lajpuk rFkk vkac/ku-I
1
lajpuk rFkk vkac/ku Structure and Bonding
1-0 izLrkouk & nqfu;k dsoy jlk;u ls gh cuh gS lcdks ekywe gS fd ge ik¡p rRo
ls cus gS] isM+] ikS/ks rFkk tho tarq] ekuo lc es jlk;fud fØ;k gh gksrh gSA dkcZfud
jlk;u esa dkcZu ds ;kSfxd ftles lgla;ksth ca/k gksrs gS] mldk v/;;u fd;k tkrk gSA
ekuo 'kjhj dh lajpuk esa T;knkrj dkckZfud jlk;u gh gksrs gSA blhfy, dkcZfud
jlk;u cgqr mi;ksxh gSA bl ,dd eas dkcZfud jlk;u ds cgqr egRoiw.kZ va’k gS]
ftldh tkudkjh ls ge dkcZfud jlk;u le> ldrs gSA dkcZu dh rhu ladj.k voLFkk
gSA dkcZu ijek.kq foHké izdkj ls tqM+dj yk[kksa ;kSfxd cukrs gSA
1-1 & ,d ,dd ds izFke Hkkx v/;;u ds i'pkr~ vki
fofHké izdkj ds vkca/k cuus ds dkj.k crk ldsaxs(
lgla;ksth vkca/k ds la;kstdrk vkca/k fl)kar dh O;k[;k dj ldsaxs(
lgla;ksthd vkca/kksa ds fn’kkRed xq.kksa dh izkxqfDr dj ldsaxs(
fofHké izdkj ds mu ladj.kksa ds chp varj Li"V dj ldsaxs] ftuesa s. p rFkk d{kd
lfEefyr gksa rFkk v.kqvksa dh vkd`fr;ksa dh vkjsf[kr dj ldsaxs(
gkbMªkstu vkca/k dh ladYiuk dh O;k[;k dj ldsaxsA
1-2 nks izdkj ds d{kd gksrs gS] ‘s’ ,oa p d{kd d{kdksa ds vfrO;kiu ds vuqlkj nks izdkj lgla;ksth vkca/k gksrs gS &
(i) flXek () vkca/k rFkk
(ii) ikbZ ()vkca/k
1-2-1 flXek () vkca/k Sigma bond & bl izdkj dk lgla;ksth vkca/k] vkca/kh
d{kdksa ds varukZfHkdh; v{k ij fljsokj (Head on) vfrO;kiu ;k v{kh; (axial) vfrO;kiu dgrs gSA bl izdkj dk vkca/k] ijek.kod d{kdksa ds fuEufyf[kr esa ls fdlh
,d izdkj ds la;kstu }kjk izkIr fd, tk ldrs gSaaA
s-s vfrO;kiu & bl izdkj ds la;kstu esa nks v/kZ Hkwr d{kd varukfHkdh; v{k ij
vfrO;kiu djrs gSA tSlk uhsps fn[kk;k x;k gSA
+
s d{kd s d{kd s-s vfrO;kiu
s-p vfrO;kiu & bl izdkj dk vfrO;kiu ,d ijek.kq dks v/kZ Hk`r s d{kd rFkk
nwljs ijek.kq dks v/kZ Hk`r p d{kd ds chp gksrk gSA
+
s d{kd p d{kd s-p vfrO;kiu
p-p vfrO;kiu & bl izdkj dk vfrO;kiu nks ijek.kqvkas ds v/kZ Hkr p d{kdksa ds
chp gksrk gSA
p d{kd p d{kd pp vfrO;kiu
1-2-2 ikbZ ¼½ vkca/k Pi bond & ikbZ vkca/k ds cuus ds vkf.od d{kd bl izdkj
vfrO;kiu djrs gSa fd muds v{k ,d nwljs ds lekarj rFkk varukZfHkdh; d{k ls yacor~
gksrs gSaA bl izdkj ik’oZ vfrO;kiu ds QyLo:i fufeZr d{kd esa ijek.kqvksa ds ry ds
Åij rFkk uhsps nks IysVuqek vkosf’kr vHkz gksrs gSaA
lajpuk rFkk vkac/ku-I
2
+ vFkok
p d{kd p d{kd pp vfrO;kiu
ewyr% vkca/k dh izcyrk vfrO;kiu dh lhek ij fuHkZj djrh gSA flXek vkca/k esa d{kdksa
dk vfrO;kiu vf/kd gksrk gSA blfy, flXek vkca/k] ikbZ vkca/k ¼ftlesa de vfrO;kiu
gksrk gS½ dh rqyuk esa vf/kd izcy gksrk gSA blds vykok ;g tkuuk Hkh egRoiw.kZ gS fd
nks ijek.kqvksa ds chp ikbZ vkca/k dHkh vdsyk ugha ik;k tkrk gSA ;g lnSo flXek vkca/k
ds lkFk gh gksrk gSA ;g lnSo mu v.kqvksa esa ik;k tkrk gS] ftuesa f}vkca/k ;k f=vkca/k
mifLFkr gksrs gSaA
tc nks ijek.kq ikl vkrs gSa] rc muds d{kdksa esa vfrO;kiu gksrk gSA ;g
vfrO;kiu d{kdksa ds xq.kksa ds vuqlkj /kukRed] _.kkRed ;k 'kwU; gks ldrk gSaA s rFkk
p ijek.kq d{kdksa dh fofHké voLFkk,¡] ftuds QyLo:i /kukRed ;k _.kkRed ;k 'kwU;
vfrO;kiu gksrk gSa] fp= 1-1 esa n’kkZbZ xbZ gSA
lgla;ksth vkca/k ds fojpu ds eq[; dkjd ds :i esa vfrO;kiu dh dlkSVh
leukfHkdh; fo"keukfHkdh; f}ijek.kqd v.kqvksa rFkk cgqijek.kqd v.kqvksa ij leku :i ls
/kukRed vfrO;kiu _.kkRed vfrO;kiu
ppz
(a)
ppz
(e)
p
z
s (b)
p
z
s (f)
p
z
p (c)
p
z
p (g)
z
pp
z
pp
(d) 'kwU; vfrO;kiu (h)
z
s
p (i)
z
pp (j)
fp=&1-1 % s rFkk p ijek.kq d{kdksa ds /kukRed] _.kkRed rFkk 'kwU; vfrO;kiuA
lajpuk rFkk vkac/ku-I
3
ykxw gksrk gSA blds vfrfjDr CH4, NH3 rFkk H2O tSls cgqijek.kqd v.kqvksa dh
vkdfr;ksa dks la;kstdrk vkca/k fl)kar ds vk/kkj ij Li"V djuk vko’;d gSA ge tkurs
gSa fd CH4, NH3 rFkk H2O v.kqvksa dh vkd`fr Øe’k% prq"Qydh; fijkfeMh rFkk eqM+h
gqbZ gksrh gSA vr% ;g tkuuk jkspd gksxk fd D;k bu T;kferh; vkd`fr;ksa dks d{kd
vfrO;kiu ds vk/kkj ij Li"B fd;k tk ldrk gSA
loZizFke ge eSFksu (CH4) ds v.kq ij fopkj djrs gSA ryLFk voLFkk
(Ground State) esa dkcZu dk bysDVªkWu foU;kl 1s2
2s2 2p
2 gS] tks mÙksftr voLFkk esa
2 1 1 1 11 2 2 2 2x y zs s p p p gks tkrk gSA blds mÙkstu ds fy, vko’;d ÅtkZ dh iwfrZ
ladfjr d{kdksa rFkk gkbMªkstu ds chp vfrO;kiu ds QyLo:i eqDr vfrfjDr ÅtkZ ls
gksrh gSA dkcZu ds pkj ijek.kq d{kd] ftuesa ls izR;sd esa ,d v;qfXer bysDVªkWu
mifLFkr gksrk gSA ftlesa pkjksa HCH dks.k prq"Qydh; gksrs gSa rFkk izR;sd dk eku
109-5o gksrk gSA blls Li"V gksrk gS fd dsoy d{kdksa ds vfrO;kiu ds vk/kkj ij CH4
ds vkca/kksa ds fn’kkRed xq.kksa dks Li"V ugha fd;k tk ldrk gSA
1-3 ladj.k ds egRoiw.kZ y{k.k & ladj.k ds eq[; y{k.k bl izdkj gSa &
1- ladj d{kdksa dh la[;k ladj.k dh izfØ;k esa Hkkx ysus okys d{kdksa dh la[;k ds
cjkcj gksrh gSA
2- ladj d{kd lnSo leku ÅtkZ ds gksrs gSaA
3- ladj d{kd LFkk;h vkca/k esa 'kq) d{kdksa dh vis{kk vf/kd l{ke gksrs gSaA
4- ladj d{kd LFkk;h O;oLFkk ikus ds fy, f=foe esa fof’k"V fn’kkvksa esa funsZf’kr gksrs gSaA
blfy, ladj.k dk izdkj v.kq dh T;kfefr n’kkZrk gSA
5- ijek.kq ds la;kstdrk d{k ds d{kd ladfjr gksrs gSaA
6- ladfjr gksus okys d{kdksa dh ÅtkZ yxHkx leku gksuh pkfg,A
7- ladj.k ds fy, bysDVªku dk mÙkstu vko’;d ugha gSaA
8- ;g vko’;d ugh gS fd dsoy v/kZ&Hk`r d{kd gh ladj.k esa Hkkx ysaA dHkh&dHkh
la;kstdrk d{k ds iw.kZ Hkwr rFkk [kkyh d{kd Hkh ladfjr gks ldrs gSaA
s rFkk p d{kdksa ds ladj.k fuEufyf[kr izdkj ds gksrs gSa &
1.3.1 sp ladj.k bl izdkj ds ladj.k esa ,d s rFkk ,d p d{kd ladfjr gksdj nks
leku sp ladj d{kdks dk fuekZ.k djrs gSaA z&v{k ij ladj.k d{kdksa dks ikus gsrq] sp
ladj.k ds fy, s rFkk pz d{kd mi;qDr gksrs gSaA izR;sd sp ladj d{kd esa 50%
s&y{k.k rFkk 50% p&y{k.k gksrk gSA ;fn fdlh v.kq esa dsaUnzh; ijek.kq ds la;kstdrk
d{k ds d{kd sp ladfjr gksrs gSa rFkk nks ijek.kqvksa esa vkca/k cukrs gSa] rks v.kq dks
jSf[kd T;kfefr gksrh gSA bl izdkj ds ladj.k dks ^fod.kZ ladj.k* Hkh dgrs gSaA
sp ladj d{kdksa ds nks mHkjs gq, /ku yksc ¼ikfy½ rFkk vR;ar NksVs _.k yksc
foijhr fn’kkvksa esa z-v{k dh vksj n`"V gksrs gSaA blds dkj.k izHkkoh vfrO;kiu gksrk gS]
ftlds QyLo:i izcyrj vkca/k fufeZr gksrs gSaA
C C
H 1s H 1s
sp sp
C
C
2py
2py
2px2px
(a) (b)
lajpuk rFkk vkac/ku-I
4
H
H
C
C
(c)
fp=&1-2 % ,Fkkbu esa flXek rFkk ikbZ vkca/kksa dk cuuk
sp ladj.k okys v.kqvksa ds mnkgj.k
C2H2 esa sp
ladj.k & ,Fkkbu v.kq ds cuus esa nksuksa dkcZu ijek.kq sp ladj.k n’kkZrs
gSA muij nks&nks vladfjr rFkk (2py d{kd 2px) d{kd gksrs gSA
,d dkcZu ijek.kq dk sp ladj d{kd nwljs dkcZu ijek.kq ds sp ladj d{kd ls
v{kh; vfrO;kiu }kjk C – C flXeksa vkca/k cukrk gSA cps gq, ladj d{kd gkbMªkstu ds
v/kZ&Hk`r 1s d{kdksa ls v{kh; vfrO;kiu }kjk flXek vkca/k cukrs gSaA nksuks dkcZu
ijek.kqvksa ij mifLFkr nks&nks vladfjr d{kd ik’oZ vfrO;kij }kjk nks ikbZ vkca/k cukrs
gSaA bl izdkj bFkkbu esa nks dkcZu ijek.kqvksa ds chp mifLFkr f= vkca/k] ,d flXek
rFkk nks ikbz vkca/kks la cuk gksrk gS] tSlk fp= 1-2 esa n’kkZ;k x;k gSA
X
Y
z
X
Y
z
180
z
jSf[kd
¼d½ sp ladj
d{kd
fp=&1-3 % ¼d½ s rFkk p d{kdksa }kjk sp ladj d{kdksa dk fuekZ.k
1.3.2 sp2 ladj.k & bl izdkj ds ladj.k esa ,d s d{kd rFkk nks p d{kd ladfjr
gksdj rhu leku sp2 ladj d{kdksa dk fuekZ.k djrs gSaA
(s+px+pz)
z
120o
ladjsp2
fp=&1-4 % sp2 ladj d{kdksa dk fuekZ.k
C2H4 esa sp
2 ladj.k & ,Fkhu v.kq ds cuus esa dkcZu ijek.kq dk ,d sp2
ladj d{kd
ls v{kh; vfrO;kiu }kjk C – C flXek vkca/k cukrk gS] tcfd izR;sd dkcZu ijek.kq ds
vU; nks sp2
ladj d{kd gkbMªkstu ijek.kqvksa ds lkFk sp2
– S flXek vkca/k cukrs gSaA
,d dkcZu ijek.kq dk vladfjr d{kd 2px vFkok 2py
nwljs dkcZu ijek.kq ds leku
d{kd ds lkFk ik’oZ (Sidewise) vfrO;kiu }kjk nqcZy vkca/k cukrk gSa ftlesa dkcZu
rFkk gkbMªkstu ijek.kqvksa ds ry ds Åij rFkk uhps leku bysDVªkWu vHkz gksrk gSA
lajpuk rFkk vkac/ku-I
5
,Fkhu v.kq esa C – C ds e/; ,d sp2 – sp
2 ladfjr d{kdksa esa flXek ()
vkca/k rFkk ,d ikbZ vkca/k ¼ftldh yackbZ 134 pm gksrh gS] tks p d{kdksa ds e/; gksrk gS½
ladj.k esa iz;ksx ugh gksrs ,oa v.kq ds ry ds yacor gksrs gSaA C–H vkca/k esa (sp2–s)
flXek () vkca/k dh yackbZ 108 pm gksrh gSa H–C–H ,oa H–C–C vkca/k dks.k Øe’k%
117-6 o 121
o gksrk gSA
,Fkhu v.kq esa flXek () ,oa ikbZ () vkca/kksa dk cuuk fp= 1-4 rFkk 1-5 esa
n’kkZ;k x;k gSA
CC
H
H
H
H
2p
H H
HH
¼[k½ ¼x½
2p
CC
H
HH
H
CC
H
H
H
H
2p2p
¼?k½ ¼M½
fp=&1-5 % ,Fkhu esa flXek rFkk vkca/kksa dk cuuk
1.3.3 (III) sp3 ladj.k & bl izdkj ds ladj.k dh O;k[;k CH4 v.kq ds mnkgj.k
}kjk dh tk ldrh gSA blesa lgla;ksth d{k ds ,d s d{kd rFkk p d{kdksa ds ladj.k
ls pkj sp3 ladj d{kd curs gSaA ;s d{kd leku ÅtkZ rFkkk vkdkj ds gksrs gSaA izR;sd
sp3 d{kd esa 25% s y{k.k rFkk 75% p-y{k.k gksrk gSA sp
3 ladj.k }kjk izkIr pkj
sp3 ladj d{kd prq"kQyd ds pkj dksuksa dh vksj gksr gSA tSlk fp= 1-7 esa n’kkZ;k x;k
gSa] sp3 ladj d{kdksa ds chp dks.k dk eku 109.5
o gksrk gSA
C2H6 v.kq esa sp
3 ladj.k & baFksu ds v.kq esa dkcZu ds nksuks dkcZu sp3
ladfjr gksrs
gSaA dkcZu ijek.kq ds pkj sp3
ladj d{kdksa esa ijek.kq ls ,d] vU; dkcZu ijek.kq ds ,d
sp3
ladj d{kd esa v{kh; vfrO;kiu }kjk sp3
– sp3 flXek vkca/k cukrs gSa] tcfd
izR;sd dkcZu ijek.kq ds vU; rhu sp3
ladj d{kd gkbMªkstu ijek.kqvksa ds 1s d{kdks ds
lkFk sp3
– s flXek vkca/k cukrs gSA blds ifj.kkeLo:i bFksu esa C – C
vkca/k yackbZ
154 pm vkSj C – H vkca/k yackbZ 109pm
gksrh gSA
C CH H
H 1s H 1s
H 1sH 1s
¼d½ fp=&1-6 % ,Fkhu esa flXek rFkk vkca/kksa dk cuuk
lajpuk rFkk vkac/ku-I
6
C
CH4
y
z
x
s+px+py+pz
109.5o
+
+
+
+
ladjsp3
+ H+H
+
+
H
H
v.kq
fp=&1-7 % dkcZu ds s, px, py vkSj pz ijek.kq d{kdksa ds lfEeJ.k ls sp3 ladj
d{kdksa dk fuekZ.k rFkk CH4 dk fojpuA
1-4-1 vkca/k yEckbZ Bond length
fdlh v.kq esa vkcaf/kr ijek.kqvksa ds ukfHkdks ds chp lkE;koLFkk nwjh ^vkca/k yackbZ*
dgykrh gSA vkca/k yackbZ LisDVªeh] ,Dl fdj.k foorZu rFkk bysDVªku foorZu (Electron
Diffraction) fof/k;ksa dh lgk;rk ls Kkr dh tkrh gSaA bu rduhdksa dk v/;;u vki
mPp d{kkvksa esa djsaxsA vkcaf/kr ;qXe dk izR;sd ijek.kq vkca/k yackbZ esa ;ksxnku nsrk gS
¼fp= 1-8½A lgla;ksth vkca/k esa izR;sd ijek.k dk ;ksxnku ml ijek.kq dh ^lgla;ksth
f=T;k* dgykrh gSA
vkcaf/kr voLFkk esa fdlh ijek.kq ds ØksM] tks layXu ijek.kq ds ØksM ds laidZ esa
gksrk gS] fd f=T;k mldh lgl;aksth f=T;k ekuh tkrh gSA lgla;ksth f=T;k ,d gh
v/kq esa vkcaf/kr nks le:i ijek.kqvksa ds chp dh nwjh dk vk/kk Hkkx gksrh gSA okaMjoky
rBrA
A B
fp=&1-8 % lgla;ksth v.kq AB esa vkca/k yackbZ R = rA + rB tgk¡ R vkca/k yackbZ gS
rFkk rA o rB Øe’k% A o B ijek.kqvksa dh lgla;ktsh f=T;k,¡ gSaA
f=T;k vukcaf/kr voLFkk esa la;ksth dks’k lfgr ijek.kq dk lexz vkdkj fu:fir djrh
gSA okaMjoky f=T;k Bksl voLFkk esa fofHké v.kqvksa ds nks le:i ijek.kqvksa ds chp dh
nwjh dk vk/kk Hkkx gksrh gsA Dyksjhu v.kq ds fy, lagla;ksth rFkk okaMj oky f=T;kvksa dks
fp= 1-9 esa n’kkZ;k x;k gSA
lajpuk rFkk vkac/ku-I
7
360 pm
rvdw 180 pm
rc = 99 pm
198 pm
fp=&1-9 % Dyksjhu ds v.kq gsrq lgla;ksth ,oa okaMjoky f=T;k,¡A vanj ds o`r Dyksjhu
ds ijek.kq dk vkdkj bafxr djrs gSaA rc ,oa rvdw Øe’k% okaMjoky vkSj
lgla;ksth f=T;k,¡ n’kkZrs gSaA
dqN ,dy] f} rFkk f= vkca/kksa dh vkSlr yackb;k¡ lkj.kh&v eas nh xbZ gSaA dqN
lkekU; v.kqvksa dh vkca/k yackb;k¡ lkj.kh&c esa nh xbZ gSa] tcfd dqN lkekU; rRoksa dh
lgla;ksth f=T;k,¡ lkj.kh&l esa Øec) dh xbZ gSA
lkj.kh v & dqN ,dy] f} rFkk f= vkca/kksa dh vkSlr yckb;k¡
vkca/k dk izdkj lgla;ksth vkca/k yackbZ
(pm)
O – H 96
C – H 107
N – O 136
C – O 143
C – N 143
C – C 154
C = O 121
N = O 122
C = C 133
C = N 138
C N 116
C C 120 lkj.kh c & dqN lkekU; v.kqvksa dh vkca/k yackb;k¡
v.kq vkca/k yackbZ
(pm)
H2 (H – H) 74
F2 (F – F) 144
Cl2 (Cl – Cl) 199
Br2 (Br – Br) 228
I2 (I – I) 267
M2 (N N) 109
O2 (O = O) 121
HF (H – F) 92
HCl (H – C) 127
HBr (H – Br) 141
HI (H – I) 160
lajpuk rFkk vkac/ku-I
8
lkj.kh l & lg la;ksth f=T;k,¡ * rcov/(pm)
H 37
C 77(1) N 71(1) O 66(1) F 64
67(2) 65(2) 57(2) Cl 99
60(3) 55(3)
P 110 S 104(1) Br 114
95(2)
As 121 Se 104 1 133
Sb 141 Te 137
*fn, x, eku ,dy vkca/kksa ds fy, gSA vU; izdkj ds vkca/kksa dks dks"Bd esa n’kkZ;k x;k gSA
1-4-2 vkca/k dks.k Bond Angle
fdlh v.kq ds dsUnzh; ijek.kq ds vklikl mifLFkr vkca/ku bysDVªkWu ;qXe dks
/kkj.k djus okys vkWfcZVyksa ds chp cuus okys dks.k dks ^vkca/k dks.k* dgrs gSaA vkca/k
dks.k dks fMxzh ds :i esa O;Dr fd;k tkrk gS rFkk izk;ksfxd rkSj ij LisDVªeh fof/k;ksa }kjk
Kkr fd;k tkrk gSA vkca/k dks.k v.kq ds dsUnzh; ijek.kq ds vklikl vkWfcZVyksa ds forj.k
dh tkudkjh nsrk gSA vr% blls ges v.kq@tfVy vk;u dh vkd`fr dks Kkr djus es
lgk;rk feyrh gSA tSls ty ds v.kq esa H – O – H vkca/k dks.k dk bl izdkj
fu:fir fd;k tkrk gSA
O
H H
::
104.5o
1-4-3 vkca/k ÅtkZ Bond Energy
xSlh; fLFkfr esa nks ijek.kqvksa ds chp fof’k"V vkca/kksa ds ,d eksy rks rksM+us ds
fy, vko’;d ÅtkZ dks ^vkca/k ,aFkSYih* dgrs gSaA vkca/k ,aFkSYih dk ek=d kJ mol–1
gksrk gSA mnkgj.kkFkZ gkbMªkstu ds v.kq esa H–H vkca/k dh vkca/k ,FkSYih 435.8 kJ
mol–1
gksrh gS] vFkkZr~
H2(g) H(g) + H(g) : aH = 435.8 kJ mol–1
blh izdkj cgqvkca/ku okys ijek.kqvksa ¼tSls O2 rFkk N2½ ds fy, vkca/k ,FkSYih
gksxh
O2 (O = O) (g) O(g) + O(g) : aH = 498 kJ mol–1
N2 (N = N) (g) N(g) + N(g) : aH = 946.0 kJ mol–1
;g rF; egRoiw.kZ gS fd ;fn vkca/k fo?kVu ,aFkSYih vf/kd gS] rks vkca/k vf/kd
izcy gksxkA HCl tSls ,d fo"ke ukfHkdh; f}ijek.kqd v.kq ds fy,
HCl (g) H(g) + Cl(g) : aH = 431.0 kJ mol–1
cgqijek.kqd v.kqvksa esa vkca/k lkeF;Z dk fu/kkZj.k vf/kd tfVy gksrk gSA
mnkgj.kkFkZ H2O v.kq esa nks O – H vkca/kksa ds fo{Nsnu gsrq vko’;d ÅtkZ leku ugha
gSA
H2O(g) H(g) + OH(g) : aH1 = 502 kJ mol–1
OH(g) H(g) + O(g) : aH2 = 427 kJ mol–1
lajpuk rFkk vkac/ku-I
9
H ekuksa esa varj ;g n’kkZrk gS fd ifjofrZr jklk;fud ifjfLFkfr ds dkj.k
f}rh; O – H vkca/k esa dqN ifjorZu vkrk gSA ;gh dkj.k O – H gS fd vkca/k dh
,aFkSYih fofHké v.kqvksa ¼tSls C2H5OH ,sFksukWy½ rFkk ty esa fHké gksrh gSA blhfy,
cgqijek.kqd v.kqvksa esa ek/; vFkok vkSlr vkca/k ÅtkZ uked in dk iz;ksx fd;k tkrk gSA
bls izkIr djus ds fy, dqy vkca/k fo;kstu ,FkSYih ds eku dks foPNsfr vkca/kksa dh la[;k
}kjk foHkkftr fd;k tkrk gSA
mnkgj.k ds fy, ty v.kq esa O – H vkca/k dh vkSlr vkca/k ,aFkSYih
1502 427
464.52
kJ mol
1-4-4 vkca/k dksfV (Bond order)
vkca/k dksfV dks vkca/kh vkf.od d{kdksa ,oa izfr vkca/kh vkf.od d{kdksa esa
mifLFkr bysDVªkWuksa dh la[;k ds varj ds vk/ks ds :i esa ifjHkkf"kr fd;k tkrk gS &
vkca/k dksfV 1
2b aN N
vkca/k dksfV fdlh v.kq esa mifLFkr lgla;ksth vkca/k dh la[;k crkrh gSA
vkca/k dksfV ls vkca/k dh izd`fr rFkk yackbZ dh tkudkjh izkIr gksrh gSA
lgla;ksth vkca/k dh ywbl O;k[;k ds vuqlkj fdlh v.kq esa nks ijek.kqvksa ds
e/; vkca/kksa dh la[;k vkca/k dksfV (Bond Order) dgykrh gSA mnkgj.k d fy, H2
¼ftlesa ,d lgHkkftr bysDVªkWu ;qXe gS½] O2 (ftlesa nks lgHkkftr bysDVªkWu ;qXe gksrs
gSa½ rFkk N2 (ftlesa rhu lgHkkftr bysDVªkWu ;qXe gksrs gSa½ ;s vkca/k dksfV Øe’k% 1] 2 rFkk
3 gSA blh izdkj CO esa tgk¡ ij dkcZu rFkk vkWDlhtu ds chp rhu lgHkkftr ;qXe gSa]
vkca/k dksfV 3 gSA N2 dh vkca/k dksfV 3 gS rFkk bldk aH eku 946 kJ mol–1
gSA tks
fdlh f} ijek.koh; v.kq ds fy, lokZf/kd gSA
lebysDVªkWuh v.kqvksa rFkk vk;uksa esa vkca/k dksfV leku gksrh gSA mnkgj.k ds fy,
F2 rFkk O2 esa vkca/k dksfV 1 rFkk 2 gSA
blh izdkj N2, CO rFkk NO+ dh vkca/k dksfV 3 gSA v.kqvksa ds LFkkf;Ro dks
le>us ds fy, ,d mi;ksxh lkekU; lglaca/k ;g gS fd vkca/k dksfV c<+us ij vkca/k
,FkSYih c<+rh gS] tcfd vkca/k yackbZ ?kVrh gSA
1-4-5 vuqukn lajpuk,¡
izk;ksfxd fu/kkZfjr izkpyksa (Parameters) ds lanHkZ esa fdlh v.kq ds fu:i.k ds
fy, ,d ywbl lajpuk dbZ ckj i;kZIr ugha gksrh gSA mnkgj.kkFkZ vkst+ksu v.kq dks
fuEufyf[kr lajpukvksa ¼I o II½ }kjk leki :i ls fu:fir fd;k tk ldrk gSA
lajpuk rFkk vkac/ku-I
10
O
O O
..
:: ::..
O
O O
..
::..
..
..
O
O O
148 pm 121 pm121 pm
148 pm
III
III
148 pm128 pm
fp=&1-10 % O3 v.kq dh vuqukn lajpuk,¡
1.4.5.1 CO2 v.kq dh lajpuk
CO2 ds v.kq esa dkcZu vkWDlhtu vkca/k dh yackbZ dk izk;ksfxd eku 115 pm
gSA f}&vkca/k (C=O) rFkk dkcZu&vkWDlhtu f=vkca/k (C=O) dh yackb;k¡ Øe’k%
121pm rFkk 110 pm gSaA CO2 esa dkcZu&vkWDlhtu vkca/k dh yackbZ (115pm),
(C=O) rFkk (C=O) dh lkekU; yackb;ksa ds chp gksrh gSA blls ;g Li"V gksrk gS fd
CO2 v.kq dh okLrfod lajpuk dks dsoy ,d ywbl lajpuk ds vk/kkj ij iznf’kZr ugha
fd;k tk ldrkA vr% ;g vko’;d gks tkrk gS fd blds fy, ,d ls vf/kd ywbl
lajpuk,¡ fy[kh tk,¡ rFkk CO2 dh lajpuk dks bu fofgr lajpukvksa ¼I, II rFkk III½ ds
ladj ds :i esa iznf’kZr fd;k tk,A
:O :::
.. ..
C :: C : O+
::..
..O C :. :. :O
+:.:. C ::
..
..O I II III
fp=&1-11 % CO2 v.kq eas vuqukn lajpuk,¡ I., II rFkk III rhu fofgr lajpukvksa dks
n’kkZrs gSaA
vuqukn v.kq dks LFkkf;Ro iznku djrk gS] D;ksafd vuqukn ladj dh ÅtkZ fdlh Hkh
fofgr lajpuk dh ÅtkZ ls de gksrh gSA
vuqukn ds dkj.k vkca/kksa ds y{k.k vkSlr eku izkIr djrs gSaA bl izdkj O3 v.kq esa
vuqukn ladj :i III dh ÅtkZ] dsukfudy :i I rFkk II dh ÅtkZ ds eku ls Hkh
de gksrh gSA
vuqukn ladYiuk ls lacaf/kr dbZ Hkzk¡fr;k gSa] ftudk fuokj.k vko’;d gSA vkidks Lej.k
jgs fd &
okLro esa fofgr lajpukvksa dk dksbZ vfLrRo ugha gksrk gSA
,slh ugh gksrk fd v.kq dqN le; ds fy, fdlh fofgr lajpuk ds :i esa mifLFkr
jgrk gS] tcfd vU; le; fdlh nwljh fofgr lajpuk dks viukrk gSA
fofgr lajpukvksa ls pyko;oksa ¼dhVks rFkk bukWy½ ds e/; ike, tkus okys lkE; tSlk
dksbZ lkE; ugha gksrk gSA
okLrfod :i esa v.kq dh dsoy ,d lajpuk gksrh gS] tks fofgr lajpukvksa dh
vuqukn ladj gksrh gS] tks fofgr lajpukvksa dh vuqukn ladj gksrh gSA mls dsoy
,d ywbl lajpuk }kjk iznf’kZr ugha fd;k tk ldrk gSA
fdlh vkca/k dk lkS izfr’kr vk;fud ;k lgla;ksth gksuk ,d vkn’kZ fLFkfr gSA ijarq okLro
esa dksbZ Hkh vkca/k ;kSfxd iw.kZ :i ls lgla;ksth ;k vk;fud ugha gksrk gSA ;gk¡ rd fd
nks gkbMªkstu ijek.kqvksa ds chp cuus okys lgla;ksth vkca/k dh izd`fr Hkh vkaf’kd :i ls
vk;fud gksrh gSA
lajpuk rFkk vkac/ku-I
11
CH4, NH3 rFkk H2O tSls cgqijek.kqd v.kqvksa esa vkca/k cuus ds e/; lkFk
v.kq dh T;kfefr Hkh egRoiw.kZ gksrh gSA mnkgj.k ds fy, CH4 ds v.kq dh vkd`fr
prq"Qydh; D;ks gksrh gS vkSj HCH vkca/k dks.k dk eku 109o.5
o D;ks gksrk gS\ vFkok
NH3 v.kq dh vkd`fr fijkfeMh D;kas gksrh gS\
^la;kstdrk vkca/k fl)kar* ds vk/kkj ij CH4, NH3, H2O vkfn cgqijek.kqd
v.kqvksa esa vkca/k fojpu rFkk muds fn’kkRed xq.kksa dks ijek.kq d{kdksa ds ladj.k rFkk
vfrO;kiu dh lgk;rk ls Li"V fd;k tk ldrk gSA
1-4-6 gkbMªkstu ca/k Hydrogen bond
ukbVªkstu] vkWDlhtu rFkk ¶yqvksjhu ;s rhu vR;f/kd fo|qr _.kkRed rRo tc ijek.kq
lgla;kstd vkca/k }kjk gkbMªkstu ijek.kq ls tqM+s gksrs gS] rc lgla;ksth vkca/k ds
bysDVªku vf/kd fo|qr _.kkRed rRo dh vksj LFkkukarfjr gks tkrs gSaA QyLo:i izkIr
vkaf’kd /kukosf’kr gkbMªkstu ijek.kq fdlh nwljs fo|qr _.kkRed ijek.kq ds lkFk ,d u;k
vkca/k cukrk gSA bl vkca/k dks ^gkbMªkstu vkca/k* dgrs gSaA ;g vkca/k lgla;ksth vkca/k
ls nqcZy gksrk gSA mnkgj.kkFkZ HF esa ,d v.kq ds gkbMªkstu ijek.kq rFkk nwljs v.kq ds
¶yqvksjhu ijek.kq ds chp gkbMªkstu vkca/k curk gSA bl bl izdkj n’kkZ;k tk ldrk gSA
…..…H
– F
…..…H
– F
…..…H
– F
;gk¡ ij gkbMªkstu vkca/k nks ijek.kqvksa ds chp ,d lsrq dk dk;Z djrk gS] tks
,d ijek.kq dks lgla;kstd vkca/k rFkk nwljs dks gkbMªkstu vkca/k }kjk tksM+dj j[krk gSA
gkbMªkstu vkca/k dks MkWVsM js[kk ¼---------½ }kjk n’kkZrs gSa] tcfd lgla;kstu vkca/k dks Bksl
js[kk ¼&½ }kjk n’kkZrs gSaA bl izdkj gkbMªkstu vkca/k dks ml vkd"kZ.k cy ds :i esa
ifjHkkf"kr fd;k tk ldrk gS] tks ,d v.kq ds gkbMªkstu ijek.kq dks nwljs v.kq ds fo|qr
_.kkRed ijek.kq ¼F, O ;k N½ ls cka/krk gSA
tc gkbMªkstu ijek.kq fdlh izcy fo|qr _.kkRed rRo ‘X’ ls vkcaf/kr gksrk gS]
tks lgHkkftr bysDVªkWu ;qXe gkbMªkstu ijek.kq ls nwj gks tkrk gSA ifj.kkeLo:i
gkbMªkstu ijek.kq nwljs ijek.kqvksa ‘X’ ds lkis{k vR;f/kd fo|qr /kukRed gks tkrk gSA
pw¡fd bysDVªkWu ‘X’ ijek.kq dks vksj LFkkukarfjr gks tkrs gS] blfy, gkbMªkstu ijek.kq
/kukRed vkos’k () xzg.k djrk gS] tcfd ‘X’ ijek.kq ij vkaf’kd _.kkRed vkos’k
() vk tkrk gSA blls ,d f}/kqzoh v/kq izkIr gksrk gS] ftlds chp fLFkj oS|qr cy gksrk
gSA bls bl izdkj n’kkZ;k tk ldrk gSA
+ - +
H X......H X......H X
gkbMªkstu vkca/k dk ifj.kke ;kSfxd dh HkkSfrd voLFkk ij fuHkZj djrk gSA
Bksl voLFkk esa ;g vf/kdre gksrk gS rFkk xSlh; voLFkk es aU;wureA bl rjg ls
gkbMªkstu vkca/k ;kSfxdksa dh lajpuk rFkk xq.k/keksZ dks izcyrk ls izHkkfor djrs gSaA
gkbMªkstu vkca/k nks izdkj ds gksrs gs &
(i) varj&v.kqd gkbMªkstu vkca/k
(ii) varjk&v.kqd gkbMªkstu vkca/k
(i) varj&v.kqd gkbMªkstu vkca/k & ;s vkca/k leku vFkok fofHké ;kSfxdksa ds nks
vyx&vyx v.kqvksa ds chp curs gSaA mnkgj.kkFkZ& HF v.kq] ,YdksgkWy ;k ty ds
v.kqvksa ds chp gkbMªkstu vkca/kA
(ii) varjk&v.kqd gkbMªkstu vkca/k & ;s vkca/k ,d gh v.kq esa mifLFkr
gkbMªkstu ijek.kq rFkk vf/kd fo|qr _.kkRed ijek.kq (F,O,N) ds chp curk gSA
mnkgj.kkFkZ& o-ukbVªksfQukWy esa gkbMªkstu] tks vkWDlhtu ds e/; jgrk gSaA
lajpuk rFkk vkac/ku-I
12
OH
N
O
O
fp=&1-12 % o&ukbVªksfQukWy v.kq esa varj v.kqd gkbMªkstu vkca/k
1-4-7 ok.Mj okYl vU;ksU; fØ;k,¡ VANDER WAALS
INTERACTIONS
ok.Mj okYl cy lgla;kstd v.kqvksa ;k ijek.kqvksa ds e/; yxus okys nqcZy
vkd"kZ.k cy gksrs gSa tks jklk;fud vkca/k dh vuqifLFkfr esa izHkkoh gksrs gSaA ;s cy fofHké
vU;ksU; cyks ds QyLo:i mRié gksrs gSa rFkk /kqzoh; o v/kqzoh; nksuksa izdkj ds v.kqvksa
¼ijek.kqvksa o vk;uksa½ ds e/; dk;Z djrs gSaA bu vU;ksU; cyks dks ok.Mj okYl vU;ksU;
fØ;k,¡ dgrs gSaA dqN izeq[k vU;ksU; fØ;k,¡ (interactions) fuEu izdkj dh gksrh gS &
fp=&1-13 % mnklhu ijek.kq% /kukRed vkSj _.kkRed vkos’k ds dsUnz laikrh
(i) f}/kqzzo&f}/kqzo vkd"kZ.k & ;s cy ,sls v.kqvksa esa ik;s tkrs gSa ftuesa LFkk;h f}/kqzo gksrk
gS( tSls&HCl, NF3, CO, H2O vkfnA bl izdkj ds nks v.kq tc ,d&nwljs ds lEidZ
esa vkrs gSa rc bl izdkj O;ofLFkr gks tkrs gSa fd muds e/; vf/kdre vkd"kZ.k gksA bl
voLFkk esa foijhr vkosf’kr dsUnz ,d&nwljs ds fudVre gksrs gSA ;s cy eq[;r;k Bksl
voLFkk esa vkSj dqN gn rd nzo voLFkk esa ik;s tkrs gSaA
(ii) f}/kqzzo&izsfjr f}/kqzo vkd"kZ.k & tc ,d LFkk;h f}/kqzo fdlh v/kqzoh; v.kq ds fudV
vkrk gS rc og izsj.k ds }kjk v/kqzoh; v.kq esa Hkh /kqzork mRié dj nsrk gS ftlls ;g Hkh
;g f}/kqzo ds leku vkpj.k djus yxrk gSA vc ;s nksuksa f}/kqzo ,d&nwljs dks vkdf"kZr
djus yxrs gSaA ;g cy /kqzoh; foys; dk v/kqzoh; foyk;dksa esa foys;rk dk mÙkjnk;h gSA
(iii) y.Mu cy ;k rkR{kf.kd f}/kqzzo&izsfjr f}/kqzo vU;ksU; fØ;k & ;g ,d izdkj
dh nqcZy vU;ksU; cy tks v/kqzoh; v.kqvksa okyh xSlksa( tSls& H2, O2, Cl2, N2, CO2 rFkk
,d ijek.kqd mRd"V xSlksa( tSls& He, Ne, Ar vkfn esa dk;Z djrh gS vkSn budh nzo o
Bksl voLFkk ds fy, mÙkjnk;h gksrh gSA bl vU;ksU; fØ;k ds dkj.k nqcZy varjk.kqd
vkd"kZ.k cy ¼ok.Mj&okYl cy½ mRié gksrs gSa tks v/kqzoh; (non polar) v.kqvksa ds e/;
dk;Z djrs gSa vkSj mUgsa ijLij ck¡/krs gSA bldk eku 2 ls 10 kcal/mole gksrk gSA bls
rkR{kf.kd (instantaneous) f}/kzqo&izsfjr f}/kqzo vU;ksU; fØ;k rkR{kf.kd&rkR{kf.kd
vU;ksU; fØ;k Hkh dgrs gSaA
lkekU;r;k fdlh v/kqzoh mnklhu v.kq ;k ijek.kq esa /kukRed vkSj _.kkRed
vkos’k ds dsUnz laikrh (coincide) gksrs gSa ftlds dkj.k buesa dksbZ f}/kqzo vk?kw.kZ ugha
gksrk gSA vfirq fdlh Hkh {k.k bysDVªkWuksa ds ukfHkd ds pkjksa vksj lrr ;kn`fPNd xfr
(random motion) ds dkj.k bysDVªkWu vHkz esa fo:i.k (distortion) gks tkrk gS
ftlls v.kq esa /kzqork (polarity) mRié gks tkrh gSA bls rkR{kf.kd /kzqork
(instantaneous polarity) dgrs gSaA rkR{kf.kd /kzqork okyk ijek.kq ;k v.kq vius
vklikl ds nwljs v.kq esa /kzqork (polarity) izsfjr djrs gSA
lajpuk rFkk vkac/ku-I
13
1-5-1 Inclusion Compounds
tc nks ;kSfxd la;ksx djds ,slk mRikn cukrs gSa ftlesa nksuksa ;kSfxdksa dk leLr
nzO;eku fufgr jgrk gS] ,sls mRikn dks ;ksxksRikn ;k ;ksxkRed ;kSfxd (addition
compound) dgrs gSaA ;ksxkRed ;kSfxd vusd izdkj ds gksrs gSa tSls &
(i) ;ksxkRed ;kSfxd tks vkd"kZ.k cyksa ds }kjk curs gSa tSls&bysDVªku nkrk&xzkgh
ladqy ¼vkos’k LFkkukUrj.k ladqy½] Charge transfer complex, ØkÅu bZFkj
ladqy] fØIVsV vkfnA
(ii) ;ksxkRed ;kSfxd tks HkkSfrd izxzg.k ;k fiatju (trapping) ls curs gSa]
tSls&lekos’ku ;kSfxd (inclusion compounds), DySFkzsV vkfnA buesa vfHkdkjh
;kSfxdksa ds e/; dksbZ jklk;fud vkca/ku LFkkfir ugha gksrk gS] cfYd nqcZy ok.Mj
okYl cy ;k HkkSfrd izxzg.k gksrk gSA
lekos’ku ;kSfxdksa dk fuekZ.k es nks izdkj ds ;kSfxdksa ls gksrk gS ftuesa ls ,d
vfrFks; ;k gksLV (host) vkSj nwljk vfrfFk (guest) gksrk gSA vfrfFk gksLV fØLVy ds
ySfVl ds e/; fjDr LFkku esa izos’k dj tkrk gS vkSj lekos’ku ;kSfxd cukrk gSA gksLV
?kVd dh xqfgdk (cavity) dh vkdfr vkSj fnd~LFkku ds vk/kkj ij lekos’ku ;kSfxd
vusd izdkj ds gksrs gsa ftuesa ls nks izeq[k fuEufyf[kr gS &
(v) okfgdk ;k uky (channel or canal) lekos’ku ;kSfxdA
(c) DySFkzsV ;k fiatfjr (cage) lekos’ku ;kSfxdA
1-5-2 Channel or Canal Inclusion
Compounds
lekos’ku ;kSfxd os gSa ftudh okfgdk ;k dSuky ds leku vkdfr gksrh gSA
;wfj;k lekos’ku (inclusion) ;kSfxdksa dk ,d izeq[k vfrFks; (host) ;wfj;k gSA lk/kkj.k
fØLVyh; ;wfj;k f}leyack{k (tetragonal) :i esa fØLVyhd`r gksrk gS] fdUrq tc fdlh
vfrfFk dh mifLFkfr esa fØLVyhd`r gksrk gS rc ;g ,d vf/kd [kqyh gqbZ "kV~dks.kh;
ySfVl lajpuk (hexagonal lattice) ds :i esa yEch okfgdk (channel) cukdj mlds
fnd~&LFkku (space) esa vfrfFk dks ?ksjrs gq, fØLVyhdr gksrk gSA ;g ns[kk x;k gS fd
okfgdk (channel) dk O;kl djhc (5o
A ) gksrk gS fd og vius vanj dsoy lh/kh Ja[kyk
okys C6 ls mPp gkbMªksdkcZuksa ;k muds O;qRiéksa dks vius vanj lek;ksftr dj ldsA cM+s
vkdkj okys 'kkf[kr Ja`[kyk okys leko;oh bu NksVh xqfgdkvksa (cavities) esa lek;ksftr
ugha gks ikrs gSaA bl xq.k dk mi;ksx ;wfj;k ds }kjk ,sYdsyksa dk mlds 'kkf[kr Ja[kyk
okys leko;fo;ksa ls i`Fkd djus esa fd;k tkrk gSA ;wfj;k ds lekos’ku ;kSfxdksa dk mi;ksx
jsflfed feJ.k dk fo;kstu (resolution) djus ds fy, Hkh fd;k tkrk gSA tSls ( ) 2&czkseksvkWDVsu ;wfj;k ds lkFk nks fHké lekos’ku ;kSfxd cukrk gS ftudks izHkkftr fØLVy
ds }kjk i`Fkd~ dj ysrk gSA ¼fp= 1-14½
okfgdk
;wfj;k ¼vfrFks;½
n&,Ysdu
fp=&1-14 % ;wfj;k esa vfrfFk v.kq
lajpuk rFkk vkac/ku-I
14
1-5-2-1 Clatherates of cage inclusion
compounds
;g Hkh ,d izdkj ds lekos’ku ;kSfxd gSaA buesa vfrFks; v.kq (host
molecule) lhfer lkbt dk vkf.od iatj (molecular cage) cukrs gSaA bu iatjksa
esa vfrfFk v.kq (guest molecules) dSn gks tkrs gSaA vfrfFk v.kq dk lkbt bu iatjksa
ls NksVk gksrk gSA gkbMªksfDouksu rFkk vU; QhukWy DySFkzsV ;kSfxdksa dh ,d cM+h la[;k ds
fy, vfrFks; (host) ds :i esa dk;Z djrs gSaA mnkgj.kkFkZ] tc fDoukWy dk fØLVyu
gksrk gS rc blds rhu v.kq gkbMªkstu vkca/kksa ds }kjk ijLij feydj ,d iatj (cage)
dk fuekZ.k djrs gSa ftlesa vfrfFk ¼tSls&Ar, Xe, Kr vkfn½ dk ,d v.kq lek tkrk gSA
tc vf/kd nkc ij Ar, Kr ;k Xe dks fDoukWy ds tyh; foy;u esa ls izokfgr
djds mldk fØLVyu fd;k tk;s rks DysFkzsV ;kSfxd izkIr gksrs gSaA fDoukWy ds fØLVy
tkyd esa ;g xSl ¼Ar, Xe, Kr vkfn½ HkkSfrd :i ls f?kj tkrh gSA bu ;kSfxdksa esa
fDoukWy ds v.kq gkbMªkstu vkca/kksa ds }kjk fiatjkuqek lajpuk cuk ysrs gSa ftlls mlds
e/; fNnz jg tkrs gSaA bUgh fNnzksa esa mRd`"V xSl ds v.kq Q¡l tkrs gSaA vkxZu ds lkFk
cus DySFkzsV ;kSfxd Ar[C6H4(OH)2]3 dh lajpuk fp=&1-15 esa nh x;h gSA fDoykWy ds
vfrfjDr vU; inkFkks± ds v.kq] tSls&ty Hkh mRd"V xSlksa ds lkFk DySFkzsV ;kSfxd cukrk
gS] tSls Ar.6H2O, Kr.6H2O, Xe.6H2OA QhukWy&mRd`"V xSl ;kSfxd ,oa iSjk
ØhlkWy mRd`"V xSl ;kSfxd Ar.C6H5OH, (C7H8O6)6Xe Hkh DySFkzsV ;kSfxdksa ds
mnkgj.k gSaA dSuky ;kSfxdksa ds vleku buds fØLVy ySfVl esa vfrfFk ds izos’k djus ds
ckn Hkh dqN LFkku fjDr jgrk gSA ;gk¡ ij Hkh dsoy mi;qDr vkeki ds vfrfFk v.kq dh
fiatfjr (trapped) gksrs gSA
OH
O
OH
O Ar
A4 O
OHOH
H
H
fp=&1-15 % fDoukWy v.kqvksa }kjk fufeZr DySFkzsV Ar[C6H4(OH)2]3 dh lajpuk
1-5-3 Charge Transfer Complex
bysDVªkWu&lao`) (electron-rich) v.kq ¼ftls nkrk] D dgrs gS½ vkSj bysDVªkWu
U;wu (electron-poor) v.kq ¼ftls xzkgh] A dgrs gSa½ dks 1%1 ds vuqikr esa feykus ls cus
vkf.od ;ksxksRikn (molecular adducts) dks vkos’k LFkkukUrj.k ladqy dgykrs gSaA
bysDVªkWu nkrk og v.kq gksrk gS tks vukcaf/kr (non-bonding) vFkok bysDVªkWuksa dk
nku dj ldrk gS rFkk bysDVªkWu U;wu og ;kSfxd gksrk gS tks bUgsa xzg.k dj ldrk gSA ;s
ladqy fuEu vuquknh :iksa ds ladj (hybrid) ds :i esa ekus x;s gSa %
D + A D AD A
+
(I) (II)
ladqy esa lajpuk I dk ;ksxnku eq[; :i ls gksrk gSA blesa nkrk vkSj xzkgh ds
e/; QkWeZy lgla;kstd cU/k mifLFkr ugha gksrk gS rFkk bu v.kqvksa ¼D o A ds e/;½ esa
ijLij yxus okyk ca/ku cy (binding force) nqcZy dqykWeh (coulombic) cy gks
ldrk gSA nkrk vkSj xzkgh ds e/; vkd"kZ.k cyksa ds dkj.k bl izdkj LFkkfir gq,
vkcU/ku dks vkos’k&LFkkukUrj.k ladqy vU;ksU; fØ;k dgrs gSaA mnkgj.kkFkZ] eslsfVyhu vkSj
1]3]5&VªkbukbVªkscsathu ijLij la;ksx djds 1]1&LFkkukUrj.k ladqy cukrs gSaA eslsfVyhu esa
lajpuk rFkk vkac/ku-I
15
rhu&CH3 lewg gksrs gSa tks izcy $1 izHkko ds dkj.k csUthu oy; dks bysDVªkWu /kuh cuk
nsrs gSaA bls ge nkrk v.kq (D) dgrs gSaA tc ;g bysDVªkWu U;wu ;kSfxd
2]4]6&VªkbukbVªksfQukWy ds lEidZ esa vkrk gS rc vkos’k LFkkukUrj.k ladqy cu tkrk gSA
ukbVªks lewg ds izcy&I o &M izHkko ds dkj.k csathu oy; vR;Ur bysDVªkWu U;wu gks
tkrk gSA bls ge xzkgh (acceptor) v.kq dgrs gSaA _.kkosf’kr nkrk v.kq (D) ls
bysDVªkWfud vkos’k dk LFkkukUrj.k xzkgh v.kq (A) dh vksj gks tkrk gS vkSj ladqy dk
fuekZ.k gks tkrk gSA vkos’k LFkkukUrj.k ladqy dks nks izdkj dh lajpukvksa dk vuquknh
ladj ds :i esa ekurs gSaA ,d lajpuk vukca/kh (non-bonding) gS ftlesa eslsfVyhu
dh _.kkosf’kr oy; vkSj VªkbukbVªkscsathu dh /kukosf’kr oy; ijLij ok.Mj okYl cy
}kjk ca/kh gksrh gS vkSj nwljh ca/kh lajpuk D gS ftlesa mPpre Hkjs gq, &d{kdksa
(HOMO) ls bysDVªkWuksa dk LFkkukUrj.k A ds fuEure fjDr d{kdksa (LUMO) esa gks tkrk gSA
CH
3
CH3
CH3
NO2
NO2
O2N
CH3
CH3
CH3
NO2
NO2
O2N
OH OH
+
eslsfVyhu fiØfjad vEy vkos’k LFkkukUrj.k ladqy
nkrk (D) xzkgh (A) (D+, A–) ¼bysDVªkWu /kuh v.kq½ ¼bysDVªkWu U;wu½
;ksxkRed ;kSfxdksa ¼vkos’k&LFkkukUrj.k ladqy½ dk lcls izeq[k mnkgj.k fiØsV gS
tks fd fifØd vEy ¼2]4]6&VªkbukbVªksfQukWy½ dh ,sjkseSfVd gkbMªksdkcZu ds lkFk fØ;k ls
curk gSA ,sjkseSfVd gkbMªksdkcZuksa ds vfrfjDr ,sjkseSfVd ,sehu] ,fyQSfVd ,sehu] ,sYdhu
rFkk vU; ;kSfxd Hkh fifØd vEy ds lkFk bl izdkj ds ;ksxkRed ;kSfxd cukrs gSaA ;s
;ksxkRed mRikn fuf’pr xyukad okys Bksl gksrs gS ftudk mi;ksx bu ;kSfxdksa ds fiØsV
cukdj igpku djus esa dke vkrs gSA
1-5-4 izsjf.kd izHkko rFkk {ks=h; izHkko Inductive Effect and Field
Effects
lgla;kstd vkcU/k nks izdkj ds gksrs gSA ,d v/kqzoh; (non-polar) tSlk fd
gkbMªkstu (H–H) vkfn esa gksrk gS vkSj nwljk /kqzoh; (polar) tSlk fd H–Cl, CH3–Cl vkfn esa gksrk gSA /kqzoh; lgla;kstd vkca/k esa lk>s dk bysDVªkWu tksM+k nksuk sa ijek.kqvksa ds
chp esa fo|eku u jgdj ml ijek.kq dh vksj foLFkkfir gks tkrk gS tks vf/kd _.kfo|qrh
gksrk gSA bl dkj.k mPp fo|qr~ _.kkRed (electronegative) ijek.kq ij rfud _.k
vkos’k vkSj nwljs ijek.kq ij rfud /ku vkos’k mRié gks tkrk gSaA lgHkkftr bysDVªkWu tksM+s
dk mPp _.kfo|qrh1 (electronegative) ijek.kq dh vksj bl izdkj ds bysDVªku
foLFkkiu dks izsjf.kd izHkko dgrs gSaA
H : H H : Cl H3C – Cl C – Cl
Non-polar bond polar covalent bond
Cl– dh _.kfo|qr~rk dkcZu ijek.kq dh vis{kk vf/kd gS] blfy, C1–Cl vkca/k
dk bysDVªkWu ;qXe Dyksjhu dh vksj foLFkkfir gks tkrk gSA QyLo:i Dyksjhu ijek.kq
vkaf’kd _.k (negative) vkos’k;qä vkSj dkcZu ijek.kq (C1) rfud /ku vkos’k;qä gks
tkrk gSA vc pw¡fd C1 ij vkaf’kd /ku vkos’k gS] blfy, ;g C1–C2 cU/k ds bysDVªkWu
;qXe dks viuh vksj vkdf"kZr djrk gS ftlds QyLo:i C2 ij Hkh vkaf’kd /kukos’k mRié
gks tkrk gSa] fdUrq bldk eku C1 ds $ vkos’k dh vis{kk de gksxkA blh izdkj C2
/kukosf’kr gksus ds dkj.k C2–C3 cU/k ds bysDVªkWu ;qXe dks viuh vksj vkdf"kZr djrk gS
lajpuk rFkk vkac/ku-I
16
ftlds QyLo:i C3 ij Hkh vkaf’kd /kukos’k mRié gks tkrk gS ftldk eku C2 ds $
vkos’k dh vis{kk de gksrk gSA blh izdkj ;g izHkko vkxs Hkh lapkfjr gksrk gS vkSj C4 ij Hkh {kh.k lk $ vkos’k mRié gks tkrk gSA bl izdkj izsjf.kd izHkko iwjh dkcZu Ja`[kyk esa
lapkfjr (transmit) gks tkrk gS] fdUrq lzksr (source) ls tSls&tSls nwjh c<+rh gS bldk
izHkko de gksrk tkrk gSA O;kogkfjd rkSj ij bldk izHkko nwljs dkcZu ijek.kq ds ckn
lekIr gks tkrk gSA izsjf.kd izHkko dks ,d I v{kj ;k ,sls MS’k (dash) ds }kjk O;ä
djrs gSa ftlds chp esa rhj dk fpUg ( ) gksrk gSA ;g rhj de _.kfo|qrh
ijek.kq ls vf/kd _.kqfo|qrh ijek.kq dh vksj funsZf’kr jgrk gS] tSlk fd fuEu mnkgj.k esa
iznf’kZr gS &
H3C H
2C H
2C H
2C Cl
1234
n&C;wfVy DyksjkbM
– I izHkko Mkyus okys lewg ;k bysDVªkWu vkdf"kZr djus okys lewg ¼?kVrk gqvk Øe½
+ +
3 3 2 2 6 5NR NR NO SO R CN COOH F Cl Br I OR OH C H
+ I izHkko Mkyus okys lewg ;k bysDVªkWu izfrdf"kZr djus okys lewg ¼?kVrk gqvk Øe½
3 3 3 2 2 5 3O COO (CH ) C (CH ) CH C H CH
izsjf.kd izHkko ds }kjk fdlh vkca/k esa /kqzohdj.k gksrk gSa vfirq vkca/kksa ds
/kqzohdj.k esa ,d nwljk izHkko Hkh dk;Z djrk gS ftls {ks=h; izHkko (field effect) dgrs
gSaA ;g izHkko f}d LFkku (space) ;k foyk;d ds v.kqvksa ds }kjk dk;Z djrk gSaA ;s nksuksa
izHkko ¼izsjf.kd ,oa {ks=h; izHkko½ la;qDr :i ls ca/kksa ds /kzqohdj.k dks izHkkfor djrs gSaA
izsjf.kd izHkko fdlh dkcZu Ja[kyk esa vkca/kksa ds lgkjs dk;Z djrk gSa tcfd {ks=h; izHkko
fnd~&LFkku (space) ;k foyk;d ds v.kqvks ds }kjk dk;Z djrk gSA izsjf.kd izHkko vkSj
{ks=h; izHkko ds e/; varj djuk dfBu dk;Z gS vFkkZr~ ;g fuf’pr djuk eqf’dy gS fd
veqd vkcU/k ds /kzqohdj.k esa fdruk ;ksxnku izsjf.kd izHkko dk gS vkSj fdruk {ks=h; izHkko
dk gSA izsjf.kd izHkko dsoy vkca/kksa dh izd`fr ij fuHkZj djrk gS] tcfd {ks=h; izHkko v.kq
dh T;kfefr ij fuHkZj djrk gSA fups mnkgj.k esa nksuksa leko;fo;ksa esa Dyksjhu ijek.kqvksa
dk –COOH lewg ds bysDVªkWuksa ds viksgu (withdrawl) ij vFkkZr~ vEyh;rk ij
leku izHkko iM+uk pkfg, D;ksafd leko;oh I esa Dyksjhu ijek.kq lewg ds vf/kd fudV gSaA
bu nksuksa leko;fo;ksa dh vEyh;rk esa {ks=h; izHkko ds dkj.k varj gksrk gSA leko;oh I
esa _.kkosf’kr Dyksjhu (Cl–) vEy ds ,suk;u ds _.kkos’k ds vf/kd fudV gksus ds dkj.k
,suk;u dks vLFkk;h cukrk gS ftlls leko;oh I dk vEyh; y{k.k de gks tkrk gSA
leko;oh I dk pKa eku 6-07 gS] tcfd II dk 5-67 gSA
COOH
ClH
HCl
COOH
HCl
ClH
I pKa=6.07 II pKa=5.67
izsjf.kd izHkko ds leku {ks=h; izHkko Hkh egRoiw.kZ gksrk gS] rFkk ;g mldh vis{kk
vf/kd egRoiw.kZ gksrk gSA izLrqr esa vf/kdka’k izdj.kksa esa nksuksa izHkkoksa dks la;qDr :i ls
lajpuk rFkk vkac/ku-I
17
laKku esa fy;k x;k gSA izsjf.kd izHkko ds LFkku ij {ks=h; izHkko 'kCn dks iz;qDr djuk
vf/kd mi;qDr gSA
lajpuk rFkk vkac/ku-I
18
1-5-5 vuqukn fl)kar Resonance Theory
vuqukn ds izeq[k vfHkxghr (postulates) fuEufyf[kr gSaA bu vfHkxghrksa ds
vk/kkj ij ;g fuf’pr fd;k tk ldrk gS fd vHkqd ;kSfxd fdu&fdu fofgr
(canonical) ;k ;ksxnkuh lw=ksa dk vuqukn ladj gksxk rFkk vuqukn ladj esa fdl fofgr
lw= dk ;ksxnku vf/kd gksxk vkSj fdldk deA
1- tc fdlh v.kq dks nks ;k nks ls vf/kd ,sls bysDVªkWfuDl lw=ksa ds }kjk iznf’kZr fd;k
tkrk gS tks bysDVªkWuksa dh O;oLFkk esa varj j[krs gSa] rc ;g ekuk tkrk gS fd v.kq esa
vuqukn laHko gSA v.kq dks lHkh lajpukvksa dk vuqukn ladj ekuk tkrk gSA buesa ls
dksbZ Hkh lajpuk v.kq dh okLrfod lajpuk dks fu:fir ugha djrh gS fdUrq izR;sd
lajpuk vuqukn ladj ¼okLrfod lajpuk½ esa ;ksxnku nsrh gSA
2- izR;sd ;ksxnkuh lajpuk (contributing structure) esa v;qfXer bysDVªkWuksa dh la[;k
leku gksuh pkfg,A
3- ;ksxnkuh lajpuk dk LFkkf;Ro ftruk vf/kd gksrk gS mldk vuqukn ladj esa ;ksxnku
mruk gh vf/kd gksrk gS] tSls&fuEu mnkgj.k esa d¡dqys lw= dk ;ksxnku vf/kd gS]
D;ksafd ;g vf/kd LFkk;h gksrk gSA
Kekule structures Dewars structures
4- tc ;ksxnkuh lajpuk,¡ leku ;k yxHkx leku gksrh gSa rc vuqukn egRoiw.kZ gksrk gSA
5- vuquknh ladj dk LFkkf;Ro fdlh Hkh ;ksxnkuh lajpuk dh rqyuk esa vf/kd gksrk gSA
lcls vf/kd LFkk;h ;ksxnkuh lajpuk dh ÅtkZ vkSj ladj (hybrid) dh ÅtkZ ds
varj dks vuqukn ÅtkZ (resonance energy) ;k vLFkkuhdj.k ÅtkZ
(delocalization energy) dgrs gSaA
6- ;ksxnkuh lajpukvksa dh ÅtkZvksa esa ftruk de varj gksrk gS] ladj dh vuqukn ÅtkZ
mruh vf/kd gksrh gSA
7- /kqzoh; lajpukvksa ¼vk;fud lajpukvksa½ dk LFkkf;Ro v/kzqoh; lajpukvksa dh rqyuk esa
de gksrk gS blfy, ladj esa budk ;ksxnku de gksrk gSA
8- ftl ;ksxnkuh lajpuk ¼dSuksfudy lw=½ esa ca/kksa dh la[;k ftruh vf/kd gksrh gS
mldk LFkkf;Ro mruk gh vf/kd gksrk gSA
9- fdlh ladj v.kq ds fy, ftrus vf/kd la;kstdrk cU/k lw= fy[ks tk ldrs gSa mldk
LFkkf;Ro mruk vf/kd gksxkA
1-5-5-1 (i) vkcU/k yEckbZ Bond length de gksrh gS & vuquknh ladj ¼okLrfod lajpuk½ esa vkcU/k yEckbZ dSuksfudy lw= }kjk visf{kr
vkcU/k yEckbZ ls de gksrh gSA mnkgj.kkFkZ] ,fFky DyksjkbM esa C–Cl vkcU/k yEckbZ
1.76o
A (176pm) gksrh gS] fdUrq vuqukn ds dkj.k foukby DyksjkbM esa ;g nwjh
1.72o
A (172pm) gksrh gSA
1-5-5-2 vuquknh ÅtkZ Resonance Energy dh mifLFkfr&vuquknh gkbfczM dh
ÅtkZ lcls vf/kd LFkk;h dSuksfudy lw= }kjk x.kuk dh x;h ÅtkZ ls de gksrh gSA
nksuksa ÅtkZvksa ds varj dks vuquknh ÅtkZ dgrs gSaA ;g ÅtkZ dh og ek=k gS tks rc u"V
gksrh gS tc dSuksfudy lw= ladj :i xzg.k djrk gSA vr% fdlh v.kq ds cuus dh
okLrfod Å"ek dSuksfudy lw= }kjk x.kuk dh x;h Å"ek ls de gksrh gSA mnkgj.kkFkZ]
CO2 ds cuus dh okLrfod Å"ek 300 kcal/mole gS] fdUrq lw= (O=C=O) ds vuqlkj
dkcZu MkbvkWDlkbM ds cuus dh Å"ek 336 kcal/mole gksrh gSA
lajpuk rFkk vkac/ku-I
19
1-5-5-3 LFkkf;Ro Stability & vkcU/k yEckbZ esa deh vkSj ÅtkZ dh deh dkcZfud
;kSfxd dks vfrfjDr LFkkf;Ro iznku djrh gSA vr% dkcZfud ;kSfxd vius dSuksfudy
lw= ls visf{kr LFkkf;Ro ls vf/kd LFkk;h gksrk gSA
1-5-6 Hyperconjugation
tc dksbZ C–H vkcU/k fdlh vlar`Ir dkcZu ¼–C=C– ;k >C=O vkfn½ ds lkFk tqM+k
jgrk gS rc C–H vkcU/k vlar`Ir i)fr ds lkFk la;qXeu dj ysrk gSA ,slh fLFkfr esa C–
H vkcU/k ds ¼flXek½ bysDVªkWu f}cU/k ¼;k vlar`Ir i)fr½ ds &bysDVªkWu ds lkFk
la;qXeu dj ysrs gSaA bls gkbijdUtwxs’ku1 dgrs gSaA bls &dUtwxs’ku Hkh dgrs gSaA
blesa &dkcZu ls vlar`Ir dkcZu dh vksj &bysDVªkWuksa dk LFkkukUrj.k gksrk gS vkSj lkFk
gh lkFk f}cU/k dk /kzqohdj.k gks tkrk gSA bl izdkj gkbijdUtwxs’ku esa f}cU/k ds
p&vkWfcZVyksa vkSj fudVorhZ C–H cU/k ds &vkWfcZVyksa ¼&vkcU/k vkWfcZVy½ ds e/;
vfrO;kiu gks tkus ds dkj.k &bysDVªkWuksa dk vLFkkuhdj.k delocalisation gks tkrk gS
tSlk fd vkxs iznf’kZr fd;k x;k gS &
C
H
C C
H
H
H-BOND
-BOND
p-d{kdCONJUGATION
fp=&1-16 % gkijdUtwxs’ku vFkkZr la;qXeu dk vkWfcZVy fu:i.k
bysDVªkWuksa ds LFkkukUrj.k ds QyLo:i tks vk;fud :i mRié gksrs gSa os vuqukn
ds }kjk LFkkf;Ro izkIr dj ysrs gSaA mnkgj.kkFkZ] izksfiyhu esa la;qXeu
¼gkbijdUtwxs’ku½ ds QyLo:i mRié gq, vk;fud :iksa dks uhps iznf’kZr fd;k x;k gSA
bUgsa gkbijdUtwxsfVo lajpuk,¡ dgrs gSaA ;s :i vuqukn ds }kjk LFkkf;Ro izkIr dj ysrs
gSaA
C
H
H
H CH CH2 C
H+
H
H CH CH2
izksfiyhu (I) (II)
C
H
H
H+
CH CH2 C
H
H
H CH CH2
+
(III) (IV)
izksfiyhu dk f}/kqzo vk?kw.kZ (dipole moment) 0.4 D gksrk gS tks bl rF; dh
iqf"V djrk gS fd izksfiyhu ds vuqukn ladj esa vk;fud :iksa (hyperconjugative
structures) dk Hkh ;ksxnku gksrk gSA gkbijdUtwxs’ku vuqukn ds leku gS vkSj blesa
;kSfxd vis{kkd`r vf/kd LFkk;h gks tkrk gSA mnkgj.kkFkZ] izksfiyhu ,fFkyhu dh rqyuk esa
vf/kd LFkk;h gksrk gS D;ksafd ;g pkj lw=ksa I, II, III o IV dk gkbfczM gS] tcfd ,fFkyhu
dk dsoy ,d lw= gksrk gSA lw= II, III o IV esa ls fdlh esa Hkh C o H ds e/; dksbZ
vkcU/k ugha gS blfy, gkbijdUtwxs’ku dks fcuk vkcU/k dk vuqukn (no bond
resonance) Hkh dgrs gSaA
lajpuk rFkk vkac/ku-I
20
mi;qZDr lajpukvksa esa ;|fi eqDr izksVkWu dks iznf’kZr fd;k x;k gS fdUrq ;g
&bysDVªkWu vHkz ds lkFk dkQh etcwrh ls c¡/kk jgrk gS blfy, v.kq ls vyx gksus ds
fy, Lora= ugha gksrk gSA
vuqukn vkSj gkbijdUtwxs’ku esa izeq[k varj ;g gS fd vuqukn esa &bysDVªkWu ;k
n-bysDVªkWu ¼,dkdh bysDVªkWu ;qXe½ Hkkx ysrs gSa] tcfd gkbijdUtwxs’ku esa dsoy C–H
cU/k ds flXek bysDVªkWu fudVorhZ vlar`Ir fudk; vFkok vlgHkkftr p&d{kd ds lkFk
vkaf’kd la;qXeu (partial conjugation) n’kkZrs gSaA ;g ,d LFkk;h izHkko gS tks izsjf.kd
izHkko ls izcy gksrk gSA bldk eku &dkcZu ls layXu H–C cU/kksa dh la[;k ij fuHkZj
djrk gSA budh la[;k ftruh vf/kd gksrh gS] gkbijdUtwxs’ku izHkko mruk izcy gksrk
gSA vr% fofHké ,sfYdy lewgksa ds gkbijdUtwxs’ku izHkko dk izcyrk Øe fuEufyf[kr
gksrk gS &
CH3 > CH3 – CH2 > –CH(CH3)2 > C–(CH3)3
esfFky ,fFky vkblksizksfiy r`rh;d C;wfVy
¼nks gkbMªkstu½ ¼,d gkbMªkstu½ ¼dksbZ gkbMªkstu ugha½
vfirq izsjf.kd izHkko dh izcyrk dk Øe blds foijhr gksrk gSA
(CH3)3C – > (CH3)2CH – > CH3CH2 – > CH3 –
1-5-7 gkijdUtwxsfVo izHkko dk egRo Importance of Hyperconjugative effect gkbijdUtwxsfVo izHkko vuqukn izHkko dh rqyuk esa nqcZy gksrk gS fdUrq ;g
dkcZfud v.kqvksa ds vusd HkkSfrd o jklk;fud xq.kksa dks izHkkfor djrk gS ,oa muds
O;ogkj dks Li"V djrk gSA dqN xq.kksa dk o.kZu ;gk¡ fd;k x;k gS &
1.5.7.1 ,sfYdy lew gkbijdUtwxs’ku ds vk/kkj ij ,sjkseSfVd
izfrLFkkiu ,sfYdy lewgksa dk fn’kkRed izHkko Li"V fd;k tk ldrk gSA ,sfYdy lewg o-
o p-fn’kkRed gksrs gSaA esfFky lewg $I izHkko ds lkFk&lkFk izcy gkbijdUtwxsfVo izHkko
Mkyrk gSA gkbijdUtwxs’ku ds dkj.k vkWFkksZ ij iSjk LFkkuksa ij bysDVªkWu ?kuRo dh of)
gksrh gS ftlds dkj.k VkWyqbZu dk ukbVªhdj.k ¼bysDVªksfQfyd izfrLFkkiu½ o- o p-LFkkuksa ij gksrk gSA
C
H
HH C
H
H+
H
:
C
H
H+
H
:
..
C
H
H+
H
fp=&1-17 % VkWyqbZu dh fofHké gkbijdUtwxsfVo lajpuk,¡
tSlk fd igys mYys[k fd;k x;k gS fd gkbijdUtwxsfVo izHkko $ I izHkko dh
rqyuk esa izcy gksrk gS blfy, ,sfYdy csUthi esa bysDVªksfQfyd izfrLFkkiu blh izHkko ds
}kjk fu/kkZfjr gksrk gSA fofHké ,sfYdy lewgksa dk $ I izHkko dk Øe fuEufyf[kr gksrk
gS&
CH3 – < CH3 – CH2 – < (CH3)2CH – < (CH3)3C –
fdUrq gkbijdUtwxsfVo izHkko dk Øe fuEu gksrk gS &
CH3 – > CH3 – CH2 – > (CH3)2CH – > (CH3)3C –
bldh iqf"V p&vkblksizksfiy VkWyqbZu ds ukbVªhdj.k ls gksrh gSA ukbVªhdj.k ij
ukbVªks lewg esfFky lewg ds lkis{k o&LFkku ij izos’k djrk gSA
lajpuk rFkk vkac/ku-I
21
CH3
CH3
CH
CH3
CH3
CH
NO2
CH3
CH3
c.HNO3
;g rHkh lEHko gS] tcfd gkbijdUtwxsfVo izHkko $I izHkko dh rqyuk esa vf/kd
izcy gksA esfFky lewg ds rhu -H vkSj vkblksizksfiy lewg dk dsoy ,d -H csathu
ds bysDVªkWuksa ds lkFk la;qXeu djrs gSaA vr% esfFky lewg vf/kd izHkko’kkyh
gkbijdUtwxsfVo izHkko Mkyrk gSA
1.5.7.2 dkcksZdsVk;uksa ,oa eqDr ewydksa dk LFkkf;Ro & fofHké dkcksZdsVk;uksa vkSj eqDr
ewydksa ds vkisf{kd LFkkf;Ro dk fuEu Øe ik;k tkrk gS &
r`rh;d > f}rh;d > izkFkfed
bldk Li"Vhdj.k gkbijdUtwxs’ku ds vk/kkj ij fuEu izdkj ls fd;k tk ldrk
gS&
tc H–C cU/k fdlh ,sls ijek.kq ls tqM+k jgrk gS ftlds ikl vlgHkkftr p-
vkfcZVy gksrk gS ¼tSls&eqDr ewyd] dkcksZdsVk;u vkfn½ rc Hkh H–C cU/k ds
bysDVªkWuksa dk gkbijdUtwxs’ku ds dkj.k foLFkkuhdj.k (delocalisation) gks tkrk gSA
bls CH3CH2 ¼,fFky dkcksZdsVk;u½ dk mnkgj.k ysdj le>k tk ldrk gSA
C C
H
H
H
H
Hvfrla;qXeu
fjDr 2p&d{kd
fp=&1-18 % ,fFky /kuk;u esa vfrla;qXeu n’kkZrk d{kd vkjs[k
esfFky lewg dk ,d C–H vkca/k /kukosf’kr dkcZu ds fjDr p&d{kd ds ry
ds lajs[k.k esa gks tkrk gS ftlds dkj.k iw.kZ iwfjr C–H vkcU/k vkWfcZVy /kukosf’kr
dkcZu ds fjDr pvkWfcZVy dk vfrO;kiu dj ysrk gS vkSj C–H vkca/k ds bysDVªkWu
fjDr pd{kd esa foLFkkuhd`r gks tkrs gSaA QyLo:i ,fFky ewyd vkSj ,fFky
dkcksZdsVk;u ds fy, fofHké ;ksxnkuh lw= ;k dSuksfudy lw= fy[ks tk ldrs gSaA
C
H
H
H C
H
H
C
H
H
H C
H
H
C
H
H
H C
H
H
C
H
H
H C
H
H
(I) (II) (III)
,fFky dkcksZdsVk;u (1o) ds fofHké gkbijdUtwxsfVo :i
C
H
H
H C
H
H
C
H
H
H C
H
H
C
H
H
H C
H
H
C
H
H
H C
H
H
.
.
.
.
(I) (II)
,fFky ewyd (1o) ds fofHké gkbijdUtwxsfVo :i
mi;qZDr lajpukvksa ls Li"V gS fd dkcksZdsVk;u o eqDr ewyd nksuksa dh
gkbijdUtwds’ku ds }kjk LFkkf;Ro izkIr dj ysrs gSA gkbijdUtwxs’ku ds }kjk
lajpuk rFkk vkac/ku-I
22
vkblksizksfiy ¼f}rh;d½ vkSj t-C;wfVy dsVk;u Hkh LFkkf;Ro izkIr djrs gSa D;ksafd buds fy,
Hkh vusd gkbijdUtwxsfVo lajpuk,¡ iznf’kZr dh tk ldrh gSA vkblksizksfiy dsVk;u 6
vkSj t-C;wfVy 9 ;ksxnkuh lajpukvksa dk gkbfczM gksrk gSA pw¡fd V’kZjh C;wfVy ¼;k V’kZjh
,sfYdy½ dkcksZdsVk;u f}rh;d ,sfYdy dh rqyuk esa vf/kd ;ksxnkuh lajpukvksa vkSj
f}rh;d ,sfYdy izkFkfed dh rqyuk esa mlls vf/kd ;ksxnkuh lajpukvksa dk ladj gksrk gS
blfy, ,sfYdy dsVk;uksa ds LFkkf;Ro dk Øe 3o > 2
o > 1
o gksrk gSA
C
H
H
H C
H
C
H
H
H C
H
H
H C
H
C
H
H
H C
H
H
H C C H
H
H
H
vkfn
vkblksizksfiy dkcksZdsVk;u (2o) ds fofHké gkbijdUtwxsfVo :i
C
H
H
H C C
H
H
H
H
C HH
C
H
H
H C C
H
H
H
H
C HH
C
H
H
H C C
H
H
H
H
C HH
vkfn
V’kZjh C;wfVy dkcksZdsVk;u (3o) ds fofHké gkbijdUtwxsfVo :i
izkFkfed] f}rh;d vkSj rrh;d ,sfYdy ewydksa ds fy, Hkh fofHké
gkbijdUtwxsfVo :i fy[ks tk ldrs gSaA izkFkfed ,sfYdy ewyd 3] f}rh;d ,sfYdy
ewyd 6 vkSj r`rh;d ,sfYdy ewyd 9 cU/k foghu gkbijdUtwxsfVo :iksa dk ladj gksrk gS
blfy, buds LFkkf;Ro dk Øe fuEufyf[kr gksrk gS
r`rh;d > f}rh;d > izkFkfed > esfFky
1-6 dkcZfud vfHkfØ;kvksa dh fØ;kfof/k MECHANISM OF ORGANIC REACTIONS
1-6-1 dkcZfud fØ;kfof/k esa eqM+s gq, rhj dk ladsru Curved arrow notation
in organic reaction mechanism
dkcZfud vfHkfØ;k esa izk;% iqjkus ca/kksa dk fo[k.Mu vkSj u;s vkca/kksa dk fuekZ.k
gksrk gSA lgla;kstd vkca/k dks izk;% ,d MS’k (–) ls iznf’kZr djrs gSa rFkk bysDVªkWuksa ds
,d ;qXe ds vfHkxeu ;k LFkkukUrj.k dks eqM+s gq, rhj ( ) ds }kjk] tcfd eNyh ds
dk¡Vs okys rhj ( ) ds }kjk ,d bysDVªkWu dk LFkkukUrj.k iznf’kZr djrs gSaA
(i) X Y X + Y
. .
eqDr ewyd
Cl : Cl.
2Cl
(ii)
X Y X + Y :
..
..:
,
:
..(CH
3)3
Cl (CH3)3C Cl::
....
..+
(iii)
X Y X + Y ,
X Y X Y
eqM+k gqvk rhj ;qXe cU/k ds &bysDVªkWuksa ds LFkkukUrj.k dks izdV djrk gSA
(i) esa X – Y cU/k dk fonyu gksus ij lgla;kstd vkca/k ds bysDVªkWu ;qXe dk ,d&,d
bysDVªkWu X o Y ijek.kqvksa ik pyk tkrk gSA mnkgj.k (ii) esa bysDVªkWu ;qXe dk
vfHkxeu Y ijek.kq dh vksj gks tkrk gS ftlls Y ij _.kkRed vkos’k vkSj X ij
lajpuk rFkk vkac/ku-I
23
/kukRed vkos’k mRié gksrk gSA mnkgj.k (iii) esa bysDVªkWu ;qXe dk X ijek.kq dh vksj
vfHkxeu gks tkrk gS vkSj X ij _.kkRed vkos’k vkSj Y ij /kukRed vkos’k mRié gks
tkrk gSA dkcZfud jlk;u esa f}’kh"kZ 'kjksa (double headed arrows ) dk mi;ksx
v.kqvksa dh lajpuk iznf’kZr djus ds fy, fd;k tkrk gSA ;g f}’kh"kZ 'kj ;g iznf’kZr djrk
gS fd fdlh v.kq dh lajpuk dsoy ,d lw= ds leku u gksdj fofHké lajpukvksa ds
;ksxnku ls cuh gksrh gSA tSls fuEu mnkgj.k esa csUthu v.kq dh lajpuk fuEu dSuksfudy
lw=ksa esa ls fdlh Hkh ,d ds leku ugha gksrh gS cfYd lHkh lajpukvksa (I ls V) ls
dqN&dqN feyrh tqyrh gksrh gSA
I II III IV V
fp=&1-19 % csathu eas vuqukn
vr% fofHké lajpukvksa esa vuqukn dh fLFkfr O;Dr djus ds fy, f}’kh"kZ 'kj j[k
fn;k tkrk gSA ;g rhj nks v.kqvksa ;k lajpukvksa ds e/; xfrd lkE; iznf’kZr ugha djrk
gS cfYd ;g lq>ko nsrk gS fd v.kq dks dsoy ,d lajpuk dh rqyuk esa fofHké lajpukvksa
ds vquuknh ladj ds :i esa O;Dr djuk vf/kd mi;qDr gSA ;g f}’kh"kZ 'kj bysDVªkWuksa ds
vfHkxeu dks iznf’kZr ugha djrk gSA
1-6-2 Homolytic and Heterolytic
Bond Fission
dkcZfud vfHkfØ;k esa dkcZfud v.kq Hkkx ysrs gSa rc bu v.kqvksa ds iqjkus
lgla;kstd vkcU/k VwV tkrs gSa vkSj u;s vkcU/k cu tkrs gSaA blds ifj.kkeLo:i gh u;s
v.kq curs gSaA lgla;kstd vkcU/k nks izdkj ls VwV ;k fonfyr gks ldrk gS&lefer o
vlefer izdkj lsA
1.6.2.1 Homolytic Fission of
Homolysis & bl izdkj ds fonyu esa lk>s ds nksuksa bysDVªkWuksa dk cfU/kr ijek.kqvksa esa
cjkcj&cjkcj foHkktu gks tkrk gS vFkkZr~ cU/k ls tqM+s gq, nksuksa ijek.kq ;k lewg
viuk&viuk lk>s dk bysDVªkWu ysdj vyx gks tkrs gS vkSj nks eqDr ewyd mRié gks tkrs
gSA
R X R X. . R + X
. .
;k
gkseksfyfVd
fonyudksbZ v.kq
eqDr ewyd
Cl Cl. . Cl + Cl
. .
gkseksfyfVd fonyu
UV izdk'k
Dyksjhu eqDr ewyd
eqDr ewyd mnklhu ijek.kq ;k ijek.kqvksa dk ,slk lewg gksrk gS ftlds ikl
viuk lk>s dk bysDVªkWu ijek.kq ;k v.kq (odd electron atom or molecule) Hkh dgrs
gSA
dqN dkcZfud eqDr ewydksa ds mnkgj.k fuEufyf[kr gS &
CH
H
H
.
CC6H
5
C6H
5
C6H
5
.
.C
6H
5
Qsfuy ewyd
CC6H
5
O
.O
esfFky ewyd VªkbQsfuyesfFky ewyd csatkW;ykWDlh ewyd
1.6.2.2 Heterolytic
fission&blesa lgla;kstd ca/k dk fo[k.Mu vlefer :i ls gksrk gS vFkkZr~ lk>s dk
lajpuk rFkk vkac/ku-I
24
bysDVªkWu tksM+k fdlh ,d ijek.kq ;k [k.M ds lkFk pyk tkrk gS vkSj nks vkos’k;qDr
vk;u curs gSaA
R X R X R+
: X
..:
..:;k +
dsVk;u ,suk;u
R R R R R :: R:..
:
;k +dsVk;u,suk;u
tc fo[k.Mu es nks vk;u curs gSA ftl ij /ku vFkok _.k fo|qr vkos’k gks
ldrk gSA tc dsVk;u R+ esa /ku vkos’k dkcZu ijek.kq ij mifLFkr jgrk gS rc bls
dkcksZfu;e vk;u ;k dkcksZdsVk;u dgrs gSaA ,sls dkcZu ijek.kq dh ckáre d{kk esa 6
bysDVªkWu gksrs gSa( tSls &
CH
H
H
Cl CH
H
H
Cl:..
:..
+
esfFky DyksjkbM esfFky dkcksZdsVk;u DyksjkbM vk;u
tc ,suk;u R– esa _.k vkos’k dkcZu ijek.kq ij gksrk gSa] rc bls dkcsZfu;u
dgrs gSaA bl dkcZu ij _.k vkos’k blfy, jgrk gSa] D;ksafd blesa ,d fcuk lk>k fd;k
gqvk bysDVªkWu tksM+k jgrk gSA blesa dkcZu ijek.kq dh ckárd d{kk esa 8 bysDVªkWu gksrs
gSaA
CR
H
H
:Et CR
H
H
Et
..CH
3CH
3CH
3
CH
3, ++
dkcsZfu;u
dkcksZdsVk;u ,oa dkcZ,suk;u dk foLr`r o.kZu vkxs vfHkfØ;k’khy e/;orhZ ds
vUrxZr fd;k x;k gSA dHkh&dHkh nks lgla;kstd cU/kksa dk fonyu gksrk gS vkSj nks lewg
;k ijek.kq ,d gh dkcZu ls i`Fkd gksrs gSa ftuesa ls ,d bysDVªkWu jfgr vFkok nksuksa
ijek.kq ,d&,d bysDVªkWu ysdj i`Fkd gks tkrs gSA bl izdkj izkIr gq, fo|qr mnklhu
vo’ks"k dks dkchZu (carbene) dgrs gSaA dkchZu vR;Ur fØ;k’khy mnklhu Lih’kht gksrs gSa
ftuds dkcZu ijek.kq ds la;kstdrk dks’k esa N% bysDVªkWu gksrs gSaA bu N% bysDVªkWuksa esa ls
nks vlgHkkftr (unshared) gksrs gSaA esfFkyhu (:CH2) lcls ljy dkchZu gSA
. .
CR
R'
Y
:X CR
R'
R'R C : CH2
XY;k ;k esfFkyhu
dkchZu
dkchZu nks izdkj ds gksrs gS&flaXysV o fVªIysVA flaXysV dkchZu (:CH2) esa
vlgHkkftr bysDVªkWu ;qxy (paried) ds :i esa jgrs gSaA bldk O;ogkj dkcksZdsVk;u ds
leku gksrk gSA ;g vR;f/kd vLFkk;h gksrk gSSA fVªIysV dkchZu (CH2) esa vlgHkkftr
bysDVªkWu v;qfXer (unparied) jgrs gSaA bldk O;ogkj eqDr ewyd ds leku gksrk gSA
H2C : Singlet vlgHkkftr bysDVªkWu ;qfXer
CH H.
. Triplet
vlgHkkftr bysDVªkWu v;qfXer
lajpuk rFkk vkac/ku-I
25
1-6-3 vfHkdeZdksa ds izdkj Types of Reagents
dkcZfud ;kSfxdksa esa fo"keka’k vi?kVu (heterolysis) }kjk bysDVªksfQfyd
¼bysDVªksQkby½ vkSj U;wfDyvksfQfyd ¼U;wfDyvksQkby½ curs gSA
1-6-3-1 bysDVªksfQfyd ¼bysDVªkWuLusgh½ vfHkdeZd Electrophilic
Reagents
vfHkdeZd ftudh bysDVªkWuksa ds izfr cU/kqrk (affinity) vf/kd gksrh gS vFkok tks
vfHkfØ;k esa bysDVªkWuksa dks xzg.k djrs gSaA bysDVªksfQfyd vfHkdeZd fdlh v.kq ds ml
LFkku ij fØ;k djrk gS tgk¡ ij mldk ¼fØ;k/kkj dk½ bysDVªkWu ?kuRo vf/kd gksrk gS
vkSj tgk¡ ls og bysDVªkWu ;qXe izkIr dj ldrk gSA ;s izk;% /kukosf’kr vk;u ¼2NO ,
Cl+, Br
+, R
vkfn½ gksrs gSa] fdUrq dqN bysDVªksfQfyd vfHkdeZd mnklhu v.kq Hkh gksrs
gSa ftuesa bysDVªkWu U;wu (electron deficient) ijek.kq gksrs gSa] tSls& AlCl3, BF3,
SnCl4, FeCl3 vkfnA bUgsa yqbl vEy (electron pair acceptor) Hkh dgrs gSaA lHkh
bysDVªksfQfyd vfHkdeZdksa esa ,d ;k ,d ls vf/kd ,sls ijek.kq gksrs gSa ftudh ckáre
d{kk esa vkB ls de bysDVªkWu gksrs gSaA blh izdkj vEy vkSj dkcksZdsVk;u Hkh
bysDVªksfQfyd gksrs gSaA dqN bysDVªksfQfyd vfHkdeZd fuEukafdr gSa &
3 2H, H O, R; NO , Cl
, 3Br, NO, SO
, AlCl3, BF3, ZnCl2, FeCl3
1-6-3-2 U;wfDyvksfQfyd ¼ukfHkdLusgh½ vfHkdeZd Nucleophilic
Reagents
vfHkdeZd ftuesa bysDVªkWu ?kuRo vf/kd gksrk gS vFkok vf/kd gksrk gS vFkok
U;wfDy;l ds izfr mPp cU/kqrk gksrh gS vFkok tks vfHkfØ;k esa bysDVªkWu nku nsrs gSaA ;s
vfHkdeZd fdlh v.kq ds lkFk mlds ml LFkku ij fØ;k djrs gSa tgk¡ ij bysDVªkWu ?kuRo
de gksrk g S ¼vFkkZr~ /ku vkos’k gksrk gS½A dqN U;wfDyvksfQfyd vfHkdeZd fuEufyf[kr gSa&
..OH, RO, CN, Cl , I , R ,.. ..
..: : : : CCH ¼,slsfVykbM vk;u½
;s izk;% _.k vkosf’kr vk;u ¼OH–, CN
– vkfn½ vFkok ,sls mnklhu v.kq gksrs
gSa ftuesa NO, S, Cl, Br, I ds de&ls&de ,d lgHkkftr bysDVªkWu ;qXe (unshared
pair of electrons) vo’; mifLFkr jgrk gS] tSls &
H O H, C2H
5O H, NH
3, R
3N, R S H
..
..
..
.. .. ..
..
..
1-6-4 dkcZfud vfHkfØ;kvksa ds izdkj Types of Organic
Reactions
izeq[k izdkj dh dkcZfud vfHkfØ;k fuEufyf[kr gS &
¼1½ izfrLFkkiu vfHkfØ;k,¡
¼2½ ;ksxkRed ;k vfHkfØ;k,¡
¼3½ foyksiu vfHkfØ;k,¡
¼4½ iqufoZU;kl vfHkfØ;k,¡
¼5½ vkf.od vfHkfØ;k,¡
1-6-4-1 izfrLFkkiu vfHkfØ;k,¡ Substitution Reaction
vfHkfØ;k ftlesa fdlh ;kSfxd dk dksbZ ijek.kq ;k lewg nwljs ijek.kq ;k lewg
ls bl izdkj izfrLFkkfir gksrk gS fd ;kSfxd dh vkarfjd jpuk esa dksbZ ifjorZu ugha vkrk
gSA u;k izos’kh lewg mlh dkcZu ds lkFk layXu gksrk gS ftlls vyx gksus okyk ijek.kq
lajpuk rFkk vkac/ku-I
26
;k lewg tqM+k gqvk FkkA fØ;k ds QyLo:i cus u;s ;kSfxd dks izfrLFkkiu mRikn dgrs
gSaA
H NO2
cH2SO
4
cHNO3
cSathu ukbVªkscSathu
izfrLFkkiu mRikn
;g fØ;k eqDr ewyd] bysDVªksQkby ;k U;wfDyvksQkby ds }kjk gksrh gSA
gSykstuhdj.k] ukbVªhdj.k] lYQksuhdj.k vkfn bl izdkj ds bysDVªksfQyd izfrLFkkiu
vfHkfØ;kvksa ds mnkgj.k gSaA ,sYdsu vkSj ,sjkseSfVd gkbMªksdkcZu bl izdkj dh vfHkfØ;k,¡
iznf’kZr djrs gSaA
(i) eqDr ewyd izfrLFkkiu & ;g eqDr ewyd ds vkØe.k ds }kjk gksrk gSA
2Cl Cl Clhv
,sYdsu bl izdkj dh vfHkfØ;k,¡ iznf’kZr djrs gSA mnkgj.kkFkZ&,sYdsu dk
Dyksjhuhdj.k
4 3Cl CH CH HCl
3 2 3CH Cl CH Cl Cl
bR;kfn
(ii) bysDVªksfQfyd izfrLFkkiu Electrophilic substitution & ;g fØ;k
bysDVªksQkby( tSls& 2NO , Cl vkfn ds vkØe.k ds }kjk gksrh gS rFkk ,sjkseSfVd
;kSfxd bl izdkj dh vfHkfØ;k,¡ iznf’kZr djrs gSaA budk mPp bysDVªkWu ?kuRo
bysDVªksQkby dks vkdf"kZr djrk gSA
HNO3 + H
2SO
4H
3O + HSO
4 + NO
2
H
NO2
NO2
HSO4
2
+ NO2
bl izdkj dh vfHkfØ;kvksa dks SE ls O;Dr djrs gSaA
(iii) U;wfDyvksfQfyd izfrLFkkiu & ;g fØ;k U;wfDyvksQkby ¼ukfHkdLusgh½ ds
vkØe.k ds }kjk gksrh gSA tSls&,sfYdy gSykbM dh izfrLFkkiu vfHkfØ;kA
Nu: + R X Nu + X:R
;s vfHkfØ;k,¡ ,d ls vf/kd izdkj dh fØ;kfof/k ds }kjk gksrh gSa] tSls& SN1 o
SN2A
+R X R X
Nu + R NuR (SN
1)
;k Nu + R X Nu R + X[Nu.....R.....X] (SN1)
1.6.4.2 ;ksxkRed vfHkfØ;k,¡ Addition Reactions
vfHkfØ;k ftlesa v.kq vkil esa la;ksx djds dsoy ,d fØ;kQy nsrs gSaA u;s
inkFkZ dks ;ksxkRed mRikn dgrs gSaA bl izdkj dh vfHkfØ;k,¡ ,sYdhu] ,sYdkbu]
lajpuk rFkk vkac/ku-I
27
dkcksZfuy ;kSfxdksa vkfn esa gksrh gS ftuesa f}d ;k f=d vkcU/k gksrs gSaA okLro easa ;g
budk fof’k"V xq.k gS ladyu vfHkfØ;k esa fdlh f}&vkca/k okys v.kq esa nks ijek.kqvksa ;k
lewgksa dk ;ksx gksrk gSA izfrLFkkiu vfHkfØ;k ds leku ;s vfHkfØ;k,¡ Hkh bysDVªksQkby]
U;wfDyvksQkby ;k eqDr ewyd ds vkØe.k }kjk gksrh gSA bysDVªkWu Lusgh rFkk eqDr
ladyu vfHkfØ;k,¡ lkekU;r% ,sYdhuksa o ,sYdkbuksa easa gksrh gSa tcfd ukfHkd Lusgh ladyu
vfHkfØ;k,¡ fo"ke ijek.kq okys f}&vkca/kksa ij gksrh gSa] tSls&dkcksZfuy ;kSfxdksa esaA
(i) bysDVªksfQfyd ;ksx
CH2
CH2
Br2
CH2Br
CH2Br
CH2 + H
+
CH2 CH
2CH
3
CH
2BrCH
3
Br
+
HBr
ijkDlkbMksa dh mifLFkfr esa HBr dk ;ksx eqDr ewyd fØ;kfof/k ds }kjk gksrk
gSA
(ii) U;wfDyvksfQfyd ;ksx
C OCH3
CH3
C
O
CN
CH3
CH3
C
OH
CN
CH3
CH3
HCN
CN
H+
1.6.4.3 foyksiu vfHkfØ;k,¡ Elimination Reactions
vfHkfØ;k ftlesa fdlh v.kq esa ls nks ijek.kq ;k lewg foyksfir gks tkrs gSa vFkkZr
fudy tkrs gSa vkSj ,d vfrfjDr vkcU/k cu tkrk gSA foyksiu fØ;k esa nks ijek.kq ;k
lewg nks fudVorhZ dkcZu ijek.kqvksa ij ls fudy tkrs gSa vkSj ,d u;k f}vkcU/k ¼;k
f=vkcU/k½ cu tkrk gSA mnkgj.kkFkZ] ,sYdksgkWyksa dk vEy mRizsfjr futZyu rFkk ,sfYdy
gSykbMksa dk {kkjd mRizsfjr fogkbMªksgSykstuhdj.kA
C
R
R
R
R
X
C
R
R R
R
C
Y
C XY+
mijksDr foyksiu 1] 2 vFkok &foyksiu dgykrk gS] tSls &
(i) ,sYdksgkWy dk vEy mRizsfjr futZyu
..CH2
OH +CH3
H..
CH2
OH2CH
2 ..
CH
2CH2
H H
CH2
CH2
- H2O
;k 3 2 2 2 2
HCH CH OH CH CH H O
(ii) ,sfYdy gSykbM {kkjd mRiszfjr fogkbMªksgSykstuhdj.k
lajpuk rFkk vkac/ku-I
28
CH2
ClCH2
CH2CH
2HHOCl
H2O +
;k 3 2 2 2 2CH CH Cl KOH Alc. CH CH KCl H O
blds vfrfjDr nks lewgksa vFkok nks ijek.kqvksa dk foyksiu ,d gh dkcZu ijek.kq
ls Hkh gks ldrk gSA bl voLFkk esa bls &foyksiu ¼;k 1]1 foyksiu½ dgrs gSaA bl voLFkk
esa fØ;k’khy Lih’kht dkchZu curh gSA mnkgj.k ds fy,
CHCl3
CCl3
:CCl2 + Cl
OH-
-H2OMkbDyksjksdkchZu
1.6.4.4 iqufoZU;kl vfHkfØ;k,¡ Rearrangement Reactions
vfHkfØ;k,sa ftuesa dksbZ ijek.kq ;k lewg v.kq ds vanj gh ,d ijek.kq ls nwljs
ijek.kq ij vfHkxeu (migrate) dj tkrk gSA dkcZfud vfHkfØ;kvksa esa os iqufoZU;kl
vfHkfØ;k,¡ cgqr lkekU; gS ftuesa dksbZ lewg ,d dkcZu ls gVdj fudVorhZ nwljs dkcZu
ijek.kq ij pyk tkrk gSA bls 1]2-shift dgrs gSaA bl izdkj dh vfHkfØ;kvksa esa visf{kr
mRikn ds LFkku ij ,d leko;oh mRikn izkIr gksrk gSA mnkgj.kkFkZ] tc 2] 2&MkbesfFky
C;wVsu&1] 2&MkbvkWy dk vEy mRizsfjr futZyu gksrk gS tc iqufoZU;kflr mRikn
(rearranged product) 2, 2-MkbesfFkyC;wVsu&2&vksu ¼fiukdkWyksu½ izkIr gksrk gSA blesa
,d esfFky lewg fudVorhZ dkcZu ij pyk tkrk gSA
CH3
C
OH
CH3 CH
3
CH3
C
OHH
-H2O
CH3
C
CH3
CH3 CH
3C
O
fiukdkWy fiukdksyhu
1.6.4.5 vkf.od vfHkfØ;k,¡ Molecular Reactions
vfHkfØ;k,sa ftuesa lgla;kstd vkcU/k varj&v.kqd :i (intermolecularlarly)
esa ;k vUrjk&v.kqd :i (intramolecularly) esa pØh; laØe.k voLFkk (Cyclic
transition states) dk fuekZ.k djrs gq, iqufoZU;flr (reorganize) gks tkrs gSaA blesa
vk;fud e/;orhZ ;k ewyd e/;orhZ dk dksbZ ;ksxnku ugha gksrk gS rFkk vEyksa vkSj {kkjdksa
dk dksbZ izHkko ugh iM+rk gSA ;s vfHkfØ;k,¡ Å"ek ;k izdk’k ds izHkko ds }kjk gksrh gSa
rFkk vR;f/kd LVhfj;ksLisflfQd gksrh gSaA mnkgj.kkFkZ]
h ;k
C;wVkMkbbZu laØe.k voLFkk lkbDyksC;wVhu
+
C;wVkMkbbZu ,Fkhu laØe.k voLFkk lkbDyksgsDlhu
lajpuk rFkk vkac/ku-I
29
1-7 dkcZfud vfHkfØ;kvksa esa ÅtkZ dk fopkj Energy Consideration in Organic Reactions
1-7-1 Å"ekxfrdh vk/kkj Thermodynamics process
jklk;fud vfHkfØ;kvksa dks ,d lkE; izØe (equilibrium process) ds :i esa
ekuk tk ldrk gS ftudk lkE; fcUnq vfHkdkjdksa ,oa mRiknksa dh vkisf{kd ÅtkZvksa ls
fu/kkZfjr gksrk gSA os vfHkfØ;k,¡ tks mRiknksa dh fn’kk esa fcYdqy Hkh vxzlj ugha gksrh gSa] o s
Hkh lkE; izØe esa gksrh gSaA buds fy, lkE; fLFkjkad dk eku 'kwU; gksrk gSA ,d
jklk;fud vfHkfØ;k rHkh vkxs c<+rh gS ;k lHkh lEié gksrh gS tc bldk vuqdwy lkE;
gksrk gS vFkkZr~ tc mRikn vfHkdkdjksa dh rqyuk esa vf/kd LFkk;h gksrs gSaA
jklk;fud vfHkfØ;k dk lkE; fLFkjkad ,UFkSYih ifjorZu (H) rFkk ,.VªkWih
ifjorZu (S) ij fuHkZj djrk gSA ,UFkSYih ifjorZu Å"ek dh og ek=k gS tks rc mRié
gksrh ;k vo’kksf"kr gksrh gS tc vfHkdkjd dk ,d eksy] mRikn ds ,d eksy esa ifjofrZr
gksrk gS rFkk ,.VªkWih ifjorZu ÅtkZ dh og ek=k gS tks mRiknksa esa fØ;kdkjdksa dh rqyuk
esa O;oLFkk ¼;kn`fPNdrk&randomness½ c<+kus esa iz;qDr gksrh gS ¼;k mRlftZr gksrh gS½A
tc ,.VªkWih ifjorZu dks ije rki ds lkFk O;Dr fd;k tkrk gS rc eqDr ÅtkZ ifjorZu
dks fuEu lehdj.k ds }kjk O;Dr fd;k tk ldrk gS & bles eqDr ÅtkZ ifjorZu] G
= H – TS
vfHkfØ;k ds vxz fn’kk esa gksus ds fy, ;k Lor% (spontaneous) gksus ds fy,
mlesa gksus okyk eqDr ÅtkZ ifjorZu (G) _.kkRed gksuk pkfg;s vFkkZr mRiknksa dh eqDr
ÅtkZ] vfHkdkjdksa dh eqDr ÅtkZ ls de ugha gksuh pkfg;s vFkok ;g dg ldrs gSa fd vxz
fn’kk esa vfHkfØ;k rHkh gksrh tc G dk eku _.kkRed gksxk vFkkZr tc fudk; esa ls
ÅtkZ mRlftZr gksxhA G dk /kukRed eku ;g bafxr djrk gS fd vfHkfØ;k esa foijhr
fn’kk (backward direction) esa vxzflr gksus dh izofÙk gSA pw¡fd ,.VªkWih fdlh fudk;
dh ;knfPNdrk (randomness) rFkk vO;oLFkk dh eki gS blfy, dksbZ fudk; rc
lcls vf/kd LFkk;h gksrk gS tc bldh ;knfPNdrk (randomness) ;k ,.VªkWih vf/kd
gksrh gSA blls ;g fu"d"kZ fudyrk gS fd os vfHkfØ;k,¡ ftuesa mRiknksa esa vkf.od Loh’kht
dh la[;k vfHkdkjdksa dh rqyuk esa de gksrh gS os ljyrk ls ugh gksuh pkfg;sA izk;ksfxd
rkSj ij ;g ns[kk Hkh x;k gS fd bl izdkj dh vfHkfØ;k,¡ rHkh gksrh gSa tc H dk eku
_.kkRed gks ¼vFkkZr~ vfHkfØ;k Å"ek{ksih gks½ vkSj bruk T;knk gks fd G dk eku
_.kkRed gksA blds foijhr tc mRiknksa esa vkf.od Lih’kht dh la[;k vfHkdkjdksa dh
rqyuk esa c<+rh gS rc ,.VªkWih esa o`f) gksrh gS vkSj in TS dk eku bruk vf/kd gks
tkrk gS fd vfHkfØ;k vxz fn’kk esa gksus yxrh gS pkgs vfHkfØ;k Å"ek{ksih (exothermic)
u Hkh gksA tc lHkh inkFkZ ekud voLFkkvksa ¼25oC o 1 ok;qe.Myh; nkc½ esa gSa rc eqDr
ÅtkZ ifjorZu dh lehdj.k dks fuEu izdkj ls fy[kk tk ldrk gS &
Go–H
oTS
o
ew/kk±d (superscript) esa 'kwU; (zero) ;g iznf’kZr djrk gS fd inkFkZ ekud
voLFkk esa gSA lkE; fLFkjkad K vkSj Go vkil esa fuEu izdkj lacaaf/kr gksrs gSa &
Go = – RT In K = – 2.303 RT log K
tcfd In K=K dk izkdfrd ykWxsfjFe rFkk T=dsfYou esa rkiA
mijksDr lehdjk.k ds vuqlkj lkE; fLFkjkad K dk eku ¼mldk ifjek.k½ ;g
fu/kkZfjr djrk gS fd lkE; fdl fn’kk esa gksxk&mRiknksa vFkok vfHkdkjdksa dh vksjA Go
lajpuk rFkk vkac/ku-I
30
dk _.kkRed eku K ds vf/kd eku ds laxr gksrk gSA K dk vf/kd eku vfHkfØ;k ds
iw.kZrk dh vksj ladsr djrk gSA
1-7-2 xfrd vk/kkj Kinetic process
jklk;fud v.kqxfrdh eq[;r% vfHkfØ;k ds osx ls lacaf/kr gksrh gSA ;|fi G
ds _.kkRed eku ls gedks ;g irk pyrk gS fd veqd vfHkfØ;k vxz fn’kk esa vxzflr
gkssus ds fy, Å"kkxfrdh; (thermodynamically) :i ls vuqdwy gS fdUrq ;g irk ugha
pyrk gS fd vfHkfØ;k ds laiaé gksus dh nj D;k gksxhA ;g xfrdh; ekiu ls lEHko gksrk
gSA xfrdh; v/;;u vfHkfØ;kvksa dh nj rFkk mlds fofHké fØ;kdkjjh Lih’kht dh
lkUnzrkvksa ij fuHkZjrk ds lkFk laca/k Hkh izdV djrk gSA v.kqxfrdh dk mi;ksx vfHkfØ;k
dh fØ;kfof/k dk fu.kZ; djus esa Hkh fd;k tkrk gSA vf/kdka’k dkcZfud vfHkfØ;k,¡
cgqinh; (multistep) vfHkfØ;k,¡ gksrh gSa ftudk ,d in tks fd lcls ean (slow) gksrk gS nj fu/kkZjd in gksrk gSA xfrdh; ekiu ls ;g Kkr gks tkrk gS fd bi in esa
dkSu&lh Lih’kht Hkkx ys jgh gSA lkekU;r% fdlh vfHkfØ;k dh nj mu Lih’kht dh
lkUnzrkvksa ds xq.kuQy ds lekuqikrh gksrh gS tks nj fu/kkZjd in esa Hkkx ysrs gSaA
xfrdh; ekiu esa fdlh vfHkfØ;k dh izxfr dks mRiknksa ds izdV gksus vFkok
vf/kdkjdksa ds yqIr gksus dks ekWuhVj djds ns[kk tk ldrk gSA bls fdlh vuqekiuh fof/k
}kjk lh/ks (directly) vFkok vfHkfØ;k fudk; ds viorZukad (refractive index)
izdkf’kr ?kuRo bR;kfn tSls fdlh HkkSfrd xq.k esa ifjorZu ds }kjk ijks{k (indirectly) :i
ls ekik tk ldrk gSA
1-8 Reactive Intermediates
dkcZfud vfHkfØ;k,¡ cgqinh; gksrh gS ftuesa ls dqN Lih’kht e/;orhZ ds :i esa
curh gSaA ;s e/;orhZ lkekU; lgla;kstd ;kSfxd] vk;u ;k ewyd gksrs gS ftudk
vk;qdky cgqr de gksrk gSA ;s brus LFkk;h ughsa gksrs gSa fd bUgs foyx fd;k tk ldsA
;gk¡ ij dqN lkekU; e/;ofrZ;ksa dk o.kZu fd;k x;k gS &
lfØ; e/;dksa dk fuekZ.k ,oa LFkkf;Ro Formation and Stability of
Reaction Inter mediates & dkcZu eq[;r;k pkj vLFkk;h o lfØ; e/;orhZ
(reactive intermeidate) cukrk gS tks vusd vfHkfØ;kvksa esa e/;orhZ (intermediate) ds :i esa dk;Z djrs gSa] tSls &
C
:C
C.
C
.
.:C ;k
dkcksZdsVk;u dkcZ,suk;u eqä ewyd dkchZu
,sjkbu
R N : ukbVªhu
1-8-1 dkcksZdsVk;u Carbocation
dsVk;u ftuesa /ku vkos’k dkcZu ij mifLFkr jgrk gSA mls dkcksZdsVk;u dgrs
gSA ;s dsVk;u fdlh lgla;kstd vkca/k ds fo"kekad fonyu ij mRié gksrs gSaA bl
dkcZu dh ckárd d{kk esa 6 bysDVªkWu gksrs gSaA /kukosf’kr dkcZu ijek.kq ls layXu
,sfYdy ewydksa dh la[;k ds vk/kkj ij ;s rhu izdkj ds izkFkfed] f}rh;d ,oa r`rh;d
gksrs gSaA dkcksZdsVk;u vR;f/kd fØ;k’khy gksrs gS vkSj fdlh Hkh ,sls v.kq ds lkFk 'kh?kzrk
ls fØ;k dj ysrs gSa tks lgla;kstd cU/k cukus ds fy, vko’;d bysDVªkWu tksM+k ns ldrk
gSA vr% ;s bysDVªksfQfyd gksrs gSaA dkcksZdsVk;u vR;Ur vLFkk;h gksrs gSa fdUrq tc
/kukosf’kr dkcZu ls ,slk ewyd tqM+k gksrk gS tksfd /kukosf’kr dkcZu ds vkos’k dks de
djrk gS ¼$ I izHkko½ rks bukd LFkkf;Ro c<+ tkrk gSA vr% fofHké dkcksZdsVk;uksa ¼,sfYdy
dsVk;uksa½ ds LFkkf;Ro dk Øe fuEufyf[kr vFkkZr~ r`rh;d] f}rh;d o izkFkfed gksrk gS]
lajpuk rFkk vkac/ku-I
31
D;ksafd ,sfYdy ewyd $ I izHkko ds }kjk dkcZu ds /kukos’k dks de djrs gSa vFkkZr~
vLFkkfur (delocalise) djrs gSaA
R
C
R
R
R
C
H
R
H
C
H
R
H
C
H
H> > >
3o 2
o 1
o esfFky
H
H
:..C..
H
CH3
H
:..C..
H
CH3
:..C
H
CH3
:
CH3
:..C
CH3
CH3
:
dkcksZdsVk;u esfFky 1o ,fFky 1
o vkblksizksfiy 2
o r`rh;d C;wfVy 3
o
bysDVªkWu vkdf"kZr djus okys lewg( tSls&2NO , CN
vkfn ;fn /ku vkosf’kr
dkcZu ls tqM+s gksrs gSa rks ;s dkcksZdsVk;u dk LFkkf;Ro de dj nsrs gSaA
dkcksZdsVk;u vuqukn ds }kjk Hkh LFkkf;Ro izkIr dj ysrs gSa] D;ksafd$vkos’k
vLFkkfur (delocalise) gks tkrk gS] tSls&,sfyy dkcksZdsVk;u] izksfiy dkcksZdsVk;u dh
vis{kk vf/kd LFkk;h gksrk gSA
2 2 2 2CH CH CH CH CH CH
allyl carbocation
izksfiy dkcksZdsVk;u 3 2 2CH CH CH
esa vuqukn lEHko ugha gSA
blh izdkj csaftfyd dkcksZdsVk;u 6 5 2C H CH
Hkh vuqukn ds }kjk LFkkf;Ro
izkIr dj ysrk gSA
H
2C
CH2 CH
2
CH2
vr% fofHké dkcksZdsVk;uksa ds LFkkf;Ro dk Øe fuEufyf[kr gksrk gS &
csaftfyd ~ 3o > ,sfyfyd ~ 2
o > 1
o > CH3
vfirq budh fØ;k’khyrk dk Øe blds foijhr gksrk gSA
,sfYdy izfrLFkkfir dkcksZdsVk;uksa ds mPp LFkkf;Ro dk dkj.k eq[;r;k
vfrla;qXeu gSA
1-8-1-1 dkcksZdsVk;uksa ds cukus dh fof/k;k¡ Methods of Preparation of Carbocations
(a) vlefer fonyu }kjk & By hetrolytic fission
(C
6H
5)3C Cl
H2SO
4(C
6H
5)3C + Cl::
..
..
VªkbQsfuy esfFky DyksjkbM ¼jaxghu½ VªkbQsfuy esfFky dsVk;u ¼ihyk½
lajpuk rFkk vkac/ku-I
32
(b) vlar`Ir ;kSfxdksa ij vEuksa ds ;ksx ls & ,sYdhu] dkcksZfuy ;kSfxd rFkk ukbVªkby
izksfVd foy;u ;k yqbZl vEy esa ?kqydj dkcksZdsVk;u cukrs gSaA
C O + H
OHC
OHC
H+
R CH CH
2CH
3RCH
C N + H C N H
+
(c) ,sYdksgkWy] bZFkj] ,LVj] ,sfYMgkbM] dhVksu ds izksVksuhdj.k ds ckn futZyu ls &
.. R O H + H.. ROH
2R + H
2O
,sYdksgkWy
.. R O R' + H.. R O R'..
H
R'..:O
H
R
R'..:O
H
R
+
bZFkj
(d) ,sfYdy gSykbMksa ij vEyksa ds ;ksx ls vFkok lqij vEyksa vkfn dh fØ;k ls &
R :..
..Cl
H ClR H
R ::
..
..Cl H+ +
R :..
..Cl AlCl
3 ClR
R :..
..Cl AlCl
3AlCl
3AlCl
4+ + ;k
yqbZl vEy
FRR SbF
5SbF
4 ++
1-8-1-2 lalwpu Detection & vfHkfØ;k ds nkSjku vfHkfØ;k feJ.k ds nmr v/;;u ls
dkcksZdsVk;u ds cuus dk izR;{k izek.k izkIr gksrk gSA nmr }kjk buds vf/kd LFkk;h :i
esa iqufoZU;kflr gksus dk Hkh izek.k feyrs gSA
1-8-1-3 dkcksZdsVk;uksa dh vfHkfØ;k,¡ Reactions of Carbocations
dkcksZdsVk;u vusd izdkj dh vfHkfØ;k,¡ iznf’kZr djrs gSa] ftuesa ls fuEufyf[kr izeq[k gS(
(1) tksfd vfHkfØ;k esa bysDVªkWu ;qXe dk nku dj lds &
XR
R : X+
lajpuk rFkk vkac/ku-I
33
dkcksZdsVk;u U;wfDyvksfQfyd vfHkdeZd
CH
3CH
:OHCH3
(CH3)2CH OH+
vkblksizksfiy ,sYdksgkWy
:..
..
(CH
3)3C OH
2
OH2
(CH3)
3C
- HOH(CH
3)
3C
+
V’kZjh C;wfVy dkcksZdsVk;u izksVksusVsM VªkbesfFky dkfcZukWy r`rh;d&C;wfVy ,sYdksgkWy
(2) izksVkWu dk fudVorhZ dkcZu ijek.kq ls foyksiu & blesa /kukosf’kr dkcZu ds
fudV dkcZu ijek.kq ls izksVkWu ;k vU; ijek.kq dk dsVk;u ds :i esa foyksiu gksrk gS vkSj
/kukosf’kr dkcZu &dkcZu ls ,d bysDVªkWu tksM+s dks viuh vksj vkdf"kZr djds vkcU/k
cuk ysrk gS( tSls &
C
:OHH2C H
CH3
H3C
-H2O
OHC
CH3
CH3
H2C
(3) gkbMªkstu ds lkFk ;ksx &
R H : R' RH R'
(4) ,sYdhu ds lkFk ;ksx & mPprj dkcksZdsVk;u curk gSA
C
CH3
CH3
CH3 CH
2CH
2C
CH3
CH3
CH3 CH
2CH
2+
(5) vkf.od iqufoZU;kl Molecular Rearrangements & dkcksZdsVk;u vusd
fØ;kvksa esa bl izdkj iqufoZU;kflr gksrs gSa fd igys ls vf/kd LFkk;h dkcksZdsVk;u cu
tkrs gSA fofHké dkcksZdsVk;uksa ds LFkkf;Ro dk fuEu Øe ls gksrk gS &
r`rh;d > f}rh;d > izkFkfed
izkFkfed dkcksZdsVk;u iqufoZU;kl ds }kjk f}rh;d dkcksZdsVk;u esa vkSj f}rh;d
dkcksZusVk;u r`rh;d esa ifjofrZr gksrk gSA bu iqufoZU;klksa esa gkbMªkstu gkbMªkbM vk;u
ds :i esa rFkk ,sfYdy ;k ,sfjy ewyd dk LFkkukUrj.k ,sfYdy ;k ,sfjy ,suk;u ds :i
esa /kukosf’kr dkcZu ds fudV okys dkcZu ls /kukosf’kr dkcZu ij gksrk gSA tSls &
3 2 2 2 3 2 3CH CH CH CH CH .CH CH.CH
¼izkFkfed dkcksZdsVk;u½ ¼vf/kd LFkk;h f}rh;d dkcksZdsVk;u½
CH3
CH3.CH
2.CH
2CH
2
CH3
CH3.CH
2CH.CH
3
¼de LFkk;h izkFkfed½ ¼vf/kd LFkk;h 2o dkcksZdsVk;u½
lajpuk rFkk vkac/ku-I
34
C
CH3
CH3
C
H
CH3
CH3
CH3
CH3
CH CH3
C
CH3
esfFky ewyd
LFkkukUrj.k
¼f}rh;d½ ¼r`rh;d½
vusd dkcZfud vfHkfØ;k,¡ bUgha iqufoZU;klksa ds }kjk gh gksrh gSA
1-8-2 dkcsZfu;u Carbanion
,suk;u ftlesa _.k vkos’k dkcZu ij jgrk gS] dkcsZfu;u (Carbanion) dgykrk
gSA bldk fuekZ.k Hkh lgla;kstd vkcU/k ds fo"kekax fonyu ls gksrk gS
CH
3CH
3CH
3CH
3+
,sls dkcZu dh ckáre d{kk eas 8 bysDVªkWu ¼4 bysDVªkWu ;qXe½ gksrs gSa ftuesa ls rhu
bysDVªkWu ;qXe rks cfU/kr gksrs gSa vkSj ,d bysDVªkWu ;qXe vcfU/kr (non-bonded) ;k ,dkdh bysDVªkWu ;qXe ds :i esa gksrk gSA tSls &
CH
3:
CH
2CH3
CHCH3
CH3
..
esfFky dkcsZfu;u ,fFky dkcsZfu;u vkblksizksfiy dkcsZfu;u
C(CH
3)
3:
CH2
: CH O
r`rh;d C;wfVy dkcsZfu;u
1-8-2-1 dkcsZfu;uksa dk cuuk Formation of Carbanions
dqN dkcZfud ;kSfxd izcy yqbZl {kkjdksa dh mifLFkfr esa izksVhu [kksdj dkcsZfu;u
cukr gSA ftu dkcZfud ;kSfxdksa esa cgq&cU/k (multiple) ;qDr lewg gksrs gSa os viuk
&gkbMªkstu izcy {kkjd dh mifLFkfr esa izksVkWu (H+) ds :i es R;kx dj vuqukn
LFkk;h dkcsZfu;u cukrs gSa( mnkgj.kkFkZ &
CH3
N O
O
- H
CH2
N O
OCH
2N O
O{kkjd
CH3
C- H
N CH2
C N CH2
C N{kkjd
CH3
C- H
CH2
C H CH2
C H
O O O
H{kkjd
CH CH + : NH
2:C CH + : NH
3
C(C6H
5)
3: + H
2O(C
6H
5)
3CH
OH
lajpuk rFkk vkac/ku-I
35
VªkbQsfuy esFksu VªkbQsfuy esfFky dkcsZfu;u
;s rc Hkh curs gS tc dksbZ U;wfDyvksQkby fdlh dkcZu&dkcZu vkca/k ij ;ksx djrk gSA
C2H
5O + CH
2 CH C N
C2H
5OCH
2 CH C N
C2H
5OCH
2 CH C N
1-8-2-2 xq.k Properties
dkcsZfu;uksa ds vkisf{kd LFkkf;Ro dk Øe fuEufyf[kr gksrk gS &
esfFky > izkFkfed > f}rh;d > r`rh;d
buesa $ I izHkko Mkyus okys ,sfYdy lewg dsUnzh; dkcZu ijek.kq ij bysDVªkWu
?kuRo esa o`f) dj nsrs gSaA ftlls dkcsZfu;u ds LFkkf;Ro esa àkl gksrk gSA la;qXeu
(conjugation) o vuqukn ds }kjk Hkh dkcsZfu;u LFkkf;Ro izkIr djrs gSa] tSls&,sfyy
,suk;u rFkk csafty dkcsZfu;u dk la;qXeu ds dkj.k LFkkf;RoA ;s lk/kkj.k ,sfYdy lewgksa
dh rqyuk esa vf/kd LFkk;h gksrs gSaA
:CH2
CH2
CH2
CH2
CH2CHCH
2
..CH
2CHCH2
..
budk lalwpu LisDVªksLdkWih fof/k }kjk gksrk gSA buds vfLrRo dk izek.k vusd
jklk;fud fØ;kvksa ds }kjk izkIr gksrk gSA
C..
CH3 > H
3C
..CH
2 > H > H
3C
H3C
CH3
C :
CH3
CH3
1-8-2-3 dkcsZfu;uksa dh vfHkfØ;k,¡ Reactions of Carbanion
;s vusd ;ksxkRed vkSj izfrLFkkiu fØ;k esa e/;orhZ ds :i esa Hkkx ysrs gSa] tSls&
(1) ;ksxkRed fØ;k & dkcsZfu;u ,sfYMgkbM ds dkcksZfuy lewg ij ;ksxkRed fØ;k djrs
gSa vkSj vius vlgHkkftr bysDVªkWu ;qXe ds }kj vkcU.k cukrs gSaA
: CH2C
O
H
CH3
C
H
O CH3
C
O
H
CH2 C O
H
+
dkcksZfuy ;kSfxd
dkcsZfu;u
;g ;ksx dkcksZfuy lewg ds vfrfjDr dkcksZfuy lewg ds l;qXeu esa fLFkr
vlar`Ir dkcZu ij Hkh gksrk gSA
lajpuk rFkk vkac/ku-I
36
,sYMksy la?kuu] ukosusty vfHkfØ;k vkSj Dystu&f’eV la?kuu] MhdeSu la?kuu
vkfn esa dkcsZfu;u dk ;ksx gksrk gSA
(2) izfrLFkkiu vfHkfØ;k & vusd izfrLFkkiu vfHkfØ;kvksa esa Hkkh dkcsZfu;u Hkkx ysrs gSa]
tSls&eSyksfud ,LVj ds lksfM;e yo.k ls cuk gqvk dkcsZfu;u ,sfYdy gSykbM ds lkFk
fØ;k djds gSykstu dks izfrLFkkfir dj nsrk gS vkSj ,sfYdy eSyksfud ,LVj cukrk gSA
OC2H
5
C O
OC2H
5
C O
Na HC ICH3
OC2H
5
C O
OC2H
5
C O
C CH3 + NalH+
lksfM;ks eSyksfud ,LVj ,sfYdy eSyksfud ,LVj
blds vfrfjDr vusd vfHkfØ;k,¡] tSls&oqVZt vfHkfØ;k] gSyksQkWeZ vfHkfØ;k]
dhVksuksa dk gSykstsuhdj.k vkfn esa dkcsZfu;u e/;orhZ (intermediate) ds :i esa curs
gSaA
1-8-3 eqDr ewyd Free Radicals
tc fdlh lgla;kstd vkca/k dk leka’k fo[k.Mu ;k gkseksfyfVd vkcU/k fo[k.Mu
(hemolytic fission) gksrk gS rc nks fo|qr mnklhu [k.M mRié gksrs gSa ftuds ikl
viuk&viuk lk>s dk bysDV ªkWu gksrk gSA bu ij dksbZ vkos’k ugha gksrk gS vkSj bUgsa eqDr
ewyd dgrs gSaA mUgsa fo"ke (odd) bysDVªkWu ijek.kq ;k v.kq Hkh dgrs gSaA
R . . XXR R + X
. .
;kgkseksfyfVd
dksbZ v.kq eqDr ewyd
Cl . . Cl Cl + Cl. .UV izdk'k
eqä ewyd mnklhu ijek.kq ;k ijek.kqvksa dk ,slk lewg gksrk gS ftlds ikl
viuk lk>s dk bysDVªkWu gksrk gSA bUgsa fo"ke bysDVªkWu ijek.kq ;k v.kq (odd electron
atom or molecule) Hkh dgrs gSA
dqN dkcZfud eqä ewydksa ds mnkgj.k fuEufyf[kr gS &
C
H
H
H .
C
C6H
5
C6H
5
C6H
5.
C
6H
5
.
C
O
OC6H
5
.
esfFky ewyd VªkbQsfuy esfFky
ewyd
Qsfuy ewyd ctk;ykWDlh ewyd
Benzyloxy
1-8-3-1 eqä ewydksa dk fojpu Formation of free radicals
(1) ÅtkZ ds iz;ksx ls & dqN dkcZfud ;kSfxd lk/kkj.k izdk’k esa] dqN dkcZfud ;kSfxd
lw;Z ds izdk’k (UV light) esa rFkk VsVªkesfFky ySM mPp rki ij vi?kfVr gksdj eqä
ewyd mRié djrs gSaA
lajpuk rFkk vkac/ku-I
37
Cl Cl Cl Cl. . .lw;Z dk izdk'k
+ ;k 2Cl
CO CH
3CH
3CH
3CO
. .
CH3
UV izdk'k
+
,slhVksu
CH
3CO
..CH
3CO
UV izdk'k
+
Pb + CH
3
.(CH
3)4Pb
.
4zmPp rki
(2) xksEcxZ dh jklk;fud fof/k }kjk&csUthu esa cuk;s x;s Vªkb,sfjy DyksjksesFksu ds
foy;u esa edZjh ;k flYoj Mkydj dbZ fnuksa ds fy, NksM+ nsus ij VªkbQsfuy eqä ewyd
izkIr gksrk gSA
6 5 6 53 3C H C Cl Ag C H C AgCl
VªkbQsfuy esfFky ewyd
1-8-3-2 eqä ewyd dk LFkkf;Ro Stability of Free Radicals
eqä ewyd dk LFkkf;Ro dkcksZdsVk;u ds LFkkf;Ro ds leku gksrk gSA LFkkf;Ro
dk Øe fuEufyf[kr gksrk gS &
VªkbQsfuy esfFky > MkbQsfuy esfFky > csafty > ,sykby > r`rh;d ,sfYdy >
f}rh;d ,sfYdy > izkFkfed ,sfYdy > esfFkyA
tks Hkh dksbZ dkjd dsUnzh; ijek.kq ds fo"ke bysDVªkWu ds vLFkkuhdj.k
(delocalisation) esa lgk;d gksrk gS og eqä ewyd dk LFkkf;Ro c<+k nsrk gSA la;qXeu
vFkok vuqukn ds }kjk vusd eqä ewyd LFkkf;Ro izkIr djrs gS( tSls&Vªk;Qsfuy esfFky
ewyd vuqukn ds }kjk fuEu izdkj ls LFkkf;Ro izkIr djrk gS &
C . C
.
C
.
C
.
rFkk vU; lajpuk,¡
blh izdkj csfUtfyd vkSj ,ykbfyd ewyd Hkh vuqukn ds }kjk LFkkf;Ro izkIr
djrs gS vkSj ;s ,sfYdy ewydksa dh rqyuk esa vf/kd LFkk;h gksrs gSaA
.
CH2 H
2C .H
2C
.
CH2
.
2 2 2 2CH CH CH CH CH CH
lajpuk rFkk vkac/ku-I
38
1-8-3-3 eqä ewydksa dh vfHkfØ;k,¡ Reactions of Free Radicals
(i) la;ksx dk ;qXeu & nks leku ;k fHké ewyd ijLij la;ksx dj ysrs gS vkSj mnklhu
v.kq cukrs gSaA
Cl Cl Cl Cl
3 3 3 3CH CH CH CH
esfFky eqä ewyd
3 3CH Cl CH Cl
esfFky Dyksjhu
ewyd ewyd
(ii) vlekuqikru Disproportionation & nks eqä ewyd ijLij bl izdkj fØ;k
djrs gSa fd ,d ewyd nwljs dks viuk gkbMªkstu ijek.kq ns nsrk gS vkSj nksuksa LFkkf;Ro
izkIr dj ysrs gSaA bl vfHkfØ;k esa ,d eqä ewyd nwljs ewyd ds }kjk vipf;r gksrk gSA
3 2 2 3 3 3 2 2CH CH CH CH CH CH CH CH
,fFky eqä ewyd
(iii) vikgj.k Abstractions & eqä ewyd fdlh lar`Ir dkcZu dkcZfud v.kq ds lkFk
fØ;k djds mlesa ls ,d gkbMªkstu ijek.kq ¼vFkkZr~ gkbMªkstu eqDr ewyd½ dk vikgj.k
(abstraction) dj ysrk gS vkSj u;k eqDr ewyd mRié gksrk gSA
3 3Cl H CH HCl CH
esFksu
23 2 5 4 5CH H C H CH C H
1-8-4 dkchZu Carbenes
;s mnklhu f}la;kstd dkcZu e/;orhZ gksrs gSa tks ,d izdkj ds f}la;kstu eqä
eqyd gksrs gSa] tSls 2CH
¼esfFkyhu½ vkSj 2CCl
vkfnA dkchZu ds dkcZu ds
ckáre d{kk esa 6 bysDVªkWu gksrs gSaA buesa ls pkj bysDVªkWu cfU/kr bysDVªkWu ;qXeksa
(bonded electron pairs) ds :i esa vFkkZr nks bysDVªkWu ;qXeksa ds :i esa gksrs gSa vkSj
'ks"k nks bysDVªkWu ;k rks ,d ,dkdh bysDVªkWu ;qXe ds :i esa ,d ladfjr vkWfcZVy (sp2)
esa gksrs gSa (Singlet carbene) vFkok ,d&,d bysDVªkWu ds :i esa vyx&vyx
vladfjr p&vkfcZVy esa gksrs gSa (triplet carbene)A vr% dkchZu nks izdkj ds gksrs
gS&flXysV dkchZu rFkk fVªIysV dkchZu (triplet carbene)A flaXysV dkchZu dk dkcZu
sp2&ladfjr voLFkk es gksrk gS rhu sp
2&vkWfcZVyksa esa ls nks cfU/kr bysDVªkWu ;qXeksa
(bonded electron pairs) }kjk nks lewgksa ls tqM+sa jgrs gSaA ,d sp2&ladj vkWfcZVy esa
,d ,dkdh bysDVªkWu ;qXe jgrk gS rFkk vladfjr p&vkfcZVy fjä jgrk gSA
C
R
R' sp2
p-ORBITAL(UNHYBRIDISED)
sp2 (UNHYBRIDISED)
C
R
R'
p-ORBITAL
sp HYBRIDISED
p-ORBITAL
p-ORBITAL
,dd (Singlet) f=dd (Triplet)
fp=&1-20 % flaXysV ,oa fVªIysV dkchZu
lajpuk rFkk vkac/ku-I
39
fVªIysV dkchZu dk dkcZu sp&ladfjr voLFkk esa gksrk gSA blds nks cfU/kr
bysDVªkWu tksM+s bu nks sp&ladfjr vkWfcZVy esa gksrs gSaA bUgh vkWfcZVyksa ds }kjk ;g nks
,sfYdy lewgksa ;k vU; ijek.kqvksa ls tqM+k gksrk gSA ,sls dkcZu esa nks vladfjr
(unhybridised) p&vkfcZVy gksrs gSaA buesa ,d&,d v;qfXer bysDVªkWu jgrk gSA bu
bysDVªkWuksa ds pØ.k lekUrj (parallel spins) fn’kk esa gksrs gSaA vr% nksuksa gh izdkj ds
dkchZuksa ds dkczu ds ckáre d{k esa 6 bysDVªkWu gksrs gSaA buds dkcZu dks viuk v"Vd
iwjk djus ds fy, nks bysDVªkWuksa dh vkSj vko’;drk iM+rh gSa] blfy, ;s ,d
bysDVªksfQfyd vfHkdeZd ds leku O;ogkj djrs gSA
1-8-4-1 fojpu Formation
lkbDyksizksisu (I) rFkk vkWDlhjsuksa ds izdk’k jklk;fud ;k rkih; vi?kVu ls &
C
H3C
6
H
CH2
CH2
H2C : + C
6H
5CH CH
2;k
h
(1)dkchZu
C
H3C
6
H
CHC6H
5
O
C6H
5HC : + HC C
6H
5
Oh
budh lgk;rk ls vusd lkbDyksizksisu O;qRié cuk;s x;s gSaA lkbDyksgsDlhu
¼,sYdhu½ dh mifLFkfr esa MkbDyksjksdkcZu mRié djus ij ,d f}pØh; mRikn izkIr gksrk
gSA
KOH
CHCl3
Cl
Cl
7]7&MkbDyksjh ckbZlkboyh [4,1,0] gsIVsu
vusd dkchZu Mkb,stks ;kSfxdksa vkSj dhVhu ds vi?kVu ls mRié gksrs gSaA
H2C : + : N N :N :NCH
2N :NCH
2 ..
h
Mkb,stksesFksu
C H2C : + : C O :OCH
2 ..
..
;k
h
dhVksu
lalwpu & budk lalwpu bysDVªkWu izpØ.k vuqukn (ESR) v/;;u ds }kjk lQyrkiwoZd
fd;k x;k gSA budk izxzg.k (trapping) ,sYdksgkWy ds –OH vkca/k esa vUrfuZos’k
(insertion) ds }kjk fd;k x;k gSA
1-8-4-2 vfHkfØ;k,¡ Reactions
;s eq[; :i ls nks izdkj dh vfHkfØ;k,¡ iznf’kZr djrs gSaA ;s vfHkfØ;k,¡
gSa&,sYdhu ds lkFk pØh; ladyu (cyclo-addition) rFkk vkca/k esa vUrfuZos’k
(insertion)A
lajpuk rFkk vkac/ku-I
40
C C H2C : C C
CH2
+,sYdhu
C
H
H
R H C
R'
: C
H
H
R C
R
R'
H
R
+vkca/k esa vUrfuZos'k
;s vusd vfHkfØ;kvksa tSls jkbej&Vheu (Riemer-Tiemann) vfHkfØ;k esa
e/;orhZ ds :i esa curs gSaA
1-8-5 ,sjkbu Arynes
,sjkbu ;k csUtkbu os ,sjkseSfVd e/;orhZ gSa ftuesa ,d QkWeZy dkcZu&dkcZu
f=;d vkca/k gksrk gSA bldk izeq[k mnkgj.k csatkbu ¼1]2&fMgkbMªkscsathu½ gS ftls
,slhfVyhu ds lerqY; ekuk tk ldrk gSA
vfirq bldk f=d vkca/k ,slhfVyhu ds f=d vkca/k ds leku ugha gksrk gSa tgk¡ ij nks sp
ladfjr vkWfcVy nks vkca/k cukrs gS vkSj nks vladfjr (unhybridised) p&vkfcZVy
nks &vkcU/k cukrs gSaA ,slhfVyhu ds leku lajpuk csatkbu ds fy, lEHko ugha gSa]
D;ksfd csathu oy; "kV~dks.kh; gksrk gSA laHkor% csatkbu dk u;k vfrfjDr &vkcU/k nks
fudVorhZ dkcZu ijek.kqvksa ds sp2 vkWfcVyksa ds ik’oZorhZ vfrO;kiu ls curk gS ftuds v{k
casthu fjax ds ry esa gh gksrs gSaA ;g vkcU/k csUthu fjax ds &vkf.od vkWfcVy ds
ykfEcd (orthogonal) gksrk gS rFkk ,sjkseSfVd fjax ds Åij o uhps fLFkr vHkz ds lkFk
cgqr de vU;ksU; fØ;k n’kkZrk gSA sp2
fp=&1-21 % csUtkbu dh lajpuk
sp2&vkfcZVyksa ds ik’oZorhZ vfrO;kiu ls cuk &vkcU/k vR;f/kd vLFkk;h gksrk
gS blfy, csUtkbu vfr fØ;k’khy o vLFkk;h gksrk gSA
csUtkbu vusd vfHkfØ;kvksa esa e/;orhZ ds :i esa curs gSaA mnkgj.kkFkZ] izcy
{kkjd dh mifLFkfr esa ,sfjy gSykbM viuh 1]2&fLFkfr;ksa ls HX dk ,d v.kq foyksfir
djds csUtkbu cukrs gSa tks miyC/k U;wfDyvksQkby ds lkFk vfHkfØ;k djds iqu% ,sjkseSfVd
fudk; mRié djrk gSA tSls&czkseks csathu ds lkFk veksfu;k dh fØ;kA
Br
H
: NH2 Br : NH
3+ +
,sfjy gSykbMcsUtkbu
: NH3
NH2
H
H
NH2
+
csUtkbu
+
,sfuyhu
veksfu;k
¼U;wfDyvksQkby½
lajpuk rFkk vkac/ku-I
41
1-8-6 ukbVªhu Nitrenes
dkchZu ds leku] ukbVªhu bysDVªkWu U;wu rFkk mnklhu Loh’kht gksrs gS ftlesa
ukbVªkstu ijek.kq ds cká d{k esa bysDVªkWuksa dk dsoy "kVd (sextet) gksrk gSA ;s nks laHko :iksa esa jg ldrs gSa ftUgsa flaXysV o fVªIysV dgrs gSaA
R N : . .
.
R N
. .
flaXysV fVªIysV
ukbVªhu vusd vfHkfØ;kvksa] tSls&gkWQeSu] dfVZ;l] f’eV vkSj ykWlsu iqufoZU;klksa
vkfn esa ,sfYdy] ,sfly O;qRié ds :i eas e/;orhZ ds :i esa curs gSaA
1-8-6-1 lajpuk Structure
esfFkyhu ¼dkchZu½ ds leku ukbVªhu ,dd (singlet) vFkok f=d voLFkk esa ik;s
tkrs gSaA ,dd esa ukbVªkstu ijek.kq sp2-ladfjr voLFkk esa gksrk gSA bl voLFkk esa
bysDVªkWuksa ds nks ;qXe sp2&vkfcZVyksa esa rFkk ,d bysDVªkWu fuEu ÅtkZ ds vladfjr
p&d{kd gksrk gS tcfd f=d voLFkk esa ukbVªkstu sp&ladfjr voLFkk esa gksrk gSA
fVªIysV esa izR;sd vladfjr p&vkWfcZVy esa ,d&,d bysDVªkWu gksrk gS rFkk ,dkdh
bysDVªkWu ;qXe sp&vkfcZVy esa gksrk gSA
:R N..
:R
.R N
:R
..
.
Nsp2
p-ORBITALfjDr
,dd ukbVªhu (sp2)
N sp
fVªIysV ukbVªhu (sp)
p
p
sp2
1-8-6-2 vfHkfØ;k,¡ Reactions
(i) ;qXeu Coupling – ,sfjy ukbVªhu ;qXeu vfHkfØ;kvksa ds }kjk ,stks ;kSfxd cukrs gSaA
2Ar N 2Ar N N Ar
. .
. .
;g fo’okl fd;k tkrk gS fd ;g fØ;k fVªIysV :i ds }kjk gksrh gSA
(ii) gkbMªkstu dk vikgj.k Abstraction of Hydrogen & ukbVªhu C–H vkca/k
ls gkbMªkstu dk vikgj.k djds izkFkfed ,sehu mRié djrs gSaA vfHkfØ;k ds igys in es
af=d ukbVªhu] fØ;k/kkj (substrate) ls gkbMªkstu dk vikgj.k djds ,d vehuks ewyd o
,d dkcZu ewyd nsrk gSA ;g ,sehuksa ewyd nwljs gkbMªkstu dk vikgj.k djds izkFkfed
,sehu nsrk gSA
C
H
H
H.
C..
NAr :.
[Ar ].N H
H
H
:+ +
.C..
Ar.N H H .CAr NH
2
izkFkfed ,sehu
+ +
lajpuk rFkk vkac/ku-I
42
(iii) iqufoZU;kl Rearrangement & ukbVªhu vf/kdrj ,sls iqufoZU;kl iznf’kZr djrs
gSa ftuesa 1]2&LFkkukUrj.k (1,2-shift) }kjk ,sfYdy] ,sfjy vFkok H– dk dkcZu ls
ukbVªkstu ij vfHkxeu gksrk gSA bl rjg ds iqufoU;kl dk ,d egRoiw.kZ mnkgj.k
gkWQeku iqufoZU;kl gS ftlesa ,d vEy ,sekbM] czksehu rFkk tyh; lksfM;e gkbMªkWDlkbM
ls vfHkfØ;k djds ,d izkFkfed ,sehu nsrk gSA
..
.C
O
R NH2 NaOH
Br2
..C
O
R N
Br
H OH
..C
O
R N.. Br
Br
RNH2
CO2 COH NHR
O
C N
O
R CR N
O
..
..
H2O
,sehu
vkblkslk;usV
,sfly ukbVªhu
1-9 vfHkfØ;kvksa dh fØ;kfof/k fu/kkZj.k dh fof/k;k¡ Methods of determination of Reaction Mechanism
vfHkfØ;k fØ;kfof/k ds fu/kkZj.k fof/k;ksa esa ls izeq[k fof/k;k¡ gSa&mRikn dk foyxu
(isolation), leLFkkfud izHkko (isotopic effect) f=foejklk;fud
(stereochemical) v/;;u vkfnA buesa ls fdlh ,d vFkok lHkh ls izkIr tkudkjh o
xfrd MkVk dks feykdj vfHkfØ;k ds fy, ,d laHko fØ;kfof/k dks izLrkfor fd;k tk
ldrk gSA
1.9.1 Product Analysis
fdlh vfHkfØ;k dh fØ;kfof/k izLrkfor djus ls igys vfHkfØ;k ls feyus okys
lHkh mRiknksa dk] mudh vkisf{kd ek=kvksa lfgr] vfHkfu/kkZj.k djuk vR;Ur vko’;d gksrk
gSA mnkgj.kkFkZ] leko;oh ,sykbfyd DyksjkbMksa ds ty&vi?kVu ls ,d feJ.k izkIr
gksrk gS ftlesa 85% r`rh;d ,sYdksgkWy vkSj 15% izkFkfed ,sYdksgkWy gksrk gSA pw¡fd
mRikn dk la?kVu nksuksa n’kkvksa esa leku jgrk gS blfy, ;g izLrkfor fd;k tk ldrk gS
fd nksuksa gSykbM ,d&lk e/;orhZ (common intermediate) cukrs gSaA bl vk/kkj ij
;g vfHkfØ;k SN1 fØ;kfof/k ds vuqlkj gksuh pkfg;sA nksuksa n’kkvksa esa e/;orhZ dh leku
vuquknh lajpuk;sa curh gSaA
Cl
(CH3)
2C CH CH
2Cl
(CH3)
2C CH CH
2
(CH3)
2C CH CH
2
(CH3)
2C CH CH
2
(CH3)
2C CH
CH2OH
OH
(CH3)
2 C CH CH
2
1&Dyksjks&2&esfFkyC;wV&2&bZuizkFkfed ,sYdksgkWy (15%)
3&Dyksjks&3&esfFkyC;wV&1&bZu e/;orhZ dkcksZdsVk;u r`rh;d ,sYdksgkWy (85%)
e/;orhZ vius fdlh Hkh :i (i) ;k (ii) ds }kjk vkxs fØ;k djds ,sYdksgkWy nsrk gSA
lajpuk (ii) r`rh;d dkcksZdsVk;u gksus ds dkj.k vf/kd LFkk;h gksrh gS blfy, vkxs dh
vfHkfØ;k eq[;r% blh lajpuk ds vuqlkj gksrh gS vkSj r`rh;d ,sYdksgkWy 85% ek=k esa curk gSA
lajpuk rFkk vkac/ku-I
43
blh izdkj esFksu ds izdk’k Dyksjhuhdj.k ij vU; mRiknksa ds lkFk&lkFk FkksM+h
ek=k esa ,Fksu Hkh curk gSA ;g eqDr ewyd fØ;kfof/k ls gh lEHko gSA vr% ;g vfHkfØ;k
¼esFksu dk Dyksjhuhdj.k½ eqDr ewyd fØ;kfof/k ds }kjk gksuh pkfg;sA
2Cl hv 2Cl
I
4 3Cl CH CH HCl
P
3 2 3CH Cl CH Cl Cl
P
3 4CH HCl CH Cl
P
3 3 2 6CH CH C H
T
2Cl Cl Cl
T
I=Initiation P=Propogation T=Termination
1.9.2 e/;orhZ dh mifLFkfr Kkr djds
dkcZfud vfHkfØ;k,¡ vf/kdka’kr% e/;orhZ (intermediate) cukrs gSaA e/;orhZ LFkk;h Lih’kht gksrs gSaA budh mifLFkfr dh igpku budks foyx djds vFkok fdlh
;kSfxd ds }kjk izxzfgr (trap) djds vFkok LisDVªeh fof/k ls dh tk ldrh gS vkSj
vfHkfØ;k dh fØ;kfof/k dk vuqeku yxk;k tk ldrk gSA
1.9.2.1 e/;orhZ dk foyxu ,oa vfHky{k.ku Intermediate Isolation and
Characterisation & gkWQeSu iqufoZU;kl vfHkfØ;k esa rhu e/;orhZ N&czkseks,sekbM
(RCONHBr), bldk ,suk;u (RCONBr–) rFkk vkblkslkbvkusV (RNCO) foyx
fd;s x;s gSaA vr% bl vfHkfØ;k ds fy, ,slh fØ;kfof/k izLrkfor dh tk ldrh gS tks
bu e/;ofrZ;ksa dk cuuk Li"V dj ldsA
R CONH2
RNH2
(Br2 + NaOH)
NaOBr
2 2RCONH NaOBr RCONHBr RCO N Br RNCO RNH
1.9.2.2 e/;oehZ dk LisDVªeh vfHkfu/kkZj.k & e/;orhZ dk cuuk o [kiuk nkuksa rhoz gksa
rc mldk foyxu djuk dfBu gksrk gSA ,sls esa vojDr LisDVªe (IR), ukfHkdh; pqEcdh;
vuqukn (NMR), bysDVªkWu pØ.k vuqukn (ESR) vFkok jkeu LisDVªfefr vkfn fof/k;ksa
ls dqN mi;ksx tkukdjh izkIr dh tk ldrh gSA mnkgj.k ds fy,] jkeu LisDVªfefr }kjk
ukbVªhdj.k feJ.k (H2SO4 + HNO3) esa NO2+ vk;u ¼ukbVªksfu;e vk;u½ ds lalwpu
(detection) }kjk blds }kjk ,sjkseSfVd gkbMªksdkcZu dh ukbVªhdj.k vfHkfØ;k esa e/;orhZ
gksus ds Li"V izek.k izkIr gksrs gSaA
1.9.2.3 e/;orhZ dk izxzg.k Trapping & ,sls ;kSfxd dks tks fof’k"V :i ls lafnX/k
e/;orhZ ls fØ;k djrk gks] vfHkfØ;k feJ.k esa Mkydj e/;orhZ dks izxzfgr (trap) fd;k
tk ldrk gSA mnkgj.kkFkZ] dkchZu dks lkbDyksgSDlhu ds }kjk lkbDyksizksisu O;qRié ds :i
esa izxzfgr fd;k tk ldrk gSA
CH2
N N
N2
H2C : C
H
HlkbDyksizksisu O;qRié
h
dkcZdsVk;uksa ds izxzg.k esa lkekU;r% ukfHkdLusfg;ksa dk mi;ksx gksrk gSA ,sYdhu
esa gSykstu ds ladyu ds le; dkcksZdsVk;u ds e/;orhZ ds :i esa cuus dk lh/kk izek.k
lajpuk rFkk vkac/ku-I
44
bl izs{k.k ls izkIr gksrk gS fd tc ;g vfHkfØ;k vU; ukfHkdLusfg;ksa dh mifLFkfr esa dj
tkrh gS rc mRiknksa dk feJ.k izkIr gksrk gS] tSls &
Br+
CH2 + Br
2/AcOHCH
2CH
2CH
2BrCH
2CH
2OCH
3
CH3O
BrCH2CH
2Br
BrCH2CH
2I
I
Br
1.9.3 leLFkkfudh; v/;;u
vfHkfØ;k iFk o fØ;kfof/k ds v/;;u esa leLFkkfudksa dk nks vyx&vyx rjhdksa
ls mi;ksx fd;k tkrk gSA ;s vuqKkid (tracers) o izfrLFkkih (substituents) ds :i
esa mi;ksx esa yk, tkrs gSA buesa izfrLFkkih dk izHkko xfrdh; gksrk gSA
1.9.3.1 leLFkkfudh; vadu & leLFkkfudh; vadu (isotopic lebelling) esa v.kq ds
dqN ijek.kqvksa dks leLFkkfudksa }kjk izfrLFkkfir fd;k tkrk gSA fQj vfHkfØ;k ds iw.kZ
gksus ds mijkUr mRiknksa dk vafdr Lih’kht ds fy, fo’ys"k.k fd;k tkrk gSA mnkgj.kkFkZ]
,LVj ds ty&vi?kVu dh fØ;kfof/k Kkr djus ds fy, O18
leLFkkfud dk mi;ksx
fd;k x;k gSA ,sfey ,slhVsM (CH3COOC5H11) dk H2O18
dh mifLFkfr esa
ty&vi?kVu djus ij vukafdr (non-labelled) ,sfey ,sYdksgkWy rFkk vafdr ,slhfVd
vEy izkIr gksrk gSA
18 18
3 5 11 2 3 5 11CH COOC H H O CH COO H C H OH
bl izs{k.k ds vk/kkj ij og fu"d"kZ fudkyk tk ldrk gS fd ,LVj ds
ty&vi?kVu esa ,sfly&vkWDlhtu vkcU/k fo[kafMr gksrk gS] ,sfYdy&vkWDlhtu ugha gksrk
gSA
CH3
COH H
O C5H
11CH
3COO H + C
5H
11OH
1818
acyl-oxygen fission
CH3
C
O
OHH CH3COOH + C
5H
11OHO C
5H
11
18 18
alkyl-oxygen fission
lkekU;r% gkbMªkstu (H2, T
3) dkcZu (
13C,
14C) vFkok vkWDlhtu (
17O ;k
18O) ds leLFkkfud iz;ksx esa yk;s tkrs gSaA
1.9.4 f=foejklk;fud izek.k
vfHkdkjdksa o mRiknksa ds f=foe jklk;fud v/;;u }kjk vusd vfHkfØ;kvksa dh
vfHkfØ;k fØ;kfof/k ds ckjs esa egRoiw.kZ tkudkjh izkIr dh tk ldrh gSA tc fdlh /kzqo.k
?kw.kZd (optically active) ;kSfxd ds vlefer (asymmetric) dsUnz ij vfHkfØ;k gksrh
gS tc mRikn /kqzo.k ?kw.kZd gks ldrk gS vkSj ugha HkhA nwljh laHkkouk dks jsflehdj.k
(racemisation) dgrs gSA ,slk vDlj mu vfHkfØ;kvksa esa gksrk gS tgk¡ fØ;kdkjd
fo?kfVr gksdj ryh; e/;orhZ (Planner intermediate) nsrk gSA e/;orhZ vfHkdeZd ds
lkFk fdlh Hkh ik’oZ (side) esa fØ;k dj ldrk gSA blls ;k rks foU;kl ifjofrZr gks
tkrk gS vFkok /kkfjr (retained) jgrk gSA mnkgj.kkFkZ] tc /kqzo.k r`rh;d ,sfYdy
gSykbM dk ty&vi?kVu fd;k tkrk gS rc ,slsfed mRikn curk gS tks fuEu fØ;k fof/k
lajpuk rFkk vkac/ku-I
45
(SN1) ds vuqlkj dkcksZdsVk;u ¼leryh;½ ds e/;orhZ ds :i esa cuus dk vuqeksnu djrk
gSA dkcksZdsVk;u ds cuus ds ckn vxys in esa –OH lewg /kukosf’kr dkcZu ls fdlh Hkh
ik’oZ (side) es tqM+dj jslsfed feJ.k cukrk gSA
C ClC2H
5
C6H
5
CH3
aq. acetoneC OHC
2H
5
C6H
5
CH3
C
C6H
5
CH3
C2H
5
C C2H
5OH
C6H
5
CH3
Cl
+H2O
+
(+) isomer carbocation dl jslsfed feJ.k
tc 2&czkseksvkWDVsu ds ,d /kqzo.k ?kw.kZd leko;oh dk {kkjdh; ty&vi?kVu
fd;k tkrk gS rc /kqzo.k ?kw.kZd ,sYdksgkWy izkIr gksrk gSA ;g rHkh lEHko gS tc OH–
vk;u dkcZu ij Br– vk;u dh foijhr fn’kk ls vkØe.k djrk gS vkSj dkcksZdsVk;u
e/;orhZ ds :i esa u curk gksA ,slh fLFkfr esa vfHkfØ;k lfEefyr (concerted) :i esa
gksrh gS ¼SN2 fØ;kfof/k½ vkSj foU;kl dk O;qRØe.k (inversion) gks tkrk gSA
C BrHHO
CH3
H13
C6
HO ..... C ..... Br
C6H
13
CH3
H
C HOH
CH3
C6H
13
/kqzo.k ?kw.kZd
¼foijhr foU;kl½
f=foejklk;fud v/;;u }kjk ;ksxkRed] foyksiu rFkk iqufoZU;kl vfHkfØ;kvksa ds
ckjs esa egRoiw.kZ tkudkjh izkIr gksrh gSA mnkgj.kkFkZ] ;g ik;k x;k gS fd fll&MkbDyksjks
,fFkyhu dk Dyksjks ,slhfVyhu esa :ikUrj.k VªkUl leko;oh dh rqyuk esa 20 xquk vf/kd
xfr ls gksrk gS ftlls ;g Li"V gksrk gS fd os E2 vfHkfØ;k,¡ rhoz osx ls gksrh gS ftuesa
fu"dkflr gksus okys lewg fll dh vis{kk VªkUl fLFkfr esa fLFkr gksrk gSA
C
H
Cl
C
Cl
H
OH
fastC CCl H C
Cl
H
C
Cl
Hcis trans
OH
slow
1.9.5 xfrd izek.k Kinetic Evidence
xfrd (Kinetic) v/;;u ls vfHkfØ;k dh fØ;kfof/k ds ckjs esa Li"V tkudkjh
izkIr ugha gksrh gS fdUrq vfHkfØ;k dh dksfV ds ckjs esa fuf’pr tkudkjh izkIr gks tkrh gS
tks fd lEHkkfor fØ;kfof/k;ksa esa ls lgh fØ;kfof/k dk p;u djus esa lgk;d gksrh gSA
tSls] esfFky czksekbM dk gkbMªkWDlkbM vk;u }kjk ty&vi?kVu ds fy, fuEu osx&O;atd
izkIr gksrk gS &
- [CH3Br]
dtk [CH
3Br] [OH]
blls Li"V gksrk gS fd esfFky czksekbM ds ty&vi?kVu dh fØ;kfof/k bl
izdkj dh gksxh ftlesa osx fu/kkZjd in esa OH– vk;u dk Hkh ;ksxnku gksxkA vr% ;g
,d f} v.kqd f}rh; dksfV (SN2) vfHkfØ;k gS ftls fuEukafdr izdkj n’kkZ;k tk ldrk
gS&
lajpuk rFkk vkac/ku-I
46
HO ..... C ..... BrHO + CH3 Br Br + CH
3 OH
H
HHeUn rhoz
blh izdkj r`rh;d C;wfVy czksekbM ds fy, fuEu osx O;atd izkIr gksrk gS &
3 3
3 3
CH CBrCH CBr
dt
blls izdV gksrk gS fd osx fu/kkZjd in esa OH– dk dksbZ ;ksxnku ugha gksrk
gSA vr% ;g ,d&v.kqd izFke dksfV (SN1) dh vfHkfØ;k gksxh tks fuEu izdkj gksrh gS &
(CH
3)
3CBr (CH
3)
3C + BreUn
(CH
3)
3C + OH (CH
3)
3C
OHrhoz
mi;qZDr izs{k.k rFkk f=foejklk;fud izek.k ds vk/kkj ij nksuksa izdkj ds ,sfYdy
gSykbMksa ds {kkjdh; ty&vi?kVu ds fy, fHké fØ;kfof/k;k¡ (SN1 o SN
2) ekU; dh
x;h gSA
1- Check your progress I fuEu es dkSu lk izHkko LFkkbZ ugh gS &
A. izsjf.kd B.ehlksesfjd C.bysDVªksesfjv D.,sjksesfVd
II fcuk ca/k vuqukn dk nwljk uke gS
A.izsjf.kd izHkko B.ehlksesfjd izHkko C.bysDVªksesfjd izHkko D.vfrla;qXeu
III ,sjkseSfVd ;kSfxd esa fdrus bysDVªkWu gksrs gS\
A.(4n+2) B.(4n+3) C.(4n+1) D.(4n+4)
IV fuEu es ls dkSu lk ;kSfxd gkbMªkstu ca/k ugh cukrk gS
A.H2O B.C2H5OH C.CH3COOH D.C6H6
V H3C–CH=CH–C CH es ck;h ls nkfguh vksj dkcZu ijek.kqvksa dk ladj.k
D;k gS\
A. sp3,sp
2,sp
2,sp,sp B. sp
3,sp
2,sp
2,sp,sp
3
C. sp3,sp,sp,sp
2,sp
2 D. sp
2,sp,sp
2,sp,sp
3
VI ladsru n’kkZrk gS &
A.bysDVªksesfVd izHkko B.izsjf.kd izHkko C.vuqukn D.vfrl;qXeu
VII CH4 v.kq esa fuEufyf[kr ca/k gksrs gS &
A.leryh; B.prq"Qydh; C.fijkfeMh D.iapHkqth;
VIII CH2=CH2 v.kq esa fuEufyf[kr ca/k gksrs gS &
A. 6 B. 5 C. 4 D. 4
IX fdl dkcZu ladfjr voLFkk esa =.kfc/kqrk lokZf/kd gksrh gS
A. sp B. sp2 C. sp
3 D. sp
2d
2
X lkbDyksisUVkMkbZfuy ,suk;u esa fdrus bysDVªku gksrs gS
A. 2 B. 6 C. 10 D. 4
Short question -
I lekfur rFkk vlekfur ca/k fo[kaMu dks mnkgj.k lfgr le>kb,A
II fiatj ;kSfxd D;k gS\ ;s ijukyk ladqy ls fdl izdkj fHké gS\
III vkos’k LFkkukUrj.k ;kSfxd D;k gS\ buds egRo fyf[k,A
IV lfØ; e/;d D;k gS\ muds fuekZ.k rFkk fØ;k ds ckjs esa o.kZu dhft,A
lajpuk rFkk vkac/ku-I
47
V U;wfDyksQkby ,oa bysDVªksQkby esa mnkgj.k lfgr varj Li"V dhft,A
VI fofHké izdkj dh dkcZfud vfHkfØ;kvksa ds mnkgj.k fyf[k,A
VII vfHkfØ;k dh fØ;kfof/k fu/kkZfjr djus dh fof/k;ksa dk o.kZu dhft,A
1-11 Unit (Summary) dkcZu ds S rFkk P d{kdksa ds vfrO;kiu ls ca/k curs gSa ca/k S-S, S-P rFkk
PP fljs okj vfrO;kiu ls curs gS rFkk ca/k PP d{kdksa ds yaccr vfrO;kiu ls curs
gSaA dkcZu es rhu izdkj ds ladj.k gksrs gSa (i) SP (ii) SP2 rFkk (iii) SP
3 mnkgj.k
CH CH esa SP.CH2=CH2 esa SP2 rFkk CH4 esa SP
3 ladj.k gksrk gSaA foHké
ladj.k ds dkj.k dkcZu yk[kksa ;kSfxd cukrk gSA foHké izdkj ds ca/k dh vkca/k yEckbZ Hké
gksrh gS] fofHké lg la;ksth ca/k dh f=T;k,¡ Hkh vyx&vyx gksrh gSA v.kkqsa esa vkca/k
dks.k dh fHké gksrs gSA ca/k dh vkca/k ÅtkZ] ml ca/k dks rksM+us esa yxus okyh ÅtkZ dks
dgrs gSA vkca/k dksfV nks ijek.kqvksa ds cht fdrus ca/k gksrs gS] og n’kkZrk gSA dqN v.kq
ds foHké lajpuk,¡ gksrh gS ftlesa dsoy bysDVªkWu dh LFkkiuk esa dsoy varj gksrk gS
mudks vuquknh lajpuk, dgrs gSA ikuh ds v.kq esa gkbMªkstu ca/k gksrk gSA ;g nks izdkj
ds gksrs gS varj v.kqd rFkk var; v.kqdA ok.Mj okYl oy lgla;kstd v.kqvksa ;k
ijek.kqvksa ds e/; yxus okyk nqcZy vkd"kZ.k cy gSaA lekos’ku ;kSfxd % okfgdk ;k uky
;k DySFkzsV ;k fiatj izdkj dks gksrs gSA vkos’k LFkkukUrj.k ladqy esa ,d v.kq nkrk rFkk 3
,d v.kq xzkgh gksrk gSA
lgla;kstd vkca/k esa foHké izdkj ds izHkko gksrk gS tSls fd izsjf.kd rFkk {ks=h;
izHkko] vfrla;qXeu] ehlksesfjd ,oa bysDVªksesfVd izHkko lgla;kstd vkcU/k nks izdkj ls
fonyu djrk gSA leka’k vkSj fo"keka’k vkca/k fonyu ftlls vyx&vyx izdkj dh
dkcZfud vfHkfØ;kvksa dh fØ;k fof/k gksrh gSA blesa bysDVªksfQyd rFkk U;wfDyksfQfyd
vfHkedZ fØ;k djrs gS rFkk foHké izdkj dh dkcZfud vfHkfØ;k gksrh gSA Å"ekxfrdh ,oa
xfrd v/kkj ls dkcZfud vfHkfØ;kvksa esa fopkj fd;k tk ldrk gSA dbZ dkcZfud
vfHkfØ;k esa vyx&vyx e/;orhZ gksrs gS tSls dkcsZdsVk;u] dkcZ,suk;u] eqDr ewyd]
dkchZu] ,sjkbu ukbVªhu vkfnA mRikn dk fo’ys"k.k] e/;orhZ dh mifLFkfr Kkr djds]
leLFkkfudh; v/;u] f=foHk jklk;fud izek.k rFkk xfrd izek.k ls vfHkfØ;kvksa dh
fØ;kfof/k dk fu/kkZj.k fd;k tkrk gSA
1- Ans to check your progress
I C.bysDVªksesfjv II D.vfrla;qXeu III A.(4n+2) IV D.C6H6 V A.
sp3,sp
2,sp
2,sp,sp VI C.vuqukn VII B.prq"Qydh; VIII B. 5 IX
A. sp X B. 6
1-13 dqN mi;ksxh iqLrdsa Suggested reading/Reference
1. Organic Chemistry, Volume 1, I.L. Finar, ELBS Longman.
Fundamentals of Organic Chemistry , T.W. Graham Solomons, John
Wiley & Sons, Inc. Chapters 3, 11&13.
2. Organic Chemistry, Volume I, S.M. Mukherji, S.P. Singh, R.P.
Kapoor, Wiley Eastern Limited, New Delhi.
3. Organic Chemistry, Robert T.Morrison and Robert N.Boyd,
Prentice-Hall of India, Pvt. Ltd. New Delhi.
4. Advanced Organic Chemistry, B., S. Bahl and Arun Bahl, S. Chand
& Company Ltd. New Delhi.
5. Organic Chemistry, M.K. Jain, Shoban Lal Nagin Chand & Co.,
Delhi.
lajpuk rFkk vkac/ku-I
48
2-0 izLrkouk dkcZfud ;kSfxdksa dk f=foe jlk;u
2-
bl bdkbZ dk e/;;u djus ls vki fuEu 'kh"kZdks dh tkudkjh izkIr dj ldsxsA
1- leko;ork rFkk mlds izdkjA
2- f=foe leko;ok rFkk mlds izdkjA
3- T;kferh; leko;ok rFkk mlds izdkj] foU;kl dk fu/kkZj.k
4- izdkf’k; leko;ok rFkk mnkgj.k
5- lery /kqfor izdk’k
6- /kzqo.k ?kw.kZdÙkk
7- fof’k"V ?kw.kZu
8- fdjSfyVh
9- leferh ds rRo
10- vizfrfcEc :i rFkk mlds izdkj
11- ,ihej
12- izfrfcEc :iksa dk izFkDdj.k
13- jsflehdj.k
14- okYMu izfrykseu
15- foU;kl rFkk mlds izdkj
16- la:i.k rFkk fu:fir djus dh fof/k;k¡
17- ,Fksu] n&C;wVsu rFkk lkbDyksgsDlsu ds la:i.k
2-2 leko;ork
nks ;k nks ls vf/kd ,sls ;kSfxd ftuds v.kqlw= leku gks] leko;oh (isomers) dgykrs
gS rFkk ;s ifj?kVuk leko;ork (isomerization) dgykrh gSA
leko;ork dh [kkst 1820 esa ykfcx rFkk Ogksyj n~okjk dh xbZ FkhA mUgksus nks
;kSfxd flYoj lkbusV (AgCNO) rFkk flYoj QYehusV (AgONC) dks izkIr fd;k Fkk
ftlesa ijek.kq la[;k¡ leku FkhA
leko;kfo;ksa ds HkkSfrd o jlk;fud nksuksa gh xq.kksa esa fHkérk gksrh gSA fdlh
dkcZfud ;kSfxd ds xq.k mudh lajpuk ij fuHkZj djrs gSaA lajpuk ls rkRi;Z ;kSfxd esa
mifLFkr vkca/kksa ds Øe ls vFkok ;kSfxd esa mifLFkr fdlh ijek.kq dh vU; ijek.kqvksa ds
lkFk lyaXurk ls gksrk gSA
leko;ork nks izdkj dh gksrh gS &
¼v½ lajpukRed leko;ork
¼c½ f=foe leko;ork
leko;rrk
lajpuk leko;ork f=foe leko;ork
J[kayk LFkku fØ;kRed e/;ko;rk pyko;ork oy; J[kayk
izdkf’kd T;kferh; la#ih;
2-2-1 lajpuk leko;ork (Structural isomerism)
lajpuk rFkk vkac/ku-I
49
tc nks ;k nks ls vf/kd ;kSfxdks ds v.kqlw= leku ijarq lajpuk lw= fHké gks] rks
mUgsa laajpuk leko;oh dgrs gSa rFkk bls lajpuk leko;ork dgrs gSaA
mnkgj.k & lw= C3H7Cl ds nks leko;oh n&izksfiy DyksjkbM rFkk vkblksizksfiy
DyksjkbM laHko gSaA
C3H7Cl CH3CH2CH2Cl
Cl
CH3
CHCH3
v.kqlw= n&izksfiy DyksjkbM vkblks izksfiy DyksjkbM
lajpuk leko;ork ds 6 izdkj gksrs gSA
2-2-2 J[kayk leko;ork (Chain isomerism)
,sls ;kSfxd ftuds vq.klw= leku ijarq muesa mifLFkr dkcZu ijek.kqvksa ds vkil
esa tqM+us ds Øe esa fHkérk gks] vFkok dkcZu ijek.kq lh/kh vFkok 'kk[kk ;qDr J[kayk ds #i
esa O;ofLFkr gks] J[kayk leko;oh dgykrs gSa rFkk bls J[kayk leko;ork dgrs gSaA
mnkgj.k (a) lw= C4H10 nks leko;kfo;ksa ds #i esa izkIr gSA
C4H10 CH3CH2CH2CH3
CH3
CH3
CHCH3
v.kqlw= n&C;qVsu vkblks C;qVsu
(b) C5H12 ds 3 leko;oh gSaA
C5H12 : v.kqlw=
CH3 – CH2CH2CH2CH3
n&C;qVsu
CH3
CH3
CHCH3
CH3
CH3
CCH3
CH3
vkblks isUVsu fu;ks isUVsu
2-2-3 LFkku leko;ork (Position Isomerism)
,sls ;kSfxd ftuds vq.klw= leku] ijarq muesa mifLFkr izfrLFkkid ijek.kqvksa
(substituent atoms) ;k leqgksa dk dkcZu J[kayk esa tqM+us dk LFkku fHké&fHké gks]
LFkku leko;oh dgykrs gSa rFkk bls LFkku leko;ork dgrs gSaA
mnkgj.k (a) C3H7OH ds nks leko;oh gSaA
C3H7OH CH3CH2CH2OH
OH
CH3
CHCH3
v.kqlw= n&izksfiy ,Ydksgy vkblks izksfiy ,Ydksgy
(b) tk;yhu (C8H10) ds 3 leko;oh gSaA
lajpuk rFkk vkac/ku-I
50
C8H10 :
CH3
CH3
CH3
CH3
CH3
CH3
v.kqlw= vkFkksZtk;yhu esVk vk;yhu iSjk tk;yhu
2-2-4 fØ;kRed leko;ork@vfHky{kdh; leko;ork (Functional Isomerism)
,sls ;kSfxd ftuds vq.klw= leku] ijarq muesa fHké&fHké izdkj ds fØ;kRed lewg
mifLFkr gksa] fØ;kRed leko;oh dgykrs gSa rFkk bls fØ;kRed leko;ork dgrs gSaA
mnkgj.k &
(a) C3H6O : C2H5 CHO CH3COCH3 v.kqlw= izksfivkWu ,fYMgkbM ,lhVksu
(b) C3H9N CH3CH2CH2NH2 CH3NHC2H5 CH3N(CH3)2
v.kqlw= izksfiy,ehu ,fFkyesfFky,ehu VªkbesfFky,ehu ¼izkFkfed½ ¼f}rh;d½ ¼r`rh;d½
2-2-5 e/;ko;rk leko;ork (Metamerism)
,sls ;kSfxd ftuds vq.klw= leku] ijarq muesa mifLFkr fØ;kRed lewgks ls tqM+us
okys ,fYdy leqgksa esa fHkérk gks] e/;ko;h dgykrs gS rFkk bls e/;ko;rk dgrs gSaA
bl izdkj dh leko;ork ltkrh; Js.kh ds lnL;ksa n~okjk iznf’kZr dh tkrk gSA
mnkgj.k &
(a) C4H10O CH3 O C3H7 C2H5 O C2H5 v.kqlw= esfFkyizksfiybZFkj Mk;,fFkybZFkj
(b) C4H11N CH3 NH C3H7 C2H5 NH C2H5 v.kqlw= esfFkyizksfiy,ehu Mk;,fFky,ehu
2-2-6 pyko;ork (Tautomerism)
leko;ork ftlesa ;kSfxd dk O;ogkj bl izdkj dk gksrk gS fd ekuksa mldh nks
izdkj dh lajpuk,¡ ;k #i gks] pyko;ork dgykrh gSA rFkk buesa fofHké #iksa dks
(Tautomers) pyko;oh dgrs gSA
bl izdkj dh leko;ork ,d gkbMªkstu ijek.kq ds 1]3 LFkkuksa ij fLFkr nks
cgqla;ksxh (Polyvalent) ijek.kqvksa ds chp esa nksyu (Oscillation) djus ls mRié gksrh
gSA gkbMªkstu ijek.kqvksa ds nksyu ds lkFk lkFk leko;kfo;ksa ds ca/kksa esa Hkh ifjorZu gksrk
gSA
mnkgj.k &
(a)
H O N O H NO
O
ukbVªkbV #i ukbVªks #i
(b) ,flVks,flfVd ,LVj ds nks leko;oh] dhVksfud #i rFkk buksfyd #i gksrs gS bls
buksy leko;ork dgrs gSA
lajpuk rFkk vkac/ku-I
51
O
CCH3
CH2
COOC2H
5
OH
CCH3 CH COOC
2H
5
dhVksu #i buksy #i
92.1% 7.9%
2-2-7 oy; J[kayk leko;ork (Ring chain isomerism) bl izdkj dh leko;ork esa leko;oh foor J[kayk (Open chain) rFkk lao`r
J[kayk (closed chain) okys gksrs gSaA
mnkgj.k
(a) CH CH
2CH
3 CH
2CH
2
CH2
izksihyhu lkbDyksizksisu
(b) CH CH
2CHCH2
CH2
CH2
CH2
CH2
1]2] Mk;C;qVhu lkbDyksC;qVsu
2-3 f=foe leko;ork
tc nks ;k nks ls vf/kd ;kSfxdksa ds v.kqlw= rFkk lajpuk lw= ,d leku gksa ijarq
muds ijek.kq ;k ijek.kq leqgksa dh f=foe esa O;koLFkk fHké gks rks mUgsa f=foe leko;oh
dgrs gSA bls f=foe leko;ork dgrs gSaA
f=foe leko;fo;ksa ds ijek.kq vFkok lewgksa ds tqM+us dk Øe ,d leku gksrk gS
ijUrq os f=foe esa vyx&vyx vkdk’kh; foU;kl ?ksjrs gSaA
f=foe leko;ork dks nks oxksZ esa ckaVk tkrk gSaA
(I) la#ih; leko;ork (Conformational isomerism)
bl izdkj dh leko;ork] fdlh v.kq ds ,dy vkoa/kksa ls vkcaf/kr ijek.kqvksa
vFkok leqgksa ds eqDr ?kw.kZu ds dkj.k fHké f=foe foU;kl xzg.k djus ls mRié gksrh gSaA
,sls izR;sd foU;kl dks la#i.k (conformation) dgrs gSaA
la#i.k lkekU; rki ij ,d nwljs esa ,dy ca/k ds pkjksa vksj eqDr ?kw.kZu ds
nokjk izkIr gksrs gS bUgs ,d nwljs ls izFkd djuk dfBu gksrk gSA mnkgj.k & ,Fksu rFkk
C;qVsu ds la#i.k A
(II) foU;klh leko;ork (Configuration isomerism)
;g mu f=foe leko;fo;ksa ds n~okjk iznf’kZr dh tkrh gS] ftUgsa vkca/kksa ds rksM+s
fcuk ,d nwljs ls ifjofrZr ugha fd;k tk ldrk gSA bUgsa T;kferh; rFkk izdkf’kd
lek;ork esa oxhZd`r fd;k tkrk gSA
(a) T;kferh; leko;ork (Geomerical isomerism)
og f=foe leko;ork tks f}vkca/k ¼;k pØh; lajpuk½ tSls n`.k lajpuk ds pkjksa
vksj leqgksa ds izfrcaf/kr ?kw.kZu ds dkj.k fHké foU;kl izkIr dj ysus ls mRié gksrh gS]
lajpuk rFkk vkac/ku-I
52
mls T;kferh; leko;ork dgrs gSA ,sls leko;fo;ksa dk ,d nwljs esa vklkuh ls
varjifjorZu laHko ugha gksrk gSA
(b) (Optical isomerism)
;g leko;ork vk.kfod vleferh ds dkj.k mRié gksrh gSA ,sls lekofo;ksa ds
jlk;fud rFkk vf/kdk’kar% HkkSfrd xq.k leku gksrs gS ijarq lery /kqzfor izdk’k ds izfr
fHké O;ogkj gksrs gSA
vr% f=foe leko;ork eq[;r% 3 izdkj dh gksrh gSaA
(I) izdkf’k; leko;ork
(II) T;kferh; leko;ork
(III) la#ih; leko;ork
2-4
izdkf’kd leko;ork ds v.kqlw= rFkk lajpuk lw= rks leku gksrs gS fdUrq ,d
leko;oh dks nwljs leko;oh ij v/;kjksfir ugha fd;k tk ldrk gSA
H
CH3
C2H5
C2H5
Cl
H
Cl
fp= 2.1 % 2&DyksjksC;qVsu ds izdkf’kd leko;oh
tSls ,d ;kSfxd] ftlesa ,d dkcZu ijek.kq pkj vleku leqgksa ;k ijek.kqvksa ls vkcfU/kr
gSA pwfd dkcZu ijek.kqvksa dh la;kstdrk prq"Qydh; #i f}d foU;kflr gS] mlls tqM+s
pkj vleku leqgksa dks nks #iksa esa O;ofLFkr fd;k tk ldrk gS vFkkZr nks vyx&vyx
foU;kl gks ldrs gSaA
fdlh ;kSfxd ds ijek.kq ;k ijek.kq leqgksa dh vkdk’kh; O;koLFkk dks foU;kl
(configuration) dgrs gSaA
mnkg.kkFkZ 2 DyksjksC;qVsu ds nks izdkf’kd leko;fo;ksa dks n’kkZ;k x;k gSa tks ,d nwljs ds
ihNs gSA budk v/;kjksi.k vlEHko gS vr% ;s ,d nwljs ds f=foe leko;oh gSaA bl
f=foe lajpuk esa CH3 i`"B oØ ds ihNs gSA C2H5 i"B ry ij rFkk Cl rFkk H i`"B ry ds mij gSaA ifj.kker% nks izFkd foU;kl tks ,d nwljs ij v/;kjksfir ugha gksrs gSaA
budk uke 2 DyksjksC;qVsu dsoy budh ljapuk dks iznf’kZr djrk gS vkdk’kh; foU;kl dks
ughaA ;s leko;oh izdk’kh; leko;oh (Optical isomers) dgykrs gSaA budk (plane
polarized light) lery /kzqfor izdk’k ds izfr O;ogkj fHké gksrk gSA
lajpuk rFkk vkac/ku-I
53
2-4- (Plane polarized light) izdk’k dk lapj.k (Propagation) ,d rjax ds #i esa gksrk gSA rFkk lk/kkj.k
izdk’k esa bldh rjaxksa ds daiu lHkh ryksa esa lapj.k js[kk ds yEcor gksrs gSA tc ,sls
izdk’k dh fdj.k dks fdlh (optical device) izdk’kh; ;qfDr ls xqtkjk tkrk gS rc
fuxZrdj.k (Emergent ray) dsoy ,d gh ry esa dafir gksrh gS bl izdkj dk izdk’k
tks ,d gh ry esa dafir gksrk gS (plane polarized light) lery /kqzfor izdk’k
dgykrk gSA rFkk ry (plane of polarization) /kzqo.k ry dgykrk gSA
.
lkekU; izdk’k fudkWyfizTe lery /kqzfor izdk’k vk¡[k
fp= 2.2 % leery&/kqzfor izdk’k
2-4-2 /kqzo.k ?kw.kZdrk (Optical activity) tc lery /kqzfor izdk’k dks cgqr fof’k"V inkFkZ ¼ek/;e½ esa ls xqtkjk tkrk gS]
rks fuxZr izdk’k ,d vU; lery esa daiu djrs gq, ik;k tkrk gS vFkkZr bl ek/;e ds
fof’k"V xq.k ds dkj.k /kzqo.k lery ck¡;h ;k nk¡;h vksj ?kwerk gSA
vr% ,slk inkFkZ ¼ek/;e½ tks /kqzfor izdk’k ds /kqzo.k lery dk ?kw.kZu
(Rotation) djrk gSA /kzqo.k ?kw.kZd inkFkZ (Optically active substance) dgykrk gSA
rFkk ;g ?kVuk /kzqo.k ?kw.kZdrk (Optical activity) dgykrh gSA
tks leko;oh lery /kqzfor izdk’k ds ry dks nk¡;h vksj (clock wise ) ?kqekrs
gSaA mUgsa nf{k.k /kqo.k ?kw.kZd (Dextro rotatary )dgrs gSa mUgsa d ;k ?ku (+) fpUg ls
iznf’kZr djrs gSA tks leko;oh lery /kqzfor izdk’k ds ry dks ck¡;h vksj ?kqek nsrs gSa mls
oke/kzqo.k ?kw.kZd ;k leavo rotary dgrs gSA bUgsa L&v{kj ;k _.k (–) fpUg ls iznf’kZr
djrs gSaA
tks leko;rh lery /kqzfor izdk’k ds ry dks fdlh Hkh fn’kk esa ugha ?kqekrs gSa
mUgsa /kqzo.k vk?kw.kZd (Optical inactive) dgrs gSaA ;s ehlksa (Meso) ;k jslsfed
(Racemic) ;kSfxd gksrs gSaA
phuh] Xywdkst] ysfDVd vEy] VkVZfjd vEy vkfn /kzqo.k ?kww.kZd inkFkZ gSaA dqN
vdkcZfud ;kSfxd ds fØLVy tSls& lksfM;e vFkok iksVsf’k;e ds czksesV ;k vk;ksMsV Hkh
/kqzo.k ?kw.kZd inkFkZ gSA
lkekU;
izdk’k
fudkWy
fizTe
lery
/kzqfor izdk’k
izdkf’kd lfØ; inkFkZ
fo’ys"kd okekorZ?kw.kZu
(Anti clock
wise)
nf{k.kkorZ ?kw.kZu
(Clock wise)
fp= 2.3 % /kqzo.k ?kw.kZdrk dk vkjs[kh; izn’kZu
lajpuk rFkk vkac/ku-I
54
2-4-3 /kqzo.k ?kw.kZdrk dk ekiu (Measurement of Optical
activity)
/kqzo.kekih (Polarameter) & /kqzo.kekih ds eq[; fuEufyf[kr Hkkx gksrs gSa &
(i) izdk’k dk ,d L=ksr ¼lk/kkj.kr;k lksfM;e ySEi½
(ii) ,d /kzqod (Polarizer)
(iii) ,d uyh /kqzo.k ?kw.kZd inkFkZ ;k mlds tyh; foy;u dks j[kus gsrqA
(iv) ,d fo’ys"kd (Analyser)
(v) ?kw.kZu dks.k dks ekius ds fy, ,d oÙkkdkj LdsyA
/kqzo.k ?kw.kZd ;kSfxd dk mi;qDr foyk;d esa ekud foy;u ¼Kkr 'kfDr okyk
foy;u½ cukdj dkap dh izs{k.k uyh (Observation tube) esa Hkj fn;k tkrk gSa rFkk
o`Ùkkdkj Ldsy (Circular scale) ij ?kw.kZu dks.k (Angle of rotation) () dk
ikB~;kad uksV dj ysrs gSaA
2-4-4 (Specific rotation)
dksbZ izdk’k leko;oh lery /kzqfor izdk’k ds ry dks fturs va’k ls ?kqekrk gS]
mls ?kw.kZu dks.k (angle of rotation) dgrs gSA fdlh foy;u dh ?kw.kZu 'kfDr
(Rotation power) dks fof’k"V ?kw.kZu (specific rotation) ds #i esa O;Dr fd;k
tkrk gSaA
cl
ifsz {kr ?k.w kuZ
fof'k"V ?kw.kZu
tgk¡ l = /kqzo.kekih uyh dh MslhehVj esa yackbZ
c = foy;u dh xzke izfr ?ku lseh esa lkUnzrkA
fof’k"V ?kw.kZu dks n’kkZrs le; rki rFkk izdk’k dk rjax nS)Z Hkh fy[krs gSaA
vr% ot
D l c
fof’k"V ?kw.kZu og dks.k gS tks bdkbZ lkUnzrk rFkk bdkbZ yEckbZ okys foy;u n~okjk mRié
gksrk gSA
mnkgj.k & 20oC rki ij lqØksl foy;u ds fy,
20
65.5o
o
D
D = lksfM;e ySEi dh D js[kk [=5890Ao]
+ fpUg = Dextro–rotation nf{k.kkorhZ ?kw.kZu
2-4-5 ?kqzo.k ?kw.kZork ds dkj.k (Cause of optical activity)
(i) fØLVyh; lajpuk ds dkj.k & vkajsxks us loZizFke DokVZ~t ds nks fØLVyh; :iksa
dks ns[kk tks ,d nwljs ds izfrfcEc :i Fks ijUrq ,d nwljs ij v/;kjksfir ugha gksrs Fks
mUgksus ik;k fd ;s lery ?kqzfor izdk’k dks ck¡;h ;k nk¡;h vksj ?kqek nsrs gS ijUrq mUgsa
fi?kaykus ij ;s optically inactive ¼/kzqo.k vk?kw.kZd½ gks tkrs gSaA vr% /kqzo.k ?kw.kZrk
lajpuk rFkk vkac/ku-I
55
fØLVyksa dk xq.k gksrk gSA vU; mnkgj.k% lksfM;e czksesV vkSj lksfM;e vk;ksMsV dk foys;
vFkok fi?kyh voLFkkA
(ii) vk.kfod lajpuk ds dkj.k (Optical activity due to molecular
structure)& vusd /kzqo.k ?kw.kZd dkcZfud inkFkZ dh lajpuk dk v/;;u djus ij ik;k
x;k fd buesa ,d vlefer dkcZu ijek.kq vo’; ik;k tkrk gS vlefer dkcZu ijek.kq ls
rkRi;Z ,sls dkcZu ijek.kq ls gS ftldh pkjksa l;kstdrk,¡ fHké gksaA
mnkgj.k &
COOH
CH H
CH3
COOH
CH OH
CH3
CH3
CCH3 H
COOH
izksfi;ksfud vEy ySfDVd vEy vkblksC;qfjfjd vEy
(Optically inactive) (Optically active) (Optically inactive)
COOH
CH H
H
CH3+ H
Xykbdkfyd vEy
(Optically inactive)
2-4-6 fdjSfyVh (Chirality)
dksbZ inkFkZ vFkok v.kq tks vius niZ.k izfrfcEc (Mirror image) ij v/;kjksfir
(Super impose) ugha gksrkA fdjSy v.kq dgykrk gSA fdjSy v.kq folefer
(Disymmetric) gksrs gS] buesa ?kqzo.k ?kw.kZdrk ikbZ tkrh gS ?kzqo.k ?kw.kZd ;kSfxd esa
fdjSy dsUnz izk;% vlefer dkcZu ijek.kq gksrs gSaA
2-4-7 vlefer dkcZu ijek.kq (Asymmetric carban atom)
dkcZu prq"la;kstd (Tetravalent) gksrs gS ;fn dkcZu dh pkjksa la;kstdrk,¡
pkj fofHké ,d laa;kstdh; ijek.kq ;k leqgksa ls tqM+h gks] tSls C* abcd rks ,sls dkcZu
| C* | vlefer dkcZu ijek.kq ;k fdjSy dkcZu dgrs gSa
mnkgj.kkFkZ& 2&,sehuks C;qVsu esa ,d fdjSy dkcZu gSA
H
CCH3 C
2N
5
NH2
*
lajpuk rFkk vkac/ku-I
56
2-4-8 leferh ds rRo (Elements of symmetry)
fdlh v.kq esa fdjSfyVh dk xq.k mifLFkr gksus ds fy, mlesa fdjSy dsUnz ;k
ijek.kq dk mifLFkr gksuk vko’;d gksrk gSA ijUrq dbZ ,sls ;kSfxd Hkh gSa ftuesa fdjSy
dsUnz vuqifLFkr gksrs gq, Hkh v.kq fdjSy gksrk gS rFkk dbZ ;kSfxdksa esa fdjSy ijek.kq rks gS]
ijUrq muesa izfrfcEc :firk fn[kkus dh {kerk ugha gSA
fdlh v.kq dh fdjSfyVh mlesa leferh ds rRoksa dh vuqifLFkfr ij vk/kkfjr gSA
2-4-8-1 leferh dk ry
2-4-8-2 leferh dk dsUnz
2-4-8-3 leferh dk ,dkUrj v{k
2-4-8-1 leferh dk ry (A plane of symmetry)
;fn fdlh v.kq dks fdlh ry esa nks cjkcj Hkkxksa es foHkkftr dj fn;k tk,]
rFkk nksuksa foHkkftr v/kZHkkx vkil esa ,d nwljs ds izfrfcEc gksa] v.kq esa lefefr dk ry
mifLFkr gksrk gSaA ,sls v.kq /kqzo.k vk?kw.kZd gksrs gSaA mnkgj.k VkVZfjd vEy dk ehlks#iA
blesa vlefer dkcZu ijek.kq mifLFkr gS] ijUrq ;g vlefer v.kq ugha gSA blesa
lefefr dk ry gksus ls ;s lefer gks tkrk gS rFkk ;s Optically inactive gksrk gSA
C
OH
C
OH
H
H
COOH
COOH
C
OH
C
OH
HOOC H
HOOCH II & Hkkx
I & Hkkx
2-4-8-2 lefefr dk dsUnz (Centre of symmetry)
;fn fdlh v.kq esa mifLFkr fdlh fcUnq ls ,d fn’kk esa [khpha xbZ js[kk ls izkIr
lewg vFkok fcUnq] ml fcUnq ls foijhr ijUrq mruh gh nwjh ij [khph xbZ js[kk n~okjk izkIr
lewg ;k fcUnq leku gks rks ;g dgk tk;sxk fd bl v.kq esa lefefr dsUnz mifLFkr gSA
mnkgj.k & 2]4&Mk;esfFky lkbDyksC;qVsu&1] 3 Mk;dkcksZfDlfyd vEy
COOH
COOH
CH3
H
HH
H
CH3
fp= 2.4 & lefefr dk dsUnz
2-4-8-3 lefefr dk ,dkUrj v{k (Alternative axis of symmetry)
v.kq dks mlds fdlh v{k ls 360o/n ls fdlh dks.k ij ?kqekdj v{k ds yEcor
mldk ijkorZu djrs gSaA ;fn ijkofrZr lajpuk viuh ewy lajpuk ds leku gksrh gS] rks
;g dgk tkrk gS fd v.kq esa n&QksYM ,dkUrj v{kh; lefefr gSaA
mnkgj.k&1]2 Mk;Dyksjks] 2]4&Mk;¶yksjks lkbDyksC;qVsu esa nks QksYM ,dkUrj v{kh;
lefefr gSA
lajpuk rFkk vkac/ku-I
57
H
H
H
H
F
F
Cl
Cl
H
H
H
H
F
Cl
F
Cl
H
H
H
H
F
Cl
Cl
F
2
v{k ds lkFk
?kw.kZu180o
fp= 2.5 & QksYM ,dkUrj v{kh; lefefr
2-5
lk/kkj.kr;k ftu ;kSfxd esa n fdjSy dsUnz ¼;k vlefer dkcZu ijek.kq½ gksrs gSa
rks mlds lEHkkfor ;fn fdlh ;kSfxd esa fofHké vlefer dkcZu ijek.kqvksa dh la[;k n gS
rc ml ;kSfxd ds /kqzo.k ?kw.kZd :iksa dh la[;k 2n gksxhA vr% ;fn fdlh ;kSfxd esa 2
fHké vlefer dkcZu ijek.kq ;k fdjSy dsUnz gS rc blds laHkkfor leko;fo;ks dh la[;k
2n=2
2=4 gksxh fdUrq ;fn vlefer dkcZu ijek.kq vkil esa leku gS tSlk fd VkVZfjd
vEy esa gS rc ;kSfxd 2n fu;eksa dk ikyu ugha djrk gS vkSj 2
n ls de leko;oh ik;s
tkrs gSaA
2.5.1 ,d vlefer dkcZu ijek.kq ;qDr ¼,d fdjSy dsUnz½ ;kSfxd
ySfDVd vEy & (CH3 – C
*HOH – COOH)
ySfDVd vEy esa ,d vlefer dkcZu ijek.kq gS bls nks varfj{k foU;kl n~okjk
iznf’kZr fd;k tk ldrk gS ;s nksuksa foU;kl ,d nwljs ds izfrfcEc :i gS rFkk ,d nwljs
ij v/;kjksfir ugha gks ldrs gSaA
COOH
OHH
CH3
H
CH3
COOH
HO
okeh; ?kw.kZd@(&)ySfDVd vEy nf{k.kh ?kw.kZd@(+) ySfDVd vEy
fp= 2.6 & ySfDVd vEy esa izdkf’k; leko;ork
lajpuk rFkk vkac/ku-I
58
vr% ySfDVd vEy 3 :iksa esa ik;k tkrk gS &
(a) (+) d&ySfDVd vEy & ;g lery /kqzfor izdk’k ds ry dks nk;ha vksj ?kqekrk
gSaA ;g ekal ls izkIr fd;k tkrk gSA lk/kkj.k ySfDVd vEy tks fd jslsfed :i
esa gksrk gS mls isfuflfy;e Xyksde nokjk fo;ksftr djds Hkh izkIr fd;k tkrk gS
isfuflfy;e XykSde l&#i dks u"V dj nsrk gS rFkk d&#i 'ks"k cprk gSA
(b) (–)-l-ySfDVd vEy & ;g lery /kqzfor izdk’k ds ry dks ckW;h vksj ?kqekrk gS
;g lqØksl dk fd.ou djus ij izkIr gksrk gSA
(c) ( ) –dl-ySfDVd vEy & ;g d rFkk l #i dk levk.kfod feJ.k (50% d +
50%l) gksrk gSA ;g lery /kqzfor izdk’k ds izfr fuf"Ø; (Optically
inactive) gksrs gSa bls jslsfed feJ.k Hkh dgrs gSA
2.5.2 nks vlefer dkcZu ijek.kq ;qDr ¼nks fdjSy dsUnz½ ;kSfxd
mnkgj.k & VkVZfjd vEy& VkVZfjd vEy esa vlefer dkcZu ijek.kqvksa dh la[;k nks gksrh
gSA
CH (OH) COOH
CH (OH) COOH*
*
H OH
HHO
COOH
HOOC
H OH
OHH
COOH
COOH
H OH
OHH
COOH
HOOC
(+) VkVZfjd vEy (I) &VkVZfjd vEy (II) eslksVkVZfjd vEy (III)
COOH
CH OH
COH H
COOH
COOH
COH H
CH OH
COOH
COOH
CH OH
CH OH
COOH d(+) VkVZfjd vEy l (&) VkVZfjd vEy eslksVkVZfjd vEy
fp= 2.7 & VkVZfjd vEy esa izdkf’kd leko;ork
lajpuk (I) o (II) vkil esa izfrfcEc #i (Enantiomer) gSA ;s ,d nwljs ij
v/;kjksfir ugha gksrs gSaA ;s nksuksa lajpuk,¡ vlefer gSA lajpuk (III) lefer gSA bls
ehlks leko;oh dgrs gSaA
;s fuEu :iksa esa izkIr gksrk gS
(a) d(+) VkVZfjd vEy & ;g lery /kzqfor izdk’k dks nka;h vksj ?kqekrk gSA
(b) l (&) VkVZfjd vEy & ;g lery /kzqfor izdk’k dh cka;h vksj ?kqekrk gSA
(c) ehlksVkVZfjd vEy & ;g /kqzo.k vk?kw.kZd (optically inactive) gksrk gSA bls
izkIr djus ds fy, d VkVZfjd vEy dks ty ds lkFk 170oC ij xeZ fd;k tkrk
gSA
(d) d–l vFkok jslsfed VkVZfjd vEy & ;g d rFkk l dks lev.kqd ek=k ¼50% d
rFkk 50% l½ dk feJ.k gksrk gSA ;g /kqzo.k vk?kw.kZd gksrk gSA
lajpuk rFkk vkac/ku-I
59
2-5-3 izfrfcEc :i (Enantiomers)
,sls ;kSfxd ds tksM+s tks ,d nwljs ds ni.kZ izfrfcEc (Mirror image) gksrs gSa
,oa ,d nwljs ij v/;kjksfir (Super impose) ugha gksrs gSaA izfrfcEc :i
(Enantiomers enatio=opposite, mesose-part) dgykrs gSaA
buds HkkSfrd rFkk jlk;fud xq.kksa esa lekurk gksrh gS dsoy lery /kzqfor izdk’k
,oa /kzqo.k ?kw.kZd vfHkdeZdksa ds izfr budk O;ogkj fHké gksrk gSA ,d izfrfcEc :i lery
/kqzfor izdk’k ds ry dks nkW;h vksj ,oa nwljk ckW;h vksj ?kwf.kZr djrk gSA buds ?kw.kZu dh
ek=k leku] fdUrq fn’kk foijhr gksrh gSA
mnkgj.kkFkZ& d&ySfDVd vEy ,oa l&ySfDVd vEy
d&VkVZfjd vEy rFkk l&VkVZjd vEy
COOH
OHH
CH3
H
CH3
COOH
HO
l, () ySfDVd vEy d, (+) ySfDVd vEy
fp= 2.8 & ySfDVd vEy ds izfrfcEc :i
2-5-4 nks vlefer dsUnz ;qDr fdjSy v.kq (Chiral molecule with two stereogenic center)
mnkgj.k & fluSfed vEy MkbczksekbM
* *
6 5C H CH Br . CHBr . COOH
blds pkj /kqzo.k ?kw.kZd ik;s tkrs gSaA
COOH
C BrH
C6H
5
C BrH
COOH
C HBr
C6H
5
C HBr
Mirror
I II
COOH
C HBr
C6H
5
C BrH
COOH
C BrH
C6H
5
C HBr
Mirror
III IV
Two enantiomers Two enantiomers
2-5-5 nks vlefer dsUnz ;qDr vfdjSy v.kq (Achiral molecule with two stereogenic center)
lajpuk rFkk vkac/ku-I
60
mnkgj.k & VkVZfjd vEy
* *
HOOC CHOH CHOH COOH
VkVZfjd vEy dk fuEukafdr f=foe foU;klksa esa iznf’kZr dj ldrs gSaA
COOH
C HOH
COOH
C OHH
COOH
C OHH
COOH
C HOH
Mirror
(I) (II)
Enantiomers (non-super imposable)
COOH
C OHH
COOH
C OHH
COOH
C HOH
COOH
C HOH
Mirror
(III) (IV)
COOH
C HOH
COOH
C HOH
Super imposable (identical) Meso compound (III) (IV)
lajpuk I rFkk II vkil esa izfrfcEc :i (enantiomers) gS] ;s /kqzo.k ?kw.kZd
gksrs gSA mudk ,d nwljs esa ifjorZu vFkok v/;kjksi.k C–C ca/k ds ?kw.kZu ls ugha gks
ldrk gSA lajpuk III o IV vkil esa leku gSA budk ,d nwljs esa ifjorZu o
v/;kjksi.k gks tkrk gS vr% ;s /kzqo.k v?kw.kZd gksrs gSaA ;g VkVZfjd vEy dk eslks :i
(Meso form) dgykrk gSA vr% eslks :i esa nks vlefer dkcZu ijek.kq gksrs gq, Hkh
;g vfdjSy v.kq gksrk gSaA
2-5-6 vizfrfcEc :i (Diastereomers)
,sls f=foe leko;oh (stereo isomers), tks vkil esa ,d nwljs ds niZ.k
izfrfcEc ugha gksrs gSa] vizfrfcEc :i dgykrs gSaA
mnkgj.k& fluSfed vEy MkbczksekbM dks fuEukafdr f=foe foU;klksa ls iznf’kZr djrs gSa &
COOH
C BrH
C6H
5
C BrH
COOH
C HBr
C6H
5
C HBr
COOH
C BrH
C6H
5
C HBr
COOH
C HBr
C6H
5
C BrH
(I) (II) (III) (IV)
lajpuk rFkk vkac/ku-I
61
mi;qDr lajpukvksa esa (I) o (IV), II o (III) vkSj II o (IV) ,d nwljs ds vizfrfcEc
:i gSaA blh izdkj T;kferh; leko;oh Hkh vizfrfcEc :i gksrs gSaA tSls eSysbd rFkk
¶;qesfjd vEyA
C COOHH
C COOHH
C HHOOC
C COOHH
eSysbd vEy (Cis) ¶;wesfjd vEy (Trans)
¼vizfrfcEc :i½
vizfrfcEc :i ds HkkSfrd o jlk;fud xq.k Li"V% fHké&fHké gksrs gSaA
2-5-7 fFkz;ks ,oa ,fjFkzks vizfrfcEc :i (Threo and Erythro Distereo isomers)
;kSfxd ds Cabd, Cabe tSls lkekU; lw= okys ljapukvksa ds pkj leko;fo;ksa
ds fy, ,d fo’ks"k ukedj.k fd;k x;k gSA ,sls ;kSfxdksa ds nks leku leqgksa ¼a rFkk b½ tc ,d gh rjg gksrs gSa] rks bUg s bfjFkzks iwoZyEu ls rFkk foijhr fn’kk esa gksus ls ßfFkz;ksÞ
iwoZyXu ls ladsru djrs gSaA
mnkgj.k&VsVªksl ds fuEukafdr pkj /kzqo.k ?kw.kZd :i iznf’kZr gSa &
CHO
OHH
CH2OH
OHH
Mirror
CHO
HOH
CH2OH
HOH
(I) (II)
() - Erythrose (+) - Erythrose
CHO
HOH
CH2OH
OHH
CHO
OHH
CH2OH
HOH
(III) (IV)
() - Therose (+) - Therose
2-5-8 eslks ;kSfxd (Meso compounds)
eslks ;kSfxd /kqzo.k v?kw.kZd (optically inactive) gksrs gSa] blesa vlefer dkcZu
ijek.kq ¼vlefer dsUnz½ gksrs g, Hkh vius niZ.k izfrfcEc ls ;s v/;kjksfir gks tkrs gSA
eslks ;kSfxdks esa lefefr ds rRo ik;s tkrs gSa rFkk v.kq vkarfjd izfrdkfjrk (Internal
compensation) ds dkj.k vfØ; (Inactive or Meso) gks tkrk gSA
eslks VkVZfjd vEy ,oa eslks 2]3&MkbDyksjks C;qVsu ds mnkgj.kksa ls bls le>k tk
ldrk gSA blesa lefefr ds ry (Plane of symmertry) ik;h tkrh gSA vFkkZr v.kq
lajpuk rFkk vkac/ku-I
62
dks ,d ry ls nks cjkcj v/kZ Hkkxksa esa foHkDr fd, tkus ij nksuksa v/kZHkkx vkil esa ,d
nwljs ds izfrfcEc :i gksrs gSaA bl izdkj v.kq vius vki esa lefer gks tkrk gS rFkk
izdkf’kr :i ls vfØ; gks tkrk gSA v.kq ds mijh v/kZ Hkkx dk ?kw.kZu fupys v/kZ&Hkkx ds
?kw.kZu dks fo:) fn’kk esa leku ek=k esa lek;ksftr dj nsrk gSA bldh vkarfjd
izfrdkfjrk (Internal compensation) ds dkj.k v.kq /kqzo.k v?kw.kZd (Optically
inactive) gks tkrk gSA
COOH
C OHH
COOH
C OHH
CH3
C ClH
CH3
C ClH
Meso Tartaric acid Meso 2,3-dichlorobutane
2-5-9 ,ihej (Epimers)
,ihej ,sls ;kSfxd gksrs gSa ftues ,d ls vf/kd fdjSy dkcZu ijek.kq mifLFkr
jgrk gS ysfdu ;s fdlh ,d dkcZu ij] ds foU;kl esa jgrs gSaa] dkcksZgkbMªsV esa ,slh 'kdZjk,¡
tks ,d dkcZu ij] ds foU;kl esa fHké gksrh gS] ,ihej dgykrh gSA
mnkgj.k& D&Xywdkst rFkk D&eSukslA buds foU;kl dsoy ,d dkcZu C5 ij fHké gksrs gSaA
CHO
C OHH
CH2OH
C HOH
C OHH
C OHH
1
2
3
4
5
6
CHO
C HOH
CH2OH
C HOH
C OHH
C OHH
1
2
3
4
5
6
D&Xywdkst D&eSukst
lajpuk rFkk vkac/ku-I
63
2-6 izfrfcEc :ikas dk izFkDdj.k
2-6-1 fo;kstu (Resolution)
jslsfed feJ.k dh mlds izfrfcEc :i (Enontiomers) d rFkk l esa izFkd djus
dh fof/k fo;kstu (Resolution) dgykrh gSA fdlh ;kSfxd dk dksbZ ,d izfrfcEc :i
dks izkIr djuk izk;% dfBu gksrk gS vr% izfrcEch :iksa dk HkkSfrd xq.k leku gksus ls Hkh
bUgs izFkDdj.k dh lkekU; fof/k;ksa n~okjk vyx&vyx ugha fd;k tk ldrk gSA bUgs
i`Fkd djus gsrq fo’ks"k fof/k;ksa dk iz;ksx fd;k tkrk gS ftuesa ls dqN fuEu gSa &
2-6-2 ;kfU=d izFkDdj.k (Mechanical separation)
bl fof/k dk loZizFke iz;ksx lu~ 1848 esa ik’pj us fd;k FkkA d rFkk l leko;fo;ksa dh fuf’pr Li"V lajpuk gksrh gSA vr% budh vkdfr Hkh fHké&fHké gksrh gSA
bUgs lw{en’khZ dh lgk;rk ls gkFk ls i`Fkd dj ldrs gSaA
2-6-3 tSo jlk;fud fof/k
ik’pj us lu~ 1859 esa bl fof/k dk vfo"dkj fd;k FkkA ;g fof/k bl fl)kar ij
vk/kkfjr gS fd lw{e thoksa tSls&cSDVhfj;k] ;hLV] QQw¡nh vkfn ,slh izdfr ds gksrs gSa ftUgsa
jslsfed feJ.k esa feykus ij fdlh ,d leko;oh dks u"V dj nsrs gS rFkk nwljk foy;u
esa 'ks"k jgrk gSA tSls&isfuflfy;e XywdSe dks d / l VkVZfjd vEy esa feykus ij d :i
u"V gks tkrk gSA rFkk l :i foy;u esa 'ks"k jg tkrk gSA
2-6-4 yo.k cukus dh fof/k n~~okjk (Salt formation method)
fo;kstu dh ;g loksZÙke fof/k gSA bl fof/k esa fdlh jslsfed vEy dks fdlh
/kqzo.k ?kw.kZd {kkj ls ,oa jslsfed {kkj dks /kqzo.k ?kw.kZd vEy ls vfHkdr djrs gSA vfHkdr
djus ij nks izdkj ds yo.k izkIr gksrs gSa ;s yo.k vizfrfcEch :i (Diastero
isomers) gksrs gSA bUgsa izHkkth fØLVyu n~okjk vyx fd;k tkrk gS] fQj HCl n~okjk
ty vi?kVu djds d rFkk l leko;fo;ksa dks vyx&vyx dj ysrs gSaA
mnkgj.kkFkZ &
(d+l) + 2d dd + d l vEy dk jslsfed {kkjd yo.k yo.k
feJ.k /kqzo.k ?kw.kZd ¼/kzqo.k ?kw.kZd yo.k
(Diastereisomers)
2H Odl HCl l dd
eqDr /kqzo.k ?kw.kZd {kkjd dk DyksjkbM
vEy
dd HCl d dcl
eqDr /kqzo.k ?kw.kZd {kkjd dk DyksjkbM
vEy
2-6-5 xfrd fof/k
;g fof/k bl fl)kar ij vk/kkfjr gS fd jslhesV dks ,d ,sls /kzoq.k inkFkZ ls
vf/kdr fd;k tkrk gS] tks jslhesV ds izfrfcEc :iksa esa fHké&fHké xfr;ksa ls fØ;k djrk
gSA vfHkfØ;k djus ds i'pkr~ izkIr ,d MkbLVhfj;ksej dh lkUnzrk nwljs ls vf/kd gksxh
vkSj bl rjg vkaf’kd fo;kstu gks ldrk gSA mnkgj.kkFkZ] tc es.Msfyd vEy ds ,slsfed
lajpuk rFkk vkac/ku-I
64
feJ.k dks ¼&½ esUFkkWy (Menthol) ls vfHkd`r fd;k tkrk gS] rc ¼$½ vEy vis{kkdr
rhoz xfr ls fØ;k djrk gS vr% vfHkfØ;k esa i;kZIr ek=k esa esUFkk¡y feyk;k tk, rks izkIr
Mk;LVhfj;kselZ ds feJ.k esa ¼&½ esfFky ¼$½ es.MsysV dh ek=k vf/kd gksxhA ifj.kke Lo:i
ewy ¼$]&½ vEy esa ¼&½ vEy dh ek=k ¼$½ vEy dh vis{kk vf/kd gksxh vFkkZr es.Msfyd
vEy dk vkaf’kd fo;kstu gks tkrk gSA
2-6-6 o.kZys[kh fof/k (Chromatographic method)
bl fof/k esa /kqzo.k ?kw.kZd inkFkksZ dks fdlh /kzqo.k vf/k’kks"kd ij o.kkZRed :i ls
vo’kksf"kr fd;k tkrk gSA ysDVkst] Åu vkfn dks vf/k’kks"kdksa ds :i esa iz;qDr fd;k tkrk
gSA es.Msfyd vEy] Vªkstj {kkj (Troger’s base) vkfn dks fo;ksftr djus esa blh fof/k
dk mi;ksx fd;k tkrk gSA
2-6-7- jsflehdj.k (Racemisation)
fdlh /kqzo.k ?kw.kZd ¼d vFkok l½ ;kSfxd dks v?kw.kZd ,slsfed feJ.k (dl) feJ.k esa
ifjofrZr djus dh izfØ;k dks jsflehdj.k dgrs gSaA bl izfØ;k dks fuEu fyf[kr izdkj
ls izsfjr fd;k tkrk gSA tSls& (i) ;kSfxd dks rhozrk ls xeZ djds] tSls&,fey ,Ydksgy] fiuhu vkfnA
(ii) ty ds lkFk xeZ djds] tSls&VkVZfjd vEy dks ty ds lkFk xeZ djus ij jslsfed
feJ.k o ehlks vEy izkIr gksrs gSaA
(iii) {kkj ds laaidZ eas j[kdj] tSls d&ysfDVd vEyA
(iv) lkaUnz H2SO4 n~okjk] tSls&cSysfjd vEyA
ykWosjh ds vuqlkj] jslsehdj.k dh fØ;kfof/k esa vlefer v.kq dk leko;ohdj.k
gksrk gS vkSj ,d vLFkk;h e/;orhZ ;kSfxd curk gS] tks lefer v.kq gksrk gSA ;g 'kh?kzrk
ls iquZfoU;kl nokjk dl feJ.k cukrk gSA iquZfoU;kl gksus ij nksuksa :iksa d ,oa l ds cuus
dh laHkkouk jgrh gSA vr% dsoy d ;k l u cudj dl feJ.k curk gSA mnkgj.kkFkZ&
ySfDVd vEy ds jslsehdj.k dks fuEukfyf[kr izzdkj ls iznf’kZr fd;k tk ldrk gS &
CH3
C OHH
C OHO
CH3
C O
C OHOH
H
d&ySfDVd vEy vLFkkbZ
CH3
C OHH
C OHO
CH3
C HOH
C OHO
+
d&#i l&#i
fp= 2.9 ySfDVd vEy d-l feJ.k
lajpuk rFkk vkac/ku-I
65
2-6-8 okYMu izfrykseu (Walden inversion-optical inversion)
;g ,d izfrfcEc :i ds nwljs izfrfcEc :i esa ifjorZu dh fof/k gSA tc fdlh
vlefer dkcZu ijek.kq ls tqM+s izfrLFkkih (substituents) dks fdlh vU; ijek.kq ;k
lewg ls izfrLFkkfir djrs gS rc u;s cus ;kSfxd dk foU;kl ;k rks vifjofrZr jgrk gS
vFkok izkjafHkd inkFkZ ds lkis{k foijhr gks tkrk gS tc izfrLFkkiu fØ;k ds lkFk&lkFk
foU;kl esa Hkh izfrykseu (Inversion) gksrk gS rc bl okYMu izfrykseu dgrs gSA
foU;kl es ifjorZu ds lkFk&lkFk ;kSfxd dh ?kw.kZu dh fn’kk esa Hkh ifjorZu vk tkrk gS]
fdUrq ;g vko’;d ugha gSA bl ?kVuk dks loZizFke okYMu us lu~ 1893 esa voyksfdr
fd;k FkkA mnkgj.kkFkZ] tc ¼$½ eSfyd vEy dks PCl5 ds lkFk vfHkd`r djrs gSa rc
¼&½ Dyksjks lfDlfud vEy izkIr gksrk gSA blesa cl lh/ks gkFk dh vksj gksrk gSA blh
izdkj (+) Dyksjks lfDlfud vEy tyh; KOH dh vfHkfØ;k nokjk (+) eSfyd vEy
nsrk gS fdUrq ue AgOH dh fØ;k nokjk ¼&½ eSfyd vEy mRié gksrk gSA
CH2COOH
C HOH
COOH
CH2COOH
C ClH
COOH
PCl5
AgOH AgOH
CH2COOH
C HCl
COOH
CH2COOH
C OHH
COOHPCl
5
2KOH
izfrykseu
¼$½ eSfyd vEy
(I)
dkssbZ izfrykseu
ugha
(II)
dkssbZ izfrykseu
ugha
KOH
izfrykseu
¼$½ DyksjkslkfDlfud
vEy
¼&½ eSfyd vEy
izfrykseu dk gksuk iz;qDr fd, x, vfHkdkjdksa] vfHkfØ;k esa Hkkx ysus okys
;kSfxdksa dh izd`fr] foyk;d vkSj rki ij fuHkZj djrk gSA vusd ,fYdy gSykbMksa dh
izfrLFkkiu fØ;k,¡ tks fd SN2 fØ;kfof/k n~okjk gksrh gS muesa okYMu izfrykseu gks tkrk
gSaA buesa okYMu izfrykseu ds QyLo:i dHkh&dHkh ?kw.kZu dh fn’kk cny tkrh gS tSls
¼&½ 2&czkseks vkDVsu dk ¼$½ 2&vkDVkukWy esa ifjorZu &
Br
C6H
13
H
CH3
H
C6H
13
HO
CH3
OH
() Bromo-Octanane (+) –Octanol
() = 36.0o () = 10.3
o
lajpuk rFkk vkac/ku-I
66
NaICH
3CH
2CH CH
3
Br
CH3CH
2CH CH
3
I,lhVksu
2&czkseksC;qVsu 2&vk;ksMksC;qVsu
¼$½ leko;o ¼&½ leko;o
izfrykseu dh fof/k vHkh Hkh vfuf’pr gS vkSj Li"V ugha gqbZ gSA
2-7 vkisf{kd ,oa fujis{k foU;kl (Relative and Absolute Configuration)
fdlh v.kq ds fofHké ijek.kqvksa ;k ijek.kq leqgksa dh f=foe esa O;koLFkk
(Arrangment of atoms of groups in space) foU;kl (configuration) dgykrh
gSA
fdlh izdk’kh; leko;ork dks iw.kZ :i ls O;Dr dju s ds fy, mlds ?kw.kZu dh
fn’kk rFkk mldk foU;kl izdV djuk vko’;d gSA ?kw.kZu dh fn’kk Dextro ;k leavo
izdV djus ds fy, vaxzsth ds NksVs v{kj d rFkk l dk mi;ksx fd;k tkrk gS ;fn
leko;oh nf{k.k /kqzo.k gks rks mls d ls vkSj ;fn oke /kzo.kZ ?kw.kZd gks rks mls l ls O;Dr
djrs gSaA d rFkk l ds LFkku ij (+) rFkk () fpUg dk Hkh mi;ksx djrs gSsaA
2-7-1 vkisf{kd fof/k (Relative configuration)
fdlh leko;oh ds foU;kl dks D rFkk L ladsruksa nokjk iznf’kZr djus dh fof/k
vkisf{kd foU;kl (Relative configuration) dh fof/k dgykrh gS tks fd D rFkk L
fXylfjy ,fYMgkbM ds foU;kl ij vk/kkfjr gSA bl fof/k esa v.kq dk foU;kl Kkr djus
ds fy, fXylfjy ,fMgkbM dks ekud inkFkZ ds :i esa pquk tkrk gSA ;g fuEu Points ij vk/kkfjr gSA
I. dkcZu dh prq"Qydh; izd`fr ds vk/kkj ij fXylfjy ,fYMgkbM ds foU;kl dks
iz{ksI; lw=ksa (Projections formula) dh lgk;rk ls fuEu izdkj ls izdV fd;k
tkrk gS &
CHO
C OHH
CH2OH
CHO
C HOH
CH2OH
(I) (II)
blesa I foU;kl (+) fXylfjy,fYMgkbM rFkk II () fXylfjy,fYMgkbM dks fu:ifr
djrk gS ,fey fQ’kj us I dks D rFkk II foU;kl dks L v{kj ls fu:fir fd;kA
II. D-fXylfjy,fYMgkbM esa vlefer dkcZu ijek.kq ls layXu &OH lewg lh/ks gkFk
dh vksj rFkk L&fXylfjyk,fYMgkbM esa ck¡, gkFk dh vksaj gksrk gSA
III. tks leko;oh D&fXylfjy,fYMgkbM esa ifjofrZr fd;k tk ldrk gS og
D&ifjokj dk rFkk tks L&fXylfjy ,fYMgkbM esa ifjofrZr fd;k tk ldrk gS
og L&ifjokj dk lnL; gksxkA
lajpuk rFkk vkac/ku-I
67
C OHH
CH2OH
C H
CH2OH
OH
(D-series) (l-series)
IV. ;fn fdlh ;kSfxd esa ,d ls vf/kd vlefer dkcZu ijek.kq gSa rc blds ,d
vlefer dsUnz fdjSy dk fXyljy ,fYMgkbM ds lkFk laca/k ns[kk tkrk gS rFkk
vU; ds foU;kl }kjk dkcZu ds lkis{k fu/kkZfjr fd, tkrs gSA mnkgj.k&Xywdkst esa
;g dkcZu C5 gS tks fd CH2OH lewg ds fudVre gSA
H
OH
OH
OH
OH
CHO
CH2OH
H
H
H
5
4
3
2
1
D-series
V. foU;kl fu/kkZfjr djrs le; ;g rF; Li"V :i ls le> ysuk pkfg, fd leko;oh
ds foU;kl o ?kw.kZu dh fn’kk esa dksbZ laca/k ugha gksrk gSA D&foU;kl okyk
leko;oh oke /kzqo.k ?kw.kZd gks ldrk gS rFkk L&foU;kl okyk leko;oh nf{k.k
/kzqo.k ?kw.kZd gks ldrk gSA mnkgj.k D&fXylfjy ,fYMgkbM vkDlhdj.k ij
fXylfjy vEy nsrk gS ftldk D&foU;kl gksrk gS ijUrq og okeh; /kzqo.k ?kw.kZd
gksrk gSA
OH
CHO
H
CH2OH
OH
COOH
H
CH2OH
Br2 / H
2O
D (+) fZXylfjy,fYMgkbM D (-) fXylfjd vEy
lhek, ¡
bl fof/k n~okjk vf/kdka’k f=foe leko;fo;ksa ds foU;kl dks izdV fd;k tk ldrk gS
ijUrq mu leko;fo;ksa ds foU;kl dh O;k[;k ugha dh tk ldrh tks fXylfjy
,fYMgkbM ls lacaf/kr ugha gksrs A
bl fof/k n~okjk gkbMªkDlh ;kSfxdksa ds foU;kl izdV djus ds fy, iz{ksI; lw= dh
m/okZ/kj js[kk ij lcls mij og lewg j[kk tkrk gS tks lcls vf/kd lqxerk ls
vkDlhd`r gksrk gS&ySfDVd vEy esa ;g lewg &COOH gSA
lajpuk rFkk vkac/ku-I
68
2-7-2 fujsis{k foU;kl rFkk R o S ladsru (Absolute configuration/R and S system of nomenclature)
dqN v.kqvksa ds foU;kl ds fu/kkZj.k ds fy, D rFkk L i)fr ykxw ugha dh tk
ldrh mnkgj.k ds :i esa &
Br
C
Cl
HF
buds vykok ,sls v.kq ftlesa ,d ls vf/kd fdjSy dsUnz gksrs gSa] dk fu/kkZj.k Hkh
D rFkk L i)fr n~okjk ugha fd;k tk ldrk gS bl izdkj ds v.kqvksa ds fy, ,d ubZ
i)fr dks fn;k x;k ftls R, S ifjikVh dgrs gSaA ;g i)fr dku&bUxksYM&fizyksx
(Cahn-Ingold prelog) ds n~okjk izLrkfor dh xbZ FkhA
I. bl fof/k n~okjk ukedj.k fuEu inksa esa gksrk gSA ftl dkcZu ijek.kq dk foU;kl
fu/kkZfjr djuk gksrk gS mlls tqM+s pkjksa izfrLFkkfi;ksa dk igpku djds mUgsa vxzrk
ds ?kVrs gq, Øe esa 1] 2] 3 o 4 vad iznku fd, tkrs gSA vxzrk ls rkRi;Z muds
ijek.kq Øekad ls gksrk gSA
Br
Cl
F
I1
2
3
4
Br
I
F
Cl1
2
3
4
II. v.kq dks leprq"Qydh; :i esa bl izdkj fy[krs gSa fd lcls vxzrk dk ijek.kq ;k
lewg gekjh nf"V ls lcls nwj jgsA fQj 'ks"k rhuks leqgksa dk ?kVuk Øe
¼1 2 3½ ns[krs gSaA ;fn ?kVrk gqvk vxzrk dk Øe ?kM+h dh fn’kk esa vFkkZr
Clockwise gksrk gS rks og bl dkcZu dk R foU;kl vkSj ;fn ?kVrk gqvk vxzrk
dk Øe ?kM+h dh foijhr fn’kk vFkkZr anti clack wise gksrk gS rks blesa
s&foU;kl gksrk gSA
1
2
3
4
Br
ClI
F
I
1
2
3
Br
Cl
F4
R foU;kl S foU;kl
fp= 2.10 & v.kq I, Br, Cl F dk prq"Qydh; izn’kZu
prq"Qydh; :i dks iz{ksI; lw= (Projection formula) ds n~okjk Hkh iznf’kZr fd;k tk
ldrk gSA prq"Qydh; :i esa tks lewg gekjh n`f"V ls lcls nwj gksrk gS mls iz{ksI; lw=
dh m?okZ/kj js[kk esa uhsps dh vksj iznf’kZr fd;k tkrk gSA
lajpuk rFkk vkac/ku-I
69
C
OH
CHOHOH2C
H
prq"Qydh; :i
v.kq dh f=f=eh; lajpuk dh dYiuk fd, fcuk Hkh fd’kj iz{ksI; lw=ksa dh lgk;rk ls
foU;kl dk fu/kkZj.k fd;k tk ldrk gSA blds fy, fd’kj iz{ksI; (projection
formula) dks bl izdkj fy[kk tkrk gS fd lcls de vxzrk dk ijek.kq dk lewg
m/okZ/kj js[kk esa lcls uhps jgsA blds fy, dHkh&dHkh leqgksa dh fLFkfr esa Hkh
ifjorZu djuk gksrk gSA ;fn ,d ckj nks leqgksa dh fLFkfr esa ifjorZu djrs gS rks
izfrfcEc:ih (Enantiomer) izkIr gksrs gSaA nks ckj ifjorZu ls ewy foU;kl izkIr
gksrk gSA fQj buesa pkSFks izfrLFkkih dh mis{kk djrs gq, 1 ls 2 gksrs gq, 3 iFk dk
vuqjs[k.k n~okjk foU;kl fu/kkZfjr fd;k tkrk gS tSls igys crk;k tk pqdk gSA
2-7-3 vuqØe fu;e (Sequence Rule)
vlefer dkcZu ijek.kqvksa ls tqM+s gq, ijek.kqvksa dh vkisf{kd vxzrk Kkr djus ds fy,
vusd fu;e gS ftuesa ls izeq[k fu;e fuEu gS &
I. ;fn vlefer dkcZu ijek.kq ls pkj fHké ijek.kq tqM+s gq, gS rc ml ijek.kq dks
mPpre vxzrk nh tkrh gS ftldk ijek.kq Øekad vf/kdre gksrk gSA mnkgj.k
czkseksDyksjks vk;ksMksesFksu (C, H, Cl, Br, I) esa vxzrk dk ?kVrk gqvk Øe (I),
(Br), (Cl), (H) gksxkA ;fn ,d gh rRo ds leLFkkfud vlefer dkcZu ls tqM+s
gks rks vf/kd nzO;eku okys leLFkkfud dks mPp vxzrk (High priority) dh
tkrh gSA mnkgj.k &
D
C
H
BrCH3
mnkgj.k esa vxzrk dk ?kVuk gqvk Øe Br, C, D, H gksxkA
II. ;fn fu;e I ds vuqlkj nks leqgksa dh vkisf{kd vxzrk dk fu’p; djuk laHko u gks
rks bu leqgksa ds vxys ijek.kqvksa dh rqyuk djds vkisf{kd vxzrk fuf’pr dh tkrh
gS mnkgj.k ;fn fdlh vlefer dkcZu ls CH2CH3 ¼,fFky½ rFkk esfFky
(CH3) lewg tqM+s gks rks pawfd izFke ijek.kq C gS rFkk bldk ijek.kq Øekad H
dh vis{kk vf/kd gS blfy, C2H5 dh vxzrk CH3 dh vis{kk vf/kd gksxhA
H
C
Cl
CH2CH
3CH
CH3
CH3
3&Dyksjks&2&esfFky isUVsu
III. f}ca/k ;k f=;d cU/k ls tqM+k gqvk ijek.kq ,sls nks ;k rhu ijek.kqvksa ds lerqY;
gksrk gS fdUrq ;fn nks ;k nks ls vf/kd ,sls ijek.kq vyx&vyx fdlh ijek.kq es
tqM+s gksa rks bu ijek.kqvksa dh vxzrk mu ijek.kqvksa dh vis{kk mPp gksrh gS tks
f}ca/k ;k f=;d ca/k ls tqM+s gksrs gSaA
lajpuk rFkk vkac/ku-I
70
vr%
C O
H
lerqY; gksxk C O
H
O
ds
mnkgj.k
CH
2
C OHH
C OH
OH
bles ls OH lewg dh vxzrk mPpre gksxhA blds ckn CHO lewg ds O, O, H
dh vxzrk CH2OH lewg ds H, H, O ls vf/kd gksxhA vr% vxzrk dk ?kVrk Øe
fuEu gksxk&
OH, CHO, CH2OH, H
2-8 T;kferh; leko;or (Geometrical Isomerism)
2-8-1 izLrkouk
T;kferh; leko;ork (Geometerical isomerism) og leko;ork gS] tks
vksyhQhuksa ¼dkcZu&dkcZu f}ca/k½ esa ik;h tkrh gSA blesa f}ca/k ds pkjksa vksj mifLFkr
lewgksa dh vleku O;oLFkk ls gh leko;oh laHko gSA
mnkgj.k & 1]2 MkbDyksjks ,FksuA blds nks f=foe leko;oh :i laHko gSA
C C
Cl
H
Cl
H
C C
H
Cl
Cl
H
(I) (II)
lei{k :i (Cis form) foi{k :i (Trans form)
nksuksa leko;fo;ksa ds lajpuk lw= leku gS ijarq ,d leko;oh dk nwljs ij
v/;kjksi.k lHHko ugha gksrk gSA
tc leku lewg] ;qXe ca/k ds ,d vksj fLFkr gks rks mls lei{k (Cis) rFkk tc
leku lewg ,dkUrj Øe esa fLFkr gks rks mls foi{k (Trans form) :i dgrs gSaA
mnkgj.kkFkZ
(i) Cis&MkbDyksjks bFkhyhu vkSj trans-MkbDyksjks bFkhyhu
C
C
Cl
Cl
H
H
C
C
Cl
HH
Cl
Cis-MkbDyksjks bFkhyhu Trans-MkbDyksjks bFkhyhu
(ii) MkbesfFky bFkhyhu
lajpuk rFkk vkac/ku-I
71
C HCH3
C HCH3
C HCH3
C CH3
H
Cis – form Trans – form
(iii) pØh; ;kSfxd & lkbDyks izksisu MkbdkcksZfDlfyd vEy
C
C C
COOH
HH
HOOC
H
H
C
C C
H
COOHH
HOOC
H
H
Cis – form Trans – form
2-8-2 T;kferh; leko;ork dk dkj.k
T;kferh; leko;ork izfrcaf/kr ?kw.kZu (hindered rotation) ds dkj.k mRié
gksrh gSA bls okUV gkZQ ds varfj{k fl)kar ;k dkcZu dh leprq"Qydh; izd`fr
(tetrahedral) izd`fr dks /;ku esa j[krs gq, lfDlfud vEy dk mnkgj.k ls Li"V fd;k
FkkA
H
C
H
COOHH
C COOHH
H
C
H
HHOOC
C COOHH
(I) (II)
dkcZu dh leprq"Qydh; izd`fr ds vk/kkj ij lfDlfud vEy dk v.kq nks
f=foe O;oLFkkvksa n~okjk iznf’kZr fd;k tkrk gSA ;s nksuksa :i rHkh laHko gS tc dkcZu
ijek.kqvksa dks vkil esa tksM+us okyk ca/k n`.k (rigid) gks vFkkZr u eqM+us okyk gksA blls
;g fu"d"kZ fudyrk gS fd ,dy ca/k ls layXu dkcZu ijek.kq vius lk{ks ds v{k ds pkjksa
vksj ?kwe tkrs gSa vkSj lfDlfud vEy ;k rks lajpuk (I) ;k (II) xzg.k djrk gS vFkok
:i (I) o (II) ,d nwljs esa ifjofrZr gks tkrs gSaA lfDlfud vEy ds nksuksa prq"Qyd
(tetrahedron) ,d nwljs ls dsoy ,d gh fcUnq ls tqM+s gksrs gSaA
C1
Ha
Hb
Ha
Hb
C2
f}vkca/k ds izfrcaf/kr ?kw.kZu ds dkj.k T;kferh; leko;ork dk mRié gksuk
vkfcZVy laydYiuk ds vk/kkj ij Hkh Li"V fd;k tk ldrk gSA pwfd C ijek.kqvksa ds
lajpuk rFkk vkac/ku-I
72
e/; mifLFkr f}ca/k ,d flXek () rFkk ,d () ikbZ ca/k ls cuk gksrk gSA blesa ikbZ
() ca/k dk fuekZ.k nks dkcZu ijek.kqvksa ds vladfjr &vkWfcZVyksa ds e/; ik’oZorhZ
vfrO;kiu ls gksrk gS &
Bond
Bond
vc ;fn f}caf/kr dkcZu ijek.kqvksa esa ls ,d dks fLFkj j[krs gS rFkk nwljs dks ?kqek;k tk,
rc p&vkfcZVyksa ds e/; vfrO;kiu lekIr gks tk,xk vFkkZr ca/k fo[kafMr gks tk,xk
ca/k dks fo[kafMr djus ds fy, 251 KJ mol&1
mtkZ dh vko’;drk gksrh gS tks lkekU;
rki ij v.kqvksa ds ijLij Vdjkus ls izkIr ugha gksrhA QyLo:i dkcZu&dkcZu f}ca/k ds
pkjksa vksj eqDr ?kw.kZu laHko ugh gks ikrk vFkkZr izfr caf/kr jgrk gSA bl izfrcaf/kr ?kw.kZu
ds dkj.k f}caf/kr dkcZu ijek.kqvksa ls layXu ijek.kqvksa ;k lewgksa dh vkisf{kd fLFkfr fLFkj
gks tkrh gS] ftl fLFkfr esa dksbZZ lewg ;k ijek.kq f}caf/kr C&ijek.kq ls tqM+rk gS mlh
fLFkfr esa jgrk gS vkSj nks leko;oh mRié gks tkrs gSaA mnkgj.kkFkZ&fuEu izdj.k esa C2 ds
lkis{k C1 dk ?kw.kZu izfrcaf/kr jgus ls fuEu leko;oh mRié gksrs gSaA
C1
Ha
Hb
Ha
Hb
C2
T;kferh; leko;ork f}ca/k ls ;qDr ;kSfxdks ds vfrfjDr dqN pØh; ;kSfxdks esa Hkh ik;h
tkrh gS D;ksafd buesa eqDr ?kw.kZu ugha gks ikrk gSA
2-8-3 T;kferh; leko;fo;ksa ds foU;kl dk fu/kkZj.k
2-8-3-1 T;kferh; leko;fo;ksa dk E, Z fof/k ls ukedj.k
fll Vªkal fof/k ls lHkh izdkj ds T;kferh; leko;fo;ksa ds foU;kl dks izdV djuk
laHko ugha gSA fuEukafdr VªkbZ ,oa VsVªk izfrLFkkfir ,fFkyhu O;qRiéksa ds foU;kl
fllVªkal fof/k ls izdV ugha fd, tk ldrs gSa &
C
C
BrCH3
H Cl
C
C
ClBr
CH3
H
1 czkseks] 2&Dyksjks izksihu 1&czkseks] 1&Dyksjks izksihu
mi;qDr ;kSfxdksa ds foU;kl dk fu/kkZj.k djus gsrq] E, Z fof/k dk mi;ksx fd;k tkrk gSA
buesa fuEu inksa dk ikyu fd;k tkrk gS &
(a) ;qXe ca/k ls layXu ijek.kqvksa ;k lewgksa dks vuqØe fu;ekuqlkj vxzrk Øe izFke
(1) ,oa f}rh; (2) n~okjk lwfpr djrs gSaA vxzrk dk fu/kkZjd dkUg bUxksYM
lajpuk rFkk vkac/ku-I
73
izhykWx ds R–S ukedj.k esa iz;qDr ojh;rk Øe ds vk/kkj ij fd;k tkrk gSA
¼mPpre ijek.kq {kkj okys ijek.kq dks mPpre vxzrk vkfn½A
(b) fQj nkuksa dkcZu ijek.kq ls layXu mPp vxzrk okys leqgksa ;k ijek.kqvksa dk
forj.k ns[krs gSA ;fn mPp vxzrk okys lewg ;qXe ca/k ds ,d vksj gksrs gSa] rc
bl :i dks foU;kl Z (Zusamen, German, Means-together) ls izdV
djrs gSa vkSj ;fn mPp vxzrk okys ijek.kq ;k lewg foijhr i{kksa ij gksrs gSa] rc
blds foU;kl gks E (Entgegen German means opposite) ls izdV djrs
gSaA
mnkgj.k
C
C
HCH3
I Cl
1 2
21
C
C
HCH3
Br Cl
1 2
21
(Z)&1&Dyksjks] 1&vk;ksMks izksihu (Z)&1&czkseks] 1&Dyksjks izksihu
C
C
BrI
CH3
Cl
1 2
2 1
C
C
BrCH3
H Cl
12
2 1
(E)&1&czkseks] 1&vk;ksMks] (Z)&1&Dyksjks] 2&czkseks izksihu
2&Dyksjks izksihu
2-8-3-2 vkfDleksa esa T;kferh; leko;ork (Geometrical isomerism of
oximes)
dkcZu ijek.kq dh rjg ukbVªkstu ijek.kq ds la;kstdrk ca/k Hkh f=foe (space)
esa forfjr jgrs gSA rFkk fdUgh nks ca/kksa ds e/; 107o dk dks.k gksrk gSA vr% ,fYMgkbMks
ds vkfDleksa R–CH=N–OH tSls ;kSfxdks ftuesa dkcZu ijek.kq N&ijek.kq ds lkFk
Ja[kfyr gS] T;kferh; leko;ork iznf’kZr djrs gSaA f}/kqzo vk?kw.kZ rFkk vojDr LisDVªk ds
v/;;u ls veksfu;k v.kq dks fijkfeMh :i es iznf’kZr djrs gSaA N&ijek.kq dks fijkfiM
ds 'kh"kZ ij rFkk H&ijek.kqvksa dks vk/kkj ds fljksa ij iznf’kZr djrs gSaA
vkfDleksa esa &H rFkk &OH leqgksa dks ;qXe ca/k ds ,d vksj rFkk foijhr
O;ofLFkr jgrs gSaA bl izdkj izkIr nks f=foe leko;kfo;ksa (stereoisomers) dks flu
(syn) ¼led{k ds rqY;½ rFkk ,fUV (anti) foi{k ds rqY; dgrs gSaA ,sYMkfDle ds nks
leko;kfo;ksa dks fuEukafdr izdkj ls fy[k ldrs gSaA
C
N
HR
OH
C
N
HR
OH syn – aldoxime anti – aldoxime
lajpuk rFkk vkac/ku-I
74
blh izdkj ls csUtsfYMgkbM ds nksuksa leko;fo;ksa dk foU;kl fuEu izdkj ls gS &
C HC6H
5
N OH
C HC6H
5
OH N syn – benzaldoxime anti – benzaoldoxime
fefJr dhVksuksa (Mixed ketones) ds vkfDle Hkh T;kferh; leko;ork iznf’kZr djrs
gSa&
C R'R
N OH
C R'R
OH N
Two stereoisomers of Ketoximes
ljy dhVksuks ds vkfDleksa ftuesa R rFkk R’ leku gSa] T;kferh; leko;ork iznf’kZr ugha
djrs gSaA
2-8-3-3 ,fylkbfDyd ;kSfxdksa esa T;kferh; leko;ork
,fylkbfDyd O;qRiéksa esa f}&vkca/k ds pkjksa vksj izfrcaf/kr ?kw.kZu ds dkj.k
iznf’kZr T;kferh; leko;ork dh HkkaWfr nz.k <k¡ps okys ,fylkbfDyd ;kSfxd dh T;kferh;
leko;ork iznf’kZr djrs gSaA oy; dh mifLFkfr ds dkj.k fjax ls tqM+s dkcZu ijek.kq ds
e/; eqDr ?kw.kZu ugha gks ikrk gS ftlls T;kferh; leko;oh mRié gks tkrs gSaA vpØh;
;kSfxdksa ds leku pØh; ;kSfxdksa ds T;kferh; leko;fo;ksa dks fll o Vªkal ds n~okjk
O;Dr fd;k tkrk gSA bu nksuksa izdkj ds leko;fo;ksa esa eq[; varj ;g gS fd ;s /kzqo.k
?kw.kZdrk Hkh iznf’kZr dj ldrs gSA ik¡p lnL;h; oy; rd ds oy; leryh; gksrs gS
oy; ds izR;sd dkcZu ls layXu nks lewgksa esa ls ,d oy; ds Åij rFkk nwljk uhps
yacor fLFkr gksrk gSA
pØh; leko;ork iznf’kZr djus okys pØh; ;kSfxd bl izdkj gSa &
H
H
CH3
H
CH3
H
H
H
H
CH3
CH3
H
fll&1] 2&MkbesfFky lkbDyksizksisu Vªkal&1] 2&MkbesfFky lkbDyksizksisu
Cl
H
Cl
H
H
Cl
Cl
H
fll&1] 2&MkbDyksjks lkbDyksisUVsu Vªkal&1] 2&MkbDyksjks lkbDyksisUVsu
2-9 la:i.k leko;ork (Conformational isomerism)
2-9-1 izLrkouk (Conformational Isomerism) la:i.k (Conformation)
lajpuk rFkk vkac/ku-I
75
;s dkcZu ijek.kq tks ,d nwljs ls ,dy ca/k n~okjk tqM+s gksrs gSa os vius v{k ds
pkjksa vksj ?kweus ds fy, Lora= gksrs gSaA ,dy ca/k ls vkcaf/kr dkcZu ijek.kqvksa ds eqDr
?kw.kZu ds dkj.k fdlh ,Ydsu ;k izfrLFkkfir ,Ydsu ds v.kq dh f=foe (space) esa vusd
O;oLFkk,¡ laHko gksrh gSa ftUgsa dkWudkSesZ’ku (conformation) dgrs gSaA ,Ydsu ds v.kq esa
C–C ,dy ca/kksa ds eqDr ?kw.kZu (Free rotation) ds dkj.k muds vusd la:ih
(conformers) mRié gks tkrs gSA
fdlh v.kq ds os leko;oh tks mlds ,d ;k ,d ls vf/kd ,dy ca/k ds ?kw.kZu
ls mRié gksrs gSa] la:i.k (Conformation) ;k ?kw.kk±d leko;oh (Rotational
Isomers) dgykrs gSaaA
2-9-2 dkcZfud ;kSfxdksa esa la:i.kks dks fu:fir djus dh fof/k;k¡
2-9-2-1 lkWgklZ iz{ksi lw= (Sawhorse Projection Formula)
;g dkcZfud v.kq dh lajpuk dks f=foeh; (Three dimentional) :i esa
iznf’kZr djus dk rjhdk gSaA blesa v.kq dks mij ;k nkfguh vksj ls ns[kk tkrk gSA blesa
nks dkcZu ijek.kq dks tksM+us okys dsUnzh; ca/k ¼eq[; ca/k½ dks dkxt ds ry esa gh ,d
lh/kh js[kk n~okjk fu:fir djrs gSa tks nkfguh vksj FkksM+k >qdh gksrh gSaA lkeus okys dkcZu
dh uhps ck;ha vksj okys dkcZu ds :i esa vkSj nwj okys dkcZu dks mij nkfguh vksj okys
dkcZu ds :i esa iznf’kZr fd;k tkrk gSA
C
H
H H
C
H
H H
H
H
H
H
H H
(a) Eclipsed (b) Staggered
izR;sd dkcZu rhu lewgksa ;k ijek.kqvksa ds lkFk rhu js[kkvkasa n~okjk layXu jgrk gS
rFkk ;s js[kk,¡ ,d nwljs ds lkFk 120o dk dks.k cukrh gSaA
mi;qDr nks la:iksa dks ,d vPNs rjhds ls (c) rFkk (d) n~okjk Hkh iznf’kZr fd;k
tk ldrk gSA nksuksa dkcZu ijek.kqvksa dks tksM+us okyk ca/k dkxt ds ry ij rFkk] xgjh
js[kk ry ds mij o uhps fcUnqfdr js[kk,¡ iz{ksfir jgrh gSaA
H
H H
H
H H
H
H
H
H
H H
(c) (d)
2-9-2-2 U;qesu iz{ksi.k (Newman projections)
blesa v.kq dks lkeus ls voyksfdr fd;k tkrk gSA n`f"V ds fudV okys dkcZu dks
,d fcUnw ls iznf’kZr fd;k tkrk gS rFkk blls tqM+s rhu leqgksa rFkk ijek.kqvksa dks rhu
js[kkvksa ls iznf’kZr fd;k tkrk gS tks fd ,d nwljs ds lkFk 120o dk dks.k cukrh gSA
n`f"V ls nwj okys dkcZu dks ,d NksVs ls o`r ds n~okjk iznf’kZr fd;k tkrk gS rFkk bl
lajpuk rFkk vkac/ku-I
76
dkcZu ls tqM+s rhu lewgksa dks o`r dh ifjf/k ls layXu rhu NksVh&NksVh js[kkvksa ls iznf’kZr
fd;k tkrk gS ;s js[kk,¡ ,d nwljs ls 120o dk dks.k cukrh gSaaA
H
H
H
H
H H
H
H
H
H
H
H Eclipsed Staggered
fp= 2.11&,Fksu ds Eclipsed vkSj Staggered la:iksa dk U;qesu iz{ksi.kksa ds n~okjk izn’kZu
2-9-2- (Fischer projection formula)
,d ls vf/kd fdjsy dsUnzks okys v.kq ds foU;kl dks crkus ds fy, teZu
jlk;uK us ,d ifjikVh izLrqr dh ftls fQ’kj iz{ksi lw= (Fischer projection
formula) dgk tkrk gSA fQ’kj iz{ksi lw=ksa dk v/;;u djus ls igys] ,d vU; izdkj ds
fu:i.k ls ifjfpr gksuk vko’;d gksrk gS ftls lan’kZ vkjs[k.k (Perspective drawing) dgrs gSaA bl izdkj ds fu:i.k dk mi;ksx v.kqvksa dh f=foeh; lajpukvksa dks nks foekvksa
eas fu:fir djus ds fy, fd;k tkrk gSA fp= 2-11 eas ,sls lanHkZ vkjs[k.k dks fn[kk;k
x;k gSA fQ’kj iz{ksi lw= dks vPNh rjg ls le>us ds fy, vki ,d ,sls v.kq dk ekMy
cukb, ftlls prq"dydh; dkcZu ijek.kq ij pkj fHké&fHké izfrLFkkih layXu gksA vc
vki bl ekWMy dks bl izdkj ns[ksa fd vkidh vksj fufnZ"V nks izfrLFkkih {kSfrt ry
(horizontal plain) esa gks vkSj vkils nwj okys vU; nks izfrLFkkih m/okZ/kj ry
(vertical plain) gks tSlk fd fp= (a) esa iznf’kZr fd;k x;k gSA fp= (b) esa vki ns[ksxsa
fd {kSfrt rFkk m/okZ/kj ry ds chp dks.k ledks.k gSA blfy, {kSfrt ry esa fLFkr
izfrLFkkih vkSj m/okZ/kj ry esa fLFkr izfrLFkkih ledks.k ij gksrs gSA vr% izfrLFkkfi;ksa ds
bu nks lsVksa ds nks js[kkvksa dks ,d nwljs ds ledks.k ij [khap dj ,d ry esa fu:fir dj
ldrs gSaA blds ckn bu js[kkvksa ij bu izfrLFkkfi;ksa dks mu LFkkuksa ij fy[kk tkrk gS
tSls os izs{kd dks fn[kkbZ nsrs gSa vFkkZr oks tks izfrLFkkih izs{kd ds cka;h vksj gksrs gSA mUgas
ck;ha vksj fy[krs gSa rFkk tks nk;h vksj gksrs gSa mUgs nk;ha vksj fy[krs gSa rFkk mij rFkk
uhsps ds vksj ds izfrLFkkfi;ksa dks mij rFkk uhsps dh vksj fy[kk tkrk gS tSlk fd fp= (c)
esa fn[kk;k x;k gSA fp= (c) dks vksj vf/kd ljy rjhds ls fp= (d) n~okjk iznf’kZr fd;k
vk ldrk gS tks fd fQ’kj iz{ksi lw= gSA fQ’kj iz{ksiksa esa fdjsy dsUnzksa dks ugha fn[kk;k
tkrk gS vkSj mls {kSfrt rFkk m/okZ/kj js[kkvksa ds izfrPNsn fcUnq (Point of
intersection) ij fLFkr ekuk tkrk gSA
. .C
OH
H
C2H
5
CH3
C
OH
CH3
C2H
5
H
(a) (b) ry ftlesa esfFky vkSj ry ftlesa gkbMªkstu ijek.kq vkSj
,fFky lewg fo|eku gS gkbMªkfDly lewg fo|eku gSa
lajpuk rFkk vkac/ku-I
77
OH
CH3
C2H
5
H
OH
CH3
C2H
5
H
(d) fQ’kj iz{ksi lw=
(c)
2.12 & fdlh v.kq dk fQ’kj iz{ksi lw= fy[kuk
2-9-2-4 ¶ykbax ost lw=
dkcZfud v.kqvksa dh f=foeh; lajpuk dks f}foeh; leryh lajpuk ds :i esa ,d
vU; izdkj ls Hkh iznf’kZr fd;k tk ldrk gS mls ¶ykbax ost lw= dgrs gSaA blesa
lgla;kstd vkca/kksa dks dku ;k oSt (Wedge) ds :i esa iznf’kZr fd;k tkrk gSA leqgksa
;k izfrLFkkfi;ksa dh f=foe jlk;uh (stereochemical) O;oLFkk iznf’kZr djus ds fy,
izk;% nks Qyu (Wedge) iz;qDr fd, tkrs gSaA
(i) Bksl Qyu (Solid wedge)& Bksl Qyu n~okjk iznf’kr vkca/k ;g n’kkZrs gS fd
izfrLFkkih ;k lewg dkxt ds ry ds ckgj (out of the plane of the paper) vxzkUr
isz{kd dh vksj gSA
(ii) gYds Qku (Light wedge)& gYds Qku mu vkca/kksa dks n’kkZrs gSa tks vkca/k dkxt
ds ry ds ihNs ;k uhsps (Inside the plain or below the plain) gksrs gSaA bUgsa
dHkh&dHkh dashed Qku (lllll) ds n~okjk iznf’kZr fd;k tkrk gSA
Br
Br
Br
Br
H
3C
CH3
H
H
Tsons-1, 3-Dimethylcyclohexane
1
2345
6
7
OH
OH
CH3
CH3
4, 5-Dimethylheptane 2, 3-Diol
2-9-3 ,Fksu ds la:i.k (Conformational analysis of Ethane)
,Fksu ds v.kq esa nks dkcZu ijek.kq ijLij ca/k n~okjk tqM+s jgrs gSa vkSj izR;sd
dkcZu rhu&rhu gkbMªkstu ijek.kqvksa ls tqM+k jgrk gSA &ca/k csyukdkj lefefr dk
lajpuk rFkk vkac/ku-I
78
gksrk gS bl dkj.k ,d esfFky lewg dks fLFkj j[krs gq, nwljs dkcZu lewg dks dkcZu dkcZu
ca/k ij ?kqek;k tk ldrk gS ftlls ,Fksu v.kq dh vufxur u;h lajpuk,sa mRié gks tkrh
gS ftUgs ,Fksu ds la:i.k dgrs gSaA
bu la:i.kksa esa nks pje (Extreme) la:i.k gksrs gSa igyk xzflr (Eclipsed)
o lkUrfjr (Staggered)A xzflr (Eclipsed) la:i.k esa ,d dkcZu ijek.kq ls tqM+s
gkbMªkstu ijek.kq nwljs dkcZu ijek.kq ls tqM+s gkbMªkstu ijek.kqvksa dks lkeus ls <d ysrs
gSa rFkk lkarfjr (Staggered) la:ih esa ,d nwljs ds e/; esa fLFkr gksrs gSaA iw.kZr;k
lkarfjr :i xzflr :i ds esfFky lewg dks vf/kdre 60o ?kqekus ij izkIr gksrs gSA xzflr
la:i.k rFkk iw.kZr;k lkarfjr la:i.k ds e/; vusd lkUrfjr la:i.k laHko gksrs gS ftUgs
fo"ke&ryh; la:i.k (Skew conformation) dgrs gSaA ,Fksu esa lkarfjr la:i.k]
xzflr la:i.k dh vis{kk 12.13 KJ mol
mtkZ ls vf/kd LFkk;h gksrk gS D;ksfd bu
la:i.k esa gkbMªkstu ijek.kq ,d nwljs ls vf/kdre nwjh ij gksrs gSa ftlls buds e/;
U;wure izfrd"kZ.k gksrk gS ,Fksu ds bu nksuksa :iksa dh mtkZvksa esa varj de gksrk gSA
lkekU; rki ij ,Fksu v.kq vf/kdk’kar% lkUrfjr :i esa gh jgrk gS D;ksafd ;g bldk lcls
LFkk;h :i gSA
H
H H
H
H H
HH
HH
HH
Sawhorse Newman
Eclipsed
H
H
H
H
H H
H
H
H
H
H
H
Sawhorse Newman
Staggesed
fp= 2-13 & ,Fksu esa la:i.k
fp= ls Li"V gksrk gS fd xzflr la:i.k dh mtkZ lkarfjr la:i.k ls 12.13 KJ mol
vf/kd gksrh gSA
lajpuk rFkk vkac/ku-I
79
lajpuk rFkk vkac/ku-I
80
,Fksu v.kq ds vusd dkWUQkWesZ’ku laHko gSa tks f}ry dks.k ds eku ij fuHkZj djrs gSaA
xzflr :i ls izkjaHk djds ;fn lkeus okys dkcZu dks fLFkj j[krs gq, ihNs okys dkcZu dks
60o ls ?kqek;k tkrk gSA rc lkUrfjr :i izkIr gksrk gSA blh izdkj ls lkUrfjr rFkk
xzflr :iksa dk ,d nwljs esa varjifjorZu gksrk jgrk gSA
2-9-4 n&C;qVsu ds la:i.k
n-C;qVsu (CH3–CH2–CH2–CH3) dks ,Fksu (CH3–CH3) dk ,slk Mk;esfFky
O;qRié ekuk tkrk gS ftlds izR;sd dkcZu dk ,d&,d gkbMªkstu esfFky ls izfrLFkkfir gks
x;k gSA C;qVsu ds vusd dkWUQkWesaZ’ku C2 rFkk C3 Øe la[;k okys dkcZu ijek.kqvksa n~okjk
cuk;s x, C–C vkca/k ds ?kw.kZu ls izkIr gksrs gSaA ;fn C2 dks fLFkj j[krs gq, C3 dks
?kqek;k tk, rks fofHké dkWUQkWesZ’ku izkIr gksrs gSaA tc nksuksa dkcZu ijek.kq ds nksuksa lewg
vkeus&lkeus gksrs gSaA rc iw.kZ xzflr :i (I) izkIr gksrk gS bl fLFkfr esa nksuksa esfFky
lewg xzflr gksrs gSA bl voLFkk es izfrd"kZ.k cy vf/kd gksrk gS rFkk v.kq mPpre mtkZ
ij vkSj lcls de LFkk;h gksrk gSA C2–C3 ca/k dks 120o ds dks.k ls ?kqekus ij nks xzflr
:i II rFkk III izkIr gksrs gS] ftlesa CH3 rFkk H xzflr gksrs gSA blfy, ;g dkWUQkWesaZ’ku
I dh vis{kk FkksM+k de mtkZ okyk gksrk gSA iw.kZ xzflr :i I dks 180o ds dks.k ls ?kqekus
ij lakrfjr (staggered) :i IV izkIr gksrk gS ftls izfrdkWUQkWesZ’ku
(anticonformation) dgrs gSaA bleasa nksuks dkcZuksa ds esfFky lewg ,d nwljs ls
vf/kdre nwjh ij gksrs gS ftlds dkj.k buesa U;wure izfrd"k.k gksrk gSA ;g C;qVsu dk
lcls LFkk;h :i gSA lkUrfjr :i dksa Øe’k% 120o ij ?kqekus ls nks lkUrfjr :i V rFkk
VI vkSj izkIr gksrs gSaA buesa ,d dkcZu dk esfFky lewg vkSj gkbMªkstu ijek.kq ds e/;
jgrk gSA bu :iksa dks xkW’k dkWUQkWesZ’ku dgrs gSA ;s iw.kZr% lkUrfjr :i dh vis{kk de
LFkk;h gksrs gSaA vr% C;wVsu ds eq[; la:i.k vxz gksrs gS &
(i) iw.kZr;k xzflr (I)
(ii) xzflr (Eclipsed) II o III
(iii) iw.kZr;k lkUrfjr (staggered) ;k izfr dkWUQkWesZ’ku
(iv) xkW’k :i (Gauch forms) ;k fo"keryh;
C;qVsu ds mtkZ vkjs[k ls izdV gksrk gS fd izfr rFkk fo"keryh; dkWUQkWesZ’kuksa ds e/; mtkZ
varj yxHkx 3.64 KJ mol
gksrh gSA lkekU; rki ij 72% izfr dkWUQkWesZ’ku rFkk
28% fo"keryh; dkWUQkWWesZ’ku dk feJ.k gksrk gSA
C;qVsu ds lkWgklZ rFkk U;qesu iz{ksiksa dks uhps fu:fir fd;k x;k gSA
H
CH3
H
CH3
H H
CH
3
H H
HH
CH3
lksgklZ izs{ksi U;wesu iz{ksi
fp= esa C;qVsu ds dkWUQkWesZ’kuksa dh fLFkfrt mtkZ ds :ikarjksa dks fn[kk;k x;k gS ;s
dkWUQkWusZ’ku Øe’k% 60o dks.k ds ?kw.kZu ij mRié gksrs gSA
lajpuk rFkk vkac/ku-I
81
lajpuk rFkk vkac/ku-I
82
2-9-5 lkbDyksgsDlsu ds la:i.k (Conformations of Cylohexane)
,Ydsuksa ds leku lkbDyks,Ydsuksa esa Hkh la:ih; leko;ork ik;h tkrh gSA ;fn ge
lkbDyksgsDlsu dk ,d ekWMy cuk, ftuesa 6 sp3 ladj dkcZu ijek.kq ,d le"kBHkqt
(Regular hexagon) cukrs gSa rks ;g vuqHko fd;k tkrk gS fd v.kq ds dks.k ruko ds
vfrfjDr] layXu dkcZu ijek.kqvksa ij fLFkr gkbMªkstu ijek.kqvksa dk xzflr foU;kl gksrk
gSaA
&dkcZu ijek.kq &gkbMªkstu ijek.kq
fp= 2.16 & lkbDyksgSDlsu dk ruko okyk leryh; dkWUQkesZ’ku tks xzflr gkbMªkstuksa
dks iznf’kZr djrk gSA
lsDls (Sachse) us 1890 esa crk;k fd lkbDyksgsDlsu ds nks vleryh; ekWMy
laHko gS tks dks.k ruko ls eqDr gksrs gSa bUgs dqlhZ rFkk ukSdk (Chair and boat) dkWUQkWesZ’ku dgrs gSaA ;s lkbDyksgsDlsu ds la:i.k gksrs gSaA
;s ,d izdkj ds ,Ydsuksa ds Øe’k% lkUrfjr rFkk xzflr la:i.k gksrs gSaA dqlhZ
rFkk ukSdk :i eas ls dqlhZ :i vis{kkd`r vf/kd LFkk;h gksrk gSA bu nksuksa :iksa dh mtkZvksa
esa yxHkx 44KJ Mol
mtkZ dk varj gksrk gSA ukSdk :i esa ,Fksu ds xzflr :i ds
leku] fudVorhZ dkcZuksa ds gkbMªkstu ijek.kq vfr fudV gksus ds dkj.k izfrd"kZ.k djrs gSa
blds foijhr dqlhZ :i esa lkUrfjr :i ds leku gkbMªkstu ijek.kq nwj&nwj fLFkr gksrs gSa
ftlls izfrd"kZ.k de gksrk gSA
H
H
H
HH
HH
H
H
H
H
H
HH
H
H
H
H
H
H
H
H
H
H
dqlhZ dkWUQkWesZ’ku ukSdk dkWUQkWesZ’ku
2-9-5-1 lkbDyksgSDlsu esa v{kh; rFkk fuj{kh; ca/k (Axial and Equatiorial
Bonds)
lkbDyksgSDlsu eq[;r;k dqlhZ :i esa gh ik;k tkrk gS D;ksafd dqlhZ la:i.k] ukSdk
la:i.k dh rqyuk esa vf/kd LFkk;h gksrk gSA
lkbDyksgSDlsu ds dqlhZ la:i.k (Chair conformations) esa nks izdkj ds
gkbMªkstu gksrs gSaA
(I) v{kh; (Axial) gkbMªkstu ijek.kq
(II) fuj{kh; (Equatorial) gkbMªkstu ijek.kq
(I) v{kh; gkbMªkstu ijek.kq (Axial hydrogen atoms)& ;s N% gkbMªkstu
ijek.kq oy; ds ry ds yEc ds lekarj v{k esa fo|eku gksrs gSaA rhu gkbMªkstu
lajpuk rFkk vkac/ku-I
83
ijek.kq oy; ds ry ds mij rhu ,dkarj dkcZu ijek.kqvksa ij rFkk 2 vU; rhu
gkbMªkstu ijek.kq oy; ds ry ds uhps 'ks"k ,dkUrj dkcZu ijek.kqvksa ij fo|eku
jgrs gSA bu gkbMªkstu ijek.kqvksa dks dkcZu ijek.kq ls la;ksftr djus okys ca/kksa
dks v{kh; ca/k dgrs gSaA bUgsa ‘a’ v{kj ls iznf’kZr fd;k tkrk gSA
(II) fuj{kh; gkbMªkstu ijek.kq (Equatorial hydrogen atoms)& ;s N%
gkbMªkstu ijek.kq oy; ds ry esa mifLFkr gksrs gSaA ftu ca/kksa n~okjk ;s gkbMªkstu
ijek.kq fjax ds lkFk tqM+s jgrs gSa mUgsa fuj{kh; ca/k (Equatorial bond) dgrs gSaA
bUgs ‘e’ v{kj n~okjk iznf’kZr fd;k tkrk gSA
aa
aa
a
a
e
e
e e
e
e
fp= 2.17 v{kh; rFkk fuj{kh; gkbMªkstu ijek.kqvksa dks iznf’kZr djrk gqvk
lkbDyksgsDlsu dk dqlhZ la:i.k
lkbDyksgSDlsu ¼dqlhZ la:i.k½ esa oy; ds yphysiu ds dkj.k v{kh; gkbMªkstu ijek.kq
fuj{kh; gkbMªkstu esa rFkk fuj{kh; gkbMªkstu ijek.kq] v{kh; (axial) esa ifjofrZr gksrs jgrs gSaA
aa
aa
a
a
e
e
e
eee
fp= 2.18 lkbDyksgSDlsu oy; ¼dqlhZ :i½ dk yphykiu ftlds dkj.k v{kh;
H&ijek.kq fuj{kh; H&ijek.kq esa ifjofrZr gksrs gSaA
blds vfrfjDr ukSdk dkWUQkWesZ’ku esa] ukSdk ds vxys rFkk fiNys Hkkx esa fLFkr nks
gkbMªkstuks dks ¶ySxiksy (Flagpole) gkbMªkstu dgrs gSaA ftuds chp dh nwjh 183pm gksrh gSA ukSdk dkWUQkWesZ’ku esa vU;ksu fØ;kvksa ds dkj.k tks ruko mRié gksrk gS rks og
dqN ek=k esa O;korZ ukSdk (twist boat) dkWUQkWesZ’ku ;k fo"keryh ukSdk (stew boat) dkWUQkWesZ’ku eas de gks tkrk gSA O;korZ ukSdk :i] ukSdk :i ls vf/kd LFkk;h] ijarq dqlhZ
dkWUQkWesZ’ku ls de LFkk;h gksrk gSA oy; ds yphysiu ds dkj.k oy; izfrorZu (ring
flipping) iz—e n~okjk dqlhZ dkWUQkWesZ’ku nwljs dqlhZ dkWUQkWesaZ’ku esa Hkh ifjofrZr gks ldrk
gSA oy; ifjorZu ds fy, 14.7 KJ mol
mtkZ dh vko’;drk gksrh gS tks lkekU;
rki ij gh izkIr gks tkrh gSA blfy, lkekU; rki ij Hkh varjk:ikUrj.k cgqr rhoz gksrk
gSA oy; izfrorZu ds dkj.k ewy dqlhZ dkWUQkZesZ’ku esa tks izfrLFkkih v{kh; Fks os izfrofrZr
dqlhZ dkWUQkWesZ’ku esa fuj{kh; gks tkrs gSa rFkk tks fuj{kh; gksrs gSa os v{kh; esa ifjofrZr gks
tkrs gSaA ;g /;ku nsus ;ksX; gS fd bl ifjorZu esa u rks vkca/k VwVrk gS u gh curk gSA
lkbDyksgSDlsu ds fofHké dkWUQkWesZ’kuksa ls lac) mtkZ ekuksa dh fp= esa iznf’kZr fd;k x;k
gSA
lajpuk rFkk vkac/ku-I
84
lajpuk rFkk vkac/ku-I
85
2-9-5-
lkbDyksgSDlsu oy; ds dqlhZ :i ds izR;sd dkcZu ijek.kq ds nks ca/k rqY; ugha
gksrs gSa* buesa ls ,d v{kh; vkSj nwljk fuj{kh; ca/k gksrk gSA vr% ;g vk’kk dh tkrh gS
fd lkbDyksgSDlsu ds nks dqlhZ la:i.kksa ds laxr nks leko;oh esfFky lkbDyksgSDlsu ¼,d
izfrLFkkih lkbDyksgSDlsu½ Kkr gksxsaA fdUrq buesa ls ,d la:i.k ik;k tkrk gSA esfFky
lkbDyksgSDlsu ds dqlhZ dkWUQkWesZ’ku esa esfFky leqg (CH3) dh v{kh; vFkok fuj{kh;
fLFkfr gks ldrh gSaA
CH3
H
a
CH3
H
e
v{kh; fuj{kh;
ge tkurs gS fd oy; izfrorZu ls ,d dqlhZ dkWUQkWfeZ’ku ls nwljs dqlhZ
dkWUQkWesZ’ku esa ifjorZu gks ldrk gS vr% esfFky lkbDyksgSDlsu ds dqlhZ :iksa esa oy;
izfrorZu gks ldrk gSA oy; izfrorZu ls bu nks :iksa dk varZjk:ikarj.k gks tkrk gS vkSj
esfFky leqg v{kh; ls fuj{kh; fLFkfr esa rFkk fuj{kh; ls v{kh; fLFkfr esa pyk tkrk gS ;s
nks f=foe leko;oh MkbLVhfj;ksej gksrs gSaA vr% budh mtkZ,¡ vkSj LFkkf;Ro vyx&vyx
gksrs gSaA tc esfFky lewg v{kh; fLFkfr esa gksrk gS rc ;g C3 rFkk C5 dkcZu ijek.kqvksa
ls layXu v{kh; gkbMªkstuksa ds vis{kkd`r fudV gksrk gSA esfFky lewg ds gkbMªkstu vkSj
C3 vFkok C5 ds gkbMªkstu ijek.kq ds chp dh nwjh] nks gkbMªkstuksa ds ckUMj okYl
f=T;kvksa ds ;ksx ls de gksrh gS blfy, okUMjokYl izfrd"kZ.k esfFky lkbDyksgSDlsu ds
v{kh; dkWUQkWesZ’ku dks vLFkk;h cuk nsrs gSa tcfd fuj{kh; dkWUQkWesZ’ku esa esfFky lewg
fuj{kh; fLFkfr xzg.k djrk gS vkSj gkbMªkstu v{kh; fLFkfrA esfFky lewg dh vis{kk
gkbMªkstu dk vkHkko de gksus ds dkj.k og de okUMjokYl izfrd"kZ.kksa dk vuqHko djrk
gSA bl izdkj ,d izfrLFkkfir lkbDyksgSDlsu dk fuj{kh; dkWUQkWesZ’ku] v{kh; dkWUQkWesZ’ku
dh vis{kk vf/kd LFkk;h gksrk gS vkSj esfFky lkbDyksgSDlsu ds vf/kdka’k v.kq fuj{kh;
la:i.k dh fn’kk esa fo|eku jgrs gSsA
CH3
1
2
3
4
5
6
H
H
CH3
HH
H 12
3
4 5
6H
H
v{kh; CH3 vkSj C3 o C5 ij v{kh;
gkbMªkstuksa ds chp okUMjokYl izfrd"kZ.k
C1 gkbMªkstu vkSj C3 vkSj C5 ij v{kh; gkbMªkstuksa ds vis{kkdr okUMjokYl
izfrd"kZ.k
2.10 (Objective Questions)
1- fuEu esa ls dkSu lk ;kSfxd pyko;ork n’kkZrk gSA
(a) 3CH CHCl COOH (b) 3 2CH CO CH COOH
(c) HOOC CH CH COOH (d) 3CH CO COOH
2 fuEu esa ls dkSu lk ;kSfxd izdkf’kd leko;ork iznf’kZr djsaxk &
(a) QkfeZd vEy (b) vkDlsfyd vEy (c) ySfDVd vEy
3- fdjSy v.kq &
(a) vlefer v.kq gksrs gS
(b) esa ,d dkcZu ij pkj fofHké oxZ caf/kr gksrs gSa
(c) izdkf’kd leko;ork iznf’kZr djrs gSa
(d) mi;qDr lHkh dFku lR; gS
lajpuk rFkk vkac/ku-I
86
4- (+) vkSj (–) ySfDVd vEy gSa &
(a) izfrfcEc :i (b) ,ihej (c) MkbLVhfj;ksej (d) e/;korhZ 5- fuEu esa ls dkSu lk /kzqo.k ?kw.kZd gS &
(a) CH3 – CHCl – COOH (b) CH2Cl – CH2 – COOH
(c) CH2OH – CH2 – COOH (d) CH2Cl – CH2 – CH2Cl
(Theoritical questions)
1- lkbDyks,Ydsu esa la:i.k dks le>kb,A
2- v{kh; rFkk fo"kqor ca/k D;k gksrs gSa\
3- lkbDyksgSDlsu ds la:i.kksa dk iw.kZ foospu dhft,A
4- fuEu ij fVIi.kh fyf[k, &
(i) lkgkslZ lw=A
(ii) U;wesu lw=A
(iii) fQ’kj lw=A
5- f=foe leko;ork ds izdkjksa dks mnkgj.k lfgr le>kb,A
6- leko;ork fdls dgrs gSa\ buds fofHké izdkjksa ij fuca/k fyf[k,A
7- /kzqo.k ?kw.kZdrk ls vki D;k le>rs gS\ bls iznf’kZr djus ds fy, fdlh ;kSfxd esa
fdu xq.kksa dk gksuk vko’;d gSA
8- lefefr ds rRo D;k gS\ laf{kIr esa o.kZu dhft,A
9- izdkf’kd leko;ork D;k gksrh gS mnkgj.k lfgr o.kZu dhft,A
10- fuEufyf[kr ij fVIi.kh fyf[k, &
(a) ukedj.k dh R o S i)fr
(b) vuqØe fu;e
11- fuEu ;kSfxdksa ds uke ,oa i)fr ds fu;eksa ds vuqlkj fyf[k,A
C
C
HCH3
H Cl
C
C
HH5C
2
OH H
12- dkj.k Li"V dhft, &
(i) ,sYMkfDle T;kferh; leko;ork iznf’kZr djrk gSA
(ii) izksfivkfud vEy izdkf’kd leko;ork iznf’kZr ugha djrk gSa] tcfd ySfDVd vEy
izdkf’kd leko;ork iznf’kZr djrk gSA
lajpuk rFkk vkac/ku-I
87
2.11 Unit Summary lkajk'k lkj
dkcZfud ;kSfxdks dk f=foe jlk;u
1- leko;ork (Isomerization) & nks ;k nks ls vf/kd ,sls ;kSfxd ftuds v.kqlw=
leku gksa] leko;oh dgykrs gS rFkk ;s ifj?kVuk leko;ork (Isomerization) dgykrh
gSA
leko;ork ds izdkj
A. lajpuk leko;ork (i) J[kayk leko;ork (ii) L;ku leko;ork
(iii) fØ;kRed leko;ork (iv) e/;ko;rk leko;ork
(v) pyko;ork leko;ork (vi) oy; leko;ork
B. f=foe leko;ork (i) izdk’kh; leko;ork (ii) la:ih; leko;ork
(iii) T;kferh; leko;or
2- (Optical isomerism) - izdkf’k; leko;fo;ksa ds v.kqlw=
rFkk ljapuk lw= oks leku gksrs gSaA fdUrq leko;fo;ksa dks ,d nwljs esa v/;kjksfir ugha
fd;k tk ldrk gSA
2- (Plane polarized light) - izdk’k tks ,d gh ry esa
dfEir gksrk gS lery /kqzfor izdk’k dgykrk gS rFkk ry /kzqo.k ry dgykrk gSA
2-2 /kzqo.k ?kw.kZdrk (Optical activity)& os inkFkZ tks /kzqo.k izdk’k ds /kqzo.k ry dk
?kw.kZu (Rotation) djrk gS] /kqzo.k ?kw.kZd inkFkZ dgykrk gS] ;s inkFkZ /kqzo.k ?kw.kZd
inkFkZ (Optically active substance) dgykrk gS rFkk ;g ?kVuk /kqzo.k ?kw.kZdrk
(Optical activity) dgykrh gSA
tks leko;oh lery /kqzfor izdk’k ds nk;h vksj (clock wise) ?kqek nsrs gS]]
nf{k.k /kzqo.k ?kw.kZd (Dextro Rotatary) rFkk tks lery /kqzfor izdk’k ds ry dks ck;h
vksj ?kqekrs gS] oke /kzqo.k ?kw.kZd (leavo rotary) dgykrs gSaA nf{k.k /kqzo.k ?kw.kZd dks
‘d’ ;k ‘t’ fpUg ls o;k oke /kzqo.k ?kw.kZd dks ‘l’ ;k ‘&’ fpUg ls iznf’kZr djrs gSaA
2- (Specific rotation) dksbZ izdk’k leko;oh] lery /kzqfor izdk’k ds
ry dk ftrus va’k ls ?kqekrk gS mls /kzqo.k dks.k (angle of rotation) dgrs gSaA
l C
ifs jr ?kw.kZufof'k"V ?kw.kuZ
tgka l = /kqzo.kekih uyh dh Mslh ehVj esa yEckbZ
C = foy;u dh xzke izfr ?ku lseh esa lkUnzrk
2-4 fdjsfyVh (Chirality) - dksbZ inkFkZ ;k v.kq tks vius niZ.k izfrfcEc ij v/;kjksfir
ugha gksrk] fdjSy inkFkZ ;k v.kq dgykrk gS rFkk ;g xq.k fdjSfyVh dgykrh gSA bu
inkFkksZ esa /kqzo.k ?kw.kZdrk ikbZ tkrh gSA
2-5 dkcZu ijek.kq (Asymmetric carbon atom) – dkcZu prqgla;kstd gksrs gSa
;fn dkcZu dh pkjksa la;kstdrk,¡ pkj fofHké ,d la;ksth ijek.kq ;k lewg ls tqM+h gks rks
,sls dkcZu ijek.kq dks vlefer dkcZu ijek.kq ;k fdjsy dkcZu dgrs gSaA
2-6 leferh ds rRo (Element of symmetry) 2-6-1 leferh dk ry
2-6-2 leferh dk dsUnz
2-6-3 leferh dk ,dkUrj v{k
lajpuk rFkk vkac/ku-I
88
3- izfrfcEc :i (Enantiomers)& ,d ;kSfxd ds tksMs+ tks ,d nwljs ds niZ.k
izfrfcEc gksrs gS rFkk ,d nwljs ij v/;kjksfir gksrs gSaA izfrfcEc :i dgykrs gSA
mnk- d-ySfDVd vEy o l-ySfDVd vEy
4- vizfrfcEc :i (Diastereo isomers)& f=foe leko;oh tks vkil esa niZ.k
izfrfcEc ugha gksrs gsaA vizfrfcEc :i gksrs gSA
mnkgj.k & ftusfed vEy MkbczksekbM
fFkz;ks o ,fjFkzks izfrfcEc :i (Threo and Distereo isomers)& ;kSfxd ds
Cabd, Cabe tSls lkekU; lw= okys ljapukvksa ds pkj leko;fo;ksa ds fy, ,d fo’ks"k
ukedj.k fd;k x;k gSA ,sls ;kSfxdksa ds nks leku leqgksa ¼a rFkk b½tc ,d gh rjg gksrs
gSa ros bUgs ofj/kzks iwoZyXu ls rFkk foijhr fn’kk esa gksrs ls ßfFkz;ksÞ iwoZyXu ls ladsru
dgrs gSaA
mnkgj.k & VsVªksl
5- ehlksa ;kSfxd (Meso compound) & ehlks ;kSfxd /kzqo.k viw.kZd gksrs gSaA
6- ,ihej (Epimers)& ,ihej ,sls ;kSfxd gksrs gSa ftues ,d ls vf/kd fdjSy dkcZu
ijek.kq mifLFkr jgrk gS] ysfdu ;s fdlh ,d dkcZu ds foU;kl ij gksrs gSaA mnkgj.k
& D-Xywdksl o D-eSuksl
7- izfrfcXc :iksa dk izFkDdj.k
7-1 fo;kstu (Resolution) - feJ.k dh mlds izfrfcEc :i rFkk esa iz;d djus dh
fof/k fo;kstu dgykrh gSA fuEu fof/k;k¡ gksrh gSa &
7-1-1 ;kf=d izFkDdj.k 7-1-2 tSo jlk;fud fof/k
7-1-3 yo.k cukus dh fof/k nokjk 7-1-4 xfrd fof/k
7-1-5 o.kZys[kh fof/k
7-2 ,sflehdj.k (Racemisation) – fdlh /kzqo.k ?kw.kZd ¼d vFkok d½ ;kSfxd dks
v?kw.kZd ,slsfed feJ.k (dl) feJ.k eas ifjofrZr djus dh izfØ;k dks ,slsehdj.k dgrs gSaA
8- vkisf{kr rFkk fujis{k foU;kl (Relative and absolute configuration)&
fdlh v.kq ds fofHké ijek.kqvksa ;k ijek.kq leqgksa dh f=foe O;koLFkk foU;kl
(configuration) dgykrh gSA
8-1 vkisf{kd fof/k (Relative configuration) & fdlh leko;oh ds foU;kl dks D
rFkk L ladsruksa nokjk iznf’kZr djus dh fof/k vkisf{kd foU;kl (relative
configuration) dh fof/k dgykrh gS tks fd rFkk fXylfjy ,fDMgkbM ds foU;kl ij
vk/kkfjr gSA
9- T;kferh; leko;rk (Geometrical isomerism) - T;kferh; leko;ork og
leko;ork gS] tks fd vksyhdhuks esa ikbZ tkrh gSA
mnk-
C C
Cl
H
Cl
H
C C
Cl
H
H
Cl
Cis-1, 2 MkbDyksjks ,sFksu Cis-1,2 Trans-1, 2
Dichloro ethane
10- la:i.k leko;ork (Conformational isomerism) - ,dy cU/k ls vkcafU/kr
dkcZu ijek.kvksa ds eqDr ?kw.kZu ds dkj.k fdlh ,Ydsu ;k izfrLFkkfir ,Ydsu ds v.kq dh
f=foe esa vusd O;oLFkk,W lEHko gSa ftUgsa conformation dgrs gS rFkk leko;ork
conformational isomersism dgykrh gSA
lajpuk rFkk vkac/ku-I
89
2- Ans to check your progress
1-(b) 2-(c) 3-(d) 4-(a) 5-(a)
2-13 dqN mi;ksxh iqLrdsa Suggested reading/Reference
6. Organic Chemistry, Volume 1, I.L. Finar, ELBS Longman.
Fundamentals of Organic Chemistry , T.W. Graham Solomons, John
Wiley & Sons, Inc. Chapters 3, 11&13.
7. Organic Chemistry, Volume I, S.M. Mukherji, S.P. Singh, R.P.
Kapoor, Wiley Eastern Limited, New Delhi.
8. Organic Chemistry, Robert T.Morrison and Robert N.Boyd,
Prentice-Hall of India, Pvt. Ltd. New Delhi.
9. Advanced Organic Chemistry, B., S. Bahl and Arun Bahl, S. Chand
& Company Ltd. New Delhi.
10. Organic Chemistry, M.K. Jain, Shoban Lal Nagin Chand & Co.,
Delhi.
bdkbZ&III : ,Ydsu ,oa lkbDyks,Ydsu] ,jhu ,oa
,jkseSfVdrk
3-0 izLrkouk
dkcZu ijek.kqvksa ds vkil esa ca/k cuk ldus ds vf}rh; xq.k ßdsVhu'kuÞ ds
dkj.k vla[; dkcZu ijek.kq tqM+dj yach Ja[kyk okys ;kSfxd cuk ldrs gSaA vU; fdlh
Hkh rRo esa vf/kdre pkj ;k ik¡p ijek.kq gh tqM+dj J`a[kyk cuk ikrs gSaA dkcZu ijek.kqvksa
dh Ja[kyk,¡ lh/kh] 'kk[kk;qä ;k pØh; gks ldrh gSaA lh/kh ,oa 'kk[kk;qä Ja[kyk,¡ ,Ydsu
rFkk lar`Ir pØh; lajpuk,¡ lkbDyks,Ydsu dgykrh gSaA vlar`Ir pØh; lajpuk,¡ ,jhu
dgykrh gSaA
3-1 mís';
bl bdkbZ dk v/;;u djus ls vki fuEukuqlkj 'kh"kZdksa dh tkudkjh izkIr dj ldsaxsA
,Ydsu] ,Ydsuksa (CnH2n+2) dk vkb ;w ih , lh ukedj.k] 'kk[kk;qDr ,Ydsuksa ds
vkb ;w ih , lh ukedj.k ds fu;e
,sYdsuksa esa dkcZu ijek.kqvksa ds izdkj] ,fYdy lewg (CnH2n+1)
,Ydsuksa esa leko;ork&lajpukRed leko;ork
,Ydsuksa ds lzksr
,Ydsuksa ds cuus dh lkekU; fof/k;k¡] oqVZt vfHkfØ;k] dksYcs vfHkfØ;k]
dksjs&gkml vfHkfØ;k] dkckZfDlfyd vEyksa dk fodkckZfDlyhdj.k
,Ydsuksa ds HkkSfrd xq.k] ,Ydsuksa dh jklk;fud vfHkfØ;k,¡
,Ydsuksa ds eqDr ewydh; gSyksstuhdj.k dh fØ;kfof/k] ,Ydsuksa ds gSykstuhdj.k esa
nSf'kdrk] lfØ;rk ,oa oj.kh;rk A
lkbDyks,Ydsuksa dk ukedj.k] lkbDyks,Ydsuksa ds fojpu dh fof/k;k¡
lkbDyks,Ydsuksa dh jklk;fud vfHkfØ;k,¡
lajpuk rFkk vkac/ku-I
90
ck;j ruko fl)kUr ds izeq[k vfHkxzghr] lkbDyks,Ydsu ds leryh; pØ esa
ruko dh x.kuk] ck;j ruko fl)kar ds i{k esa izk;ksfxd izek.k] ck;j ruko
fl)kar dh lhek,¡] ck;j ruko fl)kar ds fojks/k esa izk;ksfxd voyksdu] ck;j
ruko fl)kar ds =qfViw.kZ vfHkxzghr
ruko jfgr oy;ksa dk fl)kar] izk;ksfxd izek.k
dsyk vkcU/k ¼lkbDyksizksisu½ A
,jhu ¼,jkseSfVd&,yhQSfVd gkbMªksdkcZu ,oa muds O;qRié½
ukedj.k % ,fjy lewg] ,jkseSfVd ukfHkd ,oa ik'oZ Ja`[kyk
csUthu dh lajpuk % v.kq lw= ,oa dsdqys lajpuk] vuquknh lajpuk] vkf.od
d{kd lajpuk
,jkseSfVdrk
gdy dk fu;e ¼4n+2 fu;e½
,jkseSfVd bysDVªksfQfyd izfrLFkkiu
,oa ladqyksa dk egRo
lfØ;d ,oa fuf"Ø;d lewg
nSf'kd izHkko ,oa vkFkksZiSjk vuqikr
fcpZ vip;u
,fYdy csathu& cukus dh lkekU; fof/k;k¡ ] vfHkfØ;k,¡
ckbQsfuy& cukus dh lkekU; fof/k;k¡ ] vfHkfØ;k,¡
3-2 ,Ydsu
dkcZu ,oa gkbMªkstu ds ;kSfxd ftuesa dsoy flXek vkcU/k gksrs gSa] lar`Ir gkbMªksdkcZu
;k ,Ydsu dgykrs gSaA fØ;k'khyrk dh deh ,oa fØ;kRed lewg dh vuqifLFkfr ds dkj.k
bUgsa iSjkfQu ¼parum-U;wu] affins-cU/kqrk½ Hkh dgk tkrk gSA bu [kqyh Ja[kyk okys
¼vpØh;½ ;kSfxdksa dh ltkrh; Js.kh dk lkekU; lw= CnH2n+2 gS] tgk¡ n ,d iw.kk±d
la[;k gSA
C
H
H
HH
H
C
HH
H109.5o
C
H
H
HH
¼d½ yqbl lajpuk ¼[k½ f=foeh; izLrqrhdj.k ¼x½ leprq"Qydh; lajpuk
¼?k½ d{kd js[kkfp= ¼M
-½ ckWy ,oa fLVd ekWMy ¼p½ Lisl fQfyax ekWMy
js[kkfp= 3-1&,Ydsuksa dh lajpuk ds izLrqrhdj.k dh fofHké i)fr;k¡&mnkgj.k ehFksu
(CH4) : izFke lnL;
lajpuk rFkk vkac/ku-I
91
lajpuk rFkk vkac/ku-I
92
lajpuk rFkk vkac/ku-I
93
3-2-2 'kk[kk;qDr ,Ydsuksa ds vkb ;w ih , lh ukedj.k ds fu;e
1- dkcZu ijek.kqvksa dh lcls yach lrr Ja[kyk dk ,Ydsu ds ^vk/kkj uke* ds :i esa
p;u rFkk 'kk[kkvksa dks ,fYdy izfrLFkkih ds :i esa ukfer djuk
CH3
CH2
CH CH3
CH3
CH3
CH2
CH CH3
CH2
CH2
CH3
pkj dkcZu ijek.kqvksa dh lh/kh Ja[kyk Ng dkcZu ijek.kqvksa dh lcls yach Ja[kyk
vk/kkj ,Ydsu&C;wVsu vk/kkj ,Ydsu&gsDlsu
2- izfrLFkkih ls fudVre fljs ls dkcZu ijek.kqvksa dks la[;kad iznku djuk
CH3
CH CH2
CH2
CH2
CH3
CH2
CH3
CH3
CH2
CH3
CH2 CH
2CH CH
3
12346 5
2 1
3 4 5 6 7
izzfrLFkkih
3- fu;e 2 ds vuqlkj la[;kad ls izfrLFkkih dh fLFkfr O;Dr djuk
CH3
CH CH2
CH2
CH2
CH3
CH2
CH3
CH3
CH2
CH3
CH2 CH
2CH CH
3
12346 5
2 1
3 4 5 6 7
2&esfFky gsDlsu 3&esfFky gsIVsu
4- ewy Ja[kyk ij ,d ls vf/kd izfrLFkkih gksus ij izR;sd dh fLFkfr la[;kad ls iznf'kZr
djrs gq, o.kZekyk ds Øe esa tekdj muds chp esa gkbQu yxkuk
CH3
CH2
CH2
CH2CH
3CH
2
CH2
CH2 CH
2CH CH
3
CH3
CH3 C
2H
5
CH3
CH3CH
2C
1 2 3 4 65 3 4 5 6 71 2
4&,fFky&2&esfFky gsDlsu 3&,fFky&3&esfFky gsIVsu
5- tc nks ;k vf/kd leku lewg mifLFkr gksa] rks Mkb] Vªkb] VsVªk] vkfn iwoZyXu ,fYdy
lewg ds igys yxk;s tkrs gSa] fdUrq ;s la[;klwpd iwoZyXu o.kZekyk ds Øe esa 'kkfey ugha
fd;s tkrss A
CH3
CH3
CH3
CH3CH CH
CCH3
CH3
CH3
CH2CH CH
2CH
3
CH3
2]3&MkbesfFky C;wVsu 2]4]4&VªkbesfFky gsDlsu
lajpuk rFkk vkac/ku-I
94
CH3
CH3
CH3
CH2CH CH
C2H
5
CH2
CH2
CH3
5&,fFky&2] 3&MkbesfFky vkDVsu
6- ;fn leku yackbzZ dh nks Ja[kyk,¡ gksa] rks ewy Ja[kyk og yh tk;sxh] ftl ij
izfrLFkkfi;ksa dh la[;k vf/kd gksA
CH2
CH
CH3
CH CH CH CH3
CH3
CH3
CH2 CH
3
CH2CH
3
5
67
12346 57
2] 3] 5&VªkbesfFky&4&izksfiy gsIVsu ¼lgh½ 4&sec-C;wfVy&2] 3&MkbesfFky gsIVsu ¼xyr½
7- ;fn izR;sd fljs ls izFke izfrLFkkih dh nwjh leku gks] rks vxys izfrLFkkih dks U;wure
vad iznku djrs gq, uke dk p;u fd;k tk;sA
CH3
CH
CH3
CH CH CH CH3
CH3 CH
3
12 3 4 65
12346 5
2] 3] 5 & VªkbesfFky gsDlsu ¼lgh½ 2] 4] 5 & VªkbesfFky gsDlsu ¼xyr½
8- ;fn ewy Ja[kyk ij tfVy izfrLFkkih ¼pkj ls vf/kd dkcZu ;qDr½ gks] rks ,sls ,fYdy
lewg dk uke dks"Vd esa fy[kk tk;s] ftlesa la[;kadu ewy Ja[kyk ls tqM+s dkcZu ls izkjaHk
fd;k tk;sA
CH2
CH CH2
CH2
CH2
CH3
CH3
CH2CH
2CH
2CH
3
CH
CH3
CHCH3
12346 57810 9
1'
3' 2'
5&¼1] 2&MkbesfFky izksfiy½ Msdsu
3-2-3 ,sYdsuksa esa dkcZu ijek.kqvksa ds izdkj
layXu dkcZu
ijek.kqvksa dh
la[;k
izdkj ladsr
mnkgj.k
CH3
CH3
CH2CHCH
3 C
CH3
CH3
3040 2010
10 10
10
prqFkZd r`rh;d f}rh;d izkFkfed
1 ;k fujad izkFkfed 1o
2 f}rh;d 2o
3 r`rh;d 3o
4 prqFkZd 4o
lajpuk rFkk vkac/ku-I
95
3-2-4 ,fYdy lewg (CnH2n+1)
,Ydsu & ,u + by ,fYdy
ewy ,Ydsu
,fYdy lewg dk lajpuk lw= lkekU; uke* IUPAC uke
laf{kIr :i izdkj
ehFksu CH3 – esfFky esfFky Me 1o
bZFksu CH3 – CH2 – ,fFky ,fFky Et 1o
izksisu CH3 – CH2 – CH2 – n-izksfiy izksfiy Pr 1o
izksisu (CH3)2 CH – vkblks&izksfiy 1&esfFky ,fFky i-Pr 2o
C;wVsu CH3(CH2)2 – CH2 – n-C;wfVy C;wfVy Bu 1o
C;wVsu (CH3)2 CH – CH2 – vkblks&C;wfVy 2&esfFky izksfiy i-Bu 1o
C;wVsu CH2CH
3C
CH3
H
sec-C;wfVy 1&esfFky izksfiy s-Bu 2o
2&
esfFky
izksisu
CH3
C
CH3
CH3
tert-C;wfVy 1]1&MkbesfFky
,fFky t-Bu 3
o
2]2&
Mkb
esfFky
izksisu
CH3
C
CH3
CH3
CH2
fu;ks&isfUVy 2]2&Mkb esfFky
izksfiy – 1
o
* cgq/kk ,fYdy lewgksa ds lkekU; uke gh iz;qä fd;s tkrs gSaA
lajpuk rFkk vkac/ku-I
96
3-2-5 ,Ydsuksa esa leko;ork & lajpukRed leko;ork
CH2
CH3
CH3(C
3H
8)
CC
C
C C
CC C C CC C
CC C C CC CC C
C
CH2
C
CC C
C
(C4H
10)
CH2
CH2
(C5H
12)
C C
CC C C C C
C
C C C C C
C
C
CC C
C
C
C
CC C
C
C
(C6H
14)
CH3CH
3
CH4
CH4
C2H
6
CH2
CH2
+
izksisu
C;wVsu
¼2 leko;oh½
++
isUVsu
¼3 leko;oh½
vkblks&isUVsu
fu;ks&isUVsu
&isUVsun
¼5 leko;oh½
gsDlsu
gsDlsu
2&esfFky isUVsu
3&esfFky isUVsu
2]3&MkbesfFky C;wVsu
2]2&MkbesfFky C;wVsu
&C;wVsun
2&esfFky izksisu
bZFksu
ehFksu
+
+
vfHkO;fä dh lqfo/kk gsrq izR;sd dkcZu ijek.kq dh prq"la;kstdrk ds fy;s vko';d
gkbMªkstu ijek.kq n'kkZ;s ugha x;s gSaA
dkcZu ijek.kqvksa dh la[;k c<+us ds lkFk leko;fo;ksa dh la[;k c<+rh tkrh gSa chl
dkcZu ;qä bdkslsu dh 3]66]319 leko;oh lajpuk,¡ laHko gSaA
3-3 ,Ydsuksa ds lzksr
izeq[k vkS|ksfxd lzksr & izVªksfy;e ,oa izkÑfrd xSl
izkÑfrd xSl & izeq[k ?kVd ehFksu
ek'kZ xSl ¼lsY;wykst dk ,u,jksfcd fd.ou½ & izeq[k ?kVd ehFksu
isVªªksfy;e & C5–C50 ¼5 ls 50 dkcZu ;qä ,Ydsu½
izkÑfrd olk vEy 2
CO C27–C37 ¼27 ls 37 dkcZu ;qä ,Ydsu½
dk"B VjisUVkbu – n–gsIVsu ikni ekse & ,sYdsu
e/kqeD[kh dk ekse & C27H56 ,oa C31H64
3-3-1 ,Ydsuksa ds cukus dh lkekU; fof/k;k¡
fØ;k/kkj vfHkdeZd ,Ydsu
lajpuk rFkk vkac/ku-I
97
LiAlH4 ;k NaBH4 ;k
Ph3SnH/Pd-C ;k Ni/H2
RCOR’
o qVZt vfHkfØ;k ¼Na@bZFkj½
dksYcs fo|qr vi?kVu
R2 Cu Li
R – X ,fYdy gSykbM
RMg X fxzxukMZ H2O ;k ROH ;k NH3 ;k RNH2 ;k C6H5OH ;k
vfHkdeZd RSH, vkfn ¼lfØ; gkbMªkstu ;qä ;kSfxd½
RL i dkcZyhfFk;e
RCOONa lksMk ykbe (NaOH/CaO) m"ek lksfM;e dkckZfDlysV
jSus Ni/H2
RCH = CH2 1. B2H6 2. CH3COOH ;k AgNO3/NaOH
RX
RCOOK
Dyhesulu vip;u (Zn–Hg/HCl)
oqYQ&fd'uj vip;u (NH2NH2 / EtONO)
dhVsku (1) 2RSH–'kq"d HCl;
(2) Ni/H2
RX
3-3-2 oqVZt vfHkfØ;k
RX + 2Na + XR bFZ kj
R – R +2 NaX
RX & ,fYdy gSykbM ¼fo'ks"kr% czksekbM ,oa vk;ksMkbM½
3RX + 6Na + 3XR’ bFZ kj R–R+R’–R’+ R’–R+6 NaX
lhek,¡ % ¼i) dsoy le dkcZu ijek.kq la[;k ds ,Ydsu cuukA
(ii) r`rh;d ,fYdy gSykbMksa ls vfHkfØ;k vlaHkoA
(iii) ehFksu ugha cukbZ tk ldrhA
laHkkfor fØ;kfof/k&
¼d½ vk;fud fØ;kfof/k ¼ek/;fed dkcZ/kkfRod ;kSfxd cuuk½
(i)
R X + 2Na NaX + R Na
(ii) R Na NaXR X
SNR RNa
2
R . . . R . . . X+ +
laØe.k voLFkk
¼[k½ eqDr ewyd fØ;kfof/k
(i) R X Na R NaX
(ii) R R R : R
RH
2 3RCH CH
R – R
2 'RCH R
'R R
lajpuk rFkk vkac/ku-I
98
leFkZu esa izek.k % 2 5C H Br dh vfHkfØ;k ls C;wVsu ds lkFk&lkFk bFksu ,oa bFkhu dk
cuuk
C2H
5Br + Na C
2H
5
C2H
5 C
2H
5
C2H
4 + C
2H
6
NaBr22 2
.
folekuqikru
;qXeu
2
3-3-3 dksYcs vfHkfØ;k
2 2 22RCOONa 2H O R R 2CO 2NaOH H fo?krq vi?kVu
fØ;kfof/k %
(i) CH3CH
2CH
2COONa CH
3CH
2CH
2COO + Na
(ii) bysDVªksM vfHkfØ;k,¡
_.kksn ij
Na e Na
2 22Na H O 2NaOH H
/kuksn ij
3 2 2 3 2 2CH CH CH COO CH CH CH COO e
3 2 2 3 2 2 2CH CH CH COO CH CH CH CO
3 2 2 3 2 342CH CH CH CH CH CH
Ikk'oZ mRikn
3 2 2 3 2 2 3 2 32CH CH CH CH CH CH CH CH CH
folekuqikru
CH3CH
2CH
2 CH3CH
2CH
2COO CH
3CH
2CH
2COOCH
2CH
2CH
3
..+
;qXeu
3-3-4 dksjs&gkml vfHkfØ;k
RX RLi R2CuLi + LiI2
-2 LiX
Li bZFkj2
Cu I
2R CuLi R 'X R R ' RC LiXu
izkFkfed
,fYdy
yhfFk;e yhfFk;e
Mkb,fYdy
D;wiszV
,fYdy gSykbM
1o ;k 2
o ;k 3
o
esfFky gSykbM ;k
izkFkfed gSykbM
lajpuk rFkk vkac/ku-I
99
fo'ks"krk,¡ % bl vfHkfØ;k ds }kjk le rFkk fo"ke nksuksa izdkj ds dkcZu ijek.kq okys ,Ydsu cuk;s
tk ldrs gSaA
mPprj ,oa 'kk[kk;qDr ,Ydsuksa ds fuek.kZ gsrq fo'ks"k mi;ksxh gSA
fØ;kfof/k %
1-
R2 Cu Li R
2 Cu Li R
2 Cu
Li+
2-
R2Cu R Cu
..2 +
dkcZ,uk;u
3-
R : R X R R X :+ +
ukfHkd
Lusgh
3-3-5 dkckZfDlfyd vEyksa dk fodkckZfDlyhdj.k
RCOONa RH + Na2 CO
3lksMkykbe@m"ek
olk vEy dk
lksfM;e yo.k
RCOONa + NaOH(CaO) CH4 + Na
2 CO
3
m"ek
3-4 ,Ydsuksa ds HkkSfrd ,oa jklk;fud xq.k
1- HkkSfrd voLFkk ,oa xa/k &
izFke pkj lnL; ¼C1 ls C4½ jaxghu] xa/kghu xSlsa rFkk C5 ls C15 jaxghu] ok"i'khy ,oa
isVªksy tSlh xa/k;qDr nzo gksrs gSaA v.kqHkkj esa o`f) ds lkFk ok"i'khyrk ,oa xa/k de gksrh
tkrh gSA mPp v.kqHkkj okys ,Ydsu jaxghu ,oa xa/kghu Bksl gksrs gSaA
2- xyukad ,oa DoFkukad & ¼d½ lh/kh Ja[kyk;qDr ,Ydsuksa ds DoFkukad v.kqHkkj c<+us ds lkFk Øe'k% c<+rs tkrs
gSaA xyukad gj CH2 lewg dh of) ds lkFk 20o ls 30
oC rd c<+rk gSA le la[;k
ds dkcZu ijek.kq okys ,Ydsuksa dk xyukad fo"ke dkcZu ijek.kq okys ,Ydsuksa dh rqyuk esa
vf/kd gksrk gSA ¼fp= 1-2½
¼[k½ leko;oh ,Ydsuksa esa 'kk[kk;qDr ,Ydsuksa dk DoFkukad lh/kh Ja[kyk okys ,Ydsuksa
ls de gksrk gS] D;ksafd 'kk[kk ;qDr ,Ydsuksa dh vkÑfr vis{kkÑr xksykdkj gksus ds dkj.k
lrg dk {ks=Qy de gks tkrk gS] ifj.kker% ok.Mj oky cy nqcZy gks tkrs gSaA
n&C;wVsu vkblks&C;wVsu
3- fof'k"V ?kuRo & v.kqHkkj c<+us ds lkFk Øe'k% c<+rk gS rFkk yxHkx 0-8 ij fLFkj gks
tkrk gSA ¼fp=1-2½
lajpuk rFkk vkac/ku-I
100
4- foys;rk % dkcZu ,oa gkbMªkstu dh _.k fo|qrrk esa vf/kd varj u gksus ds dkj.k
,Ydsu v/kzqoh; izd`fr ds gksrs gSa] vr% ty esa vfoys; fdUrq dkcZfud foyk;dksa esa foys;
gksrs gSaA
fp= % 3-2 lh/kh J`a[kyk okys ,Ydsuksa esa dkcZu ijek.kqvksa dh la[;k ¼n½ esa o`f} ds lkFk HkkSfrd fLFkjkadksa esa o`f}
3-4-1 ,Ydsuksa dh jklk;fud vfHkfØ;k,¡
,Ydsuksa esa dsoy flXek vkcU/k gksus ds dkj.k cU/k fo[k.Mu gsrq mPp ÅtkZ
¼rkih; vFkok izdk'k jklk;fud½ dh vko';drk gksrh gSA vf/kdak'k vfHkfØ;kvksa esa
ek/;fed eqDr ewyd curs gSaA ,Ydsuksa dh lfØ;rk dk Øe 3o > 2
o > 1
o gksrk gSaaA
vf/kdka'kr% vfHkfØ;k,¡ izfrLFkkiu gksrh gSa] ftuesa izfrLFkkiu dk Øe 1oH > 2
oH > 3
oH
gksrk gS] D;ksafd 1oH ijek.kqvksa dh la[;k vf/kdre gksrh gSA
lajpuk rFkk vkac/ku-I
101
3-4-2 ,Ydsuksa dh izeq[k jklk;fud vfHkfØ;k,¡
3-4-3 ,Ydsuksa ds eqDr ewydh; gSyksstuhdj.k dh fØ;kfof/k
(1) X
2 X2 .200-400oC
;k h
Ja`[kyk izkjaHku in
(2) X + RH HX + R ..
Ja`[kyk lapj.k in (3) R + X
2 RX + X..
gSykstu dh i;kZIr ek=k gksus ij in Øekad ¼2½ ,oa ¼3½ dh iqujkofÙk gksus ls ,Ydsu ds
leLr gkbMªkstu Øe'k% gSykstu ls izfrLFkkfir gks tkrs gSaA
(4) X2
X + X. .
Ja`[kyk lekiu in (5) .R + R. R R (6) R XX + X. .
eqDr ewyd fØ;kfof/k ds i{k esa izek.k &
¼d½ va/kdkj ,oa dejs ds rki ij vfHkfØ;k ugha gksrh gSA
¼[k½ mPp DokaVe n{krk Ja[kyk fØ;kfof/k dk izek.k gSA
¼x½ vkDlhtu dh mifLFkfr vfHkfØ;k esa vojks/kd gksrh gS] D;ksafd O2 ds ,fYdy eqDr
ewyd ls la;ksx ij ROO curk gS] ftldh fØ;k'khyrk R ls cgqr de gksrh gS
,oa J`a[kyk dh dM+h VwV tkrh gSA
¼?k½ VsVªkesfFky ysM ¼eqDr ewyd lzksr½ dh mifLFkfr esa fØ;k de rki ¼150oC½ ij gh
laié gks tkrh gSaA
gSykstuhdj.k esa fofHkUu gSykstuksa dh lfØ;rk dk Øe gS % F2 > Cl2 > Br2
lajpuk rFkk vkac/ku-I
102
'kq) ¶yksjhu ds lkFk foLQksVd xfr ls vfHkfØ;k gksrh gS] vr% mls ukbVªkstu ds
lkFk fefJr djuk vko';d gSA
vk;ksfMuhdj.k dfBukbZ ls gksrk gS] D;ksafd vfHkfØ;k mRØe.kh; gksrh gS %
CH4 + I
2CH
3I + HI
vr% fØ;k gsrq vkDlhdkjd vko';d gS] tks HI dks fou"V dj lds] mnkgj.kkFkZ &
vk;ksfMd vEy ;k ukbfVªd vEy A
HI + HIO3
I2 + H
2O5 33
3-4-4 ,Ydsuksa ds gSykstuhdj.k esa nSf'kdrk
gSykstuhdj.k esa fofHkUu ek=k esa leko;oh gSyks ,Ydsu curs gSaA
(i) CH3CH
2H
3C
CH2
CH2
H3C
Cl2
CH3 CH
2 CH
2 Cl
CH3CHH
3C
Cl2
CH3 CHCl CH
3
Cl.
.
.1&Dyksjksizksisu (45%)
2&Dyksjksizksisu (55%)
viksgu
1oH dk
viksgu
2oH dk
�
1o ,oa 2
o H dh la[;k ds vuqlkj ;g vuqikr 3%1 gksuk pkfg;s Fkk] vFkkZr 75%: 25%
(ii) CH3CH
2CH
3
CH3 CH
2 CH
2 CH
2
Cl2
CH3 CH
2 CH
2 CH
2 Cl
Cl2
CH3 CH
2 CHCl CH
3
ClCH
2
CH3 CH
2 CH CH
3
.
.
.28%
72%
viksgu
1oH dk
viksgu
2oH dk
1
oH ,oa 2
oH dk lkaf[;dh vuqikr 6%4 gS] vFkkZr~ 60% : 40%
(iii)
.CH
3CHCH3
Cl2
ClCH
3CH
3
CH3
CH2
C CH3
CH3
CH2 ClCH
Cl2
CH3
CH3
CH23
C CH3
CH3
CH3
C
Cl
.
.64%
viksgu
1oH dk
viksgu
3oHdk36%
1
oH ,oa 3
oH dk lkaf[;dh vuqikr 9%1 gS] vFkkZr~ 90% : 10%
fu"d"kZ & leko;oh gSykstu izfrLFkkfi;ksa dk vuqikr 1o, 2
o ;k 3
oH dh la[;k ds
ctk; muds izdkj ij fuHkZj gksrk gSA ;g ifj?kVuk nSf'kdrk dgykrh gSA
czksehuhdj.k esa nSf'kdrk vf/kd Li"Vr% fn[kkbZ nsrh gSA
(iv) CH
3 CH
2 CH
3
Br2 CH
3 CH
2 CH
2 Br + CH
3 CH Br CH
3
3% 97%
(v
)
CH3
Br2CH
3CHCH3
CH3
CH2 Br +CHCH
3
CH3
CH3CH
3C
Br1%99%
3-4-5 lfØ;rk ,oa oj.kh;rk
lajpuk rFkk vkac/ku-I
103
gSykstuhdj.k esa mRikn leko;oh gSyks,Ydsuksa dh ek=k dks izHkkfor djus okys
dkjd gS &
¼d½ izfrLFkkiuh; gkbMªkstu dh lfØ;rk dk Øe % 3oH > 2
oH > 1
oH
¼[k½ gSykstu dh oj.kh;rk dk Øe % Br2 > Cl2] tks budh lfØ;rk ds Øe ls
foijhr gksrk gSA
gSykstu RkkiØe gkbMªkstu viksgu dh lkisf{kd nj
3oH 2
oH 1
oH
Cl2 dejs ds rki ij 5 3.8 1
Br2 127oC ij 1600 82 1
fofHkUu gSyks ,Ydsu leko;fo;ksa dh yfC/k ds vuqikr dh x.kuk ,Ydsu ds gkbMªkstu
ijek.kqvksa ds vk/kkj ij fuEukuqlkj dh tk ldrh gSA
2o gSyks ,Ydsu
1o gSyks ,Ydsu
=2oH dh la[;k
1oH dh la[;k
x2oH dh lfØ;rk
1oH dh lfØ;rk
mnkgj.kkFkZ %
¼d½ n&C;wVsu 3 2 2 3CH CH CH CH dk Dyksjhuhdj.k
3 2 2 2
3 2 3
CH CH CH CH Cl 6 1 3
CH CH CHClCH 4 3.8 7.6
vFkkZr 72% 3 2 3CH CH CHClCH ,oa 28% 3 2 2 2CH CH CH CH Cl , tks
okLrfod yfC/k ds lfédV gSaA
¼[k½ 2&esfFky izksisu dk czksehuhdj.k
3 22
3 3
CH CH CH Br 9 1 9 1%
CH C Br 1 1600 1600 99%
vFkkZr~ 2&czkseks&2&esfFky izksisu dh yfC/k 99% ,oa 1&czkseks&2&esfFky izksisu dh yfC/k
1%A
3-5 lkbDyks,Ydsu
pØh; ,yhQSfVd ;k ,yhlkbfDyd gkbMªksdkcZu lkbDyks,Ydsu ;k lkbDyksiSjkfQu
dgykrs gSaA ltkrh; Js.kh dk lkekU; v.kqlw= CnH2n gS]A C3 ls C50 rd ds lnL;
Kkr gSaA ik¡p ,oa Ng dkcZu ;qDr lkbDyks,Ydsu LFkk;h gkssrs gSa] ,oa izdfr esa ik;s tkrs
gSaA rhu ,oa pkj dkcZu pØh; ;kSfxd ,Ydsu ,oa ,Ydhu ds e/;orhZ xq.k fn[kkrs gSaA
3-5-1 ukedj.k
vuds esfFkyhu bdkbZ;ksa ds tqM+dj pØ cukus ds dkj.k bUgsa ikWyhesfFkyhu Hkh
dgk tkrk gSA IUPAC ukedj.k %
¼d½ vizfrLFkkfir lkbDyks,Ydsuksa dk ukedj.k laxr ,Ydsuksa ds uke esa ^lkbDyks*
iwoZyXu tksM+dj fd;k tkrk gSA
lkj.kh lkbDyks,Ydsuksa dk ukedj.k
v.kq lw= lajpuk lw= laf{kIr
izLrqrhdj.k # lkekU; uke
vkb ;w ih , lh uke
C3H6
CH
2CH2
CH2
VªkbZesfFkyhu lkbDyksizksisu
C4H8
CH
2
CH2
H2C
H2C
VsVªkesfFkyhu lkbDyksC;wVsu
lajpuk rFkk vkac/ku-I
104
C5H10
CH
2
CH2
H2C
H2C
CH2
isUVkesfFkyhu lkbDyksisUVsu
C6H12
CH
2
CH2
CH2
H2C
H2C
CH2
gsDlkesfFkyhu lkbDyksgsDlsu
# lqfo/kk dh n`f"V ls lkbDyks,Ydsuksaa dks T;kferh; vkdkjksa ¼lecgqHkqt½ }kjk iznf'kZr
fd;k tkrk gS] ftlesa izR;sd dksa.k ,d CH2 lewg dks vfHkO;ä djrk gSA
¼[k½ izfrLFkkfi;ksa dh fLFkfr la[;kad ls bafxr dh tkrh gSA pØ ds dkcZu ijek.kqvksa dks
bl izdkj la[;kad iznku fd;s tkrs gSa] rkfd izfrLFkkfi;ksa ds fLFkfr lwpd vadksa dk
;ksx U;wure gksA
Cl
Br Br
CHCH3CH
3
1
23
4
56
CH2CH
3
CH3
1& ,fFky & 3 & esfFky lkbDyksgsDlsu ¼lgh½ 1& ,fFky & 5 & esfFky lkbDyksgsDlsu ¼xyr½
3-5-2 fojpu dh fof/k;k¡
¼1½ ÝqUM fof/k % MkbZ gSykstu ;kSfxdksa ls Na ;k Zn dh vfHkfØ;k ¼vkUrfjd oqVZt+ vfHkfØ;k½
rhu ls Ng lnL;h; pØksa gsrq mi;ksxh
CH2
CH2Br
CH2Br
NaC
2H
5OH
NaBr+ +2 2m"ek
CH2
CH2
CH2
C2H
5OHBr
BrCH2
Zn ZnBr2
m"ek+ +
¼2½ ,jkseSfVd gkbMªksdkcZuksa ds mRizsjdh; vip;u &
Dyksjks lkbDyks
izksisu 1]2&MkbZ czkseks
lkbDyks C;wVsu vkblks izksfiy
lkbDyksissUVsu
lajpuk rFkk vkac/ku-I
105
NiH2+ 3
180 200oC
¼3½ f}HkkfLed vEyksa ds csfj;e ;k dSfYl;e yo.kksa ls &
CH2
CH2
CH2
CH2
COO
COO
CH2
CH2
CH2
CH2
Ba CHg HCLZn
Ovip;u
m"ek
bl fof/k ls lkbDyks izksisu ugha cukbZ tk ldrhA
¼4½ fMdeku pØhdj.k
OZn/Hg - HCl
- CO2
O
COOH
CH2
CH2 COO C
2H
5CH
2
CH2
Na CH2
CH2
CH2
CH2
CH
COOC2H
5
CH2 COO C
2H
5
C2H
5ONa
OC
HCl/H2O
vip;u
ty vi?kVu
+
m"ek
lajpuk rFkk vkac/ku-I
106
¼5½ FkkiZ&thxyj fof/k
CH2
CH2CH
2CN
CH2CN
LiN(C2H
5)
3C=NH
-CO2 C=O
H2O/H+
C=O
CN
CH
COOH
CH2
CH2
CH2
CH2
CH2
CH2
Zn/Hg
ruq foy;u
n&iw.kk±d la[;k
m"ek
HCl
(CH2)n (CH2)n
(CH2)n (CH2)n
(CH2)n
vUrj v.kqd vfHkfØ;k dks izfrcfU/kr djus ds fy;s csUthu ;k Vkywbu ds vkf/kD; esa
ruq foy;u dk iz;ksx fd;k tkrk gSA
cM+s vkdkj ds pØh; lkbDyks,Ydsuksa ds fy;s loZJs"B fof/k gSA
¼6½ eSyksfud ,LVj la'ys"k.k ¼ifdZu fof/k½
3-5-3 jklk;fud vfHkfØ;k,¡
lkbDyks,Ydsuksa dh jklk;fud vfHkfØ;k,¡ ,Ydsuksa ds ln`'k gksrh gSaA vEy] {kkj] vkDlhdkjdksa ,oa vipk;dksa ls lkbDyks,Ydsuksa dh vfHkfØ;k ugha gksrhA
gSykstuksa ds lkFk izfrLFkkiu vfHkfØ;k,¡ %
CH2
CH2
CH
CH2
Cl2
ClBr
2
CH2
Br-HC
UV izdk'k(CH2)n
UV izdk'k
(CH2)n
(CH2)n
lajpuk rFkk vkac/ku-I
107
lkbDyksizksisu dh fof'k"V vfHkfØ;k,¡ % ;ksxkRed vfHkfØ;k,¡
CH3
CH2Br
CH2
CH
3
CH2I
CH2
CH2Cl
CH2Cl
H2C
CH2Br
CH2Br
H2C
CH
3
CH3
H2C
lkbDyksC;wVsu (i) o (ii) vfHkfØ;k,¡ nsrh gS] fdUrq (iii) gsrq 200oC rkiØe vko';d
gSA
lkbDyksisUVsu ,oa mPprj lnL; ;ksxkRed fØ;k,¡ ugha nsrsA
3-5-4 ck;j ruko fl)kUr ds izeq[k vfHkxzghr ¼lkbDyks,Ydsuksa dh vkisf{kd lfØ;rk ds Li"Vhdj.k gsrq½
¼1½ lar`Ir dkcZu leprq"Qydh; gksrk gS] vkcU/k dks.k 109o28’ (109.5
o)
¼2½ dkcZu dh la;kstdrk n`<+ ugh gksrh] vkcU/k dks.k esa fopyu laHko gS] fdUrq fopyu
ls ruko mRié gksrk gSA
¼3½ leprq"Qydh; dks.k ls fopyu ds ifjek.k esa o`f) ls v.kq dk vLFkkf;Ro c<+rk
gSA
¼4½ lkbDyks,Ydsuksa ds pØ esa leqifLFkr leLr dkcZu ,d gh lery esa gksrs gSaA
3-5-4-1 lkbDyks,Ydsu ds leryh; pØ esa ruko dh x.kuk
vkcU/k dks.k = 360
180o
o
n
¼n = pØ esa mifLFkr dkcZu ijek.kqvksa dh la[;k] 360o
n = ckº; dksa.k½
prq"Qydh; dksa.k ls fopyu (d) = 1 360
109.5 1802
oo o
n
60
24.75
109 5.
Oo
o d
js[kkfp= 3-3 lkbDyksizksisu esa vkcU/kdks.k dk fopyu
lajpuk rFkk vkac/ku-I
108
lkj.kh % lkbDyks,Ydsuksa esa lkekU; leprq"Qyd dksa.k ls fopyu (d) ,oa
izfr CH2 lewg ngu Å"ek H
lkbDyks,Ydsu pØ dh T;kferh n vkcU/k dks.k d
H#
fdyksdSykjh@eksy
lkbDyksizksisu leckgq f=Hkqtkdkj 3 60o
+24.75o
166.6 lkbDyksC;wVsu oxkZdkj 4 90
o +9.75
o 164.0
lkbDyksgsDlsu fu;fer iapHkqtkdkj 5 108o +0.75
o 158.3
lkbDyksgsDlsu fu;fer "k"BHkqtkdkj 6 120o -5.25
o 157.4
lkbDyksgsIVsu fu;fer lIrHkqtkdkj 7 128.5o -9.5
o 158.6
lkbDyksvkWDVsu fu;fer v"VHkqtkdkj 8 135o -12.75
o 158.6
,Ydsu - 109.5o
- 157.4 # vf/kd LFkk;h ;kSfxd dh ngu m"ek de gksrh gSA
3-5-4-2 ck;j ruko fl)kar ds i{k esa izk;ksfxd izek.k ¼1½ lkbDyksizksisu ds fy;s leprq"Qyd dks.k ls vf/kdre fopyu mldh vf/kd
fØ;k'khyrk] U;wure LFkkf;Ro ,oa fojpu dh tfVyrk dk Li"Vhdj.k djrk gSaA
¼2½ lkbDyksisUVsu gsrq U;wure fopyu ,oa lkbDyksgsDlsu ds fy;s vis{kkÑr de
fopyu] buds fojpu dh lqxerk] LFkkf;Ro ,oa vusd izkÑfrd ;kSfxdksa esa
mifLFkfr ls lqlaxr gSA
3-5-4-3 ck;j ruko fl)kar dh lhek,¡%ck;j ruko fl)kar ds fojks/k esa izk;ksfxd voyksdu
1- lkbDyksisUVsu lokZf/kd LFkk;h gksuk pkfg;s] fdUrq % 300
oC ij gkbMªkstuhdj.k djus ij lkbDyksisUVsu pØ [kqy tkrk gS] tcfd
lkbDyksgsDlsu pØ ugha [kqyrkA
izÑfr esa lkbDyksisUVsu dh vis{kk lkbDyksgsDlsu pØ cgqrk;r esa ik;k tkrk gSA
2- lkbDyksC;wVsu ,oa lkbDyksgsIVsu dk LFkkf;Ro leku gksuk pkfg;s] fdUrq lkbDyksgsIVsu
vf/kd LFkk;h gSA
3- lkr ls X;kjg lnL;h; pØksa dk LFkkf;Ro lkbDyksisUVsu ds leku gSA
4- ckjg ;k vf/kd lnL;h; dkcZu pØksa dk LFkkf;Ro [kqyh Ja[kyk ;kSfxdksa ds leku gh
gksrk gSA
ck;j ruko fl)kar ds =qfViw.kZ vfHkxzghr lkbDyks,Ydsuksa ds pØksa dh leryh; lajpuk dk izfriknu
prq"la;ksth dkcZu ds vkcU/k dksa.k 109.5o ls fopyu laHko ekuukA
3-5-4-4 ruko jfgr oy;ksa dk fl)kar % lk'ks&eksgj fl)kUr
3] 4 ,oa 5&lnL;h; pØksa esa dkcZu ijek.kq ,d gh lery esa gks ldrs gSa] fdUrq
6&lnL;h; ,oa cM+s pØ izdqafpr (puckered) gksrs gSaA vr% dkcZu ijek.kqvksa ds fofHkUu
ryksa esa fLFkr gksus ls leprq"Qydh; dks.k ls fopyu vko';d ugha gksrkA
dqlhZ :i ukSdk:i lkbDyksMsdsu
lkbDyksgsDlsu
js[kkfp= 3-4 lkbDyks,Ydsuksa ds izdaqfpr la:i.k
3-5-4-5 izk;ksfxd izek.k l=g ls vf/kd dkcZu ;qDr pØh; ;kSfxdksa dh fojpu fof/k fodflr dj yh xbZ
gSA
:ft+dk us 34 dkcZu ;qDr lkbDyks,Ydsu dk la'ys"k.k fd;kA
izÑfr esa cM+s pØ ;qDr LFkk;h ;kSfxd eLdksu C16H30O ,oa flosVksu
C17H30O ik;s tkrs gSaaA
lajpuk rFkk vkac/ku-I
109
cMs+ pØh; ;kSfxdksa ds la'ys"k.k esa dfBukbZ dk dkj.k mudk vLFkk;h gksuk ugha gS] oju~
,d gh v.kq ds nks Nksjksa ds fudV vkus ¼pØhdj.k½ dh rqyuk esa nks fHkUu v.kqvksa ds e/;
fØ;k ¼Ja[kyk of)½ vf/kd lgt gSA
CH2
CH2
CH2Y
CH2Y
¼d½ pØhdj.k
CH2Y
Y CH2
Y CH2
CH2
CH2 CH
2Y
Y CH2
CH2Y +
¼[k½ Ja[kyk of)
js[kk fp= 3-2-3 cM+s pØh; ;kSfxdksa dk la'ys"k.k
3-5-5 dsyk vkcU/k ¼lkbDyksizksisu½
lar`Ir ;kSfxdksa ds SP3 ladfjr d{kdksa ds e/; dksa.k 109.5
o gksrk gSaA C–C–C
vkcU/k dksa.k Hkh 109.5o gksus ij gh lek{k vfrO;kiu izHkkoh :i ls gksxk ,oa izcy ca/k
cusxkA lkbDyksizksisu esa C–C–C dksa.k 60o gh laHko gS] vr% vfrO;kiu nqcZy gksus ds
dkj.k cU/k Hkh nqcZy gksrk gSA
C
C
C
109o5o
CC
C
90o
¼d½ ¼[k½ js[kkfp= dksa.kh; ruko dk d{kdh; izLrqrhdj.k % SP
3 ladfjr d{kdksa dk
vfrO;kiu ¼d½ [kqyh Ja[kyk ;k cM+s pØksa esa izHkkoh vfrO;kiu ¼[k½ lkbDyksizksisu esa nqcZy vfrO;kiu
lkbDyksizksisu esa SP3 ladfjr d{kd vUrjukfHkdh; v{k ij gksus ds ctk; ckgj dh vksj
dsys tSlh vkÑfr esa eqM+sa gksrs gSa] vr% bl vkcU/k dks ßdsyk vkcU/kÞ dgk tkrk gSA
3-6 ,jhu ,oa ,jkseSfVdrk
csUthu ,oa mlds ltkrh; ;kSfxd] ftudk lkekU; lw= CnH2n–6 gksrk gS] ,jhu dgykrs gSaA ;s vlar`Ir ;kSfxd gksrs gSa] ftudk gkbMªkstu U;wurk lwpdkad pkj gksrk gS
vFkkZr pkj vkcU/k gksuk pkfg;sA vR;f/kd vlar`Ir gksus ds ckotwn ;s ;kSfxd
,yhQSfVd ;kSfxdksa ls de fØ;k'khy gksrs gSaA
lajpuk rFkk vkac/ku-I
110
vkjaHk esa fof'k"V xa/k ;qä ;kSfxdksa dks ,jkseSfVd ¼,jksek ;qä vFkkZr~ lqxa/k ;qä½
;kSfxd dgk x;kA orZeku esa csUthu vkSj mlds ln`'k O;ogkj iznf'kZr djus okys ;kSfxd
,jkseSfVd dgykrs gSaA oLrqr% ,sls csUthukWbM ¼cSathu ln`'k½ ,oa ukWu&csUthukWbM ;kSfxdksa
dk bysDVªkWfud foU;kl csUthu tSlk gksrk gSA
3-6-1 ukedj.k
3-6-1-1 ,jhu ¼,jkseSfVd&,yhQSfVd gkbMªksdkcZu ,oa muds O;qRié½
¼1½ lkekU;r% ewy uke csUthu fy;k tkrk gSA
¼2½ ljyre izfrLFkkfir cSathu O;qRiéksa ds fy;s lkekU;r% fo'ks"k uke iz;qä fd;s tkrs gSaA
mnkgj.kkFkZ&
CH3
VkWybu
¼esfFky csathu½
CH3
CH3
CH3
CH3
CH3
CH3
o&tkbyhu m&tkbyhu p&tkbyhu
¼o–, m–, ,oa p&MkbesfFky csathu½
OH
QhukWy
¼gkbMªkWDlh csathu½
NH
2
,fuyhu
¼,ehuks csathu½
COOH
SO3H
csatksbd vEy csathu lYQksfud vEy
CH = CH2
LVkbjhu
¼foukby csathu½
¼3½ vU; O;qRiéksa esa izfrLFkkih dk uke iwoZyXu ds :i esa csathu ds lkFk tksM+k tkrk gSA
C
2H
5
CH
2 CH
2 CH
3
CH2
CH CH3
CH3
,fFky csathu n&izksfiy csathu vkblksC;wfVy csathu
¼4½ tfVy ik'oZ Ja[kyk;qDr ;kSfxdksa dk ukedj.k Qsfuy ,Ydsu ds :i esa fd;k tkrk gSA
¼C6H5=Qsfuy½
CH CH2
CH3
CH3
HCH3C1 2 3 4 5
CH2
CH2CH
2
2&esfFky&3&Qsfuy isUVsu MkbZQsfuy ehFksu 1]2&MkbQsfuy bFksu
¼5½ f}izfrLFkkfi;ksa ds fy;s fLFkfr lwpd la[;kad ;k vkFkksZ (o-), eSVk (m-) ,oa iSjk (p-) iwoZyXu fy;s tkrs gSaA
lajpuk rFkk vkac/ku-I
111
Br
Br
COOH
NO2
OH
Cl 1]2&MkbczksekscsUthu
o&MkbczksekscsUthu
3&ukbVªkscsatksbd vEy
m&ukbVªkscsatksbd vEy
4&DyksjksfQukWy
p&DyksjksfQukWy
¼6½ cgqizfrLFkkfir csUthu O;qRiéksa esa izfrLFkkfi;ksa dh fLFkfr o.kZekyk ds Øe ,oa U;wure
laHko la[;kad }kjk nh tkrh gSA
Cl
Cl
Cl
1
2
3
45
NH2
Br
Br
O2N
6
1]2]3&VªkbDyksjks csUthu 2]4&Mkbczkseks&5&ukbVªks ,fuyhu
¼7½ ,d ls vf/kd fØ;kRed lewg mifLFkr gksus ij izeq[k fØ;kRed lewg dks izFke
la[;kad fn;k tkrk gSA ojh;rk dk Øe % – COOH, – SO3H, – COCl, –
CONH2, – CHO, – CN, – NC, >C=O, – OH, – SH, – NH2, =NH A
12
34
5
NH2
Br
COOH
NO2
6
2&vehuks&5&czkseks&3&ukbVªks
csUtksbd vEy
3-6-1-2 ,fjy lewg
,jkseSfVd gkbMªksdkcZu ls ,d ;k vf/kd gkbMªkstu foLFkkfir djus ij izkIr gksus
okys lewg ,fjy lewg dgykrs gSaA
ewy ;kSfxd
,fjy lewg
v.kq lw= lajpuk lw= uke
csUthu
(C6H6) C6H5 –
Qsfuy
Vkywbu
(CH3C6H5) CH3C6H4–
CH3 CH
3CH
3
m - o - p -
VkWfyy
csathu
(C6H6) C6H4 <
m - p - o -
Qsfuyhu
3-6-1-3 ,jkseSfVd ukfHkd ,oa ik'oZ Ja[kyk
csUthu ds izfrLFkkfir ;kSfxdksa esa Ng dkcZu ijek.kqvksa ls cuk pØ ,jkseSfVd
ukfHkd dgykrk gS rFkk bl pØ ls fdlh dkcZu ijek.kq }kjk tqM+s ,fYdy ;k vU;
lajpuk rFkk vkac/ku-I
112
,yhQSfVd lewg ik'oZ Ja`[kyk dgykrs gSaA pØ ls lh/ks tqM+s gq, vU; lewg fØ;kRed
lewg dgs tkrs gSaA
,jkseSfVdukfHkd &ik'oZ Ja[kyk ,jkseSfVd ukfHkd &fØ;kRed lewg
CH2 Cl
Cl
CH2 CH2 OH
OH
CH
2CH NH
2
CH3
NH2
3-6-2 csUthu dh lajpuk
3-6-2-1 v.kq lw= ,oa dsdqys lajpuk
dkcZu ,oa gkbMªkstu dh izfr'kr ek=k rFkk v.kqHkkj ds vk/kkj ij csUthu dk
v.kqlw= C6H6 Kkr fd;k x;kA ftlds vuqlkj dqN laHkkfor lajpuk,¡ gks ldrh FkhaA
2 2H C CH C C CH CH 2 2HC C CH CH C CH
I II
3 3H C C C C C CH
III
;s vR;f/kd vlar`Ir lajpuk,¡ vekU; dh xbZ] D;ksafd fuEufyf[kr izk;ksfxd voyksduksa
dk Li"Vhdj.k bu lajpukvksa }kjk ugha fn;k tk ldkA
¼1½ vlar`Ir ;kSfxdksa gsrq lkekU; ;ksxkRed vfHkfØ;kvksa esa Hkkx ugha ysuk &
KMnO4 / OH
Br2 / CCl
4
HX
C6H
6
Hkwjs jax dk fojatu ugha
xqykchs jax dk fojatu ugha
;ksx ugha
gSykstu vEy
¼2½ rhu ;qXe vkca/kksa dh mifLFkfr & vkf.od lw= C6H6 ds vk/kkj ij csUthu dk ;qXe vkcU/k rqY;kad ^pkj* gksuk pkfg, Fkk]
fdUrq fuEufyf[kr vfHkfØ;kvksa ds vk/kkj ij ;g ^rhu* Kkr gqvkA
C6H
6
C6H
6X
6
C6H
6O
9
C6H
12
2
csathu gsDlkgSykbMa
3O3
3H2
csathu VªkbvktksukbMa
lkbDyksgsDlsua
3X 2
mRizsjd] mPp rki ,oa nkc
¼3½ bysDVªkWuLusgh izfrLFkkiu vfHkfØ;k,¡ &
lajpuk rFkk vkac/ku-I
113
HNO3 / H
2SO
4
Br2 / FeBr
2
CH3COCl / AlCl
3C
6H
6
H2SO
4
C6H
5NO
2 + H
2O
C6H
5Br + HBr
C6H
5COCH
3 + HCl
C6H
5SO
3H + H
2O
¼czksehuhdj.k½a
¼ukbVªhdj.k½a
¼ÝhMy&Øk¶V ,lkbyhdj.k½a
¼lYQksuhdj.k½a
¼4½ izfrLFkkfir csathu leko;fo;ksa dh la[;k eksuksizfrLFkkfir csathu % dsoy ,d
f}izfrLFkfir csathu leko;oh % dsoy rhu
mijksä voyksduksa ds vk/kkj ij dsdqys ¼1865½ }kjk csUthu dh izLrkfor lajpuk &
H
H
H
H
H
H
C
C
C
C
C
C
vU; oSKkfudksa }kjk izLrkfor lajpuk,¡ tks csathu ds xq.kksa dh O;k[;k u dj ldus ds
dkj.k vekU; dj nh xbZA
Msokj
¼1867½
¼fod.kZ½
DykWml
¼1867½
¼fizTe½
ysMu cxZ
¼1869½
¼dsfUnzd½
vkeZLVªkax ,oa
ckW;j ¼1892½
¼va'k la;ksth½
Fkhy
dsdqys lajpuk ds leFkZUk esa rF;
¼1½ gsDlkesfFky csUthu ds ,Dlfdj.k v/;;u ¼layXu
fp=½ ,oa jeu LisDVªe ls lery "kV~dksa.kh; lajpuk
,oa dkcZu&dkcZu nwjh 1-39
o
A Kkr dh xbZA
¼2½ csathu ds pqEcdh; ?kw.kZu ,oa vkf.od viorZu
v/;;u }kjk rhu ,dkUrj ;qXe vkca/kksa dh iqf"V dh
xbZA
dsdqys lajpuk }kjk u le>k;s tk ldus okys rF;
1- ;ksxkRed vfHkfØ;kvksa ds LFkku ij bysDVªku Lusgh izfrLFkkiu
2- gkbMªkstuhdj.k m"ek ds vk/kkj ij vlkekU; LFkkf;Ro
;kSfxd gkbMªkstuhdj.k fØ;k
gkbMªkstuhdj.k ÅtkZ ¼fdyks
dSykjh@eksy½
vuquknh
ÅtkZ ¼fdyks
dSykjh@eksy½ ifjdfyr voyksfdr
lkbDyksgsDlhu H2
28.6
lkbDyksgsDlk
MkbbZu
2H2
28.6x2=57.2 55.4 1.8
lajpuk rFkk vkac/ku-I
114
csUthu 3H2
28.6x3=85.8 49.8 36.0
3- lHkh dkcZu&dkcZu vkca/kksa dh leku vkca/k yackbZ % X&fdj.k foorZu ls lHkh Ng
dkcZu&dkcZu vkca/kksa dh yackbZ 1-39
o
A ekih xbZ] tks ,dy vkca/k ¼1-54
o
A ½ ,oa ;qXe
vkca/k ¼1-39
o
A ½ ds e/;orhZ gSA
4-
X
X
X
X
,oa fHké leko;oh gksuk pkfg;sA
dsdqys us 1872 esa csathu dks fuEufyf[kr lajpukvksa dk lfEeJ.k crk;k] ftuesa ;qXe vkca/k
fLFkfr cnyrs jgrs gSaA
ysfou ,oa dksys us 1932 esa o&tkbyhu ds vkstksuh vi?kVu }kjk Xyk;vkDly]
ik;:osfYMgkbM ,oa Mkb,lhVy izkIr dj bl izLrko dh iqf"V dhA
CH3
CH3 O
3 COCH3
CHO CHO
CHO
ty
vi?kVua
(i)
(ii)2 +
ik;:osfYMgkbM $ Xyk;vkDlya
O3 COCH
3
COCH3
CHO
CHO
CH3
CH3
ty
vi?kVua
(i)
(ii)2+
Mkb,lhVya Xyk;vkDlya
3-6-2-2 vuquknh lajpuk
csathu ds fy;s izLrkfor dh xbZ fofHké lajpukvksa esa varj dsoy bysDVªkfud O;oLFkk esa
Fkk] fdUrq fdlh Hkh lajpuk ds }kjk csathu ds leLr xq.kksa dh O;k[;k laHko ugha FkhA
vr% vuqukn fl)kar ds vuqlkj csathu dh lajpuk fuEufyf[kr lajpukvksa (I-V) ds
;ksxnku ls cuh gqbZ vuquknh ladj lajpuk (VI) dks ekuk x;kA
1
2
3
4
5
6
I II III IV V VI
dsdqys lajpuk,¡ Msokj lajpuk,¡ vuquknh ladj
lajpuk rFkk vkac/ku-I
115
dsdqys lajpukvksa I ,oa II dk LFkkf;Ro leku gksrk gS ,oa vuquknh ladj esa budk ;ksxnku
vf/kdre gksrk gSA
vuquknh lajpuk ds }kjk csathu ds xq.kksa dk Li"Vhdj.k
1- vkca/k yackbZ & vuquknh lajpuk esa okLrfod ,dy ;k ;qXe vkca/k ugha gksrs] lHkh C
– C ca/k leku gksrs gSA
2- leko;fo;ksa dh la[;k & casthu ds vuquknh ladj (VI) esa 1] 2& ,oa 1]
6&fLFkfr;k¡ leku gksus ds dkj.k dsoy rhu f}izfrLFkkih csathu O;qRié cuuk Li"V gksrk
gSA
1,2 1,3 1,4
3- LFkkf;Ro & fdlh Hkh v.kq dk vuquknh ladj mlesa ;ksxnku nsus okyh leLr
lajpukvksa ls vf/kd LFkk;h gksrk gSA csathu ds okLrfod v.kq vkSj vuquknh lajpukvksa ¼I ;k
II½ dh ÅtkZ esa varj vuqukn ÅtkZ ¼36 fdyks dSykjh@eksy½ ds :i esa O;ä gksrk gS] tks
LFkkf;Ro ds fy;s mÙkjnk;h gSA
4- mPp vuquknh ÅtkZ ds dkj.k csathu] ,jkseSfVd xq.kksa ¼;ksxkRed fØ;kvksa ds izfr
mnklhurk½ dk izn'kZu djrh gSA
3-6-2-3 csathu dh vkf.od d{kd lajpuk
X&fdj.k foorZu ekiu ls Kkr dh xbZ vkca/k yackbZ ,oa vkca/k dks.k 120o ds
vk/kkj ij csathu ds lHkh Ng dkcZu ijek.kq sp2 ladfjr gksuk pkfg,A izR;sd dkcZu ds
rhu sp2 ladfjr d{kdksa ls &dadky curk gS] ftldh lajpuk lery "kVHkqt gksrh gSA
&dadky ds yacor~ vladfjr p&d{kd vofLFkr gksrs gSaA izR;sd p&d{kd vius
fudVorhZ nksuksa p&d{kdksa ls leku:i ls vfrO;kiu djrk gS] ftlds &dadky ds
lery ds Åij ,oa uhps pØkdkj foLFkkuhf;r bysDVªkWu vHkz &dadky cukrk gSA
C
C
C
C
C
C
H
H
H
H
H
H
C
C
C
C
C
C
H
H
H
H
H
H
120o
csaUthu dk &dadky
dadky ¼Ng &bysDVªkWuksa dk foLFkkuhdj.k½
lajpuk rFkk vkac/ku-I
116
3-6-4 ,jkseSfVdrk
csathu ,oa dqN vU; ;kSfxd vR;f/kd vlar`Irrk ¼fuEu gkbMªkstu&dkcZu vuqikr½ ,oa dbZ
&vkca/k gksus ds ckotwn] [kqyh Ja[kyk ;qDr ikWyhbZuksa dh rqyuk esa fHké ,oa vlkekU;
HkkSfrd ,oa jklk;fud xq.k iznf’kZr djrs gSA ;Fkk&
1- ;ksxkRed ,oa vkDlhdj.k vfHkfØ;kvksa ds fy;s izfrjks/k ,oa bysDVªkWu Lusgh izfrLFkkiu
vfHkfØ;kvksa dh lqxerk
2- vlkekU; LFkkf;Ro &
fuEu gkbMªkstuhdj.k m”ek
fuEu ngu m”ek
mPp vuqukn ÅtkZ ¼151 fdykstwy@eksy½
vfHkfØ;k
csathu ds fy;s
voyksfdr
lkbDyks gsDlkVªkbbZu ds
fy;s ifjdfyr
vuqukn ÅtkZ
m”ek ¼fdyks twy @ eksy½
gkbMªkstuhdj.k 209 363 154
ngu 3302 3447 145
3- ,jkseSfVd pØ ls lh/ks tqM+s gq, izfrLFkkih] tSls&Cl, OH, NH2 vkfn fHké O;ogkj
iznf’kZr djrs gSa&
RCl vR;f/kd fØ;k’khy Ar Cl csathu ls Hkh de fØ;k’khy
ROH mnklhu Ar OH nqcZy vEyh;
R NH2 veskfu;k ls vf/kd HkkfLed Ar NH2 veksfu;k ls de HkkfLed
R NH2
HNO2
R OH0-5oC
HNO2
Ar NH2
Ar N N Cl
0-5oC Mkb,tksfu;e yo.k
jkWfculu dk ,jkseSfVd k”Vd fl)kar
csUthu ds Ng dkcZu ijek.kqvksa ds lery “kMHkqt ds Åij ,oa uhps Ng
bysDVªku foLFkkuhf;r gksdj ,d lrr bysDVªkWu vHkz cukrs gSa] tks ,jkseSfVd xq.kksa dk
tud gSA
3-6-4-1 gdy dk fu;e ¼4n+2 fu;e½
gdy us 1931 esa vkf.od d{kd x.kuk ds vk/kkj ij ,jkseSfVdrk dk fl)kar
izfrikfnr fd;k] tks csathu ln`'k ¼csUthukbM½ ,oa uku&csUthukbM ;kSfxdks ,oa fofHké
vkdkjksa ds pØks ds fy;s mi;ksxh gSA izeq[k vfHkxzghr fuEukuqlkj gS &
¼1½ ,jkseSfVd ;kSfxd lery@likV gksuk pkfg;s] rkfd p&d{kdksa dk vf/kdre ,oa
izHkkoh lgik'ohZ; vfrO;kiu gkss ldsA
¼2½ pØh; fudk; esa &dadky ds Åij ,oa uhsps foLFkkuhf;r &bysDVªkWuksa }kjk
pØh; bysDVªkWu vHkz cuuk vko';d gSA
¼3½ bysDVªkWu vHkz esa dqy 4n + 2 bysDVªkWu gksuk vko';d gS] tgk¡ n ,d iw.kk±d
la[;k ¼0] 1] 2] 3] ------------] bR;kfn½ gSA
¼4½ 4nbysDVªkWu okys ikyhbZu pØh; ;kSfxd led{k [kqyh Ja[kyk ;qä ;kSfxdksa ls
Hkh de LFkk;h gksrs gSa ,oa izfr,jkseSfVd (anti aromatic) ;kSfxd dgs tkrs gSa]
mnkgj.kkFkZ &
1] 3&lkbDyksC;wVkMkbu 1] 3] 5] 7&lkbDyks vkDVkVsVªkbZu
lajpuk rFkk vkac/ku-I
117
4bysDVªkWu (n=1) 8bysDVªkWu (n=2)
csUthukbM ,jkseSfVd ;kSfxd
n 4n + 2 mnkgj.k
1 4 x 1 + 2 = 6
csathu
1 4 x 1 + 2 = 6
N
fijhMhu
2 4 x 2 + 2 = 10
us¶Fkyhu
2 4 x 2 + 2 = 10
N
fDouksyhu
3 4 x 3 + 2 = 14
,UFkszlhu
ukWu & csUthukbM ,jkseSfVd ;kSfxd
fo"ke pØh; ;kSfxd & fo"ke ijek.kq ¼X = N, O ;k S½ ds p&d{kd esa mifLFkr
,dkdh bysDVªkWu ;qXe ,jkseSfVd "k"Vd esa ;ksxnku nsrk gSA
C C
C C
X
NH
..
O..
S..
Pyrrole Furan Thiophene
3-6-4-2 ,jkseSfVd vk;u &
¼1½ lkbDyksizksisfuy /kuk;u & 2 bysDVªkWu (n = 0, 4 ₓ 0 + 2 = 2)
lajpuk rFkk vkac/ku-I
118
=
OH
Br
SbCl6
gkbMªkWDlh lkbDyksizksisfuy czksekbM lkbDyksizksisfuy gsDlkDyksjks,UVheksusV
¼LFkk;h ,jkseSfVd ;kSfxd½ ¼LFkk;h ,jkseSfVd ;kSfxd½
¼2½ lkbDyksisUVkMkbbfuy _.kk;u &
6 bysDVªkWu (n = 1, 4 x 1 + 2 = 6)
.. :
..
:
..
K+
Fe2+
ikSVsf'k;e
lkbDyksisUVkMkbbukbM Qsjkslhu
QSjkslhu ukjaxh jax dk Bksl ;kSfxd ¼xyukad 172oC½ gksrk gSA ;g lYQksuhdj.k
,lkbyhdj.k ,oa ejDw;jhdj.k vfHkfØ;k,¡ djrk gS] fdUrq ukbVªhdj.k ,oa gSykstuhdj.k esa
Qsjl vk;u dk vkWDlhdj.k gks tkrk gSA Fe ds LFkku ij vU; vk;u] ;Fkk& Co, Ni,
Ru, Os, Ti, V, bR;kfn Hkh esVykslhu yo.k cukrs gSaA
¼3½ lkbDyksgsIVkVªkbbZfuy ¼Vªksikbfy;e½ /kuk;u ¼6 bysDVªkWu½
OH
Cl
Br
Vªksikbfy;e
/kuk;u
gkbMªkDlh
Vªksikbfy;e DyksjkbM
Vªksikbfy;e
czksekbM
3-7 ,jkseSfVd bysDVªksfQfyd izfrLFkkiu
csUthu ,oa mlds O;qRiéksa esa pØ ds Åij ,oa uhps mifLFkr bysDVªkWu vHkz
bysDVªku Lusgh vfHkdeZdksa dks vkdf"kZr djrk gS ,oa gkbMªkstu vk;u ¼izksVkWu½ bysDVªkWu
Lusgh /kuk;u (E+) }kjk izfrLFkkfir dj fn;k tkrk gSA
3-7-1 fØ;kfof/k dk lkekU; izkn'kZ
¼1½ bysDVªksQkby dk mRié gksuk &
lajpuk rFkk vkac/ku-I
119
ENu E Nu
¼2½ bysDVªksQkby }kjk ,jkseSfVd pØ ij vkØe.k dj &ladqy cukuk
+ E+
E
¼3½ &ladqy dk &ladqy es ifjorZu
H
E
H
E
H
E
H
E
E
ean
sp
2 &ladqy ;k ,jhfu;e vk;u ;k OghyS.M ladqy
ladfjr dkcZu
¼4½ &ladqy ls izksVku ds fu"dklu }kjk izfrLFkkfir mRikn dk cuuk
EH
E
Nu + NuH
nzqr
laiw.kZ bysDVªkWuLusgh izfrLFkkiu vfHkfØ;k &
E
H
E
H + E
laØe.k voLFkk&I ladqy
E
H E
H+
laØe.k voLFkk&II
3-7-2 ,oa ladqyksa dk egRo
,jkseSfVd bysDVªkWu Lusgh izfrLFkkiu esa &ladqy ,d ek/;fed ds :i esa curk
gSA izk;ksfxd voyksduksa ds vk/kkj ij ik;k x;k] fd bysDVªkWu Lusgh ds lkFk dkcZu vkca/k
cukdj &ladqy cuus ls iwoZ ,d &ladqy curk gS] tks pØ ds bysDVªkWu vHkz ds izfr
vkd"kZ.k ds dkj.k curk gSA laiw.kZ izfrLFkkiu vfHkfØ;k fuEukuqlkj fn[kkbZ tk ldrh gSA
lajpuk rFkk vkac/ku-I
120
E H
E
E
+ E
E
+ H
H&ladqy
&ladqy &ladqy
fHké&fHké vfHkfØ;kvksa esa &ladqy ;k &ladqy fuekZ.k fØ;k dk osx fu/kkZfjr
djrk gSA mnkgj.k ds rkSj ij czksehuhdj.k vfHkfØ;kvksa esa &ladqy fuEkkZ.k osx fu/kkZjd
¼ean½ ij gksrk gS rFkk ukbVªksfu;e ¶yqjkscksjsV (NO2BF4) }kjk VsVªkesfFky lYQksu
foyk;d esa ,jkseSfVd gkbMªksdkcZuksa ds ukbVªhdj.k esa &ladqy fuekZ.k osx fu/kkZjd in
gksrk gSA &ladqy ;k &ladqy cuus ds egRo ds vk/kkj ij ÅtkZ vkjs[k fuEukuqlkj
n'kkZ;s tk ldrs gSaA
&ladqy fuekZ.k % osx fu/kkZjd
&ladqy fuekZ.k % osx fu/kkZjd
lajpuk rFkk vkac/ku-I
121
lajpuk rFkk vkac/ku-I
122
lajpuk rFkk vkac/ku-I
123
3-8 lfØ;d ,oa fuf"Ø;d lewg
tc dksbZ bysDVªkWu Lusgh vfHkdeZd fdlh ,jkseSfVd ukfHkd ij vkØe.k djrk gS]
rks pØ ij igys ls mifLFkr lewg vfHkfØ;k dh lqxerk ,oa vkØe.k dh fLFkfr dks
izHkkfor djrk gSA
mnkgj.kkFkZ &
CH3
CH3
NO2
CH3
NO2
CH3
NO2
HNO3 / H
2SO
4
+ +de rki ij
VkYohu (58%) o- (38%) p- (4%) m- ukbVªksVkYohu
NO2
NO2
NO2
NO2
NO2
NO2
NO2
HNO3 / H
2SO
4
+ +
ukbVªkscsathu
90oC
(6.4%) o- (0.3%) p- (93.3%) m- Mkb ukbVªkscsUthu
lfØ;dj.k ,oa nSf'kdrk ds vk/kkj ij izfrLFkkfir;ksa dks nks Jsf.k;ksa esa ckaVk tkrk gS &
¼1½ lfØ;d & tks fØ;k dh lqxerk c<+krs gSa ,oa o, p&funsZ'kd gksrs gSa] tSls &
NR2, NH2, OH, O, NHCOR, OR, OCOR, R bR;kfnA
¼2½ fuf"Ø;d & tks fØ;k dks dfBu dj nsrs gSa ,oa m&funsZ'kd gksrs gSa] tSls&
N
R3, CX3, C N, COOH, CHO, COR, COOR,
SO3H, bR;kfnA
gSykstu fo'ks"k lewg gSa] tks fuf"Ø;d gksrs gSa] fdUrq o, p-funsZ'kd gksrs gSaA
3-8-1 ,jkseSfVd bysDVªku Lusgh izfrLFkkiu esa lfØ;rk ,oa nSf'kdrk dk Li"Vhdj.k
fdlh Hkh vfHkfØ;k ds osx dh nj fØ;kdkjdksa ,oa laØe.k voLFkk dh ÅtkZvksa
ds varj vFkkZr~ ßlfØ;.k ÅtkZÞ (Ea) ij fuHkZj djrh gSA lkekU;r% ,jkseSfVd
bysDVªkWLusgh izfrLFkkiu esa &ladqy dk fuekZ.k osx fu/kkZjd in gksrk gS] vr% &ladqy
ds LFkkf;Ro dks izHkkfor djus okys dkjd gh lfØ;.k ÅtkZ dks izHkkfor djrs gSaA
lfØ;d lewg bysDVªkWu iznku izsjf.kd izHkko vFkok vuqukn izHkko }kjk djrs gSa rFkk
&ladqy /kukos'k dks ijklfjr djds &ladqy dks LFkkf;Ro iznku djrs gSaA
fuf"Ø;d lewg bysDVªkWu &ladqy ds vkd"khZ lewg gksrs gSa] tks &ladqy ij
/kukns'k dks c<+kdj mls vLFkk;h cukrs gSaA
/kukfo"V &ladqy dh vuquknh lajpukvksa ds voyksdu ls izfrLFkkfi;ksa dh
nSf'kdrk dk Li"Vhdj.k feyrk gSA
lajpuk rFkk vkac/ku-I
124
CH3
H E
CH3
H E
CH3
H E
CH3
H
E
CH3
H
E
CH3
H
E
CH3
H
E
CH3
H
E
CH3
H
E
CH3
E
(T)
(T)
m-
vkØe.k
vkØe.k
o-
VkWYohu
vkØe.k
p-
vkFkksZ ,oa iSjk fLFkfr ij vkØe.k gksus ij &ladqy dh ,d vuquknh lajpuk esa esfFky
lewg ls tqM+s dkcZu ij /kukos'k gksrk gS] rrh;d dkcksZdsVk;u gksus ds dkj.k ;g 'ks"k
lajpukvksa ¼f}rh;d dkcksZdsVk;u½ ls vf/kd LFkk;h gksrk gSA eSVk&fLFkfr esa ,slh dksbZ
vuquknh lajpuk ugha gSA o& ;k p&fLFkfr ij vkØe.k gksus ij vfrla;qXeu }kjk /kukos'k
esfFky lewg ij Hkh foLrkfjr gks ldrk gSA
H E H E
C H
H
H C
H
H
H E
C HH
H E
C H
H
H
H
H
3-8-2 fuf"Ø;d lewg gsrq vuquknh lajpuk,¡
N
H E
OON
H E
OON
H E
OO
N
H
E
OO
N
H
E
OO
N
H
E
OON
H
E
OO
N
H
E
OON
H
E
OO
N OO
(T)
(T)
p&vkØe.k
o&vkØe.k
m&vkØe.kE+
p- ,oa o- vkØe.k esa vuquknh lajpukvksa esa /kukfo"V ukbVªkstu ls tqM+s dkcZu ij /kukos'k
gksrk gS] vr% ;s lajpuk,¡ vLFkk;h gksrh gSaA
lajpuk rFkk vkac/ku-I
125
CH3
CH3
EH
CH3
H
E
H
CH3
E
NO2
EHEH
NO2
H
E
NO2
NO
2
H
E
+ E + E + E
p
om
p o m
csUthu] VkWYohu ,oa ukbVªksosUthu ds bysDVªkWu Lusgh izfrLFkkiu vfHkfØ;k esa fofHké &ladqyksa lkis{k ÅtkZ
3-8-3 gSykscsUthu ds O;ogkj dk Li"Vhdj.k
gSykstu _.kkRed izsjf.kd izHkko (–I) ds dkj.k bysDVªkWu Lusgh vfHkfØ;kvksa esa
fuf"Ø;d izHkko mRié djrh gSa] fdUrq vuquknh izHkko (+M) ds dkj.k o, p-funsZ'kd
gksrh gSaA
Cl
H E
Cl
H E
..
: :..
:
Cl
E
H
Cl
E
H
..
: :..
:
p&vkØe.k o&vkØe.k
Cl
E
H
Cl
E
H
..: :
..::
m&vkØe.k
3-8-4 nSf'kd izHkko ,oa vkFkksZiSjk vuqikr
tc ,d eksuksizfrLFkkih csathu (Ph-Y) ij bysDVªkWu Lusgh izfrLFkkiu vfHkfØ;k
dh tkrh gS] rks bysDVªkWuLusgh ( E ) igys ls mifLFkr izfrLFkkih (Y) dh fLFkfr ls
vkFkksZ ;k esVk ;k iSjk LFkku ij tqM+ ldrk gSA izfrLFkkih y ds xq.kksa ds vk/kkj ij uohu
izfrLFkkih E dh fLFkfr fu/kkZfjr gksrh gSA dqN lewgksa ds /kzqoh; izHkko ,oa nSf'kd izd`fr
fuEukuqlkj gSA
lajpuk rFkk vkac/ku-I
126
lewg lfØ;.k /kzqoh; izHkko nSf'kd
izdfr
¼1½ .... ..
O, NR2, NH2, OH
izcy
lfØ;d + R o, p
¼2½ .... .. ..
NCOR, OR, sR, O COR
e/;e
lfØ;d + R o, p
¼3½ 3, 2 3, 3 6 52CH CH CH CH CH C H
nqcZy
lfØ;d
+ I vfrla;qXeu
+ I o, p
¼4½ .... .. ..
F, Cl, Br, I
nqcZy
fuf"Ø;d – I , + R o, p
¼5½ 2 3NO , CN, SO H, 3COOH, SO R,
CHO, COR
e/;e
fuf"Ø;d – I, – R m
¼6½ 3 3CF , CCl izcy
fuf"Ø;d – I m
;|fi dqN lewg izeq[kr% o, p ,oa vU; m&funsZ'kd gksrs gSa] fdUrq lhfer ek=k esa vU;
mRikn Hkh izkIr gks ldrs gSaA
3-8-5 vkFkksZ iSjk vuqikr
fdlh eksuksizfrLFkkih csathu esa nks vkFkksZ ,oa ,d iSjk fLFkfr gksrh gS] vr%
lkaf[;dh vuqikr 2%1 gksuk pkfg, fdUrq lkekU;r% vkFkkZsizfrLFkkiu laHkkfor ls de ek=k esa
gh ik;k tkrk gSA bl folaxfr ds fy;s vusd dkjd gks ldrs gSa] tSls&izfrLFkkfi;ksa ds
/kzqoh; izHkko] foyk;d] rkieku] f=foeh; izHkko vkfnA
¼1½ f=foeh; izHkko & izk;ksfxd vkadM+ksa ds vk/kkj ij fl) gqvk gSa] fd iwoZ ls mifLFkr
izfrLFkkih ,oa izos'k djus okys izfrLFkkfi;ksa ds vkdkj dk izHkko vkFkksZ iSjk vuqikr fu/kkZfjr
djus esa izeq[k Hkwfedk j[krs gSaA
,fYdy csathu ds ukbVªhdj.k esa o / p vuqikr
izfrLFkkih (R) c<+rk
vkdkj
o&mRikn dk
%
p&mRikn dk
% o / p vuqikr
CH3 58 37 1.57
CH3 CH2 45 59 0.92
CHCH
3
CH3
30 62 0.48
(CH3)3 – C – 16 73 0.22
izfrLFkkih ds c<+rs vkdkj ds lkFk vuqikr de gksrk tkrk gSA
VkYohu ds ÝhMy Øk¶V ,fYdyhdj.k esa o&mRikn dk izfr'kr
6 5 3 6 4 3C H CH R C H CHR
vkØe.kdkjh
bysDVªku Lusgh ( R ) c<+rk vkdkj o&mRikn dk izfr'kr
CH3 – 53.8
CH3 CH2 – 45.0
CHCH
3
CH3
37.5
(CH3)3 C – 0
lajpuk rFkk vkac/ku-I
127
6 5 6 4C H Cl E C H ClE
c<+rk vkdkj E o&mRikn dk % p&mRikn dk % o / p vuqikr
Cl 39 55 0-71
2N O
30 70 0-43
Br 11 87 0-14
SO3
1 99 0-01
¼2½ bysDVªkWfud izHkko & gSykscsathu dk ukbVªhdj.k
2
6 5 6 4 2X C H X C H NONO
vkdkj &I izHkko izfrLFkkih X o&mRikn dk % p&mRikn dk % o / p vuqikr
F 12 88 0-14
Cl 30 69 0-44
Br 37 62 0-60
I 38 60 0-63
¼3½ rkiØe dk izHkko
2 4
6 5 6 4 3HO C H HO C H SO HH SO
15 – 20oC - o-mRikn dh mPp ek=k
100oC - p-mRikn dh mPp ek=k
¼4½ foyk;d dk izHkko yqbl mRiszjd dh vuqifLFkfr esa VkYohu ds gSykstuhdj.k esa foyk;d dh /kzqoh;rk
esa varj ls o/p vuqikr izHkkfor gksrk gSA
3-8-6 fcpZ vip;u
,jkseSfVd ;kSfxdksa dk vkaf'kd vip;u nzo veksfu;k ,oa vYdksgy dh mifLFkfr esa {kkj
/kkrq ¼lksfM;e] iksVsf’k;e ;k yhfFk;e½ dh fØ;k ls 1]4&lkbDyksgsDlkMkbbZu curk gSA
NH3, C
2H
5OH
Na
fØ;k fof/k &
izFke bysDVªkWu LFkkukUrj.k
Na..
.... .
bR;kfn
csUthu _.kk;u ewyd
C2H5OH
lajpuk rFkk vkac/ku-I
128
HH HH
.
.
bR;kfn
f}rh; bysDVªkWu LFkkukUrj.k Na
.
HH HH
..
..bR;kfn
HH
HH
vf/kd LFkk;h la;qfXer MkbbZu 1]3&lkbDyksgsDlkMkbbZu ds LFkku ij de LFkk;h
1]4&lkbDyksgsDlkMkbbZu cuus dk dkj.k vKkr gSA
lkekU; mnkgj.k & mRikn esa izfrLFkkih dh fLFkfr ;qXe caf/kr dkcZu ij
O CH3
O CH3
NH3, C
2H
5OH
Li
80%
CH3
CH3
O CH3
CH3
NH3, C
2H
5OH
Na
(77-95%)
viokn % mRikn esa izfrLFkkih dh fLFkfr lar`Ir dkcZu ij COOH
(i) Na, NH3, C
2H
5OH
(ii) H3O
COONa
(89-95%)
3-9 ,fYdy csathu & cukus dh lkekU; fof/k;k¡
1- oqVZt fQfVx vfHkfØ;k &
6 5 3 6 5 3C H Br + 2Na + BrCH C H CH + 2NaBr'kq"d bFZ kj
2- ,jkseSfVd vEyksa dk fodkckZDlhyhdj.k &
3 6 4 6 5 3 2 3 2CH C H COOH C H CH + Na CO + H OlkMs k ykbe
3- fefJr dhVksuksa dk DyhesUlu ;k oqYQ fd'uj vip;u &
C6H
5 COCH
3C
6H
5 CH
2 CH
3NH2NH
2
Zn+HCl
C2H5OH
lajpuk rFkk vkac/ku-I
129
4- QhukWyksa dk vip;u &
3 6 4 3 6 5CH C H OH + Zn CH C H + ZnO
5- ,jkseSfVd lYQksfud vEyksa dk ty vi?kVu &
CH3 C
6H
4 SO
3H C
6H
5 CH
3 + H
2SO
4
vfrrIr tyok"i
;k lkUnz HCl, 150oC
6- fxzxukMZ vfHkdeZd ds lkFk ,fYdy gSykbM dh fØ;k &
6 5 3 6 5 3C H Mg Br + ClCH C H CH + Mg Br Cl
7- ,Ydsuksa dk mRizsjdh; fogkbMªkstuhdj.k & gkbMªksQkfeZUx ;k mRiszjdh; fjQkfeZUx &
mPp nkc ij ,Y;wfeuk (Al2O3) vk/kkj ij Øksfe;e vkWDlkbM dh mifLFkfr esa
480&500oC ij n&gsIVsu ;k n&vkWDVsu dks xeZ djuk ¼vkS|ksfxd fof/k½
CH3 (CH
2)
5 CH
3
Al2O
3 - Cr
2O
3
CH3
480-550oC+ 4 H2
VkYohu
CH3 (CH
2)
6 CH
3
Al2O
3 - Cr
2O
3
C2H
5
CH3
CH3
480-550oC
+ 4 H2
+ 4 H2
,fFky csUthu
(o-, p-, m-) tkbyhu
3-9-1 ,fYdy csathu dh vfHkfØ;k,¡
3-9-2 ik'oZ Ja`[kyk vfHkfØ;k,¡
1- vkDlhdj.k
(a) KMnO4 ;k K2Cr2O7 ;k ruq HNO3 }kjk
CH2CH
3COOH
+ 4 [O] + CO2
CH3
CH3
COOH
COOH
[O]
lajpuk rFkk vkac/ku-I
130
C3H
7
CH3
COOH
CH3
COOH
COOH
[O] [O]
(b) bVkMZ vfHkfØ;k&Øksfey DyksjkbM (CrO2Cl2) }kjk CS2 foy;u esa vkWDlhdj.k
6 5 3 6 5 2C H CH 2[O] C H CHO + H O
6 5 2 3 6 5 2 2C H CH CH 2[O] C H CH CHO + H O
2- eqDr ewyd gSykstuhdj.k ¼mPp rki ;k izdk'k dh mifLFkfr esa½
(i)
CH3
Cl2
CH2Cl
Cl2
CHCl2
Cl2
C Cl3
VkYohu csafty csaty csatksVªkbZ
DyksjkbM DyksjkbM DyksjkbM
(ii)
CH2CH
3
Cl2
CHCl CH3
CH2 CH
2 Cl
+
eq[; mRikn
(iii)
CH2CH
3
Br2
CH Br CH3
uksV & Dyksjhu dh rqyuk esa czksehu dh oj.kh;rk mPp gksrh gSA
fØ;kfof/k
CH2CH
3
CHCH3
X2
CH2CH
2X + X
X
.
CH2CH
2
X2
CH2CH
2X + X .
.
.
csatkbfyd eqDr ewyd
¼vf/kd LFkk;h½
1o eqDr ewyd
¼de LFkk;h½
(-HX)
Xo
3-9-3 ,jkseSfVd ukfHkd ij izfrLFkkiu
lajpuk rFkk vkac/ku-I
131
CH3
NO2
CH3
NO2
HNO3, H
2SO
4
CH3
SO3H
CH3
SO3H
CH3
CH3
CH3
CH3
CH3
X
CH3
X
H2SO
4, SO
3
CH3X, Al X
3
X2 + Fe
CH3
+
+
+
+
3-9-4 ckbQsfuy
ckbQsfuy dksyrkj esa ik;k tkrk gSA ;g ,sls ,jkseSfVd gkbMªksdkcZuksa dk ljyre
mnkgj.k gS] ftuesa ,jkseSfVd pØ ,dy vkca/k }kjk tqM+s jgrs gSaA
3-9-4-1 cukus dh fof/k;k¡
¼1½ fQfVx vfHkfØ;k &
Br Br + 2NaBr+ 2Na +
20-30%
¼2½ czksekscsUthu ls ¼cq'k ,oa lg;ksxh½
BrNH
2NH
2Pd/CaCO
3 + 2HBr
80%
2{kkjh; bFksukWfyd foy;u
¼3½ mYeku ckb,fjy la'ys"k.k &
I I+ 2Na + + 2CuI
80%
¼4½ Mkb,tksfu;e yo.kksa ls &
NC
2H
5OH
CuN HSO
4
+ 2N2 + 2H2SO4
2
lajpuk rFkk vkac/ku-I
132
¼5½ xksEcxZ vfHkfØ;k &
N N Cl
+ N2 + HCl+
¼6½ fxzxukMZ vfHkfØ;k
CoCl2
Mg Br + Br + Mg Br2
¼7½ vkS|ksfxd fof/k
C6H
6C
6H
5 C
6H
5 + H
22jä rIr uyh 600-800oC
I;wfel ;k FeSO4
3-9-4-2 jklk;fud vfHkfØ;k,¡ 1- ukfHkdh; izfrLFkkiu vfHkfØ;k,¡ & ,d csathu pØ bysDVªkWu iznkrk ,oa nwljk
bysDVªku xzkgh dh rjg O;ogkj djrk gSA bysDVªkWu Lusgh o&,oa p&fLFkfr;ksa ij izos'k djrk gSA
m' o'
p'
m' o'
1
23
4
5 6
'''
'' '
1
2 3
4
56
o m
p
mo
mnkgj.k & ukbVªhdj.k
NO2
NO2
lkUnz H2SO4
lkUnz H NO3+
4&ukbVªks 2&ukbVªks
ckbQsfuy ckbQsfuy
¼eq[; mRIkkn½
2- vkWDlhdj.k
H2CrO
4COOH CO
2 + H
2O+
vYi ek=k esa eq[; mRikn
3- vkstksuh vi?kVu
(i) O3 (ii) H
2O
COOH 86%
-20oC
3-10- cks/k iz'u ¼x½
1- lgh mÙkj ij dk fu'kku yxkb;s
(i) fuEufyf[kr esa ls dkSu&lk ;kSfxd ,jkseSfVd gS\
lajpuk rFkk vkac/ku-I
133
¼v½
¼c½
¼l½
¼n½
(ii) fuEufyf[kr esa ls dkSu&lk vk;u ,jkseSfVd ugha gS\
¼v½
¼c½
¼l½
¼n½
(iii)
CH3
ds fcpZ vip;u ij dkSu&lk mRikn izkIr gksxk\
v
CH3
c
CH3
l
CH3
n
CH3
(iv) fuEufyf[kr esa ls dkSu&lk izfrLFkkih fuf"Ø;d gksus ij Hkh ,jkseSfVd bysDVªkWu
Lusgh izfrLFkkiu esa o, p&funsZ'kd gksrk gSS\
¼v½ NO2 ¼c½ CHO ¼l½ Cl ¼n½ C N
(v) fuEufyf[kr esa ls dkSu&lk lewg m&funsZ'kd gksrk gSS\
¼v½ OH ¼c½ NH2 ¼l½ OCH3 ¼n½ COOH
Loij[k iz'u@vH;kl
1- csathu ds LFkkf;Ro ,oa dkcZu&dkcZu vkca/k yackbZ ds vk/kkj ij izLrkfor vuquknh
lajpuk dk fooj.k nhft;sA
2- gdy fu;e D;k gS\ dqN ,jkseSfVd vk;uksa ds mnkgj.k nhft;sA
3- ÝhMy Øk¶V vfHkfØ;k dh fØ;kfof/k le>kb,A
4- ,jkseSfVd bysDVªkWuLusgh izfrLFkkiu esa ,oa ladqyksa dk egRo crkrs gq, ÅtkZ izØe
vkjs[k cukb;sA
5- fuEufyf[kr ds cukus dh fof/k;k¡ ,oa jklk;fud vfHkfØ;k,¡ fyf[k, &
(i) ,fYdy csathu (ii) ,Ydkbfuy csathu (iii) ckbQsfuy
vH;kl
1- fuEufyf[kr ;kSfxdksa ds lajpuk lw= fyf[k;sA
(i) 1] 2] 4&VªkbesfFky csathu
(ii) 4&gkbMªkWDlh VkWYohu
(iii) 4&vehuks&2&czkseks csatkbd vEy
(iv) 2&Qsfuy bFksukWy
2- fuEufyf[kr ,fjy ewydksa ds uke fyf[k;sA
(i)
CH3
(ii) CH2Cl
(iii) C
(iv) CH
NO2
lajpuk rFkk vkac/ku-I
134
3-10-1 cks/k iz'u d 1- lgh mÙkj ij ¼½ fu'kku yxkb;s
(i) 'kq"d bZFkj foy;u esa ,fYdy gSykbM ,oa lksfM;e /kkrq dh fØ;k ls ,Ydsu
cukus dh fof/k fdl oSKkfud us nh Fkh\
¼v½ dkSYcs ¼c½ oqVZt ¼l½ ÝsUdys.M ¼n½ fxzxukMZ
(ii) dksjs&gkml vfHkfØ;k eas ,fYdy gSykbM ds lkFk fdl vfHkdeZd dh fØ;k dh
tkrh gS\
¼v½ lksfM;e ¼c½ ftad
¼l½ yhfFk;e Mkb,fYdy dkWij ¼n½ eSXuhfl;e
(iii) lkbDyksizksisu dh czksehu ls vfHkfØ;k gksus ij D;k curk gS\
¼v½ 1]3&Mkbczkseksizksisu ¼c½ czksekslkbDyksizksisu
¼l½ ¼v½ ,oa ¼c½ nksuks ¼n½ dksbZ fØ;k ugh
(iv) ck;j ruko fl)kar ds vuqlkj fuEufyf[kr esa ls dkSu&lk lkbDyks,Ydsu
lokZf/kd LFkk;h gksrk gS\
¼v½
¼c½
¼l½
¼n½
3-10-2 fjä LFkkuksa dh iwfrZ dfj;s
(i) lksfM;e izksfivkusV dks lksMk ykbe ds lkFk xeZ djus ij -------------curh gSA
(ii) isUVsu -------------- leko;oh :iksa esa ikbZ tkrh gSA
(iii) vkblks&C;wVsu esa mifLFkr r`rh;d gkbMªkstu ijek.kqvksa dh la[;k ---------- gSA
(iv) ck;j ruko fl)kar ds vuqlkj lkbDyks isaVsu ,oa ---------- dk LFkkf;Ro leku gksuk
pkfg,A
3-10-3 Loij[k iz'u@vH;kl iz'u 1- fuEufyf[kr vfHkfØ;kvksa dh fØ;kfof/k fyf[k;sA
(i) dksYcs fo|qr vi?kVu (ii) oqVZt
2- fuEufyf[kr ij fVIi.kh fyf[k;sA
(i) ruko jfgr oy;ksa dk fl)kar (ii) dsyk vkca/k
(iii) dksjs&gkml vfHkfØ;k (iv) ,Ydsuks dk gSykstuhdj.k
(v) ,Ydsuksa ds HkkSfrd xq.k
3- ,Ydsu cukus dh dksbZ nks fof/k;k¡ fyf[k;sA
4- ,fFky vk;ksMkbM ,oa esfFky vk;ksMkbM ds bFkjh; foy;u esa lksfM;e feykus ij
dkSu&ls mRikn cusaxs\ uke ,oa jklk;fud lehdj.k fyf[k;sA
5- ck;j ruko fl)kar ,oa mldh lhek,W fyf[k;sA
6- ,Ydsuksa dh izeq[k jklk;fud vfHkfØ;k,¡ fyf[k;sA
3-10-4 vH;kl rhu leko;oh ,Ydsuksa ¼v]c]l½ dk v.kqlw= C5H12 gSA Dyksjhuhdj.k djus ij ^v* ls
dsoy ,d] ^c* ls pkj ,oa ^l* ls rhu eksuksDyksjksO;qRié C5H11Cl eq[; mRikn ds :i esa
izkIr gksrs gSaA ^v*] ^c*] ^l* ,oa C5H11Cl leko;fo;ksa ds lajpuk lw= fyf[k;sA
3-10-5 fuEufyf[kr ;kSfxdksa ds IUPAC uke fyf[k;sA
lajpuk rFkk vkac/ku-I
135
(i)
CH CH2
CH3
CHCH3 CH
2CH
3
CH3
(ii) CH
2
CH CH2
CH3
CH3
CH3
CH3
C
CH3
(iii)
CH2
CH3
CH2
CH3 CH
CH3 CH
3
CH3
C
(iv) CH CH3
CHCH3 CH
2
CH3
CH3 C
2H
5
(v)
CH3
(vi)
Cl CH3
(vii)
Br
C
CH3
CH3CH
3
3-11 bdkbZ lkj la{ksi
,Ydsu vpØh; ¼[kqyh Ja`[kyk ;qDr½ gkbMªksdkcZu gksrs gSaA dsoy ,dy vkca/k
;qDr bu lar`Ir ;kSfxdksa dh leko;oh Js.kh dk lkekU; lw= CnH2n+2 gksrk gSA ,Ydsu
eq[;r% izfrLFkkiu vfHkfØ;k,a iznf’kZr djrs gSa] ftuesa eqDr ewyd lfØ; ek/;fed curs
gSaA pØh; ,lhQSfVd gkbMªksdkcZu % lkbDyks,Ydsuksa dk lkekU; CnH2n lw= gSA buds
fuEure lnL; 3& ,oa 4& lnL;h; pØ ;qä ;kSfxd ¼lkbDyksizksisu ,oa lkbDyksC;wVsu½
vLFkk;h gksrs gSa ,oa izfrLFkkiu ds ctk; ;ksxkRed vfHkfØ;k,a djrs gSaA ftuesa pØ [kqy
tkrs gSaA buds vlkekU; vLFkkf;Ro ds fy;s ck;j ruko fl)kar izLrqr fd;k x;kA cM+s
pØksa ds fy;s ;g fl)kar vuqi;qä ik;k x;k] vr% lk’ks&eksgj }kjk ruko jfgr oy;ksa dk
fl)kar izfrikfnr fd;k x;kA ,jhu ;k ,jkseSfVd gkbMªksdkcZuksa dk lkekU; lw= CnH2n-6
gksrk gSA vR;f/kd vlar`Ir gksus ds ckn Hkh ;s ;kSfxd ;ksxkRed ds ctk; izfrLFkkiu
vfHkfØ;k,¡ iznf’kZr djrs gSa] ftudh fØ;kfof/k lkekU;r% bysDVªkWu Lugsh gksrh gSaA
,jkseSfVdrk ds xq.k ds fy;s gdy us leryh;] pØh;] ,dkUrj ;qXe vkcU/k ;qDr ;kSfxdksa
esa 4n+2 bysDVªkWuksa dh vfLFkfr dks vko’;d crk;kA ,jkseSfVd bysDVªku Lusgh
izfrLFkkiu vfHkfØ;kvksa esa pØ esa mifLFkr izfrLFkkih uohu izfrLFkkih dh nSf’kdrk ,oa
fØ;k dh xfr dks izHkkfor djrs gSaA
lajpuk rFkk vkac/ku-I
136
3-12-1 cks/k iz'uksa ds mÙkj
1- (i) ¼c½ (ii) ¼l½ (iii) ¼v½ (iv) ¼l½
2- (i) izksisu (ii) pkj (iii) ,d (iv) lkbDyksgsIVsu
3-12- mÙkj
C CH3
CH3
CH3
CH3
C CH2Cl
CH3
CH3
CH3
Cl2
^v*
CH2
H3C CH
2CH
2CH
3
Cl2
CH3
CH2
CH2
CH2Cl
CH3
CH3
CH2
C CH3
CH3
Cl
CH3
CH CH CH3
CH3
Cl
ClCH2
CH2
CH CH3
CH3
^c*
CH2
H3C CH
2CH
2CH
3
Cl2
CH3CH
2CH
2CH
2 CH2Cl
CH3CH
2 CH2
CH CH3
Cl
CH3CH
2 CH2
CH CH3
Cl
^l*
3-12-3 mÙkj & (i) 2]4&MkbesfFky gsDlsu (ii) 2]2]4&VªkbesfFky gsDlsu
(iii) 3&,fFky&2] 2&MkbesfFky isUVsu (iv) 2]3]4&VªkbesfFky gsDlsu
(v) esfFky lkbDyksgsDlsu
(vi) 1&Dyksjks&2&esfFky lkbDyksC;wVsu
(vii) 1&czkseks&3&r`rh;d C;wfVy lkbDyksisUVsu
3-12-6 cks/k iz'uksa ds mÙkj
lajpuk rFkk vkac/ku-I
137
x 1 (i) l (ii) c (iii) v (iv) l (v) n
3-12-7-1 vH;kl iz'uksa ds mÙkj
1-
(i)
CH3
CH3
CH3
(ii)
OH
CH3
(iii)
Br
NH2
COOH
(iv)
CH2 CH
2OH
2. (i) o&VkWfyy (ii) 4&Dyksjks csafty
(iii) csatks (iv) 3&ukbVªkscsaty
3-13 dqN mi;ksxh iqLrdsa
11. Organic Chemistry, Volume 1, I.L. Finar, ELBS Longman, Chapters
3, 19 & 20.
12. Fundamentals of Organic Chemistry, T.W. Graham Solomons, John
Wiley & Sons, Inc. Chapters 3, 11&13.
13. Organic Chemistry, Volume I, S.M. Mukherji, S.P. Singh, R.P.
Kapoor, Wiley Eastern Limited, New Delhi, Chapters 5, 7, 8 & 9.
14. Organic Chemistry, Robert T.Morrison and Robert N.Boyd,
Prentice-Hall of India, Pvt. Ltd. New Delhi, Chapters, 3, 12, 13 &
14.
15. Advanced Organic Chemistry, B., S. Bahl and Arun Bahl, S. Chand
& Company Ltd. New Delhi, Chapters 9, 10 & 35.
16. Organic Chemistry, M.K. Jain, Shoban Lal Nagin Chand & Co.,
Delhi, Chapters, 5, 20 & 21.
;wfuV&4 % ,YdhUl] MkbbZUl ,oa ,YdkbUl
4-0 izLrkouk
dkcZu ,oa gkbMªkstu }kjk cus ;kSfxd ftuesa ,d ;k vf/kd f}vkcU/k vFkok
f=vkcUn mifLFkr gksa] vlar`Ir gkbMªksdkczu dgykrs gSaA
4-1
lajpuk rFkk vkac/ku-I
138
bl bdkbZ dk v/;;u djus ls vki fuEukuqlkj 'kh"kZdksa dh tkudkjh izkIr dj
ldsaxs &
,Ydhuksa dk ukedj.k
,Ydhsuksa ds cukus dh fof/k;k¡
,Ydhuksa dh jklk;fud vfHkfØ;k,¡
MkbbZuksa dk ukedj.k
MkbbZuksa ds izdkj
MkbbZuksa dh lajpuk
MkbbZuksa dh cukus dh fof/k;k¡
MkbbZuksa dh vfHkfØ;k,¡
,Ydkbuksa dk ukedj.k
,Ydkbuksa dh cukus dh fof/k;k¡
,Ydkbuksa dh vfHkfØ;k,¡
4-2 ,YdhUl ¼ifjp;½
,sls gkbMªksdkcZUl ftuesa nks dkcZu ijek.kqvksa ds chp esa de ls de ,d f}ca/k
C C vo’; ik;k tkrk gS] ,YdhUl dgrs gSaA budk lkekU; lw= CnH2n gksrk gSA ,YdhUl ;ksxkRed vfHkfØ;k,W izeq[krk ls nsrs gSaA
4-2-1 ,Ydhuks ds cukus dh fof/k;k¡
4-2-1-1 vYdksgkWy ds futZyhdj.k dh fØ;k fof/k
tc vYdkWgyksa dk futZyhdj.k fd;k tkrk gS rc ,YdhUl izkIr gksrs gSA mnk-
H C
H
H
H2O + H
2C = CH
2C H
H
OH
H2SO
4
lkUnz
170oC
bZFkhu
fØ;kfof/k & ,fFky vYdksgkWy dk futZyhdj.k rhu inksa esa gksrk gS &
igyk in & ,sfFky vYdksgkWy H2SO4 ls ,d izksVkWu H
ysdj izksVkWfur vYdksgkWy
esa cny tkrk gSA
H C
H
H
C O
H
H
H H
H C
H
H
C O
H
H
H
. .
. . . .
H
+
vkWDlksfu;e vkW;u @
izksVkfur vYdksgkWy
nwljk in & izksVkWfur vYdksgkWy Lor% gh ty ,oa dkcksZfu;e vkW;u esa cny tkrk gSA
lajpuk rFkk vkac/ku-I
139
H C
H
H
CO
H
H
HH . .
. .H C
H
H
C O
H
H
H
. .
H
+
ty dkcksZfu;e vkW;u
rhljk in & 4
H SO {kkjd dkcksZfu;e vkW;u ls izksVkWu ysdj mls ,Ydhu esa cny nsrk
gSA
H C
H
H
C
H
H
H2C = CH
2 + H
2SO
4
H SO4
dkcksZfu;e vkW;u ,sYdhu ¼bZFkhu½
4-2-2-2 ,fYdy gSykbMksa dk fogkbMªksgSykstuhdj.k
bl fof/k }kjk Hkh ,Ydhu cuk, tkrs gSa &
3 2 2 2 2
CH CH Cl KOH H C CH KCl H O
,sfFky DyksjkbM vYdksgkWfyd ,Fkhu
dkWfLVd
iksVk’k
4-2-3 vYgksgkWyksa ds futZyhdj.k esa {ks= dh oj.kkRedrk (Regioselectivity)
tc vYdksgkWyksa ds futZyhdj.k ls ,Ydhu curs gS rc vYdksgkWy dk ¼chVk½
H&ijek.kq iFkd gksrk gSA tc ,d ls vf/kd H ijek.kq gksa rc ml dkcZu ls H
ijek.kq iFkd gksrk gS ftl ij gkbMªkstu ijek.kqvksa dh la[;k lcls de gksrh gSA bls
fuEu mnk- }kjk le>k tk ldrk gS &
H2SO
4
OH
CH3
CH2
CH3
CHH
2O
CH3
CH CH3
CH
CH3
CH2 CH
2CH
2&C;wVhu
¼eq[; mRikn½
1&C;wVhu
¼de ek=k½15%
85%
uksV & bl vfHkfØ;k esa ,sfYdy gSykbM ds nks fudVorhZ dkcZu ijek.kq vius
gkbMªkstu ,oa gSykstu ijek.kq [kksrs gS] vr% bls fMgkbMªksgSykstuhdj.k vfHkfØ;k
dgrs gSaA
lajpuk rFkk vkac/ku-I
140
4-2-4 lsVts+Q fu;e
ß,sfYdy gSykbMksa ds fogkbMªksgSykstuhdj.k esa mls dkcZu ijek.kq ls H&ijek.kq
foyqIr gksrk gS ftlds lkFk la;qDr H&ijek.kqvksa dh la[;k de gksrh gSAÞ mnk-
CH3
CH2 CH
3CH
Br
KOHCH
3CH CH
3CH CH3
CH2
CH2
CH
,YdksgkWyh;
+
2&C;wVhu (80%) 1&C;wVhu (20%)
4-2-5 gkWQesu foyksiu (Hofmann elimination)
prq"d veksfu;e gSykbM dks flYoj gkbMªkWDlkbM ds lkFk vfHkd`r djus ij ,d
gSykstu Lo=ra prq"d veksfu;e gkbMªkDlkbl dk Bksl fØ;kQy o flYoj gSykbM
vo{ksfir gks tkrk gSA
3 3
R R' N X AgOH R R' N OH AgX
prq"d veksfu;e prq"d veksfu;e
gSykbM gkbMªkDlkbM
prq"d veksfu;e gkbMªkWDlkbM dks rhozrk ls xje djus ij Øe’k% r`rh; ,sehu]
ikuh ,oa vYdhu izkIr gksrk gS rFkk vYdhu dh lajpuk R ij vk/kkfjr gksrh gSA
+
3 2 2 2 3 3 3 2 2 23 3HCH CH CH CH N CH O CH N CH CH CH CH H O
VªkbesfFky n C;wfVy veksfu;e r`rh;d 1&C;wVhu gkbMªkDlkbM ,sehu
4-3 vYdhUl ds jklk;fud xq.k
vYdhUl vlar`Ir gkbMªksdkcZu gksrs gSa] vr% ;s ß;ksxkRed&vfHkfØ;k,¡Þ izeq[krk ls
nsrs gSaA tSls&
4-3-1 gkbMªkstuhdj.k
vYdhUl ij gkbMªkstu dk ;ksx gkbMªkstuhdj.k dgykrk gSA bl fØ;k ds
QyLo:i vYdhUl ,YdsUl esa cny tkrs gSaA bls lckrs ,oa lsaMjsal vip;u Hkh dgrs gSaA
mnk-&
H2C CH
2
NiCH
3CH
3 + H2
200 - 300oC bZFkhu bZFksu
lajpuk rFkk vkac/ku-I
141
4-3-2 bysDVªkWuLusgh ,oa eqDr ewyd vfHkfØ;k,¡
¼v½ bysDVªkWu Lusgh vfHkfØ;k & CC
esa ,d ca/k gksrk gS] ftlds
bysDVªkWUl vkil esa f’kfFkyrk ls ca/ks jgrs gSaA vr% ca/k ,d bysDVªkWu lzksr dk dk;Z
djrk gS vkSj bl ij /kukRed vkW;u ;k bysDVªkWu U;wu vfHkdeZdksa dk rqjUr ;ksx gks tkrk
gSA mnk-
CH
2
CH2
Br
Br
CH3
CH3 Br
Br+
fØ;kfof/k & izFke in &
Br Br
CH2
CH2 Br Br
f}rh; in &
Br BrC
CBr Br
C
C
+
&ladqy
ladqy esa dk fpUg f’kfFky ca/k dks n’kkZrk gSA
r`rh; in &
Br BrC
CCC
Br
Br+
czkseksfu;e vkW;u
prqFkZ in &
CC
Br
Br CC
Br
Br
+
¼c½ eqDr ewyd vfHkfØ;k,¡ &
igyk in &
Br Br Br
.lw;Z dk izdk'k
2 czksehu eqDr ewyd
lajpuk rFkk vkac/ku-I
142
nwljk in &
CCBr.
Br C C.
+
eqDr czkseks vYdhu ewyd
rhljk in &
Br C C.
Br2 Br C C Br Br
.+ +
4-3-3 ekdksZfudkWQ fu;e
vlefer vYdhuksa esa tqM+us okys v.kq dk _.kkRed Hkkx ml dkcZu ijek.kq ls
tqMrk gS] ftl ij gkbMªkstu ijek.kqvksa dh la[;k lcls de gksrh gSA
CH2
CHCH3 H Cl
CHCH CH3
Cl
CH2H
3C CH
2Cl
+
n&izkikby DyksjkbM
¼lg&mRikn½
vkblksizksfiy DyksjkbM
¼eq[;&mRikn½
izksihu
¼,d vlefer vYdhu½
43-4 gkbMªkscksjhdj.k&vkWDlhdj.k
og vfHkfØ;k ftlesa Mkbcksjsu (B2H6) ,Ydhuksa ls ;ksx djds Vªkb,fYdy cksjsu cukrs gSa]
gkbMªkscksjhdj.k dgykrh gSA tc budk vkWDlhdj.k fd;k tkrk gS rc vYdksgy izkIr
gksrs gSaA tSls &
CH2H
3C BH
2
CH2
CH2
CH2
BH
CH3
CH2
H3CCH
2CH
2
CH2
CH3
B
CH2
CH3
CH2
H3C
H2O
2
CH3
OHCH2 H
3 BO
3
CH2
H2C
1
2BH
3B
2H
6
+
3
3 +
vkWDlhdj.k
Vªkb,fFky cksjsu
,sfFky vYdksgkWy cksfjd&vEy
+ ;k
lajpuk rFkk vkac/ku-I
143
4-3-5 vkWDlheD;Zwjhdj.k&vip;u
ß,sYdhu ty dh mifLFkfr esa eD;wZfjd ,slhVsV ls fØ;k djus ij gkbMªkWDlh
eD;wZfjy ;kSfxd cukrs gSa] tks (NaBH4 }kjk) vip;u ij ,sYdksgkWy nsrs gSaA bl lEiw.kZ
vfHkfØ;k dks vkWDlheD;wZjhdj.k&vip;u dgrs gSaAÞ
fØ;k-fof/k& ¼1½ izFke in esa dkcZu&dkcZu f}cU/k C C ij –OH rFkk
3HgO CO CH dk ;ksx gksrk gSA bl in dks vkWDlheD;wZjhdj.k
(Oxymercuration) dgrs gSaA
mnkgj.k &
OH2
Hg (OOCCH3)2CC
OH
C
HgOCOCH3
C CH3COOH++ +
dkcZu edZjh ;kSfxd
¼2½ vxys in esa 3
Hg O CO CH gkbMªkstu ls izfrLFkkfir gks tkrk gSA vr%
;g ,d izdkj ls ty;kstu vfHkfØ;k gS] fdUrq izFke ty;kstu dh rqyuk esa vf/kd
mi;ksx esa vkrh gSA bls foeD;wZjhdj.k (Demercuration) Hkh dgrs gSaA
mnkgj.k &
OH
C
HgOCOCH3
CNaBH
4
OH
C
H
C
,sYdksgkWy
uksV& ¼1½ bl vfHkfØ;k esa dkcZeD;wZjh ;kSfxd (Organo-mercurical
compound) i`Fkd ugha fd;k tkrk gS] cfYd lksfM;e cksjksgkbMªkbM }kjk vfHkfØ;k LFky ij gh vipf;r fd;k tkrk gSA
¼2½ bl vfHkfØ;k esa ty;kstu dh fØ;k ekdksZuhdkWQ ds fu;ekuqlkj gksrh gSA
mnkgj.k &
CH2
CH2
CH2 CH CH
2CH
3
Hg (OAc)2 . H
2O
CH2
CH2
CH2 CH CH
3CH
3
OH
(i)
(ii) NaBH4
gsDlsu 2&vkWy
vkWDlheD;wZjhdj.k dh fØ;k esa Hg vk;u dkcZu&dkcZu f}cU/k ij bysDVªksfQfyd
(Electrophilic) ;ksx djrk gS vkSj eD;wZjhfu;e vk;u (Mercurinium ion) curk gSA bl ij U;wfDy;ksfQfyd foyk;d ty fØ;k gksrh gS vkSj ;ksxkRed mRikn curk gSaA
C C
Hg
2+
lajpuk rFkk vkac/ku-I
144
eD;wZjhfu;e vk;u
4-3-6 ,ikWDlhdj.k tc vYdhUl dh fØ;k vkWDlhtu ls dh tkrh gS rc f}ca/k ij ,d vkWDlhtu
ijek.kq tqM+ tkrk gS vkSj pØh; vkWDlkbl ¼,ikWDlkbM½ curs gSaA
O2
H2C
H2C
OCH
2
CH2
+1
2
,fFkyhu ,sfFkyhu vkWDlkbM
¼,ikWDlkbM½
4-3-7 KMnO4 ds lkFk vkWDlhdj.k
¼v½ B.Ms KMnO4 foy;u ¼ckW;j vfHkdeZd½ }kjk & tc 1% B.Ms tyh; {kkjh;
KMnO4 foy;u ¼ckW;j vfHkdeZd½ dh fØ;k vYdhUl ls gksrh gS rc f}ca/k dk
gkbMªkbDlhyhdj.k gks tkrk gSaA vYdhUl Xyk;dkWYl esa cny tkrs gSa ,oa ckW;j vfHkdeZd
dk cSaxuh jax mM+ tkrk gSaA bl vfHkfØ;k dk mi;ksx vlar`Iirk dh ifgpku djus esa
gksrk gSA
KMnO
4
CH2
CH2
CH2
CH2 OH
OH+ [ 0 ] + H2O
{kkjh;
,sfFkyhu ,fFkyhu Xyk;dkWy
¼c½ vEyh; KMnO4 foy;u }kjk & blds lkFk ifgys Xyk;dkWy curk gS tks ckn esa
vEy ;k dhVksu cukrk gSA
CH2 OH
CH2 OH
CH2
CH2 HCOOH + HCOOH + H
2O
[ 0 ]
H2O
3 [ 0 ]
Xyk;dkWy QkfeZd vEy
4-3-8 vYdhUl dk cgqyhdj.k
cgqyhdj.k (Polymerisation) & ßog fØ;k ftlesa fdlh mRiszjd dh mifLFkrh esa
,d gh inkFkZ ds nks ;k nks ls vf/kd v.kq vkil esa tqM+dj ,d mPp v.kqHkkj okyk
;ksxkRed v.kq djrs gSa rks bl vfHkfØ;k dks cgqyhdj.k dgrs gSA u, cus ;kSfxd dks
cgqyd (polymer) dgk tkrk gSAÞ
,sYdhu Hkh cgqyhdj.k }kjk vkil esa tqM+dj cgqr gh egRoiw.kZ cgqyd cukrs gSaA
tSls &
(i) Polythene ¼ikWyhFkhu½ & tc bFkkbyhu dks mPp rki ij AlCl3 mRizsjd dh
mifLFkrh esa xje fd;k tkrk gS rc blds vusd v.kq ¼70 ls 700rd½ vkil esa la;ksx
djds ,d yach Ja[kyk okyk Bksl ;kSfxd cukrs gSa ftls ‘Polyethylene’ ;k
‘Polythene’ dgrs gSaA
CH
2n CH
2
Al Cl3 CH
2CH
2mPp rki
)( n
Ethylene Polythene
lajpuk rFkk vkac/ku-I
145
tgkW n = 70 – 700
ikWyhFkhu ,d ikjn’kZd] etcwr ,oa Bksl IykfLVd gSA bldk mi;ksx f[kykSus]
estiks’k] fo|qrjks/kh rkj (insulators), pknjsa (sheets) vkfn cukus es fd;k tkrk gSA
(ii) Polypropylene ¼ikWyhizksikbyhu½ & tc izksikbyhu dks mRiszjd dh vifLFkrh esa
xeZ fd;k tkrk gS rc ikWyhizksihyhu izkIr gksrk gSA
CH3
CH CH2
n CH3
CH2
CHmPp rkin
mRizsjd
izksfiyhu ikWyhizksfiyhu
;g ,d dBksj Bksl gS ftldk eq[; mi;ksx jLlh ,oa /kkxs cukus esa fd;k tkrk gSA
(iii) ikWyhfoukby DyksjkbM (PVC) & ;g vR;ar mi;ksxh cgqyd gS tks foukby
DyksjkbM ds cgqyhdj.k ls izkIr gksrk gSA
ClCH Cln CH
2
CH2
CH
rkin
mRizsjd
Vinyl Chloride P.V.C.
bldk mi;ksx cjlkrh Nkrs] gkFk ds nLrkus] f[kykSus rFkk Q’kZ ij fcNkus okyh pknjksa
vkfn eas gksrk gSA
4-3-9 vYdhUl esa ,ykbfyd fLFkfr ij izfrLFkkiu ;k ,sfyfyd izfrLFkkiu (Allylic Substitution)
¼1½ lk/kkj.kr;k ,sYdhu esa izfrLFkkiu ugha gksrkA
¼2½ f}cU/k (Double bond) ls layXu dkcZu ijek.kq ij mifLFkr ,sYdhu lewg
,sfyfyd lewg dgykrk gSa
¼3½ mPp rki 400&6000C ij gSykstu ¼Dyksjhu/czksehu½ dh vfHkfØ;k djkus ij
f}cU/k ij ;ksxkRed mRikn u cudj ,sfYdy lewg dk gkbMªkstu] gSykstu
}kjk izfrLFkkfir gks tkrk gS] mls ,sfyfyd gSykstuhdj.k ¼izfrLFkkiu½ dgrs
gSaaA
tSls &
H
C
H
R CH CH2
2 2CH CH CH
,sfyfyd lewg
,sYdhu
mnkgj.k&
2 3 2 2 2
400 600CH CH CH Cl CH CH CH Cl HCloC
2 3 2 2 2
400 600 BrCH CH CH Br CH CH CH HBroC
lajpuk rFkk vkac/ku-I
146
eqDr eqyd ,sfyfyd izfrLFkkiu (Free Radical Allylic Substitution)
mPprj ,sYdhu esa dkcZu&dkcZu f}vkcU/k esa ,sfYdy lewg tqM+k jgrk gSA
,sfYdy ewyd] ,sYdsu dk vo’ks"k gksrk gS] blfy, bles a ,sYdsu ds dqN xq.k] tSls&eqDr
ewyd izfrLFkkiu (Free radical substitution) vkfn ik;s tkrs gSaaA
vr% mPprj ,sYdhu esa fdlh vfHkdeZd dh fØ;k nks LFkkuksa ij gks ldrk gSA
f}cU/k (Double bond) ij ;k ,sfYdy ewyd ijA
vfHkfØ;k fdl LFkku ij gksxh] ;g iz;ksx dh voLFkk ij fuHkZj djrk gSA
mnkgj.k & izksihu dh Dyksjhu ds lkFk fØ;k&
(a) lkekU; voLFkk esa ;ksxkRed fØ;k gksrh gSA
CH
2ClCH
3CHClCH
2CHCH
3 + Cl2
lkekU;
;ksx izksihu izksfiyhu MkbDyksjkbM
(b) tc vfHkfØ;k mPp rki 5000C ij gksrh gS] rc esfFku lewg dk ,d gkbMªkstu
ijek.kq Dyksjhu ijek.kq ls izfrLFkkfir gks tkrk gS vkSj Vªkb Dyksjks izksihu ;k ,sfyy
DyksjkbM curk gSA
H
C
H
H CH CH2
CHCH2
Cl CH2+ Cl2
500oC
izfrLFkkiu+ HCl
izksihu ,sfyy DyksjkbM
Vinylic
Hydrogen
,sfyfyd gkbMªkstu
(Allylic Hydrogen)
;qXe cU/k (Double bond) ds fudV &dkcZu dks ,sfyfyd dkcZu dgrs gSaA p¡wfd
bl izfrLFkkiu esa izfrLFkkiu fØ;k ,sfyfyd dkcZu ij gksrh gS blfy, bls ,sfyfyd
izfrLFkkiu dgrs gSA bl fØ;k esa ,sfyfyd dkcZu ls tqM+k gkbMªkstu Dyksjhu ls
izfrLFkkfir gks tkrk gSA
fØ;k&fof/k (Mechanism) & mi;qZDr fØ;k eqDr ewyd }kjk lEiUu gksrh gSA
a. Cl Cl Cl.
2h
Dyksjhu v.kq eqDr Dyksjhu ewyd
b. CHCH2HCl
.
CH2
CH CH2
.
+ HCl + CH2
izksfiyhu
c. CH2
.
CHClCH2
CH2
CH CH2
.
+ Cl2+ Cl
,sfyy DyksjkbM
blh izdkj vkxs Hkh fØ;k gksrh jgrh gS tc rd fd bldk lekiu ugha gks tkrk gSA
eqDr ewyd ds cuus dh lqxerk dk Øe fuEu gksrk gS &
lajpuk rFkk vkac/ku-I
147
Allyl > 3o > 2
o > 1
o > CH
3o > Vinyl
4-3-10 bFkhyhu rFkk izksihu ds vkS|ksfxd vuqiz;ksx (Industrial Applications of Ethylene and Propene)
bFkhyhu (i) vkWDlh bFkhyhu Tokyk /kkrqvksa dks tksM+us (welding) o dkVus ds dke esa ykbZ
tkrh gSaA
(ii) ,fFky ,YdksgkWy rFkk ,fFky czksekbM ds cukus esa
CH
2
H2SO
4 CH3
CH3CH
2CH
2HSO
4
OH2
CH2
OH
(iii) dPps Qyksa dks idkus rFkk laj{kd (Preservation) esaA
(iv) csgks’kh ykus ds fy, (Anaesthetic)A
(v) eLVMZ xSl (Mustard gas) tSlh fo"kSyh xSl cukus esaA
CH2
CH2
S2Cl
2S
ClCH2
CH2
ClCH2
CH2
S+ +2
(vi) Ñf=e [kkn] ikWfyFkhu IykfLVd vkfn cukus esaA
(vii) XykbdkWy] Mkb&vkDlsu] lSykslksYo vkfn cukus esaA
izksihu
(i) izksihu ,sYdksgkWy cukus esaA
(ii) ikWyhizksihfyu cukus esaA ftxyj mRizsjd (Ziegler catalyst AlCl3–TiCl4) dh mifLFkfr esa izksihu ds cgqyhdj.k ls ikWyhizksihyhu izkIr gksrk gSA
nCH3
CH CH2
CH2
CH
CH3
izksihu
ikWyhizksihyhu
n
4-4 MkbbZUl (Dienes)
,Sls dkcZfud ;kSfxd ftuesa dkcZu ijek.kqvksa ds e/; nks f}ca/k ik, tkrs gSa
MkbbZUl dgykrs gSaA tSls &
CH
2CH CH CH
2 CH
3CH CH CH CH
2
1]3&C;wVkMkbbZu 1]3&isUVkMkbbZu
4-4-1 MkbbZUl dk ukedj.k & fu;e&1
nks ca/kks ;qDr lokZf/kd yEch dkcZu ijek.kqvksa dh Ja[yk dk p;u & mnkgj.kkFkZ &
CH3
CH2
CH CH CH CH2
CH2
CH3
CH
CH2
lajpuk rFkk vkac/ku-I
148
mi;qZDr mnkgj.k esa dkcZu ijek.kq dh rhu Ja[yk,¡ laHko gSA lokZf/kd yach Ja[yk 8
dkcZu ijek.kqvksa dh gS ysfdu blesa flQZ 1 f}ca/k mifLFkr gSA nwljh 6 dkcZu ijek.kqvksa
dh Ja[yk 1 f}ca/k okyh gSA rhljh 7 dkcZu ijek.kqvksa okyh Ja[yk ¼?ksjs ls fn[kkbZ xbZ½
esa nks f}ca/k mifLFkr gSa vr% blh dk p;u fd;k tkosxkA
fu;e & 2 % dkcZu ijek.kqvksa dh Ja[yk dk vadu &
mnkgj.k &
CH
3CH
2CH CH CH CH CH
2
1234567
mi;qDZr mnkgj.k esa f}ca/k nk,¡ rjQ ifgys iM+ jgk gS vr% vadu nk,¡ ls ckbZ rjQ fd;k
tkosxkA
fu;e&3 % izfrLFkkidksa dk mPpkj.k& ckdh izfrLFkkidksa dk mPpkj.k vaxzsth o.kZekyk ds
ojh;rk Øe esa fn;k tkrk gSA mnkgj.kkFkZ &
CH3
CH2
CH CH CH CH CH23
456
7
CH2
1
CH
CH3Cl
89
Br
4&czkseks&7&Dyksjks&3&esfFky&uksuk 1]6&MkbbZu
4-5 oxhZdj.k & MkbbZUl rhu izdkj ds gksrs gSaA
¼v½ foyfxr & tc fdlh MkbbZu esa nks f}ca?k u rks ,dkarj fLFkrh esa gksrs gS vkSj u gh
ikl&ikl fLFkr gksrs gSa rc bUgsa foyfxr MkbbZUl dgrs gSaA buesa ,ydhUl tSls xq.k
ik, tkrs gSaA mnkgj.kkFkZ &
CH
2CH CH CH
2CH
2CH CH
2
1234567
CH3
8
vkWDVk&1] 4&MkbbZu
¼c½ D;weqysVsM (Cummulated) & tc nksuksa ca/k ikl&ikl dkcZu ijek.kqvksa ij fLFkr
jgrs gSaA
mnk- &
CH
2
1 2 3
CH2
C
izksik&1] 2&MkbbZu
¼l½ la;qfXer (Conjugated) & tc nks f}ca/k ,d ,dy ca/k }kjk iFkd jgrs gSaA
mnk-
4
CH2
1 2 3
CH2
CHCH
C;wVk&1] 3&MkbbZu
4-5-1 ,yhUl dh lajpuk
,syhu 2 2H C C CH ds nks vafre dkcZu ijek.kq sp
2 ladfjr rFkk
dsUnzh; ijek.kq sp ladfjr gksrk gSA dsUnzh; dkcZu ijek.kq vius lehiorhZ dkcZu
ijek.kqvksa ls ik’oZ js[kh; (Colinear) nks ca/kksa rFkk nks ca/kksa ls layXu jgrk gSA
nksuksa &vkca/k ,d nwljs ls ry ds ledks.k ij fLFkr gksrs gSaA blesa y&vkca/k dkxt
lajpuk rFkk vkac/ku-I
149
ds ry ij rFkk x&vkca/k dkxt ds ry ij yEcor~ fLFkr gksrs gSaA f=dks.kh; voLFkk esa
z cU/k vkca/k ds ry ds ledks.k ij fLFkr gksrk gS] f=dks.kh; dkcZu esa layXu fljksa
ds lewg ,d nwljs ls ry ds yEcor~ fLFkr gksrs gSaA bl izdkj v.kq esa ;fn fljksa ds
dkcZu ij layXu nksuksa lewg vyx gksa rks v.kq esa rc v.kq vius vki esa vlefer gks tkrk
g S vkSj izdkf’kd leko;ork n’kkZrk gSA
4-5-2 C;wVkMkbbZu dh lajpuk
1- C;wVkMkb&bZu esa sp2 ladj.k gksrk gSA blfy, blds izR;sd dkcZu ij rhu sp
2
ladfjr d{kd gksrs gSa] tks ,d gh ry esa gksrs gSaA tSls ,fFkyhu esa gksrk gS vkSj ,d
vladfjr (Unhybridised) Pz d{kd gksrk gSA
2- izR;sd dkcZu ds rhu sp2
d{kd rhu ¼flXek½ cU/k cukrs gSaA nks vU; dkcZu
ijek.kqvksa ds lkFk vkSj ,d gkbMªkstu ijek.kq ds lkFk
C CHCH C
HH
HH
vc izR;sd dkcZu ij ,d vladfjr pz d{kd 'ks"k jg tkrk gSA tSlk fd uhps fn[kk;k
x;k gS &
CH CH CH2
CH2
1 2 3 4
CH CH CH2
CH2
1 2 3 4
, ,
(a) (b)
Electrons delocalised
CH CH CH2
CH2 CH CH CH
2CH
2,
(c) (d) C;wVkMkbbZu dk d{kd izfr:i
3- dkcZu ijek.kq 2 dk pz d{kd dkcZu ijek.kq 1 ;k 3 ds pz d{kd dk leku :i ls
ik’oZorhZ (Side-wise) vfrO;kiu (overlaping) dj ldrk gS ¼b o c½ A
blh izdkj rhljs dkcZu dk pz d{kd nwljs vkSj pkSFks dkcZu ds pz d{kd dk
vfrO;kiu dj ldrk gSA
QyLo:i lHkh pz d{kdksa ls feydj ,d cM+k lk vkf.od d{kd (molecular
orbital) cu tkrk gS] tks pkjksa dkcZu ijek.kqvksa ij Nk;k jgrk gSA
4- ,sls vkf.od d{kd esa fdUgha Hkh nks ijek.kqvksa ¼1]2 ;k 1]4½ ij ;ksx gks ldrk gSA
blds vfrfjDr ,sls vkf.od d{k esa pkjksa bysDVªku vLFkkfur (Delocalised) jgrs
gSA vFkkZr~ bl d{kd esa C;wVkMkbbZu ds pkjksa bysDVªku ifjHkze.k djrs gSaA
5- vLFkkuhdj.k ds QyLo:i bysDVªkuksa ds ifjHkze.k dk {ks= c<+ tkrk gS] ftlds
dkj.k C;wVkMkbbZu dk LFkkf;Ro c<+ tkrk gSA bl vLFkkfur bysDVªkWu vkf.od
lajpuk rFkk vkac/ku-I
150
d{kd ds fdUgh Hkh nks dkcZu ijek.kqvksa ij ;ksx gks ldrk gSA QyLo:i 1]2 rFkk
1]4 ;ksxkRed mRikn nksuksa curs gSaA
lajpuk rFkk vkac/ku-I
151
4-5-2-1 cukus dh fof/k;k¡ (Methods of preparatoion)
1- C;wVsu dks Øksfe;e VªkbvkWDlkbM ls xqtkjus ij]
CH
2CH
2CH
3CH
3
Cr2O
3CH CH CH
2CH
2
n&C;wVsu 1]3 C;wVkMkbbZu
2- MkbZvkWy ds futZyhdj.k ls 1]4 C;wVsu Mk;ksy dks ,slhfVyhu ls cukdj mls xeZ
djds izkIr djrs gSaA
CHCH CH
2OHHCHO CCHOCH
2+ 2mRizsjd
C;wV&2 vkbu] 1]4 MkbvkWy
CH2
CHCHCH2
CH2OHCH
2CH
2HOCH2
Ni
mRizsjd
vEyh;
2H2
C;wVsu] 1]4 MkbvkWy 1]3 C;wVkMkbbZu
3- C;wVsu 1]3 MkbvkWy ds futZyhdj.k ls Hkh 1]3 C;wVkMkbbZu curk gSA
CH2
CHCHCH2CH
2CH
2CHCH
3
OH OH
2H2O
1]3 C;wVkMkbbZu
C;wVsu] 1]3 MkbvkWy
4-5-2-2 cgqyhdj.k
MkbbZUl esa cgqyhdj.k vfHkfØ;k,¡ Hkh ns[kus dks feyrh gSaA buesa eq[;r;k izdk’k
foydhdj.k (photodimerisation) fØ;k,¡ ns[kus esa feyrh gSaA mnkgj.kkFkZ &
CH
CH
CH2
CH2
+h
VªkWl] 1]3&C;wVkMkbbZu lkbDyksC;wVhu ckblkbDyks&
$ C;wVsu
CHCH
CH2CH
2
fll&1] 3&C;wVkMkbbZu
4-5-2-3 1]2 ,oa 1]4 ;ksx
¼1½ bysDVªksfQfyd ;ksx (Electrophilic addition) & ,d la;qfXer ;kSfxd 1]3
C;wVkMkbbZu] gSykstuksaa] HBr, H2 vkfn ds lkFk ;ksx fØ;k,¡ nsrk gSA ;|fi blesa nks
f}cU/k gksrs gSa fQj Hkh dsoy ,d gh v.kq dk ;ksx gksrk gS rFkk 1%2 ;k 1%4 mRikn izkIr
gksrk gSA blfy, bls 1%2 ;ksx rFkk 1%4 ;ksx dgrs gSaA
;ksx lkekU;r% 1]2 ij gksrk gS ,oa 1%4 ij Hkh vlkekU; :i esa gksrk gSA bu
nksuksa mRiknksa dh vkisf{kd ek=k,¡ vfHkdeZd dh izd`fr] foyk;d dh izd`fr vkSj rki ij
fuHkZj djrh gSA
mnkgj.k & C;wVkMkbu ij czksehu dh fØ;k &
lajpuk rFkk vkac/ku-I
152
(i) fuEu rki (–80oC) ij 1] 2 mRikn dh ek=k vf/kd gksrh gS tcfd
(ii) mPp rki (40oC) ij 1] 4 mRikn dh ek=k vf/kd gksrh gSA
uksV & 1]2 ;ksx fdlh Hkh ,sYdhu ds f}vkcU/k ds lkekU; xq.k ds dkj.k fdUrq 1]4 ;ksx
vlkekU; :i ls gksrk gSA
CH2
CHCHCH2
CH2
CHCHH2C
Br2
Br Br
CH2
CHCHH2C
Br Br
Br2
3]4 Mkbczkseks&1 C;wVhu
¼1]2 ;ksx½
80oC
1]4 Mkbczkseks&2 C;wVhu
¼1]4 ;ksx½
1]3 C;wVkMkbbZu
80oC
uksV&lk/kkj.kr;k 1]2 rFkk 1]4 mRikn dk feJ.k izkIr gksrk gSA
vU; mnkgj.k &
(i) CH
2CHCHCH
2 CH2
CHCHBrCH3+ HBr
1] 2 ;ksx
$
CH
2BrCHCH
3CH
1] 4 ;ksx
(ii) CH
2CHCHCH
2CH
2CH
2CH
3CH+ H2
1] 2 ;ksx
$
CH
3CHCH
3CH
1] 4 ;ksx
4-5-2-4 bysDVªksfQfyd ;ksx dh fØ;k&fof/k
tc vfHkdeZd ¼tSls&Br2½ C;wVkMkbbZu ds fudV igq¡prk gS rc C;wVkMkbbZu esa
bysDVªksesfjd ifjorZu gksrk gSA rc bysDVªksfQfyd (Br+) C1 ;k C2 ls tqM+dj
dkcksZdsVk;u A ;k B cukrs gSaA
CH
2CHCHCH
2CHCH
2CH
CH2Br+ Br
Br2
A LFkk;h
;k ;k
CH
2CHCHCH
2 CH2
CHCH2
CH
Br
+ Br
B vLFkk;h
A ,d f}rh;d dkcksZdsVk;u vkSj B izkFkfed dkcksZdsVk;u gSA pw¡fd A
f}rh;d dkcksZdsVk;u gksus ds dkj.k B ¼izkFkfed dkcksZdsVk;u½ dh vis{kk vf/kd LFkk;h gS]
blfy, vis{kkdr ljyrk ls vkSj izkFkfedrk ls curk gSA
lajpuk rFkk vkac/ku-I
153
A vuqukn ds }kjk Hkh LFkkf;Ro izkIr dj ysrk gS] blfy, izFke in esa dsoy A
dkcskZdsVk;u curk gSA vxys in esa dkcksZdsVk;u A vius fdlh Hkh :i (i) ;k (ii) }kjk
Br ls la;ksx djrk gS vkSj 1]2 rFkk 1]4 ;ksxkRed mRikn curk gSA
mi;qZDr lEiw.kZ vfHkfØ;k fuEu izdkj ls iznf’kZr dh tk ldrh gS &
CH2
CHCHCH2 CH
2BrCHCHCH
2
CH2BrCHCHCH
2
1]3 C;wVkMkbbZu
+ Br2
(ii)
(i);k
CHBrCHCH
2CH
2Br CH
2Br CHCH CH
2Br+
Br2
3] 4 Mkbczkseks&1 C;wVhu 1]4 Mkbczkseks&2 C;wVhu
¼1]2 ;ksx½ ¼1]4 ;ksx½
vU; mnkgj.k & blh izdkj tc C;wVkMkbbZu ij HBr dk ;ksx gksrk gS] rc 1] 2 rFkk
1] 4 ;ksxkRed mRikn curs gSa] ftudh vkisf{kd ek=k,¡ rki ij fuHkZj djrh gSA
CH2
CHCHCH2
CH2
CHCHCH2
H Br
CH2
CHCHCH2
H Br
CH2
CHCHCH2
H Br
CH2
CHCHCH2
H Br
80% ¼1]2 ;ksx½
80oC
+
+
40oC
20% ¼1]4 ;ksx½
20% ¼1]2 ;ksx½
20% ¼1]2 ;ksx½ 80% ¼1]4 ;ksx½
HBr
4-5-2-5 eqDr ewyd ;ksx (Free radical addition)
MkbbZu (Diene) esa ;ksx fØ;k eqDr ewyd ls Hkh gksrh gSA
mnkgj.k&1]3 C;wVkMkbbZu esa Dyksjhu dk ;ksx izdk’k ;k ijkWDlkbM dh mifLFkfr esa 1]2
,oa 1]4 ;ksxkRed mRikn nsrk gSA ;g ek/;fed ,sfyfyd eqDr ewyd ds ek/;e ls gksrk
gSA
(i) J`a[kyk dk izkjaHk (Chain initiation) & eqDr ewyd dk cuuk
Cl Cl Clhv .
2
(ii) Ja[kyk dk lapj.k (Chain propagation) & ,sfyfyd eqDr ewyd dk cuuk ,oa
vuquknh LFkkf;Ro izkIr djuk &
lajpuk rFkk vkac/ku-I
154
CHCHCH2
Cl.
CH2
CHCHCH2
CH2
.Cl
CHCHCH2
CH2
.Cl
+
...(ii)
...(i)
(iii) izR;sd (i) ,oa (ii) dk DYkksjhu ls fØ;k djds Øe’k% 1] 2 ,oa 1] 4 mRikn nsrs gSaA
CHCHCH
2Cl
.
CH2
CHCHCH2
CH2
.ClCl Cl
Cl2
+
CHCHCH
2Cl
2
.
CH2
CHCHCH2
CH2
.ClCl Cl
Cl+ +
vU; mnkgj.k & tc 1]3 C;wVkMkbbZu ij fdlh ijkWvkDlkbM dh mifLFkfr esa
czkseksVªkbDyksjks esFksu dh fØ;k gksrh gS] rc C;wVkMkbbZu ij Br.CCl3 dk ;ksx gks tkrk
gSA pwfd vfHkfØ;k ijkDlkbM dh mifLFkfr esa gksrh gS blfy, ;g vfHkfØ;k eqDr ewyd
}kjk gksrh gSA bl vfHkfØ;k esa Hkh 1]2 rFkk 1]4 ;ksxkRed mRikn nksuksa curs gSaA
CHCHCH2
Br
CCl3
CH2
Br CHCHCH2
CH2
CCl3
Br
CHCHCH2
CH2
CCl3
+
1]2 ;ksxkRed mRikn
1]4 ;ksxkRed mRikn
+
ijkWDlkbM
vfHkfØ;k dh fØ;k fof/k
(i) C6H
5CO COC
6H
5C
6H
5CO
Sun light
Homolytic Fission2
.
csatk;y ijkWDlkbM csatks;y eqDr ewyd
(ii) C6H
5CO BrCCl
3C
6H
5 COBr + CCl
3+
. .
(iii) CHCHCH2
CCl3
CH2
CCl3
CHCH2
CH CH2
. .
CCl3
CHCH2
CH CH2
CCl3 + CCl
3 CHCH2
CH CH2
CCl3 CH
2BrCH
2 CH CH
.
Br
+
1]2 ;ksxkRed mRikn
1]4 ;ksxkRed mRikn
(A)
(B)
Br.CCl3
+Br.CCl3
lajpuk rFkk vkac/ku-I
155
in (iii) esa cuk gqvk eqDr ewyd A rFkk B nks :iksa dk vuquknh ladj
(Resonance Hybrid) gksrk gSA blfy, vkxs dh fØ;k blds fdlh Hkh :i ds }kjk
gksrh gS vkSj 1]2 rFkk 1]4 ;ksxkRed mRiknksa dk feJ.k curk gSA
4-6 MhYl vYMj vfHkfØ;k (Diel’s Alder Reaction)
tc la;qfXer MkbbZu dks fdlh ,sYdhu ;k izfrLFkkfir ,sYdhu ds lkFk xeZ fd;k
tkrk gS rFkk N% lnL;h; pØh; ;kSfxd curk gSA bl vfHkfØ;k dks MhYl&,sYMj
vfHkfØ;k dgrs gSaA
;g ,d egRoiw.kZ vfHkfØ;k gS] ftldk mi;ksx pØh; ;kSfxd ds la’ys"k.k esa
fd;k tkrk gSA
mnkgj.k &
CH
CH
CH2
CH2
CH2
CH2 CH
2
CH2
CH2
CH2
HC
HC+
200oC
,fFkyhu
C;wVkMkbbZu lk;Dyks gsDlhu
CH
CH
CH2
CH2
HC
HC
C
C
O
O
O
C
C
O
O
O
+50oC
1] 3&C;wVkMkbbZu eSysbd VsVªk gkbMªks FkSfyd ,sugkbMªkbM
,sugkbMªkbM
CH
CH
CH2
CH
CH2
CH2
CH
CH
CH2
CH.CHO
CH2
CH2
CHO+
,Øksyhu
VsVªk gkbMªks csatSfYMgkbM
uksV &
(i) bl vfHkfØ;k esa vk;fud :i ;k eqDr ewyd e/;orhZ ds :i ls ugha cursA ;g
fØ;k ,d gh in esa gks tkrh gS] ftlesa u, ca/kksa dk fuekZ.k rFkk iqjkus ca/kksa dk
VwVuk lkFk&lkFk gksrk gSA
(ii) fdUrq dqN oSKkfudksa ds vuqlkj&MkbbZu (Diene) ,oa MkbbZuksfQy
(Dienophile) dks izdfr ds vk/kkj ij ;g leka’ku vFkkZr~ nks eqDr ewydksa }kjk
rFkk fo"keka’ku vkSj dHkh dHkh nksukas ds lfEefyr izHkkoksa }kjk laiaé gksrh gSA
4-7 vydkbUl ¼ifjp;½
,sYdkbu vlar`Ir gkbMªksdkcZu gksrs gSa] ftuesa ,sls nks dkcZu ijek.kq vo’;
mifLFkr jgrs gSa] tks vkil esa ,d fuca/k (Triple bond) }kjk layXu jgrs gSaA
lajpuk rFkk vkac/ku-I
156
mnkgj.k &
HH CC HH CC C
H
H
,slhfVyhu ¼,Fkkbu½ esfFky ,slhfVyhu
bl ltkrh; Js.kh dk izFke lnL; ,slhfVyhu gS] blfy, f=ca/k dks ,slhfVyhu
ca/k (Acetylene bond) Hkh dgrs gSaaA
4-7-1 ukedj.k (Nomenclature)
1- ,sydkbu vlar`Ir gkbMªksdkcZu dk lkekU; lw= CnH2n–2 gksrk gSA 2- lk/kkj.k iz.kkyh ds vuqlkj izFke rhu lnL;kksa dks Øe’k% ,slhfVyhu] ,sfyyhu rFkk
ØksVksukbyhy dgrs gSaA
3- ,d vU; fof/k ds vuqlkj ,slhfVyhu ds ltkfr;ksa dks ,slhfVyhu dk O;qRié ekurs
gSaA
mnkgj.k &
lk/kkj.k uke ,slhfVyhu uke
(i) H C C H ,slhfVyhu ,slhfVyhu
(ii) 3
CH C C H ,sfyyhu esfFky ,slhfVyhu
(iii) 3 3
CH C C CH ØksVksukbyhu MkbesfFky ,slhfVyhu
4- vkbZ-;w-ih-,-lh- i)fr ds vuqlkj ,sYdsu ds uke ls vuqyXu ,su ds LFkku ij vkbu
j[k nsrs gSaA f=ca/k (Triple bond) ;qDr lcls cM+h Ja`[kyk pqu ysrs gS vkSj Ja[kyk
ds dkcZu ijek.kqvksa dk vadu (Numbering) ml Nksj (end) ls izkjaHk djrs gS]
ftls vksj ls f=ca/k fudVre gksrk gSA
,sYdkbu,sYdsu
$ vkbu
&,su
mnkgj.k &
lw= lk/kkj.k uke
,lhfVyhu uke
IUPAC uke
(i) H C C H ,slhfVyhu ,slhfVyhu ,Fkkbu
(ii) 3
CH C C H ,sfyyhu esfFky
,slhfVyhu
izksikbu
(iii) 3 3
CH C C CH ØksVksukbyhu MkbesfFky
,slhfVyhu
2&C;wVkbu
(iv)
CH3
CHCCHCH3
& vkblksizksfiy
,slhfVyhu
3&esfFky
1&C;wVkbu
(v) 3 2
CH CH C CH & ,sfFky
,slhfVyhu
1&C;wVkbu
(vi) 53 2
CH C C C H & esfFky ,fFky
,slhfVyhu
2&isaVkbu
lajpuk rFkk vkac/ku-I
157
5- ,sYdkbu esa ls ,d gkbMªkstu ,sYdkbu tkus ds ckn vo’ks"k dks ,sYdkbfuy
(Alkynyl) dgrs gSA buds uke ds vuq:i ,sYdkbu esa ds LFkku ij – ynyl j[krs gSaA
mnkgj.k &
(i) HC C ,Fkkbfuy
(ii) 3CH C C izksikbfuy
(iii) 2 5C H C C C;wVkbfuy
6- ;fn v.kq esa ,d ls vf/kd f=;d ca/k gksrs gSa] rks ,sYdsu ds izR;;&,su ds LFkku ij]
,sMkbuh (adiyne) tc nks f=ca/k gksa ,sVªkbu (atriyne) tc rhu f=ca/k gksa j[krs gSaA
mnkgj.k &
H C C C CH 2 2CH C CH CH C CH
1] 3 C;wVkMkbvkbu 1] 3] 5&gSDlkVªkbvkbu
4-7-2 ,sYdkbu dh lajpuk
,sYdkbu esa ,d C C f=d ca/k gksrk gS] ftlesa f=ca/k ls ca/ks nksuksa dkcZu
ijek.kq sp ladfjr voLFkk esa jgrs gSaA f=caa/k ,d flXek rFkk nks ikbZ ca/kksa ls
cuk gksrkA sp ladj.k ds dkj.k ,slhfVyhu v.kq dh vkdfr jSf[kd (Linear) gksrh gSA
4-8 bysDVªkWuLusgh ,oa ukfHkd Lusgh vfHkfØ;kvksa dh fØ;kfof/k
;s os vfHkfØ;k,¡ gSa] ftuesa ,sYdkbu ,d ukfHkdLusgh vfHkdeZd (Nucleophilic
Reagent) ds :i esa dk;Z djrk gSA ,sYdkbuksa ij gSykstuksa] HCl, ty o dkcZfud
vEyksa dk ;ksx vkfn blh fØ;k&fof/k ls gksrk gSA
,sYdhuksa esa nks ijek.kqvksa ds e/; ,d vkcU/k gksus ds dkj.k nks ,d la;ksth
ijek.kq ;k lewgksa ¼,d iw.kZ v.kq½ dk ;ksx gksrk gS] ijarq ,sYdkbuksa esa nks vkca/kksa ds dkj.k
pkj ,d la;ksth ijek.kqvksa ;k lewgksa ¼nks v.kqvksa½ dk ;ksx gksrk gSA
4-8-1 gkbMªkstu dk ;ksx (Addition of Hydrogen)
(i) dksyk;Mh IysfVue vFkok fufdy dh mifLFkfr esa ,sYdkbu gkbMªkstu ls la;ksx djrs
gSa vkSj ,sYdsu cukrs gSaA ;g ;ksx nks inksa esa gksrk gSA igys ,sYdhu vkSj fQj ,sYdsu
curs gSaA
H C HC H2C CH
2H
3C CH
3Ni 300oC
H2
Ni 200oC
H2
,slhfVyhu ,fFkyhu ,Fksu
C CH CH CH2
CH3CH
3CH
2CH
3CH
3
H2 H2
Pt dejs dk rki Pt
izksihu izksisu
(ii) ,sYdkbu ds vip;u ds ,sYdhu fll (Cis) vFkok VªkUl (Trans) cuus dh fØ;k
mRiszjd ij vk/kkfjr gSA
lajpuk rFkk vkac/ku-I
158
C C
R
H
H
R
C C RR
Na, NH3 Liquid
Pd/NiBC C
R
HH
R
Trans
Cis
H2
H2
bl vfHkfØ;k ls ,d gh izdkj ds f=foe leko;eh (Stero Isomers) cuk, tk ldrs
gSaA bu izfrfØ;kvksa dks f=foeoj.kh vfHkfØ;k (Stereo selective reaction) dgrs gSaA
4.8.2 gSykstu dk ;ksx (Addition of Halogen)
(i) gSykstu va/ksjs esa vfHkfØ;k,¡ djrs gSaA lw;Z dk izdk’k ,oa /kkfRod gSykbM bl
fØ;k dks mRizsfjr djrs gSaA
gSykstu dh fØ;k’khyrk fuEu Øe esa gS &
Cl > Br > I
CH
CH
Cl
Cl
SbCl4
CHCl
CHCl
CHCl2
CHCl2
Cl2
+eUn izdk'k eUn izdk'k
,slhfVyhu ,slhfVyhu
MkbDyksjkbM VsVªkDyksjkbM
1]1]2]2&VsVªkDyksjk,Fksu
osLVªkWu
m|ksxksa esa osLVªkWu] (Westron) jcj] olk vkSj okWfuZ’k bR;kfn ds fy, foyk;d ds
:i es iz;qDr gksrk gSA ;g dhVuk’kh (Insecticide) Hkh gSA
tc osLVªkWu dh ok"iksa dks xeZ ;k pwus ij izokfgr djrs gSa rc ,d vU; egRoiw.kZ
foyk;d osLVªkWlksy (Westrosol) curk gSA
CHCl2
CHCl2
CCl2
CHCl
BaCl2
CaO + HCl;k
VªkbDyksjks ,fFkyhu
(ii) v’kq) ,slhfVyhu Dyksjhu ds lkFk rhoz foLQksVd ds lkFk fØ;k djrs gSa rFkk HCl o dkcZu curs gSaA
2 2 2HC CH Cl C HCl
(iii) czksehu ty ds lkFk Mkbczkseks,fFkyhu cukrh gS vkSj bl czksehu ds lkFk VsVªkczkseks
,Fksu cukrh gSA
CH
CH
CHBr2
CHBr2
CHBr
CHBrnzo
czksehu
czksehu ty
lajpuk rFkk vkac/ku-I
159
fØ;k fof/k ¼,slhfVyhu ij Dyksjhu dk ;ksx½
,sYdhu ds leku ,sYdkbu Hkh bysDVªkWu lzksr dk dk;Z djrs gSaA tc ;ksx
djus okyk gSykstu v.kq ,sYdkbu ds fudV vkrk gS rc ,sYdkbu dk v.kq gSykstu v.kq
dks /kzqfor dj nsrk gSA gSykstu dk /kzqfor v.kq ,sYdkbu ds ca/k ds lkFk f’kfFky caf/kr
(Loosely bonded) gksdj ladqy ( complex) cukrk gSA ;g ladqy vLFkk;h gksus
ds dkj.k vi?kfVr gks tkrk gS rFkk ;ksxt (Addendum) ds bysDVªkWuLusgh
(Elecrophilic) Cl+ dks vius vanj feyk ysrk gS rFkk Cl
– vk;u vyx gks tkrk gSA
blds ifj.kkeLo:i ,d pØh; dsVk;u curk gS] ftlesa nks dkcZu ijek.kqvksa ds
e/; ,d ;qXe ca/k gksrk gSA
vc ;g izfØ;k vFkkZr~ ladqy] ladqy rFkk Cl– vk;u dk ;ksx djkbZ tkrh
gS rFkk izfrLFkkfir ,sYdsu curk gSA
CH
CH
Cl Cl
CH
CH
Cl Cl
Cl Cl Cl ClCHCH
+
ladqy (Complex)
CHCl
CHCl
Cl Cl CH
CH
Cl ClCl+
Cl
CH
CH
ladqy (Complex) ldqqy
CHCl2
CHCl2
Cl+
Cl
CHCl
CHCl
ladqy ,slhfVyhu VsVªkDyksjkbM
4-8-3 gSykstu vEyksa dk ;ksx (Addition of Halogen Acids)
(i) bl fØ;k esa igys foukby gSykbM curk gS var esa ,sfYdyhMhu gSykbM&1]1 ;ksx
ekdksZuhdkWQ ds fu;ekuqlkj gksrk gS &
H+
ClCH
CH
H
Cl
CH2
CHCl
CH3
CHCl2
+;ksx
foukby ekdksZuhdkWQ ,fFkyhMhu DyksjkbM
DyksjkbM fu;ekuqlkj 1]1
MkbDyksjks ,Fksu
lajpuk rFkk vkac/ku-I
160
fØ;k fof/k &
R C R'C XH R C C R' X
H
+ +
C C
R'
XH
RHX
CR' X2
RCH2
(ii) ijkWDlkbM dh mifLFkfr esa ekdksZuhdkWQ ds fu;e ds foijhr izdkj ls ;ksx gksrk gS]
tSls &
3 3
BrCH C CH HBr CH CH CH Br ijkWDlkbM
3CH CHBr CHBr
1]2&Mkbczkseksizksisu
4-8-4 lY¶;wfjd vEy dk ;ksx (Addition of H2SO4)
,slhfVyhu ¼vFkok dksbZ vU; ,sYdkbu½ lkUnz o B.Ms H2SO4 esa vo’kksf"kr gks
tkrk gS ,oa ,fFkyhMhu gkbMªkstu lYQsV cukrk gSA okbfuy gkbMªkstu lYQsV ek/;fed
inkFkZ ds :i esa gksrk gSA
CH
CH
H
HSO4
CH2
CH.HSO4
CH3H
2SO
4
H HSO4
.CH.(HSO
4)2
+
,slhfVyhu okbfuy gkbMªkstu ,fFkyhMhu gkbMªkstu
lYQsV lYQsV
,fFkyhMhu gkbMªkstu lYQsV dks ty ds lkFk mckyk tkrk gSA rks
,slhVSfYMgkbM (Acetaldehyde) curk gSA
CH3
CH.(HSO4)2
CH3
(-H2SO
4)
.
CH
HOH
H OHCH
3
CHOOH
OH-H
2O
2
vLFkk;h ,slhVSfYMgkbM
bl vfHkfØ;k }kjk ,slhVSfYMgkbM dks O;kikfjd ek=k esa cuk;k tkrk gSA
4-8-5 ,sYdkbu ij ty dk ;ksx vFkok ,sYdkbu dk ty;kstu (Addition of water on alkynes of hydration of alkynes)
tc fdlh ,sYdkbu dks 42% H2SO4 esa 1% HgSO4 ¼mRizsjd½ dh mifLFkfr
esa 60oC ij izokfgr fd;k tkrk gS rc ,sfYMgkbM@dhVksu curk gSA
mnkgj.k &
(i) ,slhfVyhu ds lkFk ,slhVSfYMgkbM
(ii) esfFky ,slhfVyhu ds lkFk ,slhVksu
lajpuk rFkk vkac/ku-I
161
(iii)
CH
CH
CH2
CHOH
H2SO
4 + HgSO
4CH
3CHO+ H2O
42% 1%
60oC
foukby ,slhVYMhgkbM
vYdksgkWy
(iv) izksikbu ¼esfFky ,slhfVyhu½ esa ty dk ;ksx ekdksZuhdkWQ ds fu;e ds vuqlkj gksrk gS
,oa ,slhVksu curk gSA
CH3
C CH CH3
C CH2
CH3
CO CH3
OH
+ H2O42% H2SO4 + 1% HgSO4
60oC
fØ;k fof/k (Mechanism) & blesa bysDVªksfQfyd ;ksx gksrk gSA blesa Hg vk;u
¼mRiszjd½ f=;d ca/k ds lkFk la;kstu djds ,d ladqy (complex) cukrk gSA
;g ladqy (complex) fQj ,d pØh; dsVku;u esa ifjofrZr gks tkrk gSA
pØh; dsVk;u ij fQj ty dk ;ksx gksrk gSA pØh; dsVk;u esa fcUnqfdr vkca/k ;g
iznf’kZr djrk gS fd u;k vkca/k cu jgk gS rFkk iqjku vkca/k VwV jgk gSA
lEiw.kZ fØ;k&fof/k fuEu izdkj iznf’kZr fd;k tk ldrk gS &
HC CH + Hg
H
HC CH
H C C H
:..
H C C H
Hg+
H C C H H C C H
Hg
OH OH OH2
H
H C C H
OH
2+ Hg2
Hg2
H2O
- Hg2+
+ H
- H+
4-8-6 ,slhfVd vEy dk ;ksx (Addition of acetic acid)
eD;wZfjd yo.k ¼mRizsjd½ dh mifLFkfr esa ,slhfVyhu igys foukbu ,slhVsV vkSj
fQj ,fFkyhMhu ,slhVsV curk gSA
H
CH3COO
CH
CH
HgSO4
CH2
CH.COOCH3
CH3
CH(OOC.CH3)2
CH3COOH
+
,slhfVd vEy foukby ,slhVsV ,fFkyhMhu ,slhVsV
¼foukby ,slhVsV dk mi;ksx IykfLVd m|ksx esa gksrk gSA½
,fFkyhMhu ,slhVsV xeZ djus ij ,slhVSfYMgkbM ,oa ,slhfVd ,sugkbMªkbM curk gSA
lajpuk rFkk vkac/ku-I
162
CH3
CH(OOCCH3)2
CH3
CHO
CH3CO
CH3CO
O+
600-700K
,fFkyhMhu ,slhVsV ,slhVSfYMgkbM ,slhfVd ,sugkbMªkbM
4-8-7 gkbiksDyksjl vEy ¼Dyksjhu ty½ ;ksx Addition of Hypochlorous acid (Chlorine water)
;ksx nks inksa ij ekdksZuhdkWQ ds fu;ekuqlkj gksrk gS &
(a)
CH
CH
CHOH
CHCl
CH(OH)2HO
Cl
HOCl -H2O
CHCl2
CHO
CHCl2
+
vLFkk;h MkbDyksjks
,slhVSfYMgkbM
(b)
C OH
CHCl
C
CH
HO
Cl
HOClCH3
CH3 C(OH)
2
CHCl2
CH3
+
vLFkk;h
C O
CHCl2
-H2O CH
3
1]2 MkbDyksjks ,slhVksu
fØ;k fof/k (Mechanism) & Dyksjhu OH dh vis{kk de _.kfo|qrh
(Electronegative) gS] blfy, HOCl fuEu izdkj ls /kzqfor voLFkk esa jgrk gS &
HOCl Cl OH
vkaf'kd /kzqo.k
/kzqohdj.k
vkxs ;ksx fuEukuqlkj gksrk gS &
CH
CH
Cl OHCH
CH
CH
CH
- complex
+
Cl+ OH- OH-Cl+ +
pØh; dsVk;u
- complex
CHCl
CHOH
CH
CH
CHCl
CHOH
Cl+ OH-OH-
Cl+ Cl+ OH-
CHOH
CHCl CHCl2
CH(OH)2
CHCl2
CHO
Cl OH-
+ H2O
lajpuk rFkk vkac/ku-I
163
4-8-8 vklsZfud VªkbDyksjkbM dk ;ksx (Addition of Arsenic Trichloride)
vklsZfud VªkbDyksjkbM ,slhfVyhu ds lkFk ;ksxkRed fØ;k dj &Dyksjks
foukby MkbDyksjks vklsZfud ¼yqvlkbV½ uked fo"kSyh xSl cukrh gSA
CH
CHCl AsCl
2
CHCl
CH.AsCl2
+
&Dyksjks foukby MkbDyksjks vklsZfud ¼yqvlkbV½
4-8-9 vkstksu dk ;ksx ;k vksthuhdj.k (Ozonolysis or Ozonisation)
,sYdkbu] vkstksu ds ;ksx ls vkstksukbM cukrk gSA vkstksukbM vLFkk;h gksrs gSa
vkSj ty dh fØ;k ls vi?kfVr gksdj MkbdhVksu nsrs gSaA
(a) CH
CHO
3O
CH
CH O
O CHO
CHO+ + H2O2
H.OH
,slhfVyhu ,slhfVyhu vkstksukbM Xykb vkWDlsy
(b)
C2H
5CCH3
CO
3CH
3C C
OO
O
C2H
5
H2O
izksikbu
vkstksukbM
C
2H
5 + H
2O
2COCOCH
3
esfFky ,fFky XykbvkWDly
lkFk gh lkFk Hkh curk gS] tks MkbdhVksu dks lk/kkj.k vEyksa esa vkWDlhdr dj nsrk gSA
(i)
CHO
CHO COOH
COOH
H2O
2
vkWDtsfyd vEy
(ii) C2H
5 + H
2O
2COCOCH
3CH
3COOH + C
2H
5COOH
4.8.10 ukfHkdLusgh ;ksx (Nucleophilic addition reactions)
,sYdkbu ds f=;d ca/k (Triple bond) ij bysDVªksfQfyd vfHkdeZd dk ;ksx
lqxerk ls ugha gksrk] blfy, ;g vis{kk dh tk ldrh gS fd bl ij ukfHkdLusgh
(Nucleophilic reagent) vfHkdeZd dk ;ksx Hkh gks tkrk gSA
blesa ;ksx nks inksa esa gksrk gS &
(i) gkbMªkstu lk;ukbM dk ;ksx@lk;uks ,fFkukbyhdj.k (Addition of
hydrogen cyanide/cyano ethylation& ,sYdkbu ij HCN dk ;ksx csfj;e
lk;ukbM mRizsjd dh mifLFkfr esa gksrk gSA ,slhfVyhu ds lkFk okbfuy lk;ukbM ;k
,fdyks ukbVªky curk gSA
blls la’ysf"kr /kkxk vksjyksu (Orlon) o jcj cuk;k tkrk gS &
lajpuk rFkk vkac/ku-I
164
H
CNCH
CH CH2
CH.CN+
foukby lk;ukbM
fØ;k fof/k & (a) bl vfHkfØ;k esa igys lk;ukbM vk;u (CN) dk f=;d ca/k
(Triple bond) ds dkcZu ij ;ksx gksrk gS vkSj foukby dkcsZuk;u (Vinyl carbanion) curk gSA
(b) ;g dkcsZfu;u HCN ds nwljs v.kq esa ls gkbMªkstu dk viksgu (Abstraction) dj
ysrk gSA
C HCN + H C C CH
CN
H
H CNC C
H H
HCN
,fdyks ukbVªkby
;k
foukby lk;ukbM
4-8-11 gkbMªkscksjhuhdj.k&vkWDlhdj.k
vYdhuksa ds leku vydkbUl Hkh Mkbcksjsu ls fØ;k dj ;ksxkRed ;kSfxd cukrs gSa ftudk
gkbMªkstu ijkWDlkbl ls vkWDlhdj.k djus ij ^vYdksgkWy* eq[; mRikn ds :i esa izkIr
gksrs gSaA
4-8-12 /kkrq veksfu;k vip;u
1- ,sYdkbuksa esa f=;d vkca/k okys dkcZu ijek.kq ij layXu gkbMªkstu C H
fØ;k’khy gkbMªkstu (Active hydrogen) dgykrk gSA
2- ,slhfVyhu ds v.kq esa mifLFkr gkbMªkstu vEyh; izdfr ds gSa] ftldh iqf"V fuEu
fØ;kvksa ls dh tk ldrh gSA
(i) lksfM;e ,slhfVykbM dk curk & ,slhfVyhu lksfM;e ,oa nzo veksfu;k vFkok
lksMkekbM ls fØ;k djds eksuks ,oa MkblksfM;ks ,slhfVykbM cukrh gSA
CH C H Na CH C Na
1
2
++ +
veksfu;k
nzoH2
eksuks lksfM;e ,slhfVykbM
CH C Na C C NaNa
veksfu;k
nzo
MkblksfM;e
,slhfVykbM
,slhfVyhu dks xeZ lksfM;e ij izokfgr djus ls nksuksa gkbMªkstu ijek.kq /kkrq ls ,d&,d
djds izfrLFkkfir gks tkrs gSaA
CHCH Na CH C.Na C NaCNa+180oC + 210oC ++
eksuks lksfM;e Mkb lksfM;e
,slhfVykbM ,slhfVykbM
(ii) dkij ,slhfVykbM dk cuuk & ,slhfVyhu veksfudy D;wizl DyksjkbM ds fØ;k
djds dkWij ,slhfVykbM dk yky vo{ksi nsrk gSA
lajpuk rFkk vkac/ku-I
165
CHHC Cu2Cl
2 + NH
4OH CCu C Cu2+ + 2NH4Cl + 2H2O
dkWij ,slhfVykbM
¼yky vo{ksi ½
;k
CuC
CuC
D;wizl ,slhfVykbM
(iii) flYoj ,slhfVykbM dk cuuk & veksfudy flYoj ukbVªsV ls fØ;k djds
,slhfVyhu] flYoj ,slhfVykbM dk lQsn vo{ksi nsrk gSA
CC CAg CH Ag + 2NH4NO3 + 2H2OH + 2AgNO3 + 2NH4OH
lQsn vo{ksi
;k
AgC
AgC
flYoj ,slhfVykbM
uksV & ,slhfVyhu ds eksuks ,sfYdy O;qRié Hkh ,slhfVyhu ds leku fuEu izdkj /kkfRod
O;qRié cukrs gSa] ftUgs ,sfYdukbM dgrs gS &
CCR Na
CCR Ag CCR Cu
lksfM;e ,sfYdukbM flYoj ,sfYdukbM D;wizl ,sfYdukbM
4-8-13 vkWDlhdj.k
1- f=;d ca/k dh mifLFkfr ds dkj.k ,sYdkbu 'kh?kz dh vkWDlhd`r gks tkrs gSA
2- vkWDlhdj.k ls cuus okys inkFkZ vkWDlhdj.k dh izd`fr ij fuHkZj djrs gSA
(i) ngu (Combustion) & gok ds vf/kD; esa /kq¡,nkj Tokyk ds lkFk tyrk gS] fdurq
gok ds fu;af=d izokg esa pednkj Tokyk ds lkFk tyrk gSA ;g izdk’k vk¡[kksa ds fy,
gkfudkjd gSA
2 2 2 2 2
2 50 4 2C H CO H O
(ii) {kkjh; KMnO4 }kjk vkWDlhdj.k & ,slhfVyhu vkWDtsfyd vEy esa vkWDlhdr gks
tkrk gSA
CH
CH
COOH
COOHKMnO4
+ 4(O){kkjh;
vkWDtsfyd vEy
(iii) vEyh; KMnO4 }kjk vkWDlhdj.k & f=;d ca/k (Triple bond) ij v.kq VwV tkrk
gS vkSj QkWfeZd vEy curk gSA
CH
CH+ 3(O) +H2O 2HCOOH
QkWfeZd vEy
lajpuk rFkk vkac/ku-I
166
(iv) Øksfed vEy (K2Cr2O7 + H2SO4) & blds lkFk vfHkfØ;k ls ,slhfVd vEy
nsrk gSA
H
2SO
4
CHCHK
2Cr
2O
7+ H2O + (O) CH3COOH
(v) lsfyfu;e vkWDlkbM ls vkWDlhdj.k & MkbdhVksu ;k MkbdkcksZfuy ;kSfxd cukrk gSA
(vi) lsfyfu;e vkWDlkbM ls vkWDlhdj.k & MkbdhVksu ;k MkbdkcksZfuy ;kSfxd cukrk gSA
2R C C R SeO R CO CO R Se
2H C C H SeO CHO CHO Se
3 3 2 3 3CCH C C CH SeO CH O CO CH Se
C;wVkMkbuksu
4-8-14 cgqyhdj.k
fHké&fHké voLFkkvksa esa ,sYdkbu fHké&fHké cgqyd cukrs gSaA
pØh; cgqyhdj.k (Cyclic polymerisation) – (i) tc ,slhfVyhu vFkok blds fdlh
ltkr dks yky rIr (Red hot) /kkfRod uyh esa izokfgr fd;k tkrk gS rc casthu vFkok
bldk dksbZ ltkr gkbMªksdkcZu curk gS (Bertholet, 1862) A
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
CH
150o
can uyh es xeZ
+
csathu
4-9 ,slhfVyhu ds vEyh; LoHkko dk Li"Vhdj.k (Explaination of acidity nature of acetylene)
,slhfVyhu ds gkbMªkstu ijek.kq ds vEyh; LoHkko dks nks izdkj ls Li"V fd;k
tk ldrk gS &
(a) _.kfo|qrrk (Electronegativity) ds vk/kkj ij
(b) ,suk;u ds LFkkf;Ro (Stability of Anion) ds vk/kkj ij
4.9.1 _.kfo|qrrk ds vk/kkj ij vEyh; izd`fr dk Li"Vhdj.k
¼1½ ladj.k ds fu;ekuqlkj] ßfdlh ijek.kq ds ladj d{kd (Hybrid orbital) esa s d{kd
ftruk vf/kd gksrk gS] og ijek.kq mruh gh vf/kd _.kfo|qrh (Electronegative) gksrk gS] D;ksafd vkcaf/kr bysDVªkWu ;qXe ijek.kq ukfHkd ds mruk gh fudV jguk
pkgrk gSAÞ
vr% sp gkbfczM vkWfcZVy dh _.kfo|qrrk sp2 ,oa sp
3 gkbfczM vkWfcZVyksa dh
vis{kk vf/kd gksrh gSA
¼2½ ,slhfVyhu esa gkbMªkstu ijek.kq dkcZu ds sp ladfjr vkWfcZVy ls tqM+k jgrk gS]
tcfd ,Fksu es sp3 ladfjr vkfcZVy ls ,oa ,fFkyhu esa sp
2 ladfjr vkWfcZVy ls tqM+k
jgrk gSA
lajpuk rFkk vkac/ku-I
167
¼3½ pw¡fd sp ladfjr vkfcZVy esa s y{k.k vf/kd gksrk gS (50%)A blfy, sp ladfjr
dkcZu ijek.kq dh _.kfo|qrrk sp2 ,oa sp
3 ladfjr dkcZu dh vis{kk vf/kd gksrh gSA
¼4½ sp ladfjr dkcZu ijek.kq dh _.kfo|qrrk vf/kd gksus ds dkj.k ,slhfVyhu ds C–H
ca/k ¼sp-s ca/k½ ds bysDVªkWu dkcZu ds ukfHkd ds vf/kd fudV vkSj gkbMªkstu ds
ukfHkd ls nwj jgrs gSaA ifj.kkeLo:i gkbMªkstu ijek.kqvksa esa izk sVkWu ds :i esa eqDr
gksus dh izofÙk mRié gks tkrh gS vkSj ,slhfVyhu esa vEyh; xq.k iznf’kZr djus yxrk
gSA
4.9.2 ,suk;u ds LFkkf;Ro ds vk/kkj ij vEyh; izd`fr dk Li"Vhdj.k
(i) ,slhfVyhu esa dkcZu sp ladfjr voLFkk esa gksrk gS vkSj C o H ds chp esa sp–s ca/k gksrk gS A
(ii) gkbMªkstu ijek.kq dk izksVhu ds :i esa vyx gksus ij sp–s ca/k dk bysDVªkWu tksM+k
sp ladfjr vkWfcZVy esa jgrk gS] tcfd ,sYdsu esa sp3 ladfjr vkWfcZVy esa rFkk
,sYdhu esa sp2 ladfjr vkWfcZVy esa jgrk gSA
(iii) sp vkWfcZVy ds bysDVªkWu sp3 rFkk sp
2 dh vis{kk ukfHkd ds vf/kd fudV jgrs gSa]
blfy, 1&,sYdkbu ¼,slhfVyhu½ esa ls gkbMªkstu ds foyksiu ds ckn cuk ,suk;u
vis{kkd`r vf/kd LFkk;h gksrk gSA
QyLo:i 1&,sYdkbu vEyh; xq.k izdV djus yxrk gS] tcfd ,sYdsu ,oa
,sYdhu esa vEyh; xq.k ugha ik;k tkrkA
4-10 iz”u
1- ekdksZuhdkWQ fu;e ls izksuhu ,oa HBr ds ;ksx ls curk gSA
a. izksfiy czksekbM b. vkblks izksfiy czksekbM
c. ckseks izksisu d. vkblks czkseks izksisu
2- ,fYdy gSykbM ds fo|nMªks gSykstuhdj.k ls gksrh gS rks --------------------------------
lkbukbM izkIr gksrk gSA
a. ,Ydsu b. ,Ydhu c. ,Ydkbu d. bfyy
3- tc ,lhfVyhu ij HCN dh vfHkfdz;k gksrh gS rks ----------------------------
lkbukbM izkIr gksrk gSA
a. ,fYdy b. ,fjy c. foukby d. ,YdkbUl
4- MhYl ,UMj vfHkfdz;k ls lkbDyks ----------- izkIr gksrs gSA
a. ,sYdsu b. ,fjy c. ,Ydkbu d. ,YdkbUl
lajpuk rFkk vkac/ku-I
168
4-11 Unit Summary bdkbZ lk”ka”k
dkcZu ,oa gkbMªkstu }kjk cus ;kSfxd ftuesa ,d ;k vf/kd f}vkcU/k vFkok f=vkcUn
mifLFkr gksa] vlar`Ir gkbMªksdkczu dgykrs gSaA budk lkekU; lw= CnH2n gksrk gSA
,YdhUl ;ksxkRed vfHkfØ;k,W izeq[krk ls nsrs gSaA tc vYdkWgyksa dk futZyhdj.k fd;k
tkrk gS rc ,YdhUl izkIr gksrs gSA vlefer vYdhuksa esa tqM+us okys v.kq dk _.kkRed
Hkkx ml dkcZu ijek.kq ls tqMrk gS] ftl ij gkbMªkstu ijek.kqvksa dh la[;k lcls de
gksrh gSA tc vYdhUl dh fØ;k vkWDlhtu ls dh tkrh gS rc f}ca/k ij ,d vkWDlhtu
ijek.kq tqM+ tkrk gS vkSj pØh; vkWDlkbl ¼,ikWDlkbM½ curs gSaA tc 1% B.Ms tyh;
{kkjh; KMnO4 foy;u ¼ckW;j vfHkdeZd½ dh fØ;k vYdhUl ls gksrh gS rc f}ca/k dk
gkbMªkbDlhyhdj.k gks tkrk gSaA vYdhUl Xyk;dkWYl esa cny tkrs gSa ,oa ckW;j vfHkdeZd
dk cSaxuh jax mM+ tkrk gSaA bl vfHkfØ;k dk mi;ksx vlar`Iirk dh ifgpku djus esa
gksrk gSA vYdhUl esa cgqyhdj.k fdz;k gksrh gS vYdhUl esa ,ykbfyd fLFkfr ij
izfrLFkkiu ;k ,sfyfyd izfrLFkkiu gksrk gSA fla;qfXer MkbZbZUl esa 1-2 ,oa 1-4 ;ksx fdz;k gksrh
gSA vYdkbZUl esa bysDVªkWuLusgh ,oa ukfHkd Lusgh vfHkfØ;kvksa gksrh gSA ,slhfVyhu ds
vEyh; LoHkko gksrk gSA
4-12 iz”u mRrj
1- vkbZlksa izksfiy czksekbM
2- ,Ydhu
3- foukby
4- ,Ydhu
4-13 dqN mi;ksxh iqLrdsa Suggested reading/Reference
17. Organic Chemistry, Volume 1, I.L. Finar, ELBS Longman.
Fundamentals of Organic Chemistry , T.W. Graham Solomons, John
Wiley & Sons, Inc. Chapters 3, 11&13.
18. Organic Chemistry, Volume I, S.M. Mukherji, S.P. Singh, R.P.
Kapoor, Wiley Eastern Limited, New Delhi.
19. Organic Chemistry, Robert T.Morrison and Robert N.Boyd,
Prentice-Hall of India, Pvt. Ltd. New Delhi.
20. Advanced Organic Chemistry, B., S. Bahl and Arun Bahl, S. Chand
& Company Ltd. New Delhi.
21. Organic Chemistry, M.K. Jain, Shoban Lal Nagin Chand & Co.,
Delhi.
lajpuk rFkk vkac/ku-I
169
,sfYdy ,oa ,sfjy gSykbM [Alkyl and Aryl halides]
5-0 izLrkouk
lar`Ir gkbMªksdkcZuksa ds gSykstu O;qRié ,fYdy gSykbM dgykrs gSaA gSykstu
ijek.kqvksa dk vU; ijek.kqvksa ;k lewgksa }kjk foLFkku laHko gksus ds dkj.k bu ;kSfxdksa ds
vusd lka’ysf"kd vuqiz;ksx gksrs gSaA budk foyk;dksa ds :i esa Hkh iz;ksx fd;k tkrk gSA
,sjkseSfVd gkbMªksdkcZuksa ds gSykstu O;qRié ,fjy gSykbM dgykrs gSaA
5-
bl bdkbZ ds v/;;u ls vki fuEukuqlkj 'kh"kZdksa dh tkudkjh izkIr dj ldsaxsA
,fYdy gSykbM
oxhZdj.k
ukedj.k
cukus dh lkekU; fof/k;k¡
HkkSfrd ,oa jklk;fud xq.k
,fjy gSykbM
ukedj.k
cukus dh lkekU; fof/k;k¡
HkkSfrd ,oa jklk;fud xq.k
5-2- ,sfYdy gSykbM [Alkyl Halides]
ßgkbMªksdkcZu ds gSykstu O;qRiUu os ;kSfXkd gSa] tks fdlh lar`Ir ¼,sYdsu½ ;k
vlar`Ir ¼,sYdhu ;k ,sYdkbu½ gkbMªksdkcZu ds ,d ;k ,d ls vf/kd gkbMªkstu ijek.kqvksa
ds mrus gh gSykstu ijek.kqvksa }kjk izfrLFkkiu ls curs gSaAÞ ,sYdsu ds eksuks gSykstu
O;qRiUu ß,sfYdy gSykbMÞ dgykrs gSA
fdlh ,sYdsu ds gkbMªkstu ijek.kq] gSykstu ijek.kq ls izfrLFkkfir gksrs gS] mudh
la[;k ds vk/kkj ij budk oxhZdj.k fd;k x;k gSA tSls&
,d ijek.kq izfrLFkkfir gks & eksuks [Mono] gSykstu O;qRiUUk
nks ijek.kq izfrLFkkfir gks & Mkb [Di] gSykstu O;qRiUu
rhu ijek.kq izfrLFkkfir gks & Vªkb [Tri] gSykstu O;qRiUUk
pkj ijek.kq izfrLFkkfir gks & VsVªk [Tetra] gSykstu O;qRiUu
ikWp ijek.kq izfrLFkkfir gks & isaVk [Penta] gsSykstu O;qRiUUk
vkSj vf/kd ijek.kq izfrLFkkfir gks & ikWfy [Poly] gSykstu O;qRiUu
mnkgj.k ds fy, esFksu ds gkbMªkstu ijek.kqvksa dks Dyksjhu ijek.kqvksa ls izfrLFkkfir djus
ij cus fofHkUu Dyksjhu O;qRiUu fuEu izdkj gS &
CH3Cl CH2Cl2 CHCl3 CCl4
eksuksDyksjksesFksu MkbDyksjksesFksu VªkbDyksjksesFksu V~sVªkDyksjksesFksu
5-2-1 eksuksgSykstu O;qRiUu vFkok ,sfYdy gSykbM~l [Monohalogen Derivatives or Alkyl Halides]
lajpuk rFkk vkac/ku-I
170
,sYdsuksa ds eksuksgSykstu O;qRiUu ,sfYdy gSykbM~l Hkh dgykrs gSA ,sfYdy
gSykbMksa dks gSykstu vEyksa dk O;qRiUu Hkh ekuk tkrk gSA ;fn gSyktu vEy ds
gkbMªkstu ijek.kq dks ,sfYdy lewg }kjk izfrLFkkfir fd;k tkrk gS rks ,d ,sfYdy
gSykbM izkIr gksrk gSA
HH X R X
+R,sfYdy gSykbMgSykstu vEy
,sfYdy gSykbMksa dk O;kid lw= R X vFkok CnH2n+1X gSA R ,d
,sfYdy lewg gS tks fd CnH2n+1 gSA X ,d gSykstu ijek.kq Cl, Br, I ;k F gSA
5-2-2 ,sfYdy gSykbMksa dk oxhZdj.k [Classification of Alkyl
Halides]
,sfYdy gSykbMksa dks rhu oxkZs esa foHkkftr fd;k x;k gS
¼1½ izkFkfed vFkok 1o ,sfYdy gSykbM [Primary or 1o alkyl halides]
buesa gSykstu ijek.kq izkFkfed dkcZu ijek.kq ls layXu jgrk gSaA mnkgj.k &
CH3 – CH2 – CH2 – CH2 – Br
CHCH
3CH
2Br
CH3
n&C;qfVy czksekbM vkblks C;wfVy czksekbM
¼1 czkseks C;wVsu½ 1 czkseks&2 esfFky izksisu
¼2½ f}rh;d vFkok 2o ,sfYdy gSykbM [Secondary or 2o alkyl halides]
buesa gSykstu ijek.kq 2o dkcZu ijek.kq ls layXu jgrk gSA
CH2CH
3CH CH
3
Br
CHCH
3CH
3
Cl
sec&C;qfVy czksekbM vkblks izksfiy DyksjkbM
¼2 czkseks C;wVsu½ 2&Dyksjks izksisu
¼3½ r`rh;d vFkok 3o ,sfYdy gSykbM~l [Tertiary or 3o alkyl halides]
buesa gSykstu ijek.kq 3o dkcZu ls layXu jgrk gSA
Cl
CH3
CH3
CH3
C
r`rh;d C;wfVy DyksjkbM
2&Dyksjks&2 esfFky izksisu
5-2-3 ukedj.k [Nomenclature]
¼1½ lkekU; fof/k & ,sfYdy gSykbM dk uke blesa mifLFkr ,sfYdy ewyd ds uke ij
fd;k tkrk gSA tSls &
CH3Cl & esfFky DyksjkbM
C2H5Br & ,fFky czksekbM
C3H7Br & izksfiy czksekbM
C3H7I & izksfiy vk;ksMkbM
C4H9X & C;wfVy gSykbM
buesa igys ,sfYdy lewg mlds ckn gSykstu dks gSykbM fy[kk tkrk gSA tSls &
Cl & Dyksjhu dks DyksjkbM
Br & czksehu dks czksekbM
lajpuk rFkk vkac/ku-I
171
F & ¶yksjhu dks ¶yqvksjkbM
I & vk;ksMhu dks vk;ksMkbM
X & gSykstu dks gSykbM
eksuks gSykstu O;qRiUuks esa gSykstu ijek.kq izkFkfed [P ;k 1o] f}rh;d [S ;k 2
o]
r`rh;d dkcZu ijek.kq [T ;k 3o] ls layXu gks ldrk gSA bl vk/kkj ij bUgs Øe’k%
izkFkfed [Primary], f}rh;d [Secondary] ,oa r`rh;d [Tertiary] ,sfYdy gSykbMks
esa oxhZd`r fd;k x;k gSA
¼2½ IUPAC ukedj.k & IUPAC uke i}fr ds vuqlkj &
(a) ,sfYdy gSykbMksa dks muds laxr ,sYdsuksa dk gSykstu izfrLFkkfir mRikn ekurs gSA
(b) gSykstu ijek.kq dh fLFkfr fn[kkus ds fy, dkcZu ijek.kq dh Øe la[;k dk mi;ksx
djrs gS ftlls ;s tqM+s jgrs gSA ftl dkcZu ijek.kq ls gSykstu tqM+k gksrk gS] mls
U;wUkre vad iznku djrk gSA fuEu lkj.kh esa dqN ,sYdsuksa ds eksuks gSykstu
O;`RiUuksa ds lw=] lekU; rFkk IUPAC uke fn;s x;s gS &
lw= [Formula]
lkekU; uke [Common Name]
IUPAC uke [IUPAC Name]
CH3Cl esfFky DyksjkbM DyksjksesFksu
3 2CH CH Cl ,fFky DyksjkbM Dyksjks,sFksu
3 2 2CH CH CH Cl n-izksfiy DyksjkbM 1&Dyksjksizksisu
3 3CH CHCl CH vkblks izksfiy DyksjkbM 2&Dyksjksizksisu
3 2 2 2CH CH CH CH Cl n-C;wfVy DyksjkbM 1&DyksjksC;wVsu
CHCH3
CH2
Cl
CH3
vkblks C;wfVy DyksjkbM 2&esfFky 1&Dyksjksizksisu
CH
2CH3
CH CH3
Cl
f}rh;d C;wfVy
DyksjkbM 2&DyksjksC;wVsu
CH3
CH3
CH3
Cl
C
r`rh;d C;wfVy
DyksjkbM
2&Dyksjks&2 esfFky
izksisu
leko;ork [Isomerism] mPprj ,fYdy gSykbM eq[;r% nks izdkj dh leko;ork iznf’kZr djrs gS &
¼1½ LFkku leko;ork [Position Isomerism]
¼2½ Ja[kyk leko;ork [Chain Isomerism]
¼1½ LFkku leko;ork & ;g ,sfYdy lewg dh dkcZu Ja[kyk ij gSykstu ijek.kq dh
fHkUUk fLFkfr;ksa ds dkj.k mRiUUk gksrh gSA
¼a½ CH
2CH3
CH2
CH2
Cl2 134
izkFkfed C;wfVy DyksjkbM ;k 1 Dyksjks C;wVsu
¼b½ CH
2CH3
CH CH3
Cl
2 134
f}rh;d C;wfVy DyksjkbM ;k 2 Dyksjks C;wVsu
¼2½ Ja[kyk leko;ork & ;g leko;ork leo;oh ;kSfxdksa dh dkcZu&Ja[kykvksa esa
varj gksus ls gksrh gSA
lajpuk rFkk vkac/ku-I
172
CH2CH
3CH
2CH
2Cl
2 134
2 13
CHCH3
CH2
Cl
CH3
1&Dyksjks C;wVsu
¼n&C;wfVy DyksjkbM½
1&Dyksjks 2 esfFky izksisu
¼vkblks C;wfVy DyksjkbM½
5-3 cukus dh fof/k;k¡ [Methods of preparation]
5-3-1 ,sYdsuksa ds lh/ks gSykstuhdj.k ls (From direct Halogenation of
Alkanes)
lw;Z ds izdk’k vFkok mRizsjd dh mifLFkfr esa ,saYdsuksa dh Dyksjhu vFkok czksehu ls
vfHkfØ;k gksus ij Øe’k% ,sfYdy DyksjkbM vkSj ,sfYdy czksekbM izkIr gksrs gSA ,sYdsuksa esa
gkbMªkstu ijek.kq ds gSykstu ijek.kq }kjk izfrLFkkiu Øe bl izdkj gS t > s > p
CH2CH
3ClCH
3CH3
+ HCl+ Cl225oC
izdk'k
CH2BrCH
3CH
3CH3
+ HBr+ Br225oC
izdk'k
CH3CH
2CH
3CH
2CH2
CH3
Cl CH3
CH
Cl
+ Cl225oC
izdk'k+ CH3
izksfiy DyksjkbM vkblksizksfiy DyksjkbM
45% 55%
gSykstu dh lfØ;rk dk Øe bl izdkj gS &
F > > > Cl > Br > > > I
vFkkZr ¶yksjhu dh rhozrk lokZf/kd] Dyksjhu o czksehu dh fØ;k’khyrk esa varj vf/kd ugh
,oa vk;ksMhu lcls de fØ;k’khy gksrk gSA
vk;ksMhuhdj.k dh fØ;k mRØe.kh; gksrk gSSA fØ;k esa cuh HI ,sfYdy gSykbM
dks vipf;r dj nsrk gSA
CH
4 + I
2CH
3I + HI
vk;ksMhuhdj.k dh fØ;k fdlh vkDlhdkj.k dh mifLFkfr tSls
HIO3/HNO3/HgO esa gksrh gS] tks HI dk vkDlhsdj.k dj nsrk gS vkSj fØ;k
mRØe.kh; ugh jgrhA
5HI + 5 HIO3 3I2 + 3H2O
2HI + 2 HNO3 2H2O + I2
CH4 + I2 3 3/HNO HIO
CH3I + HI
¶yksjhu dh fØ;k dHkh Hkh lh/kh ugh djkrs] D;ksfd blls foLQksV gks tkrk gSA
CH4 + 2 F2 4HF + C
lajpuk rFkk vkac/ku-I
173
5-3-2 ,sYdhuksa ds lkFk gkbMªkstu gSykbMksa ds la;ksx ls (From Addition of
HX with Alkenes)
tc ,sYdhuksa ij gSykstu vEyksa dk ;ksx gksrk gS rks ,fYdy gSykbM izkIr gksrs gSaA
CH2 = CH2 + HI CH3 – CH2I
vlefer ,sfYdu ij gSykstu vEyksa [HCl, HBr, HI] dk ;ksx ekdksZuhdkWd ds
fu;ekuqlkj gksrk gSA bl fu;e ds vuqlkj ß;ksxdkjh v.kq dk _.kkRed Hkkx f}d cU/k ds ml dkcZu ijek.kq ij tkrk gS] ftl ij gkbMªkstu ijek.kqvksa dh de la[;k layXu gksrh gSAÞ
CH
2 + HCHCH
3 CH3
CH
Br
Br CH3
2 czkseksizksisu
ijUrq dkcZfud ijkWDlkbM dh mifLFkfr ea vlefur ,sYdhu ij HBr dk ;ksx
ekdksZuhdkWd fu;e ds fo:} gksrk gSA ;g izHkko ijDlkbM izHkko vFkok [kjS’k izHkko
[Kharsch effect] dgykrk gSA
CH
2 + HCHCH
3 CH2BrCH
2Br
(C6H
5CO)
2O
2CH3
1 czkseks izksisu
5-3-3 ,sYdksgkWyksa ls (From alcohols)
,sYdksgkWy ds –OH lewg X dks ¼gSykstu½ ijek.kq }kjk foLFkkfir djus ls
,sfYdu gSykbM izkIr gksrs gksrk gSA
;g foLFkkiu fuEu vfHkdeZd }kjk fd;k tk ldrk gS &
(A) ,sYdksgkWy ij vEyksa dh fØ;k ls &
(a) ;g fØ;k futZy ZnCl2 vFkok lkUnz H2SO4 dh mifLFkfr esa dh tkrh gSA
ClROHRZnCl
2
+ H2O+ HClfutZy
OHC2H
5 ZnCl2
C2H
5Cl + H2O+ HCl
futZy
(b) ,sfYdy czksekbM izkIr djus ds fy, ,sYdksgkWy dks HBr ,oa lkanz H2SO4 dh
mifLFkfr es xeZ djrs gS vFkok ,sYdksgkWy dks KBr ,oa lkanz H2SO4 ds feJ.k ds
lkFk xeZ djrs gSA
2 5 2 5 22 4
H SOC H OH HBr C H Br H O
lkanz
2 4 4 2
RefluxR OH KBr H SO RBr KHSO H O
(c) ,sfYdy vk;ksMkbM cukus ds fy, ,sYdksgkWy dk fLFkj DoFkukadh HI ds lkFk Ik’p
okgu [Refluxing] fd;k tkrk gSA
3 2 3 2 2CH CH OH HI CH CH I H O
lajpuk rFkk vkac/ku-I
174
(B) ,sYdksgkWy ij QkLQksjl gSykbMks dh fØ;k ls&
(a) R–OH + PCl5 Reflux R – Cl + POCl3 + HCl
(b) R–OH ds lkFk PCl3 dh fØ;k ls &
3R–OH + PCl3 Reflux 3 RCl + H3PO3
(c) QkLQksjl Vªkb vk;ksMkbM ;k Vªkb czksekbM vfHkfØ;k ds le; ¶ykLd esa gh cuk;s
tkrs gSA vfHkfØ;k ¶ykLd esa ,sYdksgkWy vkSj yky QkLQksjl dk feJ.k ysdj czksehu
;k vk;ksMhu Mkyk tkrk gSA
2P + 3I2 2PI3
3C2H5 – OH + PI3 3C2H5 I + H3PO3
5-3-4 olk vEyksa ds jtr yo.kksa ls [From Silver Salts of Fatty acids]
fdlh olk&vEy ;k jtr yo.k Dyksjhu ;k czksehu ds lkFk lk/kkj.k rki ij vfHkfØ;k
dj ,sfYdy gSykbM cukrk gSA ;g vfHkfØ;k gqalfMdj vfHkfØ;k dgykrh gSA
mngkj.k &
R – COOAg + Cl2 R – Cl + CO2 + AgCl
CH2COOAg + Br2 CH3 – Br + CO2 + AgBr
5-3-5 gSykbM fofue; }kjk [By halide exchange]
tc ,sfYdy gSykbMksa dh vfHkfØ;k tSls&czkseks vFkok Dyksjks ,sYdsuksa dh ,slhVksu vFkok
esFkukWy esa lksfM;e vk;ksMkbM foy;u ds lkFk dh tkrh gS rks vk;ksMks,sYdsu izkIr gksrs
gSA
C2H5 – Br + NaI , slhVkus C2H5I + NaBr
5-3-6 jkbtksu dh fof/k [Rydon’s method]
,sYdksgkWy ij VªkbQsfuy QkLQsV dh mifLFkfr esa czksehu dh fØ;k ls ,sfYdy czksekbM izkIr
gksrk gSA
R – OH + Br2 + [C6H5O]3 PO RBr + BrPO [OC6H5]2 + C6H5OH
5-4 ,sfYdy gSykbMksa ds lkekU; xq.k [General properties of alkyl halides]
5-4-1 HkkSfrd xq.k [Physical Properties]
¼1½ HkkSfrd voLFkk [Physical state] - bl Js.kh ds dqN fuEurj ,sfYdy gSykbM
tSls CH3Cl, CH3Br rFkk CH3CH2Cl dejs ds rki ij xSl gS tcfd C18
rd ds ,fYdy gSykbM nzo gksrs gSA C18 ls mPp ,sfYdy gSykbM Bksl gksrs gSA
¼2½ jax vkSj xU/k [Colour and Smell] ’kq} voLFkk esa ;s jaxghu ryk ehBh xa/k okys
gksrs gSA
¼3½ foys;rk [Solubility] ,sfYdy gSykbM /kzqoh v.kq gksrs gS ,oa ty esa vfoys; gSA
bldk dkj.k ;g gS fd ,sfYdy gSykbM u rks ty ds lkFk gkbMªkstu cU/k cuk
ldrs gS vkSj u gh ty ds e/; igys ls mifLFkr gkbMªkstu cU/kks dks rksM+ ldrs
gSA
¼4½ xyukad rFkk DoFkukad [Melting and Boiling Points] ,sfYdy gSykbMksa ds
xyukad vkSj DoFkukad yxHkx leku v.kqekj okys ,sYdsuksa ds xyukadks rFkk
DoFkukadks ls vf/kd gksrs gSA ;g mudh vYi /kzqoh izd`fr ds dkj.k gksrk gSA vius
lajpuk rFkk vkac/ku-I
175
vf/kd vk.kfod nzO;eku ds dkj.k leku dkcZu ijek.kqvksa okys ,sYdsuksa dh vis{kk
,sfYdy gSykbMksa ds DoFkukad mPprj gksrs gSA
5-4-2 jklk;fud xq.k [Chemical properties] 5-4-2-1 ,sfYdy gSykbMks dh ukfHkd Lusgh izfrLFkkiu vfHkfØ;kvksa dh fØ;k&fof/k [Mechanism of Nucleophilic Substitution Reactions of Alkyl Halides]
,sfYdy gSykbMks esa gSykstu ijek.kq ml dkcZu dh vis{kk vf/kd fo/kqr_.kh gS]
ftlds lkFk og layXu gSA ifj.kkeLo:Ik dkcZu ijek.kq vkaf’kd /kukos’k rFkk gSykstu
ijek.kq vkaf’kd _.kkos’k xzg.k dj ysrk gSA
C Cl:
;k C X
dkcZu ijek.kq ij vkaf’kd /kukos’k gksus ds dkj.k ukfedLusgh bysDVªku U;wu
[electron, deficient] dkcZu ijek.kq ij vkØe.k dj vf/kd nqcZy ukfed&Lusgh gSykbM
vk;u dks foLFkkfir dj nsrk gSaA tc gSykbM vk;u ls vf/kd izcy ukfedLusgh ,sfYdy
gSykbM ds /kukosf’kr dkcZu ijek.kq ds fudV igaqprk gS rks gSykstu ijek.kq viu s vkcU/kh
bysDVªku ;qXe lfgr foLFkkfir gks tkrk gS vkSj dkcZu ijek.kq rFkk vUnj izos’k djus okys
ukfedLusgh ds e/; ,d vkcU/k cu tkrk gSA
: :Nu R X R Nu X foyk;d
ß,slh vfHkfØ;k;sa ftuesa ,d vf/kd izcy ukfedLusgh ,d vf/kd nqcZy
ukfedLusgh dks foLFkkfir djrk gS ukfedLusgh vfHkfØ;k;sa dgykrh gSA og ijek.kq vFkok
lewg tks fd vkcU/kh bysDVªku ;qXe ds lkFk fudy tkrk gS] vof’k"V lewg [leaving
group] dgykrk gSAÞ
5-4-2-2 ukfHkdLusgh izfrLFkkiu vfHkfØ;kvksa ds izdkj [Types of nucleophilic Substitution Reactions]
ukfHkdLusgh vfHkfØ;k,W nks izdkj dh gksrh gS &
¼1½ ,d v.kqd ukfedLusgh izfrLFkkiu vfHkfØ,W [Unimolecular nucleophilic
substitution reaction] SN1 vfHkfØ;k,W
¼2½ f} v.kqd ukfedLusgh izfrLFkkiu vfHkØ;k,W [Bimolecular nucleophilic
substitution reactions] SN2 vfHkfØ;k,A
¼1½ ,d v.kqd izfrLFkkiu vfHkfØ;k SN1
SN1 eas S = Substitution
N = Nucleophilic
1 = Unimolecular bu vfHkfØ;kvksa esa vfHkfØ;k dh nj dsoy ,sfYdy gSykbM ds lkUnz.k ij fuHkZj djrh
gSA ;g fØ;k nks inksa esa gksrh gSA
¼1½ igyk in [First step] - bl in esa ,sfYdy gSykbM dk fo"kHkkaxh fonyu gksrk
gSA ,oa dkcksZdSVk;u izkIr gksrk gSA
R X
/khek
R+ X+ dkcksZfu;e gSykbM
vk;u vk;u
lajpuk rFkk vkac/ku-I
176
¼2½ nwljk in [Second step] nwljs in esa dkcksZdsVk;u] ukfedLusgh ds lkFk rqjUr
vfHkfØ;k djds izfrLFkkiu mRikn cukrk gSA
R OH R OH rhoz
Li"Vhdj.k & vfHkfØ;k esa izFke in nwljs in dh vis{kk /khek gksrk gSA bldk
dkj.k ;g gs fd izFke in esa cuk dkcksZfu;e vk;u vLFkk;h gksrk gSA vfHkfØ;k ds osx
dk fu/kkZj.k /khesa in }kjk gksrk gS vr% izFke in laiw.kZ fØ;k dk osx fu/kkZj.k in gksrk
gSA pwafd osx fu/kkZjd in esa vfHkdkjdksa dk dsoy ,d v.kq ¼,sfYdy gSykbM½ Hkkx ysrk gS
bl dkj.k bls ,d v.kqd ukfHkd Lusgh izfrLFkkiu SN1 dgk tkrk gSA
vfHkfØ;k dh nj [RX]
vfHkfØ;k dh nj = k [RX]
mnkgj.k lkekU;r% r`rh;d ,sfYdy gSykbM SN1 }kjk vfHkfØ;k djrs gSA
Cl
CH3
CH3
CCH3
CH3
CH3
CCH3
Cl
/khek
+
r`rh;d dkcksZfu;e vk;u
OH
CH3
CH3
CCH3
CH3
CH3
CCH3
+ OH
rhoz
r`rh;d C;wfjy ,sYdksgkWy
¼2½ f} v.kqd ukfHkdLusgh izfrLFkkiu vfHkfØ;k SN2
SN2
esa & S = Substitution
N = Nucleophilic
2 = Bimolecular
SN2
vfHkfØ;k;s ,dy in vfHkfØ;k,¡ gksrh gS bldk rkRi;Z ;g fd ,sfYdy
gSykbM rFkk ukfHkd Lusgh nksuks gh vfHkfØ;k ds nj fu/kkZjd in esa vfHkfØ;k esa Hkkx ysrs
gSaA
....... .......R X O H HO R X HO R X
/khek rhoz
Li"Vhdj.k & pwafd ;g ,d i{kh; izde gS vr% tSls gh u;k ca/k curk gS] igys okyk
ca/k VwV tkrk gSA vfHkfØ;k esa ,d ,slk e/;orhZ curk gS ftlesa dkcZu ij fu"dkflr
gksus okys lewg ,oa izos’k djus okys lewg nksuks gh v)Z vkcaf/kr [Half bonded] gS bl
e/;orhZ dks laØe.k voLFkk [Transition state] dgrs gSA bl vfHkfØ;kvksa esa vfHkfØ;k
dh nj ,sfYdy gSykbM ,oa ukfHkd Lusgh nksuks gh ds lkUnz.k ij fuHkZj jgrh gSA
vfHkfØ;k dh nj [R–X] [OH–]
vfHkfØ;k dh nj = k [R–X] [OH–]
mnkgj.k & esfFky czksekbM dk {kkjh; ty vi?kVu dh vfHkfØ;k fuEu izdkj iznf’kZr dh
tk ldrh gSA
H O C : Br
H
H
H
OH C Br
H H
H
OH : Br
HH
H
C+/khek rhoz
+
lajpuk rFkk vkac/ku-I
177
pwafd bl ukfHkd Lusgh izfrLFkkiu vfHkfØ;k esa vfHkdkdksa ds nks v.kw ¼,sfYdy
gSykbM ,o aukfHkd Lusgh½ vfHkfØ;k fu/kkZfj.k in esa Hkkx ysrs gs blfy;s ;g f}v.kqd
ukfHkd Lusgh izfrLFkkiu vfHkfØ;k dgykrh gSA
5.4.2.3 SN1 rFkk SN
2 vfHkfØ;k esa varj [Difference between SN
1 and SN
2 Mechanism]
Ø SN1 fØ;kfof/k [SN
1 mechanism] SN
2 fØ;kfof/k [SN2 mechanism]
1 ;g nks inh; izde gS ;g ,d inh; izde gS
2 ,d v.kqd ;k izFke dksfV dh
vfHkfØ;k gSA
,d f}v.kqd vFkkZr f}rh; dksfV dh
vfHkfØ;k gSA
3 blesa cus mRikn dk jslhehdj.k gksrk
gS vFkkZr jsflfed feJ.k curk gSA
bl vfHkfØ;k esa cus mRikn ds v.kq dh
T;kfefr izkjafHkd v.kq ds foijhr gksrh gS
vFkkZr v.kq dk foU;kl izrhykseu gksrk gSA
4 laØe.k voLFkk ugh gksrh gS laØe.k voLFkk gksrh gS
5 dkcksZfu;d vk;u curk gSA dkcksZfu;d vk;u ugh curk gSA
6 mPp /kqzork okys foyk;d vuqdwy gksrs
gSA
fuEu /kqzork okys foyk;d vuqdwy gksrs gSA
7 vfHkfØ;k esa ,sfYdy gSykbMks dk
lfØ;rk Øe gksrk gS & r`rh;d >
f}rh;d > izkFkfed > esfFky gSykbM
vfHkfØ;k esa ,sfYdy gSykbMks dk lfØ;rk
Øe gksrk gS &esfFky gSykbM >
izkFkfed > f}rh;d > rrh;d ,ssfYdy
gSykbM
mtkZ js[kk fp= [Energy Profile Diagram] 5-4-2-3-1 SN
1 vfHkfØ;k dk mtkZ js[kkfp= & ;g fuEu js[kkfp= }kjk iznf’kZr fd;k
x;k gS ;g nks inksa esa gksus okyh vfHkfØ;k ds fy, gSA
SN1 vfHkfØ;k gsrq mtkZ js[kkfp=
bl vfHkfØ;k ds izFke in esa ,sfYdy gSykbM dk vkeuhdj.k gksrk gS ;g ean
in gksrk gSA
Br
CH3
CH3
CCH3
CH3
CH3
CCH3
Brean
+
lajpuk rFkk vkac/ku-I
178
r`rh;d C;wfVy czksekbM r`rh;d C;wfVy /kuk;u
nwljs in esa ukfHkd Lusgh vfHkdeZd dh r`rh;d C;wfVy /kuk;u ls fØ;k gksrh
gs ;g rhoz fØ;k ij gSA
OH
CH3
CH3
CCH3
CH3
CH3
CCH3
OH
rhoz
+
mijksDr fp= n’kkZrk gS fd dkcksZfu;e ds fuekZ.k esa vf/kdre vko’;d mtkZ
yxrh gS ,oa mlds cuus ds ckn ukfHkd Lusgh vfHkdeZd ds lky Rofjr fØ;k gksdj
mRikn curk gSA
5-4-2-3-2 SN2 vfHkfØ;k dk mtkZ js[kkfp= & ;g fuEu js[kkfp= }kjk iznf’kZr fd;k
x;k gS ;g vfHkfØ;k ,d in esa gksrh gS bl izdkj dh vfHkfØ;k esa dksbZ ek/;fed ;ksfxd
ugh curk gS ijUrq ,d laØe.k voLFkk vkrh gSA
SN2 vfHkfØ;k gsrq mtkZ js[kkfp=
bl vfHkfØ;k esa ukfHkd Lusgh dk vkØe.k ihNs ls gksrk gS rFkk gSykbM vk;u
lkeus ls fudyrk gS ifj.kke Lo:i SN2 vfHkfØ;kvksa esa foU;kl dk izfrykseu gksrk gSA
C
H
OH C Br OH
H
CBr
HH HH
H
HH
BrOH +
+
laØke.k voLFkk
mijksDr fp= n’kkZrk gS fd lfØ;.k mtkZ gh ek= mtkZ (E) fufeÙk vojks/k gS
rFkk ,d ukfHkd Lusgh vfHkfØ;k gsrq vko’;d gksrk gSA dkcZu ijek.kq ij tqM+s lewgks dh
la[;k vFkok vkdkj c<+us ij E dk eku c<+rk gSA
5-4 ,sfYdy gSykbMks dh ukfHkd&Lusgh izfrLFkkiu vfHkfØ;k, [Nucleophilic substitution Reaction in Alkyl Halides]
5-4-1 - (a) ,sfYdy gSykbM dh fØ;k 'kq"d bZFkj dh mifLFkfr eas
lksfM;e ds lkFk dh tk, rks ,sYdsu curs gSA ;g fØ;k o`VZ~t vfHkfØ;k dgykrh gSA
lajpuk rFkk vkac/ku-I
179
2 2R X Na X R R R NaX 'kq"d bFZ kj
3 3 3 32 2CH Br Na Br CH CH CH NaBr 'kq"d bFZ kj
¼b½ ,sfYdy gSykbM dh fØ;k 'kq"d bZFkj ds LFkku ij Zn dh mifLFkfr esa gks rks
Hkh ,sYdsu curk gSA ;g fØ;k ÝSadyS.M vfHkfØ;k dgykrh gSA
2
ZnR X Zn X R R R ZnX
2 5 2 5 2 5 2 5 2
ZnC H Br Zn Br C H C H C H ZnBr
5-4-2 ,sfYdy gSykbMksa ij lksfM;e ,FkkukbM dh
vfHkfØ;k }kjk mPprj ,Ydkbu izkIr gksrs gSA
2 5 2 5C H I Na C C H C H C C H NaI
1 C;wVkbu
5-4-3 ¼1½ lksfM;e ,sYdkWDlkbM dh fØ;k ls&,sfYdy gSykbM ij
lksfM;e ,sYdkWDlkbM dh fØ;k ls bZFkj izkIr gksrs gSA
3 3 3 3CH I NaO CH CH O CH NaI
lksfM;e esFkkWDlkbM MkbesfFky bZFkj
flyoj vkDlkbM dh fØ;k ls & ,sfYdy gSykbM ij flYoj vkDlkbM dh
vfHkfØ;k }kjk bZFkj curs gSA
3 2 3 3 3 2CH I Ag O CH I CH O CH AgI
5-4-4 ,sfYdy gSykbMksa ij tyh;
dkfLVd iksVk’k (KOH) ;k mcyrs gq;s ty esa fuyfEcr flYoj vkDlkbM dh fØ;k
ls ,sYdksgkWy izkIr gksrs gSA
2 5 2 5C H Cl KOH C H OH KCl
tyh;
3 2 2 32 2CH I Ag O H O CH OH AgI
5-4-5 ,sfYdy gSykbMksa dks Bksl ;k ,sYdksgkWfyd
KCN ds lkFk xeZ djus ij ,fYdy lkbukbM curs gSA
R I KCN R CN KI
3 3CH I KCN CH CN KI
bl vfHkfØ;k dk mi;ksx ltkrh; Js.kh ds vkjksg.k esa vFkkZr Ja[kyk esa ,d
dkcZu ijek.kq tksM+us esa gksrk gSA
5-4-6 k esa & ,sfYdy gSykbMksa ij flYoj
lk;ukbM dh vfHkfØ;k ls vk;lkslk;ukbM curs gSA
R I AgCN R N C+ + AgI
I AgCN N CCH
3CH
3+ + AgI
5-4- tc ,sfYdy gSykbMksa dks veksfu;k ds tyh;
vFkok ,sYdksgkWyh foy;u ds lkFk ,d can uyh esa 100oC ij xeZ fd;k tkrk gS] rc
fofHké ,sehu rFkk prq"d veksfu;e yo.k dk feJ.k curk gSA
2 5 3 2 5 2C H Br NH C H NH HBr
,sfFky ,sehu ¼izkFkfed ,sehu½
lajpuk rFkk vkac/ku-I
180
2 5 2 2 5 2 5 2 5C H NH BrC H C H NH C H
MkbZ ,fFky ,sehu ¼f}rh;d ,sehu½
C2H
5NH C
2H
5Br C
2H
5
C2H
5
C2H
5
C2H
5N+
VªkbZ ,sfFky ,sehu ¼r`rh;d ,sehu½
Br C2H
5
C2H
5
C2H
5
C2H
5N +
2 5 4C H N Br
VsVªk ,sfFky veksfu;e czksekbM
¼prq"d veksfu;e ;kSfxd½
5-4-8 ukbVªks ,sYdsu dk cuuk & flYoj ukbVªsV ds lkFk ,sfYdy gSykbM dh
vfHkfØ;k }kjk ukbVªks ,sYdsu izkIr gksrs gSA
3 2 3 2CH I AgNO CH NO AgI
5-4-9 ,sfYdy gSykbM ikSVsf’k;e ukbVªkbV ds lkFk
,sfYdy ukbVªkbM cukrs gSA
3 2 3CH I KNO CH O N O KI
esfFky ukbVªkbM
5-4-10 Fkk;ks,sYdksgkWy ;k edsZIVuksa dk la tc ,sfYdy gSykbM dks tyh;
iksVSf’k;e gkbMªkstu lYQkbM ds lkFk xeZ fd;k tkrk gS] rc Fkk;ks ,sYdksgkWy ;k edsZIVu
curs gSA
3 3CH I KSH CH SH KI
Fkk;ks ,sYdksgkWy
5-4- ,sfYdy gSykbM dh fØ;k lksfM;e ;k iksVSf’k;e
lYQkbM ls djk;h tkrh gS] rks Fkk;ks bZ;j izkIr gksrs gSA
3 2 3 3 3 2CH I Na S CH I CH S CH NaI
Mkb esfFky Fkk;ks bZFkj
5-4-12 futZy AlCl3 dh mifLFkfr esa ,sfYdy gSykbM]
cSathu ds lkFk fØ;k dj ,sfYdy cSthu cukrs gSA
CH3I + C
6H
6 AlCl3
C6H
6 CH
3 + HI
futZy
esfFky cSathu@VkWyqbZu
5-4- esfFky ,sYdksgkWy ;k ,slhVksu dh
mifLFkfr esa ,sfYdy DyksjkbM lksfM;e vk;ksMkbM ls fØ;k dj ,sfYdy vk;ksMkbM cukrk
gSA
3 3CH CI NaI CH I NaCI
5-4-14 ,sfYdy gSykbM eSXuhf’k;e] fyfFk;e]
ftad] ySM vkfn ds lkFk ’kq"d bZFkj dh mifLFkfr esa fØ;k dj dkcZ/kkfRod ;ksfxd cukrs
gSA
lajpuk rFkk vkac/ku-I
181
3 3CH I Mg CH MgI
'kq"d bFZ kj
,sfYdy eSXuhf’k;e gSykbM
2 5 2 52C H Br Li C H Li LiBr 'k"q d bZFkj
,fFky yhfFk;e
2 5 2 5 222C H Br Zn C H Zn ZnBr
'kq"d bZFkj
Mkb,sfFky ftax
2 5 2 5 44 4 4 3C H Br PbNa C H Pb NaBr Pb
'k"q d bFZ kj
lksfM;e ySM VsVªk,fFky ySM
feJ/kkrq TEL
5-5 ikWyh gSykstu ;ksfxd (Poly Halogen Compounds)
tc fdlh dkcZu ;ksfxd esa ,d ls vf/kd gSykstu ijek.kq mifLFkr gks rks os ikWyh
gSykstu ;ksfxd dgykrs gS tSls&Mkb gsykstu O;qRiUu] Vªkb gSykstu O;qRiUUk] VsVªkgSykstu
O;qRiUUk vkfnA
5-5-1 DyksjksQkeZ vFkok VªkbDyksjksesFksu (Chloroform or
Trichloromethane)
DyksjksQkeZ ty vi?kVu djus ij QkWfeZd vEy nsrk gS] blfy, bldk uke DyksjksQkeZ
j[kk x;k gSA bldh fu’psrd fØ;k dh [kkst loZizFke flEilu us 1815 esa dh vkSj rHkh
ls ;g vc rd fu’psrd ds :i esa iz;ksx gks jgk gSA
5-5-1-2 cukus dh fof/k;k (Methods of Preparation)
5-5-1-2-1 d fof/k & nksuks gh Lrj ij ,fFky ,sYdksgkWy vFkok
,slhVksu ij fojatd pw.kZ o ty dh vfHkfØ;k }kjk DyksjksQkeZ cuk;k tkrk gSA
fojatd pw.kZ ty dh fØ;k ls Dyksjhu ,oa dSfYl;e gkbMªkDlkbM cukrk gSA
2 22Ca OCl Cl H O Ca OH Cl
fojatd pw.kZ
(A) ,sYdksgkWy ls DyksjksQkeZ & Dyksjhu ,sYdksgkWy ds lkFk nks izdkj ls dk;Z djrk gSA
(a) vkDlhdj.k ds :Ik esa (b) Dyksjksuhdkjd ds :Ik esa
(i) fojatd pw.kZ ls izkIr Dyksjhu] ,sYdksgkWy dks ,slsVSfYMgkbM esa vkDlhdr djrh gSA
3 2 2 3 2CH CH OH Cl CH CHO HCl
,slsVSfYMgkbM
(ii) ,lsfVYMgkbM ds Dyksjhuhdj.k ls DyksjSy izkIr gksrk gSA
3 2 33 3CH CHO Cl CCl CHO HCl
DyksjSy
(iii) DyksjSy dSfYl;e gkbMªkDlkbM }kjk ty vi?kfVr gksdj DyksjksQkeZ cukrk gSA
3 2 3 22 ( ) 2CCl CHO Ca OH CHCl HCOO Ca
DyksjksQkeZ
,slhVksu ls DyksjksQkeZ&
¼1½ igys ,slhVksu] Dyksjhu ls fØ;k dj VªkbDyksjks,slhVksu cukrk gSA
3 3 2 3 33 3CH COCH Cl CCl COCH HCl
lajpuk rFkk vkac/ku-I
182
VªkbDyksjks,slhVksu
¼2½ VªkbDyksjks,slhVksu] dSfYl;e gkbMªkDlkbM }kjk ty vi?kfVr gksdj DyksjksQkeZ cukrk
gSA
3 3 3 32 22 2CCl COCH Ca OH CHCl CH COO Ca
DyksjksQkeZ
,d xksy isanh ds ¶ykLd eaas 100xzke] fojtad pw.kZ ,oa 200 ml ty
ls cuh gqbZ ysbZ ysrs gSA blesa 25ml ,fFky ,YdksgkWy ;k ,slhVksu Mkydj ckyw m"ed ij
/khjs&/khjs xeZ djrs gSSA
DyksjksQkeZ ty lfgr vklfor gksdj xzkgh ¶ykLd esa ,df=r gks tkrk gSA ty
ls Hkkjh gksus ds dkj.k DyksjksQkeZ uhps cSB tkrk gS rFkk izFkd ijr cuk ysrk gSA ,d
izFkddkjh dhi dh lgk;rk ls DyksjksQkeZ dh fupyh ijr dks vyx dj fy;k tkrk gSA
bl izdkj izkIr DyksjksQke Z v’kq} gksrk gSA bl v’kq} DyksjksQkeZ dks ruq NaOH foy;u
vkSj ty ls /kksdj laxfyr dSfYl;e DyksjkbM ij lq[kk ysrs gSA bldk iqu% vklou
djus ij 60&62oC ij ’kq} DyksjksQkeZ izkIr gksrk gSA
5-5-1-2-2 DyksjygkbMªsV dks lksfM;e gkbMªkDlkbM
foy;u ds lkFk vklfor djus ij ’kq} DyksjksQkeZ izkIr gksrk gSA
3 2 3CCl CHO H O NaOH CHCl HCOONa vklou
DyksjksQkeZ lksfM;e QkesZV
5-5-1-2-3 vkS/kksfxd fof/k;k¡ & ¼i½ esFksu ds Dyksjhuhdj.k }kjk & lw;Z ds /kaq/kys izdk’k dh mifLFkrh esa esFksu dh
Dyksjhu ls fØ;k djkus ij DyksjksQkeZ izkIr gksrk gSA
lw;Z dk
/kqa/kyk izdk'k
CHCl3 + HClCH4 + 3Cl2
¼ii
vkS/kksfxd Lrj ij DyksjksQkeZ] dkcZu VsVªkDyksjkbM ds ykSg pw.kZ vkSj ty ds }kjk vkaf’kd
vip;u ls izkIr fd;k tkrk gSA
4 32
/2
Fe H OCCl H CHCl HCl
bl izdkj izkIr DyksjksQkeZ ’kq} ugh gksrk] blfy, bldk mi;ksx foyk;d ds :Ik
fd;k tkrk gSA
¼iii½ fo/kqr vi?kVd }kjk & tyh; ,slhVhu vFkok ,sYdksgkWy esa cus gq;s 20% NaCl dk fo|qr vi?kVu }kjk ’kq} DyksjksQkeZ izkIr gksrk gSA
vfHkfØ;k,W fuEu inksa esa gksrh gS &
¼i½ vk;uu
lajpuk rFkk vkac/ku-I
183
NaCl Na+ + Cl
¼ii½ dSyksM ij lksfM;e ty ls fØ;k djrk gSA
Na+ + e
Na
2Na + 2H2O 2NaOH + H2
¼iii½ ,uksM ij eqDr gqbZ Dyksjhu ,sYdksgkWy vFkok ,slhVksu ds lkFk fØ;k dj DyksjSy
vFkok VªkbDyksjks,lhVksu curh gSA
Cl e Cl
2 Cl Cl2
C2H5OH + Cl2 CH3CHO + 2HCl
CH3CHO + 3Cl2 CCl3CHO + 3HCl
CH3COCH3 + 3Cl2 CCl3COCH3 + 3HCl
in (iii) esa cuk DyksjSy ;k VªkbDyksjks ,slhVksu in (ii) esa cus NaOH ls vfHkfØ;k dj
DykjksQkeZ cukrk gSA
CCl3CHO + NaOH CHCl3 + HCOONa
CCl3CO CH3 + NaOH CHCl3 + CH3COONa
5-5-1-2 HkkSfrd xq.k (Physical Properties) ¼1½ DyksjksQkeZ ,d jaxghu] e/kqj xa/k okyk xk<+k ok"i’khy nzo gSA
¼2½ DoFkuakd 61oC ,ao ok"i ?kuRo 1-485 gSA
¼3½ ty esa cgqr de ?kqyu’khy gS] fdUrq bZFkj ,oa ,sYdksgkWy esa vR;ar ?kqyu’khy gSA
¼4½ ;g ,sjksesfVd ;ksfxdksa dh Hkk¡rh /kwfey Tokyk nsrk gqvk tyrk gS
¼5½ dkcZfud inkFkZ tSls & rSy] olk rFkk jsftu vkfn ds fy, foyk;d ds :Ik esaA
¼6½ blds ok"i dk fo’olu (Inhalation) djus ij vLFkk;h vpsr voLFkk mRiUu
gksrh gS] blfy, bldk mi;ksx fu’psrd ds :Ik esa gksrk gSA
5-5-1-3 jklk;fud xq.k (Chemical properties)
¼1½ vkDlhdj.k & ok;q rFkk izdk’k dh mifLFkfr esa DyksjksQkeZ dk /khjs&/khjs vkDlhdj.k
gks tkrk gS vkSj ,d fo"ksyh xSl QWkLthu ;k dkcksZfuy DyksjkbM cukrk gSA
ok;q rFkk
lw;Z dk izdk'k
2CHCl3 + O2 2COCl2 + 2HCl
ok;q dk vf/kD;
lw;Z dk izdk'k
4CHCl3 + 3O2 4COCl2 + Cl2 + 2H2O
(Anaesthetic chloroform) & [kqys ok;qe.My ;k [kqyh ’kh’kh
esa j[ks DyksjksQkeZ esa vkDlhdj.k gksus ds dkj.k ,d fo"kyh xSl QkLthu curh gSA vr%
,sls DyksjksQkeZ dks vLirkyksa esa fu’psrd ds :Ik esa iz;ksx esa ugh yk;k tk ldrk A
vr,o fu’psrd ds :Ik esa iz;qDr gksus okys DyksjksQkeZ dks j[kus ds fy, fuEu lko/kkfu;kW
cjrh tkrh gS &
¼1½ bls dkWp dh uhys ;k Hkwjs jax dh cksry esa eqg rd Hkjdj MkV yxkdj j[kk
tkrk gSA ,slk djus ls izdk’k rFkk ok;q nksuksa dh izHkko ugh gksrk gSA
¼2½ bles yxHkx 1% ,fFky ,sYdksgkWy feyk fn;k tkrk gS ftlls ;g
DyksjksQkeZ dk vkDlhdj.k jksd nsrk gS vkSj ;fn vkDlhd`r gksdj QkWLthu
cus Hkh oks og ,sYdksgkWy ls vfHkfØ;k djds ,fFky dkcksZusV cuk nsrk gS tks
fd fo"ksyk ;ksfxd ugh gSA
2 2 5 2 5 322COCl C H OH C H CO HCl
,fFky dkcksZusV
lajpuk rFkk vkac/ku-I
184
¼2½ vip;u Reduction - ¼1½ ftad rFkk dh mifLFkfr esa vip;u gksus ij esfFkyhu
DyksjkbM curk gSA
3 2 2
/2 Zn HClCHCl H CH Cl HCl
esfFkyhu DyksjkbM
¼2½ ftad rFkk ty ds lkFk vip;u ij ehFksu curk gSA
3 4
/26 3
Zn H OCHCl H CH HCl
¼3½ ty vi?kVu (Hydrolysis) lkUnz KOH ds tyh; foy;u ds lkFk mckyus
ij DyksjksQkeZ dk ty vi?kVu gks tkrk gS vkSj iksVsf’k;e QkesZV curk gSA
CHCl3 + 3 KOH CH(OH)3 + 3KCl
CH(OH)3 HCOOH + H2O
HCOOH + KOH HCOOK + H2O
CHCl3 + 4 KOH HCOOK + 3KCl + H2O iksVsf’k;e QkesZV
¼4½ Dyksjksuhdj.k (Chlorination) lw;Z ds /kqa/kys izdk’k esa Dyksjhu ls DyksjksQkeZ
fØ;k djds dkcZu VsVªkDyksjkbM cukrk gSA
CHCl3 + Cl
2CCl
4 + HCl
lw;Z dk /kaq/kyk
izdk'kdkcZu VsVªk
DyksjkbM
¼5½ ukbVªhdj.k (Nitration) lkUnz ukbfVªd vEy dh DyksjksQkeZ ls vfHkfØ;k gksus ij
DyksjksfiØfju uked vfr fo"ksyk inkFkZ curk gSA
CHCl3 + HNO3 CCl3 NO2 + H2O DyksjksfifØu
¼6½ dkcZy ,sehu vfHkfØ;k (Carbylamine reaction) tc DyksjksQkeZ dks fdlh
,yhQsfVd ;k ,sjksesfVd izkFkfed vehu rFkk ,sYdksgkWyh; dkfLVd iksVk’k ds lkFk xeZ
fd;k tkrk gS rks ,d vR;ar nqxZU/k;qDr inkFkZ vkblkslk;ukbM curk gS bl inkFkZ dks
dkfcZy ,sehu dgrs gSA
CHCl3 + C
2H
5 NH
2 + KOH C
2H
5N C + KCl + H
2O33 3
,fFky vkblks lk;ukbM
CHCl3 + C
6H
5 NH
2 + KOH C
6H
5N C + KCl + H
2O3
Qsfuy vkblks lk;ukbM
¼7½ ,slhVksu ds lky la?kuu (Condesation with acetone) DyksjkQkeZ ,slhVksu
ds lkFk vfHkfØ;k djds DyksjhVksu cukrk gS ;g ,d funzkdkjh inkFkZ ds :i esa dke vkrk
gSA
CCl3
C
OH
CH3
CH3
KOHC
O
CH3
CH3 CHCl
3+
DyksjhVksu
¼8½ fogSykstuhdj.k (Dehalogenation) jtr pw.kZ ds lkFk mPp rki ij xeZ djus
ls fogSykstuhdj.k }kjk ,slsfVyhu izkIr gksrk gSA
CHCl3 + 6Ag + CHCl3 CHCH + 6AgCl
lajpuk rFkk vkac/ku-I
185
¼9½ jkbej VheSu vfHkfØ;k (Reimer Tiemann Reaction) tc DyksjksQkeZ vkSj
Qhuky dks 60-70oC ij izcy {kkj KOH ds lkFk xeZ fd;k tkrk gS rks
lSfyflYMhgkbM eq[; mRikn ds :i esa izkIr gksrk gSA
OH OH
CHO
+ CHCl3 + 3KOH + 3KCl + 2H2O
lSfyflYMhgkbM
mi;ksx (Uses) ¼1½ iz;ksx’kkyk esa foyk;d ds :i esA
¼2½ 'kq"d /kqykbZ (Dry cleaning) esa A
¼3½ 30% bZFkj ds lkFk feykdj 'kY; deZ esa ,d lkekU; fu’psrd ds :i esaA
¼4½ izkFkfed ,sehuksa ds ijh{k.k esaA
¼5½ jksxk.kquk’kd ds :i esaA
DyksjksQkeZ dh 'kq)rk dk ijh{k.k (Test for Purity of chloroform) ¼1½ 'kq) DyksjksQkeZ flyoj ukbVªsV ds lkFk dksbZ vo{ksi ugh nsrkA
¼2½ lkanz H2SO4 ds lkFk fgykus ij ihyk jax ugh nsrkA
¼3½ uhys fyVel dks yky ugh djrkA
5-6 dkcZu VsVªkDyksjkbM (Carbon tetrachloride)
5-6-1 cukus dh fof/k;k¡ (Methods of preparation)
¼1½ ehFksu ds Dyksjhuhdj.k }kjk & bls ehFksu ds Dyksjhuhdj.k }kjk cuk;k tk ldrk
gSA
CH4 + 4Cl2 h CCl4 + 4HCl
¼2½ dkcZu MkbZ lYQkbM ij Dyksjhu dh fØ;k ls & tc dkcZu Mkb lYQkbM ,oa
Dyksjhu dh fØ;k mRizsjd yksgs] vk;ksMhu vFkok ,sUVheuh isUVkDyksjkbM dh mifLFkfr esa
dh tkrh gS rks dkcZu VsVªkDyksjkbM curk gSA
CS2 + Cl2 o20 40 C CCl4 + S2Cl2
2 S2Cl2 + CS2 CCl4 + 6S
¼3½ DyksjksQkeZ ij Dyksjhu dh fØ;k }kjk & DyksjksQkeZ ij lw;Z ds izdk’k esa vFkok
mRizsjd vk;ksMhu dh mifLFkfr esa Dyksjhu dh fØ;k }kjk dkcZu VsVªkDyksjkbM izkIr fd;k
tk ldrk gSA
CHCl3 + Cl2 idz k'k CCl4 + HCl
5-6-2 HkkSfrd xq.k (Physical properties)
¼1½ ;g ,d jaxghu] nqxZU/k;qDr Hkkjh nzo gSA
¼2½ bldk DoFkukad 77oC gSA
¼3½ ty esa vfoys; fdUrq ,sYdksgkWy] bZFkj vkfn dkcZfud foyk;dks esa foys;A
¼4½ ;g vToyu’khy ,oa fo"ksyk gksrk gSA
¼5½ bldk fof’k"V ?kuko 1-585 gSA
5-6-3 jklk;fud xq.k (Chemical Properties)
¼1½ vip;u & yksg pw.kZ rFkk ty ds lkFk mip;u ij DyksjksQkeZ cuk gSA
CCl4 + 2H 2Fe/H O
CHCl3 + HCl
¼2½ Hkki ds lkFk vfHkfØ;k & bldh ok"i mPp rki ij Hkki ds lkFk vfHkfØ;k dj
QkLthu cukrk gSA
lajpuk rFkk vkac/ku-I
186
CCl4 + H2O o500 C COCl2 + 2HCl
ØkfLVd iksVk’k ds lkFk ty
vi?kfVr gksdj iksVsf’k;e dkcksZusV nsrk gSA
Cl
C
Cl
ClCl
OH
C
OH
OHOH+ 4KOH + 4KCl
vkxkeh 2H2O
K2CO3 + H2OCO2 + 2KOH
¼4½ jkbej VheSu vfHkfØ;k
{kkj dh mifLFkfr esa Qhuky ds lkFk vfHkfØ;k dj lSfyflfyd vEy cukrk gSA
OH OH
COOH
+ CCl4 + 4KOH + 4KCl + 2H2O
lSfyflfyd vEy
mi;ksx (Uses) ¼1½ ik;jhu ds uke ls ,d vfXu’kked ds :i esaA
¼2½ rsy] olk] jsftu vkfn ds fy, ,d foyk;d ds :i esaA
¼3½ ,d iz;ksx’kkyk vfHkdeZd ds :i esaA
¼4½ ,d dhVuk’kd ryk vukt /kwezd ds :i esaA
¼5½ d`fe fu"dklu vkS"kf/k ds :i esaA
¼6½ 'kq"d /kqykbZ esaA
5-7 ,sfjy gSykbM [Aryl Halides]
ß,sjkSfed gkbMªksdkcZu ¼cSathu vkSj mlds ltkrh;] VkWyqbZu] tkbyhu vkfn½ rFkk
gSykstu dh vfHkfØ;k ls cus mRikn ,sjkseSfVd gSykstu ;kSfxd dgykrs gSAÞ ;s nks izdkj
ds gksrs gS &
(A) ;ksxkRed gSykstu ;kSfxd
(B) izfrLFkkfir gSykstu ;kSfxd
5-7-1 ;ksxkRed gSykstu ;kSfxd [Addition Halogen Compound]
os ,sjksesfVd gSykstu O;qRié tks ,sjksesfVd gkbMªksdkcZu ds cSathu fjax ds
dkcZu&dkcZu f}ca/k ij gSykstu ijek.kqvksa ds ;ksx ls curs gSA
bl izdkj ds ;kSfxd vLFkk;h gksrs gSA Mkb ,oa VsVªk ;ksfxd ugh curs gS dsoy
gsDlk O;qRié gh curs gSA ;k lw;Z ds izdk’k esa cSathu ls fØ;k dj ;ksxkRed ;kSfxd
cukrs gSA tSls&cSathu gSDlk DyksjkbM] cSathu gSDlkczksekbM
ClHCCHCl
CHCl
CHCl
CHCl
ClHCC
6H
6Cl
6
UV+
lw;Z dk izdk'k
3Cl2vFkok
vFkok
lajpuk rFkk vkac/ku-I
187
cSathu cSathu gSDlkDyksjkbM
blh izdkj cSathu gSDlkczksekbM
BrHCCHBr
CHBr
CHBr
CHBr
BrHCC
6H
6Br
6
UV+
lw;Z dk izdk'k
3Br2vFkok
vFkok
cSathu gSDlkczksekbM
5-7-2 izfrLFkkfir gSykstu ;kSfxd [Substituted Hallogen Compound]
ßos gSykstu O;qRié ftuesa] gSykstu ijek.kqvksa dk gkbMªkstu ijek.kqvksa dh txg
izfrLFkkiu gksrk gS izfrLFkkfir gSykstu ;kSfxd dgykrs gSaAÞ ;s nks izdkj ds gksrs gS &
(i) ukHkdh; izfrLFkkiu mRikn
(ii) ik’oZ Ja[kyk izfrLFkkiu mRikn
(i) ukHkdh; izfrLFkkiu mRIkkn ;k ,sfjy gSykbM [Nuclear substitution
compounds or Aryl halides]
os gSykstu ;kSfxd tks cSUthu ukfHkd ds gkbMªkstu ijek.kq dks gSykstu ijek.kq
}kjk izfrLFkkfir djus ij curs gS] tSls &
Cl
CH3
Cl
Br
I
Dyksjks cSathu o-Dyksjks VkWywbZu czksekscSathu vkbMks cSathu
Br
Br
Cl
Cl
p-MkbczksekscSathu o-MkbDyksjkscSathu
(ii) ;k ,sjSfYdy gSykbM ;k ,sfjy gSyks ,sYdsu [Side Chain Substitution Product or Aralkyl Halide or Aryl
Halo Alkane]
;s os ;kSfxd gS ftlesa gSykstu ijek.kq ,sjkseSfVd ;kSfxd dh ik’oZ Ja[kyk ls tqM+k
gksrk gSA tSls&
CH2Cl
CHCl2
CCl3
cSfUty DyksjkbM cSUty DyksjkbM cSUtks DyksjkbM
mi;qZDr lHkh ;ksfxdkasa esa ,d ,sjSfYdy ewyd gksrk gS vr% ;s ,sjSfYdy gSykbM Hkh
dgykrs gSA buesa gSykstu ijek.kq ,sfYdy gSykbMksa dh vi s{kk vf/kd fØ;k’khy gksrs gSA
lajpuk rFkk vkac/ku-I
188
5-8 ,sfjy gSykbM ;k ukfHkdh; gSykstu O;qRié
[Aryl Halides or Nuclear Halogen derivatives]
5-8-1 cukus dh lkekU; fof/k;k¡ [General methods of Preparation]
(1) izR;{k gSykstuhdj.k [By Direct Halogenation] - ;g fof/k Dyksjks rFkk czkseks
O;qRié cukus ds fy;s mi;qDr gSA tc ,sjkseSfVd] gkbMªksdkcZu gsykstu [Cl2 ;k Br2] ds
lkFk dejs ds rki ij va/ksjs esa fdlh gSykstu okgd [Fe, I, P vkfn] dh mifLFkfr esa
fØ;k djrk gS] rc ,fjy gSykbM curk gSA Qssfjd gSykbMks rFkk ,Y;weksfu;e gSykbMksa dk
mi;ksx Hkh fd;k tkrk gSA gSykstu o gkbMªksdkcZu dk vuqikr cjkcj (1:1) gks rks
eksuksgsykstu O;qRié curk gSA
Cl2
FeCl3
AlCl3
Cl
+;k
+ HCl
cSathu DyksjkscSathu
fØ;kfof/k [Mechanism]
;g fof/k fuEufyf[kr inksa esa iw.kZ gksrh gS &
(i) +
3 4Cl Cl AlCl Cl AlCl
Dyksjksfu;e
vk;u
(ii) Dyksjhfu;e vk;u bysDVªku Lusgh vfHkdeZd gksrk gS tks fd cSathu] ukfHkd ij
vkØe.k djrk gSA ;g ,d ean vfHkfØ;k gS] ftlesa Dyksjhu layXu dkcksZfu;e vk;u
curk gSA ;g dkcksZfu;e vk;u vuqukn }kjk LFkkf;Ro izkIr djrk gSA blds 4bysDVªku
dk foLFkkiuhdj.k gksdj vuqukn ladj cu tkrk gSA
Cl
ClH
ClH
ClH
ClH
+ +
(iii) vuqukn ladj 4AlCl dh mifLFkfr esa izksVku R;kxdj Dyksjks cSathu cukrk gSA ;g
,d rhoz vfHkfØ;k gSA
AlCl4
ClClH
HCl + AlCl3++ +
;fn Dyksjhu dh ek=k vf/kd gks tk, rks eksuks ds LFkku ij Mkb izfrLFkkfir
gSykstu O;qRié cu tkrk gSA
Cl2
Cl
ClFeCl
3
AlCl3
Cl
Cl
+ +;k
cSathu vf/kD; o-MkbDyksjks cSathu p-Mkb Dyksjks cSathu
lajpuk rFkk vkac/ku-I
189
vk;ksMks&O;qRié & lh/ks vk;ksMksuhdj.k ls ugh cukrs] D;ksfd fØ;k vØe.kh; gks tkrh
gSA blfy;s bls fdlh vkDlhdkjd tSls HIO3/HNO3 dh mifLFkfr esa vk;ksMhuhdj.k
fd;k tkrk gSA
(1) C
6H
6 + I
2C
6H
5I + HI
fØ;k mRØe.kh; gSA
(2) 6 6 2 3 6 5 2C H 2I HIO 5 C H I 3H O
(2) QkLQksjl isaVk DyksjkbM ,oa QhukWy ls fØ;k & QkLQksjl isaVk
DyksjkbM@QkLQksjl isaVk czksekbM Qhuky ls fØ;k djkus ij Dyksjks@czksek cSathu izkIr
gksrk gSA
6 5 5 6 5 3C H OH PCl C H Cl POCl HCl
6 5 5 6 5 3C H OH PBr C H Br POBr HBr
(3) gSykstu vEyksa ls & ,sjksesfVd gSykstu vEyksa ds lksfM;e vo.k dks lksMkykbe ds
lkFk xeZ djus ij ,sfjy gSykbM curk gSA
Cl C
6H
4COONa + NaOH
CaOCl C
6H
5Na
2CO
3
lksMkykbe
+
Dyksjks lksfM;e cSatks,V
(4) Mkbtksfu;e yo.kksa ls ;k ls.Mes;j vfHkfØ;k }kjk [From Diazonium
salts of by Sandmayer’s reaction – tc fdlh Mkbtksfu;e yo.k dh D;wizl
DyksjkbM@czksekbM rFkk mlds laxr gSykstu vEy ds HCl/HBr lkFk xeZ djrs gS rks
Mkb,tks lewg gSykstu ijek.kq }kjk izfrLFkkfir gks tkrk gSA
(i) 6 5 2 6 5 2
CuCl/HClC H N Cl C H Cl N CuCl
6 5 2 6 5 2
CuBr/HBrC H N Cl C H Br N CuCl
(ii) vk;Mks O;qRié cukus ds fy;s Mkbtksfu;e yo.k dks KI foy;u ds lkFk xeZ djrs gSA
6 5 2 6 5 2C H N Cl KI C H I N KCl
(iii) ¶yksjks ;ksfxd ckjks¶yqvksfjd vEy dh fØ;k ls curs gS &
6 5 2 4 6 5 2 4C H N Cl HBF C H N BF HCl
6 5 2 4 6 5 3 2C H N BF C H F BF N xe Z dju s ij
(5) gkbiksgSyl vEy dh fØ;k ls [From Hypohallous Acids] & cSUthu ,oa
mlds ltkrh; dh mifLFkfr esa gkbiksczksel vEy ds lkFk vfHkfØ;k djkus ij czkseks O;qRié
cukrk gSA
2 2Br H O HBr HOBr
6 5 6 5 2C H H HO Br C H Br H O
3 3HBr AgNO AgBr HNO
(6)
[From silver or Pot. salt of Aromatic acids] & ,sjksesfVd yo.kksa ds 'kq"d
jtr ;k iksVsf’;e yo.kksa ij czksehu dh fØ;k ls ,fjy czksekbM ;ksfxd curk gSA
6 5 2 6 5 2C H COOAg Br C H Br CO AgBr
lajpuk rFkk vkac/ku-I
190
(7) ,sjkseSfVd vEyksa dk gSyksfodkcksZDlhyhdj.k [Halodecarboxylation of
Acids] & vk;ksMhu ,oa izdk’k dh mifLFkfr esa ,sjksesfVd dkcksZfefyd vEyksa dh ySM
VsVªk,lhVsV ds lkFk fØ;k djkus ij ,d lkFk fodkcksZf>yhdj.k ,oa vk;ksMhuhdj.k gksrk
gSA
C6H
6 COOH + I
2 [CH3COO]
4 Pb
LightC
6H
5I + C
6H
4I2 + CO
2
5-8-2 ukfHkd Lusgh ,sjkseSfVd izfrLFkkiu vfHkfØ;k;sa [Nuceophilic Aromiatic Substitution Reaction]
,sjksesfVd fajax ds dkcZu ls tqM+s gq, gkbMªkstu ;k vU; dksbZ lewg dsk fdlh
U;wfDyvksfQfyd vfHkdeZd }kjk izfrLFkkiu U;wfDyvksa fQfyd ,sjksfefVd izfrLFkkiu dgrs
gSA lk/kkj.k ,sfjy gSykbM] ,sfYdy gSykbM dh rqyuk esa ukfHkd&Lusgh izfrLFkkiu ds izfr
fuf"Ø; gksrs gSA ;s dsoy vf/kd izcy n’kkvksa vkSj ifjfLFkfr;ksa esa gh ukfHkd Lusgh
vfHkfØHkZdksa }kjk izfrLFkkfir gksrs gsA ;s vfHkfØ;k,¡ izcy {kkjks dh mifLFkfr esa gksrh gSA
,sfjy gSykbM esa ;g nks izdkj ls gksrk gS &
(1) SN2 f} v.kqd foLFkkiu fØ;kfof/k [Biomolecular displacement mechanism]
(2) csUtkbu e/;orhZ fØ;k fof/k [Benzyne intermediate mechanism]
(1) SN2 f} v.kq foLFkkiu fØ;kfof/k [Bimolecular displacement
mechanism]
bl fØ;k fof/k }kjk izfrLFkkiu mu ;ksfxdksa esa gksrk gS] ftuesa dksbZ bysDVªku
vkd"kZd lewg Hkh yxk gksrk gS] tSls ukbVªksDyksjks csUthu esa Dyksjhu dk izfrLFkkiuA
fØ;k nks inksa esa gksrh gS] igys in esa ukfHkd Lusgh vfHkdeZd ukfHkd ds dkcZu ijek.kq
ij vkØe.k djrk gS vkSj ,d dkcsZfu;e [Carbanion] cukrk gSA ;g dkcsZfu;e vk;u
rhu lajpukvksa I, II, III dk vuqukn ladj gksrk gSA
nwljs in esa dkcsZfu;e esa ls _.kkRed vk;u ¼DyksjkbM vk;u½ fudy tkrk gS
vkSj mRikn cu tkrk gSA iSjk ukbVªksDyksjks csUthu ds ty&vi?kVu djus ij p-ukbVªksQhuky curk gSA
(i)
Cl
NO2
OH
OHCl
NO2
OHCl
NO2
OHCl
NO2
Slow
NO2
OHCl
+
I II III
(ii)
OHCl
NO2
Fast
Cl
OH
NO2
Carbanion
[Explanation for the observed reactivity and orientation in this
reaction]
,slh ukfHkd Lusgh fØ;k dh dqy nj dkcsZfu;e vk;u ds cuus dh nj ij fuHkZj
djrh gSA dkcsZfu;e vk;u dk LFkkf;Ro ftruk vf/kd gksxk] mruh gh vf/kd lqxerk ds
og cusxkA _.kkos’k dks ifj{ksfir djus okys dkjd( tSls&izsjf.kd izHkko vFkok vuqukfnd
lajpuk rFkk vkac/ku-I
191
izHkko laØe.k voLFkk ds izkjafHkd dkcsZfu;e vk;u dk LFkk;hdj.k djrs gSA ;fn
DyksjkscsUthu ij ukfHkd Lugsh OHds vkØe.k }kjk cus dkcsZfu;e vk;u dh rqyuk
p&ukbVªksDyksjks csUthu ij OH vk;u ds vkØe.k }kjk cus dkcsZfu;e vk;u (I) ls dh
tkrh gS rks dkcsZfu;e vk;u dk vf/kd LFkkf;Ro gksrk gSA bysDVªku vkdf"kZr lewg
mifLFkr gksus ds dkj.k izcy&I izHkko ,sjksfefVd fjax ds _.kkos’k dk LFkk;hdj.k djrs gS
rFkk ,fjy gSykbMksa esa ukfHkd izfrLFkkiu ljyrk ls gksrk gSA blds foijhr bysDVªku
izfrd"kZd lewg e/;orhZ dkcsZfu;e vk;u dk vLFkk;hdj.k djrs gSA vr,o bysDVªku
izfrd"kZd lewgksa dh mifLFkfr esa ukfHkd Lusgh izfrLFkkiu vfHkfØ;k ean gks tkrh gSA
(2) cSatkbu e/;orhZ fØ;kfof/k ;k foyksiu ;ksx fØ;kfo/kh [Benzyne
intermediate mechanism or Elimination addition mechanism]
csUtkbu vfHkfØ;k fof/k }kjk ukfHkd Lusgh izfrLFkkiu dsoy vfHkfØ;k’khy ;ksfxd
esa laHko gS] ftlesa SN2 fØ;kfof/k }kjk izfrLFkkiu laHko ugh gksrk gSA
mnkgj.kkFkZ&ukbVªksDyksjks cSathu esa Dyksjhu dk OH }kjk izfrLFkkiu SN2 }kjk ljyrk ls
gks tkrk gS] fdUrq DyksjkscSathu esa Cl dk OH }kjk dh LFkkiu cgqr dfBukbZ ls gksrk
gSA ,sls fØ;k’khy ;ksfxdksa esa izfrLFkkiu fØ;k fdlh izcy {kkj dh mifLFkrh esa ljyrk
ls djkbZ tk ldrh gSA ;g fØ;k cSUtkbu fØ;k fof/k }kjk gksrh gSA ;g nks inksa esa
gksrh gSA igys in esa fujkdj.k [Elimination] gksrk gS] nwljs in esa ;ksx
[Addition] gksrk gSA bldks fujkdj.k ;ksxkRed fØ;kfof/k Hkh dgrs gSA
mnkgj.kkFkZ&DyksjkscSathu dks lskMkekbM ds nzo veksfu;k ds ?kksy ds lkFk fØ;k djkus ij
Dyksjhu dk NH2 lewg }kjk izfrLFkkiu gks tkrk gSA
(1) foyksiu ;k fujkdj.k [Elimination]
(i)
H
Cl
NH2
Cl
NH3+ +
(ii)
Cl
Cl+
Benzyne
(2) ;ksx [Addition]
(i) NH3
NH2
..+
(ii)
NH2
NH3
NH2
H
NH2.. + +
,suhyhu
foyksiu in esa gkbMªkstu DyksjkbM dk foyksiu gksrk gS ,oa csatkbu curk gS
tcfd ;ksx ij esa csUtkbu e/;orhZ ij Øe’k% 2NH rFkk H dk ;ksx gksrk gS blfy;s
bl ukfHkd Lusgh izfrLFkkiu dh iw.kZ vfHkfØ;k dh fØ;kfof/k dks foyksiu ;ksx fØ;kfof/k
[elimination addition mechanism] dgk tkrk gSA bl vfHkfØ;k esa cus csUtkbu
e/;orhZ esa ,d dkcZu&dkcZu f=d cU/k gksrk gS ftlesa fd ,d u;k dkcZu&dkcZu cU/k
sp2 d{kdksa ds ik’oZ vfrO;kiu }kjk curk gSA ;g u;k cU/k nqcZy gksrk gS rFkk csUtkbu
,d cgqr vf/kd fØ;k’khy v.kq gksrk gSA
,sfjy gSykbM nks lewgksa dh vfHkfØ;k;s nsrs gS &
lajpuk rFkk vkac/ku-I
192
(A) gSykstu ijek.kq dh vfHkfØ;k;sa (B) ukHkdh; vfHkfØ;k;sa
5.8.3 gSykstu ijek.kq dh vfHkfØ;k,¡
(1) ,sfjy gSykbM] ,sfYdy gSykbM dh rqyuk esa de fØ;k’khy gksrs gS] D;ksfd buesa
gSykstu ijek.kq eslksesfjd izHkko ds dkkj.k ukfHkd ds lkFk vR;Ur n`<rkiwoZd tqM+k jgrk
gSA blfy;s ;g OH, NH2, CN vkfn lewgksa }kjk lqxerk ls foLFkkfir ugh fd;k tk
ldrk gSA dsoy dqN fo"ks’k n’kkvksa esa gsykstu ijek.kq dk foLFkkiu gks ldrk gSA
(1) gSykstu ijek.kq dk &NH2 lewg }kjk foLFkkiu & tc DyksjkcSathu dks tyh;
veksfu;k ds lkFk D;wizl vkDlkbM dh mifLFkrh esa 200oC ,oa mPp nkc ij xeZ djrs
gS] rc gSykstu ijek.kq ,sehu lewg }kjk foLFkkfir gks tkrk gSA
C6H
5Cl + NH
3 + Cu
2O C
6H
5NH
2 + CuCl + H
2O2 2 2
mPp nkc
200oC
Dyksjkscsathu ,sfuyhu
(2) gSykstu ijek.kq dk &SH lewg }kjk foLFkkiu & iksVsf’k;e gkbMªkstu lYQkbM
ds lkFk xeZ djus ij Fkk;ks QhukWy curk gSA
C
6H
5Cl + KSH C
6H
5SH + KCl
Fkk;ks QhukWy
(3) gSykstu ijek.kq dk &CN lewg }kjk foLFkkiu & Dyksjkscsathu dks dkij
lk;ukbM ds lkFk fijhMhu dh mifLFkfr esa 200oC ij xeZ djus ls Qsfuy lk;ukbM
curk gSA
C6H
5Cl + CuCN C
6H
5CN + CuCl
fijhMhu
200oC
Qsfuy lk;ukbM
(4) gSykstu ijek.kq dk &OH lewg }kjk foLFkkiu&tc Dyksjkscsathu ds lksfM;e
gkbMªkDlkbM ds tyh; foy;u ds lkFk mPp nkc o 300oC ij xeZ djrs gS rks QhukWy
izkIr gksrk gSA
C6H
5Cl + NaOH C
6H
5OH + NaCl
mPp nkc
300oC
(5) gSykstu ijek.kq dk &OR lewg }kjk foLFkkiu & tc Dyksjkscsathu dks
,sYdkDlkbM tSls esFkkDlkbM ;k lksfM;e ,FkkDlkbM ds lkFk xeZ djrs gs] rks gSykstu
dk ,sYdkDlkbM }kjk foLFkkiu gks tkrk gSA
6 5 2 5 6 5 2 5C H Cl NaOC H C H O C H NaCl
,sfFky Qsfuy bZFkj
6 5 3 6 5 3C H Cl NaOCH C H O CH NaCl
(2) oqVZ~t fQfVx vfHkfØ;k [Wurtz – Fitting Reaction]
(a) ,sfjy gSykbM ds bZFkjh; foy;u dks lksfM;e ,oa ,sfYdy gSykbM dks lkFk xeZ djus
ij ,sfYdy cSathu izkIr gksrk gSA
lajpuk rFkk vkac/ku-I
193
C6H
5Br + Na + CH
3Br C
6H
5 CH
3 + NaBr2
VkyqbZu
'kq"d bZFkj
;g fØ;k oqVZ~t fQfVx vfHkfØ;k dgykrh gSA
(b) tc ,sfjy gSykbM bZFkj dh mifLFkfr esa lksfM;e ds lkFk djrk gS rc MkbQsfuy
curk gSA ;g vfHkfØ;k fQfVax vfHkfØ;k dgykrh gSA
C6H
5Br + Na + C
6H
5Br C
6H
5 C
6H
5 + NaBr2
MkbQsfuy
2
(3) mYeku vfHkfØ;k [Ulmann’s Reaction] tc vk;Mkscsathu dks Cu pw.kZ ds
lkFk 200oC ij ,d can uyh esa xeZ fd;k tkrk gS] rks MkbQsfuy curk gSaA
C6H
5I + Cu + C
6H
5I C
6H
5 C
6H
5 + CuI2
MkbQsfuy
2200oC
can uyh
(4) fxzxukMZ vfHkdeZd dk cuuk [Formation of Grignard reagents] ,sfjy
gSykbM dks 'kq"d bZFkj dh mifLFkfr esa eSXuhf’k;e /kkrq ds lkFk vfHkfØ;k djkus ij
fxzxukMZ vfHkdeZd curk gSA
C6H
5Br + Mg C
6H
5MgBr
'kq"d bZFkj
(5) vip;u [Reduction] ,sfjy gSykbM dk fufdy ,sY;qehfu;e feJ /kkrq ,oa {kkj
vFkok lksfM;e veyxe ,oa ,sYdksgkWy }kjk vipf;r djus ij gkbMªksdkcZu curk gSA
C6H
5Cl + H
NaOHC
6H
6 + HCl
Ni / Al2
5.8.4 ukHkdh; vfHkfØ;k;s
gSykstu lewg vkWFkksZ rFkk iSjk funsZ’kd gksrs gS vr% vkus okys lewg dks vius ls
vkWFkksZ o iSjk LFkku ij izfrLFkkfir gksus dk funsZ’k djrs gSA vr% ,sfjy gSykbM dk
gSykstuhdj.k] ukbVªhdj.k o lYQksuhdj.k djus ij u;k lewg O ;k P LFkku ij vkrk
gSA
(1) gSykstuhdj.k [Haogenation]
Cl2
Cl
Cl
Cl
Cl
Cl
+ +
Dyksjkscsathu o&MkbDyksjks cSathu p&MkbDyksjks csathu
(2) lYQksuhdj.k [Sulphonation]
lajpuk rFkk vkac/ku-I
194
H2SO
4
Cl
SO3H
Cl
SO3H
Cl
lkUnz
+
o-Dyksjks csathu p-Dyksjks csathu
lYQksfud vEy lYQksfud vEy
(3) ukbVªhdj.k [Nitration]
H2SO
4
Cl Cl
NO2
Cl
NO2
HNO3
lkUnz
+¼lkUnz½+
o-ukbVªks Dyksjks p-ukbVªks Dyksjks
csathu csathu
5-9 [Side Chain Hallogen Substituted Derivatives]
bu ,sjksesfVd gSykstu ;ksfxdksa esa ,sjksesfVd oy; dh ik’oZ Ja[kyk ds gkbMªkstu
ijek.kq gSykstu ijek.kq }kjk izfrLFkkfir gksrs gSA ,sls ;ksfxdks dks ,sfYdy gSykbMksa ds
,fjy O;qRié ekuk tk ldrk gSA D;ksfd buds jklk;fud xq.k ,sfYdy gSykbMksa ls feyrs
gSA bu ;kSfxdks dk gSykstu ijek.kq] ,sfYdy gSykbMksa ds gSykstu ijek.kq dh rqyuk esa
vf/kd lfØ; gksrk gSA bu ;ksfxdksa dks lh/ks gSyksthuhdj.k }kjk cuk;k tk ldrk gSA
mnkgj.kkFkZ tc Dyksjhu ;k czksehu dks lw;Z ds izdk’k dh mifLFkrh esa gSykstu okgd dh
vuqifLFkrh esa VkWywbZu ds mcyrs gq;s foy;u esa izokfgr fd;k tkrk gS rks esfFky eyd esa
gkbMªkstu ijek.kq Dyksjhu ijek.kq ls ,d&,d djds izfrLFkkfir gks tkrs gSa ,oa csafty
DyksjkbM] csaty DyksjkbM rFkk csatksVªkb DyksjkbM curk gSA
CH3
Cl2
CH2Cl
Cl2
CHCl2
Cl2
CCl3
lw;Z dk izdk'k lw;Z dk izdk'k lw;Z dk izdk'k
h h h
VkWywbZu csafty DyksjkbM csaty DyksjkbM csatksVªkb
DyksjkbM
tc ik’oZ Ja[kyk esfFky ewyd ls cM+h gksrh gS tSls –CH3–CH2– rc igys rFkk
LFkkuksa ij ,d lkFk Dyksjhuhdj.k gksrk gS vkSj var esa isaVk Dyksjks ,fFky csathu curk
gSA
CH2
Cl2
CH3
CHCl CH3
CH2
Cl2
CH2Cl CCl
2 . CCl
3
+
Dyksjks ,fFky Dyksjks isaVk Dyksjks
cSathu ,fFky cSathu ,fFky cSathu
lajpuk rFkk vkac/ku-I
195
tc fdlh gkbMªksdkcZu esa ,d ls vf/kd ik’oZ Ja[kyk tqM+h gks rks lHkh dk gSyksthuhdh.k
gksrk gSA
Cl2
C6H
4
CH3
CH3 Cl
2
C6H
4
CH2Cl
CH3
C6H
4
CH2Cl
CH2Cl
HCl HCl
lajpuk rFkk vkac/ku-I
196
5-9-1 csfUty DyksjkbM [C6H5CH2Cl] [Benzyl chloride]
cukus dh fof/k;k¡ [Methods of Preparation]
yk fof/k [Laboratory Method] & iz;ksx’kkyk esa csfUty DyksjkbM dks
VkWywbZu dk lh/kk Dyksjhuhdj.k djds cuk;k tkrk gSA mcyrh gqbZ VkWywbZu esa izdk’k dh
mifLFkrh esa Dyksjhu dh fuf’pr ek=k izokfgr djus ij csfUty DyksjkbM izkIr gksrk gSA
CH3
Cl2
CH2Cl
+izdk'k
+ HCl
¼2½ csathu ds DyksjhesfFkyhdj.k }kjk
CH2Cl
ZnCl2
+ H2O + CH2O + HCl
¼3½ VkWywbZu ij dkcZu ijkDlkbM dh mifLFkfr esa lYQwfjy DyksjkbM dh vfHkfØ;k }kjk
cuk;k tk ldrk gSA
CH3 CH
2Cl
dkcZfud ijDlkbM
+ HCl + SO2 + SO2Cl2
5-9-2 HkkSfrd xq.k [Physical Properties]
1- ;g ,d jaxghu] Hkkjh nzo gS ftldk DoFkukad 179oC gSA
2- blesa vfiz; xa/k gksrh gSA
3- ty esa vfoys; fdUrq dkcZfud foyk;uksa esa foys; gSA
4- bldh ok"i vkW[kks rFkk ukd dh 'ysf"ed f>fYy;kas ij izHkko Mkyrh gSA
5-9-3 jklk;fud xq.k [Chemical Properties]
;g ,sjkseSfVd ;ksfxdksa ,oa ,sfYdy gSykbMksa dh lHkh vfHkfØ;k;sa nsrk gSa rFkk
,sfYdy gSykbM dh vis{kk vf/kd fØ;k’khy gSA cSafty DyksjkbM dh vf/kd fØ;k’khyrk
csafty dkcksZfu;e vk;u ds vuqukn LFkk;hdj.k ds dkj.k gSA
(A) os vfHkfØ;k,¡ ftlesa csafty DyksjkbM ,oa ,fYdy DyksjkbM lekurk j[krs gSa
1- tyh; KOH vFkok ty ds lkFk mckyus dh fØ;k [Action of aq. KOH
or boiling with water] % csafty ,sYdkgkWy izkIr gksrk gSA
6 5 2 6 5 2C H CH Cl KOH C H CH OH KCl
csafty DyksjkbM csafty ,sYdksgkWy
6 5 2 2 6 5 2C H CH Cl H O C H CH OH HCl
2- ,sYdksgkWyh KCN dh fØ;k [Action of alcoholic KCN] : csafty lk;ukbM
curk gS &
6 5 2 6 5 2C H CH Cl KCN C H CH CN KCl
lajpuk rFkk vkac/ku-I
197
csafty DyksjkbM csafty lk;ukbM
3- veksfu;k ds tyh; vFkok ,sYdksgkWyh foy;u dh vfHkfØ;k [Action of
alcoholic or aqueous solution of NH3] : csfty ,sehu curk gSA
6 5 2 3 6 5 2 2 4C H CH Cl 2NH C H CH NH NH Cl
4- olk vEyks ds jtr yo.k dh fØ;k [Action of silver salt of fatty acids] % flYoj ,slhVsV ds lkFk fØ;k djus ij csafty ,slhVsV izkIr gksrk gSA
3 6 5 2 3 2 6 5CH COOAg C H CH Cl CH COOCH C H AgCl
csafty ,slhVsV
5- 'kq"d bZFkj dh mifLFkfr esa lksfM;e ls fØ;k [Action of sodium in the
presence of dry ether] oqVZt vfHkfØ;k [Wurtz reaction] bl vfHkfØ;k esa
Mkbcsafty izkIr gksrk gSA
6 5 2 6 5 2 6 5 2 2 6 5C H CH Cl 2Na C H CH Cl C H CH CH C H NaCl
Mkbcsafty
6- Dyksjkscsathu ds lkFk oqVZ~t fQfVx vfHkfØ;k [Wurtz fitting reaction with
chlorobenzene] bl vfHkfØ;k esa MkbQhesy ehFksu izkIr gksrh gSA
6 5 2 6 5 6 5 2 6 5C H CH Cl 2Na C H Cl C H CH C H 2NaCl
MkbQsfuy ehFksu
7- lksfM;e ,sYdkWDlkbMksa dh fØ;k [Action of sodium alkoxides] csafty
DyksjkbM lksfM;e ,ykDlkbM ls fØ;k djds bZFkj cukrk gSA
6 5 2 6 5 6 5 2 2 5C H CH Cl C H ONa C H CH OC H NaCl
csafty bZFkj
8- mYeku dh vfHkfØ;k [Ulman’s reaction] csafty DyksjkbM Cu dh mifLFkfr esa
fØ;k djds Mkbcsafty nsrk gSA
6 5 2 6 5 2 6 5 2 2 6 5 2 2C H CH Cl 2Cu C H CH Cl C H CH CH C H Cu Cl
Mkbcsafty
9- 'kq"d bZFkj dh mifLFkfr esa Mg ls fØ;k [Reaction with ether in
presence of dry ether] 'kq"d bZFkj dh mifLFkfr esa eSXuhf’k;e ds lkFk vfHkfØ;k
djds fxzxukMZ vfHkdeZd cukrk gSA
6 5 2 6 5 2C H CH Cl Mg C H CH MgCl 'kq"d bZFkj
10- vip;u [Reaction] uotkr gkbMªkstu dh mifLFkfr esa mipf;r gksdj VkWywZu
cukrk gSA
6 5 2 6 5 3C H CH Cl 2[H] C H CH HCl uotkr gkbMkª ts u
11- vkDlhdj.k [Oxidation]
(a) 60% ukbfVªd vEy ds lkFk vkDlhdj.k ij csatksbd vEy nsrk gSA
6 5 2 3 6 5 2 2 3C H CH Cl 2HNO C H COOH H O N O HCl
(b) KMnO4 ds lkFk vkDlhdj.k ij csatksbd vEy nsrk gSA
lajpuk rFkk vkac/ku-I
198
COOHCH2Cl
KMnO4
(c) D;wfiz; vFkok ySM ukbVªsV }kjk vkDlhdj.k djus ij csatSfYMgkbM curk gSA
6 5 2 3 6 5 2 2 2 322C H CH Cl Pb NO 2C H CHO PbCl H O N O
5-9-4 ,sjksesfVd ;ksfxd ds leku vfHkfØ;k;s
csafty DyksjkbM dh Dyksjhu eqDr ik’oZ Ja[kyk vkFkksZ ,oa iSjk funsZ’kd gksrh gS
vr% cSathu ukfHkd esa foLFkkfir gksus okyk nwljk lewg bl ik’oZ Ja[kyk ds vkFkksZ o iSjk
dk fLFkfr ij tkosxkA Dyksjhuhdj.k] ukbVªhdj.k o lYQksuhdj.k djus ij izR;sd n’kk esa
vkFkksZ o iSjk mRikn izkIr gksrs gSA
(i) ukbVªhdj.k [Nitration]
CH2Cl
NO2
CH2Cl CH
2Cl
NO2
HNO3
H2SO
4
+lkUnz
lkUnz
o&ukbVªks csafty p&ukbVªks csafty
DyksjkbM DyksjkbM
(ii) Dyksjhuhdj.k [Chlorination]
CH2Cl
Cl
CH2Cl CH
2Cl
Cl
Cl2
Fe+
o-Dyksjks csafty p-Dyksjks csafty
DyksjkbM DyksjkbM
(iii) lYQksuhdj.k [Sulphonation]
CH2Cl
SO3H
CH2Cl CH
2Cl
SO3H
H2SO
4
+lkUnz
csafty DyksjkbM csafty DyksjkbM
o-lYQksfud vEy p-lYQksfud vEy
mi;ksx %
(1) bldk mi;ksx csafty ,sYdksgkWy] csafty ,sehu ,oa cSatsfYMgkbM cukus ds fuekZ.k esa
;g ,d izkFkfed inkFkZ gSA
(2) dkcZfud ;ksfxdks esa csafty lewg izfrLFkkfir dkjus esa bldk mi;ksx gksrk gSA
5-9-5 csaty DyksjkbM ;k csaftfyMhu DyksjkbM [Benzal chloride or Benzylidene chloride]
cukus dh fof/k;k [Methods of preparation]
lajpuk rFkk vkac/ku-I
199
(1) mcyrs gq, VkWybZu esa rc rd Dyksjhu izokfgr djrs gS tc rd fd mlds Hkkj esa
csafty DyksjkbM ,oa VkWybZu ds v.kqHkkjksa esa vUrj ds cjkcj of) u gks tk;sA
6 5 3 2 6 5 2C H CH 2Cl C H CHCl 2HCl
(2) csatSfYMgkbM ij PCl5 dh vfHkfØ;k }kjk csaty DyksjkbM cuk;k tk ldrk gSA
6 5 5 6 5 2 3C H CHO PCl C H CHCl POCl
HkkSfrd xq.k [Physical properties] & jaxnho nzo gS] bldk DoFkukad 207oC gS]
bldh xa/k vfiz; gksrh gSA
jklk;fud xq.k
(1) ;g pwus ds ikuh ds lkFk mckyus ij csaUtSfYMgkbM curk gSA
6 5 2 6 5 22 2C H CHCl Ca OH C H CH OH CaCl
6 5 6 5 22C H CH OH C H CHO H O
¼2½ lksfM;e ,slhVsV ds lkFk vfHkfØ;k djus ij ;g fluSfed vEy nsrk gSA
6 5 2 3 6 5C H CHCl CH COONa C H CH CHCOONa 2HCl
6 5 6 5C H CH CHCOONa HCl C H CH CHCOOH HCl
fluSfed vEy
¼3½ vkDlhdj.k djus ij cSatksbd vEy nsrk gSA
C6H
5CHCl
2 KMnO4
HNO3
C6H
5COOH
¼4½ casthu ukfHkd dh vfHkfØ;k, [Reactions of the Benzene nucleus] % izfrLFkkiu vfHkfØ;k;sa ukbVªhdj.k] gSyksthuhdj.k o ukbVªhdj.k djus ij ;g o, m rFkk
p rhuks gh izfrLFkkfir mRikn cukrk gSA
5-9-6 csatksVªkbDyksjksbM ;k Qhfuy DyksjksQkeZ [Benzotrichloride or phenyl chloroform]
cukus dh fof/k [Method of Preparation] – mcyrh gqbZ VkWybZu esa i zdk’k dh
mifLFkfr esa rc rd Dyksjhu izokfgr djrs gSa tc rd fd mlds Hkkj esa vkSj vf/kd of)
ugh gksrh gS csatksVªkbDyksjkbM izkIr gksrk gSA
6 5 3 2 6 5 3C H CH 3Cl C H CCl 3HCl
HkkSfrd xq.k & ;g ,d jaxghu nzo gS] bldk DoFkukad 213oC gSA
jklk;fud xq.k [Chemical properites]
¼1½ tc bls pwus ds ikuh ds lkFk mckyk tkrk gS rks cstksbZd vEy izkIr gksrk gSA
2
6 5 3 2 6 5 3
Ca(OH)C H CCl 3H O C H C OH
6 5 6 5 23C H C OH C H COOH H O
¼2½ csathu ukfHkd dh vfHkfØ;k gS ukHkdh; izfrLFkkiu ij ;g Hkh csaty DyksjkbM dh
Hkkafr o, m rFkk p rhuks gh mRikn nsuk gSA ¼3½ vkDlhdj.k djus ij csatksbd vEy izkIr gksrk gSA
C6H
5 CCl
3C
6H
5 COOH
O
HNO3 ;k {kkjh; KMnO4
lajpuk rFkk vkac/ku-I
200
[Difference between the
nuclear and side chain halogen derivatives]
¼1½ ukHkdh; gSykstu O;qRiéksa esa gSykstu ijek.kq csathu ukfHkd ls n`<+rkiwoZd tqM+k jgrk gS
rFkk –OH, –NH2, –CN ;k lewgksa }kjk vklkuh ls izfrLFkkfir ugh fd;k tk ldrkA
;s ;ksfxd ik’oZ Ja[kyk gSykstu O;qRiéksa dh vis{kk vf/kd LFkk;h gksrs gSA ik’oZ Ja[kyk
gSykstu O;qRié mi;qZDr lewgksa }kjk vklkuh ls izfrLFkkfir gks tkrs gS rFkk os ,fYdy
gSykbMks tSlk O;ogkj djrs gSA nksuksa izdkj ds gSykstu O;qRiéks esa varj dh O;k[;k
vuqukn ds vk/kkj ij dh tk ldrh gSA Dyksjkscsathu dks fuEufyf[kr lajpukvksa dk
vuqukn ladj ekuk tkrk gSaA
Cl :..
: Cl :..
: Cl :..
Cl :..
Cl :..
+ + +
Dyksjkscsathu esa C – Cl dh ca/k yEckbZ 1-70 A
o gksrh gS] tcfd esfFky DyksjkbM
es ;g yEckbZ 1-76Ao gSA ;g cU/k yEckbZ C – Cl rFkk C = Cl cU/kksa dh e/;orhZ gSA
vr% DyksjkscSthu esa C – Cl cU/k dk y?kqdj.k vuqukn ds dkj.k gh gksrk gSA bl izdkj
nksuksa ijek.kq vf/kd n`<+rk ls tqM+s jgrs gS vkSj Dyksjhu dk izfrLFkkiu dfBu gksrk gSA
csafty DyksjkbM esa csafty vk;u Dyksjhu ds fudy tkus ds ckn gh vuqukn }kjk
LFkk;hd`r gksrk gSA
CH2Cl CH
2
Cl
+
CH2 CH
2CH
2CH
2 CH2
bl izdkj vuqukn] LFkk;hdj.k csafty vk;u Dyksjhu ds vU; lewg }kjk gksus
okys izfrLFkkiu dks vklku cuk nsrk gSA
¼2½ ukHkdh; gSykstu O;qRiéksa dk lkekU; n’kkvksa esa ty vi?kVu ugh gksrk] tcfd ik’oZ
Ja[kyk gSykstu O;qRié ty vi?kfVr gks tkrs gSA
6 5 2 2 6 5 2C H CH Cl H O C H CH OH HCl
csafty ,sYdksgksy
6 5 2 2 6 5C H CHCl 2H O C H CHO HCl
csatSfYMgkbM
6 5 3 2 6 5C H CCl 3H O C H COOH HCl
csatksbd vEy
¼3½ ukHkdh; gSykstu O;qRiéksa dk vkDlhdj.k djus ij ukfHkd ls layXu gSykstu ijek.kq
vizHkkfor jgrk gS] ijUrq tc gSykstu ijek.kq ik’oZ Ja[kyk esa mifLFkr jgrk gS rks lEiw.kZ
ik’oZ Ja[kyk &COOH lewg esa vkDlhd`r gks tkrh gSA
lajpuk rFkk vkac/ku-I
201
Cl
COOHCH3
ClO
KMnO4 or HNO
3
o&Dyksjks cSatksbd vEy
O
KMnO4 or HNO
3
Cl
CH3
Cl
COOH
p&Dyksjks cSatksbd vEy
O
KMnO4 or HNO
3
CH2Cl
COOHCH2Cl
CCl3 csatksbd vEy
5-9-7 ,sfYdy gSykbMks dh ,fyy] okbfuy ,oa ,fjy gSykbMks ds lkis{k
[Relative Reactivities of Alkyl Halides, Allyl vinyl and Aryl Halides]
,sfjy gSykbM esa gSykstu ijek.kq ,sfYdy gSykbM ds gSykstu ijek.kq dh rqyuk esa
de fØ;k’khy gksrk gS ftlds dkj.k ;g NH3, KCN, NaOH vkfn vfHkdeZdksa ds izfr
de fØ;k’khy gksrk gSA foukby gSykbM [CH2 = CH – X] esa Hkh gSykstu ijek.kq bu
vfHkdeZdksa ds izfr cgqr de fØ;k’khyrk iznf’kZr djrk gSA ,sfYdy gSykbMksa esa ca/k dh
/kqzork ds dkj.k v.kq ukfHkdLusgh vfHkdeZdksa ds izfr fØ;k’khy gks tkrk gS vkSj dbZ izdkj
dh izfrLFkkiu fØ;k,¡ nsrk gSA ,sfYdy gSykbM ds leku ,sfyy gSykbM [CH2 = CH –
CH2 – X]] okbfuy gSykbM [CH2 = CH – X] vkSj ,fjy gSykbM [Ar–X] lHkh eas
/kzqoh; cU/k gksrk gS fdUrq lHkh esa gSykstu ijek.kq dh fØ;k’khyrk vyx&vyx gksrh gSA
,sfYdy gSykbMksa dh rqyuk esa okbfuy gSykbM ,oa ,fjy gSykbM de fØ;k’khy gksrs gS
tcfd ,sfyy gSykbM vkSj ,sjSfYdy gSykbM cgqr vf/kd fØ;k’khy gksrs gSA bldk dkj.k
budh lajpukvksa ds vk/kkj ij le>k;k tk ldrk gSA
(A) ,sfyy ,oa ,sjSfYdy g ,sfyy DyksjkbM esa
Dyksjhu ijek.kq okbfuy DyksjkbM rFkk ,sfYdy DyksjkbM ds Dyksjhu ijek.kq dh rqyuk esa
vf/kd fØ;k’khy gksrk gS D;ksfd ,sfyy dkcksZdsVk;u vuqukn ds dkj.k vf/kd LFkkf;Ro
izkIr dj ysrk gSA
CH2
ClCHCH2
CH2
CHCH2
Cl
eUn+
CH
2CHCH
2CH
2CHCH
2
lajpuk rFkk vkac/ku-I
202
,sfyy dkcksZdsVk;u ,d la;qfXer /kuk;u gksus ds dkj.k blesa vuqukn laHko gksrk
gS vr% DyksjkbM vk;u [kksdj ;g ljyrk ls cu tkrk gSA ,sfYdy gSykbM esa ,sfYdy
dkcksZdsVk;u vuqukn ds }kjk LFkkf;Ro izkIr ugh djrk gS blfy;s ;g dfBurk ls curk gS
,oa SN1 vfHkfØ;kvksa esa ,sfyy gSykbM dh rqyuk esa de fØ;k’khyrk n’kkZrk gSA
csfUty DyksjkbM ds vk;uu ls csfUty dkcksZdsVk;u dk ,sfyy dkcksZdsVk;u ds
leku vuqukn }kjk LFkk;hdj.k gks tkrk gS ijUrq ;g ,fyy dkcksZdsVk;u dh rqyuk esa
vf/kd LFkk;h gksrk gSA QyLo:i csfUty DyksjkbM] ,sfyy DyksjkbM ls vf/kd fØ;k’khy
gksrk gSA
CH2Cl
SlowCl
+
CH2
CH2
CH2
CH2
++
(B) okbfuy DyksjkbM ds
Dyksjhu ijek.kq ij rhu ,dkdh bysDVªku ;qXe mifLFkr gksrs gS tks dkcZu&dkcZu f}ca/k ds
lkFk la;qXeu gSA vr% blesa ls ,d bysDVªe ;qXe dk f}caU/k dh vksj foLFkkiu gks tkrk gS
ftlds dkj.k okbfuy DyksjkbM dh fuEu nks vuqukfnr lajpuk ds gks tkrh gSA
ClCHCH2
ClCHCH2
:
..
..
..:
I II
mijksIr nksuks lajpukvksa ls irk pyrk gS fd DYkksjhu ijek.kq dkcZu ds lkFk ,d
,sls vkcU/k }kjk tqM+k jgrk gS ftlesa vkaf’kd f}ca?k xq.k gksrk gSA bldh iq"Vh bldh cU/k
yEckbZ 1-69Ao ls gksrh gS tks fd ,sfYdy gSykbM esa C–X cU/k yEckbZ 1-77A
o ls de
gksrh gSA pwafd Dyksjhu ijek.kq ij vkaf’kd /kukns’k vk tkrk gS ftlds dkj.k bldk
DyksjkbM (Cl–) ds :i esa fu"dklu dfBu gks tkrk gSA vr% foukby DyksjkbM ,sfYdy
DyksjkbM dh rqyuk esa de fØ;k’khy gksrk gSA
okbfuy DyksjkbM ds leku Dyksjkscsathu esa Hkh +M izHkko ds dkj.k dkcZu
Dyksjhu vkca/k esa vkf’kad f}cU/k xq.k vk tkrk gS ftlls dkcZu&dkcZu oU/k dh yEckbZ de
gks tkrh gSA Dyksjks csathu esa dkcZu Dyksjhu cU/k yEckbZ okbfuy DyksjkbM ds leku 1-
69Ao gksrh gSA bl cU/k dks rksM+us ds fy;s vis{kkd`r vf/kd mtkZ dh vko’;drk gksrh gSA
vr% Dyksjkscsathu okMfuy gSykbM ds leku ,sfYdy gSykbM ls de fØ;k’khy gksrk gSA
Cl Cl Cl Cl Cl
::..
:..
:..
:..
:..
Dyksjkscsathu [+M izHkko ds dkj.k] dh vuquknh lajpuk,¡
vr% vuquknh lajpukvks ds dkj.k Dyksjkscsathu esa C–Cl cU/k dk vk;uu gksuk
vkSj Cl– ds :i esa eqDr gksuk dfBu gksrk gSA
5-9-8 Mh-Vh-Vh- (D.D.T.) [P,P '– [Dichloro Diphenyl Trichloro Ethane]
cukus dh fof/k & Dyksjkscsathu dk lkUnz H2SO4 dh mifLFkfr esa Dyksjy ds lkFk xeZ
djus ij D.D.T. curk gSA
lajpuk rFkk vkac/ku-I
203
ClH
ClH
CH3CH O
H2SO
4
Cl
Cl
CH3CH
lkUnz
p, p ' -MkbDyksjks MkbQsfuy VªkbDyksjks
,sFksu ;k D.D.T.
xq.k & 1- ;g ty esa vfoys; o vok"i’khy gSA
2- ;g lQsn Bksl gksrk gS ,oa bldk xyukad 109-110oC gksrk gSA \
3- O;kikfjd D.D.T. ,d 'kq) ;ksfxd ugh gSA ;g 70% P, P ' -leko;oh]]
10&15% o, p ' leko;oh ,oa 'ks"k o, o ' leko;oh gksrk gSA
mi;ksx & f}rh; fo’o ;q) ds ckn bldk iz;ksx vf/kd izpfyr gqvkA ;g izeq[kr%
dhVk.kqvksa rFkk muds ykokZ dks u"V djus esa leFkZ gSA
bldk fpM+dko foy;u ;k pw.kZ ds :i esa djus ls ePNj] eD[kh] [kVey] fiLlw]
fo"kSys dhsM+s frypês rFkk Qyksa o lfCt;ksa dks u"V djus okys dhM+s o muds ykokZ [kRe gks
tkrs gSA
gkfu ¼nq"ifj.kke½ ?kjsyw dk;ksZ] d`f"k dk;ksZ o vU; dk;ksZ esa blds cqjs izHkko iM+rs gSA
tSls 'kjhj esa nkus iM+uk] gkFk iSj esa [kqtykgV gksuk] 'kjhj esa pdrs iM+uk vf/kd lw?kus ls
?kcjkgV] detksjh o flj esa Hkkjhiu gksuk vkfnA bu cqjs izHkko ds dkj.k gh bldk
izpyu /khj&/khjs de gksrk tk jgk gSA
5-9-10 ch-,p-lh- [B.H.C.] ;k csUthu gsDlk DyksjkbM [Benzene Hexa
Chloride]
tc lw;Z ds izdk’k ;k ijkcSaxuh izdk’k dh mifLFkfr eas csathu esa Dyksjhu xSl
vf/kdrk esa izokfgr dh tkrh gS rks csathu ds rhuksa f}vkca/k Cl ijek.kqvksa ds ;ksx ds
dkj.k lar`Ir gks tkrs gS ,oa csathu gsDlk DyksjkbM curk gSA
Cl
Cl
Cl
Cl
ClCl
+ 3Cl2
lw;Z izdk'k ;k
ijkcSaxuh fdj.ks
csathu gSDlkDyksjkbM
csathu gsDlkDyksjkbM ds vkB laHko f=foe leko;oh :i gksrs gS] ftlesa ls dsoy
,d gh :i ( ) vlefer gksrk gS ,oa bldk nks izdk’kh; leko;fo;ksa ea fo;kstu fd;k
tk ldrk gSA blds vkBksa :i csathu fjax esa H o Cl dh fofHké O;oLFkkvksa ds dkj.k
mRié gksrs gSA blds Kkr vkB :iksa esa ls pkj 'kq) voLFkk esa izkIr fd;s x;s gSA :i
izcy dhVuk’kh gS rFkk D.D.T. dh vis{kk vf/kd fØ;k’khy gSA
bls xSesDlhu] xSesu] 666-fy.Msu vkfn O;kikfjd ukeksa ls tkuk tkrk gSA
CH
CH
Cl
Cl
CH
CH
Cl
Cl
CH Cl
CH Cl
lajpuk rFkk vkac/ku-I
204
- leko;h
xq.k [Properties] ;g lQsn jax dk fØLVyh; Bksl gS bldk 112&113oC xyukad gS
bldk leko;oh ty es vU; leko;fo;ksa dh vis{kk de foys; gSA blds lHkh
leko;fo;ksa dks izFkd djuk dfBu gksrk gSA {kkj ds lkFk xeZ djus ij vi?kfVr gksdj
Vªkb Dyksjks csathu cukrk gSA
mi;ksx ¼1½ B.H.C. dk izHkko D.D.T. ls Hkh vf/kd rhoz xfr ls gksrk gSA xSsesDesu
ikoMj ;k ty esa foy;u cukdj fipdkjh ls fpM+dko djus ls dhVk.kq o
blds ykokZ ej tkrs gS ,oa 'ks"k dk fodk’k dqN fnu ds fy, :d tkrk
gSA
¼2½ tw jksx esa Hkh bldk mi;ksx fd;k tkrk gSA
¼3½ pkjikbZ] fcLrj] est] dqlhZ vkfn esa mifLFkr [kVeyksa dks ekjus ;k Hkxkus
esa] xeZ ty esa cuk foy;u iz;ksx fd;k tkrk gSA
gkfu & bls law?kus ls 'kjhj dh Luk;q raf=dk f’kfFky gksus yxrh gS ,oa vf/kdrk ls blds
fu’olu ls e`R;q gks ldrh gSA blds laidZ esa ?kcjkgV o xehZ dk vuqHko gksrk gSA
lko/kkfu;ka & bls fNM+drs le; ukd o eq¡g dks <ddj j[kuk pkfg,A fNM+dko
#d&#ddj djuk pkfg, ftlls nok ds laidZ esa vf/kd nsj rd u jgsA fNM+dko ds
i'pkr iwjs 'kjhj dh lQkbZ Bhd ls dj ysuk pkfg;sA
5-9-11 ÝhvkWu [Freon]
esFksu rFkk ,Fksu ds ikyh Dyksjks¶yqvksa O;Rié dks ÝhvkWu vFkok lh-,Q-lh-]
Dyksjks¶yksjks dkcZu dgrs gSA budk mi;ksx iz’khrd ds :i esa fd;k tkrk gSA fdlh
ÝhvkWu esa dkcZu rFkk ¶yksvksjhu ds vuqikr ds vuqlkj mldk fof’k"V ÝhvkWu ukekdj.k
fd;k tkrk gSA
mnkgj.k &
CFCl3 CF2Cl2 C2F2Cl4
1:1 1:2 1:1:2 ÝhvkWu&11 ÝhvkWu&12 ÝhvkWu&112
lcls egRoiw.kZ ÝhvkWu MªkbDyksjks Mkb¶yksjks esFksu gS bls ÝhvkWu&12 Hkh dgrs
gSA bls ,fUVeuh VªkbDyksjkbM vkSj dkcZu VsVªkDyksjkbM dks SbCl3 mRizsjd dh mifLFkfr
esa xeZ djds cukrs gSA
4 3 2 2 3
SbClF3CCl 2SbF 2CCl 2SbCl 5
3 3F2SbCl 6HF 2Sb 6HCl
ÝhvkWu ,d nzo gSA vk stksu ijr ds fouk’k ds fy;s eq[; #i ls DyksjksQksjks
dkcZfud ;ksfxd vFkkZr CFC ftEesnkj gSA ;s vfØ;] jaxghu] xU/kghu] vToyu’khy
rFkk ok;qe.My esa yEch vof/k rd cus jgus okys jlk;u gSA iFoh ds fupys okrkoj.k
vFkkZr 'kksHke.My [troposphere] esa CFC fcuk vi?kfVr gq, yxHkx lkS lky rd
ekStwn jg ldrs gSA
mi;ksx & ¼i½ ikbjsu ds uke ls vkx cq>kus ds fy;s iz;qDr fd;k tkrk gSA
¼ii½ bldk mi;ksx okrkuqdwyu esa rFkk iz’khrd ds :i esa gksrk gSA
¼iii½ bldk mi;ksx izlk/ku dh lkexzh ij¶;we] Lizs vkfn esa gksrk gSA
¼iv½ ;g rsy] clk] jsftu vkfn ds fy, ,d mÙke foyk;d ds :i esa iz;qDr gksrk gSA
5-10 iz”u
1- DyksjksQkeZ esa vkDlhdj.k ls curk gSA
lajpuk rFkk vkac/ku-I
205
a. COCl2 b. CO2Cl2 c. COCl3 d. COCl4
2- fuEu esa ls dkSu lk gSyksQkeZ vfHkfdz;k nsrk gSA
a. C6H6 b. CH3COOH c. C3H8 d. CH3COCH3
3- dkfcZy ,ehu vfHkfdz;k dks --------------- ijh{k.k ds uke ls tkurs gSA
a. vkbZlks lkbukbM b. lkbukbM c. DyksQekZ d. ,ehu
4- DykscSthu dh fuEu ls fdz;k }kjk DDT izkIr gksrk gSA
a. lY¶;wfjd vEy b. Dyksjy c. Dyksjhu d. DykslsQkeZ
5- VsVªk ¶yksjks ,fFkyhu dk cgqyd gSA
a. ik¡yhFkhu b. Vs¶yk¡u c. ik¡yh LVkbjhu d. ikyh foukby DyksjkbM
5-11 Unit Summary bdkbZ lkajk'k
lar`Ir gkbMªksdkcZuksa ds gSykstu O;qRié ,fYdy gSykbM dgykrs gSaA gSykstu ijek.kqvksa
dk vU; ijek.kqvksa ;k lewgksa }kjk foLFkku laHko gksus ds dkj.k bu ;kSfxdksa ds vusd
lka’ysf"kd vuqiz;ksx gksrs gSaA budk foyk;dksa ds :i esa Hkh iz;ksx fd;k tkrk gSA
,sjkseSfVd gkbMªksdkcZuksa ds gSykstu O;qRié ,fjy gSykbM dgykrs gSaA ßgkbMªksdkcZu ds
gSykstu O;qRiUu os ;kSfXkd gSa] tks fdlh lar`Ir ¼,sYdsu½ ;k vlar`Ir ¼,sYdhu ;k ,sYdkbu½
gkbMªksdkcZu ds ,d ;k ,d ls vf/kd gkbMªkstu ijek.kqvksa ds mrus gh gSykstu ijek.kqvksa
}kjk izfrLFkkiu ls curs gSaAÞ ,sYdsu ds eksuks gSykstu O;qRiUu ß,sfYdy gSykbMÞ dgykrs
gSA mPprj ,fYdy gSykbM eq[;r% nks izdkj dh leko;ork iznf’kZr djrs gS ¼1½ LFkku
leko;ork ¼2½ Ja[kyk leko;ork
,sfYdy gSykbMks dh ukfHkd Lusgh izfrLFkkiu vfHkfØ;kvksa gksrh gSA ukfHkdLusgh vfHkfØ;k,W
nks izdkj dh gksrh gS ¼1½ ,d v.kqd ukfedLusgh izfrLFkkiu vfHkfØ,W SN1 vfHkfØ;k,W
¼2½ f} v.kqd ukfedLusgh izfrLFkkiu vfHkØ;k,W SN2 vfHkfØ;k, gksrh gSA
,sfYdy gSykbMks dh ukfHkd&Lusgh izfrLFkkiu vfHkfØ;k, gksrh gSA
,sjkSesfVd gkbMªksdkcZu ¼cSathu vkSj mlds ltkrh;] VkWyqbZu] tkbyhu vkfn½ rFkk gSykstu
dh vfHkfØ;k ls cus mRikn ,sjkseSfVd gSykstu ;kSfxd dgykrs gSAÞ ;s nks izdkj ds gksrs
gS ;ksxkRed gSykstu ;kSfxd izfrLFkkfir gSykstu ;kSfxd dgykrs gSA ukfHkd Lusgh
,sjkseSfVd izfrLFkkiu vfHkfØ;k;sa gksrh gS ,sjksesfVd gSykstu ;ksfxdksa esa ,sjksesfVd oy; dh
ik’oZ Ja[kyk ds gkbMªkstu ijek.kq gSykstu ijek.kq }kjk izfrLFkkfir gksrs gSA ,sls ;ksfxdks
dks ,sfYdy gSykbMksa ds ,fjy O;qRié ekuk tk ldrk gSA ,sfjy gSykbM esa gSykstu
ijek.kq ,sfYdy gSykbM ds gSykstu ijek.kq dh rqyuk esa de fØ;k’khy gksrk g ,sfYdy
gSykbMksa dh rqyuk esa okbfuy gSykbM ,oa ,fjy gSykbM de fØ;k’khy gksrs gS tcfd
,sfyy gSykbM vkSj ,sjSfYdy gSykbM cgqr vf/kd fØ;k’khy gksrs gSA
5-12 iz'u ds mRrj
1- COCl2
2- CH3COCH3
3- vkblksa lkbukbM
4- Dyksjy
5- Vs¶yk¡u
lajpuk rFkk vkac/ku-I
206
4-13 dqN mi;ksxh iqLrdsa Suggested reading/Reference
22. Organic Chemistry, Volume 1, I.L. Finar, ELBS Longman.
Fundamentals of Organic Chemistry , T.W. Graham Solomons, John
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