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4/10/2013
1
HA HU C I CNG
Ging vin: Ths. Uy Nhn
Email: [email protected]
NI DUNGPhn I. I CNG HA HC HU C
1 Cu trc electron v lin kt ha hc trong hp cht hu c
2 Cc hiu ng electron trong hp cht hu c
3 ng phn v cu dng
4 Cc loi phn ng trong ha ha c
5 Cc phng php ha hc v vt l xc nh cc hp cht hu c
Phn II. HYDROCACBON
6 Alkan hydrocacbon no
7 Cycloalkan
8 Alken Hydrocarbon etylenic
9 Alkin Hydrocarbon acetylenic
10 Aren Hydrocarbon thm
11 Hp cht hydrocacbon a nhn thm
Phn III. HP CHT A CHC V N CHC
12 Dn xut halogen
13 Dn cht c kim
14 Alcol
15 Phenol
16 Ete
17 Aldehid Ceton
18 Acidcarboxylic v dn cht
19 Amin
Phn IV. HP CHT THIN NHIN
21 Alkaloid
22 Acid nucleic
23 Terpen
24 Steroid
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I : I CNG V HA HC HU C
Ha hc hu c l ha hc ca cc hp cht cha Carbon
- S lng cc HC Hu c rt ln hn so vi HC V c
- a s cha 2 n 4 nguyn t. Ngoi ra cn cha P, S, halogen, kim loi
- Phn ln l hp cht cng ha tr
- t bn di tc dng ca nhit
- Tan km trong nc, tan trong dung mi hu c
- Phn ng thng chm, hiu sut thp v cho phn ng ph
1. Tnh cht chung ca cc hp cht hu c
2. Xc nh c cu hp cht hu c
2.1. C lp v tinh ch : - Ly trch bng dung mi
- Li cun hi nc
- Chng ct phn on
- Kt tinh
- Thng hoa
- Sc k,.
2.2. Xc nh cng thc phn t
CxHyOzNt :
bt bo ha :2
2)2( +-= ii
vn
2.3. Xc nh cng thc cu to
Phng php ha hc : xc nh sn carbon v nhm nh chc
Phng php vt l : IR, UV, MS, RMN, nhiu x tia X
12xC%
=y
H%=
14zN%
=16tO%
= ...........100
= M
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PHNG PHP CHNG CT
Chng ct n Chng ct li cun hi nc
SC K CT
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PH UV
XC NH CU TRC BNG CNG HNG T HT NHN
Bruker Advance 500 MHz
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XC NH CU TRC BNG CNG HNG T HT NHN
I.1 : TNH NG PHN
ong phan
ong phan phang ong phan lap the
P v tr P cau tao P cau trang P cau hnhHo bien
P hnh hoc P quang hoc
P cis (Z) P trans (E)
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ng phn l nhng hp cht c cng cng thc phn t nhng
cng thc khai trin khc nhau.
1. ng phn phng
1.1. ng phn v tr
H3C OH H3CCH3
OHC4H9OH
H3COH
CH3 OH
H3C CH3
CH3
1-Butanol 2-Butanol
Isobutanol tert-Butanol
Cng CTPT, cng nhm chc nhng khc sn carbon
hoc khc v tr nhm chc
1.2. ng phn cu to
( = 1)
Cng CTPT nhng cng thc khai trin ca chng mang cc
nhm chc khc nhau
1.3. S h bin
C4H8O
CH3CH CHCH2OH CH3CH2CH2-CHO CH3CH2CCH3
2-Butenol
O
Butanal Butanon
OH CH2OH
O
CH3H3C O
Ciclobutanol Hidroximetilciclopropan 1,2-Dimetiloxiran Tetrahidrofuran
O OHOHO
N
NN
N
OH
NH2H
N
NN
N
OH
NH2H
Lactam LactiminGuanin
Ceton Enol
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2. ng phn lp th
2.1. Cng thc lp th
C tp chng sp3
2.1.1. Thuyt carbon t din
2.1.2. Cng thc phi cnh
edb
a
C
be
d
a
C
Ni C-a v C-b trong mt phngNi C-d hng ra ngoi mt phngNi C-e hng ra sau mt phng
a
d b f
eg
f
g ea
bd
2.1.3. Cng thc chiu Newman
2.1.4. Cng thc chiu Fischera
C
b
d e
a
d
b
e
CH3
COOHHOH
CH3
COOH
OHH
CH3
H
COOHOH
CH3
OH
OHHOOC
2 ni nm ngang : hng ra trc mt phng2 ni thng ng : hng ra sau mt phng
2.1.5. Chuyn i t CT phi cnh sang Fischer
CH3
HBr
C2H5
Cl H C2H5
Cl H
HBr
CH3
CH3
H Br
ClH
C2H5
Tri qua Phi qua
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ng phn cu trng
Cu trng l cc dng khc nhau ca mt cu hnh, l kt qu do s
quay quanh mt ni n trong phn t
Cu trng i lch Cu trng che khut
2.2.1. Cu trng cc hp cht khng vng
- Cu trng lch : cu trng bn lch v cu trng i lch
- Cu trng che khut : che khut ton phn v che khut mt phn
i lch Bn lch Che khut ton phn
Cl
H H Cl
HH
Cl
H HCl
HH
Cl
H H H
ClH
H
H ClCl
HH
Cl
H H
Cl
HH
Cl
H H
H
ClH
Cl
HH
Cl
HH
Cl
HH
H
ClH
Che khut mt phn
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CU TRNG CC HP CHT VNG
Cu trng gh Cu trng tu
Cu trng bn Cu trng khng bn
e (equatorial) : ni xch o
a (axial) : ni trc
a : ni hng xung mt phng trung bnh ca vng
b : ni hng ln trn mt phng trung bnh ca vng
Cu trng bn
Nhm th v tr xch o c cu trng bn hn
Nhm th ln u tin v tr xch o
Nhm t-butil lun v tr xch o
CH3
t-C4H9C2H5
H
CH3
CH3H
H
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2.3. ng phn cu hnh
2.3.1. ng phn hnh hc
ng phn cis trans
ng phn E - Z
a) Alcen
cis-2-buten
HH
H
CH3
H
H3C
H
H
CH3
H3C1
23
4
trans-2-buten
HH
H
C2H5
H
H3C
H
H
C2H5
H3C
Z-2-penten E-2-penten
ng phn hnh hc v ng phn quang hc
20
Khng c ng phn hnh hc
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21
NG PHN E,Z
u l ng phn cis, ng phn trans ?
22
Quy tc Cahn-Ingold-Prelog
Quy tc 1
Quy tc 2
Sp xp theo s hiu nguyn t
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23
Quy tc 3
Quy tc 4
Tng ng
Tng ng
2.3.2. ng quang hc
a) Tnh quang hot : tnh cht lm xoay mt phng nh sng phn cc phng mt gc a.
Cht t trin : lm quay mt phng nh sng phn cc v bn tay tri
K hiu : (-) hoc l
Cht hu trin : lm quay mt phng nh sng phn cc v bn tay phi
K hiu : (+) hoc d
'
100
lclc
t
D
aaa ==
ld
t
D
aa =
Dung dch
Cht lng
a : gc quay quan st (nng lc trin quang)l : di ng cha muc : nng dung dch (g/ml) ; c : g/100ml)d : t trng cht lng tinh cht (g/ml)T : nhit khi o (C)D : nh sng n sc ca n natrium (l = 589 nm)
b) Carbon th tnh : carbon phi i xng _ carbon mang 4 nhm th
khc nhau
K hiu : C*
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25
A chiral opbject
ng phn quang hc
Nonsuperimposable
mirror image
An achiral opbject
26
Quang hot
Khng quang hot
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27
L carbon mang bn nhm th khc nhau
Carbon bt i xng C*
C tnh quang hot
(chiral)
- i phn (i hnh ) : cng thc lp th i xng nhau qua gng phng
- Xuyn lp th phn (bn i hnh) : CTLT khng i xng nhau qua gng
Nhng hp cht c cng cng thc khai trin trong mt phng nhng
cng thc lp th khc nhau
COOH
HO H
CH3
COOH
H OH
CH3
COOH
H OH
OH H
COOH
COOH
H OH
H OH
COOH
Hnh nh hai i phn Hai xuyn lp th phn ca acid tartric
Cc ng phn quang hc c ho tnh v l tnh ging nhau
Tnh quang hot khc nhau do hot tnh sinh hc khc nhau
c) ng phn quang hc
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29
HOT TNH SINH HC HAI I PHN
30
HOT TNH SINH HC HAI I PHN
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ng phn quang hc c cha C th tnh : C*abde
d) Xc nh cu hnh R - S (R : rectus, phi ; S : sinister, tri)
- Xp cc phi t a, b, d, e theo th t u tin da vo quy tc chui (a b d e)
- Quan st vin nhn C* theo chiu t C* n phi t c u tin thp nht
- Xc nh chiu i t a n b ri n d. Nu chiu quay theo chiu kim ng h : R
ngc chiu kim ng h : S
b
a
d
e
d
a
b
e
R S
Quy tc chui (Cahn-Ingold-Prelog )
- Da theo bc s nguyn t : -I -Br -Cl SH -OH -NH2 -CH3 -H
- ng v c khi lng ln th u tin hn : 18O 17O 16O
- Ni ba Ni i Ni n
- i in t t do c u tin thp nht
- Cis Trans
Mt cht c n carbon th tnh 2n ng phn quang hc
COOH
H OH
OH H
COOH
COOH
HO H
H OH
COOH
COOH
H OH
H OH
COOH
Acid meso-tartric Acid (+)-tartric Acid (-)-tartric
ng phn quang hc khng cha C th tnh : trong trng hp ca alen, spiran v biphenil
i vi hp cht c 2 tm C th tnh, dng meso c tm thy ch khi 4 nhm gn trn C th tnh ny ging ht 4 nhm gn trn C th tnh cn li.
Y
A B
A B
Z
Y
B A
B A
Z
Y
A B
B A
Z
Y
B A
A B
Z
eritro treo
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Hnh chiu Fisher v ng phn D v L
C
C HHO
CH2OH
1
2
3
H
O
C
C OHH
CH2OH
1
2
3
H
O C
C HHO
C OHH
C HHO
C HHO
CH2OH
1
2
3
4
5
6
H
O
C
C OHH
C HHO
C OHH
C OHH
CH2OH
1
2
3
4
5
6
H
O
L-Glucose D-Glucose
(L-Gliceraldehid) (D-Gliceraldehid)
Nhm OH gn ln carbon bt i xng c s th t ln nht quay sang phi
l ng phn D, ngc li l ng phn (i phn) L.
(L-Serin)
C
C HH 2N
CH 2O H
1
2
3
H
O
C
C NH 2H
C HH
C 6H 5
1
2
3
4
H
O
(D-Phenilanalin)
Nhm NH2 gn ln carbon bt i
xng c s th t nh nht quay
sang phi l ng phn D, ngc li
l ng phn (i phn) L.
CIII : C CU IN T CA HP CHT HU C
1. Vn o nguyn t
Vn o : s, p, d, f
z
x
y
z
y
x x
y
z
s px py pz
p
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z
x
y
z
y
x x
y
z
s px py pz
2 px 2 py 2 pz2s2
2 px 2 py 2 pz2s2
Lai ha sp3, gc ni 109,5
Trng thi c bn :
Trng thi kch thch :
2. Tp chng vn o
Lai ha sp2, gc ni 120
Lai ha sp, gc ni 180
z
x
y
z
y
x x
y
z
s px py pz
z
x
y
z
y
x x
y
z
s pxpy pz
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Ni C-H Ni C-C
H
H
H
H
C C
H
H
H
H
S to ni ca C lai ha sp3
S to ni ca C lai ha sp2
Ni C-C v C-H Ni
Ni
S to ni ca C lai ha sp
C CHCC HH H
Ni Ni
3. Tnh phn cc v tnh kh phn cc
A A A : A
Cng ha tr khng phn cc (ng cc)
A B A: B
m in ca A > B
- +
Cng ha tr phn cc (ng cc)
Trong cng chu k, tng dn t tri sang phI.
Trong cng phn nhm, gim dn t trn xung di.
Ni C-H c xem nh khng phn cc.
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3.1. Moment lng cc
Tnh phn cc ca nI A-B c biu th bng moment lng cc
Vector nm trn trc lin nhn, hng t cc dng n cc m v c module
A B- +
= x r
r : chiu di nI A-B
: thng c tnh bng Debye-
+
C
Cl
HH
H
C
Cl
ClCl
Cl
Clorometan (=1.87D) Tetraclorometan (=0D)
Hiu ng in t
Hieu ng cam Hieu ng cong hng Hieu ng sieu tiep cach
Hieu ng ien t
+I -I +R -R
CC C X
+ ++ -
Hiu ng cm : hin tng nguyn t c m in cao ht in t ca
nguyn t c m in thp hn thng qua ni
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Hiu ng cm I (Inductive) :
- Halogen : -F > -Cl > -Br > -I
- Nhm mang in tch dng : -NR3 -PR3 -SR2Amonium Phosphonium Sulfonium
- Nhm trung ha c hiu ng I yu : -NH2 -OH -OR
-SH, -C6H5, -CH=CH2
Hiu ng cm I :
Cc nhm rt in t c hiu ng -I
N
O
O
S
O
OH
O
- Nhm trung ha c ni lng cc c hiu ng I yu hn nhm mang in tch dng
- Nhm carbonil c hiu ng I yu : -CHO, -COOH, -COR
Trong cng chu k, -I tng dn t phI qua tri
-NR2 < -OR < -F
Trong cng phn nhm, -I gim dn t trn xung di
in tch dng cng ln hay tp chng cng c nhiI tnh s, -I cng mnh
-NH3 > -NH2
C CH CH CH2>
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Hiu ng cm +I :
Cc nhm cho (y) in t c hiu ng +I
sp3 < sp2 < sp :
C
H
H
H
C
CH3
H
H
C
CH3
H
CH3
C
CH3
CH3
CH3
Cc nguyn t mang in tch m c hiu ng +I mnh : -O- < -S-
Hiu ng cm nh hng n moment lng cc, n tnh acid-baz ca
phn t, hat phn ng v nh hng phn ng.
Nhm y in t lm gim tnh acid, nhm ht in t lm tng tnh acid.
+I cng ln khi nguyn t mang in tch m c kch thc cng ln
Hiu ng cng hng R (resonance)
S di chuyn in t trng thi tnh trong nhng phn t c ni a
tip cch gi l hiu ng cng hng.NH2 NH2 NH2 NH2
Qui tc vit cng thc cng hng
Hai c cu cng hng ch khc nhau cch sp xp cc i in
t, v tr tng i ca cc nguyn t trong phn t khng thay i.
Hai c cu cng hng c cng s in t kt i.
C cu cng phI ph hp vi c cu in t ngai bin ca
nguyn t.
Cng thc c s nI cng ha tr cng nhiu th cng bn.
Cng thc cng hng kh bn vI in tch m nm trn nguyn t
c m in ln.
Cng thc cng hng vI hai in t cng du trn 2 nguyn t k
cn khng bn.
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Hiu ng cng hng R :
Nhm rt in t ca ni i C=C tip cch gy hiu ng -R
V d : C=O, -NO2, CN, RCOO-
HC CH N
O
OHC CH N
O
O
HC CH C
O
HC CH C
O
HC CH C
O
O R
HC CH C
O
O R
Trong 1 chu k, m in cng ln, -R cng mnh (-COR > CNR2).
in tch dng trn nguyn t cng ln, -R cng mnh.
Hiu ng cng hng +R :
Nhm cho i in t c lp ca mnh v pha ni i C=C tip
cch gy hiu ng +R
V d : -OR, -halogenur
HC CH O R HC O RCH
HC CH Cl HC ClCH
in tch m cng ln, +R cng mnh (-O- > -OR).
m in cng ln, +R cng km (-NR2 > -OR > -F).
Vn o p c mc nng lng cng cao, +R cng km (-F>-Cl>-Br>-I).
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-R, -I +R, -I +R, +I
-NO2, -CN, -CHO,-COR, -COOH,-COOR, -CONR2,-COCl, -C
-NR2, -NH2, -OR, -OH, -NHCOR, -F, -Cl, -Br, -I
-S-, -O-
=CR
Hiu ng cng hng nh hng n :
- di ni : hiu ng cng hng lm cho ni n k ni a ngn hn ni
n bnh thng v ni a th di hn di bnh thng.
- Moment lng cc.
Hiu ng siu tip cch
Nhm alkil gn trn C bt bo ha ca mt ni i hoc nhn benzen c
th cho in t nh hiu ng cng hng. i in t ca ni n C-H
v tr i vi C bt bo ha c tnh linh ng nn c th gy ra hiu
ng cng hng tng t nh in t p ca nguyn t halogen trong
halogenur vinil
R
CR
H
C CR2
R R
CR C CR2
R
C
H
H H C
H
H C
H
H
Hiu ng siu tip cch nh hng n di ni, moment lng cc v
bn tng i ca alcen.
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ACID - BAZ
Thuyt Brontested Lowry : Acid : cho proton H+
Baz : nhn proton
Acid Baz lien hp + H
HCl, phenol, HCOOH, CH3NO2
CH3O-, Ph-NH2, CH3OH
Acid lien hpBaz + H
Cht lng tnh : va c tnh acid, va tnh baz
-OH, -SH, -NH-
C OHH3C
O
-H
(H2O)C OH3C
O
+H
(H2SO4)C OHH3C
O
H
Lc acid - baz
+ H2OAH H3O + A
[A-][H3O+]
[AH]Ka pKa = -logKa
pKa cng nh, acid cng mnh
+ H2OB OH + BH
[BH][OH-]
[B-]Kb pKb = -logKb
pKa + pKb = 14
pH : pH = -log[H+]
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Cc yu t nh hng n lc acid - baz
- Nhm I lm tng tnh acid v lm gim tnh baz
H-CH2-C-O-H
O
O2N-CH2-C-O-H
O
pKa = 4,76 pKa = 1,68
- Nhm R lm tng tnh acid v lm gim tnh baz
- Trong mt chu k t tri sang phi, tnh acid tng v tnh baz gim
Tnh acid tng : CH4 < NH3 < H2O < HF
Tnh baz gim : CH3- < NH2
- < OH- < F-
- Trong mt phn nhm t trn xung di, tnh acid tng v tnh baz gim
Tnh acid : HF < HCl < HBr < HI
- Hiu ng lp th : s hin din cc nhm c kch thc ln trong
phn t c th che khut tm acid hoc tm baz hoc lm tr ngi hiu
ng lp th lm nh hng n tnh acid - baz
N
MeMe
Me
MeMe
MeN
Tnh baz :
- Ni hidrogen
O OH
OH
O OH
O
COOH
OH
pKa1 = 3,0 pKa2 = 13,4 pKa1 = 4,5
pKa2 = 9,8
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CIV : HIDROCARBON
Cc cht ch cha 2 nguyn t C v H
I. Alcan : CnH2n+2
I.1. Danh php : -an
CH4 : metan ; C2H6 : etan ; C7H16 : heptan ; C10H22 : decan
H3C CH
CH3
CH3CH2 CH
CH3
H3C C
CH3
CH3
H3C C
CH3
CH2
CH3
i-Propil s-Butil t-Butil Neopentil
CH3 CH2 CH2 CH
Et
CH CH2 CH3
Me
1 2 3 4 5 6 7CH3 CH2 CH
Et
CH CH2 CH3
Me
1 2 3 4 5 6
4-Etil-3-metilheptan 3-Etil-4-metilhexan
Qui tc gi tn :
- Chn dy di nht lm dy chnh. Nu hai dy cng chiu di chn dy
c nhiu nhnh lm dy chnh.
- nh s cc nguyn t C ca dy chnh lm th no cc C mang dy
nhnh c ch s nh nht.
- Khi c nhiu nhnh v tr tng ng, nhnh c ch s nh c chn
theo mu t.
3-Etil-4-metilhexan
CH3 CH2 CH
Et
CH CH2 CH3
Me
1 2 3 4 5 6
CH3 CH2 CH
Me
CH CH2 CH3
Et
1 2 3 4 5 6
4-Etil-3-metilhexan
L tnh : khng phn cc, tan trong dung mi hu c
- Dy thng : si v t trng tng theo s C, n = 1 - 4 : cht kh t thngn = 5 - 7 : cht lngn >10 : cht rn
- Dy nhnh : tnh d bay hi tng theo s dy nhnh.
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CnH2n+23n + 1
2O2 nCO2 + (n+1) H2O + Q+
Ha tnh
1. S t chy
R-H + X2t
R-X + HX
2. Halogen ha alcan
iu ch
1. Hon nguyn halogenur alkil
R-X + 2H R-H + HX
Dng hidrogen ang sinh :
Dng LiAlH4 :
4 R-X + LiAlH4 4 R-H + LiX + AlX3
nh sng
x
2. Phng php Grignard
RMgX + H2O RH + 1/2 MgX2 + 1/2 Mg(OH)2
3. Tng hp Wurtz
2 RX + 2 Na R-R + 2 NaX
4. Hidrogen ha alcan, alcin
R-CH=CH2 + H2Pt
R-CH2-CH3
R-CH2-CH3 + H2R-CH CHPt
5. Hon nguyn cc hp cht carbonil
Phng php Clemmensen
R C R'
O
Zn-Hg / HCl
tCR-CH2-R'
Phng php Wolff-Kishner
R C R'
O
NH2-NH2 / OH-
tCR-CH2-R'
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II. Alcen : -en hoc ilen (tn thng thng) : CnH2n
Dy di nht c cha ni i v ni i v tr nh nht
CH2=CH2 CH3CH2CH=CH2 C
CH3
CH CH2CHCH2=CH-CH=CH2
EtilenEten
Butilen1-Buten
1,3-Butadien 2-Metil-1,3-butadien(isopren)
CH2=CH- CH3-CH=CH- CH2=CH-CH2- CH3-CH=CH-CH2-
Etenil(vinil)
1-Propenil 2-Propenil(alil)
2-Butenil(crotil)
Ha tnh
1. Cng tc cht i xng
Hidrogen ha
R-CH2-CH2-R'R=CH-CH=R' + H2Ni Raney
Halogen ha : Cl Br I
R-CHBr-CHBr-R'R=CH-CH=R' + Br2CCl4
Ozon ha
RC CH
R'
R"
CH
OO
CO
R"R
R'
+ O3 CH
OO
C
O
R"R
R'
Zn, H2OR
CR'
O + R"CH=O + H2O2
Ozonid
4/10/2013
30
2. Cng tc cht bt i xng
Qui tc Markownikoff : nguyn t H hay phn mang in tch dngca tc cht s gn vo C ca ni i mang nhiunguyn t H nht v phn mang in tch m sgn vo C ca ni i mang t nguyn t H nht.
Qui tc Kharash: vi s hin din ca peroxid, nguyn t H ca tc chts gn vo C ca ni i mang t nguyn t H nht theoc ch gc t do (ch nh hng i vi HBr).
CH3 CH CH2 + HBr CH3 CH CH2
H Br
ROOR
CH3 CH CH2 + HBr CH3 CH CH2
Br H
CH3 CH CH2 + H2SO4 CH3 CH CH3
OSO3H
Oxid ha
R CH CH CH3 CH CH
OH OH
R'KMnO4 long
OH-R'
iu ch
1. T alcol
2. T halogenur alkil
R-CH2-CH-CH3
OH
R-CH =CH-CH3 R-CH2-CH =CH2+H+,
- H2O
+R-CH-CH-CH3
XR'
OH-R-C=CH-CH3
R'
R-C-CH =CH2
R'
SPC SPP
SPC SPP
Qui tc Zaitzeff : sn phm chnh l alcen mang nhiu nhm tr hon nht
3. Kh X2 ca a-dihalogenur alkil
+R-CH-CH-R'
XX
R-CH =CH-R' ZnX2+ Zn
4/10/2013
31
ALCIN - CnH2n-2 : -in
CH C HC C CH2
Etinil 2-Propinil
CH CH CH C CH3
Etin Propil
Acetilen Metilacetilen
Propargil
Ha tnh
1. Phn ng cng
Cng hidrogen
C CR R' + H2 CH CHR R'Ni
C CR R' + 2 H2 CH2 CH2R R'Ni
C CR R' + H2
Na hay Li
NH3 long
Pd/C
C C
H
R
R'
H
C C
H
R
H
R'
trans
cis
Cng halogen
C CR H+ Br2
C C
Br
R
H
Br
+ Br2R-CBr2-CHBr2
4/10/2013
32
Cng nc
C CHR + H2OHgSO4
H2SO4 longR C CH2
OH
R C
O
CH3
Cng hidracid
C CHRHCl
R-CCl=CH2HI
R-CICl=CH2
C CHRHCl
R-CCl=CH2HCl
R-CCl2-CH3
Oxid ha
C CR R'O
RCOOH + R'COOH
Phn ng ca acetilen n hon
C CHR + Na C CNaR + 1/2 H2
C CHR + KNH2 C CKR + 1/2 NH3
iu ch
1. T carbur calcium vi nc
CaC2 + 2 H2O C2H2 + Ca(OH)2
2. T vic- hay gem-dihalogenur
RCHBr-CHBr-CH3NaNH2 / NH3 R CH2 C CH
R CH2 CHCl2NaNH2 / NH3
R C CH
3. T tetrahalogenur
R C CR C
X
X
C
X
X
R' + 2 Zn R' + 2 ZnX2
x
4/10/2013
33
AREN
Me CH = CH2
Me Me
Toluen Stiren Cumen
Me
Me
Me
Me
Me
Me
o-Xilen m-Xilen p-Xilen
CH2 Ph3C- Ph-CH2=CH-
Phenil Benzil Tritil Stiril
Ha tnh
Cng hidrogen
+ 3 H2Ni
, p
Cng halogen
+ 3 Cl2h
Cl
Cl
Cl
Cl
Cl
Cl
Cng ozon
1. Phn ng cng
1/ O3
2/ Zn, H2O3 OHC-CHO + 2 H2O2
4/10/2013
34
2. Phn ng tr hon thn in t
Halogen ha
+ Cl2AlCl3
Cl
Nitro ha
NO2HNO3 , H2SO4 + H2O
Sulfon ha
SO3H
+ H2OH2SO4
Alkil ha
+ R-ClAlCl3
R
+ HCl
Acil ha
+ R-CO-ClAlCl3
CO-R
+ HCl
+ (R-CO)2OAlCl3
CO-R
+ RCOOH
4/10/2013
35
3. S nh hng ca phn ng tr hon thn in t trn nhn hng phng
G (+I, +R) : nh hng orto, para
Me
HNO3 , H2SO4
Me
NO2
Me
NO2G (-I, -R) : nh hng meta
NO2
H2SO4
NO2
SO3H
G halogen (-I, +R) : nh hng orto, para
Cl Cl Cl
NO2
HNO3 , H2SO4NO2
+
Me
OCH3
Br2 , FeBr3
Me
OCH3
Br
HNO3 , H2SO4+
Me Me
NO2NO2
O2N
Me
NO2NO2
Me
NO2
NO2
+
G1 rt in t, G2 cho in t Ph thuc G1
x
x
4/10/2013
36
iu ch
Pt - Al2O3
250 oC
Cr2O3- Al2O3
250 oC
Me
n-Heptan
x
CV : HALOGENUR ALKIL v HP CHT GRIGNARD
I.1. Danh php- Dy C di nht lm dy chnh, dy chnh phi cha cc nhm nh chc nu c.
- nh s cc C sao cho cc nhm th c s th t nh nht.- Nu c nhiu nhm th halogen ging nhau, dng tip u ng di, tri, tetra
- Nu c nhiu nhm th khc nhau, nh s v tr vn theo quy tc chung nhng vit theo mu t.
CH3-CH-CH2-CH-CH-CH2-CH3 CH3-CH-CH2-CH-CH-CH2-CH3
Me
Me
Br1
2
3 4
5 6 7 1 2
3 4
5
6 7
Me
Me
Br
5-Bromo-2,4-dimetilheptan 2-Bromo-4,5-dimetilheptan
Cl-CH2-CH2-CH-CH-CH3
Br
Me1 2 3
4
5
6
3-Bromo-1-cloro-4-metilpentan
CH3-CH-CH2-CH2-CH-CH3
Me Br
12345
2-Bromo-5-metilhexan
I. Halogenur alkil
4/10/2013
37
I.2. Phn ng
I.2.1. Phn ng th thn hch
Nu-: tc cht thn hch (cht giu in t c tnh baz, l hp cht hu
c, v c, ion m hoc phn t trung ha in.
Nu-: alkoxid natrium, mui ca acid hu c, acetilur
phn ng : R-Cl < R-Br < R-Ihalogenur nht cp > nh cp > tam cp
R-X + Nu-
R-Nu + X-baz
CH3O Na + R-CH2-Br R-CH2-OCH3 + NaBr
R'COO Na + R-CH2-Br R-CH2-O-CO-R' + NaBr
R'C C Na + R-CH2-Br R-CH2C CR' + NaBr
I.2.2. Phn ng kh
CH3CH2CHCH3
Br
EtONa
EtOHCH3CH=CHCH3 + CH3CH2CH=CH2
81% 19%
I.3. iu ch
phn ng : halogenur tam cp > nh cp > nht cp
I.3.1. T alcan, alcen, alcin tc dng vi hidracid hoc halogen
I.3.2. T alcol tc dng vi SOCl2, PCl5 hoc HX
R-OH + HX R-X + H2O
phn ng : alcol tam cp > nh cp > nht cp
R-CH2-OH + SOCl2 R-CH2-Cl + SO2 + HCl
R-CH2-OH + PCl5 R-CH2-Cl + POCl3 + HCl
4/10/2013
38
II. Hp cht Grignard : RMgX
RMgX + H2O RH + 1/2 MgX2 + 1/2 Mg(OH)2
II. 1. Phn ng
Vi nc :
Vi alcol, phenol :
RMgX + R'-OH R-H + R'OMgX
Vi acid :
RMgX + R'-COOH R-H + R'COOMgX
Vi alcin :
RMgX + R'C CH R-H + R'C CMgX
II.1.1. Vi hp cht c hidrogen acid
II.1.2. Phn ng cng
Vi dioxid carbon :
RMgX + CO2 RCOOMgX RCOOH
Vi aldehid, ceton :
RMgX + H-CHO
RMgX + R'-CHO
R-CH2-OMgX RCH2OH
R-CH-OMgX
R'
R-CH-OH
R'
RMgX + R'-C-R"
O
R-C-OMgX
R'
R"
R-C-OH
R'
R"
Vi dn xut ca acid carboxilic
RMgX + R'-C-O-R"
O
R-C-OMgX
R'
OR"
R'-C-R
O
R'-C-R
ORMgX
R-C-OMgX
R'
R
R-C-OH
R'
R
4/10/2013
39
II.2. iu ch
RMgXR-X + Mgeter khan
CVI : ALCOL PHENOL - ETER
I. ALCOL : R-OH
C
R
H
H
OH C
R
R'
H
OH C
R
R'
R"
OH
Alcol nht cp Alcol nh cp Alcol tam cp
CH3-CH2-OH CH3-CH-OH
CH3CH3-CH-CH2-OH
CH3 CH2-OH
Alcol benzilAlcol etil Alcol isopropil Alcol isobutil
Metilcarbinol Dimetilcarbinol Iospropilcarbinol Phenilcarbinol
IUPAC : - dy C di nht cha nhm OH- C-OH mang s v tr nh nht
CH3-CH-CH-CH2-OH
CH3Cl
1234
3-Cloro-2-metilbutanol
CH3-CH-CH=CH-CH-OH
Cl CH2-CH3
12
34567
6-Cloro-3-heptenol
4/10/2013
40
1. Phn ng
1.1. Phn ng ct t ni C-O
Vi hidracid :
R-OH + HX R-X + H2O
phn ng : - alil, benzil > acol III > alcol II > alcol I- HI > HBr > HCl
CH3CH2CH2OHHCl, ZnCl2
tCH3CH2CH2Cl
CH3-C-CH3
CH3
OH
HCl conc.CH3-C-CH3
CH3
Cl
Vi trihalogenur phosphor (PBr3, PI3) :
CH3CH2CH2OH CH3CH2CH2Br
CH3-C-H
CH3
OH
CH3-C-H
CH3
Cl
PBr3
P+I2
Phn ng do s t ni O-H
R-OH + Na RONa + 1/2 H2
R-OH + R'MgX R-OMgX + R'H
mnh acid : H2O > ROH > C2H2 > NH3 > RHCH3OH > alcol I > alcol II > alcol III
Tnh acid - baz
Phn ng ester ha
R-OH + R'COOH R'COOR + H2OH+
phn ng : CH3OH > alcol I > alcol II > alcol III
R-OH + (R'CO)2O R'COOR + R'COOHH+
R-OH + R'COCl R'COOR + HClPiridin
R-OH + SO2ClMe SO2ORMeOH- (piridin)
clorur tosil
4/10/2013
41
Vi clorur tionil :
ROH + SOCl2 RCl + SO2 + HCl
Vi tc cht kh nc :
C
H
C
OH
-H2O C C
phn ng : alcol III > alcol II > alcol I
Tc cht kh nc : - H2SO4, t
- acid Lewis : Al2O3, t
- POCl3 trong pyridin
OH
POCl3
Piridin, 0C
Phn ng oxid ha :
RCH2OH[O]
RCHO[O]
RCOOH
R-CH-OH[O]
R'
RCOR'
R-C-OH
R'
R''
[O]
Tc cht oxid ha : - Cu, 325 oC- KMnO4, OH
-
- K2Cr2O7, H2SO4- CrO3, CH3COOH
4/10/2013
42
Phenol
OH OH
OH
OH
OH
OH
OH
Phenol Catechol Resorcinol Hidroquinon
OH
COOH
OH
NO2O2N
NO2
OH
OCH3
CHO
Acid salicilic Acid picric Vanilin
Acid o-hidroxibenzoic
Phn ng do s t ni ArO-H
OH
NaOH
ONa
+ H2O
S to thnh eter
NaOHAr-OH ArONa RX ArOR + NaX
S to thnh ester
ArOH + RCOCl RCOOAr + HCl
ArOH + (RCO)2O RCOOAr + RCOOH
Chuyn v Fries
OCOEt
AlCl3
OH
COEt
OH
+
COEt
4/10/2013
43
OH
NO2
NO2
O2N
PCl5
Cl
NO2
NO2
O2N
Phn ng t ni Ar-OH
Phn ng trn vng hng phng
Nitro ha
OH
NO2
NO2
O2N
OH
HNO3 conc.
+
OH
NO2
OH
HNO3 dilution
OH
NO2
20C
Sulfon ha
OH
SO3H
OH
OH
SO3H
H2SO4
15 - 20C
100C
100C
Halogen ha
OH
Br2, H2O
OH
BrBr
Br
OH
Br2, CS2, 0C
OH
Br
4/10/2013
44
Alkil ha Friedel-Craft
OH OH
t-Bu
t-BuCl+HF
Nitroso ha
OH OH
NO
NaNO2, H2SO4, 7- 8C
Phn ng Koble-Schmitt
OH OH
1. NaOH
2. CO2, 125C, 100 atm
3. H3O+
COOH
Phn ng Reimer - Tiemann
OH OH
1. CHCl3, NaOH, H2O, 70C
2. H3O+
CHO
Vi Formaldehid
OH
+ HCHOt
OH OH
OH
OH
Nha Bakelit
HO Ar'N2+
Cl+ HO N NAr'
Phn ng ghp cp vi mui diazonium
4/10/2013
45
S C- v O-alkil ha
ONa
+ CH2=CH-CH2Br
aceton
C6H6
OCH2CH=CH2
OH
CH2CH=CH2
200C P chuyn v Claisen
Phn ng oxid ha
OH
O2
O
O
+ H2O
Benzoquinon
Eter : R-O-R
OO
OO O
O
oxiran oxetan oxolan oxan dioxan
tetrahidrofuran
Tn thng thng
Dng t eter t sau tn gc ca nhm th
CH3CH2-O-CH2CH3 Ph-O-Ph
Etil eter (dietil eter) Phenil eter
Xem eter nh mt dn xut alkoxi ca hidrocarbon
O CH3
1
2
3
4
OCH3H3CO
4-metoxi-1-ciclohexen 1,4-Dimetoxibenzen
4/10/2013
46
Phn ng
R-O-R' + HX R-OH + R'XtC
phn ng : HI > HBr > HCl
Phn ng m vng epoxid
OH3O
+
H2C CH2
OH OH
OHO
OHH3O+
iu ch : PP Williamson
+ R'-X ROR' + XRO
ALDEHID & CETON
CR
O
H R'
Nhom carbonil
Aldehid Ceton
CR
O
R
R' + -
120o
C O
Hp cht mang nhm C=O
4/10/2013
47
I. Danh php
1. Aldehid
a. Tn dn xut t acid
Thay the -ic hoac -oic trong ten thong thng cua acid carboxilic tng ng bang -aldehid.
HCHO CH3CHO CH3CH2CH2CHO
CHO CHO
OH
CH3CH
2CH
2CHCHO
CH3
Formaldehid Acetaldehid Butiraldehid
Benzaldehid Salicilaldehid a-Metilvaleraldehid
b. Tn theo h thng
Them -al vao sau ten hidrocarbon co cung so carbon. Nhom nh chc carbonil luon luon co ch so v tr la 1
CH3
CH3CH
2CHCH
2CHO
3-Metilpentanal
2. Ceton
a. Ceton chi phng
at ten hai nhom tr hoan, gan vao nhom nh chc carbonil, trc t ceton.
O O
CH3CH2CCH3 PhCH2CCH3
Metil etil ceton Metil benzil ceton
4/10/2013
48
b. Ceton hng phng
Goi ten theo ten thong thng cua acid carboxilic tng ng, thay ic hoac oic bang ophenon
O
C
O O
CH3-C CH
3CH
2CH
2-C
Acetophenon Benzophenon n-Butirophenon
c. Tn theo h thng
Them -on sau ten hidrocarbon tng ng. Nguyen t carbon cua nhom carbonil luon luon mang ch so nho nhat
O
O O
CH3CCH
3 CH3CH2CCH3
Propanon Butanon Ciclohexanon
d. Tn thng thng
O
OOCH3-C-CH3 CH3-C-C-CH3
O O
Aceton Diacetil Quinon
O
O O
Menton Camphor Jasmon
4/10/2013
49
II. iu ch
1. Aldehid
Cu , 200-300oCR-CH2-OH R-CHO
Phn ng oxid ha alcol nht cp
K2Cr
2O
7 , H
2SO
4 R-CHO
R-CH2-OH
Phn ng oxid ha metilaren
Ar-CH3 + CrO3 Ar-CH(OAc)2 Ar-CHOH2OAc2O
Ar-CH3 + Cl
2Ar-CHCl
2Ar-CHO
H2OAc2O
Phan ng Rosenmund
R-C=O R-CHO RCH2OH
Cl
H2
S-QuinolinPd-SO4
H2
CHOH
2 , xuc tac
COCl
4/10/2013
50
II. iu ch
2. Ceton
OH
K2Cr2O7 , H2SO4
O
OOH
CrO3 hay K2Cr2O7R-CH-R' R-C-R'
Oxid ha alcol nh cp
Mentol Menton
Ar-H +
RCOClAlCl3
ArCOCl
O
Ar- C - R
O
Ar- C - Ar
Phn ng acil ha Friedel-Crafts
R' -Li
RCOCl hay ArCOCl
R' -CuLiCuX
R'
R - C - R' Ar - C -R'hay
OO
Phn ng gia clorur acid v hp cht c kim
4/10/2013
51
III. Phn ng
1. Phn ng do nhm Carbonil
a. Phn ng cng thn hch
R C O
Z R' C
Z
R
O
R'
Z
R
O
R' C
OH
H2O
ZR'
C
O
O_
_
R
Cong acid cianhidric
C O + HCNOH
CCN
cianohidrin
Cong bisulfit natrium
C O + NaHSO3
SO3NaC
OHSan pham cong bisulfit
Cong amoniac NH3
3HCHO + 3NH3
3 HCHON
N
N
N
N N
N
CH2OH
CH2OH
HOH2C
3 CH2
OH
NH2
NH NH
NHNH
3
NH NH
NH
Hexametilentetramin
Cong cac dan xuat cua amoniac
C O + H2N G H2O+C N G C NH G
OH
4/10/2013
52
Cong alcol
C OROH, H
COH
OR
ROH, HC
OR
OR
Aldehid
Ceton
Hemiacetal
Hemicetal
Acetal
Cetal
Cong RMgX
C O
H
R1
+ R-MgX CR1
H
O
R
H2OCR1
H
OH
R
MgX
Formaldehid
Aldehid
Ceton
Alcol 1
Alcol 2
Alcol 3
b. Phn ng oxid ha
Aldehid[O]
Ceton
- Thuc th Tollens (AgNO3/NH3)
R-CHO + 2 Ag(NH3)2OH 2 Ag + R-COONH4 3 NH3 H2O+ +
R-CHO + 2 Cu(OH)2 Cu2O + H2O+R-COOH
C O
R
R1
ORCOOH R1COOH+
- Thuc th Fehling
4/10/2013
53
c. Phn ng hon nguyn
Hoan nguyen thanh alcol
Hoan nguyen thanh hidrocarbon
H2, Ni, to
H3CCH CH CHO
H3CCH CH CHOLiAlH4
H3CCH2CH2CH2OH
H3CCH CH CH2OH
R C R
O
Z n -H g/H C l
H 2N -N H 2/K O H
R C H 2 R
R C H 2 R
Phan ng Cannizzarro
2 HCHONaOH 50%
HCOONa CH3OH+
CHO
NO2
2NaOH 35%
COONa
NO2
+
CH2OH
NO2
4/10/2013
54
2. Phn ng do Ha
a. Phn ng hologen ha
H 3CCO CH 3 + C l2B
CH 3C O C H 2C l H C l+
O Br2 O H B r
Br
+ +
b. Phn ng haloform
R-COCH3 + +
+ +
3 NaOX R-COCX3 3 NaOH
NaOH R-COOH CHX3R-COCX3
Haloform
c. Phn ng xc hp aldol
d. Phn ng Perkin
H C
O
CH3 + H C
O
CH3B
CH3HC
H2C
OH
CHO CH3 CH CH CHO
Ph-CHO (CH3CO)2O1) CH3COONa, 175
oC
2) H2OPh-CH=CH-COOH+
4/10/2013
55
Acid carboxylic v dn xut
1. Acid carboxylic
1.1. C cu
R-COOH Ar-COOH
CH2=CH-COOH
Acid acrylic
CH3-CH2-COOH
Acid propionic
Ph-COOH
Acid benzoic
HOOC-CH2-COOH
Acid malonic
1.2. Danh php
a. Tn thng thng
CH3-COOH
H3CCHCH2COOH
H3C
COOH
Acid acetic Acid isovaleric Acid benzoic
b. Tn theo h thng
Tn hydrocarbon chi phng + -oic
C H 3-C O O H
H 3CC H C H 2C O O H
H 3C
A cid eta n o ic A c id 3 -m ety lb u ta n o ic
1.3. iu ch
a. Acid formic
1.3.1. Trong k ngh
+CO + NaOH
p, HCOONa H3O HCOOH
4/10/2013
56
b. Acid acetic
Acetylen + H2OH2SO4, HgSO4 H3CCHO
O2, xc tc CH3COOH
C2H5OH[O]
H3CCHOO2, xc tc
CH3COOH
C2H5OH + O2Men dm
CH3COOH
c. Acid bo
RCOOR + NaOH RCOONa + ROH
RCOOR + H2O RCOOH + ROHH+
1.3.2. Trong phng th nghim
RCH2OH[O] [O]
RCHO RCOOH
RXMg CO2
RMgX RCOOMgX
(ArX)
RCOOHH+
(ArCOOH)
Ar-RKMnO4 hoc K2Cr2O7
Ar-COOH
1.4. Phn ng
a. Tnh acid
Nhm gy hiu ng rt in t (-I, -R) lm tng tnh acid
CH3COOH, Cl2CHCOOH, C6H5COOH, C2H5COOH
4/10/2013
57
b. Phn ng Hell-Volhard-Zelinski
CH3COOH + Br2P
BrCH2COOH
c. Kh nhm carboxyl
d. Phn ng to peracid
CH4 CO2+CH3COONa
NO2
NO2
O2N
COOH
NO2
NO2
O2N
+ H-O-O-HR C
O
OH R C
O
O OH + H2O
2. Dn xut ca acid carboxylic
2.1. C cu
+ H2OR C
O
A R C
O
OH + HA
S thay th nhm OH ca acid bng mt nhm khc, v s thy gii
cho tr li acid ban u.
Ester, anhidrid acid, clorur acid, amid
2.2. Danh php
a. Ester
Thay ui ic trong tn acid bng at tip theo l tn gc alkyl
tng ng vi alcol
CH3-COOC2H5 COOCH3
Acetat etylBenzoat etyl
4/10/2013
58
b. Clorur acid
Clorur + tn nhm acyl tng ng
CH3 C
O
Cl
Clorur acetyl Clorur benzoyl
C
O
Cl
c. Anhidrid acid
Thay t acid trong tn acid bng anhidrid
O
O
O
Anhidrid phtalic
CH3 C
O
O
C
O
CH3
Anhidrid acetic
d. AmidThay vn ic trong tn acid bng -amid
HCONH2
Formamid
H2C=CH-CONH2
Acrylamid
2.3. iu ch
a. Clorur acid
RCOOH + PCl5 RCOCl + HCl + POCl3
3 RCOOH + PBr3 3 RCOBr + H3PO3
RCOOH + SOCl2 RCOCl + HCl + SO2
4/10/2013
59
b. Ester
RCOOH + ROH RCOOR + H2O
RCOOH + CH2N2 RCOOCH3 + N2
RCOO- + RX RCOOR + X-
Trans ester ha
RCOOR + ROH RCOOR + ROH
RCOCl + ROH RCOOR + HCl
Phn ng Schotten - Baumann
(RCO)2O + ROH RCOOR + RCOOH
c. Anhidrid
RCOOH + RCOCl RCOOCOR + HCl
O
O
O
Anhidrid phtalic
O
O
OH
OH
Acid phtalic
200 oC
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d. Amid
RCOCl + 2 NH3 RCONH2 + NH4Cl
RCOCl + 2 NH2R RCONHR + RNH3Cl
RCOOH + NH3 RCOO- NH4
+ RCONH2to
RCN + H2O RCONH2
2.4. Phn ng
a. Thy gii
+ H2OR C
O
A R C
O
OH + HA
R C
O
AR'MgX
R C
R'
R'
O R C
R'
R'
OHH2O
MgX
H+
1) OH- 2) H3O+
b. Phn ng vi tc cht Grignard
c. Hon nguyn
R C
O
A1) LiAlH4
2) H3ORCH2OH
1) LiAlH4
2) H3ORCH2NH2RCONH2
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d. Phn ng sc hp Claisen
Hai ester c Ha, di tc dng ca baz mnh s sc hp cho
ra b-cetoester
C2H5OHCH3COOC2H5C2H5ONa CH3COCH2COOC2H5 +
Amin Mui Diazonium
1. Amin
1.1. C cu Danh php
a. C cu
R-NH2 R2-NH R3-N R4N+
Amin 1o Amin 2o Amin 3o Mui amonium
b. Danh php
b1- Amin chi phng
- Tn thng thng: tn cc nhm tr hon alkil t trc t amin
(CH3)3NCH3 CH2HC
NH2
CH3CH3 CH2 NH2
Etylamin Sec-Butylamin Trimetylamin
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- Amin phc tp: gi theo h thng IUPAC (International Union of Pure and
Applied Chemistry). Nhm NH2 c gi nh l mt nhm th: amino
CH3 CH2 CH
NH2
CH2 CH3 CH3 CH2 CH2 CH
N
CH3
CH3C2H5
3-Aminopentan 2-(N-Etil-N-metilamino)pentan
b2- Amin hng phng
NH2 NH2
CH3
NH2
NH2
NH
Anilin m-Toluidin o-Phenilendiamin Diphenilamin
b3- Mui amonium
(CH3)4N Cl2
(C2H5)2N(CH3)2 OH(C6H5NH3)2 SO4
Clorur tetrametilamonium Sulfat anilium Hidroxid dimetildietilamonium
1.2. iu ch
a. Hon nguyn hp cht nitro
Ar-NO2
R-NO2
Kim loi, H+ hay H2, xc tcAr-NH2
R-NH2
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b. Amoniac gii hay amin gii halogenur
NH3RX
RNH3 XNH3 RNH2
RXR2NH
RXR3N R4N X
RX
Cl
NO2O2N
NO2
NH3
NH2
NO2O2N
NO2
Amin 1o Amin 2o Amin 3o Mui amonium t cp
CH3
ClKNH2, NH3
CH3
NH2
Clorur piril Piramid
c. Amin ha hon nguyn
C O + NH3-H2O
C NHH2
xtC NH2
H
CH3(CH2)5CHONH3, H2, Ni
CH3(CH2)5CH2NH2
C CH3Ph
O
NH3, H2, NiCHPh
NH2
CH3
Acetophenon
Imin
Heptanal Heptilamin
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d. Hidrogen ha hp cht nitril
R C NH2, Pt
R CH2 NH2
Cl-H2C-(CH2)2-CH2Cl NC-(CH2)4-CNNaCN H2, Ni
H2N-H2C-(CH2)2-CH2NH2
CH2Cl
NaCN
CH2CN CH2CH2NH2
H2, Ni
Nitril Amin 1o
1,4-Diclorobutan Adiponitril Hexametilendiamin
Clorur benzil Phenilacetonitril b-Pheniletilamin
e. Phn ng gim cp Hofmann ca amid
CONH2
Br
Br2 / NaOH
NH2
Br
N K
O
O
R-X H2O
NaOHNR
O
O
COOH
COOH
RNH2+
f. iu ch amin nht theo phn ng Gabriel
C NH2R
O
Br2 / NaOHR-NH2
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g. Amin nh, tam hng phng
+ C6H5NH2220oC, 6 atm (C6H5)2NH + NH4 ClC6H5NH3 Cl
Ph2NHLi
Ph2NLiPhI, CuI
Ph3N
R-NH2 R-NH3H
OH
1.3. Phn ng
a. Tnh baz
R-NH2 + HCl R-NH3Cl
b. Tc dng vi anhidrid v clorur acid
R-NH2 + (R'CO)2O R
'CONHR + R-COOH
R-NH2 + R'COCl R'CONHR + HCl
R-NH2 + HONO +R N N R N2H2O R-OH H+
c. Tc dng vi acid nitro
Amid N-tr hon
- Amin nht cp
Ph-NH2HONO, 0 oC
Ph N N
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- Amin nh cp
R2-NH + HONO R2N N O
Ph-NHCH3 + HONO Ph N N CH3
N O
N(CH3)2
+ HONO
N(CH3)2
NO
+ H2O
- Amin tam cp
p-Nitroso-N,N-dimetilanilin
Amin chi phng: to dialkilnitrosoamin
Amin hng phng: to N-nitroso
d. Oxid ha
PhN H 2O
PhN O 2
(C H 3)3NO
(C H 3)3N O
R4N XAg2O R4N OH + AgX
Oxid amin tam
CH3 N
CH3
CH3
CH2CH2CH3 OH CH3 N
CH3
CH3
+ CH3 CHCH2 + H2O
e. Phn ng ca mui amonium