反応例 10.3 アルコールとアルデヒドの酸化反応...反応例 10.3 アルコールとアルデヒドの酸化反応 第二級アルコールからケトンの生成 Cl
反応例 9.1 カルボン酸誘導体の反応応例 9.1 カルボン酸誘導体の反応...
Transcript of 反応例 9.1 カルボン酸誘導体の反応応例 9.1 カルボン酸誘導体の反応...
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RCOOR RCOOH
E. L. Eliel, M. T. Fisk, T. Prosser, Org. Synth., Coll. Vol. 4, 169 (1963).
OEt
Cl
O
PhOH
Cl
O
Ph
HCl
reflux, 1.5 h
CH3COOH
reflux, 3 h
R. C. Cambie, D. S. Rutledge, Org. Synth., Coll. Vol. 6, 348 (1988).
95-100%
O
O
Me
Me
O
O
NaOH
EtOH
H2O
OH
OH
reflux, 2 h
EtOH
92-97%
O. Ort, Org. Synth., Coll. Vol. 8, 522 (1993).
O
Ph
Cl
OKOH
OH
Ph
RCOOH RCOOR
OH
OH
O
PhOEt
OH
O
Ph
HCl
reflux, 5 h
EtOH
E. L. Eliel, M. T. Fisk, T. Prosser, Org. Synth., Coll. Vol. 4, 169 (1963).
reflux, 4 h 93%
P. Kalaritis, R. W. Regenye, Org. Synth., Coll. Vol. 8, 258 (1993).
H2SO4
OH
O
FEtOH
OEt
O
F
-
OH
OH
O
+
HO
Cl
POCl3
80 C, 4 h
OH
O
OCl
N. G. Gaylord, P. M. Kamath, Org. Synth., Coll. Vol. 4, 178 (1963).
55-62%
RCOCl RCOOR
Ph
O
HOCl
Cl
+
55 215 C
A. H. Ford-Moore, Org. Synth., Coll. Vol. 4, 84 (1963).
Ph
O
OCl
89-91%
CH2Cl2
M. Braun, S. Graf, S. Herzog, Org. Synth., Coll. Vol. 9, 507 (1998).
HOOH
Ph
H Ph
Ph
O
ClMe+
N
OOH
Ph
H Ph
Ph
Me
O
0 C rt, 4 h 92%
OH NaH
Et2O
S. H. Montgomery, M. C. Pirrung, C. H. Heathcock, Org. Synth., Coll. Vol. 7, 190 (1990).
Et2O
0 C
Et
O
Cl
0 C, 1.5 h
O
O
Et
96-97%
G. P. Crowther, E. M. Kaiser, R. A. Woodruff, C. R. Hauser, Org. Synth., Coll. Vol. 6, 259 (1988).
rt, 15 hMe
Cl
O
t-BuOLi
Et2O
+
Me
OBu-t
O
79-82%
reflux, 7.5 h
Et2O
63-67%
R. E. Ireland, M. Chaykovsky, Org. Synth., Coll. Vol. 5, 171 (1973).
PCl5+C
O
OH
N
reflux, 2 h
rt, 15 h
PhNMe2
t-BuOH
C
O
OBu-t
N
-
(RCO)2O RCOOR
25 C, 6 h
94-98%
R. P. Hanzlik, Org. Synth., Coll. Vol. 6, 560 (1988).
OH
O
O
O
MeMe
N
O Me
O
+0 C rt
D. R. Deardorff, C. Q. Windham, C. L. Craney, Org. Synth., Coll. Vol. 9, 487 (1998).
HO O O
O
O
MeMe
Me
O
N
HN
O O Me
O
Me
O
96-98%
toluene
reflux, 24 h
K. Furuta, K. Iwanaga, H. Yamamoto, Org. Synth., Coll. Vol. 8, 141 (1993).
84%
O
O
O
OH
+O
O
O
OTsOH
+reflux, 18 h
90%
C. Hubschwerlen, J.-L. Specklin, Org. Synth., Coll. Vol. 9, 13 (1998).
N
O
O
OH
O
SOCl2 N
O
O
Cl
O
H. C. J. Ottenheijm, M. W. Tijhuis, Org. Synth., Coll. Vol. 7, 467 (1990).
+Me
O
OH
H OMe
Cl ClO
25 50 CMe
O
Cl
O
44-50%
-
reflux, 7.5 h
C6H6
82-94%
E. C. Taylor, A. Mckillop, G. H. Hawks, Org. Synth., Coll. Vol. 6, 549 (1988).
Ph
PhOH
O
SOCl2+
Ph
PhCl
O
75-80%
G. A. Olah, S. J. Kuhn, Org. Synth., Coll. Vol. 5, 66 (1973).
Cl
O
HF
rt, 1 h 3040 C, 1 h
F
O
70 C, 1.5 h
B. Vassel, W. G. Skelly, Org. Synth., Coll. Vol. 4, 154 (1963).
98-100%
SOCl2Me2N
O
OH
+
Cl
Me2N
O
Cl
+
Cl
Cl
O
H ONa
OEt2O
MeMe O
O
H
O
L. I. Krimen, Org. Synth., Coll. Vol. 6, 8 (1988).
rt, 5.5 h+
HO
HO
OH
OH
O
O
+
H2SO4
reflux
10 min
EtOH
O
O
O
MeMeO
AcO
AcO
O
O71-77%
R. L. Shriner, C. L. Furrow, Jr., Org. Synth., Coll. Vol. 4, 242 (1963).
RCOOH RCONR2
-
CH3 OH
O
CH3 ONH4
O
CH3 NH2
O+ (NH4)2CO3
!"
210~216 C
87~90%
G.H. Coleman, A.M. Alvarado, Org. Synth., Coll. Vol. 1, 3 (1941).
HN
CH3
!
NCH3
CHO
+ HCO2Htoluene
93~97%
L.F. Fieser, J.E. Jones, Org. Synth., Coll. Vol. 3, 590 (1955).
NH2 C NHCO2H +
O
C. N. Webb, Org. Synth., Coll. Vol. 1, 82 (1941).
R. J. Johnson, L. T. Sandborn, Org. Synth., Coll. Vol. 1, 111 (1941).
NH2
AcOH
reflux, 2 h
HN
O
Me
RCOOR RCONR2
ClCH2 C OCH2CH3
O
ClCH2 C NH2
ONH
4OH
05 C
+ CH3CH2OH
W. A. Jacobs, M. Heidelberger, Org. Synth., Coll. Vol. 1, 153 (1941).
NCCH2 C OCH2CH3
O
NCCH2 C NH2
O
+ CH3CH2OHNH3
B. B. Corson, R. W. Scott, C. E. Vose, Org. Synth., Coll. Vol. 1, 179 (1941).
CH3 CH C OCH2CH3
O
OH
CH3 CH C NH2
O
OH
liq. NH3
J. Kleinberg, L. F. Audrieth, Org. Synth., Coll. Vol. 3, 516 (1955).
-
C CH2 C OCH2CH3
O O
C CH2 C NH
O OPhNH2
135 C
C. F. H. Allen, W. J. Humphlett, Org. Synth., Coll. Vol. 4, 80 (1963).
CH3CH2O
O
O
OCH2CH3
H2N
O
O
NH2
NH4OH
NH4Cl
D. T. Mowry, J. M. Butler, Org. Synth., Coll. Vol. 4, 486 (1963).
(RCO)2O RCONR2
+
40 C reflux
EtOH
O
O
O
MeMe
92-97%
K. E. Krakowiak, J. S. Bradshaw, Org. Synth., Coll. Vol. 9, 34 (1998).
HO O NH2 HO O NH
Me
O
H2NCH2 C OH
O
NHCH2 C OH
O(CH3CO)2O, H2O
CH3C
O
R. M. Herbst, D. Shemin, Org. Synth., Coll. Vol. 2, 11 (1943).
RCOCl RCONR2
0 C
NaOH
77-81%
C. S. Marvel, W. A. Lazier, Org. Synth., Coll. Vol. 1, 99 (1941).
NH
Ph
O
Cl
+Ph
O
N
H2O
PhCH2O CCl
O
PhCH2O C
OH2NCH2CO2H
NaOH
NHCH2CO2H
H. E. Carter, R. L. Frank, H. W. Johnston, Org. Synth., Coll. Vol. 3, 167 (1955).
-
OMeO
OH + SOCl2
DMF
cat.Et2NH
THF
OMeO
NEt2
X. Wang, S. O. de Silva, J. N. Reed, R. Billadeau, E. J. Griffen, A. Chan, V. Snieckus, Org. Synth., Coll.
Vol. 9, 559 (1998).
(CH3)2CH CCl
O
(CH3)2CH C
O
NH2NH4OH
R. E. Kent, S. M. McElvain, Org. Synth., Coll. Vol. 3, 490 (1955).
C(CH2)8C Cl
OO
CH3O C(CH2)8C NH2
OO
CH3ONH4OH
8 C W. S. Bishop, Org. Synth., Coll. Vol. 3, 613 (1955).
CH3CH2 CCl
O
CH3CH2 C
O
N O
CH2Cl2
ON
R. B. Lettan, II, B. C. Milgram, K. A. Scheidt, Org. Synth., Annual Vol. 84, 22 (2007).
Br (CH2)10CO2HK2CO3
(CH2)10
O
C O DMSO100 C, 1 h
C. Galli, L. Mandolini, Org. Synth., Coll. Vol. 6, 698 (1988).
79~83%
CHO
O
OPh3P=CHCO2Me
OO
CO2Me
OO
HO
MeOH, 0 C
H2SO4/MeOH
room temp., 2 h
78%
(trans 10%)
~100%
J. Mann, A.C. Weymouth-Wilson, Org. Synth., Coll. Vol. 10, 152 (2004).
!"#$$#%&'()**+,
-
HO2C
H2N
H
CO2HOO
H
CO2H
L-glutamic acid
NaNO2/H2SO4
(S)-(+)
70%
O.H. Gringore, F.P. Rouessac, Org. Synth., Coll. Vol. 6, 698 (1988).
CO2
NH
CH3
O
CO2HCH3NH2
H2O
CO2
N
CH3
+NH3CH3
N
CH3
CH3O
+NH3CH3
H2 / Ni
74~77%
R.L. Frank, W.R. Schmitz, B. Zeidman, Org. Synth., Coll. Vol. 3, 328 (1955).
CO2H
H2N !
HN
O
cis and trans
Dowtherm
!"#$%
81~84%
W.M. Peariman, Org. Synth., Coll. Vol. 5, 670 (1973).
C. Y. Meyers, L. E. Miller, Org. Synth., Coll. Vol. 4, 39 (1963).
reflux, 1 h
90%
NH
O
HCl
H2O Amberlite
resin
HO
O
NH2
11