反応例 9.1 カルボン酸誘導体の反応...naoh etoh h2o oh oh reflux, 2 h etoh 92-97% o....
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反応例 9.1 カルボン酸誘導体の反応
エステルの加水分解: 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
エステルの生成
カルボン酸から: 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%
酸ハロゲン化物から: 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
酸無水物から: (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
酸ハロゲン化物の合成
+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 30–40 °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–
酸無水物の合成
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).
アミドの生成
カルボン酸から: 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
エステルから: RCOOR → RCONR2
ClCH2 C OCH2CH3
O
ClCH2 C NH2
ONH
4OH
0–5 °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).
酸無水物から: (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).
酸塩化物から: 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).
ラクトンの生成
Br (CH2)10–CO2HK2CO3
(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 O
O
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).
ラクタムの生成
CO2–
NH
CH3
O
CO2H CH3NH2
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).
ラクタムの加水分解
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
(還元的アミノ化:11章)
(イオン交換)