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
Ph OH
Cl
O Ph HCl
reflux, 1.5 h CH
3COOH
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
H
2O
OH OH
reflux, 2 h EtOH
92-97%
O. Ort, Org. Synth., Coll. Vol. 8, 522 (1993).
O Ph
Cl
O KOH
OH Ph
エステルの生成
カルボン酸から
： RCOOH → RCOOR OH
OH
O
Ph OEt
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).
H
2SO
4OH
O
F EtOH OEt
O
F
OH OH O
+ HO
Cl
POCl
380 °C, 4 h
OH O
O Cl
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
HO Cl
Cl +
55 – 215 °C A. H. Ford-Moore, Org. Synth., Coll. Vol. 4, 84 (1963).
Ph O
O Cl
89-91%
CH
2Cl
2M. Braun, S. Graf, S. Herzog, Org. Synth., Coll. Vol. 9, 507 (1998).
HO OH
Ph H Ph
Ph
O Cl
+ Me N
O OH
Ph H Ph
Ph Me
O
0 °C – rt, 4 h 92%
OH NaH
Et
2O
S. H. Montgomery, M. C. Pirrung, C. H. Heathcock, Org. Synth., Coll. Vol. 7, 190 (1990).
Et
2O 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 h Me
Cl O
t-BuOLi
Et
2O +
Me
OBu-t O
79-82%
reflux, 7.5 h Et
2O
63-67%
R. E. Ireland, M. Chaykovsky, Org. Synth., Coll. Vol. 5, 171 (1973).
PCl
5C +
O OH N
reflux, 2 h rt, 15 h PhNMe
2t-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
Me Me
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
Me Me
Me O
N H N
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 TsOH O
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
SOCl
2N
O
O
Cl O
H. C. J. Ottenheijm, M. W. Tijhuis, Org. Synth., Coll. Vol. 7, 467 (1990).
Me + O
OH
H OMe Cl Cl O
25 – 50 °C Me
O Cl O
44-50%
reflux, 7.5 h C
6H
682-94%
E. C. Taylor, A. Mckillop, G. H. Hawks, Org. Synth., Coll. Vol. 6, 549 (1988).
Ph
Ph OH
O
SOCl
2+
Ph
Ph Cl
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%
SOCl
2Me
2N
O OH +
Cl
–Me
2N O
Cl +
Cl
–酸無水物の合成
Cl O
H ONa
O
Et2O
Me Me O
O
H O
L. I. Krimen, Org. Synth., Coll. Vol. 6, 8 (1988).
rt, 5.5 h +
HO HO
OH OH O
O
+
H
2SO
4reflux 10 min
EtOH O
O O
Me
Me O
AcO AcO
O
71-77% O 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 → RCONR
2CH
3OH O
CH
3ONH
4O
CH
3NH
2O + (NH
4)
2CO
3 !"210~216 ˚C
87~90%
G.H. Coleman, A.M. Alvarado, Org. Synth., Coll. Vol. 1, 3 (1941).
H N CH
3!
N CH
3CHO
+ HCO
2H toluene
93~97%
L.F. Fieser, J.E. Jones, Org. Synth., Coll. Vol. 3, 590 (1955).
NH
2C NH
CO
2H +
O
C. N. Webb, Org. Synth., Coll. Vol. 1, 82 (1941).
R. J. Johnson, L. T. Sandborn, Org. Synth., Coll. Vol. 1, 111 (1941).
NH
2AcOH reflux, 2 h
H N
O Me
エステルから
： RCOOR → RCONR
2ClCH
2C OCH
2CH
3O
ClCH
2C NH
2NH
4OH O
0–5 °C + CH
3CH
2OH W. A. Jacobs, M. Heidelberger, Org. Synth., Coll. Vol. 1, 153 (1941).
NCCH
2C OCH
2CH
3O
NCCH
2C NH
2O
+ CH
3CH
2OH NH
3B. B. Corson, R. W. Scott, C. E. Vose, Org. Synth., Coll. Vol. 1, 179 (1941).
CH
3CH C OCH
2CH
3O
OH
CH
3CH C NH
2O OH liq. NH
3J. Kleinberg, L. F. Audrieth, Org. Synth., Coll. Vol. 3, 516 (1955).
C CH
2C OCH
2CH
3O O
C CH
2C NH
O O
PhNH
2135 °C
C. F. H. Allen, W. J. Humphlett, Org. Synth., Coll. Vol. 4, 80 (1963).
CH
3CH
2O O
O
OCH
2CH
3H
2N O
O NH
2NH
4OH
NH
4Cl
D. T. Mowry, J. M. Butler, Org. Synth., Coll. Vol. 4, 486 (1963).
酸無水物から
： (RCO)
2O → RCONR
2+
40 °C – reflux EtOH O
O O
Me Me
92-97%
K. E. Krakowiak, J. S. Bradshaw, Org. Synth., Coll. Vol. 9, 34 (1998).
HO O NH
2HO O N
H Me O
H
2NCH
2C OH O
NHCH
2C OH (CH
3CO)
2O, H
2O O
CH
3C O
R. M. Herbst, D. Shemin, Org. Synth., Coll. Vol. 2, 11 (1943).
酸塩化物から
： RCOCl → RCONR
20 °C NaOH
77-81%
C. S. Marvel, W. A. Lazier, Org. Synth., Coll. Vol. 1, 99 (1941).
N H
Ph O
Cl +
Ph O
N H
2O
PhCH
2O CCl O
PhCH
2O C H
2NCH
2CO
2H O
NaOH NHCH
2CO
2H
H. E. Carter, R. L. Frank, H. W. Johnston, Org. Synth., Coll. Vol. 3, 167 (1955).
O MeO
OH + SOCl
2DMF cat.
Et
2NH THF
O MeO
NEt
2X. Wang, S. O. de Silva, J. N. Reed, R. Billadeau, E. J. Griffen, A. Chan, V. Snieckus, Org. Synth., Coll.
Vol. 9, 559 (1998).
(CH
3)
2CH CCl O
(CH
3)
2CH C O
NH
2NH
4OH
R. E. Kent, S. M. McElvain, Org. Synth., Coll. Vol. 3, 490 (1955).
C(CH
2)
8C Cl O O
CH
3O C(CH
2)
8C NH
2O O
CH
3O NH
4OH
8 °C
W. S. Bishop, Org. Synth., Coll. Vol. 3, 613 (1955).
CH
3CH
2CCl O
CH
3CH
2C O
N O
CH
2Cl
2O N
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 (CH
2)
10–CO
2H
K2CO3
(CH
2)
10O C O
DMSO100 ˚C, 1 h
C. Galli, L. Mandolini, Org. Synth., Coll. Vol. 6, 698 (1988).
79~83%
CHO O O
Ph3P=CHCO2Me
O O
CO
2Me
O O
HO
MeOH, 0 ˚CH2SO4/MeOH room temp., 2 h
78%
(trans 10%)
~100%
J. Mann, A.C. Weymouth-Wilson, Org. Synth., Coll. Vol. 10, 152 (2004).
!"#$$#%&'()**+,
HO
2C
H
2N H
CO
2H O O
H CO
2H
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
CO
2–NH CH
3O
CO
2H
CH3NH2H2O
CO
2–N CH
3+
NH
3CH
3N
CH
3CH
3O
+
NH
3CH
3 H2 / Ni74~77%
R.L. Frank, W.R. Schmitz, B. Zeidman, Org. Synth., Coll. Vol. 3, 328 (1955).
CO
2H
H
2N !
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
H
2O Amberlite
resin
HO O
NH
2（還元的アミノ化：11章）
（イオン交換）
