反応例 11.2 イミンの生成と関連反応および Wittig 反応反応例 11.2...
7
反応例 11.2 イミンの生成と関連反応および Wittig 反応 イミンの合成 CHO CH NPh PhNH 2 15 min + 84~87% L. A. Bigelow, H. Eatough, Org. Synth., Coll. Vol. 1, 80 (1941). NH 2 CH 3 CHO + N CH 3 CH C. F. H. Allen, J. VanAllan, Org. Synth., Coll. Vol. 3, 827 (1955). CHO CH 3 NH 2 CH NCH 3 + benzene 87~95% R. B. Moffett, Org. Synth., Coll. Vol. 4, 605 (1963). CHO NO 2 PhNH 2 ! NO 2 NPh CH 87~94% + 1 h J. I. G. Cadogan, R. K. Mackie, Org. Synth., Coll. Vol. 5, 941 (1973). R. L. Danheiser, I. Okamoto, M. D. Lawlor, T. W. Lee, Org. Synth., Vol. 80, 160 (2003). 88% + rt, 2 h MgSO 4 PhCHO OCH 3 H 2 N CH 2 Cl 2 OCH 3 N Ph
Transcript of 反応例 11.2 イミンの生成と関連反応および Wittig 反応反応例 11.2...
反応例 11.2 イミンの生成と関連反応および Wittig反応
イミンの合成
CHO CH NPhPhNH2
15 min
+
84~87% L. A. Bigelow, H. Eatough, Org. Synth., Coll. Vol. 1, 80 (1941).
NH2
CH3
CHO+ N
CH3
CH
C. F. H. Allen, J. VanAllan, Org. Synth., Coll. Vol. 3, 827 (1955).
CHO CH3NH2 CH NCH3+
benzene
87~95% R. B. Moffett, Org. Synth., Coll. Vol. 4, 605 (1963).
CHO
NO2
PhNH2
!
NO2
NPhCH
87~94%
+
1 h
J. I. G. Cadogan, R. K. Mackie, Org. Synth., Coll. Vol. 5, 941 (1973).
R. L. Danheiser, I. Okamoto, M. D. Lawlor, T. W. Lee,
Org. Synth., Vol. 80, 160 (2003).
88%
+
rt, 2 h
MgSO4PhCHOOCH3
H2N CH2Cl2
OCH3
N
Ph
H
O
N-t-Bu+ t-BuNH2
benzene, !
78~94%
W.D. Emons, A.S. Pagano, Org. Synth., Coll. Vol. 5, 191 (1973).
D. J. Weix, J. A. Ellman, Org. Synth., Vol. 80, 157 (2005).
98%EtOH
OHO
OH
NH2
OH
under Ar, 2 h
OH
N
オキシム
J. L. LaMattina, R. T. Suleske, Org. Synth., Vol. 64, 19 (1985).
66-69%
0-5°C, 2 h
NH2OH-HCl
Naq. NaOHMe
O
NMe
N OH
J. D. White, D. J. Wardrop, K. F. Sundermann, Org. Synth., Vol. 79, 125 (2002).
79% rt, 20 min
NH2OH
EtOH, pyridine
O
O
N
O
OH
ヒドラゾン
V. G. Nenajdenko, V. N. Korotchenko, A. V. Shastin, E. S. Balenkova,
Org. Synth., Vol. 82, 93 (2005).
81-88%
reflux, 3 h
NH2NH2
EtOHMe
O
Me
N NH2
ClCl
X. Creary, Org. Synth., Vol. 64, 207 (1985).
87-93%
+ rt
MeOHPhCHO NH2NHTs PhCH NNHTs
エナミンの合成
O
HN OTsOH N
O
+
toluene, !72~80%
S. Hünig, E. Lücke, W. Brenninger, Org. Synth., Coll. Vol. 5, 808 (1973).
ON
+
98%
HN
benzene, reflux
R.B. Woodward, I.J. Pachter, M.L. Scheinbaum, Org. Synth., Coll. Vol. 6, 496 (1988).
J. Oh, C. Ziani-Cherif, J.-P. Choi, J. K. Cha, Org. Synth., Vol. 78, 212 (2000).
99%
O
Cl NH
MgSO4
rt, overnight
N
Cl
OTsOH
N
xylene, reflux78~82%
R.D Burpitt, J.G. Thweatt, Org. Synth., Coll. Vol. 5, 277 (1973).
+ HN
CHO
CHO
CH3
CH3
HN
HN
CH3
CH3 H
N
N
+
Y. Chan, W.W. Epstein, Org. Synth., Coll. Vol. 6, 496 (1988).
+toluene, reflux
V.V. Kane, M. Jones, Jr., Org. Synth., Coll. Vol.7, 473 (1990).
93.6%
N2, !
94~95%
Y. Hamada, T. Shioiri, Org. Synth., Vol. 78, 191 (1984).
quant.
NH
4A MS12 O
+Et2OBF3, toluene
reflux, 20 h
12N
CH3
CO2Et
O
CH3
CO2Et
NHPh
+ PhNH2AcOH (cat.)
benzene, !
76~80%
G.A Reynolds, C.R. Hauser, Org. Synth., Coll. Vol. 3, 374 (1955).
還元的アミノ化
CH3 NH2PhCHO
CH3 N=CHPh CH3 NHCH2PhH2 (1000 psi)
Raney Ni / Et2O
89~94%
C.F.H. Allen, J. VanAllan, Org. Synth., Coll. Vol. 3, 827 (1955).
Ph CH3
O
Ph CH3
NH2
+ NH3
H2 (3500~5000 psi)
Raney Ni, 150 ˚C
52%
J.C. Robinson, Jr., H.R. Snyder, Org. Synth., Coll. Vol. 3, 717 (1955).
CH3 CH3
O
H2NOH+
H2 (25 psi)
PtO2 / EtOHCH3 N
H
OH
CH3
94~95%
E.M. Hancock, A.C. Cope, Org. Synth., Coll. Vol. 3, 501 (1955).
ONaBH3CN / KOH
MeOH
NMe2
+ Me2NH·HCl
52~54%
R.F. Borch, Org. Synth., Coll. Vol. 6, 499 (1988).
Wolff-Kishner還元
HO2C(CH2)4C(CH2)4CO2H
OH2NNH2
KOH
HO2C(CH2)9CO2H
87~93%
L.J. Durham, L,J, McLeod, Org. Synth., Coll. Vol. 4, 510 (1963).
Ph Ph
NNH2 t-BuOK
DMSO
PhCH2Ph
90%
D.J. Cram, M.R.V.Sahyun, G.R. Knox, J. Am. Chem. Soc., 84, 1734 (1962).
O
t-Bu
NaBH3CN
t-Bu
+ TsNHNH2
77%
R.O. Hutchins, B.E. Maryanoff, C.A. Milewski, J. Am. Chem. Soc., 93, 1793 (1971).
Clemmensen 還元
OH
C(CH2)5CH3
O
Zn(Hg)
HClOH
CH2(CH2)5CH3
81~86%
R.R. Read, J. Wood, Jr., Org. Synth., Coll. Vol. 3, 444 (1955).
CHOCH3O
HO
Zn(Hg)
HCl
CH3CH3O
HO 60~67%
R. Schwarz, H. Hering, Org. Synth., Coll. Vol. 4, 203 (1963).
Wittig 反応
O
Ph3P CH2
!
Ph3P–CH3 Br–
Et2O
BuLi
CH2
Ph3P CH2
+
35~40%
Ph3P + CH3Br
+
G. Wittig, U. Schöllkopf, Org. Synth., Coll. Vol. 5, 751 (1963).
t-BuOK
CHO
Me2NPh3P CCl2
Ph3P CCl2
HC
Me2N
CCl2
Ph3P + CHCl3heptane
<5 ̊ C, 1 h
+heptane, 10 ˚C
39~56%
A.J. Speziale, K.W. Ratts, D.E. Bissing, Org. Synth., Coll. Vol. 5, 361 (1963).
PhCH CHCH2Cl + Ph3P
PhCH CHCH2PPh3 Cl–LiOEt
EtOH
PhCH CHCH2PPh3 Cl–
PhPh
+
+
PhCHO +
xylene, reflux
60~67%
R.N. McDonald, T.W. Campbell, Org. Synth., Coll. Vol. 5, 49 (1963).
CHOPh3P
Cl–CF2–CO2NaHC
CF2
diglyme, ! 67~79%
S.A. Fuqua, W.G. Duncan, R.M. Silverstein, Org. Synth., Coll. Vol. 5, 49 (1963).
CF3
O
Ph3P
Cl–CF2–CO2Na CCF2
CF3
diglyme, 140 ̊ C 50~60%
F.E. Harkes, D.J. Burton, Org. Synth., Coll. Vol. 5, 949 (1963).
Cl
O
Ph3P C
H
CO2Et
Et3N
CH2Cl2
C C
H
CH3
C
CO2Et
H
+
62~64%
R.W. Lang, H.-J. Hansen, Org. Synth., Coll. Vol. 7, 232 (1990).
