反応例
19.1
芳香族求核置換反応（ベン ゼン誘導体）
付加−脱離反応
Cl
O 2N
NH2
NH 3, NH4 OAc
170 ˚C
NO 2
O2N
NO 2
68~76%
F.B. Welles, C.F.H. Allen, Org. Synth., Coll. Vol. 2, 221 (1943).
Cl
O 2N
NO2
NHNH2
H2NNH2·H2SO4,KOAc
EtOH, reflux, 1 h
O 2N
NO 2
81~85%
C.F.H. Allen, Org. Synth., Coll. Vol. 2, 228 (1943).
NO 2
NO2
Cl
NH2
NH4OH/H2O
NO2 100 ˚C, 1 h
KO3S
NO 2
KO3S
NO 2
NH2
H2 SO4/H2O
reflex, 6 h
NO2
30~36%
H.P. Schultz, Org. Synth., Coll. Vol. 4, 364 (1963).
Cl
Cl
O 2N
NH3/HOCH2CH2OH
140 ˚C, 3 h
NO2
H2 N
NH2
O 2N
NO2
88~95%
J.H. Boyer, R.S. Burks, Org. Synth., Coll. Vol. 5, 1067 (1973).
I
I
K2CO3
DMF
F
NO2
Ph
NO 2
NH2
+ HO
Ph
NaH
DMF
H
N
I
O
NO 2
OH
80%
Ph
NH2
80%
R.Beugelmans, A. Bigot, J. Zhu, Tetrahedron Lett., 35, 5649 (1994).
NO2
OH
NO2
F HO
+
OH
OH
O
NO2
O
K 2CO3
DMF
MeO2C
MeO2C
CO2Me
CO 2Me
CO 2Me
80%
R.Beugelmans, G.P. Singh, J. Zhu, Tetrahedron Lett., 34, 7741 (1993).
Cl
S
Na2 S/EtOH
reflux, 2 h
NO2
S
NO2 O2N
M.T. Bogert, A. Stull,
Org. Synth., Coll. Vol. 1, 220 (1941).
56~66%
Cl
SNa
Na2S/H2O
reflux, 20 h
O 2N
SNa
Na 2S/H 2O
!
O 2N
70 ˚C, 2 h
H2N
S S
30% H 2O2
H2 N
NH2
58~64%
C.C. Price, G.W. Stacy, Org. Synth., Coll. Vol. 3, 86 (1955).
Cl
O2N
NO2
SCH2Ph
PhCH2 SH, pyridine
MeOH, reflux, 16 h
O 2N
NO2
81~86%
N. Kharasch, R.B. Langford, Org. Synth., Coll. Vol. 5, 474 (1973).
F
F
F
F
+ NC
F
CO 2Et
110~120 ˚C, 4 h
F
F
H 2SO4, AcOH
H 2O, reflux, 15 h
K 2CO3/DMF
F
CN
F
F
F
F
F
CO 2Et
CN
F
F
F
71~75%
R. Filler, S.M. Woods,
Org. Synth., Coll. Vol. 6, 873(1988).
脱離−付加（ベンザイン）機構
Br
O- t-Bu
t-BuOH/DMSO
+ t-BuOK
>130 ˚C, 1 min
42~46%
R.V. Sahyun, D.J. Cram, Org. Synth., Coll. Vol. 5, 926 (1973).
CH3
CH3
CH3
NaOH
+
350 ˚C
OH
Cl
OH
CH3
CH3
NaNH 2
CH3
+
!"NH 3
Cl
NH2
NH2
CH3
CH3
Cl
CH3
NH2
NaNH 2
+
!"NH 3
CH3
NH2
CH3
CH3
NaNH2
Cl
!"NH3
CH3
NH2
+
+
NH2
NH2
OCH3
OCH3
Cl
NaNH2
!"NH3
NH2
CF3
CF3
Cl
NaNH2
!"NH3
OH
NH2
OH
NaNH2
!"NH3
NH2
Br
F
+
Br
Mg
THF
28%
G. Wittig, Org. Synth., Coll. Vol. 4, 964 (1963).