反応例
芳香族求電子置換 反 応（ベンゼン誘導体）
16.1
（縮合多環芳香族の反応については 20.1 を参照のこと）
ハロゲン化
NO2
Br
Br2, Fe
NO2
J.R.Johnson, C.G. Gauerke,
Org. Synth., Coll. Vol. 1, 123 (1941).
140 ˚C
60~75%
OH
OH
Br 2
CS 2, 5 ˚C
R. Adams, C.S. Marvel,
Org. Synth., Coll. Vol. 1, 128 (1941).
Br
80~84%
CH3
CH3
Br 2, Fe
0 ˚C
CH3
Br
W.A. Wisansky, S. Ansbacher,
Org. Synth., Coll. Vol. 3, 138 (1955).
CH3
94~97%
CH3
CH3
Br
Br2
CH3
CH3 CCl4, 10 ˚C
CH3
CH3
L.I.Smith,
Org. Synth., Coll. Vol. 2, 95 (1943).
79~82%
NHAc
AcOH
CH3
NHAc
Br2
CH3
Br
J.R.Johnson, L.T. Sandborn,
Org. Synth., Coll. Vol. 1, 111 (1941).
Br
OH
AcOH
O 2N
HO
OH
CO 2H
OH
Br 2
Br2
AcOH
O2N
Br
HO
OH
Br
W.W. Hartman, J.B. Dickey,
Org. Synth., Coll. Vol. 2, 173!(1943).
R.B. Sandin. R.A. McKee,
CO 2H Org. Synth., Coll. Vol. 2, 100!(1943).
Br2
Br
Br
R.E. Buckles, N.G. Wheeler, Org. Synth., Coll. Vol. 4, 256 (1963).
Br
NH2
NH2
Br2
HCl, H2O
Br
Br
Br
G.H.Coleman, W.F. Talbot,
Org. Synth., Coll. Vol. 4, 545 (1963).
1) NaNO2, H2SO4
2) H2SO4, EtOH, !
Br
Br
Br
HO 2C
NH2
HO2C
Br 2
HCl, H2O
NH2
Br
40~50 ˚C
Br
Br
NaNO2, H2SO4
M.M. Robison, B.L. Robison,
Org. Synth., Coll. Vol. 4,!947 (1963).
HO 2C
50% H3 PO2
AcOH, H2O
Br
–10 to 5 ˚C
Br
70~80%
Cl
NH2
NH2
Cl2
CO 2H
HCl, H2 O
Cl
CO 2H
I
I2, HNO3
E.R. Atkinson, D.M. Murphy, J.E. Lufkin,
Org. Synth., Coll. Vol. 4,!872 (1963).
F.B. Dains, R.Q. Brewster,
Org. Synth., Coll. Vol. 1, 323 (1941).
50 ˚C
86~87%
I
NH2
O 2N
NH2
ICl, AcOH
!
O 2N
I
R.B. Sandin, W.V. Drake, F. Leger,
Org. Synth., Coll. Vol. 2, 196!(1943).
ニトロ化
O
O
HNO3,
H2SO4
CH3
O2N
CH3
B.B. Corson, R.K. Hazen,
Org. Synth., Coll. Vol. 2, 434 (1943).
0 ˚C
55 %
O
O
HNO3 ,
H 2SO4
OMe
O2N
OMe
O. Kamm, J.B. Segur,
Org. Synth., Coll. Vol. 1, 372!(1941).
5~15 ˚C
81~85%
CH2CN
HNO3,
H2SO4
CH2CN
20 ˚C
G.R. Robertson,
Org. Synth., Coll. Vol. 1, 396!(1941).
O 2N
50~54%
!"#$%&'()*+,
CH3
CH3
HNO3
CH3
CH3
Ac2O, AcOH
20 to 50 ˚C
CH3
G.Powell, F.R. Johnson,
Org. Synth., Coll. Vol. 2, 449!(1943).
NO2
CH3
74~76%
CO 2H
!" HNO3
H2SO4
70 to 100 ˚C, 4 h
140 ˚C, 3 h
O2N
CO2H
NO2
R.Q. Brewster, B. Williams, R. Phillips,
Org. Synth., Coll. Vol. 3, 337!(1955).
54~58%
CHO
CHO
HNO3
Ac2O, AcOH
NO2
36~46%
R.E. Buckles, M.P. Bellis,
Org. Synth., Coll. Vol. 4, 722!(1963).
CH3
CH3
HNO3
H2SO4, AcOH
–15 to –10 ˚C
(CH3)2CH
(CH3) 2CH
NO 2
78~82%
!8%" p-nitrotoluene#$%&
K.A. Kobe, T.F. Doumani, Org. Synth., Coll. Vol. 3, 653!(1955).
NH2
NHAc
Ac2O
MeO
NHAc
HNO3
MeO
MeO
NO2
75~79%
NH2
KOH, H 2O
MeOH
Cl
Cl
MeO
2 KNO3
H2 SO4
130 ˚C
P.E. Fanta, D.S. Tarbell,
Org. Synth., Coll. Vol. 3, 661!(1955).
NO 2
Cl
Cl
O 2N
NO2
J.H. Boyer, R.S. Buriks,
Org. Synth., Coll. Vol. 5, 1067!(1973).
70~71.5%
NO 2
CH3
CH3
2 NO2+ BF4–
SO2 !
CN
O 2N
CN
G.A. Olah, S.J. Kuhn,
Org. Synth., Coll. Vol. 5, 480!(1973).
48~53%
MeO
CHO
MeO
CHO
HNO3
MeO
MeO
C.A. Fetscher,
Org. Synth., Coll. Vol. 4, 735!(1963).
NO 2
73~79%
スルホン化
CH3
NH2
H2 SO4
H 2O
CH3
NH3HSO 4
!
HO 3S
CH3
NH2
C.F.H. Allen, J.A. VanAllan, Org. Synth., Coll. Vol. 3, 824!(1955).
OH
OH
100 ˚C, 3 h
HO3S
SO 3H
Br
Br2
40~50 ˚C
ONa
NaOH
H2SO4
NaO3S
SO3Na
Br
OH
NaO3S
Br
SO3Na
+
OH
H2SO4
HO 3S
OH
H 3O
SO3H
200 ˚C
40~43%
R.C. Hudson, M.M. Ballard, Org. Synth., Coll. Vol. 2, 97!(1943).
NHAc
NHAc
HOSO2Cl
S. Smiles, J. Stewart,
Org. Synth., Coll. Vol. 1, 8 (1941).
ClO2S
Friedel-Crafts アルキル化
CH3
+ 2 CH3Cl
CH3
AlCl 3
!
CH3
CH3
CH3
CH3
L.I. Smith, Org. Synth., Coll. Vol. 2, 248 (1943).
Br
Ph
CH3
AlCl 3
+
O
!
CH3
Ph
O
Br2
benzene
E.M. Schultz, S. Mickey,
Org. Synth., Coll. Vol. 3, 343 (1955).
CH3
O
+
H2SO4
C6 H6
B.B. Corson, V.N. Ipatieff,
Org. Synth., Coll. Vol. 2, 151 (1943).
+
Cl
H2SO4
Cl
W.T. Smith, Jr., J.T. Sellas,
Org. Synth., Coll. Vol. 4, 702 (1963).
C6 H6
NH2·HCl
NH2·HCl
AcOH
+ Ph 3COH
!
NH2
NaOH
H2O
Ph3C
Ph3C
B. Witten, E.E. Reid, Org. Synth., Coll. Vol. 4, 47 (1963).
Friedel-Crafts アシル化
CH3
CH3
O
AlCl3
+
CH3
(CH3) 2CH
Cl
CS 2
–5 to 5 ˚C
CH3
(CH3) 2CH
O
C.F.H. Allen, Org. Synth., Coll. Vol. 2, 3 (1943).
NHAc
NHAc
O
+ Cl
AlCl3
Cl
CS 2 !
Cl
O
J.L. Leiserson, A. Weissberger, Org. Synth., Coll. Vol. 3, 183 (1955).
O
NMe2
NMe2
O
Cl
+ Cl
AlCl3
CS2
reflux, 1 h Me2N
O
O
38~42%
C. Tüzün, M. Ogliaruso, E.I. Becker, Org. Synth., Coll. Vol. 5, 111 (1973).
O
O
+
O
AlCl3
C6H6
C.E. Olson, A.R. Bader, G.D. Johnson,
Org. Synth., Coll. Vol. 4, 898 (1963).
!
91~96%
O
O
Cl
AlCl3
CS2 !
E.L. Martin, L.F. Fieser,
Org. Synth., Coll. Vol. 2, 569 (1943).
74~91%
SOCl2
!
O
OH
O
O
OH
!""#$
H.R. Snyder, F.X. Werber,
Org. Synth., Coll. Vol. 3, 798 (1955).
!
75~86%
O
O
+
O
CO 2H
AlCl3
C6 H6
O
reflux, 30 min
77~82%
O
O
+
O
CO 2H
AlCl 3
C6H 6
O
L.F. Somerville, C.F.H. Allen,
Org. Synth., Coll. Vol. 2, 81 (1943).
!
50~85%
O. Grummitt, E.L. Becker, C. Miesse,
Org. Synth., Coll. Vol. 3, 109 (1955).
O
CH3
O
+
CO2H
AlCl3
PhCH 3
90 ˚C, 2.5 h
O
O
CH3
96%
L.F. Fieser, Org. Synth., Coll. Vol. 1, 517 (1941).
O
CO 2H
CH3
!"H2 SO4
100 ˚C, 2 h
O
81~90%
O
L.F. Fieser, Org. Synth., Coll. Vol. 1, 353 (1941).
OH
O
!H2SO4
B(OH)3
+
O
O
OH
O
OH
200 ˚C, 3.5 h
O
Cl
68~74%
L.A. Bigelow, H.H. Reynolds, Org. Synth., Coll. Vol. 1, 476 (1941).
HO
OH
HO
OH
ZnCl 2
+ AcOH
CH3
AcOH !
S.R. Cooper,
Org. Synth., Coll. Vol. 3, 761 (1955).
O
Vilsmeier 反応
NMe2
NMe2
O
1) POCl 3
+
H
NMe2
2) AcONa
H 2O
O
O
H
P
Cl
Cl
Cl
O
H
NMe2
–
Cl
Cl
CHO
H
C
E. Champaigne, W.L. Archer,
Org. Synth., Coll. Vol. 4, 331 (1963).
O
POCl2
+
NMe2
H
NMe2
H
H OPOCl2
Cl
+
Cl
NMe2
Cl H
H C NMe2
NMe2
H2O
+
NMe2
NMe2
NMe2
!"#$%&"&'()*
NMe2
O
NMe2
NHPh
+
NMe2
POCl3
NPh
NMe 2
HCl
C.D. Hurd, C.N. Webb,
Org. Synth., Coll. Vol. 1, 217 (1941).
H2O
O
ハロアルキル化
CH3
CH3
H2C O
HCl
CH3
CH3
CH2Cl
55 ˚C
CH3
CH3
OH
OH
O 2N
R.C. Fuson, N. Rabjohn,
Org. Synth., Coll. Vol. 3, 557 (1955).
CH2(OCH3 )2
HCl, H2SO4, 70 ˚C
O2N
CH2Cl
C.A. Buehler, F.K. Kirchner, G.F. Deebel, Org. Synth., Coll. Vol. 3, 557 (1955).
MeO
MeO
O
OH
H2C O
AcOH, HCl
80~90 ˚C
MeO
MeO
O
O
J. Finkelstein, A. Brossi,
Org. Synth., Coll. Vol. 6, 471 (1988).