8
GATAULLIN ET AL.
4.3 | (4-Bromophenyl)[(2E)-1-methylbut-
2-en-1-yl]amine (2b)
4.5 | N-{2-bromo-6-[(2E)-1-methylbut-
2-en-1-yl]phenyl}-
4-methylbenzenesulfonamide (3a)
The 4-chloro-2-pentene (6 g, 58.1 mmol) was added to
4-bromaniline (10 g, 58.14 mmol) in Et3N (30 ml). The
reaction mixture was heated in a water bath at 80ꢁC for
2 hours. The excess of Et3N was evaporated under
Tosylchloride (0.57 g, 3 mmol) was added to a solution of
compound 1a[18] (0.65 g, 2.7 mmol) in dry pyridine
(2 ml). The reaction mixture was kept for 24 hours at
20ꢁC. Water (30 ml) was added and mixed for 30 minutes.
The solvent was evaporated in vacuo; H2O (30 ml) and
CH2Cl2 (60 ml) were added to the remaining stock,
shaken in a separatory funnel, the organic phase was sep-
arated, washed consequently with 10% HCl (10 ml) and
water (10 ml), and dried over Na2SO4. After removal of
the solvent in vacuo, the remaining stock (≈1.5 g) was
purified by chromatography on a silica gel column (5 g,
C6H6 as eluent). Yield 1.0 g (93%). Compound 3a was
slowly crystallized from ethanol. MS, m/z (Ir, %): (Scan
E+) 394, 396 [M + H]+ (100); (Scan E−) 392, 394
[M − H]− (100). NMR spectrum 1H (CDCl3), δ, ppm: 1.28
d (3H, CH3, J 6.8 Hz), 1.66 d (3H, CH3, J 4.2 Hz), 2.42 s
reduced pressure on
a rotary evaporator; to the
remaining mixture CH2Cl2 (60 ml) was added, then satu-
rated NaHCO3 aqueous solution (2 × 100 ml), and the
mixture was gently shaken in a separatory funnel until
CO2 emission ceased. The organic layer was dried over
KOH, decanted from the desiccant, the solvent was evap-
orated on a rotor evaporator. The reaction product was
isolated by distillation in vacuo, b. p. 124-127ꢁC
(2 mm Hg). Yield 11 g (78%). MS, (20 eV), m/z (Ir, %):
213, 215 [M-C5H8 + CH3CN + H]+ (100), 240, 242
[M + H]+ (55), 254, 256 (50), 281, 283 [M + CH3CN + H]+
(100). IR, ν, cm−1:3413 (NH), 1593, 1495, 1316, 965, 812,
1
678, 650, 624, 596, 504, 487. H NMR, CDCl3, δ, ppm:
1
0
1.27 d (3H, CH3, J 6.6 Hz), 1.67 d (3H, CH3, J 6.2 Hz),
(3H, CH3), 4.27-4.30 m (1H, H ), 5.44-5.57 m (2H,
1
2
0
3
0
0
3.83-3.90 m (1H, H ), 3.61 br. s (1H, NH), 5.35-5.61 m
H C CH ), 6.42 s (1H, NH), 7.11 dt (1Harom., J 2.5,
J 7.9 Hz), 7.21-7.30 m (4Harom.), 7.56 dd (2Harom., J 1.8,
J 8.3 Hz). Found, %: C 54.70; H 4.96; Br 20.01; N 3.44; S
7.93. C18H20BrNO2S. Calculated, %: C 54.83; H 5.11; Br
20.26; N 3.55; S 8.13.
2
3
0
0
(2H, H C CH ), 6.47 d (2Harom., J 8.6 Hz), 7.22 d
(2Harom., J 8.6 Hz). 13C NMR, CDCl3, δ, ppm: 17.63, 21.91
1
1
4
0
(2CH3), 50.50 (C ), 108.50, 146.49 (C , C ), 114.91, 131.74
(C2.6, C3.5), 125.47, 133.85 (C , C ). Found, %: C 54.88; H
5.74; Br 33.09; N 5.70. C11H14BrN. Calculated, %: C 55.02;
H 5.88; Br 33.27; N 5.83.
2
3
0
0
4.6 | N-{4-bromo-2-[(2E)-1-methylbut-
2-en-1-yl]phenyl}-
4-methylbenzenesulfonamide (3b)
4.4 | (2-Chlorophenyl)[(2E)-1-methylbut-
2-en-1-yl]amine (2h)
N-{4-bromo-2-[(2E)-1-methylbut-2-en-1-yl]phenyl}-
(2-Chlorophenyl)[(2E)-1-methylbut-2-en-1-yl]amine (2h)
was synthesized as described for compound 2b from 30 g
(235 mmol) of 2-chloroaniline and 24.6 g (235 mmol) of
chloropentene. The reaction product was isolated by dis-
tillation in vacuo, b. p. 116-117ꢁC (2 mm Hg). Yield 40 g
(87%). MS, m/z (Ir, %): 169 [M-Cl]+ (100), 196 [M + H]+
(70), 210 (50), 237 [M + CH3CN + H]+ (65). IR, ν,
cm−1:3364 (NH), 1599, 109, 1325, 1032, 965, 740. 1H
NMR, CDCl3), δ, ppm: 1.34 d (3H, CH3, J 6.5 Hz), 1.68 d
4-methylbenzenesulfonamide (3b) was synthesized as
described for compound 3a, by the interaction of
alkenylaniline 2b (0.9 g, 3.45 mmol) and TsCl (0.86 g,
4.5 mmol) in pyridine (3 ml). Chromatographic purifica-
tion on a silica gel column (eluent—C6H6) gave 1.11 g
(75%) of sulfonylamide 3b, viscous oil, Rf 0.43 (C6H6). MS
(20 eV), m/z (Ir, %): 392, 394 [M − H¯] (100). IR, ν,
cm−1:3278 (NH), 1483, 1332,1164, 1091, 814, 664,
1
585, 568, 546. Н NMR, CDCl3, δ, ppm: 0.98 d (3Н, СН3,
1
0
(3H, CH3, J 6.5 Hz), 3.96 quintet (1H, H , J 6.5 Hz), 4.26
J 7.0 Hz), 1.64 d (3Н, СН3, J 5.6 Hz), 2.39 s (3Н, СН3),
2
3
1
0
0
0
br. s (1H, NH), 5.40-5.70 m (2H, H C CH ), 6.60 d.t
(1Harom., J 1.2, J 7.8 Hz), 6.67 d (1Harom., J 8.0 Hz), 7.10 d.
t (1Harom., J 1.3, J 8.0 Hz), 7.25 d.d (1Harom., J 1.2,
J 7.8 Hz). 13C NMR, CDCl3, δ, ppm: 17.64, 22.03 (2СH3),
3.08 quintet (1Н, Н , J 7.0 Hz), 5.25-5.35 m (2Н,
2
3
0
0
Н C CН ), 6.71 s (1Н, NH), 7.22-7.24 m (3Н, Нarom.),
7.28 s (2H, Нarom.), 7.60 d (2H, Нarom., J 8.2 Hz). 13С
NMR, CDCl3, δ, ppm: 17.82, 19.69, 21.48 (3СH3), 36.71
1
1
3
5
6
0
0
0
0
0
50.30 (С ), 112.20, 116.80, 125.31, 127.58, 129.02, 133.63
(С ), 125.98, 126.09, 130.06, 130.29, 133.83 (С , С , С ,
3
4
5
6
2
3
1
2
2
3
(С , С , С , С , С , C ), 119.50, 143.29 (C , C ). Found,
%: C 67.37; H 7.05; Cl 17.88; N 6.97. C11H14ClN. Calcu-
lated, %: C 67.51; H 7.21; Cl 18.12; N 7.16.
С , С ), 127.10, 129.64 (С2,6, С3 5), 119.82, 133.28,
00
00
00 00
1
4
1
2
4
0
0
0
136.35, 140.04, 143.94 (С , С , С , С , С ). Found, %: C
54.66; 4.98; Br 20.03; 3.42; 7.96.
H
N
S