6
S. A. AL-JADAAN ET AL.
Anal. Calc. for C16H16N2.H2O: C, 75.57; H, 7.13; N, 11.01. Found: C, 75.47; H, 7.05; N,
10.87%. IR (KBr, cm−1): 3310b, 3075w, 2888w, 2845w, 1660s, 1615s, 1560s, 1265s, 752s.
1H NMR (DMSO-d6, δ / ppm): 2.21 (s, 6H, CH3); 7.26(t, J = 8.8, 1.0 Hz, Ar-H); 7.33(t,
4H, J = 8.5, 1.1 Hz, Ar-H);7.48(d, 4H, J = 7.9 Hz, Ar-H). 13C NMR (DMSO-d6, δ / ppm):
23.9(CH3), 118.5 (C-2,6), 122.0 (C-3,5), 128.0(C-4), 139.0(C-1), 168.1(C N).
The following compounds were prepared similarly using the appropriate N-
(1chloroethylidene)arylamine:
N-(3-(4-Chlorophenylimino)butan-2-ylidene)-4-chlorobenzamine
(2).
White solid, 63% yield, m.p. 169–171◦C (Lit.[16] 175◦C, Lit.17 177◦C). Anal. Calc. for
C16H14Cl2N2.H2O: C, 59.46; H, 4.99; N, 8.67. Found: C, 59.01; H, 4.98; N, 8.21%.
IR(KBr, cm−1):3300b, 3080w, 2950w, 2850w, 1671s, 1620m, 1553s, 1268s,770m. H
1
NMR(DMSO-d6, δ / ppm): 2.05(s, 6H, CH3); 7.29 (d, 4H, J = 7.6 Hz, Ar-H); 7.66
(d, 4H, J = 7.6 Hz, Ar-H). 13C NMR(DMSO-d6, δ / ppm): 23.9 (CH3), 120.0 (C-2,6),
126.0(C-3,5), 128.1(C-4), 138.2(C-1), 168.3(C N). EI-MS m/z (M+) 304.
N-(3-(4-Methylphenylimino)butan-2-ylidene)-4-methylbenzenamine (3).
White solid, 76%, m.p. 140–141◦C. Anal. Calc. for C18H20N2·H2O: C, 76.56; H, 7.85; N,
9.92. Found: C, 76.28; H, 7.66; N, 10.27%. IR(KBr, cm−1): 3085w, 2900w, 2800w, 1663s,
1615m, 1555s, 1260s, 750s. 1H NMR(DMSO-d6, δ / ppm): 2.20(s, 6H, CH3-Ar); 2.34(s, 6H,
CH3); 7.12(d, 4H, J = 7.7 Hz, Ar-H); 7.37(d, 4H, J = 7.5 Hz, Ar-H). 13C NMR(DMSO-d6,
δ / ppm): 20.4 (CH3), 23.83(CH3-Ar), 118.0(C-2,6), 128.1(C-3,5), 131.2(C-4), 136.0(C-1),
167.9(C N). EI-MS m/z (M+) 264.
N-(3-(4-Nitrophenylimino)butan-2-ylidene)-4-nitrobenzenamine
(4).
White solid, 73% yield, m.p. 118–120◦C. Anal. Calc. for C16H14N4O4.2H2O: C, 53.04;
H, 5.01; N, 15.46. Found: C, 52.69; H, 4.93; N, 15.35%. IR(KBr, cm−1): 3305b, 3090w,
2900w, 2850w, 1677s, 1617m, 1562s, 1266s, 748s. 1H NMR(DMSO-d6, δ / ppm):
2.16 (s, 6H, CH3) 7.81(d, 4H, J = 8.8 Hz, Ar-H); 8.21(d, 4H, J = 8.8 Hz, Ar-H).
13C NMR(DMSO-d6, δ / ppm): 24.2(CH3), 112.0(C-2,6), 125.1(C-3,5), 135.2 (C-1),
155.0(C-1), 169.0(C N).
N-(3-(2-Chloro-4-methylphenylimino)butan-2-ylidene)-2-chloro-4-
methylbenzenamine (5). To a solution of N-(3-(4-methylphenylimino)butan-2-
ylidene)-4-methylbenzenamine (3) (0.27 g; 1 mmol) in dry diethyl ether (15 mL) was
added slowly with stirring a solution of thionyl chloride (0.36 g; 3 mmol) in diethyl ether
(10 mL) at 5◦C. The mixture was stirred further for 1 h at room temperature; the pale yellow
solution then filtered. The solvent was allowed to evaporate at room temperature and a
pale yellow precipitate was obtained. The product was recrystallized from chloroform and
hexane (3:2) to give compound 5 as a very pale yellow solid in 67% yield; m.p. 117–119◦C.
Anal. Calc. for C18H18Cl2N2.H2O: C, 61.56; H, 7.74; N, 7.97. Found: C, 61.09; H, 5.65;
N, 7.63%. IR(KBr, cm−1): 3320b, 3092w, 2970w, 2845w, 1677s, 1658m, 1565s, 1270s,
765s. 1H NMR(DMSO-d6, δ / ppm): 2.15(s, 6H, CH3-Ar); 2.34(s, 6H, CH3); 7.12 (d, 2H,
J = 7.6 Hz, ArH); 7.25(s, 2H, ArH); 7.36 (d, 2H, J = 1.2 Hz, Ar-H).
N-(3-(2-Bromo-4chlorophenylimino)butan-2-ylidene)-2-bromo-4-chloro
benzenamine (6). To
a
solution of N(3(4chlorophenylimino)butan2ylidene)4
chlorobenzamine (2) (0.30 g; 1 mmol) in dry diethyl ether(20 mL) was added
dropwise a solution of bromine (0.48 g; 3 mmol) in dry diethyl ether (20 mL). The yellow
solution was stirred for 2 h at room temperature. Evaporation of the solvent at room
temperature yielded a yellow precipitate of compound 6. Recrystallization of the product
from chloroform and ether (7:3) gave a yellow solid in 70% yield.