ACCEPTED MANUSCRIPT
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H and 5 Ar-H). 13C-NMR (δ, ppm): 48.3 (CH3), 119.9 (CN), 89.1, 102.2, 110.8, 118.3, 121.4,
127.5, 128.8, 130.4, 132.8, 133.3, 146.3, 161.9, 167.2 (Ar C). Anal. Calcd. for C17H14N4
(274.32): C, 74.43; H, 5.14; N, 20.42. Found: C, 74.80; H, 5.09; N, 20.12.
4.1.2.2. 6-(3,4-Dimethoxyphenyl)-2-amino-4-(1-methyl-1H-pyrrol-2-yl)-nicotinonitrile (7).
1H-NMR (δ, ppm): 3.45 (s, 3H, N-CH3), 3.89 (s, 6H, 2 OCH3), 5.06 (s, 2H, NH2), 6.44 (s, 1H,
pyridine C5-H), 6.81-7.26 (m, 6H, 3 pyrrole-H and 3 Ar-H). 13C-NMR (δ, ppm): 47.9 (CH3), 54.2
(OCH3), 56.6 (OCH3), 118.3 (CN), 89.7, 101.9, 111.2, 116.3, 120.9, 126.6, 129.1, 131.2, 133.6,
134.1, 145.6, 162.5, 167.9 (Ar C). Anal. Calcd. for C19H18N4O2 (334.37): C, 68.25; H, 5.43; N,
16.76. Found: C, 68.53; H, 5.23; N, 16.93.
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4.1.2.3. 2-Amino-4-(1-methyl-1H-pyrrol-2-yl)-6-(2-thienyl)nicotinonitrile (8). H-NMR (δ,
ppm): 3.46 (s, 3H, N-CH3), 5.07 (s, 2H, NH2), 6.42 (s, 1H, pyridine C5-H), 6.79-7.20 (m, 6H, 3
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pyrrole-H and 3 thiophene-H). C-NMR (δ, ppm): 48.1 (CH3), 118.6 (CN), 89.1, 101.2, 110.2,
118.3, 121.9, 126.5, 130.4, 141.8, 146.3, 161.9, 167.2 (Ar C). Anal. Calcd. for C15H12N4S
(280.35): C, 64.26; H, 4.31; N, 19.98; S, 11.44. Found: C, 64.41; H, 4.42; N, 20.28; S, 11.63.
4.1.2.4.
2-Amino-8-methyl-4-(1-methyl-1H-pyrrol-2-yl)-5,6,7,8-tetrahydroquinoline-3-
carbonitrile (9). 1H-NMR (δ, ppm): 1.36 (s, 3H, CH3), 1.62-2.37 (m, 6H, C5,6,7-H), 2.86 (m, 1H,
C8-H), 3.36 (s, 3H, N-CH3), 5.06 (s, 2H, NH2), 6.89-7.21 (m, 3H, 3 pyrrole-H). 13C-NMR (δ,
ppm): 21.1 (CH3), 22.1, 27.6, 31.2, 38.4 (C5,6,7,8), 46.2 (CH3), 118.7 (CN), 88.1, 102.2, 110.8,
117.3, 121.4, 145.7, 163.8, 164.2, (Ar C). Anal. Calcd. for C16H18N4 (266.34): C, 72.15; H, 6.81;
N, 21.04. Found: C, 72.33; H, 7.06; N, 21.16.
4.1.3.
N-((3-cyano-8-methyl-4-(1-methyl-1H-pyrrol-2-yl)-5,6,7,8-tetrahydroquinolin-2-
yl)carbamothioyl)benzamide (10).
Conventional heating: to a mixture of the 2-amino-8-methyl-4-(1-methyl-1H-pyrrol-2-yl)-
5,6,7,8-tetrahydroquinoline-3-carbonitrile 9 (1.33 g, 5 mmol) and K2CO3 (0.9 g, 6.5 mmol) in
dry acetone (20 mL), a solution of benzoyl isothiocyanate (0.82 g, 5 mmol) in dry acetone (5
mL) was added. The resultant reaction mixture was heated under reflux for 2 h, then left for an
overnight at room temperature, concentrated to half its volume and allowed to cool in the
refrigerator for 4 h. The separated solid product was filtered, washed with diethyl ether and
crystallized from ethanol.