9-Cyano-8-methyl-6-oxo-2,3,4,6-tetrahydropyrido[2,1-b][1,3]thiazine (2). Yield 1.73 g (84%);
mp 224-225°C. IR spectrum, ν, cm-1: 2214 (C≡N), 1675 (C=O). 1H NMR spectrum, δ, ppm (J, Hz): 6.03 (1H, s,
H-7); 3.98 (2H, t, J = 5.5, NCH2); 3.25 (2H, t, J = 6.3, SCH2); 2.20 (5H, m, CH3 and CH2). Mass spectrum, m/z
(Irel, %): 206 [M]+ (100); 205 (17), 191 (48), 178 (224), 173 (20), 150 (23). Found, %: C 58.03; H 5.12; N 13.40.
C10H10N2OS. Calculated, %: C 58.23; H 4.89; N 13.58.
7,9-Dicyano-6-oxo-3,4,6,7-tetrahydro-2H-spirocyclohexane-1',8-pyrido[2,1-b][1,3]thiazine
(3a).
Yield 1.98 g (69%); mp 144-146°C. IR spectrum, ν, cm-1: 2247 (C(7)–C≡N), 2200 (C≡N), 1680 (C=O). 1H NMR
spectrum, δ, ppm (J, Hz): 4.58 (1H, s, H-7); 3.71-3.96 (2H, m, NCH2); 2.14 (2H, t, J = 5.1, SCH2); 1.28-1.90
(12H, m, (CH2)6). Mass spectrum, m/z (Irel, %): 287 [M]+ (79), 272 (8), 258 (26), 244 (98), 231 (100), 206 (27),
179 (38), 56 (48). Found, %: C 62.50; H 6.16; N 14.52. C15H17N3OS. Calculated, %: C 62.69; H 5.96; N 14.62
7,9-Dicyano-6-oxo-3,4,6,7-tetrahydro-2H-spiro(4'-methylcyclohexane)-1',8-pyrido[2,1-b][1,3]thiazine
(3b). Yield 2.08 g (69%); mp 152-164°C. IR spectrum, ν, cm-1: 2246 (C(7)–C≡N), 2208 (C≡N), 1678 (C=O).
1H NMR spectrum, δ, ppm (J, Hz): 4.71 (1H, s, H-7); 3.94 and 3.68 (both 1H, both t, J = 6.3, NCH2); 3.13 and
3.07 (both 1H, both t, J = 6.5, SCH2); 2.11 (2H, t, J = 5.8, CH2); 1.88-1.15 (9H, m, CH and (CH2)4); 0.91 (3H, d,
J = 4.7, CH3). Found,%: C 63.60; H 6.28; N 14.07. C16H19N3OS. Calculated, %: C 63.76; H 6.35; N 13.94.
6-Amino-7,9-dicyano-8-phenyl-3,4-dihydro-2H,8H-pyrido[2,1-b][1,3]thiazine (4). Yield 2.21 g
1
(75%); mp 216-218°C. IR spectrum, ν, cm-1: 3182, 3308, 3455 (NH2), 2202 (C≡N), 1647 (δ NH2). H NMR
spectrum, δ, ppm (J, Hz): 7.02-7.40 (5H, m, C6H5); 6.05 (2H, br. s, NH2); 4.04 (1H, s, H-8); 3.93 and 3.49
(both 1H, both m, NCH2); 2.98 (2H, t, J = 5.0, SCH2); 2.29 and 2.10 (both 1H, both m, CH2). Found, %:
C 64.99; H 5.02; N 18.87. C16H14N4S. Calculated, %: C 65.28; H 4.79; N 19.03.
5-Cyano-6-mercapto-3-methoxycarbonyl-4-(2-thienyl)-3,4-dihydropyridin-2(1H)-one
(5)
was
obtained according to our procedure [10]. Yield 2.35 g (80% ); mp 158-160°C (ethanol). IR spectrum, ν, cm-1:
3345 (N-H), 2202 (C≡N), 1742 (C=O), 1685 (CONH). 1H NMR spectrum, δ, ppm (J, Hz): 8.70 (1H, br. s, NH);
7.34 (2H, dd, J = 1.4 and J = 4.3, H-5 thienyl); 6.93 (1H, m, H-4 thienyl); 6.87 (1H, m, H-3 thienyl); 4.20 (1H,
d, J = 6.15, H-3); 3.62 (3H, s, CH3); 3.58 (1H, br. s, SH); 3.52 (1H, d, J = 6.15, H-4). Mass spectrum, m/z
(Irel, %): 296 [M+2]+ (5), 295 [M+1]+ (9), 294 [M]+ (35), 267 (48), 235 (100), 195 (63), 137 (47), 100 (72), 58
(60). Found, %: C 49.12; H 3.15; N 9.64. C12H10N2O3S2. Calculated, %: C 48.97; H 3.42; N 9.52.
5-Cyano-6-mercapto-4-methyl-2(1H)-pyridinone (6) was characterized in our previous work [11].
3,5-Dicyano-6-mercapto-3,4-dihydrospiro(cyclohexane-1',4-pyridin)-2(1H)-one (7a) and 3,5-dicyano-
6-mercapto-3,4-dihydrospiro(4'-methylcyclohexane-1',4-pyridin)-2(1H)-one (7b) were characterized in our
previous work [12]. N-Methylmorpholinium 6-amino-3,5-dicyano-4-phenyl-1,4-dihydro-2-pyridinethiolate
(8) was characterized in our previous work [13].
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