TABLE 2. Spectral Characteristics of Compounds 1-5
Com-
pound
IR spectrum, ν, cm-1
1Н NMR spectrum, δ, ppm (J, Hz )*
1b
1640, 1655 (C=O); cis-isomer: 2.06 (2.1H, s, COCH3); 2.37 (2.1H, s, 6-CH3);
2258 (C≡N); 3250
(NH)
4.90-5.10 (0.7Н, m, Н-3 and Н-4); 7.0-7.7 (2.8Н, m, C6H4);
12.12 (0.7H, br. s, NH) trans-isomer: 2.14 (0.9Н, s, СОCH3);
2.45 (0.9Н, s, 6-CH3); 4.37 and 4.81 (0.3Н, d and d, J = 3.4,
Н-3 and Н-4); 7.0-7.7 (1.2Н, m, C6H4); 12.40 (0.3H, s, NH)
2a
2b
2c
1654 (C=O); 2194
2.06 (3H, s, COCH3); 2.33 (3H, s, 6-CH3); 3.06-3.17 (2Н, m,
(C≡N); 3128, 3240, SCH2); 3.54-3.70 (2Н, m, CH2Cl); 3.70-3.88 (1H, m, СН-ОН);
3274 sh. (NH, ОН) 4.66 (1Н, s, H-4); 6.00 (1Н, br. s, ОH); 7.1-7.4 (5Н, m, C6H5);
9.52 (1Н, s, NH)
1655 (C=O); 2196
2.04 (3H, s, COCH3); 2.34 (3H, s, 6-CH3); 2.88-3.20 (2Н, m,
(C≡N); 3130, 3215, SCH2); 3.50-3.66 (2Н, m, CH2Cl); 3.88-4.27 (2H, m, СН-ОН);
3490 (NH, ОН)
5.28 (1Н, s, H-4); 7.10-7.50 (4Н, m, C6H4);
8.68 and 8.74 (1Н, s and s, NH)
1617, 1628 sh.
(C=O); 2202
2.16 (3H, s, COCH3); 2.40 (3H, s, 6-CH3); 3.04-3.24 (2Н, m,
SCH2); 3.50-3.70 (2Н, m, CH2Cl); 4.10-4.37 (2H, m, СН-ОН );
(C≡N); 3152, 3252 4.82 (1Н, s, H-4); 7.40-8.20 (4Н, m, C6H4);
(NH, ОН)
8.82 and 8.93 (1Н, s and s, NH)
3a
3b
3c
4a
1682 (C=O); 2204
(C≡N); 3412 (NH,
ОН)
1.90 (3H, s, COCH3); 2.36 (3H, s, 6-CH3); 3.37-3.57 (4Н, m
and m, SCH2 and CH2N); 3.56-3.78 (1H, m, СН-ОН );
4.80 (1Н, s, H-8); 5.32 (1Н, m, ОH); 7.15-7.40 (5Н, m, C6H5)
1670 (C=O); 2200
1.90 (3H, s, COCH3); 2.34 (3H, s, 6-CH3); 3.36-3.62 (4Н, m
(C≡N); 3418 (ОН) and m, SCH2 and CH2N); 3.56-3.82 (1H, m, СН-ОН);
5.27 (1Н, s, H-8); 5.32 (1Н, m, ОH); 7.20-7.55 (4Н, m, C6H4)
1672 (C=O); 2195
(C≡N); 3444,
3544 (ОН)
2.01 (3H, s, COCH3); 2.42 (3H, s, 6-CH3); 3.36-3.66 (4Н, m
and m, SCH2 and CH2N); 4.60-4.88 (1H, m, СН-ОН );
5.08 (1Н, s, H-8); 5.37 (1Н, m, ОH); 7.80-8.20 (4Н, m, C6H4)
1665, 1736 (C=O); 1.92 (3H, s, 7-COCH3); 2.10 (3H, s, OCOCH3);
2198 (C≡N) 2.40 (3H, s, 6-CH3); 3.09-3.53 (2Н, m, SCH2); 3.96-4.42 (2H, m,
CH2N); 4.52-4.82 (1H, m, H-3); 4.68 (1Н, s, H-8);
7.10-7.40 (5Н, m, C6H5)
4b
4c
5
1664, 1736 (C=O); 1.94 (3H, s, 7-COCH3); 2.10 (3H, s, OCOCH3);
2194 (C≡N) 2.38 (3H, s, 6-CH3); 3.08-3.56 (2Н, m, SCH2); 3.97-4.46 (2H, m,
CH2N); 4.54-4.83 (1H, m, H-3); 5.38 (1Н, s, H-8);
7.10-7.50 (4Н, m, C6H4)
1677, 1746 (C=O); 1.98 (3H, s, 7-COCH3); 2.12 (3H, s, OCOCH3);
2188 (C≡N)
2.44 (3H, s, 6-CH3); 3.15-3.59 (2Н, m, SCH2);
3.97-4.43 (2H, m, CH2N); 4.52-4.82 (1H,
m, H-3); 4.85 (1Н, s, H-8); 7.40-8.20 (4Н, m, C6H4)
1665 (C=O);
1.35-1.75 [6H, s, (CH2)3]; 2.02 (3H, s, CO CH3CH3);
2200 (C≡N); 3120, 2.25-2.45 [4H, m, +N(CH2)2]; 2.36 (3H, s, 6-CH3);
3496 (NH, OH)
2.50-2.67 (2H, m, CH2N); 2.70-2.92 (2Н, m, SCH2);
3.70-4.10 (2H, m, CН-ОН);
5.28 (1Н, s, H-4); 7.4-7.5 (4Н, m, C6H4); 9.30 (1H, s, NH)
_______
1
* The H NMR spectra for compounds 2a-c, 4b,c, and 5 were taken in
CDCl3; the rest were taken in DMSO-d6.
5-Acetyl-2-(1-chloro-2-hydroxy-3-propyl)-3-cyano-6-methyl-4-phenyl-1,4-dihydropyridine (2a). A
mixture of 1,4-dihydropyridine-2(3H)-thione 1a (0.54 g, 2 mmol) [4], sodium bicarbonate (0.19 g, 2.2 mmol),
and epichlorohydrin (0.20 ml, 2.4 mmol) in ethanol (10 ml) was stirred for 24 h at room temperature. The
sodium bicarbonate was filtered out, the filtrate was concentrated down and treated with petroleum ether. The
precipitate was filtered out and washed with ethanol (cooled down to 0°C) (2 ml) and water (10 ml). We
obtained 0.49 g (68%) of the colorless compound 2a with mp 202-203°C.
Compounds 2b and 2c (light yellow) were obtained similarly from thiones 1b and 1c in 59 and 45%
yields.
1192