J = 15.2, C=CHCOH); 6.37 (1H, dd, J = 15.2, J = 9.9, CHCH=CH); 7.30-7.52 (3H, m, C6H5); 7.58 (2H, d,
J = 7.8, C6H5); 11.25 (1H, s, NH), 14.11 (1H, s, OH). 13C NMR spectrum (DMSO-d6), δ, ppm: 22.87 (CH3),
23.00 (=CCH2), 26.95 (CH3), 27.04 (CH3), 31.33 (CHCH2CH2), 32.58 (CH2CH2C), 53.98 (CHCH=CH), 102.29
(CH=COH), 122.11 (CH=CHCH2), 128.36 (CH=CHCOH), 131.17 (CH=CHCOH), 132.93 (CH3C=CH), 124.54,
1
126.55, 129.01, 138.79 (C6H5), 166.73 (COH), 189.97 (C=S). H NMR spectrum (DMSO-d6), δ, ppm (J, Hz),
ketone form: 0.84 (3H, s, CH3); 0.87 (3H, s, CH3); 1.10-1.23 (1H, m, =CHCH2CHH); 1.30-1.43 (1H, m,
=CHCH2CHH); 1.49 (3H, s, CH3); 1.94-2.03 (2H, m, =CHCH2CHH); 2.34 (1H, d, J = 9.6, CHCH=CH); 4.20
(2H, s, CSCH2CO); 5.46 (1H, s, C=CHCH2); 6.13 (1H, d, J = 15.8, C=CHCO); 6.71 (1H, dd, J = 15.8, J = 9.9,
CHCH=CH); 7.30-7.52 (3H, m, C6H5); 7.81 (2H, d, J = 7.8, C6H5); 11.76 (1H, s, NH). 13C NMR spectrum
(DMSO-d6), δ, ppm: 22.87 (CH3), 23.08 (=CCH2), 26.77 (CH3), 27.94 (CH3), 31.14 (=CHCH2CH2), 32.86
(CH2CH2C), 53.89 (CHCH=CH), 58.72 (CH2CS), 122.70 (C=CHCH2), 132.19 (CH3C=CH), 139.83
(CH=CHCO), 123.27, 126.55, 129.08, 140.48 (C6H5), 149.34 (CH=CHCO), 193.63 (C=O), 195.14 (C=S).
Found, %: C 73.03; H 7.45; N 4.15; S 10.16. C20H25NOS. Calculated, %: C 73.35; H 7.96; N 4.28; S 9.79.
3-Hydroxy-7,11-dimethyldodeca-2,4,6,10-tetraenethioic Acid Phenylamide (2c). Yield 65%. Dark
oil. IR spectrum (thin layer), νmax, cm-1: 3276-3164 (NH, OH), 1738 (C=O), 1612-1556 (C=C−OH, C=C), 1060
1
(C=S). H NMR spectrum (CDCl3), δ, ppm (J, Hz), enol form: 1.86 (6H, s, CH3); 2.02 (3H, s, CH3); 2.08-2.25
(4H, m, 2CH2); 4.94-5.04 (1H, m, =CHCH2); 5.60 (1H, s, CHCOH); 5.73 (1H, d, J =14.6, =CHCOH); 5.94 (1H,
d, J = 11.3, =CHCH=); 7.14-7.36 (8H, m, C6H5, =CHCH=CH); 7.39-7.49 (4H, m, C6H5); 8.12 (1H, br. s, NH),
14.57 (1H, s, OH). 13C NMR spectrum (CDCl3), δ, ppm: 17.47 (CH3), 17.71 (CH3), 25.70 (CH3), 26.39
(CHCH2CH2), 40.42 (CH2CH2C), 103.80 (C=COH), 120.48 (=CHCH=), 123.02 (CHCOH), 123.74 (C=CHCH2),
132.58 (C=CHCH2), 123.38, 125.33, 126.81, 137.89 (C6H5), 141.03 (CH3CCH2), 142.90 (C=CHCOH), 171.20
(C−OH), 197.13 (C=S). 1H NMR spectrum (CDCl3), δ, ppm (J, Hz), ketone form: 1.88 (6H, s, CH3); 2.02 (3H, s,
CH3); 2.08-2.25 (4H, m, 2CH2); 4.24 (2H, s, CH2CS); 5.04-5.16 (1H, m, =CHCH2); 6.07 (1H, d, J = 11.3,
=CHCH=); 6.15 (1H, d, J =14.9, =CHCOH); 7.14-7.36 (8H, m, C6H5, =CHCH=CH); 7.39-7.49 (4H, m, C6H5);
11.21 (1H, br. s, NH). 13C NMR spectrum (CDCl3), δ, ppm: 17.71 (CH3), 21.06 (CH3), 25.70 (CH3), 26.95
(CHCH2CH2), 40.66 (CH2CH2C), 60.42 (CH2CS), 121.86 (=CHCH=), 124.25 (CHCO), 132.17 (C=CHCH2),
123.48, 125.11, 126.50, 138.73 (C6H5), 155.26 (C=CHCOH), 190.54 (C=S), 193.55 (C=O). Found, %: C 73.23;
H 7.65; N 4.13; S 10.08. C20H25NOS. Calculated, %: C 73.35; H 7.69; N 4.28; S 9.79.
2-Phenyl-6-phenylamino-2,3-dihydrothiopyran-4-one (3a). Yield 54%. Pale yellow solid;
mp 195-197°C (toluene). IR spectrum (KBr), νmax, cm-1: 3212 (NH), 1590 (C=O, C=C), 1550-1500 (NH, C−N,
C=C), 1444 (C−H), 1262 (NH). 1H NMR spectrum (DMSO-d6), δ, ppm (J, Hz): 2.65 (1H, dd, J = 16.2, J = 2.8,
CHH); 3.02 (1H, dd, J = 16.1, J = 3.0, CHH); 4.77 (1H, dd, J = 12.7, J = 2.5, Ph−CH); 5.67 (1H, s, =CH); 7.10
(1H, t, J = 7.3, N−Ph); 7.19 (2H, d, J = 8.0, N−C6H5); 7.26-7.40 (5H, m, C−C6H5, N−C6H5); 7.45 (2H, d, J = 7.5,
C−C6H5); 9.41 (1H, s, NH). 13C NMR spectrum (100 MHz, DMSO-d6), δ, ppm: 44.38 (CH2), 45.03 (CH), 98.55
(=CH), 123.53, 125.13, 128.12, 128.58, 129.18, 129.53, 138.76, 139.33 (2 C6H5), 160.92 (=C), 192.20 (C=O).
Found, %: C 72.49; H 5.29; N 4.89; S 11.20. C17H15NOS. Calculated, %: C 72.57; H 5.37; N 4.98; S 11.40.
6-Phenylamino-2-(2,6,6-trimethylcyclohex-2-enyl)-2,3-dihydrothiopyran-4-one (3b). Yield 90%.
Pale yellow solid; mp 193-197°C (heptane–toluene). IR spectrum (CHCl3), νmax, cm-1: 3400 (NH), 1608 (C=O,
C=C), 1550-1500 (NH, C−N, C=C), 1252 (NH). 1H NMR spectrum (CDCl3), δ, ppm (J, Hz): 0.84 (3H, s, CH3);
0.95 (3H, s, CH3); 1.12-1.17 (1H, m, CCHHCH2); 1.56 (1H, dd, J = 22.4, J = 9.3, CCHHCH2); 1.69 (1H, s,
CCHC); 1.81 (3H, s, CH3); 1.97 (2H, s, =CCH2); 2.53 (1H, t, J = 15.8, COCHH); 2.87 (1H, t, J = 15.6,
COCHH); 3.80 (1H, d, J = 14.1, SCH); 5.48 (1H, s, C=CHCH2); 5.72 (1H, s, C=CHCO); 7.05-7.10 (3H, m,
C6H5); 7.11-7.27 (2H, m, C6H5). 13C NMR spectrum (CDCl3), δ, ppm: 22.27 (=CCH2), 26.37 (CH3), 27.08
(CH3), 28.41 (CH3), 30.38 (=CCH2CH2), 33.27 (CH2C), 43.53 (SCH), 47.89 (CH2CO), 53.46 (=CCH), 99.62
(CCHCO), 123.34, 125.51, 129.45, 138.30 (C6H5), 124.76 (=CCH2), 132.29 (C=CCH2), 162.35 (SC=CH),
195.33 (C=O). Found, %: C 73.33; H 7.48; N 4.20; S 9.65. C20H25NOS. Calculated, %: C 73.35; H 7.69; N 4.28;
S 9.79.
178