Int. J. Mol. Sci. 2021, 22, 2462
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6: 1, the second column: SiO2, chloroform), gave pale yellow solid in 90% yield. Mp. 137–
1
138 ◦C (petroleum ether: ethyl acetate). H NMR (400 MHz, CDCl3):
6.4 Hz 1H, 6-C
δ
2.72 (dd, J = 13.8,
H-3), 3.07 (dd, J = 13.8, 3.8 Hz, 1H,
-3), 4.86 (ddt, J = 6.4, 3.1, 3.8 Hz, 1H,
CH-6), 5.90 (dd, J = 5.1, 3.1 Hz, 1H, =CH-4), 7.00–7.14 (m, 2H, C6H5), 7.24–7.34 (m, 3H,
C6H5), 7.34–7.53 (m, 5H, C6H5), 9.26 (br. s, 1H, NH). 13C NMR (101 MHz CDCl3):
40.00
HH), 2.79 (dt, J = 23.2, 3.1 Hz, 1H, CH
6-CH ), 3.48 (ddd, J = 23.2, 5.1, 3.1 Hz, 1H, CH
H
H
δ
(CH2-3), 40.83 (6-CH2), 58.3 (CH-6), 120.60 (=CH-4), 126.00, 127.23, 128.55, 129.03, 130.05
(C6H5), 134.27 (=C-5), 135.22, 137.27 (C6H5), 199.5 (C=S). GC-MS (EI, 70 eV): m/z = 279
(27), [M+], 188 (100), 154 (19), 128 (29), 91 (16). HRMS (ESI-TOF): m/z calcd for C18H18NS
[M+H]+, 280.1160; found: 280.1161.
(6RS)-6-Benzyl-1-methyl-5-phenyl-3,6-dihydropyridine-2(1H)-thione (S7): The crude
product purified twice by column chromatography (the first column: SiO2, n-hexane: ethyl
1
acetate, 6: 1, the second column: SiO2, chloroform), gave dark red oil in 78% yield. H
NMR (400 MHz, CDCl3):
δ
2.22 (ddd, J = 22.6, 3.5, 2.2 Hz, 1H, C
HH-3), 2.78 (dd, J = 13.9, 4.1
Hz, 1H, 6-C H), 3.18 (dd, J = 13.9, 4.5 Hz, 1H, 6-CH
H
H
), 3.51 (ddd, J = 22.4, 5.7, 1.9 Hz, 1H,
CHH-3), 3.62 (d, J = 0.8 Hz, 3H, N-CH3), 4.92 (dddd, J = 4.5, 4.1, 3.4, 1.9 Hz, 1H, CH-6), 5.9
(dd, J = 5.7, 2.2 Hz, 1H, =CH-4), 6.78–7.06 (m, 2H, C6H5), 7.12–7.31 (m, 3H, C6H5), 7.32–7.48
(m, 5H, C6H5). 13C NMR (101 MHz CDCl3):
δ 37.64 (6-CH2), 42.46 (CH2-3), 42.73 (NCH3),
66.24 (CH-6), 121.50 (=CH-4), 125.85, 127.39, 128.22, 128.29, 129.04, 130.13 (C6H5), 134.66
(=C-5), 134.73, 137.06 (C6H5), 197.40 (C=S). GC-MS (EI, 70 eV): m/z = 293 (22), [M+], 202
(100), 170 (6), 128 (11), 91 (8), 65 (63), 42 (8). HRMS (ESI-TOF): m/z calcd for C19H20NS
[M+H]+, 294,1316; found: 294,1314.
(4RS)-4-Benzyl-5-(4-fluorophenyl)-3,4-dihydropyridine-2(1H)-thione (S8): The crude
product purified twice by column chromatography (the first column: SiO2, n-hexane: ethyl
acetate, 10: 1, the second column: SiO2, chloroform), gave yellow solid in 90% yield. Mp.
◦
1
144–147 C (hexane: ethyl acetate). H NMR (400 MHz, CDCl3):
δ
2.57 (dd, J = 13.7, 10.7 Hz,
H-3), 2.96 (dddd, J = 10.7, 6.2, 4.0, 1.8 Hz, 1H,
-3), 6.50 (d, J = 4.6 Hz, 1H, =CH-6), 7.02–7.12 (m,
1H, 4-C
H
H), 2.73–2.84 (m, 2H, 4-CHH,
C
H
CH-4), 3.20 (dd, J = 17.2, 1.5 Hz, 1H, CH
H
2H, C6H5), 7.15–7.46 (m, 7H, C6H5), 9.95 (br. s, 1H, NH). 13C NMR (101 MHz CDCl3):
δ
35.99 (CH-4), 37.16 (4-CH2), 41.85 (CH2-3), 115.89 (d,2JC-F = 21.6 Hz, CH-30, CH-50), 120.05
(=CH-6), 126.22 (=C-5), 126.59 (C6H5), 126.73 (d,3 JC-F = 8.0 Hz, CH-20, CH-60), 128.50
(C6H5), 129.50 (C6H5), 132.40 (d, JC-F = 3.4 Hz, C-10), 138.32 (C6H5), 162.24 (d, JC-F
=
4
1
247.9 Hz, C-40), 197.71 (C=S). GC-MS (EI, 70 eV): m/z = 279 (37) [M+], 207(14), 206 (100),
173 (9), 172 (21), 146 (30), 91 (17). HRMS (ESI-TOF): m/z calcd for C18H17FNS [M+H]+,
298.1066; found: 298.1064.
(4RS)-4-Benzyl-5-(3,4-difluorophenyl)-3,4-dihydropyridine-2(1H)-thione (S9): The
crude product purified twice by column chromatography (the first column: SiO2, n-hexane:
ethyl acetate, 8: 1, the second column: SiO2, chloroform), gave yellow solid in 95% yield.
1
Mp. 142–149 ◦C (hexan: ethyl acetate). H NMR (400 MHz, CDCl3):
δ
= 2.58 (dd, J = 13.6,
), 2.92 (dddd, J = 10.5, 6.4, 4.2, 1.5,
1H, CH-4), 3.22 (dd, J = 16.8, 1.5 Hz, 1H, CHH-3), 6.51 (d, J = 4.6 Hz, 1H, =CH-6), 7.00–7.46
10.5 Hz, 1H, 4-CHH), 2.73–2.84 (m, 2H, CHH-3, 4-CHH
(m, 8H, ArH), 9.76 (s, 1H, NH). 13C NMR (101 MHz CDCl3):
δ 35.93 (CH-4), 37.29 (4-CH2),
41.99 (CH2-3), 114.02 (d, 2J = 18.2 Hz, CH-20), 117.75 (d, 2J = 17.4 Hz, CH-50), 120.85 (d, 5J
= 1.5 Hz, =CH-6), 121.06 (dd, J = 6.1, 03.4 Hz, CH-60), 125.11 (=C-5), 126.73, 128.58, 129.51
0
(C6H5), 133.62 (dd, J = 5.9, 4.3 Hz, C-1 ), 138.11 (C6H5), 148.41 (dd, J = 250.7, 12.6 Hz, C-3 ),
150.68 (dd, J = 248.9, 12.5 Hz, C-40), 198.1 (C=S). GC/MS (EI, 70 eV): m/z = 316 (6) [M+],
315 (27), [M+], 225 (14), 224 (100), 191 (8), 190 (20), 164 (25), 163 (6), 91 (21), 65 (7). HRMS
(ESI-TOF): m/z calcd for C18H16F2NS [M+H]+, 316.0972; found: 316.0981.
(4RS)-4-Benzyl-5-(4-chlorophenyl)-3,4-dihydropyridine-2(1H)-thione (S10): The crude
product purified twice by column chromatography (the first column: SiO2, n-hexane: ethyl
acetate, ◦3: 1, the second column: SiO2, chloroform), gave yellow solid in 78% yield. Mp.
1
161–163 C (hexane: ethyl acetate). H NMR (400 MHz, CDCl3):
δ 2.57 (dd, J = 13.6, 10.7 Hz,
1H, 4-C
H
H), 2.73–2.84 (m, 2H, 4-C
H
H, CH
H
H
-3), 2.97 (dddd, J = 10.7, 6.1, 4.0, 1.8 Hz, 1H,
-3), 6.55 (d, J = 4.6 Hz, 1H, =CH-6), 7.13–7.44
CH-4), 3.21 (ddd, J = 17.1, 1.8, 0.9 Hz, 1H, CH