PAPER
One-Pot Synthesis of 5-Alkylthio-3H-1,2-Dithiole-3-Thiones: Advantages and Scopes
1753
MS (EI): m/z (%) = 210 (5, M+ + 2), 209 (3, M+ + 1), 208 (24, M+),
173 (0.5, M+ 33), 166 (4, M+ 42), 143 (1, M+ 65), 103 (4), 102
(3), 101 (40, M+ 107), 64 (3, M+ 144), 57 (19), 45 (50), 44 (13),
43 (96), 42(12), 41 (100), 32 (38).
IR (KBr): = 3026, 2953, 2921, 2843, 1472, 1442, 1296, 1259,
1227, 1186, 1045, 910, 837, 722, 660, 556, 524 cm .
1H NMR (200 MHz, CDCl3): = 0.89 (t, 6.9 Hz, 3 H), 1.15 1,48 (s
and m, 14 H), 1.78 (m, 7.3 Hz, 2 H), 3.11 (t, 7.3 Hz, 2 H), 7.00 (s, 1
H).
13C NMR (50 MHz, CDCl3): = 14.09, 22.64, 28.62, 28.81, 28.94,
29.24, 29.38, 29.46, 31.85, 35.90, 135.27, 174.70, 212.81.
1
UV (isooctane):
242 nm (3.68).
(log ) = 422 (3.70), 320 (4.03), 254 (3.76),
max
HRMS: m/z calcd for C6H8S4: 207.95089, found: 207.95111.
5-Butylthio-3H-1,2-dithiole-3-thione (Table 2, Entry 5)
Yield: 1.080 g (32%); mp 47 48 °C (Lit.14 mp 47 48 °C).
MS (EI): m/z (%) = 307 (2), 306 (10, M+), 273 (7, M+ 33), 241 (8,
M+ 65), 180 (12, M+ 126), 169 (4), 168 (12), 167(45), 166 (55,
M+ 140), 157 (4), 155 (4), 135 (10), 133 (9), 102 (10), 101 (100,
M+ 205), 100 (9), 89 (9), 87 (8), 71 (17), 57 (30), 55 (11), 43 (12),
42 (65), 41 (87, M+ 265).
IR (KBr): = 2963, 2925, 2854, 1445, 1287, 1173, 1032, 912, 657,
1
552 cm .
1H NMR (200 MHz, CDCl3): = 0.96 (t, 7.3 Hz, 3 H), 1.48 (m, 7.6
Hz. 2 H), 1.77 (m, 7.3 Hz, 2 H), 3.12 (t, 7.3 Hz, 2 H), 7.01 (s 1 H).
13C NMR (50 MHz, CDCl3): = 13.46, 21.81, 30.74, 35.55, 135.09,
174.99, 212.59.
UV (isooctane):
242 nm (3.74).
(log ) = 422 (3.75), 320 (4.09), 254 (3.82),
max
HRMS: m/z calcd for C13H22S4: 306.06438, found: 306.05990
5-Benzylthio-3H-1,2-dithiole-3-thione (Table 2, Entry 9)
Yield: 0.763 g (19%); mp 113 115 °C (Lit.13d mp 117 118 °C).
MS (EI) : m/z (%) = 224 (9, M+ + 2), 223 (6, M+ + 1), 222 (46, M+),
180 (2, M+ 42), 166 (17, M+ 56), 165 (2, M+ 57), 157 (8, M+
65), 103 (11), 102 (7), 101 (100, M+ 121), 100 (5), 97 (6), 85
(11), 71 (15), 69 (12), 57 (55, M+ 165), 45 (8), 41 (37).
IR (KBr): = 3050, 2970, 2940, 1499, 1452, 1296, 1233, 1190,
1
1076, 1041, 915, 837, 774, 707, 660, 551, 520 cm .
UV/vis (isooctane):
(3.89), 243sh nm (3.81).
(log ) = 422 (3.82), 320 (4.15): 254
1H NMR (200 MHz, CDCl3): = 4.31 (s, 2H), 7.00 (s, 1H), 7.37 (s,
5H).
max
HRMS: m/z calcd for C7H10S4: 221,96654, found: 221,96655.
13C NMR (50 MHz, CDCl3): = 40.24, 128.59, 128.94, 129.10,
134.00, 136.24, 172.73, 212.89.
MS (EI): m/z (%) = 258 (3), 257 (3), 256 (19, M+), 165 (1, M+ 91),
103 (4), 102 (3), 101 (47, M+ 155), 92 (8), 91 (100, M+ 165), 90
(2), 89 (7), 77 (3), 76 (4), 69 (6), 65 (18, M+ 191), 57 (9), 51 (7),
45 (11) 39 (12).
5-Hexylthio-3H-1,2-dithiole-3-thione (Table 2, Entry 6)
Yield: 0.864 g (22%); mp 42.5 43.5 °C.
IR (KBr): = 3057, 3020, 2948, 2833, 1467, 1431, 1374, 1290,
1253, 1212, 1181, 1040, 1019, 967, 905, 847: 733, 660, 560, 524
1
cm .
UV (isooctane):
242 nm (4.17).
(log ) = 422 (4.06), 320 (4.38), 254 (4.19),
1H NMR (200 MHz, CDCl3): = 0.91 (t, 6.6 Hz, 3 H), 1.32 1.48
(m, 6 H), 1.78 (m, 7.3 Hz, 2 H), 3.11 (t, 7.3 Hz, 3 H), 6.99 (s, 1 H).
max
HRMS: m/z calcd for C10H7S4: 255.95089, found: 255.95033.
13C NMR (50 MHz, CDCl3): = 13.90, 22.39, 28.27, 28.75, 31.07,
35.90, 135.24, 174.70, 212.76.
5-(2-Ethoxy)ethylthio-3H-1,2-dithiole-3-thione (Table 2, Entry
10)
MS (EI): m/z (%) = 252 (4, M+ + 2), 251 (4, M+ + 1), 250 (26, M+),
217 (3, M+ 33), 194 (2, M+ 56), 193 (4), 192 (3), 185 (8, M+
65), 169 (1), 168 (4), 167 (8), 166 (22, M+ 84), 165 (16), 142 (2),
135 (6), 134 (4), 133 (7), 118 (1), 117 (5), 116 (5), 115 (5), 114 (2),
101 (100, M+ 149), 89 (7), 87 (5), 76 (4), 69 (14) 57 (14), 55 (10),
45 (11), 43 (28, M+ 207), 41 (27), 39 (13).
Yield: 0.187 g (5%); mp 40 41 °C.
IR (KBr): = 2979, 2947, 1442, 1374, 1353, 1310, 1285, 1190,
1133, 1112, 1040, 918, 819, 698, 672, 650, 551, 520 cm .
1H NMR (200 MHz, CDCl3): = 1.22 (t, 7 Hz, 3 H), 3.31 (t, 6.2 Hz,
2 H), 3.55 (q, 7 Hz, 2 H), 3.74 (t, 6.1 Hz, 2 H), 7.05 (s, 1 H).
1
UV (isooctane):
242 nm (4.00).
(log ) = 422 (4.02), 320 (4.36), 254 (4.09),
13C NMR (50 MHz, CDCl3): = 15.01, 35.96, 66.88, 68.07, 136.04,
173.81, 213.01.
max
HRMS: m/z calcd for C9H14S4: 249.99784, found: 249.99914.
MS (EI): m/z (%) = 241 (8), 240 (7), 239 (45) 238 (30, M+), 237 (3),
193 (2, M+ 45), 181 (11), 180 (10), 179 (10, M+ 59), 178 (30),
177 (4), 169 (10), 168 (12), 167 (55), 166 (65), 165 (8, M+ 73),
104 (4), 103 (13), 102 (15), 101 (100, M+ 137), 100 (20), 89 (9),
73 (10), 69 (12), 59 (16), 57 (13), 46 (12), 45 (37), 44 (9).
5-Octylthio-3H-1,2-dithiole-3-thione (Table 2, Entry 7)
Yield: 1.222 g (28%); mp 51 52 °C (Lit.14 mp 51 52 °C).
IR (KBr): = 3046, 2962, 2929, 2851, 1455, 1294, 1175, 1043, 911,
1
660, 554 cm .
UV (isooctane):
(3.85).
(log ) = 421 (3.76), 319 (4.08), 254 nm
1H NMR (200 MHz, CDCl3): = 0,87 (t, 6.4 Hz, 3 H), 1.2 1.5 (s
and m, 10 H), 1.79 (m, 7 Hz, 2 H), 3.13 (t, 7.1 Hz, 2 H), 7.04 (s, 1 H).
max
HRMS: m/z calcd for C7H10OS4: 237.96145, found: 237.96181.
13C NMR (50 MHz, CDCl3): = 14.04, 22.57, 28.60, 28.80, 28.90,
29.01, 31.67, 35.92,135.24, 174.80, 212.73.
5-Ethylthio-4-methyl-3H-1,2-dithiole-3-thione (Table 2, Entry
14)
MS (EI): m/z (%) = 281 (1), 280 (7), 279 (2), 278 (M+), 245 (8, M+
33), 235 (2, M+ 43), 213 (15, M+ 65), 170 (2), 169 (8), 168
(15), 167 (41), 166 (71, M+ 112), 157 (6), 135 (13), 133 (10), 115
(2), 103 (12), 102 (8), 101(100, M+ 177), 100 (7), 89 (7), 87 (8),
85 (4), 71 (10), 69 (20), 57 (23), 55 (17), 43 (22), 41(24).
Yield: 0.196 g (6%); mp: 92 93 °C.
IR (KBr) = 1442, 1363, 1322, 1254, 1254, 1097, 1082, 1019, 962,
920, 790, 743, 712, 660, 620, 514 cm .
1H NMR (200 MHz, CDCl3): = 1.5 (t, 7.7 Hz, 3 H), 2.19 (s, 3 H),
3.24 (q, 7.7 Hz, 2 H).
13C NMR (50 MHz, CDCl3): = 14.39, 16.09, 28.27, 140.72,
168.23, 211.09.
1
UV (isooctane): max (log ) = 422 (3.84), 320 (4.19), 254 (3.90),
242sh nm (3.81).
HRMS: m/z calcd for C11H16S8: 278.02914, found: 278.02927.
5-Decylthio-3H-1,2-dithiole-3-thione (Table 2, Entry 8)
Yielde: 1.201 g (25%); mp 49 50 °C.
MS (EI): m/z (%) = 212 (2), 211 (3), 210 (21) 209 (22), 208 (100,
M+), 207 (100), 193(5, M+ 15), 192 (4), 181 (5), 180 (10), 179 (24,
Synthesis 2000, No. 12, 1749–1755 ISSN 0039-7881 © Thieme Stuttgart · New York