SOLVENT-FREE SYNTHESIS OF THIOPHENOL
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2,5-Dihydroxylthiophenol (2d). White solid, mp: 117–118 ꢀC (lit.[20] mp:
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118 ꢀC). H NMR (400 MHz, CDCl3): d ¼ 3.10 (s, 1H), 4.53 (s, 1H), 5.70 (s, 1H),
6.69–7.26 (m, 3H)[21]; MS (EI): m=z (rel. int.) 142 (100), 113 (26), 97 (6), 81 (23),
69 (5), 53 (10), 39 (2).
2-Ethoxythiophenol (2e). Light yellow liquid, 1H NMR (400 MHz, CDCl3):
d ¼ 1.48 (t, 3H), 3.88 (s, 1H), 4.04–4.11 (q, 2H), 6.80–6.85 (m, 2H), 7.04–7.10 (m,
1H), 7.22–7.25 (m, 1H); 13C NMR (100 MHz, CDCl3) d ¼ 17.5, 63.4, 126.2, 120.3,
112.1, 118.5, 129.8, 155.4; MS (EI): m=z (rel. int.) 154 (100), 139 (5), 126 (97), 109
(5), 97 (88), 84 (10), 69 (14), 53 (12), 39 (5), 29 (4). EI-HRMS calcd. for C8H10OS
(Mþ): 154.0452; found: 154.0454.
2-Methyl-4-fluorothiophenol (2f). Colorless liquid. 1H NMR (400 MHz,
CDCl3): d ¼ 2.32 (s, 3H), 3.20 (s, 1H), 6.75–6.81 (m, 1H), 6.86–6.90 (m, 1H),
7.20–7.25 (m 1H);13C NMR (100 MHz, CDCl3) d ¼ 20.0, 112.4, 116.2, 129.2,
131.1, 143.5, 159.1; MS (EI): m=z (rel. int.) 142 (98), 109 (100), 97 (9), 83 (9), 69
(6), 57 (6), 45 (7). EI-HRMS calcd. for C7H7FS (Mþ): 142.0252; found: 142.0255.
3,5-Dimethylthiophenol (2g). Colorless liquid. 1H NMR (400 MHz,
CDCl3): d ¼ 2.33 (s, 6H), 3.44 (s, 1H), 6.86 (s, 1H), 6.98 (s, 2H)[18]; MS (EI): m=z
(rel. int.) 138 (65), 123 (9), 105 (100), 91 (14), 77 (23), 63 (9), 39 (17).
3-Fluoro-4-methoxythiophenol (2h). Colorless liquid. 1H NMR (400 MHz,
CDCl3): d ¼ 3.43 (s, 1H), 3.84 (s, 3H), 6.82 (t, 1H, J ¼ 11.4 Hz), 7.04–7.12 (m, 2H)[22]
;
MS (EI): m=z (rel. int.) 158 (100), 143 (97), 126 (3), 115 (28), 95 (6), 83 (5), 69 (6),
57 (4), 45 (5).
2-Methyl-5-chlorothiophenol (2i). Colorless liquid. 1H NMR (400 MHz,
CDCl3): d ¼ 2.27 (s, 3H), 3.33 (s, 1H), 7.00–7.07 (m, 2H), 7.24 (d, 1H, J ¼ 8.0 Hz);
13C NMR (100 MHz, CDCl3) d ¼ 21.6, 125.0, 130.2 (2C), 130.8, 134.9, 140.3; MS
(EI): m=z (rel. int.) 158 (100), 125 (77), 99 (3), 89 (30), 77 (11), 63 (10), 53 (3), 45
(11). EI-HRMS calcd. for C7H7ClS (Mþ): 157.9957; found: 157.9959.
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2,5-Difluorothiophenol (2j). Colorless liquid. H NMR (400 MHz, CDCl3):
d ¼ 3.70 (s, 1H), 6.79–6.84 (m, 1H), 6.97–7.07 (m, 2H);13C NMR (100 MHz, CDCl3)
d ¼ 114.0, 116.4, 117.2, 121.3, 158.7, 160.1; MS (EI): m=z (rel. int.) 146 (100), 126
(68), 101 (39). EI-HRMS calcd. for C6H4F2S (Mþ): 146.0002; found: 146.0003.
3,5-Bis(trifluoromethyl)thiophenol (2k). Colorless liquid. 1H NMR
(400 MHz, CDCl3): d ¼ 3.70 (s, 1H), 7.64 (s, 1H), 7.68 (s, 2H)[23]; MS (EI): m=z
(rel. int.) 246 (100), 226 (56), 207 (5), 182 (41), 157 (28), 132 (19), 114 (5), 99 (8),
69 (53), 45 (21), 20 (2).
3-Trifluoromethylthiophenol (2l). Colorless liquid. 1H NMR (400 MHz,
CDCl3): d ¼ 3.57 (s, 1H), 7.24–7.43 (m, 3H), 7.51 (s, 1H)[18]; MS (EI): m=z (rel.
int.) 178 (100), 158 (60), 145 (12), 133 (9), 114 (36), 95 (8), 82 (7), 69 (36), 57 (10),
45 (22), 28 (5).
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3-Methyl-4-fluorothiophenol (2m). Colorless liquid. H NMR (400 MHz,
CDCl3): d ¼ 2.21 (s, 3H), 3.38 (s, 1H), 6.84–6.90 (m, 1H), 7.04–7.13 (m, 2H); 13C
NMR (100 MHz, CDCl3) d ¼ 15.1, 115.4, 124.0, 126.3, 127.8, 128.0, 158.7; MS