Tao et al.
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S-(p-tolyl) benzothioate (3a)89: A pale white crystalline 123.1, 21.5ppm. HRMS (ESI-TOF) calcd for C15H12F3OS
solid; yield 95% (42.3mg); m.p. 75–77°C; 1H NMR [M+H]+: 297.0561; found: 297.0542.
(400MHz, CDCl3): δ 7.91 (d, J=7.6Hz, 2H), 7.46 (t,
S-(p-tolyl) pyridine-3-carbothioate (3h): A pale white
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J=7.6Hz, 1H), 7.34 (t, J=7.6Hz, 2H), 7.29 (d, J=8.0Hz, crystalline solid; yield 47% (21.5mg); m.p. 80–82°C; H
2H), 7.14 (d, J=8.0Hz, 2H), 2.28 (s, 3H) ppm. 13C NMR NMR (400MHz, CDCl3): δ 8.74 (d, J=4.8Hz, 1H), 7.95
(100MHz, CDCl3): δ 190.5, 139.8, 136.8, 135.1, 133.6, (d, J=7.6Hz, 1H), 7.86 (t, J=7.2Hz, 1H), 7.57–7.52 (m,
130.2, 128.8, 127.5, 123.9, 21.4ppm. HRMS (ESI-TOF) 1H), 7.41 (d, J=7.6Hz, 2H), 7.27 (d, J=7.6Hz, 2H), 2.40
calcd for C14H13OS [M+H]+: 229.0687; found: 229.0690. (s, 3H) ppm. 13C NMR (100MHz, CDCl3): δ 192.4, 151.9,
S-(p-tolyl) 4-methylbenzothioate (3b)90: A pale white 149.3, 139.7, 137.5, 135.0, 130.2, 128.1, 124.7, 120.9,
crystalline solid; yield 77% (37.3mg); m.p. 123.5–124.5°C; 21.5ppm. HRMS (ESI-TOF) calcd for C13H12NOSNa
1H NMR (400MHz, CDCl3): δ 7.91 (d, J=8.0Hz, 2H), [M+Na]+: 252.0459; found: 252.0455.
7.38 (d, J=8.0Hz, 2H), 7.27–7.23 (m, 4H), 2.41 (s, 3H),
S-(p-tolyl) furan-2-carbothioate (3i): A pale white crys-
2.39 (s, 3H) ppm. 13C NMR (100MHz, CDCl3): δ 190.2, talline solid; yield 80% (34.9mg); m.p. 74–76°C; 1H NMR
144.6, 139.8, 135.2, 134.3, 130.2, 129.5, 127.7, 124.1, (400MHz, CDCl3): δ 7.60 (s, 1H), 7.38 (d, J=8.0Hz, 2H),
21.8, 21.5ppm. HRMS (ESI-TOF) calcd for C15H15OS 7.29–7.17 (m, 3H), 6.55 (dd, J=3.2, 1.6Hz, 1H), 2.39 (s,
[M+H]+; 243.0844; found: 243.0840.
3H) ppm. 13C NMR (100MHz, CDCl3): δ 179.2, 150.5,
S-(p-tolyl) 4-methoxybenzothioate (3c)91: A pale white 146.5, 140.1, 135.2, 130.2, 122.7, 116.2, 112.5, 21.5ppm.
crystalline solid; yield 75% (38.7mg); m.p. 63–65°C; H HRMS (ESI-TOF) calcd for C12H11O2S [M+H]+:
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NMR (400MHz, CDCl3): δ 7.99 (d, J=8.8Hz, 2H), 7.38 219.0479; found: 219.0465.
(d, J=8.0Hz, 2H), 7.25 (d, J=8.0Hz, 2H), 6.94 (d,
S-(p-tolyl) naphthalene-2-carbothioate (3j): A pale
J=8.8Hz, 2H), 3.86 (s, 3H), 2.39 (s, 3H) ppm. 13C NMR white crystalline solid; yield 81% (45.1mg); m.p. 119–
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(100MHz, CDCl3): δ 189.2, 166.1 (d, JC-F =255.2Hz), 121°C; H NMR (400MHz, CDCl3): δ 8.59 (s, 1H), 8.01
140.0, 135.1, 133.1 (d, 4JC-F =2.6Hz), 130.3, 130.1 (d, 3JC- (dd, J=8.4, 1.6Hz, 1H), 7.96 (d, J=8.0Hz, 1H), 7.87 (t,
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F =9.3Hz), 123.6, 116.0 (d, JC-F =22.1Hz), 21.5 ppm. J=8.4Hz, 2H), 7.63–7.48 (m, 2H), 7.43 (d, J=8.0Hz, 2H),
HRMS (ESI-TOF) calcd for C15H15O2SNa [M+Na]+: 7.27 (d, J=8.0Hz, 2H), 2.40 (s, 3H) ppm. 13C NMR
281.0612; found: 281.0599.
(100MHz, CDCl3): δ 190.6, 139.9, 136.0, 135.2, 134.1,
S-(p-tolyl) 4-fluorobenzothioate (3d): A pale white crys- 132.6, 130.2, 129.7, 129.0, 128.70, 128.67, 127.9, 127.1,
talline solid; yield 91% (44.8mg); m.p. 71–73°C; 1H NMR 124.0, 123.4, 21.5ppm. HRMS (ESI-TOF) calcd for
(400MHz, CDCl3): δ 8.06–8.02 (m, 2H), 7.38 (d, J=8.0Hz, C18H15OS [M+H]+: 279.0844; found: 279.0847.
2H), 7.27–7.24 (m, 2H), 7.14 (t, J=8.4Hz, 2H), 2.39 (s,
S-(4-methoxyphenyl) benzothioate (4a)92: A pale white
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3H) ppm. 19F NMR (376MHz, CDCl3): δ −104.26ppm. 13C crystalline solid; yield 65% (31.5mg); m.p. 92–94°C; H
NMR(100MHz, CDCl3):δ189.2, 166.1(d, JC-F =255.2Hz), NMR (400MHz, CDCl3): δ 8.02 (d, J=7.2Hz, 2H), 7.59 (t,
140.0, 135.1, 133.1 (d, J=2.6C-F Hz), 130.3, 130.1 J=7.2Hz, 1H), 7.47 (t, J=7.8Hz, 2H), 7.41 (d, J=8.8Hz,
(d, JC-F =9.3Hz), 123.6, 116.0 (d, JC-F =22.1Hz), 21.5ppm. 2H), 6.98 (d, J=8.8Hz, 2H), 3.84 (s, 3H) ppm. 13C NMR
HRMS (ESI-TOF) calcd for C14H12FOSNa [M+Na]+: (100MHz, CDCl3): δ 191.1, 160.9, 136.8, 136.7, 133.7,
269.0412; found: 269.0394.
128.8, 127.6, 118.0, 115.1, 55.5ppm. HRMS (ESI-TOF)
S-(p-tolyl) 4-chlorobenzothioate (3e): A pale white crys- calcd for C14H13O2SNa [M+Na]+: 267.0456; found:
talline solid; yield 88% (46.1mg); m.p. 84–86°C; 1H NMR 267.0465.
(400MHz, CDCl3): δ 7.95 (d, J=8.4Hz, 2H), 7.43 (d,
S-(4-(tert-butyl)phenyl) benzothioate (4b): A pale white
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J=8.4Hz, 2H), 7.37 (d, J=8.0Hz, 2H), 7.30–7.22 (m, 2H), crystalline solid; yield 71% (38.4mg); m.p. 77–79°C; H
2.39 (s, 3H) ppm. 13C NMR (100MHz, CDCl3): δ 189.5, NMR (400MHz, CDCl3): δ 8.03 (d, J=7.2Hz, 2H), 7.59 (t,
140.1, 140.0, 135.2, 135.1, 130.3, 129.1, 128.9, 123.5, J=7.2Hz, 1H), 7.46–7.43 (m, 6H), 1.34 (s, 9H) ppm. 13C
21.5ppm. HRMS (ESI-TOF) calcd for C14H12ClOS NMR (100MHz, CDCl3): δ 190.6, 152.9, 136.9, 134.8,
[M+H]+: 263.0297; found: 263.0309.
133.7, 128.8, 127.6, 126.5, 124.0, 34.9, 31.4ppm. HRMS
S-(p-tolyl) 4-bromobenzothioate (3f): A pale white crys- (ESI-TOF) calcd for C17H19OS [M+H]+: 271.1157; found:
talline solid; yield 87% (53.1mg); m.p. 93–95°C; 1H NMR 271.1157.
(400MHz, CDCl3): δ 7.79 (d, J=8.4Hz, 2H), 7.53 (d,
S-(o-tolyl) benzothioate (4c): A yellow oily liquid; yield
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J=8.4Hz, 2H), 7.29 (d, J=8.0Hz, 2H), 7.24–7.12 (m, 2H), 84% (38.4mg); H NMR (400MHz, CDCl3): δ 8.05 (d,
2.32 (s, 3H) ppm. 13C NMR (100MHz, CDCl3): δ 189.7, J=7.2Hz, 2H), 7.59 (t, J=7.2Hz, 1H), 7.48 (t, J=7.6Hz,
140.1, 135.6, 135.1, 132.1, 130.3, 129.0, 128.7, 123.4, 3H), 7.41–7.33 (m, 2H), 7.32–7.20 (m, 1H), 2.40 (s, 3H)
21.5ppm. HRMS (ESI-TOF) calcd for C14H12BrOS ppm. 13C NMR (100MHz, CDCl3): δ 189.7, 142.8, 136.9,
[M+H]+: 306.9792; found: 306.9780.
136.5, 133.7, 130.9, 130.3, 128.8, 127.7, 126.9, 126.8,
S-(p-tolyl) 4-(trifluoromethyl)benzothioate (3g): A pale 20.9ppm. HRMS (ESI-TOF) calcd for C14H13OS [M+H]+:
white crystalline solid; yield 76% (45.1mg); m.p. 103– 229.0687; found: 229.0685.
105°C; 1H NMR (400MHz, CDCl3): δ 8.11 (d, J=8.0Hz,
S-(4-fluorophenyl) benzothioate (4d)91: A pale white
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2H), 7.74 (d, J=8.0Hz, 2H), 7.39 (d, J=7.6Hz, 2H), 7.28 crystalline solid; yield 87% (40.4mg); m.p. 51–52°C; H
(d, J=7.6Hz, 2H), 2.41 (s, 3H) ppm. 19F NMR (376MHz, NMR (400MHz, CDCl3): δ 8.01 (d, J=7.2Hz, 2H), 7.61 (t,
CDCl3): δ −63.09ppm. 13C NMR (100MHz, CDCl3): δ J=7.2Hz, 1H), 7.51–7.45 (m, 4H), 7.15 (t, J=8.8Hz, 2H)
189.9, 140.3, 139.7, 135.1, 135.0 (q, 2JC-F =32.8Hz), 130.4, ppm. 19F NMR (376MHz, CDCl3): δ −111.02ppm. 13C
127.9, 125.9 (q, JC-F =3.6Hz), 123.6 (q, JC-F =272.7Hz), NMR(100MHz,CDCl3):δ190.2,163.8(d,1JC-F =250.1Hz),
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