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The Journal of Organic Chemistry
(s). HRMS (ESI) for C13H11NOS [M+H]+: calcd 230.0634,
MHz, CDCl3) δ -63.10 (s). HRMS (ESI) for C15H11F3OS
[M+H]+: calcd 297.0555, found 297.0548.
found 230.0627.
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S-(p-tolyl) 4,4,4-trifluorobutanethioate (3h): Colorless liq-
uid (25.4 mg, 41%). H NMR (500 MHz, CDCl3) δ 7.19 (d, J
S-(p-tolyl) pyridine-2-carbothioate (3o): White solid (42.9
mg, 75%). 1H NMR (500 MHz, CDCl3) δ 8.66 (d, J = 4.5 Hz,
1H), 7.87 (d, J = 7.8 Hz, 1H), 7.78 (td, J = 7.7, 1.5 Hz, 1H),
7.48 – 7.44 (m, 1H), 7.33 (d, J = 8.0 Hz, 2H), 7.19 (d, J = 8.0
Hz, 2H), 2.32 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 192.29
(s), 151.66 (s), 149.07 (s), 139.59 (s), 137.31 (s), 134.80 (s),
130.00 (s), 127.99 (s), 124.46 (s), 120.69 (s), 21.32 (s). HRMS
(ESI) for C13H11NOS [M+H]+: calcd 230.0634, found
230.0627.
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= 8.1 Hz, 2H), 7.13 (d, J = 8.0 Hz, 2H), 2.84 – 2.78 (m, 2H),
2.46 – 2.35 (m, 2H), 2.28 (s, 3H). 13C NMR (126 MHz, CDCl3)
δ 195.21 (s), 140.14 (s), 134.45 (s), 130.17 (s), 125.72 (q, J =
275.94 Hz), 123.22 (s), 35.63 (q, J = 2.8 Hz), 29.21 (q, J =
30.3 Hz), 21.32 (s). 19F NMR (471 MHz, CDCl3) δ -66.62 (s).
HRMS (ESI) for C11H11F3OS [M+H]+: calcd 249.0555, found
249.0548.
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S-(p-tolyl) 4-fluorobenzothioate (3i): White solid (16.0 mg,
26%). H NMR (500 MHz, CDCl3) δ 8.00 – 7.96 (m, 2H),
S-(p-tolyl) thiophene-2-carbothioate (3q): White solid (53.2
mg, 91%). 1H NMR (500 MHz, CDCl3) δ 7.80 (dd, J = 3.7, 0.7
Hz, 1H), 7.54 (dd, J = 4.9, 0.7 Hz, 1H), 7.31 (d, J = 8.0 Hz,
2H), 7.16 (d, J = 7.9 Hz, 2H), 7.04 (dd, J = 4.7, 4.1 Hz, 1H),
2.30 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 182.42 (s),
141.34 (s), 139.89 (s), 134.92 (s), 133.04 (s), 131.43 (s),
130.03 (s), 127.91 (s), 123.23 (s), 21.31 (s). HRMS (ESI) for
C12H10OS2 [M+H]+: calcd 235.0246, found 235.0239.
S-(p-tolyl) 4-methoxybenzothioate (3r): White solid (34.8
mg, 54%). 1H NMR (500 MHz, CDCl3) δ 7.92 (d, J = 8.8 Hz,
2H), 7.31 (d, J = 8.0 Hz, 2H), 7.18 (d, J = 7.6 Hz, 2H), 6.87 (d,
J = 8.8 Hz, 2H), 3.79 (s, 3H), 2.32 (s, 3H). 13C NMR (126
MHz, CDCl3) δ 189.02 (s), 163.86 (s), 139.60 (s), 135.08 (s),
129.99 (s), 129.63 (s), 129.40 (s), 123.97 (s), 113.82 (s), 55.49
(s), 21.34 (s). HRMS (ESI) for C15H14O2S [M+H]+: calcd
259.0787, found 259.0780.
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7.31 (d, J = 8.1 Hz, 2H), 7.20 (d, J = 8.1 Hz, 2H), 7.11 – 7.07
(m, 2H), 2.34 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 189.19
(s), 166.01 (d, J = 255.4 Hz), 139.97 (s), 135.01 (s), 132.98 (d,
J = 3.0 Hz), 130.15 (s), 130.02 (d, J = 9.4 Hz), 123.42 (s),
115.87 (d, J = 22.2 Hz), 21.38 (s). 19F NMR (471 MHz, CDCl3)
δ -104.32 (s). HRMS (ESI) for C14H11FOS [M+H]+: calcd
247.0587, found 247.0583.
S-(p-tolyl) 3-fluorobenzothioate (3j): White solid (43.1 mg,
70%). 1H NMR (500 MHz, CDCl3) δ 7.74 (d, J = 7.8 Hz, 1H),
7.61 (d, J = 9.1 Hz, 1H), 7.37 (td, J = 8.0, 5.6 Hz, 1H), 7.30 (d,
J = 8.0 Hz, 2H), 7.23 – 7.17 (m, 3H), 2.32 (s, 3H). 13C NMR
(126 MHz, CDCl3) δ 189.48 (s), 162.64 (d, J = 248.5 Hz),
140.04 (s), 138.59 (d, J = 6.7 Hz), 134.90 (s), 130.35 (d, J =
7.7 Hz), 130.16 (s), 123.20 (s), 123.17 (s), 120.48 (d, J = 21.4
Hz), 114.25 (d, J = 23.0 Hz), 21.35 (s). 19F NMR (471 MHz,
CDCl3) δ -111.33 (s). HRMS (ESI) for C14H11FOS [M+H]+:
calcd 247.0587, found 247.0581.
S-(p-tolyl) 4-chlorobenzothioate (3k): White solid (37.3 mg,
57%). 1H NMR (400 MHz, CDCl3) δ 7.89 (d, J = 8.6 Hz, 2H),
7.38 (d, J = 8.3 Hz, 2H), 7.31 (d, J = 7.9 Hz, 2H), 7.20 (d, J =
8.0 Hz, 2H), 2.33 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
189.49 (s), 140.01 (s), 139.95 (s), 135.00 (s), 134.95 (s),
130.16 (s), 129.01 (s), 128.79 (s), 123.28 (s), 21.37 (s).
S-(p-tolyl) 4-bromobenzothioate (3l): White solid (19.1 mg,
25%). 1H NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.2 Hz, 2H),
7.55 (d, J = 8.7 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 7.20 (d, J =
9.1 Hz, 2H), 2.34 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
189.72 (s), 140.03 (s), 135.44 (s), 134.95 (s), 132.00 (s),
130.18 (s), 128.89 (s), 128.63 (s), 123.24 (s), 21.38 (s).
S-(p-tolyl) 4-hydroxybenzothioate (3s): White solid (34.8
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mg, 57%). H NMR (500 MHz, DMSO-d6) δ 10.63 (s, 1H),
7.85 (d, J = 8.7 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.28 (d, J =
8.0 Hz, 2H), 6.90 (d, J = 8.7 Hz, 2H), 2.35 (s, 3H). 13C NMR
(126 MHz, DMSO) δ 187.90 (s), 163.44 (s), 139.78 (s),
135.54 (s), 130.42 (s), 130.14 (s), 127.48 (s), 124.10 (s),
116.22 (s), 21.32 (s). HRMS (ESI) for C14H12O2S [M+H]+:
calcd 245.0631, found 245.0624.
S-(p-tolyl) 4-(tert-butyl)benzothioate (3t): White solid (13.5
mg, 19%). 1H NMR (500 MHz, CDCl3) δ 7.89 (d, J = 8.5 Hz,
2H), 7.44 – 7.40 (m, 2H), 7.32 (d, J = 8.1 Hz, 2H), 7.19 (d, J =
5.9 Hz, 2H), 2.33 (s, 3H), 1.28 (s, 9H). 13C NMR (126 MHz,
CDCl3) δ 190.17 (s), 157.41 (s), 139.68 (s), 135.04 (s), 134.03
(s), 130.04 (s), 127.37 (s), 125.66 (s), 123.93 (s), 35.19 (s),
31.07 (s), 21.37 (s). HRMS (ESI) for C18H20OS [M+H]+: calcd
285.1308, found 285.1304.
S-(p-tolyl) 4-ethylbenzothioate (3u): White solid (23.7 mg,
37%). 1H NMR (500 MHz, CDCl3) δ 7.87 (d, J = 8.2 Hz, 2H),
7.31 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.2 Hz, 2H), 7.19 (d, J =
8.2 Hz, 2H), 2.64 (q, J = 7.6 Hz, 2H), 2.33 (s, 3H), 1.19 (t, J =
7.6 Hz, 3H). 13C NMR (126 MHz, CDCl3) δ 190.18 (s), 150.63
(s), 139.67 (s), 135.03 (s), 134.29 (s), 130.03 (s), 128.18 (s),
127.62 (s), 123.91 (s), 28.98 (s), 21.35 (s), 15.19 (s). HRMS
(ESI) for C16H16OS [M+H]+: calcd 257.0995, found 257.0989.
S-(p-tolyl) 4-acetylbenzothioate (3v): White solid (27.7 mg,
41%). 1H NMR (500 MHz, CDCl3) δ 8.02 (d, J = 8.3 Hz, 2H),
7.97 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 8.0 Hz, 2H), 7.21 (d, J =
7.9 Hz, 2H), 2.58 (s, 3H), 2.34 (s, 3H). 13C NMR (126 MHz,
CDCl3) δ 197.29 (s), 190.12 (s), 140.50 (s), 140.12 (s), 139.93
(s), 134.86 (s), 130.20 (s), 128.57 (s), 127.63 (s), 123.11 (s),
26.88 (s), 21.37 (s). HRMS (ESI) for C16H14O2S [M+H]+:
calcd 271.0787, found 271.0782.
S-(p-tolyl) 4-iodobenzothioate (3m): White solid (22.1 mg,
25%). 1H NMR (400 MHz, CDCl3) δ 7.77 (d, J = 8.2 Hz, 2H),
7.66 (d, J = 8.1 Hz, 2H), 7.31 (d, J = 7.9 Hz, 2H), 7.20 (d, J =
8.3 Hz, 2H), 2.33 (s, 3H). 13C NMR (101 MHz, CDCl3) δ
189.70 (s), 139.71 (s), 137.67 (s), 135.69 (s), 134.63 (s),
129.85 (s), 128.44 (s), 122.90 (s), 101.03 (s), 21.07 (s). HRMS
(ESI) for C14H11IOS [M+H]+: calcd 354.9648, found 354.9644.
S-(p-tolyl) furan-2-carbothioate (3n): White solid (34.3 mg,
63%). 1H NMR (500 MHz, CDCl3) δ 7.53 (d, J = 0.8 Hz, 1H),
7.31 (d, J = 8.1 Hz, 2H), 7.19 – 7.16 (m, 3H), 6.48 (dd, J = 3.5,
1.7 Hz, 1H), 2.32 (s, 3H). 13C NMR (126 MHz, CDCl3) δ
179.08 (s), 150.36 (s), 146.35 (s), 139.94 (s), 135.04 (s),
130.07 (s), 122.48 (s), 116.10 (s), 112.34 (s), 21.33 (s). HRMS
(ESI) for C12H10O2S [M+H]+: calcd 219.0474, found 219.0469.
S-(p-tolyl) pyridine-3-carbothioate (3p): Colorless liquid
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(27.5 mg, 48%). H NMR (500 MHz, CDCl3) δ 9.17 (s, 1H),
8.75 (d, J = 2.7 Hz, 1H), 8.19 (dt, J = 8.0, 1.9 Hz, 1H), 7.36
(dd, J = 7.9, 4.9 Hz, 1H), 7.32 (d, J = 8.1 Hz, 2H), 7.21 (d, J =
8.0 Hz, 2H), 2.34 (s, 3H). 13C NMR (126 MHz, CDCl3) δ
189.29 (s), 153.89 (s), 148.58 (s), 140.23 (s), 134.88 (s),
134.72 (s), 132.33 (s), 130.23 (s), 123.60 (s), 122.60 (s), 21.36
S-(p-tolyl) 2-cyanobenzothioate (3w): White solid (34.8 mg,
55%). 1H NMR (500 MHz, CDCl3) δ 8.09 (d, J = 7.4 Hz, 1H),
7.78 – 7.74 (m, 1H), 7.64 (tdd, J = 15.1, 10.8, 4.2 Hz, 2H),
7.33 (d, J = 8.0 Hz, 2H), 7.20 (d, J = 7.9 Hz, 2H), 2.33 (s, 3H).
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