JOURNAL OF CHEMICAL RESEARCH 2018 461
1H), 7.20 (d, J = 8.0 Hz, 2H), 7.15 (d, J = 8.8 Hz, 2H), 1.28 (s, 9H),
1.26 (s, 9H); 13C NMR (101 MHz, CDCl3): δ 156.1, 153.4, 151.2, 149.5,
132.0, 130.9, 129.5, 129.4, 128.2, 126.5, 126.2, 125.7, 123.6, 120.7,
116.7, 111.7, 34.7, 34.6, 31.4, 31.37. HRMS (EI) m/z calcd for C28H30OS2
[M]: 446.1738; found: 446.1722.
2,3-Bis(p-tolylthio)benzo[b]thiophene (3m): White solid; yield 61
mg (54%); m.p. 75.3–78.1 °C; 1H NMR (400 MHz, CDCl3): δ 7.72 (d,
J = 7.2 Hz, 1H), 7.63 (d, J = 7.2 Hz, 1H), 7.43 (d, J = 8.0 Hz, 2H), 7.29
(m, 1H), 7.25 (d, J = 6.0 Hz, 1H), 7.16 (d, J = 8.0 Hz, 2H), 7.06 (d,
J = 8.4 Hz, 2H), 7.00 (d, J = 8.0 Hz, 2H), 2.36 (s, 3H), 2.26 (s, 3H);
13C NMR (101 MHz, CDCl3): δ 147.1, 140.6, 139.5, 139.3, 135.7, 133.3,
132.8, 130.3, 130.0, 129.9, 127.7, 125.1, 124.8, 123.03, 123.0, 122.0,
21.4, 21.1. HRMS (EI) m/z calcd for C22H18S3 [M]: 378.0571; found:
378.0554.
135.5, 134.4, 130.5, 129.6, 125.9, 122.2, 120.8, 119.1, 110.7, 100.0, 21.0,
12.3.
3-Methyl-2-(p-tolylthio)-1H-indole (5c)35: White solid; yield 18 mg
(24%); m.p. 100.1–100.6 °C (lit.35 m.p. 93–95 °C); 1H NMR (400 MHz,
CDCl3): δ 7.89 (s, 1H), 7.59 (t, J = 7.0 Hz, 1H), 7.29–7.21 (m, 2H),
7.15–7.11 (m, 1H), 7.05–6.97 (m, 4H), 2.40 (d, J = 6.8 Hz, 3H), 2.27
(d, J = 6.0 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ 136.9, 135.9, 133.4,
130.0, 128.6, 127.2, 123.5, 122.4, 119.7, 119.5, 119.4, 110.9, 21.0, 9.6.
7-Nitro-3-(p-tolylthio)-1H-indole (5d): Yellow solid; yield 70 mg
1
(82%); m.p. 177.2–179.7 °C; H NMR (400 MHz, CDCl3): δ 10.09
(s, 1H), 8.21 (d, J = 8.8 Hz, 1H), 7.95 (d, J = 8.0 Hz, 1H), 7.67 (d,
J = 2.4 Hz, 1H), 7.23 (d, J = 8.0 Hz, 1H), 7.04 (d, J = 8.4 Hz, 2H), 7.00
(d, J = 8.4 Hz, 2H), 2.26 (s, 3H); 13C NMR (101 MHz, CDCl3): δ 135.6,
134.3, 133.6, 132.7, 132.5, 130.1, 129.8, 128.0, 127.0, 120.4, 120.3,
106.6, 21.0. HRMS (EI) m/z calcd for C15H12N2O2S [M]: 284.0619;
found: 284.0609.
2,3-Bis((4-methoxyphenyl)thio)benzo[b]thiophene (3n): White
1
solid; yield 48 mg (39%); m.p. 127.2–127.9 °C; H NMR (400 MHz,
CDCl3): δ 7.73 (d, J = 8.0 Hz, 1H), 7.60 (d, J =8.0 Hz, 1H), 7.52 (d, J
= 8.8 Hz, 2H), 7.29 (t, J = 7.6 Hz, 1H), 7.24 (m, 1H), 7.19 (d, J = 8.8
Hz, 2H), 6.90 (d, J = 8.8 Hz, 2H), 6.76 (d, J = 8.8 Hz, 2H), 3.82 (s,
3H), 3.73 (s, 3H); 13C NMR (101 MHz, CDCl3): δ 160.8, 158.5, 148.4,
140.8, 139.1, 136.0, 130.2, 126.8, 125.1, 124.4, 123.5, 122.6, 122.2,
121.9, 115.2, 114.8, 55.5, 55.4. HRMS (EI) m/z calcd for C22H18O2S3
[M]: 410.0469; found: 410.0446.
5-Nitro-3-(p-tolylthio)-1H-indole (5e)31: Yellow solid; yield
1
50 mg (59%); m.p. 169.6–171.2 °C (lit.31 m.p. 204–207 °C); H NMR
(400 MHz, CDCl3): δ 8.80 (s, 1H), 8.57 (d, J = 2.0 Hz, 1H), 8.16 (dd,
J = 9.0, 2.2 Hz, 1H), 7.63 (d, J = 2.4 Hz, 1H), 7.48 (d, J = 9.0 Hz,
1H), 7.06 (d, J = 8.4 Hz, 2H), 7.01 (d, J = 8.2 Hz, 2H), 2.26 (s, 3H);
13C NMR (101 MHz, CDCl3): δ 136.9, 135.4, 134.0, 129.8, 128.3, 127.2,
122.7, 118.2, 116.7, 104.5, 103.2, 21.1.
2,3-Bis((4-(t-butyl)phenyl)thio)benzo[b]thiophene (3o): White
solid; yield 116 mg (87%); m.p. 104.6–107.3 °C; 1H NMR (400 MHz,
CDCl3): δ 7.75 (d, J = 9.2 Hz, 1H), 7.64 (d, J = 6.8 Hz, 1H), 7.45 (d,
J = 8.4 Hz, 2H), 7.35 (d, J = 8.4 Hz, 2H), 7.29 (m, 1H), 7.26 (m, 1H),
7.20 (d, J = 8.4 Hz, 2H), 7.08 (d, J = 8.4 Hz, 2H), 1.31 (s, 9H), 1.25 (s,
9H); 13C NMR (101 MHz, CDCl3): δ 152.2, 148.9, 146.9, 140.6, 139.6,
132.9, 132.8, 130.2, 127.3, 126.6, 126.2, 125.1, 124.8, 123.4, 123.1,
122.0, 34.8, 34.5, 31.41, 31.4. HRMS (EI) m/z calcd for C28H30S3 [M]:
462.1510; found: 462.1515.
3-(p-Tolylthio)-1H-indole-7-carbonitrile (5f): White solid; yield
33 mg (41%); m.p. 175.5–178.3 °C; H NMR (400 MHz, CDCl3): δ
8.78 (s, 1H), 7.68–7.62 (m, 2H), 7.52 (dd, J = 0.8, 0.8 Hz, 1H), 7.29 (d,
J = 8.0 Hz, 1H), 7.10 (d, J = 8.2 Hz, 2H), 7.00 (d, J = 8.0 Hz, 2H),
2.25 (s, 3H); 13C NMR (101 MHz, CDCl3): δ 136.9, 135.4, 135.4, 133.9,
129.8, 128.6, 128.3, 127.3, 122.7, 118.1, 116.6, 104.7, 103.3, 21.1. HRMS
(EI) m/z calcd for C16H12N2S [M]: 264.0721; found: 264.0710.
1
Acknowledgements
2,3-Bis((4-fluorophenyl)thio)benzo[b]thiophene (3p): White solid;
yield 60 mg (52%); m.p. 75.8–78.1 °C; H NMR (400 MHz, CDCl3):
We gratefully acknowledge financial support of this work
by the National Natural Science Foundation of China (No.
21563025), and the Program for Changjiang Scholars and
Innovative Research Team in University (No. IRT_15R46), and
Yangtze River Scholar Research Project of Shihezi University
(No. CJXZ201601).
1
δ 7.75–7.70 (m, 1H), 7.66 (dd, J = 2.0, 1.6 Hz, 1H), 7.50 (dd, J = 5.2,
5.2 Hz, 2H), 7.35–7.27 (m, 2H), 7.12 (dd, J = 5.2, 5.2 Hz, 2H), 7.04 (t,
J = 8.6 Hz, 2H), 6.89 (t, J = 8.6 Hz, 2H); 13C NMR (101 MHz, CDCl3):
δ 164.6, 162.8, 162.1, 160.3, 146.3, 140.3, 139.5, 135.33, 135.3, 131.22,
131.2, 129.7, 129.6, 128.7, 128.6, 125.4, 125.2, 123.7, 123.0, 122.2,
116.9, 116.7, 116.4, 116.2. HRMS (EI) m/z calcd for C20H12F2S3 [M]:
386.0069; found: 386.0054.
Electronic Supplementary Information
The ESI associated with this paper can be found at:
1,2-Di-p-tolyldisulfane (3aa)33: White solid; yield 24 mg (33%); m.p.
1
39–40 °C (lit.33 m.p. 39–40 °C); H NMR (400 MHz, CDCl3): δ 7.38
(d, J = 8.0 Hz, 4H), 7.10 (d, J = 8.0 Hz, 4H), 2.32 (s, 6H).
Received 11 July 2018; accepted 7 August 2018
Paper 1805520
Published online: 3 September 2018
S-(p-tolyl)-4-methylbenzenesulfonothioate (3ab)34: White solid;
yield 52 mg (62%); m.p. 76.0–76.8 °C (lit.34 m.p. 76.7–77.5 °C);
1H NMR (400 MHz, CDCl3): δ 7.46 (d, J = 8.4 Hz, 2H), 7.24 (d, J = 8.4
Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H), 2.42 (s, 3H),
2.38 (s, 3H).
References
S-(4-methoxyphenyl)-4-methylbenzenesulfonothioate (3ac)34: White
solid; yield 53 mg (60%); m.p. 126.5–127.2 °C (lit.34 m.p. 127.2–128.0 °C);
1H NMR (400 MHz, CDCl3): δ 7.46 (d, J = 8.4 Hz, 2H), 7.27 (d, J = 8.4
Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 6.84 (d, J = 9.2 Hz, 2H), 3.83 (s, 3H),
2.42 (s, 3H).
1
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HRMS (ESI) m/z calcd for C23H22NS2 [M + H]+: 376.11882; found:
+
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2-Methyl-3-(p-tolylthio)-1H-indole (5b)31: White solid; yield 30 mg
(39%); m.p. 98.7–96.9 °C (lit.31 m.p. 94–96 °C); H NMR (400 MHz,
1
CDCl3): δ 8.14 (s, 1H), 7.54 (d, J = 7.8 Hz, 1H), 7.31 (d, J = 8.0 Hz,
1H), 7.17 (td, J = 8.0, 7.6, 1.2 Hz, 1H), 7.13–7.08 (m, 1H), 6.95 (s, 4H),
2.49 (s, 3H), 2.23 (s, 3H); 13C NMR (101 MHz, CDCl3): δ 141.0, 135.8,
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