Lee et al.
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without purification. DMF and DIPEA were dried with CaH2.
Indium, InCl3, and Xantphos were purchased. All reactions were
monitored by TLC using silica gel 60 F254 precoated glass plates
and purifications were performed by column chromatography
2,5-Di(4-methoxyphenylthio)pyridine (2f): white solid; mp
112 °C; H NMR (400 MHz, CDCl3) δ 8.28 (s, 1H), 7.50 (d,
1
J = 8.65 Hz, 2H), 7.34 (d, J = 8.68 Hz, 2H), 7.24 (d, J = 8.38
Hz, 1H), 6.94 (d, J = 8.65 Hz, 2H), 6.85 (d, J = 8.68 Hz, 2H),
6.68 (d, J = 8.38 Hz, 1H), 3.83 (s, 3H), 3.79 (s, 3H); 13C NMR
(100 MHz, CDCl3) δ 161.1, 160.9, 160.4, 150.0, 137.9, 137.6,
135.1, 124.3, 121.4, 121.1, 115.7, 115.5, 55.8; IR (film) 3434,
1592, 1550, 1494, 1412, 1249 cm-1; HRMS (EI) calcd for
C19H17NO2S2 m/z 355.0701 [Mþ], found m/z 355.0700.
1
using silica gel 60 (0.04-0.063 mm, 230-400 mesh). H NMR
and 13C NMR spectra were recorded on 400 MHz spectrometer
using deuterated chloroform as solvent and chemical shift values
(δ) are reported in part per million relative to TMS as internal
standard. High-resolution mass spectra and infrared spectra were
recorded on each spectrometer.
2,5-Di(4-fluorophenylthio)pyridine (2g): white solid; mp 72 °C;
1H NMR (400 MHz, CDCl3) δ 8.33(s, 1H), 7.56 (dd, J = 8.31,
8.4 Hz, 2H), 7.37-7.31 (m, 3H), 7.11 (dd, J = 8.5, 8.58 Hz, 2H),
Synthetic Procedure of 4,40-Bis(p-tolylthio)biphenyl (3b). To a
solution of Pd(OAc)2 (4.5 mg, 4 mol %) and Xantphos (12.1 mg,
4.2 mol %) in DMF (1.0 mL) was added 4,40-dibromo-1,10-
biphenyl (156 mg, 0.5 mmol) in DMF (0.5 mL) at 25 °C under
nitrogen atmosphere. After being stirred for 5 min, (4-Me-
C6H4S)3In (164.7 mg, 0.34 mmol) and DIPEA (87.0 μL, 0.5
mmol) in DMF (1.0 mL) was transferred via double-ended needle,
and the mixture was stirred at 100 °C for 4 h. The reaction mixture
was quenched with NaHCO3 (satd aq). The aqueous layer was
extracted with ether (3 ꢀ 20 mL), and the combined organic layers
werewashedwithwaterandbrine, driedwithMgSO4, filtered, and
concentrated under reduced pressure. The residue was purified by
silica gel column chromatography to give 3b (167.4 mg, 84%) as
white solid: mp 159 °C; 1H NMR (400 MHz, CDCl3) δ 7.45 (d,
J = 8.36 Hz, 2H), 7.34 (d, J = 8.00 Hz, 2H), 7.30 (d, J = 8.36 Hz,
2H), 7.16 (d, J = 8.00 Hz, 2H), 2.35 (s, 3H); 13C NMR (100 MHz,
CDCl3) δ 138.9, 138.2, 136.9, 132.9, 131.4, 130.6, 130.3, 127.8,
21.6; IR (film) 3431, 809 cm-1; HRMS (EI) calcd for C26H22S2
m/z 398.1163 [Mþ], found m/z 398.1164.
7.00 (dd, J = 8.31, 8.4 Hz, 2H), 6.80 (d, J = 8.41 Hz, 1H); 13
C
NMR (100 MHz, CDCl3) δ 160.7, 150.8, 139.6, 138.8, 137.9,
135.2, 131.7, 130.7, 130.5, 130.2, 129.3, 126.3, 121.1, 21.3, 21.1;
IR (film) 3441, 1588, 1489, 1224 cm-1; HRMS (EI) calcd for
C17H11F2NS2 m/z 331.0301 [Mþ], found m/z 331.0301.
5-(tert-Butylthio)-2-(4-methoxyphenylthio)pyridine (2h):
1
white solid; mp 95 °C; H NMR (400 MHz, CDCl3) δ 8.48 (s,
1H), 7.56-7.53 (m, 3H), 6.98 (d, J = 8.7 Hz 2H), 6.73 (d, J = 8.4
Hz, 1H), 3.85 (s, 3H), 1.25 (s, 9H); 13C NMR (100 MHz, CDCl3)
δ 168.1, 161.3, 156.8, 145.4, 137.8, 125.2, 120.9, 120.2, 115.8,
55.8, 46.7, 31.2; IR (film) 3434, 1592, 1550, 1494, 1412, 1249
cm-1; HRMS (EI) calcd for C16H19NOS2 m/z 305.0908 [Mþ],
found m/z 305.0910.
2-(Isopropylthio)-5-(p-tolylthio)pyridine (2i): pale yellow oil;
1H NMR (400 MHz, CDCl3) δ 8.39 (s, 1H), 7.40 (d, J = 8.5 Hz,
1H), 7.24 (d, J = 8.1 Hz, 2H), 7.12 (d, J = 8.1 Hz, 2H), 7.06 (d,
J = 8.5 Hz, 1H), 3.95 (sep, J = 6.7 Hz, 1H), 2.33 (s, 3H), 1.39 (d,
J = 6.7 Hz, 6H); 13C NMR (100 MHz, CDCl3) δ 158.3, 151.1,
138.5, 137.6, 131.3, 131.2, 130.1, 128.5, 122.9, 35.3, 23.1, 21.1;
IR (neat) 3435, 1560, 1492, 1443, 1349 cm-1; HRMS (EI) calcd.
for C15H17NS2 m/z 275.0802 [Mþ], found m/z 275.0804.
4,40-Di(phenylthio)-1,10-biphenyl20 (3a): yellow solid; mp
2,5-Di(propylthio)pyridine (2a): yellow oil; 1H NMR (400
MHz, CDCl3) δ 8.42 (s, 1H), 7.48 (d, J = 8.45 Hz, 1H), 7.09
(d, J = 8.45 Hz, 1H), 3.13 (t, J = 7.35 Hz, 2H), 2.82 (t, J = 7.35
Hz, 2H), 1.73 (sextet, J = 7.35 Hz, 2H), 1.67 (sextet, J = 7.35
Hz, 2H), 1.04 (t, J = 7.35 Hz, 3H), 1.00 (t, J = 7.35 Hz, 3H); 13
C
1
NMR (100 MHz, CDCl3) δ 157.7, 151.0, 138.5, 128.2, 122.1,
37.0, 32.3, 22.7, 22.6, 13.5, 13.2; IR (film) 3435, 2962, 2870, 1566
cm-1; HRMS (EI) calcd for C11H17NS2 m/z 227.0802 [Mþ],
found m/z 227.0804.
113 °C; H NMR (400 MHz, CDCl3) δ 7.50 (d, J = 8.28 Hz,
2H), 7.41-7.37 (m, 4H), 7.35-7.31 (m, 2H), 7.29-7.27 (m, 1H);
13C NMR (100 MHz, CDCl3) δ 138.9, 135.4, 135.35, 131.3,
131.1, 129.3, 127.6, 127.3; IR (film) 3435, 1645, 1476 cm-1
.
2,5-Di(isopropylthio)pyridine18 (2b): yellow oil; 1H NMR (400
MHz, CDCl3) δ 8.47 (s, 1H), 7.53 (d, J = 8.14 Hz, 1H), 7.10 (d,
J = 8.14 Hz, 1H), 3.97 (sep, J = 6.75 Hz, 1H), 3.24 (sep, J = 6.75
9,10-Di(phenylthio)anthracene21 (3c): yellow solid; mp 215 °C;
1H NMR (400 MHz, CDCl3) δ 8.95 (d, J = 6.82 Hz, 2H), 7.57
(d, J = 6.82 Hz, 2H), 7.12 (dd, J = 7.92, 7.24 Hz, 2H), 7.04 (dd,
J = 7.92, 7.24 Hz, 1H), 6.96 (d, J = 7.24 Hz, 2H), 3.80 (s, 6H);
13C NMR (100 MHz, CDCl3) δ 138.7, 135.6, 130.3, 129.4, 128.1,
Hz, 1H), 1.40 (d, J = 6.75 Hz, 6H), 1.27 (d, J = 6.75 Hz, 6H); 13
C
NMR (100 MHz, CDCl3) δ 158.8, 153.4, 140.8, 126.6, 122.5, 39.3,
35.2, 23.14, 23.12; IR (film) 3435, 2961, 1564, 1449 cm-1
.
127.8, 126.9, 125.6; IR (film) 3434, 1643 cm-1
.
2,5-Di(tert-butylthio)pyridine (2c): white solid; mp 63 °C; 1H
NMR (400 MHz, CDCl3) δ 8.57(s, 1H), 7.62 (d, J = 8.04 Hz,
1H), 7.23 (d, J = 8.04 Hz, 1H), 1.55 (s, 9H), 1.29 (s, 9H); 13C
NMR (100 MHz, CDCl3) δ 159.9, 156.2, 144.2, 125.9, 125.6,
48.0, 46.3, 30.9, 30.8; IR (film) 1433, 1363 cm-1; HRMS (EI)
calcd for C13H21NS2 m/z 255.1115 [Mþ], found m/z 255.1118.
2,4-Di(4-methoxyphenylthio)-1-methoxybenzene (3d): white
solid; mp 79 °C; H NMR (400 MHz, CDCl3) δ 7.35 (d, J =
1
8.69 Hz, 2H), 7.20 (d, J = 8.88 Hz, 2H), 7.02 (d, J = 8.42 Hz,
1H), 6.85 (d, J = 8.69 Hz, 2H), 6.77 (d, J = 8.88 Hz, 2H), 6.75
(d, J = 8.42 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 160.2,
159.3, 154.2, 136.5, 133.9, 129.3, 129.1, 128.5, 127.7, 125.8,
121.5, 115.1, 114.7, 110.8, 56.0, 55.3; IR (film) 3435, 1592,
1493, 1288 cm-1; HRMS (EI) calcd for C21H20O3S2 m/z
384.0854 [Mþ], found m/z 384.0850.
1
2,5-Di(phenylyhio)pyridine19 (2d): yellow oil; H NMR (400
MHz, CDCl3) δ 8.41 (s, 1H), 7.61-7.58 (m, 2H), 7.44-7.40 (m,
5H), 7.30 (d, J = 4.34 Hz, 4H), 6.82 (d, J = 8.26 Hz, 1H); 13
C
NMR (100 MHz, CDCl3) δ 160.7, 151.7, 139.7, 135.1, 134.9,
130.7, 130.6, 129.7, 129.4, 129.3, 128.5, 127.4, 121.5; IR (film)
2,7-Di(p-tolylthio)-9,9-dimethyl-9H-fluorene (3e): white solid;
mp 138 °C; 1H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 7.98 Hz,
2H), 7.38 (s, 2H), 7.29 (d, J = 7.96 Hz, 4H) 7.22 (d, J = 7.98 Hz,
2H), 7.13 (d, J = 7.96 Hz, 4H), 2.34 (s, 6H), 1.40 (s, 6H); 13C
NMR (100 MHz, CDCl3) δ 154.9, 137.9, 137.7, 135.9, 132.5,
131.8, 130.5, 130.2, 129.8, 128.9, 125.3, 120.9, 47.4, 27.4, 21.6;
IR (film) 3435, 2960, 1600, 1491 cm-1; HRMS (EI) calcd. for
C29H26S2 m/z 438.1476 [Mþ], found m/z 438.1479.
3434, 3058, 1560, 1475 cm-1
.
2,5-Di(p-tolylthio)pyridine (2e): white solid; mp 52 °C; 1H
NMR (400 MHz, CDCl3) δ 8.35 (s, 1H), 7.47 (d, J = 8.06 Hz,
2H), 7.33 (d, J = 8.54 Hz, 2H), 7.24-7.21 (m, 4H), 7.11 (d, J =
8.08 Hz, 2H), 6.75 (d, J = 8.54 Hz, 1H), 2.38 (s, 3H), 2.32 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 160.7, 150.8, 139.6, 138.8, 137.9,
135.2, 131.7, 130.7, 130.5, 130.2, 129.3, 126.3, 121.1, 21.3, 21.1;
IR (film) 3435, 1560, 1492, 1443, 1349 cm-1; HRMS (EI) calcd
for C19H17NS2 m/z 323.0802 [Mþ], found m/z 323.0799.
3,4-Di(4-methoxyphenylthio)thiophene (3f): white solid; mp
1
157 °C; H NMR (400 MHz, CDCl3) δ 7.33 (d, J = 8.86 Hz,
4H), 7.00 (s, 2H), 6.85 (d, J = 8.86 Hz, 4H), 3.80 (s, 6H); 13C
NMR (100 MHz, CDCl3) δ 159.4, 134.3, 133.4, 125.5, 125.2,
(18) Testaferri, L.; Tiecco, M.; Tingoli, M.; Bartoli, D.; Massoli, A.
Tetrahedron 1985, 41, 1373.
(19) Markley, L. D.; Tong, Y. C.; Wood, S. G. U.S. Patent 4371537, 1983.
(20) Wang, Z. Y.; Hay, A. S. Tetrahedron Lett. 1990, 31, 5685.
(21) Hacker, N. P.; Larson, C. E. U.S. Patent 4760013, 1988.
764 J. Org. Chem. Vol. 76, No. 3, 2011