Organometallics
ARTICLE
7.49 (1H, dd, J = 1.6, 7.6 Hz), 7.56 (4H, t, J = 7.6 Hz), 7.57 (1H, dd, J =
1.6, 7.6 Hz), 8.11 (4H, d, J = 7.6 Hz); 13C NMR (100 MHz, DMSO-d6)
δ 126.5, 127.6, 127.7, 128.6, 131.1, 132.6, 135.7, 137.7, 140.6, 173.5.
Anal. Calcd for C20H14BiBrS: C, 39.22; H, 2.56. Found: C, 39.19;
H, 2.41.
7.34 (1H, dt, J = 1.6, 7.6 Hz), 7.39 (1H, dt, J = 1.6, 7.6 Hz), 7.48 (1H, dd,
J = 1.6, 7.6 Hz), 7.55 (4H, d, J = 7.6 Hz), 7.63 (1H, dd, J = 1.6, 7.6 Hz),
7.88 (1H, dd, J = 1.6, 7.6 Hz); 13C NMR (100 MHz, CDCl3) δ 21.5,
121.2, 126.4, 127.6, 128.1, 129.4, 131.3, 131.9, 132.7, 136.4, 137.2, 137.6,
138.9, 139.4, 139.8, 154.5, 165.0. Anal. Calcd for C26H22BiBrS: C, 47.65;
H, 3.38. Found: C, 48.02; H, 3.44.
Diphenyl[2-(2-bromophenylthio)phenyl]bismuthane (5b):
colorless solid; yield 43%; mp 72ꢀ73 °C; 1H NMR (400 MHz, CDCl3)
δ 6.60 (1H, dd, J = 1.6, 7.6 Hz), 6.93 (1H, dt, J = 1.6, 7.6 Hz), 6.96 (1H,
dt, J = 1.6, 7.6 Hz), 7.29 (2H, t, J = 7.6 Hz), 7.36 (4H, t, J = 7.6 Hz), 7.36
(1H, dt, J = 1.6, 7.6 Hz), 7.41 (1H, dt, J = 1.6, 7.6 Hz), 7.48 (1H, dd, J =
1.6, 7.6 Hz), 7.66 (1H, dd, J = 1.6, 7.6 Hz), 7.67 (4H, d, J = 7.6 Hz), 7.87
(1H, dd, J = 1.6, 7.6 Hz); 13C NMR (100 MHz, CDCl3) δ 121.2, 126.5,
127.6 (ꢁ2), 128.2, 129.5, 130.5, 132.0, 132.7, 136.5, 137.5, 139.0, 139.5,
139.6, 158.4, 165.5. Anal. Calcd for C24H18BiBrS: C, 45.95; H, 2.89.
Found: C, 46.06; H, 2.88.
Bis(4-chlorophenyl)[2-(2-bromophenylthio)phenyl]bis-
muthane (5c): colorless solid; yield 43%; mp 105ꢀ106 °C; 1H NMR
(400 MHz, CDCl3) δ 6.51ꢀ6.54 (1H, m), 6.91ꢀ6.97 (2H, m), 7.29
(4H, d, J = 8.0 Hz), 7.35ꢀ7.47 (3H, m), 7.55 (4H, d, J = 8.0 Hz), 7.68
(1H, dd, J = 1.6, 7.6 Hz), 7.81 (1H, dd, J = 1.6, 7.6 Hz); 13C NMR (100
MHz, CDCl3) δ 121.2, 126.7, 127.7, 128.0, 129.8, 130.6, 132.3, 132.8,
134.0, 137.0, 138.8, 138.9, 139.1, 139.2, 156.0, 165.4. Anal. Calcd for
C24H16BiBrCl2S: C, 41.40; H, 2.32. Found: C, 41.79; H, 2.41.
Bis(4-methylphenyl)[2-(2-methylphenylthio)phenyl]bis-
muthane (7a): colorless solid; yield 79%; mp 111ꢀ112 °C; 1H NMR
(400 MHz, CDCl3) δ 2.32 (6H, s), 2.33 (3H, s), 6.89 (1H, dd, J = 1.2,
7.6 Hz), 6.99 (1H, dt, J = 1.2, 7.6 Hz), 7.07 (1H, dt, J = 1.2, 7.6 Hz), 7.16
(1H, dd, J = 1.2, 7.6 Hz), 7.17 (4H, d, J = 7.6 Hz), 7.23 (1H, dt, J = 1.6,
7.6 Hz), 7.30 (1H, dt, J = 1.6, 7.6 Hz), 7.43 (1H, dd, J = 1.6, 7.6 Hz), 7.57
(4H, d, J = 7.6 Hz), 7.79 (1H, dd, J = 1.6, 7.6 Hz); 13C NMR (100 MHz,
CDCl3) δ 20.5, 21.5, 126.3, 126.6, 129.1, 129.3, 130.2, 130.6, 131.3,
134.2, 136.7, 137.0, 137.2, 137.6, 139.1, 141.0, 154.0, 162.5. Anal. Calcd
for C27H25BiS: C, 54.91; H, 4.27. Found: C, 54.99; H, 4.34.
Bis(4-chlorophenyl)(2-bromophenylthio)bismuthane (4c):
yellow solid; yield 40%; mp 101ꢀ102 °C; 1H NMR (400 MHz, CDCl3)
δ 6.98 (1H, dt, J = 1.6, 7.6 Hz), 7.11 (1H, dt, J = 1.6, 7.6 Hz), 7.47 (1H,
dd, J = 1.6, 7.6 Hz), 7.49 (4H, d, J = 8.4 Hz), 7.57 (1H, dd, J = 1.6,
7.6 Hz), 7.99 (4H, d, J = 8.4 Hz); 13C NMR (100 MHz, CDCl3) δ 127.4,
128.4, 130.9, 131.7, 133.0, 134.9, 136.3, 137.0, 138.8, 165.5. Anal. Calcd
for C18H12BiBrCl2S: C, 34.86; H, 1.95. Found: C, 34.82; H, 1.85.
Bis(4-methylphenyl)(2-methylphenylthio)bismuthane (6a).
yellow solid; yield 69%; mp 79ꢀ80 °C; 1H NMR (400 MHz, CDCl3)
δ 2.34 (6H, s), 2.42 (3H, s), 6.97ꢀ7.04 (2H, m), 7.14 (1H, dd, J = 1.2,
7.6 Hz), 7.35 (4H, d, J = 7.6 Hz), 7.35 (1H, dd, J = 1.2, 7.6 Hz), 7.95 (4H,
d, J = 7.6 Hz); 13C NMR (100 MHz, CDCl3) δ 21.6, 22.3, 126.0, 126.8,
130.0, 132.2, 135.2, 136.1, 137.3, 138.2, 141.6, 163.4. Anal. Calcd for
C21H21BiS: C, 49.03; H, 4.11. Found: C, 48.82; H, 4.10.
Reaction of Diaryl(arylthio)bismuthanes with Benzyne.
General Procedure. Method A: To a solution of diaryl(arylthio)-
bismuthane (0.3 mmol) in acetonitrile (3 mL) were added benzyne
precursor 2 (0.6 mmol) and CsF (1.5 mmol) at room temperature. The
reaction mixture was allowed to react at this temperature for 24 h. The
reaction was quenched with brine (5 mL), and the mixture was extracted
with ethyl acetate (5 mL ꢁ 3). The combined extracts were dried over
anhydrous sodium sulfate and evaporated to leave a residue, which was
chromatographed on silica gel with hexaneꢀethyl acetate (15:1) to give
the product. Method B: To a solution of diaryl(arylthio)bismuthane
(0.3 mmol) in THF (3 mL) were added benzyne precursor 2 (0.6 mmol),
KF (0.9 mmol), and 18-crown-6 (0.9 mmol) at 0 °C. The reaction
mixture was allowed to react at this temperature for 1 h and then at room
temperature for 11 h. The reaction was quenched with brine (5 mL), and
the mixture was extracted with ethyl acetate (5 mL ꢁ 3). The combined
extracts were dried over anhydrous sodium sulfate and evaporated to
leave a residue, which was chromatographed on silica gel with hexaneꢀ
ethyl acetate (15:1) to give the product.
Bis(4-methylphenyl)[2-(phenylthio)phenyl]bismuthane (3a):
colorless solid; yield 60%; mp 74ꢀ75 °C; 1H NMR (400 MHz, CDCl3)
δ 2.31 (6H, s), 7.08ꢀ7.11 (3H, m), 7.16 (2H, d, J = 7.4 Hz), 7.17 (4H, d,
J = 7.2 Hz) 7.24 (1H, dt, J = 1.2, 7.4 Hz), 7.31 (1H, dt, J = 1.2, 7.4 Hz),
7.57 (4H, d, J = 7.2 Hz), 7.57 (1H, dd, J = 1.2, 7.4 Hz), 7.80 (1H, dd, J =
1.2, 7.4 Hz); 13C NMR (100 MHz, CDCl3) δ 21.5, 125.9, 128.5, 128.9,
129.0, 131.1, 131.3, 135.2, 137.2, 137.6, 138.0, 139.0, 140.7, 154.1, 163.5.
Anal. Calcd for C26H23BiS: C, 54.17; H, 4.02. Found: C, 54.27; H, 4.05.
Diphenyl[2-(phenylthio)phenyl]bismuthane (3b): colorless
solid; yield 67%; mp 65ꢀ66 °C; 1H NMR (400 MHz, CDCl3) δ 7.09ꢀ
7.13 (3H, m), 7.19 (2H, t, J = 7.2 Hz), 7.28ꢀ7.40 (8H, m), 7.60 (1H, dd,
J = 1.2, 7.4 Hz), 7.69 (4H, d, J = 7.2 Hz), 7.79 (1H, dd, J = 1.2, 7.4 Hz);
13C NMR (100 MHz, CDCl3) δ 126.1, 127.6, 128.6, 129.0, 129.3, 130.5,
131.3, 135.4, 137.7, 137.9, 139.1, 140.8, 158.1, 164.1. Anal. Calcd for
C24H19BiS: C, 52.56; H, 3.49. Found: C, 52.45; H, 3.45.
Bis(4-chlorophenyl)[2-(phenylthio)phenyl]bismuthane (3c):
colorless solid, yield 65%; mp 60ꢀ61 °C; 1H NMR (400 MHz, CDCl3)
δ 7.06 (2H, d, J = 7.4 Hz), 7.12 (1H, t, J = 7.4 Hz), 7.18 (2H, t, J =
7.4 Hz), 7.32 (4H, d, J = 8.0 Hz), 7.33ꢀ7.40 (2H, m), 7.57 (4H, d, J =
8.0 Hz), 7.63 (1H, dd, J = 1.2, 7.4 Hz), 7.74 (1H, dd, J = 1.2, 7.4 Hz); 13C
NMR (100 MHz, CDCl3) δ 126.2, 128.3, 129.1, 129.6, 130.8, 131.6,
134.0, 135.8, 137.4, 138.7, 139.0, 140.4, 155.7, 164.1. Anal. Calcd for
C24H17BiCl2S: C, 46.69; H, 2.78. Found: C, 46.39; H, 2.77.
Bis(4-methylphenyl)[2-(4-methoxyphenylthio)phenyl]bis-
muthane (9a): colorless solid; yield 27% based on the starting 4-me-
1
thoxythiophenol (0.2 mmol); mp 103ꢀ104 °C; H NMR (400 MHz,
CDCl3) δ 2.34 (6H, s), 3.77 (3H, s), 6.77 (2H, d, J = 9.2 Hz), 7.16ꢀ7.20
(3H, m), 7.20 (4H, d, J = 8.0 Hz), 7.27 (1H, dt, J = 1.6, 7.6 Hz), 7.44 (1H,
dd, J = 1.6, 7.6 Hz), 7.60 (4H, d, J = 8.0 Hz), 7.74 (1H, dd, J = 1.6, 7.6 Hz);
13C NMR (100 MHz, CDCl3) δ 21.5, 55.3, 114.7, 127.5, 128.9, 130.1,
131.2, 131.3, 132.5, 133.1, 137.2, 137.5, 137.7, 138.7, 143.4, 158.9. Anal.
Calcd for C27H25BiOS: C, 53.47; H, 4.15. Found: C, 53.39; H, 4.21.
Synthesis of Arylbis(arylthio)bismuthanes. General Pro-
cedure. A typical example is exemplified by the synthesis of 12a. To a
solution of thiophenol (6 mmol) in methanol (5 mL) was added sodium
methoxide (7.2 mmol) at room temperature, and the resulting solution
was stirred for 30 min. To this solution thus obtained was added drop-
wise a suspension of dichloro(4-methyllphenyl)bismuthane (3 mmol),
prepared from tris(4-methylphenyl)bismuthane (1 mmol) and bismuth-
(III) chloride (2 mmol) in diethyl ether (10 mL) by stirring for 1 h at
room temperature, and the reaction mixture was stirred for 2 h at room
temperature. The reaction was quenched with brine (10 mL), and the
mixture was extracted with ethyl acetate (10 mL ꢁ 3). The combined
extracts were dried over anhydrous sodium sulfate and evaporated to
leave a residue, which was recrystallized from methanol to give 12a.
(4-Methylphenyl)bis(phenylthio)bismuthane (12a): yellow
solid; yield 47%; mp 158ꢀ159 °C (lit.18 155 °C); 1H NMR (400 MHz,
CDCl3) δ 2.35 (3H, s), 7.11 (2H, t, J = 7.2 Hz), 7.20 (4H, t, J = 7.2 Hz),
7.33 (4H, d, J = 7.2 Hz), 7.55 (2H, d, J = 7.2 Hz), 8.28 (2H, d, J = 7.2 Hz);
13C NMR (100 MHz, DMSO-d6) δ 21.5, 125.3, 128.2, 133.0, 134.3,
137.0, 138.0, 138.6, 190.9. Anal. Calcd for C19H17BiS2: C, 44.02; H, 3.31.
Found: C, 43.79; H, 3.33.
Bis(4-methylphenyl)[2-(2-bromophenylthio)phenyl]bis-
muthane (5a): colorless solid; yield 46%; mp 104ꢀ105 °C; 1H NMR
(400 MHz, CDCl3) δ 2.31 (6H, s), 6.59 (1H, dd, J = 1.6, 7.6 Hz), 6.92
(1H,dt,J=1.6,7.6Hz),6.96(1H,dt,J= 1.6, 7.6 Hz), 7.16 (4H, d, J=7.6Hz),
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dx.doi.org/10.1021/om200228x |Organometallics 2011, 30, 4532–4538