6
1
Ethyl 2-(phenylthio)acetate (6a): Colorless oil; H NMR (CDCl3,
1-Phenyl-2-(phenylthio)ethanone (6m): Yellow solid, Mp: 50-51 oC;
1H NMR (CDCl3, 400 MHz): δ 7.99 (t, J = 8.4 Hz, 1H), 7.59-
7.41 (m, 8H), 7.17 (s, 1H), 2.60 (s, 2H); 13C NMR (CDCl3, 100
MHz): δ 191.9, 132.7, 129.3, 128.8, 128.7(2C), 128.4, 126.6,
122.3, 19.0. Ms (EI) m/z = 228.1 (M+).
400 MHz): δ 7.41 (d, J = 8.0 Hz, 2H), 7.30 (t, J = 7.4Hz, 2H),
7.23 (t, J = 7.2 Hz, 1H), 4.19-4.14 (m, 2H), 3.64 (s, 2H), 1.22 (t,
J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ 169.9, 135.1,
130.1, 129.2, 127.1, 61.7, 36.9, 14.2; Ms (EI) m/z = 196.1 (M+).
1
o
Ethyl 2-(p-tolylthio)acetate (6b): Colorless oil; H NMR (CDCl3,
2-(Benzylthio)-1-phenylethanone (6n): Yellow solid, Mp: 89-90 C;
400 MHz): δ 7.33 (d, J = 8.0 Hz , 2H), 7.10 (d, J = 7.6 Hz , 2H),
4.18-4.12 (m, 2H), 3.58 (s, 2H), 2.32 (s, 3H), 1.22 (t, J = 7.0 Hz,
3H); 13C NMR (CDCl3, 100 MHz): δ 169.9, 137.3, 131.2, 131.0,
129.8, 61.5, 37.4, 21.1, 14.1; Ms (EI) m/z = 210.1 (M+).
Ethyl 2-((4-methoxyphenyl)thio)acetate (6c): Colorless oil; 1H
NMR (CDCl3, 400 MHz): δ 7.42 (d, J = 8.8 Hz, 2H), 6.84(d, J =
8.8 Hz, 2H)ꢁ4.17-4.11 (m, 2H), 3.80 (s, 3H), 3.51 (s, 2H), 1.22
(t, J = 7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ 170.1, 159.8,
134.4, 125.1, 114.8, 61.5, 55.5, 38.8, 14.2; Ms (EI) m/z = 226.1
(M+).
Ethyl 2-((4-chlorophenyl)thio)acetate (6d): Colorless oil; 1H NMR
(CDCl3, 400 MHz): δ 7.35 (d, J = 8.4 Hz, 2H), 7.27 (d, J = 8.0
Hz, 2H); 4.19-4.14 (m, 2H), 3.60 (s, 2H), 1.23 (t, J = 7.2 Hz,
3H); 13C NMR (CDCl3, 100 MHz): δ 169.6, 133.6, 133.3, 131.6,
129.3, 61.8, 37.0, 14.2; Ms (EI) m/z = 230.0 (M+).
Ethyl 2-(benzylthio)acetate (6e): Colorless oil; 1H NMR (CDCl3, 400
MHz): δ 7.34-7.32 (m, 4H), 7.28-7.24 (m, 1H), 4.21-4.15 (m,
2H), 3.83 (s, 2H), 3.06 (s, 2H), 1.29 (t, J = 7.2 Hz, 3H); 13C
NMR (CDCl3, 100 MHz): δ 170.6, 137.4, 129.3, 128.7, 127.4, 61.4,
36.4, 32.4, 14.3; Ms (EI) m/z = 210.1 (M+).
1H NMR (CDCl3, 400 MHz): δ 7.93 (d, J = 7.6 Hz, 2H), 7.60-
7.56 (m, 1H), 7.49-7.44 (m, 3H), 7.37-7.30 (m, 5H), 3.76 (s,
2H), 3.68 (s, 2H); 13C NMR (CDCl3, 100 MHz): δ 194.5, 137.3,
135.4, 133.4, 129.3, 128.7(2C), 128.6, 127.3, 36.1, 35.9. Ms (EI)
m/z = 242.1 (M+).
4.5 Typical procedure for the synthesis of thioethers:
Under N2 atmosphere, a solution of complex 1 (68.7 mg, 5
mol%) in THF (3.0 mL), zinc dust (80 mg, 1.2 mmol), diphenyl
disulfide (109 mg, 0.5 mmol), and 1-bromopentane (166 mg, 1.1
mmol) were added. Then the mixture was stirred for 2 h at room
temperature, monitored by thin-layer chromatography (TLC).
The resulting reaction mixture was diluted with diethyl ether (10
mL × 3), filtered, and evaporated, and then the residue was
subjected to column chromatography using petroleum ether:ethyl
acetate as eluent (30:1) to afford the pure product 8a.
1
8a-8h are known compounds,3b, 6a, 6g, 10c and H NMR, 13C NMR
and Ms spectral data are summarized as follows:
1
Pentyl(phenyl)sulfane (8a): Colorless oil; H NMR (CDCl3, 400
MHz): δ 7.25-7.21 (m, 2H), 7.19-7.17 (m, 2H), 7.07 (t, J = 7.2
Hz, 1H), 2.83 (t, J = 7.4 Hz, 2H), 1.61-1.54 (m, 2H), 1.36-1.22
(m, 4H), 0.82 (t, J = 7.0 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ
137.2, 128.9 (2C), 125.7, 33.7, 31.1, 28.9, 22.4, 14.1; Ms (EI)
m/z = 180.1 (M+).
Methyl 2-(phenylthio)propanoate (6f): Colorless oil; 1H NMR
(CDCl3, 400 MHz): δ 7.46-7.44 (m, 2H), 7.31-7.25 (m, 3H),
3.82-3.77 (m, 1H), 3.67 (s, 3H), 1.48 (d, J = 5.2 Hz, 3H); 13C
NMR (CDCl3, 100 MHz): δ 173.2, 133.2(2C), 129.1, 128.2, 52.4,
45.4, 17.6; Ms (EI) m/z = 196.1 (M+).
1
Isobutyl(phenyl)sulfane (8b): Colorless oil; H NMR (CDCl3, 400
Methyl 2-(p-tolylthio)propanoate (6g): Colorless oil; 1H NMR
(CDCl3, 400 MHz): δ 7.35 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 8.0
Hz, 2H), 3.74-3.69 (m, 1H), 3.66 (s, 3H), 2.33 (s , 3H), 1.45 (d, J
= 7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ 173.2, 138.6,
134.0, 129.8, 129.2, 52.3, 45.6, 21.3, 17.5; Ms (EI) m/z = 210.1
(M+).
MHz): δ 7.26-7.20 (m, 2H), 7.19-7.16 (m, 2H), 7.07 (t, J = 7.2
Hz, 1H), 2.73 (d, J = 6.8 Hz, 2H), 1.84-1.74 (m, 1H), 0.96 (d, J =
6.8 Hz, 6H); 13C NMR (CDCl3, 100 MHz): δ 137.5, 128.9 (2C),
125.7, 42.7, 28.4, 22.2; Ms (EI) m/z = 166.1 (M+).
Allyl(phenyl)sulfane (8c): Colorless oil; 1H NMR (CDCl3, 400
MHz): δ 7.28-7.22 (m, 2H), 7.21-7.18 (m, 2H), 7.11 (t, J = 7.2
Hz, 1H), 5.85-5.76 (m, 1H), 5.06 (d, J = 16.8 Hz, 1H), 5.00 (d, J
= 10.0 Hz, 1H), 3.48 (d, J = 6.8 Hz, 2H); 13C NMR (CDCl3, 100
MHz): δ 136.0, 133.7, 129.9, 128.9, 126.3, 117.8, 37.3; Ms (EI)
m/z = 150.1 (M+).
Phenethyl(phenyl)sulfane (8d): Colorless oil; 1H NMR (CDCl3, 400
MHz): δ 7.37-7.16 (m, 10H), 3.17 (t, J = 7.8 Hz, 2H), 2.92 (t, J =
8.0 Hz, 2H); 13C NMR (CDCl3, 100 MHz): δ 140.3, 136.5, 129.3,
129.1, 128.8, 128.7, 128.6, 128.5, 126.6, 126.1, 35.8, 35.2; Ms
(EI) m/z = 214.1(M+).
Methyl 2-((4-chlorophenyl)thio)propanoate (6h): Colorless oil; 1H
NMR (CDCl3, 400 MHz): δ 7.30 (d, J = 8.4 Hz, 2H), 7.20 (d, J =
8.4 Hz, 2H), 3.71-3.65 (m, 1H), 3.60 (s, 3H), 1.39 (d, J = 7.2 Hz,
3H); 13C NMR (CDCl3, 100 MHz): δ 172.9, 134.6, 131.6, 129.8,
129.2, 52.4, 45.3, 17.4; Ms (EI) m/z = 230.0 (M+).
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1-(Phenylthio)propan-2-one (6i): Colorless oil; H NMR (CDCl3,
400 MHz): δ 7.35-7.26 (m, 4H), 7.24-7.19 (m, 1H), 3.67 (s, 2H),
2.28 (s, 3H); 13C NMR (CDCl3, 100 MHz): δ 203.7, 134.8, 129.7,
129.3, 127.0, 44.8, 28.1; Ms (EI) m/z = 166.1 (M+).
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(Naphthalen-2-ylmethyl)(phenyl)sulfane (8e): white solid; mp: 49-50
1-(p-tolylthio)propan-2-one (6j): Colorless oil; H NMR (CDC13,
1
oC; H NMR (CDCl3, 400 MHz): δ 7.84-7.76 (m, 3H), 7.70 (s,
400 MHz): δ 7.25 (d, J = 8.0 Hz, 2H), 7.10 (d, J = 8.0 Hz, 2H),
3.61 (s, 2H), 2.31 (s, 3H), 2.26 (s, 3H); 13C NMR (CDCl3, 100
MHz): δ 203.7, 137.3, 130.9, 130.5, 130.0, 45.4, 28.1, 21.1; Ms (EI)
m/z = 180.1 (M+).
1H), 7.50-7.46 (m, 3H), 7.34 (d, J = 7.2 Hz, 2H), 7.26 (t, J = 7.4
Hz, 2H), 7.19 (t, J = 7.2 Hz, 1H), 4.29 (s, 2H); 13C NMR (CDCl3,
100 MHz): δ 136.4, 135.0, 133.4, 132.7, 130.2, 129.0, 128.4,
127.8 (2C), 127.5, 127.1, 126.6, 126.3, 125.9, 39.6; Ms (EI) m/z
= 250.1 (M+).
1-((4-Methoxyphenyl)thio)propan-2-one (6k): Colorless oil; 1H NMR
(CDCl3, 400 MHz): δ 7.35 (d, J=8.8 Hz, 2H), 6.84 (dꢁJ = 8.8
Hz, 2H), 3.79 (s, 3H), 3.55 (s, 2H), 2.26 (s, 3H); 13C NMR
(CDCl3, 100 MHz): δ 203.5, 159.7 133.8, 124.7, 115.0, 55.5, 46.7,
28.2 Ms (EI) m/z = 196.1 (M+).
o-Nitrophenyl pentyl sulfide (8f): Yellow oil;1H NMR (CDCl3, 400
MHz): δ 8.10 (d, J = 8.0 Hz, 1H), 7.47 (t, J = 7.8 Hz, 1H), 7.33
(d, J = 8.4 Hz, 1H), 7.16 (d, , J = 7.6 Hz, 1H), 2.87 (t, J = 7.4 Hz,
2H), 1.70-1.63 (m, 2H), 1.44-1.36 (m, 2H), 1.34-1.25 (m, 2H),
0.85 (t, J = 7.2 Hz, 3H); 13C NMR (CDCl3, 100 MHz): δ 146.1,
138.4, 133.5, 126.6, 126.2, 124.3, 32.4, 31.3, 27.6, 22.3, 14.0; Ms
(EI) m/z = 225.1 (M+).
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1-((4-Chlorophenyl)thio)propan-2-one (6l): Colorless oil; H NMR
(CDCl3, 400 MHz): δ 7.26 (s, 4H), 3.65 (s, 2H), 2.27 (s, 3H); 13
C
NMR (CDCl3, 100 MHz): δ 203.1, 133.2, 133.1, 131.0, 129.4, 44.8,
28.1. Ms (EI) m/z = 200.0 (M+).
(4-Chlorophenyl)(pentyl)sulfane (8g): Colorless oil; 1H NMR (CDCl3,
400 MHz): δ 7.24 (s, 4H), 2.89 (t, J = 7.4 Hz, 2H), 1.67-1.59 (m,