The Journal of Organic Chemistry
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4-Chlorophenyl Phenyl Sulfide (1f and 2x).6p Following
4-Ethoxyphenyl Phenyl Sulfide (2g).18 Following general
procedure A, a light yellow oil. H NMR (300 MHz, CDCl3) δ 7.40
(d, J = 8.9 Hz, 2H), 7.25−7.10 (m, 5H), 6.87 (d, J = 8.8 Hz, 2H), 4.03
(q, J = 7.0 Hz, 2H), 1.41 (t, J = 7.0 Hz, 3H). 13C NMR (75 MHz,
CDCl3) δ 159.3, 138.7, 135.4, 128.91, 128.2, 125.7, 124.1, 115.5, 63.6,
14.8.
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general procedure A, colorless oil. H NMR (300 MHz, CDCl3) δ
7.33−7.28 (m, 5H), 7.27−7.25 (m, 4H). 13C NMR (75 MHz, CDCl3)
δ 135.1, 134.7, 133.0, 132.0, 131.4, 129.4, 129.3, 127.5.
4-Fluorophenyl Phenyl Sulfide (1g).17 Following general
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procedure A, colorless oil. H NMR (300 MHz, CDCl3) δ 7.40−35
(m, 2H), 7.28−7.21 (m, 5H), 7.02 (t, J = 8.7 Hz, 2H). 13C NMR (75
MHz, CDCl3) δ 164.1, 160.8, 136.7, 134.2, 134.1, 130.2, 130.0, 129.2,
126.8, 116.6, 116.3.
4-Ethoxyphenyl 4-Fluorophenyl Sulfide (2h). Following
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general procedure A, colorless oil. H NMR (300 MHz, CDCl3) δ
7.35 (d, J = 8.9 Hz, 2H), 7.25−7.15 (m, 2H), 6.95 (t, J = 8.7 Hz, 2H),
6.87 (d, J = 8.9 Hz, 2H), 4.03 (q, J = 7.0 Hz, 2H), 1.42 (t, J = 7.0 Hz,
3H). 13C NMR (75 MHz, CDCl3) δ161.6 (d, J = 245.9 Hz), 159.1,
134.5, 133.2 (d, J = 3.3 Hz), 131.0 (d, J = 8.0 Hz), 125.0, 116.0 (d, J =
22.0 Hz), 115.5, 63.6, 14.8. HRMS calcd for C14H13FOS (M+)
248.0671; found 248.0675.
4-(Phenylthio)benzoic Acid (1h).8b Following general procedure
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B, white soild, mp 173.4−174.1 °C. H NMR (300 MHz, CDCl3) δ
9.09 (brs, 1H), 7.95 (d, J = 8.7 Hz, 2H), 7.53−7.50 (m, 2H), 7.44−
7.40 (m, 3H), 7.20 (d, J = 8.7 Hz, 2H). 13C NMR (75 MHz, CDCl3) δ
171.6, 146.0, 134.1, 131.9, 130.7, 129.7, 128.9, 127.2, 126.4.
4-Phenylsulfanyl-phenol (1i).6p Following general procedure B,
a light yellow soid, mp 50.2−50.6 °C. 1H NMR (300 MHz, CDCl3) δ
7.36 (d, J = 8.7 Hz, 2H), 7.28−7.12 (m, 5H), 6.83 (d, J = 8.7 Hz, 2H),
5.11 (brs, 1H). 13C NMR (75 MHz, CDCl3) δ 155.8, 138.3, 135.4,
128.8, 128.1, 125.7, 124.3, 116.4.
4-Ethoxyphenyl 3-Methylphenyl Sulfide (2i). Following
general procedure A, a light yellow oil. 1H NMR (300 MHz,
CDCl3) δ 7.40 (d, J = 8.9 Hz, 2H), 7.13 (t, J = 7.6 Hz, 1H), 7.03 (s,
1H), 6.99−6.95 (m, 2H), 6.89 (d, J = 8.8 Hz, 2H), 4.05 (q, J = 7.0 Hz,
2H), 2.28 (s, 3H), 1.43 (t, J = 7.0 Hz, 3H). 13C NMR (75 MHz,
CDCl3) δ 159.1, 138.7, 138.3, 135.2, 128.9, 128.8, 126.7, 125.5, 124.4,
115.5, 63.6, 21.3, 14.8. HRMS calcd for C15H16OS (M+) 244.0922;
found 244.0919.
2-Methylphenyl Phenyl Sulfide (1j and 2v).6p Following
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general procedure A, colorless oil. H NMR (300 MHz, CDCl3) δ
7.31−7.13 (m, 9H), 2.38 (s, 3H). 13C NMR (75 MHz, CDCl3) δ
140.0, 136.3, 133.8, 133.1, 130.7, 129.7, 129.2, 128.0, 126.8, 126.4,
20.6.
4-Phenylphenyl Phenyl Sulfide (2j).19 Following general
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procedure D, white solid, mp 69.9−70.6 °C. H NMR (300 MHz,
CDCl3) δ 7.57−7.50 (m, 4H), 7.44−7.22 (m, 10H). 13C NMR (75
MHz, CDCl3) δ 140.3, 140.0, 135.8, 135.0, 131.3, 131.2, 129.3, 128.9,
127.9, 127.5, 127.2, 127.0.
2-(Phenylthio)benzoic Acid (1k).4b Following general procedure
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B, white soild, mp 166.5−167.0 °C. H NMR (300 MHz, CDCl3) δ
9.79 (brs, 1H), 8.14 (dd, J = 7.8, 1.6 Hz, 1H), 7.61−7.57 (m, 2H),
7.46−7.44 (m, 3H), 7.31−7.25 (m, 1H), 7.15 (td, J = 7.6, 1.1 Hz, 1H),
6.81 (dd, J = 8.2, 1.0 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ 171.7,
144.6, 135.8, 133.1, 132.2, 132.1, 129.8, 129.3, 127.2, 125.4, 124.3.
2,6-Dimethylphenyl Phenyl Sulfide (1l).5j Following general
4-Phenylphenyl 4-Methylphenyl Sulfide (2k). Following
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general procedure D, colorless oil. H NMR (300 MHz, CDCl3) δ
7.59− 7.56 (m, 2H), 7.51 (d, J = 8.6 Hz, 2H), 7.44−7.41 (m, 2H),
7.38−7.33 (m, 5H), 7.17 (d, J = 7.9 Hz, 2H), 2.37 (s, 3H). 13C NMR
(75 MHz, CDCl3) δ 140.6, 139.5, 137.8, 136.5, 132.5, 131.4, 130.3,
130.2, 129.0, 127.9, 127.5, 127.1, 21.3. HRMS calcd for C19H16S (M+)
276.0973; found 276.0965.
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procedure A, colorless oil. H NMR (300 MHz, CDCl3) δ 7.30−7.27
(m, 1H), 7.25−7.19 (m, 4H), 7.12−7.07 (m, 1H), 6.98−6.98 (m, 2H),
2.47 (s, 6H). 13C NMR (75 MHz, CDCl3) δ 143.9, 138.1, 130.5,
129.3, 128.9, 128.5, 125.7, 124.6, 21.8.
4-Phenylphenyl 3-Methylphenyl Sulfide (2l). Following
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general procedure D, colorless oil. H NMR (300 MHz, CDCl3) δ
2-(Phenylthio)thiophene (1m).5j Following general procedure A,
colorless oil. 1H NMR (300 MHz, CDCl3) δ 7.45 (dd, J = 5.4, 1.3 Hz,
1H), 7.29−7.13 (m, 6H), 7.05 (dd, J = 5.4, 3.6 Hz, 1H). 13C NMR (75
MHz, CDCl3) δ 138.7, 136.1, 131.3, 131.2, 129.0, 128.0, 127.2, 126.1.
2-Phenylsulfanyl-benzothiazole (1n).4b Following general
7.57−7.49 (m, 4H), 7.44−7.32 (m, 5H), 7.23−7.19 (m, 3H), 7.07 (s,
1H), 2.31 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 140.4, 139.8, 139.2,
135.3, 135.2, 132.0 131.0, 129.1, 128.9, 128.5, 128.2, 127.8, 127.5,
127.0, 21.3. HRMS calcd for C19H16S (M+) 276.0973; found
276.0968.
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procedure C, colorless oil. H NMR (300 MHz, CDCl3) δ 7.79 (d,
4-Methylthiophenyl Phenyl Sulfide (2m).20 Following general
J = 8.1 Hz, 1H), 7.66−7.63 (m, 2H), 7.55 (d, J = 8.0 Hz, 1H), 7.42−
7.26 (m, 4H), 7.16 (td, J = 7.5, 1.1 Hz, 1H). 13C NMR (75 MHz,
CDCl3) δ 169.5, 153.8, 135.5, 135.3, 130.3, 129.8, 126.1, 124.3, 121.9,
120.7.
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procedure A, colorless oil. H NMR (300 MHz, CDCl3) δ 7.31−7.17
(m, 9H), 2.46 (s, 3H). 13C NMR (75 MHz, CDCl3) δ 138.2, 136.5,
132.3, 131.5, 130.2, 129.2, 127.2 126.8, 15.8.
4-Methylthiophenyl 4-Fluorophenyl Sulfide (2n). Following
4-Trifluoromethylphenyl Phenyl Sulfide (2c).5j Following
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general procedure A, colorless oil. H NMR (300 MHz, CDCl3) δ
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general procedure A, colorless oil. H NMR (300 MHz, CDCl3) δ
7.33−7.29 (m, 2H), 7.26−7.12 (m, 4H), 6.99 (t, J = 8.7 Hz, 2H), 2.46
(s, 3H). 13C NMR (75 MHz, CDCl3) δ162.2 (d, J = 247.4 Hz), 137.9,
133.2 (d, J = 8.1 Hz), 132.4, 131.3, 131.0 (d, J = 3.3 Hz), 127.3, 116.4
(d, J = 22.0 Hz), 15.8. HRMS calcd for C13H11FS2 (M+) 250.0286;
found 250.0290.
4-Methylthiophenyl 3-Methylphenyl Sulfide (2o). Following
general procedure A, colorless oil. 1H NMR (300 MHz, CDCl3) δ 7.30
(d, J = 8.5 Hz, 2H), 7.21−7.03 (m, 6H), 2.48 (s, 3H), 2.31 (s, 3H).
13C NMR (75 MHz, CDCl3) δ 139.0, 138.0, 136.0, 132.1, 131.9, 131.0,
129.0, 127.8, 127.5, 127.2, 21.3, 15.8. HRMS calcd for C14H14S2 (M+)
246.0537; found 246.0542.
7.50−7.47 (m, 4H), 7.41−7.38 (m, 3H), 7.27 (d, J = 10.6 Hz, 2H).
13C NMR (75 MHz, CDCl3) δ 142.9, 133.5, 132.6, 129.7, 128.6, 128.3,
127.9, 125.82 (q, J = 3.8 Hz), 122.3.
3-(Phenylthio)benzoic acid (2d).5k Following general procedure
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B, yellow solid, mp 107.7−108.4 °C. H NMR (300 MHz, CDCl3) δ
10.04 (brs, 1H), 8.05 (t, J = 1.6 Hz, 1H), 7.95 (dt, J = 7.7, 1.3 Hz, 1H),
7.56−7.46 (m, 1H), 7.43−7.32 (m, 6H). 13C NMR (75 MHz, CDCl3)
δ 171.7, 137.7, 135.3, 134.2, 132.1, 131.6, 130.3, 129.5, 129.3, 128.4,
127.9.
3-Ttrifluoromethoxyphenyl Phenyl Sulfide (2e). Following
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general procedure A, colorless oil. H NMR (300 MHz, CDCl3) δ
4-(m-Tolylthio)benzoic Acid (2p). Following general procedure
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7.44−7.27 (m, 5H), 7.23 (s, 1H), 7.14 (d, J = 7.9 Hz, 1H), 7.07 (s,
1H), 7.02 (d, J = 8.1 Hz, 1H). 13C NMR (75 MHz, CDCl3) δ 149.7,
139.5, 133.5, 132.7, 130.1, 129.5, 128.2, 127.6, 122.1, 121.7, 118.7.
HRMS calcd for C13H9F3OS (M+) 270.0326; found 270.0321.
3-Ttrifluoromethoxyphenyl 4-Fluorophenyl Sulfide (2f).
B, white solid, mp 166.4−167.2 °C. H NMR (300 MHz, CDCl3) δ
8.89 (brs, 1H), 7.97 (d, J = 8.5 Hz, 2H), 7.37−7.21 (m, 6H), 2.39 (s,
3H). 13C NMR (75 MHz, CDCl3) δ 171.6, 146.3, 139.7, 134.7, 131.4,
131.2, 130.6, 129.8, 129.5, 127.1, 126.2, 21.3. HRMS calcd for
C14H12O2S (M+) 244.0558; found 244.0556.
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4-(Phenylthio)benzonitrile (2q).6p Following general procedure
Following general procedure A, colorless oil. H NMR (300 MHz,
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CDCl3) δ 7.42 (dd, J = 8.9, 5.2 Hz, 2H), 7.22 (t, J = 4.0 Hz, 1H),
7.07−6.97 (m, 5H). 13C NMR (75 MHz, CDCl3) δ 162.9 (d, J = 249.2
Hz), 139.5, 135.3 (d, J = 8.3 Hz), 135.0, 130.1, 128.6, 127.0, 126.5,
116.74 (d, J = 22.0 Hz). HRMS calcd for C13H8F4OS (M+) 288.0232;
found 288.0234.
A, a light yellow oil. H NMR (300 MHz, CDCl3) δ 7.53−7.41 (m,
7H), 7.17 (d, J = 8.7 Hz, 2H). 13C NMR (75 MHz, CDCl3) δ 145.7,
134.5, 132.4, 130.9, 129.9, 129.4, 127.4, 118.8, 108.8.
3-(Phenylthio)benzonitrile (2r).5j Following general procedure
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D, a light yellow oil. H NMR (300 MHz, CDCl3) δ 7.47−7.31 (m,
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dx.doi.org/10.1021/jo300100x | J. Org. Chem. 2012, 77, 2878−2884