The Journal of Organic Chemistry
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EtOAc in hexanes) afforded the title compound as a colorless oil
(0.094 g, 85%). Spectral data were consistent with reported values:34
TLC Rf = 0.7 (10% EtOAc in hexanes); 1H NMR (400 MHz, CDCl3)
δ 7.35−7.29 (m, 4H), 7.28−7.22 (m, 5H); 13C NMR (100 MHz,
CDCl3) δ 135.2, 134.8, 133.1, 132.1, 131.4, 129.5, 129.4, 127.6.
(Perfluorophenyl)(phenyl)sulfane (11). Title compound was
prepared according to general procedure A from pentafluorothiophe-
nol (0.067 mL, 0.50 mmol), NCS (0.073 g, 0.55 mmol) and PhZnBr
(1.3 mmol, 1.7 mL). Purification by flash column chromatography (3%
EtOAc in hexanes) afforded the title compound as a colorless
crystalline solid (0.114 g, 84%). Spectral data were consistent with
reported values:37 TLC Rf = 0.6 (5% EtOAc in hexanes); mp 45−48
°C; 1H NMR (400 MHz, CDCl3) δ 7.35 (m, 2H), 7.32−7.24 (m, 3H);
13C NMR (125 MHz, CDCl3) δ 148.7 (m), 146.7 (m), 143.2 (m),
141.2 (m), 139.0 (m), 136.9 (m), 133.1, 130.7, 129.6, 128.1, 109.1
(m); 19F NMR (376 MHz, CDCl3) δ −131.9 (dd, J = 24.7 Hz, 7.0 Hz,
2F), −151.6 (t, J = 20.9 Hz, 1F), −160.6 (td, J = 22.2 Hz, 6.7 Hz, 2F);
IR (neat) 1482, 1093, 971 cm−1; HRMS (TOF MS CI+) m/z calcd for
C12H5F5S (M)+ 276.0032, found 276.0025.
(4-Methoxyphenyl)(phenyl)sulfane (12). Title compound was
prepared according to general procedure A from 4-methoxybenzene-
thiol (0.062 mL, 0.50 mmol), NCS (0.073 g, 0.55 mmol) and PhZnBr
(1.3 mmol, 1.7 mL). Purification by flash column chromatography
(10% EtOAc in hexanes) afforded the title compound as a colorless oil
(0.071 g, 66%). Spectral data were consistent with reported values:34
TLC Rf = 0.5 (10% EtOAc in hexanes); 1H NMR (400 MHz, CDCl3)
δ 7.40 (d, J = 8.5 Hz, 2H), 7.22−7.11 (m, 5H), 6.87 (d, J = 8.6 Hz,
2H), 3.77 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 159.8, 138.7,
135.4, 129.0, 128.2, 125.8, 124.3, 115.0, 55.3.
procedure B to afford 57% yield (determined by 1H NMR in
comparison to the internal standard phenyltrimethylsilane). Spectral
data were consistent with reported values:39 TLC Rf = 0.5 (30%
1
EtOAc in hexanes); H NMR (500 MHz, CDCl3) δ 7.70 (m, 2H),
7.59 (m, 1H), 7.47−7.42 (m, 3H), 7.39 (m, 1H), 7.27−7.21 (m, 2H);
13C NMR (100 MHz, CDCl3) δ 163.4, 152.0, 142.1, 134.5, 130.0,
129.8, 127.3, 124.5, 124.4, 119.2, 110.2.
2-(Phenylthio)pyrimidine (17). Title compound was prepared
according to general procedure A from 2-mercaptopyrimidine (0.056
g, 0.50 mmol), NCS (0.073 g, 0.55 mmol) and PhZnBr (1.3 mmol, 1.7
mL). Purification by flash column chromatography (20% EtOAc in
hexanes) afforded the title compound as a colorless oil (0.081 g, 86%).
Spectral data were consistent with reported values:40 TLC Rf = 0.3
(30% EtOAc in hexanes); 1H NMR (500 MHz, CDCl3) δ 8.47 (d, J =
5.0 Hz, 2H), 7.63 (m, 2H), 7.44 (m, 3H), 6.95 (t, J = 5.0 Hz, 1H); 13C
NMR (125 MHz, CDCl3) δ 172.9, 157.7, 135.4, 129.45, 129.43, 129.3,
117.1.
1-Phenyl-5-(phenylthio)-1H-tetrazole (18). Title compound
was prepared according to general procedure A from 1-phenyl-1H-
tetrazole-5-thiol (0.089 g, 0.50 mmol), NCS (0.073 g, 0.55 mmol) and
PhZnBr (1.3 mmol, 1.7 mL). Purification by flash column
chromatography (30% EtOAc in hexanes) afforded the title compound
as a colorless crystalline solid (0.102 g, 80%): TLC Rf = 0.4 (30%
EtOAc in hexanes); mp 129−133 °C; 1H NMR (400 MHz, CDCl3) δ
7.57−7.53 (m, 7H), 7.42−7.36 (m, 3H); 13C NMR (125 MHz,
CDCl3) δ 153.7, 134.0, 133.7, 130.5, 130.1, 129.86, 129.85, 126.9,
124.5; IR (neat) 3067, 2922, 1498, 1412, 1389, 1240 cm−1; HRMS
(TOF MS ES+) m/z calcd for C13H10N4S (M + Na)+ 277.0524, found
277.0524.
(4-Nitrophenyl)(phenyl)sulfane (13). Title compound was
prepared according to general procedure A from 4-nitrobenzenethiol
(0.082 g, 0.50 mmol), NCS (0.073 g, 0.55 mmol) and PhZnBr (1.3
mmol, 1.7 mL). Purification by flash column chromatography (10%
EtOAc in hexanes) afforded the title compound as a colorless oil
(0.042 g, 37%). Spectral data were consistent with reported values:34
TLC Rf = 0.4 (5% EtOAc in hexanes); 1H NMR (400 MHz, CDCl3) δ
8.06 (dt, J = 9.6 Hz, J = 2.2 Hz, 2H), 7.53 (m, 2H), 7.46 (m, 3H), 7.18
(dt, J = 9.6 Hz, J = 2.2 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ
148.6, 145.4, 134.8, 130.5, 130.1, 129.7, 126.7, 124.1.
2-Phenyl-5-(phenylthio)-1,3,4-oxadiazole (19). Title com-
pound was prepared according to general procedure A from 5-
phenyl-1,3,4-oxadiazaole-2-thiol (0.089 g, 0.50 mmol), NCS (0.073 g,
0.55 mmol) and PhZnBr (1.3 mmol, 1.7 mL). Purification by flash
column chromatography (20−50% EtOAc in hexanes) afforded the
title compound as a white solid (0.089 g, 70%). Spectral data were
consistent with reported values:41 TLC Rf = 0.5 (20% EtOAc in
1
hexanes); H NMR (500 MHz, CDCl3) δ 7.94 (d, J = 7.0 Hz, 2H),
7.67 (m, 2H), 7.51−7.39 (m, 6H); 13C NMR (125 MHz, CDCl3) δ
166.4, 162.9, 133.7, 131.9, 129.9, 129.8, 129.1, 127.1, 126.8, 123.5.
1-Methyl-2-(phenylthio)-1H-imidazole (20). Title compound
was prepared according to general procedure A from 2-mercapto-1-
methylimidazole (0.057 g, 0.50 mmol), NCS (0.073 g, 0.55 mmol) and
PhZnBr (1.3 mmol, 1.7 mL). Purification by flash column
chromatography (10% EtOAc in hexanes) afforded the title compound
as a colorless oil (0.081 g, 95%). Compound 20 was also prepared
from PhMgBr according to general procedure B to afford 59% yield
(determined by 1H NMR in comparison to the internal standard
phenyltrimethylsilane). Spectral data were consistent with reported
values:39 TLC Rf = 0.2 (30% EtOAc in hexanes); 1H NMR (500 MHz,
CDCl3) δ 7.25 (m, 2H), 7.18−7.13 (m, 4H), 7.06 (d, J = 1.0 Hz, 1H),
3.62 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 138.1, 135.0, 130.2,
129.3, 128.0, 126.6, 123.9, 33.9.
4-Phenylsulfanylacetophenone (14). Title compound was
prepared according to general procedure A from 1-(4-sulfanylphenyl)-
ethan-1-one (60 μL, 0.50 mmol), NCS (0.073 g, 0.55 mmol) and
PhZnBr (1.3 mmol, 2.6 mL). Purification by flash column
chromatography (5% EtOAc in hexanes) afforded the title compound
as a pale yellow solid (0.072 g, 63%). Spectral data were consistent
with reported values:38 TLC Rf = 0.3 (5% EtOAc in hexanes); H
1
NMR (400 MHz, CDCl3) δ 7.81 (d, J = 8.5 Hz, 2H), 7.50−7.47 (m,
2H), 7.40−7.38 (m, 3H), 7.20 (d, J = 8.5 Hz, 2H), 2.54 (s, 3H); 13C
NMR (125 MHz, CDCl3) δ 197.3, 145.0, 134.5, 134.0, 132.1, 129.8,
129.0, 128.9, 127.5, 26.5; IR (neat) 2922, 1677, 1589, 690 cm−1.
2-Phenylthiobenzothiazole (15). Title compound was prepared
according to general procedure A from 2-mercaptobenzothiazole
(0.084 g, 0.50 mmol), NCS (0.073 g, 0.55 mmol) and PhZnBr (1.3
mmol, 1.7 mL). Purification by flash column chromatography (15%
EtOAc in hexanes) afforded the title compound as a colorless oil
(0.087 g, 71%). Compound 15 was also prepared from PhMgBr
according to general procedure B to afford 65% yield (determined by
1H NMR in comparison to the internal standard phenyltrimethylsi-
lane). Spectral data were consistent with reported values:39 TLC Rf =
0.5 (30% EtOAc in hexanes); 1H NMR (400 MHz, CDCl3) δ 7.87 (d,
J = 8.4 Hz, 1H), 7.72 (m, 2H), 6.63 (d, J = 8.0 Hz, 1H), 7.52−7.43 (m,
3H), 7.38 (m, 1H), 7.25 (m, 1H); 13C NMR (125 MHz, CDCl3) δ
169.8, 154.0, 135.6, 135.4, 130.6, 130.01, 129.98, 126.2, 124.4, 122.0,
120.9.
2-(4-Methoxyphenylthio)pyrimidine (21). Title compound was
prepared according to general procedure B from 2-mercaptopyr-
imidine (0.056 g, 0.50 mmol), NCS (0.073 g, 0.55 mmol) and (4-
OMe)PhMgBr (1.3 mmol, 1.8 mL). Purification by flash column
chromatography (20−30% EtOAc in hexanes) afforded the title
compound as a white solid (0.082 g, 75%). Spectral data were
consistent with reported values:40 TLC Rf = 0.4 (30% EtOAc in
1
hexanes); H NMR (400 MHz, CDCl3) δ 8.47 (d, J = 4.4 Hz, 2H),
7.54 (d, J = 8.0 Hz, 2H), 6.95 (m, 3H), 3.83 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 173.5, 160.6, 157.6, 137.1, 120.0, 116.8, 114.9, 55.4.
2-(4-(Trifluoromethyl)phenylthio)pyrimidine (22). Title com-
pound was prepared according to general procedure B from 2-
mercaptopyrimidine (0.056 g, 0.50 mmol), NCS (0.073 g, 0.55 mmol)
and (4-CF3)PhMgBr (1.3 mmol, 2.1 mL). Purification by flash column
chromatography (10−30% EtOAc in hexanes) afforded the title
compound as a colorless oil (0.110 g, 86%): TLC Rf = 0.6 (30%
2-Phenylthiobenzoxazole (16). Title compound was prepared
according to general procedure A from 2-mercaptobenzoxazole (0.076
g, 0.50 mmol), NCS (0.073 g, 0.55 mmol) and PhZnBr (1.3 mmol, 1.7
mL). Purification by flash column chromatography (15% EtOAc in
hexanes) afforded the title compound as a colorless oil (0.093 g, 82%).
Compound 16 was also prepared from PhMgBr according to general
1
EtOAc in hexanes); H NMR (400 MHz, CDCl3) δ 8.51 (d, J = 4.8
Hz, 2H), 7.76 (d, J = 8.0 Hz, 2H), 7.67 (d, J = 8.0 Hz, 2H), 7.02 (t, J =
1950
dx.doi.org/10.1021/jo402586v | J. Org. Chem. 2014, 79, 1947−1953