The Journal of Organic Chemistry
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116.8, 116.3; HRMS (ESI-TOF) calcd for C12H10NaO2S 241.0299 [M
+ Na+], found 241.0295.
benzoquinone (2162.8 mg, 20.0 mmol) in MeOH (30 mL) was stirred
at room temperature for 2 h. The reaction was monitored by TLC.
MeOH was removed in vacuo, and the residue was subjected to flash
chromatography (silica gel/hexane−EtOAc, 10:1 then 3:1 v/v) to give
2g in 96% yield (4458.2 mg, 19.2 mmol): yellow solid; mp 63.5−64.0
Preparation of 2-((2-Bromophenyl)thio)benzene-1,4-diol
(2b). A mixture of 2-bromothiophenol (3.8 mL, 31.5 mmol) and
1,4-benzoquinone (3242.1 mg, 30.0 mmol) in MeOH (50 mL) was
stirred at room temperature for 6 h. The reaction was monitored by
TLC. MeOH was removed in vacuo, and the residue was subjected to
flash chromatography (silica gel/hexane−EtOAc, 10:1 then 3:1 v/v) to
give 2b in 93% yield (8276.6 mg, 27.9 mmol): white solid; mp 126.5−
1
°C; H NMR (500 MHz, CDCl3) δ 7.08−7.04 (m, 4H), 6.98 (d, J =
3.0 Hz, 1H), 6.93 (d, J = 8.8 Hz, 1H), 6.84 (dd, J = 8.8, 3.0 Hz, 1H),
6.11 (s, 1H), 4.63 (s, 1H), 2.29 (s, 3H); 13C NMR (126 MHz, DMSO-
d6) δ 151.0, 148.5, 137.4, 132.1(2C), 131.3, 130.7 (2C), 122.6, 117.5,
116.7, 115.5, 21.2; HRMS (ESI-TOF) calcd for C13H12NaO2S
255.0456 [M + Na+], found 255.0460.
Preparation of 2-(Naphthalen-2-ylthio)benzene-1,4-diol
(2h). A mixture of 2-thionaphthol (810.3 mg, 5.06 mmol) and 1,4-
benzoquinone (538.5 mg, 4.98 mmol) in MeOH (10 mL) was stirred
at room temperature for 3 h. MeOH was removed in vacuo, and the
residue was subjected to flash chromatography (silica gel/hexane−
EtOAc, 10:1 then 3:1 v/v) to give 2h in 24% yield (301.2 mg, 1.20
mmol): yellow solid; mp 62.5−62 °C; 1H NMR (500 MHz, CDCl3) δ
7.76 (d, J = 8.0 Hz, 1H), 7.72 (dd, J = 8.8, 1.9 Hz, 1H), 7.66 (d, J = 7.8
Hz, 1H), 7.53 (s, 1H), 7.49−7.39 (m, 2H), 7.23 (dt, J = 8.7, 2.1 Hz,
1H), 7.04 (t, J = 2.6 Hz, 1H), 6.98 (dd, J = 8.8, 2.1 Hz, 1H), 6.90 (dt, J
= 8.8, 2.6 Hz, 1H), 6.12 (d, J = 2.1 Hz, 1H), 4.58 (d, J = 2.0 Hz, 1H);
13C NMR (126 MHz, CDCl3) δ 150.4, 148.7, 133.5, 132.6, 131.8,
1
127.0 °C; H NMR (500 MHz, CDCl3) δ 7.53 (dd, J = 7.9, 1.4 Hz,
1H), 7.12 (td, J = 7.7, 1.4 Hz, 1H), 7.05−6.99 (m, 2H), 6.98 (s, 1H),
6.93 (dd, J = 8.8, 3.0 Hz, 1H), 6.64 (dd, J = 8.0, 1.6 Hz, 1H), 6.00 (s,
1H), 4.74 (s, 1H); 13C NMR (126 MHz, DMSO-d6) δ 150.9 (2C),
138.3, 133.3, 128.7, 128.7, 127.5, 121.6, 121.2, 118.5, 117.4, 116.8;
HRMS (ESI-TOF) calcd for C12H9BrNaO2S 318.9404 [M + Na+],
found 318.9397.
Preparation of 2-((3-Bromophenyl)thio)benzene-1,4-diol
(2c). A mixture of 3-bromothiophenol (3.9 mL, 33.0 mmol) and
1,4-benzoquinone (3242.0 mg, 30.0 mmol) in MeOH (50 mL) was
stirred at room temperature for 12 h. The reaction was monitored by
TLC. MeOH was removed in vacuo, and the residue was subjected to
flash chromatography (silica gel/hexane−EtOAc, 10:1 then 3:1 v/v) to
give 2c in 97% yield (8686.7 mg, 29.2 mmol): white solid; mp 109−
110 °C; 1H NMR (500 MHz, CDCl3) δ 7.29 (dt, J = 7.9, 1.3 Hz, 1H),
7.22 (t, J = 1.8 Hz, 1H), 7.10 (t, J = 7.9 Hz, 1H), 7.01−6.98 (m, 2H),
6.97 (s, 1H), 6.91 (dd, J = 8.9, 2.9 Hz, 1H), 6.00 (s, 1H), 4.57 (s, 1H);
13C NMR (126 MHz, DMSO-d6) δ 150.8, 150.4, 139.8, 131.5, 130.4,
128.8, 128.6, 128.2, 127.7, 127.2, 126.8, 126.2, 120.4, 118.0, 116.4,
115.8; HRMS (ESI-TOF) calcd for C16H12NaO2S 291.0456 [M +
Na+], found 291.0457.
Preparation of 2-(Pyridin-2-ylthio)benzene-1,4-diol (2i). A
mixture of 2-mercaptopyridine (564.1 mg, 5.05 mmol) and 1,4-
benzoquinone (536.2 mg, 5.0 mmol) in MeOH (50 mL) was stirred at
room temperature for 3.5 h. The reaction was monitored by TLC.
MeOH was removed under reduced pressure, and the residue was
subjected to flash chromatography (silica gel/EtOAc) to give 2i in
97% yield (1060.0 mg, 4.83 mmol): yellow solid; mp 91.5−92.0 °C;
1H NMR (500 MHz, CDCl3) δ 8.41 (d, J = 4.4 Hz, 1H), 7.59 (td, J =
7.8, 1.8 Hz, 1H), 7.23 (d, J = 7.9 Hz, 1H), 7.12 (dd, J = 7.6, 5.1 Hz,
1H), 7.07−6.95 (m, 2H), 6.85 (dd, J = 8.8, 2.9 Hz, 1H), 4.98−4.46
(br, 1H), 3.80−3.38 (br, 1H); 13C NMR (126 MHz, CD3OD) δ 162.5,
152.8, 152.1, 149.9, 138.8, 123.4, 122.4, 121.3, 120.1, 118.4, 116.9;
HRMS (ESI-TOF) calcd for C11H9NNaO2S 242.0252 [M + Na+],
found 242.0257.
Preparation of 2-Phenylsulfanyl-1,4-dimethoxybenzene
(3a). Under a nitrogen atmosphere, a solution of 2a (4365.4 mg,
20.0 mmol) in dry THF (100 mL) was added to a suspension of NaH
(2456.9 mg, 60%, 61.4 mmol) in THF (100 mL) over 15 min at 0 °C.
MeI (12.5 mL, 200 mmol) was added to the reaction mixture at 0 °C,
and the resulting solution was stirred at the same temperature for an
additional 15 min and at room temperature for 24 h. Saturated
NH4Claq (100 mL) was added, and THF was removed by rotary
evaporator. The aqueous solution extracted with EtOAc (40 mL × 3).
The organic phases were combined, washed with brine (50 mL), and
dried over Na2SO4. After filtration, the organic phase was concentrated
in vacuo. The residue was purified by flash chromatography (silica gel/
hexane−EtOAc, 7:1 v/v) to give 3a in 93% yield (4578.9 mg, 18.6
mmol): yellow oil; 1H NMR (500 MHz, CDCl3) δ 7.32 (d, J = 7.5 Hz,
2H), 7.27−7.19 (m, 3H), 6.76 (d, J = 8.8 Hz, 1H), 6.66 (dd, J = 8.9,
3.0 Hz, 1H), 6.53 (d, J = 3.0 Hz, 1H), 3.76 (s, 3H), 3.59 (s, 3H); 13C
NMR (126 MHz, CDCl3) δ 154.0, 151.5, 133.8, 132.2 (2C), 129.3
(2C), 127.5, 125.8, 116.8, 112.5, 111.9, 56.5, 55.6; HRMS (ESI-TOF)
calcd for C14H14NaO2 269.0612 [M + Na+], found 269.0615.
Preparation of 2-(2-Bromophenyl)sulfanyl-1,4-dimethoxy-
benzene (3b). Under a nitrogen atmosphere, a solution of 2b
(7429.4 mg, 25.0 mmol) in dry THF (50 mL) was added to a
suspension of NaH (3174.5 mg, 60%, 79.4 mmol) in THF (50 mL)
over 15 min at 0 °C. MeI (7.8 mL, 125.0 mmol) was added to the
reaction mixture at 0 °C, and the resulting solution was stirred at the
same temperature for an additional 15 min and at room temperature
for 12 h. Saturated NH4Cl aq (50 mL) was added, and THF was
removed by using a rotary evaporator. The aqueous solution extracted
with EtOAc (50 mL × 3). The organic phases were combined, washed
with brine (100 mL), and dried over Na2SO4. After filtration, the
129.2, 127.6, 122.7, 120.5, 118.0, 117.8, 117.3; HRMS (ESI-TOF)
calcd for C12H9BrNaO2S 318.9404 [M + Na+], found 318.9404.
Preparation of 2-((4-Bromophenyl)thio)benzene-1,4-diol
(2d). A mixture of 4-bromothiophenol (1039.7 mg, 5.5 mmol) and
1,4-benzoquinone (539.9 mg, 5.0 mmol) in MeOH (10 mL) was
stirred at room temperature for 18 h. The reaction was monitored by
TLC. MeOH was removed in vacuo, and the residue was subjected to
flash chromatography (silica gel/hexane−EtOAc, 10:1 then 3:1 v/v) to
give 2d in 98% yield (1458.3 mg, 4.9 mmol): yellow solid; mp 115.5−
1
116.0 °C; H NMR (500 MHz, CDCl3) δ 7.35 (d, J = 7.6 Hz, 2H),
7.00−6.95 (m, 3H), 6.95 (d, J = 4.8 1H), 6.88 (dd, J = 8.8, 3.0 Hz,
1H), 6.02 (s, 1H), 4.74 (s, 1H); 13C NMR (126 MHz, DMSO-d6) δ
150.8, 149.8, 136.0, 132.5 (2C), 131.5 (2C), 119.8, 119.6, 119.1, 117.3,
117.1; HRMS (ESI-TOF) calcd for C12H9BrNaO2S 318.9404 [M +
Na+], found 318.9405.
Preparation of 2-((4-Chlorophenyl)thio)benzene-1,4-diol
(2e). A mixture of 4-chlorothiophenol (4355.0 mg, 30.3 mmol) and
1,4-benzoquinone (3243.5 mg, 30.0 mmol) in MeOH (50 mL) was
stirred at room temperature for 6 h. The reaction was monitored by
TLC. MeOH was removed in vacuo, and the residue was subjected to
flash chromatography (silica gel/hexane−EtOAc, 10:1 then 3:1 v/v) to
give 2e in 87% yield (6602.4 mg, 26.1 mmol): white solid; mp 119.5−
120 °C; 1H NMR (500 MHz, CDCl3) δ 7.22 (d, J = 8.6 Hz, 1H), 7.04
(d, J = 9.0 Hz, 2H), 6.98 (d, J = 3.0 Hz, 1H), 6.96 (d, J = 8.8 Hz, 1H),
6.89 (dd, J = 8.9, 3.0 Hz, 1H), 6.01 (s, 1H), 4.55 (s, 1H); 13C NMR
(126 MHz, DMSO-d6) δ 150.9, 149.8, 135.4, 131.6 (2C), 131.4 (2C),
129.7, 119.5, 119.4, 117.2, 117.1; HRMS (ESI-TOF) calcd for
C12H9ClNaO2S 274.9910 [M + Na+], found 274.9906.
Preparation of 2-((2-Methylphenyl)thio)benzene-1,4-diol
(2f). A mixture of o-thiocresol (3.7 mL, 31.5 mmol) and 1,4-
benzoquinone (3242.7 mg, 30.0 mmol) in MeOH (50 mL) was stirred
at room temperature for 6 h. The reaction was monitored by TLC.
MeOH was removed in vacuo, and the residue was subjected to flash
chromatography (silica gel/hexane−EtOAc, 10:1 then 3:1 v/v) to give
2f in 100% yield (6954.4 mg, 29.9 mmol): white solid; mp 51.5−52.0
1
°C; H NMR (500 MHz, CDCl3) δ 7.17 (d, J = 7.9 Hz, 1H), 7.12−
7.00 (m, 2H), 6.99−6.91 (m, 2H), 6.87 (dd, J = 8.7, 3.0 Hz, 1H), 6.76
(dd, J = 7.8, 1.4 Hz, 1H), 5.97 (s, 1H), 4.64 (s, 1H), 2.43 (s, 3H); 13C
NMR (126 MHz, DMSO-d6) δ 150.7, 148.5, 138.9, 133.6, 131.7,
130.7, 127.6, 127.0, 120.8, 117.1, 116.4, 115.3, 20.1; HRMS (ESI-
TOF) calcd for C13H12NaO2S 255.0456 [M + Na+], found 255.0454.
Preparation of 2-((4-Methylphenyl)thio)benzene-1,4-diol
(2g). A mixture of p-thiocresol (2653.2 mg, 21.4 mmol) and 1,4-
F
dx.doi.org/10.1021/jo402522y | J. Org. Chem. XXXX, XXX, XXX−XXX