10.1002/cmdc.201600593
ChemMedChem
FULL PAPER
boron tribromide according to general procedure for ether cleavage.
Purification by CC (petroleum ether:ethyl acetate = 3:1) gave the title
compound as a yellow solid, 72% yield, mp 175-177 °C. 1H NMR (400
MHz, Acetone-d6) δ 8.94 (s, 2H), 7.50 (m, 2H), 7.26 (d, J = 8.4 Hz, 2H),
7.17 (m, 4H). 13C NMR (100 MHz, Acetone-d6) δ 152.14, 149.24, 146.13,
134.02, 127.46, 118.48, 117.48, 115.93. HRMS (MALDI/DHB) calcd for
C16H11F2O2Se (M + H+) 351.9947 found 351.9946.
2H), 7.49 (d, J = 8.4 Hz, 2H), 7.48 (d, J = 8.0 Hz, 1H), 6.92 (d, J = 8.4 Hz,
2H), 6.87 (d, J = 8.0 Hz, 2H). 13C NMR (100 MHz, CD3OD) δ 159.10,
158.82, 149.74, 141.81, 131.61, 131.42, 128.85, 128.10, 127.36, 116.88,
116.43, 116.33, 108.08. HRMS (MALDI/DHB) calcd for C16H12BrO2Se (M
+ H+) 394.9237 found 394.9240.
3-Bromo-2,5-bis(4-hydroxy-2-methylphenyl)selenophene
(6b).
Compound 6b was prepared by 3-bromo-2,5-bis(4-methoxy-2-
methylphenyl)selenophene (6b) and boron tribromide according to
general procedure for ether cleavage. Purification by CC (petroleum
ether:ethyl acetate = 3:1) gave the title compound as a yellow solid, 79%
yield, mp 52-54 °C. 1H NMR (400 MHz, Acetone-d6) δ 8.59 (s, 2H), 7.26
(d, J = 8.4 Hz, 1H), 7.15 (d, J = 7.6 Hz, 2H), 6.81 (t, J = 8.8 Hz, 2H), 6.75
(d, J = 8.4 Hz, 2H), 2.41 (s, 3H), 2.23 (s, 3H). 13C NMR (100 MHz,
Acetone-d6) δ 154.89, 154.57, 149.50, 141.47, 129.88, 128.46, 127.44,
126.79, 126.68, 125.59, 125.07, 107.38, 16.67, 16.62. HRMS
(MALDI/DHB) calcd for C18H16BrO2Se (M + H+) 422.9548 found 422.9553.
3,4-Bis(4-hydroxyphenyl)selenophene (4a). Compound 4a was
prepared by 3,4-bis(4-methoxyphenyl)selenophene (3a) and boron
tribromide according to general procedure for ether cleavage. Purification
by CC (petroleum ether:ethyl acetate = 3:1) gave the title compound as a
blue solid, 61% yield, mp 144-147°C. 1H NMR (400 MHz, Acetone-d6) δ
8.24 (s, 2H), 7.76 (s, 2H), 6.85 (d, J = 8.4 Hz, 4H), 6.59 (d, J = 8.4 Hz,
4H). 13C NMR (100 MHz, Acetone-d6) δ 157.31, 144.98, 131.00, 128.54,
115.75. HRMS (MALDI/DHB) calcd for C16H13O2Se (M + H+) 317.2253,
found 317.2259.
3,4-Bis(4-hydroxy-2-methylphenyl)selenophene (4b). Compound 4b
was prepared by 3,4-bis(4-methoxy-2-methyl phenyl)selenophene (3b)
and boron tribromide according to general procedure for ether cleavage.
Purification by CC (petroleum ether:ethyl acetate = 3:1) gave the title
compound as a yellow solid, 51% yield, mp 151-153 °C. 1H NMR (400
MHz, Acetone-d6) δ 8.20 (s, 2H), 7.84 (s, 2H), 6.83 (d, J = 8.0 Hz, 2H),
6.58 (d, J = 7.6 Hz, 2H), 6.52 (d, J = 7.2 Hz, 2H), 6.50 (d, J = 7.2 Hz, 6H),
2.01 (s, 6H). 13C NMR (100 MHz, Acetone-d6) δ 157.14, 145.56, 138.21,
132.37, 128.53, 117.31, 112.95, 20.63. HRMS (MALDI/DHB) calcd for
C18H17O2Se (M + H+) 345.0394, found 345.0398.
3-Bromo-2,5-bis(4-hydroxy-3-methylphenyl)selenophene
(6c).
Compound 6c was prepared by 3-bromo-2,5-bis(4-methoxy-3-
methylphenyl)selenophene (5c) and boron tribromide according to
general procedure for ether cleavage. Purification by CC (petroleum
ether:ethyl acetate = 3:1) gave the title compound as a blue solid, 82%
yield, mp 155-157 °C. 1H NMR (400 MHz, DMSO-d6) δ 9.68 (s, 2H), 7.21
(d, J = 8.4 Hz, 2H), 7.10 (s, 1H), 6.72 (s, 2H), 6.68 (d, J = 8.0 Hz, 1H),
6.66 (d, J = 8.4 Hz, 1H), 2.36 (s, 3H), 2.17 (s, 3H). 13C NMR (100 MHz,
Acetone-d6) δ 156.93, 156.64, 149.47, 141.43, 132.30, 129.07, 128.63,
128.49, 128.41, 127.51, 126.05, 125.52, 125.24, 116.09, 115.62, 107.50,
16.27, 16.23. HRMS (MALDI/DHB) calcd for C18H16BrO2Se (M + H+)
422.9548 found 422.9553.
3,4-Bis(4-hydroxy-3-methylphenyl)selenophene (4c). Compound 4c
was prepared by 3,4-bis(4-methoxy-3-methylphenyl)selenophene (3c)
and boron tribromide according to general procedure for ether cleavage.
Purification by CC (petroleum ether : ethyl acetate = 3:1) gave the title
compound as a blue solid, 68% yield, mp 148-151 °C. 1H NMR (400 MHz,
Acetone-d6) δ 8.21 (s, 2H), 7.88 (s, 2H), 6.98 (s, 2H), 6.75 (d, J = 8.4 Hz,
2H), 6.69 (d, J = 8.4 Hz, 2H), 2.14 (s, 6H). 13C NMR (100 MHz, Acetone-
d6) δ 155.20, 145.11, 132.33, 130.84, 128.33, 128.21, 124.55, 114.97,
16.35. HRMS (MALDI/DHB) calcd for C18H17O2Se (M + H+) 345.0394,
found 345.0395.
3-Bromo-2,5-bis(4-hydroxy-3,5-dimethylphenyl)selenophene
(6d).
Compound 6d was prepared by 3-bromo-2,5-bis(4-methoxy-3,5-
dimethoxyphenyl)selenophene (5d) and boron tribromide according to
general procedure for ether cleavage. Purification by CC (petroleum
ether:ethyl acetate = 3:1) gave the title compound as a blue solid, 86%
yield, mp 199-201 °C. 1H NMR (400 MHz, DMSO-d6) δ 7.64 (d, J = 8.4
Hz, 2H), 7.39 (s, 1H), 7.25 (s, 4H), 2.29 (s, 6H), 2.28 (s, 6H). 13C NMR
(100 MHz, Acetone-d6) δ 154.88, 154.56, 149.50, 141.48, 129.89, 128.46,
127.45, 126.69, 125.59, 125.07, 107.38, 16.70, 16.65. HRMS
(MALDI/DHB) calcd for C20H20BrO2Se (M + H+) 450.9864 found 450.9866.
3,4-Bis(3-fluoro-4-hydroxyphenyl)selenophene (4d). Compound 4d
was prepared by 3,4-bis(3-fluoro-4-methoxy phenyl)selenophene (3d)
and boron tribromide according to general procedure for ether cleavage.
Purification by CC (petroleum ether:ethyl acetate = 3:1) gave the title
compound as a blue solid, 58% yield, mp 167-169 °C. 1H NMR (400 MHz,
CDCl3) δ 8.76 (s, 2H), 8.01 (s, 2H), 6.95 (d, J = 8.4 Hz, 2H), 6.91 (d, J =
7.6 Hz, 1H), 6.67 (d, J = 7.2 Hz, 1H), 6.82 (d, J = 8.4 Hz, 1H). 13C NMR
(100 MHz, CDCl3) δ 151.79, 144.66, 143.56, 131.39, 129.92, 126.19,
118.35, 117.38. HRMS (MALDI/DHB) calcd for C16H11F2O2Se (M + H+)
352.9892, found 352.9895.
3-Bromo-2,5-bis(3-chloro-4-hydroxyphenyl)selenophene
(6e).
Compound 6e was prepared by 3-bromo-2,5-bis(3-chloro-4-methoxy-
phenyl)selenophene (5e) and boron tribromide according to general
procedure for ether cleavage. Purification by CC (petroleum ether:ethyl
acetate = 3:1) gave the title compound as a gray solid, 72% yield, mp 98-
100 °C. 1H NMR (400 MHz, Acetone-d6) δ 9.33 (s, 2H), 7.64 (d, J = 8.8
Hz, 2H), 7.52 (s, 1H), 7.44-7.39 (m, 2H), 7.08 (d, J = 8.8 Hz, 2H). 13
NMR (100 MHz, Acetone-d6) δ 156.19, 149.19, 129.12, 129.05, 125.77,
125.43, 125.20, 116.00. HRMS (MALDI/DHB) calcd for C16H10Cl2O2Se
(M + H+) 462.8326 found 450. 8327.
C
3,4-Bis(2-fluoro-4-hydroxyphenyl)selenophene (4e). Compound 4e
was prepared from 3,4-bis(2-fluoro-4-methoxy phenyl)selenophene (3e)
and boron tribromide according to general procedure for ether cleavage.
Purification by CC (petroleum ether:ethyl acetate = 3:1) gave the title
compound as a blue solid, 54% yield, mp 168-171 °C. 1H NMR (400 MHz,
Acetone-d6) δ 8.08 (s, 2H), 7.01 (s, 2H), 6.57 (d, J = 8.4 Hz, 1H), 6.55 (d,
J = 8.4 Hz, 1H), 6.52 (d, J = 8.4 Hz, 2H), 13C NMR (100 MHz, CDCl3) δ
163.73, 161.32, 155.95, 140.16, 132.01, 131.91, 105.39, 102.64. HRMS
3-Bromo-2,5-bis(4-fluoro-5-hydroxyphenyl)selenophene
Compound 6f was prepared by 3-bromo-2,5-bis(4-fluoro-5-
(6f).
methoxyphenyl)selenophene (5f) and boron tribromide according to
general procedure for ether cleavage. Purification by CC (petroleum
ether:ethyl acetate = 3:1) gave the title compound as a yellow solid, 70%
yield, mp 80-82 °C. 1H NMR (400 MHz, DMSO-d6) δ 10.26 (s, 1H), 10.22
(s, 1H), 7.63 (s, 1H), 7.26 (d, J = 8.8 Hz, 1H), 7.24 (d, J = 8.4 Hz, 1H),
7.16 (d, J = 8.4 Hz, 2H), 7.12 (d, J = 8.4 Hz, 1H), 7.03 (d, J = 8.4 Hz, 1H),
7.01 (d, J = 8.4 Hz, 2H). 13C NMR (100 MHz, Acetone-d6) δ 148.0, 145.7,
143.3, 141.0, 130.2, 121.5, 119.4, 118.4, 117.5, 117.3, 117.1, 116.9,
116.8, 116.6, 116.0. HRMS (MALDI/DHB) calcd for C16H10BrF2O2Se (M +
H+) 430.1023 found 430.1025.
(MALDI/DHB) calcd for C16H11F2O2Se (M
352.9895.
+
H+) 352.9892, found
3-Bromo-2,5-bis(4-hydroxyphenyl)selenophene (6a). Compound 6a
was prepared by 3-bromo-2,5-bis(4-methoxyphenyl)selenophene (5a)
and boron tribromide according to general procedure for ether cleavage.
Purification by CC (petroleum ether:ethyl acetate = 3:1) gave the title
compound as a blue solid, 68% yield, mp 193-195 °C. 1H NMR (400 MHz,
DMSO-d6) δ 9.91 (s, 1H), 9.89 (s, 1H), 7.56 (s, 1H), 7.52 (d, J = 8.0 Hz,
3-Bromo-2,5-bis(2-fluoro-4-hydroxyphenyl)selenophene
Compound 6g was prepared from 3-bromo-2,5-bis(4-fluoro-5-
(6g).
14
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