2-Methyl-4-(phenylseleno)phenol (entry 10): From 2-methyl-
phenol, method A, 1 h, yield 76%, mp 59–60 ЊC, C13H12OSe
(C,H), Mϩ 264 (80Se). 1H NMR (ppm): 7.40–7.15, m, 7 H; 6.70,
d (8 Hz), 1H, 4.86, s, 1H; 2.21, s, 3H.
NMR (ppm): 8.04, s, 2H; 7.45–7.25, m, 10H, 7.22, s, 1H, 3.78,
s, 3H.
3,5-Dimethyl-2,4-bis(phenylseleno)phenol (entries 28, 44):
By-product (2%) in the preparation of 3,5-dimethyl-4-(phenyl-
seleno)phenol (entry 33), mp 100–101 ЊC (hexane), C20H18OSe2
(C,H), Mϩ 434 (80Se2). 1H NMR (ppm): 7.20–7.10, m, 5H; 7.17,
s, 5H; 7.02, s, 1H, 9.92, s, 1H, 2.74, s, 3H; 2.51, s, 3H.
2,6-Dimethyl-4-(phenylseleno)phenol (entry 11): From
2,6-dimethylphenol, method A, 1 h, yield 37%, mp 29–30 ЊC
1
(pentane), C14H14OSe (C,H), Mϩ 278 (80Se). H NMR (ppm):
7.35–7.12, m, 7H; 4.73, s, 1H; 2.19, s, 6H.
1-Methoxy-4-(phenylseleno)benzene (entry 12): ref. 5.
4-(Phenylseleno)phenol (entry 13): ref. 5.
2,6-Bis(phenylseleno)phenol (entry 29): From phenol,
method D, yield 37%, mp 59–61 ЊC (pentane), C18H14OSe2
1
(C,H), Mϩ 406 (80Se2). H NMR (ppm): 7.47–7.20, m, 12H;
1-Methoxy-2-methyl-4-(phenylseleno)benzene (entry 14):
From 2-methylanisole, method C, 10 min, yield 92%, mp 57–58
ЊC (pentane), C14H14OSe (C,H), Mϩ 278 (80Se).1H NMR (ppm):
7.43, dd (2ϩ8 Hz, 1H; 7.39, d (2 Hz), 1H; 7.35–7.31, m, 2H;
7.25–7,17, m, 3H; 6.78, d (8 Hz), 1H; 3.82, s, 3H; 4.41, s, 3H.
3-Chloro-4-(phenylseleno)phenol (entry 15): From 3-chloro-
phenol, method B, 1 h, yield 55%, oil, purified by chromato-
6.85, s, 1H; 6.72, t (7.5 Hz), 1H.
1-Methoxy-3,5-dimethyl-4-(phenylseleno)benzene (structure
6, entry 30): From 3,5-dimethylanisole, method A, 3 days, yield
79%, mp 82–84 ЊC (pentane), C15H16OSe (C,H), Mϩ 292 (80Se).
1H NMR (ppm): 7.09, s, 5H; 6.73, s, 2H; 3.79, s, 3H; 2.45, s, 6H.
3,5-Dimethyl-4-(phenylseleno)phenol (entry 31): From
3,5-dimethylphenol, method A, 2 h, yield 76%, mp 91–92 ЊC
1
1
graphy (silica gel 60/hexane–75% dichloromethane). H NMR
(hexane), C14H14OSe (C,H), Mϩ 278 (80Se). H NMR (ppm):
(ppm): 7.48–7.40, m, 2H; 7.35–7.20, m, 3H; 7.08, d (9 Hz),
1H; 6.91, d (2 Hz), 1H, 6.57, dd (9ϩ2 Hz), 1H; 5.24, s, 1H.
4-Bromo-1-methoxy-2-(phenylseleno)benzene (entry 16):
From 4-bromoanisole, method C, 90 min, yield 22%, mp 92–93
ЊC (MeOH), C13H11BrOSe (C,H), Mϩ 342 (78Se81Br ϩ 80Se79Br).
1H NMR (ppm): 7,65–7.55, m, 2H; 7.40–7.30, m, 3H; 7.25,
dd (8ϩ2 Hz), 1H; 6.21, d (2 Hz), 1H; 6.68, d (8 Hz), 1H; 3.85,
s, 3H.
7.09, s, 5H; 6,66, s, 2H; 5,29, s, 1H; 2.40, s, 6H.
Methyl 4-hydroxy-3-(phenylseleno)benzoate (entry 34):
Byproduct (6%) in the preparation of methyl 4-hydroxy-3,5-
bis(phenylseleno)benzoate (entry 29), mp 88–89 ЊC (hexane),
C14H12O3Se (C,H), Mϩ 308 (80Se).1H NMR (ppm): 8.35, d
(2 Hz), 1H; 8.02, dd (2 ϩ10 Hz), 1H; 7.22, s, 5H; 7.06, d
(10 Hz); 1H; 6.94, s, 1H; 3.87, s, 3H.
4-Methyl-2-(phenylseleno)phenol (entry 35): From 4-methyl-
phenol, method B, 30 min, oil, C13H12OSe (C,H), Mϩ 264 (80Se).
1H NMR (ppm): 7.34, d (2 Hz), 1H; 7.19, s, 5H; 7.14, dd (2 ϩ8
Hz), 1H; 6.95, d (8 Hz), 1H; 6.25, s, 1H; 2.26, s, 3H.
2,3-Dimethyl-4-(phenylseleno)phenol (structure 2, entry 18):
From 2,3-dimethylphenol, method A, 50 min, yield 75%,
1
mp 72–73 ЊC (hexane), C14H14OSe (C,H), Mϩ 278 (80Se). H
NMR (ppm): 7.36, d (8 Hz), 1H; 7.21, s, 5H; 5.56, d (8 Hz), 1H;
5.10, s, 1H; 2,41, s, 3H; 2.22, s, 3H.
1,4-Dimethoxy-2,5-bis(phenylseleno)benzene (structure 5,
2-(Phenylseleno)phenol (entry 37): From phenol, method D,
yield 40%, oil, C12H10OSe (C,H), Mϩ 250 (80Se). 1H NMR
(ppm): 7.60, dd (2ϩ8 Hz), 1H; 7,33, dt (2ϩ8 Hz), 1H; 7.18, s,
5H; 7.05, dd (2ϩ8 Hz), 1H; 6.85, dt (2ϩ8 Hz), 1H; 4.73, s, 1H.
2-Methyl-6-(phenylseleno)phenol (entry 38): From 2-methyl-
phenol, method D, yield 31%, mp 29–30 ЊC (pentane), C13H12-
OSe (C,H), Mϩ 264 (80Se). 1H NMR (ppm): 7.47, dd (1.5ϩ8 Hz),
1H; 7.19, s-br., 6H; 6.78, t (8 Hz), 1H; 6.52, s, 1H; 2.29, s, 3H.
3-Chloro-6-(phenylseleno)phenol (entry 39): From 3-chloro-
phenol, method D, yield 10%, mp 35–36 ЊC (pentane),
C12H9ClOSe (C,H), Mϩ 284 (35Cl80Se). 1H NMR (ppm): 7.53, d
(8 Hz), 1H; 7.19, s 5H, 7.13, d (2 Hz); 1H; 6.99; dd (2ϩ8 Hz),
1H; 6.47, s, 1H.
entry 19): From 1,4-dimethoxybenzene, method C, yield 64%,
1
mp 177–179 ЊC, C20H18O2Se2 (C,H), Mϩ 450 (80Se2). H NMR
(ppm): 7.60–7.50, m, 4H; 7.40–7.25, m, 6H; 6.54, s, 2H; 3.58,
s, 6H.
1-Methoxy-4-methyl-2-(phenylseleno)benzene (structure 8,
entry 20): From 4-methylanisole, method B, 24 h, yield 79%,
1
mp 71–73 ЊC (pentane), C14H14OSe (C,H), Mϩ 278 (80Se). H
NMR (ppm): 7.60–7.55, m, 2H; 7.35–7.30, m, 3H; 7.00, dd
(1.5ϩ8 Hz, 1H; 6.84, d (1.5 Hz), 1H; 6.77, d (8 Hz), 1H; 3.86,
s, 3H; 2.17, s, 3H.
3,5-Dimethyl-2,4,6-tris(phenylseleno)phenol (entries 21, 32):
From 3,5-dimethyl-4-(phenylseleno)phenol, method A, 4 days,
yield 37%, mp 175–177 ЊC (dichloromethane–hexane), C26H22-
3,5-Dimethyl-2,6-bis(phenylseleno)phenol (entry 40): From
3,5-dimethylphenol, method D, yield 67%, mp 119–121 ЊC
(hexane), C20H18OSe2 (C,H), Mϩ 434 (80Se2).1H NMR (ppm):
7.23, s, 1H; 7.16, s, 5H; 9.91, s, 1H; 2.46, s, 6H.
1
OSe3 (C,H), Mϩ 588 (78Se80Se2). H NMR (ppm): 7.55, s, 1H;
7.16, s, 15H; 2.84, s, 6H.
4,6-Bis(phenylseleno)benzene-1,3-diol (structure 3, entry 41):
From 4-(phenylseleno)benzene-1,3-diol, method A, 15 min,
yield 56%, mp 121–122 ЊC (dichloromethane–hexane), C18H14-
O2Se2 (C,H), Mϩ 422 (80Se2). 1H NMR (ppm): 7.96, s, 1H; 7.19,
s, 10H; 6.82, s, 1H; 6.62, s, 2H.
1,3-Dimethoxy-4,6-bis(phenylseleno)benzene (entry 23):
From 1,3-dimethoxybenzene, method A, 24 h, yield 87%,
mp 91–92 ЊC (dichloromethane-hexane), C20H18O2Se2 (C,H),
1
Mϩ 450 (80Se2). H NMR (ppm): 7.35–7.25, m, 4H; 7.20–7.10,
m, 6H; 7.06, s, 1H; 6.46, s, 1H; 3.81, s, 6H.
4,6-Bis(phenylseleno)-3-methoxyphenol (structure 1, entries
4-(Phenylseleno)benzene-1,3-diol (structure 7, entry 43):
From benzene-1,3-diol, method A, 30 min, yield 35%, mp
112–113 ЊC (dichloromethane–pentane), C12H10O2Se (C,H),
24, 42): From 3-methoxyphenol, method A, 10 min, yield 49%,
mp 78–80 ЊC, C19H16O2Se2 (C,H), Mϩ 436 (80Se2). H NMR
Mϩ 266 (80Se). H NMR (ppm): 7.50, d (8 Hz), 1H; 7.18, s,
1
1
(ppm): 7.57, s, 1H; 7.30–7.35, m, 2H; 7.25–7.15, m, 3H; 7.14, s,
5H, 6.64, s, 1H; 6.51, s, 1H; 3.81, s, 3H.
5H; 6.58, d (2 Hz), 1H; 6,50, s, 1H; 6.41, dd (2ϩ8 Hz), 1H; 5.32,
s, 1H.
2,5-Dimethyl-4-(phenylseleno)phenol (structure 9, entry 25):
3,5-Dimethyl-2-(phenylseleno)phenol (entry 45): From 3,5-
dimethylphenol, method D, yield 40%, mp 58–59 ЊC (pentane),
C14H14OSe (C,H), Mϩ 278 (80Se). 1H NMR (ppm): 7.14, s, 5H;
6.76, s, 1H; 6.70, s, 1H; 6,67, s, 1H; 2.39, s, 3H; 2.30, s, 3H.
From 2,5-dimethylphenol, method A, 15 min, yield 89%,
1
mp 63–64 ЊC, C14H14OSe (C,H), Mϩ 278 (80Se). H NMR (in
DMSO-d6) (ppm): 9.63, s, 1H; 7.34, s, 1H; 7.25–7.12, m, 5H;
6.83, s, 1H; 2.25, s, 3H; 2.09, s, 3H.
1,3-Dimethoxy-4-(phenylseleno)benzene (entry 26): From
1,3-dimethoxybenzene, method A, 24 h, yield 59%, mp 28–29
X-Ray crystallography
1
ЊC, C14H14O2Se (C,H), Mϩ 294 (80Se). H NMR (ppm): 7.45–
Single crystal data were collected on crystals cooled to 122.0(5)
K on an Enraf-Nonius CAD4 diffractometer.12 The employed
radiation was obtained from a graphite monochromator. Data
reductions were performed with the DREADD package.13
All reflections were corrected for background, Lorentz and
polarisation effects. The data sets were scaled to account for the
7.30, m, 2H; 7.25–7.15, m, 4H; 6.48, d (2 Hz); 1H; 6.41, dd (2ϩ8
Hz), 1H; 3.80, s, 3H; 3.78, s, 3H.
Methyl 4-hydroxy-3,5-bis(phenylseleno)benzoate (entry 27):
From methyl 4-hydroxybenzoate, method B, 4 days, yield 66%,
mp 103–104 ЊC (hexane), C20H16O3Se2 (C,H), Mϩ 464(80Se2). 1H
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 1 0 5 3 – 1 0 6 0
1059