10.1002/adsc.201900641
Advanced Synthesis & Catalysis
and oxazole (0.069 g, 1 mmol), product 3c was obtained in
17% yield (0.046 g) as a white solid: mp 265-267 °C. 1H
NMR (400 MHz, CDCl3): 8.25 (d, J = 8.6 Hz, 2H), 7.86
(d, J = 8.6 Hz, 2H), 7.83 (d, J = 8.6 Hz, 2H), 7.78 (d, J =
8.6 Hz, 2H), 7.68 (s, 1H). 13C NMR (100 MHz, CDCl3):
160.6, 150.7, 133.1, 132.9, 131.5, 130.7, 127.1, 126.8,
124.8, 118.5, 118.3, 114.4, 112.4. LRMS calcd for M+
C17H9N3O 271, found 271.
g, 2 mmol) and 2-(4-methoxyphenyl)oxazole 13b (0.175 g,
1 mmol), product 25 was obtained in 85% yield (0.235 g)
as a yellow solid: mp 175-177 °C. 1H NMR (400 MHz,
CDCl3): 8.04 (d, J = 8.6 Hz, 2H), 7.77 (d, J = 8.6 Hz,
2H), 7.71 (d, J = 8.6 Hz, 2H), 7.55 (s, 1H), 7.00 (d, J = 8.6
Hz, 2H), 3.88 (s, 3H). 13C NMR (100 MHz, CDCl3):
162.6, 161.9, 148.8, 132.8, 132.1, 128.3, 126.2, 124.2,
119.6, 118.6, 114.4, 111.2, 55.5.
Anal. Calcd for
C17H12N2O2 (276.30): C, 73.90; H, 4.38. Found: C, 74.15;
(8c):[7a]
H, 4.28. LRMS calcd for M+ C17H12N2O2 276, found 276.
2,5-Bis(4-(trifluoromethyl)phenyl)oxazole
Following procedure C,
from
4-
(trifluoromethyl)bromobenzene (0.675 g, 3 mmol) and
oxazole (0.069 g, 1 mmol), product 8c was obtained in
60% yield (0.214 g) as a white solid: mp 127-129 °C. 1H
NMR (400 MHz, CDCl3): 8.24 (d, J = 8.5 Hz, 2H), 7.84
(d, J = 8.5 Hz, 2H), 7.77 (d, J = 8.5 Hz, 2H), 7.72 (d, J =
8.5 Hz, 2H), 7.60 (s, 1H). 13C NMR (100 MHz, CDCl3):
160.5, 150.6, 132.3 (q, J = 32.7 Hz), 130.8 (m), 130.6 (q, J
= 32.7 Hz), 130.2 (m), 126.7, 126.1 (q, J = 3.8 Hz), 125.9
(q, J = 3.8 Hz), 125.5, 124.4, 123.8 (q, J = 272.0 Hz),
123.7 (q, J = 272.0 Hz). LRMS calcd for M+ C17H9F6NO
357, found 357.
4-(5-(4-Methoxyphenyl)oxazol-2-yl)benzonitrile
(26):
Following procedure A, from 4-bromoanisole (0.374 g, 2
mmol) and 4-(oxazol-2-yl)benzonitrile 3b (0.170 g, 1
mmol) at 150 °C, product 26 was obtained in 86% yield
(0.237 g) a yellow solid: mp 157-159 °C. 1H NMR (400
MHz, CDCl3): 8.18 (d, J = 8.6 Hz, 2H), 7.76 (d, J = 8.6
Hz, 2H), 7.66 (d, J = 8.6 Hz, 2H), 7.38 (s, 1H), 6.99 (d, J =
8.6 Hz, 2H), 3.87 (s, 3H). 13C NMR (100 MHz, CDCl3):
160.3, 158.6, 152.6, 132.6, 131.3, 126.4, 126.0, 122.7,
120.2, 118.4, 114.6, 113.2, 55.4.
Anal. Calcd for
C17H12N2O2 (276.30): C, 73.90; H, 4.38. Found: C, 73.85;
H, 4.51. LRMS calcd for M+ C17H12N2O2 276, found 276.
2,5-Bis(4-chlorophenyl)oxazole
(9c):[27]
Following
procedure C, from 4-bromochlorobenzene (0.573 g, 3
mmol) and oxazole (0.069 g, 2 mmol), product 9c was
obtained in 71% yield (0.206 g) as a white solid: mp 146-
148 °C. 1H NMR (400 MHz, CDCl3): 8.03 (d, J = 8.4
Hz, 2H), 7.64 (d, J = 8.4 Hz, 2H), 7.46 (d, J = 8.4 Hz, 2H),
7.43 (s, 1H), 7.42 (d, J = 8.4 Hz, 2H). 13C NMR (100
MHz, CDCl3): 160.4, 150.5, 136.6, 134.4, 129.3, 129.2,
127.6, 126.3, 125.7, 125.4, 123.9. LRMS calcd for M+
C15H9Cl2NO 289, found 289.
5-(4-Fluorophenyl)-2-(4-methoxyphenyl)oxazole (27):
Following procedure A, from 4-bromofluorobenzene
(0.350 g, 2 mmol) and 2-(4-methoxyphenyl)oxazole 13b
(0.175 g, 1 mmol), product 27 was obtained in 77% yield
(0.207 g) as a white solid: mp 131-133 °C. 1H NMR (400
MHz, CDCl3): 8.03 (d, J = 8.6 Hz, 2H), 7.67 (dd, J = 8.6,
5.2 Hz, 2H), 7.34 (s, 1H), 7.13 (t, J = 8.6 Hz, 2H), 6.99 (d,
J = 8.6 Hz, 2H), 3.87 (s, 3H). 13C NMR (100 MHz,
CDCl3): 162.6 (d, J = 248.5 Hz), 161.4, 161.3, 149.9,
127.9, 125.9 (d, J = 8.2 Hz), 124.5 (d, J = 3.3 Hz), 122.9
(d, J = 1.3 Hz), 120.2, 116.0 (d, J = 22.1 Hz), 114.3, 55.4.
Anal. Calcd for C16H12FNO2 (269.28): C, 71.37; H, 4.49.
Found: C, 71.56; H, 4.20. LRMS calcd for M+ C16H12NO2
269, found 269.
2,5-Bis(4-fluorophenyl)oxazole
(10c):[28]
Following
procedure C, from 4-bromofluorobenzene (0.525 g, 3
mmol) and oxazole (0.069 g, 2 mmol), product 10c was
obtained in 73% yield (0.188 g) as a white solid: mp 154-
1
156 °C. H NMR (400 MHz, CDCl3): 8.09 (dd, J = 8.2 ,
5.3 Hz, 2H), 7.69 (dd, J = 8.2, 5.3 Hz, 2H), 7.37 (s, 1H),
7.22-7.12 (m, 4H). 13C NMR (100 MHz, CDCl3): 165.5,
162.9 (d, J = 249.1 Hz), 161.8 (d, J = 250.2 Hz), 150.7,
128.5 (d, J = 8.7 Hz), 126.2 (d, J = 8.2 Hz), 124.4, 123.9,
123.2, 116.3 (d, J = 22.1 Hz), 116.2 (d, J = 22.1 Hz).
LRMS calcd for M+ C15H9F2NO 257, found 257.
5-(4-(tert-Butyl)phenyl)-2-(4-methoxyphenyl)oxazole
(28): Following procedure A, from 1-bromo-4-tert-
butylbenzene (0.426 g,
2
mmol) and 2-(4-
methoxyphenyl)oxazole 13b (0.175 g, 1 mmol), product 28
was obtained in 81% yield (0.249 g) as a white solid: mp
111-113 °C. 1H NMR (400 MHz, CDCl3): 8.04 (d, J =
8.6 Hz, 2H), 7.64 (d, J = 8.4 Hz, 2H), 7.46 (d, J = 8.4 Hz,
2H), 7.36 (s, 1H), 7.00 (d, J = 8.6 Hz, 2H), 3.87 (s, 3H),
1.36 (s, 9H). 13C NMR (100 MHz, CDCl3): 161.3, 161.0,
151.5, 150.9, 127.9, 125.8, 125.4, 123.9, 122.8, 120.4,
114.2, 55.4, 34.8, 31.2. Anal. Calcd for C20H21NO2
(307.39): C, 78.15; H, 6.89. Found: C, 77.89; H, 6.98.
LRMS calcd for M+ C20H21NO2 307, found 307.
2,5-Diphenyloxazole (11c):[27] Following procedure C,
from bromobenzene (0.471 g, 3 mmol) and oxazole (0.069
g, 2 mmol), product 11c was obtained in 69% yield (0.152
g) as a white solid: mp 78-80 °C. 1H NMR (400 MHz,
CDCl3): 8.12 (d, J = 8.4 Hz, 2H), 7.73 (d, J = 8.4 Hz,
2H), 7.51-7.42 (m, 6H), 7.34 (t, J = 7.8 Hz, 1H). 13C NMR
(100 MHz, CDCl3): 161.3, 151.4, 130.5, 129.1, 129.0,
128.6, 128.2, 127.6, 126.4, 124.4, 123.6. LRMS calcd for
M+ C15H11NO 221, found 221.
2,5-Bis(4-methoxyphenyl)oxazole (13c):[27] Following
procedure C, from 4-bromoanisole (0.561 g, 3 mmol) and
oxazole (0.069 g, 2 mmol), product 13c was obtained in
53% yield (0.149 g) as a white solid: mp 143-145 °C. 1H
NMR (400 MHz, CDCl3): 8.03 (d, J = 8.4 Hz, 2H), 7.63
(d, J = 8.4 Hz, 2H), 7.28 (s, 1H), 6.99 (d, J = 8.4 Hz, 2H),
7.97 (d, J = 8.4 Hz, 2H), 3.87 (s, 3H), 3.85 (s, 3H). 13C
NMR (100 MHz, CDCl3): 161.3, 160.8, 159.8, 150.9,
127.9, 125.7, 121.9, 121.2, 120.6, 114.5, 114.3, 55.5 (2C).
LRMS calcd for M+ C17H15NO3 281, found 281.
4-(2-(4-Fluorophenyl)oxazol-5-yl)benzonitrile
(29):
Following procedure B, from 4-bromofluorobenzene
(0.350 g, 2 mmol) and 4-(oxazol-5-yl)benzonitrile 3a
(0.170 g, 1 mmol), product 29 was obtained in 79% yield
(0.208 g) as a white solid: mp 209-211 °C. 1H NMR (400
MHz, CDCl3): 8.11 (dd, J = 8.6, 5.3 Hz, 2H), 7.79 (d, J =
8.5 Hz, 2H), 7.73 (d, J = 8.5 Hz, 2H), 7.57 (s, 1H), 7.19 (t,
J = 8.6 Hz, 2H). 13C NMR (100 MHz, CDCl3): 164.4 (d,
J = 252.2 Hz), 161.6, 149.4, 132.8, 131.8, 128.7 (d, J = 8.7
Hz), 126.2, 124.3, 123.2 (d, J = 3.3 Hz), 118.5, 116.2 (d, J
= 22.2 Hz), 111.6. Anal. Calcd for C16H9FN2O (264.26):
C, 72.72; H, 3.43. Found: C, 72.89; H, 3.62. LRMS calcd
for M+ C16H9FN2O 264, found 264.
2,5-Di(naphthalen-1-yl)oxazole (21c):[29] Following
procedure C, from 1-bromonaphthalene (0.621 g, 3 mmol)
and oxazole (0.069 g, 2 mmol), product 21c was obtained
4-(2-(4-(tert-Butyl)phenyl)oxazol-5-yl)benzonitrile (30):
Following procedure B, from 1-bromo-4-tert-butylbenzene
(0.426 g, 2 mmol) and 4-(oxazol-5-yl)benzonitrile 3a
(0.170 g, 1 mmol), product 30 was obtained in 77% yield
1
in 81% yield (0.260 g) as a yellow solid: mp 96-98 °C. H
1
NMR (400 MHz, CDCl3): 9.42 (d, J = 8.6 Hz, 1H), 8.44
(d, J = 8.2 Hz, 1H), 8.36 (d, J = 8.0, 1.1 Hz, 1H), 8.00 (d, J
= 8.2 Hz, 1H), 7.96-7.87 (m, 4H), 7.72-7.53 (m, 7H). 13C
NMR (100 MHz, CDCl3): 161.5, 150.3, 134.0, 134.0,
131.3, 130.3, 130.2, 129.6, 128.8, 128.6, 127.9, 127.7,
127.2, 126.8, 126.5, 126.4, 126.3, 126.2, 125.5, 125.4,
125.1, 125.0, 123.9. LRMS calcd for M+ C23H15NO 321,
found 321.
(0.232 g) as a yellow solid: mp 157-159 °C. H NMR (400
MHz, CDCl3): 8.03 (d, J = 8.4 Hz, 2H), 7.79 (d, J = 8.5
Hz, 2H), 7.71 (d, J = 8.5 Hz, 2H), 7.57 (s, 1H), 7.52 (d, J =
8.4 Hz, 2H), 1.37 (s, 9H). 13C NMR (100 MHz, CDCl3):
162.6, 154.5, 149.1, 132.8, 132.0, 126.4, 126.3, 125.9,
124.3, 124.1, 118.6, 111.3, 35.0, 31.2. Anal. Calcd for
C20H18N2O (302.38): C, 79.44; H, 6.00. Found: C, 79.65;
H, 5.82. LRMS calcd for M+ C20H18N2O 302, found 302.
4-(2-(4-Methoxyphenyl)oxazol-5-yl)benzonitrile
(25):
5-([1,1'-Biphenyl]-2-yl)-2-(4-methoxyphenyl)oxazole
(31a): Following procedure A, from 2-bromobiphenyl
Following procedure A, from 4-bromobenzonitrile (0.364
9
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