The Journal of Organic Chemistry
Article
HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C14H16BrNNa
300.0358; found 300.0309.
as the eluent) to give pure product P52 as a colorless oil (0.981 g,
80%). H NMR (400 MHz, CDCl3): δ 6.88−6.74 (m, 3H), 3.89 (s,
3H), 3.87 (s, 3H), 3.63 (d, J = 7 Hz, 1H), 2.37−2.22 (m, 1H), 1.90−
1.79 (m, 1H), 1.77−1.47 (m, 6H), 1.40−1.28 (m, 1H). 13C{1H}
NMR (101 MHz, CDCl3): δ 149.3, 148.8, 128.4, 120.9, 120.0, 111.4,
110.7, 45.4, 42.2, 31.0, 30.4, 25.0, 25.0.
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2-Cyclohexyl-2-(3-chlorophenyl)acetonitrile (P81).27 The crude
product was purified by column chromatography (silica as the
stationary phase and a mixture of hexanes and Et2O (9.8:0.2) as the
1
eluent) to give pure product P81 as a white solid (0.793 g, 68%). H
2-Cyclopentyl-2-(4-chlorophenyl)acetonitrile (P62).29 The crude
product was purified by column chromatography (silica as the
stationary phase and a mixture of hexanes and Et2O (9.8:0.2) as the
eluent) to give pure product P62 as a colorless oil (0.714 g, 65%). 1H
NMR (400 MHz, CDCl3): δ 7.38−7.31 (m, 2H), 7.30−7.22 (m, 2H),
3.70 (d, J = 7 Hz, 1H), 2.36−2.21 (m, 1H), 1.89−1.78 (m, 1H),
1.77−1.48 (m, 6H), 1.38−1.25 (m, 1H). 13C{1H} NMR (101 MHz,
CDCl3): δ 134.5, 134.0, 129.2, 129.1, 120.2, 45.3, 42.0, 31.0, 30.3,
25.0, 24.9.
2-Cyclopentyl-2-(3,4-methylenedioxyphenyl)acetonitrile (P102).
The crude product was purified by column chromatography (silica
as the stationary phase and a mixture of hexanes and ethylacetate
(9.8:0.2) as the eluent) to give pure product P102 as a colorless oil
(0.858 g, 75%). 1H NMR (400 MHz, CDCl3): δ 6.82−6.72 (m, 3H),
5.95 (s, 2H), 3.59 (d, J = 7 Hz, 1H), 2.32−2.18 (m, 1H), 1.90−1.78
(m, 1H), 1.75−1.45 (m, 6H), 1.35−1.22 (m, 1H). 13C{1H} NMR
(101 MHz, CDCl3): δ 148.1, 147.3, 129.6, 121.1, 120.7, 108.5, 108.0,
101.4, 45.3, 42.1, 30.9, 30.3, 24.9, 24.9. HRMS (ESI-TOF) m/z: [M +
Na]+ calcd for C14H15NO2Na 252.0995; found 252.0988.
2-Cycloheptyl-2-phenylacetonitrile (P13). Crude product was
purified by column chromatography (silica as the stationary phase
and a mixture of hexanes and ethylacetate (9.8:0.2) as the eluent) to
give pure product P13 as a colorless oil (0.916 g, 86%). 1H NMR (400
MHz, CDCl3): δ 7.40−7.27 (m, 5H), 3.74 (d, J = 7 Hz, 1H), 2.03−
1.90 (m, 1H), 1.84−1.63 (m, 4H), 1.61−1.35 (m, 8H). 13C{1H}
NMR (101 MHz, CDCl3): δ 135.1, 128.7, 127.9, 127.8, 120.3, 44.6,
44.4, 33.1, 30.6, 27.7, 27.7, 26.1, 25.9. HRMS (ESI-TOF) m/z: [M +
Na]+ calcd for C15H19NNa 236.1410; found 236.1414.
NMR (400 MHz, CDCl3): δ 7.27−7.17 (m, 3H), 7.15−7.04 (m, 1H),
3.54 (d, J = 7 Hz, 1H), 1.84−1.48 (m, 6H), 1.28−0.97 (m, 5H).
13C{1H} NMR (101 MHz, CDCl3): δ 136.7, 134.8, 130.1, 128.3,
126.3, 119.6, 44.0, 42.8, 31.3, 29.5, 25.9, 25.8, 25.8.
2-Cyclohexyl-2-(3-trifluromethylphenyl)acetonitrile (P91).27
Compound P91 was synthesized according to the general procedure
C. The crude product was purified by column chromatography (silica
as the stationary phase and a mixture of hexanes and Et2O (9.5:0.5) as
the eluent) to give the pure product as a colorless oil (0.560 g, 42%).
1H NMR (400 MHz, CDCl3): δ 7.71−7.37 (m, 4H), 3.71 (d, J = 7
Hz, 1H), 1.91−1.60 (m, 6H), 1.27−1.05 (m, 5H). 13C{1H} NMR
(101 MHz, CDCl3): δ 135.9, 131.5, 129.5, 125.0, 124.9, 119.5, 44.3,
42.9, 31.3, 29.5, 26.0, 25.8, 25.8.
2-Cyclohexyl-2-(3,4-methylenedioxyphenyl)acetonitrile (P101).
The crude product was purified by column chromatography (silica
as the stationary phase and a mixture of hexanes and Et2O (9.5:0.5) as
the eluent) to give pure product P101 as a colorless oil (0.876 g, 72%).
1H NMR (400 MHz, CDCl3): δ 6.81−6.67 (m, 3H), 5.98 (s, 2H),
3.51 (d, J = 7 Hz, 1H), 1.92−1.56 (m, 6H), 1.28−1.00 (m, 5H).
13C{1H} NMR (101 MHz, CDCl3): δ 148.1, 147.4, 128.4, 121.5,
120.3, 108.4, 108.3, 101.4, 44.0, 42.9, 31.1, 29.8, 26.0, 25.9, 25.9.
HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C15H17NO2Na
266.1157; found 266.1165.
2-Cyclohexyl-2-(2-napthyl)acetonitrile (P111).19a The crude prod-
uct was purified by column chromatography (silica as the stationary
phase and a mixture of hexanes and ethylacetate (9.8:0.2) as the
eluent) to give pure product P111 as a white solid (0.994 g, 80%). 1H
NMR (400 MHz, CDCl3): δ 7.90−7.75 (m, 4H), 7.56−7.46 (m, 2H),
7.41−7.34 (m, 1H), 3.81 (d, J = 7 Hz, 1H), 1.97−1.59 (m, 6H),
1.28−1.00 (m, 5H). 13C{1H} NMR (101 MHz, CDCl3): δ 133.3,
132.9, 132.1, 128.8, 128.0, 127.8, 127.2, 126.8, 126.5, 125.6, 120.3,
44.6, 42.9, 31.5, 29.9, 29.7, 26.1, 26.0, 25.9.
2-Cycloheptyl-2-(3-methylphenyl)acetonitrile (P43). The crude
product was purified by column chromatography (silica as the
stationary phase and a mixture of hexanes and ethylacetate (9.8:0.2)
as the eluent) to give pure product P43 as a colorless oil (0.954 g,
1
84%). H NMR (400 MHz, CDCl3): δ 7.32−7.17 (m, 2H), 7.15−
2-Cyclopentyl-2-phenylacetonitrile (P12).28 The crude product
was purified by column chromatography (silica as the stationary phase
and a mixture of hexanes and ethylacetate (9.0:1.0) as the eluent) to
give pure product P12 as a colorless oil (0.778 g, 84%). 1H NMR (400
MHz, CDCl3): δ 7.40−7.27 (m, 5H), 3.72 (d, J = 7 Hz, 1H), 2.38−
2.24 (m, 1H), 1.91−1.80 (m, 1H), 1.78−1.48 (m, 6H), 1.40−1.29
(m, 1H). 13C{1H} NMR (101 MHz, CDCl3): δ 136.0, 129.0, 128.0,
127.7, 120.6, 45.4, 42.6, 31.1, 30.3, 25.0, 24.9.
2-Cyclopentyl-2-(4-methylphenyl)acetonitrile (P32). The crude
product was purified by column chromatography (silica as the
stationary phase and a mixture of hexanes and Et2O (9.7:0.3) as the
eluent) to give pure product P32 as a colorless oil (0.747 g, 75%). 1H
NMR (400 MHz, CDCl3): δ 7.27−7.11 (m, 4H), 3.67 (d, J = 7 Hz,
1H), 2.39−2.24 (m, 4H), 1.90−1.79 (m, 1H), 1.77−1.47 (m, 6H),
1.40−1.28 (m, 1H). 13C{1H} NMR (101 MHz, CDCl3): δ 137.8,
133.0, 129.7, 127.6, 120.9, 45.4, 42.4, 31.1, 30.4, 25.0, 25.0, 21.2.
HRMS (ESI-TOF) m/z: [M + Na]+ calcd for C14H17NNa 222.1253;
found 222.1250.
7.05 (m, 3H), 3.70 (d, J = 7 Hz, 1H), 2.05−1.88 (m, 1H), 1.86−1.66
(m, 4H), 1.65−1.30 (m, 8H). 13C{1H} NMR (101 MHz, CDCl3): δ
138.6, 135.1, 128.7, 128.6, 125.1, 120.5, 44.7, 44.5, 33.2, 30.7, 27.8,
27.8, 26.2, 26.1, 21.4. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C16H21NNa 250.1566; found 250.1566.
2-Cycloheptyl-2-(3,4-dimethoxyphenyl)acetonitrile (P53). The
crude product was purified by column chromatography (silica as
the stationary phase and a mixture of hexanes and ethylacetate
(7.5:2.5) as the eluent) to give pure product P53 as a colorless oil
(0.930 g, 68%). 1H NMR (400 MHz, CDCl3): δ 6.88−6.75 (m, 3H),
3.89 (s, 3H), 3.87 (s, 3H), 3.64 (d, J = 7 Hz, 1H), 1.97−1.86 (m,
1H), 1.85−1.65 (m, 4H), 1.61−1.34 (m, 8H). 13C{1H} NMR (101
MHz, CDCl3): δ 149.3, 148.8, 127.7, 120.7, 120.5, 111.3, 111.0, 56.1,
56.1, 44.7, 44.5, 33.1, 30.9, 28.0, 27.9, 26.3, 26.3. HRMS (ESI-TOF)
m/z: [M + Na]+ calcd for C17H23NO2Na 296.1621; found 296.1627.
2-Cycloheptyl-2-(4-chlorophenyl)acetonitrile (P63). The crude
product was purified by column chromatography (silica as the
stationary phase and a mixture of hexanes and ethylacetate (9.8:0.2)
as the eluent) to give pure product P63 as a colorless oil (0.867 g,
2-Cyclopentyl-2-(3-methylphenyl)acetonitrile (P42). The crude
product was purified by column chromatography (silica as the
stationary phase and a mixture of hexanes and ethylacetate (9.8:0.2)
as the eluent) to give pure product P42 as a colorless oil (0.727 g,
1
70%). H NMR (400 MHz, CDCl3): δ 7.38−7.31 (m, 2H), 7.28−
7.22 (m, 2H), 3.70 (d, J = 7 Hz, 1H), 1.99−1.87 (m, 1H), 1.81−1.63
(m, 4H), 1.61−1.32 (m, 8H). 13C{1H} NMR (101 MHz, CDCl3): δ
134.1, 133.9, 129.4, 129.3, 120.0, 44.7, 44.4, 33.3, 30.8, 27.9, 27.9,
26.3, 26.1. HRMS (ESI-TOF) m/z: [M + Na]+ calcd for
C15H18ClNNa 270.1020; found 270.1023.
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73%). H NMR (400 MHz, CDCl3): δ 7.25−7.20 (m, 1H), 7.16−
7.07 (m, 3H), 3.67 (d, J = 7 Hz, 1H), 2.43−2.21 (m, 4H), 1.90−1.79
(m, 1H), 1.75−1.48 (m, 6H), 1.40−1.28 (m, 1H). 13C{1H} NMR
(101 MHz, CDCl3): δ 138.8, 135.9, 128.9, 128.4, 124.8, 120.8, 45.4,
42.5, 31.1, 30.4, 25.0, 25.0, 21.5. HRMS (ESI-TOF) m/z: [M + Na]+
calcd for C14H17NNa 222.1253; found 222.1249.
2-Cycloheptyl-2-(3,4-methylenedioxyphenyl)acetonitrile (P103).
The crude product was purified by column chromatography (silica
as the stationary phase and a mixture of hexanes and ethylacetate
(9.0:1.0) as the eluent) to give pure product P103 as a pale-yellow oil
(0.940 g, 73%). 1H NMR (400 MHz, CDCl3): δ 6.80−6.68 (m, 3H),
5.95 (s, 2H), 3.60 (d, J = 7 Hz, 1H), 1.96−1.83 (m, 1H), 1.83−1.61
2-Cyclopentyl-2-(3,4-dimethoxyphenyl)acetonitrile (P52).28 The
crude product was purified by column chromatography (silica as the
stationary phase and a mixture of hexanes and ethylacetate (8.5:1.5)
H
J. Org. Chem. XXXX, XXX, XXX−XXX