H. Doucet, M. Santelli et al.
(0.01 mmol) afforded 32a and 32b, after evaporation of the solvent 21.3, 14.1 ppm. C12H13NO (187.24): calcd. C 76.98, H 7.00; found
FULL PAPER
and filtration of the crude material through silica gel, as a 27:73
mixture of isomers (as determined by H NMR of the crude mix-
C 77.07, H 6.87.
1
(Z)-3-Ethoxy-3-(2-fluorophenyl)acrylonitrile (36a) and (E)-3-
Ethoxy-3-(2-fluorophenyl)acrylonitrile (36b, Table 4, Entry 9): The
reaction of 1-bromo-2-fluorobenzene (0.175 g, 1 mmol), 3-ethoxy-
acrylonitrile (0.194 g, 2 mmol) and NaHCO3 (0.168 g, 2 mmol)
with the palladium complex (0.01 mmol) afforded 36a and 36b, af-
ter evaporation of the solvent and filtration of the crude material
through silica gel, as a 26:74 mixture of isomers (as determined by
1H NMR of the crude mixture) in 78% (0.149 g) isolated yield (36b
was a white solid with a m.p. = 180 °C). These isomers were sepa-
rated by chromatography on silica gel. (Z)-36a: 1H NMR
(300 MHz, CDCl3): δ = 7.45 (t, J = 7.5 Hz, 1 H), 7.40 (t, J =
7.5 Hz, 1 H), 7.19 (t, J = 7.5 Hz, 1 H), 7.12 (m, 1 H), 4.95 (s, 1 H),
4.34 (q, J = 7.0 Hz, 2 H), 1.40 (t, J = 7.0 Hz, 3 H) ppm. (E)-36b:
1H NMR (300 MHz, CDCl3): δ = 7.50 (t, J = 7.5 Hz, 1 H), 7.43
(t, J = 7.5 Hz, 1 H), 7.19 (t, J = 7.5 Hz, 1 H), 7.13 (m, 1 H), 4.75
(s, 1 H), 4.00 (q, J = 7.0 Hz, 2 H), 1.43 (t, J = 7.0 Hz, 3 H) ppm.
13C NMR (75 MHz, CDCl3): δ = 169.8, 159.8 (d, J = 248.5 Hz),
132.4 (d, J = 8.6 Hz), 130.4 (d, J = 2.3 Hz), 124.1 (d, J = 3.4 Hz),
121.8 (d, J = 12.0 Hz), 117.5, 116.3 (d, J = 21.3 Hz), 74.0, 65.9,
14.0 ppm. C11H10FNO (191.20): calcd. C 69.10, H 5.27; found C
69.02, H 5.31.
ture) in 84% (0.213 g) isolated yield (32b was a white solid with a
m.p. of 105 °C). These isomers were separated by chromatography
on silica gel. (Z)-32a: H NMR (300 MHz, CDCl3): δ = 7.99 (s, 1
1
H), 7.85 (m, 2 H), 7.53 (dd, J = 8.1 and 1.9 Hz, 1 H), 7.20–7.10
(m, 2 H), 5.05 (s, 1 H), 4.59 (q, J = 7.0 Hz, 2 H), 3.94 (s, 3 H), 1.49
1
(t, J = 7.0 Hz, 3 H) ppm. (E)-32b: H NMR (300 MHz, CDCl3): δ
= 8.23 (s, 1 H), 7.85–7.75 (m, 3 H), 7.20–7.10 (m, 2 H), 4.64 (s, 1
H), 4.01 (q, J = 7.0 Hz, 2 H), 3.92 (s, 3 H), 1.48 (t, J = 7.0 Hz, 3
H) ppm. 13C NMR (75 MHz, CDCl3): δ = 172.6, 159.0, 135.9,
130.4, 128.2, 127.9, 126.8, 124.9, 123.7, 119.5, 119.1, 105.5, 69.4,
65.5, 55.3, 14.2 ppm. C16H15NO2 (253.30): calcd. C 75.87, H 5.97;
found C 75.84, H 6.07.
(Z)-3-Ethoxy-3-phenylacrylonitrile (33a) and (E)-3-Ethoxy-3-phen-
ylacrylonitrile (33b, Table 4, Entry 5): The reaction of iodobenzene
(0.204 g, 1 mmol), 3-ethoxyacrylonitrile (0.194 g, 2 mmol) and
NaHCO3 (0.168 g, 2 mmol) with the palladium complex
(0.01 mmol) afforded 33a and 33b, after evaporation of the solvent
and filtration of the crude material through silica gel, as a 40:60
1
mixture of isomers (as determined by H NMR of the crude mix-
ture) in 80% (0.139 g) isolated yield as an oil. These isomers were
separated by chromatography on silica gel. (Z)-33a: 1H NMR
(300 MHz, CDCl3): δ = 7.58–7.30 (m, 5 H), 4.94 (s, 1 H), 4.54 (q,
J = 7.0 Hz, 2 H), 1.45 (t, J = 7.0 Hz, 3 H) ppm. (E)-33b: 1H NMR
(300 MHz, CDCl3): δ = 7.75 (d, J = 8.2 Hz, 2 H), (m, 3 H), 4.60
(s, 1 H), 3.99 (q, J = 7.0 Hz, 2 H), 1.46 (t, J = 7.0 Hz, 3 H) ppm.
These compounds were characterized by hydrolysis into the corre-
sponding ketone 33c.
(Z)-3-Ethoxy-3-(naphthalen-1-yl)acrylonitrile (37a) and (E)-3-
Ethoxy-3-(naphthalen-1-yl)acrylonitrile (37b, Table 4, Entry 10):
The reaction of 1-bromonaphthalene (0.207 g, 1 mmol), 3-ethoxy-
acrylonitrile (0.194 g, 2 mmol) and NaHCO3 (0.168 g, 2 mmol)
with the palladium complex (0.01 mmol) afforded 37a and 37b, af-
ter evaporation of the solvent and filtration of the crude material
through silica gel, as a 75:25 mixture of isomers (as determined by
1H NMR of the crude mixture) in 81% (0.181 g) isolated yield as
an oil. These isomers were separated by chromatography on silica
gel. (Z)-37a: 1H NMR (300 MHz, CDCl3): δ = 7.92 (d, J = 8.3 Hz,
1 H), 7.85 (m, 2 H), 7.64 (d, J = 7.0 Hz, 1 H), 7.60–7.47 (m, 3 H),
4.90 (s, 1 H), 4.07 (q, J = 7.0 Hz, 2 H), 1.43 (t, J = 7.0 Hz, 3 H)
ppm. 13C NMR (75 MHz, CDCl3): δ = 174.0, 133.6, 131.0, 130.9,
130.4, 128.5, 127.7, 126.9, 126.3, 124.9, 124.6, 117.8, 74.2, 65.8,
14.1 ppm. C15H13NO (223.27): calcd. C 80.69, H 5.87; found C
80.48, H 5.97. (E)-37b: 1H NMR (300 MHz, CDCl3): δ = 8.00–7.85
(m, 3 H), 7.62–7.45 (m, 4 H), 4.71 (s, 1 H), 3.93 (q, J = 7.0 Hz, 2
H), 1.25 (t, J = 7.0 Hz, 3 H) ppm.
(Z)-3-Ethoxy-3-(4-methoxyphenyl)acrylonitrile (34a) and (E)-3-
Ethoxy-3-(4-methoxyphenyl)acrylonitrile (34b, Table 4, Entry 7):
The reaction of 4-bromoanisole (0.187 g, 1 mmol), 3-ethoxyacry-
lonitrile (0.194 g, 2 mmol) and NaHCO3 (0.168 g, 2 mmol) with
the palladium complex (0.01 mmol) afforded 34a and 34b, after
evaporation of the solvent and filtration of the crude material
through silica gel, as a 24:76 mixture of isomers (as determined by
1H NMR of the crude mixture) in 85% (0.173 g) isolated yield as
an oil. These isomers were separated by chromatography on silica
1
gel. (Z)-34a: H NMR (300 MHz, CDCl3): δ = 7.48 (J = 8.5 Hz, 2
H), 6.88 (d, J = 8.5 Hz, 2 H), 4.86 (s, 1 H), 4.53 (q, J = 7.0 Hz, 2
H), 3.84 (s, 3 H), 1.44 (t, J = 7.0 Hz, 3 H) ppm. (E)-34b: 1H NMR
(300 MHz, CDCl3): δ = 7.75 (J = 8.5 Hz, 2 H), 6.93 (d, J = 8.5 Hz,
2 H), 4.52 (s, 1 H), 3.98 (q, J = 7.0 Hz, 2 H), 3.84 (s, 3 H), 1.45 (t,
J = 7.0 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ = 172.2,
161.7, 129.6, 125.5, 119.2, 113.7, 68.4, 65.3, 55.4, 14.1 ppm.
C12H13NO2 (203.24): calcd. C 70.92, H 6.45; found C 71.10, H
6.45.
(Z)-3-Ethoxy-3-(o-tolyl)acrylonitrile (38a) and (E)-3-Ethoxy-3-(o-
tolyl)acrylonitrile (38b, Table 4, Entry 11): The reaction of 2-bro-
motoluene (0.171 g, 1 mmol), 3-ethoxyacrylonitrile (0.194 g,
2 mmol) and NaHCO3 (0.168 g, 2 mmol) with the palladium com-
plex (0.01 mmol) afforded 38a and 38b, after evaporation of the
solvent and filtration of the crude material through silica gel, as a
1
77:23 mixture of isomers (as determined by H NMR of the crude
mixture) in 77% (0.144 g) isolated yield (38b was a white solid with
a m.p. 149 °C). These isomers were separated by chromatography
on silica gel. (Z)-38a: H NMR (300 MHz, CDCl3): δ = 7.40–7.20
(Z)-3-Ethoxy-3-(m-tolyl)acrylonitrile (35a) and (E)-3-Ethoxy-3-(m-
tolyl)acrylonitrile (35b, Table 4, Entry 8): The reaction of 3-bromo-
toluene (0.171 g, 1 mmol), 3-ethoxyacrylonitrile (0.194 g, 2 mmol)
and NaHCO3 (0.168 g, 2 mmol) with the palladium complex
(0.01 mmol) afforded 35a and 35b, after evaporation of the solvent
and filtration of the crude material through silica gel, as an 11:89
1
(m, 4 H), 4.70 (s, 1 H), 3.98 (q, J = 7.0 Hz, 2 H), 2.34 (s, 3 H),
1.43 (t, J = 7.0 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ =
174.8, 136.2, 133.3, 130.6, 130.3, 129.0, 125.8, 117.9, 72.8, 65.5,
19.3, 14.0 ppm. C12H13NO (187.24): calcd. C 76.98, H 7.00; found
1
mixture of isomers (as determined by H NMR of the crude mix-
1
C 76.81, H 6.82. (E)-38b was not isolated in pure form: H NMR
ture) in 81% (0.152 g) isolated yield as an oil. These isomers were
(300 MHz, CDCl3): δ = 4.51 (s, 1 H) ppm.
separated by chromatography on silica gel. (Z)-35a: 1H NMR
(300 MHz, CDCl3): δ = 4.90 (s, 1 H) ppm. (E)-35b: 1H NMR (Z)-3-Ethoxy-3-(2,4,6-trimethylphenyl)acrylonitrile (39a) and (E)-3-
(300 MHz, CDCl3): δ = 7.56 (m, 2 H), 7.32 (t, J = 7.3 Hz, 1 H), Ethoxy-3-(2,4,6-trimethylphenyl)acrylonitrile (39b, Table 4, Entry
7.28 (m, 1 H), 4.58 (s, 1 H), 3.98 (q, J = 7.0 Hz, 2 H), 2.39 (s, 3
H), 1.45 (t, J = 7.0 Hz, 3 H) ppm. 13C NMR (75 MHz, CDCl3): δ
= 172.8, 138.1, 133.1, 131.7, 128.4, 128.3, 125.1, 118.8, 69.8, 65.4,
12): The reaction of 1-bromo-2,4,6-trimethylbenzene (0.195 g,
1 mmol), 3-ethoxyacrylonitrile (0.194 g, 2 mmol) and NaHCO3
(0.168 g, 2 mmol) with the palladium complex (0.01 mmol) af-
3130
www.eurjoc.org
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2007, 3122–3132