The Journal of Organic Chemistry
NOTE
1H NMR spectrum, the vinylic proton on the β-carbon of (Z)-isomer
appears upper field than the same proton of the E-isomer.8a
(major): Rf 0.87 (toluene); 1H NMR (500 MHz, CDCl3) δ 7.63
(d, J = 8.0 Hz, 2H), 7.40À7.28 (m, 5H), 7.20 (d, J = 8.0 Hz, 2H),
6.93 (s, 1H), 3.70 (s, 2H), 2.38 (s, 3H); 13C NMR (125 MHz, CDCl3) δ
144.0, 140.5, 136.6, 130.8, 129.5, 128.89, 128.85, 128.7, 127.3, 118.9,
109.4, 42.2, 21.4. This product spectroscopically matched that of the
2-Methyl-3-phenylacrylonitrile (4a). Column chromatography
(Hex/EtOAc = 99/1) yielded 4a (118 mg, 83%, Z/E = 70:30). Z-Isomer
(major): Rf 0.81 (toluene); 1H NMR (300 MHz, CDCl3) δ 7.72À7.68
(m, 2H), 7.44À7.36 (m, 3H), 6.94 (apparent s, 1H), 2.16 (d, J = 1.2 Hz,
3H); 13C NMR (75 MHz, CDCl3) δ 144.0, 133.8, 129.8, 128.8, 128.4,
119.2, 106.1, 22.2. This product spectroscopically matched that of the
1
known compound.8c E-Isomer (minor): Rf 0.80 (toluene); H NMR
(300 MHz, CDCl3) δ 7.38À7.19 (m, 10H), 3.83 (s, 2H), 2.38 (s, 3H);
13C NMR (75 MHz, CDCl3) δ 145.3, 139.9, 136.5, 130.9, 129.5, 129.0,
128.9, 128.3, 127.2, 120.5, 112.9, 35.5, 21.4; HRMS (TOF MS ES+)
calcd for C17H15NNa 256.1102 [M + Na]+, found 256.1096.
1
known compound.8i E-Isomer (minor): Rf 0.76 (toluene); H NMR
(300 MHz, CDCl3) δ 7.46À7.31 (m, 5H), 7.21 (apparent s, 1H), 2.15
(d, J = 1.5 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 144.2, 134.0, 129.27,
129.24, 128.6, 121.2, 109.6, 16.7. This product spectroscopically
matched that of the known compound.15
2-Methyl-3-(4-nitrophenyl)acrylonitrile (4g). Column chro-
matography (Hex/EtOAc = 99/1) yielded 4g (151 mg, 80%, Z/E =
1
81:19). Z-Isomer (major): Rf 0.79 (toluene); H NMR (300 MHz,
CDCl3) δ 8.26 (d, J = 8.7 Hz, 2H), 7.84 (d, J = 8.7 Hz, 2H), 7.01
(apparent s, 1H), 2.23 (d, J = 7.5 Hz, 3H); 13C NMR (75 MHz, CDCl3)
δ 148.1, 141.3, 139.7, 129.2, 124.0, 118.1, 111.1, 22.3. This product
spectroscopically matched that of the known compound.8i E-Isomer
(minor): Rf 0.75 (toluene); 1H NMR (300 MHz, CDCl3) δ 8.28 (d, J =
8.7 Hz, 2H), 7.49 (d, J = 8.7 Hz, 2H), 7.26 (apparent s, 1H), 2.17 (d, J =
1.5 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 147.7, 141.8, 140.0, 130.0,
123.9, 120.1, 113.7, 17.0; HRMS (TOF MS ES+) calcd for C10H8N2O2-
Na 211.0483 [M + Na]+, found 211.0476.
2-Benzylidenebutanenitrile (4b). Column chromatography
(Hex/EtOAc = 99/1) yielded 4b (111 mg, 71%, Z/E = 70:30). Z-
Isomer (major): Rf 0.86 (toluene); 1H NMR (300 MHz, CDCl3) δ
7.74À7.70 (m, 2H), 7.45À7.36 (m, 3H), 6.94 (apparent s, 1H), 2.44
(qd, J = 7.5, 1.2 Hz, 2H), 1.26 (t, J = 7.5 Hz, 3H); 13C NMR (75 MHz,
CDCl3) δ 142.4, 133.8, 129.8, 128.7, 128.5, 118.7, 112.9, 29.6, 13.0;
HRMS (TOF MS ES+) calcd for C11H11NNa 180.0789 [M + Na]+,
found 180.0818. E-Isomer (minor): Rf 0.83 (toluene); 1H NMR (300
MHz, CDCl3) δ 7.44À7.20 (m, 6H), 2.54À2.47 (m, 2H), 1.26 (t, J =
7.5 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 143.6, 134.1, 129.2,
129.1, 128.7, 120.2, 117.2, 22.9, 12.8; HRMS (TOF MS ES+) calcd
for C11H11NNa 180.0789 [M + Na]+, found 180.0787.
3-(4-Methoxyphenyl)-2-(4-methylbenzyl)acrylonitrile
(4h). Column chromatography (toluene) yielded 4h (190 mg, 72%, Z-
1
isomer only). Z-Isomer (major): Rf 0.86 (toluene); H NMR (300
MHz, CDCl3) δ 7.72 (d, J = 8.7 Hz, 2H), 7.18 (s, 4H), 6.92 (d, J = 8.7
Hz, 2H), 6.89 (s, 1H), 3.84 (s, 3H), 3.64 (s, 2H), 2.36 (s, 3H); 13C NMR
(75 MHz, CDCl3) δ 160.9, 143.3, 136.8, 133.7, 130.4, 129.5, 128.7,
126.3, 119.3, 114.1, 107.9, 55.3, 41.7, 21.1. This product spectro-
scopically matched that of the known compound.8f
2-Benzyl-3-phenylacrylonitrile (4c). Column chromatography
(Hex/EtOAc = 99/1) yielded 4c (185 mg, 84%, Z/E = 86:14). Z-Isomer
(major): Rf 0.92 (toluene); 1H NMR (500 MHz, CDCl3) δ 7.75À7.73
(m, 2H), 7.42À7.29 (m, 8H), 6.98 (s, 1H), 3.72 (s, 2H); 13C NMR (125
MHz, CDCl3) δ 144.0, 136.4, 133.5, 130.1, 128.89, 128.87, 128.8, 128.7,
127.3, 118.7, 110.8, 42.2. This product spectroscopically matched that of
the known compound.8d E-Isomer (minor): Rf 0.86 (toluene); 1H
NMR (500 MHz, CDCl3) δ 7.41À7.24 (m, 11H), 3.82 (s, 2H); 13C
NMR (125 MHz, CDCl3) δ 145.2, 136.4, 133.7, 129.5, 129.0, 128.9,
128.8, 128.3, 127.2, 120.2, 114.1, 35.5; HRMS (TOF MS ES+) calcd for
C16H13NNa 242.0946 [M + Na]+, found 242.0941.
2-Benzylidenepent-4-enenitrile (4d). Column chromatogra-
phy (Hex/EtOAc = 99/1) yielded 4d (140 mg, 83%, Z/E = 70:30). Z-
Isomer (major): Rf 0.88 (toluene); 1H NMR (500 MHz, CDCl3) δ 7.73
(apparent d, J = 7.0 Hz, 2H), 7.42À7.40 (m, 3H), 6.96 (s, 1H),
5.93À5.87 (m, 1H), 5.29À5.25 (m, 2H), 3.14 (d, J = 6.5 Hz, 2H);
13C NMR (125 MHz, CDCl3) δ 143.9, 133.6, 132.8, 130.1, 128.8, 128.6,
118.8, 118.6, 109.5, 40.0. This product spectroscopically matched that of
the known compound.16 E-Isomer (minor): Rf 0.84 (toluene); 1H
NMR (500 MHz, CDCl3) δ 7.42À7.30 (m, 6H), 5.97À5.90 (m, 1H),
5.30À5.26 (m, 2H), 3.21 (d, J = 5.5 Hz, 2H); 13C NMR (125 MHz,
CDCl3) δ 145.1, 133.7 132.4, 129.5, 129.0, 128.7, 120.2, 118.2, 113.0,
33.9; HRMS (TOF MS ES+) calcd for C12H11NNa 192.0789 [M +
Na]+, found 192.0786.
2-(4-Methylbenzyl)-3-phenylacrylonitrile (4e). Column
chromatography (Hex/EtOAc = 99/1) yielded 4e (208 mg, 89%,
Z/E = 88:12). Z-Isomer (major): Rf 0.90 (toluene); 1H NMR
(500 MHz, CDCl3) δ 7.73 (apparent d, J = 6.0 Hz, 2H), 7.41À7.39
(m, 3H), 7.18 (s, 4H), 6.95 (s, 1H), 3.67 (s, 2H), 2.36 (s, 3H); 13C
NMR (125 MHz, CDCl3) δ 143.8, 137.0, 133.6, 133.3, 130.0, 129.6,
128.80, 128.77, 128.65, 118.7, 111.1, 41.8, 21.1. This product
spectroscopically matched that of the known compound.8f E-Isomer
(minor): Rf 0.85 (toluene); 1H NMR (300 MHz, CDCl3) δ
7.40À7.36 (m, 6H), 7.15 (s, 4H), 3.78 (s, 2H), 2.35 (s, 3H); 13C
NMR (75 MHz, CDCl3) δ 145.0, 136.9, 133.8, 133.3, 129.6, 129.5,
129.0, 128.8, 128.2, 120.3, 114.3, 35.1, 21.1; HRMS (TOF MS ES+)
calcd for C17H15NNa 256.1102 [M + Na]+, found 256.1097.
2-Benzyl-3-(p-tolyl)acrylonitrile (4f). Column chromatography
(Hex/EtOAc = 99/1) yielded 4f (224 mg, 96%, Z/E = 88:12). Z-Isomer
3-(4-Chlorophenyl)-2-(4-methylbenzyl)acrylonitrile (4i).
Column chromatography (Hex/EtOAc = 99/1) yielded 4i (240 mg,
90%, Z/E = 86:14). Z-Isomer (major): Rf 0.94 (toluene); 1H NMR (500
MHz, CDCl3) δ 7.66 (d, J = 8.5 Hz, 2H), 7.36 (d, J = 8.5 Hz, 2H), 7.18
(s, 4H), 6.89 (s, 1H), 3.67 (s, 2H), 2.36 (s, 3H); 13C NMR (75 MHz,
CDCl3) δ 142.2, 137.0, 135.8, 133.0, 132.0, 129.9, 129.6, 129.0, 128.8,
118.4, 111.7, 41.7, 21.0. This product spectroscopically matched that of
the known compound.8f E-Isomer (minor): Rf 0.89 (toluene); 1H NMR
(300 MHz, CDCl3) δ 7.39À7.10 (m, 9H), 3.75 (s, 2H), 2.35 (s, 3H);
13C NMR (75 MHz, CDCl3) δ 143.6, 137.0, 135.6, 132.9, 132.1, 130.3,
129.7, 129.1, 128.1, 120.1, 114.9, 35.1, 21.1; HRMS (TOF MS ES+)
calcd for C17H14ClNNa 290.0713 [M + Na]+, found 290.0713.
2-(2-Chlorobenzylidene)hexanenitrile (4j). Column chroma-
tography (Hex/EtOAc = 99/1) yielded 4j (168 mg, 72%, Z/E = 85:15).
1
Z-Isomer (major): Rf 0.93 (toluene); H NMR (300 MHz, CDCl3)
δ 7.94À7.90 (m, 1H), 7.44À7.26 (m, 4H), 2.45 (t, J = 7.2 Hz, 2H),
1.71À1.65 (m, 2H), 1.41À1.35 (m, 4H), 0.93 (t, J = 7.2 Hz, 3H); 13C
NMR (75 MHz, CDCl3) δ 139.9, 133.8, 132.3, 130.7, 129.6, 129.2,
127.1, 118.2, 115.1, 35.9, 30.8, 27.7, 22.3, 14.0. This product spectro-
scopically matched that of the known compound.8g E-Isomer (minor):
Rf 0.91 (toluene); 1H NMR (300 MHz, CDCl3) δ 7.46À7.21 (m, 5H),
2.35À2.30 (m, 2H), 1.65À1.60 (m, 2H), 1.29À1.26 (m, 4H), 0.87 (t,
J = 6.9 Hz, 3H); 13C NMR (75 MHz, CDCl3) δ 141.2, 133.9, 132.5,
130.3, 130.0, 129.9, 126.6, 119.7, 118.1, 30.9, 29.3, 27.6, 22.2, 13.9;
HRMS (TOF MS ES+) calcd for C14H16ClNNa 256.0869 [M + Na]+,
found 256.0864.
2-Methyl-5-phenylpent-2-enenitrile (4k). Column chroma-
tography (Hex/EtOAc = 20/1) yielded 4k (149 mg, 87%, Z/E = 11:89).
E-Isomer (major): Rf 0.81 (toluene); 1H NMR (300 MHz, CDCl3) δ
7.31À7.12 (m, 5H), 6.32 (dt, J = 7.5, 0.8 Hz, 1H), 2.71 (t, J = 7.5 Hz,
2H), 2.45 (dt, J = 7.5, 7.5 Hz, 2H), 1.72 (d, 0.8 Hz, 3H); 13C NMR (75
MHz, CDCl3) δ 146.9, 140.1, 128.4, 128.2, 126.2, 120.4, 109.8, 34.0,
30.1, 14.6; HRMS (TOF MS ES+) calcd for C12H13NNa 194.0946 [M +
Na]+, found 194.0940. Z-Isomer (minor): Rf 0.85 (toluene); 1H NMR
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dx.doi.org/10.1021/jo201280x |J. Org. Chem. 2011, 76, 8053–8058