2-Allyl-2-[(E)-1-phenylhexa-1,5-dien-3-yl]malononitrile [Table 2,
entry 11]. Pale yellow liquid. nmax/cmÀ1 3082, 3028, 2982,
2957, 2852, 2247, 1642, 1494, 1441, 1417, 989, 970. H NMR
Ethyl 2-allyl-2-cyano-3-(4-(trifluoromethoxy)phenyl)hex-5-
enoate (mixture of two isomers) [Table 2, entry 18]. Colorless
liquid. nmax/cmÀ1 3015, 2983, 2933, 2244, 1742, 1510, 1442,
1
1
(300 MHz, CDCl3) d (ppm): 2.40–2.72 (m, 5H), 5.01–5.12
(m, 2H), 5.28–5.36 (m, 2H), 5.45–5.78 (m, 1H), 5.83–5.94
(m, 1H), 6.48 (d, J = 15.7 Hz, 1H), 7.21–7.33 (m, 6H). 13C
NMR (75 MHz, CDCl3) d (ppm): 36.0, 40.2, 41.9, 49.2, 114.1,
114.8, 118.6, 123.1, 123.3, 126.6 (2C), 128.7, 128.9, 129.0 (2C),
133.4, 135.4, 137.2. Anal Calcd for C18H18N2: C 82.41, H 6.92,
N 10.68%. Found: C 82.26, H 6.74, N 10.76%.
1261, 1225, 1167, 923. H NMR (300 MHz, CDCl3) d (ppm):
0.91 (t, J = 7.0 Hz, 3H), 1.38 (t, J = 7.0 Hz, 3H), 2.41–2.46
(m, 2H), 2.72–2.89 (m, 6H), 3.09–3.18 (m, 2H), 3.88 (q, J =
7.0 Hz, 2H), 4.30 (q, J = 7.0 Hz, 2H), 4.90–5.31 (m, 8H),
5.40–5.51 (m, 2H), 5.77–5.85 (m, 2H), 7.15–7.23 (m, 4H),
7.35–7.43 (m, 4H). 13C NMR (75 MHz, CDCl3) d (ppm):
13.5, 14.1, 34.8, 36.7, 40.6, 41.2, 50.1, 50.6, 54.7, 55.5, 62.4,
62.9, 117.7, 117.8, 117.9 (2C), 118.7, 120.7 (4C), 120.8, 121.0,
121.2, 122.1, 130.3 (4C), 130.4, 130.5, 134.1, 135.7, 136.5,
148.8, 148.9, 167.2, 168.4. Anal Calcd for C19H20F3NO3:
C 62.12, H 5.49, N 3.81%. Found: C 62.32, H 5.27, N 4.29%.
2-Allyl-2-[(E)-1-(2-methoxyphenyl)hexa-1,5-dien-3-yl]malono-
nitrile [Table 2, entry 12]. Pale yellow liquid. nmax/cmÀ1 3007,
2957, 2926, 2872, 2854, 2247, 1601, 1585, 1494, 1454, 1438,
1292, 1262, 1047. 1H NMR (300 MHz, CDCl3) d (ppm):
2.39–2.48 (m, 2H), 2.68–3.03 (m, 3H), 3.82 (s, 3H), 4.96–5.46
(m, 4H), 5.71–5.90 (m, 2H), 6.52 (d, J = 15.8 Hz, 1H),
6.88–6.94 (m, 3H), 7.26–7.31 (m, 2H). 13C NMR (75 MHz,
CDCl3) d (ppm): 36.3, 40.5, 43.1, 51.3, 55.3, 114.2 (2C), 114.7,
115.4, 118.5, 121.2, 123.1, 128.8, 130.2, 133.4, 136.5, 137.4,
160.0. Anal Calcd for C19H20N2O: C 78.05, H 6.89, N 9.58%.
Found: C 77.88, H 6.76, N 9.37%.
Methyl
4,4-dicyano-2-methylene-5-phenylhept-6-enoate
[Scheme 2, 2a]. Colorless liquid. nmax/cmÀ1 2957, 2924, 2872,
2854, 2247, 1726, 1634, 1442, 1303, 1163. 1H NMR (300 MHz,
CDCl3) d (ppm): 2.57 (dd, J1 = 13.9 Hz, J2 = 0.6 Hz, 1H),
2.88–2.96 (m, 3H), 3.14 (dd, J1 = 11.2 Hz, J2 = 4.3 Hz, 1H),
3.77 (s, 3H), 4.94–5.10 (m, 2H), 5.45–5.54 (m, 1H), 5.95
(s, 1H), 6.52 (s, 1H), 7.33–7.41 (m, 5H). 13C NMR (75 MHz,
CDCl3) d (ppm): 36.2, 37.1, 43.6, 52.4, 52.5, 114.2, 115.1,
118.6, 129.1 (2C), 129.2 (3C), 131.9, 133.0, 133.4, 135.0, 166.1.
HRMS Calcd for C18H18N2O2 [M + Na]+: 317.1266. Found:
317.1261.
2-Allyl-2-(1-cyclohexylbut-3-enyl)malononitrile [Table 2,
entry 14]. Colorless liquid. nmax/cmÀ1 2933, 2856, 2245, 1657,
1543, 1485, 1344, 1261, 989, 933. 1H NMR (300 MHz, CDCl3)
d (ppm): 1.25–1.35 (m, 2H), 1.62–1.93 (m, 8H), 2.15 (broad,
2H), 2.47–2.48 (m, 2H), 2.79 (d, J = 7.1 Hz, 2H), 5.05–5.23
(m, 2H), 5.36–5.45 (m, 2H), 5.87–5.93 (m, 2H). 13C NMR
(75 MHz, CDCl3) d (ppm): 25.8, 26.3, 28.2, 30.7, 32.6, 36.9,
40.8, 41.1, 43.1, 48.4, 112.2, 115.3, 117.8, 123.1, 128.8, 136.5.
Anal Calcd for C16H22N2: C 79.29, H 9.15, N 11.56%. Found:
C 79.01, H 8.99, N 11.38%.
Methyl 4,4-dicyano-2-methylene-5-(thiophen-2-yl)-oct-7-enoate
[Scheme 2, 2b]. Colorless liquid. nmax/cmÀ1 3080, 3003, 2953,
2850, 2247, 1724, 1634, 1441, 1305, 1163. 1H NMR (300 MHz,
CDCl3) d (ppm): 2.72 (d, J = 14.0 Hz, 1H), 2.77–3.01 (m, 3H),
3.48 (dd, J1 = 11.6 Hz, J2 = 3.5 Hz, 1H), 3.79 (s, 3H),
5.02–5.16 (m, 2H), 5.52–5.62 (m, 1H), 5.99 (s, 1H), 6.55
(s, 1H), 7.06 (dd, J1 = 5.1 Hz, J2 = 3.6 Hz, 1H), 7.12–7.14
(m, 1H), 7.34 (d, J = 5.1 Hz, 1H). 13C NMR (75 MHz,
CDCl3) d (ppm): 36.8, 37.9, 43.9, 48.1, 52.5, 113.9, 114.7,
118.9, 126.3, 127.4, 127.9, 131.9, 132.9 (2C), 137.2, 166.0.
HRMS Calcd for C16H16N2O2S [M + Na]+: 323.0830.
Found: 323.0830.
2-Allyl-2-(2-methylpent-4-en-2-yl)malononitrile [Table 2,
entry 15]. Colorless liquid. nmax/cmÀ1 2974, 2936, 2918, 2245,
1663, 1465, 1440, 1390, 1379, 1207, 991, 937. 1H NMR
(500 MHz, CDCl3) d (ppm): 1.21 (s, 6H), 2.32 (d, J = 12.2
Hz, 2H), 2.61 (d, J = 12.3 Hz, 2H), 5.15–5.23 (m, 2H),
5.39–5.45 (m, 2H), 5.45–5.79 (m, 1H), 5.94–5.97 (m, 1H).
13C NMR (125 MHz, CDCl3) d (ppm): 22.5 (2C), 36.5, 40.8,
42.3, 49.1, 114.7 (2C), 120.2, 122.7, 129.7, 131.9. Anal Calcd
for C12H16N2: C 76.55, H 8.57, N 14.88%. Found: C 76.35,
H 8.41, N 14.68%.
Methyl
4,4-dicyano-2-methylene-5-styrylhept-6-enoate
[Scheme 2, 2c]. Pale yellow liquid. nmax/cmÀ1 3082, 3028,
3005, 2982, 2912, 2247, 1726, 1631, 1442, 1305, 1163, 970.
1H NMR (300 MHz, CDCl3) d (ppm): 2.38–2.55 (m, 1H),
2.74–2.81 (m, 2H), 2.95–3.09 (m, 2H), 3.80 (s, 3H), 5.13–5.23
(m, 2H), 5.71–5.76 (m, 1H), 5.97–6.06 (m, 1H), 6.60 (s, 1H),
6.63 (d, J = 15.5 Hz, 1H), 7.34–7.46 (m, 6H). 13C NMR
(75 MHz, CDCl3) d (ppm): 36.0, 36.9, 42.6, 50.6, 52.5, 113.9,
114.6, 118.7, 123.4, 126.8 (2C), 128.5, 129.0 (2C), 131.9, 133.0,
133.4, 135.5, 137.6, 166.1. HRMS Calcd for C20H20N2O2
[M + Na]+: 343.1422. Found: 343.1421.
Ethyl 2-allyl-2-cyano-3-p-tolylhex-5-enoate (mixture of two
isomers) [Table 2, entry 17]. Colorless liquid. nmax/cmÀ1 3007,
2982, 2926, 2243, 1742, 1641, 1443, 1298, 1225, 1145, 993. H
1
NMR (300 MHz, CDCl3) d (ppm): 0.94 (t, J = 7.1 Hz, 3H),
1.33 (t, J = 7.1Hz, 3H), 2.29 (s, 3H), 2.33 (s, 3H), 2.37–2.44
(m, 2H), 2.70–2.83 (m, 6H), 3.02–3.17 (m, 2H), 3.88 (q, J =
7.1 Hz, 2H), 4.29 (q, J = 7.1 Hz, 2H), 4.86–5.28 (m, 8H),
5.43–5.49 (m, 2H), 5.76–5.82 (m, 2H), 7.07–7.26 (m, 8H). 13C
NMR (75 MHz, CDCl3) d (ppm): 13.6, 14.2, 21.0, 21.1, 34.8,
36.7, 40.5, 41.2, 50.5, 50.9, 55.0, 55.8, 62.2, 62.8, 117.4, 118.0,
118.2, 120.4, 120.9, 128.8 (4C), 129.1 (4C), 129.4, 130.7, 130.8,
133.9, 134.5, 134.7, 134.8, 137.5, 137.9, 167.4, 168.7. Anal
Calcd for C19H23NO2: C 76.73, H 7.80, N 4.71%. Found:
C 76.55, H 7.63, N 4.67%.
Methyl
[Scheme 2, 3a]. White crystalline solid. mp 100–102 1C;
max/cmÀ1 3032, 2953, 2850, 2251, 1715, 1659, 1456, 1437,
5,5-dicyano-4-phenylcyclohex-1-enecarboxylate
n
1278, 1261, 1236, 1105, 1078. 1H NMR (500 MHz, CDCl3)
d (ppm): 2.70–2.75 (m, 1H), 2.86–2.92 (m, 1H), 2.97–3.02
(m, 1H), 3.18–3.28 (m, 1H), 3.27 (d, J = 18 Hz, 1H), 3.75
(s, 3H), 7.17–7.19 (m, 1H), 7.35–7.37 (m, 5H). 13C NMR
(125 MHz, CDCl3) d (ppm): 29.3, 34.8, 37.2, 45.3, 52.3,
c
This journal is The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2011
New J. Chem., 2011, 35, 430–437 435