10316
N. V. Lukashev et al. / Tetrahedron 57 (2001) 10309±10317
3
818H, d, JPH11.5 Hz; PCMe3); 1.01 86H, t, J7.0 Hz,
N, 12.09. C15H20N2 requires C, 78.90; H, 8.83; N, 12.27%],
Rf 8benzene) 0.35; nmax8luqiud ®lm) 2850±2830 8br), 2190,
1625, 1600.
2
CH2CH3); dC 8100.6 MHz, CDCl3): 132.7 8d, JPC
3
3
44.3 Hz, Cv), 114.4 8d, JPC3.2 Hz, JCH13.4 Hz,
1
1
CN), 102.8 8d, JPC16.8 Hz, JCH152.0 Hz, HCv),
1
1.2.2. (E)-2-(Diethylamino)-3-(4-methylphenyl)-2-butene-
nitrile (E-10a). dH 8400 MHz, CDCl3): 7.35 82H, m, CHAr),
7.13 82H, m, CHAr), 2.64 84H, q, J7.2 Hz, NCH2), 2.33
83H, s, MeAr); 2.32 83H, s, CH3Cv); 0.93 86H, t, J7.2 Hz,
CH2CH3); dC 8100.6 MHz, CDCl3): 146.5 8ArCv), 138.0
8MeCAr), 135.7 8CArCv), 128.6 8CHAr), 127.9 8CHAr),
119.7 8NCv), 115.1 8CN), 48.1 8NCH2), 21.9 8CH3Cv),
21.2 8MeAr), 12.9 8CH2CH3).
44.5 8NCH2), 31.8 8d, JPC17.6 Hz, PCMe3), 29.3 8d,
2JPC13.7 Hz, PCMe3), 12.4 8CH2CH3); dP 8161.9 MHz,
CDCl3): 15.9.
1.1.22. (Z)-3-[Di(tert-butyl)phosphino]-2-(diethylamino)-
2-propenenitrile (Z-7b). dH 8400 MHz, CDCl3): 5.16 81H,
2
5
d, JPH4.9 Hz, HCv), 3.34 84H, dq, J6.9 Hz, JPH
3
2.4 Hz, NCH2), 1.11 818H, d, JPH11.6 Hz; PCMe3), 1.09
86H, t, J6.9 Hz, CH2CH3); dC 8100.6 MHz, CDCl3): 130.3
2
3
3
1.2.3. (Z)-2-(Diethylamino)-3-(4-methylphenyl)-2-butene-
nitrile (Z-10a). dH 8400 MHz, CDCl3): 7.28 82H, m, CHAr),
7.18 82H, m, CHAr), 2.74 84H, q, J7.2 Hz, NCH2), 2.35
83H, s, MeAr), 2.23 83H, s, CH3Cv), 1.05 86H, t, J7.2 Hz,
CH2CH3). dC 8100.6 MHz, CDCl3): 153.2 8ArCv), 138.9
8MeCAr), 136.0 8CArCv), 129.1 8CHAr), 127.5 8CHAr),
119.0 8NCv), 114.7 8CN), 48.8 8NCH2), 21.2 8MeAr),
19.9 8CH3Cv); 13.1 8CH2CH3).
8d, JPC20.8 Hz, Cv), 117.0 8d, JPC9.1 Hz, JCH
1
1
7.3 Hz, CN), 108.9 8d, JPC27.5 Hz, JCH151.9 Hz,
4
1
HCv), 45.9 8d, JPC12.1 Hz, NCH2), 32.5 8d, JPC
2
18.3 Hz, PCMe3), 29.1 8d, JPC15.2 Hz, PCMe3), 12.9 8d,
5JPC3.0 Hz, CH2CH3); dP 8161.9 MHz, CDCl3): 6.1.
1.1.23. O,O-Diethyl 2-cyano-2-(diethylamino)ethenyl-
phosphonate (9). A colourless oil 80.198 g, 76%);
[Found: C, 51.13; H, 7.98; P, 12.32. C11H21N2O3P requires
1.2.4. 2-(Diethylamino)-3-(4-methoxyphenyl)-2-butene-
nitrile (10b). Mixture of Z/E isomers with 60:40 ratio; a
colourless oil 80.055 g, 76%); [Found: C, 74.10; H, 8.34;
N, 11.02. C15H20N2O requires C, 73.74; H, 8.25; N,
11.47%]; Rf 0.27 8benzene); nmax8liquid ®lm) 2960±2850
8br), 2190, 1625, 1605.
C, 50.76; H, 8.13; P, 11.90%]; nmax8liquid ®lm) 2970±2850
.
8br), 2275, 1565 cm21
1.1.24. O,O-Diethyl (E)-2-cyano-2-(diethylamino)ethenyl-
phosphonate (E-9). dH 8400 MHz, CDCl3): 4.54 81H, d,
3
2JPH5.6 Hz, HCv), 4.11 84H, dq, J7.1 Hz, JPH
1.5 Hz, POCH2), 3.34 84H, q, J7.2 Hz, NCH2), 1.34 86H,
1.2.5.
(E)-2-(Diethylamino)-3-(4-methoxyphenyl)-2-
t, J7.1 Hz, OCH2CH3), 1.17 86H, t, J7.2 Hz, NCH2CH3);
2
butenenitrile (E-10b). dH 8400 MHz, CDCl3): 7.52 82H,
m, CHAr), 6.85 82H, m, CHAr), 3.80 83H, s, OCH3), 2.66
84H, q, J7.2 Hz, NCH2), 2.33 83H, s, CH3Cv), 0.94
86H, t, J7.2 Hz, CH2CH3); dC 8100.6 MHz, CDCl3):
159.4 8MeOCAr), 145.8 8ArCv), 130.7 8CArCv), 129.7
8CHAr), 119.1 8NCv), 115.3 8CN), 113.2 8CHAr), 55.2
8MeOAr), 48.1 8NCH2), 21.7 8CH3Cv), 12.8 8CH2CH3).
dC 8100.6 MHz, CDCl3): 132.3 8d, JPC12.2 Hz, Cv),
3
3
1
111.8 8d, JPC8.5 Hz, JCH12.9 Hz, CN), 87.1 8d, JPC
1
2
212.1 Hz, JCH155.9 Hz, HCv), 61.9 8d, JPC6.1 Hz,
3
OCH2), 45.3 8NCH2), 15.9 8d, JPC7.6 Hz, OCH2CH3),
12.2 8NCH2CH3); dP 8161.9 MHz, CDCl3): 16.2.
1.1.25. O,O-Diethyl (Z)-2-cyano-2-(diethylamino)ethenyl-
phosphonate (Z-9). dH 8400 MHz, CDCl3): 4.50 81H, d,
3
2JPH2.3 Hz, HCv), 4.08 84H, dq, J7.0 Hz, JPH
1.2.6. (Z)-2-(Diethylamino)-3-(4-methoxyphenyl)-2-butene-
nitrile (Z-10b). dH 8400 MHz, CDCl3): 7.36 82H, m, CHAr),
6.90 82H, m, CHAr), 3.81 83H, s, OCH3); 2.73 84H, q,
J7.3 Hz, NCH2), 2.23 83H, s, CH3Cv), 1.04 86H, t, J
7.3 Hz, CH2CH3); dC 8100.6 MHz, CDCl3): 160.1
8MeOCAr), 152.8 8ArCv), 131.1 8CArCv), 129.0 8CHAr),
118.5 8NCv), 114.9 8CN), 113.8 8CHAr), 55.3 8MeOAr),
48.8 8NCH2), 19.9 8CH3Cv), 13.1 8CH2CH3).
1.4 Hz, OCH2), 3.58 84H, q, J7.1 Hz, NCH2), 1.35 86H,
t, J7.0 Hz, OCH2CH3), 1.24 86H, t, J7.1 Hz, NCH2CH3);
2
dC 8100.6 MHz, CDCl3): 132.7 8d, JPC9.2 Hz, Cv),
3
3
1
115.0 8d, JPC27.5 Hz, JCH8.4 Hz, CN), 86.7 8d, JPC
1
2
206.0 Hz, JCH156.9 Hz, HCv), 61.8 8d, JPC6.1 Hz,
3
OCH2), 45.6 8NCH2), 15.6 8d, JPC7.6 Hz, OCH2CH3),
13.0 8NCH2CH3); dP 8161.9 MHz, CDCl3): 13.5.
1.2. Suzuki coupling of 3-bromo-2-(diethylamino)-2-
butenenitrile with arylboronic acidsÐgeneral
procedure
Acknowledgements
We are grateful to INTAS 99-01541 and Russian Founda-
tion for Basic Research 8N 98-03-32975 and 01-03-33144)
for ®nancial support.
In a ¯ask equipped with re¯ux condenser and gas inlet
0.3 mmol of 5a, 0.33 mmol of arylboronic acid, 0.9 mmol
K2CO3 were dissolved in 3 mL of THF and 1 mL of water
under atmosphere of Ar. 12.0 mmol Pd8PPh3)4 84 mol%)
was added and the solution was stirred at re¯ux for 24 h.
Solvents were evaporated in vacuum and the residue was
puri®ed by column chromatography on silica with benzene
as eluent.
References
1. De Kimpe, N.; Verhe, R.; De Buyck, L.; Schamp, N. Chem.
Ber. 1983, 116, 3846±3857 and references cited therein.
2. 8a) Lukashev, N. V.; Zhichkin, P. E.; Kazankova, M. A.;
Beletskaya, I. P. Tetrahedron Lett. 1993, 34, 1331±1334.
8b) Beletskaya, I. P.; Kazankova, M. A. Polyhedron 2000,
19, 597±598.
1.2.1.
2-(Diethylamino)-3-(4-methylphenyl)-2-butene-
nitrile (10a). Mixture of Z/E isomers with 61:39 ratio; a
colourless oil 80.054 g, 78%); [Found: C, 78.67; H, 9.10;
3. 8a) Jackson, W. R.; Lovel, C. G. Aust. J. Chem. 1983, 36,