8460
Acknowledgements
This work was supported by a grant from the Rhoˆne Poulenc Industrialisation. We also thank
Ghizlaine Baraka and Fabien Bonnette for their participation to this work, respectively, as
Maˆıtrise and Maste`re students.
References
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13. Typical procedure: to a solution of nickel complex Ni(PPh3)3 (0.5 mmol), generated in situ and under nitrogen
from NiBr2(PPh3)3 (0.5 mmol), PPh3 (1 mmol) and Zn (1.5 mmol), in dry tetrahydrofuran, were added the aryl
halide (5 mmol) and the malononitrile anion (5.5 mmol), preliminary prepared from malononitrile (5.5 mmol)
and t-BuOK (11 mmol). The mixture was heated to 60°C with stirring for an appropriate time. After quenching
with dilute hydrochloric acid, the product was extracted with diethylether. Purification by silica gel column
chromatography (ethyl acetate/hexane, 10/90), followed by recrystallization from hexane afforded the corre-
sponding arylmalonitrile. a-(p-Trifluoromethyphenyl)malononitrile: 80% in isolated yield (entry 9); mp=97°C
1
(hexane); H NMR (200.1 MHz, CDCl3) l 5.17 (s, 1H), 7.69 (d, J=8.3 Hz, 2H), 7.81 (d, J=8.3 Hz, 2H); 13C
NMR (50.3 MHz, CDCl3) l 27.9, 111 (CN), 123.3 (q, J=271 Hz, CF3), 127.1 (q, J=3.75 Hz, CꢀCꢀCF3), 127.8,
130.0, 133.0 (q, J=35 Hz, CꢀCF3); IR (KBr) w 2880, 2260, 2255, 1925, 1805, 1690, 1629, 1422, 1335, 1240, 1210,
1170, 1140, 1080, 1025, 930, 860, 800, 772, 670 cm−1; MS (EI, 70 eV): m/z (%)=210 (M+, 30), 190 (13), 183 (9),
159 (14), 141 (100), 114 (9), 87 (7), 75 (15). Anal. calcd for C10H5F3N2: C, 57.14; H, 2.38; N, 13.32. Found: C,
56.90; H, 2.39; N, 13.21. a-(p-Cyanophenyl)malononitrile: isolated yield: 60% (entry 6).
.