Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

Chapitre VI
(s, p-C of OC-Ph), 131.8 (s, p-C of P-Ph), 133.6 (d, 3 JPC = 8.9 Hz, m-C of P-Ph), 142.0 (d,
3 JPC = 14.0 Hz, ipso-C of OC-Ph), 184.4 (s, CO); 31 P{ 1 H} NMR (CDCl3, 121.5 MHz): δ 30.9.
Synthesis of (benzoylmethylene)phenyldi(n-butyl)phosphorane 9
4.300 g (21.60 mmol) of α-bromoacetophenone were added to a solution of 4.800 g
(21.60 mmol) of phenyldi(n-butyl)phosphine in 30 mL of toluene and stirred for 24 h at room
temperature. The solvent was then removed with a canula and the phosphonium salt was
washed with toluene (40 mL) and dried under vacuum (the phosphonium salt has not been
characterized by 31 P NMR or 1 H NMR). The dried salt was dissolved in a mixture of 100 mL
of distilled water and 50 mL of MeOH and an aqueous solution of NaOH (2.0 M) was added
to the solution until pH 8 was reached. The solution became cloudy and 9 settled overnight as
a red oil, it was washed with water and dried under vacuum overnight. Yield: 6.900 g, 94 %.
1 H NMR (300 MHz, CDCl3): δ 0.87 (6H, t, 3 JHH = 6.9 Hz, CH3), 1.43 (8H, m, CH2-CH2), 1.32
(4H, m, P-CH2), 3.99 (1H, d, 2 JPH = 22.6 Hz), 7.36 (2H, m, aromatic H), 7.49-7.55 (3H, m,
aromatic H), 7.70-7.77 (3H, m, aromatic H), 7.91-7.95 (2H, m, aromatic H); 13 C{ 1 H} NMR
(CDCl3, 75.5 MHz): δ 13.7 (s, CH3), 23.6 (d, 1 JPC = 57.0 Hz, P-CH2), 24.0 (d, 2 JPC = 15.6 Hz,
P-CH2-CH2), 24.4 (d, 3 JPC = 3.6 Hz, CH2-CH3), 46.0 (d, 1 JPC = 108.1 Hz, P-CH), 126.5 (d,
1 JPC = 82.0 Hz, ipso-C of P-Ph), 126.6 (s, CH of OC-Ph), 127.8 (s, CH of OC-Ph), 129.1-
129.3 (overlapping s of CH of OC-Ph and d of o-C of P-Ph), 131.2 (d, 3 JPC = 8.7 Hz, m-C of
P-Ph), 131.9 (d, 4 JPC = 2.6 Hz, p-C of P-Ph), 141.5 (d, 3 JPC = 13.7 Hz, ipso-C of OC-Ph),
185.15 (d, 4 JPC = 3.5 Hz, CO); 31 P{ 1 H} NMR (CDCl3, 121.5 MHz): δ 19.5.
Synthesis of (benzoylmethylene)diphenyl(n-butyl)phosphorane 10
This compound was prepared using a method similar to that described for 9 by
reaction of 1.680 g (8.40 mmol) of α-bromoacetophenone with 2.040 g (8.40 mmol) of
diphenyl(n-butyl)phosphine (the phosphonium salt has not been characterized by 31 P NMR or
1 H NMR). Yield: 2.800 g, 92%. 1 H NMR (300 MHz, CDCl3): δ 0.88 (3H, t, 3 JHH = 7.2 Hz,
CH3), 1.40-1.60 (4H, m, CH2-CH2), 1.78 (2H, m, P-CH2), 4.23 (1H, d, 2 JPH = 23.4 Hz), 7.35
(3H, m, aromatic H), 7.45-7.56 (6H, m, aromatic H), 7.70-7.78 (4H, m, aromatic H) and 7.95
(2H, m, aromatic H); 13 C{ 1 H} NMR (CDCl3, 75.5 MHz): δ 13.7 (s, CH3), 24.1 (d, 1 JPC =
110.9 Hz, P-CH2), 24.2 (d, 2 JPC = 16.7 Hz, P-CH2-CH2), 24.7 (d, 3 JPC = 3.1 Hz, CH2-CH3),
47.9 (d, 1 JPC = 47.9 Hz, P-CH), 126.9 (s, CH of OC-Ph), 127.8 (s, p-C of OC-Ph), 128.6 (d,
1 JPC = 88.0 Hz, ipso-C of P-Ph), 129.0 (d, 2 JPC = 11.6 Hz, m-C of P-Ph), 129.3 (s, CH of OC-
16