My PhD dissertation - Institut Fresnel

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Dibutyl-tert-butylphosphine (26e): Analogously prepared from chlorodibutylphosphine
(25b; 20 g, 0.11 mol) and tert-butyllithium (0.11 mol) in pentane (79 mL); colorless liquid;
b.p. 72 - 73 °C/2.8 Torr; yield: 13.0 g (58%).
1 H NMR: δ = 1.4 (m, 9 H), 1.2 (m, 3 H), 1.02 (d, J = 11.2 Hz, 9 H), 0.9 (m, 6 H)
ppm.
13 C NMR: δ = 42.9 (d, J = 14 Hz), 30.1 (d, J = 18 Hz), 27.4 (d, J = 13 Hz), 24.2
(d, J = 16 Hz), 15.5 (d, J = 3 Hz), 13.9 (d, J = 8 Hz) ppm.
31 P NMR: δ = 0.8 ppm.
C12H27P (202.32) calcd. C 71.24% H 13.45%
found C 71.32% H 13.35%.
Dibutylmethylphosphine (26f): Analogously prepared from dibutylchlorophosphine (25b;
16 g, 90 mmol); colorless liquid; b.p. 63 - 64 °C/15 Torr; yield: 12.0 g (84%).
1 H NMR: δ = 1.3 - 0.9 (m, 18 H), 0.81 (d, J = 3.7 Hz, 3H) ppm.
13 C NMR: δ = 32.6 (d, J = 12.0 Hz), 28.4 (d, J = 13.8 Hz), 24.6 (d,
J = 10.9 Hz), 14.4 (d, J = 16.1 Hz), 13.8 ppm.
31 P NMR: δ = -43.7 ppm.
C9H21P (160.24) calcd. C 67.46% H 13.21%
found C 67.41% H 13.13%.
Butyldiethylphosphine (26g): A solution of butyllithium (0.13 mol) in hexane (0.11 mL)
was added slowly to a solution of diethylchlorophosphine (25g; 16 g, 0.13 mol) in diethyl
ether (50 mL) at -75 °C. The salts were then filtered under inert atmosphere and the usual
direct distillation protocol was applied to give a colorless liquid; b.p. 65 - 66 °C/46 Torr (ref.
[156] b.p. 106 - 107 °C/100 Torr); yield: 9.49 g (51%).
1 H NMR: δ = 1.7 (m, 1 H), 1.4 (m, 9 H), 1.17 (dt, J = 15.6, 7.6 Hz, 1 H), 1.06 (symm.
m, 5 H), 0.9 (m, 3 H) ppm.