My PhD dissertation - Institut Fresnel

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Di-tert-butylisopropylphosphine (26b): Analogously prepared from Chlorodi-tert-
butylphosphine (25a; 18 g, 0.10 mol) and freshly prepared isopropylmagnesium chloride
(0.10 mol) in tetrahydrofuran (50 mL); colorless liquid; b.p. 41 - 43 °C/4.9 Torr (ref. [154] b.p.
81 - 83 °C/11 Torr); yield: 9.85 g (52%).
1 H NMR: δ = 1.4 (m, 1 H), 1.12 (d, J = 11.0 Hz, 18 H), 1.02 (d, J = 11.2 Hz, 6 H)
ppm.
13 C NMR: δ = 35.9 (d, J = 40 Hz), 30.8 (d, J = 13 Hz), 27.8 (d, J = 17 Hz), 23.2
(d, J = 12 Hz) ppm.
31 P NMR: δ = 31.6 ppm.
Di-tert-butylmethylphosphine (26c): A solution of methyllithium (90 mmol) in diethyl ether
(59 mL) was added slowly to a solution of di-tert-butylchlorophosphine (25a; 16 g, 90 mmol)
in diethyl ether (90 mL) at -75 °C. The salts were removed by filtration under inert
atmosphere and the direct distillation protocol was applied to give a colorless liquid; b.p. 50 -
52 °C/13 Torr (ref. [155] b.p. 58 °C/12 Torr); yield: 8.99 g (63%).
1 H NMR: δ = 0.83 (d, J = 4.5 Hz, 3 H), 1.04 (d, J = 10.6 Hz, 18 H) ppm.
13 C NMR: δ = 30.5 (d, J = 21.0 Hz), 29.5 (d, J = 14.1 Hz), 3.2 ppm.
31 P NMR: δ = 11.2 ppm.
Dibutylneopentylphosphine (26d): Analogously prepared from dibutylchlorophosphine
(25b; 22 g, 0.12 mol) and freshly prepared neopentylmagnesium bromide (0.12 mol) in
diethyl ether (0.10 L); colorless liquid; b.p. 84 - 85 °C/1.1 Torr; yield: 16.8 g (65%).
1 H NMR: δ = 1.5 - 1.3 (m, 10 H), 1.2 (s, 2 H), 0.98 (s, 9 H), 0.9 (m, 8 H) ppm.
13 C NMR: δ = 31.5 (d, J = 6 Hz), 30.9 (d, J = 9 Hz), 30.1 (d, J = 64 Hz), 24.3 (d,
J = 14 Hz), 24.2 (d, J = 4 Hz), 13.7 (d, J = 20 Hz) ppm.
31 P NMR: δ = 50.1 ppm.