My PhD dissertation - Institut Fresnel

31 P NMR: δ = 53.4 ppm.
92
C16H31OP (270.39) calcd. C 71.07% H 11.56%
found C 71.01% H 11.53%.
Methyldiisopropylphosphine oxide (27h): Analogously prepared from
Methyldiisopropylphosphine (26k; 4.8 g, 36 mmol) and 30% hydrogen peroxide solution
(10 mL); colorless liquid; b.p. 70 - 71 °C/3.1 Torr (ref. [161] b.p. 116 - 117 °C/20 Torr); yield:
4.63 g (86%).
1 H NMR: δ = 1.98 (symm. m, 2 H), 1.31 (d, J = 11.5 Hz, 3 H), 1.23 (dd, J = 14.9,
7.4 Hz, 6 H), 1.16 (dd, J = 15.5, 7.2 Hz, 6 H) ppm.
13 C NMR: δ = 25.6 (d, J = 67 Hz), 16.0 (d, J = 2 Hz), 15.1 (d, J = 3 Hz), 7.6 (d,
J = 62 Hz) ppm.
31 P NMR: δ = 60.6 ppm.
Di-tert-butylmethylphosphine oxide (27i): In a two necked flask equipped with a reflux
condenser, iodomethane (0.3 mL, 0.7 g, 4.0 mmol) was added at 25 °C, to a solution of
methyldi-tert-butylphosphinite (7.0 g, 40 mmol) in tetrahydrofuran (20 mL). The mixture was
then vigorously stirred until the white precipitate redisolved. After 1 h, the solvent and excess
of reagent were evaporated and the residue directly distilled to afford a colorless liquid which
spontaneously crystallized into white needles; b.p. 72 - 73 °C/0.85 Torr (ref. [162] b.p.
57 °C/0.02 Torr); m.p. 23 - 25 °C; yield: 5.50 g (79%).
1 H NMR: δ = 3.72 (d, J = 10 Hz, 3 H), 1.17 (d, J = 16 Hz, 18 H) ppm.
13 C NMR: δ = 51.3 (d, J = 7 Hz), 24.2, 8.5 (d, J = 85) ppm.
31 P NMR: δ = 58.4 ppm.
Dibutylmethylphosphine oxide (27j): Prepared following a procedure described by G.M.
Kosolapoff and R.F. Struck [163] , starting from methylphosphonic dichloride ( 6.7 g, 50 mmol)
and butylmagnesium bromide (0.11 mol) in tetrahydrofuran (45 mL); white needles; b.p. 133
- 135 °C/0.49 Torr; m.p. 32 - 34 °C (ref. [163] m.p. 34 - 35 °C); yield: 7.45 g (84%).