My PhD dissertation - Institut Fresnel

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1 H NMR: δ = 1.7 (m, 4 H), 1.6 (m, 4 H), 1.4 (m, 4 H), 1.42 (d, J = 12.1 Hz, 3 H),
0.94 (t, J = 7.0 Hz, 6 H) ppm.
13 C NMR: δ = 29.7 (d, J = 67 Hz), 24.2 (d, J = 14 Hz), 23.9 (d, J = 4 Hz), 13.9 (d,
J = 66 Hz), 13.6 ppm.
31 P NMR: δ = 48.8 ppm.
tert-Butyldimethylposphine oxide (27k): A solution of tert-butylphosphonic dichloride (8.7
g, 50 mmol) in diethyl ether (50 mL) was added dropwise to methylmagnesium bromide (0.10
mol) in diethyl ether (35 mL) at 10 °C. The brown mixture was then stirred at 25 °C for 1 h
until it became homogeneous and solvent was removed and replaced by hexanes (50 mL).
Filtration of the salts and evaporation of the solvent gave a brown oil which was distilled
under vacuum to afford a colorless liquid; b.p. 58 - 61 °C/0.33 Torr (ref. [162] b.p. 90 -
94 °C/2 Torr); yield: 4.55 g (68%).
1 H NMR: d = 2.13 (d, J = 11.8 Hz, 6 H), 1.49 (d, J = 15.2 Hz, 9 H) ppm.
13 C NMR: d = 51.5 (d, J = 7 Hz), 24.4, 8.4 (d, J = 85) ppm.
31 P NMR: d = 48.9 ppm.
3.3 Tetraalkylphosphonium Halides
Dibutyldimethylphosphonium iodide (28a): Iodomethane (0.40 mL, 1.0 g, 7.0 mmol) was
added dropwise to a solution of dibutylmethylphosphine (26f; 1.1 g, 7.0 mmol) in diethyl
ether (6.0 mL) at 0 °C. The reaction mixture was allowed to warm up to 25 °C and the
precipitate formed was filtered under inert atmosphere. The solid obtained was recrystallized
from diethyl ether to afford white prisms; m.p. 168 - 169 °C; yield: 2.10 g (99%).
1 H NMR: δ = 2.5 (m, 4 H), 2.18 (d, J = 13.6 Hz, 6 H), , 1.5 (m, 8 H), 0.98 (t, J =
7.1 Hz, 6 H) ppm.