Anthony KERMAGORET - THESES ET MEMOIRES DE L'UDS

5. Experimental
Chapitre VI
General Considerations. All solvents were dried and freshly distilled under nitrogen
and degased under argon prior to use using common techniques. All manipulations were
carried out using Schlenk techniques under argon atmosphere. The 1 H, 31 P{ 1 H} and 13 C{ 1 H}
NMR spectra were recorded at 300.13, 121.5 and 75.5 MHz , respectively, on a Bruker
AC300 instrument. Gas chromatographic analyses were performed on a Thermoquest
GC8000 Top series gas chromatograph using a HP Pona column (50 m, 0.2 mm diameter, 0.5
µm film thickness). The compounds [Ni(COD)2] 62 and ylid 3 53 were prepared according to the
literature. Some details of the synthesis and analytical data for known compounds are given
below because of slight modifications or new data introduced.
Synthesis of diphenyl(t-butyl)phosphine 63
3.05 mL (17.00 mmol) of PPh2Cl were dissolved in 40 mL of a mixture pentane/THF
(3/1) and cooled to -78 °C. 10 mL of a t-BuLi solution in pentane (1.7 mol·L -1 , 17.00 mmol)
were slowly added and the solution was stirred overnight from -78 °C to room temperature.
The white precipitate of LiCl was eliminated by filtration with a canula and the solvents were
removed under reduced pressure. The brown oil obtained was distilled under reduced pressure
(140 °C, 0.8 mBar). The phosphine was isolated as a colorless liquid. Yield: 2.630 g, 64%. 1 H
NMR (300 MHz, CDCl3): δ 1.22 (9H, d, 3 JPH = 12.6 Hz, CH3), 7.36 (3H, m, aromatic H) and
7.60 (2H, m, aromatic H); 31 P{ 1 H} NMR (CDCl3, 121.5 MHz): δ 19.1 (s)
Synthesis of diphenyl(n-butyl)phosphine 64
4.60 mL (25.60 mmol) of PPh2Cl were dissolved in 30 mL of diethylether and cooled
to -78 °C. 16 mL of a t-BuLi solution in pentane (1.6 mol·L -1 , 25.60 mmol) were slowly
added and the solution was stirred overnight from -78 °C to room temperature. The white
precipitate of LiCl was eliminated by filtration with a canula and the solvents were removed
under reduced pressure. The yellow oil obtained was distilled under reduced pressure (135 °C,
0.8 mBar). The phosphine was isolated as a colorless liquid. Yield: 4.270 g, 73%. 1 H NMR
(300 MHz, CDCl3): δ 0.90 (3H, d, 3 JPH = 7.7 Hz, CH3), 1.44 (4H, m, CH2-CH2), 2.04 (2H, m,
P-CH2), 7.31 – 7.46 (5H, m, aromatic H); 31 P{ 1 H} NMR (CDCl3, 121.5 MHz): δ -14.8 (s)
Synthesis of phenyldi(t-butyl)phosphine 65
2.28 mL (17.00 mmol) of PPhCl2 were dissolved in 40 mL of pentane and cooled to -
78 °C. 20 mL of a t-BuLi solution in pentane (1.7 mol·L -1 , 34.00 mmol) were slowly added
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