My PhD dissertation - Institut Fresnel
My PhD dissertation - Institut Fresnel
My PhD dissertation - Institut Fresnel
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1 H NMR: δ = 6.96 (s, 3 H), 6.94 (d, J = 8.6 Hz, 3 H), 2.27 (s, 18 H) ppm.<br />
74<br />
13 C NMR: δ = 139.9, 135.0 (d, J = 12.1 Hz), 129.3, 94.3 (d, J = 16.3 Hz),<br />
20.9 ppm.<br />
31 P NMR: δ = -5.7 ppm.<br />
2.2 Furanylphosphines<br />
Tris(5-methyl-2-furyl)phosphine (8): At -75 °C, butyllithium (90 mmol) in hexanes (61 mL)<br />
was added dropwise to a solution of 2-methylfuran (8.1 mL, 7.4 g, 90 mmol) in<br />
tetrahydrofuran (90 mL) in order to keep the temperature below –70 °C. After further 30 min<br />
at -75 °C, triethyl phosphite (5.2 mL, 5.0 g, 30 mmol) was added. After evaporation of the<br />
volatiles, the solid residue was crystallized from toluene to afford white platelets; m.p. 85 -<br />
86 °C; yield: 22.8 g (92%).<br />
1 H NMR: δ = 6.66 (dd, J = 2.9, 1.6 Hz, 3 H), 5.98 (symm. m, 3 H), 2.33 (s, 9 H)<br />
ppm.<br />
13 C NMR: δ = 124.6 (d, J = 22 Hz), 121.9 (d, J = 22 Hz), 107.5 (d, J = 9 Hz),<br />
106.8 (d, J = 6 Hz), 14.0 ppm.<br />
31 P NMR: δ = 73.1 ppm.<br />
MS : 291 (29%, M + +NH3), 275 (7%, M + +1), 193 (100%), 151 (55%).<br />
C15H15O3P (274.25) calcd. C 65.69% H 5.51%<br />
found C 65.63% H 5.50%.<br />
Tris(2-benzofuryl)phosphine (9): Benzofuran (16 mL, 18 g, 0.15 mol) in tetrahydrofuran<br />
(0.30 L) was treated with a solution of butyllithium (0.15 mol) in hexanes (0.10 L) at -75 °C.<br />
The white suspension formed was vigorously stirred for 2 h until Gilman color test II<br />
revealed the absence of remaining alkyllithium in the reaction mixture. Triethyl phosphite<br />
(8.7 mL, 8.3 g, 50 mmol) was added to the white suspension and the reaction mixture was<br />
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