My PhD dissertation - Institut Fresnel

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allowed to reach ambient temperature. The volatiles were removed under vacuum and the
resulting solid suspended in hot ethanol (50 mL). The solid was collected by filtration,
washed with cold ethanol (40 mL) and recrystallized from ethanol to afford the product as
colorless needles; m.p. 151 - 153 °C (ref. [63] m.p. 152 - 153 °C); yield: 17.5 g (92%).
1 H NMR: δ = 7.57 (d, J = 7.6, 3 H), 7.53 (dd, J = 8.3, 0.6 Hz, 3 H), 7.32 (ddd,
J = 8.3, 7.6, 1.3 Hz, 3 H), 7.26 (dd, J = 1.9, 0.9 Hz, 3 H), 7.22 (dd, J = 7.3, 0.6 Hz,
3 H) ppm.
13 C NMR: δ = 158.5 (d, J = 4 Hz), 151.1 (d, J = 5 Hz), 128.2 (d, J = 7 Hz), 126.0,
123.4, 121.9, 118.6 (d, J = 22 Hz), 112.0 ppm.
31 P NMR: δ = -68.5 ppm.
Tris[5-(1,3-dioxolan-2-yl)-2-furyl]phosphine (11): At – 75 °C, butyllithium (0.11 mol) in
hexanes (67 mL) was added dropwise in the course of 1 h, to a solution of
2-(2-furyl)-1,3-dioxolane [94] (19; 15 g, 0.11 mol) in tetrahydrofuran (0.20 L) in order to keep
the temperature below –70 °C. Triethyl phosphite (6.1 mL, 5.8 g, 35 mmol) was slowly added
to the dark green mixture during 30 min. The volatiles were removed under reduced pressure
and the residue dissolved in ethyl acetate (0.15 L). After addition of water (0.10 L), phases
were separated and the aqueous layer was extracted with ethyl acetate (70 mL). The combined
organic phases were dried with sodium sulfate and evaporated to afford brown crystals which
were treated with activated charcoal in hot ethanol and recrystallized from methanol to give
colorless prisms; m.p. 110 - 112 °C; yield: 10.4 g (68%).
1 H NMR (acetone-d6) : δ = 6.84 (dd, J = 3.2, 1.6 Hz, 3 H), 6.54 (dd, J = 3.2,
1.6 Hz, H ), 5.92 (s, 3 H), 4.03 (symm. m., 12 H) ppm.
13 C NMR (acetone-d6) : δ = 158.4 (d, J = 3 Hz), 149.6 (d, J = 1 Hz), 122.6 (d,
J = 22 Hz), 110.3 (d, J = 6 Hz), 98.1, 65.8 ppm.
31 P NMR (acetone-d6) : δ = - 73.8 ppm.
MS : 449 (4%, M + +1), 311 (21%), 173 (39%), 141 (100%), 73 (15%).