My PhD dissertation - Institut Fresnel

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C21H21O9P (448.36) calcd. C 56.25% H 4.72%
found C 56.27% H 4.74%.
Tris(5-formyl-2-furyl)phosphine (12): Pyridinium chloride (0.70 g, 6.0 mmol) and
tris[5-(1,3-dioxolan-2-yl)-2-furyl] phosphine (20; 9.0 g, 20 mmol) were heated under reflux for 20 h in a
mixture of acetone (80 mL) and water ( 5.0 mL). The reaction mixture was then allowed to cool down to
25 °C and acetone was removed under reduced pressure. Ethyl acetate (80 mL) and a saturated aqueous
solution of sodium bicarbonate (40 mL) were added and the phases were separated. The organic layer
was dried with sodium sulfate and the solvent was evaporated to afford slightly colored crystals.
Recrystallization from ethyl acetate afforded colorless prisms; m.p. 127 - 129 °C; yield: 5.44 g (88%).
1 H NMR (acetone-d6) : δ = 9.73 (d, J = 1.0 Hz, 1 H), 7.51 (dd, J = 3.5, 1.3 Hz,
1 H), 7.22 (dd, J = 3.5, 1.0 Hz, 1 H ) ppm.
13 C NMR (acetone-d6) : δ = 178.9, 158.2 (d, J = 3 Hz), 153.4 (d, J = 7 Hz), 124.8
(d, J = 19 Hz), 122.1 (d, J = 5 Hz) ppm.
31 P NMR (acetone-d6) : δ = - 66.6 ppm.
C15H9O6P (316.20) calcd. C 56.98% H 2.87%
found C 57.05% H 2.91%.
Tris(5-hydroxymethyl-2-furyl)phosphine (13): At 0 °C, sodium borohydride (1.5 g, 39
mmol) was added in one portion to a solution of tris(5-formyl-2-furyl)phosphine (21; 4.2 g,
13 mmol) in tetrahydrofuran (40 mL). The suspension was then stirred at 25 °C for 6 h
before water (30 mL) was added. Phases were separated and the aqueous layer was extracted
twice with ethyl acetate (25 mL). The combined organic layers were dried with sodium sulfate
and evaporated under reduced pressure to afford a white solid. Recrystallization from ethanol
gave colorless prisms; m.p. 165 - 167 °C; yield: 3.60 g (86%).
1 H NMR (acetone-d6) : δ = 6.77 (dd, J = 3.2, 1.6 Hz, 3 H), 6.34 (symm. m, 3 H ),
4.55 (d, J = 6.1 Hz, 6 H), 4.32 (t, J = 6.1 Hz, 3 H) ppm.
13 C NMR (acetone-d6) : δ = 161.6 (d, J = 3 Hz), 147.8 (d, J = 2 Hz), 122.6 (d, J =
21 Hz), 109.1 (d, J = 6 Hz), 56.7 ppm.