One-Pot Reaction To Form Hydrophosphorylated Fullerenes from C₆₀ and Ph_3–n PCl _n /ROH

Abstract

Hydrophosphorylated fullerene derivatives were readily prepared in one step by treating C₆₀ with Ph₃– _n PCl _n (n = 1–3) and ROH (R = H, alkyl). The one-pot reaction could be performed under mild conditions with moderate to good yields. Dichlorophenylphosphine and alcohols exhibited unexpected reactivity towards C₆₀. A possible reaction mechanism involving the formation of P(III)–OH in situ was proposed to explain the experimental results.

Key words

one-pot reaction - hydrophosphorylation - fullerenes - alcohols - dichlorophenylphosphine

• References and Notes


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• 17 Ethoxy(phenyl)phosphoryl[60]fullerene (3a) EtOH (41 μL, 0.70 mmol), pyridine (55.8 μL, 0.70 mmol), and PhPCl₂ (94.2 μL, 0.70 mmol) were added sequentially to a stirred solution of C₆₀ (51.0 mg, 0.071 mmol) in toluene (25 mL). The mixture was stirred at r.t. for 30 min, then heated to 70 °C for 10 min. The organic layer was washed with H₂O (2 × 20 mL) and concentrated under vacuum. The residue was purified by chromatography (silica gel, PE) to collect recovered C₆₀ [yield: 9.9 mg (73%)]; subsequent elution [toluene–EtOAc (10:1)] gave product 3a as a brown solid; yield (37.4 mg, 59%). ¹H NMR (400 MHz, CDCl₃): δ = 8.33–8.28 (m, 2 H), 7.76–7.72 (m, 1 H), 7.69–7.64 (m, 2 H), 7.29 (d, J _P–H = 32 Hz, 1 H), 4.77–4.73 (m, 1 H), 4.63–4.59 (m, 1 H), 1.69–1.65 (t, 3 H). ³¹P NMR (162 MHz, CDCl₃): δ = 38.72. ESI-MS: m/z [M + H]⁺ calcd for C₆₈H₁₂O₂P: 891.0569; found: 891.0573.