Diphenyl(methoxymethyl)phosphine

Abstract

[43139-94-2] C14H15OP (MW 230.26) InChI = 1S/C14H15OP/c1-15-12-16(13-8-4-2-5-9-13)14-10-6-3-7-11-14/h2-11H,12H2,1H3 InChIKey = NTZMQOXRONKNAZ-UHFFFAOYSA-N (one-carbon homologation of hindered ketones to the corresponding aldehydes via the methyl enol ethers1) Physical Data: bp 134–135 °C/0.25 mmHg);2 n20D 1.6085;3 1H NMR (CDCl3) δ 7.70–7.20 (m), 4.14 (d, J = 8 Hz), 3.38 (s).2 Solubility: sol THF, ether. Preparative Methods: from the reduction of diphenyl(methoxymethyl)phosphine oxide with Hexachlorodisilane (50% yield)2 or Lithium Aluminum Hydride (ca. 50% yield).7 Nucleophilic addition of methoxymethylmagnesium chloride to diphenylchlorophosphine3 furnishes the reagent 1 in 80% yield. An alternative synthesis (eq 1), which is suitable for large scale preparation, involves reductive lithiation of diphenylchlorophosphine with 2.2 equiv of Lithium in liquid ammonia, followed by trapping of the phosphide anion at low temperature with Chloromethyl Methyl Ether (caution: carcinogen).1 Workup of the reaction is performed under argon. (1) Handling, Storage, and Precautions: stench. Undergoes oxidation to the phosphine oxide on standing in air.