Darstellung, Eigenschaften und Reaktivität von 2-, 3- und 4-Chloracyl(diphenyl)phosphanoxiden / Preparation, Properties and Reactivity of 2-, 3- and 4-Chloroacyl(diphenyl)phosphane Oxides

Abstract

<jats:p>The highly reactive chloroacyl(diphenyl)phosphane oxides RC(O)-P(O)Ph<jats:sub>2</jats:sub> (2a-d, g) [R = HCCl<jats:sub>2</jats:sub> (a), CCl<jats:sub>3</jats:sub> (b), CH<jats:sub>3</jats:sub>CHCl (c), CH<jats:sub>3</jats:sub>CCl<jats:sub>2</jats:sub> (d), ClCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub> (e), CH<jats:sub>3</jats:sub>CHClCH<jats:sub>2</jats:sub> (f), ClCH<jats:sub>2</jats:sub>(CH<jats:sub>2</jats:sub>)<jats:sub>2</jats:sub> (g)] are obtained by oxidation of the thermally labile chloroacyl(diphenyl)- phosphanes RC(O)-PPh<jats:sub>2</jats:sub> (1a-d, g) with molecular oxygen in ether at low temperatures. While hydrolysis leads to a complete decomposition of 2a-d, g, the oxidation of 1a, c, e-g with oxygen in the presence of HP(O)Ph<jats:sub>2</jats:sub> yields the diphosphorylated alcohols RC[P(O)Ph<jats:sub>2</jats:sub>]<jats:sub>2</jats:sub>OH (3a, c, e-g). 3e, f can be interpreted as trapping products of the not isolable oxides 2e, f. In tetrachloroethene a partial transformation of 3a into the phosphinate RC[P(O)Ph<jats:sub>2</jats:sub>][OP(O)Ph<jats:sub>2</jats:sub>]H can be observed which can be followed <jats:sup>31</jats:sup>P{<jats:sup>1</jats:sup>H}-NMR spectroscopically. In solution the alcohols 3c, e-g decompose to give HP(O)Ph<jats:sub>2</jats:sub> and the corresponding phosphane oxides 2c, e-g. </jats:p>