Ciba Specialty Chemicals Corporation

Daniel Stein

Hansjörg Grützmacher

Jean-Pierre Wolf

Peter Murer

Stephan Burkhardt

Souâd Boulmaâz

Jens Geier

Markus Scherer

Hartmut Schönberg

Kurt Dietliker

Reinhard Sommerlade

The invention relates to a process for the preparation of (bis)acylphosphanes of formula I, wherein n and m are each independently of the other 1 or 2; R1 if n=1, is e.g. unsubstituted or substituted C-Calkyl or C-Calkenyl, or phenyl, R1 if n=2, is e.g. a divalent radical of the monovalent radical defined above; R2 is e.g. C-Calkyl, C-Ccycloalkyl, C-Calkenyl, mesityl, phenyl, naphthyl; R3 is one of the radicals defined under R; the process comprises the steps a) contacting e.g. elemental phosphorous [P]&#x221e;, P(Hal)with a reducing metal optionally in the presence of a catalyst or an activator in a solvent to obtain metal phosphides MeP or Me'P, wherein Me is an alkali metal and Me&#x2032; is an earth alkali metal or to obtain metal polyphosphides b) optionally adding a proton source, optionally in the presence of a catalyst or an activator to obtain metal dihydrogen phosphides MePH; c) subsequent acylation reaction with m acid halides of formula III or m carboxylic acid esters of formula IV or, in case that in formula I m=1, with one carboxylic ester of formula IV followed by one acid halide of formula III or vice versa, wherein R is the residue of an alcohol and Ris as defined above; d) alkylation reaction subsequent reaction with an electrophilic agent RHal or other electrophilic agents to obtain the compounds of formula I. An oxidation step may follow to obtain mono- and bisacylphosphane oxides or mono- and bisacylphosphane sulfides, which are used as photoinitiators. 

Process for preparing acylphosphanes and derivatives thereof

The present invention relates to a new, selective process for the preparation of mono- and bisacylphosphanes of formula (I) n and m are each independently of the other 1 or 2; R, if n=1, is e.g. phenyl R, if n=2, is e.g. C-Calkylene or phenylene; Ris e. g. C-Calkyl, phenyl or substituted phenyl; Ris e. g. C-Calkyl, by (1) reacting a phosphorous halide of formula IIa or a phosphorous halide oxide of formula (IIb) or a phosphorous halide sulfide of formula (IIc) with an alkali metal in a solvent in the presence of a proton source; (2) subsequent reaction with m acid halides of formula (III) An oxidation step may follow to obtain mono- and bisacylphosphane oxides or mono- and bisacylphosphane sulfides. 

The invention relates to a process for the preparation of cycloorganylphosphanes of formula 1 (RP)by reaction of dihalo(organyl)phosphanes of formula RPHalwith: a) activated zinc in an organic solvent, or with: b) an alkali metal or alkaline earth metal in a non-polar organic solvent in the presence of an activator, wherein Ris C&#x2013;Calkyl; C&#x2013;Ccycloalkyl, aryl or heteroaryl, Hal is F, Cl, Br or I, and n is a number from 3 to 20. The invention relates also to novel di(alkali metal/alkaline earth metal) oligophosphanediides and to the use thereof in the preparation of organophosphorus compounds.

Process for the synthesis of cycloorganylphosphanes and di(alkyli metal/alkaline earth metal) oligophosphanediides

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Seelze, Germany

Daniel Stein