Ciba Specialty Chemicals Corporation

Ciba-geigy Corporation

Gebhard Hug

Jean-Pierre Wolf

David G Leppard

Urs Schwendimann

Eugen Eichenberger

Manfred Kohler

Beat Michael Aebli

René Kaeser

Werner Rutsch

Ljubomir Misev

René´ Kaeser

A description is given of processes for the preparation of mono- and bisacylphosphines and of mono- and bisacylphosphine oxides and mono- and bisacylphosphine sulfides, which comprises first reacting organic P-monohalogenophosphines or P,P-dihalogenophosphines, or mixtures thereof, with an alkali metal or magnesium in combination with lithium, where appropriate in the presence of a catalyst, and then carrying out the reaction with acid halides and, in the case of the process for the preparation of oxides, carrying out an oxidation step and, in the case of the preparation of sulfides, reacting the phosphines so obtained with sulfur. It is characteristic, inter alia, that the processes are carried out without isolation of the intermediates.

Process for the preparation of acylphosphines, acyl oxides and acyl sulfides

The invention relates to dimer and multimer form of BAPO compounds of the formula (I) dimer and multimer forms of MAPO compounds of the formula (II) wherein R, R, and Rindependently of one another are unsubstituted or substituted C&#x2013;Calkyl, benzyl, C&#x2013;Calkoxy, C&#x2013;Ccycloalkyl or C&#x2013;Caryl; Q is a di- tri or tetravalent arylene residue; n is 1&#x2013;4, m is 0&#x2013;2, n+m is 2, 3 or 4, with the proviso, that Rand Rare different from each other. The invention further relates to a process for the preparation of dimer or multimer forms of BAPO compounds of the formula (I) and of dimer or multimer forms of MAPO compounds of the formula (II), characterized in the (n+m) equivalents of a dimetalated-phosphine RP(M)is reacted with one equivalent of a di- or polycarboxylic acid halogenide to form an intermediate of the formula III the intermediate is then reacted either with (n+m) equivalents of a further carboxylic acid halogenide (R&#x2014;CO-Hal) or with a halogenide R-Hal, the reaction products are then oxidized to form phosphine oxides of the formula I or II 

Multimer forms of mono-and bis-acylphosphine oxides

Compounds of formula (I), wherein A is S or O; x is 0 or 1; a is SRor N(R)(R); Rand Rare C&#x2013;Calkyl, OR, CFor halogen; R, Rand Rare hydrogen, C&#x2013;Calkyl, ORor halogen; or two of the radicals RRRRand/or Rtogether form C&#x2013;Coalkylene uninterrupted or interrupted by O, S or NR; R, RRand Rare hydrogen, C&#x2013;Calkyl; C&#x2013;Calkyl which is interrupted one or more times by non-consecutive O atoms and unsubstituted or substituted by OH and/or SH, or R, R, Rand Rg are OR; halogen; or phenyl unsubstituted or substituted one or more times by C-Calkyl; R, Rand Rare e.g. hydrogen; X is e.g. (II), and R; have one of the meanings given for Rand R; and R', R&#x2032; and Rs&#x2032; have one of the meanings given for R, Rand R; are suitable as photoinitiators, especially for irradiation with light of relatively long wavelengths 

Bathochromic mono- and bis-acylphosphine oxides and sulfides and their use as photoinitiators

Compounds of the formula (I), in which E is O or S; and x is 0 or 1, A is cyclopentyl, cyclohexyl, naphthyl, biphenylyl, anthracyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring, where the mentioned radicals are unsubstituted or substituted by halogen, C&#x2013;Calkyl or C&#x2013;Calkoxy; or A is a group formula (II) R is C&#x2013;Calkyl, unsubstituted or substituted, C&#x2013;Calkyl which is interrupted once or more than once by nonconsecutive O, S or NRand which is unsubstituted or substituted, C&#x2013;Calkenyl which is uninterrupted or interrupted once or more than once by nonconsecutive O, S or NRand which is unsubstituted or substituted, C&#x2013;Ccycloalkenyl which is uninterrupted or interrupted once or more than once by nonconsecutive O, S or NRand which is unsubstituted or substituted; C&#x2013;Carylalkyl which is unsubstituted or substituted on the aryl group. C&#x2013;Ccycloalkyl which is uninterrupted or interrupted once or more then once by O, S or NRand which is unsubstituted or substituted, C&#x2013;Carylcycloalkyl or C&#x2013;Carylcycloalkenyl; or, R is a group of the formula (III) W is a bond, &#x2014;CO&#x2014;O&#x2014; or &#x2014;CO&#x2014;N(R)&#x2014;; L a di-tri-or tetravalent linking group, n is a number of 2,3 or 4; 

Multimer forms of acylphosphines and their derivatives

Compounds of the formula Iin which or unsubstituted or substituted cyclopentyl, cyclohexyl, naphthyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring; Rand Rare C-Calkyl, OR, CFor halogen; R, Rand Rare hydrogen, C-Calkyl, ORor halogen; Ris unsubstituted or substituted C-Calkyl, C-Calkyl, which is interrupted by O, S or NRand is unsubstituted or substituted; C-Calkenyl, uninterrupted or interrupted by O, S or NRand unsubstituted or substituted; unsubstituted or substituted C-Carylalkyl; C-Ccycloalkyl, uninterrupted or interrupted by O, S and/or NR; or C-Carylcycloalkyl; Ris C-Calkyl, C-Ccycloalkyl, phenyl, benzyl or C-Calkyl, interrupted by O or S and unsubstituted or substituted; Rand Rare hydrogen, C-Calkyl, C-Ccycloalkyl, phenyl, benzyl or C-Calkyl, interrupted by O atoms and unsubstituted or substituted; or Rand Rtogether are C-Calkylene, uninterrupted or interrupted by O, S or NR; Ris hydrogen, phenyl, C-Calkyl or C-Calkyl, interrupted by O or S and unsubstituted or substituted; and M is hydrogen, Li, Na or K; are valuable intermediates for the preparation of unsymmetrical bisacylphosphine oxides and monoacylphosphine oxides.

Organometallic monoacylalkylphosphines

Organometallic monoacylarylphosphines

Acylphosphine oxides

Compounds of formula I ##STR1## wherein n is 0 or 1, p is a number from 1 to 8,

Benzoyl-substituted phosphabicycloalkanes and

Bisacylphosphine sulfides of formula I ##STR1## wherein R.sub.1 is unsubstituted C.sub.1 -C.sub.18 or C.sub.1 -C.sub.8 alkyl which is substituted by phenyl, --CN, C.sub.1 -C.sub.12 alkoxy or halogen, C.sub.2 -C.sub.18 alkenyl, unsubstituted C.sub.5 -C.sub.8 cycloalkyl or C.sub.5 -C.sub.8 cycloalkyl which is substituted by C.sub.1 -C.sub.12 alkyl, C.sub.1 -C.sub.12 alkoxy or halogen, unsubstituted C.sub.6 -C.sub.12 aryl or C.sub.6 -C.sub.12 aryl which is substituted by halogen, C.sub.1 -C.sub.12 alkyl or C.sub.1 -C.sub.12 alkoxy, or a 5- or 6-membered aromatic heterocyclic radical which contains oxygen, sulfur and/or nitrogen and is unsubstituted or substituted by halogen, C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy, and

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Rheinfelden, Switzerland

Gebhard Hug