Phenyl alkyl ketone substituted by cyclic amine and a process for the preparation thereof

A process for the preparation of a photoinitiator of formula IV

• or the acid addition salt thereof, wherein:
• R1 and R2 together are straight-chain or branched, unsubstituted C3-C20alkylene optionally interrupted by one or more than one —O—, —S— or —N(R4) group and/or optionally substituted by hydroxy, C1-C4alkoxy, hydroxymethyl, C1-C4alkoxymethyl, —COO(C1-C4alkyl) or phenyl;
• R3 is straight-chain or branched C2-C20alkyl which is unsubstituted or substituted by C1-C4alkoxy, phenoxy, cyclohexyl or phenyl,
• R4 is hydrogen, C1-C3alkyl, C3-C5alkenyl, C7-C9phenylalkyl, C1-C4hydroxyalkyl or phenyl;
• R5 is either
• (a) a radical of formula
• wherein p is 0 or 1, or
• (b) a radical of formula
• wherein q is 0, 1, 2 or 3, or
• c) a radical of formula
• wherein Ar is a phenyl, naphthyl, furyl, thienyl or pyridyl radical which is unsubstituted or substituted by halogen, OH, C1-C12alkyl, or by C1-C4alkyl which is substituted by OH, halogen, —N(R12)2, C1-C12alkoxy, —COO(C1-C18alkyl), —CO(OCH2CH2)nOCH3 or —OCO(C1-C4)-alkyl;
• by C1-C12-alkoxy, or by C1-C4alkoxy which is substituted by —COO(C1-C18alkyl) or —CO(OCH2CH2)nOCH3;
• or by —(OCH2CH2)nOH, —(OCH2CH2)nOCH3, C1-C8alkylthio, phenoxy, —COO(C1-C18alkyl), —CO(OCH2CH2)nOCH3, phenyl or benzoyl, wherein n is 1-20, in which formulae
• R12 is hydrogen, C1-C8alkyl, C3-C5alkenyl, C7-C9phenylalkyl, C1-C4hydroxyalkyl or phenyl,
• R8 is hydrogen, C1-C8alkyl or phenyl, and
• R9, R10 and R11 are each independently of one another hydrogen or C1-C4alkyl, or R9 and
• R10 taken together are C3-C7alkylene,
• R6 is hydrogen, C1-C12alkyl;
• C2-C4alkyl which is substituted by hydroxy, C1-C4alkoxy, —CN or —COO(C1-C4alkyl);
• C3-C5alkenyl, C5-C12cycloalkyl or C7-C9phenylalkyl,
• R7 is C1-C12alkyl;
• C2-C4alkyl which is substituted by hydroxy, C1-C4alkoxy, —CN or —COO(C1-C4alkyl);
• C3-C5alkenyl, C5-C12cycloalkyl, C7-C9phenylalkyl, phenyl, or phenyl which is substitued by halogen, C1-C12alkyl, C1-C4alkoxy or —COO(C1-C4alkyl), or R7, together with R3, is C1-C7alkylene, C7-C10phenylalkylene, o-xylylene, 2-butenylene or C2-C3oxaalkylene or azaalkylene, or
• R6 and R7 together are C3-C7alkylene optionally interrupted by —O—, —S—, —CO— or —N(R13)—or optionally substituted by hydroxy, C1-C4alkoxy or —COO(C1-C4alkyl), wherein R13 is hydrogen, C1-C12alkyl which may be interrupted by one or more than one —O—;
• C3-C5alkenyl, C7C9phenylalkyl, C1-C4hydroxyalkyl, —CH2CH2CN, —CH2CH2COO(C1-C4alkyl), C2-C8alkanoyl or benzoyl,
• by aminolysis of a p-halophenyl alkyl ketone of formula II
• with a cyclic amine of formula III
• in water at a temperature of at least 130° C., in which formulae X is a halogen atom and R1, R2 and R3 are as defined above, to a cyclic amine-substituted phenyl alkyl ketone of formula
• halogenation of this phenyl alkyl ketone compound of formula I, reaction with an amine of formula
• subsequent reaction with a compound introducing R5, and Stevens rearrangement under basic conditions.