Compounds of the formula I (I), in whichAr is a group or unsubstituted or substituted cyclopentyl, cyclohexyl, naphthyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring; R1 and R2 are C1-C20alkyl, OR11, CF3 or halogen; R3, R4 and R5 are hydrogen, C1-C20alkyl, OR11 or halog
Compounds of the formula I (I), in whichAr is a group or unsubstituted or substituted cyclopentyl, cyclohexyl, naphthyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring; R1 and R2 are C1-C20alkyl, OR11, CF3 or halogen; R3, R4 and R5 are hydrogen, C1-C20alkyl, OR11 or halogen; R6 is unsubstituted or substituted C1-C24alkyl, C2-C24alkyl, which is interrupted by O, S or NR14 and is unsubstituted or substituted; C2-C24alkenyl, uninterrupted or interrupted by O, S or NR14 and unsubstituted or substituted; unsubstituted or substituted C7-C24arylalkyl; C4-C24cycloalkyl, uninterrupted or interrupted by O, S and/or NR14; or C8-C24arylcycloalkyl; R11 is C1-C20alkyl, C3-C8cycloalkyl, phenyl, benzyl or C2-C20alkyl, interrupted by O or S and unsubstituted or substituted; R12 and R13 are hydrogen, C1-C20alkyl, C3-C8cycloalkyl, phenyl, benzyl or C2-C20alkyl, interrupted by O atoms and unsubstituted or substituted; or R12 and R13 together are C3-C5alkylene, uninterrupted or interrupted by O, S, or NR14; R14 is hydrogen, phenyl, C1-C12alkyl or C2-C12alkyl, 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.
대표청구항▼
1. A process for the preparation of compounds of the formula III in whichA is O or S; x is 0 or 1; Ar is a group or Ar is cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring, where the radicals cyclopentyl, cyclohexyl, naphthyl, an
1. A process for the preparation of compounds of the formula III in whichA is O or S; x is 0 or 1; Ar is a group or Ar is cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring, where the radicals cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and 5- or 6-membered heterocyclic ring are unsubstituted or substituted by halogen, C1-C4alkyl and/or C1-C4alkoxy;R1 and R2 independently of one another are C1-C20alkyl, OR11, CF3 or halogen; R3, R4 and R5 independently of one another are hydrogen, C1-C20alkyl, OR11 or halogen; or in each case two of the radicals R1, R2, R3, R4 and R5 together form C1-C20alkylene which can be interrupted by O, S or ?NR14; R6 is C1-C24alkyl, unsubstituted or substituted by C5-C24cycloalkenyl, phenyl, CN, C(O)R11, C(O)OR11, C(O)N(R14)2, OC(O)R11, OC(O)OR11, N(R14)C(O)N(R14), OC(O)NR14, N(R14)C(O)OR11, cycloalkyl, halogen, OR11, SR11, N(R12)(R13) or C2-C24alkyl which is interrupted once or more than once by nonconsecutive O, S or NR14 and which is unsubstituted or substituted by phenyl, OR11, SR11, N(R12)R13), CN, C(O)R11, C(O)OR11, C(O)N(R14)2 and/or C2-C24alkenyl which is uninterrupted or interrupted once or more than once by nonconsecutive O, S or NR14 and which is unsubstituted or substituted by OR11, SR11 or N(R12)(R13);C5-C24cycloalkenyl which is uninterrupted or interrupted once or more than once by non-consecutive O, S or NR14 and which is unsubstituted or substituted by OR11, SR11 or N(R12(R13); C7-C24arylalkyl which is unsubstituted or substituted on the aryl group by C1-C12alkyl, C1-C12alkoxy or halogen; C4-C24cycloalkyl which is uninterrupted or interrupted once or more than once by O, S and/or NR14 and which is unsubstituted or substituted by OR11, SR11 or N(R12)(R13); or C8-C24arylcycloalkyl or C8-C24arylcycloalkenyl; R11 is H, C1-C20alkyl, C2-C20alkenyl, C3-C8cycloalkyl, phenyl, benzyl or C2-C20alkyl which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted by OH and/or SH; R12 and R13 independently of one another are hydrogen, C1-C20alkyl, C3-C8cycloalkyl, phenyl, benzyl or C2-C20alkyl, which is interrupted once or more than once by O or S and which is unsubstituted or substituted by OH and/or SH; or R12 and R13 together are C3-C5alkylene which is uninterrupted or interrupted by O, S or NR14; Z1 is C1-C24alkyl, which is unsubstituted or substituted once or more than once by OR15, SR15, N(R16)(R17), phenyl, halogen, CN, ?N?C=A, and/or or Z1 is C2-C24alkyl which is interrupted once or more than once by O, S or NR14 and which can be substituted by OR15, SR15, N(R16)(R17), phenyl, halogen, or Z1 is C1-C24alkoxy, which is substituted once or more than once by phenyl, CN, ?N?C=A, or Z1 is unsubstituted C3-C24cycloalkyl or C3-C24cycloalkyl substituted by C1-C20alkyl, OR11, CF3 or halogen; unsubstituted C2-C24alkenyl or C2-C24alkenyl substituted by C6-C12aryl, CN, (CO)OR15 or (CO)N(R18)2; or Z1 is C3-C24cycloalkenyl or is one of the radicals or Z1 is C1-C24alkylthio, in which the alkyl radical is uninterrupted or interrupted once or more than once by nonconsecutive O or S, and is unsubstituted or substituted by OR15, SR15 and/or halogen; with the proviso that Z1 and R6 are not identical;A1 is O, S or NR18a; Z2 is C1-C24alkylene; C2-C24alkylene interrupted once or more than once by O, S or NR14; C2-C24alkenylene; C2-C24alkenylene interrupted once or more than once by O, S or NR14; C3-C24cycloalkylene; C3-C24cycloalkylene interrupted once or more than once by O, S or NR14; C3-C24cycloalkylene; C3-C24cycloalkylene interrupted once or more than once by O, S or NR14; where the radicals C1-C24alkylene, C2-C24alkylene, C2-C24alkenylene, C3-C24cycloalkylene and C3-C24cycloalkenylene are unsubstituted or are substituted by OR11, SR11, N(R12)(R13) and/or halogen; or Z2 is one of the radicals where these radicals are unsubstituted or are substituted on the aromatic by C1-C20alkyl; C2-C20alkyl which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted by OH and/or SH; OR11, SR11, N(R12)(R13), phenyl, halogen, NO2, CN, (CO)?OR11, (CO)?R11, (CO)?N(R12)(R13), SO2R24, OSO2R24, CF3 and/or CCl3;or Z2 is a group Z3 is CH2, CH(OH), CH(CH3) or C(CH3)2; Z4 is S, O, CH2, C?O, NR14 or a direct bond; Z5 is S, O, CH2, CHCH3, C(CH3)2, C(CF3)2, SO, SO2, CO; Z6 and Z7 independently of one another are CH2, CHCH3 or C(CH3)2; r is 0, 1 or 2; s is a number from 1 to 12; g is a number from 0 to 50; t and p are each a number from 0 to 20; E, G, G3 and G4 independently of one another are unsubstituted C1-C12alkyl or C1-C12alkyl substituted by halogen, or are unsubstituted phenyl or phenyl substituted by one or more C1-C4alkyl; or are C2-C12alkenyl; R11a is C1-C20alkyl substituted once or more than once by OR15 or or is C2-C20alkyl which is interrupted once or more than once by nonconsecutive O atoms and is unsubstituted or substituted once or more than once by OR15, halogen or or R11a is C2-C20alkenyl, C3-C12alkynyl; or R11a is C3-C12cycloalkenyl which is substituted once or more than once by halogen, NO2, C1-C6alkyl, OR11 or C(O)OR16; or C7-C16arylalkyl or C8-C16arylcycloalkyl;R14 is hydrogen, phenyl, C1-C12alkoxy, C1-C12alkyl or C2-C12alkyl which is interrupted once or more than once by O or S and which is unsubstituted or substituted by OH and/or SH; R15 has one of the meanings given for R11 or is a radical R16 and R17 independently of one another have one of the meanings given for R12 or are a radical R18 is hydrogen, C1-C24alkyl, C2-C12alkenyl, C3-C8cycloalkyl, phenyl, benzyl; C2-C20alkyl which is interrupted once or more than once by O or S and which is unsubstituted or substituted by OH; R18a and R18b independently of one another are hydrogen; C1-C20alkyl, which is substituted once or more than once by OR15, halogen, styryl, methylstyryl, ?N?C=A or or C2-C20alkyl, which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted once or more than once by OR15, halogen, styryl, methylstyryl or or R18a and R18b are C2-C12alkenyl; C5-C12cycloalkyl, which is substituted by ?N?C=A or ?CH2?N?C=A and is additionally unsubstituted or substituted by one or more C1-C4alkyl; or R18a and R18b are C6-C12aryl, unsubstituted or substituted once or more than once by halogen, NO2, C1-C6alkyl, C2-C4alkenyl, OR11, ?N?C=A, ?CH2?N?C=A or C(O)OR18; or R18a and R18b are C7-C18arylalkyl; or R18a and R18b together are C8-C16arylcycloalkyl; or R18a and R18b independently of one another are Y3 is O, S, SO, SO2, CH2, C(CH3)2, CHCH3, C(CF3)2, CO or a direct bond; R19, R20, R21, R22 and R23 independently of one another are hydrogen, C1-C20alkyl; C2-C20alkyl, which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted by OH and/or SH; or R19, R20, R21, R22 and R23 are OR11, SR11, N(R12)(R13), NO2, CN, SO2R24, OSO2R24, CF3, CCl3, halogen; or phenyl which is unsubstituted or substituted once or more than once by C1-C4alkyl or C1-C4alkoxy; or in each case two of the radicals R19, R20, R21, R22 and R23 together form C1-C20alkylene which is uninterrupted or interrupted by O, S or ?NR14; R24 is C1-C12alkyl, halogen-substituted C1-C12alkyl, phenyl, or phenyl substituted by OR11 and/or SR11; with the proviso that R6 and Z1 are not identical; (1) by reaction of an acyl halide of the formula IV in whichAr is as defined above, and X is Cl or Br; with a dimetalated organophosphine of the formula V in whichR6 is as defined above; and M1 is Na, Li or K; in the molar ratio of approximately 1:1;(2) subsequent reaction of the product with a compound of the formula VI or VI′Z1-X??(VI) Z1-X′??(VI′), in whichZ1 is as defined above ; and X is as defined above; and X′ is ?N?C=A, ?N?C?N=Z1, or ?CHO;with the proviso that, Z1 is not identical to R6; in the molar ratio of approximately 1:1; and, in the case where Z1 is not a group (v), (w) or C1-C12alkylthio, and(3) optionally subsequent oxidation or sulfurization of the resulting phosphine compounds.2. A photocurable composition comprising(a) at least one ethylenically unsaturated photopolymerizable compound and (b) at least one compound of the formula III as prepared in a process according to claim 1 as photoinitiator. 3. A photocurable composition according to claim 2, comprising, in addition to components (a) and (b), further photoinitiators (c) and/or further additives (d).4. A photocurable composition as claimed in claim 3, comprising, as further photoinitiator (c), at least one compound of the formula VIII, IX, X, XI in whichR25 is hydrogen, C1-C18alkyl, C1-C18alkoxy, ?OCH2CH2?OR29, morpholino, SCH3, a group n has a value from 2 to 10; G1 and G2 independently of one another are end groups of the polymeric unit, in particular hydrogen or CH3; R26 is hydroxyl, C1-C16alkoxy, morpholino, dimethylamino or ?O(CH2CH2O)m?C1-C16alkyl; R27 and R28 independently of one another are hydrogen, C1-C6alkyl, phenyl, benzyl, C1-C16alkoxy or ?O(CH2CH2O)m?C1-C16alkyl, or R27 and R28 together with the carbon atom to which they are bonded form a cyclohexyl ring; m is a number from 1-20; where R26, R27 and R28 are not all C1-C18alkoxy or ?O(CH2CH2O)m?C1-C16alkyl at the same time, and R29 is hydrogen, R30 and R32 independently of one another are hydrogen or methyl; R31 is hydrogen, methyl or phenylthio, where the phenyl ring of the phenylthio radical is unsubstituted or substituted by C1-C4alkyl in the 4-, 2-, 2,4- or 2,4,6-position; R33 and R34 independently of one another are C1-C20alkyl, cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenyl, where these radicals are unsubstituted or are substituted by halogen, C1-C12alkyl and/or C1-C12alkoxy, or R33 is an S- or N-containing 5- or 6-membered heterocyclic ring, or are R35 is cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenyl, these radicals being unsubstituted or substituted by halogen, C1-C4alkyl and/or C1-C4alkoxy, or R35 is an S- or N-containing 5- or 6-membered heterocyclic ring; R36 and R37 independently of one another are unsubstituted cyclopentadienyl or cyclopentadienyl substituted once, twice or three times by C1-C18alkyl, C1-C18alkoxy, cyclopentyl, cyclohexyl or halogen; and R38 and R39 independently of one another are phenyl which is substituted in at least one of the two ortho positions relative to the titanium-carbon bond by fluorine atoms or CF3, and which on the aromatic ring may contain, as further substituents, unsubstituted pyrrolinyl or pyrrolinyl substituted by one or two C1-C12alkyl, di(C1-C12alkyl)aminomethyl, morpholinomethyl, C2-C4alkenyl, methoxymethyl, ethoxymethyl, trimethylsilyl, formyl, methoxy or phenyl; or polyoxaalkyl, or R38 and R39 are R40, R41 and R42 independently of one another are hydrogen, halogen, C2-C12alkenyl, C1-C12alkoxy, C2-C12alkoxy interrupted by one to four O atoms, cyclohexyloxy, cyclopentyloxy, phenoxy, benzyloxy, unsubstituted phenyl or phenyl substituted by C1-C4alkoxy, halogen, phenylthio or C1-C4-alkylthio; or biphenyl, where R40 and R42 are not both hydrogen at the same time and in the radical at least one radical R40 or R42 is C1-C12alkoxy, C2-C12alkoxy interrupted by one to four O atoms, cyclohexyloxy, cyclopentyloxy, phenoxy or benzyloxy;E1 is O, S or NR43; and R43 s C1-C8alkyl, phenyl or cyclohexyl. 5. A process for the photopolymerization of nonvolatile monomeric, oligomeric or polymeric compounds having at least one ethylenically unsaturated double bond, which comprises irradiating a composition according to claim 2 with light in the range from 200 to 600 nm.6. A process according to claim 5 for the preparation of pigmented and nonpigmented surface coatings, printing inks, screen printing inks, offset printing inks, flexographic printing inks, powder coatings, printing plates, adhesives, dental materials, optical waveguides, optical switches, colour testing systems, composite materials, gel coats, glass-fibre cable coatings, screen printing stencils, resist materials, colour filters, for the encapsulation of electrical and electronic components, for the preparation of magnetic recording materials, of three-dimensional objects by means of stereolithography, of photographic reproductions, image recording material, for holographic recordings, for the preparation of decolouring materials, for the preparation of image recording materials using microcapsules.7. A coated substrate which has been coated on at least one surface with a composition according to claim 2.8. A process for the photographic production of relief images in which a coated substrate according to claim 7 is subjected to imagewise exposure and then the unexposed portions are removed with a solvent.9. A process for the preparation of compounds of the formula III, in whichA is O or S; x is 0 or 1; Ar is a group or Ar is cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring, where the radicals cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and 5- or 6-membered heterocyclic ring are unsubstituted or substituted by halogen, C1-C4alkyl and/or C1-C4alkoxy;R1 and R2 independently of one another are C1-C20alkyl, OR11, CF3 or halogen; R3 R4 and R5 independently of one another are hydrogen, C1-C20alkyl, OR11 or halogen; or in each case two of the radicals R1, R2, R3, R4 and R5 together form C1-C20alkylene which can be interrupted by O, S or ?NR14; R6 is C1-C24alkyl, unsubstituted or substituted by C5-C24cycloalkenyl, phenyl, CN, C(O)R11, C(O)OR11, C(O)N(R14)2, OC(O)R11, OC(O)OR11, N(R14)C(O)N(R14), OC(O)NR14, N(R14)C(O)OR11, cycloalkyl, halogen, OR11, SR11, N(R12)(R13) or C2-C24alkyl which is interrupted once or more than once by nonconsecutive O, S or NR14 and which is unsubstituted or substituted by phenyl, OR11, SR11, N(R12)(R13), CN, C(O)R11, C(O)OR11, C(O)N(R14)2 and/or C2-C24alkenyl which is uninterrupted or interrupted once or more than once by nonconsecutive O, S or NR14 and which is unsubstituted or substituted by OR11, SR11 or N(R12)(R13);C5-C24cycloalkenyl which is uninterrupted or interrupted once or more than once by non-consecutive O, S or NR14 and which is unsubstituted or substituted by OR11, SR11 or N(R12)(R13); C7-C24arylalkyl which is unsubstituted or substituted on the aryl group by C1-C12alkyl, C1-C12alkoxy or halogen; C4-C24cycloalkyl which is uninterrupted or interrupted once or more than once by O, S and/or NR14 and which is unsubstituted or substituted by OR11, SR11 or N(R12)(R13); or C8-C24arylcycloalkyl or C8-C24arylcycloalkenyl; R11 is H, C1-C20alkyl, C2-C20alkenyl, C3-C8cycloalkyl, phenyl, benzyl or C2-C20alkyl which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted by OH and/or SH; R12 and R13 independently of one another are hydrogen, C1-C20alkyl, C3-C8cycloalkyl, phenyl, benzyl or C2-C20alkyl, which is interrupted once or more than once by O or S and which is unsubstituted or substituted by OH and/or SH; or R12 and R13 together are C3-C5alkylene which is uninterrupted or interrupted by O, S or NR14; Z1 is C1-C24alkyl, which is unsubstituted or substituted once or more than once by OR15, SR15, N(R16)(R17), phenyl, halogen, CN, ?N?C=A, and/or or Z1 is C2-C24alkyl which is interrupted once or more than once by O, S or NR14 and which can be substituted by OR15, SR15, N(R16)(R17), phenyl, halogen, or Z1 is C1-C24alkoxy, which is substituted once or more than once phenyl, CN, ?N?C=A, or Z1 is unsubstituted C3-C24cycloalkyl or C3-C24cycloalkyl substituted by C1-C20alkyl, OR11, OF3 or halogen; unsubstituted C2-C24alkenyl or C2-C24alkenyl substituted by C6-C12aryl, CN, (CO)OR15 or (CO)N(R18)2; or Z1 is C3-C24cycloalkenyl or is one of the radicals or Z1 is C1-C24alkylthio, in which the alkyl radical is uninterrupted or interrupted once or more than once by nonconsecutive O or S, and is unsubstituted or substituted by OR15, SR15 and/or halogen; with the proviso that Z1 and R6 are not identical;A1 is O, S or NR18a; Z2 is C1-C24alkylene; C2-C24alkylene interrupted once or more than once by O, S or NR14; C2-C24alkenylene; C2-C24alkenylene interrupted once or more than once by O, S or NR14; C3-C24cycloalkylene; C3-C24cycloalkylene interrupted once or more than once by O, S or NR14; C3-C24cycloalkylene; C3-C24cycloalkenylene interrupted once or more than once by O, S or NR14; where the radicals C1-C24alkylene, C2-C24alkylene, C2-C24alkenylene, C3-C24cycloalkylene and C3-C24cycloalkenylene are unsubstituted or are substituted by OR11, SR11, N(R12)(R13) and/or halogen; or Z2 is one of the radicals where these radicals are unsubstituted or are substituted on the aromatic by C1-C20alkyl; C2C20alkyl which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted by OH and/or SH; OR11, SR11, N(R12)(R13), phenyl, halogen, NO2, CN, (CO)?OR11, (CO)?R11, (CO)?N(R12)(R13), SO2R24, OSO2R24, CF3 and/or CCl3;or Z2 is a group Z3 is CH2, CH(OH), CH(CH3) or C(CH3)2; Z4 is S, O, CH2, C?O, NR14 or a direct bond; Z5 is S, O, CH2, CHCH3, C(CH3)2, C(CF3)2, SO, SO2, CO; Z6 and Z7 independently of one another are CH2, CHCH3 or C(CH3)2; r is 0, 1 or 2; s is a number from 1 to 12; q is a number from 0 to 50; t and p are each a number from 0 to 20; E, G, G3 and G4 independently of one another are unsubstituted C1-C12alkyl or C1-C12alkyl substituted by halogen, or are unsubstituted phenyl or phenyl substituted by one or more C1-C4alkyl; or are C2-C12alkenyl; R11a is C1-C20alkyl substituted once or more than once by OR15 or or is C2-C20alkyl which is interrupted once or more than once by nonconsecutive O atoms and is unsubstituted or substituted once or more than once by OR15, halogen or or R11a is C2-C20alkenyl, C3-C12alkynyl; or R11a is C3-C12cycloalkenyl which is substituted once or more than once by halogen, NO2, C1-C8alkyl, OR11 or C(O)OR18; or C7-C16arylalkyl or C8-C16arylcycloalkyl;R14 is hydrogen, phenyl, C1-C12alkoxy, C1-C12alkyl or C2-C12alkyl which is interrupted once or more than once by O or S and which is unsubstituted or substituted by OH and/or SH; R15 has one of the meanings given for R11 or is a radical R16 and R17 independently of one another have one of the meanings given for R12 or are a radical R18 is hydrogen, C1-C24alkyl, C2-C12alkenyl, C3-C8cycloalkyl, phenyl, benzyl; C2-C20alkyl which is interrupted once or more than once by O or S and which is unsubstituted or substituted by OH; R18a and R18b independently of one another are hydrogen; C1-C20alkyl, which is substituted once or more than once by OR15, halogen, styryl, methylstyryl, ?N?C=A or or C2-C20alkyl, which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted once or more than once by OR15, halogen, styryl, methylstyryl or or R18a and R18b are C2-C12alkenyl; C5-C12cycloalkyl, which is substituted by ?N?C=A or ?CH2?N?C=A and is additionally unsubstituted or substituted by one or more C1-C4alkyl; or R18a and R18b are C6-C12aryl, unsubstituted or substituted once or more than once by halogen, NO2, C1-C6alkyl, C2-C4alkenyl, OR11, ?N?C=A, ?CH2?N?C=A or C(O)OR18; or R18a and R18b are C7-C16arylalkyl; or R18a and R18b together are C8-C16arylcycloalkyl; or R18a and R18b independently of one another are Y3 is O, S, SO, SO2, CH2, C(CH3)2, CHCH3, C(CF3)2, (CO), or a direct bond; R19, R20, R21, R22 and R23 independently of one another are hydrogen, C1-C20alkyl; C2-C20alkyl, which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted by OH and/or SH; or R19, R20, R21, R22 and R23 are OR11, SR11, N(R12)(R13), NO2, CN, SO2R24, OSO2R24, CF3, CCl3, halogen; or phenyl which is unsubstituted or substituted once or more than once by C1-C4alkyl or C1-C4alkoxy; or in each case two of the radicals R19, R20, R21, R22 and R23 together form C1-C20alkylene which is uninterrupted or interrupted by O, S or ?NR14; R24 is C1-C12alkyl, halogen-substituted C1-C12alkyl, phenyl, or phenyl substituted by OR11 and/or SR11; with the proviso that R6 and Z1 are not identical;(1) by reaction of an acyl halide of the formula IV in whichAr is as defined above, and X is Cl or Br; with an unsymmetrical phosphine of the formula VII in whichR6 is as defined above, and Z1 is as defined above with the proviso that R6 and Z1 are not identical; in the molar ratio of approximately 1:1, in the presence of a base or an organolithium compound, to give the corresponding acylphosphine; and(2) optionally subsequent oxidation or sulfurization of the thus obtained acylphosphine.10. A photocurable composition comprising(a) at least one ethylenically unsaturated photopolymerizable compound and (b) at least one compound of the formula III as prepared in a process according to claim 9 as photoinitiator. 11. A process for the preparation of compounds of the formula III in whichA is O; x is 1; Ar is a group or Ar is cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl or an O-, S- or N-containing 5- or 6-membered heterocyclic ring, where the radicals cyclopentyl, cyclohexyl, naphthyl, anthracyl, biphenylyl and 5- or 6-membered heterocyclic ring are unsubstituted or substituted by halogen, C1-C4alkyl and/or C1-C4alkoxy;R1 and R2 independently of one another are C1-C20alkyl, OR11, CF3 or halogen; R3, R4 and R5 independently of one another are hydrogen, C1-C20alkyl, OR11 or halogen; or in each case two of the radicals R1, R2, R3, R4 and R5 together form C1-C20alkylene which can be interrupted by O, S or ?NR14; R6 is C1-C24alkyl, unsubstituted or substituted by C5-C24cycloalkenyl, phenyl, CN, C(O)R11, C(O)OR11, C(O)N(R14)2, OC(O)R11, OC(O)OR11, N(R14)C(O)N(R14), OC(O)NR14, N(R14)C(O)OR11, cycloalkyl, halogen, OR11, SR11, N(R12)(R13) or C2-C24alkyl which is interrupted once or more than once by nonconsecutive O, S or NR14 and which is unsubstituted or substituted by phenyl, OR11, SR11, N(R12)(R13), CN, C(O)R11, C(O)OR11, C(O)N(R14)2 and/or C2-C24alkenyl which is uninterrupted or interrupted once or more than once by nonconsecutive O, S or NR14 and which is unsubstituted or substituted by OR11, SR11 or N(R12)(R13);C5-C24cycloalkenyl which is uninterrupted or interrupted once or more than once by nonconsecutive O, S or NR14 and which is unsubstituted or substituted by OR11, SR11 or N(R12)(R13); C7-C24arylalkyl which is unsubstituted or substituted on the aryl group by C1-C12alkyl, C1-C12alkoxy or halogen; C4-C24cycloalkyl which is uninterrupted or interrupted once or more than once by O, S and/or NR14 and which is unsubstituted or substituted by OR11, SR11 or N(R12)(R13); or C8-C24arylcycloalkyl or C8-C24arylcycloalkenyl; R11 is H, C1-C20alkyl, C2-C20alkenyl, C3-C8cycloalkyl, phenyl, benzyl or C2-C20alkyl which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted by OH and/or SH; R12 and R13 independently of one another are hydrogen, C1-C20alkyl, C3-C8cycloalkyl, phenyl, benzyl or C2-C20alkyl, which is interrupted once or more than once by O or S and which is unsubstituted or substituted by OH and/or SH; or R12 and R13 together are C3-C5alkylene which is uninterrupted or interrupted by O, S or NR14; Z1 is C1-C24alkyl, which is unsubstituted or substituted once or more than once by OR15, SR15, N(R16)(R17), phenyl, halogen, CN, ?N?C=A, and/or or Z1 is C2-C24alkyl which is interrupted once or more than once by O, S or NR14 and which can be substituted by OR15, SR15, N(R16)(R17), phenyl, halogen, or Z1 is C1-C24alkoxy, which is substituted once or more than once by phenyl, CN, ?N?O=A, orZ1 is unsubstituted C3-C24cycloalkyl or C3-C24cycloalkyl substituted by C1-C20alkyl, OR11, CF3 or halogen; unsubstituted C2-C24alkenyl or C2-C24alkenyl substituted by C6-C12aryl, CN, (CO)OR15 or (CO)N(R16)2; or Z1 is C3-C24cycloalkenyl or is one of the radicals or Z1 is C1-C24alkylthio, in which the alkyl radical is uninterrupted or interrupted once or more than once by nonconsecutive O or S, and is unsubstituted or substituted by OR15, SR15 and/or halogen;A1 is O, S or NR18a; Z2 is C1-C24alkylene; C2-C24alkylene interrupted once or more than once by O, S or NR14; C2-C24alkenylene; C2-C24alkenylene interrupted once or more than once by O, S or NR14; C3-C24cycloalkylene; C3-C24cycloalkylene interrupted once or more than once by O, S or NR14; C3-C24cycloalkylene; C3-C24cycloalkenylene interrupted once or more than once by O, S or NR14; where the radicals C1-C24alkylene, C2-C20alkylene, C2-C24alkenylene, C3-C24cycloalkylene and C3-C24cycloalkenylene are unsubstituted or are substituted by OR11, SR11, N(R12)(R13) and/or halogen; or Z2 is one of the radicals where these radicals are unsubstituted or are substituted on the aromatic by C1-C20alkyl; C2-C20alkyl which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted by OH and/or SH; OR11, SR11, N(R12)(R13), phenyl, halogen, NO2, CN, (CO)?OR11, (CO)?R11, (CO)?N(R12)(R13), SO2R24, OSO2R24, CF3 and/or CCl3;or Z2 is a group Z3 is CH2, CH(OH), CH(CH3) or C(CH3)2; Z4 is S, O, CH2, C?O, NR14 or a direct bond; Z5 is S, O, CH2, CHCH3, C(CH3)2, C(CF3)2, SO, SO2, CO; Z6 and Z7 independently of one another are CH2, CHCH3 or C(CH3)2; r is 0 or 2; s is a number from 1 to 12; q is a number from 0 to 50; t and p are each a number from 0 to 20; E, G, G3 and G4 independently of one another are unsubstituted C1-C12alkyl or C1-C12alkyl substituted by halogen, or are unsubstituted phenyl or phenyl substituted by one or more C1-C4alkyl; or are C2-C12alkenyl; R11a is C1-C20alkyl substituted once or more than once by OR15 or or is C2-C20alkyl which is interrupted once or more than once by nonconsecutive O atoms and is unsubstituted or substituted once or more than once by OR15, halogen or or R11a is C2-C20alkenyl, C3-C12alkynyl; or R11a is C3-C12cycloalkenyl which is substituted once or more than once by halogen, NO2, C1-C6alkyl, OR11 or C(O)OR18; or C7-C16arylalkyl or C8-C16arylcycloalkyl;R14 is hydrogen, phenyl, C1-C12alkoxy, C1-C12alkyl or C2-C12alkyl which is interrupted once or more than once by O or S and which is unsubstituted or substituted by OH and/or SH; R15 has one of the meanings given for R11 or is a radical R16 and R17 independently of one another have one of the meanings given for R12 or are a radical R18 is hydrogen, C1-C24alkyl, C2-C12alkenyl, C3-C8cycloalkyl, phenyl, benzyl; C2-C20alkyl which is interrupted once or more than once by O or S and which is unsubstituted or substituted by OH; R18a and R18b independently of one another are hydrogen; C1-C20alkyl, which is substituted once or more than once by OR15, halogen, styryl, methylstyryl, ?N?C=A or or C2-C20alkyl, which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted once or more than once by OR15, halogen, styryl, methylstyryl or or R18a andR18b are C2-C12alkenyl; C5-C12cycloalkyl, which is substituted by ?N?C=A or ?CH2?N?C=A and is additionally unsubstituted or substituted by one or more C1-C4alkyl; or R18a and R18b are C6-C12aryl, unsubstituted or substituted once or more than once by halogen, NO2, C1-C8alkyl, C2-C4alkenyl, OR11, ?N?C=A, ?CH2?N?C=A or C(O)OR18; or R18a and R18b are C7-C16arylalkyl; or R18a and R18b together are C8-C16arylcycloalkyl; or R18a and R18b independently of one another are Y3 is O, S, SO, SO2, CH2, C(CH3)2, CHCH3, C(CF3)2, (CO), or a direct bond; R19, R20, R21, R22 and R23 independently of one another are hydrogen, C1-C20alkyl; C2-C20alkyl, which is interrupted once or more than once by nonconsecutive O atoms and which is unsubstituted or substituted by OH and/or SH; or R19, R20, R21, R22 and R23 are OR11, SR11, N(R12)(R13), NO2, CN, SO2R24, OSO2R24, CF3, CCl3, halogen; or phenyl which is unsubstituted or substituted once or more than once by C1-C4alkyl or C1-C4alkoxy; or in each case two of the radicals R19, R20, R21, R22 and R23 together form C1-C20alkylene which is uninterrupted or interrupted by O, S or ?NR14; R24 is C1-C12alkyl, halogen-substituted C1-C12alkyl, phenyl, or phenyl substituted by OR11 and/or SR11; by (1) reaction of the compound of the formula (I) in whichAr, R1, R2 R3, R4, R5, R6, R11, R12, R13 and R14 are as defined above; and M is hydrogen, Li, Na or K with phosgene to give the corresponding phosphine chloride (Ii) (2) subsequent reaction with an alcohol to give the compound of the formula (Iii) in whichR is the radical of an alcohol, in particular C1-C12alkyl, C5-C8cycloalkyl or benzyl; and (3) reaction of the resulting compound of the formula (Iii) with an organoylhalideZ1-X, in whichZ1 is as defined above, but is not identical to R6 from the formula (I), and X is Cl or Br, to give the compound of the formula III.12. A photocurable composition comprising(a) at least one ethylenically unsaturated photopolymerizable compound and (b) at least one compound of the formula III as prepared in a process according to claim 11 as photoinitiator.
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