Oxime ester photoinitiators

A compound of the formula I, II or III

• wherein
• R2 is hydrogen, C1-C20alkyl which C1-C20alkyl optionally contains one or more C—C multiple bonds;
• C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14 and which uninterrupted or interrupted C3-C10cycloalkyl optionally contains one or more C—C multiple bonds;
• or R2 is C1-C20cycloalkyl which is substituted by one or more halogen, OR11, COOR11, NR12R13, C1-C20heteroaryl, C1-C20heteroaryl-(CO)O,C1-C20heteroaryl-S, CONR12R13,
• phenyl or by phenyl which is substituted by SR10, OR11 or NR12R13, which substituted C1-C20alkyl optionally contains one or more C—C multiple bonds;
• or R2 is C2-C20alkyl which is interrupted by one or more O and/or optionally is substituted by one or more halogen, OR11, COOR11, NR12R13, C1-C20heteroaryl, C1-C20heteroaryl-(CO)O, C1-C20heteroaryl-S, CONR12R13,
• phenyl or by phenyl which is substituted by SR10, OR11, or NR12R13, which interrupted C2-C20alkyl optionally contains C—C multiple bonds;
• or R2 is unsubstituted phenyl, naphthyl or C1-C20heteroaryl;
• or are phenyl, naphthyl or C1-C20heteroaryl which is substituted by one or more C1-C12alkyl, C2-C12alkenyl, C2-C12alkynyl, phenyl, halogen, CN, NO2, SR10, OR11, NR12R13 or by C3-C10cycloalkyl which optionally is interrupted by O,CO or NR14;
• or R2 is C2-C20alkanoyl, or benzoyl which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, SR10, OR11 or NR12R13;
• or R2 is C2-C12alkoxycarbonyl which optionally is interrupted by one or more O and/or optionally is substituted by one or more OH;
• or R2 is phenoxycarbonyl which is unsubstituted or substituted by one or more C1-C6alkyl, halogen, phenyl, SR10, OR11 or NR12R13;
• or R2 is are NR12R13 or
• or R2 is form a ring with one of the C-atoms of the phenyl or naphthyl ring to which the group
• is attached, wherein said formed ring is unsubstituted or substituted;
• R″2 has one of the meanings given for R2 or is
• R″′2 has one of the meanings given for R2 or is
• R1 is hydrogen, (CO)R″2, C1-C20alkoxycarbonyl, phenyl-C1-C4alkyl, C1-C20alkyl which optionally is substituted by one or more halogen, COOR11 or CONR12R13;
• or R1 is C2-C20alkyl which is interrupted by O, CO or NR14;
• or is C2-C12alkenyl which optionally is interrupted by O, CO or NR14, or is C4-C8cycloalkenyl or C2-C12alkinyl;
• or R1 is benzoyl, naphthoyl, phenyloxycarbonyl or naphtyloxycarbonyl;
• or is benzoyl, naphthoyl, phenyloxycarbonyl or naphtyloxycarbonyl each of which is substituted by one or more C1-C20alkyl, C1-C4haloalkyl, SR10, OR11, NR12R13, halogen, phenyl, COOR11, CONR12R13, CN, NO2 or by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or R1 is C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14, or is C3-C10cycloalkylcarbonyl which optionally is interrupted by O, CO or NR14, or is C3-C10cyclo-alkyloxycarbonyl which optionally is interrupted by O, CO or NR14;
• or R1 is unsubstituted phenyl or naphthyl, or is phenyl or naphthyl which is substituted by one or more C1-C20alkyl, C1-C4haloalkyl, SR10, OR11, NR12R13, halogen, phenyl, COOR11, CONR12R13, CN, NO2, or by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• R6, R7, R8, R′6, R′7, R′8, R″6, R″7, R″′6 and R″′7 independently of one another are hydrogen, halogen,
• C1-C20alkyl, C2-C20alkyl which is interrupted by O, CO or NR14, or are C2-C12alkenyl which optionally is interrupted by O, CO or NR14, or are C4-C8cycloalkenyl, C2-C12alkinyl, phenyl-C1-C4alkyl, CN, NO2 or C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or R6, R7, R8, R′6, R′7, R′8, R″6, R″7, R″′6 and R″′7 are phenyl which is unsubstituted or substituted by one or more C1-C20alkyl, halogen, CN, SR10, OR11 or NR12R13;
• or R6, R7, R8, R′6, R′7, R′8, R″6, R″7, R″′6 and R″′7 are (CO)R′2, SR10, OR11, SOR10, SO2R10 or NR12R13, wherein the substituents (CO)R′2, OR11, SR10 and NR12R13 optionally form 5- or 6-membered rings via the radicals R10, R11, R12 R13, and/or R′2 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring;
• or R″6 and R″7 in formula II together are C1-C6alkylene or C2-C6alkenylene to form a bicyclic ring together with the phenyl to which they are attached, wherein said bicyclic ring optionally is substituted by one or more C1-C20alkyl, or by C2-C20alkyl which is interrupted by O, CO or NR14, or said bicyclic ring optionally is substituted by C1-C4haloalkyl, SR10, OR11, NR12R13, halogen, phenyl, COOR11, CONR12R13, CN, NO2, or C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• provided that the group
• is attached to either ring;
• or R″′6 and R″′7 in formula III together are C2-C6alkylene or C2-C6alkenylene to form a bicyclic ring together with the phenyl to which they are attached, wherein said bicyclic ring optionally is substituted by one or more C1-C20alkyl, by C2-C20alkyl which is interrupted by O, CO or NR14, or said bicyclic ring optionally is substituted by C1-C4haloalkyl, SR10, OR11, NR12R13, halogen, phenyl, COOR11, CONR12R13, CN, NO2, or by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• provided that one or more groups (CO)R′″2 are attached to either ring;
• R′2 is hydrogen, C1-C20alkyl which C1-C20alkyl optionally contains one or more C—C multiple bonds;
• C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14 and which uninterrupted or interrupted C3-C10cycloalkyl optionally contains one or more C—C multiple bonds;
• or R2 and R′2 are C1-C20alkyl which is substituted by one or more halogen, OR11, COOR11, NR12R13, C1-C20heteroaryl, C1-C20heteroaryl-(CO)O, C1-C20heteroaryl-S, CONR12R13,
• phenyl or by phenyl which is substituted by SR10, OR11 or NR12R13, which substituted C1-C20alkyl optionally contains one or more C—C multiple bonds;
• or R2 and R′2 are C2-C20alkyl which is interrupted by one or more O and/or optionally is substituted by one or more halogen, OR11, COOR11, NR12R13, C1-C20heteroaryl, C1-C20heteroaryl-(CO)O, C1-C20heteroaryl-S, CONR12R13,
• phenyl or by phenyl which is substituted by SR10, OR11, or NR12R13, which interrupted C2-C20alkyl optionally contains C—C multiple bonds;
• or R2 and R′2 are unsubstituted phenyl, naphthyl or C1-C20heteroaryl;
• or are phenyl, naphthyl or C1-C20heteroaryl which is substituted by one or more C1-C12alkyl, C2-C12alkenyl, C2-C12alkynyl, phenyl, halogen, CN, NO2, SR10, OR11, NR12R13 or by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or R2 and R′2 are C2-C20alkanoyl, or benzoyl which is unsubstituted or substituted by one or more C1-C6alkyl, phenyl, SR10, OR11 or NR12R13;
• or R2 and R′2 are C2-C12alkoxycarbonyl which optionally is interrupted by one or more O and/or optionally is substituted by one or more OH;
• or R2 and R′2 are phenoxycarbonyl which is unsubstituted or substituted by one or more C1-C6alkyl, halogen, phenyl, SR10, OR11 or NR12R13;
• or R2 and R′2 are NR12R13 or
• or R2 and R′2 form a ring with one of the C-atoms of the phenyl or naphthyl ring to which the group (CO)R′2 is attached, wherein said formed ring is unsubstituted or substituted;
• R9 is hydrogen, C3-C8cycloalkyl, C2-C5alkenyl, C1-C20alkoxy, unsubstituted C1-C20alkyl or C1-C20alkyl which is substituted by one or more halogen, phenyl, C1-C20alkylphenyl and/or CN;
• or R9 is phenyl or naphthyl, both of which are unsubstituted or substituted by one or more C1-C6alkyl, halogen, CN, OR11, SR10 and/or NR12R13;
• or R9 is benzyloxy or phenoxy both of which are unsubstituted or substituted by one or more C1-C6alkyl and/or halogen;
• R10 is hydrogen, C1-C20alkyl, C3-C12alkenyl, C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14,
• or R10 is phenyl-C1-C4alkyl or is C1-C20alkyl which is substituted by OH, SH, CN, C3-C6alkenoxy, C1-C20heteroaryl, C1-C20heteroaryl-(CO)O, C1-C20heteroaryl-S,
• —OCH2CH2(CO)O(C1-C4alkyl),—O(CO)-(C1-C4alkyl), —O(CO)-phenyl, —(CO)OH or —(CO)O(C1-C4alkyl);
• or R10 is C2-C20alkyl which is interrupted by one or more O or S;
• or R10 is —(CH2CH2O)nH, —(CH2CH2O)n(CO)—(C1-C8alkyl), C2-C8alkanoyl, benzoyl, C3-C12alkenyl or C3-C6alkenoyl;
• or R10 is phenyl, naphthyl or C1-C20heteroaryl, each of which is unsubstituted or substituted by one or more halogen, C1-C12alkyl, C1-C12alkoxy, phenyl-C1-C3alkyloxy, phenoxy, C1-C12alkylsulfanyl, phenylsulfanyl, —N(C1-C12alkyl)2, diphenylamino, —(CO)O(C1-C8alkyl) or by (CO)N(C1-C8alkyl)2;
• or R10 is phenyl, naphtyl or C1-C20heteroaryl which forms a 5- or 6-membered ring with the phenyl ring to which the SR10 is attached via a direct bond, C1-C4alkylene, O, S, NR14 or CO, wherein said phenyl or naphthyl is unsubstituted or substituted by one or more C1-C20alkyl, C2-C20alkyl which is interrupted by O, CO or NR14, or is substituted by C3-C10cycloalkyl which is optionally interrupted by O, CO or NR14, or is substituted by halogen, C1-C20alkoxy, C1-C20alkylcarbonyl or phenylcarbonyl;
• n is an integer from 1-12;
• R11 is hydrogen, C1-C20alkyl which optionally is substituted by one or more halogen;
• or
• R11 is —(CH2CH2O)nH, —(CH2CH2O)n(CO)-(C-C8alkyl), C1-C8alkanoyl, C3-C12alkenyl, C3-C12alkenoyl, phenyl-C1-C4alkyl or is C2-C20alkyl which is interrupted by one or more O;
• or is C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or R11 is C1-C20alkyl which is substituted by OH, SH, CN, C3-C6alkenoxy, C1-C20heteroaryl, C1-C20heteroaryl-(CO)O, C1-C20heteroaryl-S, —OCH2CH2CN, —OCH2CH2(CO)O(C1-C4alkyl),
• —O(CO)-(C1-C4alkyl), —O(CO)-phenyl, —(CO)OH or —(CO)O(C1-C4alkyl);
• or R11 is benzoyl which is unsubstituted or substituted by one or more C1-C6alkyl, halogen, OH or C1-C4alkoxy;
• or R11 is phenyl, naphthyl or C1-C20heteroaryl each of which is unsubstituted or substituted by one or more halogen, OH, C1-C12alkyl, C3-C10cycloalkyl or C1-C12alkoxy;
• R12 and R13 independently of one another are hydrogen, C1-C20alkyl, C2-C20alkyl which is interrupted by O, CO or NR14, or are C2-C4hydroxyalkyl, C1-C12alkoxy, phenyl-C1-C4alkyl, (CO)R15, C2-C10alkoxyalkyl, C3-C5alkenyl or C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or R12 and R13 are phenyl or naphthyl, each of which is unsubstituted or substituted by one or more C1-C20alkoxy, (CO)R15, phenyl, NR16R17, SR10, OR11, C1-C20alkyl, by C2-C20alkyl which is interrupted by O, CO or NR14 or are substituted by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or R12 and R13 independently of each other are C2-C5alkylene or C2-C5alkenylene which is attached to one of the C-atoms of the phenyl or naphthyl ring to which the NR12R13 is attached, wherein said C2-C5alkylene or C2-C5alkenylene optionally is interrupted by O, CO or NR14;
• or
• R12 and R13 independently of one another are phenyl which is attached via a direct bond to the phenyl ring on which the NR12R13 is positioned;
• or
• R12 and R13 together with the N-atom to which they are attached form a 5-or 6-membered saturated or unsaturated ring which optionally is interrupted by O, N or NR14, and which ring is unsubstituted or substituted by one or more C1-C20alkyl, C1-C20alkoxy, ═O, SR10, OR11, NR16R17, (CO)R15, NO2, CN, phenyl or by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or
• R12 and R13 together with the N-atom to which they are attached form a heteroaromatic ring system, which heteroaromatic ring system is unsubstituted or substituted by one or more C1-C20alkyl, C1-C20alkoxy, ═O, SR10, OR11, NR16R17, (CO)R15, NO2, CN, phenyl or by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• R14 is hydrogen, C1-C20alkyl, C3-C8cycloalkyl, phenyl or (CO)R15;
• R15 is hydrogen, OH, C1-C20alkyl, C1-C4haloalkyl, C2-C20alkyl which is interrupted by O, CO or NR14, or is C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14, or is phenyl-C1-C4alkyl, SR10, OR11 or NR12R13;
• or R15 is phenyl, naphthyl or C1-C20heteroaryl all of which are unsubstituted or substituted by one or more SR10, OR11, NR12R13,
• CN, NO2, halogen, C1-C20alkyl, C1-C10haloalkyl, by C2-C20alkyl which is interrupted by O, CO or NR14 or are substituted by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• R16 and R17 independently of each other are hydrogen, C1-C20alkyl, C3-C10cycloalkyl or phenyl;
• or
• R16 and R17 together with N-atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring, which optionally is interrupted by O, S or NR14;
• or R16 and R17 independently of one another are C2-C5alkylene or C2-C5alkenylene which is attached to one of the C-atoms of the phenyl or naphthyl ring to which the NR16R17 is attached, wherein said C2-C5alkylene or C2-C5alkenylene optionally is interrupted by O, CO or NR15, and to which C2-C5alkylene or C2-C5alkenylene optionally a benzene ring is condensed;
• R18, R19, R20, R′18, R′19, and R′20 independently of one another are hydrogen, halogen,
• C1-C20alkyl, C2-C20alkyl which is interrupted by O, CO or NR14, or are C2-C12alkenyl which optionally is interrupted by O, CO or NR14, or are C4-C8cycloalkenyl, C2-C12alkinyl, phenyl-C1-C4alkyl, CN, NO2 or C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or R18, R19, R20, R′18, R′19, and R′20 are phenyl which is unsubstituted or substituted by one or more C1-C20alkyl, halogen, CN, SR10, OR11 or NR12R13;
• or R18, R19, R20, R′18, R′19, and R′20 are (CO)R′2, SR10, OR11, SOR10, SO2R10 or NR12R13, wherein the substituents (CO)R′2, OR11, SR10 and NR12R13 optionally form 5- or 6-membered rings via the radicals R10, R11, R12 R13, and/or R′2 with further substituents on the phenyl ring or with one of the carbon atoms of the phenyl ring;
• R″18 and R″19 independently of each other have one of the meanings as given for R″6 and
• R″7;
• and
• R′″18 and R′″19 independently of each another have one of the meanings as given for R′″6 and R′″7;
• R21 is COOR11, CONR12R13 or (CO)R9;
• or R21 has one of the meanings as given for R15;
• R22 is COOR11, CONR12R13 or (CO)R9;
• or R22 has one of the meanings as given for R12 and R13;
• X is O, S, SO or SO2;
• X2 is a direct bond, C1-C20alkylene which optionally is interrupted by O, CO or NR14, and which uninterrupted or interrupted C1-C20alkylene is unsubstituted or substituted by one or more halogen, OR11, COOR11, NR12R13, C1-C20heteroaryl, C1-C20heteroaryl-(CO)O, C1-C20heteroaryl-S, CONR12R13,
• phenyl or by phenyl which is substituted by halogen, C1-C20alkyl, C1-C4haloalkyl, SR10, OR11, or NR12R13, and which unsubstituted or substituted, interrupted or non-interrupted C1-C20alkylene optionally contains one or more C—C multiple bonds;
• m is an integer 1 or 2;
• R23 has one of the meanings as given for R9;
• R24 is hydrogen, C1-C20alkyl;
• C2-C20alkenyl;
• C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14, or R24 is C3-C10cycloalkenyl;
• C1-C20alkyl which is substituted by one or more halogen, OR11, COOR11, NR12R13, C1-C20heteroaryl, C1-C20heteroaryl-(CO)O, C1-C20heteroaryl-S, CONR12R13,
• or by phenyl;
• or R24 is C2-C20alkyl which is interrupted by one or more O and/or optionally is substituted by one or more halogen, OR11, COOR11, NR12R13, C1-C20heteroaryl, C1-C20heteroaryl-(CO)O, C1-C20heteroaryl-S, CONR12R13,
• or by phenyl;
• or R24 is phenyl, naphthyl or C1-C20heteroaryl, all of which optionally are substituted by one or more C1-C12alkyl, phenyl, halogen, C1-C4haloalkyl, CN, NO2, SR10, OR11, NR12R13 or by C3-C10cycloalkyl which optionally is interrupted by O, CO or NR14;
• or R24 is C2-C20alkanoyl, or benzoyl which is unsubstituted or substituted by one or more C1-C6alkyl, halogen, phenyl, SR10, OR11 or NR12R13;
• or R24 is C2-C12alkoxycarbonyl which optionally is interrupted by one or more O and/or optionally is substituted by one or more OH;
• or R24 is phenoxycarbonyl which is unsubstituted or substituted by one or more C1-C6alkyl, C1-C4haloalkyl, halogen, phenyl, SR10, OR11 or NR12R13;
• or R24 is NR12R13;
• or R24 forms a ring with one of the C-atoms of the phenyl or naphthyl ring to which the group
• is attached, wherein said formed ring is unsubstituted or substituted;
• or
• R24 is
• provided that
• R2 in formula III and R″2 in formula II
• (i) are NR12R13 or
• (ii) form a ring with one of the C-atoms of the phenyl or naphthyl ring to which the corresponding group
• ,(CO)R′2 or (CO)R″′2 is attached;
• (iii) are C1-C20alkyl which is substituted by one or more C1-C20heteroaryl, C1-C20heteroaryl-(CO)O, C1-C20heteroaryl-S or
• ;
• or
• (iv) are unsubstituted or substituted C1-C20heteroaryl.