Oxime ester photoiniators having a combined structure

Compounds of the formulae I, II and III

• wherein
• R1 is hydrogen, C3–C8cycloalkyl or C1–C12alkyl which is unsubstituted or substituted by one or more halogen, phenyl and/or CN;
• or R1 is C2–C5alkenyl;
• or R1 is phenyl which is unsubstituted or substituted by one or more C1–C6alkyl, halogen, CN, OR3, SR4 and/or NR5R6;
• or R1 is C1–C8alkoxy, benzyloxy;
• or phenoxy which is unsubstituted or substituted by one or more C1–C6alkyl and/or halogen;
• R2 and R2′ independently of each other are hydrogen;
• unsubstituted C1–C20alkyl or C1–C20alkyl substituted by one or more halogen, OR3, phenyl and/or phenyl substituted by OR3, SR4 and/or NR5R6;
• or R2 and R2′ are C3–C8cycloalkyl;
• or are C2–C20alkyl interrupted by one or more —O— and/or optionally substituted by one or more halogen, OR3, phenyl and/or phenyl substituted by OR3, SR4 and/or NR5R6;
• or R2 and R2′ are phenyl which is unsubstituted or substituted by one or more C1–C6alkyl, phenyl, halogen, OR3, SR4 and/or NR5R6;
• or R2 and R2′ are C2–C20alkanoyl or benzoyl which is unsubstituted or substituted by one or more C1–C6alkyl, phenyl, OR3, SR4 and/or NR5R6;
• or R2 and R2′ are C2–C12alkoxycarbonyl optionally interrupted by one or more —O— and/or optionally substituted by one or more hydroxyl groups;
• or R2 and R2′ are phenoxycarbonyl which is unsubstituted or substituted by C1–C6alkyl, halogen, phenyl, OR3, SR4 and/or NR5R6;
• or R2 and R2′ are CN, —CONR5R6, NO2, C1–C4haloalkyl, S(O)m—C1–C6alkyl;
• S(O)m-phenyl which optionally is substituted by C1–C12alkyl or SO2—C1–C6alkyl;
• or are SO2O-phenyl which optionally is substituted by C1–C12alkyl;
• or are diphenyl phosphinoyl or di-(C1–C4alkoxy)-phosphinoyl;
• or R2 and R2′ are a group
• Ar1 is phenyl, naphthyl, benzoyl or naphthoyl, each of which is substituted 1 to 7 times by halogen, C1–C12alkyl, C3–C8cycloalkyl, benzyl and/or phenoxycarbonyl;
• or each of which is substituted by phenyl or by phenyl which is substituted by one or more OR3, SR4 and/or NR5R6;
• or each of which is substituted by C2–C12alkoxycarbonyl optionally interrupted by one or more —O— and/or optionally substituted by one or more hydroxyl groups;
• or each of which is substituted by OR3, SR4, SOR4, SO2R4 and/or NR5R6, wherein the substituents OR3, SR4 or NR5R6 optionally form 5- or 6-membered rings via the radicals R3, R4, R5 and/or R6 with further substituents on the phenyl or naphthyl ring;
• or each of which is substituted by a group
• provided that
• if R2 is not a group (A), (B) or (C), then Ar1 is phenyl, naphthyl, benzoyl or naphthoyl, each of which is substituted by at least one group —(CO)R7, (D), (E) or (F);
• Ar2 is phenylene, naphthylene, phenylenedicarbonyl or naphthylenedicarbonyl, each of which is substituted 1 to 4 times by halogen, C1–C12alkyl, C3–C8cycloalkyl, benzyl, OR3, SR4, SOR4, SO2R4 and/or NR5R6;
• or each of which is substituted by a group —(CO)R7, (D), (E) or (F);
• provided that
• if R2 or R2′ is not a group (A), (B) or (C) and Ar2 is phenylene, naphthylene, phenylenedicarbonyl or naphthylenedicarbonyl, then Ar2 is substituted by at least one of the groups —(CO)R7, (D), (E) or (F);
• if R2 is not hydrogen or a group (A), (B) or (C), each of which is substituted by at least one of the groups —(CO)R7, (D), (E) or (F), Ar2 additionally is
• each of which is unsubstituted or substituted 1 to 4 times by halogen, C1–C12alkyl, benzyl, OR3, SR4 and/or NR5R6;
• or each of which is substituted by a group, —(CO)R7, (D), (E) or (F);
• if R2 is a group (A), (B) or (C), Ar2 additionally is
• each of which is unsubstituted or substituted by 1 to 4 times by halogen, C1–C12alkyl, benzyl, OR3, SR4 and/or NR5R6;
• or each of which is substituted by a group —(CO)R7, (D), (E) or (F);
• unsubstituted or substituted by 1 to 6 times by halogen, C1–C12alkyl, benzyl, OR3, SR4 and/or NR5R6, wherein the substituents OR3, SR4 or NR5R6 optionally form 5- or 6-membered rings via the radicals R3, R4, R5 and/or R6 with one of the carbon atoms of the phenyl or naphthyl ring;
• or each of which is substituted by a group —(CO)R7, (D), (E) or (F);
• Ar3 is phenyl, naphthyl or coumarinyl, each of which is substituted 1 to 7 times by halogen, C1–C12alkyl, C3–C8cycloalkyl, benzyl and/or phenoxycarbonyl;
• or each of which is substituted by phenyl or by phenyl which is substituted by one or more OR3, SR4 and/or NR5R6;
• or each of which is substituted by C2–C12alkoxycarbonyl optionally interrupted by one or more —O— and/or optionally substituted by one or more hydroxyl groups;
• or each of which is substituted by OR3, SR4, SOR4, SO2R4 and/or NR5R6;
• M1 is C1–C20alkylene, which is optionally interrupted by one or more —O— and/or optionally substituted by one or more halogen, OR3, phenyl or phenyl substituted by OR3, SR4 and/or NR5R6;
• or M1 is phenylene or naphthylene, each of which is unsubstituted or substituted by one or more C1–C6alkyl, phenyl, halogen, OR3, SR4 and/or NR5R6;
• or M1 is a group
• (H), which is optionally substituted 1 to 4 times by halogen, C1–C12alkyl, benzyl, OR3, SR4, SOR4, SO2R4 and/or NR5R6, wherein the substituents OR3, SR4 or NR5R6 optionally form 5- or 6-membered rings via the radicals R3, R4, R5 and/or R6 with one of the carbon atoms of the other phenyl ring;
• provided that
• if Ar1 is phenyl, naphthyl, benzoyl or naphthoyl, each of which is not substituted by a group —(CO)R7, (D), (E) or (F), then M1 is a group (G) or (H), which is optionally substituted 1 to 4 times by halogen, C1–C12alkyl, benzyl, OR3, SR4, SOR4, SO2R4 and/or NR5R6, wherein the substituents OR3, SR4 or NR5R6 optionally form 5- or 6-membered rings via the radicals R3, R4, R5 and/or R6 with one of the carbon atoms of the other phenyl ring;
• M2 is a direct bond, C1–C10alkylene or cyclohexylene;
• or M2 is C1–C10alkylene or C1–C10alkylene-X—, each of which is optionally interrupted by one or more —O— and/or optionally substituted by one or more halogen, OR3, phenyl or phenyl substituted by OR3, SR4 and/or NR5R6;
• or M2 is phenylene, naphthylene or phenylene-X—, each of which is unsubstituted or substituted by one or more C1C6alkyl, phenyl, halogen, OR3, SR4 and/or NR5R6;
• or M2 is C1–C10alkylene-C(O)—X—, C1–C10alkylene-X—C(O)—, phenylene-C(O)—X— or C1–C10alkylene-phenylene-X—;
• M3 and M3′ independently each other are a direct bond, C1–C10alkylene or cyclohexylene;
• or M3 and M3′ are C1–C10alkylene or C1–C10alkylene-X—, each of which is optionally interrupted by one or more —O— and/or optionally substituted by one or more halogen, OR3, phenyl or phenyl substituted by OR3, SR4 and/or NR5R6;
• or M3 and M3′ are phenylene, naphthylene or phenylene-X—, each of which is unsubstituted or substituted by one or more C1–C6alkyl, phenyl, halogen, OR3, SR4 and/or NR5R6;
• or M3 and M3′ are C1–C10alkylene-C(O)—X, C1–C10alkylene-X—C(O)—, phenylene-C(O)—X—, C1–C10alkylene-phenylene-X— or phenylene-(CO)-phenylene;
• provided that
• M3 and M3′ are not C1–C10alkylene-X—, phenylene-X— or C1–C10alkylene-phenylene-X—, if Ar1 is naphthyl, naphthoyl or 2-R3O-phenyl, each of which is not substituted by a group —(CO)R7, (D), (E) or (F);
• M4 and M4′ independently of each other are a direct bond, —O—, —S—, —NR5′— or —CO—;
• or M4 and M4′ are —Y—(C1–C10alkylene)-Y′— which is optionally interrupted by one or more —O— and/or optionally substituted by one or more halogen, OR3, phenyl or phenyl substituted by OR3, SR4 and/or NR5R6;
• or M4 and M4′ are —Y-phenylene-Y′— or —Y— naphthylene-Y′—, each of which is unsubstituted or substituted by one or more C1–C6alkyl, phenyl, halogen, OR3, SR4 and/or NR5R6;
• or M4 and M4′ are —Y—(C1–C4alkylene)-O-phenylene-O—(C1–C4alkylene)-Y′— or —Y—(C1–C4alkylene)-O-naphthylene-O—(C1–C4alkylene)-Y′—;
• or M4 and M4′ are —X—C1–C10alkylene-X—C(O)— which is optionally interrupted by one or more —O—;
• or M4 and M4′ are a group
• which is optionally substituted 1 to 4 times by halogen, C1–C12alkyl, benzyl, OR3, SR4, SOR4, SO2R4 and/or NR5R6, wherein the substituents OR3, SR4 or NR5R6 optionally form 5- or 6-membered rings via the radicals R3, R4, R5 and/or R6 with one of the carbon atoms of the other phenyl ring or that of the phenyl or naphthyl ring attached to this group;
• M4″ is a direct bond, —O—, —S—, —NR5′— or —CO—;
• or M4″ is —Y—(C1–C10alkylene)-Y′— which is optionally interrupted by one or more —O— and/or optionally substituted by one or more halogen, OR3, phenyl or phenyl substituted by OR3, SR4 and/or NR5R6;
• or M4″ is —Y-phenylene-Y′— or —Y— naphthylene-Y′—, each of which is unsubstituted or substituted by one or more C1–C6alkyl, phenyl, halogen, OR3, SR4 and/or NR5R6;
• or M4″ is —X—C1–C10alkylene-X—C(O)— which is optionally interrupted by one or more —O—;
• X and X′ independently each other are —O—, —S— or —NR5—;
• Y and Y′ independently each other are a direct bond, —O—, —S— or —NR5—;
• R3 is hydrogen, C1–C20alkyl or phenyl-C1–C3alkyl;
• or R3 is C1–C8alkyl which is substituted by —OH, —SH, —CN, C3–C6alkenoxy, —OCH2CH2CN, —OCH2CH2(CO)O(C1–C4alkyl), —O(CO)—(C1–C4alkyl), —O(CO)-phenyl, —(CO)OH and/or —(CO)O(C1–C4alkyl);
• or R3 is C2–C12alkyl which is interrupted by one or more —O—;
• or R3 is —(CH2CH2O)n+1H, —(CH2CH2O)n(CO)—(C1–C8alkyl), C1–C8alkanoyl, C2–C12alkenyl, C3–C6alkenoyl, C3–C8cycloalkyl;
• or R3 is benzoyl which is unsubstituted or substituted by one or more C1–C6alkyl, halogen, —OH and/or C1–C4alkoxy;
• or R3 is phenyl or naphthyl each of which is unsubstituted or substituted by halogen, —OH, C1–C12alkyl, C1–C12alkoxy, phenoxy, C1–C12alkylsulfanyl, phenylsulfanyl, —N(C1–C12alkyl)2 and/or diphenylamino;
• n is 1–20;
• R4 is hydrogen, C1–C20alkyl, C2–C12alkenyl, C3–C8cycloalkyl, phenyl-C1–C3alkyl;
• or R4 is C1–C8alkyl which is substituted by —OH, —SH, —CN, C3–C6alkenoxy, —OCH2CH2CN, —OCH2CH2(CO)O(C1–C4alkyl), —O(CO)—(C1–C4alkyl), —O(CO)-phenyl, —(CO)OH or —(CO)O(C1–C4alkyl);
• or R4 is C2–C12alkyl which is interrupted by one or more —O— or —S—;
• or R4 is —(CH2CH2O)n+1H, —(CH2CH2O)n(CO)—(C1–C8alkyl), C1–C8alkanoyl, C2–C12alkenyl, C3–C6alkenoyl;
• or R4 is benzoyl which is unsubstituted or substituted by one or more C1–C6alkyl, halogen, —OH, C1–C4alkoxy or C1–C4alkylsulfanyl;
• or R4 is phenyl or naphthyl, each of which is unsubstituted or substituted by halogen, C1–C12alkyl, C1–C12alkoxy, phenyl-C1–C3alkyloxy, phenoxy, C1–C12alkylsulfanyl, phenylsulfanyl, —N(C1–C12alkyl)2, diphenylamino, —(CO)O(C1–C8alkyl), —(CO)—C1–C8alkyl or (CO)N(C1–C8alkyl)2;
• R5 and R6 independently of each other are hydrogen, C1–C20alkyl, C2–C4hydroxyalkyl, C2–C10alkoxyalkyl, C2–C5alkenyl, C3–C8cycloalkyl, phenyl-C1–C3alkyl, C1–C8alkanoyl, C3–C12-alkenoyl, benzoyl;
• or R5 and R6 are phenyl or naphthyl, each of which is unsubstituted or substituted by C1–C12alkyl, benzoyl or C1–C12alkoxy;
• or R5 and R6 together are C2–C6alkylene optionally interrupted by —O— or —NR3— and/or optionally substituted by hydroxyl, C1–C4alkoxy, C2–C4alkanoyloxy or benzoyloxy;
• R5′ is hydrogen, C1–C20alkyl, C2–C4hydroxyalkyl, C2–C10alkoxyalkyl, C2–C5alkenyl, C3–C8cycloalkyl, phenyl-C1–C3alkyl, C2–C8alkanoyl, C3–C12alkenoyl, benzoyl;
• or R5′ is phenyl or naphthyl, each of which is unsubstituted or substituted by C1–C12alkyl or C1–C12alkoxy;
• or R5′ is a group
• R7 is hydrogen, C1–C20alkyl;
• C1–C8alkyl which is substituted by halogen, phenyl, —OH, —SH, —CN, C3–C6alkenoxy, —OCH2CH2CN, —OCH2CH2(CO)O(C1–C4alkyl), —O(CO)—(C1–C4alkyl), —O(CO)-phenyl, —(CO)OH or —(CO)O(C1–C4alkyl);
• or R7 is C2–C12alkyl which is interrupted by one or more —O—;
• or R7 is —(CH2CH2O)n+1H, —(CH2CH2O)n(CO)—(C1–C8alkyl), C2–C12alkenyl or C3–C8cycloalkyl;
• or R7 is phenyl, biphenylyl or naphthyl, each of which optionally is substituted by one or more C1–C6alkyl, halogen, CN, OR3, SR4, SOR4, SO2R4 or NR5R6, wherein the substitutents OR3, SR4 or NR5R6 optionally form 5- or 6-membered rings via the radicals R3, R4, R5 and/or R6 with one of the carbon atoms of the phenyl, biphenylyl or naphthyl ring;
• R8, R9, R8′ and R9′ independently of each other are hydrogen, C1–C12alkyl optionally substituted by one or more halogen, phenyl, CN, —OH, —SH, C1–C4alkoxy, —(CO)OH or —(CO)O(C1–C4alkyl);
• or R8, R9, R8′ and R9′ are phenyl optionally substituted by one or more C1–C6alkyl, halogen, CN, OR3, SR4 or NR5R6;
• or R8, R9, R8′ and R9′ are halogen, CN, OR3, SR4, SOR4, SO2R4 or NR5R6, wherein the substituents OR3, SR4 or NR5R6 optionally form 5- or 6-membered rings via the radicals R3, R4, R5 and/or R6 with one of the carbon atoms of the phenyl, naphthyl, benzoyl or naphthoyl group of Ar1 or that of the substituent R7 or one of the carbon atoms of the naphthylene or phenylene group of M3;
• or R8 and R9 or R8′ and R9′ together are a group
• R10, R11, R12 and R13 independently of one another are hydrogen, C1–C12alkyl optionally substituted by one or more halogen, phenyl, CN, —OH, —SH, C1–C4alkoxy, —(CO)OH or —(CO)O(C1–C4alkyl);
• or R10, R11, R12 and R13 are phenyl optionally substituted by one or more C1–C6alkyl, halogen, CN, OR3, SR4 or NR5R6;
• or R10, R11, R12 and R13 are halogen, CN, OR3, SR4 or NR5R6;
• and
• R14 and R15 independently of each other are hydrogen, C1–C12alkyl optionally substituted by one or more halogen, phenyl, CN, —OH, —SH, C1–C4alkoxy, —(CO)OH or —(CO)O(C1–C4alkyl);
• or R14 and R15 are phenyl optionally substituted by one or more C1–C6alkyl, halogen, CN, OR3, SR4 or NR5R6;
• provided that
• (i) if Ar1 is phenyl, which is substituted by a group (E) and is not additionally substituted by a group (D) or (F), and R2 is hydrogen, then M4 is no direct bond, S or NR5
• (ii) if Ar1 is naphthyl, which is substituted by a group (E) and is not additionally substituted by a group (D) or (F), then M4 is no direct bond, S, O or NR5;
• (iii) if M4 is O and R2 is hydrogen, then Ar1 is not phenyl which is substituted by a group (E) and is not additionally substituted by a group (D) or (F) and simultaneously substituted by OR3 at the ortho position or by SR4, NR5R6, phenyl, —(CO)R7 or SO2R7;
• (iv) if Ar, is phenyl, which is substituted by —(CO)R7 and is not additionally substituted by a group (D) or (F), then R2 is not hydrogen;
• (v) if Ar, is phenyl, which is substituted by —(CO)R7 and is not additionally substituted by a group (D) or (F), and R2 is not hydrogen, then R7 is not phenyl or C1–C11alkyl;
• (vi) if Ar1 is naphthyl, which is substituted by —(CO)R7 and is not additionally substituted by a group (D) or (F), then R7 is not phenyl or C1–C11alkyl.