Oxime ester photoinitiators

Abstract

Oxime ester compounds of the formula I, II, III, IV or V ##STR00001##
wherein
Z is for example ##STR00002##
Z.sub.1 for is NO.sub.2, unsubstituted or substituted C.sub.7-C.sub.20 aroyl or unsubstituted or substituted C.sub.4-C.sub.20heteroaroyl; provided that at least one Z.sub.1 is other than NO.sub.2; Z.sub.2 is for example unsubstituted or substituted C.sub.7-C.sub.20aroyl; R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 for example are hydrogen, halogen, or unsubstituted or substituted C.sub.1-C.sub.20alkyl, unsubstituted or substituted C.sub.6-C.sub.20aryl, or unsubstituted or substituted C.sub.4-C.sub.20heteroaryl; R.sub.9, R.sub.10, R.sub.11, R.sub.12 and R.sub.13 for example are hydrogen, halogen, OR.sub.16, unsubstituted or substituted C.sub.1-C.sub.20alkyl; provided that R.sub.9 and R.sub.13 are neither hydrogen nor fluorine; R.sub.14 is for example unsubstituted or substituted C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl Q is for example C.sub.6-C.sub.20arylene or C.sub.3-C.sub.20heteroarylene; Q.sub.1 is —C.sub.1-C.sub.20alkylene-CO—; Q.sub.2 is naphthoylene; Q.sub.3 is for example phenylene; L is for example O-alkylene-O—; R.sub.15 is for example hydrogen or C.sub.1-C.sub.20alkyl; R.sub.20 is for example hydrogen, or unsubstituted or substituted C.sub.1-C.sub.20alkyl; are effective photoinitiators.

Claims

1. A compounds of formula III ##STR00198## wherein: Z.sub.1 independently of each other are C.sub.7-C.sub.20 aroyl or C.sub.4-C.sub.20 heteroaroyl, where C.sub.7-C.sub.20 aroyl or C.sub.4-C.sub.20 heteroaroyl is unsubstituted or substituted by one or more identical or different R.sub.10; R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 independently of each other are hydrogen, halogen, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19, or C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by one or more halogen, OR.sub.16, COOR.sub.16, CONR.sub.18R.sub.19 or NR.sub.18R.sub.19; or R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 independently of each other are C.sub.6-C.sub.20 aryl, or C.sub.4-C.sub.20 heteroaryl, each of which is unsubstituted or substituted by one or more C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.4 haloalkyl or halogen; R.sub.10 is hydrogen, halogen, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19, CN, NO.sub.2 or C.sub.2-C.sub.20 alkyl which is interrupted by one or more O, S or NR.sub.21, wherein the interrupted C.sub.2-C.sub.20 alkyl is unsubstituted or substituted by one or more halogen, OR.sub.16, COOR.sub.16, SR.sub.17, CONR.sub.18R.sub.19, C.sub.6-C.sub.20aryl, C.sub.3-C.sub.20 heteroaryl or C.sub.3-C.sub.20 cycloalkyl, C.sub.3-C.sub.20 cycloalkyl interrupted by one or more O, S, NR.sub.21; or R.sub.10 is C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by one or more halogen, OR.sub.16, SR.sub.17, COOR.sub.16, CONR.sub.18R.sub.19, NR.sub.18R.sub.19, phenyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.20 heteroaryl or M; R.sub.14 is C.sub.6-C.sub.20 aryl or C.sub.3-C.sub.20 heteroaryl each of which is unsubstituted or substituted by one or more phenyl, halogen, C.sub.1-C.sub.4 haloalkyl, CN, NO.sub.2, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19, PO(OC.sub.kH.sub.2k+1).sub.2, SO—C.sub.1-C.sub.10 alkyl, SO.sub.2—C.sub.1-C.sub.10 alkyl, M, ##STR00199##  or by C.sub.2-C.sub.20 alkyl which is interrupted by one or more O, CO, S, C(O)O, OC(O), phenylene, naphthylene or by NR.sub.21, or each of which C.sub.6-C.sub.20 aryl or C.sub.3-C.sub.20 heteroaryl is substituted by one or more C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by one or more halogen, COOR.sub.16, CONR.sub.18R.sub.19, phenyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.3-C.sub.20 heteroaryl, C.sub.6-C.sub.20 aryloxycarbonyl, C.sub.3-C.sub.20 heteroaryloxycarbonyl, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19 or by M; Q.sub.1 is a direct bond, C.sub.1-C.sub.20 alkylene, C.sub.1-C.sub.20 alkenylene, which C.sub.1-C.sub.20 alkylene OR C.sub.1-C.sub.20 alkenylene are unsubstituted or substituted by one or more halogen, OR.sub.16, COOR.sub.16, NR.sub.18R.sub.19, C.sub.1-C.sub.20 heteroaryl, CONR.sub.18R.sub.19, ##STR00200##  phenyl or by phenyl substituted by halogen, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.4 haloalkyl, OR.sub.16, SR.sub.17, or NR.sub.18R.sub.19; or Q.sub.1 is C.sub.3-C.sub.10 cycloalkylene or C.sub.3-C.sub.10 cycloalkenylene, both of which optionally are interrupted by O, CO or NR.sub.21; or Q.sub.1 is C.sub.2-C.sub.20 alkylene interrupted by one or more O or C.sub.2-C.sub.20 alkenylene interrupted by one or more O, which interrupted C.sub.2-C.sub.20 alkylene or C.sub.2-C.sub.20 alkenylene is unsubstituted or substituted by one or more halogen, OR.sub.16, COOR.sub.16, NR.sub.18R.sub.19, C.sub.1-C.sub.20 heteroaryl, CONR.sub.18R.sub.19, ##STR00201##  phenyl or by phenyl substituted by halogen, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.4 haloalkyl, OR.sub.16, SR.sub.17, or NR.sub.18R.sub.19; or Q.sub.1 is phenylene, naphthylene, coumarinylene or C.sub.1-C.sub.20 heteroarylene, each of which is unsubstituted or substituted by one or more C.sub.1-C.sub.12 alkyl, phenyl, halogen, C.sub.1-C.sub.4 haloalkyl, CN, NO.sub.2, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19 or by C.sub.3-C.sub.10 cycloalkyl which optionally is interrupted by O, CO or NR.sub.21; or Q.sub.1 is phenylene-O* or naphthylene-O*, each of which is unsubstituted or substituted by one or more C.sub.1-C.sub.6 alkyl, halogen, phenyl, OR.sub.16, SR.sub.17, or NR.sub.18R.sub.19; or Q.sub.1 is C.sub.1-C.sub.20 alkylene-CO* or phenylene-CO* which is unsubstituted or substituted by one or more C.sub.1-C.sub.6 alkyl, halogen, phenyl, OR.sub.16, SR.sub.17, or NR.sub.18R.sub.19; or Q.sub.1 is C.sub.1-C.sub.20alkylene-O—CO* which is optionally interrupted by one or more O and which interrupted or uninterrupted C.sub.1-C.sub.20 alkylene-O—CO* is unsubstituted or substituted by one or more OH; or Q.sub.1 is phenylene-O—CO* which is unsubstituted or substituted by one or more C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.4 haloalkyl, halogen, phenyl, OR.sub.16, SR.sub.17, or NR.sub.18R.sub.19; or Q.sub.1 is ##STR00202## p is an integer 1 or 2; where the asterix in the definitions for Q.sub.1 denotes the bond to L; M is ##STR00203## G is NO.sub.2 or —COR.sub.28; L is C.sub.1-C.sub.20 alkylene, C.sub.2-C.sub.12 alkenylene, O-phenylene-O, O-naphthylene-O, S—C.sub.1-C.sub.20 alkylene-S, S-phenylene-S, S-naphthylene-S, C.sub.2-C.sub.20alkylene which is interrupted by one or more groups selected from the group consisting of O, S, CO, (CO)O, O(CO), phenylene and naphthylene, or L is O—C.sub.1-C.sub.20 alkylene-O, O—C.sub.2-C.sub.20alkylene-O which is interrupted by one or more groups selected from the group consisting of O, S, CO, (CO)O, O(CO), phenylene and naphthylene, or L is S—C.sub.2-C.sub.20 alkylene-S which is interrupted by one or more groups selected from the group consisting of O, S, CO, (CO)O, O(CO), phenylene and naphthylene, wherein all radicals L as defined are unsubstituted or substituted by one or more halogen; R″.sub.14 is C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by phenyl or by phenyl which is substituted by one or more halogen, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.4 haloalkyl, OR.sub.16, SR.sub.17 or by NR.sub.18R.sub.19; or R″.sub.14 is C.sub.2-C.sub.20 alkyl which is interrupted by one or more O, CO, S, C(O)O, OC(O), phenylene, naphthylene or NR.sub.21, wherein the interrupted C.sub.2-C.sub.20 alkyl is unsubstituted or substituted by one or more halogen, OR.sub.16, COOR.sub.16, CONR.sub.18R.sub.19, phenyl or by phenyl which is substituted by OR.sub.16, SR.sub.17 or by NR.sub.18R.sub.19; or R″.sub.14 is CN, CONR.sub.18R.sub.19, NO.sub.2, C.sub.1-C.sub.4 haloalkyl, S(O).sub.m—C.sub.1-C.sub.6 alkyl; S(O).sub.m-phenyl which is unsubstituted or substituted by C.sub.1-C.sub.12 alkyl or SO.sub.2—C.sub.1-C.sub.6 alkyl; or R″.sub.14 is SO.sub.2O-phenyl which is unsubstituted or substituted by C.sub.1-C.sub.12 alkyl; or is diphenyl phosphinoyl or di-(C.sub.1-C.sub.4 alkoxy)-phosphinoyl; or R″.sub.14 is C.sub.6-C.sub.20 aryl or C.sub.3-C.sub.20 heteroaryl each of which is unsubstituted or substituted by one or more phenyl, halogen, C.sub.1-C.sub.4 haloalkyl, CN, NO.sub.2, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19, PO(OC.sub.kH.sub.2k+1).sub.2, SO—C.sub.1-C.sub.10 alkyl, SO.sub.2—C.sub.1-C.sub.10 alkyl, or by C.sub.2-C.sub.20 alkyl which is interrupted by one or more O, CO, S, C(O)O, OC(O), phenylene, naphthylene or by NR.sub.21, or each of which is substituted by one or more C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by one or more halogen, COOR.sub.16, CONR.sub.18R.sub.19, phenyl, C.sub.3-C.sub.8cycloalkyl, C.sub.3-C.sub.20heteroaryl, C.sub.6-C.sub.20aryloxycarbonyl, C.sub.3-C.sub.20heteroaryloxycarbonyl, OR.sub.16, SR.sub.17 or by NR.sub.18R.sub.19; R.sub.15 is C.sub.3-C.sub.8 cycloalkyl, C.sub.2-C.sub.5 alkenyl, C.sub.1-C.sub.20 alkoxy or C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by one or more halogen, phenyl, C.sub.1-C.sub.20 alkylphenyl or CN; k is an integer 1-10; m is an integer 1 or 2; R′.sub.14 has one of the meanings as given for R.sub.14 or is C.sub.1-C.sub.20 alkyl; R′.sub.15 has one of the meanings as given for R.sub.15; X.sub.1 is O, CO, S or a direct bond; X.sub.2 is O, S, SO or SO.sub.2; X.sub.3 is O, S or NR′.sub.20; R.sub.16 is hydrogen, phenyl-C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.20 alkyl, which is unsubstituted or substituted by one or more halogen, OH, SH, CN, C.sub.3-C.sub.6 alkenoxy, O(C.sub.1-C.sub.4 alkyl), OCH.sub.2CH.sub.2CN, OCH.sub.2CH.sub.2(CO)O(C.sub.1-C.sub.4alkyl), O(CO)—(C.sub.1-C.sub.4alkyl), O(CO)—(C.sub.2-C.sub.4)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C.sub.1-C.sub.4alkyl), C.sub.3-C.sub.20cycloalkyl, SO.sub.2—(C.sub.1-C.sub.4haloalkyl), O(C.sub.1-C.sub.4haloalkyl), O(C.sub.1-C.sub.20arylene)-M, or by C.sub.3-C.sub.20cycloalkyl which is interrupted by one or more O; or R.sub.16 is C.sub.2-C.sub.20alkyl which is interrupted by one or more O, S or NR.sub.21, which interrupted C.sub.2-C.sub.20alkyl is unsubstituted or substituted by O—C.sub.6-C.sub.20arylene-M, in which O—C.sub.6-C.sub.20arylene-M, the arylene is unsubstituted or substituted by one or more C.sub.1-C.sub.6alkyl or O(C.sub.1-C.sub.6alkyl); or R.sub.16 is (CH.sub.2CH.sub.2O).sub.n+1H, (CH.sub.2CH.sub.2O).sub.n(CO)—(C.sub.1-C.sub.8alkyl), C.sub.1-C.sub.8alkanoyl, C.sub.2-C.sub.12alkenyl, C.sub.3-C.sub.6alkenoyl, or C.sub.3-C.sub.20cycloalkyl which is uninterrupted or interrupted by one or more O, S, CO or NR.sub.21; or R.sub.16 is C.sub.1-C.sub.8alkyl-C.sub.3-C.sub.10cycloalkyl which is uninterrupted or interrupted by one or more O; or R.sub.16 is benzoyl which is unsubstituted or substituted by one or more C.sub.1-C.sub.6alkyl, halogen, OH, or C.sub.1-C.sub.3alkoxy; or R.sub.16 is phenyl, naphthyl or C.sub.3-C.sub.20heteroaryl, each of which is unsubstituted or substituted by one or more halogen, OH, C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, CN, NO.sub.2, phenyl-C.sub.1-C.sub.3alkyloxy, phenoxy, C.sub.1-C.sub.12alkylsulfanyl, phenylsulfanyl, N(C.sub.1-C.sub.12alkyl).sub.2, diphenylamino or ##STR00204## n is 1-20; R.sub.17 is hydrogen, C.sub.2-C.sub.12alkenyl, C.sub.3-C.sub.20cycloalkyl or phenyl-C.sub.1-C.sub.3alkyl, wherein the C.sub.2-C.sub.12alkenyl, C.sub.3-C.sub.20cycloalkyl or phenyl-C.sub.1-C.sub.3alkyl is uninterrupted or interrupted by one or more O, S, CO or NR.sub.21; or R.sub.17 is C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more OH, SH, CN, C.sub.3-C.sub.6alkenoxy, OCH.sub.2CH.sub.2CN, OCH.sub.2CH.sub.2(CO)O(C.sub.1-C.sub.4alkyl), O(CO)—(C.sub.2-C.sub.4)alkenyl, O(CO)—(C.sub.1-C.sub.4alkyl), O(CO)-phenyl or COOR.sub.16 or S—C.sub.6-C.sub.20arylene-M; or R.sub.17 is C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more OH, SH, CN, C.sub.3-C.sub.6alkenoxy, OCH.sub.2CH.sub.2CN, OCH.sub.2CH.sub.2(CO)O(C.sub.1-C.sub.4alkyl), O(CO)—(C.sub.2-C.sub.4)alkenyl, O(CO)—(C.sub.1-C.sub.4alkyl), O(CO)-phenyl or COOR.sub.16; or R.sub.17 is C.sub.2-C.sub.20alkyl which is interrupted by one or more O, S, CO or NR.sub.21, which interrupted C.sub.2-C.sub.20alkyl is unsubstituted or substituted by S—C.sub.6-C.sub.20arylene-M; or R.sub.17 (CH.sub.2CH.sub.2O).sub.nH, (CH.sub.2CH.sub.2O).sub.n(CO)—(C.sub.1-C.sub.8alkyl), C.sub.2-C.sub.8alkanoyl or C.sub.3-C.sub.6alkenoyl; or R.sub.17 is benzoyl which is unsubstituted or substituted by one or more C.sub.1-C.sub.6alkyl, halogen, OH, C.sub.1-C.sub.4alkoxy or C.sub.1-C.sub.4alkylsulfanyl; or R.sub.17 is phenyl, naphthyl or C.sub.3-C.sub.20heteroaryl, each of which is unsubstituted or substituted by one or more halogen, C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.12alkoxy, CN, NO.sub.2, phenyl-C.sub.1-C.sub.3alkyloxy, phenoxy, C.sub.1-C.sub.12alkylsulfanyl, phenylsulfanyl, N(C.sub.1-C.sub.12alkyl).sub.2, diphenylamino, (CO)O(C.sub.1-C.sub.8alkyl), (CO)—C.sub.1-C.sub.8alkyl, (CO)N(C.sub.1-C.sub.8alkyl).sub.2 or ##STR00205## R.sub.18 and R.sub.19 independently of each other are hydrogen, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.4hydroxyalkyl, C.sub.2-C.sub.10alkoxyalkyl, C.sub.2-C.sub.5alkenyl, C.sub.3-C.sub.20cycloalkyl, phenyl-C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.8alkanoyl, C.sub.1-C.sub.8alkanoyloxy, C.sub.3-C.sub.12alkenoyl, SO.sub.2—(C.sub.1-C.sub.4haloalkyl) or benzoyl; or R.sub.18 and R.sub.19 are phenyl, naphthyl or C.sub.3-C.sub.20heteroaryl, each of which is unsubstituted or substituted by one or more halogen, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.20alkoxy, C.sub.1-C.sub.12alkyl, benzoyl or C.sub.1-C.sub.12alkoxy; or R.sub.18 and R.sub.19 together with the N-atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is uninterrupted or is interrupted by O, S, or NR.sub.21, and which 5- or 6-membered saturated or unsaturated ring is unsubstituted or substituted by one or more C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20alkoxy, ═O, OR.sub.16, SR.sub.17, NR.sub.31R.sub.32, COR.sub.41, NO.sub.2, halogen, C.sub.1-C.sub.4-haloalkyl, CN, phenyl, ##STR00206##  or by C.sub.3-C.sub.20 cyclalkyl which is uninterrupted or is interrupted by one or more O, S, CO or NR.sub.21; or R.sub.18 and R.sub.19 together with the N-atom to which they are attached form a group ##STR00207## R.sub.20 is hydrogen, COR.sub.41 or C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more halogen, OR.sub.16, SR.sub.17, COOR.sub.16, CONR.sub.18R.sub.19, NR.sub.18R.sub.19, PO(OC.sub.kH.sub.2k+1).sub.2 or M; or R.sub.20 is C.sub.2-C.sub.20alkyl which is interrupted by one or more O, CO, C(O)O, OC(O) or NR.sub.21, wherein the interrupted C.sub.2-C.sub.20alkyl is unsubstituted or substituted by one or more halogen, OR.sub.16, SR.sub.17, COOR.sub.16, CONR.sub.18R.sub.19, NR.sub.18R.sub.19 or M; or R.sub.20 is C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl each of which is unsubstituted or substituted by one or more phenyl, halogen, C.sub.1-C.sub.4haloalkyl, CN, NO.sub.2, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19, M, Z, ##STR00208##  or by C.sub.1-C.sub.20alkyl which is interrupted by one or more O, S or NR.sub.21, or each of which C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl is substituted by one or more C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more halogen, COOR.sub.16, CONR.sub.18R.sub.19, phenyl, C.sub.3-C.sub.8cycloalkyl, C.sub.3-C.sub.20heteroaryl, C.sub.6-C.sub.20aryloxycarbonyl, C.sub.3-C.sub.20heteroaryloxycarbonyl, OR.sub.16, SR.sub.17 or NR.sub.18R.sub.19; R.sub.21 is hydrogen, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.4haloalkyl or C.sub.2-C.sub.20alkyl which is interrupted by one or more O, CO, C(O)O or OC(CO), or R.sub.21 is COR.sub.41, phenyl-C.sub.1-C.sub.4alkyl or C.sub.3-C.sub.5cycloalkyl which is uninterrupted or is interrupted by one or more O or CO, or R.sub.21 is phenyl or naphthyl both of which are unsubstituted or substituted by one or more C.sub.1-C.sub.20alkyl, halogen, C.sub.1-C.sub.4haloalkyl, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19 or ##STR00209## R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26 or R.sub.27 independently of each other are hydrogen, COR.sub.41, NO.sub.2 or ##STR00210##  or one of R.sub.22, R.sub.23 or R.sub.24 and one of R.sub.25, R.sub.26 or R.sub.27 together with X.sub.3 and the phenyl rings to which they are attached form a heteroaromatic ring system; R.sub.28 is C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl each of which is unsubstituted or substituted by one or more phenyl, halogen, C.sub.1-C.sub.4haloalkyl, CN, NO.sub.2, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19 or by C.sub.2-C.sub.20 alkyl which is interrupted by one or more O, S or NR.sub.21, or each of which C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl is substituted by one or more C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more halogen, COOR.sub.16, CONR.sub.8R.sub.9, phenyl, C.sub.3-C.sub.8cycloalkyl, C.sub.3-C.sub.20heteroaryl, C.sub.6-C.sub.20aryloxycarbonyl, C.sub.3-C.sub.20heteroaryloxycarbonyl, OR.sub.16, SR.sub.17 or NR.sub.8R.sub.9; R.sub.29 is COOR.sub.16, CONR.sub.18R.sub.19, (CO)R.sub.16; or R.sub.29 has one of the meanings given for R.sub.18 and R.sub.19; R.sub.30 is COOR.sub.16, CONR.sub.18R.sub.19, (CO)R.sub.16; or R.sub.30 has one of the meanings given for R.sub.16; R.sub.33, R.sub.34, R.sub.35, R.sub.36, R.sub.37, R.sub.38, R.sub.39 and R.sub.40 independently of each other are hydrogen, ##STR00211##  NO.sub.2, COR.sub.41, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.4haloalkyl, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19, halogen, CN, phenyl or C.sub.3-C.sub.20cycloalkyl which is uninterrupted or is interrupted by one or more O, S, CO or NR.sub.21; or R.sub.35 and R.sub.36 or R.sub.37 and R.sub.38 or both, R.sub.35 and R.sub.36 and R.sub.37 and R.sub.38 are ##STR00212## R.sub.41 is C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl each of which is unsubstituted or substituted by one or more phenyl, halogen, C.sub.1-C.sub.4haloalkyl, CN, NO.sub.2, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19 or by C.sub.2-C.sub.20alkyl which is interrupted by one or more O, S or NR.sub.21, or each of which C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl is substituted by one or more C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more halogen, COOR.sub.16, CONR.sub.18R.sub.19, phenyl, C.sub.3-C.sub.8cycloalkyl, C.sub.3-C.sub.20heteroaryl, C.sub.6-C.sub.20aryloxycarbonyl, C.sub.3-C.sub.20heteroaryloxycarbonyl, OR.sub.16, SR.sub.17 or NR.sub.18R.sub.19; or R.sub.41 is ##STR00213## or R.sub.41 is hydrogen, OH, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.2-C.sub.20alkyl which is interrupted by one or more O, CO or NR.sub.21, or R.sub.41 is C.sub.3-C.sub.20cycloalkyl which is uninterrupted or is interrupted by O, S, CO or NR.sub.21; R.sub.42 is hydrogen, C.sub.3-C.sub.8cycloalkyl, C.sub.2-C.sub.5alkenyl, C.sub.1-C.sub.20alkoxy or is C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more halogen, phenyl, C.sub.1-C.sub.20alkylphenyl or CN; or R.sub.42 is phenyl or naphthyl, both of which are unsubstituted or substituted by one or more C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.4haloalkyl, halogen, CN, OR.sub.16, SR.sub.17 or NR.sub.18R.sub.19; or R.sub.42 is benzyloxy or phenoxy both of which are unsubstituted or substituted one or more C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.4haloalkyl or hydrogen.

2. A compound according to claim 1, wherein Z.sub.1 is C.sub.7-C.sub.20aroyl, which is unsubstituted or substituted by one or more identical or different R.sub.10; R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are hydrogen; R.sub.10 is hydrogen R.sub.14 is C.sub.6-C.sub.20aryl which is unsubstituted or substituted by one or more NO.sub.2, OR.sub.16, NR.sub.18R.sub.19 or C.sub.1-C.sub.20alkyl which C.sub.1-C.sub.20 alkyl is unsubstituted or substituted by SR.sub.17; Q.sub.1 is C.sub.1-C.sub.20 alkylene; M is ##STR00214## G is —COR.sub.28; L is O—C.sub.1-C.sub.20alkylene-O, O—C.sub.2-C.sub.20alkylene-O which is interrupted by one or more O; R″.sub.14 is C.sub.1-C.sub.20alkyl or C.sub.6-C.sub.20aryl which C.sub.6-C.sub.20aryl is unsubstituted or substituted by C.sub.1-C.sub.20alkyl; R.sub.15 is C.sub.1-C.sub.20alkyl; R′.sub.14 is C.sub.1-C.sub.20 alkyl; R′.sub.15 is C.sub.1-C.sub.20alkyl; X.sub.3 together with R.sub.24 and R.sub.27 and the phenyl rings to which they are attached forms a heteroaromatic ring system; R.sub.16 is C.sub.1-C.sub.20alkyl, which is unsubstituted or substituted by one or more halogen, OH, O(C.sub.1-C.sub.4alkyl), O(CO)—(C.sub.1-C.sub.4alkyl) or O(C.sub.1-C.sub.20arylene)-M; or R.sub.16 is C.sub.2-C.sub.20alkyl which is interrupted by one or more O, which interrupted C.sub.2-C.sub.20alkyl is substituted by O—C.sub.6-C.sub.20arylene-M, in which O—C.sub.6-C.sub.20arylene-M, the arylene is unsubstituted or substituted by O(C.sub.1-C.sub.6alkyl); or R.sub.16 is C.sub.1-C.sub.8alkanoyl; R.sub.17 is C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by COOR.sub.16; R.sub.18 and R.sub.19 independently of each other are C.sub.1-C.sub.20alkyl, or R.sub.18 and R.sub.19 together with the N-atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is uninterrupted or is interrupted by O, or R.sub.18 and R.sub.19 together with the N-atom to which they are attached form a group ##STR00215## R.sub.22, R.sub.23, R.sub.25 and R.sub.26 are hydrogen, R.sub.24 and R.sub.27 together with X.sub.3 and the phenyl rings to which they are attached form a heteroaromatic ring system; R.sub.28 is C.sub.6-C.sub.20aryl which is unsubstituted or substituted by C.sub.1-C.sub.20alkyl; R.sub.33, R.sub.35, R.sub.36, R.sub.37, R.sub.38 and R.sub.40 independently of each other are hydrogen; R.sub.34 is ##STR00216## R.sub.39 is COR.sub.41; R.sub.41 is C.sub.6-C.sub.20aryl which is unsubstituted or substituted by C.sub.1-C.sub.20alkyl.

3. A compound according to claim 2, wherein Z.sub.1 is C.sub.7-C.sub.20aroyl, which is substituted by R.sub.10; R″.sub.14 is C.sub.1-C.sub.20alkyl or C.sub.6-C.sub.20aryl which is substituted by C.sub.1-C.sub.20alkyl; R.sub.16 is C.sub.1-C.sub.20alkyl, which is unsubstituted or substituted by one or more halogen, OH, O(C.sub.1-C.sub.4alkyl), O(CO)—(C.sub.1-C.sub.4alkyl) or O(C.sub.1-C.sub.20arylene)-M; or R.sub.16 is C.sub.2-C.sub.20 alkyl which is interrupted by one or more O, which interrupted C.sub.2-C.sub.20 alkyl is substituted by O—C.sub.6-C.sub.20arylene-M, in which O—C.sub.6-C.sub.20arylene-M, the arylene is substituted by O(C.sub.1-C.sub.6alkyl); or R.sub.16 is C.sub.1-C.sub.8alkanoyl; R.sub.17 is C.sub.1-C.sub.20 alkyl which is substituted by COOR.sub.16; R.sub.18 and R.sub.19 independently of each other are C.sub.1-C.sub.20alkyl, or R.sub.18 and R.sub.19 together with the N-atom to which they are attached form a 6-membered saturated ring which is uninterrupted or is interrupted by O, or R.sub.18 and R.sub.19 together with the N-atom to which they are attached form a group ##STR00217## R.sub.24 and R.sub.27 together with X.sub.3 and the phenyl rings to which they are attached form a carbazolyl ring system; R.sub.28 is C.sub.6-C.sub.20aryl which is substituted by C.sub.1-C.sub.20 alkyl; R.sub.41 is C.sub.6-C.sub.20aryl which is substituted by C.sub.1-C.sub.20alkyl.

4. A photopolymerizable composition comprising (a) at least one ethylenically unsaturated photopolymerizable compound and (b) as photoinitiator, at least one compound of claim 1.

5. The photopolymerizable composition according to claim 4, wherein (a) is a resin obtained by the reaction of a saturated or unsaturated polybasic acid anhydride with a product of the reaction of an epoxy resin and an unsaturated monocarboxylic acid.

6. The photopolymerizable composition according to claim 4, further comprising at least one photoinitiator (c), and/or other additives (d).

7. The photopolymerizable composition according to claim 6, comprising further additive (d), additive (d) comprising a pigment or a mixture of pigments or a mixture of one or more pigments with one or more dyes.

8. The photopolymerizable composition according to claim 6, comprising further additive (d), additive (d) comprising a dispersant or a mixture of dispersants.

9. The photopolymerizable composition according to anyone of claim 6, comprising further additive (d), additive (d) comprising at least one photo sensitizer compound selected from the group consisting of benzophenone, benzophenone derivatives, thioxanthone, thioxanthone derivatives, anthraquinone, anthraquinone derivatives, coumarin and coumarine derivatives.

10. The photopolymerizable composition according to claim 4, comprising 0.05 to 25% by weight of photoinitiator (b).

11. The photopolymerizable composition according to claim 4, further comprising a binder polymer (e).

12. A process for the photopolymerization of compounds containing ethylenically unsaturated double bonds, which comprises irradiating the composition according to claim 4 electromagnetic radiation in the range from 150 to 600 nm, or with electron beam or with X-rays.

13. The process according to claim 12 for producing pigmented and nonpigmented paints and varnishes, powder coatings, printing inks, printing plates, adhesives, dental compositions, gel coats, photoresists, for encapsulating electrical and electronic components, for producing magnetic recording materials, micromechanical parts, waveguides, optical switches, plating masks, colour proofing systems, glass fibre cable coatings, screen printing stencils, three-dimensional objects by means of stereolithography, image recording materials for holographic recordings, microelectronic circuits, decolorizing materials, formulations containing microcapsules.

14. A process for the preparation of a compound according to claim 1, comprising reacting the corresponding oxime compound of formula IIIA ##STR00218## wherein Z.sub.1, Q.sub.1, L, R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, and R.sub.14 are as defined in formula III, with an acyl halide of the formula 2 or an anhydride of the formula 3 ##STR00219## wherein Hal is a halogen, and R.sub.15 is as defined in formula III, in the presence of a base or a mixture of bases.

15. A color filter prepared by providing red, green and blue picture elements and optionally a black matrix, all comprising a photosensitive resin and a pigment on a transparent substrate and providing a transparent electrode either on the surface of the substrate or on the surface of the color filter layer, wherein said photosensitive resin comprises a polyfunctional acrylate monomer, an organic polymer binder and a compound of claim 1.

16. A coated substrate which is coated on at least one surface with a composition according to claim 4.

17. A process for the photographic production of relief images, in which a coated substrate according to claim 16 is subjected to imagewise exposure and then the unexposed portions are removed with a developer.

18. A compound of the formula IIIA ##STR00220## wherein Z.sub.1 independently of each other are C.sub.7-C.sub.20 aroyl or C.sub.4-C.sub.20 heteroaroyl, where C.sub.7-C.sub.20 aroyl or C.sub.4-C.sub.20 heteroaroyl is unsubstituted or substituted by one or more identical or different R.sub.10; R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 independently of each other are hydrogen, halogen, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19, or C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by one or more halogen, OR.sub.16, COOR.sub.16, CONR.sub.18R.sub.19 or NR.sub.18R.sub.19; or R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and R.sub.6 independently of each other are C.sub.6-C.sub.20 aryl, or C.sub.4-C.sub.20 heteroaryl, each of which is unsubstituted or substituted by one or more C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.4 haloalkyl or halogen; R.sub.10 is hydrogen, halogen, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19, CN, NO.sub.2 or C.sub.2-C.sub.20 alkyl which is interrupted by one or more Q, S or NR.sub.21, wherein the interrupted C.sub.2-C.sub.20 alkyl is unsubstituted or substituted by one or more halogen, OR.sub.16, COOR.sub.16, SR.sub.17, CONR.sub.18R.sub.19, C.sub.6-C.sub.20aryl, C.sub.3-C.sub.20 heteroaryl or C.sub.3-C.sub.20 cycloalkyl, C.sub.3-C.sub.20 cycloalkyl interrupted by one or more Q, S, NR.sub.21; or R.sub.10 is C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by one or more halogen, OR.sub.16, SR.sub.17, COOR.sub.16, CONR.sub.18R.sub.19, NR.sub.18R.sub.19, phenyl, C.sub.3-C.sub.8-cycloalkyl, C.sub.3-C.sub.20 heteroaryl or M; R.sub.14 is C.sub.6-C.sub.20 aryl or C.sub.3-C.sub.20 heteroaryl each of which is unsubstituted or substituted by one or more phenyl, halogen, C.sub.1-C.sub.4 haloalkyl, CN, NO.sub.2, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19, PO(OC.sub.kH.sub.2k+1).sub.2, SO—C.sub.1-C.sub.10 alkyl, SO.sub.2—C.sub.1-C.sub.10 alkyl, M, ##STR00221##  or by C.sub.2-C.sub.20 alkyl which is interrupted by one or more O, CO, S, C(O)O, OC(O), phenylene, naphthylene or by NR.sub.21, or each of which C.sub.6-C.sub.20 aryl or C.sub.3-C.sub.20 heteroaryl is substituted by one or more C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by one or more halogen, COOR.sub.16, CONR.sub.18R.sub.19, phenyl, C.sub.3-C.sub.8 cycloalkyl, C.sub.3-C.sub.20 heteroaryl, C.sub.6-C.sub.20 aryloxycarbonyl, C.sub.3-C.sub.20 heteroaryloxycarbonyl, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19 or by M; Q.sub.1 is a direct bond, C.sub.1-C.sub.20 alkylene, C.sub.1-C.sub.20 alkenylene, which C.sub.1-C.sub.20 alkylene OR C.sub.1-C.sub.20 alkenylene are unsubstituted or substituted by one or more halogen, OR.sub.16, COOR.sub.16, NR.sub.18R.sub.19, C.sub.1-C.sub.20 heteroaryl, CONR.sub.18R.sub.19, ##STR00222##  phenyl or by phenyl substituted by halogen, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.4 haloalkyl, OR.sub.16, SR.sub.17, or NR.sub.18R.sub.19; or Q.sub.1 is C.sub.3-C.sub.10 cycloalkylene or C.sub.3-C.sub.10 cycloalkenylene, both of which optionally are interrupted by O, CO or NR.sub.21; or Q.sub.1 is C.sub.2-C.sub.20 alkylene interrupted by one or more O or C.sub.2-C.sub.20 alkenylene interrupted by one or more O, which interrupted C.sub.2-C.sub.20 alkylene or C.sub.2-C.sub.20 alkenylene is unsubstituted or substituted by one or more halogen, OR.sub.16, COOR.sub.16, NR.sub.18R.sub.19, C.sub.1-C.sub.20 heteroaryl, CONR.sub.18R.sub.19, ##STR00223##  phenyl or by phenyl substituted by halogen, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.4 haloalkyl, OR.sub.16, SR.sub.17, or NR.sub.18R.sub.19; or Q.sub.1 is phenylene, naphthylene, coumarinylene or C.sub.1-C.sub.20 heteroarylene, each of which is unsubstituted or substituted by one or more C.sub.1-C.sub.12 alkyl, phenyl, halogen, C.sub.1-C.sub.4 haloalkyl, CN, NO.sub.2, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19 or by C.sub.3-C.sub.10 cycloalkyl which optionally is interrupted by O, CO or NR.sub.21; or Q.sub.1 is phenylene-O* or naphthylene-O*, each of which is unsubstituted or substituted by one or more C.sub.1-C.sub.6 alkyl, halogen, phenyl, OR.sub.16, SR.sub.17, or NR.sub.18R.sub.19; or Q.sub.1 is C.sub.1-C.sub.20 alkylene-CO* or phenylene-CO* which is unsubstituted or substituted by one or more C.sub.1-C.sub.6 alkyl, halogen, phenyl, OR.sub.16, SR.sub.17, or NR.sub.18R.sub.19; or Q.sub.1 is C.sub.1-C.sub.20alkylene-O—CO* which is optionally interrupted by one or more O and which interrupted or uninterrupted C.sub.1-C.sub.20 alkylene-O—CO* is unsubstituted or substituted by one or more OH; or Q.sub.1 is phenylene-O—CO* which is unsubstituted or substituted by one or more C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.4haloalkyl, halogen, phenyl, OR.sub.16, SR.sub.17, or NR.sub.18R.sub.19; or Q.sub.1 is ##STR00224## p is an integer 1 or 2; where the asterix in the definitions for Q.sub.1 denotes the bond to L; M is ##STR00225## G is NO.sub.2 or —COR.sub.28; L is C.sub.1-C.sub.20 alkylene, C.sub.2-C.sub.12 alkenylene, O-phenylene-O, O-naphthylene-O, S—C.sub.1-C.sub.20 alkylene-S, S-phenylene-S, S-naphthylene-S, C.sub.2-C.sub.20alkylene which is interrupted by one or more groups selected from the group consisting of O, S, CO, (CO)O, O(CO), phenylene and naphthylene, or L is O—C.sub.1-C.sub.20 alkylene-O, O—C.sub.2-C.sub.20alkylene-O which is interrupted by one or more groups selected from the group consisting of O, S, CO, (CO)O, O(CO), phenylene and naphthylene, or L is S—C.sub.2-C.sub.20 alkylene-S which is interrupted by one or more groups selected from the group consisting of O, S, CO, (CO)O, O(CO), phenylene and naphthylene, wherein all radicals L as defined are unsubstituted or substituted by one or more halogen; R″.sub.14 is C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by phenyl or by phenyl which is substituted by one or more halogen, C.sub.1-C.sub.20 alkyl, C.sub.1-C.sub.4 haloalkyl, OR.sub.16, SR.sub.17 or by NR.sub.18R.sub.19; or R″.sub.14 is C.sub.2-C.sub.20 alkyl which is interrupted by one or more O, CO, S, C(O)O, OC(O), phenylene, naphthylene or NR.sub.21, wherein the interrupted C.sub.2-C.sub.20 alkyl is unsubstituted or substituted by one or more halogen, OR.sub.16, COOR.sub.16, CONR.sub.18R.sub.19, phenyl or by phenyl which is substituted by OR.sub.16, SR.sub.17 or by NR.sub.18R.sub.19; or R″.sub.14 is CN, CONR.sub.18R.sub.19, NO.sub.2, C.sub.1-C.sub.4 haloalkyl, S(O).sub.m—C.sub.1-C.sub.6alkyl; S(O).sub.m-phenyl which is unsubstituted or substituted by C.sub.1-C.sub.12 alkyl or SO.sub.2—C.sub.1-C.sub.6 alkyl; or R″.sub.14 is SO.sub.2O-phenyl which is unsubstituted or substituted by C.sub.1-C.sub.12 alkyl; or is diphenyl phosphinoyl or di-(C.sub.1-C.sub.4 alkoxy)-phosphinoyl; or R″.sub.14 is C.sub.6-C.sub.20 aryl or C.sub.3-C.sub.20 heteroaryl each of which is unsubstituted or substituted by one or more phenyl, halogen, C.sub.1-C.sub.4 haloalkyl, CN, NO.sub.2, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19, PO(OC.sub.kH.sub.2k+1).sub.2, SO—C.sub.1-C.sub.10 alkyl, SO.sub.2—C.sub.1-C.sub.10 alkyl, or by C.sub.2-C.sub.20 alkyl which is interrupted by one or more O, CO, S, C(O)O, OC(O), phenylene, naphthylene or by NR.sub.21, or each of which is substituted by one or more C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by one or more halogen, COOR.sub.16, CONR.sub.18R.sub.19, phenyl, C.sub.3-C.sub.8cycloakyl, C.sub.3-C.sub.20heteroaryl, C.sub.6-C.sub.20aryloxycarbonyl, C.sub.3-C.sub.20heteroaryloxycarbonyl, OR.sub.16, SR.sub.17 or by NR.sub.18R.sub.19; R.sub.15 is C.sub.3-C.sub.8 cycloalkyl, C.sub.2-C.sub.5 alkenyl, C.sub.1-C.sub.20 alkoxy or C.sub.1-C.sub.20 alkyl which is unsubstituted or substituted by one or more halogen, phenyl, C.sub.1-C.sub.20 alkylphenyl or CN; k is an integer 1-10; m is an integer 1 or 2; R′.sub.14 has one of the meanings as given for R.sub.14 or is C.sub.1-C.sub.20 alkyl; R′.sub.15 has one of the meanings as given for R.sub.15; X.sub.1 is O, CO, S or a direct bond; X.sub.2 is O, S, SO or SO.sub.2; X.sub.3 is O, S or NR′.sub.20; R.sub.16 is hydrogen, phenyl-C.sub.1-C.sub.3 alkyl, C.sub.1-C.sub.20 alkyl, which is unsubstituted or substituted by one or more halogen, OH, SH, CN, C.sub.3-C.sub.6 alkenoxy, O(C.sub.1-C.sub.4 alkyl), OCH.sub.2CH.sub.2CN, OCH.sub.2CH.sub.2(CO)O(C.sub.1-C.sub.4alkyl), O(CO)(C.sub.1-C.sub.4alkyl), O(CO)—(C.sub.2-C.sub.4)alkenyl, O(CO)-phenyl, (CO)OH, (CO)O(C.sub.1-C.sub.4alkyl), C.sub.3-C.sub.20cycloalkyl, SO.sub.2—(C.sub.1-C.sub.4haloalkyl), O(C.sub.1-C.sub.4haloalkyl), O(C.sub.1-C.sub.20arylene)-M, or by C.sub.3-C.sub.20cycloalkyl which is interrupted by one or more O; or R.sub.16 is C.sub.2-C.sub.20alkyl which is interrupted by one or more O, S or NR.sub.21, which interrupted C.sub.2-C.sub.20alkyl is unsubstituted or substituted by O—C.sub.6-C.sub.20arylene-M, in which O—C.sub.6-C.sub.20arylene-M, the arylene is unsubstituted or substituted by one or more C.sub.1-C.sub.6alkyl or O(C.sub.1-C.sub.6alkyl); or R.sub.16 is (CH.sub.2CH.sub.2O).sub.n+1H, (CH.sub.2CH.sub.2O).sub.n(CO)—(C.sub.1-C.sub.8alkyl), C.sub.1-C.sub.8alkanoyl, C.sub.2-C.sub.12alkenyl, C.sub.3-C.sub.6alkenoyl, or C.sub.3-C.sub.20cycloalkyl which is uninterrupted or interrupted by one or more O, S, CO or NR.sub.21; or R.sub.16 is C.sub.1-C.sub.8alkyl-C.sub.3-C.sub.10cycloalkyl which is uninterrupted or interrupted by one or more O; or R.sub.16 is benzoyl which is unsubstituted or substituted by one or more C.sub.1-C.sub.6alkyl, halogen, OH, or C.sub.1-C.sub.3alkoxy; or R.sub.16 is phenyl, naphthyl or C.sub.3-C.sub.20heteroaryl, each of which is unsubstituted or substituted by one or more halogen, OH, C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12alkoxy, CN, NO.sub.2, phenyl-C.sub.1-C.sub.3alkyloxy, phenoxy, C.sub.1-C.sub.12alkylsulfanyl, phenylsulfanyl, N(C.sub.1-C.sub.12alkyl).sub.2, diphenylamino or ##STR00226## n is 1-20; R.sub.17 is hydrogen, C.sub.2-C.sub.12alkenyl, C.sub.3-C.sub.20cycloalkyl or phenyl-C.sub.1-C.sub.3alkyl, wherein the C.sub.2-C.sub.12alkenyl, C.sub.3-C.sub.20cycloalkyl or phenyl-C.sub.1-C.sub.3alkyl is uninterrupted or interrupted by one or more O, S, CO or NR.sub.21; or R.sub.17 is C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more OH, SH, CN, C.sub.3-C.sub.6alkenoxy, OCH.sub.2CH.sub.2CN, OCH.sub.2CH.sub.2(CO)O(C.sub.1-C.sub.4alkyl), O(CO)—(C.sub.2-C.sub.4)alkenyl, O(CO)—(C.sub.1-C.sub.4alkyl), O(CO)-phenyl or COOR.sub.16 or S—C.sub.6-C.sub.20arylene-M; or R.sub.17 is C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more OH, SH, CN, C.sub.3-C.sub.6alkenoxy, OCH.sub.2CH.sub.2CN, OCH.sub.2CH.sub.2(CO)O(C.sub.1-C.sub.4alkyl), O(CO)—(C.sub.2-C.sub.4)alkenyl, O(CO)—(C.sub.1-C.sub.4alkyl), O(CO)-phenyl or COOR.sub.16; or R.sub.17 is C.sub.2-C.sub.20alkyl which is interrupted by one or more O, S, CO or NR.sub.21, which interrupted C.sub.2-C.sub.20alkyl is unsubstituted or substituted by S—C.sub.6-C.sub.20arylene-M; or R.sub.17(CH.sub.2CH.sub.2O).sub.nH, (CH.sub.2CH.sub.2O).sub.n(CO)—(C.sub.1-C.sub.8alkyl), C.sub.2-C.sub.8alkanoyl or C.sub.3-C.sub.6alkenoyl; or R.sub.17 is benzoyl which is unsubstituted or substituted by one or more C.sub.1-C.sub.6alkyl, halogen, OH, C.sub.1-C.sub.4alkoxy or C.sub.1-C.sub.4alkylsulfanyl; or R.sub.17 is phenyl, naphthyl or C.sub.3-C.sub.20heteroaryl, each of which is unsubstituted or substituted by one or more halogen, C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.12alkoxy, CN, NO.sub.2, phenyl-C.sub.1-C.sub.3alkyloxy, phenoxy, C.sub.1-C.sub.12alkylsulfanyl, phenylsulfanyl, N(C.sub.1-C.sub.12alkyl).sub.2, diphenylamino, (CO)O(C.sub.1-C.sub.8alkyl), (CO)—C.sub.1-C.sub.8alkyl, (CO)N(C.sub.1-C.sub.8alkyl).sub.2 or ##STR00227## R.sub.18 and R.sub.19 independently of each other are hydrogen, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.4hydroxyalkyl, C.sub.2-C.sub.10alkoxyalkyl, C.sub.2-C.sub.5alkenyl, C.sub.3-C.sub.20cycloalkyl, phenyl-C.sub.1-C.sub.3alkyl, C.sub.1-C.sub.8alkanoyl, C.sub.1-C.sub.8alkanoyloxy, C.sub.3-C.sub.12alkenoyl, SO.sub.2—(C.sub.1-C.sub.4haloalkyl) or benzoyl; or R.sub.18 and R.sub.19 are phenyl, naphthyl or C.sub.3-C.sub.20heteroaryl, each of which is unsubstituted or substituted by one or more halogen, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.20alkoxy, C.sub.1-C.sub.12alkyl, benzoyl or C.sub.1-C.sub.12alkoxy; or R.sub.18 and R.sub.19 together with the N-atom to which they are attached form a 5- or 6-membered saturated or unsaturated ring which is uninterrupted or is interrupted by O, S, or NR.sub.21, and which 5- or 6-membered saturated or unsaturated ring is unsubstituted or substituted by one or more C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20alkoxy, ═O, OR.sub.16, SR.sub.17, NR.sub.31R.sub.32, COR.sub.41, NO.sub.2, halogen, C.sub.1-C.sub.4-haloalkyl, CN, phenyl, ##STR00228##  or by C.sub.3-C.sub.20cyclalkyl which is uninterrupted or is interrupted by one or more O, S, CO or NR.sub.21; or R.sub.18 and R.sub.19 together with the N-atom to which they are attached form a group ##STR00229## R.sub.20 is hydrogen, COR.sub.41 or C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more halogen, OR.sub.16, SR.sub.17, COOR.sub.16, CONR.sub.18R.sub.19, NR.sub.18R.sub.19, PO(OC.sub.kH.sub.2k+1).sub.2 or M; or R.sub.20 is C.sub.2-C.sub.20alkyl which is interrupted by one or more O, CO, C(O)O, OC(O) or NR.sub.21, wherein the interrupted C.sub.2-C.sub.20alkyl is unsubstituted or substituted by one or more halogen, OR.sub.16, SR.sub.17, COOR.sub.16, CONR.sub.18R.sub.19, NR.sub.18R.sub.19 or M; or R.sub.20 is C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl each of which is unsubstituted or substituted by one or more phenyl, halogen, C.sub.1-C.sub.4haloalkyl, CN, NO.sub.2, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19, M, Z, ##STR00230##  or by C.sub.1-C.sub.20alkyl which is interrupted by one or more O, S or NR.sub.21, or each of which C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl is substituted by one or more C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more halogen, COOR.sub.16, CONR.sub.18R.sub.19, phenyl, C.sub.3-C.sub.8cycloalkyl, C.sub.3-C.sub.20heteroaryl, C.sub.6-C.sub.20aryloxycarbonyl, C.sub.3-C.sub.20heteroaryloxycarbonyl, OR.sub.16, SR.sub.17 or NR.sub.18R.sub.19; R.sub.21 is hydrogen, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.4haloalkyl or C.sub.2-C.sub.20alkyl which is interrupted by one or more O, CO, C(O)O or OC(CO), or R.sub.21 is COR.sub.41, phenyl-C.sub.1-C.sub.4alkyl or C.sub.3-C.sub.8cycloakyl which is uninterrupted or is interrupted by one or more O or CO, or R.sub.21 is phenyl or naphthyl both of which are unsubstituted or substituted by one or more C.sub.1-C.sub.20alkyl, halogen, C.sub.1-C.sub.4haloalkyl, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19 or ##STR00231## R.sub.22, R.sub.23, R.sub.24, R.sub.25, R.sub.26 or R.sub.27 independently of each other are hydrogen, COR.sub.41, NO.sub.2 or ##STR00232##  or one of R.sub.22, R.sub.23 or R.sub.24 and one of R.sub.25, R.sub.26 or R.sub.27 together with X.sub.3 and the phenyl rings to which they are attached form a heteroaromatic ring system; R.sub.28 is C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl each of which is unsubstituted or substituted by one or more phenyl, halogen, C.sub.1-C.sub.4haloalkyl, CN, NO.sub.2, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19 or by C.sub.2-C.sub.20alkyl which is interrupted by one or more O, S or NR.sub.21, or each of which C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl is substituted by one or more C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more halogen, COOR.sub.16, CONR.sub.18R.sub.19, phenyl, C.sub.3-C.sub.8cycloalkyl, C.sub.3-C.sub.20heteroaryl, C.sub.6-C.sub.20aryloxycarbonyl, C.sub.3-C.sub.20heteroaryloxycarbonyl, OR.sub.16, SR.sub.17 or NR.sub.18R.sub.19; R.sub.29 is COOR.sub.16, CONR.sub.18R.sub.19, (CO)R.sub.16; or R.sub.29 has one of the meanings given for R.sub.18 and R.sub.19; R.sub.30 is COOR.sub.16, CONR.sub.18R.sub.19, (CO)R.sub.16; or R.sub.30 has one of the meanings given for R.sub.16; R.sub.33, R.sub.34, R.sub.35, R.sub.36, R.sub.37, R.sub.38, R.sub.39 and R.sub.40 independently of each other are hydrogen, ##STR00233##  NO.sub.2, COR.sub.41, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.4haloalkyl, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19, halogen, CN, phenyl or C.sub.3-C.sub.20cycloalkyl which is uninterrupted or is interrupted by one or more O, S, CO or NR.sub.21; or R.sub.35 and R.sub.36 or R.sub.37 and R.sub.38 or both, R.sub.35 and R.sub.36 and R.sub.37 and R.sub.38 are ##STR00234## R.sub.41 is C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl each of which is unsubstituted or substituted by one or more phenyl, halogen, C.sub.1-C.sub.4haloalkyl, CN, NO.sub.2, OR.sub.16, SR.sub.17, NR.sub.18R.sub.19 or by C.sub.2-C.sub.20alkyl which is interrupted by one or more O, S or NR.sub.21, or each of which C.sub.6-C.sub.20aryl or C.sub.3-C.sub.20heteroaryl is substituted by one or more C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more halogen, COOR.sub.16, CONR.sub.18R.sub.19, phenyl, C.sub.3-C.sub.8cycloakyl, C.sub.3-C.sub.20heteroaryl, C.sub.6-C.sub.20aryloxycarbonyl, C.sub.3-C.sub.20heteroaryloxycarbonyl, OR.sub.16, SR.sub.17 or NR.sub.18R.sub.19; or R.sub.41 is ##STR00235## or R.sub.41 is hydrogen, OH, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.4haloalkyl, C.sub.2-C.sub.20alkyl which is interrupted by one or more O, CO or NR.sub.21, or R.sub.41 is C.sub.3-C.sub.20cycloalkyl which is uninterrupted or is interrupted by O, S, CO or NR.sub.21; R.sub.42 is hydrogen, C.sub.3-C.sub.8cycloakyl, C.sub.2-C.sub.5alkenyl, C.sub.1-C.sub.20alkoxy or is C.sub.1-C.sub.20alkyl which is unsubstituted or substituted by one or more halogen, phenyl, C.sub.1-C.sub.20alkylphenyl or CN; or R.sub.42 is phenyl or naphthyl, both of which are unsubstituted or substituted by one or more C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.4haloalkyl, halogen, CN, OR.sub.16, SR.sub.17 or NR.sub.18R.sub.19; or R.sub.42 is benzyloxy or phenoxy both of which are unsubstituted or substituted one or more C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.4haloalkyl or hydrogen.

Description

EXAMPLE 1

Synthesis of [9-(2-ethyl-hexyl)-6-(acetoxyimino-o-tolyl-methyl)-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanone

1.a Synthesis of [9-(2-ethyl-hexyl)-6-(2-methyl-benzoyl)-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanone

(1) ##STR00142##

(2) To 9-(2-ethyl-hexyl)-9H-carbazole (1.40 g; 5.00 mmol) in CH.sub.2Cl.sub.2 (50 mL) are added 2,4,6-trimethylbenzoyl chloride (0.91 g; 5.00 mmol) and AlCl.sub.3 (0.69 g; 5.15 mmol) at 0° C. After stirring for 3 h at 0° C., AlCl.sub.3 (0.69 g; 5.15 mmol) and o-toluoyl chloride (0.80 g; 5.15 mmol) are added at 0° C., and the mixture is stirred at room temperature overnight. The reaction mixture is poured into ice-water, and the crude product is extracted twice with CH.sub.2Cl.sub.2. The combined organic layer is washed with H.sub.2O and brine, dried over MgSO.sub.4, and concentrated and dried in vacuo to give a beige solid as a crude product (2.08 g). The product is used for the next reaction without further purification. The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 0.81 (t, 3H), 0.92 (t, 3H), 1.21-1.42 (m, 8H), 2.05 (m, 1H), 2.13 (s, 6H), 2.34 (s, 3H), 4.20 (m, 2H), 6.94 (s, 2H), 7.27-7.37 (m, 4H), 7.41-7.45 (m, 3H), 7.98-8.02 (m, 2H), 8.56 (br, 1H), 8.57 (s, 1H).

1.b Synthesis of [9-(2-ethyl-hexyl)-6-(hydroxyimino-o-tolyl-methyl)-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanone

(3) ##STR00143##

(4) To [9-(2-ethyl-hexyl)-6-(2-methyl-benzoyl)-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanone (2.00 g; 3.78 mmol) in pyridine (10 mL) are added hydroxylammonium chloride (0.52 g; 7.55 mmol) at 120° C., and then the mixture is stirred at 120° C. overnight. After it is cooled at room temperature, the reaction mixture is poured into water, and the crude product is extracted twice with CH.sub.2Cl.sub.2. The combined organic layer is washed with water and brine and dried over MgSO.sub.4. After CH.sub.2Cl.sub.2 is removed by concentration, the crude product is recrystallized with a mixed solvent of CH.sub.2Cl.sub.2 (2 mL) and n-hexane (10 mL) to give a beige solid. It is collected by filtration, and washed with n-hexane, and then it is dried to give a beige solid (0.66 g; 31%). The product is composed of an isomeric mixture, and the structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 0.82 (m), 1.25 (m), 2.02 (m), 2.12 (s), 2.25 (s), 2.36 (s), 4.20 (m), 6.92 (s), 7.20 (d), 7.33-7.745 (m), 7.65 (br), 7.89 (br), 8.16 (s), 8.55 (br).

1.c Synthesis of [9-(2-Ethyl-hexyl)-6-(acetoxyimino-o-tolyl-methyl)-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanone

(5) ##STR00144##

(6) To [9-(2-ethyl-hexyl)-6-(hydroxyimino-o-tolyl-methyl)-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanone in AcOEt (ethyl acetate) (5 mL) are added triethylamine (0.36 g; 3.54 mmol) and acetyl chloride (0.28 g; 3.54 mmol) at 0° C. Then the mixture is stirred at 0° C. for 1 h. The reaction mixture is poured into ice-water, and the crude product is extracted with AcOEt. The combined organic layer is washed with H.sub.2O and brine, dried over MgSO.sub.4, and concentrated and dried in vacuo to give a yellow resin as a crude product. The crude product is composed of an isomeric mixture according to .sup.1H-NMR spectrum. The crude product is purified by column chromatography on silica gel eluting with a mixed solvent of CH.sub.2Cl.sub.2 and n-hexane (4:1) to obtain a pale yellow solid (0.49 g, 69%). The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). □δ[ppm]: 0.82 (t, 3H), 0.92 (t, 3H), 2.02 (m, 1H9, 2.06 (s, 3H), 2.12 (s, 6H), 2.19 (s, 3H), 2.36 (s, 3H), 4.20 (m, 2H), 6.93 (s, 2H), 7.14 (dd, 1H), 7.30-7.43 (m, 5H), 7.71 (br, 1H), 8.00 (br, 1H), 8.32 (br, 1H), 8.52 (br, 1H).

EXAMPLES 2-11

(7) In case of the compounds of example 2-5, the corresponding di-ketone intermediates are prepared according to the procedure as described in example 1.a with the corresponding aroyl chloride using 9-(2-ethyl-hexyl)-9H-carbazole or 9-ethyl-9H-carbazole as a starting material, and then the oxime and the oxime ester are prepared according to the procedures as disclosed in examples 1.b and 1.c. In case of the compound of example 6, the corresponding di-ketone is prepared by reaction of [6-(2-chloromethyl-benzoyl)-9-ethyl-9H-carbazol-3-yl]-(2,4,6-trimethyl-phenyl)-methanone with ethyl mercaptoacetate, and then the oxime and the oxime ester are prepared according to the procedures as disclosed in examples 1.b and 1.c. The corresponding diketone intermediates of the compounds of examples 7-11 are prepared by reacting mono- or di-fluorinated diketone intermediate with the corresponding nucleophiles. Then, the oxime and the oxime ester are prepared according to the procedures as disclosed in examples 1.b and 1.c. The compounds of the examples 2, 3, 5, 6, 7, 9 and 11 are obtained as an isomeric mixture, but the compounds of the other examples are obtained as a single component.

(8) TABLE-US-00001 TABLE 1 .sup.1H-NMR Example Ar.sub.1 Ar.sub.2 R δ [ppm]  2 1.48 (t, 3H), 2.12 (s, 6H), 2.18 (s, 3H), 2.36 (s, 3H), 4.38 (q, 2H), 6.93 (s, 2H), 7.13 (d, 1H), 7.28-7.45 (m, 5H), 7.73 (br, 1H), 7.99 (br, 1H), 8.34 (br, 1H), 8.52 (br, 1H)  3 0 0.80-0.98 (m), 1.18-1.48 (m), 2.01 (s), 2.05 (m), 2.16 (s), 2.18 (s), 2.22 (s), 3.72 (s), 4.17 (m), 6.67 (d), 7.14 (d), 7.20-7.44 (m), 7.59 (d), 7.66 (d), 7.97 (d), 8.05 (d), 8.21 (s), 8.33 (s), 8.54 (s), 8.61 (s)  4 0.78-0.96 (m), 1.18-1.45 (m), 2.03 (m), 2.10 (s), 2.12 (s), 2.35 (s), 4.19 (m), 6.93 (s), 7.37-7.44 (m), 7.56 (d), 7.68 (br), 8.00 (br), 8.24 (br), 8.40 (d), 8.52 (br)  5 0.82-0.98 (m), 1.20- 1.48 (m), 2.05 (s), 2.06 (s), 2.13 (s), 2.16 (s), 2.23 (s), 2.36 (s), 4.22 (m), 6.93 (s), 7.15 (d), 7.23-7.45 (m), 7.46-7.59 (m), 7.95 (br), 8.20 (s), 8.41 (br), 8.56 (br)  6 0 1.21 (t), 1.46 (t), 2.05 (s), 2.12 (s), 2.36 (s), 3.06 (d), 3.71 (d), 4.09 (q), 4.40 (m), 6.93 (s), 7.20 (d), 7.36-7.42 (m), 7.50 (t), 7.61 (d), 7.73 (br), 8.00 (br), 8.22 (s), 8.35 (br), 8.52 (br)  7 0.81-1.02 (m), 1.10- 1.52 (m), 2.04 (m), 2.08 (s), 2.12 (s), 2.16 (s), 2.35 (s), 3.24 (m), 3.32 (m), 3.86 (m), 3.89 (m), 4.19 (m), 4.22 (m), 6.84 (d), 6.92 (s), 6.96 (d), 6.96 (d), 7.34-7.54 (m), 7.74 (br), 7.98 (s), 8.04 (br), 8.25 (s), 8.48 (br)  8 1.46 (t), 2.08 (s), 2.12 (s), 2.36 (s), 3.18 (s), 3.48 (t), 3.50 (s), 3.81 (t), 4.04 (t), 4.21 (t), 4.38 (q), 6.60 (d), 6.67 (s), 6.93 (s), 7.04 (d), 7.36 (d), 7.40 (d), 7.74 (br), 8.04 (br), 8.33 (s), 8.50 (br)  9 1.48 (t), 2.12 (s), 2.19 (s), 2.36 (s), 4.11 (t), 4.42 (q), 5.03 (m), 6.88 (d), 6.93 (s), 7.18 (t), 7.41 (d), 7.48 (d), 7.49 (d), 7.61 (d), 7.72 (d), 7.93 (br), 8.08 (s), 8.55 (br) 10 0 1.46 (t), 2.07 (s), 2.09 (s), 2.12 (s), 2.36 (s), 4.38- 4.45 (m), 6.93 (s), 7.07 (d), 7.20 (d), 7.38 (d), 7.53 (m), 7.78 (br), 7.96 (br), 8.25 (br), 8.55 (br) 11 1.44 (t), 2.06 (s), 2.11 (s), 2.19 (s), 2.36 (s), 3.90 (t), 4.20-4.50 (m), 6.93 (s), 7.07 (d), 7.20 (d), 7.30- 7.56 (m), 7.60 (d), 7.63 (d), 7.82 (br), 8.12 (br), 8.25 (br), 8.56 (br)

EXAMPLE 12

[1-[4-[3-[N-acetoxy-C-phenyl-carbonimidoyl]-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]phenyl]ethylideneamino] acetate

12.a 1-(4-carbazol-9-ylphenyl)ethanone

(9) ##STR00176##

(10) To carbazole (5.02 g; 30.0 mmol) in DMSO (50 mL) is added 4-fluoroacetophenone (3.45 g; 25.0 mmol) and K.sub.2CO.sub.3 (10.4 g; 75.2 mmol), and the mixture is stirred at 135° C. overnight. The mixture is poured into water to afford a precipitate, which is isolated by filtration and washed with water. The crude product thus obtained is further purified by recrystallization from TBME (tert-butyl methyl ether), giving the product as a light brown solid. The structure is confirmed by the .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 2.71 (s), 7.32 (d), 7.41-7.50 (m), 7.72 (d), 8.15 (d), 8.21 (d).

12.b 1-[4-[3-benzoyl-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]phenyl]ethanone

(11) ##STR00177##

(12) To 1-(4-carbazol-9-ylphenyl)ethanone (5.73 g; 20.0 mmol) in CH.sub.2Cl.sub.2 (50 mL) are added 2,4,6-trimethylbenzoyl chloride (3.84 g; 21.0 mmol) and AlCl.sub.3 (5.60 g, 42.0 mmol) at 0° C. After stirring over night at room temperature, AlCl.sub.3 (2.80 g, 21.0 mmol) and benzoyl chloride (2.95 g, 21.0 mmol) are added at 0° C., and the mixture is stirred at room temperature overnight. The reaction mixture is poured into ice-water, and the crude product is extracted twice with CH.sub.2Cl.sub.2. The combined organic layer is washed with water and brine, dried over MgSO.sub.4. After CH.sub.2Cl.sub.2 is removed by concentration, the crude product is purified by column chromatography on silica gel eluting with a mixed solvent of CH.sub.2Cl.sub.2 and n-hexane (1:1) to obtain a pale white solid (2.25 g, 21%). The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 2.14 (s), 2.39 (s), 2.72 (s), 6.94 (s), 7.43-7.58 (m), 7.58-7.68 (m), 7.70-7.80 (m), 7.82-7.89 (m), 7.97 (d), 8.02 (d), 8.11 (d), 8.26 (d), 8.28 (d), 8.60 (br), 8.64 (s).

12.c [9-[4-[N-hydroxy-C-methyl-carbonimidoyl]phenyl]-6-[N-hydroxy-C-phenyl-carbonimidoyl]carbazol-3-yl]-(2,4,6-trimethylphenyl)methanone

(13) ##STR00178##

(14) To 1-[4-[3-benzoyl-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]phenyl]ethanone (1.10 g; 2.00 mmol) in pyridine (5 mL) is added hydroxylammonium chloride (0.81 g; 12.0 mmol) at 100° C., and then the mixture is stirred at 100° C. overnight. After it is cooled at room temperature, the reaction mixture is poured into water, and the crude product is extracted twice with AcOEt (ethyl acetate). The combined organic layer is washed with water and brine and dried over MgSO.sub.4. After AcOEt is removed by concentration, the crude product is purified by column chromatography on silica gel eluting with a mixed solvent of AcOEt and n-hexane (1:2) to obtain a pale white solid (2.48 g, 22%). The product is composed of an isomeric mixture, and the structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 2.12 (s), 2.33 (s), 2.40 (s), 6.88 (s), 7.30-7.66 (m), 7.88 (d), 7.90 (d), 7.99 (br), 8.20 (s), 8.55 (br).

12.d [1-[4-[3-[N-acetoxy-C-phenyl-carbonimidoyl]-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]phenyl]ethylideneamino] acetate

(15) ##STR00179##

(16) To [9-[4-[N-hydroxy-C-methyl-carbonimidoyl]phenyl]-6-[N-hydroxy-C-phenyl-carbonimidoyl]carbazol-3-yl]-(2,4,6-trimethylphenyl)methanone (0.24 g; 0.42 mmol) in AcOEt (5 mL) are added triethylamine (0.43 g; 4.24 mmol) and acetyl chloride (0.34 g; 4.24 mmol) at 0° C. Then the mixture is stirred at 0° C. for 3 hours. The reaction mixture is poured into ice-water, and the crude product is extracted with AcOEt. The combined organic layer is washed with H.sub.2O and brine, dried over MgSO.sub.4, and concentrated. The crude product is purified by column chromatography on silica gel eluting with a mixed solvent of AcOEt and n-hexane (1:1) to obtain a pale yellow solid (0.28 g, 74%). The product is composed of an isomeric mixture, and the structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 2.11 (s), 2.13 (s), 2.31 (s), 2.32 (s), 2.35 (s), 2.36 (s), 2.50 (s), 2.51 (s), 6.93 (s), 6.94 (s), 7.31-7.54 (m), 7.58-7.69 (m), 7.98 (br), 8.01-8.08 (m), 8.41 (s), 8.55 (br).

EXAMPLE 13

[[2-[6-[2-[N-acetoxy-C-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-carbonimidoyl]phenoxy]-2,2,3,3,4,4,5,5-octafluoro-hexoxy]phenyl]-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]methylene]amino acetate

13.a [9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-(2-fluorophenyl)methanone

(17) ##STR00180##

(18) To 9-ethyl-9H-carbazole (8.50 g; 43.5 mmol) in CH.sub.2Cl.sub.2 (200 mL) are added 2,4,6-trimethylbenzoyl chloride (8.35 g; 45.7 mmol) and AlCl.sub.3 (6.37 g; 47.8 mmol) at 0° C. After stirring for 20 minutes, AlCl.sub.3 (6.53 g; 48.9 mmol) is added and 2-fluorobenzoyl chloride (7.26 g; 45.7 mmol) is added dropwise, and then the mixture is stirred at room temperature for 5 hours. The reaction mixture is poured into ice-water, and the crude product is extracted twice with CH.sub.2Cl.sub.2. The combined organic layer is washed with water and brine, dried over MgSO.sub.4. After 100 mL of n-hexane is added there, CH.sub.2Cl.sub.2 is removed by concentration to give a white solid. It is collected by filtration, and washed with n-hexane, and then it is dried to give a white solid (17.82 g; 88%). The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 1.49 (t), 2.13 (s), 2.38 (s), 4.42 (q), 6.94 (s), 7.21 (t), 7.32 (t), 7.44 (d), 7.46 (d), 7.53-7.62 (m), 8.25 (br), 8.04 (d), 8.56 (br), 8.60 (s); .sup.19F-NMR spectrum (CDCl.sub.3). δ[ppm]: −111.75.

13.b [2-[6-[2-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazole-3-carbonyl]phenoxy]-2,2,3,3,4,4,5,5-octafluoro-hexoxy]phenyl]-[9-ethyl-6-(2,4,6-trimethylbenzoyl)-carbazol-3-yl]methanone

(19) ##STR00181##

(20) To [9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-(2-fluorophenyl)methanone (1.86 g; 4.01 mmol) in pyridine (10 mL) are added 2,2,3,3,4,4,5,5,-octafluoro-1,6-hexanediol (0.47 g; 1.8 mmol) and sodium hydroxide (0.24 g; 6.0 mmol) at 80° C. The mixture is stirred overnight. The reaction mixture is poured into ice-water, the crude product is extracted twice with AcOEt. The combined organic layer is washed with water and brine, dried over MgSO.sub.4. After AcOEt is removed by concentration, the crude product is recrystallized with a mixed solvent of CH.sub.2Cl.sub.2 (2 mL) and n-hexane (10 mL) to give a beige solid. It is collected by filtration, and washed with n-hexane, and then it is dried to give a beige solid (0.44 g; 21%). The product is composed of an isomeric mixture, and the structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 1.42 (t), 2.10 (s), 2.37 (s), 4.22 (t), 4.35 (q), 6.92 (s), 7.19 (t), 7.34-7.50 (m), 7.92 (s), 7.94 (br), 8.50 (s), 8.51 (br).

13.c [9-ethyl-6-[C-[2-[6-[2-[C-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-N-hydroxy-carbonimidoyl]phenoxy]-2,2,3,3,4,4,5,5-octafluoro-hexoxy]phenyl]-N-hydroxy-carbonimidoyl]carbazol-3-yl]-(2,4,6-trimethylphenyl)methanone

(21) ##STR00182##

(22) To [2-[6-[2-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazole-3-carbonyl]phenoxy]-2,2,3,3,-4,4,5,5-octafluoro-hexoxy]phenyl]-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]methanone (0.44 g; 0.38 mmol) in pyridine (5 mL) are added hydroxylammonium chloride (0.16 g; 2.30 mmol) at 100° C., and then the mixture is stirred at 100° C. overnight. After it is cooled at room temperature, the reaction mixture is poured into water, and the crude product is extracted twice with AcOEt (ethyl acetate). The combined organic layer is washed with water and brine and dried over MgSO.sub.4. After AcOEt is removed by concentration, the crude product is purified by column chromatography on silica gel eluting with a mixed solvent of AcOEt and n-hexane (1:1) to obtain a pale white solid (0.28 g, 63%). The product is composed of an isomeric mixture, and the structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 1.23 (t), 2.11 (m), 2.32 (s), 2.35 (s), 4.32-4.64 (m), 6.91 (s), 7.06-7.42 (m), 7.42 (d), 7.46-7.56 (m), 7.75 (br), 7.80-7.91 (m), 7.93 (s), 8.00 (s), 8.37 (s), 8.63 (br).

13.d [[2-[6-[2-[N-acetoxy-C-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]carbonimidoyl]phenoxy]-2,2,3,3,4,4,5,5-octafluoro-hexoxy]phenyl]-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]methylene]amino acetate

(23) ##STR00183##

(24) To [9-ethyl-6-[C-[2-[6-[2-[C-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-N-hydroxy-carbonimidoyl]phenoxy]-2,2,3,3,4,4,5, 5-octafluoro-hexoxy]phenyl]-N-hydroxy-carbonimidoyl]carbazol-3-yl]-(2,4,6-trimethylphenyl)methanone (0.28 g; 0.24 mmol) in AcOEt (5 mL) are added triethylamine (0.24 g; 2.4 mmol) and acetyl chloride (0.19 g; 2.4 mmol) at 0° C. Then the mixture is stirred at 0° C. for 4 hours. The reaction mixture is poured into ice-water, and the crude product is extracted with AcOEt. The combined organic layer is washed with H.sub.2O and brine, dried over MgSO.sub.4, and concentrated. The crude product is purified by column chromatography on silica gel eluting with a mixed solvent of AcOEt and n-hexane (1:1) to obtain a pale yellow solid (0.16 g, 54%). The product is composed of an isomeric mixture, and the structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 1.22 (m), 2.01 (s), 2.08 (s), 2.11 (s), 2.16 (s), 2.34 (s), 2.35 (s), 4.05 (t), 4.33 (m), 6.80 (m), 6.92 (s), 6.98 (m), 7.16 (s), 7.28-7.54 (m), 7.60(d), 7.64(d), 7.71 (br), 7.95 (br), 8.02 (s), 8.28 (br), 8.52(br).

EXAMPLE 14

[[2-[6-[2-[N-acetoxy-C-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]carbonimidoyl]phenoxy]hexoxy]phenyl]-[9-ethyl-6-(2,4,6-trimethylbenzoyl)-carbazol-3-yl]methylene]amino acetate

(25) ##STR00184##

(26) The corresponding dimer intermediate of diketone is prepared according to the procedure as disclosed in example 13.b with 1,6-hexanediol instead of 2,2,3,3,4,4,5,5,-octafluoro-1,6-hexanediol, and then the oxime and oxime ester are prepared the same procedure as 13.c and 13.d respectively. The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 0.78 (m), 1.15 (m), 1.39 (t), 2.00 (s), 2.10 (s), 2.35 (s), 3.60 (m), 4.31(q), 6.85(d), 6.92 (s), 7.03 (t), 7.12(d), 7.28(d), 7.32-7.42 (m), 7.65 (br), 7.96 (br), 8.30 (br), 8.50(br).

EXAMPLE 15

[[4-[6-[4-[N-acetoxy-C-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-carbonimidoyl]phenoxy]-2,2,3,3,4,4,5,5-octafluoro-hexoxy]phenyl]-[9-ethyl-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]methylene]amino acetate

(27) ##STR00185##

(28) The corresponding diketone intermediate is prepared according to the procedure as disclosed in example 13.a with 4-fluorobenzoyl chloride instead of 2-fluorobenzoyl chloride, and then the dimer of diketone, oxime and oxime ester are prepared the same procedure as 13.b, 13.c and 13.d respectively. The product is composed of an isomeric mixture, and the structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 1.47 (t), 1.52 (t), 2.10 (s), 2.12 (s), 2.34 (s), 3.38 (t), 4.36-4.66 (m), 6.90-6.98 (m), 7.04-7.12 (m), 7.14-7.48 (m), 7.50 (s), 7.60(d), 7.72 (br), 8.01 (s), 8.04 (br), 8.28 (br), 8.52(br).

EXAMPLE 16

[[9-[2-[2-[2-[3-[N-acetoxy-C-(o-tolyl)carbonimidoyl]-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]ethoxy]ethoxy]ethyl]-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-(o-tolyl)methylene]amino acetate

16.a o-Tolyl-[6-(2,4,6-trimethylbenzoyl)-9H-carbazol-3-yl]methanone

(29) ##STR00186##

(30) To 9-benzyl-9H-carbazole (2.50 g; 9.72 mmol) in CH.sub.2Cl.sub.2 (50 mL) are added 2,4,6-trimethylbenzoyl chloride (1.86 g; 10.2 mmol) and AlCl.sub.3 (1.48 g; 11.1 mmol) at 0° C. After stirring for 2 hours, AlCl.sub.3 (1.55 g; 11.6 mmol) is added and o-toluoyl chloride (1.58 g; 10.2 mmol) is added dropwise, and then the mixture is stirred at room temperature overnight. To the mixture AlCl.sub.3 (1.51 g; 11.3 mmol) is added, and the reaction mixture is stirred for 1 hour at 50° C. The reaction mixture is poured into ice-water, and the crude product is extracted twice with CH.sub.2Cl.sub.2. The combined organic layer is washed with water and brine, dried over MgSO.sub.4. After CH.sub.2Cl.sub.2 is removed by concentration, the crude product is purified by column chromatography on silica gel eluting with CH.sub.2Cl.sub.2 to obtain a white solid (2.23 g, 53%). The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 2.00 (s), 2.22 (s), 2.31 (s), 6.96 (s), 7.25 (t), 7.31 (d), 7.36 (d), 7.41 (t), 7.43 (t), 7.45 (t), 7.61 (t), 7.63 (d), 7.73 (br), 7.78 (d), 7.79 (d), 8 54 (s), 8.55 (s).

16.b [9-[2-[2-[2-[3-(2-methylbenzoyl)-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]ethoxy]-ethoxy]ethyl]-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-(o-tolyl)methanone

(31) ##STR00187##

(32) To o-Tolyl-[6-(2,4,6-trimethylbenzoyl)-9H-carbazol-3-yl]methanone (1.62 g; 3.76 mmol) in DMA (20 mL) are added triethylene glycol bis(p-toluenesulfonate) (0.90 g; 2.0 mmol) and potassium parbonate (1.11 g; 8.39 mmol). After stirring overnight at room temperature, the reaction mixture is poured into ice-water, and the crude product is extracted twice with AcOEt. The combined organic layer is washed with water and brine, dried over MgSO.sub.4. After AcOEt is removed by concentration, the crude product is purified by column chromatography on silica gel eluting with CH.sub.2Cl.sub.2 to obtain a white solid (1.60 g, 87%). The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 2.01 (s), 2.24 (s), 2.33 (s), 3.33 (s), 3.72 (t), 4.37 (t), 6.92 (s), 7.16-7.44 (m), 7.86-8.04 (m), 8.50 (s), 8.53 (s).

16.c [6-[N-hydroxy-C-(o-tolyl)carbonimidoyl]-9-[2-[2-[2-[3-[N-hydroxy-C-(o-tolyl)carbonimidoyl]-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]ethoxy]ethoxy]ethyl]carbazol-3-yl]-(2,4,6-trimethylphenyl)methanone

(33) ##STR00188##

(34) To [9-[2-[2-[2-[3-(2-methylbenzoyl)-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]ethoxy]ethoxy]ethyl]-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-(o-tolyl)methanone (1.50 g; 1.53 mmol) in pyridine (10 mL) is added hydroxylammonium chloride (7.32 g; 12.0 mmol) at 120° C., and then the mixture is stirred at 120° C. overnight. After it is cooled at room temperature, the reaction mixture is poured into water, and the crude product is extracted twice with AcOEt (ethyl acetate). The combined organic layer is washed with water and brine and dried over MgSO.sub.4. After AcOEt is removed by concentration, the crude product is purified by column chromatography on silica gel eluting with a mixed solvent of CH.sub.2Cl.sub.2 and AcOEt (5:1) to obtain a white solid (0.50 g, 33%). The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 2.07 (s), 2.21 (s), 2.35 (s), 3.33 (s), 3.68 (t), 4.32 (t), 6.90 (s), 7.15 (d), 7.26-7.40 (m), 7.69 (br), 7.87 (br), 8.07 (s), 8.53 (br).

16.d [[9-[2-[2-[2-[3-[N-acetoxy-C-(o-tolyl)carbonimidoyl]-6-(2,4,6-trimethylbenzoyl)-carbazol-9-yl]ethoxy]ethoxy]ethyl]-6-(2,4,6-trimethylbenzoyl)carbazol-3-yl]-(o-tolyl)methylene]amino acetate

(35) ##STR00189##

(36) To [6-[N-hydroxy-C-(o-tolyl)carbonimidoyl]-9-[2-[2-[2-[3-[N-hydroxy-C-(o-tolyl)carbonimidoyl]-6-(2,4,6-trimethylbenzoyl)carbazol-9-yl]ethoxy]ethoxy]ethyl]carbazol-3-yl]-(2,4,6-trimethylphenyl)methanone (0.50 g; 0.50 mmol) in THF (5 mL) are added triethylamine (0.20 g; 2.0 mmol) and acetyl chloride (0.15 g; 1.9 mmol) at 0° C. Then the mixture is stirred at 0° C. for 1.5 hours. The reaction mixture is poured into ice-water, and the crude product is extracted with AcOEt. The combined organic layer is washed with H.sub.2O and brine, dried over MgSO.sub.4, and concentrated. The crude product is purified by column chromatography on silica gel eluting AcOEt to obtain a white solid (0.36 g, 67%). The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 2.09 (s), 2.15 (s), 2.17 (s), 2.35 (s), 3.31 (s), 3.69 (t), 4.32 (t), 6.91 (s), 7.09 (d), 7.26-7.41 (m), 7.66 (br), 7.96 (br), 8.31 (br), 8.49 (br).

EXAMPLE 17

[[6-[2-[2-[2-[2-[2-[6-[N-acetoxy-C-(o-tolyl)carbonimidoyl]-9-ethyl-carbazole-3-carbonyl]-3-ethoxy-phenoxy]ethoxy]ethoxy]ethoxy]-6-ethoxy-benzoyl]-9-ethyl-carbazol-3-yl]-(o-tolyl)methylene]amino acetate

17.a ethyl 2-ethoxy-6-[2-[2-[2-(3-ethoxy-2-ethoxycarbonyl-phenoxy)ethoxy]-ethoxy]ethoxy]benzoate

(37) ##STR00190##

(38) To ethyl 6-ethoxy-2-hydroxybenzoate (5.00 g; 23.8 mmol) in DMA (50 mL) are added triethylene glycol bis(p-toluenesulfonate) (5.48 g; 12.0 mmol) and potassium parbonate (9.86 g; 71.4 mmol). After stirring at 80° C. for 3 hours, the reaction mixture is poured into water, and the crude product is extracted twice with AcOEt. The combined organic layer is washed with water and brine, dried over MgSO.sub.4. After AcOEt is removed by concentration and dried under vacuo, a white solid is obtained (2.62 g, 34%). The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]:1.30-1.39 (m), 3.68 (s), 3.81 (t), 4.04 (q), 4.14 (t), 4.36 (q), 6.53 (d), 7.22 (t)

17.b 2-[2-[2-[2-(2-carboxy-3-ethoxy-phenoxy)ethoxy]ethoxy]ethoxy]-6-ethoxy-benzoic acid

(39) ##STR00191##

(40) To ethyl 2-ethoxy-6-[2-[2-[2-(3-ethoxy-2-ethoxycarbonyl-phenoxy)ethoxy]ethoxy]ethoxy]benzoate (2.60 g; 4.89 mmol) in a mixed solvent of methanol (30 mL) and H.sub.2O (60 mL) is added sodium hydroxide (4.08 g; 102 mmol). After stirring at 100° C. overnight, the reaction mixture is cooled at room temperature. The mixture is acidified with concentrated hydrochloric acid to pH=3.0 and the crude product is extracted twice with AcOEt. The combined organic layer is washed with water and brine, dried over MgSO.sub.4. After AcOEt is removed by concentration, the crude product is purified by column chromatography on silica gel eluting with AcOEt to obtain a white solid (0.83 g, 35%). The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 1.44 (t), 3.88 (s), 3.91 (t), 4.09-4.20 (m), 6.53 (d), 6.59 (d), 7.28 (t).

17.c [6-[2-ethoxy-6-[2-[2-[2-[3-ethoxy-2-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-carbonyl]phenoxy]ethoxy]ethoxy]ethoxy]benzoyl]-9-ethyl-carbazol-3-yl]-(o-tolyl)methanone

(41) ##STR00192##

(42) To 2-[2-[2-[2-(2-carboxy-3-ethoxy-phenoxy)ethoxy]ethoxy]ethoxy]-6-ethoxy-benzoic acid (0.83 g; 1.7 mmol) in CH.sub.2Cl.sub.2 (10 mL) are added oxalyl chloride (0.68 g; 5.36 mmol) and 1drop o DMF. After stirring for 2 hours, CH.sub.2Cl.sub.2 is removed by concentration, and the crude product is dried under vacuo. To 9-ethyl-9H-carbazol (0.68 g, 3.5 mmol) in CH.sub.2Cl.sub.2 are added AlCl.sub.3 (0.51 g; 3.8 mmol) and o-toluoyl chloride (0.56 g; 3.6 mmol) at 0° C. After stirring for 1 hour, AlCl.sub.3 (0.58 g; 4.3 mmol) and the acid chloride prepared above are added at 0° C., and then the mixture is stirred at room temperature for 3 hours. The reaction mixture is poured into ice-water, and the crude product is extracted twice with CH.sub.2Cl.sub.2. The combined organic layer is washed with water and brine, dried over MgSO.sub.4. After CH.sub.2Cl.sub.2 is removed by concentration, the crude product is purified by column chromatography on silica gel eluting with a mixed solvent of CH.sub.2Cl.sub.2 and AcOEt (5:1) to obtain a white solid (1.04 g, 56%). The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 1.13 (t), 1.43 (t), 2.31 (s), 2.93 (s), 3.30 (t), 3.88 (t), 4.00 (q), 4.35 (q), 6.54 (d), 6.63 (d), 7.24-7.44 (m), 7.94 (d), 7.97 (d), 8.53 (s).

17.d [2-ethoxy-6-[2-[2-[2-[3-ethoxy-2-[9-ethyl-6-[N-hydroxy-C-(o-tolyl)carbonimidoyl]carbazole-3-carbonyl]phenoxy]ethoxy]ethoxy]ethoxy]phenyl]-[9-ethyl-6-[N-hydroxy-C-(o-tolyl)carbonimidoyl]carbazol-3-yl]methanone

(43) ##STR00193##

(44) To [6-[2-ethoxy-6-[2-[2-[2-[3-ethoxy-2-[9-ethyl-6-(2-methylbenzoyl)carbazole-3-carbonyl]phenoxy]ethoxy]ethoxy]ethoxy]benzoyl]-9-ethyl-carbazol-3-yl]-(o-tolyl)methanone (1.03 g; 0.935 mmol) in pyridine (10 mL) is added hydroxylammonium chloride (0.41 g; 5.8 mmol) at 120° C., and then the mixture is stirred at 120° C. overnight. After it is cooled at room temperature, the reaction mixture is poured into water, and the crude product is extracted twice with AcOEt (ethyl acetate). The combined organic layer is washed with water and brine and dried over MgSO.sub.4. After AcOEt is removed by concentration, the crude product is purified by column chromatography on silica gel eluting with a mixed solvent of CH.sub.2Cl.sub.2 and AcOEt (3:1) to obtain a white solid (0.45 g, 44%). The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 1.12 (t), 1.37 (t), 2.22 (s), 2.92 (s), 3.29 (t), 3.88 (t), 3.97 (q), 4.27 (q), 6.53 (d), 6.61 (d), 7.17 (d), 7.24-7.40 (m), 7.58 (d), 7.88 (d), 8.16 (s), 8.54 (s).

17.e [[6-[2-[2-[2-[2-[2-[6-[N-acetoxy-C-(o-tolyl)carbonimidoyl]-9-ethyl-carbazole-3-carbonyl]-3-ethoxy-phenoxy]ethoxy]ethoxy]ethoxy]-6-ethoxy-benzoyl]-9-ethyl-carbazol-3-yl]-(o-tolyl)methylene]amino acetate

(45) ##STR00194##

(46) To [2-ethoxy-6-[2-[2-[2-[3-ethoxy-2-[9-ethyl-6-[N-hydroxy-C-(o-tolyl)carbonimidoyl]carbazole-3-carbonyl]phenoxy]ethoxy]ethoxy]ethoxy]phenyl]-[9-ethyl-6-[N-hydroxy-C-(o-tolyl)carbonimidoyl]carbazol-3-yl]methanone (0.42 g; 0.38 mmol) in THF (10 mL) are added triethylamine (0.12 g; 1.2 mmol) and acetyl chloride (0.15 g; 1.9 mmol) at 0° C. Then the mixture is stirred at 0° C. for 2 hours. The reaction mixture is poured into ice-water, and the crude product is extracted with AcOEt. The combined organic layer is washed with H.sub.2O and brine, dried over MgSO.sub.4, and concentrated. The crude product is purified by column chromatography on silica gel eluting AcOEt to obtain a white solid (0.38 g, 84%). The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 1.13 (t), 1.39 (t), 2.04 (s), 2.17 (s), 2.92 (s), 3.30 (t), 3.88 (t), 3.98 (q), 4.30 (q), 6.53 (d), 6.62 (d), 7.11 (d), 7.26-7.42 (m), 7.70 (d), 7.92 (d), 8.27 (s), 8.52 (s).

EXAMPLE 18

[[6-[2-[2-[2-[2-[[1-[6-[N-acetoxy-C-(o-tolyl)carbonimidoyl]-9-(2-ethylhexyl)-carbazole-3-carbonyl]-2-naphthyl]oxy]ethoxy]ethoxy]ethoxy]naphthalene-1-carbonyl]-9-(2-ethylhexyl)carbazol-3-yl]-(o-tolyl)methylene]amino acetate

(47) ##STR00195##

(48) The corresponding dimer intermediate of the diketone is prepared according to the procedure as disclosed in example 17.c with the corresponding diketone, and then the oxime and oxime ester are prepared according to the same procedure as 17.d and 17.e respectively.

(49) The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 0.82 (t), 0.85 (t), 1.14-1.40 (m), 1.85 (s), 1.95 (m), 2.04 (s), 3.13 (s), 3.39 (t), 4.06 (t), 4.10 (d), 7.10 (d), 7.26-7.42 (m), 7.53 (d), 7.74 (d), 7.82 (d), 7.89 (d), 7.90 (d), 8.19 (s), 8.56 (s).

EXAMPLE 19

[[2-[6-[2-[N-acetoxy-C-[6-(2-ethoxynaphthalene-1-carbonyl)-9-(2-ethyl-hexyl)carbazol-3-yl]carbonimidoyl]phenoxy]hexoxy]phenyl]-[6-(2-ethoxy-naphthalene-1-carbonyl)-9-(2-ethylhexyl)carbazol-3-yl]methylene]amino acetate

(50) ##STR00196##

(51) The corresponding dimer intermediate of the diketone is prepared according to the procedure as disclosed in example 13.b with the corresponding diketone, and then the oxime and oxime ester are prepared according to the same procedure as 13.c and 13.d respectively.

(52) The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 0.82 (t), 0.85 (t), 1.09 (t), 1.22-1.40 (m), 1.95 (m), 2.05 (s), 3.63 (t), 4.08 (t), 4.13 (d), 6.85 (d), 7.04 (t), 7.11 (d), 7.26-7.42 (m), 7.54 (d), 7.73 (d), 7.84 (d), 7.94 (d), 7.95 (d), 8.18 (s), 8.57 (s).

EXAMPLE 20

[[9-[2-[2-[2-[3-[N-acetoxy-C-(2-methoxyphenyl)carbonimidoyl]-6-(2-ethoxy-naphthalene-1-carbonyl)carbazol-9-yl]ethoxy]ethoxy]ethyl]-6-(2-ethoxy-naphthalene-1-carbonyl)carbazol-3-yl]-(2-methoxyphenyl)methylene]-amino acetate

(53) ##STR00197##

(54) The corresponding dimer intermediate of the diketone is prepared according to the procedure as disclosed in example 16.b with the corresponding diketone, and then the oxime and oxime ester are prepared according to the same procedure as 16.c and 16.d respectively.

(55) The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3). δ[ppm]: 1.10 (t), 2.05 (s), 3.25 (s), 3.62 (t), 3.70 (s), 4.09 (q), 4.26 (t), 7.02 (d), 7.03 (t), 7.08 (d), 7.26-7.34 (m), 7.46 (t), 7.49 (d), 7.76 (d), 7.80 (d), 7.88 (d), 7.92 (d), 8.20 (s), 8.57 (s).

APPLICATION EXAMPLES

Example A1: Sensitivity Tests

(56) A photocurable composition for a sensitivity test is prepared by mixing the following components:

(57) TABLE-US-00002 11.0 parts by weight of REGAL ® 400 pigment black (provided by CABOT), 11.0 parts by weight of EFKA ® 4046, dispersant for pigment provided by BASF), 10.3 parts by weight of Ripoxy ® SPC1000, alkaline soluble poylmer (provided by SHOWA DENKO), 3.6 parts by weight of dipentaerythritol penta-/hexa-acrylate ((DPHA), provided by SIGMA-ALDRICH) 1.0 parts by weight of photoinitiator 48.5 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) 15.6 parts by weight of cyclohexanone

(58) All operations are carried out under yellow light. The compositions are applied to a glass plate using a spincoater. The solvent is removed by heating at 80° C. for 10 minutes in a convection oven. The thickness of the dry film is approximately 1.2 μm. A stepwedge pattern mask with 9 linear steps and 9 logarithmic steps of different optical density (Edumund Optics, EIA GrayScale Pattern Slide) is placed on the resist directly. Exposure is carried out using a 250W super high pressure mercury lamp (USH-IO, USH-250BY) at a distance of 15 cm. A total exposure dose measured by an optical power meter (ORC UV Light Measure Model UV-M02 with UV-35 detector) on the glass filter is 500 mJ/cm.sup.2. After exposure, the exposed film is developed with an alkaline solution (5% aqueous solution of DL-A4, YOKOHAMA OILS & FATS) for 10 seconds after break time at 28° C. by using a spray type developer (AD-1200, MIKASA). Break time is the development time of the unexposed region. The necessary UV dose for full curing (i.e. the pattern is not dissolved with the alkaline solution) is calculated from the residual thickness of each step after development. The smaller the value of the dose, the more sensitive is the tested initiator. The results are listed in Table 2.

(59) TABLE-US-00003 TABLE 2 photoinitiator of example necessary UV dose for full curing 1 39 mJ/cm.sup.2 2 32 mJ/cm.sup.2 3 42 mJ/cm.sup.2 4 37 mJ/cm.sup.2 6 35 mJ/cm.sup.2 7 37 mJ/cm.sup.2 8 22 mJ/cm.sup.2 9 39 mJ/cm.sup.2 10 32 mJ/cm.sup.2 11 33 mJ/cm.sup.2 12 28 mJ/cm.sup.2 13 15 mJ/cm.sup.2 14 15 mJ/cm.sup.2 15 29 mJ/cm.sup.2 16 18 mJ/cm.sup.2 17 19 mJ/cm.sup.2 18 22 mJ/cm.sup.2 19 23 mJ/cm.sup.2 20 20 mJ/cm.sup.2