JPH0583588B2 - - Google Patents
Info
- Publication number
- JPH0583588B2 JPH0583588B2 JP60225175A JP22517585A JPH0583588B2 JP H0583588 B2 JPH0583588 B2 JP H0583588B2 JP 60225175 A JP60225175 A JP 60225175A JP 22517585 A JP22517585 A JP 22517585A JP H0583588 B2 JPH0583588 B2 JP H0583588B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- less carbon
- substituted
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 125000004432 carbon atom Chemical group C* 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 8
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 6
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 claims description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims description 4
- PYWQACMPJZLKOQ-UHFFFAOYSA-N 1,3-tellurazole Chemical compound [Te]1C=CN=C1 PYWQACMPJZLKOQ-UHFFFAOYSA-N 0.000 claims description 4
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 4
- 125000004423 acyloxy group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- KXNQKOAQSGJCQU-UHFFFAOYSA-N benzo[e][1,3]benzothiazole Chemical compound C1=CC=C2C(N=CS3)=C3C=CC2=C1 KXNQKOAQSGJCQU-UHFFFAOYSA-N 0.000 claims description 4
- WMUIZUWOEIQJEH-UHFFFAOYSA-N benzo[e][1,3]benzoxazole Chemical compound C1=CC=C2C(N=CO3)=C3C=CC2=C1 WMUIZUWOEIQJEH-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 36
- 239000013078 crystal Substances 0.000 description 26
- -1 vinylmethyl group Chemical group 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 239000000975 dye Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RZGQBLWMLLDDKL-UHFFFAOYSA-N 2,6-dimethylpyran-4-thione Chemical compound CC1=CC(=S)C=C(C)O1 RZGQBLWMLLDDKL-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 3
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 3
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical group C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 2
- ZLLOWHFKKIOINR-UHFFFAOYSA-N 5-phenyl-1,3-thiazole Chemical compound S1C=NC=C1C1=CC=CC=C1 ZLLOWHFKKIOINR-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AMTXUWGBSGZXCJ-UHFFFAOYSA-N benzo[e][1,3]benzoselenazole Chemical group C1=CC=C2C(N=C[se]3)=C3C=CC2=C1 AMTXUWGBSGZXCJ-UHFFFAOYSA-N 0.000 description 2
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BREUOIWLJRZAFF-UHFFFAOYSA-N 1,3-benzothiazol-5-ol Chemical compound OC1=CC=C2SC=NC2=C1 BREUOIWLJRZAFF-UHFFFAOYSA-N 0.000 description 1
- ORIIXCOYEOIFSN-UHFFFAOYSA-N 1,3-benzothiazol-6-ol Chemical compound OC1=CC=C2N=CSC2=C1 ORIIXCOYEOIFSN-UHFFFAOYSA-N 0.000 description 1
- KZWJUNXNZGVOOS-UHFFFAOYSA-N 1,3-benzothiazole-5-carbonitrile Chemical compound N#CC1=CC=C2SC=NC2=C1 KZWJUNXNZGVOOS-UHFFFAOYSA-N 0.000 description 1
- RBIZQDIIVYJNRS-UHFFFAOYSA-N 1,3-benzothiazole-5-carboxylic acid Chemical compound OC(=O)C1=CC=C2SC=NC2=C1 RBIZQDIIVYJNRS-UHFFFAOYSA-N 0.000 description 1
- UPPYOQWUJKAFSG-UHFFFAOYSA-N 1,3-benzoxazol-5-ol Chemical compound OC1=CC=C2OC=NC2=C1 UPPYOQWUJKAFSG-UHFFFAOYSA-N 0.000 description 1
- SAHAKBXWZLDNAA-UHFFFAOYSA-N 1,3-benzoxazol-6-ol Chemical compound OC1=CC=C2N=COC2=C1 SAHAKBXWZLDNAA-UHFFFAOYSA-N 0.000 description 1
- ALUQMCBDQKDRAK-UHFFFAOYSA-N 2,3,3a,4-tetrahydro-1,3-benzothiazole Chemical compound C1C=CC=C2SCNC21 ALUQMCBDQKDRAK-UHFFFAOYSA-N 0.000 description 1
- GBBJPBIYHSMRHL-UHFFFAOYSA-M 2,3-dimethyl-1,3-benzoxazol-3-ium;4-methylbenzenesulfonate Chemical compound C1=CC=C2[N+](C)=C(C)OC2=C1.CC1=CC=C(S([O-])(=O)=O)C=C1 GBBJPBIYHSMRHL-UHFFFAOYSA-M 0.000 description 1
- JKTQHJKAIBONLQ-UHFFFAOYSA-N 2-amino-4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C(N)=C1 JKTQHJKAIBONLQ-UHFFFAOYSA-N 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- YVORRVFKHZLJGZ-UHFFFAOYSA-N 4,5-Dimethyloxazole Chemical compound CC=1N=COC=1C YVORRVFKHZLJGZ-UHFFFAOYSA-N 0.000 description 1
- UWSONZCNXUSTKW-UHFFFAOYSA-N 4,5-Dimethylthiazole Chemical compound CC=1N=CSC=1C UWSONZCNXUSTKW-UHFFFAOYSA-N 0.000 description 1
- ODKHOKLXMBWVOQ-UHFFFAOYSA-N 4,5-diphenyl-1,3-oxazole Chemical compound O1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 ODKHOKLXMBWVOQ-UHFFFAOYSA-N 0.000 description 1
- QBQQTGIZSOGZBT-UHFFFAOYSA-N 4,5-diphenyl-1,3-selenazole Chemical compound [se]1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 QBQQTGIZSOGZBT-UHFFFAOYSA-N 0.000 description 1
- BGTVICKPWACXLR-UHFFFAOYSA-N 4,5-diphenyl-1,3-thiazole Chemical compound S1C=NC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 BGTVICKPWACXLR-UHFFFAOYSA-N 0.000 description 1
- NDUHYERSZLRFNL-UHFFFAOYSA-N 4,6-dimethyl-1,3-benzoxazole Chemical compound CC1=CC(C)=C2N=COC2=C1 NDUHYERSZLRFNL-UHFFFAOYSA-N 0.000 description 1
- IFEPGHPDQJOYGG-UHFFFAOYSA-N 4-chloro-1,3-benzothiazole Chemical compound ClC1=CC=CC2=C1N=CS2 IFEPGHPDQJOYGG-UHFFFAOYSA-N 0.000 description 1
- GQPBBURQQRLAKF-UHFFFAOYSA-N 4-ethyl-1,3-oxazole Chemical compound CCC1=COC=N1 GQPBBURQQRLAKF-UHFFFAOYSA-N 0.000 description 1
- XQPAPBLJJLIQGV-UHFFFAOYSA-N 4-methoxy-1,3-benzothiazole Chemical compound COC1=CC=CC2=C1N=CS2 XQPAPBLJJLIQGV-UHFFFAOYSA-N 0.000 description 1
- PIUXNZAIHQAHBY-UHFFFAOYSA-N 4-methyl-1,3-benzothiazole Chemical compound CC1=CC=CC2=C1N=CS2 PIUXNZAIHQAHBY-UHFFFAOYSA-N 0.000 description 1
- PUMREIFKTMLCAF-UHFFFAOYSA-N 4-methyl-1,3-oxazole Chemical compound CC1=COC=N1 PUMREIFKTMLCAF-UHFFFAOYSA-N 0.000 description 1
- BJATXNRFAXUVCU-UHFFFAOYSA-N 4-methyl-1,3-selenazole Chemical compound CC1=C[se]C=N1 BJATXNRFAXUVCU-UHFFFAOYSA-N 0.000 description 1
- NTFMLYSGIKHECT-UHFFFAOYSA-N 4-phenyl-1,3-oxazole Chemical compound O1C=NC(C=2C=CC=CC=2)=C1 NTFMLYSGIKHECT-UHFFFAOYSA-N 0.000 description 1
- MLBGDGWUZBTFHT-UHFFFAOYSA-N 4-phenyl-1,3-selenazole Chemical compound [se]1C=NC(C=2C=CC=CC=2)=C1 MLBGDGWUZBTFHT-UHFFFAOYSA-N 0.000 description 1
- KXCQDIWJQBSUJF-UHFFFAOYSA-N 4-phenyl-1,3-thiazole Chemical compound S1C=NC(C=2C=CC=CC=2)=C1 KXCQDIWJQBSUJF-UHFFFAOYSA-N 0.000 description 1
- HYXKRZZFKJHDRT-UHFFFAOYSA-N 5,6-dimethoxy-1,3-benzothiazole Chemical compound C1=C(OC)C(OC)=CC2=C1SC=N2 HYXKRZZFKJHDRT-UHFFFAOYSA-N 0.000 description 1
- QMUXKZBRYRPIPQ-UHFFFAOYSA-N 5,6-dimethyl-1,3-benzothiazole Chemical compound C1=C(C)C(C)=CC2=C1SC=N2 QMUXKZBRYRPIPQ-UHFFFAOYSA-N 0.000 description 1
- RWNMLYACWNIEIG-UHFFFAOYSA-N 5,6-dimethyl-1,3-benzoxazole Chemical compound C1=C(C)C(C)=CC2=C1OC=N2 RWNMLYACWNIEIG-UHFFFAOYSA-N 0.000 description 1
- ODSGKKPRKQLYDA-UHFFFAOYSA-N 5-(trifluoromethyl)-1,3-benzothiazole Chemical compound FC(F)(F)C1=CC=C2SC=NC2=C1 ODSGKKPRKQLYDA-UHFFFAOYSA-N 0.000 description 1
- KFDDRUWQFQJGNL-UHFFFAOYSA-N 5-bromo-1,3-benzothiazole Chemical compound BrC1=CC=C2SC=NC2=C1 KFDDRUWQFQJGNL-UHFFFAOYSA-N 0.000 description 1
- DUMYZVKQCMCQHJ-UHFFFAOYSA-N 5-chloro-1,3-benzoselenazole Chemical compound ClC1=CC=C2[se]C=NC2=C1 DUMYZVKQCMCQHJ-UHFFFAOYSA-N 0.000 description 1
- YTSFYTDPSSFCLU-UHFFFAOYSA-N 5-chloro-1,3-benzothiazole Chemical compound ClC1=CC=C2SC=NC2=C1 YTSFYTDPSSFCLU-UHFFFAOYSA-N 0.000 description 1
- VWMQXAYLHOSRKA-UHFFFAOYSA-N 5-chloro-1,3-benzoxazole Chemical compound ClC1=CC=C2OC=NC2=C1 VWMQXAYLHOSRKA-UHFFFAOYSA-N 0.000 description 1
- GYXTWUJZURSNCF-UHFFFAOYSA-M 5-chloro-3-ethyl-2-methyl-1,3-benzothiazol-3-ium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1=C(Cl)C=C2[N+](CC)=C(C)SC2=C1 GYXTWUJZURSNCF-UHFFFAOYSA-M 0.000 description 1
- GWKNDCJHRNOQAR-UHFFFAOYSA-N 5-ethoxy-1,3-benzothiazole Chemical compound CCOC1=CC=C2SC=NC2=C1 GWKNDCJHRNOQAR-UHFFFAOYSA-N 0.000 description 1
- MHWNEQOZIDVGJS-UHFFFAOYSA-N 5-ethoxy-1,3-benzoxazole Chemical compound CCOC1=CC=C2OC=NC2=C1 MHWNEQOZIDVGJS-UHFFFAOYSA-N 0.000 description 1
- CEPRZYJDQRSAOJ-UHFFFAOYSA-N 5-ethoxybenzo[g][1,3]benzothiazole Chemical compound C12=CC=CC=C2C(OCC)=CC2=C1SC=N2 CEPRZYJDQRSAOJ-UHFFFAOYSA-N 0.000 description 1
- ZRMPAEOUOPNNPZ-UHFFFAOYSA-N 5-fluoro-1,3-benzoxazole Chemical compound FC1=CC=C2OC=NC2=C1 ZRMPAEOUOPNNPZ-UHFFFAOYSA-N 0.000 description 1
- AHIHYPVDBXEDMN-UHFFFAOYSA-N 5-methoxy-1,3-benzoselenazole Chemical compound COC1=CC=C2[se]C=NC2=C1 AHIHYPVDBXEDMN-UHFFFAOYSA-N 0.000 description 1
- PNJKZDLZKILFNF-UHFFFAOYSA-N 5-methoxy-1,3-benzothiazole Chemical compound COC1=CC=C2SC=NC2=C1 PNJKZDLZKILFNF-UHFFFAOYSA-N 0.000 description 1
- IQQKXTVYGHYXFX-UHFFFAOYSA-N 5-methoxy-1,3-benzoxazole Chemical compound COC1=CC=C2OC=NC2=C1 IQQKXTVYGHYXFX-UHFFFAOYSA-N 0.000 description 1
- VGUKLAIGOXRABB-UHFFFAOYSA-N 5-methoxybenzo[g][1,3]benzothiazole Chemical compound C12=CC=CC=C2C(OC)=CC2=C1SC=N2 VGUKLAIGOXRABB-UHFFFAOYSA-N 0.000 description 1
- LDDVDAMRGURWPF-UHFFFAOYSA-N 5-methyl-1,3-benzoselenazole Chemical compound CC1=CC=C2[se]C=NC2=C1 LDDVDAMRGURWPF-UHFFFAOYSA-N 0.000 description 1
- SEBIXVUYSFOUEL-UHFFFAOYSA-N 5-methyl-1,3-benzothiazole Chemical compound CC1=CC=C2SC=NC2=C1 SEBIXVUYSFOUEL-UHFFFAOYSA-N 0.000 description 1
- UBIAVBGIRDRQLD-UHFFFAOYSA-N 5-methyl-1,3-benzoxazole Chemical compound CC1=CC=C2OC=NC2=C1 UBIAVBGIRDRQLD-UHFFFAOYSA-N 0.000 description 1
- ZYMHCFYHVYGFMS-UHFFFAOYSA-N 5-methyl-1,3-oxazole Chemical compound CC1=CN=CO1 ZYMHCFYHVYGFMS-UHFFFAOYSA-N 0.000 description 1
- RLYUNPNLXMSXAX-UHFFFAOYSA-N 5-methylthiazole Chemical compound CC1=CN=CS1 RLYUNPNLXMSXAX-UHFFFAOYSA-N 0.000 description 1
- LUDNKXQULYIPDQ-UHFFFAOYSA-N 5-phenyl-1,3-benzoselenazole Chemical compound C=1C=C2[se]C=NC2=CC=1C1=CC=CC=C1 LUDNKXQULYIPDQ-UHFFFAOYSA-N 0.000 description 1
- AAKPXIJKSNGOCO-UHFFFAOYSA-N 5-phenyl-1,3-benzothiazole Chemical compound C=1C=C2SC=NC2=CC=1C1=CC=CC=C1 AAKPXIJKSNGOCO-UHFFFAOYSA-N 0.000 description 1
- NIFNXGHHDAXUGO-UHFFFAOYSA-N 5-phenyl-1,3-benzoxazole Chemical compound C=1C=C2OC=NC2=CC=1C1=CC=CC=C1 NIFNXGHHDAXUGO-UHFFFAOYSA-N 0.000 description 1
- YPYPBEGIASEWKA-UHFFFAOYSA-N 5-phenyl-1,3-oxazole Chemical compound O1C=NC=C1C1=CC=CC=C1 YPYPBEGIASEWKA-UHFFFAOYSA-N 0.000 description 1
- YJOUISWKEOXIMC-UHFFFAOYSA-N 6-bromo-1,3-benzothiazole Chemical compound BrC1=CC=C2N=CSC2=C1 YJOUISWKEOXIMC-UHFFFAOYSA-N 0.000 description 1
- AIBQGOMAISTKSR-UHFFFAOYSA-N 6-chloro-1,3-benzothiazole Chemical compound ClC1=CC=C2N=CSC2=C1 AIBQGOMAISTKSR-UHFFFAOYSA-N 0.000 description 1
- GKJSZXGYFJBYRQ-UHFFFAOYSA-N 6-chloroquinoline Chemical compound N1=CC=CC2=CC(Cl)=CC=C21 GKJSZXGYFJBYRQ-UHFFFAOYSA-N 0.000 description 1
- AJAKVPMSAABZRX-UHFFFAOYSA-N 6-ethoxyquinoline Chemical compound N1=CC=CC2=CC(OCC)=CC=C21 AJAKVPMSAABZRX-UHFFFAOYSA-N 0.000 description 1
- VDOYSQQOKJDYDR-UHFFFAOYSA-N 6-ethylquinoline Chemical compound N1=CC=CC2=CC(CC)=CC=C21 VDOYSQQOKJDYDR-UHFFFAOYSA-N 0.000 description 1
- AHOIGFLSEXUWNV-UHFFFAOYSA-N 6-methoxy-1,3-benzothiazole Chemical compound COC1=CC=C2N=CSC2=C1 AHOIGFLSEXUWNV-UHFFFAOYSA-N 0.000 description 1
- FKYKJYSYSGEDCG-UHFFFAOYSA-N 6-methoxy-1,3-benzoxazole Chemical compound COC1=CC=C2N=COC2=C1 FKYKJYSYSGEDCG-UHFFFAOYSA-N 0.000 description 1
- IVKILQAPNDCUNJ-UHFFFAOYSA-N 6-methyl-1,3-benzothiazole Chemical compound CC1=CC=C2N=CSC2=C1 IVKILQAPNDCUNJ-UHFFFAOYSA-N 0.000 description 1
- SZWNDAUMBWLYOQ-UHFFFAOYSA-N 6-methylbenzoxazole Chemical compound CC1=CC=C2N=COC2=C1 SZWNDAUMBWLYOQ-UHFFFAOYSA-N 0.000 description 1
- RXEDQOMFMWCKFW-UHFFFAOYSA-N 7-chloro-1,3-benzothiazole Chemical compound ClC1=CC=CC2=C1SC=N2 RXEDQOMFMWCKFW-UHFFFAOYSA-N 0.000 description 1
- NCPZTZXDHOIMDV-UHFFFAOYSA-N 7-methoxybenzo[e][1,3]benzothiazole Chemical compound C1=CC2=CC(OC)=CC=C2C2=C1SC=N2 NCPZTZXDHOIMDV-UHFFFAOYSA-N 0.000 description 1
- RNAAXKYOTPSFGV-UHFFFAOYSA-N 8-fluoroquinoline Chemical compound C1=CN=C2C(F)=CC=CC2=C1 RNAAXKYOTPSFGV-UHFFFAOYSA-N 0.000 description 1
- NGQVHYQMKZKLAM-UHFFFAOYSA-N 8-methoxybenzo[e][1,3]benzothiazole Chemical compound C12=CC(OC)=CC=C2C=CC2=C1N=CS2 NGQVHYQMKZKLAM-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 241001061127 Thione Species 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- MWGUHVCAWGDKNU-UHFFFAOYSA-N benzo[f][1,3]benzoselenazole Chemical compound C1=CC=C2C=C([se]C=N3)C3=CC2=C1 MWGUHVCAWGDKNU-UHFFFAOYSA-N 0.000 description 1
- HJLDPBXWNCCXGM-UHFFFAOYSA-N benzo[f][1,3]benzothiazole Chemical compound C1=CC=C2C=C(SC=N3)C3=CC2=C1 HJLDPBXWNCCXGM-UHFFFAOYSA-N 0.000 description 1
- GYTPOXPRHJKGHD-UHFFFAOYSA-N benzo[f][1,3]benzoxazole Chemical compound C1=CC=C2C=C(OC=N3)C3=CC2=C1 GYTPOXPRHJKGHD-UHFFFAOYSA-N 0.000 description 1
- IEICFDLIJMHYQB-UHFFFAOYSA-N benzo[g][1,3]benzoselenazole Chemical compound C1=CC=CC2=C([se]C=N3)C3=CC=C21 IEICFDLIJMHYQB-UHFFFAOYSA-N 0.000 description 1
- IIUUNAJWKSTFPF-UHFFFAOYSA-N benzo[g][1,3]benzothiazole Chemical compound C1=CC=CC2=C(SC=N3)C3=CC=C21 IIUUNAJWKSTFPF-UHFFFAOYSA-N 0.000 description 1
- BVVBQOJNXLFIIG-UHFFFAOYSA-N benzo[g][1,3]benzoxazole Chemical compound C1=CC=CC2=C(OC=N3)C3=CC=C21 BVVBQOJNXLFIIG-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- AINBZKYUNWUTRE-UHFFFAOYSA-N ethanol;propan-2-ol Chemical compound CCO.CC(C)O AINBZKYUNWUTRE-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 239000000990 laser dye Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002916 oxazoles Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- WWANKXYUVUCOMI-UHFFFAOYSA-N pyran-4-thione Chemical compound S=C1C=COC=C1 WWANKXYUVUCOMI-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Description
本発明は一般式〔〕で表わされる新規なメチ
ン染料に関する。
The present invention relates to a novel methine dye represented by the general formula [ ].
【化】
(式中、nは0又は1,mは1、又は2を表わ
す。R1は未置換のアルキル基またはアルコキシ
基もしくはフエニル基で置換されたアルキル基を
表わし、R2は一般式〔〕で表わされる基を表
わす。Zはチアゾール、ベンゾチアゾール、ナフ
トチアゾール、オキサゾール、ベンゾオキサゾー
ル、ナフトオキサゾール、ベンゾセレナゾール、
テルラゾール、3,3−ジアルキルインドレニ
ン、2−ピリジン、4−ピリジンおよび2−キノ
リンから選ばれる複素環を形成するに必要な原子
群を表わし、それらの環はメチル基、メトキシ
基、エトキシ基、トリフルオロメチル基及び塩素
原子から選ばれる基で置換されていてもよい。X
はアニオンを表わす。pは1または2を表わ
し、染料が分子内塩を形成するときはpは1であ
る。)[Formula, n represents 0 or 1, m represents 1 or 2, R 1 represents an unsubstituted alkyl group or an alkyl group substituted with an alkoxy group or a phenyl group, R 2 represents the general formula [ ] represents a group. Z is thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, benzoselenazole,
Represents a group of atoms necessary to form a heterocycle selected from tellurazole, 3,3-dialkylindolenine, 2-pyridine, 4-pyridine, and 2-quinoline, and these rings include a methyl group, a methoxy group, an ethoxy group, It may be substituted with a group selected from a trifluoromethyl group and a chlorine atom. X
represents an anion. p represents 1 or 2, and p is 1 when the dye forms an inner salt. )
【式】
(式中、R11,R12は無置換アルキル基、また
は置換基として、シアノ基、ハロゲン原子、もし
くは炭素数8以下のアルコキシカルボニル基で置
換された炭素数18以下のアルキル基を表わし、ま
たR11とR12が連結して5員環または6員環を形
成してもよい。R13,R14は水素原子、無置換ア
ルキル基、置換もしくは無置換のアミノ基、カル
ボキシル基、シアノ基、ヒドロキシ基、ハロゲン
原子、炭素数8以下のアルコキシカルボニル基、
炭素数2〜8のアルコキシ基、炭素数8以下のア
シルオキシ基、カルバモイル基、スルフアモイル
基を表わし、またR11またはR12とR13またはR14
が連結して5員環または6員環を形成してもよ
い。但し、R13及びR14の少なくとも1つは置換
もしくは無置換のアミノ基、カルボキシ基、シア
ノ基、ヒドロキシ基、ハロゲン原子、炭素数8以
下のアルコキシカルボニル基、炭素数2〜8のア
ルコキシ基、炭素数8以下のアシルオキシ基、カ
ルバモイル基、スルフアモイル基を表わす。
一般式〔〕で表わされる化合物の各置換基は
次に示す置換基が好ましい。
即ちR1は、炭素数18以下の無置換アルキル基
(例えばメチル基、エチル基、プロピル基、ブチ
ル基、ペンチル基、オクチル基、デシル基、ドデ
シル基、オクタデシル基、ビニルメチル基、シク
ロヘキシル基など)、または炭素数8以下のアル
コキシ基、(例えばメトキシ基、エトキシ基、ベ
ンジルオキシ基、フエネチルオキシ基など)、で
置換された炭素数18以下のアルキル基が好まし
い。
前記一般式〔〕で表わされる基中の好ましい
置換基を記載する。
R11,R12,R13,R14で表わされる無置換アル
キル基としては炭素数1から12の無置換アルキル
基例えばメチル基、エチル基、ピロプル基、ブチ
ル基、ヘキシル基、オクチル基、デシル基、ドデ
シル基、ビニルメチル基などが好ましい。
R11,R12で表わされる置換アルキル基の置換
基としてのハロゲン原子は例えばフツ素原子、塩
素原子など、また炭素数8以下のアルコキシカル
ボニル基は例えばメトキシカルボニル基、エトキ
シカルボニル基、フエノキシカルボニル基、ベン
ジルオキシカルボニル基などが挙げられる。
R13,R14で表わされるハロゲン原子は例えば
フツ素原子、塩素原子など、また炭素数8以下の
アルコキシカルボニル基は例えばメトキシカルボ
ニル基、エトキシカルボニル基、フエノキシカル
ボニル基、ベンジルオキシカルボニル基など;ま
た炭素数2〜8のアルコキシ基は例えばエトキシ
基、ベンジルオキシ基、フエネチルオキシ基な
ど;また炭素数8以下のアシルオキシ基は例えば
アセチルオキシ基、プロピオニルオキシ基など;
またカルバモイル基は例えばカルバモイル基、
N,N−ジメチルカルバモイル基、モルホリノカ
ルバモイル基、ピペリジノカルバモイル基など;
スルフアモイル基は例えばスルフアモイル基、
N,N−ジメチルスルフアモイル基、モルホリノ
スルホニル基、ピリジノスルホニル基などが挙げ
られる。
R13,R14の無置換または置換アミノ基として
は、[Formula] (In the formula, R 11 and R 12 are unsubstituted alkyl groups, or as substituents, an alkyl group with 18 or less carbon atoms substituted with a cyano group, a halogen atom, or an alkoxycarbonyl group with 8 or less carbon atoms. In addition, R 11 and R 12 may be linked to form a 5-membered ring or a 6-membered ring. R 13 and R 14 are a hydrogen atom, an unsubstituted alkyl group, a substituted or unsubstituted amino group, or a carboxyl group. , cyano group, hydroxy group, halogen atom, alkoxycarbonyl group having 8 or less carbon atoms,
It represents an alkoxy group having 2 to 8 carbon atoms, an acyloxy group having 8 or less carbon atoms, a carbamoyl group, or a sulfamoyl group, and R 11 or R 12 and R 13 or R 14
may be linked to form a 5-membered ring or a 6-membered ring. However, at least one of R 13 and R 14 is a substituted or unsubstituted amino group, carboxy group, cyano group, hydroxy group, halogen atom, alkoxycarbonyl group having 8 or less carbon atoms, an alkoxy group having 2 to 8 carbon atoms, Represents an acyloxy group, carbamoyl group, or sulfamoyl group having 8 or less carbon atoms. Each substituent of the compound represented by the general formula [] is preferably the substituent shown below. That is, R 1 is an unsubstituted alkyl group having 18 or less carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, decyl group, dodecyl group, octadecyl group, vinylmethyl group, cyclohexyl group, etc.). ), or an alkyl group having 18 or less carbon atoms substituted with an alkoxy group having 8 or less carbon atoms (eg, methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.). Preferred substituents in the group represented by the above general formula [] will be described. Examples of unsubstituted alkyl groups represented by R 11 , R 12 , R 13 , and R 14 include unsubstituted alkyl groups having 1 to 12 carbon atoms, such as methyl group, ethyl group, pyropur group, butyl group, hexyl group, octyl group, and decyl group. A dodecyl group, a vinylmethyl group, and the like are preferred. Examples of the halogen atom as a substituent for the substituted alkyl group represented by R 11 and R 12 include fluorine atom and chlorine atom, and examples of the alkoxycarbonyl group having 8 or less carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, and phenoxycarbonyl group. Examples include carbonyl group and benzyloxycarbonyl group. The halogen atoms represented by R 13 and R 14 include, for example, a fluorine atom and a chlorine atom, and the alkoxycarbonyl groups having 8 or less carbon atoms include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a phenoxycarbonyl group, a benzyloxycarbonyl group, etc. Also, alkoxy groups having 2 to 8 carbon atoms include, for example, ethoxy, benzyloxy, and phenethyloxy groups; and acyloxy groups having 8 or less carbon atoms include, for example, acetyloxy and propionyloxy groups;
Further, the carbamoyl group is, for example, a carbamoyl group,
N,N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.;
The sulfamoyl group is, for example, a sulfamoyl group,
Examples include N,N-dimethylsulfamoyl group, morpholinosulfonyl group, and pyridinosulfonyl group. As unsubstituted or substituted amino groups for R 13 and R 14 ,
【式】
異なつていてもよく、水素原子、炭素数1〜4の
低級アルキル基(例えばメチル基、エチル基、プ
ロピル基、ブチル基等)、炭素数2〜8のアシル
基(例えばアセチル基、プロピオニル基、ベンゾ
イル基など)が好ましい。
またR17とR18で環を形成してもよい。
Zで形成される複素環はチアゾール核(例えば
チアゾール、4−メチルチアゾール、4−フエニ
ルチアゾール、5−メチルチアゾール、5−フエ
ニルチアゾール、4,5−ジメチルチアゾール、
4,5−ジフエニルチアゾール、4,(2−チエ
ニル)チアゾール等)、ベンゾチアゾール核(例
えばベンゾチアゾール、4−クロロベンゾチアゾ
ール、5−クロロベンゾチアゾール、6−クロロ
ベンゾチアゾール、7−クロロベンゾチアゾー
ル、4−メチルベンゾチアゾール、5−メチルベ
ンゾチアゾール、6−メチルベンゾチアゾール、
5,6−ジメチルベンゾチアゾール、5−ブロモ
ベンゾチアゾール、6−ブロモベンゾチアゾー
ル、5−トリフルオロメチルベンゾチアゾール、
5−フエニルベンゾチアゾール、4−メトキシベ
ンゾチアゾール、5−メトキシベンゾチアゾー
ル、6−メトキシベンゾチアゾール、5−カルボ
キシベンゾチアゾール、5−シアノベンゾチアゾ
ール、5−フルオロメンゾチアゾール、5−エト
キシベンゾチアゾール、テトラヒドロベンゾチア
ゾール、5,6−ジメトキシベンゾチアゾール、
5−ヒドロキシベンゾチアゾール、6−ヒドロキ
シベンゾチアゾール等)〓、ナフトチアゾール核
(例えばナフト−〔1,2−d〕チアゾール、ナフ
ト〔2,1−d〕チアゾール、ナフト〔2,3−
d〕チアゾール、5−メトキシナフト〔2,1−
d〕チアゾール、5−エトキシナフト〔2,1−
d〕チアゾール、8−メトキシナフト〔1,2−
d〕チアゾール、7−メトキシナフト〔1,2−
d〕チアゾール等)、オキサゾール核(例えば4
−メチルオキサゾール、5−メチルオキサゾー
ル、4−フエニルオキサゾール、4,5−ジフエ
ニルオキサゾール、4−エチルオキサゾール、
4,5−ジメチルオキサゾール、5−フエニルオ
キサゾール等)、ベンゾオキサゾール核(例えば
ベンゾオキサゾール、5−クロロベンゾオキサゾ
ール、5−メチルベンゾオキサゾール、5−フエ
ニルベンゾオキサゾール、6−メチルベンゾオキ
サゾール、5,6−ジメチルベンゾオキサゾー
ル、4,6−ジメチルベンゾオキサゾール、5−
メトキシベンゾオキサゾール、5−エトキシベン
ゾオキサゾール、5−フルオロベンゾオキサゾー
ル、6−メトキシベンゾオキサゾール、5−ヒド
ロキシベンゾオキサゾール、6−ヒドロキシベン
ゾオキサゾール等)、ナフトオキサゾール核(例
えばナフト〔1,2−d〕オキサゾール、ナフト
〔2,1−d〕オキサゾール、ナフト〔2,3−
d〕オキサゾール等)、セレナゾール核(例えば
セレナゾール、4−メチルセレナゾール、4−フ
エニルセレナゾール、4,5−ジフエニルセレナ
ゾール等)、ベンゾセレナゾール核(例えばベン
ゾセレナゾール、5−クロロベンゾセレナゾー
ル、5−メチルベンゾセレナゾール、5−メトキ
シベンゾセレナゾール、5−フエニルベンゾセレ
ナゾール等)、ナフトセレナゾール核(例えばナ
フト〔1,2−d〕セレナゾール、ナフト〔2,
1−d〕セレナゾール、ナフト〔2,3−d〕セ
レナゾール等)、テルラゾール核(例えばベンゾ
テルラゾール、5−メチルベンゾテルラゾール、
5,6−ジメチルベンゾテルラゾール、ナフト
〔1,2−d〕テルラゾール、ナフト〔2,1−
d〕テルラゾール、ナフト〔2,3−d〕テルラ
ゾール、6−メトキシナフト〔1,2−d〕テル
ラゾール、等)、3,3−ジアルキルインドレニ
ン核(例えば3,3−ジメチルインドレニン、
3,3,5−トリメチルインドレニン、5−クロ
ロ−3,3−ジメチルインドレニン、5−エトキ
シカルボニル−3,3−ジメチルインドレニン
等)、2−ピリジン核(例えばピリジン、5−メ
チルピリジン等)、4−ピリジン核(例えばピリ
ジン等)、2−キノリン核(例えば6−エトキシ
キノリン、6−エチルキノリン、6−クロロキノ
リン、8−フルオロキノリンなど)、
X
はアニオンを表わし、具体的には、クロラ
イド、ブロミド、ヨージド、チオシアナート、パ
ークロラート、パラトルエンスルホナート、テト
ラフルオロボラートが好ましい。
一般式〔〕に示す化合物は種々の合成法によ
り合成することができるが、例えば以下の反応式
に示すように、活性メチル基を有する複素環四級
塩誘導体と2,6−ジメチル−4H−ピラン−4
−チオンとの反応により得た中間体〔A〕とアル
デヒド類との縮合反応により得ることができる。[Formula] may be different and include a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), an acyl group having 2 to 8 carbon atoms (e.g. acetyl group) , propionyl group, benzoyl group, etc.) are preferred. Further, R 17 and R 18 may form a ring. The heterocycle formed by Z has a thiazole nucleus (e.g. thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole,
4,5-diphenylthiazole, 4,(2-thienyl)thiazole, etc.), benzothiazole nuclei (e.g. benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole) , 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,
5,6-dimethylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-trifluoromethylbenzothiazole,
5-phenylbenzothiazole, 4-methoxybenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-carboxybenzothiazole, 5-cyanobenzothiazole, 5-fluoromenzothiazole, 5-ethoxybenzothiazole, Tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole,
5-hydroxybenzothiazole, 6-hydroxybenzothiazole, etc.), naphthothiazole nuclei (e.g. naphtho-[1,2-d]thiazole, naphtho[2,1-d]thiazole, naphtho[2,3-
d] Thiazole, 5-methoxynaphtho[2,1-
d] Thiazole, 5-ethoxynaphtho[2,1-
d] Thiazole, 8-methoxynaphtho[1,2-
d] Thiazole, 7-methoxynaphtho[1,2-
d] thiazole, etc.), oxazole nucleus (e.g. 4
-Methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole,
4,5-dimethyloxazole, 5-phenyloxazole, etc.), benzoxazole nuclei (e.g. benzoxazole, 5-chlorobenzoxazole, 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5, 6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 5-
methoxybenzoxazole, 5-ethoxybenzoxazole, 5-fluorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.), naphthoxazole core (e.g. naphtho[1,2-d]oxazole) , naphtho[2,1-d]oxazole, naphtho[2,3-
d] Oxazole, etc.), selenazole core (e.g. selenazole, 4-methylselenazole, 4-phenylselenazole, 4,5-diphenylselenazole, etc.), benzoselenazole nucleus (e.g. benzoselenazole, 5-chlorobenzo selenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5-phenylbenzoselenazole, etc.), naphthoselenazole core (e.g. naphtho[1,2-d]selenazole, naphtho[2,
1-d]selenazole, naphtho[2,3-d]selenazole, etc.), tellurazole core (e.g. benzotelllazole, 5-methylbenzotelllazole,
5,6-dimethylbenzotellazole, naphtho[1,2-d]telllazole, naphtho[2,1-
d] tellurazole, naphtho[2,3-d]tellazole, 6-methoxynaphtho[1,2-d]tellazole, etc.), 3,3-dialkylindolenine core (e.g. 3,3-dimethylindolenine,
3,3,5-trimethylindolenine, 5-chloro-3,3-dimethylindolenine, 5-ethoxycarbonyl-3,3-dimethylindolenine, etc.), 2-pyridine nucleus (e.g. pyridine, 5-methylpyridine, etc.) ), 4-pyridine nucleus (e.g. pyridine etc.), 2-quinoline nucleus (e.g. 6-ethoxyquinoline, 6-ethylquinoline, 6-chloroquinoline, 8-fluoroquinoline etc.), X represents an anion, specifically: , chloride, bromide, iodide, thiocyanate, perchlorate, paratoluenesulfonate, and tetrafluoroborate are preferred. The compound represented by the general formula [] can be synthesized by various synthetic methods. For example, as shown in the reaction formula below, a heterocyclic quaternary salt derivative having an active methyl group and 2,6-dimethyl-4H- Piran-4
- It can be obtained by a condensation reaction between intermediate [A] obtained by reaction with thione and aldehydes.
【化】[ka]
【化】
上記の反応式中、R1,R2,Z,P,nおよび
mは一般式〔〕で説明したものと同意義であ
る。また、X1
,X2
,X
はアニオンを表わ
す。
本発明の新規メチン染料は堅牢性に優れ、フイ
ルター用染料として有効であり、また写真感材用
の染料、増感色素として有効である。またこれら
の染料は砕木パルプ及び漂白亜硫酸パルプからの
混合物ならびに純粋なパルプを染色し、実際上完
全に染着する。更にこれらの染料はエキシマレー
ザー、Nd:YAGレーザーの第2高調波または第
3高調波などの励起方法で励起することにより近
赤外から赤外領域にレーザー光を得ることがで
き、堅牢性がよく、エネルギー変換効率の高い高
性能のレーザー色素として作用する。
以下に本発明の一般式〔〕で表わされる化合
物の具体例を記すが、これのみに限定されるもの
ではない。embedded image In the above reaction formula, R 1 , R 2 , Z, P, n and m have the same meanings as explained in the general formula [ ]. Moreover, X 1 , X 2 , and X represent anions. The novel methine dye of the present invention has excellent fastness and is effective as a dye for filters, and also as a dye for photographic materials and a sensitizing dye. These dyes also dye mixtures from groundwood pulp and bleached sulphite pulp, as well as pure pulp, and are virtually completely dyed. Furthermore, these dyes can be excited by excitation methods such as excimer laser, second harmonic or third harmonic of Nd:YAG laser, etc., to obtain laser light in the near-infrared to infrared region, and their fastness is improved. It often acts as a high-performance laser dye with high energy conversion efficiency. Specific examples of the compound represented by the general formula [] of the present invention are shown below, but the invention is not limited thereto.
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】[ka]
【化】
次に本発明による化合物の合成例を以下の実施
例により、詳細に説明する。
実施例 1
(中間体〔A〕の合成)
1−(1) 3−エチル−2−{(2,6−ジメチル−
4H−ピラン−4−イリデン)メチル}ベ
ンゾチアゾリウム p−トルエンスルホナ
ート
3−エチル−2−メチルベンゾチアゾリウム
p−トルエンスルホナート24.4gと2,6−ジメ
チル−4H−ピラン−4−チオン10.6gを150℃で
15時間加熱反応後、反応混合物にメタノール50
ml、次いでアセトン100ml、酢酸エチル300mlを加
え、室温下撹拌すると結晶が析出した。結晶を
取し、少量のアセトンで洗つたのち、室温下メタ
ノール50mlアセトン100ml、酢酸エチル300mlの混
合溶媒中に結晶を加え、30分撹拌後取し、アセ
トンで洗うと目的物12.7gを得た。(収率40%)
褐色結晶、mp160〜165℃(分解)
1−(2) 5−メチル−3−エチル−2−{(2,6
−ジメチル−4H−ピラン−4−イリデン)
メチル}ベンゾチアゾリウム p−トルエ
ンスルホナート
5−メチル−3−エチル−2−メチルベンゾチ
アゾリウム p−トルエンスルホナー13.4gと2,
6−ジメチル−4H−ピラン−4−チオン5.6gを
150℃で15時間加熱反応後、反応混合物にメタノ
ール50ml、次いでアセトン60ml、酢酸エチル120
mlを加え、室温下撹拌すると結晶が析出した。結
晶を取し、少量のアセトンで洗つたのち、室温
下メタノール50mlアセトン60ml、酢酸エチル120
mlの混合溶媒中に結晶を加え、30分撹拌後取
し、アセトンで洗うと目的物3.5gを得た。(収率
20%)
褐色結晶、mp244〜246℃(分解)
1−(3) 5−クロロ−3−エチル−2−{(2,6
−ジメチル−4H−ピラン−4−イリデン)
メチル}ベンゾチアゾリウム p−トルエ
ンスルホナート
5−クロロ−3−エチル−2−メチルベンゾチ
アゾリウム p−トルエンスルホナート31.7gと
2,6−ジメチル−4H−ピラン−4−チオン
12.9gを150℃で15時間加熱反応後、反応混合物に
メタノール50ml、次いでアセトン100ml、酢酸エ
チル300mlを加え、室温下撹拌すると結晶が析出
した。結晶を取し、少量のアセトンで洗つたの
ち、室温下メタノール50ml、アセトン100ml、酢
酸エチル30mlの混合溶媒中に結晶を加え、30分撹
拌取し、アセトンで洗うと目的物23.5gを得た。
(収率58%)
褐色結晶、mp265〜268℃(分解)
1−(4) 3−エチル−2−{(2,6−ジメチル−
4H−ピラン−4−イリデン)メチル}−ナ
フト〔2,1−d〕チアゾリウム パーク
ロラート
3−エチル−2−メチルナフト〔2,1−d〕
チアゾリウム p−トルエンスルホナート1.9gと
2,6−ジメチル−4H−ピラン−4−チオン
0.7gを150℃で10時間加熱反応後、反応混合物に
メタノール8ml、次いでアセトン12mlを加え均一
溶液とした。この溶液に過塩素酸ナトリウム1.2g
(水20ml溶液)を滴下し、室温下1時間撹拌する
と結晶が析出した。結晶を取し、少量のアセト
ンで洗浄した後、室温下水15ml、アセトン15mlの
混合溶媒中に結晶を加え、15分撹拌後、取し、
アセトンで洗うと、目的物0.4gを得た。(収率19
%)
褐色結晶、mp245〜250℃(分解)
1−(5) 3−エチル−2−{(2,6−ジメチル−
4H−ピラン−4−イリデン)メチル}ナ
フト〔1,2−d〕チアゾリウムパークロ
ラート
3−エチル−2−メチルナフト〔1,2−d〕
チアゾリウムp−トルエンスルホナート1.9gと
2,6−ジメチル−4H−ピラン−4−チオン
0.7gから1−(4)と同様な方法で目的物0.55gを得
た。(収率27%)
褐色結晶、mp228〜230℃(分解)
1−(6) 3−メチル−2−{(2,6−ジメチル−
4H−ピラン−4−イリデン)メチル}ベ
ンゾオキサゾリウムパークロラート
2,3−ジメチルベンゾオキサゾリウムp−ト
ルエンスルホナート1.5gと2,6−ジメチル−
4H−ピラン−4−チオン0.7gを150℃で10時間加
熱反応後、反応混合物にメタノール15ml、次いで
アセトン12mlを加え均一溶液とした。この溶液に
過塩素酸ナトリウム1.2g(水20ml溶液)を滴下し、
室温下1時間撹拌すると結晶が析出した。結晶を
取し、少量のアセトンで洗浄した後、室温下水
15ml、アセトン15mlの混合溶媒中に結晶を加え、
15分撹拌後、取し、アセトンで洗うと、目的物
0.24gを得た。(収率15%)
褐色結晶、mp280℃以上(分解)
実施例 2
(化合物−1)
3−エチル−2−{(2,6−ジメチル−4H−
ピラン−4−イリデン)メチル}ベンゾチアゾリ
ウムp−トルエンスルホナート4.0g、2−アミノ
−4−ジメチルアミノベンゾアルデヒド4.2gを無
水酢酸150ml中に加え、油浴上100℃で60分間加熱
還流させた。室温まで冷却後、メタノール/クロ
ロホルム=1/5(V/V)の混合溶媒を用いて、
シリカゲルカラムを通して精製し、得られた結晶
をエタノール200mlに加え、均一溶液とした。こ
の溶液に過塩素酸ナトリウム2g(水50ml溶液5を
適下し、室温下1時間撹拌すると結晶が析出し
た。結晶を取し、エタノール−イソプロパノー
ルから3回再結晶を行ない目的物1.7gを得た。
褐色結晶、mp270℃以上(分解)
λMeOH nax608nm,εMeOH nax=4.80×104
実施例 3
以下に示すメチン染料も、前述の一般的な合成
方法及び実施例2〜3に示した合成方法と同様に
合成し、得られた化合物のλMeOH nax値及び結晶の色
調を第1表に示した。embedded image Next, synthesis examples of the compounds according to the present invention will be explained in detail with reference to the following examples. Example 1 (Synthesis of intermediate [A]) 1-(1) 3-ethyl-2-{(2,6-dimethyl-
4H-pyran-4-ylidene)methyl}benzothiazolium p-toluenesulfonate 3-ethyl-2-methylbenzothiazolium
24.4 g of p-toluenesulfonate and 10.6 g of 2,6-dimethyl-4H-pyran-4-thione at 150℃
After heating reaction for 15 hours, methanol 50% was added to the reaction mixture.
ml, then 100 ml of acetone and 300 ml of ethyl acetate were added and stirred at room temperature to precipitate crystals. After collecting the crystals and washing them with a small amount of acetone, the crystals were added to a mixed solvent of 50 ml of methanol, 100 ml of acetone, and 300 ml of ethyl acetate at room temperature, stirred for 30 minutes, collected, and washed with acetone to obtain 12.7 g of the desired product. . (Yield 40%) Brown crystals, mp160-165℃ (decomposition) 1-(2) 5-methyl-3-ethyl-2-{(2,6
-dimethyl-4H-pyran-4-ylidene)
Methyl}benzothiazolium p-toluenesulfonate 5-methyl-3-ethyl-2-methylbenzothiazolium p-toluenesulfoner 13.4g and 2,
5.6 g of 6-dimethyl-4H-pyran-4-thione
After heating the reaction at 150°C for 15 hours, add 50 ml of methanol to the reaction mixture, then 60 ml of acetone, and 120 ml of ethyl acetate.
ml and stirred at room temperature to precipitate crystals. After taking the crystals and washing them with a small amount of acetone, add 50 ml of methanol, 60 ml of acetone, and 120 ml of ethyl acetate at room temperature.
The crystals were added to ml of mixed solvent, stirred for 30 minutes, collected, and washed with acetone to obtain 3.5 g of the desired product. (yield
20%) Brown crystals, mp244-246℃ (decomposition) 1-(3) 5-chloro-3-ethyl-2-{(2,6
-dimethyl-4H-pyran-4-ylidene)
Methyl}benzothiazolium p-toluenesulfonate 31.7 g of 5-chloro-3-ethyl-2-methylbenzothiazolium p-toluenesulfonate and 2,6-dimethyl-4H-pyran-4-thione
After heating reaction of 12.9 g at 150° C. for 15 hours, 50 ml of methanol, then 100 ml of acetone and 300 ml of ethyl acetate were added to the reaction mixture, and the mixture was stirred at room temperature to precipitate crystals. After collecting the crystals and washing them with a small amount of acetone, the crystals were added to a mixed solvent of 50 ml of methanol, 100 ml of acetone, and 30 ml of ethyl acetate at room temperature, stirred for 30 minutes, and washed with acetone to obtain 23.5 g of the desired product. .
(Yield 58%) Brown crystals, mp265-268℃ (decomposition) 1-(4) 3-ethyl-2-{(2,6-dimethyl-
4H-pyran-4-ylidene)methyl}-naphtho[2,1-d]thiazolium perchlorate 3-ethyl-2-methylnaphtho[2,1-d]
Thiazolium p-toluenesulfonate 1.9g and 2,6-dimethyl-4H-pyran-4-thione
After heating and reacting 0.7 g at 150° C. for 10 hours, 8 ml of methanol and then 12 ml of acetone were added to the reaction mixture to form a homogeneous solution. 1.2g of sodium perchlorate in this solution
(20 ml of water solution) was added dropwise and stirred at room temperature for 1 hour to precipitate crystals. After collecting the crystals and washing them with a small amount of acetone, the crystals were added to a mixed solvent of 15 ml of sewage water and 15 ml of acetone at room temperature, stirred for 15 minutes, and then collected.
After washing with acetone, 0.4 g of the target product was obtained. (yield 19
%) Brown crystals, mp245-250℃ (decomposition) 1-(5) 3-ethyl-2-{(2,6-dimethyl-
4H-pyran-4-ylidene)methyl}naphtho[1,2-d]thiazolium perchlorate 3-ethyl-2-methylnaphtho[1,2-d]
Thiazolium p-toluenesulfonate 1.9g and 2,6-dimethyl-4H-pyran-4-thione
From 0.7g, 0.55g of the target product was obtained in the same manner as in 1-(4). (Yield 27%) Brown crystals, mp228-230℃ (decomposition) 1-(6) 3-Methyl-2-{(2,6-dimethyl-
4H-pyran-4-ylidene)methyl}benzoxazolium perchlorate 1.5 g of 2,3-dimethylbenzoxazolium p-toluenesulfonate and 2,6-dimethyl-
After a heating reaction of 0.7 g of 4H-pyran-4-thione at 150° C. for 10 hours, 15 ml of methanol and then 12 ml of acetone were added to the reaction mixture to form a homogeneous solution. Add 1.2 g of sodium perchlorate (20 ml of water solution) to this solution,
After stirring for 1 hour at room temperature, crystals were precipitated. After taking the crystals and washing them with a small amount of acetone, place them under water at room temperature.
Add the crystals to a mixed solvent of 15 ml and acetone,
After stirring for 15 minutes, remove and wash with acetone to obtain the desired product.
Obtained 0.24g. (Yield 15%) Brown crystals, mp280℃ or higher (decomposition) Example 2 (Compound-1) 3-ethyl-2-{(2,6-dimethyl-4H-
Add 4.0 g of pyran-4-ylidene)methyl benzothiazolium p-toluenesulfonate and 4.2 g of 2-amino-4-dimethylaminobenzaldehyde to 150 ml of acetic anhydride, and heat under reflux on an oil bath at 100°C for 60 minutes. I let it happen. After cooling to room temperature, using a mixed solvent of methanol/chloroform = 1/5 (V/V),
The crystals obtained by purification through a silica gel column were added to 200 ml of ethanol to form a homogeneous solution. 2 g of sodium perchlorate (50 ml of water solution 5) was added dropwise to this solution and stirred for 1 hour at room temperature to precipitate crystals. The crystals were collected and recrystallized three times from ethanol-isopropanol to obtain 1.7 g of the desired product. Brown crystals, mp 270℃ or higher (decomposed) λ MeOH nax 608 nm, ε MeOH nax = 4.80 The compound was synthesized in the same manner as the synthesis method, and the λ MeOH nax value and crystal color tone of the obtained compound are shown in Table 1.
【表】【table】
Claims (1)
す。R1は未置換のアルキル基またはアルコキシ
基もしくはフエニル基で置換されたアルキル基を
表わし、R2は一般式〔〕で表わされる基を表
わす。Zはチアゾール、ベンゾチアゾール、ナフ
トチアゾール、オキサゾール、ベンゾオキサゾー
ル、ナフトオキサゾール、ベンゾセレナゾール、
テルラゾール、3,3−ジアルキルインドレニ
ン、2−ピリジン、4−ピリジンおよび2−キノ
リンから選ばれる複素環を形成するに必要な原子
群を表わし、それらの環はメチル基、メトキシ
基、エトキシ基、トリフルオロメチル基及び塩素
原子から選ばれる基で置換されていてもよい。X
はアニオンを表わす。pは1または2を表わ
し、染料が分子内塩を形成するときはpは1であ
る。) 【式】 (式中、R11,R12は無置換アルキル基、また
は置換基として、シアノ基、ハロゲン原子、もし
くは炭素数8以下のアルコキシカルボニル基で置
換された炭素数18以下のアルキル基を表わし、ま
たR11とR12が連結して5員環または6員環を形
成してもよい。R13,R14は水素原子、無置換ア
ルキル基、置換もしくは無置換のアミノ基、カル
ボキシル基、シアノ基、ヒドロキシ基、ハロゲン
原子、炭素数8以下のアルコキシカルボニル基、
炭素数2〜8のアルコキシ基、炭素数8以下のア
ルオキシ基、カルバモイル基、スルフアモイル基
を表わし、またR11またはR12とR13またはR14が
連結して5員環または6員環を形成してもよい。
但し、R13及びR14の少なくとも1つは置換もし
くは無置換のアミノ基、カルボキシ基、シアノ
基、ヒドロキシ基、ハロゲン原子、炭素数8以下
のアルコキシカルボニル基、炭素数2〜8のアル
コキシ基、炭素数8以下のアシルオキシ基、カル
バモイル基、スルフアモイル基を表わす。[Claims] 1. A methine dye represented by the following general formula []. [Formula, n represents 0 or 1, m represents 1 or 2, R 1 represents an unsubstituted alkyl group or an alkyl group substituted with an alkoxy group or a phenyl group, R 2 represents the general formula [ ] represents a group. Z is thiazole, benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, benzoselenazole,
Represents a group of atoms necessary to form a heterocycle selected from tellurazole, 3,3-dialkylindolenine, 2-pyridine, 4-pyridine, and 2-quinoline, and these rings include a methyl group, a methoxy group, an ethoxy group, It may be substituted with a group selected from a trifluoromethyl group and a chlorine atom. X
represents an anion. p represents 1 or 2, and p is 1 when the dye forms an inner salt. ) [Formula] (In the formula, R 11 and R 12 are unsubstituted alkyl groups, or alkyl groups having 18 or less carbon atoms substituted with a cyano group, a halogen atom, or an alkoxycarbonyl group having 8 or less carbon atoms as a substituent. and R 11 and R 12 may be linked to form a 5- or 6-membered ring. R 13 and R 14 are hydrogen atoms, unsubstituted alkyl groups, substituted or unsubstituted amino groups, carboxyl group, cyano group, hydroxy group, halogen atom, alkoxycarbonyl group having 8 or less carbon atoms,
Represents an alkoxy group having 2 to 8 carbon atoms, an alkoxy group having 8 or less carbon atoms, a carbamoyl group, or a sulfamoyl group, and R 11 or R 12 and R 13 or R 14 are linked to form a 5- or 6-membered ring. You may.
However, at least one of R 13 and R 14 is a substituted or unsubstituted amino group, carboxy group, cyano group, hydroxy group, halogen atom, alkoxycarbonyl group having 8 or less carbon atoms, an alkoxy group having 2 to 8 carbon atoms, Represents an acyloxy group, carbamoyl group, or sulfamoyl group having 8 or less carbon atoms.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60225175A JPS6284158A (en) | 1985-10-09 | 1985-10-09 | Novel methine dye |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60225175A JPS6284158A (en) | 1985-10-09 | 1985-10-09 | Novel methine dye |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6284158A JPS6284158A (en) | 1987-04-17 |
JPH0583588B2 true JPH0583588B2 (en) | 1993-11-26 |
Family
ID=16825127
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60225175A Granted JPS6284158A (en) | 1985-10-09 | 1985-10-09 | Novel methine dye |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6284158A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2105298A1 (en) | 2008-03-28 | 2009-09-30 | Fujifilm Corporation | Negative-working lithographic printing plate precursor and method of lithographic printing using same |
-
1985
- 1985-10-09 JP JP60225175A patent/JPS6284158A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2105298A1 (en) | 2008-03-28 | 2009-09-30 | Fujifilm Corporation | Negative-working lithographic printing plate precursor and method of lithographic printing using same |
Also Published As
Publication number | Publication date |
---|---|
JPS6284158A (en) | 1987-04-17 |
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