JP4473572B2 - Coumarin compounds - Google Patents
Coumarin compounds Download PDFInfo
- Publication number
- JP4473572B2 JP4473572B2 JP2003524995A JP2003524995A JP4473572B2 JP 4473572 B2 JP4473572 B2 JP 4473572B2 JP 2003524995 A JP2003524995 A JP 2003524995A JP 2003524995 A JP2003524995 A JP 2003524995A JP 4473572 B2 JP4473572 B2 JP 4473572B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- ring
- coumarin compound
- coumarin
- 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
- 125000000332 coumarinyl group Chemical class O1C(=O)C(=CC2=CC=CC=C12)* 0.000 title description 11
- -1 coumarin compound Chemical class 0.000 claims description 114
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N benzo-alpha-pyrone Natural products C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 claims description 91
- 229960000956 coumarin Drugs 0.000 claims description 88
- 235000001671 coumarin Nutrition 0.000 claims description 88
- 150000001875 compounds Chemical class 0.000 claims description 42
- 125000004122 cyclic group Chemical group 0.000 claims description 19
- 239000006096 absorbing agent Substances 0.000 claims description 17
- 239000000891 luminescent agent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000003504 photosensitizing agent Substances 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 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 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 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 claims description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical group O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 claims description 3
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical group C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 claims description 3
- 125000002346 iodo group Chemical group I* 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical group C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 2
- QYMGRIFMUQCAJW-UHFFFAOYSA-N 1,2-dihydropyrazine Chemical group C1NC=CN=C1 QYMGRIFMUQCAJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims 2
- KDUIUFJBNGTBMD-DLMDZQPMSA-N [8]annulene Chemical group C/1=C/C=C\C=C/C=C\1 KDUIUFJBNGTBMD-DLMDZQPMSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 description 78
- 238000006116 polymerization reaction Methods 0.000 description 23
- 238000010521 absorption reaction Methods 0.000 description 19
- 239000000975 dye Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000003287 optical effect Effects 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000000859 sublimation Methods 0.000 description 11
- 230000008022 sublimation Effects 0.000 description 11
- 238000004043 dyeing Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 150000004775 coumarins Chemical class 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000008033 biological extinction Effects 0.000 description 7
- 238000007796 conventional method Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000010355 oscillation Effects 0.000 description 4
- 238000005092 sublimation method Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 0 CN(*)c(cc1)cc(O2)c1C(CC(C(Oc1c3)=O)=C(C4)c1ccc3N(*)*)=C4C2=O Chemical compound CN(*)c(cc1)cc(O2)c1C(CC(C(Oc1c3)=O)=C(C4)c1ccc3N(*)*)=C4C2=O 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000007523 nucleic acids Chemical class 0.000 description 3
- 102000039446 nucleic acids Human genes 0.000 description 3
- 108020004707 nucleic acids Proteins 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical group [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- HWEQKSVYKBUIIK-UHFFFAOYSA-N cyclobuta-1,3-diene Chemical group C1=CC=C1 HWEQKSVYKBUIIK-UHFFFAOYSA-N 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 230000007423 decrease 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
- 238000004821 distillation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000002510 isobutoxy group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])O* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 2
- 125000005921 isopentoxy group Chemical group 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 125000001400 nonyl 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])[H] 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 230000002165 photosensitisation Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000006308 propyl amino group Chemical group 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 125000005920 sec-butoxy group Chemical group 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical group [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
技術分野
この発明はクマリン化合物に関するものであり、とりわけ、光吸収剤、発光剤として有用な新規なクマリン化合物に関するものである。
背景技術
情報化時代の到来に伴い、光化学的重合が多種多様の分野で頻用されるようになり、今では、その用途は、合成樹脂の分野を越えて、塗料、印刷用刷版、印刷回路、集積回路などの情報記録や電子機器の分野にまでおよぶようになった。光化学的重合は、重合性化合物を光照射によって重合させる技術であって、大別すると、重合性化合物を直接光照射し、活性化させることによって重合を開始させる光重合と、光増感剤を共存させた状態で光照射し、光増感剤の活性種を生成させることによって重合性化合物を重合させる光増感重合とがある。いずれの光化学的重合も、重合の開始及び停止が露出光源の点滅によって制御可能であり、また、露出光源の強度や波長を選択することによって重合度や重合速度を容易に制御できる特徴がある。しかも、光化学的重合は、一般に、重合開始のエネルギーが低いために、低温でも重合が可能である。印刷用刷版やホログラフィーなどの情報記録の分野においては、光化学的重合のこのような利点が買われて、アルゴンイオンレーザー、ヘリウムイオンレーザー、Ｎｄ−ＹＡＧレーザーなどの第二高調波などの可視光を照射することによって重合させることのできる光重合性組成物の需要が急速に高まっている。
光重合性組成物へ配合される重合性化合物や重合開始剤は、その多くが紫外線だけを吸収することから、光重合性組成物を可視光で重合させようとすると、光増感剤が不可欠の技術要素となる。光増感剤が備えるべき特性としては、可視領域における分子吸光係数（以下、分子吸光係数を「ε」と略記することがある。）が大きいこと、諸種の重合性化合物や重合開始剤を増感し得ること、増感効率が高いこと、溶剤に対する溶解性と他の配合成分との相溶性に優れていること、そして、安定であることが挙げられる。代表的な光増感剤として、例えば、特開昭５４−１５１０２４号公報に開示されたメロシアニン色素、特開昭５８−２９８０３号公報に開示されたシアニン色素、特開昭５９−５６４０３号公報に開示されたスチルベン色素、特開昭６３−２３９０１号公報に開示されたクマリン誘導体、特開昭６４−３３１０４号公報に開示されたメチレンブルー誘導体、特開平６−３２９６５４号公報に開示されたピラン誘導体などが挙げられるが、これらはいずれも一長一短があり、前述したごとき諸特性を常に発揮し得るようなものは未だ見出されていない。そこで、光化学的重合の新しい適用分野である、例えば、情報記録や電子機器の分野においては、重合性化合物、バインダー樹脂などの、用途に応じた光増感剤以外の材料を先ず選択し、次いで、多種多様の有機化合物のなかからそれらの重合性化合物や重合開始剤に適合するものを試行錯誤的に検索しているというのが現状である。
斯かる状況に鑑み、この発明の課題は、可視光を吸収する新規な有機化合物を提供することによって、光重合性組成物を調製するに当って、選択し得る光増感剤の幅を広げることを課題とする。
発明の開示
この課題を解決すべく、本発明者がクマリン化合物に着目し、鋭意研究し、検索したところ、クマリン骨格を有し、可視光を吸収し得る互いに同じか異なる２以上の原子団が、環状構造を形成しつつ、互いに結合してなるクマリン化合物は、可視領域に吸収極大を有し、可視領域における分子吸光係数が大きく、可視光を効率良く吸収することから、光化学的重合において重合性化合物や重合開始剤を増感させるための材料として極めて有用であることを見出した。加えて、斯かるクマリン化合物は可視領域に発光極大を有し、励起すると可視光を発光することから、斯かる性質を具備する有機化合物を必要とする諸分野において有利に用い得ることが判明した。
すなわち、この発明は、クマリン骨格を有し、可視光を吸収し得る互いに同じか異なる２以上の原子団が、環状構造を形成しつつ、互いに結合してなるクマリン化合物を提供することによって前記課題を解決するものである。
さらに、この発明は、斯かるクマリン化合物を含んでなる光吸収剤を提供することによって前記課題を解決するものである。
さらに、この発明は、斯かるクマリン化合物を含んでなる発光剤を提供することによって前記課題を解決するものである。
さらに、この発明は、フェノール化合物と１，３−ジケトン化合物とを反応させる工程を経由するクマリン化合物の製造方法を提供することによって前記課題を解決するものである。
発明を実施するための最良の形態
この発明の実施の形態について説明すると、既述のとおり、この発明は、クマリン骨格を有し、可視光を吸収し得る互いに同じか異なる２以上の原子団が、環状構造を形成しつつ、互いに結合してなるクマリン化合物に関するものである。この発明でいう原子団とは、クマリン骨格（ベンゾ−α−ピロンとも言い、シス型のα−ヒドロキシ桂皮酸のラクトンに当る。）を有し、かつ、各原子団がそれ自身で可視光、とりわけ、波長３８０乃至７８０ｎｍの光を吸収し得るものを意味する。斯かる原子団は、珪素原子、窒素原子、酸素原子、硫黄原子、セレン原子、テルル原子などのヘテロ原子を含むか含まない、例えば、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、オキシ基、メチレンジオキシ基、エチレンジオキシ基、トリエチレンジオキシ基、チオ基、イミノ基、シラニレン基などの二価基により環状構造、好ましくは、四員環乃至八員環を形成しつつ、互いに結合し合って、単一分子としてのこの発明によるクマリン化合物を生成する。用途にもよるけれども、例えば、発光剤や光化学的重合、太陽電池などにおける光増感剤として用いる場合、複数の原子団として、ともにクマリン骨格を有するものの、吸収域が互いに異なるものを採用するとともに、それらの原子団を共役多重結合を有さず、原子団同士をして実質的に電子共鳴させない環状構造により連結するときには、同一分子内にありながら、各々の原子団が吸収域の異なる、互いに独立した吸光、発色団として機能できることとなり、その結果として、この発明によるクマリン化合物が光吸収剤、発光剤として作用し得る波長域を適宜に調節したり拡大することができることとなる。また、複数の原子団として、ともにクマリン骨格を有するものの、吸収域は互いに同様のものを採用する一方、それらの原子団を共役多重結合を有さず、原子団同士をして実質的に電子共鳴させない環状構造により連結するときには、クマリン化合物が吸収剤、発光剤として作用し得る波長域を調節したり拡大することはできないものの、分子内に斯かる原子団をただ一つ有するものと比較して、１分子あたりの吸光、発色能を大きくすることができる。
この発明によるクマリン化合物のより具体的な例としては、例えば、一般式１又は一般式２で表されるものが挙げられる。
一般式１：
一般式１及び一般式２におけるＺ１及びＺ２は、クマリン骨格を有し、可視光を吸収し得る複数の原子団を互いに結合させる環状構造を表す。好ましい環状構造は、例えば、珪素原子、窒素原子、酸素原子、硫黄原子、セレン原子、テルル原子などのヘテロ原子を含むか含まない、例えば、シクロブタジエン環、シクロペンタジエン環、シクロヘキサジエン環、シクロヘプタジエン環、シクロオクタジエン環、ジオキシン環、ジヒドロジシリン環（ジヒドロジシラベンゼン環）、ジヒドロピラジン環などの四員環乃至八員環であり、このうちで、特に好ましいのは、環状構造を形成しつつ、互いに結合する２以上の原子団をして互いに実質的に電子共鳴させない、例えば、シクロブタジエン環、シクロペンタ−１，３−ジエン環、シクロヘキサ−１，４−ジエン環、シクロヘプタ−１，４−ジエン環、シクロオクタ−１，５−ジエン環、［１，４］ジオキシン環、１，４−ジヒドロ−［１，４］ジシリン環（１，４−ジヒドロ−［１，４］ジシラベンゼン環）、１，４−ジヒドロピラジン環などの共役多重結合を有しない環状構造である。環状構造が共役多重結合を有するクマリン化合物は、各々の原子団が互いに独立した吸光、発色団として機能しないものの、その環状構造が飽和メチレン基を有しないクマリン化合物は、化学的に安定で、耐環境性が大きいことから、安定な光吸収剤や発光剤が必要とされる用途において極めて有用である。なお、斯かる環状構造は、この発明の目的を逸脱しない範囲で、例えば、メチル基、エチル基などの脂肪族炭化水素基、メトキシ基、エトキシ基などのエーテル基、フルオロ基、クロロ基などのハロゲン基、さらには、ヒドロキシ基、カルボキシ基などの置換基を１又は複数有していてもよい。
用途にもよるけれども、光吸収剤、発光剤として特に好ましいのは、クマリン骨格の７位にアミノ基を有する一般式７又は一般式８で表されるクマリン化合物であり、一般式７及び一般式８において、Ｒ１、Ｒ２、Ｒ４乃至Ｒ６及びＲ８は、それぞれ独立に、水素原子か、あるいは、一般式１又は一般式２におけると同様の置換基を表す。Ｒ９乃至Ｒ１２は、それぞれ独立に、水素原子か、あるいは、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ｔｅｒｔ−ペンチル基、ヘキシル基、イソヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基などの脂肪族炭化水素基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘキセニル基などの脂環式炭化水素基、フェニル基、ビフェニリル基、ナフチル基などの芳香族炭化水素基、さらには、それらの組合せによる炭化水素基を表し、斯かる炭化水素基における水素原子は、その１又は複数が、例えば、メトキシ基、トリフルオロメトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、アリールオキシ基、ブトキシ基、イソブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ペンチルオキシ基、イソペンチルオキシ基、ヘキシルオキシ基、フェノキシ基、ベンジルオキシ基などのエーテル基、ヒドロキシ基、シアノ基などによって置換されていてもよい。Ｒ９乃至Ｒ１２における炭化水素基は、それらが結合する窒素原子を含んで、Ｒ２、Ｒ４、Ｒ６又はＲ８が結合する炭素原子と結合し合って、例えば、モルホリン環、ユロリジン環などの環状構造を形成していてもよく、この場合、Ｒ２、Ｒ４、Ｒ６及び／又はＲ８は見掛け上存在しないこととなる。なお、一般式７及び一般式８におけるＺ１及びＺ２は、一般式１及び一般式２におけると同様の四員環乃至八員環を表す。
一般式７：
化学式１：
一般式３：
溶剤としては、例えば、ペンタン、ヘキサン、シクロヘキサン、オクタン、ベンゼン、トルエン、キシレンなどの炭化水素類、四塩化炭素、クロロホルム、１，２−ジクロロエタン、１，２−ジブロモエタン、トリクロロエチレン、テトラクロロエチレン、クロロベンゼン、ブロモベンゼン、α−ジクロロベンゼンなどのハロゲン化物、メタノール、エタノール、１−プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、イソブチルアルコール、イソペンチルアルコール、シクロヘキサノール、エチレングリコール、プロピレングリコール、２−メトキシエタノール、フェノール、ベンジルアルコール、クレゾール、ジエチレングリコール、トリエチレングリコール、グリセリンなどのアルコール類及びフェノール類、ジエチルエーテル、ジイソプロピルエーテル、テトラヒドロフラン、テトラヒドロピラン、１，４−ジオキサン、アニソール、１，２−ジメトキシエタン、ジエチレングリコールジメチルエテール、ジシクロヘキシル−１８−クラウン−６、メチルカルビトール、エチルカルビトールなどのエーテル類、酢酸、無水酢酸、トリクロロ酢酸、トリフルオロ酢酸、無水プロピオン酸、酢酸エチル、炭酸ブチル、炭酸エチレン、炭酸プロピレン、ホルムアミド、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、ヘキサメチル燐酸トリアミド、燐酸トリメチルなどの酸及び酸誘導体、アセトニトリル、プロピオニトリル、スクシノニトリル、ベンゾニトリルなどのニトリル類、ニトロメタン、ニトロベンゼンなどのニトロ化合物、ジメチルスルホキシド、スルホランなどの含硫化合物、水などが挙げられ、必要に応じて、これらは適宜組合せて用いられる。
溶剤を用いる場合、一般に、溶剤の量が多くなると反応の効率が低下し、反対に少なくなると、均一に加熱・攪拌するのが困難になったり、副反応が起り易くなる。したがって、溶剤の量を重量比で原料化合物全体の１００倍まで、通常、５乃至５０倍にするのが望ましい。原料化合物の種類や反応条件にもよるけれども、反応は１０時間以内、通常、０．５乃至５時間で完結する。反応の進行は、例えば、薄層クロマトグラフィー、ガスクロマトグラフィー、高速液体クロマトグラフィーなどの汎用の方法によってモニターすることができる。化学式１乃至化学式２９で表されるこの発明のクマリン化合物は、この方法によるか、この方法に準じて所望量を製造することができる。また、環状構造の飽和メチレン基が脱水素された、例えば、化学式３０及び化学式３１で表されるこの発明のクマリン化合物は、それぞれ、化学式３、又は化学式１５で表されるクマリン化合物を脱水素反応させることによって所望量を得ることができる。なお、一般式３乃至一般式６で表される化合物は、いずれも、汎用の方法によって得ることができる。なお、一般式３及び一般式４におけるＸ１乃至Ｘ４は適宜の脱離基であり、通常、メトキシ基、エトキシ基などのアルコキシ基、クロロ基、ヨード基などのハロゲン基、アセトキシ基、ベンゾイルオキシ基などの脂肪族カルボン酸残基又は芳香族カルボン酸残基が採用される。
斯くして得られるクマリン化合物は、用途によっては反応混合物のまま用いられることもあるけれども、通常、使用に先立って、例えば、溶解、分液、傾斜、濾過、抽出、濃縮、薄層クロマトグラフィー、ガスクロマトグラフィー、高速液体クロマトグラフィー、蒸留、昇華、結晶化などの類縁化合物を精製するための汎用の方法により精製され、必要に応じて、これらの方法は組合せて適用される。この発明のクマリン化合物を、例えば、色素レーザーにおけるレーザー作用物質として用いる場合には、使用に先立って、例えば、蒸留、結晶化及び／又は昇華などの方法により高度に精製しておくのが望ましい。
このうち、昇華は、１回の操作で高純度の結晶が容易に得られるうえに、操作に伴うクマリン化合物の損失が少なく、しかも、溶剤が結晶中に取り込まれることがないので、特に優れている。適用する昇華方法は、常圧昇華法であっても減圧昇華法であってもよいが、通常、後者の減圧昇華法が適用される。この発明のクマリン化合物を減圧昇華するには、例えば、適量のクマリン化合物を昇華精製装置内へ仕込み、装置内を１０−２Ｔｏｒｒを下回る減圧、好ましくは、１０−３Ｔｏｒｒ以下に保ちながら、クマリン化合物が分解しないように、融点を下回るできるだけ低い温度で加熱する。昇華精製へ供するクマリン化合物の純度が比較的低い場合には、不純物が混入しないように、減圧度や加熱温度を加減することによって昇華速度を抑え、また、クマリン化合物が昇華し難い場合には、昇華精製装置内へ希ガスなどの不活性ガスを通気することによって昇華を促進する。昇華によって得られる結晶の大きさは、昇華精製装置内における凝縮面の温度を加減することによって調節することができ、凝縮面を加熱温度よりも僅かに低い温度に保ち、徐々に結晶化させると比較的大きな結晶が得られる。
この発明によるクマリン化合物の用途について説明すると、この発明のクマリン化合物は、既述のとおり、可視領域に吸収極大を有し、分子吸光係数も大きいことから、重合性化合物を可視光へ露光させることによって重合させるための材料、太陽電池を増感させるための材料、光学フィルター、光記録媒体における光吸収材料、さらには、諸種の衣料を染色するための材料として多種多様の用途を有する。とりわけ、この発明のクマリン化合物の多くは、その吸収極大波長が、例えば、アルゴンイオンレーザー、クリプトンイオンレーザーなどの気体レーザー、ＣｄＳ系レーザーなどの半導体レーザー、分布帰還型若しくはブラッグ反射型Ｎｄ−ＹＡＧレーザーなどの固体レーザーをはじめとする、波長５００ｎｍ付近、詳細には、４５０乃至５５０ｎｍに発振線を有する汎用可視レーザーの発振波長に近接していることから、斯かる可視レーザーを露出光源とする光重合性組成物に光増感剤として配合することによって、ファクシミリ、複写機、プリンターなどの情報記録の分野や、フレキソ製版、グラビア製版などの印刷の分野、さらには、フォトレジストなどの印刷回路の分野において極めて有利に用いることができる。
また、この発明のクマリン化合物を、必要に応じて、紫外領域、可視領域及び／又は赤外領域の光を吸収する他の材料の１又は複数とともに、衣料一般や、衣料以外の、例えば、ドレープ、レース、ケースメント、プリント、ベネシャンブラインド、ロールスクリーン、シャッター、のれん、毛布、布団、布団地、布団カバー、シーツ、座布団、枕、枕カバー、クッション、マット、カーペット、寝袋、テント、自動車の内装材、ウインドガラス、窓ガラスなどの建寝装用品、紙おむつ、おむつカバー、眼鏡、モノクル、ローネットなどの保健用品、靴の中敷、靴の内張地、鞄地、風呂敷、傘地、パラソル、ぬいぐるみ、照明装置やブラウン管ディスプレー、液晶ディスプレー、プラズマディスプレーなどを用いる情報表示装置用のフィルター類、パネル類及びスクリーン類、サングラス、サンルーフ、電子レンジ、オーブンなどの覗き窓、さらには、これらの物品を包装、充填又は収容するための包装用材、充填用材、容器などに用いるときには、生物や物品における自然光や人工光などの環境光による障害や不都合を防止したり低減することができるだけではなく、物品の色度、色調、色彩、風合などを整えたり、物品から反射したり透過する光を所望の色バランスに整えることができる実益がある。
さらに、この発明のクマリン化合物は、可視領域に螢光極大などの発光極大を有し、励起すると可視光を発光することから、斯かる性質を具備する有機化合物を必要とする、例えば、色素レーザーにおけるレーザー作用物質としても有用である。この発明のクマリン化合物を色素レーザーに用いるときには、公知の色素系レーザー発振装置を構築する場合と同様に精製し、適宜溶剤に溶解し、必要に応じて、溶液のｐＨを適宜レベルに調整した後、レーザー発振装置における色素セル内へ封入する。この発明のクマリン化合物は、類縁化合物と比較して、可視領域において極めて広い波長域で増幅利得が得られるばかりか、耐熱性、耐光性が大きく、長時間用いても劣化し難い特徴がある。
この発明によるクマリン化合物の発光能を適用し得る他の用途としては、例えば、酵素反応、抗原抗体反応、細胞内外における信号伝達、蛋白質同士の複合体形成、蛋白質と核酸間又は核酸同士のハイブリダイゼーションなどの、生体起源の物質間にみられる特異的な反応を利用する定性分析、定量分析において、酵素、基質、抗原、抗体、可溶性受容体、蛋白質、糖脂質、核酸一般などを標識するための発光剤としての用途が挙げられる。この発明による標識された生体物質は、例えば、研究や診断の分野において極めて有用である。
以下、この発明の実施の形態につき、実施例に基づいて説明する。
実施例１ クマリン化合物
反応容器に酢酸３０ｍｌをとり、化学式３２で表される化合物１０．０ｇと化学式３３で表される化合物５．１ｇとをとり、３時間加熱還流した。反応混合物を冷却した後、析出した結晶を濾取し、クロロホルム／メタノール混液を用いて再結晶したところ、化学式３で表されるこの発明のクマリン化合物の黄色結晶が２．３ｇ得られた。
化学式３２：
別途、本例のクマリン化合物と同様のクマリン骨格を有する、化学式３４で表される類縁化合物につき、同様にして可視吸収スペクトルを測定した。類縁化合物は、図１に破線で示したとおり、波長３７９ｎｍ（ε＝１．９９×１０４）に吸収極大を示した。図１の可視吸収スペクトルとこれらの分子吸光係数は、本例のクマリン化合物が、化学式３４で表される類縁化合物と比較して、ほぼ同様の波長域の可視光を２倍強の効率で吸収することを物語っている。また、このことは、本例のクマリン化合物においては、環状構造を形成しつつ、互いに結合し合ったクマリン骨格を有する原子団が、互いに電子共鳴することなく、各々独立した吸光、発色団として機能することを物語っている。なお、ＤＳＣ分析によると、化学式３４で表される類縁化合物は、１６０℃付近に融点を有し、２００℃を越えると、重量が急激に減少した。
化学式３４：
実施例２ クマリン化合物
化学式３２で表される化合物に代えて化学式３５で表される化合物を用いた以外は実施例１におけると同様に反応させたところ、化学式１で表されるこの発明のクマリン化合物が得られた。
化学式３５：
実施例３ クマリン化合物
化学式３３で表される化合物に代えて化学式３６で表される化合物を用いた以外は実施例１におけると同様に反応させたところ、化学式１０で表されるこの発明のクマリン化合物が得られた。
化学式３６：
実施例４ クマリン化合物
化学式３２及び化学式３３で表される化合物に代えて、それぞれ、化学式３５及び化学式３７で表される化合物を用いた以外は実施例１におけると同様に反応させたところ、化学式１５で表されるこの発明のクマリン化合物が得られた。
化学式３７：
実施例５ クマリン化合物
化学式３３で表される化合物に代えて化学式３８で表される化合物を用いた以外は実施例１におけると同様に反応させたところ、化学式２５で表されるこの発明のクマリン化合物が得られた。
化学式３８：
実施例６ クマリン化合物
化学式３３で表される化合物に代えて化学式３９で表される化合物を用いた以外は実施例１におけると同様に反応させたところ、化学式２６で表されるこの発明のクマリン化合物が得られた。
化学式３９：
実施例７ クマリン化合物
反応容器にブタノール３００ｍｌをとり、化学式３で表されるクマリン化合物６．２ｇとクロラニル１５．０ｇを加え、３時間加熱環流した後、溶剤を留去した。残渣をクロロホルムに溶解し、弱アルカリ水で洗浄し、傾斜により分液し、有機層を採取し、溶剤を留去した後、析出した結晶を採取し、酢酸エチルで再結晶したところ、化学式３０で表されるクマリン化合物の結晶が３．５ｇ得られた。
可視領域に吸収極大と螢光極大を有し、安定で、耐環境性が大きい本例のクマリン化合物は、光吸収剤、発光剤として、光化学的重合、太陽電池、光学フィルター、染色、色素レーザー、分析をはじめとする諸分野において有用である。
実施例８ クマリン化合物
化学式３で表されるクマリン化合物に代えて化学式１５で表されるクマリン化合物を用いた以外は実施例７におけると同様に反応させたところ、化学式３１で表されるクマリン化合物が得られた。
可視領域に吸収極大と螢光極大を有し、安定で、耐環境性が大きい本例のクマリン化合物は、光吸収剤、発光剤として、光化学的重合、太陽電池、光学フィルター、染色、色素レーザー、分析をはじめとする諸分野において有用である。
実施例９ クマリン化合物
実施例１乃至実施例８の方法により得た８種類のクマリン化合物のいずれかを水冷式昇華精製装置内へ仕込み、常法にしたがって、装置内を減圧に保ちながら加熱することによってそれぞれ昇華精製した。
本例のクマリン化合物は、いずれも、光吸収能、発光能を有する高純度の有機化合物を必要とする諸分野において有利に用いることができる。
なお、この発明のクマリン化合物は、構造によって仕込み条件や収率に若干の違いはあるものの、例えば、上記以外の化学式１乃至化学式３１で表されるものを含めて、いずれも、実施例１乃至実施例９の方法によるか、あるいは、それらの方法に準じて所望量を製造することができる。
次に、この発明によるクマリン化合物の光増感能につき、実験に基づいて説明する。
実験例 クマリン化合物の光増感能
常法にしたがって、エチルセロソルブ９００重量部に光重合性モノマーとしてペンタエリスリトールアクリレート１００重量部、バインダー樹脂としてアクリル酸−メタアクリル酸共重合体１００重量部、重合開始剤として３，３´，４，４´−テトラ（ｔｅｒｔ−ブチルパーオキシカルボニル）ベンゾフェノン８重量部をそれぞれ配合し、さらに、光増感剤として、実施例１の方法により得た化学式３で表されるこの発明のクマリン化合物を２重量部配合することによって光重合性組成物を調製した。
常法にしたがって、この組成物を表面処理した砂目立アルミ板上に均一に塗布して感光層を形成した後、酸素による重合阻害を防止すべく、感光層の表面にポリビニルアルコール層を形成した。この感光層にグレースケールを密着させて３ｋＷ超高圧水銀灯を設置し、シャープカットオフフィルター（商品名『Ｙ４７』及び『Ｙ５２』、東芝硝子株式会社製造）、干渉フィルター（商品名『ＫＬ４９』及び『ＫＬ５４』、東芝硝子株式会社製造）及び熱線カットフィルター（商品名『ＨＡ３０』、ホーヤ株式会社製造）を組合せて得た波長５３２ｎｍ（Ｎｄ−ＹＡＧレーザーの第二高調波に相当）の可視光を照射した。その後、常法にしたがって、アルカリ系現像液により現像した後、式１に示す数式にステップタブレットｎ段目における透過率Ｔｎ、露出時間ｔ及び露出強度Ｉ０をそれぞれ代入し、光硬化したステップの段数から感度を計算した。併行して、この発明によるクマリン化合物に代えて化学式３４で表される類縁化合物を用いる光重合性組成物を調製し、これを上記と同様に処置して対照とした。結果を表１に示す。
式１：
Ｅ（ｍＪ／ｃｍ２）＝Ｉｏ（ｍＪ／ｃｍ２・秒）×Ｔｎ×ｔ（秒）
産業上の利用可能性
以上説明したとおり、この発明は新規な有機化合物の創製と、その産業上有用な性質の発見に基づくものである。この発明のクマリン化合物は、可視領域に吸収極大を有し、分子吸光係数も大きいことから、光吸収剤として光化学的重合、太陽電池、光学フィルター、染色などの諸分野において有利に用いることができる。さらに、この発明のクマリン化合物は、可視領域に発光極大を有し、励起すると可視光を発光することから、発光剤として色素レーザー、分析などの諸分野において有利に用いることができる。
斯かるクマリン化合物は、フェノール化合物と１，３−ジケトン化合物とを反応させる工程を経由するこの発明の製造方法により所望量を得ることができる。
斯くも顕著な作用効果を奏するこの発明は、斯界に貢献すること誠に多大な、意義のある発明であると言える。
【図面の簡単な説明】
図１は、この発明によるクマリン化合物（実線）と類縁化合物（破線）の可視吸収スペクトルである。Technical field
The present invention relates to a coumarin compound, and more particularly to a novel coumarin compound useful as a light absorber and a luminescent agent.
Background art
With the advent of the information era, photochemical polymerization has been frequently used in a wide variety of fields. Now, its application goes beyond the field of synthetic resins to paints, printing plates, printed circuits, and integration. It has extended to the field of information recording such as circuits and electronic equipment. Photochemical polymerization is a technique for polymerizing a polymerizable compound by light irradiation. Broadly speaking, photopolymerization that initiates polymerization by direct light irradiation and activation of the polymerizable compound, and a photosensitizer There is photosensitization polymerization in which a polymerizable compound is polymerized by irradiating light in a coexisting state to generate active species of a photosensitizer. In any photochemical polymerization, the start and stop of polymerization can be controlled by blinking of the exposure light source, and the polymerization degree and polymerization rate can be easily controlled by selecting the intensity and wavelength of the exposure light source. Moreover, since photochemical polymerization generally has a low polymerization initiation energy, it can be polymerized even at low temperatures. In the field of information recording such as printing plates and holography, such advantages of photochemical polymerization have been bought, and visible light such as second harmonics such as argon ion laser, helium ion laser, and Nd-YAG laser. The demand for photopolymerizable compositions that can be polymerized by irradiating is rapidly increasing.
Since most of the polymerizable compounds and polymerization initiators blended in the photopolymerizable composition absorb only ultraviolet rays, a photosensitizer is essential when attempting to polymerize the photopolymerizable composition with visible light. It becomes a technical element. The characteristics that the photosensitizer should have include a large molecular extinction coefficient in the visible region (hereinafter, the molecular extinction coefficient may be abbreviated as “ε”), and increases the number of polymerizable compounds and polymerization initiators. It can be perceived, the sensitization efficiency is high, the solubility in a solvent and the compatibility with other compounding components are excellent, and the stability. Representative photosensitizers include, for example, merocyanine dyes disclosed in JP-A No. 54-151024, cyanine dyes disclosed in JP-A No. 58-29803, and JP-A No. 59-56403. Disclosed stilbene dyes, coumarin derivatives disclosed in JP-A-63-23901, methylene blue derivatives disclosed in JP-A-64-33104, pyran derivatives disclosed in JP-A-6-329654, etc. However, all of these have advantages and disadvantages, and no one that can always exhibit various characteristics as described above has been found. Therefore, in the field of new application of photochemical polymerization, for example, in the field of information recording and electronic equipment, a material other than a photosensitizer such as a polymerizable compound and a binder resin is first selected, and then The present situation is that a variety of organic compounds that are suitable for those polymerizable compounds and polymerization initiators are searched by trial and error.
In view of such circumstances, an object of the present invention is to provide a novel organic compound that absorbs visible light, thereby expanding the range of photosensitizers that can be selected in preparing a photopolymerizable composition. This is the issue.
Disclosure of the invention
In order to solve this problem, the present inventor paid attention to a coumarin compound, and intensively researched and searched. As a result, two or more atomic groups having a coumarin skeleton and capable of absorbing visible light have a cyclic structure. The coumarin compounds formed by bonding with each other have a maximum absorption in the visible region, a large molecular extinction coefficient in the visible region, and absorbs visible light efficiently. It has been found that it is extremely useful as a material for sensitizing a polymerization initiator. In addition, it has been found that such a coumarin compound has an emission maximum in the visible region and emits visible light when excited, and thus can be advantageously used in various fields that require an organic compound having such properties. .
That is, the present invention provides a coumarin compound in which two or more atomic groups having the coumarin skeleton and capable of absorbing visible light are bonded to each other while forming a cyclic structure. Is a solution.
Furthermore, this invention solves the said subject by providing the light absorber containing such a coumarin compound.
Furthermore, this invention solves the said subject by providing the light-emitting agent containing such a coumarin compound.
Furthermore, this invention solves the said subject by providing the manufacturing method of the coumarin compound which goes through the process of making a phenol compound and a 1, 3- diketone compound react.
BEST MODE FOR CARRYING OUT THE INVENTION
The embodiment of the present invention will be described. As described above, the present invention includes a coumarin skeleton, and two or more atomic groups that are the same or different from each other capable of absorbing visible light form a cyclic structure, while forming a cyclic structure. The present invention relates to a coumarin compound formed by bonding. The atomic group in the present invention has a coumarin skeleton (also called benzo-α-pyrone, which corresponds to a cis-type α-hydroxycinnamic acid lactone), and each atomic group itself has visible light, In particular, it means one that can absorb light having a wavelength of 380 to 780 nm. Such atomic groups contain or do not contain hetero atoms such as silicon atom, nitrogen atom, oxygen atom, sulfur atom, selenium atom, tellurium atom, for example, methylene group, ethylene group, trimethylene group, tetramethylene group, oxy group , A methylenedioxy group, an ethylenedioxy group, a triethylenedioxy group, a thio group, an imino group, a silanylene group and the like to form a cyclic structure, preferably a 4-membered ring to an 8-membered ring, Combine to produce a coumarin compound according to the invention as a single molecule. Although it depends on the application, for example, when used as a photosensitizer in a luminescent agent, photochemical polymerization, solar cell, etc., it has a coumarin skeleton as a plurality of atomic groups, but adopts those having different absorption ranges. When these atomic groups are linked by a cyclic structure that does not have conjugated multiple bonds and does not cause substantial electronic resonance between the atomic groups, each atomic group has a different absorption range while being in the same molecule. As a result, the wavelength region in which the coumarin compound according to the present invention can act as a light absorber and a luminescent agent can be appropriately adjusted or expanded. In addition, although both have a coumarin skeleton as a plurality of atomic groups, the same absorption range is adopted for each atomic group, but these atomic groups do not have conjugated multiple bonds, and the atomic groups substantially form electrons. When linked by a ring structure that does not resonate, the wavelength range in which the coumarin compound can act as an absorber or luminescent agent cannot be adjusted or expanded, but compared with those having only one such atomic group in the molecule. Thus, the light absorption and coloring ability per molecule can be increased.
More specific examples of the coumarin compound according to the present invention include those represented by the general formula 1 or the general formula 2.
General formula 1:
Z in general formula 1 and general formula 2 1 And Z 2 Represents a cyclic structure in which a plurality of atomic groups having a coumarin skeleton and capable of absorbing visible light are bonded to each other. Preferred cyclic structures include or do not contain heteroatoms such as silicon atom, nitrogen atom, oxygen atom, sulfur atom, selenium atom and tellurium atom, for example, cyclobutadiene ring, cyclopentadiene ring, cyclohexadiene ring, cyclohepta. It is a 4-membered to 8-membered ring such as a diene ring, cyclooctadiene ring, dioxin ring, dihydrodisiline ring (dihydrodisilabenzene ring), dihydropyrazine ring, and among these, a cyclic structure is particularly preferable. While forming, two or more atomic groups bonded to each other do not substantially resonate with each other, for example, cyclobutadiene ring, cyclopenta-1,3-diene ring, cyclohexa-1,4-diene ring, cyclohepta-1 , 4-diene ring, cycloocta-1,5-diene ring, [1,4] dioxin ring, 1,4-dihydro- 1,4] Jishirin ring (1,4-dihydro - [l, 4] Jishirabenzen ring), a cyclic structure having no conjugated multiple bond such as 1,4-dihydro-pyrazine ring. A coumarin compound having a conjugated multiple bond in the cyclic structure does not function as a light-absorbing or chromophore in which each atomic group is independent, but a coumarin compound in which the cyclic structure does not have a saturated methylene group is chemically stable and resistant. Due to its large environmental properties, it is extremely useful in applications where a stable light absorber or luminescent agent is required. In addition, such a cyclic structure is within a range not departing from the object of the present invention, for example, an aliphatic hydrocarbon group such as a methyl group or an ethyl group, an ether group such as a methoxy group or an ethoxy group, a fluoro group, or a chloro group. You may have 1 or more substituents, such as a halogen group and also a hydroxy group and a carboxy group.
Although it depends on the use, a coumarin compound represented by general formula 7 or general formula 8 having an amino group at the 7-position of the coumarin skeleton is particularly preferable as a light absorber or luminescent agent. 8, R 1 , R 2 , R 4 To R 6 And R 8 Each independently represents a hydrogen atom or the same substituent as in formula 1 or formula 2. R 9 To R 12 Are each independently a hydrogen atom or, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl , Tert-pentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group and other aliphatic hydrocarbon groups, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group and other fats It represents an aromatic hydrocarbon group such as a cyclic hydrocarbon group, a phenyl group, a biphenylyl group, a naphthyl group, or a combination thereof, and one or more of the hydrogen atoms in such a hydrocarbon group are For example, methoxy group, trifluoromethoxy group, ethoxy group, propoxy group, Ether group such as sopropoxy group, aryloxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, phenoxy group, benzyloxy group, hydroxy group, It may be substituted with a cyano group or the like. R 9 To R 12 The hydrocarbon groups in include the nitrogen atom to which they are attached and R 2 , R 4 , R 6 Or R 8 May combine with the carbon atom to which is bonded to form, for example, a cyclic structure such as a morpholine ring or a urolidine ring. 2 , R 4 , R 6 And / or R 8 Apparently does not exist. In addition, Z in the general formula 7 and the general formula 8 1 And Z 2 Represents the same 4-membered to 8-membered ring as in General Formula 1 and General Formula 2.
General formula 7:
Chemical formula 1:
General formula 3:
Examples of the solvent include hydrocarbons such as pentane, hexane, cyclohexane, octane, benzene, toluene, xylene, carbon tetrachloride, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, trichloroethylene, tetrachloroethylene, chlorobenzene, Halogens such as bromobenzene and α-dichlorobenzene, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2- Alcohols and phenols such as methoxyethanol, phenol, benzyl alcohol, cresol, diethylene glycol, triethylene glycol, glycerin, die Ethers such as ruether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl-18-crown-6, methyl carbitol, ethyl carbitol, Acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, ethyl acetate, butyl carbonate, ethylene carbonate, propylene carbonate, formamide, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N -Acids and acid derivatives such as dimethylacetamide, hexamethylphosphoric triamide, trimethyl phosphate, nitriles such as acetonitrile, propionitrile, succinonitrile, benzonitrile, nitromes Examples thereof include nitro compounds such as tan and nitrobenzene, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, water, and the like, and these are used in combination as necessary.
In the case of using a solvent, generally, when the amount of the solvent increases, the efficiency of the reaction decreases. On the other hand, when the amount of the solvent decreases, it becomes difficult to uniformly heat and stir or a side reaction tends to occur. Therefore, it is desirable that the amount of the solvent is up to 100 times the weight of the raw material compound, usually 5 to 50 times. Although depending on the type of raw material compound and reaction conditions, the reaction is completed within 10 hours, usually 0.5 to 5 hours. The progress of the reaction can be monitored by a general method such as thin layer chromatography, gas chromatography, high performance liquid chromatography and the like. The coumarin compound of the present invention represented by Chemical Formula 1 to Chemical Formula 29 can be produced in a desired amount by this method or according to this method. The saturated methylene group having a cyclic structure is dehydrogenated. For example, the coumarin compound of the present invention represented by the chemical formula 30 and the chemical formula 31 is dehydrogenated to the coumarin compound represented by the chemical formula 3 or the chemical formula 15, respectively. The desired amount can be obtained. Any of the compounds represented by general formulas 3 to 6 can be obtained by a general-purpose method. X in general formula 3 and general formula 4 1 To X 4 Is an appropriate leaving group, and usually an alkoxy group such as a methoxy group or an ethoxy group, a halogen group such as a chloro group or an iodo group, an aliphatic carboxylic acid residue or an aromatic carboxylic acid such as an acetoxy group or a benzoyloxy group Residues are employed.
Although the coumarin compound thus obtained may be used as the reaction mixture depending on the application, it is usually prior to use, for example, dissolution, separation, decantation, filtration, extraction, concentration, thin layer chromatography, It refine | purifies by the general purpose method for purifying related compounds, such as a gas chromatography, a high performance liquid chromatography, distillation, sublimation, crystallization, and these methods are applied in combination as needed. When the coumarin compound of the present invention is used as, for example, a laser active substance in a dye laser, it is desirable to highly purify it by a method such as distillation, crystallization and / or sublimation before use.
Among these, sublimation is particularly excellent because high-purity crystals can be easily obtained by a single operation, and there is little loss of coumarin compounds accompanying the operation, and the solvent is not taken into the crystals. Yes. The sublimation method to be applied may be a normal pressure sublimation method or a reduced pressure sublimation method, but the latter reduced pressure sublimation method is usually applied. In order to sublimate the coumarin compound of the present invention under reduced pressure, for example, an appropriate amount of coumarin compound is charged into a sublimation purification apparatus, -2 Reduced pressure below Torr, preferably 10 -3 Heating is performed at a temperature as low as possible below the melting point so as not to decompose the coumarin compound while maintaining the pressure below Torr. When the purity of the coumarin compound to be subjected to sublimation purification is relatively low, the sublimation rate is suppressed by adjusting the degree of vacuum and heating temperature so that impurities are not mixed, and when the coumarin compound is difficult to sublimate, Sublimation is promoted by passing an inert gas such as a rare gas into the sublimation purification apparatus. The size of the crystals obtained by sublimation can be adjusted by adjusting the temperature of the condensation surface in the sublimation purification apparatus. When the condensation surface is kept at a temperature slightly lower than the heating temperature and gradually crystallized, Relatively large crystals are obtained.
The use of the coumarin compound according to the present invention will be explained. As described above, the coumarin compound of the present invention has an absorption maximum in the visible region and a large molecular extinction coefficient, so that the polymerizable compound is exposed to visible light. It has a wide variety of uses as a material for polymerizing, a material for sensitizing a solar cell, an optical filter, a light absorbing material in an optical recording medium, and a material for dyeing various types of clothing. In particular, many of the coumarin compounds of the present invention have an absorption maximum wavelength of, for example, a gas laser such as an argon ion laser or a krypton ion laser, a semiconductor laser such as a CdS laser, a distributed feedback type or a Bragg reflection type Nd-YAG laser. Since it is close to the oscillation wavelength of a general-purpose visible laser having an oscillation line at 450 to 550 nm, including a solid-state laser such as a solid-state laser, photopolymerization using such a visible laser as an exposure light source Incorporated as a photosensitizer into a photosensitive composition, the field of information recording such as facsimiles, copiers and printers, the field of printing such as flexographic and gravure plates, and the field of printed circuits such as photoresists Can be used very advantageously.
In addition, the coumarin compound of the present invention is optionally used in combination with one or more of other materials that absorb light in the ultraviolet region, visible region, and / or infrared region, as well as general clothing other than clothing, such as drape. Lace, casement, print, venetian blind, roll screen, shutter, goodwill, blanket, duvet, duvet cover, bedsheet, cushion, pillowcase, pillowcase, cushion, mat, carpet, sleeping bag, tent, automotive Interior materials, bedding products such as window glass and window glass, paper diapers, diaper covers, health supplies such as eyeglasses, monocles, ronet, shoe insoles, shoe linings, saddles, furoshiki, umbrellas, Filters for information display devices using parasols, stuffed animals, lighting devices, cathode ray tube displays, liquid crystal displays, plasma displays, etc. , Panels and screens, sunglasses, sunroofs, microwave ovens, ovens and other viewing windows, as well as packaging materials, filling materials, containers, etc. Not only can prevent or reduce obstacles and inconveniences caused by environmental light such as natural light and artificial light in the article, but also adjust the chromaticity, color tone, color, and texture of the article, and reflect or transmit light from the article. There is an actual advantage that can be adjusted to a desired color balance.
Furthermore, since the coumarin compound of the present invention has a light emission maximum such as a fluorescence maximum in the visible region and emits visible light when excited, an organic compound having such properties is required. For example, a dye laser It is also useful as a laser active substance. When the coumarin compound of the present invention is used in a dye laser, it is purified in the same manner as in the case of constructing a known dye-based laser oscillation device, dissolved in a solvent as appropriate, and the pH of the solution is adjusted to an appropriate level as necessary. And encapsulating in a dye cell in a laser oscillation device. The coumarin compound of the present invention has not only an amplification gain in an extremely wide wavelength region in the visible region but also a large heat resistance and light resistance, and has a feature that it is not easily deteriorated even when used for a long time as compared with the related compound.
Other uses to which the luminescent ability of the coumarin compound according to the present invention can be applied include, for example, enzyme reaction, antigen-antibody reaction, signal transmission inside and outside cells, formation of complex between proteins, hybridization between protein and nucleic acid, or between nucleic acids For labeling enzymes, substrates, antigens, antibodies, soluble receptors, proteins, glycolipids, nucleic acids in general, etc. in qualitative analysis and quantitative analysis using specific reactions between substances of biological origin, etc. The use as a luminescent agent is mentioned. The labeled biological material according to the present invention is extremely useful, for example, in the field of research and diagnosis.
Hereinafter, embodiments of the present invention will be described based on examples.
Example 1 Coumarin Compound
30 ml of acetic acid was placed in a reaction vessel, 10.0 g of the compound represented by Chemical Formula 32 and 5.1 g of the compound represented by Chemical Formula 33 were taken and heated to reflux for 3 hours. After cooling the reaction mixture, the precipitated crystals were collected by filtration and recrystallized using a chloroform / methanol mixture, whereby 2.3 g of yellow crystals of the coumarin compound of the present invention represented by Chemical Formula 3 were obtained.
Chemical formula 32:
Separately, a visible absorption spectrum was measured in the same manner for a similar compound represented by Chemical Formula 34 having the same coumarin skeleton as the coumarin compound of this example. The analogous compound has a wavelength of 379 nm (ε = 1.99 × 10 6) as shown by the broken line in FIG. 4 ) Shows the absorption maximum. The visible absorption spectrum of FIG. 1 and these molecular extinction coefficients indicate that the coumarin compound of this example absorbs visible light in almost the same wavelength range with a little more than twice the efficiency compared to the related compound represented by Chemical Formula 34. Tells you to do. In addition, this indicates that in the coumarin compound of this example, the atomic groups having coumarin skeletons bonded to each other while forming a cyclic structure function as independent light absorption and chromophores without electronic resonance with each other. Tells you to do. According to DSC analysis, the related compound represented by Chemical Formula 34 had a melting point in the vicinity of 160 ° C., and when it exceeded 200 ° C., the weight decreased rapidly.
Chemical formula 34:
Example 2 Coumarin Compound
When the reaction was carried out in the same manner as in Example 1 except that the compound represented by the chemical formula 35 was used instead of the compound represented by the chemical formula 32, a coumarin compound of the present invention represented by the chemical formula 1 was obtained.
Chemical formula 35:
Example 3 Coumarin Compound
When the reaction was carried out in the same manner as in Example 1 except that the compound represented by Chemical Formula 36 was used instead of the compound represented by Chemical Formula 33, a coumarin compound of the present invention represented by Chemical Formula 10 was obtained.
Chemical formula 36:
Example 4 Coumarin Compound
In place of the compound represented by Chemical Formula 32 and Chemical Formula 33, the reaction was carried out in the same manner as in Example 1 except that the compounds represented by Chemical Formula 35 and Chemical Formula 37 were used. The inventive coumarin compound was obtained.
Chemical formula 37:
Example 5 Coumarin Compound
When the reaction was carried out in the same manner as in Example 1 except that the compound represented by the chemical formula 38 was used instead of the compound represented by the chemical formula 33, a coumarin compound of the present invention represented by the chemical formula 25 was obtained.
Chemical formula 38:
Example 6 Coumarin Compound
When the reaction was carried out in the same manner as in Example 1 except that the compound represented by Chemical Formula 39 was used instead of the compound represented by Chemical Formula 33, a coumarin compound of the present invention represented by Chemical Formula 26 was obtained.
Chemical formula 39:
Example 7 Coumarin Compound
To the reaction vessel, 300 ml of butanol was added, 6.2 g of a coumarin compound represented by the chemical formula 3 and 15.0 g of chloranil were added and heated under reflux for 3 hours, and then the solvent was distilled off. The residue was dissolved in chloroform, washed with weak alkaline water, separated by decantation, the organic layer was collected, the solvent was distilled off, and the precipitated crystals were collected and recrystallized with ethyl acetate. As a result, 3.5 g of a coumarin compound crystal was obtained.
The coumarin compound of this example, which has absorption maximum and fluorescence maximum in the visible region, is stable and has high environmental resistance, is a photochemical polymerization, solar cell, optical filter, dyeing, dye laser as a light absorber and luminescent agent. It is useful in various fields including analysis.
Example 8 Coumarin Compound
When the reaction was carried out in the same manner as in Example 7 except that the coumarin compound represented by Chemical Formula 15 was used instead of the coumarin compound represented by Chemical Formula 3, a coumarin compound represented by Chemical Formula 31 was obtained.
The coumarin compound of this example, which has absorption maximum and fluorescence maximum in the visible region, is stable and has high environmental resistance, is a photochemical polymerization, solar cell, optical filter, dyeing, dye laser as a light absorber and luminescent agent. It is useful in various fields including analysis.
Example 9 Coumarin Compound
Any one of the eight types of coumarin compounds obtained by the methods of Examples 1 to 8 was charged into a water-cooled sublimation purification apparatus and sublimated and purified by heating while maintaining the interior of the apparatus at a reduced pressure according to a conventional method. .
Any of the coumarin compounds of this example can be advantageously used in various fields that require a high-purity organic compound having light absorption ability and light emission ability.
In addition, although the coumarin compound of this invention has some differences in preparation conditions and yield depending on the structure, for example, those including those represented by chemical formula 1 to chemical formula 31 other than those described above are all examples 1 to A desired amount can be produced by the method of Example 9 or according to those methods.
Next, the photosensitizing ability of the coumarin compound according to the present invention will be described based on experiments.
Experimental example Photosensitizing ability of coumarin compounds
According to a conventional method, 900 parts by weight of ethyl cellosolve, 100 parts by weight of pentaerythritol acrylate as a photopolymerizable monomer, 100 parts by weight of an acrylic acid-methacrylic acid copolymer as a binder resin, and 3,3 ′, 4, as a polymerization initiator 8 parts by weight of 4′-tetra (tert-butylperoxycarbonyl) benzophenone was blended, and 2 coumarin compounds of the present invention represented by the chemical formula 3 obtained by the method of Example 1 were used as photosensitizers. A photopolymerizable composition was prepared by blending parts by weight.
According to a conventional method, this composition is uniformly applied onto a surface-treated grained aluminum plate to form a photosensitive layer, and then a polyvinyl alcohol layer is formed on the surface of the photosensitive layer to prevent polymerization inhibition by oxygen. did. A 3kW ultra-high pressure mercury lamp is installed with this gray scale in close contact with the photosensitive layer, sharp cut-off filters (trade names “Y47” and “Y52” manufactured by Toshiba Glass Co., Ltd.), interference filters (trade names “KL49” and “ KL54 ”(manufactured by Toshiba Glass Co., Ltd.) and heat ray cut filter (trade name“ HA30 ”, manufactured by Hoya Co., Ltd.) are used to irradiate visible light with a wavelength of 532 nm (corresponding to the second harmonic of the Nd-YAG laser) did. Then, after developing with an alkaline developer according to a conventional method, the transmittance T at the nth step of the step tablet is expressed by the formula shown in Formula 1. n , Exposure time t and exposure intensity I 0 Was substituted, and the sensitivity was calculated from the number of steps of the photocured step. In parallel, a photopolymerizable composition using an analogous compound represented by Chemical Formula 34 instead of the coumarin compound according to the present invention was prepared, and this was treated in the same manner as above to serve as a control. The results are shown in Table 1.
Formula 1:
E (mJ / cm 2 ) = Io (mJ / cm 2 ・ Second) × Tn × t (second)
Industrial applicability
As described above, the present invention is based on the creation of a novel organic compound and the discovery of industrially useful properties. Since the coumarin compound of the present invention has an absorption maximum in the visible region and a large molecular extinction coefficient, it can be advantageously used as a light absorber in various fields such as photochemical polymerization, solar cells, optical filters, and dyeing. . Furthermore, since the coumarin compound of the present invention has an emission maximum in the visible region and emits visible light when excited, it can be advantageously used as a luminescent agent in various fields such as dye laser and analysis.
Such a coumarin compound can be obtained in a desired amount by the production method of the present invention through a step of reacting a phenol compound and a 1,3-diketone compound.
It can be said that this invention having such remarkable effects is a very significant invention that contributes to the world.
[Brief description of the drawings]
FIG. 1 is a visible absorption spectrum of a coumarin compound (solid line) and an analogous compound (dashed line) according to the present invention.
Claims (6)
一般式７：
Ｒ１ は、水素原子、ｔｅｒｔ−ブチル基、フェニル基、又はメトキシ基を、Ｒ ５ は、水素原子又はｔｅｒｔ−ブチル基を、Ｒ ２ 、Ｒ ４ 、Ｒ ６ 及びＲ ８ は、水素原子を、Ｚ１ は、シクロペンタジエン環、シクロヘキサジエン環、シクロオクタジエン環、シクロオクタテトラエン環、ベンゼン環、１，４−ジヒドロ−［１，４］ジシラベンゼン環、ジオキシン環、又は１，４−ジメチル−ジヒドロピラジン環を表す。Ｒ９乃至Ｒ１２は、それぞれ独立に、水素原子、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、フェニル基、又はブトキシエチル基を表す。Ｒ９乃至Ｒ１２におけるメチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、又はオクチル基は、それらが結合する窒素原子を含んで、Ｒ２、Ｒ４、Ｒ６又はＲ８が結合する炭素原子と結合し合ってユロリジン環を形成していてもよく、この場合、Ｒ２、Ｒ４、Ｒ６及び／又はＲ８は見掛け上存在しないこととなる。
一般式８において、
Ｒ １ 及びＲ ５ は、それぞれ独立に、水素原子又はシアノ基を、Ｒ ２ 、Ｒ ４ 、Ｒ ６ 及びＲ ８ は、水素原子を、Ｚ ２ は、シクロペンタジエン環又はシクロヘキサジエン環を表す。Ｒ ９ 乃至Ｒ １２ は、エチル基を表す。Ｒ ９ 乃至Ｒ １２ におけるエチル基は、それらが結合する窒素原子を含んで、Ｒ ２ 、Ｒ ４ 、Ｒ ６ 又はＲ ８ が結合する炭素原子と結合し合ってユロリジン環を形成していてもよく、この場合、Ｒ ２ 、Ｒ ４ 、Ｒ ６ 及び／又はＲ ８ は見掛け上存在しないこととなる。）A coumarin compound represented by either general formula 7 or general formula 8.
General formula 7:
R 1 represents a hydrogen atom, a tert-butyl group, a phenyl group, or a methoxy group, R 5 represents a hydrogen atom or a tert-butyl group, R 2 , R 4 , R 6, and R 8 represent a hydrogen atom, Z 1 is a cyclopentadiene ring, cyclohexadiene ring, cyclooctadiene ring, cyclooctatetraene ring, benzene ring, 1,4-dihydro- [1,4] disilabenzene ring, dioxin ring, or 1,4-dimethyl- to table a dihydro pyrazine ring. R 9 to R 12 each independently to the table a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a phenyl group, or a butoxy group. The methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, or octyl group in R 9 to R 12 includes a nitrogen atom to which they are bonded, and R 2 , R 4 , R 6 or are bound together with the carbon atom to which R 8 is attached may form a Yurorijin ring, in this case, R 2, R 4, R 6 and / or R 8 is that do with the absence apparently.
In general formula 8,
R 1 and R 5 each independently represents a hydrogen atom or a cyano group, R 2 , R 4 , R 6 and R 8 each represents a hydrogen atom, and Z 2 represents a cyclopentadiene ring or a cyclohexadiene ring. R 9 to R 12 represent an ethyl group. The ethyl group in R 9 to R 12 may include a nitrogen atom to which they are bonded, and may be bonded to a carbon atom to which R 2 , R 4 , R 6 or R 8 is bonded to form a urolidine ring. In this case, R 2 , R 4 , R 6 and / or R 8 are apparently absent. )
一般式３：
General formula 3:
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| JP3512243B2 (en) * | 1994-09-29 | 2004-03-29 | 三井化学株式会社 | Bis (3-coumaryl) thioketone compound and use thereof |
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