JPH04198924A - Nonlinear optical material having aromatic conjugate group - Google Patents
Nonlinear optical material having aromatic conjugate groupInfo
- Publication number
- JPH04198924A JPH04198924A JP32541390A JP32541390A JPH04198924A JP H04198924 A JPH04198924 A JP H04198924A JP 32541390 A JP32541390 A JP 32541390A JP 32541390 A JP32541390 A JP 32541390A JP H04198924 A JPH04198924 A JP H04198924A
- Authority
- JP
- Japan
- Prior art keywords
- group
- acid
- cyano
- represented
- group represented
- 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.)
- Pending
Links
- 230000003287 optical effect Effects 0.000 title claims abstract description 44
- 239000000463 material Substances 0.000 title claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 title claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 11
- 125000001041 indolyl group Chemical group 0.000 claims abstract description 10
- 125000001033 ether group Chemical group 0.000 claims abstract description 5
- 125000004414 alkyl thio group Chemical group 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract 2
- 125000004185 ester group Chemical group 0.000 claims description 12
- 125000003368 amide group Chemical group 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 8
- 239000006104 solid solution Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 125000000101 thioether group Chemical group 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 238000012545 processing Methods 0.000 abstract description 5
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 abstract description 4
- 238000004891 communication Methods 0.000 abstract description 4
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 abstract description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 abstract description 2
- 230000009022 nonlinear effect Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 2
- KYARBIJYVGJZLB-UHFFFAOYSA-N 7-amino-4-hydroxy-2-naphthalenesulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=CC2=CC(N)=CC=C21 KYARBIJYVGJZLB-UHFFFAOYSA-N 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- RJCQMRTZKKPRPL-UHFFFAOYSA-N s-aminosulfanyloxythiohydroxylamine Chemical group NSOSN RJCQMRTZKKPRPL-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 45
- -1 monomethylamino group Chemical group 0.000 description 15
- 239000013078 crystal Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000010287 polarization Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- VEXPFUXVCVZRLI-UHFFFAOYSA-N 2-cyano-3-(1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=CC=C2C(C=C(C(=O)O)C#N)=CNC2=C1 VEXPFUXVCVZRLI-UHFFFAOYSA-N 0.000 description 2
- MYBMSWJVQCPVJH-UHFFFAOYSA-N 2-cyano-3-(4-ethoxyphenyl)prop-2-enoic acid Chemical compound CCOC1=CC=C(C=C(C#N)C(O)=O)C=C1 MYBMSWJVQCPVJH-UHFFFAOYSA-N 0.000 description 2
- WBUHGTHUBVPUAZ-UHFFFAOYSA-N 2-cyano-3-(4-propoxyphenyl)prop-2-enoic acid Chemical compound CCCOC1=CC=C(C=C(C#N)C(O)=O)C=C1 WBUHGTHUBVPUAZ-UHFFFAOYSA-N 0.000 description 2
- CDUQMGQIHYISOP-UHFFFAOYSA-N 2-cyano-3-phenylprop-2-enoic acid Chemical compound OC(=O)C(C#N)=CC1=CC=CC=C1 CDUQMGQIHYISOP-UHFFFAOYSA-N 0.000 description 2
- XTTIQGSLJBWVIV-UHFFFAOYSA-N 2-methyl-4-nitroaniline Chemical compound CC1=CC([N+]([O-])=O)=CC=C1N XTTIQGSLJBWVIV-UHFFFAOYSA-N 0.000 description 2
- SHHUTXKPXXYFFJ-UHFFFAOYSA-N 3-(4-acetamidophenyl)-2-cyanoprop-2-enoic acid Chemical compound CC(=O)NC1=CC=C(C=C(C#N)C(O)=O)C=C1 SHHUTXKPXXYFFJ-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- LRFVTYWOQMYALW-UHFFFAOYSA-N 9H-xanthine Chemical compound O=C1NC(=O)NC2=C1NC=N2 LRFVTYWOQMYALW-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical group CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical group NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical group CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical group CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical group NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003931 anilides Chemical group 0.000 description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical group CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 150000002475 indoles Chemical class 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000004492 methyl ester group Chemical group 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 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
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical group CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- UBDXZYYYWGIRGN-VCABWLAWSA-N (2e,4e)-2-cyano-5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C(\C#N)=C\C=C\C1=CC=CC=C1 UBDXZYYYWGIRGN-VCABWLAWSA-N 0.000 description 1
- JLIDBLDQVAYHNE-IBPUIESWSA-N (s)-(+)-Abscisic acid Natural products OC(=O)\C=C(/C)\C=C\[C@@]1(O)C(C)=CC(=O)CC1(C)C JLIDBLDQVAYHNE-IBPUIESWSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DHDGPQKQIWLEJR-UHFFFAOYSA-N 2-cyano-3-(1h-indol-2-yl)prop-2-enoic acid Chemical compound C1=CC=C2NC(C=C(C(=O)O)C#N)=CC2=C1 DHDGPQKQIWLEJR-UHFFFAOYSA-N 0.000 description 1
- FZSJXTJYHQPMAJ-UHFFFAOYSA-N 2-cyano-3-(2-cyanophenyl)prop-2-enoic acid Chemical compound OC(=O)C(C#N)=CC1=CC=CC=C1C#N FZSJXTJYHQPMAJ-UHFFFAOYSA-N 0.000 description 1
- PRKAGXBESHYXLI-UHFFFAOYSA-N 2-cyano-3-(2-nitrophenyl)prop-2-enoic acid Chemical compound OC(=O)C(C#N)=CC1=CC=CC=C1[N+]([O-])=O PRKAGXBESHYXLI-UHFFFAOYSA-N 0.000 description 1
- QRDHGGUIGSKAKC-UHFFFAOYSA-N 2-cyano-3-(4-ethylphenyl)prop-2-enoic acid Chemical compound CCC1=CC=C(C=C(C#N)C(O)=O)C=C1 QRDHGGUIGSKAKC-UHFFFAOYSA-N 0.000 description 1
- BXQVWEAWOZWOFW-UHFFFAOYSA-N 2-cyano-3-(4-hexoxyphenyl)prop-2-enoic acid Chemical compound CCCCCCOC1=CC=C(C=C(C#N)C(O)=O)C=C1 BXQVWEAWOZWOFW-UHFFFAOYSA-N 0.000 description 1
- CZTSLRKUJVVEKP-UHFFFAOYSA-N 2-cyano-3-(4-hexylphenyl)prop-2-enoic acid Chemical compound CCCCCCC1=CC=C(C=C(C#N)C(O)=O)C=C1 CZTSLRKUJVVEKP-UHFFFAOYSA-N 0.000 description 1
- FVQRWRPJMYOGLD-UHFFFAOYSA-N 2-cyano-3-(4-hexylsulfanylphenyl)prop-2-enoic acid Chemical compound CCCCCCSC1=CC=C(C=C(C#N)C(O)=O)C=C1 FVQRWRPJMYOGLD-UHFFFAOYSA-N 0.000 description 1
- KMHNRJDDHTZZDZ-UHFFFAOYSA-N 2-cyano-3-(4-methoxyphenyl)prop-2-enoic acid Chemical compound COC1=CC=C(C=C(C#N)C(O)=O)C=C1 KMHNRJDDHTZZDZ-UHFFFAOYSA-N 0.000 description 1
- GCQLWWTUSMRYCP-UHFFFAOYSA-N 2-cyano-3-(4-methylsulfanylphenyl)prop-2-enoic acid Chemical compound CSC1=CC=C(C=C(C#N)C(O)=O)C=C1 GCQLWWTUSMRYCP-UHFFFAOYSA-N 0.000 description 1
- WVRIVHWJJWXSTM-UHFFFAOYSA-N 2-cyano-3-(4-nitrophenyl)prop-2-enoic acid Chemical compound OC(=O)C(C#N)=CC1=CC=C([N+]([O-])=O)C=C1 WVRIVHWJJWXSTM-UHFFFAOYSA-N 0.000 description 1
- XNPUEOWHAGJWJO-UHFFFAOYSA-N 2-cyano-3-(4-pentoxyphenyl)prop-2-enoic acid Chemical compound CCCCCOC1=CC=C(C=C(C#N)C(O)=O)C=C1 XNPUEOWHAGJWJO-UHFFFAOYSA-N 0.000 description 1
- PAQVSYQGGIWWDB-UHFFFAOYSA-N 2-cyano-3-(4-pentylsulfanylphenyl)prop-2-enoic acid Chemical compound CCCCCSC1=CC=C(C=C(C#N)C(O)=O)C=C1 PAQVSYQGGIWWDB-UHFFFAOYSA-N 0.000 description 1
- ZXANPNFEYXVUSH-UHFFFAOYSA-N 2-cyano-3-(4-propanoyloxyphenyl)prop-2-enoic acid Chemical compound CCC(=O)OC1=CC=C(C=C(C#N)C(O)=O)C=C1 ZXANPNFEYXVUSH-UHFFFAOYSA-N 0.000 description 1
- TUIVLFPJSWCXRG-UHFFFAOYSA-N 2-cyano-3-[4-(ethylamino)phenyl]prop-2-enoic acid Chemical compound CCNC1=CC=C(C=C(C#N)C(O)=O)C=C1 TUIVLFPJSWCXRG-UHFFFAOYSA-N 0.000 description 1
- HOIKEQBQSLTORE-UHFFFAOYSA-N 2-cyano-3-[4-(methylamino)phenyl]prop-2-enoic acid Chemical compound CNC1=CC=C(C=C(C#N)C(O)=O)C=C1 HOIKEQBQSLTORE-UHFFFAOYSA-N 0.000 description 1
- MNKYIXBRJIONJU-UHFFFAOYSA-N 2-cyano-5-(1h-indol-3-yl)penta-2,4-dienoic acid Chemical compound C1=CC=C2C(C=CC=C(C(=O)O)C#N)=CNC2=C1 MNKYIXBRJIONJU-UHFFFAOYSA-N 0.000 description 1
- BWBQDWNRSFTYMB-UHFFFAOYSA-N 2-cyano-5-(4-ethoxycarbonylphenyl)penta-2,4-dienoic acid Chemical compound CCOC(=O)C1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 BWBQDWNRSFTYMB-UHFFFAOYSA-N 0.000 description 1
- DJEDOINOKNGKRD-UHFFFAOYSA-N 2-cyano-5-(4-ethoxyphenyl)penta-2,4-dienoic acid Chemical compound CCOC1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 DJEDOINOKNGKRD-UHFFFAOYSA-N 0.000 description 1
- JQQAXCQLLPWSAV-UHFFFAOYSA-N 2-cyano-5-(4-ethylphenyl)penta-2,4-dienoic acid Chemical compound CCC1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 JQQAXCQLLPWSAV-UHFFFAOYSA-N 0.000 description 1
- HKROSNLOZRUYJS-UHFFFAOYSA-N 2-cyano-5-(4-ethylsulfanylphenyl)penta-2,4-dienoic acid Chemical compound CCSC1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 HKROSNLOZRUYJS-UHFFFAOYSA-N 0.000 description 1
- HDFPDZFMAWHNDE-UHFFFAOYSA-N 2-cyano-5-(4-methoxyphenyl)penta-2,4-dienoic acid Chemical compound COC1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 HDFPDZFMAWHNDE-UHFFFAOYSA-N 0.000 description 1
- PBYPLJBPGUWQQD-UHFFFAOYSA-N 2-cyano-5-(4-methylsulfanylphenyl)penta-2,4-dienoic acid Chemical compound CSC1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 PBYPLJBPGUWQQD-UHFFFAOYSA-N 0.000 description 1
- JGDNZIHVJQEOHN-UHFFFAOYSA-N 2-cyano-5-(4-propoxycarbonylphenyl)penta-2,4-dienoic acid Chemical compound CCCOC(=O)C1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 JGDNZIHVJQEOHN-UHFFFAOYSA-N 0.000 description 1
- ZIOMFUIFEKDSLH-UHFFFAOYSA-N 2-cyano-5-(4-propoxyphenyl)penta-2,4-dienoic acid Chemical compound CCCOC1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 ZIOMFUIFEKDSLH-UHFFFAOYSA-N 0.000 description 1
- ADABCPUJAVMVKV-UHFFFAOYSA-N 2-cyano-5-[4-(dibutylamino)phenyl]penta-2,4-dienoic acid Chemical compound CCCCN(CCCC)C1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 ADABCPUJAVMVKV-UHFFFAOYSA-N 0.000 description 1
- HUEHPWIGBVFOHE-UHFFFAOYSA-N 2-cyano-5-[4-(diethylamino)phenyl]penta-2,4-dienoic acid Chemical compound CCN(CC)C1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 HUEHPWIGBVFOHE-UHFFFAOYSA-N 0.000 description 1
- TVDDKIWATINVSO-UHFFFAOYSA-N 2-cyano-5-[4-(dimethylamino)phenyl]penta-2,4-dienoic acid Chemical compound CN(C)C1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 TVDDKIWATINVSO-UHFFFAOYSA-N 0.000 description 1
- KMAPISQCPQNHJL-UHFFFAOYSA-N 2-cyano-5-[4-(dipropylamino)phenyl]penta-2,4-dienoic acid Chemical compound CCCN(CCC)C1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 KMAPISQCPQNHJL-UHFFFAOYSA-N 0.000 description 1
- YQGYWMXTZWKMSV-UHFFFAOYSA-N 2-cyano-5-[4-(methylamino)phenyl]penta-2,4-dienoic acid Chemical compound CNC1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 YQGYWMXTZWKMSV-UHFFFAOYSA-N 0.000 description 1
- RNCLYNIJBTUFBP-UHFFFAOYSA-N 2-cyano-5-[4-(propanoylamino)phenyl]penta-2,4-dienoic acid Chemical compound CCC(=O)NC1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 RNCLYNIJBTUFBP-UHFFFAOYSA-N 0.000 description 1
- UBDXZYYYWGIRGN-UHFFFAOYSA-N 2-cyano-5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C(C#N)=CC=CC1=CC=CC=C1 UBDXZYYYWGIRGN-UHFFFAOYSA-N 0.000 description 1
- FOVKOWVVJCQKFA-UHFFFAOYSA-N 2-cyano-7-(1h-indol-2-yl)hepta-2,4,6-trienoic acid Chemical compound C1=CC=C2NC(C=CC=CC=C(C(=O)O)C#N)=CC2=C1 FOVKOWVVJCQKFA-UHFFFAOYSA-N 0.000 description 1
- UXLIIOFYKKTMGP-UHFFFAOYSA-N 2-cyano-7-(4-ethylsulfanylphenyl)hepta-2,4,6-trienoic acid Chemical compound CCSC1=CC=C(C=CC=CC=C(C#N)C(O)=O)C=C1 UXLIIOFYKKTMGP-UHFFFAOYSA-N 0.000 description 1
- JSPWXQJICRQIHV-UHFFFAOYSA-N 2-cyano-7-(4-methylsulfanylphenyl)hepta-2,4,6-trienoic acid Chemical compound CSC1=CC=C(C=CC=CC=C(C#N)C(O)=O)C=C1 JSPWXQJICRQIHV-UHFFFAOYSA-N 0.000 description 1
- UYGRFFLWNVJMKK-UHFFFAOYSA-N 2-cyano-7-(4-propoxyphenyl)hepta-2,4,6-trienoic acid Chemical compound CCCOC1=CC=C(C=CC=CC=C(C#N)C(O)=O)C=C1 UYGRFFLWNVJMKK-UHFFFAOYSA-N 0.000 description 1
- SSCJEUZTFDCTPM-UHFFFAOYSA-N 2-cyano-7-[4-(dimethylamino)phenyl]hepta-2,4,6-trienoic acid Chemical compound CN(C)C1=CC=C(C=CC=CC=C(C#N)C(O)=O)C=C1 SSCJEUZTFDCTPM-UHFFFAOYSA-N 0.000 description 1
- HOTXRDAJWTULIQ-UHFFFAOYSA-N 2-cyano-7-phenylhepta-2,4,6-trienoic acid Chemical compound OC(=O)C(C#N)=CC=CC=CC1=CC=CC=C1 HOTXRDAJWTULIQ-UHFFFAOYSA-N 0.000 description 1
- VSEZRLWCWGAQRC-UHFFFAOYSA-N 3-(4-acetyloxyphenyl)-2-cyanoprop-2-enoic acid Chemical compound CC(=O)OC1=CC=C(C=C(C#N)C(O)=O)C=C1 VSEZRLWCWGAQRC-UHFFFAOYSA-N 0.000 description 1
- CBWQHJYSWCDDSI-UHFFFAOYSA-N 3-(5-chloro-1h-indol-3-yl)-2-cyanoprop-2-enoic acid Chemical compound C1=C(Cl)C=C2C(C=C(C(=O)O)C#N)=CNC2=C1 CBWQHJYSWCDDSI-UHFFFAOYSA-N 0.000 description 1
- QNBSNYNKJLBCPI-UHFFFAOYSA-N 5-(4-acetamidophenyl)-2-cyanopenta-2,4-dienoic acid Chemical compound CC(=O)NC1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 QNBSNYNKJLBCPI-UHFFFAOYSA-N 0.000 description 1
- XPYYUWQVYVWUMU-UHFFFAOYSA-N 5-(4-aminophenyl)-2-cyanopenta-2,4-dienoic acid Chemical compound NC1=CC=C(C=CC=C(C#N)C(O)=O)C=C1 XPYYUWQVYVWUMU-UHFFFAOYSA-N 0.000 description 1
- ZSAPOECVQGXVKJ-UHFFFAOYSA-N 5-[4-(dimethylamino)phenyl]penta-2,4-dienoic acid Chemical compound CN(C)C1=CC=C(C=CC=CC(O)=O)C=C1 ZSAPOECVQGXVKJ-UHFFFAOYSA-N 0.000 description 1
- BNCKWHAEGJPZLX-UHFFFAOYSA-N 7-(4-butylphenyl)-2-cyanohepta-2,4,6-trienoic acid Chemical compound CCCCC1=CC=C(C=CC=CC=C(C#N)C(O)=O)C=C1 BNCKWHAEGJPZLX-UHFFFAOYSA-N 0.000 description 1
- MJELJGZNGFQXGX-UHFFFAOYSA-N C(#N)C(C(=O)O)=CC1=CC=C(C=C1)OC(CCC)=O Chemical compound C(#N)C(C(=O)O)=CC1=CC=C(C=C1)OC(CCC)=O MJELJGZNGFQXGX-UHFFFAOYSA-N 0.000 description 1
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical group CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 1
- 101100134925 Gallus gallus COR6 gene Proteins 0.000 description 1
- 229910003327 LiNbO3 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- RFRXIWQYSOIBDI-UHFFFAOYSA-N benzarone Chemical compound CCC=1OC2=CC=CC=C2C=1C(=O)C1=CC=C(O)C=C1 RFRXIWQYSOIBDI-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical group CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- DNSISZSEWVHGLH-UHFFFAOYSA-N butanamide Chemical group CCCC(N)=O DNSISZSEWVHGLH-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- HJMZMZRCABDKKV-UHFFFAOYSA-N carbonocyanidic acid Chemical compound OC(=O)C#N HJMZMZRCABDKKV-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- WCYBYZBPWZTMDW-UHFFFAOYSA-N dibutylazanide Chemical group CCCC[N-]CCCC WCYBYZBPWZTMDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical group CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004706 n-propylthio group Chemical group C(CC)S* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229940075420 xanthine Drugs 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、非線形光学材料分野、さらに詳細には大きな
二次の非線形光学物性を有する有機芳香族系材料に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to the field of nonlinear optical materials, and more particularly to organic aromatic materials having large second-order nonlinear optical properties.
［従来の技術］
非線形光学効果とは、例えばレーザ光のような強い光電
場を物質に印加した場合、その物質の電気分極応答が印
加電界の大きさの単位−次に比例する関係から、印加電
場の大きさの二次以上の高次の効果があられれることを
示す。[Prior Art] The nonlinear optical effect is based on the relationship that when a strong optical electric field such as that of a laser beam is applied to a material, the electric polarization response of the material is proportional to the unit of the applied electric field. This shows that there are effects of higher order than the second order of the magnitude of the electric field.
二次の非線形光学効果には、入射光の波長を１７２の波
長変換する第２高調波発生、１種類の波長の光を２種類
の光に変換させるパラメトリック発振、逆に２種類の波
長の光がら１種類の波長の光を発現させる二次光混合な
どがある。これらの諸特性から、非線形光学効果を有す
る材料は、将来的には光データ／情報処理や光通信シス
テムにおいて用いられる光スィッチ、光メモリ、あるい
は光信号演算処理に用いられる光双安定素子、光スィッ
チなどの素子として使用される可能性がある。一般に、
この分野においてはＬｉＮｂＯ３を中心に、無機材料が
研究検討されているが、無機材料はその性能指数があま
り大きくないこと、応答速度が小さい、形態加工性が良
くない、吸湿性が大きい、安定性が低いなどの難点から
所望の光学素子を形成するのに大きな困難を伴うことな
どの欠点があった。Second-order nonlinear optical effects include second harmonic generation, which converts the wavelength of incident light into 172 wavelengths, parametric oscillation, which converts light with one wavelength into two types of light, and conversely, converts light with two wavelengths into two types of light. There is also secondary light mixing, which produces light of one type of wavelength. Due to these properties, materials with nonlinear optical effects will be used in the future as optical switches and optical memories used in optical data/information processing and optical communication systems, as well as optical bistable elements and optical switches used in optical signal processing. It may be used as an element such as in general,
In this field, inorganic materials, mainly LiNbO3, are being researched and considered, but inorganic materials do not have a very large figure of merit, have low response speed, poor formability, high hygroscopicity, and poor stability. However, there are drawbacks such as a low optical density and great difficulty in forming a desired optical element.
近年、これらの無機材料に対して、有機材料の検討が盛
んに試みられるようになってきた。これは、有機物の応
答が主としてπ電子系の分極に準拠するので、非線形光
学効果が大きく、かつ応答速度も大きいことが確がめら
れ報告されている。In recent years, many attempts have been made to investigate organic materials in place of these inorganic materials. It has been confirmed and reported that since the response of organic substances is mainly based on the polarization of the π electron system, the nonlinear optical effect is large and the response speed is also large.
例えば、エイシーエスシンポジュウムシリーズ２３３巻
（ＡＣ３Ｓｙｍｐｏｓｉｕｍ ５ｅｒｉｅｓ Ｖｏｌ、
２３３．１９８３）に数多くの報告例がなされている。For example, AC3Symposium Series Vol. 233 (AC3Symposium 5eries Vol.
233.1983), many examples have been reported.
本発明で問題とする二次の非線形光学特性は、３階のテ
ンソルであるので、分子または結晶で対称中心が存在す
ると顕在化しない。この理由のために有機物では分子の
レベルでは大きな分子非線形感受率を有していても、固
体化、結晶化の段階ではその大きい非線形感受率を発現
させる背景となる分極の効果の故に、より安定な中心対
称のある構造が優先的に形成され、このなめに光学素子
として二次の非線形光学効果が全く発現されないという
問題点があった。The second-order nonlinear optical properties that are a problem in the present invention are third-order tensors, and therefore will not become apparent if a center of symmetry exists in the molecule or crystal. For this reason, even though organic substances have a large molecular nonlinear susceptibility at the molecular level, they become more stable at the solidification and crystallization stages due to the polarization effect that is the background that causes the large nonlinear susceptibility to appear. There is a problem in that a structure with central symmetry is preferentially formed, and as a result, no second-order nonlinear optical effect is exhibited as an optical element.
一般に、第２高調波発生能は、分子内での分極が大きく
、かつその分極の寄与が大きくなる長い共役系はど大き
くなるが、逆に共役長さが長くなると吸収波長は、長波
長側に移り、入射光の１７２波長に対応するようになる
。そうなると発生する第２高調波を吸収し、屈折率の変
化する光損傷や、光学的な変性の発生、あるいは熱エネ
ルギーの吸収による燃焼が生起することがある。従って
、単純に共役長さを延長することは有利でないことが多
い。例えば下記式（１）で示されるようなカルボキシル
基、シアノ基のごとく電子吸引性の大きい基と、更にベ
ンゼン環に種々の置換基を導入することで、分子分極を
増大させた化合物は、環内の電子配置の移動効果の結果
、大きな非線形性が期待されるが、実際にはその分子分
極の大きさのなめに反転対称中心を有する構造となり、
第２高調波の発生が観測されないことが多い。一般に生
成する結晶の構造を制御することは困難な技術であり、
特に対称中心を崩すような結晶系を作成するのは難しい
。In general, the second harmonic generation ability increases in long conjugated systems where the polarization within the molecule is large and the contribution of that polarization is large, but conversely, when the conjugation length becomes long, the absorption wavelength shifts to the longer wavelength side. , which corresponds to 172 wavelengths of incident light. If this happens, the generated second harmonics may be absorbed, resulting in optical damage that changes the refractive index, optical degeneration, or combustion due to absorption of thermal energy. Therefore, simply increasing the conjugate length is often not advantageous. For example, compounds with increased molecular polarization by introducing groups with large electron-withdrawing properties such as carboxyl groups and cyano groups as shown in the following formula (1) and various substituents into the benzene ring are Although large nonlinearity is expected as a result of the transfer effect of the electron configuration in
Generation of the second harmonic is often not observed. Generally, controlling the structure of the crystals produced is a difficult technology;
In particular, it is difficult to create a crystal system that breaks the center of symmetry.
この困難を克服するなめに本発明者は先に光学活性のキ
ラル構造を利用する発明を出願しく特願昭６３−７２０
８１号、特願昭６３−７２０８０号）、分子レベルでの
非線形感受率をそのまま結晶構造に発現させることにも
成功している。In order to overcome this difficulty, the present inventor first applied for an invention utilizing an optically active chiral structure in Japanese Patent Application No. 63-720.
No. 81, Japanese Patent Application No. 63-72080), they have also succeeded in directly expressing nonlinear susceptibility at the molecular level in the crystal structure.
一方、高い二次の非線形光学特性を有する代表的な材料
として、２−メチル−４−ニトロアニリン（ＭＮＡ＞が
ある。この化合物は本来大きい分子非線形感受率を有す
るｐ−ニトロアニリンが、分極効果で結晶化に際して反
転対称中心を形成するなめに、メチル基を導入すること
でこの形成を抑制するなめに開発された材料である。こ
のように電子供与基と電子受容基とが相互に芳香環を中
心に対象の位置にある時には、その電子の流れの効果の
ために、本質的に大きい非線形光学性能が予測されるに
も拘らず、上の理由により実際に非線形光学、特に二次
の非線形光学特性が発現することが著しく困難になるこ
とが多い。ところが、このように各々独立では、対称中
心を有する構造を発現するのに対して、本発明者は鋭意
研究の結果、双極子の相互の寄与の組合せを勘案するこ
とにより、非対称構造が発現することを見い出し本発明
に到達した。On the other hand, 2-methyl-4-nitroaniline (MNA) is a typical material with high second-order nonlinear optical properties. This material was developed to suppress the formation of a center of inversion symmetry during crystallization by introducing a methyl group.In this way, the electron donating group and the electron accepting group mutually form an aromatic ring. Although inherently large nonlinear optical performance is expected when the position of interest is centered on In many cases, it becomes extremely difficult to express optical properties. However, whereas each independent structure exhibits a structure with a center of symmetry, the present inventors have conducted extensive research and found that the mutual interaction of dipoles The present invention has been achieved by discovering that an asymmetric structure is developed by considering the combination of the contributions of the following.
即ち、本発明は下記−最大（１）
％式％（１１
［但し、ｎは０，１まなは２を表わす。Ａｒは炭素数５
〜１４の芳香族基を表わす。Ｘ、Ｙは、Ｒ１−〇−で表
わされるエーテル基、Ｒ２Ｒ３Ｎ−で表わされるアミノ
基、Ｒ４−３−で表わされるチオエーテル基、ニトリル
基、ニトロ基、−ＣＯＯＲ５，−ＱＣＯＲ６で表わされ
るエステル基、−ＣＯＮＲ７Ｒ８，−Ｎ Ｒ９ＣＯＲ１
ｏで表わされるアミド基、−Ｒｏｌで表わされる炭化水
素基（Ｒ＋〜 Ｒ１１は、同一または異なる炭素数１〜
８の炭化水素基、または水素原子を表わす）から選ばれ
る官能基で、同じでも異なっていてもよい。］で表わさ
れるカルボン酸と下記−最大（２）
％式％（２）
［但し、式中１ｎｄはインドール残基を表わし、Ｒ５０
はＲｓ 、Ｒ５２Ｎ−で表わされるアミノ基；Ｒ５３−
〇＝で表わされるアルコキシ基；Ｒ５４Ｓ−で表わされ
るアルキルチオ基；シアノ基；ニトロ基；−ＣＯＯＲｓ
５もしくは一〇 ＣＯＲ５６で表わされるエステル基
； −ＣＯＮ Ｒ５７Ｒ５８もしくは−Ｎ（Ｒ５９）
ＣＯＲ６０で表わされるアミド基；Ｒ６１で表゛わされ
る炭化水素基または水素原子； （ここで、Ｒ５１〜Ｒ
６□は同一または異なる炭素数１〜８の炭化水素基を表
わす〉を示し、ｎは○〜２の整数を示す。］
で表わされるインドール環を含むカルボン酸との固溶体
からなることを特徴とする非線形光学材料に関する。That is, the present invention provides the following - maximum (1) % formula % (11 [However, n represents 0, 1 or 2. Ar is a carbon number of 5
~14 aromatic groups. X and Y are an ether group represented by R1-〇-, an amino group represented by R2R3N-, a thioether group represented by R4-3-, a nitrile group, a nitro group, an ester group represented by -COOR5, -QCOR6, -CONR7R8, -N R9COR1
An amide group represented by o, a hydrocarbon group represented by -Rol (R+~R11 is the same or different carbon number 1~
A functional group selected from 8 (representing a hydrocarbon group or a hydrogen atom), which may be the same or different. ] and the following - maximum (2) % formula % (2) [However, in the formula, 1nd represents an indole residue, and R50
is an amino group represented by Rs, R52N-; R53-
Alkoxy group represented by 〇=; Alkylthio group represented by R54S-; Cyano group; Nitro group; -COORs
5 or 10 Ester group represented by COR56; -CON R57R58 or -N(R59)
An amide group represented by COR60; a hydrocarbon group or a hydrogen atom represented by R61; (herein, R51 to R
6□ represents the same or different hydrocarbon groups having 1 to 8 carbon atoms, and n represents an integer of ◯ to 2. ] The present invention relates to a nonlinear optical material characterized by being made of a solid solution with a carboxylic acid containing an indole ring represented by the following.
一般式（１）において、Ａｒは炭素数５〜１４の芳香族
基を示す。このＡｒとしては、例えばピリジン。In general formula (1), Ar represents an aromatic group having 5 to 14 carbon atoms. This Ar is, for example, pyridine.
ベンゼン、ビフェニル、インデン、ナフタレン。Benzene, biphenyl, indene, naphthalene.
ビフェニレン、アセナフチレン、フルオレン、フェナン
トレン、アントラセン、ベンゾフラン、ベンゾチオフェ
ン、インドール、キノリン、イソキノリン、カルバゾー
ル、キサンチンから誘導される基を挙げることができる
。就中ベンゼン、ナフタレンから誘導される基が好まし
い。また、−最大（１）において、Ｘ、Ｙは前記基を示
すが、例えばメトキシ基、エトキシ基、ｎ−プロポキシ
基。Mention may be made of groups derived from biphenylene, acenaphthylene, fluorene, phenanthrene, anthracene, benzofuran, benzothiophene, indole, quinoline, isoquinoline, carbazole, xanthine. Among these, groups derived from benzene and naphthalene are preferred. Furthermore, in (1), X and Y represent the aforementioned groups, such as a methoxy group, an ethoxy group, or an n-propoxy group.
ｎ−ブトキシ基、フェノキシ基で表わされるエーテル基
、アミノ基、モノメチルアミノ基、モノエチルアミノ基
、ジメチルアミン基、ジエチルアミノ基、ジ（ｎ−プロ
ピル）アミン基、メチルエチルアミノ基、アニリノ基、
ジフェニルアミノ基等のアミン基、メチルチオ基、エチ
ルチオ基、 ｎ −プロピルチオ基、フェニルチオ基な
どで表わされるチオエーテル基、シアノ基、ニトロ基、
Ａｒの芳香族基から誘導されるカルボン酸のメチルエ
ステル基、エチルエステル基、ｎ−プロピルエステル基
、ｎ−ブチルエステル基、フェニルエステル基のような
ＣＯＯＲ５で表わされるエステル基、あるいはアセチル
オキシ基、プロピオニルオキシ基。n-butoxy group, ether group represented by phenoxy group, amino group, monomethylamino group, monoethylamino group, dimethylamine group, diethylamino group, di(n-propyl)amine group, methylethylamino group, anilino group,
Amine groups such as diphenylamino groups, thioether groups represented by methylthio groups, ethylthio groups, n-propylthio groups, phenylthio groups, cyano groups, nitro groups,
An ester group represented by COOR5 such as a methyl ester group, an ethyl ester group, an n-propyl ester group, an n-butyl ester group, a phenyl ester group of a carboxylic acid derived from an aromatic group of Ar, or an acetyloxy group, Propionyloxy group.
ブチリルオキシ基、ベンゾイルオキシ基のような０ＣＯ
Ｒ，、で表わされるエステル基、Ａｒの芳香族基から誘
導されるカルボン酸のアンモニアとのアミド基、メチル
アミド基、エチルアミド基、ジメチルアミド基、ジエチ
ルアミド基、プロピルアミド基、ジプロピルアミド基、
ブチルアミド基２ジブチルアミド基、アニリド基のよう
な−ＣＯＮＲ７Ｒで表わされるアミド基、あるいはホル
ミルアミド基、アセチルアミド基、プロピオニルアミド
基。0CO such as butyryloxy group, benzoyloxy group
An ester group represented by R, an amide group with ammonia of a carboxylic acid derived from an aromatic group of Ar, a methylamide group, an ethylamide group, a dimethylamide group, a diethylamide group, a propylamide group, a dipropylamide group,
Butylamide group 2 Dibutylamide group, amide group represented by -CONR7R such as anilide group, or formylamide group, acetylamide group, propionylamide group.
ブチリルアミド基、ベンゾイルアミド基のようなＮ Ｒ
ｇ ＣＯＲ１ｏで表わされるアミド基、あるいはメチル
基、エチル基、ｎ−プロピル基、ｎ−ブチル基、■−ペ
ンチル基のような炭化水素基が上げられ、好適には、メ
トキシ基、エトキシ基、 ｎ −プロポキシ基、フェノ
キシ基で表わされるエーテル基、アミノ基、モノメチル
アミノ基、モノエチルアミノ基、ジメチルアミノ基、ジ
エチルアミノ基、メチルエチルアミノ基、アニリノ基で
表わされるアミノ基、メチルチオ基、エチルチオ基、フ
ェニルチオ基などで表わされるチオエーテル基。N R such as butyrylamide group, benzoylamide group
g An amide group represented by COR1o, or a hydrocarbon group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, or a -pentyl group, and preferably a methoxy group, an ethoxy group, or n - Propoxy group, ether group represented by phenoxy group, amino group, monomethylamino group, monoethylamino group, dimethylamino group, diethylamino group, methylethylamino group, amino group represented by anilino group, methylthio group, ethylthio group, A thioether group represented by a phenylthio group, etc.
シアノ基、ニトロ基、 Ａｒの芳香族基から誘導される
カルボン酸のメチルエステル基、エチルエステル基、フ
ェニルエステル基のようなｃｏｏｋで代表されるエステ
ル基、あるいはアセチルオキシ基。A cyano group, a nitro group, an ester group represented by cook such as a methyl ester group, an ethyl ester group, a phenyl ester group of a carboxylic acid derived from an aromatic group of Ar, or an acetyloxy group.
プロピオニルオキシ基、ベンゾイルオキシ基のような０
ＣＯＲ６で表わされるエステル基、Ａｒの芳香族基から
誘導されるカルボン酸のアンモニアとのアミド基、メチ
ルアミド基、エチルアミド基、ジメチルアミド基、アニ
リド基のような−ＣＯＮＲ７Ｒで表わされるアミド基、
あるいはホルミルアミド基、アセチルアミド基、ベンゾ
イルアミド基のような−Ｎ Ｒｓ ＣＯＲ１ｏで表わさ
れるアミド基、あるいはメチル基、エチル基、ｎ−プロ
ピル基のような炭化水素基である。0 such as propionyloxy group, benzoyloxy group
An amide group represented by -CONR7R such as an ester group represented by COR6, an amide group with ammonia of a carboxylic acid derived from an aromatic group of Ar, a methylamide group, an ethylamide group, a dimethylamide group, an anilide group,
Alternatively, it is an amide group represented by -NRsCOR1o such as a formylamide group, an acetylamide group, or a benzoylamide group, or a hydrocarbon group such as a methyl group, an ethyl group, or an n-propyl group.
また、−ｆｆｉ式（１）において、Ｘ、Ｙはいずれかが
水素原子の場合、水素原子以外の置換基は、−ＣＨ＝Ｃ
Ｈ−基とｐ−位または〇−位にあることが好ましく、共
に水素原子以外の場合は、ｐ−位および〇−位にあるこ
とが好ましい。In addition, in -ffi formula (1), when either X or Y is a hydrogen atom, the substituent other than the hydrogen atom is -CH=C
It is preferably located at the p-position or ○-position with the H-group, and when both are other than hydrogen atoms, it is preferably located at the p-position and the ○-position.
非線形光学効果を高めるためには、分子構造として大き
な双極子を有することが必要であり、この目的のために
一般式は、シアン基、カルボキシル基を同一炭素原子上
に存在させる。また、その分子分極が相互に干渉しあう
ためには、共役系があることが望ましいが、共役長さが
長くなると吸収極大が長波長側に伸び、入射光波長、あ
るいは第２高調波により損傷を生ずる恐れがある。この
ために、共役長は余り長くてはならない。In order to enhance the nonlinear optical effect, it is necessary to have a large dipole in the molecular structure, and for this purpose, the general formula includes a cyan group and a carboxyl group on the same carbon atom. In addition, in order for the molecular polarizations to interfere with each other, it is desirable to have a conjugated system, but as the conjugation length increases, the absorption maximum extends toward longer wavelengths, causing damage due to the incident light wavelength or second harmonic. There is a risk that this may occur. For this purpose, the conjugate length must not be too long.
−最大（１）で表わされるカルボン酸としては、例えば
次の化合物を挙げることができる。- Examples of the carboxylic acid represented by (1) include the following compounds.
３−フェニル−２−シアノプロペノン酸、３−（ｐ−ジ
メチルアミノフェニル〉−２−シアノプロペノン酸、３
−（ｐ−アミノフェニル〉−２−シアノプロペノン酸、
３−＜ｐ−ジエチルアミノフェニル）−２−シアノプロ
ペノン酸、３−＜ｐ＝ニジプロピルアミノフェニル−２
−シアノプロペノン酸、３−＜ｐ−ジブチルアミノフェ
ニル）−２−シアノプロペノン酸、３−（ｐ−モノメチ
ルアミノフェニル）−２−シアノプロペノン酸。3-phenyl-2-cyanopropenoic acid, 3-(p-dimethylaminophenyl>-2-cyanopropenoic acid, 3
-(p-aminophenyl>-2-cyanopropenoic acid,
3-<p-diethylaminophenyl)-2-cyanopropenoic acid, 3-<p=nidipropylaminophenyl-2
-cyanopropenoic acid, 3-<p-dibutylaminophenyl)-2-cyanopropenoic acid, 3-(p-monomethylaminophenyl)-2-cyanopropenoic acid.
３−（ｐ−モノエチルアミノフェニル）−２−シアノプ
ロペノン酸及びそれらのｍ−１〇−置換誘導体；
３−（ｐ−メトキシフェニル）−２−シアノプロペノン
酸、３−（ｐ−エトキシフェニル）−２−シアノプロペ
ノン酸、３−（ｐ−プロピルオキシフェニル）−２−シ
アノプロペノン酸、３−（Ｐ−ブチルオキシフェニル）
−２−シアノプロペノン酸、３−（ｐ−ペンチルオキシ
フェニル）−２−シアノプロペノン酸＋３ （ｐ−ｎ
−へキシルオキシフェニル）−２−シアノプロペノン酸
。3-(p-monoethylaminophenyl)-2-cyanopropenoic acid and their m-10-substituted derivatives; 3-(p-methoxyphenyl)-2-cyanopropenoic acid, 3-(p-ethoxy phenyl)-2-cyanopropenoic acid, 3-(p-propyloxyphenyl)-2-cyanopropenoic acid, 3-(P-butyloxyphenyl)
-2-cyanopropenoic acid, 3-(p-pentyloxyphenyl)-2-cyanopropenoic acid +3 (p-n
-hexyloxyphenyl)-2-cyanopropenoic acid.
３−（Ｐ−デカツキジフェニル〉−２−シアノプロペノ
ン酸、及びそれらのｍ−２〇−置換誘導体；３−（ｐ−
メチルチオフェニル）−２−シアノプロペノン酸、３−
（Ｐ−エチルチオフェニル）−２−シアノプロペノン酸
、３−＜ｐ−プロピルチオフェニル）−２−シアノプロ
ペノン酸、３−（ｐ−ブチルチオフェニル）−２−シア
ノプロペノンＢ、３−（ｐ−ｎ−ペンチルチオフェニル
）−２−シアノプロペノン酸、３−（ｐ−ｎ−ヘキシル
チオフェニル）−２−シアノプロペノン酸。3-(P-diphenyl〉-2-cyanopropenoic acid and m-20-substituted derivatives thereof; 3-(p-
methylthiophenyl)-2-cyanopropenoic acid, 3-
(P-Ethylthiophenyl)-2-cyanopropenoic acid, 3-<p-propylthiophenyl)-2-cyanopropenoic acid, 3-(p-butylthiophenyl)-2-cyanopropenone B, 3 -(p-n-pentylthiophenyl)-2-cyanopropenoic acid, 3-(p-n-hexylthiophenyl)-2-cyanopropenoic acid.
３−＜ｐ−デカンチオフェニｌし）−２−シアノプロペ
ノン酸、及びそれらのｍ−９〇−置換誘導体；３−（ｐ
−シアノフェニル）−２−シアノプロペノン酸、３−（
ｍ−シアノフェニル）−２−シアノプロペノン酸、３−
（ｏ−シアノフェニル）−２−シアノプロペノン酸、３
−＜ｐ−メチルオキシフェニル）−２−シアノプロペノ
ン酸、３−（ｐ−エチルオキシフェニル）−２−シアノ
プロペノン酸、３−（ｐ−プロピルオキシフェニル）−
２−シアノプロペノン酸、及びそれらのｍ−。3-<p-decanethiophenyl)-2-cyanopropenoic acids and their m-90-substituted derivatives;
-cyanophenyl)-2-cyanopropenoic acid, 3-(
m-cyanophenyl)-2-cyanopropenoic acid, 3-
(o-cyanophenyl)-2-cyanopropenoic acid, 3
-<p-methyloxyphenyl)-2-cyanopropenoic acid, 3-(p-ethyloxyphenyl)-2-cyanopropenoic acid, 3-(p-propyloxyphenyl)-
2-cyanopropenoic acids, and their m-.
〇−置換誘導体；
３−（ｐ−アセチルオキシフェニル〉−２−シアノプロ
ペノン酸、３−（ｐ−プロピオニルオキシフェニル）−
２−シアノプロペノン酸、３−（ｐ−ブタノイルオキシ
フェニル）−２−シアノプロペノン酸、及びそれらのｍ
−、ｏ−置換誘導体；
３−（ｐ−ニトロフェニル）−２−シアノプロペノン酸
、３−（ｍ−二トロフェニル〉−２−シアノプロペノン
酸、３−（ｏ−ニトロフェニル）−２−シアノプロペノ
ン酸、３−（Ｐ−ジメチルアミドフェニル）−２−シア
ノプロペノン酸、３−（ｐ−ジエチルアミドフェニル）
−２−シアノプロペノン酸、３−＜ｐ−ジプロピルアミ
ドフェニル）−２−シアノプロペノン酸、３−（ｐ−ジ
ブチルアミドフェニル）−２−シアノプロペノン酸、及
びそれらのｍ−１〇−置換誘導体；３−（ｐ−アセチル
アミノフェニル）−２−シアノプロペノン酸、３−（ｐ
−プロピオニルアミノフェニル）−２−シアノプロペノ
ン酸、及びそれらのｍ−１０〜置換誘導体；
３−＜ｐ−メチルフェニル）−２−シアノプロペノンＦ
Ｉｉ、３−（ｐ−エチルフェニル）−２−シアノプロペ
ノン酸、３−＜ｐ−プロピルフェニル）−２−シアノプ
ロペノン酸、３−＜ｐ−ブチルフェニル）−２−シアノ
プロペノン酸、３−（Ｐ−ｎ−ペンチルフェニル〉−２
−シアノプロペノン酸、３−（ｐ−ｎ−へキシルフェニ
ル）−２−シアノプロペノン酸、３−（ｐ−デカンフェ
ニル）＝２−シアノプロペノン酸、及びそれらのｍ−。〇-Substituted derivative; 3-(p-acetyloxyphenyl)-2-cyanopropenoic acid, 3-(p-propionyloxyphenyl)-
2-cyanopropenoic acid, 3-(p-butanoyloxyphenyl)-2-cyanopropenoic acid, and m
-, o-substituted derivatives; 3-(p-nitrophenyl)-2-cyanopropenoic acid, 3-(m-nitrophenyl>-2-cyanopropenoic acid, 3-(o-nitrophenyl)-2 -Cyanopropenoic acid, 3-(P-dimethylamidophenyl)-2-cyanopropenoic acid, 3-(p-diethylamidophenyl)
-2-cyanopropenoic acid, 3-<p-dipropylamidophenyl)-2-cyanopropenoic acid, 3-(p-dibutylamidophenyl)-2-cyanopropenoic acid, and their m-1〇 -Substituted derivative; 3-(p-acetylaminophenyl)-2-cyanopropenoic acid, 3-(p-acetylaminophenyl)-2-cyanopropenoic acid,
3-<p-methylphenyl)-2-cyanopropenone F
Ii, 3-(p-ethylphenyl)-2-cyanopropenoic acid, 3-<p-propylphenyl)-2-cyanopropenoic acid, 3-<p-butylphenyl)-2-cyanopropenoic acid, 3-(P-n-pentylphenyl>-2
-cyanopropenoic acid, 3-(p-n-hexylphenyl)-2-cyanopropenoic acid, 3-(p-decamphenyl)=2-cyanopropenoic acid, and their m-.
〇−置換誘導体；
で表わされる置換フェニル−２−シアノプロペノン酸誘
導体、
２−シアノ−５−フェニル−２，４−ペンタジェン酸、
２−シアノ−５−（ｐ−ジメチルアミノフェニル）−２
，４−ペンタジェン酸、２−シアノ−５−（ｐ−ジエチ
ルアミノフェニル）−２，４−ペンタジェン酸、２−シ
アノ−５−（ｐ−ジプロピルアミノフェニル）−２，４
−ペンタジェン酸、２−シアノ−５−（ｐ−ジブチルア
ミノフェニル）−２，４−ペンタジェン酸、２−シアノ
−５−（ｐ−モノメチルアミノフェニル）−２，４−ペ
ンタジェン酸、２−シアノ−５−（ｐ−アミノフェニル
）−２，４−ペンタジェン酸、及びそれらのｍ−、。〇-substituted derivative; substituted phenyl-2-cyanopropenoic acid derivative represented by: 2-cyano-5-phenyl-2,4-pentadienoic acid,
2-cyano-5-(p-dimethylaminophenyl)-2
, 4-pentadienoic acid, 2-cyano-5-(p-diethylaminophenyl)-2,4-pentadienoic acid, 2-cyano-5-(p-dipropylaminophenyl)-2,4
-Pentadienoic acid, 2-cyano-5-(p-dibutylaminophenyl)-2,4-pentadienoic acid, 2-cyano-5-(p-monomethylaminophenyl)-2,4-pentadienoic acid, 2-cyano- 5-(p-aminophenyl)-2,4-pentadienoic acid, and m-, thereof.
−置換誘導体；
２−シアノ−５−（ｐ−メチルオキシフェニル）−２，
４−ペンタジェン酸、２−シアノ−５−（ｐ−エチルオ
キシフェニル）−２，４−ペンタジェン酸、２−シアノ
−５−（ｐ−プロピルオキシフェニル）−２，４−ペン
タジェン酸、２〜シアノ−５−＜Ｐ−ブチルオキシフェ
ニル）−２，４−ペンタジェン酸、及びそれらのｍ＝、
ｏ−置換誘導体；２−シアノ−５−（ｐ−メチルチオフ
ェニル）−２，４−ペンタジェン酸、２−シアノ−５−
（ｐ−エチルチオフェニル）−２，４−ペンタジェン酸
。-Substituted derivative; 2-cyano-5-(p-methyloxyphenyl)-2,
4-Pentadienoic acid, 2-cyano-5-(p-ethyloxyphenyl)-2,4-pentadienoic acid, 2-cyano-5-(p-propyloxyphenyl)-2,4-pentadienoic acid, 2-cyano -5-<P-butyloxyphenyl)-2,4-pentadienoic acid and their m=,
o-substituted derivative; 2-cyano-5-(p-methylthiophenyl)-2,4-pentadienoic acid, 2-cyano-5-
(p-ethylthiophenyl)-2,4-pentadienoic acid.
２−シアノ−５−（ｐ−プロピルチオフェニル）＝２．
４−ペンタジェン酸、２−シアノ−５−＜ｐ−ブチルチ
オフェニル）−２，４−ペンタジェン酸。2-cyano-5-(p-propylthiophenyl)=2.
4-pentadienoic acid, 2-cyano-5-<p-butylthiophenyl)-2,4-pentadienoic acid.
及びそれらのｍ−、ｏ−置換誘導体；
２−シアノ−５−（ｐ−シアノフェニル）−２゜４−ペ
ンタジェン酸、及びそれらのｍ−、ｏ−置換誘導体；
２−シアノ−５−＜ｐ−メチｌレオキシカルボニルフェ
ニル）−２，４−ペンタジェン酸、２−シアノ−５−（
ｐ−エチルオキシカルボニルフェニル）−２，４−ペン
タジェン酸、２−シアノ−５−（ｐ−プロピルオキシカ
ルボニルフェニル）−２，４−ペンタジェン酸、２−シ
アノ−５−＜ｐ−ブチルオキシカルボニルフェニル）−
２，４−ペンタジェン酸、及びそれらのｍ−、Ｏ−？ｌ
Ｆ換誘導体； ２−シアノ−５−（ｐ−ニトロフェニル
ｉ２，４−ペンタジェン酸、及びそれらのｍ−、ｏ−置
換誘導体；
２−シアノ−５−（ｐ−ジメチルアミドフェニル）−２
，４−ペンタジェン酸、２−シアノ−５−（ｐ−ジエチ
ルアミドフェニル）−２，４−ペンタジェン酸、２−シ
アノ−５−＜ｐ−ジプロピルアミドフェニル）−２，４
−ペンタジェン酸、２−シアノ−５−（ｐ−ジブチルア
ミドフェニル）−２゜４−ペンタジェン酸、２−シアノ
−５−（ｐ−モノメチルアミドフェニル）−２，４−ペ
ンタジェン酸、２−シアノ−５−（ｐ−アミドフェニル
〉−２．４−ペンタジェン酸、及びそれらのｍ−、ｏ−
置換誘導体；
２−シアノ−５−（ｐ−アセチルアミノフェニル）−２
，４−ペンタジェン酸、２−シアノ−５−（ｐ−プロピ
オニルアミノフェニル）−２，４−ペンタジェン酸、及
びそれらのｍ−、ｏ−置換誘導体；
２−シアノ−５−（ｐ−メチルフェニル）−２゜４−ペ
ンタジェン酸、２−シアノ−５−（ｐ−エチルフェニル
）−２，４−ペンタジェン酸、２−シアノ−５−（ｐ−
プロピルフェニル）−２，４−ペンタジェン酸、２−シ
アノ−５−（ｐ−ブチルフェニル）−２，４−ペンタジ
ェン酸、及びそれらのｍ−、ｏ−置換誘導体；
で表わされる置換フェニル ２−シアノ−２，４−ペン
タジェン酸誘導体、
２−シアノ−７−フェニル−２，４，６−ヘブタトリエ
ン酸、２−シアノ−７−（ｐ−ジメチルアミノフェニル
）−２，４，６−ヘプタトリエン酸、２−シアノ−７−
（ｐ−ジエチルアミノフェニル）−２、４，６−へブタ
トリエン酸、２−シアノ−７−（ｐ−ジプロピルアミノ
フェニル）−２，４，６−ヘブタトリエン酸、２−シア
ノ−７−（ｐ−ジブチルアミノフェニル）−２，４，６
−へブタトリエン酸。and m-, o-substituted derivatives thereof; 2-cyano-5-(p-cyanophenyl)-2°4-pentadienoic acid and m-, o-substituted derivatives thereof; 2-cyano-5-<p -methyl-leoxycarbonylphenyl)-2,4-pentadienoic acid, 2-cyano-5-(
p-ethyloxycarbonylphenyl)-2,4-pentadienoic acid, 2-cyano-5-(p-propyloxycarbonylphenyl)-2,4-pentadienoic acid, 2-cyano-5-<p-butyloxycarbonylphenyl )−
2,4-pentadienoic acid and their m-, O-? l
F-substituted derivatives; 2-cyano-5-(p-nitrophenyl 2,4-pentadienoic acid and m-, o-substituted derivatives thereof; 2-cyano-5-(p-dimethylamidophenyl)-2
, 4-pentadienoic acid, 2-cyano-5-(p-diethylamidophenyl)-2,4-pentadienoic acid, 2-cyano-5-<p-dipropylamidophenyl)-2,4
-Pentadienoic acid, 2-cyano-5-(p-dibutylamidophenyl)-2°4-pentadienoic acid, 2-cyano-5-(p-monomethylamidophenyl)-2,4-pentadienoic acid, 2-cyano- 5-(p-amidophenyl>-2,4-pentadienoic acid, and their m-, o-
Substituted derivative; 2-cyano-5-(p-acetylaminophenyl)-2
, 4-pentadienoic acid, 2-cyano-5-(p-propionylaminophenyl)-2,4-pentadienoic acid, and m-, o-substituted derivatives thereof; 2-cyano-5-(p-methylphenyl) -2゜4-pentadienoic acid, 2-cyano-5-(p-ethylphenyl)-2,4-pentadienoic acid, 2-cyano-5-(p-
Substituted phenyl 2-cyano represented by -2,4-pentadienoic acid derivative, 2-cyano-7-phenyl-2,4,6-heptatrienoic acid, 2-cyano-7-(p-dimethylaminophenyl)-2,4,6-heptatrienoic acid, 2 -cyano-7-
(p-diethylaminophenyl)-2,4,6-hebutatrienoic acid, 2-cyano-7-(p-dipropylaminophenyl)-2,4,6-hebutatrienoic acid, 2-cyano-7-(p- dibutylaminophenyl)-2,4,6
- Hebutatrienoic acid.
２−シアノ−７−（ｐ−モノメチルアミノフェニル）−
２，４，６−へブタトリエン酸、２−シアノ−７−（ｐ
−モノエチルアミノフェニル）−２，４，６−へブタト
リエン酸、及びそれらのｍ−１〇−置換誘導体：
２−シアノ−７−（Ｐ−メチルオキシフェニル）−２，
４，６−へブタトリエン酸、２−シアノ−７−（ｐ−エ
チルオキシフェニル）−２，４，６−へブタトリエン酸
、２−シアノ−７−（ｐ−プロピルオキシフェニル）−
２，４，６−ヘプタトリエン酸、２−シアノー７−（ｐ
−ブチルオキシフェニル）−２、４，６−へブタトリエ
ン酸、及びそれらのｍ−。2-cyano-7-(p-monomethylaminophenyl)-
2,4,6-hebutatrienoic acid, 2-cyano-7-(p
2-cyano-7-(P-methyloxyphenyl)-2,
4,6-hebutatrienoic acid, 2-cyano-7-(p-ethyloxyphenyl)-2,4,6-hebutatrienoic acid, 2-cyano-7-(p-propyloxyphenyl)-
2,4,6-heptatrienoic acid, 2-cyano 7-(p
-butyloxyphenyl)-2,4,6-hebutatrienoic acid and their m-.
〇−置換誘導体；
２−シアノ−７−（ｐ−メチルチオフェニル）−２，４
，６−ヘプタトリエン酸、２−シアノ−７−（ｐ−エチ
ルチオフェニル）−２，４，６−ヘブタトリエン酸、２
−シアノ−７−（ｐ−プロピルチオフェニル）−２，４
，６−へブタトリエン酸、２−シアノ−７−（ｐ−ブチ
ルチオフェニル）−２，４，６−ヘブタトリエン酸、及
びそれらのｍ−、ｏ−置換誘導体：
２−シアノ−７−（ｐ−シアノフェニル）−２゜４．６
−へブタトリエン酸、及びそれらのｍ−１０−置換誘導
体：
２−シアノ−７−（Ｐ−メチｌレオキシカルボニルフェ
ニル）−２，４，６−へブタトリエン酸、２−シアノ−
７−（ｐ−エチルオキシカルボニルフェニル（−２，４
，６−ヘプタトリエン酸、２−シアノ−７−（ｐ−プロ
ピルオキシカルボニルフェニル＜ −２，４，６−ヘプ
タトリエン酸、２−シアノ−７−（ｐ−ブチルオキシカ
ルボニルフェニル（−２゜４．６−へブタトリエン酸、
及びそれらのｍ−、。〇-Substituted derivative; 2-cyano-7-(p-methylthiophenyl)-2,4
, 6-heptatrienoic acid, 2-cyano-7-(p-ethylthiophenyl)-2,4,6-heptatrienoic acid, 2
-cyano-7-(p-propylthiophenyl)-2,4
,6-hebutatrienoic acid, 2-cyano-7-(p-butylthiophenyl)-2,4,6-hebutatrienoic acid, and their m-,o-substituted derivatives: 2-cyano-7-(p- cyanophenyl)-2゜4.6
-hebutatrienoic acid and m-10-substituted derivatives thereof: 2-cyano-7-(P-methylleoxycarbonylphenyl)-2,4,6-hebutatrienoic acid, 2-cyano-
7-(p-ethyloxycarbonylphenyl(-2,4
, 6-heptatrienoic acid, 2-cyano-7-(p-propyloxycarbonylphenyl < -2,4,6-heptatrienoic acid, 2-cyano-7-(p-butyloxycarbonylphenyl (-2°4.6) -hebutatrienoic acid,
and their m-,.
−置換誘導体；
２−シアノ−７−（ｐ−アセチルオキシフェニル）−２
，４，６−ヘアタトリエン酸、２−シアノ−７−（ｐ−
プロピオニルオキシフェニル）−２，４゜６−へブタト
リエン酸、２−シアノ−７−（ｐ−ブタノイルオキシフ
ェニル）−２，４，６−へブタトリエン酸、及びそれら
のｍ−、Ｏｆ置換誘導体２−シアノ−７−（ｐ−ジメチ
ルアミドフェニル）−２，４，６−ヘプタトリエン酸、
２−シアノ−７−くｐ−ジエチルアミドフェニル） −
２，４，６−ヘプタトリエン酸、２−シアノ−７−（ｐ
−ジプロピルアミドフェニル＞−２，４，６−ヘプタト
リエン酸、２−シアノ−７−（ｐ−ジブチルアミドフェ
ニル）−２，４，６−ヘプタトリエン酸、２−シアノ−
７−（ｐ−モノメチルアミドフェニル）−２゜４．６−
へブタトリエン酸、２−シアノ−７−（ｐ−モノエチル
アミドフェニル）−２，４，６−ヘプタトリエン酸、及
びそれらのｍ−、ｏ−置換誘導体；２−シアノ−７−（
Ｐ−ニトロフェニル）−２゜４．６−ヘプタトリエン酸
、及びそれのｍ−、ｏ−置換誘導体；
２−シアノ−７−（ｐ−メチルフェニル）−２゜４．６
−へブタトリエン酸、２−シアノ−７−（Ｐ−エチルフ
ェニル＞−２，４，６−へブタトリエン酸。-Substituted derivative; 2-cyano-7-(p-acetyloxyphenyl)-2
, 4,6-hairtatrienoic acid, 2-cyano-7-(p-
propionyloxyphenyl)-2,4゜6-hebutatrienoic acid, 2-cyano-7-(p-butanoyloxyphenyl)-2,4,6-hebutatrienoic acid, and their m-, Of-substituted derivatives 2 -cyano-7-(p-dimethylamidophenyl)-2,4,6-heptatrienoic acid,
2-cyano-7-p-diethylamidophenyl) -
2,4,6-heptatrienoic acid, 2-cyano-7-(p
-dipropylamidophenyl>-2,4,6-heptatrienoic acid, 2-cyano-7-(p-dibutylamidophenyl)-2,4,6-heptatrienoic acid, 2-cyano-
7-(p-monomethylamidophenyl)-2゜4.6-
Hebutatrienoic acid, 2-cyano-7-(p-monoethylamidophenyl)-2,4,6-heptatrienoic acid, and m-, o-substituted derivatives thereof; 2-cyano-7-(
2-cyano-7-(p-methylphenyl)-2°4.6
-hebutatrienoic acid, 2-cyano-7-(P-ethylphenyl>-2,4,6-hebutatrienoic acid.
２−シアノ−７−（ｐ−プロピルフェニル）−２゜４，
６−へブタトリエン酸、２−シアノ−７−（ｐ−プチル
フェニル）−２，４，６−ヘプタトリエン酸。2-cyano-7-(p-propylphenyl)-2゜4,
6-heptatrienoic acid, 2-cyano-7-(p-butylphenyl)-2,4,6-heptatrienoic acid.
及びそれらのｍ−、ｏ−置換誘導体；
で表わされるフェニル置換 ２．４．６−へブタトリエ
ン酸誘導体、
３−く２−インドリル）−２−シアノプロペノン酸、３
−（３−インドリル）−２−シアノプロペノン酸、３−
（５−クロロ−３−インドリル）−２−シアノプロペノ
ン酸、２−シアノ−５−（２−インドリル＞ ２．４
−ペンタジェン酸、２−シアノ−５−（３−インドリル
）−２，４−ペンタジェン酸、２−シアノ−５−（５−
クロロ−３−インドリル）−２，４−ペンタジェン酸、
２−シアノ−７−（３−インドリル）−２，４，６−ヘ
ブタトリエン酸、２−シアノ−７−（２−インドリル）
−２，４，６−ヘプタトリエン酸、２−シアノ−７−（
５−クロロ−３−インドリル）−２，４，６−へブタト
リエン酸。and their m-, o-substituted derivatives; phenyl-substituted 2.4.6-hebutatrienoic acid derivatives, 3-2-indolyl)-2-cyanopropenoic acid, 3
-(3-indolyl)-2-cyanopropenoic acid, 3-
(5-chloro-3-indolyl)-2-cyanopropenoic acid, 2-cyano-5-(2-indolyl>2.4
-pentadienoic acid, 2-cyano-5-(3-indolyl)-2,4-pentadienoic acid, 2-cyano-5-(5-
chloro-3-indolyl)-2,4-pentadienoic acid,
2-cyano-7-(3-indolyl)-2,4,6-hebutatrienoic acid, 2-cyano-7-(2-indolyl)
-2,4,6-heptatrienoic acid, 2-cyano-7-(
5-chloro-3-indolyl)-2,4,6-hebutatrienoic acid.
一方、−最大（２）において、好ましい例示化合物とし
ては、３−（３−インドリル）−α−シアノプロペノン
酸、３−（２−インドリル）−α〜シアノプロペノン酸
、５−（３−インドリル）−α−シアノペンタジェン酸
−１，３、５−（２−インドリル〉〜α−シアノペンタ
ジェン酸−１，３゜あるいはインドール環の４位、５位
、７位の位置にニトロ基を置換した上記カルボン酸、メ
トキシ基、エトキシ基を置換した上記カルボン酸、メチ
ルチオエーテル基を置換した上記カルボン酸、４位にア
セチルオキシ基を置換したカルボン酸類を好ましく挙げ
ることができる。On the other hand, in maximum (2), preferred exemplary compounds include 3-(3-indolyl)-α-cyanopropenoic acid, 3-(2-indolyl)-α-cyanopropenoic acid, 5-(3-indolyl)-α-cyanopropenoic acid, indolyl)-α-cyanopentadienoic acid-1,3,5-(2-indolyl> to α-cyanopentadienoic acid-1,3° or a nitro group at the 4-, 5-, and 7-positions of the indole ring Preferred examples include the above-mentioned carboxylic acids substituted with a methoxy group, the above-mentioned carboxylic acids substituted with an ethoxy group, the above-mentioned carboxylic acids substituted with a methylthioether group, and carboxylic acids substituted with an acetyloxy group at the 4-position.
本発明の固溶体は、−最大（１）のシアノカルボン酸系
芳香族誘導体と一般式（２）のインドール環を含むシア
ノカルボン酸類とが、モル比で１：１０〜１０：１の割
合で混合したものから好ましく形成される。固溶体の形
成は溶融物、固相あるいは適当な溶媒のなかでの混合に
より実施しうる。かかる溶媒としては、エタノール、メ
タノール等のアルコール類、ジオキサン、テトラハイド
ロフラン等の環状エーテル類を好ましく挙げることがで
きる。また、溶融からコンブレタスを形成する方法が、
操作性の観点からより好ましいが、化合物の安定性の観
点から、余り高温で行うのは好ましくなく、作成する構
成する化合物の低い方の変化温度−融点付近に設定する
ことが、操作性からも安定性からも望ましい。The solid solution of the present invention includes: - a cyanocarboxylic acid aromatic derivative of maximum (1) and a cyanocarboxylic acid containing an indole ring of general formula (2) are mixed at a molar ratio of 1:10 to 10:1; It is preferably formed from Formation of the solid solution can be carried out by mixing in the melt, solid phase or in a suitable solvent. Preferred examples of such solvents include alcohols such as ethanol and methanol, and cyclic ethers such as dioxane and tetrahydrofuran. Also, the method of forming combretas from melting is
It is more preferable from the viewpoint of operability, but from the viewpoint of stability of the compound, it is not preferable to carry out the process at too high a temperature, and from the viewpoint of operability, it is preferable to set the temperature near the lower change temperature - melting point of the constituent compound to be created. It is also desirable from the standpoint of stability.
かくして得られたシアノカルボン酸系化合物とインドー
ル環を含む化合物との固溶体は、結晶の形態をとり、成
形性に優れ各種素子に賦形することが可能であり、非線
形光学応用分野に適用することができる。The thus obtained solid solution of a cyanocarboxylic acid compound and a compound containing an indole ring takes the form of a crystal, has excellent moldability, and can be shaped into various devices, and can be applied to nonlinear optics applications. I can do it.
「実施例］ 以下に実施例を用いて、本発明を更に詳しく説明する。"Example] The present invention will be explained in more detail below using Examples.
なお、実施例中％は特に断らない限り重量基準である。Note that the percentages in the examples are based on weight unless otherwise specified.
また、実施例中第２高調波の発生の測定は、次のように
行った。すなわち、ニス・ケー・クルゾ（Ｓ、 Ｋ、
Ｋｒｕｔｚ）等によるジャーナル・オブ・アプライド・
フイジクス（Ｊ、 Ａｐｐｌ。Furthermore, in the examples, the generation of second harmonics was measured as follows. That is, Nis K. Kurzo (S, K,
Journal of Applied Research by Krutz et al.
Physics (J, Appl.
Ｐｈｙｓ、 １３９巻３７９８ページ＜ １９６８年）
中に記載されている方法に準拠して、本発明の粉末に対
して行つた。入射光源として、Ｎｄ：ＹＡＧレーザ（２
ＫＷ、／２Ｈｚパルス）の１．０６μの光線を使用、ガ
ラスセル中に充填した粉末サンプルに照射し、発生した
緑色光を検知することにより行った。Phys, Volume 139, Page 3798 < 1968)
was carried out on the powder of the invention according to the method described in . Nd:YAG laser (2
This was done by irradiating a powder sample filled in a glass cell with a 1.06μ light beam (KW, /2Hz pulse) and detecting the green light generated.
実施例１ 固溶体の形成方法（Ａ）
３−（３−インドリル）−α−シアノプロペノンＭｔ１
２．Ｏｇと５−フェニル−２−シアノペンタジェン酸２
．０ｇを室温でよく混合し、窒素気流下１６０°Ｃにて
２０分靜装した。混合系は一旦液状に変化し、室温に冷
却することで固化し、結晶の形成が観測された。この状
態で粉砕し、第２高調波の発生の測定を行ったところ、
Ｎｄ−ＹＡＧレーザの第２高調波に該当する緑色の発光
が観測され、その強度は尿素の約８倍程度であった。Example 1 Method for forming solid solution (A) 3-(3-indolyl)-α-cyanopropenone Mt1
2. Og and 5-phenyl-2-cyanopentadienoic acid 2
．． 0g were mixed well at room temperature, and kept under a nitrogen stream at 160°C for 20 minutes. The mixed system once changed to a liquid state, solidified by cooling to room temperature, and the formation of crystals was observed. When we crushed it in this state and measured the generation of second harmonics, we found that
Green light emission corresponding to the second harmonic of the Nd-YAG laser was observed, and its intensity was about eight times that of urea.
実施例２ 固溶体の形成方法（Ｂ）
３−（３−インドリル）−α−シアノプロペノン酸２．
０ｇと５−（４−ジメチルアミノフェニル）ペンタジェ
ン酸２．０ｇとを室温でよく混合し、２０ｍ１のエタノ
ールを加えて、湯浴にて加熱冷却を行い針状結晶を得た
。この結晶を乳鉢でよく粉砕して、第２高調波の発生能
を測定したところ、緑色の発光が認められた。Example 2 Method for forming solid solution (B) 3-(3-indolyl)-α-cyanopropenoic acid2.
0 g and 2.0 g of 5-(4-dimethylaminophenyl)pentadienoic acid were thoroughly mixed at room temperature, 20 ml of ethanol was added, and the mixture was heated and cooled in a hot water bath to obtain needle-shaped crystals. When this crystal was thoroughly crushed in a mortar and the ability to generate second harmonics was measured, green light emission was observed.
実施例３〜６
実施例１の形成方法（Ａｌまたは実施例２の形成方法（
Ｂ）で第１表に示すインドール誘導体（１１と芳香族誘
導体（２）との固溶体を作成し、その第２高調波（ＳＨ
Ｇ）発生能を調べた。Examples 3 to 6 Formation method of Example 1 (Al or formation method of Example 2)
In B), a solid solution of the indole derivative (11) shown in Table 1 and the aromatic derivative (2) was prepared, and its second harmonic (SH
G) The developmental potential was investigated.
［発明の効果］
本発明のインドリルカルボン酸化合物と芳香族系からな
る反転対称性のない結晶化合物は、非線形効果が大きい
ので、光データ処理、情報通信または光通信システムに
おいて用いられる光スィッチあるいは光演算処理に用い
られる光双安定素子。[Effects of the Invention] The non-inversion-symmetry crystalline compound of the present invention, which is composed of an indolylcarboxylic acid compound and an aromatic system, has a large nonlinear effect, so it can be used in optical switches or optical switches used in optical data processing, information communication, or optical communication systems. Optical bistable device used for optical calculation processing.
光スィッチなどの素子として広く利用することができる
。It can be widely used as an element such as an optical switch.
Claims (1)
〜１４の芳香族基を表わす。Ｘ、Ｙは、Ｒ＿１−Ｏ−で
表わされるエーテル基、Ｒ＿２Ｒ＿３Ｎ−で表わされる
アミノ基、Ｒ＿４−Ｓ−で表わされるチオエーテル基、
ニトリル基、ニトロ基、−ＣＯＯＲ＿５、−ＯＣＯＲ＿
６で表わされるエステル基、−ＣＯＮＲ＿７Ｒ＿８、−
ＮＲ＿９ＣＯＲ＿１＿０で表わされるアミド基、−Ｒ＿
１＿１で表わされる炭化水素基（Ｒ＿１〜Ｒ＿１＿１は
、同一または異なる炭素数１〜８の炭化水素基、または
水素原子を表わす）から選ばれる官能基で、同じでも異
なっていてもよい。］で表わされるカルボン酸と 下記一般式（２） ▲数式、化学式、表等があります▼・・・（２） ［但し、式中Ｉｎｄはインドール残基を表わし、Ｒ＿５
＿０はＲ＿５＿１Ｒ＿５＿２Ｎ−で表わされるアミノ基
；Ｒ＿５＿３−Ｏ−で表わされるアルコキシ基；Ｒ＿５
＿４−Ｓ−で表わされるアルキルチオ基；シアノ基；ニ
トロ基；−ＣＯＯＲ＿５＿５もしくは−ＯＣＯＲ＿５＿
６で表わされるエステル基；−ＣＯＮＲ＿５＿７Ｒ＿５
＿８もしくは−Ｎ（Ｒ＿５＿９）ＣＯＲ＿６＿０で表わ
されるアミド基；Ｒ＿６＿１で表わされる炭化水素基ま
たは水素原子；（ここで、Ｒ＿５＿１〜Ｒ＿６＿１は同
一または異なる炭素数１〜８の炭化水素基を表わす）を
示し、ｎは０〜２の整数を示す。］ で表わされるインドール環を含むカルボン酸との固溶体
からなることを特徴とする非線形光学材料。[Claims] 1. The following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) [However, n represents 0, 1 or 2. Ar has 5 carbon atoms
~14 aromatic groups. X and Y are an ether group represented by R_1-O-, an amino group represented by R_2R_3N-, a thioether group represented by R_4-S-,
Nitrile group, nitro group, -COOR_5, -OCOR_
Ester group represented by 6, -CONR_7R_8, -
Amide group represented by NR_9COR_1_0, -R_
A functional group selected from the hydrocarbon groups represented by R_1_1 (R_1 to R_1_1 represent the same or different hydrocarbon groups having 1 to 8 carbon atoms, or hydrogen atoms), and may be the same or different. ] and the following general formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) [However, In the formula, Ind represents an indole residue, and R_5
_0 is an amino group represented by R_5_1R_5_2N-; an alkoxy group represented by R_5_3-O-; R_5
Alkylthio group represented by _4-S-; cyano group; nitro group; -COOR_5_5 or -OCOR_5_
Ester group represented by 6; -CONR_5_7R_5
An amide group represented by _8 or -N(R_5_9)COR_6_0; a hydrocarbon group or hydrogen atom represented by R_6_1; (where R_5_1 to R_6_1 represent the same or different hydrocarbon groups having 1 to 8 carbon atoms); , n represents an integer of 0 to 2. ] A nonlinear optical material comprising a solid solution with a carboxylic acid containing an indole ring represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32541390A JPH04198924A (en) | 1990-11-29 | 1990-11-29 | Nonlinear optical material having aromatic conjugate group |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32541390A JPH04198924A (en) | 1990-11-29 | 1990-11-29 | Nonlinear optical material having aromatic conjugate group |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04198924A true JPH04198924A (en) | 1992-07-20 |
Family
ID=18176569
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32541390A Pending JPH04198924A (en) | 1990-11-29 | 1990-11-29 | Nonlinear optical material having aromatic conjugate group |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04198924A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6800659B2 (en) | 2000-04-13 | 2004-10-05 | Hsc Research And Development Limited Partnership | Compounds for modulating cell proliferation |
| US7598419B2 (en) | 2004-03-26 | 2009-10-06 | Hsc Research And Development Limited Partnership | Compounds for modulating cell proliferation |
-
1990
- 1990-11-29 JP JP32541390A patent/JPH04198924A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6800659B2 (en) | 2000-04-13 | 2004-10-05 | Hsc Research And Development Limited Partnership | Compounds for modulating cell proliferation |
| US7012095B2 (en) | 2000-04-13 | 2006-03-14 | Hsc Research And Development Limited | Compounds for modulating cell proliferation |
| US7598419B2 (en) | 2004-03-26 | 2009-10-06 | Hsc Research And Development Limited Partnership | Compounds for modulating cell proliferation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH04198924A (en) | Nonlinear optical material having aromatic conjugate group | |
| EP0384364B1 (en) | A composition of nonlinear optical materials and a method for preparing the same | |
| JPH0496026A (en) | Nonlinear optical material | |
| US5312565A (en) | Nonlinear optical materials | |
| JPH0436731A (en) | Novel aromatic nonlinear optical material | |
| JPH03259126A (en) | Novel aromatic nonlinear optical material | |
| JPH0273236A (en) | Organic material exhibiting nonlinear optical effect | |
| JPH03282429A (en) | Nonlinear optical material consisting of conjugation group | |
| JPH03188425A (en) | Organic nonlinear optical element | |
| JPH0490517A (en) | Nonlinear optical material having conjugated chain | |
| JPH03230127A (en) | Aromatic nonlinear optical material | |
| JPS6321627A (en) | Deuterium substituted organic nonlinear optical compound | |
| JPH0277025A (en) | Organic material having nonlinear optical effect | |
| JPH0432822A (en) | Nonlinear optical material containing aromatic ring | |
| JPH01245230A (en) | Nonlinear optical material consisting of organic salt | |
| JPH02135427A (en) | Nonlinear optical material consisting of conjugated organic amine salt | |
| JPH0273237A (en) | Organic material exhibiting nonlinear optical effect | |
| JPH03266819A (en) | Nonlinear optical material | |
| JPH0274931A (en) | Organic material which exhibits nonlinear optical effect | |
| JP2545646B2 (en) | Non-linear optical material | |
| JP2539850B2 (en) | Nonlinear optical material and nonlinear optical element using the same | |
| Davey | The design and synthesis of high temperature chromophores for use in nonlinear optics and their incorporation into high thermal stability polyimides | |
| JPH02134623A (en) | Nonlinear optical material consisting of amine salt of heterocyclic conjugated organic compound | |
| JPH049828A (en) | Nonlinear optical material consisting of aromatic molecular composite | |
| JP2005070481A (en) | Compound, nonlinear optical material and electrooptic material |