WO1995024409A1 - Compose de spiropyrane - Google Patents
Compose de spiropyrane Download PDFInfo
- Publication number
- WO1995024409A1 WO1995024409A1 PCT/JP1995/000396 JP9500396W WO9524409A1 WO 1995024409 A1 WO1995024409 A1 WO 1995024409A1 JP 9500396 W JP9500396 W JP 9500396W WO 9524409 A1 WO9524409 A1 WO 9524409A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- atom
- compound
- hydrogen atom
- dimethylamino
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 73
- -1 acryloxyethyl Chemical group 0.000 claims abstract description 44
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 24
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 14
- 150000003839 salts Chemical group 0.000 claims abstract description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 9
- 229910052717 sulfur Chemical group 0.000 claims abstract description 6
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 125000003277 amino group Chemical group 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 14
- 150000007513 acids Chemical class 0.000 claims description 13
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 12
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 4
- 230000011987 methylation Effects 0.000 claims description 4
- 238000007069 methylation reaction Methods 0.000 claims description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract 4
- 239000001257 hydrogen Substances 0.000 abstract 4
- 150000002431 hydrogen Chemical class 0.000 abstract 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 239000011593 sulfur Chemical group 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 63
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 31
- 239000007787 solid Substances 0.000 description 29
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 150000001336 alkenes Chemical class 0.000 description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 17
- 230000003287 optical effect Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- PCVYGMFTRVWQMZ-UHFFFAOYSA-N 6-nitrospiro[1,2-dihydroindole-3,1'-cyclopropane] Chemical compound C=1C([N+](=O)[O-])=CC=C2C=1NCC21CC1 PCVYGMFTRVWQMZ-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 125000003003 spiro group Chemical group 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- BZYXYGLNJWVQPG-UHFFFAOYSA-N 1,2-benzoselenazole Chemical class C1=CC=C2C=N[se]C2=C1 BZYXYGLNJWVQPG-UHFFFAOYSA-N 0.000 description 2
- IRVKEZAFAHACEJ-UHFFFAOYSA-N 2,5-dimethyl-1,3-benzoselenazol-6-amine Chemical compound CC1=C(N)C=C2[se]C(C)=NC2=C1 IRVKEZAFAHACEJ-UHFFFAOYSA-N 0.000 description 2
- HZGFZMGOLYMNGC-UHFFFAOYSA-N 2,5-dimethyl-1,3-benzoselenazole Chemical compound CC1=CC=C2[se]C(C)=NC2=C1 HZGFZMGOLYMNGC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000003935 benzaldehydes Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- VFLAUDBIPMBMJP-UHFFFAOYSA-N n,n,2,5-tetramethyl-1,3-benzoselenazol-6-amine Chemical compound C1=C(C)C(N(C)C)=CC2=C1N=C(C)[se]2 VFLAUDBIPMBMJP-UHFFFAOYSA-N 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 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
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBMXCNPQDUJNHT-UHFFFAOYSA-N 1,6-dimethylnaphthalene Chemical compound CC1=CC=CC2=CC(C)=CC=C21 CBMXCNPQDUJNHT-UHFFFAOYSA-N 0.000 description 1
- ZENKESXKWBIZCV-UHFFFAOYSA-N 2,2,4,4-tetrafluoro-1,3-benzodioxin-6-amine Chemical group O1C(F)(F)OC(F)(F)C2=CC(N)=CC=C21 ZENKESXKWBIZCV-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 description 1
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- YIWQSZDZHGDUHA-QXMHVHEDSA-N C(=O)(C=C)C(C(=O)N)CCCCCC\C=C/CCCCCCCC Chemical compound C(=O)(C=C)C(C(=O)N)CCCCCC\C=C/CCCCCCCC YIWQSZDZHGDUHA-QXMHVHEDSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XJUZRXYOEPSWMB-UHFFFAOYSA-N Chloromethyl methyl ether Chemical compound COCCl XJUZRXYOEPSWMB-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- YGLMVCVJLXREAK-UHFFFAOYSA-N Noruron Chemical compound C12CCCC2C2CC(NC(=O)N(C)C)C1C2 YGLMVCVJLXREAK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-N Salicylic acid Natural products OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- JOYKCMAPFCSKNO-UHFFFAOYSA-N chloro benzenesulfonate Chemical compound ClOS(=O)(=O)C1=CC=CC=C1 JOYKCMAPFCSKNO-UHFFFAOYSA-N 0.000 description 1
- 229940061627 chloromethyl methyl ether Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- FKSLYSSVKFYJKE-UHFFFAOYSA-N n,n-diethylethanamine;methanol Chemical compound OC.CCN(CC)CC FKSLYSSVKFYJKE-UHFFFAOYSA-N 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002102 polyvinyl toluene Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- BEOOHQFXGBMRKU-UHFFFAOYSA-N sodium cyanoborohydride Chemical compound [Na+].[B-]C#N BEOOHQFXGBMRKU-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 1
- JYCDILBEUUCCQD-UHFFFAOYSA-N sodium;2-methylpropan-1-olate Chemical compound [Na+].CC(C)C[O-] JYCDILBEUUCCQD-UHFFFAOYSA-N 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- KXYMISZTQSOSTJ-UHFFFAOYSA-N spiro[indole-3,2'-pyran] Chemical class O1C=CC=CC11C2=CC=CC=C2N=C1 KXYMISZTQSOSTJ-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910052722 tritium Inorganic materials 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D517/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms
- C07D517/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having selenium, tellurium, or halogen atoms as ring hetero atoms in which the condensed system contains two hetero rings
- C07D517/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
Definitions
- the present invention relates to a spiropyran compound exhibiting reverse photomism.
- Photomism is a phenomenon in which light reversibly changes between two states having different absorption spectra by light, and is a typical organic compound showing this phenomenon.
- Pyropyran derivatives are best known. Specific examples and physical properties of such derivatives are described in, for example, "Photochromism” by Brown (G. H. Brown).
- Benzoselenazoline spiropyran compounds are known as typical compounds exhibiting a quenching mist. These are disclosed in Japanese Patent Application Laid-Open No. Hei 2-78686, Japanese Patent Application Laid-Open No. Hei 2-289587, Japanese Patent Publication No. Hei 3-813072, and the like. However, the maximum absorption wavelengths of these known compounds are all in the range of 500 to 600 nm, and are highly sensitive to visible light or laser light in the range of 400 to 500 ⁇ . The compound has not yet been found.
- photochromic compound a compound exhibiting photochromism
- an optical material such as an optical information recording medium or an optical filter.
- photochromic compounds have a maximum absorption wavelength of 500 nm or more as described above, and high density recording is required.
- SHG material the second high-frequency generation material
- S econd—Harmonic Generation the photochromic Compounds that are sensitive (or responsive) to light in the shorter wavelength region are also required.
- An object of the present invention is to provide a compound having a maximum absorption wavelength in the range of 400 to 500 nm and exhibiting high sensitivity to light in this wavelength range.
- the compound of the present invention is a novel compound not described in the literature, It is a salt of a benzoselenazoline-based spiropyran compound represented by the following general formula (1) (hereinafter, simply referred to as “spiropyran compound (1)”) and an acidic compound.
- R 1 represents an alkyl group having 1 to 2 ° carbon atoms, an aralkyl group, a hydroquinethyl group, an acryloxystyl group, or a methacryloquinethyl group.
- R 2 and R 4 are the same or different and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a cyano group, It represents a chloromethyl group, a trifluoromethyl group or a nitro group.
- R 3 and R 5 are the same or different, and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, an alkoxy group having 1 to 5 carbon atoms, a halogen atom, a cyano group, a tri group. It represents a chloromethyl group, a trifluoromethyl group, a nitro group, an amino group, a dimethylamino group or a getylamino group.
- R 6 and R 7 are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group, an aralkyl group, a nitrogen atom, a cyano group or a nitro group.
- R 8 is hydrogen Atom, vinyl group, group CH 2 OR 9 or group
- R 9 is water atom or an alkyl group having a carbon number of 1 ⁇ 4
- R 1 Q is hydrogen atoms Komata shows the methylation group.
- X represents an oxygen atom or a sulfur atom.
- the alkyl group having 1 to 20 carbon atoms represented by R 1 is a linear or branched alkyl group having 1 to 20 carbon atoms.
- Examples of the aralkyl groups represented by R 1 to R 7 include, for example, benzyl, 1-phenyl, 2-phenylene 3-, phenylpropyl, 4-phenylbutyl and the like.
- the phenylalkyl group may be a straight-chain or branched-chain alkyl having 1 to 4 carbon atoms, and the straight-chain or branched-chain alkyl having 1 to 4 carbon atoms may be mentioned on the phenyl ring.
- One or more of an alkyl group, a linear or branched alkoxy group having about 1 to 4 carbon atoms, a halogen atom such as chlorine, bromine and iodine, and a nitro group may be substituted.
- An alkyl group having 1 to 6 carbon atoms represented by R 2 to R 7 For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec_butyl, tert-butynole, n-pentynole, n-hexyl And straight-chain or branched-chain alkyl groups.
- Examples of the aryl group represented by R 2 to R 7 include a phenyl group and a naphthyl group, and a phenyl group is preferable. Further, on the aromatic ring of these groups, a linear or branched alkyl group having about 1 to 4 carbon atoms, a linear or branched alkoxy group having about 1 to 4 carbon atoms, chlorine, bromine, iodine One or more halogen atoms, such as a nitrogen group, etc., may be substituted.
- halogen atom represented by R 2 to R 7 examples include, for example, chlorine, bromine, iodine and the like.
- Examples of the alkyl group having 1 to 4 carbon atoms represented by R 9 include a methyl group, an ethyl group, an n-propyl group, and an iso group. Examples thereof include a linear or branched alkyl group such as a monopropyl group, an n-butyl group, a sec-butynole group, and a tert-butyl group.
- the salt of the spiropyran compound (1) with an acidic compound of the present invention (hereinafter simply referred to as “spiropyran compound salt”) has a maximum absorption wavelength in the range of 400 to 500 nm, and this wavelength region It exhibits high sensitivity to light of the same type and can be a desired photochromic compound.
- the spiropyran compound salt of the present invention usually develops a color, and rapidly loses its color by irradiation with visible light, and returns to its original colored state by irradiation with ultraviolet light or heat, so-called reverse photochromism. Show. This cycle of reverse photochromism is stably repeated and reproduced in various organic solvents and resins.
- the spiropyran compound salt of the present invention is based on the above-mentioned properties, and for example, includes a high-density optical recording material, a recording / reading element, an optical filter, an optical switch, a pH sensor, a gas sensor, It can be used as a raw material for various optical materials such as image forming materials, photosensitive materials, and nonlinear optical elements, and is expected to be used in fields such as the conversion of light energy to mechanical energy. Although not an optical material, it can also be used for decorative materials.
- spiropyran compound salt of the present invention Light sources combining semiconductor lasers and SHG materials, which could not be used because conventional compounds were insensitive, such as mercury lamps (405, 436 nm), Ar lasers
- R 1 is a methyl group, an ethyl group, an n-propyl group, an n-octadecyl group, a hydroxyxyl group, or a methyloxyl group.
- R 2 is a hydrogen atom
- R 3 is a hydrogen atom, methylation group, main butoxy group, two collected by filtration group, A Mi amino group, dimethyl Chirua Mi amino group or Jechirua Mi amino group
- R 4 is a hydrogen atom, menu butyl group or main Bok alkoxy group
- R 5 is a hydrogen atom, two collected by filtration group, ⁇ Mi amino group, dimethyl Chirua Mi amino group or Jechirua Mi amino group
- R 6 and R 7 are hydrogen atoms
- R 8 is a hydrogen atom, A salt of a vinyl group, a hydroxymethyl group or a methyroquinine methyl group, a spiropyran compound (1) in which X is an oxygen atom or a sulfur atom, and an acid compound are preferred.
- the spiropyran compound salt of the present invention is produced according to a known method, for example, by allowing an acid compound to act on the spiropyran compound (1).
- an acid compound to act on the spiropyran compound (1).
- the substituent on the aromatic ring When a spiropyran compound having an amino group (1) is used as a starting material, a salt with an acidic compound can be produced more easily.
- any acidic compound that can cause a neutralization reaction with the spiropyran compound (1) which can be regarded as an organic base
- Known ones can be widely used, and examples thereof include protonic acid and Lewis acid.
- protonic acid can be preferably used.
- a wide variety of known protic acids can be used, for example, hydrochloric acid, sulfuric acid, perchloric acid, benzenesnolefonic acid, toluenesnolefonic acid, chlorobenzenesulfonate, and sulfonate ion exchange resins.
- hydrochloric acid, sulfuric acid, toluene sulfonic acid and the like can be particularly preferably used.
- Such an acidic compound may be used in a large excess with respect to the spiropyran compound (1), but may be used as a nitrogen atom on the serenazole ring in the spiropyran compound (1) and a substituent.
- the amino group (n, where n is an integer of 0 to 2) is involved in the neutralization reaction, the amino group is usually 0.01 to 1 mol per mol of the spiropyran compound (1). It is preferable to use about (n + 5) equivalent, preferably about 0.1 to (n + 1) equivalent.
- An acidic compound is allowed to act on the spiropyran compound (1).
- the reaction can be performed without a solvent, but is preferably performed in the presence of a solvent.
- the solvent used here is not particularly limited, but for example, lower alcohols such as methanol, ethanol, propanol, etc., and tetrahydrofuran Such as ethers such as benzene, dioxane, and dimethoxetane, halogenated hydrocarbons such as dichloromethane and cross-linked form, dimethylformamide, dimethylsulfoxide and the like, and a mixed solvent thereof. be able to.
- the amount of the spiropyran compound (1) to be dissolved in these solvents is not particularly limited, but is usually about 0.1 to 30 g per 100 ml of the solvent, preferably 0.5 to 10 g. It may be about g.
- This salt-forming reaction can be carried out at the same temperature as a general salt-forming reaction, usually at any temperature from about 0 ° C. to about room temperature, but is preferably carried out at room temperature.
- the spiropyran compound salt of the present invention is formed instantaneously when the spiropyran compound (1) comes into contact with the acidic compound ( therefore, the solution formed in the solvent can be isolated without isolation). It can be used as it is, and when it is necessary to isolate it as a salt, the salt of the present invention can be extracted simply by distilling off the solvent used.
- the spiropyran compound salt of the present invention is obtained. I can do it.
- the spiropyran compound (1) which is the main raw material for obtaining the spiropyran compound salt of the present invention, itself has a maximum absorption wavelength in the wavelength range of usually 500 to 600 nm. It is a photochromic compound.
- spiropyran compound (1) is disclosed in, for example, Japanese Patent Application Laid-Open Nos. 2-78685, 2-289T87, and JP-A-3-813072. Etc. can be produced according to a known method.
- a benzoselenazolenium salt derivative represented by the general formula (2) and a 5-nitronitrosyl aldehyde derivative represented by the general formula (3) are represented by the following formula. It is easily produced by condensing with
- R 1 R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and X are as defined above.
- Y represents a halogen atom or a group R 11 S 0, —, and R 11 represents a halogen atom or a phenyl group which may have a —C 4 alkyl group as a substituent.
- examples of the halogen atom represented by Y include chlorine, bromine and iodine, and among them, iodine is preferable. Also based on Y
- R 11 S 03 When it is one, the same as the above can also be mentioned as the halogen atom represented by R 11 .
- Preferred examples of the group R 11 S 03 — include, for example, p-toluenesulfonate, p-chlorobenzenesulfonate and the like.
- a benzoselenazolenium salt derivative of the general formula (2) (hereinafter, referred to as “compound (2)”) and a 5-2-torosalicylic aldehyde derivative of the general formula (3) (hereinafter, referred to as “compound (3)”) Is generally carried out in the presence of an amine in a solvent.
- the ratio of the compound (2) to the compound (3) is not particularly limited, but the compound (2) may usually be used in an amount of about 0.9 to 1.1 mol per 1 mol of the compound (3).
- the pin known ones can be widely used.
- Lysine monorephosphorin, triethylenamine, pyridin, norethidin, 1,4-diazabinclo [2,2,2] octane, 1,5-diazabicyclo [ [4,3,0] nonane 5,1,8- diazavincro [5,4,0] ⁇ -decen- 17 and the like.
- the amount of such an amine can be appropriately selected from a wide range, but is usually about 1 to 10 times mol per 1 mol of compound (2).
- the solvent is not particularly limited as long as it can dissolve the compound (2) and the compound (3). Examples thereof include methanol, acetate, methylethylketone, ethylethyl acetate, and the like.
- Butyl acetate, dichloromethane, dimethylformamide and the like can be mentioned. This condensation reaction is carried out at a temperature ranging from room temperature to the boiling point of the solvent used, and is usually completed in about 1 to 24 hours.
- the spiropyran compound (1) thus obtained can be easily isolated and purified from the reaction mixture according to conventional separation and purification means.
- Particularly preferred compounds among the spiropyran compounds of the general formula (1) are the following compounds.
- the compound (2) which is a raw material for synthesizing the above spiropyrane compound (1), is a known compound.
- the compound (2) is preferably a 1-fold molar amount or more of the corresponding 2-methylphenylbenzoselenazole derivative. Or 1.05 to 1.5 times the molar amount of the general formula R 1 Y [wherein, and Y are as defined above.
- a solvent such as 6
- a commercially available product or a benzoselenazole derivative of a synthetic product may be used as it is, or may be used on the aromatic ring of the commercial product or the synthetic product. May be introduced.
- Introduction of a substituent can be performed according to a conventional method. For example, (a) nitration by the action of concentrated nitric acid, sodium nitrate, etc., (mouth) amination, (c) alkylation, (2) especially alkyl iodide, toluenesulfonic acid ester It can be carried out by appropriately combining known methods such as alkylation for reacting with an alkylating agent such as.
- R 6 R 7 and R 8 are the same as above.
- R 12 is a group
- R 9 and R 1 G are the same as above. ]
- the salicylic acid aldehyde derivative (3a) is reacted with chloromethyl methyl ether to obtain a 3-cyclomethylethyl-5-nitrosalicylic aldehyde derivative (4).
- M is a metal source Represents a hydrogen atom or a hydrogen atom.
- a 5-nitrosatyl aldehyde derivative (3b) in which X is an oxygen atom can be obtained.
- examples of the metal atom represented by M include an alkali metal, an alkaline earth metal, silver and the like.
- triphenylphosphine dimethyl derivative is obtained by reacting triphenylphosphine with a 3—chloromethyl aldehyde derivative (4) obtained by the above reaction formula-2.
- a base such as an alkali metal hydroxide.
- the compound (3) which is an R ° -hydroxymethyl group, can be obtained by converting the above 3—chloromethyl-5--2-torosalicylic aldehyde derivative (4) into silver nitrate or sodium bicarbonate in accordance with a conventional method. Is also produced by hydrolysis in the presence of
- the spiropyran compound salt of the present invention can be used as an optical material by mixing one or more of the salts with an appropriate matrix material such as a resin or an organic solvent.
- the matrix resin used at this time is not particularly limited as long as the salt of the present invention is uniformly dispersed.
- Specific examples of matrix resins include polymer Le acid, Po Li accession Li Le acid, Po Li meta click c ⁇ c 8 alkyl esters of Li Le acids or Po Li A click Li Le acid, Po Li accession Li Roni Application Benefits Le, Po Li accession Li Le acid A Mid, poly N, N — dimethyl acrylorea mid, vinyl polyacetate, polystyrene, poly 5 ⁇ — methyl styrene, polyvinyl toluene, polyvinyl alcohol, poly Vinyl butyral, Polyvinyl pyrrolidone, Polyvinyl chloride, Polyvinylidene chloride, Polycarbonate, Polyethylene oxide, Nylon, Polyurethane, Various types Polyrefin, ethylcellulose and the like can be mentioned.
- the compounding amount of the spirobilan compound salt of the present invention is not particularly limited and can be appropriately selected from a wide range. Usually, about 0.01 to 30% by weight of the total amount of the salt and the resin. Preferably, it should be about 0.1 to 15% by weight.
- various additives conventionally used in a composition for an optical material are added as long as the properties are not impaired. You can also.
- the resin composition containing a spirobilan compound salt of the present invention may be molded into a desired shape as it is, and may be made of, for example, metal, ceramics, plastic, paper, or the like. It may be coated on a suitable substrate such as a kind. Coating by Spinco It can be performed by various methods such as a coating method, a spray method, an immersion method, a flow coating method, and a bar coating method. A transparent protective film may be coated on the film made of the resin composition containing the spiropyran compound salt of the present invention.
- optical material containing the spiropyran compound salt of the present invention can be encapsulated according to a known method, or can be used by being enclosed in an appropriate container. This capsule can be used in admixture with resin or other matrix materials.
- those having a polymerizable group as a substituent can be prepared by homopolymerization or copolymerization with a comonomer copolymerizable therewith. It can be turned into a ma. Is a copolymerizable mono-mer, meta click Li Le acid, Accession Li Le acid, meta click of Li Le acids or accession Li Le acid (: ⁇ c 8 alkyl esters, Accession Li Roni Application Benefits Le , Acryloleic acid amide, N, N-dimethylacrylosoleamide, vinyl acetate, styrene, ⁇ -methylstyrene, vinyl toluene, etc. are preferably used.
- the polymer can also be applied to optical and mechanical elements.
- a compound which has a maximum absorption wavelength in the range of 400 to 500 nm and has high sensitivity to light in this wavelength region, and is very useful as an optical material.
- FIG. 1 is an ultraviolet-visible absorption spectrum of a compound obtained in Example 1 in a methanol solution.
- FIG. 2 is an ultraviolet-visible absorption spectrum of a compound obtained in Example 2 in a methanol solution.
- FIG. 3 is an ultraviolet-visible absorption spectrum in Example 4.
- FIG. 4 is an ultraviolet-visible absorption spectrum in Example 6.
- FIG. 5 and FIG. 6 are ultraviolet-visible absorption spectra in Example 10.
- FIG. 1 shows an ultraviolet-visible absorption spectrum of the obtained compound in a methanol solution.
- 6-dimethylamino 3,5—dimethyl-6,12 trospiro [benzoselenazoline 1, 2, 2, (2'H)-1 'benzopyran] 2.
- 71 g was suspended in a mixed solvent of 300 ml of black mouth form and 180 ml of methanol.
- To this suspension was added dropwise a 2% solution of nometanol hydrochloride (170 ml) to give a red solution.
- the solvent and excess hydrochloric acid were distilled off under reduced pressure, and the residue was thoroughly washed with getyl ether and dried to obtain brown solid 6-dimethylamino 3,5-dimethyl-6'-nitro.
- Los Spiro [Benzosé Lenazoline 2, 2 '(2' ⁇ ) -11'-benzopyran] • dihydrochloride 3.18 g was obtained (yield 100%).
- FIG. 2 shows an ultraviolet-visible absorption spectrum of the obtained compound in a methanol solution.
- 6-dimethylamino 2,3,51-methyl benzoselenazole in the dark and under nitrogen gas 0.30 g and 0.16 g of 3-hydroxymethyl-5-tol-2-ethyl aldehyde were suspended in 30 ml of dry methanol. After dropping 0.022 g of pyridin, the mixture was reacted at room temperature for 1 hour and then at 70 ° C. for 11 hours. After cooling, the precipitated solid was separated by filtration, washed with cold methanol and dried, and a dark red-brown solid, 8, -hydroxyquinethyl-6-dimethylamino 3,5-dimethyl was obtained. 0.27 g of 1,6,12-tropro [benzo-1,2,2,2, (2'H) -1 ', 1'-benzopyran] was obtained (80% yield).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95910785A EP0698608B1 (en) | 1994-03-11 | 1995-03-10 | Spiropyran compound |
US08/532,802 US5708181A (en) | 1994-03-11 | 1995-03-10 | Spiropyran compound |
DE69517886T DE69517886T2 (de) | 1994-03-11 | 1995-03-10 | Spiropyranverbindung |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6/40263 | 1994-03-11 | ||
JP4026394 | 1994-03-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995024409A1 true WO1995024409A1 (fr) | 1995-09-14 |
Family
ID=12575780
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1995/000396 WO1995024409A1 (fr) | 1994-03-11 | 1995-03-10 | Compose de spiropyrane |
Country Status (4)
Country | Link |
---|---|
US (1) | US5708181A (ja) |
EP (1) | EP0698608B1 (ja) |
DE (1) | DE69517886T2 (ja) |
WO (1) | WO1995024409A1 (ja) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7910022B2 (en) * | 2006-09-15 | 2011-03-22 | Performance Indicator, Llc | Phosphorescent compositions for identification |
JP2008524401A (ja) | 2004-12-20 | 2008-07-10 | パフォーマンス インディケーター エルエルシー | 高輝度、持続性のフォトルミネセンス配合物およびフォトルミネセンス品、ならびにその製造方法 |
US20070131949A1 (en) * | 2005-12-12 | 2007-06-14 | General Electric Company | Color tunable light-emitting devices and method of making the same |
US20070132371A1 (en) * | 2005-12-12 | 2007-06-14 | General Electric Company | Color tunable light-emitting devices and method of making the same |
US7547894B2 (en) | 2006-09-15 | 2009-06-16 | Performance Indicator, L.L.C. | Phosphorescent compositions and methods for identification using the same |
US7842128B2 (en) * | 2007-09-13 | 2010-11-30 | Performance Indicatior LLC | Tissue marking compositions |
US8039193B2 (en) * | 2007-09-13 | 2011-10-18 | Performance Indicator Llc | Tissue markings and methods for reversibly marking tissue employing the same |
US8722076B2 (en) | 2010-09-30 | 2014-05-13 | Surmodics, Inc. | Photochrome- or near IR dye-coupled polymeric matrices for medical articles |
JP5665187B2 (ja) * | 2011-02-08 | 2015-02-04 | 学校法人東京電機大学 | pH指示用共重合体、それを用いたpHモニタリング装置及びpH測定方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5215703A (en) * | 1975-07-29 | 1977-02-05 | Fuji Photo Film Co Ltd | Treatmenttfree lithographic press plate material |
JPH0278685A (ja) * | 1988-09-14 | 1990-03-19 | Mitsubishi Petrochem Co Ltd | フォトクロミック材料 |
JPH02289587A (ja) * | 1989-02-28 | 1990-11-29 | Otsuka Chem Co Ltd | ベンゾセレナゾリン系スピロピラン化合物 |
JPH02302754A (ja) * | 1989-05-18 | 1990-12-14 | Canon Inc | 光情報記録媒体 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0230024B1 (en) * | 1985-12-20 | 1991-11-21 | Matsushita Electric Industrial Co., Ltd. | Optical recording medium having a stabilized recording layer |
-
1995
- 1995-03-10 EP EP95910785A patent/EP0698608B1/en not_active Expired - Lifetime
- 1995-03-10 US US08/532,802 patent/US5708181A/en not_active Expired - Fee Related
- 1995-03-10 DE DE69517886T patent/DE69517886T2/de not_active Expired - Fee Related
- 1995-03-10 WO PCT/JP1995/000396 patent/WO1995024409A1/ja active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5215703A (en) * | 1975-07-29 | 1977-02-05 | Fuji Photo Film Co Ltd | Treatmenttfree lithographic press plate material |
JPH0278685A (ja) * | 1988-09-14 | 1990-03-19 | Mitsubishi Petrochem Co Ltd | フォトクロミック材料 |
JPH02289587A (ja) * | 1989-02-28 | 1990-11-29 | Otsuka Chem Co Ltd | ベンゾセレナゾリン系スピロピラン化合物 |
JPH02302754A (ja) * | 1989-05-18 | 1990-12-14 | Canon Inc | 光情報記録媒体 |
Non-Patent Citations (4)
Title |
---|
HIRNO, MASAFUMI, "Synthesis and Photochemical Properties of Novel Spirobenzoselenazolinobenzopyrans", Chem. Lett. 1991, Vol. 11, pages 1873-1876. * |
MIYASHITA, AKIRA, "Synthesis and Negative Potochromic Properties of Spirobenzoselenazolinobenzophyran", Chem. Express. 1993, Vol. 8, No. 2, pages 93-96. * |
NAKAO, SHINJI, "Metastable Solution Structures of Spirobenzoselenazolinobenzopyrans and their Negative Photochromic Properties", Chem. Lett. 1993, Vol. 1, pages 13-16. * |
See also references of EP0698608A4 * |
Also Published As
Publication number | Publication date |
---|---|
DE69517886T2 (de) | 2001-02-22 |
DE69517886D1 (en) | 2000-08-17 |
US5708181A (en) | 1998-01-13 |
EP0698608B1 (en) | 2000-07-12 |
EP0698608A4 (ja) | 1996-03-06 |
EP0698608A1 (en) | 1996-02-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5252742A (en) | Spiropyran compounds | |
JP3170613B2 (ja) | ベンゾセレナゾリン系ビニルスピロピラン化合物及該化合物を含む重合体 | |
EP0875509B1 (en) | Chromene compound | |
US5139707A (en) | Indolino-spiroquinoxalino oxazine photochromatic compounds, methods for their preparation, photochromic compositions and articles containing such compounds | |
US6019914A (en) | Photochromic spirooxazine compounds, their use in the field of ophthalmic optics | |
JP4301621B2 (ja) | クロメン化合物 | |
JP4256985B2 (ja) | クロメン化合物 | |
JPH0481996B2 (ja) | ||
JP2000256347A (ja) | クロメン化合物 | |
JP2000229974A (ja) | クロメン化合物 | |
JP2000219686A (ja) | クロメン化合物 | |
JP2001011066A (ja) | クロメン化合物 | |
JPH11279171A (ja) | クロメン化合物 | |
JP2000229973A (ja) | クロメン化合物 | |
JP2000344761A (ja) | クロメン化合物 | |
JP2000229975A (ja) | クロメン化合物 | |
JP2000229976A (ja) | クロメン化合物 | |
WO1995024409A1 (fr) | Compose de spiropyrane | |
EP0411157B1 (en) | Spiropyran compounds | |
JPH07300484A (ja) | スピロピラン化合物 | |
US5241027A (en) | Macromolecular spiropyran compounds | |
JPH07285931A (ja) | 新規化合物 | |
JPH0368034B2 (ja) | ||
KR101295435B1 (ko) | 신규한 페난트로파이란 유도체 및 이를 포함하는 광변색염료 | |
US5468874A (en) | Benzothiophene/indole-substituted maleimide derivatives, photochromic material comprising said derivatives and optical recording material using the same material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 08532802 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1995910785 Country of ref document: EP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWP | Wipo information: published in national office |
Ref document number: 1995910785 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 1995910785 Country of ref document: EP |