CN1247604A - 新型光致变色杂环稠合的茚并萘并吡喃 - Google Patents
新型光致变色杂环稠合的茚并萘并吡喃 Download PDFInfo
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- CN1247604A CN1247604A CN97181917A CN97181917A CN1247604A CN 1247604 A CN1247604 A CN 1247604A CN 97181917 A CN97181917 A CN 97181917A CN 97181917 A CN97181917 A CN 97181917A CN 1247604 A CN1247604 A CN 1247604A
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- Prior art keywords
- alkyl
- poly
- alkoxy
- monomer
- phenyl
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- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 36
- 150000001875 compounds Chemical class 0.000 claims abstract description 85
- 239000000463 material Substances 0.000 claims abstract description 74
- 239000000178 monomer Substances 0.000 claims description 86
- 239000002585 base Substances 0.000 claims description 70
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 40
- -1 spiro heterocyclic radical Chemical class 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 28
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 26
- 239000011737 fluorine Substances 0.000 claims description 26
- 229910052731 fluorine Inorganic materials 0.000 claims description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 24
- 239000000460 chlorine Substances 0.000 claims description 24
- 229910052801 chlorine Inorganic materials 0.000 claims description 24
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 19
- 150000004880 oxines Chemical class 0.000 claims description 19
- 239000000758 substrate Substances 0.000 claims description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- 229920000642 polymer Polymers 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 229920006395 saturated elastomer Polymers 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 13
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 12
- 150000002430 hydrocarbons Chemical group 0.000 claims description 12
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 11
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 11
- 238000007046 ethoxylation reaction Methods 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 125000001624 naphthyl group Chemical group 0.000 claims description 11
- 239000004814 polyurethane Substances 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 11
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 10
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052760 oxygen Chemical group 0.000 claims description 10
- 239000001301 oxygen Chemical group 0.000 claims description 10
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 10
- 229920001169 thermoplastic Polymers 0.000 claims description 10
- 239000004416 thermosoftening plastic Substances 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 9
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 9
- 239000011118 polyvinyl acetate Substances 0.000 claims description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 125000001544 thienyl group Chemical group 0.000 claims description 8
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical class CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 125000006559 (C1-C3) alkylamino group Chemical group 0.000 claims description 6
- 125000002733 (C1-C6) fluoroalkyl group Chemical group 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 4
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 229940081735 acetylcellulose Drugs 0.000 claims description 4
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 229920002301 cellulose acetate Polymers 0.000 claims description 4
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 4
- 125000004965 chloroalkyl group Chemical group 0.000 claims description 4
- QZHPTGXQGDFGEN-UHFFFAOYSA-N chromene Chemical compound C1=CC=C2C=C[CH]OC2=C1 QZHPTGXQGDFGEN-UHFFFAOYSA-N 0.000 claims description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 4
- 125000002541 furyl group Chemical group 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 claims description 3
- 229920008347 Cellulose acetate propionate Polymers 0.000 claims description 3
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 3
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 claims description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 3
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 3
- 229920005628 alkoxylated polyol Polymers 0.000 claims description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 3
- 238000010572 single replacement reaction Methods 0.000 claims description 3
- 229920000638 styrene acrylonitrile Polymers 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 2
- OVGIGWPHRGPBCJ-UHFFFAOYSA-N 2,3-dihydro-1H-indole 10H-phenoxazine Chemical compound C1=CC=CC=2OC3=CC=CC=C3NC12.N1CCC2=CC=CC=C12 OVGIGWPHRGPBCJ-UHFFFAOYSA-N 0.000 claims description 2
- FAQVDANXTSFXGA-UHFFFAOYSA-N 2,3-dihydro-1h-benzo[g]indole Chemical compound C1=CC=CC2=C(NCC3)C3=CC=C21 FAQVDANXTSFXGA-UHFFFAOYSA-N 0.000 claims description 2
- ITHGKFNFXCDUDC-UHFFFAOYSA-N 2,3-dihydro-1h-benzo[g]indole;2h-pyrido[2,3-h][1,2]benzoxazine Chemical compound C1=CC=CC2=C(NCC3)C3=CC=C21.C1=CC2=NC=CC=C2C2=C1C=CNO2 ITHGKFNFXCDUDC-UHFFFAOYSA-N 0.000 claims description 2
- RFPBBTGDNJHSRB-UHFFFAOYSA-N 2,3-dihydro-1h-indole;2h-pyrido[2,3-h][1,2]benzoxazine Chemical compound C1=CC=C2NCCC2=C1.C1=CC2=NC=CC=C2C2=C1C=CNO2 RFPBBTGDNJHSRB-UHFFFAOYSA-N 0.000 claims description 2
- ZLLLODBXLDFWER-UHFFFAOYSA-N 2h-chromene;2,3-dihydro-1h-indole Chemical compound C1=CC=C2NCCC2=C1.C1=CC=C2C=CCOC2=C1 ZLLLODBXLDFWER-UHFFFAOYSA-N 0.000 claims description 2
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical class C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 claims description 2
- JTSFIVQMXUDGAB-UHFFFAOYSA-N 4-thiomorpholin-4-ylmorpholine Chemical compound C1COCCN1N1CCSCC1 JTSFIVQMXUDGAB-UHFFFAOYSA-N 0.000 claims description 2
- UIYCIISWTDMWTR-UHFFFAOYSA-N C(C=C)(=O)OBrOC(C(=C)C)=O Chemical compound C(C=C)(=O)OBrOC(C(=C)C)=O UIYCIISWTDMWTR-UHFFFAOYSA-N 0.000 claims description 2
- BGKLNKCWSYLOEC-UHFFFAOYSA-N C1=CC=CC=2OC3=CC=CC=C3NC12.N1CCC2=CC=C3C(=C12)C=CC=C3 Chemical compound C1=CC=CC=2OC3=CC=CC=C3NC12.N1CCC2=CC=C3C(=C12)C=CC=C3 BGKLNKCWSYLOEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001246 bromo group Chemical group Br* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical group C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 150000002475 indoles Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- VFUGUWZYXGNQHR-UHFFFAOYSA-N 2h-1,2-benzoxazine;2,3-dihydro-1h-indole Chemical compound C1=CC=C2NCCC2=C1.C1=CC=C2C=CNOC2=C1 VFUGUWZYXGNQHR-UHFFFAOYSA-N 0.000 claims 1
- 125000004171 alkoxy aryl group Chemical group 0.000 claims 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims 1
- UEOGLANRPZAEAC-UHFFFAOYSA-N indeno-naphthopyran Chemical class O1C=CC=C2C3=C4C=C(C=CC=C5)C5=C4C=CC3=CC=C21 UEOGLANRPZAEAC-UHFFFAOYSA-N 0.000 abstract 2
- 238000006243 chemical reaction Methods 0.000 description 35
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
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- 230000003287 optical effect Effects 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
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- 238000012360 testing method Methods 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
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- UELVNOHMXFLFQI-UHFFFAOYSA-N 1-hydroxy-4-phenylnaphtho[2,1-b][1]benzofuran-3-carboxylic acid Chemical class OC(=O)C1=CC(O)=C2C(C3=CC=CC=C3O3)=C3C=CC2=C1C1=CC=CC=C1 UELVNOHMXFLFQI-UHFFFAOYSA-N 0.000 description 3
- AGZJRZQGLLTCGN-UHFFFAOYSA-N 6-oxapentacyclo[10.8.0.02,10.05,9.015,20]icosa-1(12),2,4,8,10,13,15,17,19-nonaene Chemical class C=1COC=2C=1C1=CC3=C(C1=CC=2)C=1C=CC=CC=1C=C3 AGZJRZQGLLTCGN-UHFFFAOYSA-N 0.000 description 3
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
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- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/23—Photochromic filters
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- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Pyrane Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Indole Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
本发明描述了新型的光致变色的杂环稠合的茚并萘并吡喃化合物,其含有取代或未取代的杂环,所述杂环与茚并萘并吡喃的g,h,i,n或p边稠合。这些化合物可用式(Ⅰ),(Ⅰ′)表示。本发明还描述了含有或涂有这些化合物的聚合有机基质材料。
Description
本发明涉及一些新型萘并吡喃化合物。特别是,本发明涉及新型光致变色杂环稠合茚并萘并吡喃化合物和含有这种新型茚并萘并吡喃化合物的组合物及制品。当暴露在含有紫外线的电磁辐射,例如阳光紫外照射或汞灯光线紫外照射下时,许多光致变色化合物可发生颜色的可逆变化。当停止紫外照射时,这些光致变色化合物又回到最初的颜色或无色状态。
人们已经合成了不同种类的光致变色化合物,并建议可用于需要阳光诱导的可逆颜色变化或变暗的领域。美国专利3,567,605(Becker)描述了一系列吡喃衍生物,其中包括某些苯并吡喃和萘并吡喃。这些化合物被描述为苯并吡喃的衍生物,可以发生颜色变化,例如,在温度低于约-30℃下用紫外光照射,可从无色变为橙黄色。据报道在用可见光照射该化合物或提高温度到大约0℃以上时,该化合物可逆变色为无色状态。
美国专利5,066,818描述了许多3,3-二芳基-3H-萘并[2,1-b]吡喃,其在眼科和其它应用领域具有期望的光致变色性能,即有高的呈色性和可接受的褪色性。在'818专利中通过对比实验公开了异构的2,2-二芳基-2H-萘并[1,2-b]吡喃,据报道其在激活后需太长时间才能褪色。
美国专利3,627,690描述了含有少量碱或弱至中等强度酸的光致变色的2,2-二取代-2H-萘并[1,2-b]吡喃组合物。据报道,萘并吡喃组合物中加入酸或碱都可以加快变色的萘并吡喃的褪色速率,因此使得它们可用在眼睛保护中,例如太阳镜。该专利还进一步报道了在不加入前述添加剂的情况下,2H-萘并[1,2-b]吡喃到达完全复原的褪色速率为几个小时到许多天。
美国专利4,818,096公开了紫/蓝色的光致变色苯并或萘并吡喃,此化合物在吡喃环的氧的α位具有苯基,而苯基在邻位或对位具有含氮取代基
本发明涉及新型的茚并萘并[1,2-b]吡喃化合物,它含有取代或未取代的杂环,该杂环的2,3或3,2位和茚并萘并吡喃的g,h,i,n,o或p边稠合,并且在吡喃环的3位具有特定取代基。意外发现,这些化合物的激活(显色)态在可见光区的最大吸收,即λmax(Vis)发生红移,从而产生范围为从橙色到蓝/灰色的激活颜色。
近年来,光致变色塑料,特别是用于光学领域的塑料引起了人们的广泛关注。特别是,研究了光致变色的眼用塑料透镜,因为它与玻璃透镜相比具有重量轻的优点。而且在交通工具如汽车和飞机上使用的光致变色透明材料引起了人们的兴趣,因为这种透明材料可以提供潜在的安全性。
根据本发明,现在已经发现可以制备某些新型的茚并[2,1-f]萘并[1,2-b]吡喃,其激活颜色范围为从橙色到蓝/灰色。这些化合物可描述为含有未取代、单或二取代杂环和在吡喃环的3位具有特定取代基的茚并萘并吡喃,所述杂环的2,3或3,2位和茚并萘并吡喃的g,h,i,n,o或p边稠合。所述化合物的5,6,7,8,9,10,11,12和13位碳原子上也可存在某些取代基。这些茚并萘并吡喃化合物可用下式I和I'表示,其中字母a到p为构成该化合物的各边,数字1到13为杂环稠合的茚并萘并吡喃环上原子的编号。在式I和I′中的取代基的定义中,除非另有指明,相同的符号代表同样的意思。
在式I和I'中,A可以为未取代、单取代或二取代杂环,所述杂环选自苯并噻吩并、苯并呋喃并和吲哚并,所述杂环的2,3或3,2位和茚并萘并吡喃的g,h,i,n,o或p边稠合。上述各杂环取代基可以为C1-C6烷基、C5-C7环烷基、C1-C6烷氧基、氯或氟。优选杂环A为未取代或单取代杂环,及杂环的取代基为C1-C4烷基或C1-C4烷氧基。最优选杂环A为未取代或单取代的杂环,该杂环在2,3或3,2位和茚并萘并吡喃的g或p边稠合,并且所述杂环的取代基为C1-C3烷基或C1-C3烷氧基。
在式I和I'中,R1和R2可以一起形成氧代基,具有2个氧原子和3到6个碳原子(包括螺碳原子在内)的螺杂环基,或者R1和R2可以各选自氢,羟基,C1-C6烷基,C3-C7环烷基,烯丙基,苯基,单取代苯基,苄基,单取代苄基,氯,氟,和-C(O)W基团,其中各W为羟基,C1-C6烷基,C1-C6烷氧基,苯基,单取代的苯基,氨基,单(C1-C6)烷氨基或二(C1-C6)烷氨基,或者R1和R2各自可为基团-OR5,其中各R5为C1-C6烷基,苯基(C1-C3)烷基,单(C1-C6)烷基取代的苯基(C1-C3)烷基,单(C1-C6)烷氧基取代的苯基(C1-C3)烷基,C1-C6烷氧基(C2-C4)烷基,C3-C7环烷基,单(C1-C4)烷基取代的C3-C7环烷基,C1-C6氯代烷基,C1-C6氟代烷基,烯丙基,基团-CH(R6)X,其中各R6为氢或C1-C3烷基,各X为-CN,-CF3或-COOR7,各R7为氢或C1-C3烷基,或者各R5为基团-C(O)Y,其中各Y为氢,C1-C6烷基,C1-C6烷氧基,未取代,单或二取代的芳基,苯基和萘基,苯氧基,单或二(C1-C6)烷基取代的苯氧基,单或二(C1-C6)烷氧基取代的苯氧基,氨基,单(C1-C6)烷氨基,二(C1-C6)烷氨基,苯氨基,单或二(C1-C6)烷基取代的苯氨基或者为单或二(C1-C6)烷氧基取代的苯氨基,上述每一个苯基、萘基和苄基取代基为C1-C6烷基或C1-C6烷氧基。
优选R1和R2各自选自氢,羟基,C1-C4烷基,C3-C6环烷基,氯,氟,和基团-OR5,其中各R5为C1-C3烷基,苯基(C1-C2)烷基,单(C1-C3)烷基取代的苯基(C1-C3)烷基,单(C1-C3)烷氧基取代的苯基(C1-C3)烷基,C1-C3烷氧基(C2-C4)烷基,C1-C3氯代烷基,C1-C3氟代烷基或基团-CH(R6)X,其中各R6为氢或C1-C2烷基,各X为-CN或-COOR7,而各R7为氢或C1-C2烷基,或者各R5为基团-C(O)Y,其中各Y为氢,C1-C3烷基,C1-C3烷氧基,苯基,萘基,单取代的芳基、苯基和萘基,苯氧基,单或二(C1-C3)烷基取代的苯氧基,单或二(C1-C3)烷氧基取代的苯氧基,单(C1-C3)烷氨基,苯氨基,单或二(C1-C3)烷基取代的苯氨基,或者为单或二(C1-C3)烷氧基取代的苯氨基,所述的各芳基取代基为C1-C3烷基或C1-C3烷氧基。最优选R1和R2各为氢,羟基,C1-C4烷基或基团-OR5,其中各R5为C1-C3烷基。
在式I和I'中,R3和R4可以各自为C1-C6烷基、C1-C6烷氧基、氯或氟,m和n各为整数0,1或2。优选R3和R4各自为C1-C4烷基、C1-C4烷氧基、氯或氟,且m和n各为整数0或1。最优选R3和R4各为C1-C3烷基或C1-C3烷氧基,并且m和n各为整数0或1。
式I和I'中的B和B'可各选自(i)未取代、单、二和三取代的芳基,苯基和萘基;(ii)未取代、单和二取代的芳杂环基吡啶基、呋喃基、苯并呋喃-2-基、苯并呋喃-3-基、噻吩基、苯并噻吩-2-基、苯并噻吩-3-基,二苯并呋喃基、二苯并噻吩基、咔唑基和芴基,在(i)和(ii)中所述的芳基和芳杂环基各自的取代基选自羟基、芳基、单(C1-C6)烷氧基芳基、二(C1-C6)烷氧基芳基、单(C1-C6)烷基芳基、二(C1-C6)烷基芳基、溴代芳基、氯代芳基、氟代芳基、C3-C7环烷基芳基、C3-C7环烷基、C3-C7环烷氧基、C3-C7环烷氧基(C1-C6)烷基、C3-C7环烷氧基(C1-C6)烷氧基、芳基(C1-C6)烷基、芳基(C1-C6)烷氧基、芳氧基、芳氧基(C1-C6)烷基、芳氧基(C1-C6)烷氧基、单-和二(C1-C6)烷基芳基(C1-C6)烷基、单-和二(C1-C6)烷氧基芳基(C1-C6)烷基、单-和二(C1-C6)烷基芳基(C1-C6)烷氧基、单-和二(C1-C6)烷氧基芳基(C1-C6)烷氧基、氨基、单(C1-C6)烷氨基、二(C1-C6)烷氨基、二芳基氨基、N-(C1-C6)烷基哌嗪-1-基(piperazino)、N-芳基哌嗪-1-基、氮丙啶-1-基(aziridino)、二氢吲哚-1-基(indolino)、哌啶子基、芳基哌啶子基、吗啉代、硫代吗啉代、四氢喹啉-1-基(tetrahydroquinolino)、四氢异喹啉-1-基(tetrahydroisoquinolino)、吡咯基、C1-C6烷基、C1-C6溴代烷基、C1-C6氯代烷基、C1-C6氟代烷基、C1-C6烷氧基、单(C1-C6)烷氧基(C1-C4)烷基、丙烯酰氧基、甲基丙烯酰氧基、溴、氯和氟;(iii)下式所示的基团:
其中E可以为碳或氧,D可以为氧或取代的氮,条件是当D为取代的氮时E为碳,所述的氮上的取代基选自氢、C1-C6烷基和C2-C6酰基;各R8为C1-C6烷基、C1-C6烷氧基、羟基、溴、氯或氟;R9和R10各为氢或C1-C6烷基;p为整数0,1或2;(iv)C1-C6烷基,C1-C6溴代烷基、C1-C6氯代烷基、C1-C6氟代烷基、C1-C6烷氧基(C1-C4)烷基、C3-C6环烷基、单(C1-C6)烷氧基(C3-C6)环烷基、单(C1-C6)烷基(C3-C6)环烷基、溴代(C3-C6)环烷基、氯代(C3-C6)环烷基和氟代(C3-C6)环烷基;和(v)下式所示基团:在式IIC中,X可以为氢或C1-C4烷基,Z可以选自未取代、单-和二取代的萘基、苯基、呋喃基和噻吩基,在(v)中所述各基团的取代基为C1-C4烷基、C1-C4烷氧基、溴、氟或氯;或(vi)B和B'一起形成芴-9-叉、单或二取代的芴-9-叉,或形成选自下列的基团:饱和的C3-C12螺-单环烃环、例如亚环丙基、亚环丁基、亚环戊基、亚环己基、亚环庚基、亚环辛基、亚环壬基、亚环癸基、亚环十一烷基和亚环十二烷基;饱和的C7-C12螺-二环烃环,例如,二环[2.2.1]庚叉,即亚降冰片基(norbornylidene),1,7,7-三甲基二环[2.2.1]庚叉,即亚冰片基(bornylidene)、二环[3.2.1]辛叉,二环[3.3.1]壬-9-叉和二环[4.3.2 ]十一烷和饱和C7-C12螺-三环烃环,例如三环[2.2.1.02,6]庚叉、三环[3.3.1.13,7]癸叉,即亚金刚烷基和三环[5.3.1.12,6]十二烷叉,所述各芴-9-叉的取代基选自C1-C4烷基,C1-C4烷氧基、溴、氟和氯。
更优选B和B'各选自(i)苯基、单取代苯基和二取代苯基,优选在间位和/或对位被取代;(ii)未取代、单和二取代的芳杂环基呋喃基、苯并呋喃-2-基、噻吩基、苯并噻吩-2-基、二苯并呋喃-2-基和二苯并噻吩-2-基,在(i)和(ii)中所述的苯基和芳杂环的取代基各选自羟基、芳基、芳氧基、芳基(C1-C3)烷基、氨基、单(C1-C3)烷基氨基、二(C1-C3)烷基氨基、N-(C1-C3)烷基哌嗪-1-基、二氢吲哚-1-基、哌啶子基、吗啉代、吡咯基、C1-C3烷基、C1-C3溴代烷基、C1-C3氯代烷基、C1-C3氟代烷基、C1-C3烷氧基、单(C1-C3)烷氧基(C1-C3)烷基、溴、氟和氯;(iii)式IIA和IIB所示的基团,其中E为碳,D为氧,R8为C1-C3烷基或C1-C3烷氧基,R9和R10各为氢或C1-C4烷基;p为整数0或1;(iv)C1-C4烷基,和(v)式IIC所示的基团,其中X为氢或甲基,Z为苯基或单取代苯基,所述的苯基取代基选自C1-C3烷基、C1-C3烷氧基和氟;或(vi)B和B'一起形成芴-9-叉、单取代的芴-9-叉,或选自下列的基团:饱和的C3-C8螺-单环烃环、饱和的C7-C10螺-二环烃环和饱和的C7-C10螺-三环烃环,所述的芴-9-叉取代基选自C1-C3烷基,C1-C3烷氧基、氟和氯。
最优选,B和B'各选自(i)苯基、单取代和二取代苯基;(ii)未取代、单和二取代的芳杂环基呋喃基、苯并呋喃-2-基、噻吩基和苯并噻吩-2-基,在(i)和(ii)中所述的苯基和芳杂环基的各取代基选自羟基、C1-C3烷基、C1-C3烷氧基、芳基、二氢吲哚-1-基、氟和氯;和(iii)式IIA所示的基团,其中E为碳,D为氧,R8为C1-C3烷基或C1-C3烷氧基,R9和R10各为氢或C1-C3烷基;p为整数0或1;或(iv))B和B'一起形成芴-9-叉、亚金刚烷基、亚冰片基、亚降冰片基或二环[3.3.1]壬-9-叉。
如前面所述的含有取代基R3和R4的式I和I'化合物可以通过下面所述的反应A到G制备。式V或VA化合物(分别见反应A和B)用傅氏反应(Friedel-Crafts)方法制备,如反应A所示:使合适取代的或未取代的苯甲酰氯(式IV)和可市购的取代或未取代的杂环化合物(式III)反应。参见出版物傅氏反应(Friedel-Crafts)及相关反应,George A.Olah,Interscience Publishers,1964,第3卷,第XXXI章(芳香酮的合成)和“1,2,3,4,-四氢喹啉和相关含氮杂环的区域选择性傅氏酰基化反应:对NH保护基和环大小的影响”,Ishihara,Yugi等,化学会志,Perkin Trans.1,第3401到3406页,1992年。
在反应A中,式III化合物(其中X为氧、氮或硫)和式IV化合物溶解在溶剂如二硫化碳或二氯甲烷中,在路易斯酸如三氯化铝或四氯化锡的存在下进行反应,形成相应的取代的二苯酮(式V)。
在反应B中,式VA所示的取代或未取代的酮与乙炔钠在合适的溶剂如无水四氢呋喃(THF)中反应,形成相应的式VI所示的的炔丙基醇。具有基团B或B'(除取代和未取代的苯基以外)的炔丙基醇可以用市购的酮或由酰基卤和取代或未取代的苯、萘或杂芳族化合物反应制备的酮制备。式IIC所示具有基团B或B'的炔丙基醇可以用美国专利5,274,132第二栏,第40到68行所述的方法制备。
在反应C中,式V所示的取代或未取代的酮与丁二酸的酯,例如式VII所示的丁二酸二甲酯反应。把反应物加入含有叔丁醇钾或氢化钠作为碱的溶剂如甲苯中,生成式VIII所示的Stobbe缩合的半酯。在乙酸酐存在下,半酯(VIII)环化脱水,生成式IXA和IXB所示的杂环稠合的乙酰氧基萘。通过结晶分离化合物IXA和IXB,在碱(例如氢氧化钠)的醇水溶液中水解,接着用盐酸水溶液(H+)处理,分别生成式XA或XB所示的羧基萘酚。反应C
在反应D中,式XA和XB所示的羧基萘酚在温度约为160到220℃条件下加热,在酸如磷酸存在下环化,生成式XIA和XIB所示的羟基取代的苯并稠合芴酮。参见F.G.Baddar等在化学会志,第986页(1958)中的文章。合成式XIB化合物的另外方法描述在“有机化学杂志”(J.Chem.Soc.),C.F.Koelsch,第26卷,第2590页(1961)中。
在催化量酸如十二烷基苯磺酸(DBSA)存在下,式XIA和XIB所示的化合物和式VI炔丙基醇偶联,生成式IA和IB所示的茚并稠合萘并吡喃。反应D
在反应E中,式XIA和XIB所示的化合物通过Wolff-Kishner还原反应生成结构式XIIA和XIIB所示的化合物,这些化合物与式VI所示的炔丙基醇偶联生成式IC和ID所示的茚并稠合萘并吡喃。在结构式IC和ID所示的茚并基团上示出的氢被烷基(例如R1和R2)取代可通过这些化合物与三烷基铝反应生成具有结构式IE和IF所示的化合物来实现。
与式IE和IF所示的化合物类似的化合物,其中R1和R2为烷氧基而不是烷基,或者R1和R2一起形成包含2个氧原子和3到6碳原子(包括螺碳原子在内的)的螺杂环基,可在催化量酸的存在下,通过式IA或IB化合物分别与醇或二醇反应来制备。反应E
在反应F和G中,对制备具有各种R1和R2取代基的式I和I'化合物的另外方法进行了描述。首先将反应F中式IA化合物或反应G中式IB化合物用氢化铝锂(LAH)还原,分别生成结构式IG或IL所示化合物,还原羰基的其它方法在教科书《羰基化学》(The Chemistryof the Carbonyl Group)第十一章,Saul Patai著(1966)IntersciencePublishers中有描述。
结构式IG或IL所示的化合物与具有潜在取代基R'的酰氯反应生成式IJ或IN所示的化合物。在式IA或IB化合物中,引入不同的R1和R2取代基另一条途径是通过这两种化合物各与具有潜在R取代基的格利雅(Grignard)试剂或锂试剂反应,生成式IH或IM所示的化合物。然后,在酸(例如盐酸)的存在下,式IH或IM所示的化合物和具有潜在取代基R'的醇反应,生成式IK或IP所示的化合物。反应F反应G
式I、I'、IA、IB、IC、ID、IE、IF、IG、IH、IJ、IK、IL、IM、IN和IP化合物可以用于使用有机光致变色物质的领域,例如光学透镜,如用于矫正视力的眼用透镜和平面透镜,面罩、护目镜、遮光板、照相机透镜,窗户、汽车挡风玻璃、飞机和汽车的透明物件,例如透明顶(T-roof)、侧灯和后灯,塑料薄膜和薄片,织物和涂料,例如涂料组合物,和安全文件,例如钞票、护照和驾驶执照上的检验标志,在这些方面需要证明和鉴定证明。前述的杂环稠合茚并萘并吡喃化合物显示从无色到范围为橙色到灰/蓝色的颜色变化。
本发明范围中预期的茚并萘并吡喃化合物实例包括如下的这些化合物:(a)3,3-二(4-甲氧基苯基)-16-羟基-16-乙基-16H-苯并呋喃并[2',3':7,8]茚并[2',3':3,4]萘并[1,2-b]吡喃;(b)3,3-二(4-甲氧基苯基)-16-羟基-16H-苯并呋喃并[2″,3″:6',7′]茚并[3',2':4,3]萘并[1,2-b]吡喃;和(c)3,3-二(4-甲氧基苯基)-16-羟基-16-乙基-16H-苯并呋喃并[2″,3″:6,7']茚并[3',2':4,3]萘并[1,2-b]吡喃。
本发明的有机光致变色茚并萘并吡喃化合物可以单独使用,也可以与本发明其它的茚并萘并吡喃混合使用或与一种或多种其它合适的互补性的有机光致变色物质,即在约400到700纳米范围内至少有一个最大激活吸收的有机光致变色化合物,或含有该化合物的物质混合使用;并可以掺入(例如溶解或分散在)有机聚合基质材料中,用于制备光致变色制品,当受到激发时,该制品可以显示适当的色相。
除非在操作实施例中或另有指明,在本文中所有表示波长、成分量或反应条件的数字均应理解为用术语“大约”修饰。
互补的有机光致变色化合物的实例包括其它的萘并吡喃,苯并吡喃,菲并吡喃,螺(苯并二氢吲哚)萘并吡喃,螺(二氢吲哚)苯并吡喃,螺(二氢吲哚)萘并吡喃,螺(二氢吲哚)喹啉并吡喃,螺(二氢吲哚)吡喃,螺(二氢吲哚)吩噁嗪,螺(二氢吲哚)吡啶并苯并噁嗪,螺(苯并二氢吲哚)吡啶并苯并噁嗪,螺(苯并二氢吲哚)吩噁嗪,螺(二氢吲哚)苯并噁嗪,和这些光致变色化合物的混合物。
这里描述的各种光致变色物质可以以一定量(或一定比例)应用,以使应用或掺入光致变色化合物或其混合物的有机基质材料显示出所需要的颜色,例如,当用未过滤的阳光激活时,显示基本中性的颜色,即激活的光致变色化合物尽可能显示中性色。优选为中灰色和中褐色。
中灰色在400到700纳米的可见光范围内显示吸收较为一致的光谱。中褐色显示的光谱中在400-550纳米范围的吸收稍大于在550-700纳米范围的吸收。用于表述颜色的另一方法是色度坐标,它描述了色质和亮度因子,即它的色度。在CIE系统中,通过三色激励值与其总和的比例得到色度坐标,例如x=X/(X+Y+Z)和y=Y/(X+Y+Z)。在CIE系统中所描述的颜色可以在色度图上画出,通常是色度坐标x和y的曲线图。参见“颜色技术原理”(Principlesof Color Technology),第47-52页,作者为F.W.Billmeyer,Jr.和MaxSaltzman,第二版,John Wiley and Sons,纽约(1981年)。在这里使用的近中性颜色是这样一种颜色,即在暴露于太阳照射(Air Mass 1或2)而激活到40%光透射率后,其色度坐标“x”和“y”值在如下范围(D65光源)内:x:0.260-0.400,y=0.280-0.400。
光致变色物质或含有该物质的组合物施于或掺于基质材料中的量并不是严格要求的,只要在激活时这个量足以产生裸眼可识别的光致变色效应即可。一般这个量称为光致变色量。使用的具体量经常依赖于照射时所需要的颜色强度和掺入或施加光致变色物质的方法。一般情况下,施加或掺入的光致变色物质的量越多,在一定的限度内颜色强度越大。
前面所述的光致变色化合物的相对使用量可以改变并且部分取决于这种化合物激发态颜色的相对强度和最终所需的颜色。一般来说,掺入或施加到光致变色光学基质材料中的光致变色物质的总量为约0.05到约1.0,例如从0.1到约0.45毫克/平方厘米掺入或施加光致变色物质的表面。
用本领域中描述的许多方法可以将本发明的光致变色物质施加或掺入到基质材料如有机聚合基质材料中。这些方法包括将光致变色物质溶解或分散在基质材料中,例如通过在聚合前将光致变色物质加到单体基质材料中而后原位浇铸;通过将基质材料浸入光致变色物质的热溶液中或通过热转移将光致变色物质浸入基质材料中;在基质材料的邻近层之间提供一个独立的光致变色物质层,例如作为聚合物薄膜的一部分;以及将光致变色物质涂在基质材料的表面作为涂层的一部分。术语“浸润”或“浸渗”用来表示和包括光致变色物质向基质材料内的渗透,溶剂辅助转移光致变色物质至多孔聚合物中,汽相转移和其它这种转移方式。
为了医用或装饰目的,可把相容的(化学呈彩色的(chemicallyand color-wise))色调(tints),即染料应用到基质材料中,以获得美学的效果。选用的具体染料范围很宽,依赖于以上的需求和所要获得的结果。在一个实施例中,选择的染料是为了补充激发态光致变色物质的颜色,例如,为了获得更为中性的颜色或吸收特殊波长的入射光。在另一实施例中,染料的选择是为了当光致变色物质在非激活态时,为基质材料提供所希望的色调。
通常基质材料是透明的,但也可以是半透明或者甚至是不透明的。基质材料只需要对电磁谱波中激活光致变色物质的那部分波长,即使得物质处于打开状态(open form)的紫外(UV)光波长和包括UV激发态(即打开状态)物质的最大吸收波长在内的那部分可见光谱是透明的。优选的是基质材料的颜色不能掩盖激发态光致变色物质的颜色,即颜色的变化对于观察者来说是明显的。更优选的基质材料制品为固体透明或光学清晰的材料,例如,适合于光学应用的材料如平面透镜和眼用透镜,窗户,汽车透明材料,例如挡风玻璃,飞机透明材料,塑料薄片,聚合物薄膜等。
可与这里所描述的光致变色化合物或组合物一起使用的聚合有机基质材料的实例包括:如下单体的聚合物,即均聚物和共聚物:多元醇(碳酸烯丙酯)单体、二甘醇二甲基丙烯酸酯单体、二异丙烯基苯单体、乙氧基化双酚A二甲基丙烯酸酯单体、乙二醇双甲基丙烯酸酯单体、聚(乙二醇)双甲基丙烯酸酯单体、乙氧基化苯酚甲基丙烯酸酯单体和烷氧基化多元醇丙烯酸酯单体,例如乙氧基化三羟甲基丙烷三丙烯酸酯单体;如下单体的聚合物,即均聚物和共聚物:多官能,例如单、二或多官能丙烯酸酯和/或甲基丙烯酸酯单体、聚(异丁烯酸C1-C12烷基酯),例如聚(异丁烯酸甲酯)、聚(氧化烯二异丁烯酸酯)、聚(烷氧基化苯酚甲基丙烯酸酯)、乙酸纤维素、三乙酸纤维素、乙酸丙酸纤维素、乙酸丁酸纤维素、聚(乙酸乙烯酯)、聚(乙烯醇)、聚(氯乙烯)、聚(偏二氯乙烯)、聚氨酯、热塑性聚碳酸酯、聚酯、聚(对苯二甲酸乙二醇酯)、聚(苯乙烯)、聚(α-甲基苯乙烯)、(苯乙烯-异丁烯酸甲酯)共聚物、(苯乙烯-丙烯腈)共聚物、聚乙烯醇缩丁醛和二亚烯丙基季戊四醇的聚合物,即均聚物和共聚物,特别是与多元醇(碳酸烯丙基酯)单体例如二甘醇双(碳酸烯丙基酯)和丙烯酸酯单体的共聚物。
透明的共聚物和透明聚合物的掺合物也适合于作为基质材料。优选的基质材料是由热塑性聚碳酸酯树脂制备的光学清晰的聚合有机材料。例如从双酚A和光气得到的由碳酸酯连接的树脂,商品名为LEXAN;聚酯,例如商标为MYLAR的材料;一种聚(异丁烯酸甲酯),例如商标为PLEXIGLAS的材料;多元醇(碳酸烯丙酯)单体的聚合物,特别是二甘醇双(碳酸烯丙酯)聚合物,该单体商标为CR-39,和多元醇(碳酸烯丙酯)例如二甘醇双(碳酸烯丙基酯)与其它的可共聚的单体材料的共聚物,例如与乙酸乙烯基酯的共聚物,例如80-90%的二甘醇双(碳酸烯丙酯)和10-20%的乙酸乙烯酯的共聚物,特别是80-85%的双(碳酸烯丙基酯)和15-20%的乙酸乙烯酯的共聚物,以及在美国专利4,360,653和4,994,208中描述的与带有二丙烯酸酯端官能团的聚氨酯的共聚物;如在美国专利5,200,483中描述的与端部带有烯丙基或丙烯酰基官能团的脂族聚氨酯的共聚物;聚(乙酸乙烯基酯)、聚乙烯醇缩丁醛、聚氨酯、下列单体的聚合物:二甘醇二甲基丙烯酸酯单体、二异丙烯基苯单体、乙氧基化双酚A二甲基丙烯酸酯单体、乙二醇双甲基丙烯酸酯单体、聚(乙二醇)双甲基丙烯酸酯单体、乙氧基化苯酚甲基丙烯酸酯单体和乙氧基化三羟甲基丙烷的三丙烯酸酯单体、乙酸纤维素、丙酸纤维素、丁酸纤维素、乙酸丁酸纤维素、聚(苯乙烯)和苯乙烯与异丁烯酸甲酯、乙酸乙烯基酯和丙烯腈的共聚物。
更具体的是,利用本发明光致变色茚并萘并吡喃和光学有机树脂单体制备光学清晰的聚合体,即适合于光学应用的材料,例如平面透镜和眼用透镜,窗户和汽车透明材料。这种光学清晰聚合体具有约1.48到约1.75的折射率,例如从约1.495到约1.66。特殊关注的光学树脂在PPG工业公司可以购买得到,标号为CR-307和CR-407。
本发明更具体地描述在下面的仅仅用于举例的实施例中。因为对于本技术领域中那些熟练人员来说,各种改动和变化是显而易见的。
实施例1
步骤1
二苯并呋喃(40g,0.23mol)和苯甲酰氯(0.25mol)加入到装有500ml无水二氯甲烷的反应烧瓶中并在室温下搅拌。缓慢地将无水三氯化铝(0.30mol)加入到混合物中。反应混合物被搅拌1小时,然后倾入5wt%盐酸和冰的混合物中。所得到的混合物被搅拌15分钟,用二氯甲烷萃取。分离出有机层,依次用10wt%氢氧化钠水溶液和蒸馏水洗涤。分离出有机层,用无水硫酸镁干燥。真空下除去二氯甲烷溶剂。所得到的油状产物用己烷结晶。过滤和风干回收的产物(50g)。核磁共振谱(NMR)显示产物具有与2-苯甲酰基二苯并呋喃一致的结构。
步骤2
将叔丁醇钾(35g,0.31mol)经0.5小时缓慢地加入到含有600mL甲苯,2-苯甲酰基二苯并呋喃(40g,0.15mol)和琥珀酸二甲酯(30g,0.20mol)的反应烧瓶中。所得到的糊状混合物回流2小时,之后冷却并加入约400mL的水,然后充分搅拌。分离出水层并用稀盐酸酸化,用200mL甲苯萃取。在旋转蒸发器上除去溶剂甲苯和残余叔丁醇,得到几乎定量产率的Stobbe半酯粗产物:4-(二苯并呋喃-2-基)-4-苯基-3-甲氧羰基-3-丁烯酸。此物质不需进一步提纯就可以直接用于下一步骤中。
步骤3
来自步骤2的半酯粗产物加入到含有乙酸酐(100g)和无水乙酸钠(50g)的反应烧瓶中,并将混合物回流4小时。之后冷却混合物,在旋转蒸发器上除去溶剂。所得到的残余物溶于200mL氯仿中,并进行搅拌。加入水(200mL),随后缓慢加入固体碳酸钠,直至二氧化碳停止溢出时为止。分离出有机层,用水洗涤。在旋转蒸发器上除去溶剂氯仿,得到含有1-(二苯并呋喃-2-基)-2-甲氧羰基-4-乙酰氧基-萘和1-乙酰氧基-3-甲氧羰基-4-苯基-苯并[b]萘并[1,2-d]呋喃的粘稠油状物。该物质无需进一步提纯就可以直接用于下一步骤中。
步骤4
将来自步骤3的含有1-(二苯并呋喃-2-基)-2-甲氧羰基-4-乙酰氧基-萘和1-乙酰氧基-3-甲氧羰基-4-苯基-苯并[b]萘并[1,2-d]呋喃的油状物加入到含有100mL 10wt%氢氧化钠水溶液和200mL甲醇的反应烧瓶中。混合物回流3小时,然后冷却至室温,使所需要的产物结晶出来。将所得到的晶体抽滤出来并用冷乙醇水溶液洗涤,干燥。回收的产物(15g)具有与1-羟基-3-羧基-4-苯基-苯并[b]萘并[1,2-d]呋喃一致的NMR谱图。将滤液倾入到含有大约1升冷(约4℃)稀盐酸的烧杯中,以结晶出另一所需产物。真空过滤收集到约20g结晶产物。NMR谱表明产物具有与1-(二苯并呋喃-2-基)-4-羟基-2-萘甲酸一致的结构。
步骤5
将来自步骤4的1-羟基-3-羧基-4-苯基-苯并[b]萘并[1,2-d]呋喃(10g)加入到含有10g对甲苯磺酸和50mL甲苯的反应烧瓶(装有迪安-斯达克分水器)中。所得到的混合物回流5小时。在这一时间中形成了深红色固体产物。冷却该混合物并添加200mL水。固体用刮刀弄碎,过滤并依次用水、5wt%碳酸氢钠溶液和水洗涤。所回收的红色产物(7g)具有与5-羟基-7-氧代-7H-苯并[b]茚并[2',3':5,6]萘并[1,2-d]呋喃一致的NMR谱。
步骤6
将来自步骤5的5-羟基-7-氧代-7H-苯并[b]茚并[2',3':5,6]萘并[1,2-d]呋喃(6g)加入到含有50mL无水四氢呋喃的反应烧瓶中。混合物在冰浴中冷却并在氮气氛围中保护以隔绝与水汽的接触,在搅拌下将过量的乙基格氏试剂加入到反应体系中。在另外搅拌10分钟后,加入50mL 5wt%的盐酸溶液,分离有机层,用水洗涤、无水硫酸钠干燥。在旋转蒸发器上除去溶剂四氢呋喃。在残余物中加入大约10mL乙醚使所需产物结晶出来。过滤该物质并干燥,得到4g所需产物。NMR谱显示产物具有与5,7-二羟基-7-乙基-7H-苯并[b]茚并[2',3':5,6]萘并[1,2-d]呋喃一致的结构。
步骤7
将来自步骤6的5,7-二羟基-7-乙基-7H-苯并[b]茚并[2',3':5,6]萘并[1,2-d]呋喃(3g)加入到含有2.5g 1,1-二(4-甲氧基苯基)-2-丙炔-1-醇和80mL甲苯的反应烧瓶中,将所得到的混合物在室温下进行搅拌。加入对甲苯磺酸(100mg),继续搅拌5小时。之后,将反应混合物冷却至室温,进行过滤,收集到的滤液用10wt% 氢氧化钠水溶液洗涤3次。在旋转蒸发器上除去溶剂甲苯。油状粗产物通过使用己烷∶氯仿的1∶1混合物作为洗脱液在硅胶上进行柱色谱分离。所需产物(从醚中结晶)经过滤和干燥,得到1.0g熔程为242-244℃的产物。NMR谱显示产物具有与3,3-二(4-甲氧基苯基)-16-羟基-16-乙基-16H-苯并呋喃并[2',3':7,8]茚并[2',3':3,4]萘并[1,2-b]吡喃一致的结构。
实施例2
步骤1
重复实施例1的步骤5的方法,只是使用实施例1的步骤4的1-(二苯并呋喃-2-基)-4-羟基-2-萘甲酸代替1-羟基-3-羧基-4-苯基-苯并[b]萘并[1,2-d]呋喃。NMR谱表明所得到的产物具有与7-羟基-5-氧代-5H-苯并[b]萘并[2',1':2,3]茚并[7,6-d]呋喃一致的结构。
步骤2
将来自步骤1的7-羟基-5-氧代-5H-苯并[b]萘并[2',1':2,3]茚并[7,6-d]呋喃(10g)加入到含有100mL无水四氢呋喃的反应烧瓶中并进行搅拌。将少量的氢化铝锂加入到搅拌的混合物中,直至所有的桔红色消失为止。将反应混合物再搅拌2小时,用少量的乙醇终止反应,并倾入到100mL 5wt%盐酸水溶液中。分离出有机层,并用水洗涤,过滤,之后在旋转蒸发器上除去溶剂乙醚。NMR谱显示所回收的产物具有与5,7-二羟基-5H-苯并[b]萘并[2',1':2,3]茚并[7,6-d]呋喃一致的结构。
步骤3
重复实施例1的步骤7的方法,只是使用5,7-二羟基-5H-苯并[b]萘并[2',1':2,3]茚并[7,6-d]呋喃代替5,7-二羟基-7-乙基-7H-苯并[b]茚并[2',3':5,6]萘并[1,2-d]呋喃,得到1.0g的熔程为240-241℃的结晶产物。NMR谱显示产物具有与3,3-二(4-甲氧基苯基)-16-羟基-16H-苯并呋喃并[2″,3'':6',7']茚并[3',2':4,3]萘并[1,2-d]吡喃一致的结构。
实施例3
重复实施例2的方法,只是在步骤2中用乙基格氏试剂代替氢化铝锂,得到1.0g熔程为257-259℃的结晶产物。NMR谱显示产物具有与3,3-二(4-甲氧基苯基)-16-羟基-16-乙基-16H-苯并呋喃并[2″,3'':6',7']茚并[3',2':4,3]萘并[1,2-d]吡喃一致的结构。
实施例4
A部分
通过下述方法将前面实施例的光致变色的茚并萘并吡喃引入聚合物样品中,并对其进行测试。将一定量(经计算可得到1.5×10-3摩尔浓度溶液)的茚并萘并吡喃加入到含有50g的由4份乙氧基化双酚A二甲基丙烯酸酯(BPA 2EO DMA),1份聚乙二醇600二甲基丙烯酸酯和0.033wt%2,2'-偶氮二(2-甲基丙腈)(AIBN)组成的单体掺混物的烧瓶中。通过搅拌,必要时,稍微加热,将茚并萘并吡喃溶于单体掺混物中。在获得透明溶液之后,将其倾入到具有2.2mm×6英寸(15.24cm)×6英寸(15.24cm)的内尺寸的平片模具中。密封模具,然后放入已设定经5小时的时间间隔从40℃升温至95℃的水平气流、程序可控的烘箱中,在95℃的温度下保持3小时,然后降低温度至60℃保持至少2小是地,之后结束固化循环。在模具打开之后,使用金刚刀锯将聚合物片材切成2英寸(5.1平方厘米)的测试方块。
B部分
在A部分中制备的光致变色的测试方块在光具座上测试光致变色响应速率。在光具座上测试之前,将光致变色的测试方块在365纳米紫外光下暴露约15分钟以激活光致变色化合物,然后放入76℃烘箱中约15分钟以使光致变色化合物褪色(bleach)或失活。然后将测试方块冷却至室温,在荧光室照射至少2小时,尔后遮盖至少2小时,之后在温度保持为75°F(23.9℃)的光具座上进行试验。光具座装有150瓦氙弧灯,远程遥控遮光器(shutter),用作上述弧灯散热器的硫酸铜浴,Schott WG-320nm截止滤波片(滤去短波辐射);中性密度滤光片和用于插入待测试样方块的样品架。来自钨灯的准直光束以垂直于方块的小角度通过方块。在通过方块之后,来自钨灯的光通过一只与检测器相连的适光滤片(photopic filter)。该适光滤片允许某些波长通过,以使得检测器模拟人眼的反应。检测器的输出信号用辐射计进行处理。
通过如下方法来测定光密度(ΔOD)的变化:将处于变白状态的试样方块插入样品架中,调节透射率为100%,打开氙灯的遮光器以提供紫外光辐射使试样从褪色状态改变成激化(即变暗)状态,测量激活状态下的透过率,根据式ΔOD=log(100/%Ta)来计算光密度的变化,其中%Ta是激活状态下的百分透过率并且对数是以10为底。
ΔOD/Min,表示光致变色化合物对UV光响应的灵敏度,它是在UV辐射下第一个5秒内测量的,然后以每分钟为基础来表示。在与ΔOD/min相同的条件下测定饱和光密度(OD),只是对于表1中的实施例化合物连续进行UV辐射20分钟。表1中所记录的λ最大值是可见光区中的波长,在此波长下二甘醇双(烯丙基碳酸酯)组合物中光致变色化合物的激活(变色)形式发生最大吸收。褪色速率(T 1/2)是在室温下在移走活化光源之后测试方块中茚并萘并吡喃的激活态的吸收达到最大吸收的一半时所需要的时间间隔(秒)。实施例的化合物的结果列于表1中。
表1实施例 λ最大值 ΔOD/min ΔOD@ 褪色速率化合物 (可见光) 灵敏度 饱和 (T 1/2)1 597nm 0.25 0.12 232 574nm 0.19 0.26 703 580nm 0.20 0.21 48
表1的结果表明,对于本发明的实施例化合物1-3获得了褪色速率,饱和的ΔOD以及灵敏度的数值范围,它们取决于杂环A的性质,稠合的侧边和取代基R1,R2,R3,R4,B和B'。
虽然本发明已针对特定实施方案的特定细节进行了叙述,但应该认为这些细节不是对本发明范围的限定,本发明范围至少包括在所附权利要求中。
Claims (22)
1、下式所示的茚并萘并吡喃化合物:其中(a)A为未取代、单取代或二取代的选自苯并噻吩并、苯并呋喃并和吲哚并的杂环,所述杂环的2,3位或3,2位和所述茚并萘并吡喃的g,h,i,n,o或p边稠合,所述杂环的取代基为C1-C6烷基、C5-C7环烷基、C1-C6烷氧基、氯或氟;
(b)R1和R2一起形成氧代基,具有2个氧原子和包括螺碳原子在内的3到6个碳原子的螺杂环基;或者R1和R2各为氢,羟基,C1-C6烷基,C3-C7环烷基,烯丙基,苯基,单取代的苯基,苄基,单取代的苄基,氯,氟或基团-C(O)W,其中各W为羟基,C1-C6烷基,C1-C6烷氧基,苯基,单取代的苯基,氨基,单(C1-C6)烷氨基或二(C1-C6)烷氨基;或者R1和R2各为基团-OR5,其中各R5为C1-C6烷基,苯基(C1-C3)烷基,单(C1-C6)烷基取代的苯基(C1-C3)烷基,单(C1-C6)烷氧基取代的苯基(C1-C3)烷基,C1-C6烷氧基(C2-C4)烷基,C3-C7环烷基,单(C1-C4)烷基取代的C3-C7环烷基,C1-C6氯代烷基,C1-C6氟代烷基,烯丙基,基团-CH(R6)X,其中各R6为氢或C1-C3烷基,各X为-CN,CF3或-COOR7并且各R7为氢或C1-C3烷基,或者各R5为基团-C(O)Y,其中各Y为氢,C1-C6烷基,C1-C6烷氧基,未取代,单或二取代的芳基、苯基和萘基,苯氧基,单或二(C1-C6)烷基取代的苯氧基,单或二(C1-C6)烷氧基取代的苯氧基,氨基,单(C1-C6)烷氨基,二(C1-C6)烷氨基,苯氨基,单或二(C1-C6)烷基取代的苯氨基或者为单或二(C1-C6)烷氧基取代的苯氨基,上述每一个苯基、苄基和芳基的取代基为C1-C6烷基或C1-C6烷氧基;
(c)R3和R4各为C1-C6烷基、C1-C6烷氧基、氯或氟,及m和n各为整数0、1或2;和
(d)B和B'各选自下列基团:
(i)未取代、单、二和三取代的芳基,苯基和萘基;
(ii)未取代、单和二取代的芳杂环基吡啶基、呋喃基、苯并呋喃-2-基、苯并呋喃-3-基、噻吩基、苯并噻吩-2-基、苯并噻吩-3-基,二苯并呋喃基、二苯并噻吩基、咔唑基和芴基,在(d)(i)和(ii)中所述的各芳基和芳杂环基的取代基选自羟基、芳基、单(C1-C6)烷氧基芳基、二(C1-C6)烷氧基芳基、单(C1-C6)烷基芳基、二(C1-C6)烷基芳基、溴代芳基、氯代芳基、氟代芳基、C3-C7环烷基芳基、C3-C7环烷基、C3-C7环烷氧基、C3-C7环烷氧基(C1-C6)烷基、C3-C7环烷氧基(C1-C6)烷氧基、芳基(C1-C6)烷基、芳基(C1-C6)烷氧基、芳氧基、芳氧基(C1-C6)烷基、芳氧基(C1-C6)烷氧基、单和二(C1-C6)烷基芳基(C1-C6)烷基、单和二(C1-C6)烷氧基芳基(C1-C6)烷基、单和二(C1-C6)烷基芳基(C1-C6)烷氧基、单和二(C1-C6)烷氧基芳基(C1-C6)烷氧基、氨基、单(C1-C6)烷基氨基、二(C1-C6)烷基氨基、二芳基氨基、N-(C1-C6)烷基哌嗪-1-基、N-芳基哌嗪-1-基、氮丙啶-1-基、二氢吲哚-1-基、哌啶子基、芳基哌啶子基、吗啉代、硫代吗啉代、四氢喹啉-1-基、四氢异喹啉-1-基、吡咯基、C1-C6烷基、C1-C6溴代烷基、C1-C6氯代烷基、C1-C6氟代烷基、C1-C6烷氧基、单(C1-C6)烷氧基(C1-C4)烷基、丙烯酰氧基、甲基丙烯酰氧基、溴、氯和氟;
(iii)下式所示的基团:其中E为碳或氧,D为氧或取代的氮,条件是D为取代的氮时E为碳,所述的氮上的取代基选自氢、C1-C6烷基和C2-C6酰基;各R8为C1-C6烷基、C1-C6烷氧基、羟基、溴、氯或氟;R9和R10各为氢或C1-C6烷基;p为整数0,1或2;
(iv)C1-C6烷基、C1-C6溴代烷基、C1-C6氯代烷基、C1-C6氟代烷基、C1-C6烷氧基(C1-C4)烷基、C3-C6环烷基、单(C1-C6)烷氧基(C3-C6)环烷基、单(C1-C6)烷基(C3-C6)环烷基、溴代(C3-C6)环烷基、氯代(C3-C6)环烷基和氟代(C3-C6)环烷基;以及
(v)下式所示基团:其中X为氢或C1-C4烷基,Z选自未取代、单或二取代的萘基、苯基、呋喃基和噻吩基,其中所述基团的各取代基为C1-C4烷基、C1-C4烷氧基、溴、氟或氯;或
(vi)B和B'一起形成芴-9-叉、单或二取代的芴-9-叉,或形成选自下列的基团:饱和的C3-C12螺-单环烃环、饱和的C7-C12螺-二环烃环以及饱和的C7-C12螺-三环烃环,所述的芴-9-叉的各取代基选自C1-C4烷基,C1-C4烷氧基、溴、氟和氯。
2、权利要求1的茚并萘并吡喃化合物,其中
(a)杂环A为未取代或单取代的杂环,并且所述杂环的取代基为C1-C4烷基或C1-C4烷氧基;
R1和R2各选自氢,羟基,C1-C4烷基,C3-C6环烷基,氯,氟和基团-OR5,其中各R5为C1-C3烷基,苯基(C1-C2)烷基,单(C1-C3)烷基取代的苯基(C1-C3)烷基,单(C1-C3)烷氧基取代的苯基(C1-C3)烷基,C1-C3烷氧基(C2-C4)烷基,C1-C3氯代烷基,C1-C3氟代烷基或基团-CH(R6)X,其中各R6为氢或C1-C2烷基,各X为-CN或-COOR7,各R7为氢或C1-C2烷基,或者R5为基团-C(O)Y,其中Y为氢、C1-C3烷基、C1-C3烷氧基、苯基、萘基、单取代的芳基、苯基和萘基,苯氧基,单或二(C1-C3)烷基取代的苯氧基,单或二(C1-C3)烷氧基取代的苯氧基,单(C1-C3)烷基氨基,苯氨基,单或二(C1-C3)烷基取代的苯氨基,或者为单或二(C1-C3)烷氧基取代的苯氨基,上述芳基的各取代基为C1-C3烷基或C1-C3烷氧基;
(c)R3和R4各为C1-C4烷基、C1-C4烷氧基、氯或氟,以及m和n各自为整数0或1;和
(d)B和B'各选自下列基团:
(i)苯基、单取代苯基和二取代苯基;
(ii)未取代、单和二取代的芳杂环基呋喃基、苯并呋喃-2-基、噻吩基、苯并噻吩-2-基、二苯并呋喃-2-基和二苯并噻吩-2-基,在(d)的(i)和(ii)中所述的各苯基和芳杂环的取代基选自羟基、芳基、芳氧基、芳基(C1-C3)烷基、氨基、单(C1-C3)烷氨基、二(C1-C3)烷氨基、N-(C1-C3)烷基哌嗪-1-基、二氢吲哚-1-基、哌啶子基、吗啉代、吡咯基、C1-C3烷基、C1-C3溴代烷基、C1-C3氯代烷基、C1-C3氟代烷基、C1-C3烷氧基、单(C1-C3)烷氧基(C1-C3)烷基、溴、氟和氯;
(iv)C1-C4烷基;和
(v)下式所示的基团:其中X为氢或甲基,Z为苯基或单取代苯基,所述苯基的取代基选自C1-C3烷基、C1-C3烷氧基和氟;或
(vi)B和B'一起形成芴-9-叉、单取代芴-9-叉,或选自下列的基团:饱和的C3-C8螺-单环烃环、饱和的C7-C10螺-二环烃环以及饱和的C7-C10螺-三环烃环,所述芴-9-叉的取代基选自C1-C3烷基,C1-C3烷氧基、溴、氟和氯。
3、权利要求2的茚并萘并吡喃化合物,其中
(a)杂环A为未取代或单取代的杂环,所述杂环的2,3位或3,2位和所述茚并萘并吡喃的g或p边稠合,并且所述杂环的取代基为C1-C3烷基或C1-C3烷氧基;
(b)R1和R2各为氢,羟基,C1-C4烷基或基团-OR5,其中R5为C1-C3烷基;
(c)R3和R4各为C1-C3烷基或C1-C3烷氧基,以及m和n各为整数0或1;和
(d)B和B'各选自下列基团:
(i)苯基、单取代和二取代的苯基;
(ii)未取代、单和二取代的芳杂环基呋喃基、苯并呋喃-2-基、噻吩基和苯并噻吩-2-基,在(d)(i)和(ii)中所述的苯基和芳杂环的各取代基选自羟基、C1-C3烷基、C1-C3烷氧基、芳基、二氢吲哚-1-基、氟和氯;和
(iv)B和B'一起形成芴-9-叉、亚金刚烷基、亚冰片基、亚降冰片基或二环[3.3.1]壬-9-叉。
4、选自下列的茚并萘并吡喃化合物:(a)3,3-二(4-甲氧基苯基)-16-羟基-16-乙基-16H-苯并呋喃并[2',3':7,8]
茚并[2',3':3,4]萘并[1,2-b]吡喃;(b)3,3-二(4-甲氧基苯基)-16-羟基-16H-苯并呋喃并[2″,3″:6',7']茚并
[3',2':4,3]萘并[1,2-b]吡喃;和(c)3,3-二(4-甲氧基苯基)-16-羟基-16-乙基-16H-苯并呋喃并[2″,3″:6',7']
茚并[3',2':4,3]萘并[1,2-b]吡喃。
5、一种光致变色制品,它包含聚合有机基质材料和光致变色量的权利要求1的茚并萘并吡喃化合物。
6、权利要求5的光致变色制品,其中所述的聚合有机基质材料选自聚(异丁烯酸C1-C12烷基酯)、聚(氧化烯二异丁烯酸酯)、聚(烷氧基化苯酚甲基丙烯酸酯)、乙酸纤维素、三乙酸纤维素、乙酸丙酸纤维素、乙酸丁酸纤维素、聚(乙酸乙烯酯)、聚(乙烯醇)、聚(氯乙烯)、聚(偏二氯乙烯)、热塑性聚碳酸酯、聚酯、聚氨酯、聚(对苯二甲酸乙二醇酯)、聚(苯乙烯)、聚(α-甲基苯乙烯)、(苯乙烯-异丁烯酸甲酯)共聚物、(苯乙烯-丙烯腈)共聚物、聚乙烯醇缩丁醛以及如下单体的聚合物:多元醇(碳酸烯丙酯)单体、多官能丙烯酸酯单体、多官能甲基丙烯酸酯单体、二甘醇二甲基丙烯酸酯单体、二异丙烯基苯单体、乙氧基化双酚A二甲基丙烯酸酯单体、乙二醇双甲基丙烯酸酯单体、聚(乙二醇)双甲基丙烯酸酯单体、乙氧基化苯酚甲基丙烯酸酯单体、烷氧基化多元醇丙烯酸酯单体和二亚烯丙基季戊四醇单体。
7、权利要求6的光致变色制品,其中所述的聚合有机基质材料为固体透明聚合物,选自聚(异丁烯酸甲酯)、聚(乙二醇双甲基丙烯酸酯)、聚(乙氧基化双酚A二甲基丙烯酸酯)、热塑性聚碳酸酯、聚(乙酸乙烯酯)、聚乙烯醇缩丁醛、聚氨酯以及如下单体的聚合物:二甘醇二(碳酸烯丙酯)单体、二甘醇二甲基丙烯酸酯单体、乙氧基化苯酚甲基丙烯酸酯单体、二异丙烯基苯单体和乙氧基化三羟甲基丙烷的三丙烯酸酯单体。
8、权利要求7的光致变色制品,其中光致变色化合物的含量为每平方厘米掺入或施加光致变色物质的有机基质材料表面0.05到1.0毫克。
9、权利要求8的光致变色制品,其中该制品为透镜。
10、一种含有聚合有机基质材料和光致变色量的权利要求2的萘并吡喃化合物的光致变色制品,其中所述的有机基质材料选自聚(异丁烯酸甲酯)、聚(乙二醇双甲基丙烯酸酯)、聚(乙氧基化双酚A二甲基丙烯酸酯)、热塑性聚碳酸酯、聚(乙酸乙烯酯)、聚乙烯醇缩丁醛、聚氨酯和如下单体的聚合物:二甘醇双(碳酸烯丙酯)单体、二甘醇二甲基丙烯酸酯单体、乙氧基化苯酚甲基丙烯酸酯单体、二异丙烯基苯单体和乙氧基化三羟甲基丙烷的三丙烯酸酯单体。
11、一种含有聚合有机基质材料和光致变色量的权利要求3的茚并萘并吡喃化合物的光致变色制品,其中有机基质材料选自聚(异丁烯酸甲酯)、聚(乙二醇双甲基丙烯酸酯)、聚(乙氧基化双酚A二甲基丙烯酸酯)、热塑性聚碳酸酯、聚(乙酸乙烯酯)、聚乙烯醇缩丁醛、聚氨酯和如下单体的聚合物:二甘醇双(碳酸烯丙酯)单体、二甘醇二甲基丙烯酸酯单体、乙氧基化苯酚甲基丙烯酸酯单体、二异丙烯基苯单体和乙氧基化三羟甲基丙烷的三丙烯酸酯单体。
12、一种光致变色制品,它含有光学有机树脂单体的聚合物和光致变色量的权利要求1的茚并萘并吡喃化合物。
13、权利要求12的光致变色制品,其中聚合物的折射率为约1.48到约1.75。
14、权利要求13的光致变色制品,其中聚合物的折射率为约1.495到约1.66。
15、一种光致变色制品,它组合含有固体透明的聚合有机基质材料和光致变色量的下列各化合物:(a)至少一种权利要求1的茚并萘并吡喃化合物,和(b)至少一种在约400到700纳米范围内具有至少一个最大激活吸收的其它有机光致变色化合物。
16、权利要求15的光致变色制品,其中聚合有机基质材料选自聚(异丁烯酸C1-C12烷基酯)、聚(氧化烯二甲基丙烯酸酯)、聚(烷氧基化苯酚甲基丙烯酸酯)、乙酸纤维素、三乙酸纤维素、乙酸丙酸纤维素、乙酸丁酸纤维素、聚(乙酸乙烯酯)、聚(乙烯醇)、聚(氯乙烯)、聚(偏二氯乙烯)、热塑性聚碳酸酯、聚酯、聚氨酯、聚(对苯二甲酸乙二醇酯)、聚(苯乙烯)、聚(α-甲基苯乙烯)、(苯乙烯-异丁烯酸甲酯)共聚物、(苯乙烯-丙烯腈)共聚物、聚乙烯醇缩丁醛和如下单体的聚合物:多元醇(碳酸烯丙酯)单体、多官能丙烯酸酯单体、多官能甲基丙烯酸酯单体、二甘醇二甲基丙烯酸酯单体、乙氧基化双酚A二甲基丙烯酸酯单体、二异丙烯基苯单体、乙二醇双甲基丙烯酸酯单体、聚(乙二醇)双甲基丙烯酸酯单体、乙氧基化苯酚甲基丙烯酸酯单体、烷氧基化多元醇丙烯酸酯单体和二亚烯丙基季戊四醇单体。
17、权利要求16的光致变色制品,其中聚合有机基质材料为固体透明均聚物或共聚物,选自聚(异丁烯酸甲酯)、聚(乙二醇双甲基丙烯酸酯)、聚(乙氧基化双酚A二甲基丙烯酸酯)、热塑性聚碳酸酯、聚(乙酸乙烯酯)、聚乙烯醇缩丁醛、聚氨酯和如下单体的聚合物:二甘醇双(碳酸烯丙酯)单体、二甘醇二甲基丙烯酸酯单体、乙氧基化苯酚甲基丙烯酸酯单体、二异丙烯基苯单体和乙氧基化三羟甲基丙烷的三丙烯酸酯单体。
18、权利要求15的光致变色制品,其中有机光致变色化合物(b)选自萘并吡喃,苯并吡喃,菲并吡喃,螺(苯并二氢吲哚)萘并吡喃,螺(二氢吲哚)苯并吡喃,螺(二氢吲哚)萘并吡喃,螺(二氢吲哚)喹啉并吡喃,螺(二氢吲哚)吡喃,螺(二氢吲哚)吩噁嗪,螺(二氢吲哚)吡啶并苯并噁嗪,螺(苯并二氢吲哚)吡啶并苯并噁嗪,螺(苯并二氢吲哚)吩噁嗪,螺(二氢吲哚)苯并噁嗪,以及这些光致变色化合物的混合物。
19、权利要求18的光致变色制品,其中光致变色化合物的含量为每平方厘米掺入或施加光致变色物质的有机基质材料表面0.05到1.0毫克。
20、权利要求19的光致变色制品,其中所述制品为透镜。
21、一种光致变色制品,它组合含有聚合有机基质材料,所述有机基质材料选自聚(异丁烯酸甲酯)、 聚(乙二醇双甲基丙烯酸酯)、聚(乙氧基化双酚A二甲基丙烯酸酯)、热塑性聚碳酸酯、聚(乙酸乙烯酯)、聚乙烯醇缩丁醛、聚氨酯和如下单体的聚合物:二甘醇双(碳酸烯丙酯)单体、二甘醇二甲基丙烯酸酯单体、乙氧基化苯酚甲基丙烯酸酯单体、二异丙烯基苯单体和乙氧基化三羟甲基丙烷的三丙烯酸酯单体;以及光致变色量的下列各化合物:(a)至少一种权利要求2的茚并萘并吡喃化合物,和(b)至少一种在约400到700纳米范围内具有至少一个最大激活吸收的其它有机光致变色化合物。
22、一种光致变色制品,它组合含有聚合有机基质材料,所述有机基质材料选自聚(异丁烯酸甲酯)、聚(乙二醇双甲基丙烯酸酯)、聚(乙氧基化双酚A二甲基丙烯酸酯)、热塑性聚碳酸酯、聚(乙酸乙烯酯)、聚乙烯醇缩丁醛、聚氨酯和如下单体的聚合物:二甘醇双(碳酸烯丙酯)单体、二甘醇二甲基丙烯酸酯单体、乙氧基化苯酚甲基丙烯酸酯单体、二异丙烯基苯单体和乙氧基化三羟甲基丙烷的三丙烯酸酯单体;以及光致变色量的下列各化合物:(a)至少一种权利要求3的茚并萘并吡喃化合物,和(b)至少一种在约400到700纳米范围内具有至少一个最大激活吸收的其它有机光致变色化合物。
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US08/783,343 US5698141A (en) | 1996-06-17 | 1997-01-16 | Photochromic heterocyclic fused indenonaphthopyrans |
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- 1997-09-03 WO PCT/US1997/015433 patent/WO1998032037A1/en active IP Right Grant
- 1997-09-03 CA CA002278139A patent/CA2278139C/en not_active Expired - Fee Related
- 1997-09-03 HU HU0000056A patent/HUP0000056A3/hu unknown
- 1997-09-03 IL IL13096297A patent/IL130962A0/xx unknown
- 1997-09-03 BR BR9714777-0A patent/BR9714777A/pt not_active IP Right Cessation
- 1997-09-03 DE DE69732372T patent/DE69732372T2/de not_active Expired - Lifetime
- 1997-09-03 EP EP97939746A patent/EP0958514B1/en not_active Expired - Lifetime
- 1997-09-03 AU AU41765/97A patent/AU737007B2/en not_active Ceased
- 1997-09-03 CN CN97181917A patent/CN1247604A/zh active Pending
- 1997-09-03 ES ES97939746T patent/ES2236823T3/es not_active Expired - Lifetime
- 1997-09-03 JP JP53430998A patent/JP4383544B2/ja not_active Expired - Fee Related
- 1997-09-03 NZ NZ336837A patent/NZ336837A/xx unknown
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CN100506887C (zh) * | 2004-02-06 | 2009-07-01 | 三星移动显示器株式会社 | 噻吩并[3,2-b]吲哚基聚合物及使用它的有机-电致发光装置 |
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DE69732372D1 (de) | 2005-03-03 |
CA2278139A1 (en) | 1998-07-23 |
JP4383544B2 (ja) | 2009-12-16 |
HUP0000056A3 (en) | 2001-10-29 |
IL130962A0 (en) | 2001-01-28 |
EP0958514A4 (en) | 2000-03-22 |
CO5040153A1 (es) | 2001-05-29 |
WO1998032037A1 (en) | 1998-07-23 |
HUP0000056A2 (hu) | 2000-05-28 |
DE69732372T2 (de) | 2005-12-29 |
BR9714777A (pt) | 2002-05-21 |
EP0958514B1 (en) | 2005-01-26 |
CA2278139C (en) | 2004-11-09 |
US5698141A (en) | 1997-12-16 |
ES2236823T3 (es) | 2005-07-16 |
NZ336837A (en) | 2001-03-30 |
AU4176597A (en) | 1998-08-07 |
AU737007B2 (en) | 2001-08-09 |
JP2001512434A (ja) | 2001-08-21 |
EP0958514A1 (en) | 1999-11-24 |
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