CN1277821C - 并苯衍生物及其作为染料的用途 - Google Patents
并苯衍生物及其作为染料的用途 Download PDFInfo
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- CN1277821C CN1277821C CNB028052102A CN02805210A CN1277821C CN 1277821 C CN1277821 C CN 1277821C CN B028052102 A CNB028052102 A CN B028052102A CN 02805210 A CN02805210 A CN 02805210A CN 1277821 C CN1277821 C CN 1277821C
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- Prior art keywords
- pyrimidyl
- group
- pyridyl
- alkyl
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000000975 dye Substances 0.000 title claims description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- -1 3-pyrryl Chemical group 0.000 claims description 212
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 57
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 28
- 150000003949 imides Chemical class 0.000 claims description 28
- 150000008064 anhydrides Chemical class 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 22
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 239000000049 pigment Substances 0.000 claims description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 16
- 229910000071 diazene Inorganic materials 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 15
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 13
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 13
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229920003026 Acene Polymers 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 12
- 150000001555 benzenes Chemical class 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 238000004040 coloring Methods 0.000 claims description 10
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 10
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 claims description 9
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 8
- 239000004815 dispersion polymer Substances 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000006114 decarboxylation reaction Methods 0.000 claims description 7
- 238000001228 spectrum Methods 0.000 claims description 7
- 239000004480 active ingredient Substances 0.000 claims description 6
- 239000004020 conductor Substances 0.000 claims description 6
- 239000002537 cosmetic Substances 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 6
- 239000011147 inorganic material Substances 0.000 claims description 6
- 239000000990 laser dye Substances 0.000 claims description 6
- 239000011368 organic material Substances 0.000 claims description 6
- KDDQRKBRJSGMQE-UHFFFAOYSA-N 4-thiazolyl Chemical compound [C]1=CSC=N1 KDDQRKBRJSGMQE-UHFFFAOYSA-N 0.000 claims description 5
- CWDWFSXUQODZGW-UHFFFAOYSA-N 5-thiazolyl Chemical group [C]1=CN=CS1 CWDWFSXUQODZGW-UHFFFAOYSA-N 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 239000003495 polar organic solvent Substances 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 4
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 4
- 230000001131 transforming effect Effects 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 4
- 125000000623 heterocyclic group Chemical group 0.000 claims 4
- 229960004365 benzoic acid Drugs 0.000 claims 2
- 235000010233 benzoic acid Nutrition 0.000 claims 2
- 238000010572 single replacement reaction Methods 0.000 claims 1
- 125000001072 heteroaryl group Chemical group 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 abstract 1
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 abstract 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 125000003107 substituted aryl group Chemical group 0.000 abstract 1
- 239000002585 base Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000005893 bromination reaction Methods 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000031709 bromination Effects 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 241000534944 Thia Species 0.000 description 5
- 238000013019 agitation Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000002080 perylenyl group Chemical class C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 3
- 239000010981 turquoise Substances 0.000 description 3
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 125000006219 1-ethylpentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005808 2,4,6-trimethoxyphenyl group Chemical group [H][#6]-1=[#6](-[#8]C([H])([H])[H])-[#6](-*)=[#6](-[#8]C([H])([H])[H])-[#6]([H])=[#6]-1-[#8]C([H])([H])[H] 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000003006 2-dimethylaminoethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical class CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 1
- 125000004208 3-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C([H])C(*)=C1[H] 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- AWMHRVHGKOFCNI-UHFFFAOYSA-N C(CCCC)OC(C(C)(C)C)OOCCC(C)C Chemical compound C(CCCC)OC(C(C)(C)C)OOCCC(C)C AWMHRVHGKOFCNI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CBMCZKMIOZYAHS-NSCUHMNNSA-N [(e)-prop-1-enyl]boronic acid Chemical compound C\C=C\B(O)O CBMCZKMIOZYAHS-NSCUHMNNSA-N 0.000 description 1
- ODFJOVXVLFUVNQ-UHFFFAOYSA-N acetarsol Chemical compound CC(=O)NC1=CC([As](O)(O)=O)=CC=C1O ODFJOVXVLFUVNQ-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 229910001038 basic metal oxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 150000003950 cyclic amides Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000006260 ethylaminocarbonyl group Chemical group [H]N(C(*)=O)C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004458 methylaminocarbonyl group Chemical group [H]N(C(*)=O)C([H])([H])[H] 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
- C07D491/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/04—Ortho- or peri-condensed ring systems
- C07D221/18—Ring systems of four or more rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/06—Peri-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/62—Cyclic imides or amidines of peri-dicarboxylic acids of the anthracene, benzanthrene, or perylene series
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cosmetics (AREA)
- Hydrogenated Pyridines (AREA)
- Indole Compounds (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
Abstract
本发明涉及通式(I)的并苯衍生物,其中:R是氢或被取代的或未被取代的C1-C30-烷基、芳基或杂芳基;R1是氢或溴;R2是氢或C1-C6-烷基;R3是氢、C1-C18-烷基或被取代的或未被取代的芳基或杂芳基;和n是2或3。
Description
本发明涉及通式I的新型并苯(Rylen)衍生物,
其中各变量具有下列意义:
R是氢;
C1-C30-烷基,它的碳链可以被一个或多个-O-、-S-、-NR2-、-CO-和/或-SO2-基团间隔,和它可以被羧基、磺基、羟基、氰基、C1-C6-烷氧基和/或通过氮原子键接并可包含其它杂原子且可为芳族的5-至7-元杂环基团单取代或多取代;
芳基或杂芳基,其各自可以被C1-C18-烷基、C1-C6-烷氧基、卤素、羟基、氰基、羧基、-CONHR3,-NHCOR3和/或芳基偶氮基或杂芳基偶氮基单取代或多取代,这些基团各自可以被C1-C10-烷基、C1-C6-烷氧基、卤素、羟基、氰基和/或羧基取代;
R1是氢或溴;
R2是氢或C1-C6-烷基;
R3是氢;C1-C18-烷基;芳基或杂芳基,其各自可以被C1-C8-烷基、C1-C6-烷氧基、卤素、羟基和/或氰基取代;和
n是2或3,
和涉及并苯衍生物I的制备方法和涉及它们用于着色高分子量有机和无机材料(尤其塑料、表面涂层和打印油墨)的用途,用作分散助剂,有机颜料的颜料添加剂和供制备荧光着色剂和颜料添加剂用的中间体的用途,作为装饰性化妆品中着色组分的用途,用于制备在电磁波谱的近红外区中被着色的或吸收和/或发射光的聚合物水分散体的用途,作为电子照相术的光电导体的用途,作为电致发光和化学荧光应用中的发光体的用途,作为荧光转化中的活性组分和作为激光染料的用途。
另外,本发明涉及通式III的新型并苯四羧酸单酰亚胺单酸酐
其中各变量如以上所定义,其作为用于制备并苯衍生物I的中间体,和涉及它们的制备方法和用于着色高分子量有机和无机材料的用途,作为分散助剂、有机颜料的颜料添加剂和作为中间体用于制备可聚合的着色剂和颜料添加剂的用途,作为装饰性化妆品中的着色组分的用途,用于在电磁波谱的近红外区中着色或吸收和/或发射光的聚合物水分散体的制备的用途,作为电子照相术中的光电导体的用途,作为电致发光和化学荧光应用中的发光体,作为荧光转化中的活性组分和作为激光染料的用途。
较短的并苯-3,4-二羧酰亚胺(其中在通式I中n=0或1,即相应的萘和苝衍生物)是已知的。未被取代的或在迫位(苝结构的9位)上被卤素取代的苝-3,4-二羧酰亚胺例如已描述在EP-A-636 666中,在Chimia 48,503-505页(1994)中,在EP-A-592 292中和在Dyes and Pigments 16,19-25页(1991)中。另外在苝结构中被取代的其它9-卤代苝-3,4-二羧酰亚胺已公开于WO-A-96/22332中。已知的化合物的共同特征是它们在近UV区中或可见光谱的短波区域中、即基本上在340-540纳米范围内吸收光。
本发明的目的是提供并苯衍生物,它在电磁波谱的长波区域即在红色和红外区域中吸收和发射光,并可以在迫位中特定地衍生化。
我们已经发现这一目的可通过在开始定义的通式I的叔-并苯和季-并苯衍生物来实现。
优选的并苯衍生物是从属权利要求中定义。
我们还发现了制备并苯衍生物I的方法,它包括
a)在极性有机溶剂存在下在碱性条件下将通式II的不对称的并苯四羧酸二酰亚胺进行单水解
其中R4是C5-C8-环烷基,它的碳骨架可以被一个或多个-O-、-S-和/或-NR2-基团间隔和它可以被C1-C6-烷基单取代或多取代,
b)在含叔氮的碱性化合物存在下和在过渡金属催化剂存在下将在步骤a)中形成的通式III的并苯四羧酸单酰亚胺单酸酐进行单脱羧化,
和
c)如果需要,随后让该反应产物与元素溴反应。
我们还发现了制备并苯四羧酸单酰亚胺单酸酐III的方法,它包括在极性有机溶剂存在下在碱性条件下将不对称的并苯四羧酰二亚胺II进行单水解。
我们还发现在一开始定义的通式III的并苯四羧酸单酰亚胺单酸酐作为并苯-3,4-二羧酰亚胺I的中间体的用途。
在一定程度上,我们还发现,并苯衍生物I和并苯四羧酸单酰亚胺单酸酐III同样具有在一开始提到的用途。
在通式I-III中出现的全部烷基可以是直链或支化的。如果该烷基是取代的,则它们一般携带一个或两个取代基。
可提及的合适的基团R、R1、R2、R3和R4(或它的取代基)的特定的例子是下列这些:
甲基,乙基,丙基,异丙基,丁基,异丁基,叔丁基,戊基,异戊基,新戊基,叔戊基,己基,2-甲基戊基,庚基,1-乙基戊基,辛基,2-乙基己基,异辛基,壬基,异壬基,癸基,异癸基,十一烷基,十二烷基,十三烷基,异十三烷基,十四烷基,十五烷基,十六烷基,十七烷基,十八烷基,十九烷基和二十烷基(上述名称异辛基、异壬基、异癸和异十三烷基是俗名,来源于由羰基合成法获得的醇类);
2-甲氧基乙基,2-乙氧基乙基,2-丙氧基乙基,2-异丙氧基乙基,2-丁氧基乙基,2-和3-甲氧基丙基,2-和3-乙氧基丙基,2-和3-丙氧基丙基,2-和3-丁氧基丙基,2-和4-甲氧基丁基,2-和4-乙氧基丁基,2-和4-丙氧基丁基,3,6-二氧杂庚基,3,6-二氧杂辛基,4,8-二氧杂壬基,3,7-二氧杂辛基,3,7-二氧杂壬基,4,7-二氧杂辛基,4,7-二氧杂壬基,2-和4-丁氧基丁基,4,8-二氧杂癸基,3,6,9-三氧杂癸基,3,6,9-三氧杂十一烷基,3,6,9-三氧杂十二烷基,3,6,9,12-四氧杂十三烷基和3,6,9,12-四氧杂十四烷基;
2-甲基硫基乙基,2-乙基硫基乙基,2-丙基硫基乙基,2-异丙基硫基乙基,2-丁基硫基乙基,2-和3-甲基硫基丙基,2-和3-乙基硫基丙基,2-和3-丙基硫基丙基,2-和3-丁基硫基丙基,2-和4-甲基硫基丁基,2-和4-乙基硫基丁基,2-和4-丙基硫基丁基,3,6-二硫杂庚基,3,6-二硫杂辛基,4,8-二硫杂壬基,3,7-二硫杂辛基,3,7-二硫杂壬基,2-和4-丁基硫基丁基,4,8-二硫杂癸基,3,6,9-三硫杂癸基,3,6,9-三硫杂十一烷基,3,6,9-三硫杂十二烷基,3,6,9,12-四硫杂十三烷基和3,6,9,12-四硫杂十四烷基;
2-单甲基-和2-单乙基氨基乙基,2-二甲基氨基乙基,2-和3-二甲基氨基丙基,3-单异丙基氨基丙基,2-和4-单丙基氨基丁基,2-和4-二甲基氨基丁基,6-甲基-3,6-二氮杂庚基,3,6-二甲基-3,6-二氮杂庚基,3,6-二氮杂辛基,3,6-二甲基-3,6-二氮杂辛基,9-甲基-3,6,9-三氮杂癸基,3,6,9-三甲基-3,6,9-三氮杂癸基,3,6,9-三氮杂十一烷基,3,6,9-三甲基-3,6,9-三氮杂十一烷基,12-甲基-3,6,9,12-四氮杂十三烷基和3,6,9,12-四甲基-3,6,9,12-四氮杂十三烷基;
丙-2-酮-1-基,丁-3-酮-1-基,丁-3-酮-2-基和2-乙基戊-3-酮-1-基;
2-甲基磺酰基乙基,2-乙基磺酰基乙基,2-丙基磺酰基乙基,2-异丙基磺酰基乙基,2-丁基磺酰基乙基,2-和3-甲基磺酰基丙基,2-和3-乙基磺酰基丙基,2-和3-丙基磺酰基丙基,2-和3-丁基磺酰基丙基,2-和4-甲基磺酰基丁基,2-和4-乙基磺酰基丁基,2-和4-丙基磺酰基丁基和4-丁基磺酰基丁基;
羧甲基,2-羧乙基,3-羧基丙基,4-羧基丁基,5-羧基戊基,6-羧基己基,8-羧基辛基,10-羧基癸基,12-羧基十二烷基和14-羧基十四烷基;
磺基甲基,2-磺乙基,3-磺丙基,4-磺基丁基,5-磺基戊基,6-磺基己基,8-磺基辛基,10-磺基癸基,12-磺基十二烷基和14-磺基十四烷基;
2-羟乙基,3-羟丙基,1-羟基丙-2-基,2-和4-羟基丁基,1-羟基丁-2-基和8-羟基-4-氧杂辛基;
氰基甲基,2-氰基乙基,3-氰基丙基,2-甲基-3-乙基-3-氰基丙基,7-氰基-7-乙基庚基和4,7-二甲基-7-氰基庚基;
甲氧基,乙氧基,丙氧基,异丙氧基,丁氧基,异丁氧基,仲丁氧基,叔-丁氧基,戊氧基,异戊氧基,新戊氧基,叔-戊氧基和己氧基;
氨基甲酰基,甲基氨基羰基,乙基氨基羰基,丙基氨基羰基,丁基氨基羰基,戊基氨基羰基,己基氨基羰基,庚基氨基羰基,辛基氨基羰基,壬基氨基羰基,癸基氨基羰基和苯基氨基羰基;
甲酰氨基,乙酰氨基,丙酰基氨基和苯甲酰基氨基;
氯,溴和碘;
苯基偶氮基,2-萘基偶氮基,2-吡啶基偶氮基和2-嘧啶基偶氮基;
苯基,2-萘基,2-和3-吡咯基,2-,3-和4-吡啶基,2-,4-和5-嘧啶基,3-,4-和5-吡唑基,2-,4-和5-咪唑基,2-,4-和5-噻唑基,3-(1,2,4-三唑基),2-(1,3,5-三唑基),6-喹哪啶基,3-,5-,6-和8-喹啉基,2-苯并唑基,2-苯并噻唑基,5-苯并噻二唑基,2-和5-苯并咪唑基和1-和5-异喹啉基;
2-,3-和4-甲基苯基,2,4-,2,5-,3,5-和2,6-二甲基苯基,2,4,6-三甲基苯基,2-,3-和4-乙基苯基,2,4-,2,5-,3,5-和2,6-二乙基苯基,2,4,6-三乙基苯基,2-,3-和4-丙基苯基,2,4-,2,5-,3,5-和2,6-二丙基苯基,2,4,6-三丙基苯基,2-,3-和4-异丙基苯基,2,4-,2,5-,3,5-和2,6-二异丙基苯基,2,4,6-三异丙基苯基,2-,3-和4-丁基苯基,2,4-,2,5-,3,5-和2,6-二丁基苯基,2,4,6-三丁基苯基,2-,3-和4-异丁基苯基,2,4-,2,5-,3,5-和2,6-二异丁基苯基,2,4,6-三异丁基苯基,2-,3-和4-仲-丁基苯基,2,4-,2,5-,3,5-和2,6-二仲丁基苯基和2,4,6-三仲丁基苯基,2-,3-和4-叔丁基苯基,2,4-,2,5-,3,5-和2,6-二叔丁基苯基,2,4,6-三叔丁基苯基;2-,3-和4-甲氧基苯基,2,4-,2,5-,3,5-和2,6-二甲氧基苯基,2,4,6-三甲氧基苯基,2-,3-和4-乙氧基苯基,2,4-,2,5-,3,5-和2,6-二乙氧基苯基,2,4,6-三乙氧基苯基,2-,3-和4-丙氧基苯基,2,4-,2,5-,3,5-和2,6-二丙氧基苯基,2-,3-和4-异丙氧基苯基,2,4-,2,5-,3,5-和2,6-二异丙氧基苯基和2-,3-和4-丁氧基苯基;2-,3-和4-氯苯基,和2,4-,2,5-,3,5-和2,6-二氯苯基;2-,3-和4-羟苯基和2,4-,2,5-,3,5-和2,6-二羟苯基;2-,3-和4-氰基苯基;3-和4-羧基苯基;3-和4-羧酰胺基苯基,3-和4-N-甲基羧酰胺基苯基和3-和4-N-乙基羧酰胺基苯基;3-和4-乙酰基氨基苯基,3-和4-丙酰基氨基苯基和3-和4-丁酰基氨基苯基;3-和4-N-苯基氨基苯基,3-和4-N-(邻-甲苯基)氨基苯基,3-和4-N-(间-甲苯基)氨基苯基和3-和4-N-(对-甲苯基)氨基苯基;3-和4-(2-吡啶基)氨基苯基,3-和4-(3-吡啶基)氨基苯基,3-和4-(4-吡啶基)氨基苯基,3-和4-(2-嘧啶基)氨基苯基和4-(4-嘧啶基)氨基苯基;
4-苯基偶氮基苯基,4-(1-萘基偶氮基)苯基,4-(2-萘基偶氮基)苯基,4-(4-萘基偶氮基)苯基,4-(2-吡啶基偶氮基)苯基,4-(3-吡啶基偶氮基)苯基,4-(4-吡啶基偶氮基)苯基,4-(2-嘧啶基偶氮基)苯基,4-(4-嘧啶基偶氮基)苯基和4-(5-嘧啶基偶氮基)苯基;
环戊基,2-和3-甲基环戊基,2-和3-乙基环戊基,环己基,2-,3-和4-甲基环己基,2-,3-和4-乙基环己基,3-和4-丙基环己基,3-和4-异丙基环己基,3-和4-丁基环己基,3-和4-仲-丁基环己基,3-和4-叔-丁基环己基,环庚基,2-,3-和4-甲基环庚基,2-,3-和4-乙基环庚基,3-和4-丙基环庚基,3-和4-异丙基环庚基,3-和4-丁基环庚基,3-和4-仲丁基环庚基,3-和4-叔丁基环庚基,环辛基,2-,3-,4-和5-甲基环辛基,2-,3-,4-和5-乙基环辛基,3-,4-和5-丙基环辛基,2-二氧杂环己烷基,4-吗啉基,2-和3-四氢呋喃基,1-,2-和3-吡咯烷基和1-,2-,3-和4-哌啶基。
并苯衍生物I可以理想地通过根据本发明的多步骤方法来制备,其中,在步骤a)中,在酰亚胺氮上被环烷基基团取代的不对称并苯四羧酸二酰亚胺II是被单水解的,和在步骤b)中,所形成的并苯四羧酸单酰亚胺单酸酐III被单脱羧。如果需要其中在迫位上被溴化的并苯衍生物I(R1=溴),则使在迫位上未被取代的并苯衍生物I(R1=H)在下一步骤c)中与元素溴反应。
根据本发明方法的步骤a),并苯四羧酸二酰亚胺II的环烷基取代的酰亚胺基团的水解是在极性有机溶剂和碱存在下进行的。
用作此目的的起始原料的不对称并苯四羧酸二酰亚胺II是已知的,可以按照在EP-A-592 292中和在Chem.Eur.Journal 3,219-225页(1997)中所述来制备。
合适的溶剂特别是支化的C3-C6-醇,如异丙醇、叔丁醇和2-甲基-2-丁醇。
通常,以每g的II计使用40-200g的溶剂。
合适的碱是:无机碱,尤其是碱金属和碱土金属氢氧化物,例如氢氧化钠和氢氧化钾,它们优选以水溶液或悬浮液(通常50-80%浓度,按重量计)的形式使用;和有机碱,尤其是碱金属和碱土金属醇盐,优选醇钠和醇钾,如甲醇钠、甲醇钾、异丙醇钾和叔丁醇钾,它们通常以无水形式使用。
通常,需要5-50当量的碱,基于II计。
反应温度一般是50-120℃,优选60-100℃。
水解通常在10-40小时中完成。
本方法的步骤a)有利地如下进行:
并苯四羧酸二酰亚胺II、碱和溶剂的悬浮液在强烈搅拌下被加热至所需的反应温度。当水解完成和混合物已经冷却到室温时,使用酸,例如无机酸,如盐酸,或有机酸,如乙酸,达到1-4的pH。产物被滤出,用热水洗涤和随后在大约100℃下减压干燥。
通常,在步骤a)中所获得的并苯四羧酸单酰亚胺单酸酐III已经具有高含量(>90%),使得它可以直接用于步骤b)中的脱羧。
在根据本发明方法的步骤b)中,并苯四羧酸单酰亚胺单酸酐III是在作为溶剂的含叔氮的碱性化合物存在下和在过渡金属催化剂存在下进行单脱羧。
合适的溶剂特别是高沸点的含氮碱,例如环酰胺,如N-甲基吡咯烷酮,和芳族杂环化合物,如喹啉、异喹啉和喹哪啶。
溶剂的常规用量是20-150g/每g的III。
合适的催化剂特别是过渡金属铜和锌,和尤其是它们的无机和有机盐,它们优选以无水形式使用。
优选的盐的例子是铜(I)氧化物、铜(II)氧化物、铜(I)氯化物、铜(II)乙酸盐、乙酸锌和丙酸锌,特别优选的是铜(I)氧化物和乙酸锌。
当然还可以使用所述催化剂的混合物。
通常,使用50-90mol%的催化剂,基于III计。
反应温度一般是100-250℃,尤其是160-200℃。建议使用保护气体气氛(例如氮气)。
脱羧通常在3-20小时内完成。
本方法的步骤b)理想地如下进行:
并苯四羧酸单酰亚胺单酸酐III、溶剂和催化剂的混合物在搅拌下被加热至所需的反应温度。当脱羧已完成和混合物已经冷却到室温时,反应混合物被倾倒在同样体积的低沸点醇例如甲醇中,在搅拌下添加同样量的稀无机酸,例如5-6%浓度(按重量计)的盐酸,然后产物被滤出。如果需要,该粗产物在合适的溶剂例如芳族溶剂如二甲苯中进行搅拌,过滤,用低沸点的醇洗涤和在大约75℃下减压干燥。
通过从高沸点的溶剂例如N-甲基吡咯烷酮中重结晶,使得进一步提纯是可能的。通常,这不是必需的,因为所获得的并苯衍生物I(R1=H)已经具有≥95%的含量。
对于在迫位上被溴化的并苯衍生物I(R1=溴)的制备,未被取代的并苯衍生物I可以进行根据本发明的步骤c),即立体选择性溴化。
这一溴化作用优选是在脂族单羧酸,尤其C1-C4-羧酸,如甲酸、乙酸、丙酸、丁酸或它们的混合物中,或在卤代的、脂族的或芳族的溶剂,如二氯甲烷、氯仿或氯苯中进行。
对于每g所要溴化的I,通常使用5-30g、优选15-25g的溶剂。
通常,卤化催化剂的存在不是必需的。然而,如果希望加速该溴化反应(大约1.5-2倍),则建议添加元素碘,优选用量为1-5mol%,基于I计。
通常,溴和I之间的摩尔比率是约1∶1到5∶1,优选3∶1到4∶1。
反应温度一般是0-70℃,尤其是10-40℃。
取决于底物I的反应性和碘的存在或不存在,溴化通常是在2-12小时内完成。
本方法的步骤c)理想地如下进行:
需要溴化的并苯衍生物I和溶剂的混合物在搅拌下经过15-30分钟的一段时间调节至所需的反应温度,如果需要的话添加催化剂,所需要量的溴随后经过5-10分钟的时间添加进去,然后该混合物在没有光的条件下在反应温度下搅拌2-12个小时。在使用剧烈的氮气流除去多余的溴之后,反应混合物被引入到大约同样量的脂族醇例如甲醇中,搅拌一整夜,然后将沉淀的产物滤出,洗涤,优选用相同的醇进行,然后在大约120℃下减压干燥。
通常,在步骤c)中所获得的溴化并苯衍生物I也已经具有如此高的含量(>95%),使得它们可以直接用于所希望的应用中。
根据本发明的并苯衍生物I非常适合于高分子量有机和无机材料,尤其例如塑料(特别是热塑性塑料)、表面涂层和打印油墨,和氧化层体系的均匀着色。
它们也适合用作分散助剂,有机颜料的颜料添加剂和供制备荧光着色剂和颜料添加剂用的中间体,用作装饰性化妆品中的着色组分,用于在电磁波谱的近红外区中着色或吸收和/或发射光的聚合物水分散体的制备,和用作电子照相术中的光电导体,用作电致发光和化学荧光应用中的发光体,用作荧光转化中的活性组分和用作激光染料。
用作并苯衍生物I的中间体的该并苯四羧酸单酰亚胺单酸酐III本身也可用于着色上述高分子量有机和无机材料,用作分散助剂、有机颜料的颜料添加剂和供制备可聚合的着色剂和颜料添加剂用的中间体,用作装饰性化妆品中的着色组分,用于在电磁波谱的近红外区中着色或吸收和/或发射光的聚合物水分散体的制备,和用作电子照相术中的光电导体,用作电致发光和化学荧光应用中的发光体,用作荧光转化中的活性组分和用作激光染料。
实施例
A)根据本发明的通式III的并苯四羧酸单酰亚胺单酸酐的制备
实施例1-6
将10g(x mmol)的并苯四羧酸二酰亚胺II引入到500ml的异丙醇中,然后添加40g氢氧化钾和30ml水的混合物。混合物然后在搅拌下回流t小时。
在已经冷却到室温后,反应混合物被引入到两体积份水和一体积份浓盐酸的300ml混合物中。在混合物搅拌30分钟之后,产物被滤出,用水洗涤到pH中性,然后在减压下于100℃干燥。
有关这些实验和它们的结果的更多细节示于表1。
表1
实施例 | x[mmol] | 并苯四羧酸二酰亚胺II | t[h] | 产量[g]/[%] | 外观 | m.p.[℃] |
1 | 13.2 | N-(2,6-二异丙基苯基)-N’-环己基三并苯-3,4:11,12-四羧酸二酰亚胺 | 20 | 8.9/100 | 蓝紫色,微晶 | >350 |
2 | 14.2 | N-(对-甲氧基苯基)-N’-环己基三并苯-3,4:11,12-四羧酸二酰亚胺 | 28 | 8.4/95 | 蓝黑色,无定形 | >350 |
3 | 13.1 | N-十二烷基-N’-环己基三并苯-3,4:11,12-四羧酸二酰亚胺 | 18 | 8.7/97 | 黑色,无定形 | >350 |
4 | 11.4 | N-(2,6-二异丙基苯基)-N’-环己基四并苯-3,4:13,14-四羧酸二酰亚胺 | 15 | 8.9/98 | 黑色,微晶 | >350 |
5 | 12.1 | N-(对-甲氧基苯基)-N’-环己基四并苯-3,4:13,14-四羧酸二酰亚胺 | 20 | 8.3/92 | 紫黑色,无定形 | >350 |
6 | 11.3 | N-十二烷基-N’环己基四并苯-3,4:13,14-四羧酸二酰亚胺 | 28 | 8.6/95 | 紫黑色,无定形 | >350 |
B)根据本发明的并苯衍生物I(R1=H)的制备
实施例7-12
在搅拌下将xg(7mmol)的并苯四羧酸单酰亚胺单酸酐III和7g的铜(I)氧化物在400ml喹啉中的混合物加热至220℃,然后在这一温度下保持t小时。
在已经冷却到室温后,反应溶液被引入到400ml的甲醇中,然后添加3体积份水和1体积份浓盐酸的400ml混合物。在混合物搅拌30分钟之后,产物被滤出,用水洗涤到pH中性,然后在减压下于75℃干燥。以这种方式获得的粗产物随后通过从N-甲基吡咯烷酮中重结晶而除去痕量的起始原料。
有关这些实验和它们的结果的更多细节示于表2中。
表2
实施例 | x[g] | 并苯四羧酸单酰亚胺单酸酐III | t[h] | 产量[g]/[%] | 外观 | m.p.[℃] |
7 | 4.8 | N-(2,6-二异丙基苯基)三并苯-3,4:11,12-四羧酸单酰亚胺单酸酐 | 10 | 3.7/88 | 蓝黑色,微晶 | >350 |
8 | 4.4 | N-(对-甲氧基苯基)三并苯-3,4:11,12-四羧酸单酰亚胺单酸酐 | 12 | 3.3/85 | 蓝黑色,晶体 | >350 |
9 | 4.8 | N-十二烷基三并苯-3,4:11,12-羧酸单酰亚胺单酸酐 | 15 | 3.9/90 | 黑色,无定形 | >350 |
10 | 5.6 | N-(2,6-二异丙基苯基)四并苯-3,4:13,14-四羧酸单酰亚胺单酸酐 | 15 | 4.1/80 | 黑色,微晶 | >350 |
11 | 5.2 | N-(对-甲氧基苯基)四并苯-3,4:13,14-四羧酸单酰亚胺单酸酐 | 20 | 4.3/90 | 黑色,微晶 | >350 |
12 | 5.7 | N-十二烷基四并苯-3,4:13,14-四羧酸单酰亚胺单酸酐 | 20 | 4.4/86 | 黑色,无定形 | >350 |
实施例7的分析数据:
N-(2,6-二异丙基苯基)三并苯-3,4-二羧酰亚胺:
元素分析(重量%,计算值/实测值):
C:87.25/87.4;H:5.15/5.2;N:2.3/2.2;O:5.3/5.2;
质谱(FD,8kV):m/e=605.2(M+,100%);
IR(KBr):ν=1687(s,C=O),1647(s,C=O)cm-1;
UV/VIS(NMP):λmax(ε)=580(42933),639(47376)nm。
实施例10的分析数据:
N-(2,6-二异丙基苯基)四并苯-3,4-二羧酰亚胺:
元素分析(重量%,计算值/实测值):
C:88.85/88.9;H:4.85/4.8;N:1.9/1.9;O:4.4/4.4;
质谱(FD,8kV):m/e=729.3(M+,100%);
IR(KBr):ν=1690(s,C=O),1651(s,C=O)cm-1;
UV/VIS(NMP):λmax(ε)=677(72355),740(80001)nm。
C)根据本发明的11-溴三并苯-3,4-二羧酰亚胺和13-溴四并苯-3,4-二羧酰亚胺I(R1=溴)的制备
实施例13-18
将xg(0.1mol)的并苯衍生物I悬浮在1.5升的冰醋酸中达30分钟。在1g(3.9mmol)的碘和64g(0.4mol)的溴添加后,混合物在没有光的条件下在T℃下搅拌t小时。
随后通过让剧烈的氮气流穿过该混合物,然后用1升的甲醇洗涤和在室温下搅拌一夜,从反应混合物中除去多余的溴。
沉淀的产物被滤出,首先用1.5升的甲醇洗涤和然后用水洗涤,直至洗涤液呈现中性为止,然后在减压下于120℃干燥。
有关这些实验和它们的结果的更多细节示于表3中。
表3
实施例 | x[g] | 并苯衍生物I | t[h] | T[℃] | 产量[g]/[%] | 外观 | m.p.[℃] |
13 | 60.6 | N-(2,6-二异丙基苯基)三并苯-3,4-二羧酰亚胺 | 8 | 30 | 61.6/90 | 深蓝色,晶体 | >350 |
14 | 55.2 | N-(对-甲氧基苯基)三并苯-3,4-二羧酰亚胺 | 12 | 40 | 56.7/90 | 深蓝色,微晶 | >350 |
15 | 61.4 | N-十二烷基三并苯-3,4-二羧酰亚胺 | 8 | 30 | 61.0/88 | 深蓝色,微晶 | >350 |
16 | 73.0 | N-(2,6-二异丙基苯基)四并苯-3,4-二羧酰亚胺 | 12 | 35 | 68.7/85 | 绿蓝色,晶体 | >350 |
17 | 67.6 | N-(对-甲氧基苯基)四并苯-3,4-二羧酰亚胺 | 16 | 40 | 67.9/90 | 绿蓝色,微晶 | >350 |
18 | 73.8 | N-十二烷基四并苯-3,4-二羧酰亚胺 | 12 | 35 | 67.0/82 | 绿蓝色,晶体 | >350 |
实施例13的分析数据:
11-溴-N-(2,6-二异丙基苯基)三并苯-3,4-二羧酰亚胺:
元素分析(重量%,计算值/实测值):
C:77.2/77.0;H:4.4/4.4;N:2.05/2.1;O:4.7/4.7;BR:11.7/11.8;
质谱(FD,8kV):m/e=684.6(M+,100%);
IR(KBr):ν=1686(s,C=O),1645(s,C=O)cm-1;
UV/VIS(NMP):λmax(ε)=578(46018),643(52323)nm。
实施例16的分析数据:
13-溴-N-(2,6-二异丙基苯基)四并苯-3,4-二羧酰亚胺:
元素分析(重量%,计算值/实测值):
C:80.2/80.5;H:4.2/4.2;N:1.7/1.7;O:4.0/4.1;Br:9.9/9.5;
质谱(FD,8kV):m/e=808.7(M+,100%);
IR(KBr):ν=1689(s,C=O),1650(s,C=O)cm-1;
UV/VIS(NMP):λmax(ε)=671(80081),748(88256)nm。
Claims (16)
1.通式I的并苯衍生物
其中各变量具有下列意义:
R是氢;
C1-C30-烷基,它的碳链可以被一个或多个-O-、-S-、-NR2-、-CO-和/或-SO2-基团间隔,和它可以被羧基、磺基、羟基、氰基、C1-C6-烷氧基和/或通过氮原子键接的5-至7-元杂环基团单取代或多取代,其中所述5-至7-元杂环基团选自2-和3-吡咯基,2-,3-和4-吡啶基,2-,4-和5-嘧啶基,3-,4-和5-吡唑基,2-,4-和5-咪唑基,2-,4-和5-噻唑基,3-(1,2,4-三唑基),2-(1,3,5-三唑基),6-喹哪啶基,3-,5-,6-和8-喹啉基,2-苯并噁唑基,2-苯并噻唑基,5-苯并噻二唑基,2-和5-苯并咪唑基和1-和5-异喹啉基;
苯基、2-萘基、2-吡啶基、3-吡啶基、4-吡啶基、2-嘧啶基、4-嘧啶基或5-嘧啶基,其各自可以被C1-C18-烷基、C1-C6-烷氧基、卤素、羟基、氰基、羧基、-CONHR3、-NHCOR3和/或苯基偶氮基、2-萘基偶氮基、2-吡啶基偶氮基或2-嘧啶基偶氮基单取代或多取代,这些基团各自可以被C1-C10-烷基、C1-C6-烷氧基、卤素、羟基、氰基和/或羧基取代;
R1是氢或溴;
R2是氢或C1-C6-烷基;
R3是氢;C1-C18-烷基;苯基、2-萘基、2-吡啶基、3-吡啶基、4-吡啶基、2-嘧啶基、4-嘧啶基或5-嘧啶基,其各自可以被C1-C8-烷基、C1-C6-烷氧基、卤素、羟基和/或氰基取代;和
n是2或3。
2.根据在权利要求1中所要求的通式I的并苯衍生物,其中变量具有下列意义:
R是C1-C30-烷基,它的碳链可以被一个或多个-O-、-S-、-NR2-、-CO-和/或-SO2-基团间隔,和它可以被羟基、氰基、C1-C6-烷氧基和/或通过氮原子键接的5-至7-元杂环基团单取代或多取代,其中所述5-至7-元杂环基团选自2-和3-吡咯基,2-,3-和4-吡啶基,2-,4-和5-嘧啶基,3-,4-和5-吡唑基,2-,4-和5-咪唑基,2-,4-和5-噻唑基,3-(1,2,4-三唑基),2-(1,3,5-三唑基),6-喹哪啶基,3-,5-,6-和8-喹啉基,2-苯并噁唑基,2-苯并噻唑基,5-苯并噻二唑基,2-和5-苯并咪唑基和1-和5-异喹啉基;
苯基、2-萘基、2-吡啶基、3-吡啶基、4-吡啶基、2-嘧啶基、4-嘧啶基或5-嘧啶基,其各自可以被C1-C18-烷基、C1-C6-烷氧基、羟基、氰基、-CONHR3和/或-NHCOR3单取代或多取代;
R1是氢或溴;
R2是氢或C1-C6-烷基;
R3是氢;C1-C18-烷基;苯基、2-萘基、2-吡啶基、3-吡啶基、4-吡啶基、2-嘧啶基、4-嘧啶基或5-嘧啶基,其各自可以被C1-C8-烷基、C1-C6-烷氧基或氰基取代;和
n是2或3。
4.一种制备通式III的并苯四羧酸单酰亚胺单酸酐的方法,
其中各变量具有下列意义:
R是氢;
C1-C30-烷基,它的碳链可以被一个或多个-O-、-S-、-NR2-、-CO-和/或-SO2-基团间隔和它可以被羧基、磺基、羟基、氰基、C1-C6-烷氧基和/或通过氮原子键接的5-至7-元杂环基团单取代或多取代,其中所述5-至7-元杂环基团选自2-和3-吡咯基,2-,3-和4-吡啶基,2-,4-和5-嘧啶基,3-,4-和5-吡唑基,2-,4-和5-咪唑基,2-,4-和5-噻唑基,3-(1,2,4-三唑基),2-(1,3,5-三唑基),6-喹哪啶基,3-,5-,6-和8-喹啉基,2-苯并噁唑基,2-苯并噻唑基,5-苯并噻二唑基,2-和5-苯并咪唑基和1-和5-异喹啉基;
苯基、2-萘基、2-吡啶基、3-吡啶基、4-吡啶基、2-嘧啶基、4-嘧啶基或5-嘧啶基,其各自可以被C1-C18-烷基、C1-C6-烷氧基、卤素、羟基、氰基、羧基、-CONHR3、-NHCOR3和/或苯基偶氮基、2-萘基偶氮基、2-吡啶基偶氮基或2-嘧啶基偶氮基单取代或多取代,这些基团各自可以被C1-C10-烷基、C1-C6-烷氧基、卤素、羟基、氰基和/或羧基取代;
R2是氢或C1-C6-烷基;
R3是氢;C1-C18-烷基;苯基、2-萘基、2-吡啶基、3-吡啶基、4-吡啶基、2-嘧啶基、4-嘧啶基或5-嘧啶基,其各自可以被C1-C8-烷基、C1-C6-烷氧基、卤素、羟基或氰基取代;和
n是2或3,
该方法包括在极性有机溶剂存在下在碱性条件下将通式II的不对称的并苯四羧酸二酰亚胺进行单水解,
其中R4是C5-C8-环烷基,它的碳骨架可以被一个或多个-O-、-S-和/或-NR2-基团间隔和它可以被C1-C6-烷基单取代或多取代。
5.通式III的并苯四羧酸单酰亚胺单酸酐,
其中各变量具有下列意义:
R是氢;
C1-C30-烷基,它的碳链可以被一个或多个-O-、-S-、-NR2-、-CO-和/或-SO2-基团间隔和它可以被羧基、磺基、羟基、氰基、C1-C6-烷氧基和/或通过氮原子键接的5-至7-元杂环基团单取代或多取代,其中所述5-至7-元杂环基团选自2-和3-吡咯基,2-,3-和4-吡啶基,2-,4-和5-嘧啶基,3-,4-和5-吡唑基,2-,4-和5-咪唑基,2-,4-和5-噻唑基,3-(1,2,4-三唑基,2-(1,3,5-三唑基),6-喹哪啶基,3-,5-,6-和8-喹啉基,2-苯并噁唑基,2-苯并噻唑基,5-苯并噻二唑基,2-和5-苯并咪唑基和1-和5-异喹啉基;
苯基、2-萘基、2-吡啶基、3-吡啶基、4-吡啶基、2-嘧啶基、4-嘧啶基或5-嘧啶基,其各自可以被C1-C18-烷基、C1-C6-烷氧基、卤素、羟基、氰基、羧基、-CONHR3、-NHCOR3和/或苯基偶氮基、2-萘基偶氮基、2-吡啶基偶氮基或2-嘧啶基偶氮基单取代或多取代,这些基团各自可以被C1-C10-烷基、C1-C6-烷氧基、卤素、羟基、氰基和/或羧基取代;
R2是氢或C1-C6-烷基;
R3是氢;C1-C18-烷基;苯基、2-萘基、2-吡啶基、3-吡啶基、4-吡啶基、2-嘧啶基、4-嘧啶基或5-嘧啶基,其各自可以被C1-C8-烷基、C1-C6-烷氧基、卤素、羟基和/或氰基取代;和
n是2或3。
6.根据权利要求1或2所要求的通式I的并苯衍生物用于着色高分子量有机和无机材料的用途。
7.根据在权利要求6中所要求的用途,其中塑料、表面涂层和打印油墨和氧化层体系被着色。
8.根据权利要求1或2中所要求的通式I的并苯衍生物作为分散助剂、有机颜料的颜料添加剂或供制备荧光着色剂和颜料添加剂用的中间体的用途。
9.根据权利要求1或2所要求的通式I的并苯衍生物作为装饰性化妆品中的着色组分的用途。
10.根据权利要求1或2中所要求的通式I的并苯衍生物用于制备聚合物水分散体的用途,所述聚合物水分散体是在电磁波谱的近红外区中着色或吸收和/或发射光。
11.根据权利要求1或2中所要求的通式I的并苯衍生物作为电子照相术中的光电导体、作为电致发光和化学荧光应用中的发光体、作为荧光转化中的活性组分或作为激光染料的用途。
12.根据权利要求5所要求的通式III的并苯四羧酸单酰亚胺单酸酐用于着色高分子量有机和无机材料的用途。
13.根据权利要求5所要求的通式III的并苯四羧酸单酰亚胺单酸酐作为分散助剂、有机颜料的颜料添加剂或供制备荧光着色剂和颜料添加剂用的中间体的用途。
14.根据权利要求5所要求的通式III的并苯四羧酸单酰亚胺单酸酐作为装饰性化妆品中的着色组分的用途。
15.根据权利要求5所要求的通式III的并苯羧酸单酰亚胺单酸酐用于制备聚合物水分散体的用途,所述聚合物水分散体是在电磁波谱的近红外区中着色或吸收和/或发射光。
16.根据权利要求5所要求的通式III的并苯羧酸单酰亚胺单酸酐作为电子照相术中的光电导体、作为电致发光和化学荧光应用中的发光体,作为荧光转化中的活性组分或作为激光染料的用途。
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