CN1082962C - 1,7-二芳氧基或1,7-二芳硫基取代的苝3,4,9,10-四羧酸,它们的二酐和二酰亚胺,制备方法及用途 - Google Patents
1,7-二芳氧基或1,7-二芳硫基取代的苝3,4,9,10-四羧酸,它们的二酐和二酰亚胺,制备方法及用途 Download PDFInfo
- Publication number
- CN1082962C CN1082962C CN96180038A CN96180038A CN1082962C CN 1082962 C CN1082962 C CN 1082962C CN 96180038 A CN96180038 A CN 96180038A CN 96180038 A CN96180038 A CN 96180038A CN 1082962 C CN1082962 C CN 1082962C
- Authority
- CN
- China
- Prior art keywords
- perylene
- group
- tetracarboxylic acid
- replace
- 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 - Lifetime
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- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical class C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 title abstract description 10
- 125000006159 dianhydride group Chemical group 0.000 title description 2
- -1 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic diimides Chemical class 0.000 claims abstract description 109
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 239000000049 pigment Substances 0.000 claims abstract description 18
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 13
- 125000005110 aryl thio group Chemical group 0.000 claims abstract description 7
- 239000000990 laser dye Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 239000003086 colorant Substances 0.000 claims abstract description 5
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 5
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 27
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 19
- CLYVDMAATCIVBF-UHFFFAOYSA-N pigment red 224 Chemical compound C=12C3=CC=C(C(OC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)OC(=O)C4=CC=C3C1=C42 CLYVDMAATCIVBF-UHFFFAOYSA-N 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 17
- PONZBUKBFVIXOD-UHFFFAOYSA-N 9,10-dicarbamoylperylene-3,4-dicarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=N)C2=C1C3=CC=C2C(=N)O PONZBUKBFVIXOD-UHFFFAOYSA-N 0.000 claims description 14
- 229910000071 diazene Inorganic materials 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000003880 polar aprotic solvent Substances 0.000 claims description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000000010 aprotic solvent Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 230000000269 nucleophilic effect Effects 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 150000003573 thiols Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 2
- 239000000543 intermediate Substances 0.000 abstract 1
- 150000003949 imides Chemical class 0.000 description 29
- 239000002585 base Substances 0.000 description 27
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 17
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 16
- 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 15
- 239000000047 product Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 8
- 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 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000035772 mutation Effects 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
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- ZYECOAILUNWEAL-NUDFZHEQSA-N (4z)-4-[[2-methoxy-5-(phenylcarbamoyl)phenyl]hydrazinylidene]-n-(3-nitrophenyl)-3-oxonaphthalene-2-carboxamide Chemical compound COC1=CC=C(C(=O)NC=2C=CC=CC=2)C=C1N\N=C(C1=CC=CC=C1C=1)/C(=O)C=1C(=O)NC1=CC=CC([N+]([O-])=O)=C1 ZYECOAILUNWEAL-NUDFZHEQSA-N 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 241000534944 Thia Species 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 235000010755 mineral Nutrition 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000011368 organic material Substances 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 150000003141 primary amines Chemical class 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- 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 4
- 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 4
- 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 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 4
- 239000006210 lotion Substances 0.000 description 4
- 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 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000002223 garnet Substances 0.000 description 3
- 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 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920002521 macromolecule Polymers 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
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- 125000005979 2-naphthyloxy group Chemical group 0.000 description 2
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 description 2
- 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
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
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- 230000031709 bromination Effects 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
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- 235000011181 potassium carbonates Nutrition 0.000 description 2
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- 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
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- 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
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 238000006887 Ullmann reaction Methods 0.000 description 1
- 241000545067 Venus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- RZJRJXONCZWCBN-UHFFFAOYSA-N alpha-octadecene Natural products CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 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
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction 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
- 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
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229950001891 iprotiazem Drugs 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 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
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 238000012423 maintenance Methods 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
- 239000013081 microcrystal Substances 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 125000001624 naphthyl group Chemical group 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
- 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
- BKEVGGILGWUWSB-UHFFFAOYSA-N nonan-5-amine Chemical compound CCCCC(N)CCCC BKEVGGILGWUWSB-UHFFFAOYSA-N 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 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
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010926 purge Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012265 solid product Substances 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
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 125000001544 thienyl group Chemical group 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000009156 water cure Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide 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
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- 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
- C07D493/06—Peri-condensed systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/105—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic
- C07C65/15—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups polycyclic with carboxyl groups on a condensed ring system containing more than two rings
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- C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
- C07C65/24—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups polycyclic
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- C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
- C09B5/02—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic ring being only condensed in peri position
- C09B5/022—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic ring being only condensed in peri position not provided for in one of the sub groups C09B5/04 - C09B5/20
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Abstract
1,7-二取代苝-3,4,9,10-四羧酸二酐I和苝-3,4,9,10-四羧酸Ia其中R为取代或未取代的芳氧基、芳硫基、杂芳氧基或杂芳硫基,它们的制备和作为颜料,激光染料及制备萤光染料,聚合物着色剂,颜料和颜料添加剂的前体的用途,以及它们的中间体1,7-二取代苝-3.4,9,10-四羧酸二酰亚胺(VI)。
Description
R为芳氧基、芳硫基、杂芳氧基或杂芳硫基,其中各基团可被碳
链可由一个或多个选自-O-、-S-、-NR1-、-CO-和/
或-SO2-的基团插入和/或可被-COOR1、-SO3R1、羟基、氰
基、C1-C6-烷氧基、C5-C8-环烷基或经氮连接并可含有其
他杂原子的5-到7-元杂环基取代一次或多次的C1-C30-烷
基取代一次或多次,或可被C1-C6-烷氧基、氰基、-COOR1
或-SO3R1取代一次或多次,其中R1为氢或C1-C6-烷基,涉及苝-3,4,9,10-四羧酸二酐(I)或所述酸(Ia)的制备方法,以及涉及它们作为颜料,激光染料和制备萤光染料,聚合物着色剂,颜料和颜料添加剂的前体的用途。
其中:
R为芳氧基、芳硫基、杂芳氧基或杂芳硫基,其中各基团可被碳链
可由一个或多个选自-O-、-S-、-NR1-、-CO-和/或
-SO2-的基团插入和/或可被-COOR1、-SO3R1、羟基、氰基、
C1-C6-烷氧基、C5-C8-环烷基或经氮连接并可含其他杂原
子的5-到7-元杂环基取代一次或多次的C1-C30-烷基取代
一次或多次,或可被C1-C6-烷氧基、氰基、-COOR1或-SO3R1
取代一次或多次,其中R1为氢或C1-C6-烷基,以及
R2为碳链可被一个或多个选自-O-、-S-或-CO-的基团插
入的C4-C30-烷基,或为C5-C8-环烷基或芳基,该基团可
被C1-C6-烷基或C1-C6-烷氧基取代一次或多次。该化合物为制备苝-3,4,9,10-四羧酸二酐(I)以酸(Ia)的中间体,本发明还涉及制备苝-3,4,9,10-四羧酸二酰亚胺(VI)的方法。
苝-3,4,9,10-四羧酸及其二酐为已知的制备苝基酰亚胺颜料和苝基酰亚胺染料的重要中间体,而且它们本身也适于用作高分子有机材料的着色剂或颜料。
除了可通过在约200℃下在浓硫酸中水解苝-3,4,9,10-四羧酸二酰亚胺而得到的未取代的苝-3,4,9,10-四羧酸外,令人特别感兴趣的是在苝骨架上有取代的苝四羧酸及其有用的性质,例如通过引入合适的取代基可改变溶解度,固有的颜色和萤光。
WO-A-94/25504公开了1,6,7,12-四芳氧基取代的苝-3,4,9,10-四羧酸二酐,它通过在碱性条件下在极性质子溶剂中水解相应的二酰亚胺而制备。四芳氧基取代的二酰亚胺本身已通过四氯代的二酰亚胺与芳基酯的反应得到(EP-A-227980)。
正如通常以二酐形式存在的所有苝-3,4,9,10-四羧酸一样,到目前为止尚未公开1,7-二取代苝-3,4,9,10-四羧酸如新化合物(Ia)。甚至在EP-A-39912和DRP 412122中公开的二卤代的苝-3,4,9,10-四羧酸二酰亚胺也总是不同卤代程度的产物的混合物(特别是四-、三-和单卤代产物),专一地制备二卤代二酰亚胺是不可能的。
本发明的目的是提供新的、1,7-二氧芳基和1,7-二芳硫基取代的苝-3,4,9,10-四羧酸及其二酐。
我们发现通过开始时定义的式I和Ia的1,7-二取代苝-3,4,9,10-四羧酸二酐及相应的酸(下文称为二酐I)可实现这一目的。
优选的二酐I为从属权利要求中所要求的。
另外通过制备二酐I的方法可实现该目的,该方法包括:
a)在有或无酰亚胺催化剂的存在下,在极性非质子溶剂中,使1,7
-二溴苝-3,4,9,10-四羧酸二酐(II)或1,7-二溴苝-3,
4,9,10-四羧酸(IIa)与通式III伯胺反应
R2-NH2 III
其中R2为其中碳链可被一个或多个-O-、-S-或-CO-基团
插入的C4-C30-烷基,或为C5-C8-环烷基或芳基,该基团
可被C1-C6-烷基或C1-C6-烷氧基取代一次或多次,
b)在非亲核性碱或弱亲核性碱的存在下,在惰性非质子溶剂中,使
步骤a)形成的通式IV的1,7-二溴苝-3,4,9,10-四羧酸二
酰亚胺与通式V的芳族醇或硫醇反应
H-R V以及c)在极性质子溶剂和碱的存在下,将步骤b)中形成的通式VI的1,7-二取代苝-3,4,9,10-四羧酸二酰亚胺水解
得到二酐I。
另外我们也已发现了作为二酐I中间体的前面定义的式VI的1,7-二取代苝-3,4,9,10-四羧酸二酰亚胺(下文称为苝基酰亚胺VI),以及制备苝基酰亚胺VI的方法,该方法包括制备相应的二酐I的方法的步骤a)和b)。
优选的苝基酰亚胺VI为从属权利要求中所要求保护的。
我们也已发现了制备二酐I的第二种方法,其中包括在非质子溶剂及无机碱的存在下使1,7-二溴苝-3,4,9,10-四羧酸二酐(II)或1,7-二溴苝-3,4,9,10-四羧酸(IIa)与式V芳族醇或硫醇反应。
另外,我们也已发现了分别通过在100%重量的硫酸中对苝-3,4,9,10-四羧酸二酐或苝-3,4,9,10-四羧酸进行溴化来制备1,7-二溴苝-3,4,9,10-四羧酸二酐(II)或1,7-二溴苝-3,4,9,10-四羧酸(IIa)的方法,其中包括在80-90℃在碘存在下进行溴化反应以及慢慢地计量加入溴。
另外,我们也已发现了二酐I作为颜料,激光染料及制备萤光染料,聚合物着色剂,颜料和颜料添加剂的前体的用途。
最后,我们也已发现了苝基酰亚胺VI作为对高分子有机材料和无机材料染色的颜料和染料,作为激光染料或用于电发光应用的有机材料的用途。
合适的未取代的基团R为苯氧基、苯硫基、2-萘氧基、2-萘硫基、2-,3-或4-吡啶氧基、2-,3-和4-吡啶硫基、2-,4-和5-嘧啶氧基和2-,4-和5-嘧啶硫基,其中优选苯氧基和2-萘氧基。
基团R的烷基取代基(以及烷基R1和R2)可以是直链的或支链的。
这些取代基(或它们的取代基)的特例为:
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(上述术语异辛基、异壬基、异癸基和异十三烷基是俗名,由通过氧化合成得到的链烷醇衍生-参见Ullmanns Encyklopadie der technischen Chemie,第4版,第7卷,215-217,和第11卷,435和436);
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-甲硫基乙基、2-乙硫基乙基、2-丙硫基乙基、2-异丙硫基乙基、2-丁硫基乙基、2-和3-甲硫基丙基、2-和3-乙硫基丙基、2-和3-丙硫基丙基、2-和3-丁硫基丙基、2-和4-甲硫基丁基、2-和4-乙硫基丁基、2-和4-丙硫基丁基、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、4,7-二硫杂辛基、4,7-二硫杂壬基、2-和4-丁硫基丁基、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-N-甲氨基-和2-(N-乙氨基)乙基、2-(N,N-二甲氨基)乙基、2-和3-(N,N-二甲氨基)丙基、3-异丙氨基丙基、2-和4-(N-丙氨基)丁基、2-和4-(N,N-二甲氨基)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-甲基磺酰乙基、2-乙磺酰乙基、2-丙磺酰乙基、2-异丙磺酰乙基、2-丁磺酰乙基、2-和3-甲磺酰丙基、2-和3-乙磺酰丙基、2-和3-丙磺酰丙基、2-和3-丁磺酰丙基、2-和4-甲磺酰丁基、2-和4-乙磺酰丁基、2-和4-丙磺酰丁基和4-丁磺酰丁基;
羧甲基、2-羧乙基、3-羧丙基、4-羧丁基、5-羧戊基、6-羧己基、8-羧辛基、10-羧癸基,12-羧十二烷基和14-羧十四烷基;
甲基羧甲基、乙基羧甲基、丙基羧甲基、丁基羧甲基、戊基羧甲基、己基羧甲基、甲基-2-羧乙基、乙基-2-羧乙基、丙基-2-羧乙基、丁基-2-羧乙基、戊基-2-羧乙基、己基-2-羧乙基、甲基-2-羧丙基、乙基-2-羧丙基、丙基-2-羧丙基、丁基-2-羧丙基、戊基-2-羧丙基、己基-2-羧丙基、甲基-4-羧丁基、甲基-5-羧戊基、甲基-6-羧己基、甲基-8-羧辛基、甲基-10-羧癸基、甲基-12-羧十二烷基和甲基-14-羧十四烷基;
磺基甲基、2-磺基乙基、3-磺基丙基、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;
甲磺基甲基、乙磺基甲基、丙磺基甲基、丁磺基甲基、戊磺基甲基、己磺基甲基、甲基-2-磺基乙基、乙基-2-磺基乙基、丙基-2-磺基乙基、丁基-2-磺基乙基、戊基-2-磺基乙基、己基-2-磺基乙基、甲基-3-磺基丙基、乙基-3-磺基丙基、丙基-3-磺基丙基、丁基-3-磺基丙基、戊基-3-磺基丙基和己基-3-磺基丙基、甲基-4-磺基丁基、甲基-5-磺基戊基、甲基-6-磺基己基、甲基-8-磺基辛基、甲基-10-磺基癸基、甲基-12-磺基十二烷基和甲基-14-磺基十四烷基;
2-羟乙基、2-和3-羟丙基、1-羟丙-2-基、2-和4-羟丁基、1-羟丁-2-基和8-羟基-4-氧杂辛基、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-甲基-7-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、叔丁氧基、戊氧基、异戊氧基、新戊氧基、叔戊氧基或己氧基;
环戊基、环己基、环庚基、环辛基、2-二噁烷基、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。
合适的基团R1的例子为氢和上述的C1-C6-烷基。
合适的基团R2的例子为上述C4-C30-烷基,被-O-、-S-或-CO-插入的C4-C30-烷基,以及C5-C8-环烷基基团和芳基基团,例如萘基,特别是苯基,它们可被1,2或3个上述C1-C6-烷基或C1-C6-烷氧基取代,如
2-,3-和4-甲基苯基、2,4-,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-,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-,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-,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-,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-,3,5-和2,6-异丁基苯基、2,4,6-三异丁基苯基、2-,3-和4-甲氧基苯基、2,4-,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-,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-,3,5-和2,6-二丙氧基苯基、2-,3-和4-异丙氧基苯基、2,4-和2,6-二异丙氧基苯基和2-,3-和4-丁氧基苯基。
二酐I可按新的多步反应方法制备,该方法的步骤a)中1,7-二溴苝-3,4,9,10-四羧酸二酐(II)与伯胺III反应得到相应的1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺IV,在步骤b)中将其与芳族醇或硫醇V反应得到苝基酰亚胺VI,最后在步骤c)中将其在碱性条件下水解,得到二酐I,或者,二酐I也可按新的单步反应方法制备,在该方法中,1,7-二溴苝-3,4,9,10-四羧酸二酐(II)直接与芳族醇或硫醇V反应。
但是,一般说来,在单步法变种中得到的产物含有更多的杂质。因此必须随后纯化,例如通过分级结晶或硅胶柱过滤纯化,由于这个原因,在大多数情况下优选地使用三步法变种。
按照本发明,新制备方法的前体,1,7-二溴苝-3,4,9,10-四羧酸二酐(II)可通过在100%重量的硫酸(单水合物)中选择性地对苝-3,4,9,10-四羧酸二酐进行溴化而得到。
该过程优选地包括:首先将苝-3,4,9,10-四羧酸二酐在硫酸中搅拌2到16小时,加入卤化催化剂如碘(每摩尔酐优选30-40mmol)后将该混合物加热至反应温度(通常为80到90℃)。然后滴加溴(通常需要6-10小时),每摩尔酐优选地使用2-2.5mol溴(Br2)。冷却至室温并用氮排代未反应溴,片刻以后,加水使硫酸的浓度降至约85-88%重量。
滤出沉淀出的产物,用85-88%重量的硫酸洗涤,在水中搅拌,再次滤出产物,用水洗涤,干燥,可得到1,7-二溴苝-3,4,9,10-四羧酸二酐(II)。
新的三步制备法的步骤a)中,1,7-二溴苝-3,4,9,10-四羧酸二酐(II)与伯胺的反应是在有或无酰亚胺化催化剂存在下在极性非质子溶剂中进行的。
该步骤中的合适的极性非质子溶剂为,特别是,非质子氮杂环,如吡啶、嘧啶、喹啉、异喹啉、2-甲基喹啉、N-甲基哌啶、N-甲基哌啶酮以及特别是N-甲基吡咯烷酮。
溶剂的用量不是关键,每kg(II)通常为5-20kg,优选10-15kg。
合适的酰亚胺化催化剂包括有机或无机酸,例如甲酸、乙酸、丙酸和磷酸,优选地使用高浓度的酸,以及过渡金属元素如锌,铁和铜以及镁的有机和无机盐,例如乙酸锌、丙酸锌、氧化锌,乙酸铁(II)、氯化铁(III)、硫酸铁(II)、乙酸铜(II)、氧化铜(II)和乙酸镁。当然也可使用这些催化剂的混合物。
当芳族胺反应时,酰亚胺化催化剂的存在特别有利,当脂环胺反应时也很有利,但特别是短链脂族胺反应时,通常不需催化剂。
基于(II)所使用的催化剂的量通常为5-80%重量。基于(II),优选地使用50-80%重量的有机酸,或10-40%重量的过渡金属盐和镁盐。
用于新制备方法的伯胺为所有在反应条件下稳定的胺,并且它与苝-3,4,9,10-四羧酸二酐反应形成碱性条件下可水解的二酰亚胺。
特别优选的伯胺III为十八烷胺,5-壬基胺、环戊基胺、环己基胺、环庚基胺、苯胺、4-甲基苯胺、4-乙基苯胺、4-叔丁基苯胺、3,5-二甲基苯胺、3,5-二乙基苯胺和3,5-二叔丁基苯胺。
胺III与(II)的摩尔比通常为约2∶1到4∶1,优选2.2∶1到3∶1。
步骤a)的反应温度一般为40-180℃。脂族和环脂族胺的反应温度优选60-100℃,芳族胺的反应温度优选120-160℃。
惰性气氛(例如使用氮)下反应较为有利。
新方法的步骤a)可在大气压或通常至多10巴的超过大气压的压力下进行。使用挥发性胺(沸点≤约180℃)时加压处理是特别有用的。
反应通常需要2-10小时,特别是4-7小时。
步骤a)优选地如下进行:
将1,7-二溴苝-3,4,9,10-四羧酸二酐(II),溶剂和(如果使用)催化剂装入反应器中,在室温搅拌下加入胺III,将反应装置用氮气吹洗约15分钟,搅拌下将该混合物加热至反应温度并在该温度下保持4-7小时。冷却至室温后,将反应产物滤出,用脂族醇如甲醇洗涤并干燥。
如果反应在加压下进行,所使用的反应器为压力装置,引入各组分后对其提供约1-2巴压力的氮气,然后在反应温度下加热所需的时间,然后冷却,然后对反应松压。
一般,步骤a)得到的1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺IV具有足够的纯度(>95%),可直接用于下步反应。通过将该产物溶于卤代烃如二氯甲烷、氯仿或四氯化碳中,用硅胶过滤该溶液,浓缩滤液至干可制备分析纯的产物,纯度>98%。
新的三步制备方法的步骤b)中,1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺IV与芳族醇或硫醇V的反应可在非亲性或弱亲核碱的存在下在惰性非质子溶剂中进行。
该步骤中合适的惰性非质子溶剂为,特别是,含氮杂环如吡啶、嘧啶、喹啉、异喹啉、2-甲基喹啉以及特别是,N-甲基吡咯烷酮。
溶剂的用量不是关键,每kg二酰亚胺IV通常为10-50kg,优选25-35kg。
特别合适的碱为碱金属氢氧化物,例如氢氧化钠和氢氧化钾,以及特别是碱金属碳酸盐,例如碳酸钠和碳酸钾,使用其无水形式。
每摩尔二酰亚胺一般使用2-3,优选的2.2-2.5摩尔当量的碱。
步骤b)的反应温度一般为60-180℃,特别是80-140℃。
惰性气氛(例如使用氮)下反应是有利的。
芳族醇或硫醇V与二酰亚胺IV的摩尔比一般为2∶1到3∶1,优选2.0∶1到2.2∶1。
形成苝基酰亚胺VI的反应通常持续1-5小时,特别1-2小时。
步骤b)优选地如下进行:
搅拌下将二酰亚胺IV,醇或硫醇V以及碱在溶剂中的悬浮液装入反应容器,氮气氛下将其在反应温度下加热1-2小时。将反应混合物冷却至室温并引入约3倍体积的稀无机酸,例如5-10%重量的盐酸,并将沉淀出的反应产物滤出,用水洗涤至洗液呈中性,减压干燥。
这种方法得到的苝基酰亚胺VI已足够纯(>95%),不需要进一步纯化。通过用卤代烃,如二氯甲烷或氯仿,重结晶,或通过用硅胶过滤在上述溶剂中的溶液然后浓缩滤液可得到分析纯的样品。
新的三步法的步骤c)中,在极性质子溶剂和碱的存在下,苝基酰亚胺水解成二酐I。
该步骤中特别合适的极性质子溶剂为C1-C10-链烷醇如乙醇、丙醇、正丁醇、叔丁醇、2-甲基-2-丁醇、正己醇、正癸醇以及优选异丙醇。为了加速水解反应,每摩尔苝基酰亚胺VI一般加入0.1~0.2mol的水。
溶剂的用量不是关键,每kg苝基酰亚胺VI一般使用50-200kg,优选60-80kg。
特别合适的碱为碱金属氢氧化物,如氢氧化钠和氢氧化钾,每kg苝基酰亚胺VI一般使用4-10kg,优选5-7kg。
步骤c)的反应温度一般为20-140℃,特别是40-90℃。
水解通常需要3-10小时,特别是4-6小时。
步骤c)优选地如下进行:
将苝基酰亚胺VI,溶剂和碱的混合物在所需温度下加热4-6小时并冷却至室温,将沉淀出的粗产物滤出并用醇如异丙醇或丙醇洗涤至洗液无色。为了进一步纯化,将所得二酐I转入30-100倍量的稀无机酸,例如5-12%重量的盐酸中,短暂地煮沸,冷却后过滤,用水洗涤至中性并干燥。
在单步方法变种中,1,7-二溴苝-3,4,9,10-四羧酸二酐(II)与芳族醇或硫醇V直接反应。
反应条件,如溶剂和碱的性质和量以及反应温度与三步法的步骤b)中的相似。但是V与(II)摩尔比一般为2∶1到10∶1,优选的4∶1到6∶1。另外反应时间较长,通常需要4到10小时,特别是5到7小时。
单步法优选地如下进行:
将溶剂中的1,7-二溴苝-3,4,9,10-四羧酸二酐(II),醇或硫醇V和碱加入反应容器并在氮气氛下在反应温度下加热5-7小时。冷却至50℃水,将沉淀出的反应产物滤出并用冷溶剂洗涤。然后将该固体在稀无机酸,例如5-10%重量的盐酸中搅拌,然后滗出液相,残留物用热水处理并在80-85℃搅拌约30分钟,然后将固体产物滤出,优选趁热过滤,用热水洗涤至洗液呈中性,减压干燥。
这种方法得到的产物通常含约10-15%的未反应或仅部分反应的原料(II),应进一步纯化它们,例如在合适的高沸点溶剂如N-甲基吡咯烷酮或四氯乙烷中分级结晶,或用短硅胶柱过滤粗产物在这些溶剂中的溶液。
使用新的制备方法(包括单步法变种中随后的纯化)可以步骤简单及经济的方式,以高纯度(一般>95%)和高产率(三步法一般>70%而单步法一般>55%)得到1,7-二取代苝-3,4,9,10-四羧酸二酐I。
新的二酐I非常适于作为印刷墨水,涂料组合物,特别是日光-萤光着色剂,和塑料的颜料,作为激光染料以及作为制备萤光染料,聚合物着色剂,颜料和颜料添加剂的前体。
新的苝基酰亚胺VI也可用作对高分子有机材料和无机材料染色的颜色或染料,用作激光染料或用作电发光作用的有机材料。
实施例A)1,7-二溴苝-3,4,9,10-四羧酸二酐(II)的制备
实施例1
室温下将292.5g(0.75mol)苝-3,4,9,10-四羧酸二酐(纯度>98%)和4420g 100%重量的硫酸的混合物搅拌12小时,加入7g碘,然后将该混合物加热至85℃。然后在8小时内滴加262.5g(1.64mol)溴。
将反应混合物冷却至室温,用氮气置换过量的溴,每次少许地在1小时内加入总量670g的水,使反应混合物中硫酸的浓度降至86%重量。将上述过程中加热至85℃的反应混合物冷却至室温,将沉淀出的产物用G4玻璃料过滤,用3kg 86%重量的硫酸洗涤,然后在5l水中搅拌,再次过滤,洗涤至中性,在120℃下减压干燥。
得到的370g II呈亮红色,微晶粉末状。熔点>360℃,纯度>98%,相应的产率为90%。分析数据:元素分析(%重量计算值/实测值):C:52.4/52.1;H:1.1/1.1;O:17.45/17.4;Br:29.1/29.4;IR(KBr):ν=1782+1770(s,C=O),1735+1723(s,C=O)cm-1;UV/VIS(H2SO4):λmax(ε)=408(10309),520(29410),554(43141)nm.B1)按三步法变种制备1,7-二芳氧基取代的苝-3,4,9,10-四羧酸二酐I
a)1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺(IV)的制备
实施例2到4
首先将ag酰亚胺化催化剂,然后每次少许,将总量381mmol(实施例3)中为280mmol)的胺R2-NH2(III)加入搅拌着69.9g(127mmol)实施例1得到的1,7-二溴苝-3,4,9,10-四羧酸二酐(II)在900ml N-甲基-2-吡咯烷酮中的混合物。然后反应混合物在氮气氛下加热到T℃,并在此温度下搅拌6小时。
冷却至室温后,将沉淀出的反应产物滤出,用总量为2l的甲醇洗涤并在100℃减压干燥。
表1中结出了这些实验和结果的更详细的数据。
表1
实施例 | R2 | ag | 酰亚胺化催化剂 | T[℃] | 结果 | |||
产率[g]/[%] | 纯度[%] | 外观 | m.p[℃] | |||||
2 | 环己基 | 42.8 | 乙酸 | 85 | 75.1/83 | 97 | 亮红色,微晶 | >360 |
3 | 环己基 | 21.0 | 乙酸锌 | 100 | 73.9/82 | 97 | 亮红色,微晶 | >360 |
4 | 3,5-二甲基苯基 | 17.5 | 乙酸锌 | 140 | 83.8/87 | 96 | 暗红色,微晶 | >360 |
实施例2和3分析数据:元素分析(%重量计算值/实测值):C:60.7/60.6;H:4.0/4.0;N:3.9/3.9;O:9.0/9.0;Br:22.4/22.3:IR(KBr):ν=1698(s,C=O),1655(s,C=O cm-1;UV/VIS(CHCl3):λmax(ε)=491(33411),526(50033)nm.
实施例4分析数据:元素分析(%重量计算值/实测值):C:63.5/63.2;H:3.2/3.25;N:3.7/3.7;O:8.5/8.7;Br:21.1/21.0;质量(FD):m/z=754(M+,100%);IR(KBr):ν=1696(s,C=O),1653(s,C=O)cm-1;UV/VIS(CHCl3):λmax(ε)=485(28570),532(44201)nm.
实施例5到7
分别将各20mmol的实施例2到4得到的1,7-二溴苝-3,4,9,10-四羧酸二酰亚胺(IV)加入搅拌着的450ml N-甲基吡咯烷酮中,然后依次加入6.4g(46mmol)无水碳酸钾和ag(40mmol)羟基芳香化合物V,并在120℃,在氮气氛下将该混合物加热1.5小时。
冷却至室温后,搅拌下将反应混合物加入1.5l 6%重量的盐酸。将沉淀出的产物滤出,用水洗涤至中性,并在100℃减压下干燥。
表2中结出了这些实验及其结果的更详细的数据。
表2
实施例 | R2 | R | 二酰亚胺IV来自的实施例 | ag | 羟基芳香化合物V | 结果 | |||
产率[g]/[%] | 纯度[%] | 外观 | m.p.[℃] | ||||||
5 | 环己基 | 苯氧基 | 2 | 3.8 | 苯酚 | 14.5/98 | 93 | 暗红色,结晶 | >360 |
6 | 环己基 | 对叔丁基苯氧基 | 2 | 6.0 | 对叔丁基苯酚 | 16.0/94 | 95 | 晶红色,微晶 | >360 |
7 | 3,5-二甲基苯基 | 对叔丁基苯氧基 | 4 | 6.0 | 对叔丁基苯酚 | 17.7/93 | 94 | 暗红色,微晶 | >360 |
实施例5分析数据:元素分析(%重量计算值/实测值):C:78.0/77.5;H:5.2/5.3;N:3.8/3.7;O:13.0/13.4;质量(FD):m/z=738(M+,100%);IR(KBr):ν=1695(s,C=O),1654(s,C=O)cm-1;UV/VIS(CHCl3):λmax(ε)=401(7455),513(37102),549(55004)nm.
实施例6分析数据:元素分析(%重量计算值/实测值):C:79.0/78.8;H:6.4/6.4;N:3.3/3.2;O:11.3/11.4;质量(FD):m/z=850(M+,100%);IR(KBr):ν=1697(s,C=O),1654(s,C=O)cm-1;UV/VIS(CHCl3):λmax(ε)=404(9447),512(34785),547(52117)nm.
实施例7分析数据:元素分析(%重量计算值/实测值):C:80.5/80.4;H:5.6/5.6;N:3.1/3.1;O:10.7/10.8;质量(FD):m/z=894(M+,100%);IR(KBr):ν=1699(s,C=O),1651(s,C=O)cm-1;UV/VIS(CHCl3):λmax(ε)=408(10703),511(32187),544(58330)nm.
实施例8到10
分别将各10g的实施例5、6和实施例7得到的1,7-二芳氧基苝-3,4,9,10-四羧酸二酰亚胺(VI)与1l异丙醇,65g氢氧化钾和26g水的混合物回流5小时。
冷却至室温后,将沉淀出的反应产物滤出,用异丙醇洗涤至洗液无色,然后加入到搅拌着的1l 10%重量的盐酸并迅速加热至沸点。冷却至室温以后,再将产物滤出,用水洗涤至中性并在100℃减压干燥。
表3中列出了这些实验及其结果的更详细的数据。产品纯度由UV/VIS光谱和以三氯乙酸/甲苯作为流动相的硅胶半定量薄层层析测定。
表3
实施例 | R | 二酰亚胺IV | 结果 | |||
来自的实施例 | 产率[g]/[%] | 纯度[%] | 外观 | m.p.[℃] | ||
8910 | 苯氧基对叔丁基苯氧基对叔丁基苯氧基 | 567 | 7.4/947.7/957.3/91 | 989896 | 红紫色,微晶红紫色,无定形粉末红紫色,无定形粉末 | >360>360>360 |
实施例8分析数据:元素分析(%重量计算值/实测值):C:75.0/74.8;H:2.8/2.8;O:22.2/22.3;IR(KBr):ν=1758(s,C=O),1729(s,C=O)cm-1;UV/VIS(H2SO4):λmax(ε)=415(8832),559(38103)nm.实施例9和10分析数据:元素分析(%重量计算值/实测值):C:76.7/76.6;H:4.7/4.7;O:18.6/18.7;IR(KBr):ν=1755(s,C=O),1730(s,C=O);UV/VIS(H2SO4):λmax(ε)=412(9405),561(32746)nm.B2)按单步法变种制备1,7-二(对叔丁基苯氧基)苝-3,4,9,10-四羧酸二酐(I′)
实施例11
首先,在搅拌下将8.3g(60mmol)无水碳酸钾,然后将13.65g(91mmol)对叔丁基苯酚加入10g(18.2mmol)1,7-二溴苝-3,4,9,10-四羧酸二酐(II)(实施例1)在320ml N-甲基吡咯烷酮中的悬浮液中。氮气氛下将反应混合物加热至120℃,并在此温度下搅拌6小时。
冷却至50℃后,将沉淀出的反应产物滤出,用热(50℃)N-甲基吡咯烷酮洗涤并在500ml 6%重量的盐酸中迅速搅拌。滗出上清液后,将剩下的固体与600ml水混合,并在搅拌下将该混合物在80-85℃加热0.5小时。趁热将产物滤出,用热水洗涤至中性并在120℃减压干燥。
得到8.6g红紫色粉末状I′,熔点>360℃,纯度90%,相应地产率为63%。
实施例11a
为了纯化,将10g实施例11得到的1,7-二(对叔丁基苯氧基)苝-3,4,9,10-四羧酸二酐(I′)在1l N-甲基吡咯烷酮中搅拌1小时。随后将该混合物用2l G4玻璃料过滤,该玻璃中填充了占其容积2/3的硅胶(N-甲基吡咯烷酮为流动相)。
减压蒸发N-甲基吡咯烷酮后,滤液中得到8.1g纯度>98%的红紫色,结晶粉末状I′,它的分析数据与实施例9中一致。
Claims (6)
1.通式I的1,7-二取代的苝-3,4,9,10-四羧酸二酐或式Ia所示的苝-3,4,9,10-四羧酸,其中,R为未取代的或取代的芳氧基,或芳硫基。
2.根据权利要求1的化合物,其中R为未取代的或取代的芳氧基。
3.制备权利要求1或2所要求保护的化合物的方法,该方法包括:
a)在有或无酰亚胺化催化剂的存在下,在极性非质子溶剂中,使1,7-二溴苝-3,4,9,10-四羧酸二酐(II)或1,7-二溴苝-3,4,9,10-四羧酸(IIa)与通式III的伯胺反应,
R2-NH2 III其中R2为C5-C8-环烷基或未取代的或取代的芳基,
H-R V其中,R如上所定义,以及
c)在极性质子溶剂和碱的存在下,将步骤b)中形成的通式VI的1,7-二取代苝-3,4,9,10-四羧酸二酰亚胺水解,得到化合物(I)或(Ia),或者,所述方法包括:在惰性非质子溶剂和非亲核性的或弱亲核性的碱存在下使1,7-二溴苝-3,4,9,10-四羧酸二酐(II)或1,7-二溴苝-3,4,9,10-四羧酸(IIa)与式V的芳族醇或硫醇反应,
H-R V。
5.根据权利要求4的通式VI化合物,其中:R为未取代的或取代的芳氧基,和R2为C5-C8-环烷基或未取代的或取代的苯基。
6.权利要求1或2的式I或Ia化合物作为颜料、激光染料或制备萤光染料、聚合物着色剂、颜料和颜料添加剂的前体的用途。
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1315829C (zh) * | 2005-05-10 | 2007-05-16 | 山东师范大学 | 1,7-二取代-3,4∶9,10-苝双二酰亚胺的合成方法 |
Families Citing this family (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6073004A (en) * | 1996-12-17 | 2000-06-06 | Ericsson Inc. | Emergency call initiator |
DE19805121A1 (de) | 1998-02-09 | 1999-08-12 | Basf Ag | Verfahren zur Herstellung farbstoffenthaltender, wässriger Polymerisatdispersionen |
DE19940708A1 (de) * | 1999-08-27 | 2001-03-01 | Basf Ag | Thermochrome Rylenfarbstoffe |
DE10039232A1 (de) | 2000-08-11 | 2002-02-21 | Basf Ag | Flüssigkristalline Perylen-3,4:9,10-tetracarbonsäurediimide |
DE10039643A1 (de) | 2000-08-14 | 2002-02-28 | Max Planck Gesellschaft | Funktionalisierte Perylentetracarbonsäurediimide |
DE10108601A1 (de) * | 2001-02-22 | 2002-09-05 | Basf Ag | Thermochrome Rylenfarbstoffe |
ES2244777T3 (es) | 2001-03-23 | 2005-12-16 | Basf Aktiengesellschaft | Compuestos policiclicos substituidos por terc.-alquilfenoxi. |
KR100467033B1 (ko) * | 2002-04-18 | 2005-01-24 | 주식회사 알지비케미컬 | 페릴렌 단위 형광체를 포함하는 고분자형광체를 포함하는 화학 발광조성물 |
US6986811B2 (en) * | 2003-01-31 | 2006-01-17 | Basf Aktiengesellschaft | Perylene derivatives and their application as dispersants |
EP1749316B1 (en) * | 2004-01-26 | 2016-06-29 | Northwestern University | Perylene n-type semiconductors and related devices |
DE102004048729A1 (de) * | 2004-10-05 | 2006-04-06 | Basf Ag | Verfahren zur Herstellung von halogenierten Rylencarbonsäureimiden |
DE102005032583A1 (de) | 2005-07-11 | 2007-01-25 | Basf Ag | Substituierte Rylenderivate |
DE102005037115A1 (de) | 2005-08-03 | 2007-02-08 | Basf Ag | Mehrfachchromophore |
DE102005061997A1 (de) | 2005-12-23 | 2007-07-05 | Basf Ag | Naphthalintetracarbonsäurederivate und deren Verwendung |
US8350035B2 (en) | 2006-02-17 | 2013-01-08 | Basf Aktiengesellschaft | Fluorinated rylenetetracarboxylic acid derivatives and use thereof |
EP1843407A1 (de) | 2006-04-07 | 2007-10-10 | Basf Aktiengesellschaft | Flüssig-kristalline Rylentetracarbonsäurederivate und deren Verwendung |
ATE520158T1 (de) | 2006-05-04 | 2011-08-15 | Basf Se | Verfahren zum herstellen organischer feldeffekttransistoren |
US20070259475A1 (en) * | 2006-05-04 | 2007-11-08 | Basf Aktiengesellschaft | Method for producing organic field-effect transistors |
US7569693B2 (en) * | 2006-06-12 | 2009-08-04 | Northwestern University | Naphthalene-based semiconductor materials and methods of preparing and use thereof |
EP2089398A2 (en) * | 2006-10-25 | 2009-08-19 | Polyera Corporation | Organic semiconductor materials and methods of preparing and use thereof |
JP5380296B2 (ja) * | 2006-11-17 | 2014-01-08 | ポリエラ コーポレイション | ジイミド系半導体材料ならびにジイミド系半導体材料を調製および使用する方法 |
WO2008063583A1 (en) * | 2006-11-17 | 2008-05-29 | Polyera Corporation | Acene-based organic semiconductor materials and methods of preparing and using the same |
EP2993197A1 (en) | 2006-11-29 | 2016-03-09 | Sun Chemical Corporation | Phthalocyanine colorants and their use as fluorescent security taggants |
JP2010515684A (ja) * | 2007-01-08 | 2010-05-13 | ポリエラ コーポレイション | アレーン−ビス(ジカルボキシイミド)系半導体材料、およびそれを調製するための関連する中間体を調製する方法 |
US8022214B2 (en) * | 2007-01-24 | 2011-09-20 | Polyera Corporation | Organic semiconductor materials and precursors thereof |
US8119802B2 (en) | 2007-04-24 | 2012-02-21 | Basf Aktiengesellschaft | Fluorinated dyes and their use in electrophoretic display devices |
US8399670B2 (en) | 2007-05-09 | 2013-03-19 | Yeda Research And Development Co.Ltd | Selective bromination of perylene diimides and derivatives thereof under mild conditions |
US9701784B2 (en) | 2008-03-26 | 2017-07-11 | Yeda Research And Development Co. Ltd. | Supramolecular polymers derived from perylene-diimides |
CN101289447B (zh) * | 2008-06-05 | 2011-05-04 | 大连理工大学 | 三氟甲基取代的苝双二亚胺及其制备方法 |
WO2011054731A1 (en) | 2009-11-05 | 2011-05-12 | Basf Se | Fluorescent materials |
US9623381B2 (en) | 2010-08-27 | 2017-04-18 | Yeda Research And Development Co. Ltd. | Separation of nanoparticles |
EP2608874A1 (en) | 2010-08-27 | 2013-07-03 | Yeda Research and Development Co. Ltd. | Separation of nanoparticles |
JP5976675B2 (ja) | 2011-01-05 | 2016-08-24 | 日東電工株式会社 | 波長変換ペリレンジエステル発色団および発光膜 |
US8710225B2 (en) | 2011-01-10 | 2014-04-29 | Basf Se | Thiocyanato or isothiocyanato substituted naphthalene diimide and rylene diimide compounds and their use as n-type semiconductors |
KR101844880B1 (ko) | 2011-09-26 | 2018-04-03 | 닛토덴코 가부시키가이샤 | 증대된 태양에너지 수확 효율을 위한 높은 형광 및 광-안정한 발색단 |
CN103415589B (zh) | 2011-10-05 | 2016-08-10 | 日东电工株式会社 | 具有提高日光采集效率的压敏粘附层的波长转换膜 |
EP3072887B1 (en) | 2015-03-26 | 2017-10-18 | Basf Se | N,n'-bis(2,6-diisopropylphenyl)-1,7-di(2,6-diphenylphenoxy)perylene-3,4;9,10-tetracarboximide, n,n'-bis(2,6-diisopropylphenyl)-1,6-di(2,6-diphenylphenoxy)perylene-3,4;9,10-tetracarboximide and the use thereof |
EP3101087B1 (en) | 2015-06-03 | 2018-01-17 | Basf Se | Multiple chromophores with a perylenediimide skeleton |
CN105322239A (zh) * | 2015-10-09 | 2016-02-10 | 桂林理工大学 | 含n,n’-二[2-(1,3-三甘醇甲醚基)丙基]苝二酰亚胺的电解液及其制备方法 |
CN105304947A (zh) * | 2015-10-09 | 2016-02-03 | 桂林理工大学 | 含n,n’-二[2-(1,3-四甘醇甲醚基)丙基]苝二酰亚胺的电解液及其制备方法 |
CN105304948A (zh) * | 2015-10-09 | 2016-02-03 | 桂林理工大学 | 含n,n’-二[2-(1,3-二甘醇甲醚基)丙基]苝二酰亚胺的电解液及其制备方法 |
EP3858946A1 (en) | 2020-01-29 | 2021-08-04 | Basf Se | New rylene dicarboximides |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0055363A1 (de) * | 1980-12-27 | 1982-07-07 | BASF Aktiengesellschaft | Perylentetracarbonsäurediimide und deren Verwendung |
EP0227980A2 (de) * | 1985-12-19 | 1987-07-08 | BASF Aktiengesellschaft | Fluoreszierende aroxysubstituierte Perylen-3,4,9,10-tetracarbonsäurediimide und ihre Verwendung zur flächenmässigen Konzentrierung von Licht |
WO1994025504A1 (de) * | 1993-05-04 | 1994-11-10 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Tetraaroxyperylen-3,4,9,10-tetracarbonsäurepolyimide |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE412122C (de) | 1922-12-28 | 1925-04-11 | Kalle & Co Akt Ges | Verfahren zur Darstellung von Kuepenfarbstoffen |
DE3018006A1 (de) | 1980-05-10 | 1981-11-12 | Hoechst Ag, 6000 Frankfurt | Verfahren zur herstellung von pigmenten der perylen-3,4,9,10-tetracarbonsaeurediimidreihe und ihre verwendung |
DE3933903A1 (de) * | 1989-10-11 | 1991-04-18 | Basf Ag | Fluoreszenzpigmente |
DE19500912A1 (de) * | 1995-01-13 | 1996-07-18 | Basf Ag | Elektrolumineszierende Anordnung |
DE19501737A1 (de) * | 1995-01-20 | 1996-07-25 | Basf Ag | Verfahren zur Herstellung und Reinigung von Perylen-3,4-dicarbonsäureimiden |
-
1995
- 1995-12-18 DE DE19547209A patent/DE19547209A1/de not_active Withdrawn
-
1996
- 1996-12-11 DE DE59610511T patent/DE59610511D1/de not_active Expired - Lifetime
- 1996-12-11 WO PCT/EP1996/005519 patent/WO1997022607A1/de active IP Right Grant
- 1996-12-11 EP EP96943077A patent/EP0873342B1/de not_active Expired - Lifetime
- 1996-12-11 US US09/091,262 patent/US6143905A/en not_active Expired - Lifetime
- 1996-12-11 JP JP52248297A patent/JP3926392B2/ja not_active Expired - Lifetime
- 1996-12-11 CN CN96180038A patent/CN1082962C/zh not_active Expired - Lifetime
-
2000
- 2000-08-02 US US09/631,291 patent/US6326494B1/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0055363A1 (de) * | 1980-12-27 | 1982-07-07 | BASF Aktiengesellschaft | Perylentetracarbonsäurediimide und deren Verwendung |
EP0227980A2 (de) * | 1985-12-19 | 1987-07-08 | BASF Aktiengesellschaft | Fluoreszierende aroxysubstituierte Perylen-3,4,9,10-tetracarbonsäurediimide und ihre Verwendung zur flächenmässigen Konzentrierung von Licht |
WO1994025504A1 (de) * | 1993-05-04 | 1994-11-10 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | Tetraaroxyperylen-3,4,9,10-tetracarbonsäurepolyimide |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1315829C (zh) * | 2005-05-10 | 2007-05-16 | 山东师范大学 | 1,7-二取代-3,4∶9,10-苝双二酰亚胺的合成方法 |
Also Published As
Publication number | Publication date |
---|---|
WO1997022607A1 (de) | 1997-06-26 |
DE19547209A1 (de) | 1997-06-19 |
EP0873342B1 (de) | 2003-06-04 |
US6143905A (en) | 2000-11-07 |
EP0873342A1 (de) | 1998-10-28 |
DE59610511D1 (de) | 2003-07-10 |
JP3926392B2 (ja) | 2007-06-06 |
JP2000502138A (ja) | 2000-02-22 |
CN1209131A (zh) | 1999-02-24 |
US6326494B1 (en) | 2001-12-04 |
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