CN1368496A - 制备氨基二苯基胺的方法 - Google Patents
制备氨基二苯基胺的方法 Download PDFInfo
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- CN1368496A CN1368496A CN01103439A CN01103439A CN1368496A CN 1368496 A CN1368496 A CN 1368496A CN 01103439 A CN01103439 A CN 01103439A CN 01103439 A CN01103439 A CN 01103439A CN 1368496 A CN1368496 A CN 1368496A
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- palladium
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- amine
- halogeno
- benzene
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- YHYKLKNNBYLTQY-UHFFFAOYSA-N 1,1-diphenylhydrazine Chemical compound C=1C=CC=CC=1N(N)C1=CC=CC=C1 YHYKLKNNBYLTQY-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 36
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 19
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 9
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 4
- MKARNSWMMBGSHX-UHFFFAOYSA-N 3,5-dimethylaniline Chemical group CC1=CC(C)=CC(N)=C1 MKARNSWMMBGSHX-UHFFFAOYSA-N 0.000 claims description 2
- OGIQUQKNJJTLSZ-UHFFFAOYSA-N 4-butylaniline Chemical compound CCCCC1=CC=C(N)C=C1 OGIQUQKNJJTLSZ-UHFFFAOYSA-N 0.000 claims description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 2
- LRTFPLFDLJYEKT-UHFFFAOYSA-N para-isopropylaniline Chemical compound CC(C)C1=CC=C(N)C=C1 LRTFPLFDLJYEKT-UHFFFAOYSA-N 0.000 claims description 2
- CZZZABOKJQXEBO-UHFFFAOYSA-N 2,4-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1 CZZZABOKJQXEBO-UHFFFAOYSA-N 0.000 claims 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 16
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 14
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 13
- 238000003756 stirring Methods 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 9
- 235000015320 potassium carbonate Nutrition 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000012544 monitoring process Methods 0.000 description 6
- 210000003739 neck Anatomy 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 5
- 125000001539 acetonyl group Chemical group [H]C([H])([H])C(=O)C([H])([H])* 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- -1 dicyclohexyl phosphino- Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical compound C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical class C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 1
- BGDCQZFFNFXYQC-UHFFFAOYSA-N 1-chloro-2-methyl-4-nitrobenzene Chemical compound CC1=CC([N+]([O-])=O)=CC=C1Cl BGDCQZFFNFXYQC-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- NSMZCUAVEOTJDS-UHFFFAOYSA-N 4-chloro-2-methyl-1-nitrobenzene Chemical compound CC1=CC(Cl)=CC=C1[N+]([O-])=O NSMZCUAVEOTJDS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- GVVHNTGSELIGAA-UHFFFAOYSA-N ClC1=C(C(=CC=C1)OC)C1=CC=CC=C1OC Chemical group ClC1=C(C(=CC=C1)OC)C1=CC=CC=C1OC GVVHNTGSELIGAA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- WXMZPPIDLJRXNK-UHFFFAOYSA-N butyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(CCCC)C1=CC=CC=C1 WXMZPPIDLJRXNK-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 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
- GCUVBACNBHGZRS-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopenta-2,4-dien-1-yl(diphenyl)phosphane iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.c1cc[c-](c1)P(c1ccccc1)c1ccccc1 GCUVBACNBHGZRS-UHFFFAOYSA-N 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical class [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- UPDNYUVJHQABBS-UHFFFAOYSA-N phenoxy(diphenyl)phosphane Chemical compound C=1C=CC=CC=1OP(C=1C=CC=CC=1)C1=CC=CC=C1 UPDNYUVJHQABBS-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ASUOLLHGALPRFK-UHFFFAOYSA-N phenylphosphonoylbenzene Chemical class C=1C=CC=CC=1P(=O)C1=CC=CC=C1 ASUOLLHGALPRFK-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000013014 purified material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/54—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to two or three six-membered aromatic rings
- C07C211/55—Diphenylamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
如果芳胺在钯催化剂和碱存在下与硝基卤代苯反应并随后将这样得到的产物用氢氢化,则根据本发明方法的氨基二苯基胺的制备就得到好的产率和高的纯度。
Description
本发明涉及通过在钯催化剂和碱存在下使硝基卤代苯与芳胺反应并随后将得到的中间体产物氢化制备氨基二苯基胺(aminodiphenylamines)、特别是4-氨基二苯基胺(4-ADPA)的方法。
4-氨基二苯基胺(4-ADPA)是一种重要的原料，用于合成橡胶和聚合物工业中的抗氧化剂和稳定剂(Kirk-Othmer，Encyclopedia ofChemical Technology，4th Edition，1992，Vol.3，p.424-456；Ullmann’s Encyclopedia of Industrial Chemistry，5th Edition，Vol.A3，1985，p91-111)。
4-ADPA可通过许多方法制备。一种可能的制备4-ADPA的方法是苯胺或苯胺衍生物与p-硝基氯苯在酸受体或中和剂存在下的两步反应，任选有催化剂存在。例如在DE-A 3246151、DE-A 3501698、DE-A185663、US-A 4670595、US-A 4187249、US-A 468333和US-A 4187248中描述了采用该方法的生产。第一步通常使用铜催化剂，第二步使用不同的金属成分，例如镍(参见例如US-A 5840982)。例如在US-A5576460和EP-A 846676中还描述了在钯催化剂存在下卤代的硝基苯与胺的反应。
上述文献中所述方法的缺点经常是不适当的选择性，特别在形成中间体产物期间，从而在通过氢化生成4-氨基二苯基胺以前，由于或多或少复杂的提纯步骤造成了产量损失。
因此希望提供一种制备氨基二苯基胺的方法，从芳族胺开始，通过与适合的硝基卤代苯反应并随后氢化生成的中间体产物以好的产率和提高的纯度得到需要的氨基二苯基胺。
本发明因此提供一种用于制备氨基二苯基胺的方法，通过硝基卤代苯在碱和钯催化剂存在下与芳族胺反应并随后用氢氢化得到的产物。
使用的硝基卤代苯优选那些其中相对于卤代基来说硝基在对位的。可能的卤代基是：氟、氯、溴和碘，优选氯和溴。显然，硝基卤代苯还可以被一个或多个其它取代基取代，诸如例如C1-C4烷基。自然，相对于卤代基，硝基还可以在除了对位以外的其它位，例如，可以在2或3位。
可例举的硝基卤代苯是：4-硝基-2-甲基氯苯、4-硝基-3-甲基氯苯、4-硝基氯苯、3-硝基氯苯和2-硝基氯苯。4-硝基氯苯是特别优选的。
可在根据本发明的方法中使用的芳族胺是那些已知与该反应相关的芳胺，例如苯胺、邻甲苯胺、间甲苯胺、对甲苯胺、4-乙基苯胺、4-丁基苯胺、4-异丙基苯胺、3，5-二甲基苯胺或2，4-二甲基苯胺。苯胺是优选的。自然，芳族胺还可以混合物的形式使用，特别是异构体混合物。
在根据本发明的方法中，每摩尔硝基卤代苯通常使用1-10摩尔、优选1.5-6摩尔、特别优选2-4摩尔芳族胺。
根据本发明，可使用钯催化剂，例如钯/膦配合物或其它已知的钯化合物或配合物。
适合的钯/膦配合物化合物是那些其中钯为0或II价并且膦配体是诸如三苯基膦、三邻甲苯基膦、三环己基膦、三叔丁基膦、双二苯基膦乙烷(bisdiphenylphosphine ethane)、双二苯基膦丙烷、双(二苯基膦基)丁烷、双(二环己基膦基)乙烷、双(二苯基膦基)二茂铁、5，5’-二氯-6，6’-二甲氧基联苯基-2，2’-二基-双二苯基膦、双-4，4’-二苯并呋喃-3，3’-基-双二苯基膦、1，1’-双(二苯基膦基)二苯醚或双(二苯基膦基)联萘，其中所述的苯基可被磺酸基和/或被一个或多个C1-C12烷基或C3-C10环烷基取代。此外，与聚合物结合的膦也可作为配体，例如tPP聚合物(可从市场购得)。优选使用三苯基膦作为配体。
但是，除了上述钯/膦配合物化合物以外，其它也可以用于根据本发明的方法中，例如含氮或氧的配体，诸如1，10-菲咯啉、二苯基乙烷二胺、[1，1]-联萘-2，2’-二醇(BINOL)和1，1’-联萘-2，2’-二硫醇(BINAS)，或甚至那些有两个或多个不同的诸如O、N、S的杂原子的那些。
可作为催化剂的钯化合物包括下述各类的化合物，例如：钯的卤化物、乙酸盐、碳酸盐、酮酸盐(ketonates)、硝酸盐、醋酮酸盐(acetonates)或palladacyclene，例如Pd2dba3、Pd(acac)2、Pd(OAc)2、PdCl2、(CH3CN)2Pd(NO2)Cl。Pd2dba3、Pd(acac)2、Pd(OAc)2、PdCl2是优选的。此外，在根据本发明的方法中还可使用多相的或固定的钯催化剂，即，例如那些施加在适合的惰性载体上的催化剂。
在根据本发明使用钯/膦配合物的情况下，相应的配体对钯的摩尔比约为40∶1-1∶1，优选10∶1-2∶1，特别优选8∶1-4∶1。
根据本发明，相对于使用的硝基卤代苯，钯催化剂，诸如钯/膦配合物和/或其它可使用的配合物或化合物通常的用量为0.0001％摩尔-10％摩尔，优选0.001％摩尔-5％摩尔。
可用于本发明方法中的碱是碱和/或碱土金属的碳酸盐、醇盐和/或氢氧化物，其中特别提到的应是钾和/或钠的碳酸盐、碳酸铯、甲醇钠和氢氧化钡。优选使用钾和/或钠的碳酸盐。碱可以低于化学计量量使用，或以相对硝基卤代苯当量过量最多10倍的量使用。相对于硝基卤代苯，特别优选以0.3-2倍当量的量使用碱。
用于本发明方法的碱有利的是经过研磨和/或干燥预处理。
在根据本发明的方法中，可用市售的研磨机进行研磨。研磨使比表面积急剧增加，这导致转化明显增加。在许多情况下，研磨可将比表面积增加10-20倍。
研磨后，碱的比表面积为约0.1-10m2/g，优选0.2-1m2/g(BET)。
由于在根据本发明方法中使用的碱的显著吸湿性，后者具有或多或少的显著吸收诸如水或二氧化碳的大气成分的趋势。从约30％重量的吸收大气成分的水平，可注意到对可达到的转化水平的显著影响。因此，除了研磨，还常需要指明碱的干燥。
进行碱的干燥，例如在约0.01-100mbar的减压下将其加热到约50-200℃、优选100-160℃数小时。
本发明方法的第一步可在20-250℃、优选120-180℃的温度进行。反应温度具体取决于起始产物的类型、催化剂和使用的碱。
本发明的方法可在存在和不存在适合的溶剂的两种条件下进行。可能的溶剂的例子是惰性的有机烃类，诸如二甲苯和甲苯。此外，使用的芳族胺本身可作为溶剂。
在本发明的方法中，生成的反应水，如果需要(如DE-A 26 33 811和DE-A 32 46 151)，可例如通过在适合的夹带剂帮助下蒸馏除去。
使用的溶剂的量可通过适合的初步试验容易地确定。
本发明的方法可连续地或不连续地用常规方法进行。
在本发明的方法中，芳族胺与卤代硝基芳族化合物反应后得到的反应产物用氢进行氢化，其中氢化可在已经存在的钯催化剂存在下进行，任选地加入适合的惰性催化剂载体。
显然，还可以在另外的氢化催化剂存在下进行氢化，诸如那些基于镍、钯或铂的催化剂，任选地使用适合的催化剂载体。
作为催化剂载体的适合的材料是各种形式的基于碳、元素氧化物、元素碳化物或元素盐的所有工业上常用的催化剂载体。含碳载体的例子是焦炭、石墨、碳黑或活性炭。元素氧化物催化剂载体的例子是SiO2(天然或合成的硅酸、石英)、A12O3(α、γ-Al2O3)、矾土、天然或合成的硅铝酸盐(沸石)、诸如膨润土和蒙脱石之类的叶硅酸盐、TiO2(金红石、锐钛矿)、ZrO2、MgO或ZnO。元素碳化物和盐的例子是SiC、AlPO4、BaSO4、CaCO3。原则上，合成的材料和自然来源的载体，诸如浮石、高岭土、漂白粘土、铝矾土、膨润土、硅藻土、石棉或沸石，均可使用。
可用于根据本发明可使用的催化剂的其它载体是元素周期表2-16族的元素和稀土金属(原子序数58-71)的元素混合氧化物和水合的(hydrogenated)氧化物，优选元素Al、Si、Ti、Zr、Zn、Mg、Ca、Sn、Nb和Ce的，如本领域技术人员所知，它们特别可以和其它成分通过机械混合、盐的共沉淀或经盐和/或醇盐共凝胶的方法制备。
载体可以以化学均一纯净的物质和混合物两种形式使用。块和粉末两种形式的材料均适合根据本发明作为催化剂载体使用。当负载的催化剂作为固定床安装时，载体优选以模制的产品例如球状、圆柱体、棒状、中空的圆柱体或环状形式使用。催化剂载体任选进一步通过挤压、制片被模制，任选与诸如SiO2或Al2O3之类的其它催化剂载体或粘合剂混合，并且煅烧。载体内表面积(BET表面积)为1-2000m2/g，优选10-1600m2/g，特别优选20-1500m2/g。制备和进一步加工对于本领域技术人员是公知的并构成现有技术。
活性炭和含Si、Al、Mg、Zr和Ti的材料优选作为载体材料。活性炭是特别优选的。
上述载体还可以负载钯，相对于催化剂总重量，金属含量为0.01-50％重量，优选0.1-10％重量。
上述载体材料或负载钯的载体材料相对于使用的卤代硝基苯的用量为0.01-20％重量，优选0.01-10％重量。优选使用负载钯的活性炭。
显然，氢化还可以使用其它还原方法进行，如本领域技术人员已知并例如列于“Reductions in Organic Chemistry，Second Edition，ACS Monograph 188”的。
氢化温度为约0-200℃，特别是40-150℃；压力(氢气压力)约0.1-150bar，特别是0.5-70bar，尤其优选1-50bar。
使用本发明的方法，以高选择性(＞98％)和高达99％的产率得到相应的4-氨基联苯基胺。
实施例
实施例1
首先在惰性气氛下将372.0g(4.00mol)苯胺、0.25g(0.00082mol)丙酮基醋酮酸钯(palladium acetonylacetonate)和0.86g(0.00328mol)三苯基膦加入多颈圆底烧瓶中，在室温搅拌10分钟。加入157.6g(1.00mol)4-氯硝基苯并在室温再搅拌10分钟。然后加入120.0g(0.87mol)研磨过的碳酸钾和40ml二甲苯。在充分搅拌下进行回流并分离水45分钟。气相色谱监测表明对氯硝基苯完全转化。
允许混合物冷却到85℃，用300ml水稀释。有机相在10bar的氢气压下用1.0g Pd/C(5％Pd/C)进行氢化15分钟，其中温度达到110℃。
过滤和蒸馏后，得到182g(理论量的99％)4-氨基二苯基胺。
实施例2
首先在惰性气氛下将372.0g(4.00mol)苯胺、0.20g(0.00066mol)丙酮基醋酮酸钯和0.69g(0.00263mol)三苯基膦加入多颈圆底烧瓶中，在室温搅拌10分钟。加入157.6g(1.00mol)4-氯硝基苯并在室温再搅拌10分钟。然后加入120.0g(0.87mol)研磨过的碳酸钾和40ml二甲苯。在充分搅拌下进行回流并分离水45分钟。气相色谱监测表明对氯硝基苯完全转化。
允许混合物冷却到85℃，用300ml水稀释。有机相在10bar的氢气压下用1.0g Pd/C(3％Pd/C)进行氢化11分钟，其中温度达到120℃。
过滤和蒸馏后，得到181g(理论量的98％)4-氨基二苯基胺。
实施例3
首先在惰性气氛下将372.0g(4.00mol)苯胺、0.25g(0.00082mol)丙酮基醋酮酸钯和0.86g(0.00328mol)三苯基膦加入多颈圆底烧瓶中，在室温搅拌10分钟。加入157.6g(1.00mol)4-氯硝基苯并在室温再搅拌10分钟。然后加入96.6g(0.70mol)研磨过的碳酸钾和50ml二甲苯。在充分搅拌下进行回流并分离水45分钟。气相色谱监测表明对氯硝基苯完全转化。
允许混合物冷却到85℃，用300ml水稀释。有机相在10bar的氢气压下用1.0g Pd/C(5％Pd/C负载)进行氢化14分钟，其中温度达到120℃。
气相色谱测定后，得到99％的4-氨基二苯基胺。
实施例4
首先在惰性气氛下将372.0g(4.00mol)苯胺、0.22g(0.00098mol)乙酸钯和1.04g(0.00397mol)三苯基膦加入多颈圆底烧瓶中，在室温搅拌10分钟。加入157.6g(1.00mol)4-氯硝基苯并在室温再搅拌10分钟。然后加入96.6g(0.70mol)研磨过的碳酸钾和50ml二甲苯。在充分搅拌下进行回流并分离水45分钟。气相色谱监测表明对氯硝基苯完全转化。
有机相在10bar的氢气压下氢化25分钟，其中温度达到140℃。
气相色谱测定后，得到98％的4-氨基二苯基胺。
实施例5
首先在惰性气氛下将372.0g(4.00mol)苯胺、0.30g(0.00098mol)丙酮基醋酮酸钯和1.04g(0.00397mol)三苯基膦加入多颈圆底烧瓶中，在室温搅拌10分钟。加入157.6g(1.00mol)4-氯硝基苯并在室温再搅拌10分钟。然后加入96.6g(0.70mol)研磨过的碳酸钾和50ml二甲苯。在充分搅拌下进行回流并分离水45分钟。气相色谱监测表明对氯硝基苯完全转化。
允许混合物冷却到85℃，用300ml水稀释。有机相在10bar的氢气压下氢化34分钟，其中温度达到140℃。
气相色谱测定后，得到99％的4-氨基二苯基胺。实施例6
首先在惰性气氛下将372.0g(4.00mol)苯胺、0.30g(0.00098mol)丙酮基醋酮酸钯和1.04g(0.00397mol)三苯基膦加入多颈圆底烧瓶中，在室温搅拌10分钟。加入157.6g(1.00mol)4-氯硝基苯并在室温再搅拌10分钟。然后加入96.6g(0.70mol)研磨过的碳酸钾和50ml二甲苯。在充分搅拌下进行回流并分离水45分钟。气相色谱监测表明对氯硝基苯完全转化。
允许混合物冷却到85℃，用300ml水稀释。加入2.0g活性炭后，有机相在10bar的氢气压下氢化24分钟，其中温度达到140℃。
气相色谱测定后，得到99％的4-ADPA。
实施例7
碱的预处理：
将市售的碳酸钾在厨房磨或球磨机中研磨例如约5分钟。从而，Gruessing公司生产的并用这种方法处理的碳酸钾比表面积从0.04m2/g增加到0.52m2/g，并且表现出10μm或更小的主结晶尺寸。研磨后的碳酸钾随后在1mbar的压力和150℃的温度干燥5小时。如果使用其它碱，也用类似的方法预处理。
Claims (9)
1.制备氨基二苯基胺的方法，其特征在于，在钯催化剂和碱存在下使芳胺与硝基卤代苯反应并随后将这样得到的产物用氢氢化。
2.根据权利要求1的方法，其特征在于，使用的硝基卤代苯优选其中相对于卤代基而言硝基在对位的那些。
3.根据权利要求1的方法，其特征在于，使用的芳族胺是苯胺、邻甲苯胺、间甲苯胺、对甲苯胺、4-乙基苯胺、4-丁基苯胺、4-异丙基苯胺、3，5-二甲基苯胺或2，4-二甲基苯胺。
4.根据权利要求1的方法，其特征在于，就每摩尔硝基卤代苯而言通常使用1-10摩尔芳族胺。
5.根据权利要求1的方法，其特征在于，使用钯/膦配合物作为钯催化剂。
6.根据权利要求5的方法，其特征在于，在钯/膦配合物中，膦对钯的摩尔比为40∶1-1∶1。
7.根据权利要求1的方法，其特征在于，相对于使用的硝基卤代苯而言，钯催化剂的用量为0.0001％摩尔-10％摩尔。
8.根据权利要求1的方法，其特征在于，使用的碱经过研磨和/或干燥预处理。
9.根据权利要求1的方法，其特征在于，研磨后碱的比表面积为0.1-10m2/g(BET)。
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| US8486223B2 (en) * | 2003-07-04 | 2013-07-16 | Jiangsu Sinorgchem Technology Co., Ltd. | Falling film evaporator |
| JP4500302B2 (ja) | 2003-07-04 | 2010-07-14 | チアンス・シノケム・テクノロジー・カンパニー・リミテッド | ４−アミノジフェニルアミンの製造方法 |
| US7176333B2 (en) * | 2003-07-04 | 2007-02-13 | Sinorgchem Company, Shandong | Process for preparing 4-aminodiphenylamine |
| US8686188B2 (en) | 2003-07-04 | 2014-04-01 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| WO2006011879A1 (en) * | 2004-06-30 | 2006-02-02 | Eastman Kodak Company | Process for forming an aromatic amine compound |
| CN100363330C (zh) * | 2005-05-20 | 2008-01-23 | 中国石油天然气集团公司 | 一种提高4-氨基二苯胺产率的方法 |
| US7288500B2 (en) * | 2005-08-31 | 2007-10-30 | Headwaters Technology Innovation, Llc | Selective hydrogenation of nitro groups of halonitro aromatic compounds |
| US7892299B2 (en) * | 2005-09-15 | 2011-02-22 | Headwaters Technology Innovation, Llc | Methods of manufacturing fuel cell electrodes incorporating highly dispersed nanoparticle catalysts |
| US7935652B2 (en) * | 2005-09-15 | 2011-05-03 | Headwaters Technology Innovation, Llc. | Supported nanoparticle catalysts manufactured using caged catalyst atoms |
| JP2007161619A (ja) * | 2005-12-12 | 2007-06-28 | Mitsubishi Chemicals Corp | 有機化合物の製造方法、その製造方法により得られた電子材料、並びに、それを用いた電子デバイス、電子写真感光体及び画像形成装置 |
| US7718710B2 (en) | 2006-03-17 | 2010-05-18 | Headwaters Technology Innovation, Llc | Stable concentrated metal colloids and methods of making same |
| CN102259029B (zh) | 2010-05-24 | 2014-12-10 | 江苏圣奥化学科技有限公司 | 固体碱催化剂 |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE185683C (zh) | ||||
| DE2633811C2 (de) | 1976-07-28 | 1983-11-10 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von Nitrodiphenylaminen |
| US4187248A (en) | 1977-11-23 | 1980-02-05 | Monsanto Company | Making a nitrodiarylamine by reacting an alkali metal salt of a formamide with a nitrohaloarene |
| US4187249A (en) | 1977-12-27 | 1980-02-05 | Monsanto Company | Promoting the reaction of sodium salts of formyl derivatives of aromatic amines to form nitrodiarylamines |
| DE3246151A1 (de) * | 1982-12-14 | 1984-06-14 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von 4-nitrodiphenylaminen |
| DE3501698A1 (de) | 1985-01-19 | 1986-07-24 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von 4-nitrodiphenylaminen |
| DE3504479A1 (de) | 1985-02-09 | 1986-08-14 | Bayer Ag, 5090 Leverkusen | Verfahren zur herstellung von 4-nitrodiphenylaminen |
| US5576460A (en) | 1994-07-27 | 1996-11-19 | Massachusetts Institute Of Technology | Preparation of arylamines |
| DE19650213A1 (de) | 1996-12-04 | 1998-06-10 | Hoechst Ag | Synthese von aromatischen Aminen aus Chloraromaten |
| US5840982A (en) * | 1998-06-04 | 1998-11-24 | Uniroyal Chemical Company, Inc. | Process for preparing para-phenylenediamine derivatives |
| DE19942394C1 (de) * | 1999-09-06 | 2001-02-01 | Bayer Ag | Verfahren zur Herstellung von Nitrodiphenylaminen |
-
2000
- 2000-02-09 DE DE10005601A patent/DE10005601A1/de not_active Withdrawn
-
2001
- 2001-01-29 DE DE50103049T patent/DE50103049D1/de not_active Expired - Fee Related
- 2001-01-29 EP EP01101657A patent/EP1123916B1/de not_active Expired - Lifetime
- 2001-02-02 US US09/776,104 patent/US6316673B2/en not_active Expired - Fee Related
- 2001-02-06 JP JP2001030126A patent/JP2001253855A/ja active Pending
- 2001-02-06 CA CA002334273A patent/CA2334273A1/en not_active Abandoned
- 2001-02-07 SK SK199-2001A patent/SK285005B6/sk unknown
- 2001-02-08 KR KR1020010006048A patent/KR20010078783A/ko active IP Right Grant
- 2001-02-08 CN CNB011034394A patent/CN1181044C/zh not_active Expired - Fee Related
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2003
- 2003-02-28 HK HK03101526.8A patent/HK1049327A1/zh unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP1123916B1 (de) | 2004-08-04 |
| KR20010078783A (ko) | 2001-08-21 |
| SK285005B6 (sk) | 2006-04-06 |
| EP1123916A1 (de) | 2001-08-16 |
| CA2334273A1 (en) | 2001-08-09 |
| US6316673B2 (en) | 2001-11-13 |
| DE10005601A1 (de) | 2001-08-16 |
| CN1181044C (zh) | 2004-12-22 |
| SK1992001A3 (en) | 2001-12-03 |
| HK1049327A1 (zh) | 2003-05-09 |
| US20010012906A1 (en) | 2001-08-09 |
| DE50103049D1 (de) | 2004-09-09 |
| JP2001253855A (ja) | 2001-09-18 |
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