CN1116275C - 4-氨基二苯胺的制备方法 - Google Patents
4-氨基二苯胺的制备方法 Download PDFInfo
- Publication number
- CN1116275C CN1116275C CN98116878A CN98116878A CN1116275C CN 1116275 C CN1116275 C CN 1116275C CN 98116878 A CN98116878 A CN 98116878A CN 98116878 A CN98116878 A CN 98116878A CN 1116275 C CN1116275 C CN 1116275C
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- China
- Prior art keywords
- nitrosobenzene
- alkali
- catalyzer
- catalyst
- oxide
- 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.)
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- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 title claims description 35
- 238000002360 preparation method Methods 0.000 title description 13
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 150000004703 alkoxides Chemical group 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 24
- 238000005984 hydrogenation reaction Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- -1 aromatic halohydrocarbon Chemical class 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000000010 aprotic solvent Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 229910052697 platinum Inorganic materials 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 5
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 5
- 229910001701 hydrotalcite Inorganic materials 0.000 description 5
- 229960001545 hydrotalcite Drugs 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000010948 rhodium Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052703 rhodium Inorganic materials 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 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
- 229910052792 caesium Inorganic materials 0.000 description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000003444 phase transfer catalyst Substances 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- NAMDIHYPBYVYAP-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound COCCOCCOC.COCCOCCOC NAMDIHYPBYVYAP-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- XXYMSQQCBUKFHE-UHFFFAOYSA-N 4-nitro-n-phenylaniline Chemical compound C1=CC([N+](=O)[O-])=CC=C1NC1=CC=CC=C1 XXYMSQQCBUKFHE-UHFFFAOYSA-N 0.000 description 1
- 229910017119 AlPO Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- GHVZOJONCUEWAV-UHFFFAOYSA-N [K].CCO Chemical compound [K].CCO GHVZOJONCUEWAV-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 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
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 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
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000836 magnesium aluminium oxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- KTDMLSMSWDJKGA-UHFFFAOYSA-M methyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](C)(CCC)CCC KTDMLSMSWDJKGA-UHFFFAOYSA-M 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JEUXZUSUYIHGNL-UHFFFAOYSA-N n,n-diethylethanamine;hydrate Chemical compound O.CCN(CC)CC JEUXZUSUYIHGNL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 150000004686 pentahydrates Chemical class 0.000 description 1
- GJGSXVBJZVLVSE-UHFFFAOYSA-N pentan-1-ol;potassium Chemical compound [K].CCCCCO GJGSXVBJZVLVSE-UHFFFAOYSA-N 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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Classifications
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- 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
- C07C209/38—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 nitroso groups
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- 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
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Abstract
在含氢氧化物、氧化物和/或醇盐的碱和多相催化剂的存在下,在惰性非质子性溶剂的存在下,在0至200℃温度和0.1至150巴压力下,用氢氢化亚硝基苯或亚硝基苯和硝基苯的混合物制备4-氨基二苯胺类化合物。
Description
本发明涉及4-氨基二苯胺(4-ADPA)的制备方法,该方法是在氢化催化剂和碱的存在下用氢来氢化亚硝基苯来进行的。
4-ADPA是橡胶和聚合物工业中氧化剂和稳定剂的重要中间体(Kirk-Othmer,化学技术百科全书(Encyclopedia of ChemicalTechnology),第4版,1992,Vol.3,424-447页和448-456页,Ullmann’s工业化学百科全书(Ullmann’s Encyclopedia ofIndustrial Chemistry),第5版,Vol.A3,1985,91-111页)。
4-氨基二苯胺可通过多种方法制备。对4-ADPA来说,一种可能的途径是苯胺或苯胺衍生物与对硝基氯苯的两步反应(中间体4-硝基二苯胺),该反应在酸受体或中和剂存在下并任选地在催化剂的存在下进行。下列出版物的实例描述了后一制备方法:DE-A3501698,DE-A185663,US4670595,US4187249,US468333和US4187248。该方法的缺点是此情况下反应产生的卤离子使反应器和仪器腐蚀,这必须花相当的费用处理。为此,苯胺或相应的苯胺衍生物在四烷基氢氧化铵和一定量的质子物质存在下与硝基苯反应。此时得到4-ADPA的量是令人满意的(见WO95/00324和WO9324450)。按照US5420354,4-ADPA可通过在氢化催化剂、氢化抑制剂和酸共催化剂的存在下用苯胺、硝基苯和氢反应得到,但是其产率不能令人满意。US5574187描述了由苯胺与亚硝基苯或苯基羟胺在酸的存在下反应制备4-ADPA的可能性。
但是,后面的方法的缺点是使用两种不同的离析物,它们必须在反应前即时以分离的步骤制备,这是不经济的。
也已知在多相催化剂上氢化亚硝基苯主要得到苯胺和二苯肼。未提及4-ADPA为产品(Chem.Ind.1994,Catalysis of OrganicReactions,137至149页)。
现已令人惊奇地发现,在碱和多相催化剂的存在下通过氢化亚硝基苯可得到有利的工业收率的4-ADPA。
因此,本发明提供了4-氨基二苯胺的制备方法,其特征是在含氢氧化物、氧化物和/或醇盐的碱和多相催化剂的存在下,在惰性非质子性溶剂的存在下,在0至200℃温度和0.1至150巴压力下,用氢氢化亚硝基苯或亚硝基苯和硝基苯的混合物。
无机碱如碱金属氢氧化物、碱金属氧化物、碱金属醇盐、碱土金属氢氧化物、碱土金属氧化物、碱土金属醇盐和元素周期表(新IUPAC命名)中58至71号元素的相应氢氧化物、氧化物和醇盐被认为是含氢氧化物、氧化物和/或醇盐的碱,这些碱适用于本发明的方法。实例如下:钠、钾、锂、铯、镁、钙、钡、镧和/或铈的氧化物、氢氧化物及醇盐,特别是锂、钠、钾、铯的氧化物、氢氧化物和醇盐,首选氢氧化钾、氢氧化铯、丁醇钠、甲醇钠、乙醇钠、丁醇钾、甲醇钾、丙醇钾、乙醇钾、戊醇钾。
还可考虑使用有机碱如氢氧化烷基季铵(NR4 +OH-,每个R独立地表示含1至7个碳原子的烷基、芳基或芳烷基)。可提及的实例有:四甲基氢氧化铵、三乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵、甲基三丁基氢氧化铵、甲基三丙基氢氧化铵、甲基三乙基氢氧化铵、三甲基苄基氢氧化铵。特别优选四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵和四丁基氢氧化铵。首选四甲基氢氧化铵。
还可使用上述碱的任何混合物。
与相转移催化剂联合使用无机碱也是可能的。适宜的相转移催化剂描述于,例如,W.E.Keller,Fluka-Kompendium,Vol.1,2,3,Georg Thieme Verlag,Stuttgart 1986,1987,1992。例如,上述碱可与冠醚如18-冠醚6或季铵化合物一起使用。
本发明使用的碱就每摩尔而言含水可达至多6摩尔,优选达至多3摩尔水,特别优选达至多2.5摩尔水。
本发明的碱可以以固体、熔体或在非质子性溶剂中的溶液形式或在亚硝基苯和一种或多种非质子性溶剂的混合物中加入反应混合物中。
本文中使用的碱的量就每摩尔亚硝基苯而言为0.01至3,优选0.1至2,特别是0.3至1.5摩尔。
含6至20个碳原子的芳香烃、含不多于5个氧原子和2至16个碳原子的直链或环醚、含6至20个碳原子的芳香卤代烃和含1至10个碳原子的酰胺可被看作是惰性非质子性溶剂。上述溶剂自然可互相混合使用。下面是特别适宜的溶剂:苯、甲苯、二甲苯、叔丁基甲基醚、叔戊基甲基醚、二异丙基醚、二甘醇二甲基醚、甘醇二甲基醚、二噁烷、四氢呋喃、二戊醚、氯苯、二氯苯、二甲基甲酰胺、二甲基乙酰胺和N-甲基吡咯烷酮。优选使用甲苯、二甲苯、甘醇二甲基醚、二噁烷、叔丁基甲基醚、二异丙基醚、二甘醇二甲基醚,特别优选使用甘醇二甲基醚、二噁烷、叔丁基甲基醚、二甘醇二甲基醚和甲苯。对本发明的方法来说,溶剂的量无严格限制,可具体根据反应温度和类型及所用碱和催化剂的量确定。相对于反应混合物总量,该溶剂一般的使用量为1至99%(重量),优选5至95%(重量),特别优选15至90%(重量)。
实际上,已知用于氢化反应的所有多相催化剂都是适宜的本发明方法的多相催化剂。本发明的催化剂包括存在于适宜载体上的元素周期表(新IUPAC命名)中8至10族金属或铜和/或铬,其中金属含量占总催化剂重量的0.01至50%(重量),优选0.1至10%(重量)。按照本发明,可使用含一种或多种上述金属的催化剂。如果存在多种元素,则重量百分数指各百分数的总和。优选的金属特别是铂、钯、铑和钌,其中铂、钯和铑是特别优选的。还可优选的催化剂是阮内镍和载体上的镍催化剂。
按照本发明,上述金属或其化合物也可以纯的形式作为固体使用。钯黑和铂黑可称为纯的形式的金属的例子。
通过本领域技术人员已知的多种方法制备本发明的催化剂。例如,一种或多种所述金属化合物的溶液可涂敷于用于本发明的催化剂载体上,例如通过浸渍、吸附、浸蘸、喷洒、浸渗和离子交换方法。可用已知方法将其它金属加在催化剂上。还可能通过用碱沉淀的方法将一种或多种上述金属固定在载体上。例如,碱(土)金属氢氧化物可考虑作为碱。可将一种或多种金属以任何顺序依次或同时涂敷于载体上。本发明的具体实例包括通过用适当的碱沉淀金属卤化物或金属卤化物复合物涂敷金属,并将金属化合物还原为金属。如果通过溶胶方法制备载体,在一个实例中,实际上一种或多种上述金属化合物的溶液可以以本领域技术人员已知的方式加入溶胶中。
基于碳、单质(element)氧化物、单质碳化物或单质盐的,以多种形式使用的所有常规工业催化剂载体是合适的在本发明中用作催化剂载体的物质。含碳载体有焦炭、石墨、碳黑或活性炭。单质氧化物催化剂载体的例子为二氧化硅(天然或合成硅石、石英),氧化铝(α-、γ-氧化铝),矾土,天然或合成硅铝酸盐(沸石),片状硅酸盐如膨润土和蒙脱石,二氧化钛(金红石、锐钛矿),氧化锆,氧化镁或氧化锌。单质碳化物和单质盐的实例为SiC,AlPO4,硫酸钡,碳酸钙。可主要使用合成物质和天然载体如浮石,高岭土,漂白土,铝土矿,膨润土,硅藻土,石棉或沸石。
可用于发明的其他有用的催化剂载体为元素周期表2至16族元素和稀土金属(原子序数58至71)的混合氧化物和水化氧化物,优选元素Al、Si、Ti、Zr、Zn、Mg、Ca、Zn、Nb和Ce的混合氧化物和水化氧化物,它们可尤其由盐和/或醇盐由盐的物理混合物,共沉淀或由共凝胶的方式制备,这对本领域技术人员是已知的。
混合氧化物的实例为氧化铝镁(水滑石)。
该载体可使用化学均匀纯物质或混合物。块状或粉末状物质是适用于本发明的催化剂载体。如果载体上的催化剂被置于固定床上,载体优选以模塑体形式使用,如球体、圆柱体、棒、圆筒、环等。根据个别需要决定是否通过挤压、压片,任选地与其它催化剂载体或粘合剂如二氧化硅或氧化铝混合并煅烧对催化剂载体进一步修饰。载体的内表面(BET表面)约1至2000m2/g,优选约10至1600m2/g,首选约20至1500m2/g。用于本发明的催化剂载体的制备和进一步处理对本领域技术人员是熟知的并构成现有技术。
活性炭和含硅、铝、镁、锆及钛的物质优选用作载体物质,特别优选活性炭和含硅、镁和铝的载体。
本发明的催化剂可以以批量方法的变化形式使用,与所用亚硝基苯相比,其用量为0.01至20%(重量),优选为0.01至10%(重量)。如果反应以连续的方式进行,例如在搅拌罐反应器中用粉末状催化剂或在固定床催化剂上在喷淋相(trickling phase)中,每克催化剂每小时可施用0.01至500g亚硝基苯负荷。每克催化剂每小时优选负荷0.02至300g亚硝基苯。
例如,在由硝基苯制备亚硝基苯过程中产生的亚硝基苯或亚硝基苯/硝基苯混合物可以引入本发明的方法中。亚硝基苯的含量可以是例如0.5至99%,优选0.5至98%,首选1至97%。
本发明方法的反应温度优选0至200℃,特别是25至150℃;压力(氢压)约为0.1至150巴,特别是0.5至70巴,首选1至50巴。
该反应可以在恒定的温度和恒定的压力下进行。但是,在反应过程中氢压和温度也可变化,或者在不同反应器中可不相同。当反应以分批的形式进行时,亚硝基苯、催化剂、溶剂和碱可以以任何顺序加入反应器中。特定的量使用完毕后可终止提供氢气,并在以后可再继续或不继续。
连续方法变化形式为例如在液相中用粉末状悬浮催化剂(浆)氢化,在固定床催化剂上以喷淋方式氢化或在泡罩塔中用悬浮催化剂氢化。该反应可以在本领域技术人员已知的设备中进行固相、液相和气相的接触。可特别考虑搅拌罐反应器、强迫循环反应器、母线限流器、以并流或逆流方式操作的泡罩塔或喷淋相反应器或串式喷淋相反应器,其中不同类型的反应器也可同时存在(串式)。
如果在液相中以粉末状形式使用催化剂,为了混合反应成分,使用安装有适于此目的的搅拌器的搅拌罐。可使用叶式搅拌器,多步脉冲逆流搅拌器、桨式搅拌器、锚式搅拌器或气体分散搅拌器。
本发明该方法中产生的其它物质为将亚硝基苯氢化为苯胺的中间体并可全部转化为苯胺,苯胺同样是合成很多工业终产物的有价值的起始物。
实施例
下列实施例说明了在不同压力和温度下用不同催化剂、碱和溶剂进行反应的方式。通过气相色谱(Durabond DB-5-MS;30m×0.25mmID)以正十三烷作为内标物或通过定量HPLC分析反应产物。所有试验中亚硝基苯的转化都是完全的。在氮气氛下进行后处理和样品制备。当反应导致压力下降时,手工调节自动阀门指示的氢气压力。
所用碱和催化剂是商业产品或按照下文描述制备。
由常规购买的五水合物(得自Aldrich)或25%水溶液(得自Aldrich)在80℃在水喷射并然后通过泵抽真空条件下,或在氧化磷干燥器内除水制备四甲基氢氧化铵水合物(TMAOH·xH2O)。通过酸滴定检测剩余的水分。每种情况下制剂中所用物质的含水量是特定的。
催化剂A,B的制备催化剂A(Pd,Rh和Pt催化剂)
在闭炉中在350℃将载体物质加热2小时并转移至250ml烧瓶中。在旋转薄膜蒸发器上将PdCl2,RhCl3或H2PtCl6的稀水溶液(通过稀释含25%铂的H2PtCl6的水溶液制备)加到载体物质上。选择含水量,以便使其被载体完全吸收(“早期湿润”(incipient wetnet))。然后在真空在60℃将大部分水蒸发掉,并将催化剂在120℃,小于1毫巴的压力下干燥16小时并在300℃在含10%(体积)氢气的氮气流中还原24小时。通过元素分析测定贵金属含量。
实施例号 | 类型 | 载体 | BETm2/g | 载体(g) | “M” | “H2O” | “M%” |
A1 | Pd/MgO | Aldrich | 46 | 20.0 | 1.7 | 400 | 5.1 |
A2 | Rh/HT | 水滑石Sudchemie | 134 | 15.0 | 2.0 | 60 | 3.9 |
A3 | Pt/HT | 水滑石Sudchemie | 93 | 23.8 | 5.0 | 90 | 3.8 |
“M”:PdCl2,RhCl3或H2PtCl6的溶液(25%Pt含量)的量;
“H2O”:加入水的量;(在PdCl2的情况下加入1滴浓盐酸)
“M%”:制得的催化剂的贵金属含量,以重量%表示。催化剂B(Pt/活性炭)
将475g活性炭(Norit-B-Supra,自Norit)在2600ml去离子水中浆化,将此混合物加热至50℃,并加入87.5g甲酸钠的400ml去离子水溶液。在30分钟内,滴加100g H2PtCl4溶液(25%(重量)Pt)和400ml去离子水的混合物,加入后在50℃搅拌1小时。将此催化剂抽滤,洗涤并在60℃真空干燥。实施例1至22(在常压下氢化)
实施例1
将65ml二甘醇二甲基醚、7.03g(0.055mol)TMAOH·2.0H2O和0.5g得自Engelhard的粉末状5% Pd/C催化剂3230置于250ml平圆底瓶中并加热至80℃,该瓶用氮气清洗并装备有气体分散搅拌器。温度达到后,常压下用25升/小时的氢气流置换氮气,并同时加入存在于10ml二甘醇二甲基醚中的5.89g(0.055mol)亚硝基苯。120分钟后取样并过滤,用乙醇酸中和并通过定量气相色谱分析。亚硝基苯完全转化。4-ADPA的产率为46.0%(百分率为亚硝基苯的摩尔百分率)。
实施例2
在80℃用0.5g粉末状5%Pt/C催化剂(催化剂B)重复实施例1。反应2小时后,4-ADPA的产率为48.0%。
实施例3
在80℃用0.5g粉末状5% Rh/C催化剂G10(得自Degussa)重复实施例1。反应2小时后,4-ADPA的产率为47.0%。
实施例4
在80℃用0.5g粉末状5% Pt/氧化铝催化剂(得自Aldrich)重复实施例1。反应2小时后,4-ADPA的产率为35.3%。
实施例5
在80℃用2.5g粉末状1% Pt/ZSM 5催化剂重复实施例1。反应2小时后,4-ADPA的产率为31.9%。
实施例6
在80℃用2.5g粉末状1% Pt/沸石L催化剂重复实施例1。反应6小时后,4-ADPA的产率为36.9%。
实施例7
在40℃用相同的催化剂重复实施例1。反应6小时后,4-ADPA的产率为47.9%。
实施例8
在80℃用其中加入0.99g(0.055mol)水的相同催化剂重复实施例1。反应1小时后,4-ADPA的产率为32.6%。
实施例9
在80℃用存在于75ml甲苯中的相同催化剂重复实施例1。反应6小时后,4-ADPA的产率为17.3%。
实施例10
在25℃用相同的催化剂重复实施例1。反应14小时后,4-ADPA的产率为26.1%。
实施例11
在80℃用0.5g粉末状5% Pd/氧化镁催化剂(催化剂A1)重复实施例1。反应6小时后,4-ADPA的产率为14.4%。
实施例12
在80℃用3.1g(0.055mol)氢氧化钾重复实施例1。反应1.5小时后,4-ADPA的产率为3.9%。
实施例13
在80℃用6.2g(0.055mol)叔丁醇钾重复实施例1。反应10小时后,4-ADPA的产率为3.1%。
实施例14
在80℃用6.2g(0.055mol)叔丁醇钾和8.5g(0.055mol)(H3C)4NBr重复实施例1。反应18小时后,4-ADPA的产率为9.4%。
实施例15
用2.5g(0.055mol)氢氧化钠在80℃重复实施例1。反应1小时后,4-ADPA的产率为1.0%。
实施例16
在80℃用0.5g粉末状3.9% Rh/水滑石催化剂(催化剂A2)重复实施例1。反应2小时后,4-ADPA的产率为22.0%。
实施例17
用0.5g粉末状3.8% Pt/水滑石催化剂(催化剂A3)重复实施例1。反应2小时后,4-ADPA的产率为28.3%。
实施例18(对比实施例)
在80℃用相同的催化剂而不加入碱重复实施例1。反应14小时后,4-ADPA的产率小于0.3%。
实施例19
在80℃,用1.18g(0.011mol)亚硝基苯和5.42g(0.044mol)硝基苯的混合物重复实施例1。反应1小时后,4-ADPA的产率为60.8%。
实施例20
在80℃,用2.95g(0.0275mol)亚硝基苯和3.39g(0.0275mol)硝基苯的混合物重复实施例1。反应1小时后,4-ADPA的产率为35.2%。
实施例21(加压反应)
在带四叶螺旋桨搅拌器的2升Buchi玻璃高压釜中,将133gTMAOH·2.3H2O、960ml二甘醇二甲基醚(Diglyme)和2.4g 5% Pt/C催化剂(催化剂B)加热至70℃。用氮气使高压釜惰性,并加入107.1g亚硝基苯。然后在80℃,在4巴氢压下且搅拌速度为1000rpm,氢化4.4小时。
反应完成后,将高压釜中压力降至常压,用氮气清洗高压釜,并在50℃加入去离子水500ml。形成两相。将混合物过滤,进行相分离。通过用300ml去离子水摇动4次提取有机相,然后中和。通过用400ml甲苯和50g氯化钠摇动3次提取水相。
通过定量HPLC分析有机相,发现其中含48.4g 4-ADPA(相当于亚硝基苯产率为53.0%)。
Claims (8)
1.制备4-氨基二苯胺的方法,其特征是在含氢氧化物、氧化物和/或醇盐的碱和多相催化剂的存在下,在惰性非质子性溶剂的存在下,在0至200℃温度和0.1至150巴压力下,用氢氢化亚硝基苯或亚硝基苯和硝基苯的混合物。
2.根据权利要求1的方法,其特征是氢化反应在温度25至150℃和压力0.5至70巴下进行。
3.根据权利要求1的方法,其特征是碱金属氢氧化物、碱金属氧化物、碱金属醇盐、碱土金属氢氧化物、碱土金属氧化物、碱土金属醇盐和元素周期表中58至71号元素的相应氢氧化物、氧化物和醇盐及氢氧化烷基季铵被用作含氢氧化物、氧化物和/或醇盐的碱。
4.根据权利要求1的方法,其特征是碱的用量为每摩尔亚硝基苯用0.01至3当量。
5.根据权利要求1的方法,其特征是含6至20个碳原子的芳香烃、含不多于5个氧原子和2至16个碳原子的直链或环状醚、含6至20个碳原子的芳香卤代烃和含1至10个碳原子的酰胺被用作惰性非质子性溶剂。
6.根据权利要求1的方法,其特征是相对于反应混合物的总量惰性非质子性溶剂的用量为1至99%(重量)。
7.根据权利要求1的方法,其特征是任选地存在于适宜载体上的元素周期表中8至10族金属或铜和/或铬用作多相催化剂。
8.根据权利要求1的方法,其特征是催化剂可以在分批操作中使用,就所用的亚硝基苯而言,其用量为0.01至20%(重量),或以连续操作方式每克催化剂每小时可施用0.01至500g亚硝基苯负荷。
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EP (1) | EP0895983B1 (zh) |
JP (1) | JPH11228506A (zh) |
KR (1) | KR19990023373A (zh) |
CN (1) | CN1116275C (zh) |
CA (1) | CA2244391A1 (zh) |
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DE19810929A1 (de) * | 1998-03-13 | 1999-09-16 | Bayer Ag | Verfahren zur Herstellung von 4-Aminodiphenylamin |
US6495723B1 (en) * | 2000-06-21 | 2002-12-17 | Flexsys America | Zeolite support loaded with a base material for use in the coupling of aniline and nitrobenzene |
DE10055221A1 (de) * | 2000-11-08 | 2002-05-29 | Bayer Ag | Verfahren zur Herstellung von 4-Aminodiphenylamin |
US6395933B1 (en) | 2001-07-23 | 2002-05-28 | Flexsys America, L.P. | Process for preparing 4-aminodiphenylamine intermediates |
US8686188B2 (en) | 2003-07-04 | 2014-04-01 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
ES2298762T3 (es) * | 2003-07-04 | 2008-05-16 | Sinorgchem Co., Shandong | Proceso para preparar 4-aminodifenilamina. |
US8486223B2 (en) | 2003-07-04 | 2013-07-16 | Jiangsu Sinorgchem Technology Co., Ltd. | Falling film evaporator |
US7176333B2 (en) | 2003-07-04 | 2007-02-13 | Sinorgchem Company, Shandong | Process for preparing 4-aminodiphenylamine |
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 |
JP6143057B2 (ja) * | 2013-02-12 | 2017-06-07 | 株式会社ダイセル | 1,2−ペンタンジオールの製造方法 |
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US5117063A (en) * | 1991-06-21 | 1992-05-26 | Monsanto Company | Method of preparing 4-aminodiphenylamine |
US5739403A (en) * | 1996-01-11 | 1998-04-14 | Bayer Ag | Process for the production of optionally substituted 4-aminodiphenylamines |
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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 |
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 |
US5552531A (en) * | 1992-05-22 | 1996-09-03 | Monsanto Company | Process for preparing substituted aromatic azo compounds |
US5574187A (en) * | 1994-10-06 | 1996-11-12 | Uniroyal Chemical Company, Inc. | Process of preparing para substituted phenylamines |
US5420354A (en) * | 1994-10-06 | 1995-05-30 | Uniroyal Chemical Company, Inc. | Process of preparing para phenylamines |
US5606111A (en) * | 1995-10-24 | 1997-02-25 | The United States Of America As Represented By The Secretary Of The Army | Apparatus and method for measurement of offgassing rate |
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- 1998-07-24 DE DE59803587T patent/DE59803587D1/de not_active Expired - Fee Related
- 1998-07-24 EP EP98113847A patent/EP0895983B1/de not_active Expired - Lifetime
- 1998-07-30 US US09/126,344 patent/US5932768A/en not_active Expired - Fee Related
- 1998-07-30 JP JP10228532A patent/JPH11228506A/ja active Pending
- 1998-07-31 CA CA002244391A patent/CA2244391A1/en not_active Abandoned
- 1998-08-04 CN CN98116878A patent/CN1116275C/zh not_active Expired - Fee Related
- 1998-08-05 KR KR1019980031860A patent/KR19990023373A/ko not_active Application Discontinuation
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US5117063A (en) * | 1991-06-21 | 1992-05-26 | Monsanto Company | Method of preparing 4-aminodiphenylamine |
US5739403A (en) * | 1996-01-11 | 1998-04-14 | Bayer Ag | Process for the production of optionally substituted 4-aminodiphenylamines |
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CA2244391A1 (en) | 1999-02-06 |
EP0895983B1 (de) | 2002-04-03 |
EP0895983A1 (de) | 1999-02-10 |
TW500712B (en) | 2002-09-01 |
KR19990023373A (ko) | 1999-03-25 |
CN1209430A (zh) | 1999-03-03 |
JPH11228506A (ja) | 1999-08-24 |
US5932768A (en) | 1999-08-03 |
DE59803587D1 (de) | 2002-05-08 |
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