US20020055652A1 - Process for preparing4-aminodiphenylamine - Google Patents
Process for preparing4-aminodiphenylamine Download PDFInfo
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- US20020055652A1 US20020055652A1 US10/007,014 US701401A US2002055652A1 US 20020055652 A1 US20020055652 A1 US 20020055652A1 US 701401 A US701401 A US 701401A US 2002055652 A1 US2002055652 A1 US 2002055652A1
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- Prior art keywords
- adpa
- catalyst
- process according
- aminodiphenylamine
- nitrosobenzene
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 18
- NLRKCXQQSUWLCH-UHFFFAOYSA-N nitrosobenzene Chemical compound O=NC1=CC=CC=C1 NLRKCXQQSUWLCH-UHFFFAOYSA-N 0.000 claims abstract description 12
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 9
- 150000007513 acids Chemical class 0.000 claims description 7
- -1 4-ADPA ammonium salt Chemical class 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 abstract description 4
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- DYDNPESBYVVLBO-UHFFFAOYSA-N formanilide Chemical class O=CNC1=CC=CC=C1 DYDNPESBYVVLBO-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- KGAXXYDSROIYAV-UHFFFAOYSA-N n-(4-nitrosophenoxy)-n-phenylaniline Chemical compound C1=CC(N=O)=CC=C1ON(C=1C=CC=CC=1)C1=CC=CC=C1 KGAXXYDSROIYAV-UHFFFAOYSA-N 0.000 description 1
- VWLFQZQXGSXBKM-UHFFFAOYSA-N n-(4-nitrosophenyl)-n-phenylhydroxylamine Chemical compound C=1C=C(N=O)C=CC=1N(O)C1=CC=CC=C1 VWLFQZQXGSXBKM-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
Definitions
- the invention provides a process for preparing 4-aminodiphenylamine (4-ADPA), an important starting product for synthesizing antioxidants and stabilizers in the rubber and polymer industry (Kirk-Othmer, Encyclopedia of Chemical Technology, 4th edition, 1992, Vol. A3, pages 424-456; Ullman's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A3, 1985, pages 91-111).
- 4-aminodiphenylamine can be prepared using a variety of methods.
- One possibility is the two-step (intermediate product 4-nitrodiphenylamine) reaction of aniline or aniline derivatives with p-chloronitrobenzene in the presence of an acid acceptor or a neutralizing agent and optionally in the presence of a catalyst.
- Preparation using this method is described, for example, in DE-A 3 501 698, DE-A 1 856 63, U.S. Pat. No. 4,670,595, U.S. Pat. No. 4,187,249 and U.S. Pat. No. 4,187,248.
- a disadvantage of this process is that the halide ions being produced have to be disposed of at considerable cost and the starting materials such as p-chloronitrobenzene or the corresponding formanilide derivatives have to be prepared in additional reaction steps.
- Another possibility for preparing 4-ADPA comprises the reaction of aniline or corresponding aniline derivatives with nitrobenzene in the presence of tetraalkylammonium hydroxides and in the presence of regulated amounts of protic material (see WO 95/00324 and WO 93/24250).
- the disadvantage in this case is the low thermal stability of tetraalkylammonium hydroxides, so these cannot be fully recycled to the process.
- Another possibility for preparing 4-ADPA comprises the acid-catalyzed dimerization of nitrosobenzene to 4-nitrosophenyl-diphenylhydroxylamine followed by reduction to 4-ADPA (see DE-A 1 147 237 and DE-A 2 703 919).
- the disadvantage of this process is the isolation of thermally unstable 4-nitrosophenyl-phenylhydroxylamine which is required and the effluent optionally produced by neutralization.
- the present invention provides a process for preparing 4-ADPA which is characterized in that nitrosobenzene is hydrogenated with hydrogen in the presence of a proton acid as catalyst and in the presence of a hydrogenation catalyst, optionally in the presence of an inert organic solvent, and the 4-ADPA ammonium salt thus produced is thermally decomposed, wherein 4-ADPA is produced.
- Proton acids which are suitable for the process according to the present invention are aliphatic and aromatic sulfonic acids such as methanesulfonic acid and benzenesulfonic acid, hydrogen fluoride and trifluoroacetic acid.
- the yield of 4-ADPA generally decreases with increasing water content of the acids according to the present invention, so the use of anhydrous acids is preferred.
- the acids are preferably used according to the present invention in amounts of 0.1 to 100, preferably 1 to 100 mol per mol of nitrosobenzene.
- the acids may be used either individually or in the presence of each other.
- Hydrogenation catalysts which are suitable for the process according to the present invention are virtually all heterogeneous catalysts which are known to be hydrogenation catalysts.
- Catalysts according to the present invention include metals from the 8th-10th groups of the Periodic System (according to IUPAC, new) or copper and/or chromium on suitable supports with a metal content of 0.01 to 50 wt. %, preferably 0.1 to 20 wt. %, with respect to the total weight of catalyst.
- catalysts may be used which contain one or more of the metals mentioned above.
- Preferred metals are platinum, palladium and rhodium, more preferably, platinum and palladium.
- Further preferred catalysts are Raney nickel and supported nickel catalysts.
- the metals mentioned above, or their compounds may also be used in the pure form as solids. Palladium black and platinum black may be mentioned as examples of a metal in the pure form.
- Catalysts according to the present invention may be used in amounts of 0.01 to 20 wt. %, with respect to the nitrosobenzene used, preferably in amounts of 0.01 to 10 wt. %, in batchwise process variants.
- loads of 0.01 to 500 g of nitrosobenzene per g of catalyst and per hour are used.
- reaction temperatures for the process according to the present invention are ⁇ 20° C to 50° C, preferably ⁇ 10° C to 30° C.; the hydrogen pressure is 0 . 1 to 150 bar, preferably 0.5 to 70 bar, most preferably 1 to 50 bar.
- the process according to the present invention may also be performed in the presence of organic solvents.
- Aprotic solvents which are inert to the proton acid used and under the hydrogenation conditions are preferred.
- Suitable inert organic aprotic solvents are aliphatic or aromatic hydrocarbons, linear or cyclic ethers, halogenated aliphatic or aromatic hydrocarbons or their mixtures. The following may be mentioned as suitable solvents: benzene, toluene, xylene, tert.-butyl methyl ether, dioxan, tetrahydrofuran, chloroform, methylene chloride and/or chlorobenzene.
- the amount of solvent used in the process according to the present invention is not critical. Suitable amounts may also easily be determined by appropriate preliminary trials. In the case of continuous addition of nitrosobenzene and catalyst acid, the amount of solvent used depends in particular on the solubility of nitrosobenzene in the solvent used.
- the process according to the present invention may be performed either continuously or batchwise.
- the proton acid is added to the nitrosobenzene, optionally in the presence of a solvent, and the reaction mixture obtained is then hydrogenated with hydrogen in the presence of a hydrogenation catalyst.
- Continuous process variants may be performed in equipment known to a person skilled in the art for bringing solid, liquid and gas phases into contact. Stirred tanks, forced circulation reactors, bus reactors, bubble columns operated in cocurrent or countercurrent mode or trickle phase reactors or cascades of these reactors are suitable.
- Isolation of the 4-aminodiphenylamine from the acid reaction mixture is performed in such a way that water is added to the reaction mixture, the mixture is neutralized with a base and then optionally extracted with an organic solvent.
- a preferred mode of working-up the reaction mixture comprises working up the reaction mixture by distillation after filtering off the hydrogenation catalyst. In this way, the proton acid used and optionally the solvent used can be virtually quantitatively recycled. No effluent is produced in the process according to the present invention, which is of great economic and ecological advantage.
- the 4-ADPA salt of the corresponding proton acids remaining is decomposed thermally at temperatures of about 50 to 200° C and pressures of 1013 to 0 . 05 bar in order to obtain 4-ADPA.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a process for preparing 4-aminodiphenylamine, an important starting product for synthesizing antioxidants and stabilizers in the rubber and polymer industry, by hydrogenating nitrosobenzene with hydrogen in the presence of a proton acid as catalyst and in the presence of a hydrogenating catalyst, optionally in the presence of an inert organic solvent and thermally decomposing the 4-ADPA ammonium salt produced in this way, wherein 4-ADPA is obtained.
4-aminodiphenylamine is produced in good yields and high purity by the process according to the present invention. Furthermore, no effluent is produced, which makes the process particularly economic and ecological.
Description
- The invention provides a process for preparing 4-aminodiphenylamine (4-ADPA), an important starting product for synthesizing antioxidants and stabilizers in the rubber and polymer industry (Kirk-Othmer, Encyclopedia of Chemical Technology, 4th edition, 1992, Vol. A3, pages 424-456; Ullman's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A3, 1985, pages 91-111).
- 4-aminodiphenylamine can be prepared using a variety of methods. One possibility is the two-step (intermediate product 4-nitrodiphenylamine) reaction of aniline or aniline derivatives with p-chloronitrobenzene in the presence of an acid acceptor or a neutralizing agent and optionally in the presence of a catalyst. Preparation using this method is described, for example, in DE-A 3 501 698, DE-A 1 856 63, U.S. Pat. No. 4,670,595, U.S. Pat. No. 4,187,249 and U.S. Pat. No. 4,187,248. A disadvantage of this process is that the halide ions being produced have to be disposed of at considerable cost and the starting materials such as p-chloronitrobenzene or the corresponding formanilide derivatives have to be prepared in additional reaction steps.
- Another possibility for preparing 4-ADPA comprises the reaction of aniline or corresponding aniline derivatives with nitrobenzene in the presence of tetraalkylammonium hydroxides and in the presence of regulated amounts of protic material (see WO 95/00324 and WO 93/24250). The disadvantage in this case is the low thermal stability of tetraalkylammonium hydroxides, so these cannot be fully recycled to the process.
- The one-step preparation of 4-ADPA from nitrobenzene or nitrosobenzene in the presence of hydrogen, a hydrogenating catalyst and in presence of bases provides only unsatisfactory yields of 4-ADPA (see DE-A 19 70 91 24 and DE-A 19 734 055).
- Another possibility for preparing 4-ADPA comprises the acid-catalyzed dimerization of nitrosobenzene to 4-nitrosophenyl-diphenylhydroxylamine followed by reduction to 4-ADPA (see DE-A 1 147 237 and DE-A 2 703 919). The disadvantage of this process is the isolation of thermally unstable 4-nitrosophenyl-phenylhydroxylamine which is required and the effluent optionally produced by neutralization.
- The present invention provides a process for preparing 4-ADPA which is characterized in that nitrosobenzene is hydrogenated with hydrogen in the presence of a proton acid as catalyst and in the presence of a hydrogenation catalyst, optionally in the presence of an inert organic solvent, and the 4-ADPA ammonium salt thus produced is thermally decomposed, wherein 4-ADPA is produced.
- Proton acids which are suitable for the process according to the present invention are aliphatic and aromatic sulfonic acids such as methanesulfonic acid and benzenesulfonic acid, hydrogen fluoride and trifluoroacetic acid. The yield of 4-ADPA generally decreases with increasing water content of the acids according to the present invention, so the use of anhydrous acids is preferred. The acids are preferably used according to the present invention in amounts of 0.1 to 100, preferably 1 to 100 mol per mol of nitrosobenzene. The acids may be used either individually or in the presence of each other.
- Hydrogenation catalysts, which are suitable for the process according to the present invention are virtually all heterogeneous catalysts which are known to be hydrogenation catalysts. Catalysts according to the present invention include metals from the 8th-10th groups of the Periodic System (according to IUPAC, new) or copper and/or chromium on suitable supports with a metal content of 0.01 to 50 wt. %, preferably 0.1 to 20 wt. %, with respect to the total weight of catalyst. According to the present invention, catalysts may be used which contain one or more of the metals mentioned above. Preferred metals are platinum, palladium and rhodium, more preferably, platinum and palladium. Further preferred catalysts are Raney nickel and supported nickel catalysts. According to the present invention, the metals mentioned above, or their compounds, may also be used in the pure form as solids. Palladium black and platinum black may be mentioned as examples of a metal in the pure form.
- Catalysts according to the present invention may be used in amounts of 0.01 to 20 wt. %, with respect to the nitrosobenzene used, preferably in amounts of 0.01 to 10 wt. %, in batchwise process variants. When performing the reaction in a continuous manner, for example in a stirred tank with powdered catalysts or in the trickle phase on fixed bed catalysts, loads of 0.01 to 500 g of nitrosobenzene per g of catalyst and per hour are used.
- The reaction temperatures for the process according to the present invention are −20° C to 50° C, preferably −10° C to 30° C.; the hydrogen pressure is 0.1 to 150 bar, preferably 0.5 to 70 bar, most preferably 1 to 50 bar.
- The process according to the present invention may also be performed in the presence of organic solvents. Aprotic solvents, which are inert to the proton acid used and under the hydrogenation conditions are preferred. Suitable inert organic aprotic solvents are aliphatic or aromatic hydrocarbons, linear or cyclic ethers, halogenated aliphatic or aromatic hydrocarbons or their mixtures. The following may be mentioned as suitable solvents: benzene, toluene, xylene, tert.-butyl methyl ether, dioxan, tetrahydrofuran, chloroform, methylene chloride and/or chlorobenzene. The amount of solvent used in the process according to the present invention is not critical. Suitable amounts may also easily be determined by appropriate preliminary trials. In the case of continuous addition of nitrosobenzene and catalyst acid, the amount of solvent used depends in particular on the solubility of nitrosobenzene in the solvent used.
- The process according to the present invention may be performed either continuously or batchwise. When using a batchwise procedure, the proton acid is added to the nitrosobenzene, optionally in the presence of a solvent, and the reaction mixture obtained is then hydrogenated with hydrogen in the presence of a hydrogenation catalyst. Continuous process variants may be performed in equipment known to a person skilled in the art for bringing solid, liquid and gas phases into contact. Stirred tanks, forced circulation reactors, bus reactors, bubble columns operated in cocurrent or countercurrent mode or trickle phase reactors or cascades of these reactors are suitable.
- Isolation of the 4-aminodiphenylamine from the acid reaction mixture is performed in such a way that water is added to the reaction mixture, the mixture is neutralized with a base and then optionally extracted with an organic solvent. According to the present invention, a preferred mode of working-up the reaction mixture comprises working up the reaction mixture by distillation after filtering off the hydrogenation catalyst. In this way, the proton acid used and optionally the solvent used can be virtually quantitatively recycled. No effluent is produced in the process according to the present invention, which is of great economic and ecological advantage.
- The 4-ADPA salt of the corresponding proton acids remaining is decomposed thermally at temperatures of about 50 to 200° C and pressures of 1013 to 0.05 bar in order to obtain 4-ADPA.
- In an autoclave, 21.4 g nitrosobenzene and 1 g Pd/C (5 %) are added to 100 ml of anhydrous hydrofluoric acid at 0° C. The reaction mixture is heated to 10° C and then hydrogenated under a 30 bar pressure of hydrogen. After filtering off the hydrogenation catalyst, the catalyst acid (hydrofluoric acid) is distilled off. The 4-ADPA ammonium salt remaining is decomposed thermally at 200° C and 16 mbar, wherein 17 g of 4-ADPA with a fluoride content of <0.1 % are obtained.
- 100 ml of trifluoroacetic acid are used as catalyst acid using the same procedure as in Example 1. The 4-ADPA ammonium salt obtained is thermally decomposed at 100° C. and 1 mbar, wherein 15 g of 4-ADPA are obtained.
- Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Claims (5)
1. A process for preparing 4-aminodiphenylamine (4-ADPA), comprising the step of hydrogenating nitrosobenzene with hydrogen in the presence of a proton acid as catalyst and in the presence of a hydrogenation catalyst, optionally in the presence of an inert organic solvent to form an 4-ADPA ammonium salt which is then thermally decomposed to obtain 4-ADPA.
2. A process according to claim 1 , wherein hydrogenation is performed at temperatures of −20° C to 50° C and pressures of 0.1 to 150 bar.
3. A process according to claim 1 , wherein the thermal decomposition of 4-ADPA ammonium salt is performed at temperatures of 50 to 200° C and pressures of 1013 to 0.05 mbar.
4. A process according to claim 1 , wherein said proton acids are aliphatic and aromatic sulfonic acids, hydrogen fluoride or trifluoroacetic acid.
5. A process according to claim 1 , wherein said organic solvents are aliphatic or aromatic hydrocarbons, linear or cyclic ethers, halogenated aliphatic or aromatic hydrocarbons or their mixtures.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10055221.8 | 2000-11-08 | ||
| DE10055221A DE10055221A1 (en) | 2000-11-08 | 2000-11-08 | Preparation of 4-aminodiphenylamine involves hydrogenating nitrosobenzene with hydrogen in the presence of proton catalyst and hydrogenation catalyst |
| DE10055221 | 2000-11-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| US20020055652A1 true US20020055652A1 (en) | 2002-05-09 |
| US6414192B1 US6414192B1 (en) | 2002-07-02 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/007,014 Expired - Fee Related US6414192B1 (en) | 2000-11-08 | 2001-11-06 | Process for preparing 4-aminodiphenylamine |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6414192B1 (en) |
| EP (1) | EP1205469B1 (en) |
| JP (1) | JP2002179627A (en) |
| KR (1) | KR20020035783A (en) |
| CN (1) | CN1198790C (en) |
| CA (1) | CA2361222A1 (en) |
| DE (2) | DE10055221A1 (en) |
| HK (1) | HK1047429B (en) |
| SK (1) | SK16072001A3 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050065376A1 (en) * | 2003-07-04 | 2005-03-24 | Guangqiang Shi And Nongyue Wang | Process for preparing 4-aminodiphenylamine |
| US20050240058A1 (en) * | 2003-07-04 | 2005-10-27 | Nongyue Wang And Guangqiang Shi | Process for preparing 4-aminodiphenylamine |
| US20110226606A1 (en) * | 2003-07-04 | 2011-09-22 | Jiangsu Sinorgchem Technology Co., Ltd. | Falling film evaporator |
| US8686188B2 (en) | 2003-07-04 | 2014-04-01 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| WO2013132290A3 (en) * | 2012-03-07 | 2015-08-06 | Nocil Limited | Improved process for preparing 4-aminodiphenylamine |
| US9302259B2 (en) | 2010-05-24 | 2016-04-05 | Jiangsu Sinorgchem Technology Co., Ltd. | Solid base catalyst and method for making and using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3799924B2 (en) * | 2000-01-11 | 2006-07-19 | 株式会社日立製作所 | Power circuit breaker and power plant electrical circuit device |
| US7183439B2 (en) * | 2002-12-10 | 2007-02-27 | Flexsys America L.P. | Process for preparing 4-aminodiphenylamine intermediates |
| FR3041958B1 (en) | 2015-10-06 | 2019-06-14 | Arkema France | IMPROVED PROCESS FOR THE PRODUCTION OF POLYMERIC (METH) ACRYLIC ACID |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1147237B (en) | 1961-04-06 | 1963-04-18 | Bayer Ag | Process for the preparation of N-phenyl-N- (4-nitrosophenyl) -hydroxylamine |
| DE2703919C2 (en) | 1977-01-31 | 1979-03-29 | Akzo Gmbh, 5600 Wuppertal | Process for the preparation of p-nitroso-diphenylhydroxylamines |
| 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 |
| US4404401A (en) * | 1979-02-23 | 1983-09-13 | Akzona Incorporated | Process for the preparation of para-amino-diphenylamine |
| DE3501698A1 (en) | 1985-01-19 | 1986-07-24 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING 4-NITRODIPHENYLAMINE |
| DE3504479A1 (en) | 1985-02-09 | 1986-08-14 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING 4-NITRODIPHENYLAMINE |
| US5552531A (en) | 1992-05-22 | 1996-09-03 | Monsanto Company | Process for preparing substituted aromatic azo compounds |
| DE19709124A1 (en) | 1997-03-06 | 1998-09-10 | Bayer Ag | Process for the preparation of 4-aminodiphenylamine |
| TW500712B (en) * | 1997-08-06 | 2002-09-01 | Bayer Ag | Process for the preparation of 4-aminodiphenylamine |
| DE19810929A1 (en) * | 1998-03-13 | 1999-09-16 | Bayer Ag | Process for the preparation of 4-aminodiphenylamine |
-
2000
- 2000-11-08 DE DE10055221A patent/DE10055221A1/en not_active Withdrawn
-
2001
- 2001-10-29 EP EP01125351A patent/EP1205469B1/en not_active Expired - Lifetime
- 2001-10-29 DE DE50108607T patent/DE50108607D1/en not_active Expired - Fee Related
- 2001-11-05 CA CA002361222A patent/CA2361222A1/en not_active Abandoned
- 2001-11-05 JP JP2001339663A patent/JP2002179627A/en not_active Withdrawn
- 2001-11-06 SK SK1607-2001A patent/SK16072001A3/en unknown
- 2001-11-06 US US10/007,014 patent/US6414192B1/en not_active Expired - Fee Related
- 2001-11-07 KR KR1020010069208A patent/KR20020035783A/en not_active Withdrawn
- 2001-11-08 CN CNB011378387A patent/CN1198790C/en not_active Expired - Fee Related
-
2002
- 2002-11-27 HK HK02108563.8A patent/HK1047429B/en not_active IP Right Cessation
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080039657A1 (en) * | 2003-07-04 | 2008-02-14 | Xiaogen Feng | Process for preparing 4-aminodiphenylamine |
| US7989662B2 (en) | 2003-07-04 | 2011-08-02 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| US7084302B2 (en) | 2003-07-04 | 2006-08-01 | Sinorgchem Shandong Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| US20090048465A1 (en) * | 2003-07-04 | 2009-02-19 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| US7176333B2 (en) | 2003-07-04 | 2007-02-13 | Sinorgchem Company, Shandong | Process for preparing 4-aminodiphenylamine |
| US7235694B2 (en) | 2003-07-04 | 2007-06-26 | Sinorgchem Co., Shandong | Process for preparing 4-aminodiphenylamine |
| US20070227675A1 (en) * | 2003-07-04 | 2007-10-04 | Sinorgchem Co. | Process for preparing 4-aminodiphenylamine |
| US20070232832A1 (en) * | 2003-07-04 | 2007-10-04 | Sinorgchem Co. | Process for preparing 4-aminodiphenylamine |
| US20050240058A1 (en) * | 2003-07-04 | 2005-10-27 | Nongyue Wang And Guangqiang Shi | Process for preparing 4-aminodiphenylamine |
| US20050065376A1 (en) * | 2003-07-04 | 2005-03-24 | Guangqiang Shi And Nongyue Wang | Process for preparing 4-aminodiphenylamine |
| US20060247473A1 (en) * | 2003-07-04 | 2006-11-02 | Sinorgchem Co. | Process for preparing 4-aminodiphenylamine |
| US20110226606A1 (en) * | 2003-07-04 | 2011-09-22 | Jiangsu Sinorgchem Technology Co., Ltd. | Falling film evaporator |
| US8293673B2 (en) | 2003-07-04 | 2012-10-23 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| US8486223B2 (en) | 2003-07-04 | 2013-07-16 | Jiangsu Sinorgchem Technology Co., Ltd. | Falling film evaporator |
| US8686188B2 (en) | 2003-07-04 | 2014-04-01 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing 4-aminodiphenylamine |
| US9029603B2 (en) | 2003-07-04 | 2015-05-12 | Jiangsu Sinorgchem Technology Co., Ltd. | Process for preparing alkylated p-phenylenediamines |
| US9302259B2 (en) | 2010-05-24 | 2016-04-05 | Jiangsu Sinorgchem Technology Co., Ltd. | Solid base catalyst and method for making and using the same |
| WO2013132290A3 (en) * | 2012-03-07 | 2015-08-06 | Nocil Limited | Improved process for preparing 4-aminodiphenylamine |
| US9708243B2 (en) | 2012-03-07 | 2017-07-18 | Nocil Limited | Process for preparing 4-aminodiphenylamine |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2361222A1 (en) | 2002-05-08 |
| KR20020035783A (en) | 2002-05-15 |
| DE10055221A1 (en) | 2002-05-29 |
| SK16072001A3 (en) | 2002-05-09 |
| DE50108607D1 (en) | 2006-03-30 |
| JP2002179627A (en) | 2002-06-26 |
| CN1198790C (en) | 2005-04-27 |
| CN1353106A (en) | 2002-06-12 |
| EP1205469A1 (en) | 2002-05-15 |
| US6414192B1 (en) | 2002-07-02 |
| EP1205469B1 (en) | 2006-01-04 |
| HK1047429B (en) | 2005-12-09 |
| HK1047429A1 (en) | 2003-02-21 |
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