CN1069306C - Preparation process of aminodiphenylamine - Google Patents
Preparation process of aminodiphenylamine Download PDFInfo
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- CN1069306C CN1069306C CN94113079A CN94113079A CN1069306C CN 1069306 C CN1069306 C CN 1069306C CN 94113079 A CN94113079 A CN 94113079A CN 94113079 A CN94113079 A CN 94113079A CN 1069306 C CN1069306 C CN 1069306C
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- mole
- hydrogen
- pimelinketone
- aminodiphenylamine
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- 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
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
Disclosed are a method for preparing an aromatic secondary amino compound which comprises reacting an phenylenediamines in the presence of a hydrogen moving catalyst and a nitroaniline hydrogen acceptor by the use of a sulfur-free polar solvent with cyclohexanone.
Description
The present invention relates to a kind of improved aminodiphenylamine preparation method.
The aminodiphenylamine that obtains according to the present invention is a kind of very important technical chemistry goods as raw materials such as rubber chemistry goods, dyestuffs.
The preparation method of known 4-aminodiphenylamine comprises that (P.B.Reports 77764 with obtain the rearrangement of N nitrosodiphenyl amine and reduction by nitrosification P-phenylenediamine, 27-32) and the condensation of formylaniline or Acetanilide and halogen oil of mirbane, then reduce this nitro [Journal of Organic Chemistry, 42 (10), 1786-90]. the preparation method of known 2-aminodiphenylamine comprises the rearrangement of azo-compound [Journalof organic Chemistry, 295 (1), 91-7,1985].In addition, the preparation method of known 3-aminodiphenylamine comprises reduction 3-nitrodiphenylamine.But they are difficult to be considered to be in industrial advantageous method, because they need complicated reactions steps, and a large amount of special agents and/or solvent, and/or accurate purification step.
Be known that by when having hydrogen-transfer catalyst and hydrogen acceptor to exist, making pimelinketone and phenylenediamine prepared in reaction aminodiphenylamine as the present invention.According to this method,, use alpha-methyl styrene to make pimelinketone and phenylenediamine reaction obtain aminodiphenylamine (Japanese patent application publication No. 58648/1982) simultaneously as hydrogen acceptor by in the presence of palladium catalyst.But, with in this method except that its as the hydrogen acceptor, can not be used for this reaction effectively with hydrogen acceptor contrast alpha-methyl styrene among the present invention, and in this reactive system that must be all infeeds with the form of phenylenediamine as the phenylenediamine of raw material.This reaction must be carried out under high temperature and pressure.So this method is difficult to be considered to gratifying commercial run.
In order to develop than ordinary method in industrial more favourable preparation method, the inventor studies.Found that, according at phenylenediamine (below be abbreviated as " PD ") and pimelinketone, in the polar solvent of no sulphur, reaction when having hydrogen-transfer catalyst to exist, use N-methyl-p-nitroaniline (below be abbreviated as " NA ") as hydrogen acceptor, just might obtain aminodiphenylamine (below be abbreviated as " ADPA ") with very high productive rate with utmost point demulcent condition, so with the formed PD of the NA in this reactive system as raw material, thereby derive the present invention.
An object of the present invention is to provide a kind of method of preparation aminodiphenylamine, it is included in the no sulphur polar solvent when hydrogen-transfer catalyst exists, and uses N-methyl-p-nitroaniline as hydrogen acceptor phenylenediamine and pimelinketone to be reacted simultaneously.
According to the inventive method, under extremely gentle condition, obtain ADPA with high yield.And then, can be used as the raw material in this reactive system by the PD that NA forms, any remainder of PD can be reused with this catalyzer simultaneously.
Importantly use no sulphur polar solvent in the inventive method.The example that available does not have the sulphur polar solvent comprises N, dinethylformamide, N,N-dimethylacetamide; Tetramethyl-urea; Methyl iso-butyl ketone (MIBK).Tetrahydrofuran (THF), diox and 1, the 3-dimethyl-imidazolinone; Glyme is as glycol dimethyl ether, diethylene glycol dimethyl ether and triethylene glycol dme; And phenols, as wintergreen oil, phenol, alkylphenol, as sylvan and mesitylene alcohol and alkoxyl group phenol, as 3-methoxyl group phenol and 4-methoxyl group phenol.These solvents can separately or be used in combination.
By the way, the polar solvent of sulfur-bearing presents toxication to hydrogen-transfer catalyst as dimethyl sulfoxide (DMSO) and tetramethylene sulfone, therefore need not suit.
Can use any known hydrogen-transfer catalyst in the methods of the invention.Special example comprises the nickel carried catalyst, as by having those catalyzer that Raney nickel forms, and reduced nickel or be combined in nickel on the various carriers, described carrier is as diatomite, aluminum oxide, float stone, silica gel and acid clay; Cobalt catalyst is as Raney cobalt, reduction cobalt, cobalt and cobalt/carried catalyst; Palladium catalyst is as palladium black, palladous oxide, pallamine, palladium/carbon, palladium/barium sulfate and palladium/barium carbonate; Platinum catalyst is as platinum black, colloidal state platinum, platinum plating sponge, platinum oxide, platinum sulfide and platinum/carbon; Rhodium catalyst is as colloidal state rhodium, rhodium/carbon and rhodium oxide; Platinum group catalyst is as ruthenium catalyst; The rhenium catalytic materials is as rhenium heptoxide and rhenium/carbon; The cupric chromate catalyzer; Molybdenum oxide catalyst, vanadium oxide catalyst; And tungsten oxide catalyst.In these catalyzer, preferentially use palladium catalyst.Particularly use palladium/carried catalyst, especially preferred palladium/carbon or palladium/aluminum oxide.These hydrogen-transfer catalysts are generally pressed with every mol pimelinketone 0.001-1.0 grammeatom, and preferably the ratio of 0.002-0.2 grammeatom atoms metal is used.
The method according to this invention by the condensation of PD and pimelinketone, then forms ADPA by dehydrogenation and forms Schiff's base.During operation, NA is used as the acceptor of the hydrogen that obtains.In this way, in this reactive system, NA is transformed into PD and passes through this PD and other raw material, i.e. pimelinketone reaction further forms ADPA.
At this moment, 0.67 mole of NA is convertible into every mole of Schiff's base PD.Therefore for the hydrogen that utilizes the appearance in the reactive system in full force and effect, be enough if the mol ratio of NA pimelinketone is set at 0.67.The NA abundance of this grade has the trend of the speed of response of reduction, is disadvantageous therefore.On the other hand, the mol ratio of any excessive little PD/ pimelinketone then tends to cause the further reaction of established ADPA and pimelinketone in reactive system, the result makes N, and N '-diphenyl-phenylene-diamine (below be abbreviated as " N, N '-DPPA ") produces as paying product.Avoid these shortcomings, preferably add 0.67 mole of NA and at least 0.33 mole of PD with every mole of pimelinketone, make their reactions then from the reaction beginning.More preferably remain on 1.4 moles or more with every mole of pimelinketone with ading up to, particularly 1.7 moles or more NA and PD carry out this reaction.
In the method for the invention, all raw materials can be in reacting the reaction vessel of packing into together at once when beginning.Simultaneously pimelinketone and NA are added dropwise to this hydrogen-transfer catalyst but importantly carry out this reaction, in the mixed solution of PD and no sulphur polar solvent.Much less, they can mix earlier, drip then.This may make, and PD/ pimelinketone mol ratio remains on the higher level always in the reactive system, can obtain the target product of high yield thus.
Also can be when carrying out this reaction water be distillated itself and solvent (as benzene, toluene or dimethylbenzene) by azeotropic with this reaction mixture and separate.
The general selectable range of temperature of reaction is 140-250 ℃, and preferably scope is 160-200 ℃.
The ADPA of Xing Chenging can obtain with being essentially mode reaction mixture well known in the prior art after reaction is finished like this, and these modes for example are distillation, crystallization or extraction.For example after-filtration reaction mixture, separating liquiding catalyst are thus finished in reaction.The catalyzer of Hui Shouing can be reused like this.Concentrated filtrate is to reclaim solvent.The ADPA that remains in reaction vessel can use, and promptly in some cases as the raw material of next reaction, if desired, then passes through distillation, crystallization etc. with its purification.
Talk method of the present invention particularly below by following embodiment.
Embodiment 1
At pack in the round-bottomed flask of taking back the separator of flow condenser, a thermometer and the agitator 5%pd/c (water-content 50% (weight) of 3.03g of being equipped with of 200ml, the product of N.E.Chemcat Corp.), the N,N-dimethylacetamide of 64.0g, 7.21g (0.07 mole) Ursol D (below be abbreviated as " PPD "), 19.63g (0.20 mole) pimelinketone (below be abbreviated as " CH ") and 18.42g (0.13 mole) p-Nitroaniline (below be abbreviated as " PNA ").When keeping internal temperature to be 158-162 ℃, this content of continuously stirring 5 hours.Add benzene in the meantime, thereby the water component distillation that will obtain like this falls.Make water-benzol mixture condensation in reflux exchanger of this component distillation, separate by separator then.Then with this reaction mixture cool to room temperature, and from then on filter 5%pd/c in the reaction mixture.Use gc analysis filtrate, obtain column data down thus:
The turnover ratio of CH: 99.95 (mole %CH)
The productive rate of P-ADPA: 49.87 (mole %CH)
By product N, N '-P-DPPA:36.50 (mole %CH)
The rate of recovery of dehydrogenation product not: 3.26 (mole %CH)
Embodiment 2-4
In each embodiment, reaction is carried out in the mode similar to embodiment 1, but the consumption of the PPD in embodiment 1 is shown in the amount of table 1 instead.The results are shown in table 1.Comparative example 1
Reaction is carried out in the mode similar to embodiment 1, but replaces N,N-dimethylacetamide among the embodiment with p-cymene.The results are shown in table 1.
Table 1
(PPD/PNA) the commentaries on classics P-ADPA by product of CH not dehydrogenation produce
(mole changes rate (the productive rate N that rubs, the rate of recovery of N '-P thing to/CH
Than) that %) (mole %)-DPPA (mole %) embodiment 2 1.4 100 72.57 14.21 5.14 embodiment 3 1.7 100 75.18 10.67 5.53 embodiment 4 2.0 99.93 79.51 7.13 5.06 comparative examples 1 1.0 100 28.70 1.27 45.98
Embodiment 5
At the separator of taking back flow condenser that is equipped with of 200ml, a thermometer, the pd/c of the 3.03g 5% that packs in the round-bottomed flask of a dropper and an agitator (water-content: 50% (weight); N.E.Chemcat Corp. product), 40.0gN, N-N,N-DIMETHYLACETAMIDE and 7.21g (0.07 mole) PPD.The mixing solutions that preparation is made up of the PNA of the CH of 19.63g (0.20 mole) and 18.42g (0.13 mole) is in this Dropping feeder of packing into then.The internal temperature of flask under agitation is elevated to 160 ℃, and keeps this internal temperature to be 158-162 ℃, the solution in the dropping Dropping feeder 6 hours.After being added dropwise to complete,, keep internal temperature simultaneously in the said temperature scope with the contents stirred of flask 1 hour.During this, add benzene, so that the water component distillation that obtains is fallen.With water-benzol mixture condensation in this reflux exchanger of this component distillation, separate by this separator then.Then with this reaction mixture cool to room temperature, and from then on filter 5% pd/c in the reaction mixture.With this filtrate of gc analysis, obtain column data down thus:
The turnover ratio of CH: 99.51 (mole %CH)
The productive rate of P-ADPA: 54.00 (mole %CH)
By product N, N '-P-DPPA:35.65 (mole %CH)
The rate of recovery 9.72 of dehydrogenation product (mole %CH) not
Embodiment 6-7 and comparative example 2
In each example, react in the mode similar to embodiment 5, be used to replace N,N-dimethylacetamide among the embodiment 5 but be shown in the corresponding polar solvent (embodiment 6 and 7) of table 2 or non-polar solvent (comparative example 2).The results are shown in table 2.
Table 2
The commentaries on classics P-ADPA by product of solvent C H not dehydrogenation produces
Change rate (the productive rate N that rubs, the rate of recovery of N '-P thing
You are %) (mole %)-DPPA (mole %) embodiment 61,3-dimethyl 100 56.56 29.13 9.49
Imidazolone embodiment 7 glycol ether diformazans 100 57.51 32.75 4.37
Base ether comparative example 2 p-isopropyls 100 32.13 1.36 48.98
Phenylmethane embodiment 8-12
In each embodiment, reaction is carried out in the mode similar to embodiment 5, but the add-on of PPD is made into (the PPD+PNA/CH ratio set with analog value shown in the table 3 among the embodiment 5.The results are shown in table 3.
Table 3
(PPD/PNA) the commentaries on classics P-ADPA by product of CH not dehydrogenation produce
(mole changes rate (the productive rate N that rubs, the rate of recovery of N '-P thing to/CH
Than) that %) (% by mole)-DPPA (% by mole) embodiment 8 1.187 100 75.12 22.90 2.91 embodiment 9 1.437 100 81.05 15.16 2.19 embodiment 10 1.687 100 86.87 0.67 1.71 embodiment 11 1.987 100 89.64 9.12 1.24 embodiment 12 6.950 100 92.99 1.66 5.65
Embodiment 13-15
In each embodiment, reaction is carried out in the mode similar to embodiment 5, but PPD among the embodiment 5 and PNA use mphenylenediamine (below be abbreviated as " MPD ") and m-nitraniline (below be abbreviated as " MNA ") to replace respectively, set (MPD+MNA/CH ratio with the analog value shown in the table 4.
The results are shown in table 4.
Table 4
(MPD/MNA) the commentaries on classics m-ADPA by product of CH not dehydrogenation produce
(mole changes rate (the productive rate N that rubs, the rate of recovery of N '-P thing to/CH
Than) that %) (mole %)-DPPA (mole %) embodiment 13 1.000 99.9 53.4 43.2 0.9 embodiment 14 1.417 99.9 75.0 18.5 1.3 embodiment 15 1.917 100 81.8 12.4 0.7
Embodiment 16
At the separator of taking back flow condenser that is equipped with of 200ml, a thermometer, the pd/c (water-content: 50% (weight) of adding 3.03g 5% in the round-bottomed flask of a Dropping feeder and an agitator; N.E.Chemcat Corp. product), 40.0g triglyme and 27.04g (0.25 mole) O-Phenylene Diamine.The mixing solutions that preparation is made up of the o-Nitraniline of the CH of 19.63g (0.20 mole) and 18.42g (0.13 mole), and in this Dropping feeder of packing into.Under agitation the internal temperature with flask is elevated to 170 ℃, and keeps this internal temperature at 170-173 ℃, and the solution in this Dropping feeder was dripped 15 hours.After being added dropwise to complete,, keep its internal temperature simultaneously among the said temperature scope with the contents stirred of flask 2 hours.In the meantime, add benzene, the water component distillation that obtains is fallen.Make water-benzol mixture condensation in reflux exchanger of component distillation, separate with separator then.With this reaction mixture cool to room temperature, from then on filter 5% pd/c in the reaction mixture then.With this filtrate of gc analysis, obtain down column data thus:
The turnover ratio of CH: 100 (mole %CH)
The productive rate of O-ADPA: 63.8 (mole %CH)
The not recovery of non-dehydrogenation product: 35.8 (mole %CH)
Claims (4)
1. method for preparing right-aminodiphenylamine, it be included in hydrogen-transfer catalyst exist down, in no sulphur polar solvent, use p-Nitraniline as hydrogen acceptor simultaneously, p-phenylenediamine and pimelinketone are reacted.
One kind prepare between-method of aminodiphenylamine, it be included in hydrogen-transfer catalyst exist down, in no sulphur polar solvent, use meta-nitroaniline as hydrogen acceptor simultaneously, between making-phenylenediamine and pimelinketone react.
3. method for preparing neighbour-aminodiphenylamine, it be included in hydrogen-transfer catalyst exist down, in no sulphur polar solvent, use o-nitroaniline as hydrogen acceptor simultaneously, ortho-phenylene diamine and pimelinketone are reacted.
4. according to any one method among the claim 1-3, when wherein reacting N-methyl-p-nitroaniline and pimelinketone are added drop-wise to this hydrogen-transfer catalyst, phenylenediamine and do not have in the mixed liquid of sulphur polar solvent.
Applications Claiming Priority (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP303707/1993 | 1993-12-03 | ||
| JP303707/93 | 1993-12-03 | ||
| JP30370793 | 1993-12-03 | ||
| JP307638/93 | 1993-12-08 | ||
| JP30763893 | 1993-12-08 | ||
| JP307638/1993 | 1993-12-08 | ||
| JP06071734A JP3137828B2 (en) | 1993-12-03 | 1994-04-11 | Method for producing aminodiphenylamine |
| JP071734/1994 | 1994-04-11 | ||
| JP071734/94 | 1994-04-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1109464A CN1109464A (en) | 1995-10-04 |
| CN1069306C true CN1069306C (en) | 2001-08-08 |
Family
ID=27300745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94113079A Expired - Fee Related CN1069306C (en) | 1993-12-03 | 1994-12-03 | Preparation process of aminodiphenylamine |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3137828B2 (en) |
| KR (1) | KR0138789B1 (en) |
| CN (1) | CN1069306C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20110041279A (en) * | 2009-10-15 | 2011-04-21 | 금호석유화학 주식회사 | Manufacturing method of 4,4'-bis(alkylamino)diphenylamine |
| CN102259029B (en) * | 2010-05-24 | 2014-12-10 | 江苏圣奥化学科技有限公司 | Solid alkali catalyst |
| CN106608827A (en) | 2015-10-21 | 2017-05-03 | 江苏圣奥化学科技有限公司 | Preparation method for aryl substituted p-phenylenediamine substance |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0535484A2 (en) * | 1991-10-04 | 1993-04-07 | Bayer Ag | Process for the preparation of diphenylamines |
-
1994
- 1994-04-11 JP JP06071734A patent/JP3137828B2/en not_active Expired - Fee Related
- 1994-12-02 KR KR1019940032581A patent/KR0138789B1/en not_active IP Right Cessation
- 1994-12-03 CN CN94113079A patent/CN1069306C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0535484A2 (en) * | 1991-10-04 | 1993-04-07 | Bayer Ag | Process for the preparation of diphenylamines |
Also Published As
| Publication number | Publication date |
|---|---|
| KR950017916A (en) | 1995-07-20 |
| JP3137828B2 (en) | 2001-02-26 |
| JPH07215920A (en) | 1995-08-15 |
| CN1109464A (en) | 1995-10-04 |
| KR0138789B1 (en) | 1998-05-01 |
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