CN102675129A - Catalytic synthesis method of diphenylamine compound - Google Patents
Catalytic synthesis method of diphenylamine compound Download PDFInfo
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- CN102675129A CN102675129A CN2011100580658A CN201110058065A CN102675129A CN 102675129 A CN102675129 A CN 102675129A CN 2011100580658 A CN2011100580658 A CN 2011100580658A CN 201110058065 A CN201110058065 A CN 201110058065A CN 102675129 A CN102675129 A CN 102675129A
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Abstract
Disclosed is a catalytic synthesis method of a diphenylamine compound. According to the catalytic synthesis method, through a condensation-dehydrogenation-hydrogenation process in a system, an aniline compound and a phenol compound are directly synthesized into the diphenylamine compound under a high temperature and high pressure condition and in the presence of catalytic amount of cyclohexanone and metal catalyst. The catalytic synthesis method has the advantages of being simple in process, low in cost, high in yield of products, few in side reactions and suitable for industrial production.
Description
Technical field:
The invention belongs to organic chemistry filed, relate to organic Study of synthesis method, a kind of compound method of diphenylamine compound simply and easily is provided.
Background technology:
Diphenylamine compound is basic organic chemical industry's midbody; Can be widely used in the synthetic of fine chemicals such as medicine, agricultural chemicals, dyestuff; 2-methyl-4-anisidine particularly, as the core midbody of the quick coupler of benzofuran type hot pressing, its Study of synthesis method is extensively paid close attention to always.At present, the main compound method of this compounds is following both at home and abroad:
Though these compound method technical maturities are widely used, operational path length, complex process, product yield is low, three waste discharge is high shortcoming are arranged all.
The present invention makes every effort to provide a kind of technology simple, easy to operate, and product yield is high, and quality of finished is good, and " three wastes " discharging is few, is easy to the compound method of the diphenylamine compound of suitability for industrialized production.
Summary of the invention:
The object of the present invention is to provide a kind of new diphenylamine compound compound method, this method is based on following principle:
Through condensation-dehydrogenation-hydrogenation process, realize the direct condensation of amino benzenes compounds and oxybenzene compound.Here, phenol is reaction substrate, also is the hydrogenation substrate of hydrogen that dehydrogenation reaction generates.
Based on above principle, the concrete implementation of this compound method is:
With amino benzenes compounds and phenol compound; In the presence of the cyclohexanone analog compound and hydrogenation catalyst of catalytic amount, in autoclave, be heated to 150-250 ℃ to reacting completely the cooled and filtered catalyzer; Catalyzer washing back is reusable; Through the rectification under vacuum mode, reclaim excessive phenol and catalytic amount pimelinketone, this recovery raw material can directly be reused.Collect the sintetics diphenylamine compound then.
Amino benzenes compounds involved in the present invention can be an aniline, also can be single replacement or polysubstituted alkyl, alkoxyl group, like 2-Tolylamine, 4-Tolylamine, 2, and 4-xylidine, 2-methyl-4-anisidine etc.
Phenol compound involved in the present invention is generally phenol, and substituted alkyl, alkoxyl group, halogenated phenol are like Ortho Cresol, p-cresol etc.
Because phenol is in the compound method that the present invention designed; Both having played solvent action, also is the building-up reactions raw material, is again the hydrogenated raw material of hydrogen that dehydrogenation generates simultaneously; Thereby the phenol compound consumption normally the amino benzenes compounds molar ratio 2-10 doubly, be preferably in 3-5 doubly.Pimelinketone promptly is synthesis material in this compound method, also is hydrogenation products, and its consumption and amino benzenes compounds molar ratio are 1: 0.05-0.5 is preferably in 1: 0.1-0.3.
Cyclohexanone analog compound involved in the present invention is suitable for the corresponding compound of phenol compound substituting group usually.
In the compound method provided by the present invention, hydrogenation catalyst used therein can be a metal catalyst, like skeleton Ni; Co also can be a noble metal catalyst, like palladium, platinum, rhodium etc.; Support of the catalyst can be activated carbon, lime carbonate, aluminum oxide etc.; Bullion content is preferably between the 3.0-10.0% between 1.0-10.0%, and catalyst levels is the 0.1-5% of amino benzenes compounds.
In the compound method of the present invention, condensation reaction is carried out under hot conditions usually, and temperature of reaction is preferably between 170 ℃-230 ℃ at 150 ℃-250 ℃.
In the compound method provided by the present invention, condensation product has water to generate.Water vapour produces 5-20kg/cm usually under hot conditions
2Pressure.
In the compound method provided by the present invention, after reaction is accomplished, after the cooling, again catalyst filtration, washing back are reused.
In the compound method provided by the present invention, reaction mass is directly retrieved the reaction of phenol compounds through rectification under vacuum, catalytic amount cyclohexanone analog compound, and this regenerant can directly recycle.
In the compound method provided by the present invention, reaction product directly is collected as finished product through rectifying.
Compound method provided by the present invention, with amino benzenes compounds and phenol compound direct syntehsizing diphenylamine compounds in the presence of catalyzer, this method technology is simple; Easy to operate, product yield is high, and purity is good; Almost do not have " three wastes " and generate, be very beneficial for suitability for industrialized production.
Embodiment:
Following instance is done further proof to invention, but the present invention is not limited only to following instance:
Embodiment 1:
With 93g (1.0mol) aniline, 470g (5.0mol) phenol, 9.8g (0.1mol) pimelinketone, 10g5% palladium carbon (moisture 60%) places the 1000ml autoclave; Behind the nitrogen replacement, slowly be warming up to 190 ℃ of reactions 5 hours, be chilled to 60 ℃; Usefulness again behind the filtering catalyst, catalyzer washing, the filtrate decompression distillation; Recovery there is not reaction of phenol, pimelinketone, collects pentanoic 159.7g at last, yield 94.5%.
Embodiment 2:
With 107g (1.0mol) Ortho Toluidine, 470g (5.0mol) phenol, 9.8g (0.1mol) pimelinketone; 10g5% palladium carbon (moisture 60%) places the 1000ml autoclave, behind the nitrogen replacement, slowly is warming up to 200 ℃ of reactions 5 hours; Be chilled to 60 ℃, filtering catalyst is used after the catalyzer washing again.The filtrate decompression distillation is reclaimed does not have reaction of phenol, pimelinketone, collects 2-methyldiphenylamine 175.9g at last, yield 96.1%.
Embodiment 3:
With 137g (1.0mol) 2-methyl-4-anisidine, 470g (5.0mol) phenol, 9.8g (0.1mol) pimelinketone; 10g 5% palladium carbon (moisture 60%) places the 1000ml autoclave; Behind the nitrogen replacement, slowly be warming up to 200 ℃-210 ℃ reactions 6 hours, be chilled to 60 ℃; Filtering catalyst is used after the catalyzer washing again.Phenol, the pimelinketone that there is not reaction reclaimed in the filtrate decompression distillation, collects 2-methyl-4-methoxy diphenylamine 198.7g at last, yield 93.3%.
Embodiment 4:
With embodiment 3, change 10g 5% palladium-carbon catalyst into 10g 5% platinum C catalyst (moisture 55%), get 2-methyl-4-methoxy diphenylamine 195.1g, yield 91.6%.
Claims (5)
1. the compound method of diphenylamine compound; It is characterized in that with amino benzenes compounds, phenol compound the cyclohexanone analog compound of catalytic amount is in the presence of hydrogenation catalyst; Pyrocondensation-dehydrogenation-hydrogenation; Generate the object diphenylamine compound at last, behind separating catalyst, product obtains through rectification under vacuum.
2. compound method according to claim 1 is characterized in that amino benzenes compounds is an aniline, and single the replacement or polysubstituted aniline, substituting group is alkyl, alkoxyl group.Phenol compound is a phenol, and single the replacement or polysubstituted phenol, substituting group is alkyl, alkoxyl group.The cyclohexanone analog compound is that corresponding nothing with phenol compound replaces, list replaces, polysubstituted cyclohexanone analog compound.Substituting group is alkyl, alkoxyl group.
3. compound method according to claim 1 is characterized in that aniline, phenol, cyclohexanone analog compound mol ratio are 1: 2-10: 0.05-0.5.
4. compound method according to claim 1 is characterized in that used hydrogenation catalyst is a metal catalyst, like skeleton Ni, and the Co catalyzer, noble metal catalyst, like palladium, platinum, rhodium etc., its precious metal carrier can be activated carbon, lime carbonate, aluminum oxide etc.
5. compound method according to claim 1 is characterized in that setting-up point at 150 ℃-250 ℃, and condensation reaction pressure is 5-20kg/cm
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2011100580658A CN102675129A (en) | 2011-03-11 | 2011-03-11 | Catalytic synthesis method of diphenylamine compound |
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| CN2011100580658A CN102675129A (en) | 2011-03-11 | 2011-03-11 | Catalytic synthesis method of diphenylamine compound |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817458A (en) * | 2015-03-30 | 2015-08-05 | 上海瑞年精细化工有限公司 | Method for synthesizing diphenylamine compound |
| CN109304176A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of synthetic method of cyclohexanol kind compound |
| WO2024040766A1 (en) * | 2022-08-22 | 2024-02-29 | 圣奥化学科技有限公司 | Preparation method for diaryl-p-phenylenediamine compound |
-
2011
- 2011-03-11 CN CN2011100580658A patent/CN102675129A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104817458A (en) * | 2015-03-30 | 2015-08-05 | 上海瑞年精细化工有限公司 | Method for synthesizing diphenylamine compound |
| CN109304176A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of synthetic method of cyclohexanol kind compound |
| CN109304176B (en) * | 2017-07-28 | 2021-06-11 | 中国石油化工股份有限公司 | Synthesis method of cyclohexanol compound |
| WO2024040766A1 (en) * | 2022-08-22 | 2024-02-29 | 圣奥化学科技有限公司 | Preparation method for diaryl-p-phenylenediamine compound |
| US12037303B2 (en) | 2022-08-22 | 2024-07-16 | Sennics Co., Ltd. | Method for preparing diaryl p-phenylenediamine compounds |
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Application publication date: 20120919 |