JPH07278065A - Production of 3-aminodiphenylamine - Google Patents

Abstract

PURPOSE:To easily produce 3-aminodiphenylamine in high yield and raw material efficiency by using m-dinitrobenzene as a hydrogen acceptor and reacting m-phenylenediamine with cyclohexanone in the presence of a hydrogen-transfer catalyst. CONSTITUTION:This process for the production of 3-aminodiphenylamine in high raw material efficiency comprises the reaction of (A) m-phenylenediamine with (B) cyclohexanone in the presence of (C) a hydrogen-transfer catalyst such as palladium/carrier catalyst in (D) a sulfur-free polar solvent such as DMF using (E) m-dinitrobenzene as a hydrogen acceptor, thereby converting the component E into the reaction raw material component A in the reaction system.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to an improved process for preparing 3-aminodiphenylamine. The 3-aminodiphenylamine obtained by the method of the present invention is useful as an intermediate raw material for dyes and the like.

[0002]

2. Description of the Related Art As a method for producing 3-aminodiphenylamine, a method of reducing 3-nitrodiphenylamine is known. Similar to the present invention, a method for producing aminodiphenylamine by reacting cyclohexanone and phenylenediamine in the presence of a hydrogen transfer catalyst and a hydrogen acceptor is already known. In this case, as a hydrogen acceptor, α-
There is a description that cyclohexanone and phenylenediamine can be reacted with methylstyrene using a palladium catalyst to obtain aminodiphenylamine (JP-A-57-58648).

However, in this method, α-methylstyrene, which is a hydrogen acceptor, cannot be effectively used in the reaction other than being used as a hydrogen acceptor, and the raw materials are all in the form of phenylenediamine in the system. It is difficult to say that it is a satisfactory method as an industrial production method because it must be supplied to the above and it is a reaction under high temperature and pressure.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted studies to establish a manufacturing method which is more industrially advantageous than the prior art. As a result, in the reaction of m-phenylenediamine (hereinafter abbreviated as m-MPD) with cyclohexanone in the presence of a hydrogen transfer catalyst in a non-sulfur-containing polar solvent, m-dinitrobenzene (hereinafter, By using m-DNB), 3-aminodiphenylamine (hereinafter referred to as ADP) under extremely mild conditions and in good yield.
It was found that m-MPD produced from m-DNB can be used as a raw material in the system, and the present invention has been reached.

That is, according to the present invention, in the presence of a hydrogen transfer catalyst, m
A method for producing 3-ADPA, which comprises using m-DNB as a hydrogen acceptor when -MPD and cyclohexanone are reacted in a non-sulfur-containing polar solvent.

In the method of the present invention, it is important to use a non-sulfur-containing polar solvent, for example, N, N-dimethylformamide, N, N-dimethylacetamide, tetramethylurea, methylisobutylketone, tetrahydrofuran, dioxane. , 1,3-dimethylimidazolidinone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. glymes, methyl salicylate, phenol, methylphenol, 2,4,6-
Examples include alkylphenols such as trimethylphenol, phenols such as alkoxyphenol such as 3-methoxyphenol and 4-methoxyphenol. These solvents may be used alone or in combination of two.

Sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane are not preferable because they have a poisoning effect on the hydrogen transfer catalyst.

Any known hydrogen transfer catalyst may be used in the method of the present invention. Specifically, Raney nickel, reduced nickel, nickel-containing diatomaceous earth, alumina, pumice, silica gel, acid clay and the like can be used. Nickel carrier catalysts supported on various carriers; Raney cobalt,
Cobalt catalysts such as reduced cobalt, cobalt, cobalt / support catalysts; copper catalysts such as Raney copper, reduced copper, copper / support catalysts; palladium black, palladium oxide, colloidal palladium, palladium / carbon, palladium / barium sulfate,
Palladium catalysts such as palladium and barium carbonate; platinum catalysts such as platinum black, colloidal platinum, platinum sponge, platinum oxide, platinum sulfide, platinum and carrier catalysts such as platinum and carbon; colloidal rhodium, rhodium and carbon, rhodium such as rhodium oxide. Examples include catalysts; platinum group catalysts such as ruthenium catalysts; rhenium catalysts such as dirhenium heptaoxide and rhenium-carbon; copper chromium oxide catalysts; molybdenum oxide catalysts; vanadium oxide catalysts; tungsten oxide catalysts. Among these catalysts, it is preferable to use a palladium catalyst, particularly preferably a palladium-supported catalyst, and particularly preferably palladium-carbon or palladium-alumina. The amount of these hydrogen transfer catalysts to be used is usually 0.001 to 1.0 gram atom, preferably 0.002 to 0.2 gram atom, as a metal atom, based on cyclohexanone.

In the method of the present invention, ADPA is produced by dehydrogenation reaction after forming a Schiff base by condensation of m-MPD and cyclohexanone. In the present invention, m-DNB is used as an acceptor of hydrogen generated in that case. By doing so, m-DNB becomes m- in the same reaction system.
It is converted to MPD, and the m-MPD is reacted with cyclohexanone, which is the other raw material, to further produce ADP.
A produces.

In the method of the present invention, 0.33 mol of m-DNB can be converted to m-MPD per mol of Schiff base. Therefore, in order to make effective use of the hydrogen generated in the system, it is sufficient to react at a molar ratio of m-DNB / cyclohexanone of 0.33. m-DNB
If the molar ratio of the above to cyclohexanone is more than 0.33, the reaction rate tends to decrease, which is not a good idea. Also m
If the MPD / cyclohexanone molar ratio is too low,
ADPA produced in the system and cyclohexanone further react, and N, N′-diphenyl-m-phenylenediamine (hereinafter, abbreviated as N, N′-DPPA) tends to be by-produced. In order to avoid these drawbacks, from the beginning of the reaction, 0.33 mol of m-DNB per 1 mol of cyclohexanone,
And it is preferable to add 0.67 mol or more of m-MPD for reaction. More preferably, m-DNB and mm
Total with PD is 1.4 per 1 mol of cyclohexanone
It is preferable to react in a molar amount of at least 1.7 mol.

The reaction can be carried out by a batch charging method, a dropping method or the like. For example, in the dropping method, a Schiff base is previously formed from metaphenylenediamine and cyclohexanone, and the Schiff base and metadinitrobenzene are simultaneously or mixed and then added dropwise.

In the method of the present invention, in order to remove water generated in the reaction, a method of separating from the reaction mixture while azeotropically dehydrating with a solvent such as benzene, toluene and xylene can be used. The temperature during the reaction is usually 140-
It is selected in the range of 250 ° C, preferably 160 to 200 ° C.

The produced ADPA can be obtained by treating the mixture after the reaction according to a conventional method such as distillation, crystallization and extraction. For example, the reaction completed liquid is filtered to separate the catalyst. This recovered catalyst can be reused. The filtrate is concentrated and the solvent is recovered. In some cases, ADPA in the kettle can be used as it is as the next reaction raw material, but if necessary, it is purified by distillation, crystallization or the like.

[0014]

EXAMPLES The method of the present invention will be described in detail below with reference to examples. Example 1 In a 200 ml round bottom flask equipped with a reflux condenser equipped with a separator, a thermometer, and a stirring device, 21.6 g of m-MPD,
Cyclohexanone 19.6g Diethylene glycol 40
g, and stirred for 4 hours at 155 ° C. and m-DN
B11.2 g was charged into a dropping funnel, and 200 m equipped with a reflux condenser equipped with a separator, a thermometer, and a stirring device.
In a round-bottomed 1-liter flask, 5 manufactured by NE Chemcat
A mixture of 033% 5% Pd / C (4.33 g) and diethylene glycol (25.0 g) was added dropwise at 155 ° C. over 8 hours, and then aged for 2 hours. The water produced during this time was azeotropically charged with toluene, condensed with a reflux condenser, and then separated with a separator. Then, the reaction solution was cooled to room temperature, and 5% Pd / C was filtered off from the reaction mixture solution.
When the filtrate was analyzed by gas chromatography, the conversion of cyclohexanone was 99.5 (mol% /
The yield of cyclohexanone) and ADPA is 61.2 (mo
1% / cyclohexanone), N, N′-diphenylphenylenediamine yield 28.0 (mol% / cyclohexanone), undehydrogenated product yield 10.3 (mol% /
Cyclohexanone).

Example 2 Example 1 except that the amount of m-MPD used was 43.3 g.
The same operation was performed. As a result of analysis, the conversion of cyclohexanone was 99.6 (mol% / cyclohexanone), the yield of ADPA was 74.2 (mol% / cyclohexanone), and the yield of N, N′-diphenylphenylenediamine was 14. 8 (mol% / cyclohexanone), the yield of undehydrogenated product was 10.6 (mol% / cyclohexanone).

Examples 3 to 5 and Comparative Example 1 The same operation as in Example 2 was performed except that the solvent was changed. The results are shown in Table 1.

[0017]

[Table 1]

[0018]

Industrial Applicability The method of the present invention is an industrially inexpensive m-DN.
By using B as a hydrogen acceptor, it becomes an industrially advantageous production method.

Claims (1)

[Claims] 1. When m-phenylenediamine and cyclohexanone are reacted in the presence of a hydrogen transfer catalyst in a non-sulfur-containing polar solvent, m-dinitrobenzene is used as a hydrogen acceptor. A method for producing aminodiphenylamine.