JPH0748325A - Production of aromatic sec-amino compound - Google Patents

Abstract

PURPOSE:To produce an aromatic sec-amino compound important as a raw material for rubber chemical, dye, etc., under a mild condition in high yield. CONSTITUTION:An N-cyclohexylideneamino compound of formula I (R is H, alkyl, alkoxy, NH2, OF or F; n is 0-5; R' is alkyl, phenyl, benzyl, naphthyl, furyl, furfuryl or cyclohexyl) is dehydrogenated in the presence of a hydrogen transfer catalyst (preferably palladium-carrier catalyst) and a hydrogen acceptor, preferably an olefin or a nitro compound by using a polar solvent not containing sulfur such as N,N-dimethylacetamide or p-cresol and/or a co-catalyst such as an alkali (alkaline earth) metal to give an aromatic sec-amino compound of formula II. Or, cyclohexanone or a cyclohexanone nucleus substituted compound of formula III is reacted with an amine of the formula R'-NH2 and a nitro compound of the formula R'-NO2 as a hydrogen acceptor corresponding to the amine in the polar solvent not containing sulfur to give a compound of formula II.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to an improved process for making aromatic secondary amino compounds. The aromatic secondary amino compound obtained by the method of the present invention is a very important industrial chemical as a raw material for rubber drugs and dyes.

[0002]

As a method for producing an aromatic secondary amino compound, a suitable self-condensation reaction catalyst (BF ₃ , FeCl ₂ ,
Ammonium halide salt, mineral acid) in the presence of 300 ~
A method of reacting toluidine in a liquid phase at 400 ° C.,
330-340 in the presence of triphenyl phosphite
A method of reacting cresol and toluidine at a temperature of 50 ° C. and under pressure is already known.

A method for producing an aromatic secondary amino compound by dehydrogenation of an N-cyclohexylidene amino compound has already been known. For example, a method for obtaining N-cyclohexylidene-N′-isopropyl-phenylenediamine in the presence of a dehydrogenation catalyst at a temperature of 350 ° C. or lower (UK Patent No. 989257), 300 in the presence of an oxidation catalyst such as silica or alumina. Dehydrogenation catalyst selected from the group consisting of nickel, platinum, palladium and copper-chromium alloys, a method of reacting in the gas phase while supplying oxygen or an oxygen-containing gas at ˜450 ° C. (JP-A-49-49924) To obtain 4-methyldiphenylamine by reacting at 300 to 500 ° C. in the presence of a solvent (JP-A-49-49925).
No.), a method of producing using a special nickel / chromium catalyst (Japanese Patent Publication No. 57-4623).

In the presence of a hydrogen transfer catalyst, a nitro compound is used as a hydrogen acceptor to generate amines in the system, and a cyclohexanone nucleus substitution product and an amine are reacted to produce an aromatic secondary amino compound. It is already known how to do it. For example, using a palladium catalyst, p-
A method of reacting nitrophenetol with a large excess of cyclohexanone to obtain p-ethoxydiphenylamine (British Patent No. 975097); 1 / under a palladium catalyst
3 mol of 2,6-dimethylaniline, 2/3 mol of 2,
Method of obtaining 2,6-dimethyldiphenylamine by reacting with 10% excess of cyclohexanone with respect to the total of 6-dimethylnitrobenzene and 2,6-dimethylaniline and 2,6-dimethylnitrobenzene (British Patent No. 9892)
57); 2- (alkyl or alkoxy) -4-alkoxy-nitrobenzene, 2- (alkyl or alkoxy) -4-alkoxy-aniline and cyclohexanone are reacted in the presence of a palladium catalyst. Kaihei 5-117214
No.) etc.

However, these conventional methods have drawbacks such as (1) severe reaction conditions, (2) low reaction rate, and (3) low yield. It was hard to say.

[0006]

The object of the present invention is N-
A method for producing an aromatic secondary amino compound from a cyclohexylidene amino compound or cyclohexanone (including a nuclear substitution product), which is to solve the above-mentioned problems and provide a more industrially improved method.

[0007]

Means for Solving the Problems As a result of various studies, the present inventors have found that (1) when an N-cyclohexylideneamino compound is dehydrogenated in the presence of a dehydrogenation transfer catalyst and a hydrogen acceptor, Using a sulfur-containing polar solvent and / or using a co-catalyst, (2) cyclohexanone or cyclohexanone nuclear substitution product and amines, in the presence of a hydrogen transfer catalyst, a nitro compound corresponding to the amines. By using as a hydrogen acceptor and reacting in a non-sulfur-containing polar solvent, and by adding a specific co-catalyst to this system and reacting, an aromatic secondary amino compound is obtained under extremely mild conditions and in good yield. The present invention has been achieved, and the present invention has been achieved.

One of the first inventions is the following method. General formula (1) (chemical formula 9)

[0009]

[Chemical 9]

(In the formula, R represents a hydrogen atom, an alkyl group, an alkoxy group, an amino group, a hydroxyl group, or fluorine,
n is an integer of 0-5. R'represents an alkyl group, a phenyl group, a benzyl group, a naphthyl group, a furyl group, a furfuryl group, a cyclohexyl group, an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, a cyclohexyl group, a substituted amino group, a carboxyl group, a hydroxyl group, Alternatively, it may be substituted with fluorine. ) In carrying out the dehydrogenation reaction of the N-cyclohexylidene amino compound represented by the formula (1) in the presence of a dehydrogenation transfer catalyst and a hydrogen acceptor, a non-sulfur-containing polar solvent is used, and the general formula (2) ( 10)

[0011]

[Chemical 10]

A process for producing an aromatic secondary amino compound represented by the formula (wherein R, R'and n are the same as above).

The N-cyclohexylideneamino compound used as a raw material can be easily synthesized from amines (the derivatives thereof having a substituent in the amino group) and cyclohexanone or the derivatives thereof by a known method.

In the general formula (1) (formula 9), examples of the alkyl group represented by R include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-.
Butyl, pentyl, phenylmethyl, aminomethyl, hydroxymethyl, fluoromethyl, preferably methyl and ethyl.

Examples of alkoxy are methoxy, ethoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, hexadecyloxy, aminomethoxy, fluoromethoxy, preferably methyloxy and ethyloxy. Can be mentioned.

Examples of amino groups include amino, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, tert-butylamino, pentylamino, dimethylamino, diethylamino, cyclohexylamino and acetylamino. .

Examples of the alkyl group represented by R'in the general formula (1) (formula 9) are methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-.
Examples include butyl, aminomethyl, aminoethyl, aminopropyl, 2-aminopropyl, 3-aminopropyl, aminobutyl and hydroxyethyl.

Examples of the phenyl group are phenyl, o-methylphenyl, m-methylphenyl p-methylphenyl, p-ethylphenyl, p-propylphenyl and p-.
Isopropylphenyl, p-butylphenyl, p-te
rt-butylphenyl, p-pentylphenyl, p-hexylphenyl, p-heptylphenyl, p-octylphenyl, p-nonylphenyl, p-decylphenyl,
p-dodecylphenyl, p-hexadecylphenyl,
3,4-dimethylphenyl, 2,3-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, p-methoxyphenyl, p-ethoxyphenyl, p-butoxyphenyl, p-pentyloxyphenyl , P-hexyloxyphenyl, p-heptyloxyphenyl, p-octyloxyphenyl, p-nonyloxyphenyl, p-phenyloxyphenyl, p-tolyloxyphenyl, p-acetylphenyl, p-benzoylphenyl, p-amino. Phenyl, p-methylaminophenyl, p-ethylaminophenyl, p-butylaminophenyl, p-tert-butylaminophenyl,
p-octylaminophenyl, p-dodecylaminophenyl, p-cyclohexylphenyl, p-methylcyclohexylphenyl, p-ethylcyclohexylphenyl, p-propylcyclohexylphenyl, p-hydroxyphenyl, p-carboxyphenyl and p-fluorophenyl, Preferred are phenyl and p-methylphenyl.

Examples of the benzyl group are benzyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, p-ethylbenzyl, p-propylbenzyl and p-.
Isopropylbenzyl, p-butylbenzyl, p-te
rt-butylbenzyl, p-pentylbenzyl, p-hexylbenzyl, p-heptylbenzyl, p-octylbenzyl, p-nonylbenzyl, p-decylbenzyl,
p-dodecylbenzyl, p-hexadecylbenzyl, p
-Acetylbenzyl, 3,4-dimethylbenzyl, 2,
3-dimethylbenzyl, 2,6-dimethylbenzyl,
2,4,6-trimethylbenzyl, p-methoxybenzyl, p-ethoxybenzyl, p-butoxybenzyl, p
-Pentyloxybenzyl, p-hexyloxybenzyl, p-heptyloxybenzyl, p-octyloxybenzyl, p-nonyloxybenzyl, p-phenyloxybenzyl, p-tolyloxybenzyl, p-benzoylbenzyl, p-methylamino Benzyl, p-ethylaminobenzyl, p-butylaminobenzyl, p-te
rt-butylaminobenzyl, p-octylaminobenzyl, p-dodecylaminobenzyl, p-cyclohexylbenzyl, p-methylcyclohexylbenzyl, p-
Mention may be made of ethylcyclohexylbenzyl, p-propylcyclohexylbenzyl, p-hydroxybenzyl, p-carboxybenzyl and p-fluorobenzyl.

Examples of cyclohexyl groups are cyclohexyl, o-methylcyclohexyl, m-methylcyclohexyl, p-methylcyclohexyl, p-ethylcyclohexyl, p-propylcyclohexyl, p-isopropylcyclohexyl, p-butylcyclohexyl, p-.
tert-butylcyclohexyl, p-pentylcyclohexyl, p-hexylcyclohexyl, p-heptylcyclohexyl, p-octylcyclohexyl, p-nonylcyclohexyl, p-decylcyclohexyl, p-
Dodecylcyclohexyl, p-hexadecylcyclohexyl, p-acetylcyclohexyl, 3,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl,
2,6-dimethylcyclohexyl, 2,4,6-trimethylcyclohexyl, p-methoxycyclohexyl, p
-Ethoxycyclohexyl, p-butoxycyclohexyl, p-pentyloxycyclohexyl, p-hexyloxycyclohexyl, p-heptyloxycyclohexyl, p-octyloxycyclohexyl and p-nonyloxycyclohexyl.

Preferred compounds of the general formula (1) (formula 9) are shown below. 1. N- (cyclohexylidene) methylamine 1. N- (4-methylcyclohexylidene) methylamine 3. N- (4-methyloxycyclohexylidene) methylamine 4. N- (cyclohexylidene) aniline 5. N- (2-methylcyclohexylidene) aniline 6. N- (3-methylcyclohexylidene) aniline 7. N- (4-methylcyclohexylidene) aniline 8. N- (4-ethylcyclohexylidene) aniline 9. N- (2,6-dimethylcyclohexylidene) aniline 10. N- (4-methyloxycyclohexylidene)
Aniline 11. N- (4-fluorocyclohexylidene) aniline 12. N- (4-hydroxycyclohexylidene) aniline 13. N- (cyclohexylidene) -2-methylaniline 14. N- (2-methylcyclohexylidene) -2-
Methylaniline 15. N- (3-methylcyclohexylidene) -2-
Methylaniline 16. N- (4-methylcyclohexylidene) -2-
Methylaniline 17. N- (4-ethylcyclohexylidene) -2-
Methylaniline 18. N- (2,6-dimethylcyclohexylidene)
-2-methylaniline 19. N- (4-methyloxycyclohexylidene)
-2-methylaniline 20. N- (4-fluorocyclohexylidene) -2
-Methylaniline 21. N- (4-hydroxycyclohexylidene)-
2-methylaniline 22. N- (cyclohexylidene) -3-methylaniline 23. N- (2-methylcyclohexylidene) -3-
Methylaniline 24. N- (3-methylcyclohexylidene) -3-
Methylaniline 25. N- (4-methylcyclohexylidene) -3-
Methylaniline 26. N- (4-ethylcyclohexylidene) -3-
Methylaniline 27. N- (2,6-dimethylcyclohexylidene)
-3-Methylaniline 28. N- (4-methyloxycyclohexylidene)
-3-Methylaniline 29. N- (4-fluorocyclohexylidene) -3
-Methylaniline 30. N- (4-hydroxycyclohexylidene)-
3-methylaniline 31. N- (cyclohexylidene) -4-methylaniline 32. N- (2-methylcyclohexylidene) -4-
Methylaniline 33. N- (3-methylcyclohexylidene) -4-
Methylaniline 34. N- (4-methylcyclohexylidene) -4-
Methylaniline 35. N- (4-ethylcyclohexylidene) -4-
Methylaniline 36. N- (2,6-dimethylcyclohexylidene)
-4-Methylaniline 37. N- (4-methyloxycyclohexylidene)
-4-methylaniline 38. N- (4-fluorocyclohexylidene) -4
-Methylaniline 39. N- (4-hydroxycyclohexylidene)-
4-methylaniline 40. N- (cyclohexylidene) -2,4-dimethylaniline 41. N- (2-methylcyclohexylidene) -2,
4-dimethylaniline 42. N- (3-methylcyclohexylidene) -2,
4-dimethylaniline 43. N- (4-methylcyclohexylidene) -2,
4-dimethylaniline 44. N- (4-ethylcyclohexylidene) -2,
4-dimethylaniline 45. N- (2,6-dimethylcyclohexylidene)
-2,4-dimethylaniline 46. N- (4-methyloxycyclohexylidene)
-2,4-dimethylaniline 47. N- (4-fluorocyclohexylidene)-
2,4-dimethylaniline 48. N- (4-hydroxycyclohexylidene)-
2,4-dimethylaniline 49. N- (cyclohexylidene) -4-methoxyaniline 50. N- (2-methylcyclohexylidene) -4-
Methoxyaniline 51. N- (3-methylcyclohexylidene) -4-
Methoxyaniline 52. N- (4-methylcyclohexylidene) -4-
Methoxyaniline 53. N- (4-ethylcyclohexylidene) -4-
Methoxyaniline 54. N- (2,6-dimethylcyclohexylidene)
-4-Methoxyaniline 55. N- (4-methyloxycyclohexylidene)
-4-Methoxyaniline 56. N- (4-fluorocyclohexylidene) -4
-Methoxyaniline 57. N- (4-hydroxycyclohexylidene)-
4-methoxyaniline 58. N- (cyclohexylidene) -4-hydroxyaniline 59. N- (2-methylcyclohexylidene) -4-
Hydroxyaniline 60. N- (3-methylcyclohexylidene) -4-
Hydroxyaniline 61. N- (4-methylcyclohexylidene) -4-
Hydroxyaniline 62. N- (4-ethylcyclohexylidene) -4-
Hydroxyaniline 63. N- (2,6-dimethylcyclohexylidene)
-4-Hydroxyoxyaniline 64. N- (4-methyloxycyclohexylidene)
-4-hydroxyoxyaniline 65. N- (4-fluorocyclohexylidene) -4
-Hydroxyaniline 66. N- (4-hydroxycyclohexylidene)-
4-hydroxyaniline 67. N- (cyclohexylidene) benzylamine 68. N- (2-methylcyclohexylidene) benzylamine 69. N- (3-methylcyclohexylidene) benzylamine 70. N- (4-methylcyclohexylidene) benzylamine 71. N- (4-ethylcyclohexylidene) benzylamine 72. N- (2,6-dimethylcyclohexylidene)
Benzylamine 73. N- (4-methyloxycyclohexylidene)
Benzylamine 74. N- (4-fluorocyclohexylidene) benzylamine 75. N- (4-hydroxycyclohexylidene) benzylamine 76. N- (cyclohexylidene) cyclohexylamine 77. N- (2-methylcyclohexylidene) cyclohexylamine 78. N- (3-methylcyclohexylidene) cyclohexylamine 79. N- (4-methylcyclohexylidene) cyclohexylamine 80. N- (4-ethylcyclohexylidene) cyclohexylamine 81. N- (2,6-dimethylcyclohexylidene)
Cyclohexylamine 82. N- (4-methyloxycyclohexylidene)
Cyclohexylamine 83. N- (4-fluorocyclohexylidene) cyclohexylamine 84. N- (4-hydroxycyclohexylidene) cyclohexylamine 85. N- (cyclohexylidene) -4-fluoroaniline 86. N- (2-methylcyclohexylidene) -4-
Fluoroaniline 87. N- (3-methylcyclohexylidene) -4-
Fluoroaniline 88. N- (4-methylcyclohexylidene) -4-
Fluoroaniline 89. N- (4-ethylcyclohexylidene) -4-
Fluoroaniline 90. N- (2,6-dimethylcyclohexylidene)
-4-Fluoroaniline 91. N- (4-methyloxycyclohexylidene)
-4-Fluoroaniline 92. N- (4-fluorocyclohexylidene) -4
-Fluoroaniline 93. N- (4-hydroxycyclohexylidene)-
4-Fluoroaniline 94. N- (2-methylcyclohexylidene) methylamine 95. N- (3-methylcyclohexylidene) methylamine 96. N- (4-ethylcyclohexylidene) methylamine 97. N- (2,6-dimethylcyclohexylidene)
Methylamine 98. N- (4-methyloxycyclohexylidene)
Methylamine 99. N- (4-fluorocyclohexylidene) methylamine 100. N- (4-hydroxycyclohexylidene)
Methylamine 101. N- (cyclohexylidene) -4-phenoxyaniline 102. N- (2-methylcyclohexylidene) -4
-Phenoxyaniline 103. N- (3-methylcyclohexylidene) -4
-Phenoxyaniline 104. N- (4-methylcyclohexylidene) -4
-Phenoxyaniline 105. N- (4-ethylcyclohexylidene) -4
-Phenoxyaniline 106. N- (2,6-dimethylcyclohexylidene) -4-phenoxyaniline 107. N- (4-methyloxycyclohexylidene) -4-phenoxyaniline 108. N- (4-fluorocyclohexylidene)-
4-phenoxyaniline 109. N- (4-hydroxycyclohexylidene)
-4-phenoxyaniline 110. N- (cyclohexylidene) -4-fluoroaniline 111. N- (2-methylcyclohexylidene) -4
-Fluoroaniline 112. N- (3-methylcyclohexylidene) -4
-Fluoroaniline 113. N- (4-methylcyclohexylidene) -4
-Fluoroaniline 114. N- (4-ethylcyclohexylidene) -4
-Fluoroaniline 115. N- (2,6-dimethylcyclohexylidene) -4-fluoroaniline 116. N- (4-methyloxycyclohexylidene) -4-fluoroaniline 117. N- (4-fluorocyclohexylidene)-
4-Fluoroaniline 118. N- (4-hydroxycyclohexylidene)
-4-fluoroaniline

Any known hydrogen transfer catalyst may be used as the hydrogen transfer catalyst. Specifically, Raney nickel, reduced nickel and nickel are supported on various carriers such as diatomaceous earth, alumina, pumice, silica gel and acid clay. Nickel carrier catalyst; Raney cobalt, reduced cobalt, cobalt,
Cobalt catalysts such as cobalt-supported catalysts; Raney copper, reduced copper, copper catalysts such as copper-supported catalysts; palladium black, palladium oxide, colloidal palladium, palladium-carbon,
Palladium catalysts such as palladium-barium sulfate and palladium-barium carbonate; platinum catalysts such as platinum black, colloidal platinum, platinum sponge, platinum oxide, platinum sulfide, platinum-carbon, etc .; colloidal rhodium, rhodium-carbon, Examples include rhodium catalysts such as rhodium oxide; 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. You can Among these catalysts, the palladium catalyst is preferably used, particularly the palladium-supported catalyst is preferably used, and particularly palladium-carbon and palladium-alumina are preferably used.

The amount of the hydrogen transfer catalyst used is usually 0.001 to 1.0 gram atom as a metal atom per 1 gram molecule of the N-cyclohexylidene amino compound, preferably 0.
002-0.2 gram atom is good.

In the first method of the present invention, any of various reducing materials is used as the hydrogen acceptor. Examples of the hydrogen acceptor include 1-octene, allylbenzene,
Olefins such as crotonic acid, 2,6-dimethylnitrobenzene, p-amylnitrobenzene, p-hexylnitrobenzene, p-octylnitrobenzene, p-sec
-Octylnitrobenzene, p-tert-octylnitrobenzene, p-nonylnitrobenzene, p-decylnitrobenzene, p-ethoxynitrobenzene, o-ethoxynitrobenzene, 2,6-dimethyl-4-amino-nitrobenzene, nitrobenzene, p-dinitrobenzene, m-dinitrobenzene, 4-nitrodiphenyl,
p-phenoxynitrobenzene, p-cyclohexylnitrobenzene, p-benzylnitrobenzene, nitromethane, 2-nitropropane, 1-nitronaphthalene, 2
-, 3- and 4-nitrotoluene, 4-nitroanisole, p-propylnitrobenzene, m-ethylnitrobenzene, 4-nitrobenzonitrile, p-nitroacetanilide, 4-nitrobenzoic acid, nitro compounds such as nitrocyclohexane, phenol. , Methylphenol,
Ethylphenol, isopropylphenol, butylphenol, 2,4-dimethylphenol, 2,4,6-
Examples thereof include trimethylphenol, alkylphenol such as 2,6-di-tert-butyl-4-methylphenol, and phenols such as alkoxyphenol such as 3-methoxyphenol and 4-methoxyphenol. However, in the case of phenols, it is necessary to increase the amount used,
By-products also tend to increase. It is particularly preferable to use nitrobenzene in the nitro compound as a hydrogen acceptor as a raw material for N-cyclohexylideneaniline.

The amount of hydrogen acceptor used varies depending on the kind thereof, but it is sufficient if it is 5 equivalents to the N-cyclohexylidene amino compound, and particularly in the case of olefins and nitro compounds, an equivalent amount or a 50% excess amount. Is enough. When there are few hydrogen acceptors, the amount of N-cyclohexylamine produced as a by-product tends to increase.

The hydrogen acceptor is preferably an olefin or a nitro compound from the viewpoint of volumetric efficiency of the reactor.

Examples of the non-sulfur-containing polar solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, tetramethylurea, methylisobutylketone, tetrahydrofuran, dioxane, 1,3-dimethylimidazolidinone. Glymes such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, methyl salicylate, phenol, methylphenol, alkylphenols such as 2,4,6-trimethylphenol, and phenols such as alkoxyphenol such as 3-methoxyphenol and 4-methoxyphenol. If necessary, these solvents may be mixed and used. Even with the same polar solvent, dimethyl sulfoxide, sulfolane and the like are not preferable because they have a poisoning effect on the dehydrogenation catalyst. The amount of the non-sulfur-containing polar solvent used is preferably 0.05 to 3.0 times by weight, and more preferably 0.15 to 1.5 times by weight, that of the N-cyclohexylideneamino compound.

In the above reaction, when the raw materials are charged into the reaction vessel, the solvent and the catalyst are charged and mixed in advance, and then the N-cyclohexylideneamino compound and the hydrogen acceptor are simultaneously added dropwise to carry out the reaction. This is the preferred embodiment. Of course, these may be mixed and then added dropwise.

In carrying out the dehydrogenation reaction of the above-mentioned N-cyclohexylideneamino compound in the presence of a dehydrogenation transfer catalyst and a hydrogen acceptor, alkali metal and The method of adding an alkaline earth metal compound is also one aspect of the first invention.

Alkali metal compounds and alkaline earth metal compounds added as promoters are alkali metals,
Alkaline earth metal hydroxides, carbonates, bicarbonates and the like can be used. Specific examples thereof include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and the like, among which sodium hydroxide and potassium hydroxide are preferable. . These promoters may be used alone or in combination of two or more. These cocatalysts do not necessarily have to be added to the reaction system separately from the dehydrogenation catalyst. For example, after producing a noble metal-supported catalyst, an alkali metal and / or alkaline earth metal component as an alkali metal and / or alkaline earth metal component is added. A catalyst prepared by additionally supporting a salt, a hydroxide or the like as a solution may be used.

The amount of the co-catalyst used is 2 to alkaline metal and / or alkaline earth metal based on the catalyst metal.
A range of 30% by weight is good, and preferably 5 to 20% by weight. If it is more than this, the reaction rate tends to decrease, and conversely, if it is less, the yield tends to decrease.

It is advantageous to carry out the reaction while removing water. Therefore, a method of separating from the reaction mixture by azeotropic distillation using a solvent such as benzene, toluene or xylene is suitable.

The temperature during the reaction is usually 120 to 250 ° C,
It is preferably selected in the range of 140 to 200 ° C.

The mixture obtained by the above-mentioned method is usually treated by 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 and the hydrogenated product of the hydrogen acceptor are recovered. In some cases, the aromatic secondary amino compound 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.

One of the second inventions is the following method. In the presence of a hydrogen transfer catalyst, general formula (3)

[0036]

[Chemical 11]

(In the formula, R represents a hydrogen atom, an alkyl group, an alkoxy group, an amino group, a hydroxyl group, or fluorine,
n is an integer of 0-5. ) Cyclohexanone or a substituted cyclohexanone nucleus represented by the general formula (4)

[0038]

[Chemical 12]

(In the formula, R'is an alkyl group, a phenyl group,
It represents a benzyl group, a naphthyl group, a furyl group, a furfuryl group or a cyclohexyl group, and may be substituted with an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, a cyclohexyl group, a substituted amino group, a carboxyl group, a hydroxyl group or fluorine. ) And a general formula (5) (Chemical Formula 13) corresponding to the above amines as a hydrogen acceptor.

[0040]

[Chemical 13]

(In the formula, R'is the same as the definition of the above-mentioned general formula (4).) The reaction is carried out in a non-sulfur-containing polar solvent using a nitro compound represented by the general formula ( 2)
(Chemical formula 14)

[0042]

[Chemical 14]

A process for producing an aromatic secondary amino compound represented by the formula (wherein R, R'and n are the same as above).

That is, in the present invention, in the presence of a hydrogen transfer catalyst, a cyclohexanone or a cyclohexanone nuclear substitution product, amines, and a nitro compound corresponding to the amines used as a hydrogen acceptor in the reaction are used to produce a non-sulfur-containing polar compound. A method for producing an aromatic secondary amino compound, which comprises reacting in the presence of a solvent.

Examples of the alkyl group represented by R'in the general formula (4) (formula 12) and the general formula (5) (formula 13) include methyl, ethyl, propyl, isopropyl,
Butyl, isobutyl, tert-butyl, aminomethyl, aminoethyl, aminopropyl, 2-aminopropyl, 3-aminopropyl, aminobutyl and hydroxyethyl.

Examples of the phenyl group are phenyl, o-methylphenyl, m-methylphenyl p-methylphenyl, p-ethylphenyl, p-propylphenyl and p-.
Isopropylphenyl, p-butylphenyl, p-te
rt-butylphenyl, p-pentylphenyl, p-hexylphenyl, p-heptylphenyl, p-octylphenyl, p-nonylphenyl, p-decylphenyl,
p-dodecylphenyl, p-hexadecylphenyl,
3,4-dimethylphenyl, 2,3-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, p-methoxyphenyl, p-ethoxyphenyl, p-butoxyphenyl, p-pentyloxyphenyl , P-hexyloxyphenyl, p-heptyloxyphenyl, p-octyloxyphenyl, p-nonyloxyphenyl, p-phenyloxyphenyl, p-tolyloxyphenyl, p-acetylphenyl, p-benzoylphenyl, p-amino. Phenyl, p-methylaminophenyl, p-ethylaminophenyl, p-butylaminophenyl, p-tert-butylaminophenyl,
p-octylaminophenyl, p-dodecylaminophenyl, p-cyclohexylphenyl, p-methylcyclohexylphenyl, p-ethylcyclohexylphenyl, p-propylcyclohexylphenyl, p-hydroxyphenyl, p-carboxyphenyl and p-fluorophenyl, Preferred are phenyl and p-methylphenyl.

Examples of the benzyl group are benzyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, p-ethylbenzyl, p-propylbenzyl and p-.
Isopropylbenzyl, p-butylbenzyl, p-te
rt-butylbenzyl, p-pentylbenzyl, p-hexylbenzyl, p-heptylbenzyl, p-octylbenzyl, p-nonylbenzyl, p-decylbenzyl,
p-dodecylbenzyl, p-hexadecylbenzyl, p
-Acetylbenzyl, 3,4-dimethylbenzyl, 2,
3-dimethylbenzyl, 2,6-dimethylbenzyl,
2,4,6-trimethylbenzyl, p-methoxybenzyl, p-ethoxybenzyl, p-butoxybenzyl, p
-Pentyloxybenzyl, p-hexyloxybenzyl, p-heptyloxybenzyl, p-octyloxybenzyl, p-nonyloxybenzyl, p-phenyloxybenzyl, p-tolyloxybenzyl, p-benzoylbenzyl, p-methylamino Benzyl, p-ethylaminobenzyl, p-butylaminobenzyl, p-te
rt-butylaminobenzyl, p-octylaminobenzyl, p-dodecylaminobenzyl, p-cyclohexylbenzyl, p-methylcyclohexylbenzyl, p-
Ethylcyclohexylbenzyl, p-propylcyclohexylbenzyl, p-hydroxybenzyl, p-carboxybenzyl and p-fluorobenzyl.

Examples of the cyclohexyl group are cyclohexyl, o-methylcyclohexyl, m-methylcyclohexyl, p-methylcyclohexyl, p-ethylcyclohexyl, p-propylcyclohexyl, p-isopropylcyclohexyl, p-butylcyclohexyl and p-.
tert-butylcyclohexyl, p-pentylcyclohexyl, p-hexylcyclohexyl, p-heptylcyclohexyl, p-octylcyclohexyl, p-nonylcyclohexyl, p-decylcyclohexyl, p-
Dodecylcyclohexyl, p-hexadecylcyclohexyl, p-acetylcyclohexyl, 3,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl,
2,6-dimethylcyclohexyl, 2,4,6-trimethylcyclohexyl, p-methoxycyclohexyl, p
-Ethoxycyclohexyl, p-butoxycyclohexyl, p-pentyloxycyclohexyl, p-hexyloxycyclohexyl, p-heptyloxycyclohexyl, p-octyloxycyclohexyl and p-nonyloxycyclohexyl.

Preferred compounds of the general formula (3) (formula 11) are shown below. 1. Cyclohexanone 2. 2-methylcyclohexanone 3. 3-methylcyclohexanone 4. 4-methylcyclohexanone 5. 4-ethylcyclohexanone 6. 4-octylcyclohexanone 7. 2,6-Dimethylcyclohexanone 8. 2,4-dimethylcyclohexanone 9. 4-phenylcyclohexanone 10. 4-phenylmethylcyclohexanone 11. 4-phenyloxycyclohexanone 12. 4-methyloxycyclohexanone 13. 4-nonyloxycyclohexanone 14. 4-Methylaminocyclohexanone 15. 4-dimethylaminocyclohexanone 16. 4-Acetylaminocyclohexanone 17. 4-fluorocyclohexanone 18. 4-hydroxycyclohexanone

Preferred compounds of the general formula (4) (formula 12) are shown below. 1. Methylamine 2. Ethylamine 3. Aniline 4. 2-methylaniline 5. 3-methylaniline 6. 4-methylaniline 7. 4-ethylaniline 8. 4-nonylaniline 9. 2,6-dimethylaniline 10. 2,4-dimethylaniline 11. 2,4,6-trimethylaniline 12. 4-methoxyaniline 13. 2-Methyl-4-methoxyaniline 14. 4-acetylaniline 15. 4-aminoacetanilide ananiline 16. 4-methylaminoaniline 17. 4-cyclohexylaniline 18. 4-hydroxyaniline 19. 4-carboxyaniline 20. Benzylamine 21. 4-methylbenzylamine 22. 4-octylbenzylamine 23. 2,4-dimethylbenzylamine 24. 4-methoxybenzylamine 25. Cyclohexylamine 26. 4-methylcyclohexylamine 27. 4-methoxycyclohexylamine 28. 2-naphthylamine 29. Furfurylamine 30. 4-fluoroaniline 31. 4-aminodiphenyl ether

Preferred compounds of the general formula (5) (formula 13) are shown below. 1. Nitromethane 2. Nitroethane 3. Nitrobenzene 4. 2-nitrotoluene 5. 3-nitrotoluene 6. 4-nitrotoluene 7. 4-ethylnitrobenzene 8. 4-nonylnitrobenzene 9. 2,6-dimethylnitrobenzene 10. 2,4-dimethylnitrobenzene 11. 2,4,6-trimethylnitrobenzene 12. 4-Methoxynitrobenzene 13. 2-Methyl-4-methoxynitrobenzene 14. 4-Acetylnitrobenzene 15. 4-nitroacetanilide 16. 4-methylaminonitrobenzene 17. 4-cyclohexylnitrobenzene 18. 4-hydroxynitrobenzene 19. 4-carboxynitrobenzene 20. Nitrobenzyl 21. 4-methylnitrobenzyl 22. 4-octylnitrobenzyl 23. 2,4-dimethylnitrobenzyl 24. 4-methoxynitrobenzyl 25. Nitrocyclohexane 26. 4-methylnitrocyclohexane 27. 4-methoxynitrocyclohexane 28. 2-nitronaphthalene 29. Nitrofurifuril 30. 4-fluoronitrobenzene 31. 4-nitrodiphenyl ether

In the present invention, a cyclohexanone or a cyclohexanone nucleus-substituted product represented by the general formula (3) (formula 11), an amine represented by the general formula (4) (formula 12) and a general formula (5) (formula 13) The use ratio of the nitro compound represented by () can be appropriately determined based on a molar ratio of 3: 1: 2. The nitro compounds are used here as hydrogen acceptors. By doing so, amines are generated in the reaction system, and a Schiff base is generated by a condensation reaction with the other raw material cyclohexanone or a cyclohexanone nuclear substitution product, and then dehydrogenated to form an aromatic secondary amino compound. . It is possible to convert 2/3 mol of the nitro compound per mol of the Schiff base into amines by hydrogen generated when the Schiff base is dehydrogenated.

Therefore, in order to make full effective use of the hydrogen generated in the system, it is sufficient to react with cyclohexanone or a cyclohexanone nucleus substitution product / nitro compound molar ratio of 3/2. In that case, an excessive amount of cyclohexanone or The substituted cyclohexanone nucleus tends to further react with the aromatic secondary amino compound produced in the system to produce an aromatic tertiary amino compound as a by-product. On the contrary, if the amount of nitro compounds is large, the reaction rate tends to decrease, which is not a good idea. In order to avoid these drawbacks, the molar ratio of cyclohexanone or a nucleus of cyclohexanone / amines / nitro compound is 3/1 /.
The reaction is preferably carried out at 2, and the total ratio of the nitro compound and the amines is preferably 0.9 to 1.2 mol ratio with respect to cyclohexanone or a cyclohexanone nucleus-substituted product.

As the hydrogen transfer catalyst used in the method of the present invention, any known catalyst may be used. Specifically, Raney nickel, reduced nickel, nickel-containing diatomaceous earth, alumina, pumice, silica gel, acid clay, etc. may be used. Nickel carrier catalysts supported on various carriers; Raney cobalt,
Cobalt catalysts such as reduced cobalt, cobalt, cobalt-supported catalysts; copper catalysts such as Raney copper, reduced copper, copper-supported catalysts; palladium black, palladium oxide, colloidal palladium, palladium-carbon, palladium-barium sulfate,
Palladium catalysts such as palladium-barium carbonate; platinum catalysts such as platinum black, colloidal platinum, platinum sponge, platinum oxide, platinum sulfide, platinum-carrier catalysts such as platinum-carbon; colloidal rhodium, rhodium-carbon, rhodium such as rhodium oxide. Examples thereof 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, the palladium catalyst is preferably used, particularly the palladium-supported catalyst is preferably used, and particularly palladium-carbon and palladium-alumina are preferably used.

The amount of these hydrogen transfer catalysts used is usually 0.001 to 1 to 1 gram molecule of amines as a metal atom.
1.0 gram atom, preferably 0.002-0.2 gram atom.

The method of the present invention is characterized in that a non-sulfur-containing polar solvent is used. 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. If necessary, these solvents may be mixed and used. Sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane are not preferable because they have a poisoning effect on the hydrogen transfer catalyst.

The amount of the non-sulfur-containing polar solvent used is preferably 0.1 to 6.0 times by weight, more preferably 0.3 to 6.0 times the weight of cyclohexanone or the cyclohexanone nucleus-substituted product.
It is 3.0 times the weight.

The use of an alkali metal compound and / or an alkaline earth metal compound as a cocatalyst also belongs to the second invention. The use of this co-catalyst has the effect of extending the life of the hydrogen transfer catalyst.

Alkali metal compounds and alkaline earth metal compounds added as promoters are alkali metals,
Alkaline earth metal hydroxides, carbonates, bicarbonates and the like can be used. Specific examples thereof include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate and the like, among which sodium hydroxide and potassium hydroxide are preferable. . These promoters may be used alone or in combination of two or more. These cocatalysts do not necessarily have to be added to the reaction system separately from the dehydrogenation catalyst. For example, after producing a noble metal-supported catalyst, an alkali metal and / or alkaline earth metal component as an alkali metal and / or alkaline earth metal component is added. A catalyst prepared by additionally supporting a salt, a hydroxide or the like as a solution may be used.

The amount of the co-catalyst used is 2 to alkaline metal and / or alkaline earth metal based on the catalyst metal.
A range of 30% by weight is good, and preferably 5 to 20% by weight. It is also a preferred embodiment of the present invention to add an organic acid having a logarithmic value of 3.5 to 6.0, which is the reciprocal of the acid dissociation constant, to the reaction using the cocatalyst.

The preferable range of PKa is 4.0 to 5.0. If the acid has a PKa smaller than this, the Schiff base is not stable, and if it is larger than this, the dehydrogenation reaction is inhibited. Such organic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hexanoic acid, cyclohexanecarboxylic acid, octanoic acid, crotonic acid, vinylacetic acid, benzoic acid, anisic acid, cinnamic acid, Examples include phenylacetic acid and 2-naphthoic acid. The amount of the organic acid used is 50 to 2000% by weight, preferably 70 to 800% by weight, based on the catalyst metal. The amount of these cocatalysts is adjusted by appropriately adding them together with a hydrogen transfer catalyst which is added every time if necessary.

In the presence of a hydrogen transfer catalyst and a non-sulfur-containing polar solvent,
When a nitro compound is used as a hydrogen acceptor to react with cyclohexanone or a cyclohexanone nucleus substitution product and amines while producing amines in the system to produce an aromatic secondary amino compound, the catalyst used is recovered and recovered. When used, an alkali metal compound and / or an alkaline earth metal compound as a cocatalyst, and PKa 3.5 to 6.0
It is possible to minimize the amount of the catalyst added each time and maintain the reaction rate and yield by adding the organic acid and reacting.

It is advantageous to carry out the reaction while removing water, and therefore, a method of separating from the reaction mixture by azeotropic distillation using a solvent such as benzene, toluene or xylene is suitable.

The temperature during the reaction is usually 120 to 250 ° C.,
It is preferably selected in the range of 140 to 200 ° C.

In the above reaction, when the raw materials are charged in the reaction vessel, the (auxiliary) catalyst, the solvent and the amines are charged in the vessel in advance, stirred and heated, and then cyclohexanone (nuclear substitution product) and nitro It is also a preferred embodiment to react the compounds while dropping them at the same time. Of course, the two raw materials to be dropped may be mixed and then dropped.

The mixture obtained after the reaction, which is obtained by the method described above, is usually treated by 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, the aromatic secondary amino compound 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.

[0067]

EXAMPLES The method of the present invention will be described in detail below with reference to examples. Example A1 In a 100 ml round bottom flask equipped with a reflux condenser equipped with a separator, a thermometer and a stirrer, 1.86 g of 5% Pd / C containing 50% water, manufactured by NE Chemcat, and 10 g of diethylene glycol dimethyl ether. , N-cyclohexylideneaniline 17.33 g (0.1 mol),
And 8.29 g (0.067 mol) of nitrobenzene were charged. While stirring in the reactor, raise the temperature to 160 ° C,
The reaction was carried out for 4 hours while maintaining the temperature at 158 to 162 ° C. During this time, benzene was charged into the catalyst and water produced by the reaction to be azeotropically distilled, and was condensed by a reflux condenser, and then separated by a separator. The amount of water was 1.8 g. Then, the reaction solution was cooled to room temperature, and 5% Pd / C was added from the reaction mixture solution.
Was filtered off. When the filtrate was analyzed by gas chromatography, the conversion of imine was 100% and the yield of diphenylamine was 87.6%.

Examples A2 to A8 The reaction was performed in the same manner as in Example A1 except that the diethylene glycol dimethyl ether of Example A1 was replaced with various polar solvents shown in Table 1 (Table 1). The results are shown in Table 1 (Table 1).

[0069]

[Table 1]

Example A9 The nitrobenzene of Example A1 was replaced with a hydrogen acceptor α
-A reaction was performed in the same manner as in Example A1 except that 23.87 g (0.202 mol) of methylstyrene was used. As a result, the conversion of imine was 100% and the yield of diphenylamine was 85.9%.

Comparative Example A1 The reaction was carried out in the same manner as in Example A1 except that diethylene glycol dimethyl ether was not used. As a result, the conversion of imine was 96.1% and the yield of diphenylamine was 72.3%.

Comparative Example A2 The reaction was carried out in the same manner as in Example A1 except that p-tert-butyltoluene was used as a solvent instead of diethylene glycol dimethyl ether in Example A1. As a result, the conversion of imine was 94.0% and the yield of diphenylamine was 72.6%.

Example B1 5% Pd / C containing 50% water by NE Chemcat Corporation in a 100 ml round bottom flask equipped with a reflux condenser equipped with a separator, a thermometer, and a stirrer. 57
g, N, N-dimethylformamide 22.23 g, N-
20.51 g (0.1 mol) of (4-methylcyclohexylidene) -4-methylaniline and 9.24 g (0.067 mol) of p-nitrotoluene were charged. While stirring the inside of the reactor, the temperature was raised to 140 ° C and 138 to 142 ° C.
The reaction was carried out for 4 hours while maintaining Water generated during this period and water in the catalyst were charged with benzene to cause azeotropy, and were condensed by a reflux condenser, and then separated by a separator. The amount of water was 2.9 g. 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 imine was 100% and the yield of 4,4′-dimethyldiphenylamine was 85.3%.

Examples B2 to B6 In place of N, N-dimethylformamide of Example B1, various polar solvents as shown in Table 2 (Table 2) were used, and the reaction temperature was 160 ° C. The reaction was performed as in Example B1. The results are shown in Table 2 (Table 2).

[0075]

[Table 2]

Examples B7 to B14 N- (4-methylcyclohexylidene) -of Example B1
As in Example B1, using a combination of various N-cyclohexylidene amino compounds and hydrogen acceptors as shown in Table 3 (Table 3) instead of the combination of 4-methylaniline and p-nitrotoluene. The reaction was carried out. The results are shown in Table 3 (Table 3).

[0077]

[Table 3]

Example B15 A reaction was carried out in the same manner as in Example B1 except that 23.87 g (0.202 mol) of α-methylstyrene was used as a hydrogen acceptor instead of p-nitrotoluene of Example B1. As a result, the conversion of imine was 89.1%, 4,4 '.
The yield of dimethyldiphenylamine was 82.1%.

Comparative Example B1 The reaction was performed in the same manner as in Example B1 except that N, N-dimethylformamide was not used. As a result, the conversion of imine was 51.9% and the yield of 4,4′-dimethyldiphenylamine was 37.4%.

Comparative Example B2 The N, N-dimethylformamide of Example B1 was replaced by p
The reaction was performed in the same manner as in Example B1 except that -tert-butyltoluene was used as a solvent. As a result, the conversion of imine was 49.1% and the yield of 4,4′-dimethyldiphenylamine was 35.3%.

Comparative Example B3 The reaction was performed in the same manner as in Example B7 except that N, N-dimethylformamide was not used. As a result, the conversion of imine was 31.3% and the yield of 4,2′-dimethyldiphenylamine was 15.5%.

Comparative Example B4 The reaction was performed in the same manner as in Example B9 except that N, N-dimethylformamide was not used. As a result, the conversion of imine was 12.1% and the yield of 2,4'-dimethyldiphenylamine was 4.3%.

Example C1 A 200 ml round-bottomed flask equipped with a reflux condenser equipped with a separator, a thermometer, a dropping device and a stirrer was added to NE Chemcat Corporation with 5% Pd / C3. 72
g, 20 g of diethylene glycol dimethyl ether, and N-cyclohexylideneaniline 3 in the dropping device.
4.66 g (0.2 mol), and nitrobenzene 16.
A mixed solution of 58 g (0.13 mol) was prepared. The temperature in the reactor was raised to 160 ° C. with stirring, water in the catalyst was removed, and then the solution in the dropping device was added dropwise over 4 hours while maintaining the temperature at 158 to 162 ° C. After completion of the dropping, stirring was continued for 0.5 hour while maintaining this temperature range. Water generated during this time was azeotropically distilled with benzene, condensed with a reflux condenser, and then separated with a separator. The amount of water produced is 4.8.
It was g. Then, the inside of the reactor was cooled to room temperature, and 5% Pd / C was filtered off from the reaction mixture. When the filtrate was analyzed by gas chromatography, the conversion of imine was 100% and the yield of diphenylamine was 98.5%.

Examples C2 to C9 The reaction was carried out in the same manner as in Example C1 except that the diethylene glycol dimethyl ether of Example C1 was replaced with various polar solvents shown in Table 4 (Table 4). The results are shown in Table 4 (Table 4).

[0085]

[Table 4]

Comparative Example C1 The reaction was performed in the same manner as in Example C1 except that p-tert-butyltoluene was used as a solvent instead of diethylene glycol dimethyl ether in Example C1. As a result, the conversion of imine was 35.0% and the selectivity to diphenylamine was 90.2%.

Example D1 A 100 ml round-bottomed flask equipped with a reflux condenser equipped with a separator, a thermometer, a dropping device and a stirrer was manufactured by NE Chemcat and contained 5% Pd / C 2 containing 50% water. ．
57 g, N, N-dimethylformamide 22.23 g
Was charged, and 20.51 g (0.1 mol) of N- (4-methylcyclohexylidene) -4-methylaniline and 9.24 g (0.067) of p-nitrotoluene were added to the dropping apparatus.
Mol) mixed solution was prepared and stored. The temperature in the reactor was raised to 140 ° C. with stirring, and water in the catalyst was removed.
The solution in the dropping device was dropped over 4 hours while maintaining the temperature at 8 to 142 ° C. After completion of the dropping, stirring was continued for 1 hour while maintaining this temperature range. The water produced during this time was azeotropically charged with benzene, condensed with a reflux condenser, and then separated with a separator. The amount of water produced was 4.0 g. 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 imine was 98.
6%, the yield of 4,4'-dimethyldiphenylamine is 9
It was 3.5%.

Examples D2 to D6 In place of N, N-dimethylformamide of Example D1, various polar solvents shown in Table 5 (Table 5) were used, and the reaction temperature was 160 ° C. The reaction was carried out as in Example D1. The results are shown in Table 5 (Table 5).

[0089]

[Table 5]

Examples D7 to D14 A reaction was carried out in the same manner as in Example D1 except that the combination of the N-cyclohexylideneamino compound of Example D1 and the hydrogen acceptor was changed as shown in Table 6 (Table 6). went. The results are shown in Table 6 (Table 6).

[0091]

[Table 6]

Example E1 In a 100 ml round bottom flask equipped with a reflux condenser equipped with a separator, a thermometer and a stirrer, 1.86 g of 5% Pd / C containing 50% water, manufactured by NE Chemcat. ,
0.24 g of 1N-NaOH, 10 g of diethylene glycol dimethyl ether, 17.33 g (0.1 mol) of N-cyclohexylideneaniline, and 8.29 g (0.067 mol) of nitrobenzene were charged. The temperature in the reactor was raised to 160 ° C. with stirring, and the reaction was carried out for 2 hours while maintaining the temperature at 158 to 162 ° C. Water generated during this period and water in the catalyst were charged with benzene to cause azeotropy, and were condensed by a reflux condenser, and then separated by a separator. The amount of water produced was 2.6 g. 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 imine was 100% and the yield of diphenylamine was 9%.
It was 3.0%.

Examples E2 to E8 and Comparative Examples E1 to E3 The same as Example E1 except that various polar solvents shown in Table 7 (Table 7) were used in place of the diethylene glycol dimethyl ether of Example E1. The reaction was carried out. The results are shown in Table 7 (Table 7).

[0094]

[Table 7]

Examples E9 and E10 Except that 0.24 g of 1N-NaOH obtained in Example E1 was replaced with an alkali metal compound and / or an alkaline earth metal compound as shown in Table 8 (Table 8) as a cocatalyst. Reacted in the same manner as in Example E1. The results including Example E1 are shown in Table 8 (Table 8).

[0096]

[Table 8]

Example F1 2.57 g of 5% Pd / C containing 50% water, manufactured by NE Chemcat Ltd., was placed in a 100 ml round bottom flask equipped with a reflux condenser equipped with a separator, a thermometer, and a stirrer. ,
0.30 g of 1N-NaOH, 22.23 g of N, N-dimethylformamide, 20.51 g of N- (4-methylcyclohexylidene) -4-methylaniline (0.
1 mol), and 9.24 g of p-nitrotoluene (0.
067 mol). While stirring the inside of the reactor 14
The temperature was raised to 0 ° C., and the reaction was performed for 2 hours while maintaining the temperature at 138 to 142 ° C. Water generated during this period and water in the catalyst were charged with benzene to cause azeotropy, and were condensed by a reflux condenser, and then separated by a separator. The amount of water was 3.6 g. Then, the reaction solution was cooled to room temperature, and the reaction mixture was cooled to 5
% Pd / C was filtered off. When the filtrate was analyzed by gas chromatography, the conversion of imine was 99.7.
%, The yield of 4,4′-dimethyldiphenylamine is 9
It was 0.9%.

Comparative Example F1 The reaction was performed in the same manner as in Example F1 except that N, N-dimethylformamide was not used. As a result, the imine conversion rate was 46.6%, and the yield of 4,4′-dimethyldiphenylamine was 36.0%.

Comparative Example F2 The reaction was performed in the same manner as in Example F1 except that 1N-NaOH and N, N-dimethylformamide were not used. As a result, the imine conversion rate was 45.3%, and the yield of 4,4′-dimethyldiphenylamine was 31.5%.

Examples F2 to F6 Examples F1 to F6 except that various polar solvents shown in Table 9 were used instead of N, N-dimethylformamide of Example F1 and the reaction temperature was 160 ° C. The reaction was performed similarly. The results are shown in Table 9 (Table 9).

[0101]

[Table 9]

Examples F7 to F8 In place of 0.3 g of 1N-NaOH used in Example F1, alkali metal as shown in Table 10 (Table 10) was used as a cocatalyst.
Alternatively, the reaction was performed in the same manner as in Example F1 except that the alkaline earth metal compound was used. The results are shown in Table 10 (Table 10) including Example F1.

[0103]

[Table 10]

Examples F9 to F16 N- (4-methylcyclohexylidene) -of Example F1
The reaction was performed in the same manner as in Example F1 except that the combination of 4-methylaniline and p-nitrotoluene was replaced with the combination of the N-cyclohexylideneamino compound and the hydrogen acceptor as shown in Table 11 (Table 11). went. The results are shown in Table 11 (Table 11).

[0105]

[Table 11]

Comparative Example F3 The reaction was performed in the same manner as in Example F9 except that N, N-dimethylformamide of Example F9 was not added. As a result, the imine conversion rate was 55.2%, and the yield of 4,2′-dimethyldiphenylamine was 42.3%.

Comparative Example F4 The reaction was performed in the same manner as in Example F9 except that 1N-NaOH and N, N-dimethylformamide of Example F9 were not used. As a result, the imine conversion rate was 17.0%, 4,
The yield of 2'-dimethyldiphenylamine was 12.5%.

Comparative Example F5 The reaction was performed in the same manner as in Example F11 except that N, N-dimethylformamide of Example F11 was not added. As a result, the imine conversion rate was 48.2% and the yield of 2,4′-dimethyldiphenylamine was 35.8%.

Comparative Example F6 The reaction was performed in the same manner as in Example F11 except that 1N-NaOH and N, N-dimethylformamide of Example F11 were not used. As a result, the imine conversion rate was 11.3%,
The yield of 2,4'-dimethyldiphenylamine is 3.5%
Met.

Example G1 A 100 ml round bottom flask equipped with a reflux condenser equipped with a separator, a thermometer, and a stirrer was manufactured by NE Chemcat and contained 5% Pd / C containing 50% water. 86
g, 1N-NaOH 0.24 g, N-cyclohexylideneaniline 17.33 g (0.1 mol), and nitrobenzene 8.29 g (0.067 mol) were charged. While stirring the inside of the reactor, the temperature was raised to 160 ° C.
The reaction was carried out for 3 hours while maintaining the temperature at 62 ° C. Water generated during this period and water in the catalyst were charged with benzene to cause azeotropy, and were condensed by a reflux condenser, and then separated by a separator. The amount of water was 2.7 g. 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 imine was 99.4% and the yield of diphenylamine was 86.7%.

Examples G2 to G10 and Comparative Example G1 Example G1 was carried out except that 0.24 g of 1N-NaOH of Example G1 was used and the type and / or amount of the cocatalyst was used as shown in Table 12 (Table 12). The reaction was carried out as in Example G1. The results are shown in Table 12 (Table 12) including Example G1.

[0112]

[Table 12]

Example H1 5% Pd / C containing 50% water by NE Chemcat in a 100 ml round bottom flask equipped with a reflux condenser equipped with a separator, a thermometer and a stirrer. 57
g, 1N-NaOH 0.30 g, N- (4-methylcyclohexylidene) -4-methylaniline 20.51
g (0.1 mol), and p-nitrotoluene 9.24
g (0.067 mol) were charged. The temperature in the reactor was raised to 160 ° C. with stirring, and the reaction was carried out for 3 hours while maintaining the temperature at 158 to 162 ° C. Water generated during this period and water in the catalyst were charged with benzene to cause azeotropy, and were condensed by a reflux condenser, and then separated by a separator. The amount of water is 3.0
It was g. 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 imine was 9
The yield of 8.2% and 4,4'-dimethyldiphenylamine was 85.5%.

Examples H2 to H6 Examples H2 to H6 were carried out except that 0.3 g of 1N-NaOH in Example H1 was used and the amount and / or type of cocatalyst was changed as shown in Table 13 (Table 13). The reaction was carried out as in H1. The results are shown in Table 13 (Table 13) including Example H1.

[0115]

[Table 13]

Examples H7 to H14 The reaction was performed in the same manner as in Example H1 except that the combination of the N-cyclohexylideneamino compound of Example H1 and the hydrogen acceptor was changed as shown in Table 14 (Table 14). went. The results are shown in Table 14 (Table 14).

[0117]

[Table 14]

Comparative Example H1 The reaction was performed in the same manner as in Example H1 except that 1N-NaOH was not added. As a result, the imine conversion rate was 79.9%,
The yield of 4,4′-dimethyldiphenylamine is 66.8.
%Met.

Comparative Example H2 The reaction was performed in the same manner as in Example H7 except that 1N-NaOH was not added. As a result, the conversion of imine was 61.3%,
The yield of 4,2′-dimethyldiphenylamine is 35.3.
%Met.

Comparative Example H3 The reaction was performed in the same manner as in Example H9 except that 1N-NaOH was not added. As a result, the imine conversion rate was 55.9%,
The yield of 2,4′-dimethyldiphenylamine is 34.1.
%Met.

Example I1 In a 200 ml round bottom flask equipped with a reflux condenser equipped with a separator, a thermometer, and a stirrer, 5.59 g of 5% Pd / C containing 50% water, manufactured by NE Chemcat. ,
25.68 g of diethylene glycol dimethyl ether,
Aniline 13.97 g (0.15 mol), cyclohexanone 29.44 g (0.3 mol) and nitrobenzene 2
Charge 4.87 g (0.2 mol). The temperature in the reactor was raised to 160 ° C. with stirring, and the reaction was carried out for 3 hours while maintaining the temperature at 158 to 162 ° C. Water generated during this period and water in the catalyst were charged with benzene to cause azeotropy, and were condensed by a reflux condenser, and then separated by a separator. The amount of water produced was 12.4 g. 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 100% and the yield of diphenylamine was 86.8%.

Examples I2 to I7 The reaction was performed in the same manner as in Example I1 except that various polar solvents shown in Table 15 (Table 15) were used instead of the diethylene glycol dimethyl ether of Example I1.
The results are shown in Table 15 (Table 15).

[0123]

[Table 15]

Comparative Example I1 The reaction was performed in the same manner as in Example I1 except that diethylene glycol dimethyl ether was not used. As a result, the conversion of cyclohexanone was 96.6% and the yield of diphenylamine was 76.3%.

Comparative Example I2 The reaction was carried out in the same manner as in Example I1 except that p-tert-butyltoluene was used as a solvent instead of diethylene glycol dimethyl ether in Example I1. As a result, the conversion of cyclohexanone was 91.1% and the yield of diphenylamine was 67.3%.

Example I8 Example I8 except that 32.39 g (0.39 mol) of cyclohexanone, 9.31 g (0.1 mol) of aniline and 24.62 g (0.2 mol) of nitrobenzene were used.
The reaction was carried out in the same manner as in 1. As a result, the yield of diphenylamine was 89.5%, and triphenylamine was 1.
8% and 2.9% of N-cyclohexylaniline were produced.

Example J1 In a 200 ml round bottom flask equipped with a reflux condenser equipped with a separator, a thermometer, and a stirrer, 72% of 5% Pd / C containing 50% water, manufactured by NE Chemcat Ltd. was added. ,
60.00 g of N, N-dimethylformamide, 16.07 g (0.15 mol) of p-toluidine, 33.65 g (0.3 mol) of 4-methylcyclohexanone and 27.43 g (0.2 mol) of p-nitrotoluene were added. Charged. While stirring the inside of the reactor, the temperature was raised to 140 ° C.
The reaction was carried out for 3 hours while maintaining the temperature at 42 ° C. Water generated during this period and water in the catalyst were charged with benzene to cause azeotropy, and were condensed by a reflux condenser, and then separated by a separator. The amount of water was 12.34 g. 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 rate of 4-methylcyclohexanone was 98.6.
%, The yield of ditolylamine was 91.6%.

Examples J2 to J7 Aside from the N, N-dimethylformamide of Example J1 being replaced by various polar solvents as shown in Table 16 (Table 16), and the reaction temperature being 160 ° C. Example J1
The reaction was performed in the same manner as in. The results are shown in Table 16 (Table 16).

[0129]

[Table 16]

Comparative Example J1 The reaction was performed in the same manner as in Example J1 except that N, N-dimethylformamide was not used. As a result, the conversion rate of 4-methylcyclohexanone was 51.6% and the yield of ditolylamine was 7.9%.

Comparative Example J2 The reaction was performed in the same manner as in Example J1 except that xylene was used as a solvent instead of N, N-dimethylformamide in Example J1. As a result, the conversion of p-methylcyclohexanone was 53.7% and the yield of ditolylamine was 9.37.
It was 0%.

Examples J8 to J13 Example J1 except that the raw materials shown in Table 17 (Table 17) were used instead of the combination of p-toluidine, 4-methylcyclohexanone and p-nitrotoluene of Example J1. The reaction was performed in the same manner as in. The results are shown in Table 17 (Table 17)
Shown in.

[0133]

[Table 17]

Example K1 A 200 ml round bottom flask equipped with a reflux condenser equipped with a separator, a thermometer, a dropping device, and a stirring device was manufactured by NE Chemcat Corporation and contained 5% Pd / C5. 5
9 g, diethylene glycol dimethyl ether 25.6
8 g and 13.97 g (0.15 mol) of aniline were charged, and 29.44 g (0.3
Mol) and nitrobenzene 24.87 g (0.2 mol)
The mixed solution of was prepared and stored. While stirring the inside of the reactor 1
The temperature is raised to 60 ° C. to remove the water content of the catalyst, and 158 to 162
The solution in the dropping device was added dropwise over 4 hours while maintaining the temperature at ℃. After the dropping is completed, 0.5 is maintained while maintaining this temperature range.
Stirring was continued for hours. The water produced during this time was azeotropically charged with benzene, condensed with a reflux condenser, and then separated with a separator. The amount of water produced was 12.6 g.
Then, the reaction solution was cooled to room temperature, and 5% P was added to the reaction mixture solution.
d / C was filtered off. When the filtrate was analyzed by gas chromatography, the conversion of cyclohexanone was 10
The yield of 0% and diphenylamine was 99.2%.

Examples K2 to K8 Reactions were carried out in the same manner as in Example K1 except that various polar solvents shown in Table 18 (Table 18) were used instead of the diethylene glycol dimethyl ether of Example K1.
The results are shown in Table 18 (Table 18).

[0136]

[Table 18]

Comparative Example K1 The reaction was performed in the same manner as in Example K1 except that p-tert-butyltoluene was used as a solvent instead of diethylene glycol dimethyl ether in Example K1. As a result, the conversion of cyclohexanone was 77.5% and the yield of diphenylamine was 48.5%.

Example L1 A 200 ml round-bottomed flask equipped with a reflux condenser equipped with a separator, a thermometer, a dropping device and a stirring device was manufactured by NE Chemcat Corporation and contained 5% Pd / C7. 7
2 g, N, N-dimethylformamide 60.00 g, p
Charging 16.07 g (0.15 mol) of toluidine,
33.65 g of 4-methylcyclohexanone in the dropping device
(0.3 mol) and p-nitrotoluene 27.43 g
A mixed solution of (0.2 mol) was prepared and stored. The temperature in the reactor was raised to 140 ° C. with stirring to remove the water content of the catalyst, and the solution in the dropping device was added dropwise over 6 hours while maintaining the temperature at 134 to 142 ° C. After completion of the dropping, stirring was continued for 1 hour while maintaining this temperature range. The water produced during this time was azeotropically charged with benzene, condensed with a reflux condenser, and then separated with a separator. The amount of water produced is 12.
It was 5 g. 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 rate of 4-methylcyclohexanone was 99.6% and the yield of ditolylamine was 97.7%.

Examples L2 to L7 The N, N-dimethylformamide of Example L1 was replaced with various polar solvents as shown in Table 19 (Table 19), and the reaction temperature was 160 ° C. , Example L1
The reaction was performed in the same manner as in. The results are shown in Table 19 (Table 19).

[0140]

[Table 19]

Examples L8 to L13 Instead of p-toluidine, 4-methylcyclohexanone and p-nitrotoluene of Example L1, Table 20 (Table 2)
Example L1 except that the raw materials as shown in 0) were used.
The reaction was performed in the same manner as in. The results are shown in Table 20 (Table 20).

[0142]

[Table 20]

Example M1 In a 200 ml round bottom flask equipped with a reflux condenser equipped with a separator, a thermometer and a stirrer, NE Chemcat Co., Ltd. containing 5% Pd / C of 7.72 g and 1N.
-NaOH 0.91 g (Na content 10.8 wet% / P
d), N, N-dimethylformamide 60.00 g, p
-Toluidine 16.07 g (0.15 mol), 4-methylcyclohexanone 33.65 g (0.3 mol) and p
27.43 g (0.2 mol) of nitrotoluene were charged. While stirring the inside of the reactor, the temperature was raised to 140 ° C, and 13
The reaction was carried out for 3 hours while maintaining the temperature at 8 to 142 ° C. Water generated during this period and water in the catalyst were charged with benzene to cause azeotropy, and were condensed by a reflux condenser, and then separated by a separator. The amount of water was 15.22 g. 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 4-methylcyclohexanone was 99.8.
%, And the yield of ditolylamine was 94.2%.

Example M2 A 300 ml round-bottomed flask equipped with a reflux condenser equipped with a separator, a thermometer, a dropping device and a stirrer was manufactured by NE Chemcat Corporation and contained 5% Pd / C4. 6
6 g, 1 N-NaOH 1.21 g, butyric acid 0.33 g, diethylene glycol dimethyl ether 42.80 g, aniline 23.28 g (0.25 mol) were charged, and cyclohexanone 49.07 g (0.5 mol) and nitrobenzene were added to the dropping apparatus. A mixed solution of 41.45 g (0.33 mol) was prepared and stored. 160 ° C with stirring in the reactor
Up to 158-162 to remove water in the co-catalyst
The solution in the dropping device was added dropwise over 4 hours while maintaining the temperature at ℃. After the dropping is completed, 0.5 is maintained while maintaining this temperature range.
Stirring was continued for hours. The water produced during this time was azeotropically charged with benzene, condensed with a reflux condenser, and then separated with a separator. The amount of water produced was 21.0 g.
Then, the reaction solution was cooled to room temperature, and 5% P was added to the reaction mixture solution.
d / C was filtered off. When the filtrate was analyzed by gas chromatography, the conversion of cyclohexanone was 10
The yield of 0% and diphenylamine was 99.9%.
Subsequently, using the above-mentioned recovered catalyst, as shown in Table 21 (Table 21), 5% Pd / C containing 50% water, NaOH and butyric acid were added, and the same reaction was carried out. As a result, the average additional amount of new catalyst of 5% Pd / C required to maintain the reaction rate and selectivity was about 3% of the initial usage amount.

[0145]

[Table 21]

Example M3 A 300 ml round-bottomed flask equipped with a reflux condenser equipped with a separator, a thermometer, a dropping device, and a stirring device was manufactured by NE Chemcat Corporation and contained 5% Pd / C4. 6
6 g, diethylene glycol dimethyl ether 42.8
0 g and aniline 23.28 g (0.25 mol) were charged, and cyclohexanone 49.07 g (0.5
Mol) and 41.45 g (0.33 mol) of nitrobenzene were prepared and stored. The temperature in the reactor was raised to 160 ° C. with stirring to remove the water content in the co-catalyst.
The solution in the dropping device was added dropwise over 4 hours while maintaining the temperature at 8 to 162 ° C. After completion of the dropping, stirring was continued for 0.5 hour while maintaining this temperature range. The water produced during this time was azeotropically charged with benzene, condensed with a reflux condenser, and then separated with a separator. The amount of water produced is 21.0g
Met. 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 100% and the yield of diphenylamine was 99.2%.
Met. Subsequently, using the above-mentioned recovered catalyst, 5% Pd / C was added as shown in Table 22 (Table 22), and the same reaction was carried out. As a result, the average amount of additional new catalyst of 5% Pd / C required to maintain the reaction rate and selectivity was about 15% of the initial amount used.

[0147]

[Table 22]

Example N1 A 200 ml round-bottomed flask equipped with a reflux condenser equipped with a separator, a thermometer, a dropping device and a stirring device was manufactured by NE Chemcat Corporation and contained 5% Pd / C7. 7
2g, 1N-NaOH 0.91g, butyric acid 0.55g,
60.00 g of N, N-dimethylformamide and 16.07 g (0.15 mol) of toluidine were charged, and 33.65 g (0.3 mol) of 4-methylcyclohexanone and 27.43 g (0 A mixed solution of 0.2 mol) was prepared and stored. While stirring the inside of the reactor, the temperature was raised to 140 ° C. to remove water in the catalyst.
The solution in the dropping apparatus was added dropwise over 6 hours while maintaining the temperature at 142 ° C. After completion of the dropping, stirring was continued for 1 hour while maintaining this temperature range. The water produced during this time was azeotropically charged with benzene, condensed with a reflux condenser, and then separated with a separator. The amount of water produced was 12.6 g. Then, the reaction solution was cooled to room temperature, and the reaction mixture was cooled to 5
% Pd / C was filtered off. When the filtrate was analyzed by gas chromatography, the conversion rate of 4-methylcyclohexanone was 99.8% and the yield of ditolylamine was 98.
It was 8%. Then, using the above-mentioned recovered catalyst,
As shown in the table (Table 23), 50% water content 5% Pd /
C, NaOH and butyric acid were added, and the same reaction was performed. As a result, the average additional amount of new catalyst required to maintain the reaction rate and selectivity was about 6.0% of the initial usage fee.

[0149]

[Table 23]

Example N2 A 200 ml round-bottomed flask equipped with a reflux condenser equipped with a separator, a thermometer, a dropping device, and a stirring device was manufactured by NE Chemcat Corporation and contained 5% Pd / C7. 7
2 g, N, N-dimethylformamide 60.00 g, and toluidine 16.07 g (0.15 mol) were charged, and 4-methylcyclohexanone 33.65 g (0.
3 mol) and 27.43 g of p-nitrotoluene (0.2
Mol) mixed solution was prepared and stored. The temperature in the reactor was raised to 140 ° C. with stirring to remove water in the catalyst,
The solution in the dropping apparatus was added dropwise over 6 hours while maintaining the temperature at 142 ° C. After completion of the dropping, stirring was continued for 1 hour while maintaining this temperature range. The water produced during this time was azeotropically charged with benzene, condensed with a reflux condenser, and then separated with a separator. The amount of water produced was 12.5 g. Then, the reaction solution was cooled to room temperature, and the reaction mixture was cooled to 5
% Pd / C was filtered off. When the filtrate was analyzed by gas chromatography, the conversion of 4-methylcyclohexanone was 99.6% and the yield of ditolylamine was 98.
It was 7%. Then, using the above-mentioned recovered catalyst,
As shown in the table (Table 24), the average additional amount of the new catalyst was added by about 8.3% of the initial usage fee, and the same reaction was performed to obtain the results in the same table.

[0151]

[Table 24]

[00152]

According to the present invention, under extremely mild conditions,
In addition, an aromatic secondary amino compound can be obtained in good yield.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location C07C 215/76 217/92 // C07B 61/00 300 (31) Priority claim number Japanese Patent Application No. 4 -265898 (32) Priority Day 4 (1992) October 5 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-282940 (32) Priority Day 4 (1992) October 21 (33) Priority claiming country Japan (JP) (31) Priority claiming number Japanese Patent Application No. 4-290133 (32) Priority date 4 (1992) October 28 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. Hei 4-291311 (32) Priority Day Hei 4 (1992) October 29 (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese Patent Application Hei 4-297096 (32) Priority date Hei 4 (1992) November 6 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-119975 (32) The other day Hei 5 (1993) May 21 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-121423 (32) Priority Day Hei 5 (1993) May 24 (33) ) Japan claiming priority (JP) (31) Claim number of priority Japanese Patent Application No. 5-124062 (32) Priority date 5 (1993) May 26 (33) Country claiming priority Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-126826 (32) Priority date 5 (1993) May 28 (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-126827 (32) ) Priority date 5 (1993) May 28 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 5-133273 (32) Priority date 5 (1993) June 3 (33) Japan (JP), a country claiming priority Priority Kenichi Sato 30 Mitsui Toatsu Chemical Co., Ltd. 30 Asamuta-cho, Omuta-shi, Fukuoka

Claims (10)

[Claims] 1. General formula (1) (Chemical formula 1) (In the formula, R represents a hydrogen atom, an alkyl group, an alkoxy group, an amino group, a hydroxyl group, and fluorine, and n is an integer of 0 to 5. R'is an alkyl group, a phenyl group, a benzyl group, a naphthyl group, Furyl group, furfuryl group, cyclohexyl group, alkyl group, alkoxy group, phenyl group, phenoxy group, cyclohexyl group, substituted amino group,
It may be substituted with a carboxyl group, a hydroxyl group, or fluorine. ) In the dehydrogenation reaction of the N-cyclohexylidene amino compound represented by the formula (1) in the presence of a hydrogen transfer catalyst and a hydrogen acceptor, a non-sulfur-containing polar solvent is used. 2) [Chemical 2] (In the formula, R, R ′, and n are the same as above.) A method for producing an aromatic secondary amino compound. 2. The method according to claim 1, wherein the N-cyclohexylideneamino compound and the hydrogen acceptor are simultaneously added dropwise to a non-sulfur-containing polar solvent in which a hydrogen transfer catalyst is dispersed to carry out the dehydrogenation reaction. 3. The method according to claim 1, wherein an alkali metal and / or alkaline earth metal compound is added as a cocatalyst and a dehydrogenation reaction is carried out. 4. The dehydrogenation reaction according to claim 3, wherein the cocatalyst is added to the non-sulfur-containing polar solvent together with the hydrogen transfer catalyst, and the N-cyclohexylideneamino compound and the hydrogen acceptor are simultaneously added dropwise to this mixture. Method. 5. General formula (1) (Chemical Formula 3) (In the formula, R represents a hydrogen atom, an alkyl group, an alkoxy group, an amino group, a hydroxyl group, and fluorine, and n is an integer of 0 to 5. R'is an alkyl group, a phenyl group, a benzyl group, a naphthyl group, Furyl group, furfuryl group, cyclohexyl group, alkyl group, alkoxy group, phenyl group, phenoxy group, cyclohexyl group, substituted amino group,
It may be substituted with a carboxyl group, a hydroxyl group, or fluorine. When an N-cyclohexylidene amino compound represented by the formula (4) is subjected to a dehydrogenation reaction in the presence of a hydrogen transfer catalyst and a hydrogen acceptor, an alkali metal and / or alkaline earth metal compound is added as a cocatalyst. General formula (2) (Formula 4) (In the formula, R, R ', and n are the same as the above.) The manufacturing method of the aromatic secondary amino compound. 6. The formula (3) in the presence of a hydrogen transfer catalyst.
(Chemical formula 5) [Chemical formula 5] (In the formula, R represents a hydrogen atom, an alkyl group, an alkoxy group, an amino group, a hydroxyl group, and fluorine, respectively, and n is an integer of 0 to 5.) A cyclohexanone or a cyclohexanone nucleus-substituted compound represented by the general formula ( 4) (Chemical formula 6) (In the formula, R'is an alkyl group, a phenyl group, a benzyl group,
It represents a naphthyl group, a furyl group, a furfuryl group or a cyclohexyl group, and may be substituted with an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, a cyclohexyl group, a substituted amino group, a carboxyl group, a hydroxyl group or fluorine. )
And a general formula (5) (Chemical Formula 7) corresponding to the above amines as a hydrogen acceptor. (In the formula, R'is an alkyl group, a phenyl group, a benzyl group,
It represents a naphthyl group, a furyl group, a furfuryl group or a cyclohexyl group, and may be substituted with an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, a cyclohexyl group, a substituted amino group, a carboxyl group, a hydroxyl group or fluorine. )
The reaction is carried out in a non-sulfur-containing polar solvent using a nitro compound represented by the general formula (2) (Chemical Formula 8) (In the formula, R, R ′, and n are the same as above.) A method for producing an aromatic secondary amino compound. 7. The method for producing an aromatic secondary amino compound according to claim 6, wherein the cyclohexanone or the substituted cyclohexanone nucleus and the nitro compound are reacted while being dropped into a non-sulfur-containing polar solvent in which a hydrogen transfer catalyst is dispersed. 8. The method for producing an aromatic secondary amino compound according to claim 6, wherein an alkali metal and / or alkaline earth metal compound is added as a cocatalyst and reacted. 9. The aromatic secondary amino acid according to claim 8, wherein the cocatalyst is added to a non-sulfur-containing polar solvent together with a hydrogen transfer catalyst, and cyclohexanone or a cyclohexanone nucleus-substituted product and a nitro compound are added dropwise to the mixture. Method for producing compound. 10. The aromatic secondary amino compound according to claim 8 or 9, wherein an organic acid having a logarithmic value (pKa) of 3.5 to 6.0 of the reciprocal of the acid dissociation constant is further added to the non-sulfur-containing polar solvent. Manufacturing method.