Method for preparing aromatic secondary amino compound

BACKGROUND OF THE INVENTION
(a) Field of the Invention
The present invention relates to an improved method for preparing an aromatic secondary amino compound. The present invention also relates to an improved method for the preparation of aminodiphenylamine.
The aromatic secondary amino compound obtained by the method of the present invention is an extremely important industrial chemical such as a raw material for rubber chemicals, dyes and the like.
(b) Description of the Prior Art
As methods for preparing an aromatic secondary amino compound, there are known a method in which the reaction of toluidine is carried out in a liquid phase at 300.degree. to 400.degree. C. in the presence of a suitable self-condensation type reaction catalyst (BF.sub.3, FeCl.sub.2, a salt of an ammonium halogenide, or a mineral acid), and a method in which cresol is reacted with toluidine at 330.degree. to 340.degree. C. under pressure in the presence of triphenyl phosphate.
Other methods for preparing the aromatic secondary amino compound are also known which comprise the dehydrogenation reaction of an N-cyclohexylideneamino compound. For example, there are a method for obtaining N-cyclohexylidene-N'-isopropylphenylenediamine at a temperature of 350.degree. C. or less in the presence of a dehydrogenation catalyst (British Patent No. 989257); a method in which reaction is carried out in a gaseous phase, while oxygen or an oxygen-containing gas is fed at 300.degree. to 450.degree. C. in the presence of an oxidizing catalyst such as silica or alumina (Japanese Patent Application Laid-open No. 49924/1974); a method for obtaining 4-methyldiphenylamine by reaction at 300.degree. to 500.degree. C. in the presence of a dehydrogenation catalyst selected from the group consisting of nickel, platinum, palladium and copper-chromium alloy (Japanese Patent Application Laid-open No. 49925/1974); and a method for preparing an amino compound by the use of a specific nickel/chromium catalyst (Japanese Patent Publication No. 4623/1982).
Still other methods are already known in which a nitro compound is used as a hydrogen acceptor in the presence of a hydrogen moving catalyst to produce an amine in the system, and a nucleus-substituted cyclohexanone is simultaneously reacted with the amine to prepare an aromatic secondary amino compound. For example, there are a method for obtaining p-ethoxydiphenylamine by reacting p-nitrophenetole with a large excess of cyclohexanone in the presence of a palladium catalyst (British Patent No. 975097); a method or obtaining 2,6-dimethyldiphenylamine by reacting 1/3 mol of 2,6-dimethylaniline, 2/3 mol of 2,6-dimethylnitrobenzene, and cyclohexanone in the presence of a palladium catalyst, the amount of cyclohexanone being 10% in excess of the total of 2,6-dimethylaniline and 2,6-dimethylnitrobenzene (British Patent No. 989257); and a method for preparing a diphenylamine derivative by reacting 2-(alkyl or alkoxy)-4-alkoxynitrobenzene, 2-(alkyl or alkoxy)-4-alkoxyaniline and cyclohexanone in the presence of a palladium catalyst (Japanese Patent Application Laid-open No. 117214/1993).
However, these conventional methods have drawbacks of (1) severe reaction conditions, (2) a low reaction rate, and (3) a low yield. For these reasons, they are not industrially satisfactory manufacturing methods.
Known preparation processes of 4-aminodiphenyl-amine include rearrangement and reduction of N-nitroso-diphenylamine obtained by nitrosation of p-phenylenediamine (P. B. Reports 77764, 27-32) and condensation of formanilide or acetanilide with a halonitrobenzene, followed by reduction of the nitro group [Journal of Organic Chemistry, 42(10), 1786-90]. Known preparation processes of 2-aminodiphenylamine include rearrangement of an azo compound [Journal of Organic Chemistry, 295(1), 91-7, 1985]. Further, known preparation processes of 3-aminodiphenylamine include reduction of 3-nitrodiphenylamine. They are however hardly considered as industrially advantageous processes, because they require a complex reaction step, a large amount of a special reagent and/or solvent, and/or a precise purification step.
It is also known, as in the further aspect of the present invention, to prepare aminodiphenylamine by reacting cyclohexanone and phenylenediamine in the presence of a hydrogen transfer catalyst and a hydrogen receptor. Pursuant to this process, aminodiphenylamine has been obtained by reacting cyclohexanone and phenylenediamine in the presence of a palladium catalyst while using .alpha.-methylstyrene as a hydrogen receptor (Japanese Patent Laid-Open No. 58648/1982). In this process, however, except for its use as a hydrogen receptor, .alpha.-methylstyrene cannot effectively be used for the reaction, in contrast with the hydrogen receptor in this further aspect of the present invention, and phenylenediamine as a raw material has to be supplied in its entirety into the reaction system in the form of phenylenediamine. The reaction has to be conducted at elevated temperature and pressure. This process is therefore hardly considered to be satisfactory as an industrial process.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an industrially improved method for preparing an aromatic secondary amino compound from an N-cyclohexylidene amino compound or cyclohexanone (inclusive of a nucleus-substituted compound), and according to this method, the above-mentioned problems can be solved.
As a result of various investigations, it has been found that the aromatic secondary amino compound can be obtained under extremely moderate conditions in a high yield by (1) using a sulfur-tree polar solvent and/or a cocatalyst at the time of the dehydrogenation reaction of an N-cyclohexylideneamino compound in the presence of a hydrogen moving catalyst and a hydrogen acceptor, or (2) reacting cyclohexanone or a nucleus-substituted cyclohexanone with an amine in a sulfur-free polar solvent in the presence of a hydrogen moving catalyst by the use of a nitro compound corresponding to the amine as a hydrogen acceptor, or adding a specific cocatalyst to this system and then reacting the same. In consequence, one aspect of the present invention has been attained.
In accordance with a further object, it has been found that upon reaction of phenylenediamine and cyclohexanone in the presence of a hydrogen transfer catalyst in a sulfur-free polar solvent, use of nitroaniline as a hydrogen receptor makes it possible to obtain aminodiphenylamine in a high yield under extremely mild conditions and further to use as a raw material phenylenediamine formed from nitroaniline in the reaction system, leading to the present invention.
Therefore, in a further aspect of the present invention, there is thus provided a method for the preparation of aminodiphenylamine, which comprises reacting phenylenediamine and cyclohexanone in the presence of a hydrogen transfer catalyst in a sulfur-free polar solvent while using nitroaniline as a hydrogen acceptor.
According to the method of the further aspect of the present invention, aminodiphenylamine can be obtained in a high yield under extremely mild conditions. Additionally, phenylenediamine formed from nitroaniline can be used as a raw material in the reaction system and at the same time, any surplus portion of phenylenediamine can be reused together with the catalyst.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The first aspect of the present invention is directed to a method for preparing an aromatic secondary amino compound represented by the formula (2) ##STR1## wherein each R is a hydrogen atom, alkyl group, alkoxy group, amino group, hydroxyl group or fluorine; n is an integer of from 0 to 5; and R' is an alkyl group, phenyl group, benzyl group, naphthyl group, furyl group, furfuryl group or cyclohexyl group, and R' may be substituted by an alkyl group, alkoxy group, phenyl group, phenoxy group, cyclohexyl group, amino group, substituted amino group, carboxyl group, hydroxyl group or fluorine which comprises the step of subjecting, to a dehydrogenation reaction, an N-cyclohexylideneamino compound represented by the formula (1) ##STR2## wherein R, R' and n are defined above in the presence of a hydrogen moving catalyst and a hydrogen acceptor, said method being characterized in that a sulfur-free polar solvent is used at the time of the dehydrogenation reaction.
The N-cyclohexylideneamino compound which is used as a starting material can be easily synthesized from an amine (or its derivative having an amino group with a substituent) and cyclohexanone or its derivative in accordance with a known process.
Examples of the alkyl group represented by R in the formula (1) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, phenylmethyl, amino-methyl, hydroxymethyl and fluoromethyl, and above all, methyl and ethyl are preferable.
Examples of the alkoxy group include methoxy, ethoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, hexadecyloxy, aminomethoxy and fluoromethoxy, and above all, methyloxy, ethyloxy are preferable.
Examples of the amino group 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 formula (1) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, aminomethyl, aminoethyl, aminopropyl, 2-aminopropyl, 3-aminopropyl, aminobutyl and hydoxyethyl.
Examples of the phenyl group include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, p-ethyl-phenyl, p-propylphenyl, p-isopropylphenyl, p-butylphenyl, p-tert-butylphenyl, p-pentylphenyl, p-hexylphenyl, p-heptylphenyl, p-octylphenyl, p-nonylphenyl, p-decyl-phenyl, 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-trioxyphenyl, p-acetylphenyl, p-benzoylphenyl, p-aminophenyl, m-aminophenyl, p-methylaminophenyl, p-ethylaminophenyl, p-butylaminophenyl, p-tert-butyl-aminophenyl, p-octylaminophenyl, p-dodecylaminophenyl, p-cyclohexylphenyl, p-methylcyclohexylphenyl, p-ethyl-cyclohexylphenyl, p-propylcyclohexylphenyl, p-hydroxy-phenyl, p-carboxyphenyl and p-fluorophenyl, and phenyl and p-methylphenyl are preferable.
Examples of the benzyl group include benzyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, p-ethylbenzyl, p-propylbenzyl, p-isopropylbenzyl, p-butylbenzyl, p-tert-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-methylaminobenzyl, p-ethylaminobenzyl, p-butylaminobenzyl, p-tert-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 include 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.
The preferred compounds of formula (1) are as follows:
1. N-(cyclohexylidene)methylamine
2. 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)-2-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-hdyroxycyclohexylidene)-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-hydroxyaniline
64. N-(4-methyloxycyclohexylidene)-4-hydroxyaniline
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-fluorocyclohexyliene)benzylamine
75. N-(4-hydroxycyclohexylidene)benzylamine
76. N-(cyclohexylidene)cyclohexyl
77. N-(2-methylcyclohexylidene)cyclohexyl
78. N-(3-methylcyclohexylidene)cyclohexyl
79. N-(4-methylcyclohexylidene)cyclohexyl
80. N-(4-ethylcyclohexylidene)cyclohexyl
81. N-(2,6-dimethylcyclohexylidene)cyclohexyl
82. N-(4-methyloxycyclohexylidene)cyclohexyl
83. N-(4-fluorocyclohexylidene)cyclohexyl
84. N-(4-hydroxycyclohexylidene)cyclohexyl
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-fluroaniline
90. N-(2,6-dimethylcyclohexylidene)-4-fluroaniline
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-dimethylcylohexylidene)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-methylcyclohexlidene)-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
119. N-(cyclohexylidene)-2-aminoaniline
120. N-(cyclohexylidene)-3-aminoaniline
121. N-(cyclohexylidene)-4-aminoaniline
As the hydrogen moving catalyst, there can be used any known hydrogen moving catalyst. Typical examples of the hydrogen moving catalyst include Raney nickel, reduced nickel and nickel supporting catalysts obtained by supporting nickel on various carriers such as diatomaceous earth, alumina, pumice, silica gel and acidic terra abla; cobalt catalysts such as Raney cobalt, reduced cobalt, cobalt and cobalt-carrier catalysts; copper catalysts such as Raney copper, reduced copper and copper-carrier catalysts; palladium catalysts such as palladium black, palladium oxide, colloidal palladium, palladium-carbon, palladium-barium sulfate and palladium-barium carbonate; platinum catalysts such as platinum black, colloidal platinum, platinum sponge, platinum oxide, platinum sulfide, platinum-carbon and platinum-carrier catalysts; rhodium catalysts such as colloidal rhodium, rhodium-carbon and rhodium oxide; a platinum group catalyst such as a ruthenium catalyst; rhenium catalysts such as dirhenium heptaoxide and rhenium-carbon; a copper chromium oxide catalyst; a molybdenum oxide catalyst; a vanadium oxide catalyst; and a tungsten oxide catalyst. Among these catalysts, the palladium catalyst is preferable. In particular, the palladium-carrier catalyst is preferable. Above all, the palladium-carbon and palladium-alumina are most preferable.
The amount of the hydrogen moving catalyst is usually in the range of from 0.001 to 1.0 gram atom, preferably from 0.002 to 0.2 gram atom in terms of a metallic atom per gram molecule of the N-cyclohexylideneamino compound.
In the first aspect of the present invention, any of various reducing materials is used as a hydrogen acceptor. Examples of the hydrogen acceptor include olefin compounds such as 1-octene, allylbenzene and crotonic acid; nitro compounds such as 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-aminonitrobenzene, nitrobenzene, p-dinitrobenzene, m-dinitrobenzene, 4-nitrodiphenylether, p-phenoxynitrobenzene, p-cyclohexylnitrobenzene, p-benzylnitrobenzene, nitromethane, 2-nitropropane, 1-nitronaphthalene, 2-, 3- and 4-nitrotoluenes, 4-nitroanisole, p-propylnitrobenzene, m-ethylnitrobenzene, 4-nitrobenzonitrile, p-nitroacetoanilide, 4-nitrobenzoic acid and nitrocyclohexane; phenols, for example, alkylphenols such as phenol, methylphenol, ethylphenol, isopropylphenol, butylphenol, 2,4-dimethylphenol, 2,4,6-trimethylphenol and 2,6-di-tert-butyl-4-methylphenol as well as alkoxyphenols such as 3-methoxyphenol and 4-methoxyphenol.
However, in the case that the phenol is selected, it must be used in large quantities and there is the tendency that the amounts of by-products increase. It is particularly preferable to use nitrobenzene in the above-mentioned nitro compounds as the hydrogen acceptor, because nitrobenzene can be utilized as the material of N-cyclohexylideneaniline.
The amount of the hydrogen acceptor to be used depends upon its kind, but it is 5 equivalents of the hydrogen acceptor to the N-cyclohexylideneamino compound. Particularly in the case of the olefin or the nitro compound, the amount of the hydrogen acceptor is an equivalent or 50% excess of the N-cyclohexylideneamino compound. When the hydrogen acceptor is short, the by-product of N-cyclohexylamine tends to increase. As the hydrogen acceptor, the olefin or the nitro compound is preferable from the viewpoint of the volume efficiency of a reactor.
Examples of the sulfur-free polar solvent to be used include N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, methyl isobutyl ketone, tetrahydrofuran, dioxane, 1,3-dimethylimidazolizinone, glymes such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, methyl salicylate, phenol and phenols, for example, alkylphenols such as methylphenol and 2,4,6-trimethylphenol as well as alkoxyphenols such as 3-methoxyphenol and 4-methoxyphenol. If necessary, they may be used in combinations of two or more thereof. Dimethyl sulfoxide and sulfolane are similarly within the category of the polar solvents, but they are not used because they contain sulfur which is poisonous to the dehydrogenation catalyst.
The amount of the sulfur-free polar solvent to be used is preferably 0.05-3.0 times by weight, more preferably 0.15-1.5 times by weight as much as that of the N-cyclohexylideneamino compound.
In placing the starting materials in a reactor, it is a preferable manner that the solvent and the catalyst are previously placed in the reactor and mixed, and the N-cyclohexylideneamino compound and the hydrogen acceptor are then simultaneously dropped into the reactor to carry out the above-mentioned reaction. Needless to say, alternatively, the N-cyclohexylideneamino compound and the hydrogen acceptor may be first mixed and then added into the reaction.
In the above-mentioned dehydrogenation reaction of the N-cyclohexylideneamino compound in the presence of the hydrogen moving catalyst and the hydrogen acceptor, an alkali metal compound and/or an alkaline earth metal compound can be added as a cocatalyst to the reaction system irrespective of the presence of the sulfur-free polar solvent. This is also one embodiment of the first aspect of the present invention.
Usable examples of the alkali metal compound and/or the alkaline earth metal compound which can be added as the cocatalyst are hydroxides, carbonates, bicarbonates and the like of alkali metals and alkaline earth metals. Typical examples of these compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate and sodium hydrogen carbonate. Above all, sodium hydroxide and potassium hydroxide are preferable. These cocatalysts may be used singly or in combination of two or more thereof. The cocatalyst does not have to be added to the reaction system separately from the above-mentioned dehydrogenation catalyst. For example, after a noble metal supporting catalyst has been prepared, a salt, a hydroxide or the like of an alkali metal and/or an alkaline earth metal may be additionally supported as the alkali metal component and/or the alkaline earth metal component on the noble metal supporting catalyst, and the thus formed catalyst may be used.
The amount of the cocatalyst is preferably in the range of from 2 to 30% by weight, more preferably from 5 to 20% by weight, in terms of the alkali metal and/or the alkaline earth metal, based on the weight of the catalyst metal. If the amount of the cocatalyst is in excess of this range, a reaction rate tends to deteriorate, and conversely if it is less than the range, the yield is low.
It is advantageous that the reaction is carried out under the removal of water, and thus a technique is suitable in which water is removed from the reaction mixture while azeotropic distillation is done by the use of a solvent such as benzene, toluene or xylene.
The temperature of the reaction is usually in the range of from 120.degree. to 250.degree. C., preferably from 140.degree. to 200.degree. C.
The mixture obtained by the above-mentioned method is treated in an ordinary manner such as distillation, crystallization or extraction. For example, the solution in which the reaction has already been brought to an end is filtered to separate the catalyst therefrom. The thus recovered catalyst can be reused. The resultant filtrate is concentrated to recover the solvent. The produced aromatic secondary amino compound in the reactor can be directly used without any treatment, but if necessary, it may be purified by distillation, crystallization or the like.
The second aspect of the present invention is directed to a method for preparing an aromatic secondary amino compound represented by the formula (2) ##STR3## wherein each R is a hydrogen atom, alkyl group, alkoxy group, amino group, hydroxyl group or fluorine; R' is an alkyl group, phenyl group, benzyl group, naphthyl group, furyl group, furfuryl group or cyclohexyl group, and R' may be substituted by an alkyl group, alkoxy group, phenyl group, phenoxy group, cyclohexyl group, amino group, substituted amino group, carboxyl group, hydroxyl group or fluorine; and n is an integer of from 0 to 5 which comprises the step of reacting cyclohexanone or a nucleus-substituted cyclohexanone represented by the formula (3) ##STR4## wherein R is defined above, an amine represented by the formula (4)
R'--NH.sub.2 ( 4)
wherein R' is defined above, and a nitro compound corresponding to the amine and represented by the formula (5)
R'--NO.sub.2 ( 5)
wherein R' is defined above as a hydrogen acceptor in a sulfur-free polar solvent in the presence of a hydrogen moving catalyst.
That is, the second aspect of the present invention is directed to a method for preparing an aromatic secondary amino compound which is characterized by comprising the step of reacting cyclohexanone or a nucleus-substituted cyclohexanone, an amine and a nitro compound as a hydrogen acceptor corresponding to the amine in a sulfur-free polar solvent in the presence of a hydrogen moving catalyst.
Examples of the alkyl group represented by R' in the formulae (4) and (5) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, aminomethyl, aminoethyl, aminopropyl, 2-aminopropyl, 3-aminopropyl, aminobutyl and hydoxyethyl.
Examples of the phenyl group include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, p-ethyl-phenyl, p-propylphenyl, p-isopropylphenyl, p-butylphenyl, p-tert-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-trimethyl-phenyl, p-methoxyphenyl, p-ethoxyphenyl, p-butoxyphenyl, p-pentyloxyphenyl, p-hexyloxyphenyl, p-heptyloxyphenyl, p-octyloxyphenyl, p-nonyloxyphenyl, p-phenyloxyphenyl, p-trioxyphenyl, p-acetylphenyl, p-benzoylphenyl, o-aminophenyl, m-aminophenyl, p-aminophenyl, 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, and phenyl and p-methylphenyl are preferable.
Examples of the benzyl group include benzyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, p-ethylbenzyl, p-propylbenzyl, p-isopropylbenzyl, p-butylbenzyl, p-tert-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-methylaminobenzyl, p-ethylaminobenzyl, p-butylamino-benzyl, p-tert-butylaminobenzyl, p-octylaminobenzyl, p-dodecylaminobenzyl, p-cyclohexylbenzyl, p-methylcyclo-hexylbenzyl, p-ethylcyclohexylbenzyl, p-propylcyclohexyl-benzyl, p-hydroxybenzyl, p-carboxybenzyl and p-fluorobenzyl.
Examples of the cyclohexyl group include 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.
The preferred compounds of formula (3) are as follows:
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
The preferred compounds of formula (4) are as follows:
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-aminoacetoanilide
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-methoxybenzylanline
25. cyclohexylamine
26. 4-methylcyclohexylamine
27. 4-methyloxycycloamine
28. 2-naphthylamine
29. furfurylamine
30. 4-fluoroaniline
31. 4-aminodiphenylether
32. orthophenylenediamine
33. metaphenylenediamine
34. paraphenylenediamine
The preferred compounds of formula (5) are as follows:
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-trimethylnitrobezene
12. 4-methyoxynitrobenzene
13. 2-methyl-4-methoxynitrobenzene
14. 4-acetylnitrobezene
15. 4-nitroacetoanilide
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. nitrocyclohexanone
26. 4-methylnitrocyclohexanone
27. 4-methoxynitrocyclohexanone
28. 2-nitronaphthalene
29. nitrofurfuryl
30. 4-fluoronitrobenzene
31. 4-nitrodiphenylether
32. orthonitroaniline
33. metanitroaniline
34. paranitroaniline
In the present invention, a molar ratio of the cyclohexanone or the nucleus-substituted cyclohexanone represented by the formula (3): the amine represented by the formula (4): the nitro compound represented by the formula (5) is usually 3:1:2, and this ratio can be suitably altered on the basis of the given values. The nitro compound behaves as the hydrogen acceptor to produce the amine in the reaction system, and this amine causes a condensation reaction with the cyclohexanone or the nucleus-substituted cyclohexanone which is another starting material, to produce a Schiff base. Afterward, the Schiff base is subjected to dehydrogenation, thereby producing an aromatic secondary amino compound. In the dehydrogenation of the Schiff base, hydrogen is generated, and 2/3 mol of the nitro compound per mol of the Schiff base can be converted into the amine by the thus generated hydrogen.
Therefore, in order to completely effectively utilize the hydrogen generated in the system, it is necessary to react the cyclohexanone or the nucleus-substituted cyclohexanone and the nitro compound in a molar ratio of 3:2. In this case, however, the excessive amount of the cyclohexanone or the nucleus-substituted cyclohexanone further reacts with the aromatic secondary amino compound produced in the system, so that an aromatic tertiary amino compound tends to be produced as a by-product. Conversely, if the amount of the nitro compound is excessive, the reaction rate tends to deteriorate inconveniently. For the purpose of avoiding these drawbacks, it is preferable that a molar ratio of the cyclohexanone or the nucleus-substituted cyclohexanone: the amine compound: the nitro compound is 3:1:2, and more preferably, a molar ratio of the sum of the nitro compound and the amine compound to the cyclohexanone or the nucleus-substituted cyclohexanone is in the range of from 0.9 to 1.2.
As the hydrogen moving catalyst which can be used in the method of the present invention, there can be used any known hydrogen moving catalyst. Typical examples of the hydrogen moving catalyst include Raney nickel, reduced nickel and nickel supporting catalysts obtained by supporting nickel on various carriers such as diatomaceous earth, alumina, pumice, silica gel and acidic terra abla; cobalt catalysts such as Raney cobalt, reduced cobalt, cobalt and cobalt-carrier catalysts; copper catalysts such as Raney copper, reduced copper and copper-carrier catalysts; palladium catalysts such as palladium black, palladium oxide, colloidal palladium, palladium-carbon, palladium-barium sulfate and palladium-barium carbonate; platinum catalysts such as platinum black, colloidal platinum, platinum sponge, platinum oxide, platinum sulfide, and platinum-carrier catalysts such as platinum-carbon; rhodium catalysts such as colloidal rhodium, rhodium-carbon and rhodium oxide; a platinum group catalyst such as a ruthenium catalyst; rhenium catalysts such as dirhenium heptaoxide and rhenium-carbon; a copper chromium oxide catalyst; a molybdenum oxide catalyst; a vanadium oxide catalyst; and a tungsten oxide catalyst. Among these catalysts, the palladium catalyst is preferable. In particular, the palladium-carrier catalyst is preferable. Above all, the palladium-carbon and palladium-alumina are most preferable.
The amount of the hydrogen moving catalyst to be used is usually in the range of from 0.001 to 1.0 gram atom, preferably from 0.002 to 0.2 gram atom in terms of a metallic atom per gram molecule of the amine.
The method of the present invention is characterized by using a sulfur-free polar solvent. Examples of the sulfur-free polar solvent include N,N-dimethylformamide, N,N-dimethylacetamide, tetramethylurea, methyl isobutyl ketone, tetrahydrofuran, dioxane, 1,3-dimethylimidazolizinone, glymes such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, methyl salicylate, phenol and phenols, for example, alkylphenols such as methylphenol and 2,4,6-trimethylphenol as well as alkoxyphenols such as 3-methoxyphenol and 4-methoxyphenol. If necessary, they may be used in combinations of two or more thereof. Dimethyl sulfoxide and sulfolane are similarly within the category of the polar solvents, but they are not used because they contain sulfur which is poisonous to the hydrogen moving catalyst.
The amount of the sulfur-free polar solvent to be used is preferably 0.1-6.0 times by weight, more preferably 0.3-3.0 times by weight of the cyclohexanone or the nucleus-substituted cyclohexanone.
It is also within the category of the present invention to use an alkaline metal compound and/or an alkaline earth metal compound as a cocatalyst. The use of the cocatalyst leads to the effect that the life of the hydrogen moving catalyst can be prolonged.
Usable examples of the alkali metal compound and/or the alkaline earth metal compound which can be added as the cocatalyst are hydroxides, carbonates, bicarbonates and the like of alkali metals and alkaline earth metals. Typical examples of these compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, sodium carbonate, potassium carbonate and sodium hydrogen carbonate. Above all, sodium hydroxide and potassium hydroxide are preferable. These cocatalysts may be used singly or in combinations of two or more thereof. The cocatalyst does not have to be added to the reaction system separately from the above-mentioned dehydrogenation catalyst. For example, after a noble metal supporting catalyst has been prepared, a salt, a hydroxide or the like of an alkali metal and/or an alkaline earth metal may be additionally supported as the alkali metal component and/or the alkaline earth metal component on the noble metal supporting catalyst, and the thus formed catalyst may be used.
The amount of the cocatalyst to be used is preferably in the range of from 2 to 30% by weight, more preferably from 5 to 20% by weight, in terms of the alkali metal and/or the alkaline earth metal, based on the weight of the catalyst metal.
It is also a preferable embodiment of the present invention to add, to the reaction using the above-mentioned cocatalyst, an organic acid in which a logarithm (pKa) of a reciprocal of an acid dissociation constant is in the range of from 3.5 to 6.0.
The preferable pKa of the organic acid is in the range of from 4.0 to 5.0. If the pKa of the organic acid is less than this range, the Schiff base is unstable, and if it is more than the above-mentioned range, the dehydrogenation reaction is impaired. Examples of the organic acid include acetic acid, propionic acid, butyric acid, isobutyric acid, valerianic acid, isovalerianic acid, hexanic acid, cyclohexanecarboxylic acid, octanoic acid, crotonic acid, vinylacetic acid, benzoic acid, anisic acid, cinnamic acid, phenylacetic acid and 2-naphthoic acid. The amount of the organic acid to be used is preferably in the range of from 50 to 2000% by weight, more preferably from 70 to 800% by weight based on the weight of the catalyst metal.
In the case that the nitro compound is used as the hydrogen acceptor in the presence of the catalyst of a noble metal in the group VIII and the sulfur-free solvent to produce the amine and the cyclohexanone or the nucleus-substituted cyclohexanone is simultaneously reacted with the amine to prepare the aromatic secondary amino compound, the used catalyst can be recovered and then reused. In this case, if the alkali metal compound and/or the alkaline earth metal compound as the cocatalyst and the organic acid having a pKa of 3.5 to 6.0 are added to the reaction system, the amount of the catalyst to be added in each operation can be decreased as much as possible, and a reaction rate and a yield can be maintained.
It is advantageous that the reaction is carried out under the removal of water, and thus a technique is suitable in which water is removed from the reaction mixture while azeotropic distillation is done by the use of a solvent such as benzene, toluene or xylene.
The temperature at the reaction is usually in the range of from 120.degree. to 250.degree. C., preferably from 140.degree. to 200.degree. C.
In the above-mentioned reaction, when the raw materials are placed in a reactor, it is a preferable manner that the (co)catalyst, the solvent and the amine are previously put in the reactor, stirred and then heated, and the (nucleus-substituted) cyclohexanone and the nitro compound are then simultaneously dropped into the reactor to carry out the above-mentioned reaction. Needless to say, the (nucleus-substituted) cyclohexanone and the nitro compound are first mixed and then added to the reaction.
The mixture obtained by the above-mentioned reaction is treated in an ordinary manner such as distillation, crystallization or extraction. For example, the solution in which the reaction has already been brought to an end is filtered to separate the catalyst therefrom. The thus recovered catalyst can be reused. The resultant filtrate can be concentrated to recover the solvent. The produced aromatic secondary amino compound in the reactor can be directly used without any treatment, but if necessary, it may be purified by distillation, crystallization or the like.
In accordance with the further aspect of the invention wherein aminodiphenylamine (hereinafter abbreviated as "ADPA") is prepared by reacting phenylenediamine (hereinafter abbreviated as "PD") with cyclohexanone in the presence of a hydrogen transfer catalyst in a sulfur-free polar solvent while using nitroaniline (hereinafter abbreviated as "NA") as a hydrogen acceptor, it is important to use a sulfur-free polar solvent. Examples of the sulfur-free polar solvent include N,N-dimethylformamide, N,N-dimethylacetamide; tetramethylurea; methyl isobutyl ketone, tetrahydrofuran, dioxane and 1,3-dimethylimidazolidinone; glymes such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether; and phenols such as methyl salicylate, phenol, alkylphenols such as methylphenol and 2,4,6-trimethylphenol, and alkoxyphenols such as 3-methoxyphenol and 4-methoxyphenol. These solvents can be used either singly or in combination.
Incidentally, sulfur-containing polar solvents such as dimethylsulfoxide and sulfolane exhibit poisonous action against hydrogen transfer catalysts and are hence not preferred.
Any known hydrogen transfer (moving) catalysts can be used in the process of the present invention. Specific examples include those mentioned above including nickel/carrier catalysts such as those formed by having Raney nickel, reduced nickel or nickel borne on various carriers such as diatomaceous earth, alumina, pumice, silica gel and acid clay; cobalt catalysts such as Raney cobalt, reduced cobalt, cobalt and cobalt/carrier catalysts; palladium catalysts such as palladium black, palladium oxide, colloidal palladium, palladium/carbon, palladium/barium sulfate and palladium/barium carbonate; platinum catalysts such as platinum black, colloidal platinum, platinized sponge, platinum oxide, platinum sulfide and platinum/carbon; rhodium catalysts such as colloidal rhodium, rhodium/carbon and rhodium oxide; platinum group catalysts such as ruthenium catalysts; rhenium catalysts such as dirhenium heptaoxide and rhenium/carbon; copper chromate catalysts; molybdenum oxide catalysts; vanadium oxide catalysts; and tungsten oxide catalysts. Among these catalysts, it is preferred to use a palladium catalyst. In particular, use of a palladium/carrier catalyst, notably a palladium/carbon or palladium/alumina is preferred. These hydrogen transfer catalysts can be used generally in a proportion of 0.001-1.0 gram atom, preferably 0.002-0.2 gram atom in terms of metal atoms per gram molecule of cyclohexanone.
According to the method of the further aspect of the present invention, a Schiff base is formed by condensation of PD and cyclohexanone, followed by the formation of ADPA through dehydrogenation. During the method, NA is used as a receptor for resulting hydrogen. In this manner, NA is convened to PD in the reaction system and by the reaction of the PD and the other raw material, that is, cyclohexanone, ADPA is formed further.
At this time, it is possible to convert 0.67 mole of NA to PD per mole of the Schiff base. For the full and effective utilization of hydrogen occurring in the reaction system, it is therefore sufficient if the molar ratio of NA to cyclohexanone is set at 0.67. Abundance of NA at this stage tends to result in a lower reaction velocity and is hence not beneficial. An unduly small molar ratio of PD/cyclohexanone, on the other hand, tends to cause further reaction of ADPA, which has been formed in the reaction system, with cyclohexanone so that N,N'-diphenylphenylene-diamine (hereinafter abbreviated as "N,N'-DPPA") would be by-produced. To avoid these drawbacks, it is preferred to add 0.67 mole of NA and at least 0.33 mole of PD per mole of cyclohexanone from the beginning of the reaction and then to react them. It is more preferred to conduct the reaction with the sum of NA and PD being maintained at 1.4 moles or more, especially 1.7 mole or more per mole of cyclohexanone.
In the method of this aspect of the present invention, all the raw materials can be charged together at once in a reaction vessel at the beginning of the reaction. It is however important to conduct the reaction while simultaneously adding cyclohexanone and NA dropwise into a liquid mixture of the hydrogen transfer catalyst, PD and the sulfur-free polar solvent. Needless to say, they can be mixed first and then added dropwise. This makes it possible to always maintain the PD/cyclohexanone molar ratio at a still higher level in the reaction system, thereby allowing the target product to be obtained in a high yield.
The reaction can also be conducted while separating water from the reaction mixture by azeotropically distilling it off together with a solvent such as benzene, toluene or xylene.
The reaction temperature can be selected generally from a range of 140.degree.-250.degree. C., preferably from a range of 160.degree.-200.degree. C.
The ADPA so formed can be obtained by processing the reaction mixture in a manner known per se in the art, such as distillation, crystallization or extraction, after the completion of the reaction. For example, the reaction mixture is filtered subsequent to the completion of the reaction, whereby the catalyst is separated. The catalyst so recovered can be reused. The filtrate is concentrated to recover the solvent. The ADPA left in the reaction vessel can be used, as is, as a raw material for the next reaction in some instances but, if necessary, is purified by distillation, crystallization or the like.
According to the present invention, the desired aromatic secondary amino compound can be obtained under extremely moderate conditions and in a high yield.

Now, the various aspects of the present invention will be described in detail in reference to examples.
EXAMPLE A1
In a 100 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer and a stirrer were placed 1.6 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 10 g of diethylene glycol dimethyl ether, 17.33 g (0.1 mol) of N-cyclohexylidene aniline and 8.29 g (0.067 mol) of nitrobenzene. Afterward, the reactor was heated up to 160.degree. C. with stirring, and reaction was then carried out for 4 hours by maintaining the reactor at 158.degree.-162.degree. C. During this reaction, water present in the catalyst and water produced by the reaction were removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 1.8 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of an imine was 100%, and the yield of diphenylamine was 87.6%.
EXAMPLES A2 TO A8
Reactions were carried out by the same procedure as in Example A1 except that diethylene glycol dimethyl ether in Example A1 was replaced with various polar solvents shown in Table 1.
The results are set forth in Table 1.
TABLE 1______________________________________ Conversion Yield of of Imine DiphenylamineExample Solvent (mol %) (mol %)______________________________________A2 N,N- 100.0 89.5 dimethylacetamideA3 N,N'-dimethylimida- 100.0 88.2 zolidinoneA4 p-cresol 99.3 84.1A5 N,N- 100.0 87.7 dimethylformamideA6 Tetramethylurea 99.5 87.0A7 N-methylpyrrolidone 98.9 83.8A8 Methyl salicylate 99.8 86.5______________________________________
EXAMPLE A9
Reaction was carried out by the same procedure as in Example A1 except that in place of nitrobenzene in Example A1, 23.87 g (0.202 mol) of a-methylstyrene were used as a hydrogen acceptor. As a result, the conversion of an imine was 100%, and the yield of diphenylamine was 85.9%.
COMPARATIVE EXAMPLE A1
Reaction was carried out by the same procedure as in Example A1 except that diethylene glycol dimethyl ether was not used. As a result, the conversion of an imine was 96.1%, and the yield of diphenylamine was 72.3%.
COMPARATIVE EXAMPLE A2
Reaction was carried out by the same procedure as in Example A1 except that in place of diethylene glycol dimethyl ether in Example A1, p-tert-butyltoluene was used as a solvent. As a result, the conversion of an imine was 94.0%, and the yield of diphenylamine was 72.6%.
EXAMPLE B1
In a 100 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer and a stirrer were placed 2.57 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 22.23 g of N,N-dimethylformamide, 20-51 g (0.1 mol) of N-(4-methylcyclohexylidene)-4-methylaniline and 9.24 g (0.067 mol) of p-nitrotoluene. Afterward, the reactor was heated up to 140.degree. C. with stirring, and reaction was then carried out for 4 hours by maintaining the reactor at 138.degree.-142.degree. C. During this reaction, water present in the catalyst and water produced by the reaction were removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 2.9 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of an imine was 100%, and the yield of 4,4'-dimethyldiphenylamine was 85.3%.
EXAMPLES B2 TO B6
Reactions were carried out by the same procedure as in Example B1 except that N,N-dimethylformamide in Example B1 was replaced with various polar solvents shown in Table 2 and reaction temperature was set to 160.degree. C.
The results are set forth in Table 2.
TABLE 2______________________________________ Conversion Yield of of Imine DiphenylamineExample Solvent (mol %) (mol %)______________________________________B2 N,N'- 99.4 94.9 dimethylimida- zolidinineB3 p-cresol 99.6 91.4B4 Phenol 99.5 88.3B5 Diethylene glycol 99.5 91.1 dimethyl etherB6 p-methoxyphenol 99.8 93.4______________________________________
EXAMPLES B7 TO B14
Reactions were carried out by the same procedure as in Example B1 except that in place of the combination of N-(4-methylcyclohexylidene)-4-methylaniline and p-nitrotoluene in Example B1, combinations of various N-cyclohexylidene amino compounds and hydrogen acceptors shown in Table 3 were used.
The results are set forth in Table 3.
TABLE 3______________________________________ Con- version YieldEx- N-Cyclohexylidene- Hydrogen (mol (molample amino Compound Acceptor %) %)______________________________________B7 N-(4-methylcyclohexyl- o-nitro- 96.2 90.8 idene)-2-methylaniline tolueneB8 N-(3-ethylcyclohexyl- p-nitro- 99.1 94.2 idene)-4-methylaniline tolueneB9 N-(2-methylcyclohexyl- p-nitro- 100.0 96.1 idene)-4-methylaniline tolueneB10 N-cyclohexylidene- m-nitro- 98.9 92.1 3-ethylaniline tolueneB11 N-(4-methylcyclohexyl- 4-nitro- 99.2 93.1 idene)-4-methoxyaniline anisoleB12 N-(4-methylcyclohexyl- 4-nitro- 99.3 93.2 idene)-4-phenoxyaniline diphenyl etherB13 N-(4-methoxycyclohexyl- 4-fluoro- 92.3 89.1 idene)-4-fluoroaniline nitro- benzeneB14 N-(4-methylcyclohexyl- 4-nitro- 95.6 91.1 idene)-4-hydroxyaniline phenol______________________________________
EXAMPLE B15
Reaction was carried out by the same procedure as in Example B1 except that in place of p-nitrotoluene in Example B1, 23.87 g (0.202 mol) of .alpha.-methylstyrene were used as a hydrogen acceptor. As a result, the conversion of an imine was 89.1%, and the yield of 4,4'-dimethyldiphenylamine was 82.1%.
COMPARATIVE EXAMPLE B1
Reaction was carried out by the same procedure as in Example B1 except that N,N-dimethylformamide was not used. As a result, the conversion of an imine was 51.9%, and the yield of 4,4'-dimethyldiphenylamine was 37.4%.
COMPARATIVE EXAMPLE B2
Reaction was carried out by the same procedure as in Example B1 except that in place of N,N-dimethylformamide in Example B1, p-tert-butyltoluene was used as a solvent. As a result, the conversion of an imine was 49.1%, and the yield of 4,4'-dimethyldiphenylamine was 35.3%.
COMPARATIVE EXAMPLE B3
Reaction was carried out by the same procedure as in Example B7 except that N,N-dimethylformamide was not used. As a result, the conversion of an imine was 31.3%, and the yield of 4,2'-dimethyldiphenylamine was 15.5%.
COMPARATIVE EXAMPLE B4
Reaction was carried out by the same procedure as in Example B9 except that N,N-dimethylformamide was not used. As a result, the conversion of an imine was 12.1%, and the yield of 2,4'-dimethyldiphenylamine was 4.3%.
EXAMPLE C1
In a 200 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer, a dropping device and a stirrer were placed 3.72 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd. and 20 g of diethylene glycol dimethyl ether, and in the dropping device was prepared a mixed solution of 34.66 g (0.2 mol) of N-cyclohexylidene aniline and 16.58 g (0.13 mol) of nitrobenzene. Afterward, the reactor was heated up to 160.degree. C. with stirring, and after the removal of water present in the catalyst, the solution in the dropping device was dropped over 4 hours, while a temperature of 158.degree.-162.degree. C. was maintained. After completion of the dropping, the solution was stirred for 0.5 hour, while this temperature range was maintained. Water produced during this step was removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 4.8 g. Next, the reaction solution in the reactor was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of an imine was 100%, and the yield of diphenylamine was 98.5%.
EXAMPLES C2 TO C8
Reactions were carried out by the same procedure as in Example C1 except that diethylene glycol dimethyl ether in Example C1 was replaced with various polar solvents shown in Table 4.
The results are set forth in Table 4.
COMPARATIVE EXAMPLE C1
Reaction was carried out by the same procedure as in Example C1 except that in place of diethylene glycol dimethyl ether in Example C1, p-tert-butyltoluene was used as a solvent. As a result, the conversion of an imine was 35.0%, and the selectivity of diphenylamine was 90.2%.
TABLE 4______________________________________ Conversion Yield of of Imine DiphenylamineExample Solvent (mol %) (mol %)______________________________________C2 Diethylene glycol 100.0 98.4 diethyl etherC3 N,N'-dimethylimida- 100.0 98.5 zolidinoneC4 N,N- 100.0 98.7 dimethylformamideC5 N,N- 100.0 99.0 dimethylacetamideC6 Tetramethylurea 99.0 97.0C7 N-methylpyrrolidone 91.0 89.3C8 Methyl salicylate 97.0 95.0C9 p-cresol 98.0 96.5______________________________________
EXAMPLE D1
In a 100 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer and a stirrer were placed 2.57 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd. and 22.23 g of N,N-dimethylformamide, and in the dropping device was prepared and stored a mixed solution of 20.51 g (0.1 mol) of N-(4-methylcyclohexylidene)-4-methylaniline and 9.24 g (0.067 mol) of p-nitrotoluene. Afterward, the reactor was heated up to 140.degree. C. with stirring, and after the removal of water present in the catalyst, the solution in the dropping device was dropped over 4 hours, while a temperature of 138.degree.-142.degree. C. was maintained. After completion of the dropping, the solution was stirred for 1 hour, while this temperature range was maintained. Water produced during this step was removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 4.0 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of an imine was 98.6%, and the yield of 4,4'-dimethyldiphenylamine was 93.5%.
EXAMPLES D2 TO D6
Reactions were carried out by the same procedure as in Example D1 except that N,N-dimethylformamide in Example D1 was replaced with various polar solvents shown in Table 5 and reaction temperature was set to 160.degree. C.
The results are set forth in Table 5.
TABLE 5______________________________________ Conversion Yield of of Imine DitolylamineExample Solvent (mol %) (mol %)______________________________________D2 N,N'-dimethylimida- 98.2 96.3 zolidinoneD3 p-cresol 99.1 94.1D4 Phenol 99.0 93.4D5 Diethylene glycol 98.3 95.2 dimethyl etherD6 p-methoxyphenol 99.2 95.3______________________________________
EXAMPLES D7 TO D14
Reactions were carried out by the same procedure as in Example D1 except that the combination of N-cyclohexylidene amino compound and a hydrogen acceptor in Example D1 was changed to combinations shown in Table 6.
The results are set forth in Table 6.
TABLE 6______________________________________ Con- version YieldEx- N-Cyclohexylidene- Hydrogen (mol (molample amino Compound Acceptor %) %)______________________________________D7 N-(4-methylcyclohexyl- o-nitro- 96.1 94.4 idene)-2-methylaniline tolueneD8 N-(3-ethylcyclohexyl- p-nitro- 98.1 96.5 idene)-4-methylaniline tolueneD9 N-(2-methylcyclohexyl- p-nitro- 99.7 98.5 idene)-4-methylaniline tolueneD10 N-cyclohexylidene- m-nitro- 98.8 95.9 3-ethylaniline tolueneD11 N-(4-methylcyclohexyl- 4-nitro- 98.1 94.9 idene)-4-methoxyaniline anisoleD12 N-(4-methylcyclohexyl- 4-nitro- 98.2 95.3 idene)-4-phenoxyaniline diphenyl etherD13 N-(4-methoxycyclohexyl- 4-fluoro- 90.6 89.1 idene)-4-fluoroaniline nitro- benzeneD14 N-(4-methylcyclohexyl- 4-nitro- 96.0 93.7 idene)-4-hydroxyaniline phenol______________________________________
EXAMPLE E1
In a 100 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer and a stirrer were placed 1.86 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 0.24 g of 1N-NaOH, 10 g of diethylene glycol dimethyl ether, 17.33 g (0.1 mol) of N-cyclohexylidene aniline and 8.29 g (0.067 mol) of nitrobenzene. Afterward, the reactor was heated up to 160.degree. C. with stirring, and reaction was then carried out for 2 hours by maintaining the reactor at 158.degree.-162.degree. C. During this reaction, water present in the catalyst and water produced by the reaction were removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 2.6 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of an imine was 100%, and the yield of diphenylamine was 93.0%.
EXAMPLES E2 TO E8 AND COMPARATIVE EXAMPLES E1 TO E3
Reactions were carried out by the same procedure as in Example E1 except that diethylene glycol dimethyl ether in Example E1 was replaced with various polar solvents shown in Table 7.
The results are set forth in Table 7.
TABLE 7______________________________________ Yield of Con- Di- version phenyl-Ex- Co- of Imine amineample Solvent catalyst (mol %) (mol %)______________________________________E2 N,N-dimethylacetamide NaOH 100.0 94.2E3 N,N'- NaOH 100.0 93.5 dimethylimidazolidinoneE4 p-cresol NaOH 98.8 90.4E5 N,N-dimethylformamide NaOH 100.0 92.8E6 Tetramethylurea NaOH 99.2 90.6E7 N-methylpyrrolidone NaOH 98.4 89.7E8 Methyl salicylate NaOH 99.6 92.2Comp. -- NaOH 97.5 84.8Ex. E1Comp. -- -- 92.5 68.1Ex. E2Comp. p-tert-butyltoluene NaOH 91.1 67.4Ex. E3______________________________________
EXAMPLES E9 AND E10
Reactions were carried out by the same procedure as in Example E1 except that in place of 0.24 g of 1N-NaOH in Example E1, an alkali metal compound and/or an alkaline earth metal compound shown in Table 8 was used as a co-catalyst.
The results are set forth together with those of Example E1 in Table 8.
TABLE 8______________________________________ Yield of Con- Di-Cocatalyst version phenyl- Amount* of Imine amineExample Kind (wt %/Pd) (mol %) (mol %)______________________________________E1 NaOH Na: 11.9 100.0 93.0E9 Ca(OH).sub.2 Ca: 20 100.0 92.3E10 NaOH + Mg(OH).sub.2 Na: 5 100.0 93.0 Mg: 12______________________________________ *The amount of the cocatalyst in terms of an alkali metal and/or an alkaline earth metal.
EXAMPLE F1
In a 100 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer and a stirrer were placed 2.57 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 0.30 g of 1N-NaOH, 22.23 g of N,N-dimethylformamide, 20.51 g (0.1 mol)of N-(4-methylcyclohexylidene)-4-methylaniline and 9.24 g (0.067 mol) of p-nitrotoluene. Afterward, the reactor was heated up to 140.degree. C. with stirring, and reaction was then carried out for 2 hours by maintaining the reactor at 138.degree.-142.degree. C. During this reaction, water present in the catalyst and water produced by the reaction were removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The mount of the removed water was 3.6 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of an imine was 99.7%, and the yield of 4,4'-dimethyldiphenylamine was 90.9%.
COMPARATIVE EXAMPLE F1
Reaction was carried out by the same procedure as in Example F1 except that N,N-dimethylformamide was not used. As a result, the conversion of an imine was 46.6%, and the yield of 4,4'-dimethyldiphenylamine was 36.0%.
COMPARATIVE EXAMPLE F2
Reaction was carried out by the same procedure as in Example F1 except that 1N-NaOH and N,N-dimethylformamide were not used. As a result, the conversion of an imine was 45.3%, and the yield of 4,4'-dimethyldiphenylamine was 31.5%.
EXAMPLES F2 TO F6
Reactions were carried out by the same procedure as in Example F1 except that N,N-dimethylformamide in Example F1 was replaced with various polar solvents shown in Table 9 and reaction temperature was set to 160.degree. C.
The results are set forth in Table 9.
TABLE 9______________________________________ Conversion Yield of of Imine DitolylamineExample Solvent (mol %) (mol %)______________________________________F2 N,N'- 98.5 95.2 dimethylimidazolidinoneF3 p-cresol 100.0 94.6F4 Phenol 99.3 90.6F5 Diethylene glycol 98.7 93.1 dimethyl etherF6 p-methoxyphenol 98.8 94.1______________________________________
EXAMPLES F7 AND F8
Reactions were carried out by the same procedure as in Example F1 except that in place of 0.3 g of 1N-NaOH in Example F1, an alkaline metal compound and/or an alkaline earth metal compound shown in Table 10 was used as a co-catalyst.
The results are set forth together with those of Example F1 in Table 10.
TABLE 10______________________________________ Yield of Con- Di-Cocatalyst version phenyl- Amount* of Imine amineExample Kind (wt %/Pd) (mol %) (mol %)______________________________________F1 NaOH Na: 10.7 99.7 90.9F7 Ca(OH).sub.2 Ca: 20 99.7 89.8F8 NaOH + Mg(OH).sub.2 Na: 5 100.0 90.6 Mg: 12______________________________________ *The amount of the cocatalyst in terms of an alkali metal and/or an alkaline earth metal.
EXAMPLES F9 TO F16
Reactions were carried out by the same procedure as in Example F1 except that the combination of N-(4-methyl-cyclohexylidene)-4-methylaniline and p-nitrotoluene in Example F1 was changed to combinations of N-cyclohexylidene amino compounds and hydrogen acceptors shown in Table 11.
The results are set forth in Table 11.
TABLE 11______________________________________ Con- version YieldEx- N-Cyclohexylidene- Hydrogen (mol (molample amino Compound Acceptor %) %)______________________________________F9 N-(4-methylcyclohexyl- o-nitro- 97.9 94.0 idene)-2-methylaniline tolueneF10 N-(3-ethylcyclohexyl- p-nitro- 98.3 95.2 idene)-4-methylaniline tolueneF11 N-(2-methylcyclohexyl- p-nitro- 99.8 97.1 idene)-4-methylaniline tolueneF12 N-cyclohexylidene- m-nitro- 99.1 94.7 3-ethylaniline tolueneF13 N-(4-methylcyclohexyl- 4-nitro- 98.5 93.5 idene)-4-methoxyaniline anisoleF14 N-(4-methylcyclohexyl- 4-nitro- 98.5 93.6 idene)-4-phenoxyaniline diphenyl etherF15 N-(4-methoxycyclohexyl- 4-fluoro- 90.8 88.3 idene)-4-fluoroaniline nitro- benzeneF16 N-(4-methylcyclohexyl- 4-nitro- 96.2 92.8 idene)-4-hydroxyaniline phenol______________________________________
COMPARATIVE EXAMPLE F3
Reaction was carried out by the same procedure as in Example F9 except that N,N-dimethylformamide in Example F9 was not used. As a result, the conversion of an imine was 55.2%, and the yield of 4,2'-dimethyldiphenylamine was 42.3%.
COMPARATIVE EXAMPLE F4
Reaction was carried out by the same procedure as in Example F9 except that 1N-NaOH and N,N-dimethylformamide in Example F9 were not used. As a result, the conversion of an imine was 17.0%, and the yield of 4,2'-dimethyldiphenylamine was 12.5%.
COMPARATIVE EXAMPLE F5
Reaction was carried out by the same procedure as in Example F11 except that N,N-dimethylformamide in Example F11 was not used. As a result, the conversion of an imine was 48.2%, and the yield of 2,4'-dimethyldiphenylamine was 35.8%.
COMPARATIVE EXAMPLE F6
Reaction was carried out by the same procedure as in Example F11 except that 1N-NaOH and N,N-dimethylformamide in Example F11 were not used. As a result, the conversion of an imine was 11.3%, and the yield of 2,4'-dimethyldiphenylamine was 3.5%.
EXAMPLE G1
In a 100 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer and a stirrer were placed 1.86 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 0.24 g of 1N-NaOH, 17.33 g (0.1 mol) of N-cyclohexylideneaniline, 8.29 g (0.067 mol) of nitrobenzene. Afterward, the reactor was heated up to 160.degree. C. with stirring, and reaction was then carried out for 3 hours by maintaining the reactor at 158.degree.-162.degree. C. During this reaction, water present in the catalyst and water produced by the reaction were removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 2.7 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of an imine was 99.4%, and the yield of diphenylamine was 86.7%. Examples G2 to G10 and Comparative Example G1 Reactions were carried out by the same procedure as in Example G1 except that in place of 0.24 g of 1N-NaOH in Example G1, various kinds of cocatalysts were used in various amounts as shown in Table 12.
The results are set forth together with those of Example G1 in Table 12.
TABLE 12______________________________________ Yield of Cocatalyst Conversion Diphenyl-Example/ Amount* of Imine amineComp. Example Kind (wt %/Pd) (mol %) (mol %)______________________________________Example G1 NaOH 11.9 99.4 86.7Example G2 NaOH 20 100.0 87.5Example G3 Na.sub.2 CO.sub.3 12 99.8 86.9Example G4 NaHCO.sub.3 12 99.0 86.0Example G5 KOH 6 100.0 87.6Example G6 LiOH 5 98.5 84.5Example G7 Ca(OH).sub.2 20 97.7 83.9Example G8 Mg(OH).sub.2 12 98.7 84.8Example G9 NaOH + Na: 10 99.2 85.9 Ca(OH).sub.2 Ca: 10 Example G10 KOH + K: 5 99.7 86.5 Mg(OH).sub.2 Mg: 12Comp. -- -- 90.1 69.2Example G1______________________________________ *The amount of the cocatalyst in terms of an alkali metal and/or an alkaline earth metal.
EXAMPLE HI
In a 100 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer and a stirrer were placed 2.57 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 0.30 g of 1N-NaOH, 20.51 g (0.1 mol) of N-(4-methylcyclohexylidene)-4-methylaniline and 9.24 g (0.067 mol) of p-nitrotoluene. Afterward, the reactor was heated up to 160.degree. C. with stirring, and reaction was the carried out for 3 hours by maintaining the reactor at 158.degree.-162.degree. C. During this reaction, water present in the catalyst and water produced by the reaction were removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 3.0 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of an imine was 98.2%, and the yield of 4,4'-dimethyldiphenylamine was 85.5%.
EXAMPLES H2 TO H6
Reactions were carried out by the same procedure as in Example H1 except that in place of a cocatalyst in Example H1, various kinds of cocatalysts were used in various amounts as shown in Table 13.
The results are set forth together with those of Example H1 in Table 13.
TABLE 13______________________________________ Yield of Con- Di-Cocatalyst version phenyl- Amount* of Imine amineExample Kind (wt %/Pd) (mol %) (mol %)______________________________________H1 NaOH 10.7 98.2 85.5H2 NaOH 20 98.6 86.7H3 NaOH 5 97.2 83.5H4 NaHCO.sub.3 12 98.2 85.1H5 Ca(OH).sub.2 20 96.8 82.8H6 NaOH + Ca(OH).sub.2 Na: 10 98.7 84.7 Mg: 10______________________________________ *The amount of the cocatalyst in terms of an alkali metal and/or an alkaline earth metal.
EXAMPLES H7 TO H14
Reactions were carried out by the same procedure as in Example H1 except that the combination of an N-cyclohexylidene amino compound and a hydrogen acceptor in Example H1 was changed to combinations shown in Table 14.
The results are set forth in Table 14.
TABLE 14______________________________________ Con- version YieldEx- N-Cyclohexylidene- Hydrogen (mol (molample amino Compound Acceptor %) %)______________________________________H7 N-(4-methylcyclohexyl- o-nitro- 95.2 85.3 idene)-2-methylaniline tolueneH8 N-(3-ethylcyclohexyl- p-nitro- 98.3 88.6 idene)-4-methylaniline tolueneH9 N-(2-methylcyclohexyl- p-nitro- 99.1 90.3 idene)-4-methylaniline tolueneH10 N-cyclohexylidene- m-nitro- 97.6 86.3 3-ethylaniline tolueneH11 N-(4-methylcyclohexyl- 4-nitro- 97.9 87.2 idene)-4-methoxyaniline anisoleH12 N-(4-methylcyclohexyl- 4-nitro- 98.1 87.0 idene)-4-phenoxyaniline diphenyl etherH13 N-(4-methoxycyclohexyl- 4-fluoro- 89.8 81.9 idene)-4-fluoroaniline nitro- benzeneH14 N-(4-methylcyclohexyl- 4-nitro- 91.2 82.6 idene)-4-hydroxyaniline phenol______________________________________
COMPARATIVE EXAMPLE H1
Reaction was carried out by the same procedure as Example H1 except that 1N-NaOH was not used. As a result, the conversion of an imine was 79.9%, and the yield of 4,4'-dimethyldiphenylamine was 66.8%.
COMPARATIVE EXAMPLE H2
Reaction was carded out by the same procedure as Example H7 except that 1N-NaOH was not used. As a result, the conversion of an imine was 61.3%, and the yield of 4,2'-dimethyldiphenylamine was 35.3%.
COMPARATIVE EXAMPLE H3
Reaction was carried out by the same procedure as Example H9 except that 1N-NaOH was not used. As a result, the conversion of an imine was 55.9%, and the yield of 4,2'-dimethyldiphenylamine was 34.1%.
EXAMPLE I1
In a 200 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer and a stirrer were placed 5.59 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 25.68 g of diethylene glycol dimethyl ether, 13.97 g (0.15 mol) of aniline, 29.44 g (0.3 mol) of cyclohexanone and 24.87 g (0.2 mol) of nitrobenzene. Afterward, the reactor was heated up to 160.degree. C. with stirring, and reaction was then carried out for 3 hours by maintaining the reactor at 158.degree.-162.degree. C. Water present in the catalyst and water produced during this reaction was removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 12.4 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of cyclohexanone was 100%, and the yield of diphenylamine was 86.8%.
EXAMPLE I2 TO I8
Reactions were carried out by the same procedure as in Example I1 except that diethylene glycol dimethyl ether in Example I1 was replaced with various polar solvents shown in Table 15.
The results are set forth in Table 15.
TABLE 15______________________________________ Conversion Yield of of Imine DiphenylamineExample Solvent (mol %) (mol %)______________________________________I2 N,N-dimethylacetamide 100.0 90.2I3 N,N'- 98.9 86.2 dimethylimidazolidinoneI4 p-cresol 100.0 91.7I5 N,N-dimethylformamide 100.0 91.4I6 Tetramethylurea 98.2 87.4I7 N-methylpyrrolidone 97.4 85.8______________________________________
COMPARATIVE EXAMPLE I1
Reaction was carried out by the same procedure 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
Reaction was carried out by the same procedure as in Example I1 except that in place of diethylene glycol dimethyl ether, p-tert-butyltoluene was used as a solvent. As a result, the conversion of cyclohexanone was 91.1%, and the yield of diphenylamine was 67.3%.
EXAMPLE I8
Reaction was carried out by the same procedure as in Example I1 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) nitrobenzene were used. As a result, the yield of diphenylamine was 89.5%, and 1.8% of triphenylamine and 2.9% of N-cyclohexylaniline were produced.
EXAMPLE J1
In a 200 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer and a stirrer were placed 7.72 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 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. Afterward, the reactor was heated up to 140.degree. C. with stirring, and reaction was then carried out for 3 hours by maintaining the reactor at 134.degree.-142.degree. C. Water present in the catalyst and water produced during this reaction were removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 12.34 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of 4-methylcyclohexanone was 98.6%, and the yield of ditolylamine was 91.6%.
EXAMPLES J2 TO J7
Reactions were carried out by the same procedure as in Example J1 except that N,N-dimethylformamide in Example J1 was replaced with various polar solvents shown in Table 16 and reaction temperature was set to 160.degree. C.
The results are set forth in Table 16.
TABLE 16______________________________________ Yield of Conversion DitolylamineExample Solvent (mol %) (mol %)______________________________________J2 N,N-dimethylacetamide 99.8 90.2J3 N,N'- 98.9 89.2 dimethylimidazolidinoneJ4 p-cresol 100.0 94.3J5 Diethylene glycol 98.0 89.4 dimethyl etherJ6 Tetramethylurea 98.7 87.9J7 N-methylpyrrolidone 97.4 88.8______________________________________
COMPARATIVE EXAMPLE J1
Reaction was carried out by the same procedure as in Example J1 except that N,N-dimethylformamide was not used. As a result, the conversion of 4-methylcyclohexanone was 51.6%, and the yield of ditolylamine was 7.9%.
COMPARATIVE EXAMPLE J2
Reaction was carried out by the same procedure as in Example J1 except that in place of N,N-dimethylformamide in Example J1, xylene was used as a solvent. As a result, the conversion of p-methylcyclohexanone was 53.7%, and the yield of ditolylamine was 9.0%.
EXAMPLES J8 TO J13
Reaction was carried out by the same procedure as in Example J1 except that the combination of p-toluidine, 4-methylcyclohexanone and p-nitrotoluene was replaced with materials shown in Table 17.
The results are set forth in Table 17.
TABLE 17__________________________________________________________________________ Cyclohexanone Con- (nucleus- version YieldEx- substitured Nitro- Desired (mol (molample compound) Amine Compound Compound %) %)__________________________________________________________________________J8 ##STR5## ##STR6## ##STR7## ##STR8## 97.1 90.7J9 ##STR9## ##STR10## ##STR11## ##STR12## 100.0 89.1J10 ##STR13## ##STR14## ##STR15## ##STR16## 99.5 87.1J11 ##STR17## ##STR18## ##STR19## ##STR20## 99.6 90.0J12 ##STR21## ##STR22## ##STR23## ##STR24## 98.1 89.5J13 ##STR25## ##STR26## ##STR27## ##STR28## 98.9 88.9__________________________________________________________________________
EXAMPLE K1
In a 200 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer, a dropping device and a stirrer were placed 5.59 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 25.68 g of diethylene glycol dimethyl ether and 13.97 g (0.15 mol) of aniline, and in the dropping device was prepared and stored a mixed solution of 29.44 g (0.3 mol) of cyclohexanone and 24.87 g (0.2 mol) of nitrobenzene. Afterward, the reactor was heated up to 160.degree. C. with stirring, and after the removal of water present in the catalyst, the solution in the dropping device was dropped over 4 hours, while a temperature of 158.degree.-162.degree. C. was maintained. After completion of the dropping, the solution was stirred for 0.5 hour, while this temperature range was maintained. Water produced during this step was removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 12.6 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of cyclohexanone was 100%, and the yield of diphenylamine was 99.2%.
EXAMPLES K2 TO K8
Reactions were carried out by the same procedure as in Example K1 except that diethylene glycol dimethyl ether in Example K1 was replaced with various polar solvents shown in Table 18.
The results are set forth in Table 18.
TABLE 18______________________________________ Yield of Conversion DiphenylamineExample Solvent (mol %) (mol %)______________________________________K2 N,N-dimethylacetamide 100.0 98.8K3 N,N'- 100.0 98.5 dimethylimidazolidinoneK4 p-cresol 98.9 97.1K5 N,N-dimethylformamide 100.0 99.1K6 Tetramethylurea 99.5 98.0K7 N-methylpyrrolidone 96.8 94.9K8 Methyl salicylate 98.7 96.8______________________________________
COMPARATIVE EXAMPLE K1
Reaction was carried out by the same procedure as in Example K1 except that in place of diethylene glycol dimethyl ether in Example K1, p-tert-butyltoluene was used as a solvent. As a result, the conversion of cyclohexanone was 77.5%, and the yield of diphenylamine was 48.5%.
EXAMPLE L1
In a 200 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer, a dropping device and a stirrer were placed 7.72 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 60.00 g of N,N-dimethylformamide and 16.07 g (0.15 mol) of p-toluidine, and in the dropping device was prepared and stored a mixed solution of 33.65 g (0.3 mol) of 4-methylcyclohexanone and 27.43 g (0.2 mol) of p-nitrotoluene. Afterward, the reactor was heated up to 140.degree. C. with stirring, and after the removal of water present in the catalyst, the solution in the dropping device was dropped over 6 hours, while a temperature of 134.degree.-142.degree. C. was maintained. After completion of the dropping, the solution was stirred for 1 hour, while this temperature range was kept up. Water produced during this step was removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 12.5 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of 4-methylcyclohexanone was 99.6%, and the yield of ditolylamine was 97.7%.
EXAMPLES L2 TO L7
Reactions were carried out by the same procedure as in Example L1 except that N,N-dimethylformamide in Example L1 was replaced with various polar solvents shown in Table 19 and reaction temperature was set to 160.degree. C.
The results are set forth in Table 19.
TABLE 19______________________________________ Yield of Conversion DitolylamineExample Solvent (mol %) (mol %)______________________________________L2 N,N-dimethylacetamide 99.7 97.1L3 N,N'- 99.1 96.5 dimethylimidazolidinoneL4 p-cresol 99.9 98.1L5 Diethylene glycol 98.0 96.1 dimethyl etherL6 Tetramethylurea 99.2 97.1L7 N-methylpyrrolidone 98.7 96.9______________________________________
EXAMPLES L8 TO L13
Reactions were carried out by the same procedure as in Example L1 except that p-toluidine, 4-methylcyclohexanone and p-nitrotoluene in Example L1 were replaced with various materials shown in Table 20.
The results are set forth in Table 20.
TABLE 20__________________________________________________________________________ Cyclohexanone Con- (nucleus- version YieldEx- substitured Nitro- Desired (mol (molample compound) Amine Compound Compound %) %)__________________________________________________________________________L8 ##STR29## ##STR30## ##STR31## ##STR32## 98.2 95.1L9 ##STR33## ##STR34## ##STR35## ##STR36## 99.8 97.8L10 ##STR37## ##STR38## ##STR39## ##STR40## 99.6 96.8L11 ##STR41## ##STR42## ##STR43## ##STR44## 99.8 98.8L12 ##STR45## ##STR46## ##STR47## ##STR48## 98.9 96.7L13 ##STR49## ##STR50## ##STR51## ##STR52## 99.3 96.9__________________________________________________________________________
EXAMPLE M1
In a 200 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer and a stirrer were placed 7.72 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 0.91 g of 1N-NaOH (Na content=10.8 wt %/Pd), 60.00 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. Afterward, the reactor was heated up to 140.degree. C. with stirring, and reaction was then carried out for 3 hours by maintaining the reactor at 138.degree.-142.degree. C. water present in the catalyst and water produced during this reaction were removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 15.22 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of 4-methylcyclohexanone was 99.8%, and the yield of ditolylamine was 94.2%.
EXAMPLE M2
In a 300 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer, a dropping device and a stirrer were placed 4.66 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 1.21 g of 1N-NaOH, 0.33 g of butyric acid, 42.80 g of diethylene glycol dimethyl ether and 23.28 g (0.25 mol) of aniline, and in the dropping device was prepared and stored a mixed solution of 49.07 g (0.5 mol) of cyclohexanone and 41.45 g (0.33 mol) of nitrobenzene. The reactor was heated to 160.degree. C. with stirring, and after the removal of water present in the catalyst, the solution in the dropping device was dropped over 4 hours, while a temperature of 158.degree.-162.degree. C. was maintained. After completion of the dropping, the solution was stirred for 0.5 hour, while this temperature range was kept up. Water produced during this step was removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The mount of the removed water was 21.0 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of cyclohexanone was 100%, and the yield of diphenylamine was 99.9%.
In succession, the previously recovered catalyst was used, and 5% Pd/C containing 50% of water, NAOH and butyric acid were added as shown in Table 21 and reaction was then similarly carried out. As a result, the average amount of the added new 5% Pd/C catalyst necessary to maintain a reaction rate and a selectivity was about 3% of its initial amount.
TABLE 21______________________________________ Amount Con- Select- of Added Butyric version ivityNumber of New Catalyst 1N--NaOH Acid (mol (molRecycling 5% Pd/C (g) (g) (g) %) %)______________________________________1 -- -- 0.33 100.0 99.82 -- -- 0.33 100.0 99.73 -- -- 0.33 100.0 99.74 -- -- 0.33 100.0 99.15 0.70 0.18 0.33 100.0 99.76 -- -- 0.33 99.7 98.67 0.47 0.12 0.33 100.0 99.58 -- -- 0.33 100.0 99.09 -- -- 0.33 98.7 97.310 0.23 0.06 0.33 100.0 99.3______________________________________
EXAMPLE M3
In a 300 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer, a dropping device and a stirrer were placed 4.66 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 42.80 g of diethylene glycol dimethyl ether and 23.28 g (0.25 mol) of aniline, and in the dropping device was prepared and stored a mixed solution of 49.07 g (0.5 mol) of cyclohexanone and 41.45 g (0.33 mol) of nitrobenzene. Afterward, the reactor was heated up to 160.degree. C. with stirring, and after the removal of water present in the catalyst, the solution in the dropping device was dropped over 4 hours, while a temperature of 158.degree.-162.degree. C. was maintained. After completion of the dropping, the solution was stirred for 0.5 hour, while this temperature range was maintained. Water produced during this step was removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 21.0 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of cyclohexanone was 100%, and the yield of diphenylamine was 99.2%.
In succession, the previously recovered catalyst was used, and 5% Pd/C was added as shown in Table 22 and the reaction was then similarly carried out. As a result, the average amount of the added new 5% Pd/C catalyst necessary to maintain a reaction rate and a selectivity was about 15% of its initial amount.
TABLE 22______________________________________ Amount of AddedNumber of New 5% Pd/C Conversion SelectivityRecycling Catalyst (g) (mol %) (mol %)______________________________________1 0.47 98.7 96.72 0.47 94.5 92.43 0.93 95.7 93.34 0.93 96.0 93.75 0.93 96.2 94.06 0.47 93.6 90.87 0.70 95.3 92.68 0.70 94.1 91.79 0.70 93.4 91.210 0.70 92.7 90.4______________________________________
EXAMPLE N1
In a 200 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer, a dropping device and a stirrer were placed 7.72 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 0.91 g of 1N-NaOH, 0.55 g of butyric acid, 60.00 g of N,N-dimethylformamide and 16.07 g (0.15 mol) of toluidine, and in the dropping device was prepared and stored a mixed solution of 33.65 g (0-3 mol) of 4-methylcyclohexanone and 27.43 g (0.2 mol) of p-nitrotoluene. Afterward, the reactor was heated up to 140.degree. C. with stirring, and after the removal of water present in the catalyst, the solution in the dropping device was dropped over 6 hours, while a temperature of 134.degree.-142.degree. C. was maintained. After completion of the dropping, the solution was stirred for 1 hour, while this temperature range was maintained. Water produced during this step was removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 12.6 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of 4-methylcyclohexanone was 99.8%, and the yield of ditolylamine was 98.8%.
In succession, the previously recovered catalyst was used, and 5% Pd/C containing 50% of water, NAOH and butyric acid were added as shown in Table 23 and the reaction was then similarly carried out. As a result, the average amount of the added new catalyst necessary to maintain a reaction rate and a selectivity was about 6.0% of its initial amount.
TABLE 23______________________________________ Amount Con- Select- of Added Butyric version ivityNumber of New Catalyst 1N--NaOH Acid (mol (molRecycling 5% Pd/C (g) (g) (g) %) %)______________________________________1 0.39 0.08 0.55 100.0 99.22 0.19 0.08 0.55 100.0 99.13 0.19 0.08 0.55 100.0 99.04 0.19 0.08 0.55 100.0 99.15 0.19 0.08 0.55 100.0 98.9______________________________________
EXAMPLE N2
In a 200 ml round bottom flask equipped with a reflux condenser with a separator, a thermometer, a dropping device and a stirrer were placed 7.72 g of 5% Pd/C containing 50% of water made by N.E. Chemcat Co., Ltd., 60.00 g of N,N-dimethylformamide and 16.07 g (0.15 mol) of toluidine, and in the dropping device was prepared and stored a mixed solution of 33.65 g (0.3 mol) of 4-methylcyclohexanone and 27.43 g (0.2 mol) of p-nitrotoluene. Afterward, the reactor was heated up to 140.degree. C. with stirring, and after the removal of water present in the catalyst, the solution in the dropping device was dropped over 6 hours, while a temperature of 134.degree.-142.degree. C. was maintained. After completion of the dropping, the solution was stirred for 1 hour, while this temperature range was maintained. Water produced during this step was removed from the reaction system by adding benzene to the reactor to cause azeotropy, condensing water by the reflux condenser, and then separating it by the separator. The amount of the removed water was 12.5 g. Next, the reaction solution was cooled to room temperature, and the 5% Pd/C was then removed from the reaction solution by filtration. The resultant filtrate was analyzed by the use of gas chromatography. The conversion of 4-methylcyclohexanone was 99.6%, and the yield of ditolylamine was 98.7%.
In succession, the previously recovered catalyst was used, and the new catalyst was added as much as an average amount of about 8.3% based on the initial amount as shown in Table 24 and the reaction was then similarly carried out. The results obtained were shown in the same table.
TABLE 24______________________________________ Amount of AddedNumber of New Catalyst Conversion SelectivityRecycling 5% Pd/C (g) (mol %) (mol %)______________________________________1 0.39 98.5 96.72 0.19 95.6 92.83 0.39 95.8 92.74 0.39 93.9 89.95 0.59 95.1 90.5______________________________________
The method of the further aspect of the present invention will hereinafter be described specifically by the following examples.
EXAMPLE O1
Charged in a 200-ml round bottom flask equipped with a separator-fitted reflux condenser, a thermometer and a stirrer were 3.03 g of 5% Pd/C (water content: 50 wt. %; product of N.E. Chemcat Corp.), 64.0 g of N,N-dimethylacetamide, 7.21 g (0.07 mole) of paraphenylenediamine (hereinafter abbreviated as "PPD"), 19.63 g (0.20 mole) of cyclohexanone (hereinafter abbreviated as "CH") and 18.42 g (0.13 mole) of paranitroaniline (hereinafter abbreviated as "PNA"). While maintaining the internal temperature at 158.degree.-162.degree. C., the contents were continuously stirred for 5 hours. During that period, benzene was charged so that resulting water was azeotropically distilled off. The azeotropically distilled water-benzene mixture was condensed in the reflux condenser and was then separated through the separator. The reaction mixture was then cooled to room temperature and the 5% Pd/C was filtered off from the reaction mixture. The filtrate was analyzed by gas chromatography, thereby obtaining the following data:
Conversion of CH: 99.95 (mol % per CH)
Yield of P-ADPA: 49.87 (mol per CH)
By-production of N,N'-p-DPPA: 36.50 (mol % per CH)
Recovery of non-dehydrogenated product: 3.26 (mol % per CH)
EXAMPLES O2-O4
In each example, a reaction was conducted in a similar manner to Example O1 except that the amount of PPD in Examples O2-O4 was changed as shown in Table 25. The results are presented in Table 25.
COMPARATIVE EXAMPLE 1
A reaction was conducted in a similar manner to Example O1 except for the substitution of p-cymene for N,N-dimethylacetamide in Example O1. The results are presented in Table 25.
TABLE 25__________________________________________________________________________ Recovery of un- (PPD + PNA)/CH Conversion of CH Yield of p-ADPA By-production of dehydrogenated (molar ratio) (mol %) (mol %) N,N'-p-DPPA product (mol__________________________________________________________________________ %)Example O2 1.4 100 72.57 14.21 5.14Example O3 1.7 100 75.18 10.67 5.53Example O4 2.0 99.93 79.51 7.13 5.06Comp. Ex. O1 1.0 100 28.70 1.27 45.98__________________________________________________________________________
EXAMPLE O5
Charged in a 200-ml round bottom flask equipped with a separator-fitted reflux condenser, a thermometer, a dropping device and a stirrer were 3.03 g of 5% Pd/C (water content: 50 wt. %; product of N.E. Chemcat Corp.), 40.0 g of N,N-dimethylacetamide, and 7.21 g (0.07 mole) of PPD. A mixed solution consisting of 19.63 g (0.20 mole) of CH and 18.42 g (0.13 mole) of PNA was prepared and charged in the dropping device. The internal temperature of the flask was raised to 160.degree. C. under stirring and, while maintaining the internal temperature at 158.degree.-162.degree. C., the solution in the dropping device was added dropwise over 6 hours. After the completion of the dropwise addition, the contents of the flask were stirred for 1 hour while maintaining the internal temperature within the above temperature range. During that period, benzene was charged so that resulting water was azeotropically distilled off. The azeotropically distilled water-benzene mixture was condensed in the reflux condenser and was then separated through the separator. The reaction mixture was then cooled to room temperature and the 5% Pd/C was filtered off from the reaction mixture. The filtrate was analyzed by gas chromatography, thereby obtaining the following data:
Conversion of CH: 99.51 (mol % per CH)
Yield of P-ADPA: 54.00 (mol % per CH)
By-production of N,N'-p-DPPA: 35.65 (mol % per CH)
Recovery of non-dehydrogenated product: 9.72 (mol % per CH)
EXAMPLES O6-O7 & COMPARATIVE EXAMPLE O2
In each example, a reaction was conducted in a similar manner to Example O5 except that the corresponding polar solvent (Examples O6 and O7) or the non-polar solvent (Comparative Example O2) shown in Table 26 was used instead of N,N-dimethylacetamide in Example O5. The results are presented in Table 26.
TABLE 26__________________________________________________________________________ Recovery of un- Conversion of CH Yield of p-ADPA By-production of dehydrogenated Solvent (mol %) (mol %) N,N'-p-DPPA product (mol__________________________________________________________________________ %)Example O6 1,3-Dimethyl- 100 56.56 29.13 9.49 imidazolidinoneExample O7 Diethylene glycol 100 57.51 32.75 4.37 dimethyl etherComp. Ex. O2 p-Cymene 100 32.13 1.36 48.98__________________________________________________________________________
EXAMPLES O8-O12
In each example, a reaction was conducted in a similar manner to Example O5 except that the amount of PPD in Examples O5 was changed to set the (PPD+PNA)/CH ratio at the corresponding value shown in Table 27.
The results are presented in Table 27.
TABLE 27__________________________________________________________________________ Recovery of un- (PPD + PNA)/CH Conversion of CH Yield of p-ADPA By-production of dehydrogenated (molar ratio) (mol %) (mol %) N,N'-p-DPPA product (mol__________________________________________________________________________ %)Example O8 1.187 100 75.12 22.90 2.91Example O9 1.437 100 81.03 16.16 2.19Example O10 1.687 100 86.87 0.67 1.71Example O11 1.987 100 89.64 9.12 1.24Example O12 6.950 100 92.99 1.66 5.65__________________________________________________________________________
EXAMPLES O13-O15
In each example, a reaction was conducted in a similar manner to Example O5 except that PPD and PNA in Example O5 were replaced by metaphenylenediamine (hereinafter abbreviated as "MPD") and metanitroaniline (hereinafter abbreviated as "MNA"), respectively, and the (MPD+MNA)/CH ratio was set at the corresponding value shown in Table 28.
The results are presented in Table 28.
TABLE 28__________________________________________________________________________ Recovery of un- (MPD + MNA)/CH Conversion of CH Yield of m-ADPA By-production of dehydrogenated (molar ratio) (mol %) (mol %) N,N'-p-DPPA product (mol__________________________________________________________________________ %)Example O13 1.000 99.9 53.4 43.2 0.9Example O14 1.417 99.9 75.0 18.5 1.3Example O15 1.917 100 81.8 12.4 0.7__________________________________________________________________________
EXAMPLE O16
Charged in a 200-ml round bottom flask equipped with a separator-fitted reflux condenser, a thermometer, a dropping device and a stirrer were 3.03 g of 5% Pd/C (water content: 50 wt. %; product of N.E. Chemcat Corp.), 40.0 g of triethylene glycol dimethyl ether, and 27.04 g (0.25 mole) of orthophenylenediamine. A mixed solution consisting of 19.63 g (0.20 mole) of CH and 18.42 g (0.13 mole) of orthonitroaniline was prepared and charged in the dropping device. The internal temperature of the flask was raised to 170.degree. C. under stirring and, while maintaining the internal temperature at 170.degree.-173.degree. C., the solution in the dropping device was added dropwise over 15 hours. After the completion of the dropwise addition, the contents of the flask were stirred for 2 hours while maintaining the internal temperature within the above temperature range. During that period, benzene was charged so that resulting water was azeotropically distilled off. The azeotropically distilled water-benzene mixture was condensed in the reflux condenser and was then separated through the separator. The reaction mixture was then cooled to room temperature and the 5% Pd/C was filtered off from the reaction mixture. The filtrate was analyzed by gas chromatography, thereby obtaining the following data:
Conversion of CH: 100 (mol % per CH)
Yield of O-ADPA: 63.8 (mol % per CH)
Recovery of non-dehydrogenated product: 35.8 (mol % per CH)

Number	Date	Country
4-214078	Aug 1992	JPX
4-261505	Sep 1992	JPX
4-265897	Oct 1992	JPX
4-265898	Oct 1992	JPX
4-282940	Oct 1992	JPX
4-290133	Oct 1992	JPX
4-291311	Oct 1992	JPX
4-297096	Nov 1992	JPX
5-119975	May 1993	JPX
5-121423	May 1993	JPX
5-124062	May 1993	JPX
5-126826	May 1993	JPX
5-126827	May 1993	JPX
5-133273	Jun 1993	JPX
5-303707	Dec 1993	JPX
5-307638	Dec 1993	JPX
5-071734	Apr 1994	JPX

Number	Name	Date
4046810	Moggi et al.	Sep 1977
4057581	Krall et al.	Nov 1977
5196592	Immel et al.	Mar 1993
5344987	Immel et al.	Sep 1994
5449829	Kusuda et al.	Sep 1995

Number	Date	Country
0103990	Mar 1984	EPX
49-49925	May 1974	JPX
49-49924	May 1974	JPX
57-4623	Jan 1982	JPX
5-117214	May 1993	JPX
98925	Feb 1962	GBX
975097	Nov 1964	GBX
1382206	Jun 1973	GBX

	Number	Date	Country
Parent	353379	Dec 1994
Parent	100149	Aug 1993

Method for preparing aromatic secondary amino compound

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