CA1211469A

CA1211469A - Process for preparation of 3,3'- or 3,4'- diaminodiphenylmethane

Info

Publication number: CA1211469A
Application number: CA000427659A
Authority: CA
Inventors: Keizaburo Yamaguchi; Kenichi Sugimoto; Yoshimitsu Tanabe; Saburo Kawashima; Akihiro Yamaguchi
Original assignee: Mitsui Toatsu Chemicals Inc
Current assignee: Mitsui Toatsu Chemicals Inc
Priority date: 1982-09-27
Filing date: 1983-05-06
Publication date: 1986-09-16
Also published as: JPS5955855A; GB2127400B; NL189348C; NL189348B; KR840006325A; IT8321577A0; FR2533557A1; FR2533557B1; DE3318534C2; DE3318534A1; JPH0433781B2; NL8301741A; GB2127400A; CH654295A5; IT1163504B; KR860000997B1; GB8313637D0

Abstract

Process for Preparation of 3,3'- or 3,4'-Diaminodiphenylmethane Abstract of the Disclosure Preparation of 3,3'- or 3,4'-diaminodiphenylmethane by catalytically reducing and dechlorinating, in the presence of a reduction catalyst, a dinitrobenzophenone compound having the formula wherein X is chlorine and attached to a position 4 or 6 on the benzene ring, and Y is hydrogen or chlorine with the proviso that when Y is hydrogen, the nitro group is attached to a position 3' or 4', and when Y
is chlorine, Y is attached to a position 4' and the nitro group is attached to a position 3'.

Description

a~
~L~
The present invention rélatés to a novel process for the preparation of 3,3'- or 3,4'-diaminodiphenyl~
methaneO
3,3'-Diaminodiphenylmethane and 3,4'-diamino-diphenylmethane are useful as monomers for the produc-tion of high-molecular compounds, intermediates for the production of agricultural chemicals, pharmaco-logical compounds and dyes, particularly useful as starting materials for the production of polyamides and polyimides having excellent heat resistance.
Herefore, 3,3'-diaminodiphenylmethane has been prepared by condensing 3-nitrobenzyl alcohol with nitrobenzene or condensing nitrobenzene with formal-dehyde to prepare 3,3'-dinitrodiphe~ylmethane which is then reduced in the presence of stannic chloride or iron [ L. Gatterman et al., Ber., 27, 2295 (1894);
L. Thorp et al. 9 J. Am. Chem. Soc., 37, 373 (1915);
M. Schopff et al., Ber., 27 9 2322 (1894~ ~.
3,4'-Diaminodiphenylmethane has been prepared by condensing 4-nitrobenzyl alcohol with nitrobenzene to prepare 3,4'-dinitrodiphenylmethane which is then reduced [ L. Gattarmann et al., Ber., 27, 2293 (1894) ].
However, even when the condensation reaction between benzyl alcohol and nitrobenzene or between nitrobenzene and formalin is conducted for a long period of time by using a large amount of concentrated sulfuric acid, these processes result in yields of dinitrodiphenylmethane of as low as only 20 to 30 %.
Further, dinitrodiphenylmethane must be reduced in the presence of a tin compound or iron to obtain diaminodiphenylmethane. But, it is bothersome to separate the metallic compound used for the reduction from the product and it is necessary to Pay attention lest trace amounts of the me-tal should remain in the product.
Thus the conventional processes of preparing dinitrodiphenylmethane by the known condensation reaction and reducing it to prepare diaminodiphenyl-methane have disadvantages in that they require much cost and effort for the disposal of a large amount of various waste materials to prevent them from causing environmental pollution or for the recovery of them~
and in addition thereto the desired product is obtained in a low yieldO Accordingly, these processes are industrially unfavorable from the viewpoints of economy and environmental protection.

An object of the present invention is to provide an industrially advantageous and economical process for the preparation o~ 3,3'- or 3,4'~diaminodiphenyl-methane.
Another object o~ the present invention is to provide a process for -~he preparation of 3,3'- or 3,4'-diaminodiphenylmethane in a high yield.
Still another object of the present invention is to provide a process which does not require much cost and effort as compared with the conventional processes for the disposal of a large amount of various waste materials, formed as by-products in manufacturing processes, to prevent them from causing environmental pollution and which is excellent in the viewpoint of environmental protection.
In accordance with this invention, it is possible to prepare 3,3'- or 3,4'-diaminodiphenylmethane by catalytically reducing and dechlorinating, in the presence of a reduction catalyst 9 a dinitrobenzophenone having the formula X~ ~Y

wherein X is chlorine and attached to a position 4 or 6 on the benzene ring, Y is hydrogen or chlorine with the proviso that when Y is hydrogen, the nitro ~21~ 9 , group is attached to a positinn 3~ or 4', and when Y
is chlorine, Y is attached to a position 4' and the nitro group is attached to a position 3'.
The process of the present invention has advan-tages in that it does not require much cost and effort for the disposal of a large amount of various was-te materials to prevent them from causlng environmental pollution or for the recovery of them and in addition thereto the desired product can be prepar~d in a high yield, while the conventional processes of preparing 3,3'- or 3,4'-dinitrodiphenylmethane by the known condensation reaction and reducing it require much cost and effort.
m e process of the present invention comprislng dechlorinating a dinitrochlorobenzophenone compound as ~educing its nitro groups and further converting its carbonyl group into a methylene group is not known by those skilled in the art. Therefore, -the present invention provides a novel process for the preparation of 3,3'- or 3,4'-diaminodiphenylmethane which can be prepared industrially advantageously.
~=~3 The present invention relates to a process for the preparation of 3,31_ or 3,4'-diaminodiphenylmethane by catalytically reducing and dechlorinating, in the L4~

presence of a reduction catalyst, the dinitrobenzo-phenone compound represented by the above formula to obtain 3,3'- or 3,4'-diaminodiphenylmethane hydrochlo-ride followed by neutralization with ammonia or an amine.
Typical dinitrobenzophenones that can be used as starting materials in the practice of the present invention include 3,3'-dinitro-4,41-dichlorobenzophenone, 3,3'~dinitro-6,4'-dichlorobenzophenone, 3,3'-dini-tro-6-chlorobenzophenone, 3,3'-dinitro-4-chlorobenzophenone, 3,4'-dinitro-6-chlorobenzophenone and 3,4'-dinitro~4-chlorobenzophenone.
These dinitrobenzophenones can be easily obtained by nitrating the corresponding halogenobenzophenones such as 4,4'-dichlorobenzophenone, 4-chlorobenzophenone, 4-nitro-6'-chlorobenzophenone, 4 chloro-4'-nitro benzophenone and 2,4'~dichlorobenzophenone.
For example, 3,3'-dinitro-4 9 4'-dichlorobenzo-phenone can be prepared in a yield of 95 to 98 % by nitrating 4,4'-dichlorobenzophenone ~ E. R. Kofanov e-t al., J. Org. Chem. USSR, 15, 98-lOO (1979) ].
5,3'-Dinitro-2,4'--dichlorobenzophenone can be prepared in a high yield by nitrating 2,4'-dichlorobenzophenone [ E. H. Faith et al., J. Am. Chem. Soc., 779 543 (1955) ]. 3,3'-Dinitro 4-chlorobenzophenone can be prepared in a high yield by nitrating 4-chlorobenzo-phenone ~ G. S Mironov et al., J, Org. Chem, USSR, 8, 1533 (1972) ~. 3,4'-Dinitro-4-chlorobenzophenone can be prepared by nitrating 4-halogeno~4~-nitrobenzo-phenone obtained by the condensation reaction between p-nitrobenzoyl chloride and chlorobenzene [ P. T.
Montagne et al., Ber., 49, 2267-2270 (1916); G. S.
Mironov et al,, J. Org. Chem. USSR, 8, 1538-1543 (1972) ]. 3,3l-Dini-tro-694'-dichlorobenzophenone can be prepared in a high yield by nitrating 2,4'-dichloro-benzophenone obtained by the condensation reaction - between 2-chlorobenzoyl chloride and chlorobenzene [ H. F. Faith et al., J Am. Chem. Soc., 77, 543 (1955) ].
As reduction catalysts suitable for use in the practice of the present invention, metal catalysts which are conventionally used in cataly-tic reduction may be used. Examples of the metals are nickel, palladium, platinu~l, rhodium, ruthenium9 cobalt and iron. Palladium catalyst is industrially pre~erred.
These catalysts may be used in a metallic ~o~m, but they are generally supported on a carrier such as carbon, bariu~ sulfate, silica gel or alumina.
Nickel, cobalt and copper may be used in the form of a Raney catalyst.

~ :`
~211~691 The catalyst is used in an amount of from 0.05 to 10 % by weight based on that of the starting dinitrobenzophenone. When the catalyst is used in a metallic form, the amount is usually within the range 5 of from 2 to 10 ~ by weight. When supported on a carrier, the amount is within the range of from 0.1 to 5 % by weight.
Generally~ the reaction of the present invention is conducted in an organic solvent. Any o~ organic solvents which are inert to the reaction of the pre~
sent invention may be used without particular limita-tion. Examples of such organic solvents include alcohols such as methanol, ethanol and isopropyl alcohol; glycols such as ethylene glycol and propylene glycol; ethers such as ether, dioxane, tetrahydrofuran and methyl cellosolve; aliphatic hydrocarbons such as hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrach-loride, 1,2-dichloroethane, 1,1,2-trichloroethane and tetrachloroethane; N,N-dimethylformamide and dimethyl sulfoxide. Hydrogen chloride or hydrochloric acid in a molar ratio of 1 to 2 may be previously added to these solvents to carry out the reduction of the present invention. When an organic solvent immiscible with water is employed and the reaction proceeds too slow, the reaction can be accelerated by adding a conventional phase transfer catalyst such as a qua-ternary ammonium salt or a quaternary phosphonium salt, The solvent is used in an amount sufficient to suspend the starting dinitrobenzophenones or to completely dissolve them. There is no particular upper limit for the amount of~-the solvent to be used, but the solvent is usually used in an amount o~ 0.5 to 10 times by weight that of the starting material.
The reac-tion temperature is usually within the range of from 20 to 200C, preferably 50 to 150C.
The reaction pressure is usually within the range of from atmospheric pressure to 50 kg/cm2 G.
In the practice of the present i~vention, the dinitrobenzophenone compound is suspended or dissolved in a solvent and a reduction catalyst is added there-to.
Hydrogen is introduced into the mixture with stirring at a predetermined temperature to convert the nitro groups into amino groups and the carbonyl group into a methylene group and to e~fect dechlorination, thus obtaining 3,3'- or 3,4'-diaminodiphenylmethane hydrochloride~
The reaction mixture is filtered to recover a ~Zl~L4~9 mixture composed of the desired hydrochloride and the catalyst. Then the mlxture is dissolved in a 70-90 %
aqueous isopropyl alcohol solution with heating, and filtered. The filtrate is cooled to precipitate pure 3,3'- or 3,4'-diaminodiphenylmethane hydrochloride which is then isolated by filtration. The isolated hydrochloride is dissolved in water and then neutra-lized to give free 3,3'- or 3,4'-diaminodiphenylmethane~
The progress of the reaction can be traced by the absorption of a theoretical amount of hydrogen or by means of thin layer chromatography.
me following examples ~urther illustrate the present invention in more detail.
Example 1 34.1 g (0 1 mol) of 3,3'-dinitro-4,4' dichloro-benzophenone, 3.4 g o~ 5 % Pd/C catalyst (a product of Nippon Engelhardt K.K.) and 100 m~ of dioxane were charged in a closed glass vessel equipped with a thermometer and a stirrer. While stirring the mix-ture at a temperature of 80 to ~5C, hydrogen was introduced thereinto and 21.8 ~ (0.97 mol) of hydrogen was absorbed in 10 hours. Since no more absorption of hydrogen was observed, the reaction was terminated at this point.
The reaction mixture was cooled to room tempera-ture. A precipitate was rec.overed by filtration and _ g _ ~2~

washed with 10 mB of dioxane to obtain a black filter cake. This filter cake was dissol~ed in 100 m~ of an 80 % aqueous isopropyl alcohol solution with heating.
The solution was filtered with heating to remove the catalyst. The filtrate was cooled -to precipitate 3,3'-diamino-diphenylmethane dihydrochloride as a white needle crystal. This product was recovered by filtra-tion, washed with 10 mB of a 90 ~ aqueous isopropyl alcohol solution, and dried to give 20~3 g (yield 75 ~) of pure 3,3'-diaminodiphenylmethane dihydro-chloride as a white needle crystal with m.p. above 260C.
Elementary analysis for C13H16N2Ca2:
calculated (%): C 57.6, H 6.09 N 10.3, C~ 26.1 found (%): C 57.4, H 6.1, N 10.3, CB 25.9 Example 2 34.1 g (0.1 mol) of 3j3'-dinitro 4,4'-dichlor-benzophenone, 1.5 g of 5 % Pd/C9 and 100 m~ of ethanol were charged in a closed glass vessel equipped with a thermometer and a stir~er. While stirring the mixture at a temperature of 50 to 60C 3 hydrogen was introduced thereinto and 22.9 ~ (1.02 mol) of hydrogen was absorbed in 7.5 hours. Since no more absorption of hydrogen was observed, the reaction was terminated at this point, The reaction solution was neutralized with 13.4 g (0,22 mol) of 28 % aqueous ammonia and fil-tered to remove the catalyst. The filtrate was concentrated -to give 3,3'~diaminodiphenylmethane as a brown oil. A high performance liquid chromatography revealed that the purity was 93.8 %.
This brown oil was vacuum-distilled to give 16.8 g (yield 85 %) of a fraction having a boiling point of 228 to 229C/5 mmHg. The purity was 99.9 %.
This fraction was recrystallized from benzene to give a pure product as a white prismatic crystal with m.p, of 84.5 to 85C.
Elementary analysis for C13H14N2:
calculated (%): C 78.7, H 7.1, N 14.1 found (%): C 78~7, H 7.2, N 14.1 Example 3 34.1 g (0.1 mol) of 3,3' dinitro-6,4'-dichloro-benzophenone, 1 g of palladium black catalyst and 100 mB of ethyl cellosolve were charged in a closed glass vessel equipped with a thermometer and a stirrer.
While stirring the mixture at a temperature of 75 to 80C, hydrogen was introduced thereinto and 22.3 ~
(1.0 mol) of hydrogen was absorbed in 5 hours. Since no more absorption of hy~rogen was observed, the reaction was terminated at this point. The reaction solution was neutralized with 42 g (0.21 mol) of a `~2~L~9L6~

20 % aqueous caustic soda solution and filtered to remove the catalyst. m e filtrate was concentrated and vacuum-distilled to give 15 6 g (yield 78.7 ~) of a fraction having a boiling point of 228 to 229C/
5 mmHg.
Purity: above 99.9 Example 4 15~3 g (0.05 mol) of 3,3'-dinitro-4-chloroben-zophenone, 1.5 g of 10 % Pt/C and 50 m~ of diethylene glycol dimethyl ether were charged in an autoclave.
While stirring the mixture at a temperature of 100 to 110C, hydrogen was introduced. m e reaction was conducted for two hours while keeping the pressure at 10 Kg/cm2G. After the completion of the reaction, the reaction mixture was cooled and neutralized with 3.7 g (0.06 mol) of 28 % aqueous ammonia. The catalyst was removed by filtration. The filtrate was concen~
trated and vacuum-distilled to give 7.9 g (yield 79 8 %) of a fraction having a boiling point o~ 228 to 229oc/5 mmHg.
Example 5 30.7 g (0.1 mol) of 3,3'-dinitro-4-chlorobenzo-phenone~ 1 5 g of 5 ~ Pd/C and 100 mB o~ ethanol were charged in a closed glass vessel equipped with a thermometer and a stirrer. While stirring the mixture at a temperature of 65 to 70C, hydrogen was introduced thereto and 20.1 ~ (0~9 mol) of hydrogen was absorbed in 6 hours. Since no more absorption of hydrogen was observed, the reaction was terminated at this point.
The reaction mixture was cooled to room -temperature and filtered to obtain a black filter cake. This filter cake was dissolved in lO0 mB of a 90 % aqueous isopropyl alcohol solutiQn with heating. The catalyst was removed by filtra-tion with heating. The filtrate was cooled to precipitate 3,3'-diaminodiphenylmethane hydrochloride as a crystal. This crystal was recovered by fil-tration, washed with lO m~ of isopropanol and neutralized with dilute aqueous ammonia to precipitate a white crystal. The crystal was recovered by filtra-tion and dried in vacuo to give 1603 g (yield 82.2 %) of 3,3' diaminodiphenylmethane.
Examples 6 to 9 The experiment of Example 2 was repeated except that the catalysts, the solvents, the reaction tempe-ratures and the pressures given in Table l were employed to give the desired product.

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Example 10 15.3 g (0.05 mol) of 3,4'-dinitro-4-chlorobenzo-phenone, 0.75 g of 5 % Pd/C and 50 mB of ethyl cellosolve were charged in a closed glass vessel equipped with a thermometer and a stirrer. While stirring the mixture at a temperature of 75 to 80 C, hydrogen was introduced thereinto and 10.3 ~ (0.46 mol) of hydrogen was absorbed in 13 hours. Since no more absorption of hydrogen was observed, the reaction was terminated at this point.
The reaction solution was neutralized with 3,6 g (0.06 mol) of 28 % a~ueous ammonia. The catalyst was removed by filtration. The filtrate was concentrated to obtain 3,4'-diaminodiphenylmethane as a brown oil. A high performance liquid chromatography revealed that the purity was 88.2 %.
This brown oil was vacuum-distilled to give 7.9 g (yield 79.7 %) of 3,4'-diaminodiphenylmethane having a purity of 9907 ~ according to a high performance liquid chromatography This product was recrystallized from water to give a pure product as a white needle crystal with m.p. o~
85 to 87C.
Elementary analysis for C13HlLN2:
calculated (%): C 78.7, H 7.1, N 14.1 found (%): C 7805, H 7.1, N 14~0 -:~2~4~9 Example 11 ! i m e reduction of 15.3 g (0.05 mol) of 3,4'-dinitro-4 chlorobenzophenone was conducted in a similar manner to that of Example 10. After the completion of the reaction, the catalyst was immediately removed by filtration with heating. 5.2 g (0.05 mol) of concen-tra-ted hydrochloric acid was added to the filtrate.
Upon cooling, a light brown needle crystal was preci-pitated. The crystal was recovered by filtration, washed with isopropanol, and dried to give 8.9 g ~yield 66 ~) of 3,4'-diaminodiphenylmethane hydrochloride.
This crude crystal was recrystallized ~rom aqueous isoprpanol solution to give pure 3,4~-diaminodiphenyl-methane hydrochloride as a white crystal with m.p.
above 210 C ~slowly decomposed) Elementary analysis for C13H16N2C~2:
calculated (%): C 57.6, H 6.0, N 10.3, C~ 26.1 found (%) : C 57.3, H 6.2, N 10.2, CB 25.9

Claims

What is claimed is:

1. A process for the preparation of 3,3'- or 3,4'-diaminodiphenylmethane, which comprises catalytically reducing and dechlorinating, in the presence of a reduction catalyst, a dinitrobenzophenone compound having the formula wherein X is chlorine and attached to a position 4 or 6 on the benzene ring, and Y is hydrogen or chlorine with the proviso that when Y is hydrogen, the nitro group is attached to a position 3' or 4', and when Y is chlorine, Y is attached to a position 4' and the nitro group is attached to a position 3'.

2. A process as set forth in claim 1, wherein the reduction catalyst is a metal catalyst for use in catalytic reduction.

3. A process as set forth in claim 1, wherein the catalyst is used in an amount of 0.05 to 10 % by weight based on the amount of the dinitrobenzophenone compound.

4. A process as set forth in claim 1, wherein the reaction temperature is within the range of 20 to 200°C.

5. A process as set forth in claim 1, wherein the reaction is conducted in an organic solvent.

6. A process as set forth in claim 2, wherein the metal catalyst is nickel, palladium, platinum, rhodium, ruthenium or cobalt.

7, A process as set forth in claim 6, wherein the metal catalyst is supported on a catalyst carrier.

8. A process as set forth in claim 6, wherein the metal catalyst is a Raney catalyst.

9. A process as set forth in claim 5, wherein the organic solvent is selected from the group consisting of alcohols, glycols, ethers, aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, N,N-dimethylformamide and dimethyl sulfoxide.