FR2533557A1 - PROCESS FOR THE PREPARATION OF 3,3'-OR 3,4'-DIAMINODIPHENYLMETHANE - Google Patents

Abstract

THE INVENTION RELATES TO A PROCESS FOR THE PREPARATION OF 3,3- OR 3,4-DIAMINODIPHENYLMETHANE. THIS PROCESS INCLUDES THE CATALYTIC REDUCTION AND THE DECHLORATION, IN THE PRESENCE OF A REDUCTION CATALYST, OF A DINITROBENZOPHENONE OF FORMULA: (CF DRAWING IN BOPI) IN WHICH X IS CHLORINE AND IS FIXED IN POSITION 4 OR 6 OF THE BENZENIC CORE, AND THERE IS HYDROGEN OR CHLORINE ON CONDITION THAT WHEN HYDROGEN IS THERE, THE NITRO GROUP IS FIXED IN POSITION 3 OR 4 AND WHEN IS CHLORINE THERE, IS FIXED IN POSITION 4 AND THE NITRO GROUP IS FIXED IN POSITION 3.

Description

The present invention relates to a novel method of

  preparation of 3,3 'or 3,42-diaminodiphenylmethane.

  3,3'-Diaminodiphenylmethane and 3,4 '= diaminodiphenyl

  Nylmethane are useful as monomers in the production of high molecular weight compounds, intermediate for

  production of chemicals used in agriculture,

  pharmacological and coloring matters, and particularly

  interesting as starting materials in the production of po-

  lyamides and polyimides with excellent resistance to

the heat.

  So far, 1,3-diaminodiphenylmethane has been

  prepared by condensing the alcohol 3 = nitrobenzyl with

  trobenzene or by condensing nitrobenzene with formaldehyde to prepare 3,3-dinitrodiphenylmethane which was then reduced in the presence of stannic chloride or iron. Lo Gatterman et al., Ber. 27, 2295 (1894); Lo Thorp et al., Jo Am O Chemo Soco, 37, 373 (1915) Mo Sch Spff et al., Bero, 27, 2322 (1894).

  3,4'-Diaminodiphenylmethane was prepared in

  4-nitrobenzyl alcohol with nitrobenzene to prepare 3,4-dinitrodiphenylmethane, which was later reduced / L Gattermann et al., Bero, 27, 2293 (1894). However, even if the condensation reaction between

  benzyl alcohol and nitrobenzene or nitrobenzene

  zen and formalin is conducted for a long period of time using a large amount of sulfuric acid

  concentrated, these processes give dinitrodi-

  phenylmethane as low as 20 to 30% o In addition, dini = trodiphenylmethane must be reduced in the presence of a tin or iron compound to obtain diaminodiphenylmethane But it is tedious to separate from the product the metal compound used for the reduction and we have to make sure that it stays

  the least possible traces of the metal in the product.

  Thus, conventional processes for the preparation of dinitro-

  phenylmethane by the known condensation reaction and its

  duction to obtain diai nodiphenyllet hane have disadvantages in that they require a lot of expense

  and efforts to eliminate a large

  waste to avoid environmental pollutants or their recovery, and in addition, the desired product is obtained in low yield.

  uninteresting from an industrial point of view for reasons of

  economy and protection of the environment.

  The present invention proposes to provide an advantageous and economically advantageous process from the industrial point of view for the

  preparation of 353 t or 3,4'-diaminodiphenylmethane.

  The present invention further proposes to provide a process for preparing 3,3 'or 3,41-diaminodiphenylmethane in a high yield. The present invention further proposes to provide a

  process which does not require much expense or effort

  traditional processes for the disposal of a large quantity of various wastes as by-products in manufacturing processes,

  pollute the environment, and which gives excellent performance

  from the point of view of the protection of the environment.

  According to the present invention, it is possible to prepare

  3,3 'or 3,4'-diaminodiphenylmethane by reduction of

  talytic and dechlorination, in the presence of a catalyst of

  duction, of a dinitrobenzophenone of formula: Xp CQ NO,

NO 2 O

  wherein X is chlorine and is attached at the 4 or 6 position to the benzene ring, Y is hydrogen or chlorine, provided that when Y is hydrogen, the nitro group is attached at the 3 'or 4 position 'and that when Y is chlorine, Y is fixed in position 4' and the nitro group is fixed in

position 3 '.

  The method of the present invention has advantages

  in the sense that it does not require much expense or

  for the elimination of a large quantity of various wastes in order to prevent them from polluting the environment or for their recovery and, in addition: the desired product may be

  obtained in a high yield, whereas conventional methods

  Preparation of 3,3 'or 3,4'-dinitrodiphenylmethane by the known condensation and reduction reaction requires a great deal of expense and effort

  The process of the present invention which comprises the

  chloxation of a dinitrochlorobenzophenone, the reduction of its nitro groups and further the transformation of its group

  carbonyl to a methylene group is not known to

  Accordingly, the present invention

  provides a novel process for preparing 3,39 or 3,4 '-

  The present invention relates to a preparation method which can advantageously be prepared from the industrial point of view.

  3,3 'or 3,4'-diaminodiphenylmethane by catalytic reduction.

  and dechlorination, in the presence of a reduction catalyst

  dinitrobenzophenone represented by the formula

  above to obtain the hydrochloride of 33 t 'or 3,4-diamino-

  diphenylmethane, followed by neutralization with ammonia

or an amine.

  Examples of dinitrobenzophenones that can be used

  be used as starting materials in the implementation of the pre-

  invention include 3,33 dinitro-4-dichlorobenzoate

  phenone, 3,3 '-dinitro-6,4'-dichlorobenzophenone, 3,3-dichlorobenzophenone

  dinitro-6-chlorobenzophenonei 3,3 t = dinitro-4-chlorobenzoate

  phenone, 3,4'-dinitro-6-chlorobenzophenone and 3,4 '= dinitrile

tro-4-chlorobenzophenone.

  These dinitrobenzophenones can easily be obtained

  by nitration of the corresponding halobenzophenones,

  such as 4,4'-dichlorobenzophenone, 4-chlorobenzophenol

  none, 4-nitro-6'-chlorobenzophenone, 4-chloro-4'-1-nitro-

  benzophenone and 2,4-t-dichlorobenzophenone.

  For example, 3,3, -dinitro-4,4'-dichlorobenzophenone can be prepared in 95-98% yield by nitrating 4,4'-dichlorobenzophenone / E R Kofanov et al.

  J Org Chem USSR, 15, 98-100 (1979) 5,31-dinitro-2,49-

  dichlorobenzophenone can be prepared in high yield

  by nitration of 2,4'-dichlorobenzoph 6 none / E H Faith and col-

  Laboratories, J Am Chem Soc, 77, 543 (1955) / The 3,3 '-dini

  3-chlorobenzophenone can be prepared in high yield by nitration of 4-chlorobenzophenone / G S Mironov and

  co-workers, J Org Chem USSR, 8, 1538 (1972) l 3,4 '-

  dinitro-4-chlorobenzophenone can be prepared by nitration of 4halog 6 no-4 t-nitrobenzophenone obtained by the reaction of

  condensation between p-nitrobenzoyl chloride and chlo-

  robenzene / P To Mountain and coworkers, Ber, 49, 2267-

  2270 (1916); G S Mironov et al., J Org Chem.

  USSR, 8, 1538-1543 (1972) l 3,3'-dinitrophenol-6,4'-dichlorobenzene

  zophenone can be prepared in a high yield by nitrate

  2,4 '-dichlorobenzophenone 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

  of the present invention, it is possible to use

  metal lysers that are commonly used in the r 6-

  catalytic duction Examples of the metals are nickel, palladium, platinum, rhodium, ruthenium, cobalt

  and iron From an industrial point of view, cat-

  These catalysts can be used in metallic form, but they are generally fixed on a support such as carbon, barium sulfate, silica gel or alumina. Nickel, cobalt and copper can be used.

  be used in the form of a Raney catalyst.

  The catalyst is used in an amount of 0.05 to 11 o

  by weight, relative to the starting dinitrobenzophenone,

  When the catalyst is used in metallic form, its

  amount is generally between 2 and 10% by weight.

  When it is fixed on a support, its quantity is included

between 0.1 and 5% by weight.

  In general, the reaction of the present invention is

  in an organic solvent. It is possible to use without

  In particular, any organic solvent which is inert to the reaction of the present invention. Examples of such organic solvents include alcohols such as methanol,

  ethanol, and isopropyl alcohol; glycols such as

  thylene glycol and propylene glycol; ethers such as the ether itself, dioxane, tetrahydrofuran and methylcellosolve; 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 tetrachloride, 1,2-dichloroethane, 11,2-

  trichloroethane and tetrachloroethane D NN-dimethylformamide and dimethylsulfoxide can be added in advance to

  these solvents hydrogen chloride or hydrochloric acid

  than at a molar ratio of 1 to 2 to effect the reduction

  of the present invention When an organic solvent is used

  immiscible with water and that the reaction evolves too slowly

  This reaction can be accelerated by adding a

  classical phase transfer lyser such as a deammo salt

  quaternary nium or a quaternary phosphonium salt.

  is used in sufficient quantity to

  suspension of the starting dinitrobenzophenones or for

  completely weld There is no upper limit

  how much of the solvent to use, but how much

  it is usually used in an amount of 0.5 to 10 times

the weight of the starting material.

  The reaction temperature is generally understood

  between 20 and 200 C, preferably between 50 and 150 C.

  The reaction pressure is generally between

  the atmospheric pressure and 4.9 M Pa gauge.

  In the practice of the present invention, dinitrobenzophenone is suspended or dissolved in

  a solvent and a reducing catalyst is added.

  generates hydrogen in the mixture while stirring at a predetermined temperature to convert the nitro groups to amino groups and the carbonyl group to the methylene group and to perform the dechlorination, so as to obtain the

  3,3 'or 3,4'-diaminodiphenylmethane hydrochloride.

  The reaction mixture is filtered to collect a mixture of

  mixture of the desired hydrochloride and the catalyst

  te, the mixture is dissolved in a 70-90 S aqueous solution

  isopropyl alcohol by heating and then filtering.

  colds the filtrate to precipitate the hydrochloride 3,3 '-

  or pure 3,4'-diaminodiphenylmethane which is then separated by filtration The separated hydrochloride is dissolved in water,

  then we neutralize it to obtain the 3,3 'or 3,4' -diamino-

free diphenylmethane.

  The evolution of the reaction can be followed by the ab-

  sorption of a theoretical quantity of hydrogen or by chromato-

Thin layer graph.

  The following examples illustrate the present invention

in more detail.

Example 1

  It is introduced into a closed glass container equipped with a

  thermometer and stirrer 34.1 g (0.1 mole) of 3,3 '

  4,4'-dichlorobenzophenone, 3,4 g of 5% Pd on carbon catalyst (a product of Nippon Engelhardt KK) and 10 ml of dioxane While stirring the mixture at a temperature of 85 OC, there is introduced hydrogen and is absorbed 21.8 liters (0.97 mole) of hydrogen in 10 hours Because we no longer notice hydrogen absorption, the reaction

M 3557

253355?

is over at this point.

  The reaction mixture is cooled to room temperature.

  The precipitate is filtered off and washed with 10 ml of dioxane to obtain a black filter cake. This cake is dissolved in 100 ml of an aqueous solution.

  80% isopropyl alcohol with heating.

  by heating to remove the catalyst

  the filtrate to precipitate the 3,3'-diamino dihydrochloride

  diphenylmethane in the form of white crystalline needles.

  This product is filtered off, washed with 10 ml of a 90% aqueous solution of isopropyl alcohol, and

  dried to obtain 20.3 g (75% yield) of dihydrochloride.

  3,3 '-diaminodiphenylmethane in the form of crys-

  white tallines melting above 260 C.

  Elemental analysis: C (%) H (%) N (%) C 1 (%) Calculated for C 13 H 16 N 2 C 12 57.6 6.0 10 3 26.1 Found: 5794 6.1 10.3 25.9

Example 2

  It is introduced into a closed glass container equipped with a

  thermometer and stirrer 34.1 g (0.1 mole) of 393 '-dini

  tr-4,4'-dichlorobenzophenone, 1.5 g of 5% Pd on carbon catalyst and 100 ml of ethanol. While stirring the mixture at a temperature of 50 to 60 ° C., hydrogen is introduced therein and 22.9 liters (i 102 moles) of hydrogen are absorbed in 7.5 hours.

  of hydrogen, the reaction is complete at this time.

  read the reaction solution with 13.4 g (0.22 mol) of

  aqueous ammonia at 28% and filtered to remove the catalyst

  The filtrate is concentrated to give 3,3-diaminodi

  phenylmethane in the form of a brown oil

  high performance liquid phase gas reveals purity

93.8% -

  This brown oil is distilled under vacuum to obtain

  16.8% (85% yield) of a fraction having a boiling point

  from 228 to 229 C / 666.5 Pa The purity is 99.9% o

253355?

  This fraction is recrystallized from benzene to obtain a pure product in the form of prismatic crystals.

whites melting at 84.5-85 C.

  Elemental analysis: C (%) H (%) N (%) Calculated for C 13 H 4 N 2 78.7 7.1 14,, Found: 78.7 7.2 14.1

Example 3

  We introduce in a closed glass container, equipped

  of a thermometer and a stirrer 34.1 g (O% 1 mole) of 3,3 '-

  dinitro-6,4'-dichlorobenzophenone, 1 g of palladium black catalyst and 100 ml of ethylcellosolve. While stirring the mixture at a temperature of 75 to 80.degree.

  hydrogen and 22.3 liters (1.0 mole) of hydrogen are

  in 5 hours Since we no longer notice

  Hydrogen sorption, the reaction is complete at this time.

  The reaction solution is neutralized with 42 g (0.21 mol) of 20% aqueous sodium hydroxide solution and filtered to remove the catalyst. The filtrate is concentrated and distilled under vacuum to give 15.6 g ( yield 78.7%)

  a fraction boiling at 228-229 ° C / 666.5 Pa.

Purity: greater than 99.9%.

Example 4

  15.3 g (0.05 mol) of 3,3'-dinitro-4chlorobenzophenone, 1,5 g of 10% catalyst are introduced into an autoclave.

  of charcoal Pt and 50 ml of dimethyl diethyl ether

  While stirring the mixture at a temperature of 100 to C, hydrogen is introduced.

  for two hours while maintaining the manometric pressure

  only at 0.99 M Pa At the end of the reaction, the mixture is cooled

  the reaction mixture and neutralized with 3.7 g (0.06 mol)

  28% aqueous ammonia. The catalyst is removed by filtration.

  The filtrate is concentrated and distilled under vacuum to give 7.9 g (79.8% yield) of a fraction boiling at 228-229 ° C / 666.5 Pa.

Example 5

  It is introduced into a closed glass container equipped with a

  thermometer and stirrer 30.7 g (0.1 mole) of 3,3 '

  3-chlorobenzophenone, 1.5 g of 5% Pd on carbon catalyst and 100 ml of ethanol. While stirring the mixture at 65 to 70 ° C., hydrogen is introduced and

  20.1 liters (0.9 mol) of hydrogen are absorbed in 6 hours.

  Since no hydrogen uptake 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.

  in 100 ml of a 90% aqueous solution of isopropyl alcohol

  During heating The catalyst is removed by filtration

  heating The filtrate is cooled to precipitate the chlorine

  3,3'-diaminodiphenylmethane hydrochloride in the form of

  The crystals are filtered off, washed with 1 ml of isopropanol and neutralized with dilute aqueous ammonia to precipitate white crystals. These crystals are filtered off and dried in vacuo to give

  hold 16.3 g (82.2% yield) of 3,3-diaminodiphenylmethane.

Examples 6 to 9

  The experiment of Example 2 is repeated except that the catalysts, solvents, reaction temperatures and reaction pressures indicated in

  Table 1 to obtain the desired product.

TABLE 1

Catalyst Example (g).

  No Solvent (ml) Reaction Temperature / Time (O C / h) Efficiency Pressure (% -)

1 uanomé -

tramp (M Pa) 6 Raney nickel 3,5

-110/5

0.19 0.29

  Palladium black ethyl acetate

1,100

% Pt / C% o of Pd / C ethanol

-75/12

-75/10

-75/28

benzene

pressure

muosphérique

pressure

mosphérique

0.99 1.09

p 4 w tg tg

Example 10

  It is introduced into a closed glass container equipped with a

  thermometer and stirrer 15.3 g (0.05 mol) of 3,4'-dinitrile

  3-chlorobenzophenone, 0.75 g of 5% Pd on carbon catalyst and 50 ml of ethyl cellosolve while stirring the medium.

  at a temperature of 75 to 80 o C, it introduces hy-

  and 10.3 liters (0.46 moles) of hydrogen are

  not in 13 hours Since we no longer observe absorption

  of hydrogen, the reaction is complete at this time.

  read the reaction solution with 3.6 g (0.06 mol) of ammonia

  28% aqueous ammonia The catalyst was removed by filtration.

  The filtrate is concentrated to give 3,4-diaminodiphenyl-

  methane as a brown oil High performance liquid chromatography reveals that the purity is

88.2%.

  This brown oil is vacuum distilled to give 7.9 g (yield 79.7%) of 3,4'-diaminodiphenylmethane with a purity of 99.7% according to high performance liquid chromatography. This product is recrystallized in water to obtain a

  pure product in the form of white crystalline needles

at 85-87 C.

  Elemental analysis: C (%) H (%) N (o) Calcd for C H 4 N 2: 78.7 7.1 14

13 14 2 97 7.1 14.1

* Found: 78.5 7.1 14.0

Example

  The reduction of 15.3 g (0.05 mol) of 3,4 'is carried out.

  dinitro-4-chlorobenzophenone in a manner similar to that

  of Example 10 At the end of the reaction, it is immediately removed

  Catalyst 5.2 g (0.05 mol) of concentrated hydrochloric acid were added to the filtrate. After cooling, light brown crystalline needles precipitated. The crystals were filtered off, isopropanol, and dried to obtain 8.9 g

  (yield 66%) of 3,4'-diaminodiphenylmethane hydrochloride.

  These crude crystals are recrystallized from an aqueous solution

  isopropanol to give 3,4'-diaminodihydrochloride

  pure phenylmethane in the form of white crystals melting

  above 210 C (slow decomposition).

  Elemental analysis: C (%) H (%) N (%) Cl (i) Calcd for C 13 H 16 N 2 C 1257.6 6.0 10.3 26.1 Found: 57.3 6.2 10, 2 25.9

R EVE N D I CAT I ON S

  Process for the preparation of 3,3 'or 3,4'-diaminodi

  phenylmethane, characterized in that it comprises catalytic reduction and dechlorination, in the presence of a reduction catalyst, of a dinitrobenzophenone of formula: ## STR2 ##

NO 2

  wherein X is chlorine and is attached to the 4- or 6-position of the benzene ring, and Y is hydrogen or chlorine, provided that when Y is hydrogen, the nitro group is attached at the 3-position; or 4 t, and that when Y is chlorine, Y

  4 'and the nitro group is fixed in position

3 t.

  Process according to Claim 1, characterized in that the reduction catalyst is a metal catalyst for use in catalytic reduction. Process according to Claim 1, characterized in that the catalyst is used in an amount of from 0.05 to 10%. by weight relative to the amount of dinitrobenzophenone 4 Process according to claim 1, characterized in that the reaction temperature is between 20 and 200 ° C. Process according to claim 1, characterized in that

  that the reaction is conducted in an organic solvent.

  Process according to Claim 2, characterized in that the metal catalyst consists of nickel,

  ladium, platinum, rhodium, ruthenium or cobalt.

  Method according to claim 6, characterized in that

  that the metal catalyst is fixed on a support.

  Process according to claim 6, characterized in that

  that the metal catalyst is a Raney catalyst.

  Process according to claim 5, characterized in that

  that the organic solvent is selected from the group comprising

  alcohols, glycols, ethers, hydrocarbons,

  aromatic hydrocarbons, halogenated hydrocarbons, N, N-dimethylformamide and dimethylsulfoxide.