JPH0433782B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a 3,3',4,4'-tetraaminodiphenyl compound. For more details, see the general formula () A 3,3'-dinitro-4,4'-diaminodiphenyl compound represented by (wherein, X represents O, CO, CH ₂ S or SO ₂ ) was contacted in mineral acid water in the presence of a reducing catalyst. By reducing the general formula () The present invention relates to a method for producing a 3,3',4,4'-tetraaminodiphenyl compound represented by the formula (wherein, X has the same meaning as in general formula (1)). The tetraamino compound according to the present invention is useful as a heat-resistant resin raw material or its intermediate, and in particular, in recent years, polyimide and polyimide amide resins obtained by reaction with polycarboxylic acid derivatives have been used in the aerospace industry as super heat-resistant resins. It is attracting attention in fields such as automobile-related industries and heat-resistant electrical insulation parts. Therefore, the development of an industrial method for producing these tetraamino compounds is expected. Conventionally, 3,3',4,4'-tetraamino diphenyl compounds are produced by various reduction methods of 3,3'-dinitro-4,4'-diaminodiphenyl compounds. For example, the following method is known. (a) Reduction with stannic chloride in concentrated hydrochloric acid (RTFoster et al., J. of Polym. Sci., 3 418
(1965), JKStille et al., J.of Polym.Sci., 3
1023 (1965)), (b) reduction with zinc chloride in ethanol-hydrochloric acid (J.Arient et al., Collection Czech.Chem.
Commun., 30 3718-29 (1965), (Ger); CA,
64 3729 (1966)) (c) Reduction with iron (AVIvanor et al., CA, 79 78310 (1973)), (d) Reduction with sodium sulfide in an aqueous solution of ethanol (Kado et al., Japanese Patent Publication No. 43-24655) (e) Dimethyl Catalytic reduction using Raney-nickel, Pd/c catalysts in formamide or water solvents (ERKofanor et al., J.Org.Chem of USSR 15
99 (1979)) (f) Catalytic reduction using a Pt/c catalyst in ethyl acetate (VLBell et al., J of Polym Sci 5 3056
(1967)) etc. However, by reducing the 3',3-dinitro-4,4'-diaminodiphenyl compound, 3,3',4,
4'-tetraaminodiphenyl compound in high yield,
Moreover, all of the above-mentioned methods have various difficulties in obtaining high-purity products, and at present they have not been implemented industrially. In other words, in the reduction methods using metals under strong acidity as typified by (a), (b), and (c), the waste metals used,
Disadvantages include that a large amount of expense is required for processing the waste acid, and that it is difficult to remove trace amounts of metal components from the target product. Furthermore, the yields of the target products obtained by these methods are generally low. In addition, method (d), which is a reduction method under alkaline conditions, is not economical because it requires the use of a reducing agent approximately 5 times the weight of the raw material.
It is necessary to remove a trace amount of sulfide from the target product, and in addition to processing the residue, a complicated process is required. Next, there is a method of catalytic reduction using a reduction catalyst as shown in (e) and (f). Since the solubility is extremely low, in order to proceed with the reduction reaction under a relatively low pressure of around 10 atmospheres, a large amount of a solvent such as ethyl acetate must be used, or a soluble solvent such as N,
This is done using N'-dimethylformamide. For example, when using ethyl acetate solvent,
Since the amount used is 10 to 35 times the amount of the raw material, the volumetric efficiency in the reaction is low, and the yield of the target product is only about 50 to 65%. On the other hand, the method using N,N'-dimethylformamide solvent has a major drawback in that the desired product is obtained in a dark brown color, and this coloring is difficult to remove even after repeated recrystallization. Furthermore, when these organic solvents are used, it must be said that they are extremely uneconomical as recovery of the solvents also requires expense. When an aqueous solvent is used instead of these organic solvents, the reaction conditions are a reduction reaction at a temperature of 90 to 130 °C and a high pressure of 100 atm, and the yield of the target product is also 10 to 130 °C.
It is low at around 70%. Furthermore, the concentration of the reductant is 5wt.
%, a high-pressure reactor is required to carry out this reaction, and the volumetric efficiency is low, making it uneconomical and industrially very difficult. The present inventors have proposed 3.
A method for producing 3',4,4'-tetraaminodiphenyl compound was intensively investigated. As a result, 3,
3,3',4,4'-tetraamino diphenyl compound was obtained in high yield by catalytic reduction of 3'-dinitro-4,4'-diaminodiphenyl compound in mineral acid water in the presence of a reducing catalyst. discovered that it could be manufactured,
The method of the present invention has been completed. That is, the present invention provides the general formula () 3,3'-dinitro-4,4'- (wherein, X represents O, CO, CH ₂ , S or SO ₂ )
In the presence of a catalyst that reduces the diaminodiphenyl compound,
General formula () characterized by catalytic reduction in mineral acid water (In the formula, X has the same meaning as the general formula ())
This is a method for producing a 3,3',4,4' tetraaminodiphenyl compound represented by: According to the method of the present invention, the yield of the tetraaminodiphenyl compound from the dinitrodiaminodiphenyl compound is almost quantitative. Furthermore, since the target product is obtained as a mineral acid salt, it has very good stability over time and is easy to purify by recrystallization, etc., resulting in a highly pure product. That is, since tetraaminodiphenyl compounds are generally substances that are easily colored by oxidation, both production and purification conditions are usually carried out while blocking outside air. For example, in producing tetraaminobenzophenone, ERKofanor et al.
Post-treatment steps are carried out under nitrogen or argon atmosphere (ERKofanor et al., J.Org.Chem.of
USSR., 15 99 (1979)). However, in the method of the present invention, since the mineral acid salts of these tetraminodiphenyl compounds are difficult to be colored by oxidation, the mineral acid salts are purified by recrystallization using a water solvent, etc., and then neutralized. High purity target products can be produced. The raw material used in the method of the present invention is a compound represented by the general formula (), specifically 3,
3'-dinitro-4,4'-diaminodiphenyl ether, 3,3'-dinitro-4,4'-diaminobenzophenone 3,3'-dinitro-4,4'-diaminodiphenylmethane, 3, 3′-dinitro-4,4′-
Diaminodiphenyl sulfide or 3,3'-dinitro-4,4'-diaminodiphenylsulfone, which are produced by known methods. For example, 3,3'-dinitro-4,4'-diaminodiphenyl compounds are typically produced by the following two methods. (1) General formula () (wherein, X represents O, CO, CH ₂ , S or SO ₂ ) is acetylated, then nitrated, and the general formula () (In the formula, X has the same meaning as the general formula ())
A method for producing a 3,3'-dinitro-4,4'-diaminodiphenyl compound by obtaining a 3,3'-dinitro-4,4'-diacetylamino diphenyl compound represented by and hydrolyzing the same. . (2) General formula () General formula () obtained by nitrating a 4,4'-dihalogen diphenyl compound represented by (wherein, X represents CO or SO ₂ and Y represents a halogen atom) (wherein, This is a method of manufacturing by substituting with an amino group. Specifically, 3,3'-dinitro-4,4'-diaminodiphenyl ether is prepared by the method (1) above.
% yield (RTFoster et al., J.of
Polym Sci., 3 418-419 (1965), JKStille et al.
J. of Polym Sci 3 1015 (1965). 3,3'-dinitro-4,4'-diaminobenzophenone was produced by the method (1) above with a yield of about 80% (CA, 79 78310b (1973), and by the method (2) above).
produced with a yield of over 90% (GSMironor et al.
J.Org.Chem.ofUSSR., 8 , 1538-1543 (1972)). 3,3'-dinitro-4,4'-diaminodiphenylsulfone is produced by the method (2) above (CA, 70 114832y (1969), CA, 78 , 83962z
(1973)). 3,3'-dinitro-4,4'-diaminodiphenylmethane is produced by the method (1) above in a yield of 63% (VLBell et al., J. of Polym Sci 5 3055~
3056 (1967)). 3,3'-dinitro-4,4'-diaminodiphenyl sulfide is produced by the method (1) above in a yield of 72% (JK Stille et al., J. of Polym Sci 4 556~
557 (1966)). Next, the mineral acids used in the method of the present invention include:
Sulfuric acid, hydrochloric acid or phosphoric acid, preferably sulfuric acid,
Hydrochloric acid is used. The amount of these mineral acids used is 1 to 4 equivalents, more preferably 1 to 2.5 equivalents, based on the dinitrodiaminodiphenyl compound as the raw material. In other words, it is sufficient to have the amount necessary for the raw material diamines to become mineral acid salts and to be solubilized in water.
When the amount is approximately equivalent, a 1-mineral acid salt of the dinitroaminodiphenyl compound is produced, and when it is approximately 2 equivalents, it becomes a 2-mineral acid salt of the dinitrodiaminodiphenyl compound, which is solubilized in water, and the reduction reaction proceeds. Since the solubility of the mineral salt of the dinitrodiaminodiphenyl compound in water is better for the di-mineral salt than for the mono-mineral salt, the reduction reaction proceeds faster in the di-mineral salt. If the amount of mineral acid used is 1 equivalent or less, unreacted substances remain, which is not preferable, and even if an excess amount of 4 equivalents or more is used, it does not affect the reactivity. A 0.05 to 5N solution is sufficient as the concentration of the mineral acid water; if the concentration of the mineral acid water is too dilute, the volumetric efficiency will decrease, and if it is too concentrated, the catalyst will deteriorate more quickly, which is not preferred. It is preferably used within the range of 0.5 to 3 normal. Furthermore, in the method of the present invention, there is no problem in carrying out the reaction by adding a water-miscible solvent such as methanol, ethanol, isopropanol, ethylene glycol, cellosolve, dioxane, and tetrahydrofuran to the mineral acid water. The reduction catalyst used in the method of the present invention includes metal catalysts commonly used in catalytic reduction, such as palladium, platinum, rhodium, ruthenium,
Litkel, cobalt, copper, etc. can be used. Industrially it is preferred to use palladium and platinum catalysts. Although these catalysts can be used in the metal state, they are usually used by being attached to the surface of a carrier such as carbon, barium sulfate, silica gel, or alumina, and nickel, cobalt, copper, etc. are also used as Raney catalysts. It will be done. The amount of the catalyst used is in the range of 0.01 to 20% by weight as metal based on the dinitrodiaminodiphenyl compound, and usually 2 to 10% by weight when used in the metal state.
Weight%, 0.05~ when used by adhering to a carrier
It is in the range of 5% by weight. The reaction temperature is not particularly limited. Generally 20
It is carried out at a temperature of ~100°C. Further, although the reaction proceeds satisfactorily under normal pressure, there is no problem in pressurizing the reaction to a range of normal pressure to 100 kg/cm ² ·G in order to hasten the reaction. The end point of the reaction can be determined by quantifying the amount of hydrogen uptake or by thin layer chromatography. After the completion of the reaction, if the target mineral salt is in a precipitated state, it is dissolved by adding water or by further raising the temperature, and then the catalyst can be removed by hot filtration. The reaction solution from which the catalyst has been removed is concentrated if necessary and allowed to cool to precipitate the target mineral salt. After filtering this and neutralizing it with dilute alkaline water or dilute ammonia water, 3,3',
A 4,4'-tetraaminodiphenyl compound is obtained, but if a higher purity target product is required, the mineral salt may be recrystallized again with water and then neutralized. The method of the present invention is a method that can produce high-purity 3,3',4,4'-tetraaminodiphenyl compounds at high yields and at low cost, and eliminates the problem of environmental pollution caused by waste that accompanies conventional methods. It is suitable as an industrial production method because it does not require any purification operations under complicated conditions. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 In a closed glass container equipped with a thermometer and a stirrer, 151 g (0.5 mol) of 3,3'-dinitro-4,4'-diaminobenzophenone and a 5% Pd/c catalyst (manufactured by Nippon Engelhard Co., Ltd.) were added. ) 10.6g and 1.6N hydrochloric acid aqueous solution
715 ml (1.1 mol) was charged, and hydrogen was introduced under stirring while maintaining the reaction temperature at 70 to 75°C for 15 hours.
When the reaction was carried out, 69 (3.08 mol) of hydrogen was absorbed. Since no more hydrogen absorption was observed, the reaction was terminated. Next, the temperature of the reaction solution was raised to 85° C. to dissolve the precipitated reaction product, and then the catalyst was removed by hot filtration. After filtration was concentrated under reduced pressure to remove 200 ml of water, the mixture was allowed to cool, and crystals of 3,3',4,4'-tetraaminobenzophenone hydrochloride were precipitated. This was filtered, washed with 100 ml of methanol, and then dried to obtain 137 g (yield: 87%) of pale yellow needle crystals. (A) Crystallize this hydrochloride using activated carbon,
By recrystallizing with water, pure 3,3',4,
Needle-shaped crystals of 4'-tetraaminobenzophenone hydrochloride were obtained. [Table] The 3,3',4,4'-tetraaminobenzophenone hydrochloride obtained in (B) and (A) was dissolved in water and then neutralized with dilute aqueous ammonia.
Pale yellow needle crystals of 3',4,4'-tetraaminobenzophenone were obtained. The purity determined by high performance liquid chromatography was 99.9%. Melting point: 214-215°C Example 2 33.8 g (0.1 mol) of 3,3'-dinitro-4,4'-diaminodiphenylsulfone, Laoiniskel catalyst in a closed glass container equipped with a thermometer and a stirrer.
3.4 g and 100 ml (0.3 mol) of 3N hydrochloric acid aqueous solution were charged, and the reaction temperature was increased while introducing hydrogen under stirring.
The reaction was carried out at 80-85℃ for 10 hours.
Absorbed 13.0 (0.58 mol) of hydrogen. Since no further absorption of hydrogen was observed, the reaction was terminated. Next, the reaction solution was filtered hot at the same temperature to remove the catalyst, and when it was allowed to cool, pale brown needle crystals were precipitated. This was filtered and dried to give 28.5g (yield 81%) of 3,3′4,
4'-tetraaminodiphenylsulfone hydrochloride was obtained. (A) White needle-like crystals of pure 3,3',4,4'-tetraaminodiphenylsulfone hydrochloride are obtained by recrystallizing the hydrochloride crystals from an 80% isopropyl alcohol aqueous solution using activated carbon. I got it. [Table] (B) After dissolving the 3,3',4,4'-tetraaminodiphenylsulfone hydrochloride obtained in (A) in water, the 3,3 White (slightly reddish) needle-shaped crystals of ',4,4'-tetraaminodiphenylsulfone were obtained. Purity determined by high performance liquid chromatography is 99.9%
It was hot. Melting point: 173-174.5°C Example 3 In a closed glass container equipped with a thermometer and a stirrer, 34.1 g (0.1 mol) of 3,3'-dinitro-4,4'-diaminobenzophenone and 5% Pd/c1. 7g and 1,
Charge 500 ml (0.2 mol) of 2N phosphoric acid aqueous solution and raise the reaction temperature to 60-65°C while introducing hydrogen under stirring.
When the reaction was carried out for 6 hours at a constant temperature, 13.5 hours of hydrogen was absorbed. Since no more hydrogen absorption was observed, the reaction was terminated. Next, the reaction solution was filtered hot at the same temperature to remove the catalyst, and the filtrate was concentrated under reduced pressure to distill off 400 ml of water.
When this was allowed to cool, yellow crystals of 3,3',4,4'-tetraaminobenzophenone phosphate were precipitated. The crystals were filtered, washed with 20 ml of methanol, and then dried to obtain 38.5 g (yield: 87.8%) of pale yellow needle crystals. The phosphate crystals were recrystallized from water using activated carbon to obtain needle-like crystals of pure 3,3',4,4'-tetraaminobenzophenone phosphate. [Table] Example 4 In a closed glass container equipped with a thermometer and a stirrer, 29 g (0.1 mol) of 3,3'-dinitro-4,4'-diaminodiphenyl ether, 3 g of 5% Pt/c catalyst, and 1 Charge 220ml (0.11mol) of normal sulfuric acid aqueous solution,
While introducing hydrogen under stirring, increase the reaction temperature to 80-85
When the reaction was carried out for 6 hours at ℃, the result was 13.7
(0.61 mol) of hydrogen was absorbed. Since no more hydrogen absorption was observed, the reaction was terminated. Next, the reaction solution was filtered hot at the same temperature to remove the catalyst, and after cooling by adding 200 ml of water to the filtrate, it was neutralized with a dilute aqueous caustic soda solution to precipitate light brown crystals. This is filtered, dried and 3,3′,4,
22g of 4′-tetraaminodiphenyl ether (yield
95.5%). The purity determined by high performance liquid chromatography was 98.1%. This product was recrystallized from ethanol-water using activated carbon under a nitrogen stream to obtain a pure white (slightly reddish) crystal. Melting point 150-151℃ [Table] Example 5 A reduction reaction was carried out in the same manner as in Example 4 except that 3,3'-dinitro-4,4'-diaminophenylmethane was used as the raw material. ',4,-4'-tetraaminodiphenylmethane was obtained in a yield of 96.1%. A pure product was obtained by recrystallization from ethanol water. melting point
137-139℃ Example 6 A reduction reaction was carried out in the same manner as in Example 4 except that 3,3'-dinitro-4,4'-diaminodiphenyl sulfide was used as the raw material, and 3,3'4 ,4′−
Tetraaminodiphenyl sulfide yield 89.2%
I got it from A pure product was obtained by recrystallization from ethanol-water. Melting point 102~103℃

Claims (1)

[Claims] 1 General formula () 3,3'-dinitro 4,4'- (wherein, X represents O, CO, CH ₂ , S or SO ₂ )
In the presence of a catalyst that reduces the diaminodiphenyl compound,
General formula () characterized by catalytic reduction in mineral acid water (In the formula, X has the same meaning as the general formula ())
A method for producing a 3,3',4,4'-tetraaminodiphenyl compound represented by