JPS6034944B2 - Amination method for divalent phenols - Google Patents

Description

Detailed Description of the Invention The present invention relates to a method for selectively producing corresponding aminophenols and phenylenediamines by reacting dihydric phenols with ammonia or amines. The present invention relates to a highly selective manufacturing method.

Aminophenols are used as pharmaceuticals, agricultural chemicals, dyes, rubber drugs, compounding agents for synthetic resins, or intermediates for their production.

In addition to being used for the same purposes as the aminophenols, phenylene diamines are also used as raw materials for producing polyamides for special purposes and as raw materials for modification. Conventionally, as a method for producing corresponding aminophenols and phenylenediamines by reacting dihydric phenols with ammonia or amines, there has been a method for producing corresponding aminophenols and phenylenediamines by reacting the two in a molten state in the absence of a catalyst. 28
The method proposed in U.S. Pat. No. 2,376,112 in which copper is reacted in the presence of phosphoric acid or ammonium salt of arsenic acid as a catalyst;
JP-A No. 5, which involves reacting in the presence of a catalyst consisting of cobalt or nickel halide and ammonium halide.
A method proposed in Japanese Patent Application Laid-open No. 2-42829, JP-A-52-10042, in which the reaction is carried out in the presence of stannous chloride as a catalyst.
Known methods include the method proposed in Publication No. 7 and the method proposed in JP-A-52-100428, in which the reaction is carried out in the presence of a binary catalyst consisting of stannous chloride and ammonium chloride. .

Among these methods, JP-A-48-28429, in which the reaction is carried out in the absence of a catalyst, and US Pat. No. 237, in which the reaction is carried out in the presence of an ammonium salt of phosphoric acid or arsenic acid
The method proposed in No. 6112 has a slow reaction rate, low selectivity to the desired product, and low yield thereof. Further, even when dihydric phenols are reacted with ammonia or amines in the presence of the catalysts proposed in the above-mentioned known literature, it cannot be said that the selectivity to the desired product and the yield thereof are sufficiently high.
Furthermore, in the method disclosed in JP-A-52-4282, aminophenols and phenylenediamines are co-produced with dihydric phenols other than catechol, and aminophenols cannot be selectively obtained. The present inventors have developed a method for producing corresponding aminophenols and phenylenediamines by reacting dihydric phenols with ammonia or amines, using a catalyst consisting of a specific metal phosphate and an ammonium phosphate compound. The present invention has been achieved by discovering that when the reaction is carried out in the presence of , the corresponding aminophenols and phenylenediamines can be obtained selectively and in high yields, and in particular aminophenols can be obtained with high selectivity. . That is, the present invention provides dihydric phenols c in the presence of a catalyst consisting of at least one metal compound a selected from the group consisting of zinc phosphates and nickel phosphates and an ammonium phosphate compound b. This is a method for aminating dihydric phenols, which is characterized by reacting d with ammonia, a primary amine, or a secondary amine d. In the method of the present invention, the dihydric phenols c used as reaction raw materials include, for example, unsubstituted dihydric phenols such as hydroquinone, resorcinol, and catechol: 2-methylhydroquinone, 4-methylresorcinol, 5-methylresorcin, 5-ethylresorcin, 5-isopropylresorcin, 5-n-butylresorcin, 5-sec-butylresorcin, 5-rt-butylresorcin, 3-methylcatechol, 4-methylcatechol, 4-ethyl Catechol, 4-isof. Lopylcatechol, 4-n-butylcatechol, 4-sec-butylcatechol, 4 lumps
Examples include dihydric phenols having substituents such as t-butylcatechol. Among these dihydric phenols, it is preferable to use dihydric phenols without substituents, and it is particularly preferable to apply the method of the present invention to resorcinol or hydroquinone. Further, in the method of the present invention, ammonia or amines c used as a reaction raw material are ammonia, a primary amine, or a primary amine.

Specifically, examples of ammonia include ammonia or aqueous ammonia of various concentrations, and examples of primary amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, and s-butylamine.
ec-butylamine, rt-butylamine, amylamine, hexylamine, hef. Tylamine, octylamine, nonylamine, decylamine, dodecylamine,
Examples of secondary amines include dimethylamine, diethylamine, di-propylamine, diisopropylamine, di-n-butylamine, disec-butylamine, di-rt-butylamine, diamylamine, dihexylamine, diheptylamine, and dioctyl. Examples include amine and didodecylamine. These ammonia or amines c
Among them, it is preferable to use ammonia, and it is particularly preferable to use aqueous ammonia. When ammonia water is used, it is particularly preferred to use ammonia water in a range of 10 to 4% by weight. The amount of ammonia, primary amine or secondary amine to be used is preferably 2 mol or more, particularly 3 to 7 mol, per mole of dihydric phenol. Of course, it goes without saying that ammonia, primary amines or secondary amines used in excess can be recovered and reused. In the method of the present invention, dihydric phenols c and ammonia, primary amines, or secondary amines b need to be reacted in the presence of a catalyst, and the catalysts include zinc phosphate and nickel phosphate. A catalyst consisting of at least one metal compound a selected from the group consisting of acid salts and an ammonium phosphate compound b is used.

The metal compound a of the catalyst component is at least one metal compound selected from the group consisting of zinc phosphate and nickel phosphate. When a metal compound containing ammonium ions is used as the metal compound a of the catalyst component of the present invention, it is not necessarily necessary to use another ammonium phosphate compound since it also acts as the ammonium phosphate compound b. . In the method of the present invention, specifically as the metal compound a as a catalyst component,
Examples include zinc phosphate, zinc hydrogen phosphate, and amine key bodies thereof; nickel phosphate, nickel hydrogen phosphate, and amine rust bodies thereof. In the method of the present invention, the proportion of metal compound a used as a catalyst component is usually 0.02 gram atom or more, preferably 0.0 gram atom or more in terms of metal atom per mole of dihydric phenol.
It ranges from 5 to 0.5 gram atom. In the method of the present invention, the ammonium phosphate compound b as a catalyst component is at least one selected from the group consisting of ammonium salts of phosphoric acid, primary amine salts of phosphoric acid, and secondary amine salts of phosphoric acid. It is a species compound.

More specifically, ammonium salts of phosphoric acid include:
Examples include triammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium ammonium hydrogen phosphate, and potassium ammonium hydrogen phosphate. In addition, as the primary amine salt of phosphoric acid or the secondary amine salt of phosphoric acid, phosphates, hydrogen phosphates, sodium hydrogen phosphate salts of the primary amines or secondary amines exemplified as the above-mentioned reaction raw materials, Examples include potassium hydrogen phosphate salt. Note that phosphoric acid or a hydrogen phosphate compound and ammonia, a primary amine, or a secondary amine may be charged separately to generate these exemplified ammonium compounds within the reaction system. Among these ammonium phosphate compounds c, it is preferable to use an ammonium phosphate compound corresponding to aqueous ammonia, primary amine or secondary amine d to be reacted with dihydric phenol c. That is, when using ammonia as a reaction substrate, it is preferable to use an ammonium salt of phosphoric acid, and similarly when using a primary or secondary amine as a reaction substrate, it is preferable to use an ammonium salt of phosphoric acid as a catalyst component. As ammonium compound b, preference is given to using the respective corresponding primary amine salts of phosphoric acid or secondary amine salts of phosphoric acid. The amount of ammonium phosphate compound b, which is a catalyst component, is usually 0 in terms of dihydric phenol cl mole.
．． The amount is 1 mol or more, preferably in the range of 0.2 to 2 mol. The method of the invention can be carried out in the absence of a solvent or in the presence of a solvent.

Examples of reaction solvents used include water, benzene, toluene, cyclohexane, N,N-dimethylformamide, etc., and reaction substrates such as dihydric phenols, ammonia, and primary amines. Alternatively, a secondary amine can be used in a solvent amount. When carrying out the method of the present invention, the reaction is usually carried out in a nitrogen atmosphere, but it is also possible to use other gases that are inert under the reaction conditions, such as argon or helium. In the method of the invention, a mixture consisting of a dihydric phenol c, ammonia, a primary or secondary amine d, a catalyst consisting of a metal compound a catalyst component and an ammonium compound b catalyst component, and optionally a solvent is damaged. The reaction proceeds by heating to a low temperature.

The temperature during the reaction varies greatly depending on the reaction substrate, its concentration, the type of catalyst, and its concentration, but is usually 20°C.
0 to 350°C, preferably 210 to 3000
It is in the range of C. The method of the present invention can be carried out by any of the batch, semi-continuous or continuous methods. In the method of the present invention, aminophenols can be almost selectively produced by appropriately selecting reaction conditions, aminophenols and phenylenediamines can be co-produced simultaneously, or phenylenediamines can be co-produced simultaneously. It is also possible to improve the selectivity to

For example, in general, if the molar ratio of ammonia, primary amine, or secondary amine d to dihydric phenol c is lowered and the reaction is performed under relatively low temperature conditions, the selectivity to aminophenols will improve, and the If the molar ratio is increased and the reaction is performed under relatively high temperature conditions, the selectivity to phenylenediamines will improve. In the method of the present invention, the desired product can be obtained by treating the reaction product mixture after the completion of the reaction according to a conventional method such as a distillation method or a crystallization method.

Next, the method of the present invention will be specifically explained using examples.

Examples 1 to 4, Comparative Examples 1 to 7 Resorcinol 5. female (45.4 mmol),
20 g of 20% ammonia water, the metal compound shown in Table 1 (13.2 milligram atoms as metal) and the ammonium compound shown in Table 1 (18.7 mmol) were charged, and after nitrogen substitution, a reaction was carried out at 230 qo. Ta.

After the reaction was completed, the reaction mixture was cooled and taken out, concentrated to dryness under reduced pressure, and successively extracted with ether. This extract was analyzed by gas chromatography. The conversion rate of resorcin and the selectivity of m-aminophenol and m-phenylenediamine are shown in Table 1. Table 1 Example 5 Example 1 except that the amount of Ni3(P04)2 used as a metal was 4.4 milligram atoms.
When carried out in the same manner as above, the conversion rate of resorcinol was 60 mol%, and the selectivity of m-aminophenol and m-phenylenediamine was 92 mol% and 1 mol% or less, respectively.

Example 6 The same procedure as in Example 1 was carried out except that the reaction temperature was changed to 270 oo. The conversion rate of resorcinol was 93 mol%, and the selectivity of m-aminophenol and m-phenylenediamine was 73% each. The mol% was 18 mol%.

Example 7 In Example 2, 70% ammonia water was used instead of 20% ammonia water.
% ethylamine aqueous solution 15.1 g (235 mmol) and (NH4)3P04.3 day 20 instead of E elbow day 2.
The same procedure as Example 2 was carried out except that 42.7 g (18.7 mmol) of Melon P0 was used.

As a result of analysis by gas chromatography, the conversion rate of resorcinol was 94 mol%, and at this time, the conversion rate of resorcinol was 94 mol%.
-Aminophenol and N,N'-diethyl-m-phenylenediamine were produced with selectivities of 83 mol% and 8 mol%, respectively. Example 8 Hydroquinone 5. was added to the autoclave used in Example 1.
0g (45.4 mmol), 20% ammonia water 20g
, Ni3(P04)21. Key (4.4 mm IJ mole) and (N ratio) 3P04 / Thin 203. Chicks (18.7 mmol) were prepared and reacted at 250 oo after nitrogen substitution.

Claims (1)

[Scope of Claims] 1. Divalent phenols in the presence of a catalyst consisting of at least one metal compound a selected from the group consisting of zinc phosphate and nickel phosphate and an ammonium phosphate compound b. A method for aminating divalent phenols, the method comprising reacting c with ammonia, a primary amine or a secondary amine d. 2. The method according to claim 1, wherein the phosphate of component d is used as the ammonium phosphate compound b. 3. As a catalyst, a metal compound a in the range of 0.05 to 0.5 gram atom per mole of divalent phenol c and an ammonium compound in the range of 0.2 to 2 mole as metal atom per mole of divalent phenol c. The method according to claim 1 or 2, using a catalyst consisting of b. 4. The method according to any one of claims 1 to 3, wherein resorcinol or hydroquinone is used as the divalent phenol c. 5. Process according to any one of claims 1 to 4, characterized in that the reaction is carried out at a temperature in the range 210 to 300°C.