JPS6016929B2 - Amination method for dihydric phenol - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for selectively producing 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 the corresponding aminophenols and phenylene zamines by reacting dihydric phenols with ammonia or amines, there are two methods: a method in which the reaction is carried out in the gas phase in the presence of a catalyst, and a method in which the reaction is carried out in the gas phase in the presence of a catalyst. Methods are known in which the reaction is carried out in the liquid phase with or without the presence of

However, among these methods, many catalysts have been proposed for the method of conducting the reaction in the gas phase, but all of these catalysts show considerable activity at the beginning of the reaction, but their activity decreases over time. There is a drawback that it cannot be adopted as an industrial manufacturing method because of the lowering of the temperature. When dihydric phenols are used as reaction substrates, the value is large. In addition, as a method for reacting in a liquid phase, Hakama Batsu (1973-284) involves reacting both in a molten state in the absence of a catalyst.
The method proposed in US Pat. No. 2,376,112 involves the reaction in the presence of ammonium salts of arsenic acid or phosphoric acid as a catalyst, and the method proposed in US Pat. Atsukaisho 52, in which the reaction is carried out in the presence of a scale medium consisting of a genide and an ammonium halide.
The method proposed in Japanese Patent Publication No. 142829, 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 Japanese Patent Publication No. 7, and the method proposed in Japanese Patent Application Laid-open No. 100428/1983, in which stannous chloride is reacted in the presence of a binary catalyst consisting of ammonium chloride as a catalyst. . Among these methods, the method proposed in Hakama Seki Sho 48-28429, in which the reaction is carried out in the absence of a catalyst, and the method proposed in U.S. Pat. No. 2,376,112, in which the reaction is carried out in the presence of an ammonium salt of phosphoric acid or arsenic acid. However, the reaction rate is slow, and the selectivity to the desired product and its yield are also low. 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, Tokusei Showa 52-4282
In the disclosed method, aminophenols and phenylenediamines are co-produced with dihydric phenols other than catechol, and aminophenols cannot be selectively obtained. The present inventors have discovered that in a method for producing corresponding aminophenols and phenylenediamines by reacting dihydric phenols with ammonia or amines, when the reaction is carried out in the presence of a catalyst consisting of a specific metal compound, The present invention has been achieved based on the discovery that the corresponding aminophenols and phenylenediamines can be obtained selectively and in high yields, and that aminophenols in particular can be obtained with high selectivity. That is, the present invention provides a dihydric phenol characterized by reacting dihydric phenol 'a' with ammonia, a primary amine or a secondary amine 'b} in a liquid phase in the presence of a molybdenum compound. This is an amination method.

In the method of the present invention, the dihydric phenols {a} used as reaction raw materials include, for example, dihydric phenols without substituents such as hydroquinone, resorcinol, and catechol; 2-methylhydroquinone, 4- Methylresorcin, 5-methylresorcin, 5-ethylresorcin, 5-inpropylresorcin, 5-n-butylresorcin, 5-sec-butylresorcin, 5-rt-butylresorcin, 3-methylcatechol, 4-
Methylcatechol, 4-ethylcatechol, 4-isopropylcatechol, 4-n-butylcatechol, 4-s
Examples include dihydric phenols having a substituent such as ec-butylcatechol and rt-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. Furthermore, in the method of the present invention, ammonia or amines {W,
Ammonia, primary or secondary amines.

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.
Examples include ec-butylamine, rt-butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, benzylamine, and cyclohexylamine, and examples of secondary amines include dimethylamine, diethylamine, Gin-n-fu. Lopylamine, diisopropylamine, di-n-butylamine, di-sec-butylamine,
Examples include di-tert-butylamine, diamylamine, dihexylamine, diheptylamine, dioctylamine, and didodecylamine. Among these ammonia or amines'b-, 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 water, primary amine or secondary amine used is
It is preferably 2 moles or more, particularly 3 to 7 moles. 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 'a} and ammonia, primary amines or secondary amines [
b} requires reaction in the presence of a catalyst,
At least one molybdenum compound is used as catalyst. Specific examples of molybdenum compounds include molybdenum halides, molybdenum oxides, molybdic acid, and molybdate salts. Molybdenum halides include molybdenum trichloride, molybdenum tetrachloride,
Examples include molybdenum pentachloride, molybdenum tribromide, molybdenum tetrabromide, molybdenum pentabromide, molybdenum oxychloride, molybdenum oxytrichloride, molybdenum oxytetrachloride, molybdenum oxytribromide, and the like. Examples of molybdenum oxide include molybdenum dioxide, pentamolybdenum dioxide, molybdenum trioxide, and non-stoichiometric oxides obtained by partially reducing these oxides. Examples of molybdic acid include orthomolybdic acid, paramolybdic acid, metamolybdic acid, isopolymolybdic acid produced by condensation of molybdate ions other than these compounds, and P, Fu, Si, Sn, Ti,
Zr, B, Ce, Th, Pt, Mn, Ni, Te, 1,
Examples include heteropolymolybdic acids containing metals or nonmetals such as Co, AI, Cr, Fe, Rh, and Cu. Examples of molybdates include various salts of orthomolybdic acid, paramolybdic acid, metamolybdic acid, impolymolybdic acid, and hepropolymolybdic acid, such as alkali metal salts, alkali metal salts, and other metal salts; Examples include ammonium salts, various amine salts, and various quaternary ammonium salts. Among these molybdenum compounds, it is preferable to use molybdenum oxide, molybdic acid, or ammonium salts, amine salts, and quaternary ammonium salts of molybdic acid. In the method of the present invention, the proportion of the molybdenum compound used as a catalyst component is usually 0.001 to 2 gram atoms, preferably 0.01 to 2 grams of molybdenum metal atoms per mole of dihydric phenol {a}. 1.0
It is in the gram atom range. The reaction of the invention is carried out in liquid phase and 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, 1,21-dimethylformamide, etc., and dihydric phenols, ammonia, and primary amines as reaction substrates. 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 present invention, the reaction proceeds by heating a mixture consisting of a dihydric phenol, ammonia, a primary amine or a secondary amine (tb), a molybdenum compound catalyst, and, if necessary, a solvent.

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.
None, 35,000, preferably 210 to 300
The range is 0:00 p.m. 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 produced almost selectively by appropriately selecting reaction conditions, aminophenols and phenylenediamines can be co-produced at the same time, and aminophenols and phenylenediamines can be co-produced simultaneously. Selectivity can also be improved. For example, the selectivity to aminophenols is generally improved by lowering the molar ratio of dihydric phenols (ammonia, primary amines, or secondary amines) and reacting under relatively low temperature conditions. Therefore, if the molar ratio is increased and the reaction is performed under relatively high temperature conditions, the selectivity to phenylene diamines will be improved. In the method of the present invention, 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,
The desired product is obtained. Next, the method of the present invention will be specifically explained using examples.

Examples 1 to 3 2.50 hours of resorcin, 10 minutes of 20% ammonia water, and the catalyst shown in Table 1 were placed in a stainless steel autoclave (horizontally vibrated 100 times/min) with a capacity of 50. After charging a fixed amount (9.35 milligram atoms as Mo) and purging with nitrogen, 2. The dish was reacted.

After the reaction was completed, the reaction mixture was cooled, taken out, concentrated to dryness under reduced pressure, and extracted with ethanol. This extract was analyzed by gas chromatography. Table 1 shows the conversion rate of resorcinol and the selectivity of m-aminophenol and m-phenylenediamine. Comparative Examples 1 to 4 In a stainless steel autoclave with an internal volume of 100 mm (with upper and lower lighting equipment), 5.00 g of resorcinol, 20 g of ammonia water, and 20 g of the catalyst shown in Table 1 (metal compound: 4.0 g as a metal) were added. 4 milligram atoms, hummonium compound: 18.
7 mmol) and heated at 230°C for 2 hours after purging with nitrogen. plate r
Made it react.

After the reaction was completed, the reaction mixture was cooled, taken out, concentrated to dryness under reduced pressure, extracted continuously with ether, and analyzed by gas chromatography. The results are shown in Table 1. Comparative Example 5* In Example 1, (NH
4) Reaction and post-treatment were carried out under the same conditions as in Example 1 except that 1.9 days of 3P04/insect LO was used, and the extract was analyzed by gas chromatography.

The results are shown in Table 1. Table 1 Example 4 The reaction and post-treatment were carried out under the same conditions as in Example 1, except that 2.80% of (NH4)6Mo7024.4day20 was used as a catalyst, and analyzed by gas chromatography. As a result, the conversion rate of resorcinol was 98 mol%, and the selectivity of m-aminophenol and m-phenylenediamine was 89 mol% and 5.3 mol%, respectively.

Example 5 In Example 1, 40% ammonia water was used instead of 20% ammonia water.
% ammonia water 11.0cc and as a catalyst (N ratio)
The reaction and post-treatment were carried out under the same conditions as in Example 1, except that 0.825 ta of 6Mo70 Matsu-Nagi 20 was used, and as a result of analysis by gas chromatography, the conversion rate of resorcin was 88 mol%, m-aminophenol The selectivities of m-phenylene diamiso and m-phenylene diamiso were 97 mol% and 2.5 mol%, respectively.

Example 6 In Example 5, the reaction and post-treatment were carried out under the same conditions as in Example 5, except that the resorcinol content was changed to 10.0%, and as a result of analysis by gas chromatography, the change rate of resorcinol was 84 mol%, The selectivities of m-aminophenol and m-phenylenediamine were 94 mol% and 2.5 mol%, respectively.

Examples 7 to 11 Reaction and post-treatment were carried out under the same conditions as in Example 1, except that heteropolymolybdic acid and its ammonium salt prepared by the following method were used as catalysts. and analyzed by gas chromatography.

The results are shown in Table 2. <Preparation of catalyst>[1' Preparation of ammonium 6-molybdoferrate Add 10 parts of ammonium paramolybdate to 200 parts of water and add 45 parts of ammonium paramolybdate to 200 parts of water.
Prepare a solution (1) dissolved at q0.

Apart from iron alum Fe2(S04)3(N ratio)2S04
・Make solution (0) by adding 205 yen on the 24th to 100 ml of water and dissolving it, then heating it in the oven. Strong and powerful (1) to (0)
When the solution begins to turn yellow, stop dropping and place it in a suction oven. Crystals are precipitated from this furnace liquid at 0°C. This was washed with cold water and dried to obtain 4.5 tons of ammonium 6-molybdoferrate. This compound is designated as catalyst A. (2) Preparation of ammonium polymolybdate aluminate Prepare a solution (1) by dissolving 20 parts of ammonium paramolybdate in 75 parts of water.

Ammonium alum AI2 (S○4)3 NH
4)2. Prepare a solution (n) by dissolving S○4.24408.5 in 100 parts of water. At room temperature, add (b) to (1) while shaking the candle strongly and leave it for about 1 hour. The resulting mold was washed with cold water and dried to obtain a powder of 16.1 kg. As a result of elemental analysis, the Mo/Ai atomic ratio was 6.4. This compound is designated as catalyst B. [3} Preparation of polymolybdocobaltate: Dissolve 20 parts of ammonium paramolybdate in 75 parts of water.

Dissolve 2.5 parts of cobalt dichloride in 30 parts of water. If you make an aqueous solution of the two and make it acidic by adding hydrochloric acid dropwise to the solution while shaking it vigorously at room temperature, a solid substance will form. 16. After leaving the solution to thicken, the solid matter thus formed was separated in an oven, washed and dried with cooling of about 100 cc, and 16.
Three powders were obtained. As a result of elemental analysis, the Mo/Co atomic ratio was 6.3. This compound is designated as catalyst C. '41
Preparation of Polymolypdoboric Acid It was prepared in substantially the same manner as Catalyst C in ``3''.

As a result of elemental analysis, the Mo/B atomic ratio was 12.6.
This compound is designated as catalyst ○. '51 Preparation of polymolybdosilicic acid It was prepared in almost the same manner as Catalyst C of '31.

As a result of elemental analysis, the Mo/Si atomic ratio was 20.1. This compound is designated as catalyst E. Table 2 Example 12 In Example 1, commercially available ammonium 12-molybdophosphate (N) 3P04・lamo03・Hank 201.5
The reaction and post-treatment were carried out under the same conditions as in Example 1, except that 0.0% was used as a catalyst, and as a result of analysis by gas chromatography, the conversion rate of resorcin was 95 mol%, m-aminophenol and m-phenylene. The selectivity of diamine was 93 mol% and 1.6 mol%, respectively.

Example 13 In a stainless steel autoclave with an internal volume of 50, 2.50 g of resorcinol and 11.0 c of a 40% methylamine aqueous solution
c and molybdate day 2Moo4・ratio 01. After preparing Madarayu and replacing it with nitrogen, it was heated at 240:00. The enemy reacted.

After the reaction, the same post-treatment as in Example 1 was carried out, and as a result of analysis by gas chromatography, the change rate of resorcin was 10
At this time, N-methyl-m-aminophenol and N·N'-dimethyl-m-phenylenediamine were produced in yields of 46 mol% and 42 mol%, respectively. Example 14 In Example 12, 14.0 cc of a 40% dimethylamine aqueous solution was used instead of the 40% methylamine aqueous solution, and dimethylammonium 3-molybdate [(
CH3)2N ratio] 20・Milk Moo3・Day 20 1.74
The reaction and post-treatment were carried out under the same conditions as in Example 12, except that N-
Dimethyl-m-aminophenol and N-methyl-m
-Aminophenol was produced in yields of 59 mol% and 1 mol%, respectively.

Example 15 In Example 1, 2.50% of hydroquinone was used instead of resorcinol and 6Mo702 (N ratio) was used as a catalyst.
The reaction and post-treatment were carried out under the same conditions as in Example 1, except that 4. Yama 201.65 was used, and as a result of analysis by gas chromatography, the conversion rate of hydroquinone was 95 mol%, and at this time p-aminophenol and p-phenylenediamine have selectivities of 79 mol% and 1 mol%, respectively.
Generated with.

Claims (1)

[Claims] 1. In the presence of a molybdenum compound, dihydric phenols (
a) and ammonia, primary or secondary amine (b)
A method for aminating divalent phenols, characterized by reacting them in a liquid phase. 2. The method according to claim 1, wherein the molybdenum compound is molybdenum oxide, molybdic acid, or molybdate. 3 The molybdenum compound contains 0.001 to 2 molybdenum metal atoms per mole of divalent phenol (a).
Claim 1 or 2 that is in the range of gram atoms
The method described in section. 4. The method according to any one of claims 1 to 3, wherein resorcinol or hydroquinone is used as the divalent phenol (a). 5. A method according to any one of claims 1 to 4, wherein the reaction is carried out at a temperature in the range 210 to 300°C.