JPH01265065A - Method for aminating dihydric phenols - Google Patents

Abstract

PURPOSE:To obtain the corresponding aminophenols and phenylenediamines without forming tarlike substances as a by-product, by aminating OH groups of dihydric phenols in the presence of phenols and a metal phosphate. CONSTITUTION:Hydroxyl groups of dihydric phenols (e.g., catecholamine or 2-methylhydroquinone) are aminated with an amine (e.g., ammonia, primary or secondary amine) to provide the corresponding aminophenols and phenylenediamines. In the process, phenols and a metallic phosphate are used in combination as a catalyst to suppress formation of tarlike substances as a by-product and the aimed substance is obtained in good yield without losing the didydric phenols. The amounts of the phenols (preferably phenol, etc.) and metallic phosphate (preferably dihydrogenphosphate) are respectively 2-30mol and 0.01-1mol (expressed in terms of phosphoric acid) based on 1mol dihydric phenols.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing corresponding aminophenols and phenylenediamines using dihydric phenols and amines as raw materials.

Aminophenols and phenylenediamines are useful as raw materials for dyes, medicines, agricultural chemicals, rubber products, synthetic resins, and synthetic fibers, or as raw materials for modifiers.

[Conventional technology]

The hydroxyl group of dihydric phenols is 7-minated with amines such as ammonia, primary amines or secondary amines,
Methods for producing the corresponding aminophenols and phenylenediamines are known.

For example, as a method for carrying out the above reaction in a liquid phase, JP-A No. 48-28429 discloses a method in which the reaction is carried out in a molten salt without using a catalyst, and JP-A No. 52-42829 discloses a method in which copper, Method of using cobalt or nickel halide and ammonium halide simultaneously, JP-A-55-433
No. 8 describes a method using halides of antimony, vanadium, iron or iron sulfate, iron phosphate and an ammonium compound, and JP-A-55-15412 describes a method using a phosphate of zinc or nickel and an ammonium phosphate compound. JP-A-55-108841 discloses a method using a molybdenum compound; JP-A-56-73048 describes a method in which the reaction is carried out in the presence of phenols; JP-A-60-2
No. 15654 discloses a method using a composite metal oxide containing molybdenum.

[Problem to be solved by the invention]

However, all of the previously reported methods have slow reaction rates, low selectivity to the target product, and low yields, so they are not satisfactory as methods for industrially aminating dihydric phenols. I can't say that.

In particular, when using ammonia as an aminating agent,
This tendency becomes more pronounced due to the low reactivity of ammonia.

More serious problems include the following.

In other words, in this reaction for aminating dihydric phenols,
Dihydric phenols and aminophenols, which are amination products of dihydric phenols, and phenylene diamines coexist in the reaction system. Therefore, in addition to the original purpose of the reaction between dihydric phenols and amines, reactions between dihydric phenols and amine phenols and phenylene diamines, reactions between aminophenols, and reactions between aminophenols and phenylene diamines are possible. Reactions with other substances occur simultaneously, producing tar-like substances.

This causes loss of dihydric phenols supplied as raw materials, which poses a major problem when industrially aminating dihydric phenols.

For the above reasons, none of the conventionally known techniques can be called an industrial manufacturing method.

An object of the present invention is to provide a method for aminating dihydric phenols that solves these problems of the prior art.

[Means to solve the problem]

The present inventors conducted detailed research to solve these problems. As a result, dihydric phenols are aminated with ammonia or amines such as primary and secondary amines,
When producing the corresponding aminophenols and phenylene diamines, the reaction in the presence of phenols and metal phosphates has higher activity and sufficient selection to the desired product compared to conventional methods. You can get sex,
Furthermore, we discovered that the by-product of tar-like substances can also be suppressed.
The present invention has now been completed.

That is, the present invention is characterized in that a phenol and a metal phosphate are used in aminating the hydroxyl group of a dihydric phenol with an amine to produce the corresponding aminophenols and phenylene diamines. This is a method for aminating functional phenols.

In the present invention, it is important to combine phenols and metal phosphates in the reaction system.

As the metal phosphate used in the method of the present invention, dihydrogen phosphate, those with a composition equivalent thereto, or pyrophosphates obtained by dehydrating them are preferable. Specifically, lithium dihydrogen phosphate, sodium dihydrogen phosphate,
Potassium dihydrogen phosphate, rubidium dihydrogen phosphate, cesium dihydrogen phosphate, beryllium dihydrogen phosphate, magnesium dihydrogen phosphate, calcium dihydrogen phosphate, strontium dihydrogen phosphate, barium dihydrogen phosphate, and rare earths. A composition which is a reaction product of a compound and phosphoric acid and has a P/gold metal atomic ratio of 3, such as scandium, yttrium,
Lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,
There are reaction products of hydroxides or oxides of thulium, interbium, and lutetium with phosphoric acid. Also, manganese dihydrogen phosphate, iron dihydrogen phosphate, cobalt dihydrogen phosphate, zinc dihydrogen phosphate, cadmium dihydrogen phosphate, aluminum dihydrogen phosphate, thallium dihydrogen phosphate, tin dihydrogen phosphate, phosphorus A composition of a reaction product of phosphoric acid with lead dihydrogen oxide and a compound of chromium, gallium, indium, antimony, bismuth, with a P/gold metal atomic ratio of 3, such as water of chromium, gallium, indium, antimony, bismuth There are oxides or reaction products of oxides and phosphoric acid. Also, a composition of a reaction product of nickel, a scrap compound and phosphoric acid with a P/gold metal atomic ratio of 2, such as nickel,
Reaction products include copper hydroxide or oxide and phosphoric acid.

Furthermore, the corresponding acidic birophosphates obtained by dehydrating these dihydrogen phosphates or compositions corresponding thereto can also be used. In addition, reaction products of metal compounds of the periodic table IVa and Va and phosphoric acid are also used. For example, p
/ T i = 2, P / Z r = 2, P/
Hf=2, P/V=2JP/Nb=3, P/T a
= 3, such as titanyl dihydrogen phosphate, zirconyl dihydrogen phosphate, etc., can also be used.

Additionally, phosphoric acid-hydrogen salts are also used. For example, diammonium hydrogen phosphate, beryllium hydrogen phosphate, magnesium hydrogen phosphate, calcium hydrogen phosphate, strontium hydrogen phosphate, barium hydrogen phosphate, scandium hydrogen phosphate, phosphoric acid Yttrium hydrogen, lanthanum hydrogen phosphate,
Cerium hydrogen phosphate, praseodymium hydrogen phosphate, neodymium hydrogen phosphate, promethium hydrogen phosphate, samarium hydrogen phosphate, europium hydrogen phosphate, gadolinium hydrogen phosphate, terbium hydrogen phosphate, dysprosium hydrogen phosphate, holmium hydrogen phosphate, Erbium hydrogen phosphate,
Thulium hydrogen phosphate, ytterbium hydrogen phosphate, lutetium hydrogen phosphate, chromium hydrogen phosphate, manganese hydrogen phosphate, iron hydrogen phosphate, cobalt hydrogen phosphate, nickel hydrogen phosphate, steel hydrogen phosphate, silver hydrogen phosphate , zinc hydrogen phosphate, cadmium hydrogen phosphate, mercury hydrogen phosphate, aluminum hydrogen phosphate, gallium hydrogen phosphate, indium hydrogen phosphate, thallium hydrogen phosphate, tin hydrogen phosphate, lead hydrogen phosphate, antimony hydrogen phosphate , bismuth hydrogen phosphate, etc. Also, salts of metal compounds of periodic table fVa, Va and phosphoric acid, for example, element ratio P/Ti=1, P/Z
r = 1, P/Hf = 1, P/V = 1. P/Nb
= 1.5, and a substance represented by P/Ta = 1.5 can also be used.

In addition, normal salts can also be used. For example, boron phosphate, scandium phosphate, yttrium phosphate, lanthanum phosphate,
Cerium phosphate, praseodymium phosphate, neodymium phosphate, promethium phosphate, samarium phosphate, europium phosphate, gado phosphate.

linium, terbium phosphate, dysprosium phosphate,
Examples include holmium phosphate, erbium phosphate, thulium phosphate, ytterbium phosphate, lutetium phosphate, chromium phosphate, iron phosphate, aluminum phosphate, and bismuth phosphate.

Among the phosphates of these metals, dihydrogen phosphate is preferred, and when dissolution of the catalyst in the water produced during the reaction is not preferred, phosphates of Ila, ■a, and rVa metals are preferred. It is preferable to use

The amount of these metal phosphates used as catalysts is
It is usually in the range of 0.01 to 1 mol in terms of phosphorus per 1 mol of dihydric phenols as raw materials.

In addition to phenol, specific examples of phenols used together with metal phosphates in the method of the present invention include cresol, ethylphenol, propylphenol, isopropylphenol, butylphenol, methoxyphenol, ethoxyphenol, impropoxyphenol, and fluorophenol. , chlorophenol, bromophenol, nitrophenol, and the like, as well as disubstituted phenols such as dimethylphenol, diethylphenol, and dichlorophenol.

Among these phenols, it is preferable to use phenol and monosubstituted alkylphenols and halophenols.

The amount of these phenols to be used is generally 1 to 40 mol, preferably 2 to 30 mol, per 1 mol of the dihydric phenols as raw materials.

Examples of dihydric phenols used as raw materials in the method of the present invention include unsubstituted dihydric phenols such as catechol, resorcinol, and hydroquinone, as well as 2-methylhydroquinone, 4-methylresorcinol, and 5-methylresorcinol. Methylresorcin, 3-methylcatechol, 4
- In addition to compounds in which the hydrogen atom of the aromatic nucleus of dihydric phenols having no substituents is replaced with a methyl group, such as methylcatechol, ethyl group, n-propyl group, isopropyl group, n-butyl group, 5ec- Examples include dihydric phenols having a substituent in which a butyl group or ter is substituted with an alkyl group such as a -butyl group.

The following are examples of amines such as ammonia, primary amines, and secondary amines, which are the other raw materials of the present invention. As the ammonia, ammonia or aqueous ammonia is used.

Ammonia water can be of any concentration. Examples of primary amines include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, 5ec-butylamine, t-7'' thylamine, benzylamine, β-phenylethylamine, aniline, 0-toluidine, m -) luidine, P-) luidine, etc. Examples of secondary amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-5ec-butylamine. , di-1-butylamine, methylethylamine, N-methylbenzylamine, N-ethylbenzylamine, N-methylaniline, N
Examples include -ethylaniline, diphenylamine, and N-benzylaniline.

These ammonia, primary amines, and secondary amines must not have any substituents on the amino group of these products when dihydric phenols are aminated to obtain the corresponding aminophenols and phenylenediamines. Ammonia can be used if it is desired to have a substituent, and a primary or secondary amine can be used if it is desired to have a substituent.

The amount of these amines added varies depending on the reactivity of the amine used, but when ammonia is used as the amine, it is usually in the range of 2 to 200 mol, preferably 2 to 100 mol, per 1 mol of dihydric phenol. It is.

In the method of the present invention, the reaction proceeds even without the use of a reaction solvent, but the reaction can be carried out even in the presence of a reaction solvent.As the reaction solvent, any reaction solvent that does not adversely affect the reaction may be used. Can be used. Examples of these include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, cymene, N, N-
Aprotic polar compounds such as dimethylformamide, dimethylsulfoxide, -acetonitrile, phosphine oxides such as triisopropylphosphine oxide, tri-n-phthylphosphine oxide, triphenylphosphine oxide, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, etc. Examples include aliphatic halides, aromatic halides such as fluorobenzene, difluorobenzene, chlorobenzene, and dichlorobenzene, water, and, if necessary, reaction raw materials such as ammonia, primary amines, or Secondary amines can also be used in solvent amounts.

The reaction temperature in the method of the invention varies depending on the reactivity of the amine used. For example, when ammonia is used as the amine, the reaction temperature is usually 150 to 400.
°C1 is preferably in the range of 200 to 350 °C.

In the method of the present invention, when the reaction is generally carried out batchwise, the reaction is carried out under the autogenous pressure of amines such as ammonia, primary amines and secondary amines.

For example, when ammonia is used as the amine, the range is usually 50 to 400 kg/cJ gauge. on the other hand,
When the reaction is carried out in a continuous manner, the reaction pressure can be controlled, so the reaction can be carried out even in a range above the autogenous pressure of ammonia.

The reaction pressure in this case is preferably in the range of 50 to 500 kg/d gauge.

The reaction time in the method of the present invention varies depending on the amount of catalyst used, the reaction temperature, or the reactivity of the dihydric phenols and amine, but usually about 30 minutes to 8 hours is sufficient.

The method of the present invention can be carried out by a batch method, a semi-batch method, or a continuous method. For example, in the case of a batch process, an autoclave containing metal phosphates, dihydric phenols, phenols, and optionally a reaction solvent is charged with ammonia, primary amines, and secondary amines. The reaction proceeds by adding the amine in the form of a gas, liquid, or solution, and heating, preferably with stirring.

In addition, examples of continuous methods include dihydric phenols,
The reaction is carried out by continuously feeding the phenols and optionally the reaction solvent and amine into one side of a pressure-resistant reactor filled with metal phosphate, and continuously withdrawing the reaction mixture from the other side. In one or two cases, the space velocity of the reactants is about 0.1 to about 10 g total reactants/d catalyst volume/Hr, preferably about 0.2 to 2 g total reactants/d catalyst volume/Hr. Metal phosphates can also be supported on materials such as diatomaceous earth, silica, alumina, and the like.

In the method of the present invention, in order to obtain aminophenols and phenylenediamines from the reaction product liquid after completion of the reaction, a conventional method such as a distillation method or a crystallization method may be used.

〔Example〕

Hereinafter, the method of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

In addition, in the examples, the material balance of dihydric phenol was determined by the following formula.

Material balance of dihydric phenol = ((number of moles of dihydric phenol recovered after reaction; tens of moles of aminophenol produced; number of moles of phenylenediamine tD produced) / (number of moles of dihydric phenol charged) x loo ( %) Example 1 In a stirring type SUS 316L autoclave with an internal volume of 50 d, 1.0 g of aluminum dihydrogen phosphate, 2.2 g of hydroquinone (20 m5+ol), and 1 phenol were added.
After filling the autoclave and sealing it, the inside of the autoclave was replaced with N2 gas.
After weighing g, it was connected to an autoclave and the entire amount was fed into the autoclave. The autoclave was heated in an electric furnace, and from the time the reaction temperature reached 280"C,
After the reaction was completed for 0 hours, the autoclave was cooled to room temperature and excess ammonia gas was discharged. Take out all the contents of the autoclave, filter insoluble solids such as catalyst, wash well with DMF, which is a diluting solvent, and add 50a11! to a volumetric flask. The volume was determined by gas chromatography. As a result, the conversion rate of hydroquinone was 33.0%, para-aminophenol was 5.68m+*ol (selectivity 86.1%), para-phenylenediamine 0.93mno+ (selectivity 14.1%)
is produced, and 13.40 mmol of hydroquinone
was recovered. The mass balance of hydroquinone was 100%.

Example 2 The reaction was carried out in exactly the same manner as in Example 1, except that the amount of ammonia was changed to 15 g and the amount of phenol was changed to 5 g. As a result, the conversion rate of hydroquinone was 99.0%, and the conversion rate of para-aminophenol was 15.53%.
mol (selectivity 78.4%), paraphenylenediamine 2.41 mno+ (selectivity 12.2%) was produced, and 0.19 ml 1 ol of hydroquinone was recovered.

The mass balance of hydroquinone was 90.7%.

Comparative Example 1 Except for not using phenol in Example 1,
The reaction was carried out in exactly the same manner as in Example 1.

As a result, the conversion rate of hydroquinone was 91.6%, and para-aminophenol 7.78 mmol (selectivity 4
2.4%), paraphenylenediamine 1.56 mmol
(selectivity 8.5%), hydroquinone 1
．． 67 mmol was recovered. The mass balance of hydroquinone was 5561%.

〔Effect of the invention〕

According to the present invention, dihydric phenols can be aminated with amines such as ammonia, primary amines, and secondary amines to produce corresponding aminophenols and phenylenediamines in good yield.

In addition, in conventional methods, the loss of dihydric phenols supplied as raw materials occurs due to the by-product of tar-like substances, which has been a major problem when industrially aminating dihydric phenols. According to the present invention, the by-product of tar-like substances can be suppressed, and the reaction can proceed without loss of dihydric phenols.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. A process characterized by using phenols and metal phosphates in producing the corresponding aminophenols and phenylenediamines by aminating the hydroxyl group of dihydric phenols with amines. Method for aminating dihydric phenols. 2. The method for aminating dihydric phenols according to claim 1, wherein the amine is ammonia, a primary amine or a secondary amine.