JPH062717B2 - Amination method for divalent phenols - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing corresponding aminophenols and phenylenediamines by reacting divalent phenols with ammonia or amines. The present invention relates to a selective manufacturing method.

Aminophenols are used as medicines, agricultural chemicals, dyes, rubber drugs, compounding agents for synthetic resins, or intermediates for their production. Further, phenylenediamines are used for the same purpose as the above aminophenols, and are also used as a raw material for producing or modifying a polyamide for a special purpose.

Conventionally, as a method for producing the corresponding amine phenols and phenylenediamines by reacting divalent phenols with ammonia or amines, a method of carrying out a reaction in a gas phase in the presence of a catalyst and the presence of the catalyst Alternatively, a method is known in which the reaction is performed in the liquid phase in the absence. However, although many catalysts have been proposed for the method of carrying out the reaction in the gas phase among these methods, all of these catalysts show a considerable activity in the initial stage of the reaction, but the activity becomes higher over time. However, there is a drawback that it cannot be adopted as an industrial manufacturing method because it is deteriorated. This tendency is large when divalent phenols are used as reaction substrates. Further, as a method of reacting in a liquid phase, both are reacted in a molten state in the absence of a catalyst, as disclosed in JP-A-48-284.
29, 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 as a catalyst, a halide of copper, cobalt or nickel and an ammonium halide. Reacting in the presence of a catalyst consisting of
829, the method of reacting in the presence of stannous chloride as a catalyst, and the method of JP-A-52-100427, and a binary system comprising stannous chloride and ammonium chloride as a catalyst. The method proposed in JP-A-52-100428, in which the reaction is carried out in the presence of a catalyst, is known. However, all of the methods of performing the amination reaction in the liquid phase using these conventionally known catalysts have the drawbacks that the amination reaction rate is slow, and the selectivity and yield for the target product are low. Under the circumstances, the applicant of the present invention, unlike the previously known catalyst, has a high selectivity for amination reaction and a high yield, as shown in JP-A-55-108841. We have developed a new molybdic acid catalyst as an excellent catalyst. However, since the catalyst is soluble in the reaction solution, the operation of separating the catalyst after the reaction is usually complicated for this kind of catalyst, and therefore some problems remain in industrialization. The present inventors have recognized these points, and as a result of earnestly examining improvement of a molybdic acid-based catalyst, they found that the above-mentioned drawbacks can be solved by adopting a catalyst by the following method in the amination reaction. The invention was completed.

That is, according to the present invention, a salt of molybdic acid, a molybdenum compound (A) selected from molybdic acid and molybdenum oxide, and copper, magnesium, zinc, cadmium, aluminum, gallium, titanium, zirconium,
Other than molybdenum, obtained by heating and reacting a mixture of a hydroxide or metal salt (B) of a metal other than molybdenum selected from the group consisting of tin, chromium, tungsten, iron, cobalt and nickel at a high temperature of 300 ° C. or higher. Using the mixed metal oxide having the above metal / molybdenum atomic ratio in the range of 0.1 to 50 as a catalyst, the divalent phenols (a) and ammonia, primary amine or secondary amine (b) are present in the presence of the catalyst. A method for amination of divalent phenols, which comprises reacting.

In the method of the present invention, specific examples of the divalent phenols (a) used as the reaction raw material include, for example, bidroquinone, resorcin, catechol, and other non-substituted divalent phenols; 2-methylhydroquinone, 4- Methylresorcin, 5-methylresorcin, 5-ethylresorcin, 5-isopropylresorcin, 5-n-butylresorcin, 5-sec-butylresorcin, 5-tert-
Butylresorcin, 3-methylcatechol, 4-methylcatechol, 4-methylcatechol, 4-isopropylcatechol, 4-n-butylcatechol, 4-sec-butylcatechol, 4-tert-butylcatechol and the like can be mentioned. Among these divalent phenols, it is preferable to use a divalent phenol having no substituent, 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, the ammonia or amines (b) used as the reaction raw material is ammonia, primary amine or secondary amine. Specifically, ammonia or ammonia water having various concentrations can be exemplified as the ammonia, and methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, as the primary amine, tert
-Butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, benzylamine, cyclohexylamine and the like can be exemplified, and as the secondary amine, dimethylamine, diethylamine, di-n-propylamine, Diisopropylamine, di-n-butylamine, di
Examples include sec-butylamine, ditert-butylamine, diamylamine, dihexylamine, diheptylamine, dioctylamine, didodecylamine and the like. When using ammonia water, it is preferable to use 10% by weight or more of ammonia water. The amount of ammonia, primary amine or secondary amine used is preferably 1 mol or more, and particularly preferably 1 to 7 mol, per 1 mol of the divalent phenol (a). Needless to say, ammonia, primary amine or secondary amine used in excess can be recovered and reused.

The catalyst for the amination reaction used in the method of the present invention is a molybdenum compound (A) selected from salts of molybdic acid, molybdic acid and molybdenum oxide, and hydroxides of metals other than molybdenum and salts other than molybdenum selected from salts. It is a composite metal oxide containing molybdenum obtained by heating and reacting the metal compound (B) at a high temperature. The catalyst will be described in detail below. In the method of the present invention, salts of molybdic acids used in preparing the catalyst include orthomolybdic acid, isopolymolybdic acid (paramolybdic acid, metamolybdic acid, etc.), and P, As, Si. , Ge, Sn, Ti, Zr, B, Ce, Th, Pt, Mn, N
Various salts of heteropolymolybdic acid formed by condensation of metal or non-metal ions selected from i, Te, I, Co, Al, Cr, Fe, Rh, Cu around molybdic acid, for example, alkali metal salts , Alkaline earth metal salts and other metal salts,
Examples thereof include ammonium salts, various amine salts, and various quaternary ammonium salts. Among them, it is preferable to use ammonium salts and amine salts because the yield and selectivity of the desired product are high. preferable. Molybdic acids used in the method of the present invention include ortho-molybdic acid (H ₂ MoO ₄ or H ₂ MoO ₄ · H ₂ O) as well as pyromolybdic acid, metamolybdic acid, paramolybdic acid, heteropolymolybdic acid and the like. included. In addition to molybdenum trioxide, molybdenum oxide used in the method of the present invention also includes molybdenum oxides having various valences or mixed valences such as Mo ₂ O ₅ , MoO ₂ , and molybdenum blue. .

Hydroxides of metals other than molybdenum used in preparing the catalyst of the present invention include Ib and II of the periodic table.
Among the metals belonging to the respective groups a, IIb, IIIb, IVa, IVb, Vb, VIa and VIII, Cu, Mg, Zn, Cd, Al, G
A hydroxide of the metal containing at least one selected from a, Ti, Zr, Sn, Cr, W, Fe, Co, and Ni can be exemplified, and among them, preferable hydroxides include, for example, alumina. Hydrogel, silica-alumina hydrogel, iron hydroxide and the like can be exemplified, but of these, it is preferable to use alumina hydrogel. In the case of using, for example, alumina hydrogel or the like in the hydroxide, it is also possible to use alumina hydrogel as a main component and to mix it with an appropriate amount of the above-mentioned metal hydroxide. Examples of the metal salt of a metal other than molybdenum used in preparing the catalyst of the present invention include nitrates, sulfates, chlorides, phosphates, acetates and oxalates of the various metals described above. Examples thereof include salts of various organic acids.

In preparing the catalyst of the present invention, the following method can be adopted as necessary.

(1) When a hydroxide is used as a salt of molybdic acid or a metal compound of a metal other than molybdenum, the catalyst can be usually prepared as follows. The hydroxide is impregnated with an aqueous solution of a salt of molybdic acid, or the hydroxide is added to an aqueous solution of a salt of molybdic acid, and the mixture is immersed for a suitable time, and the salt of molybdic acid is adsorbed and supported, and then filtered. Or a predetermined amount of salt of molybdic acid is supported on the metal hydroxide by a method of evaporating and drying the water of the immersion mixture by using, for example, a rotary evaporator. . After drying the supported molybdic acid salt, at a predetermined temperature and time,
The catalyst of the present invention can be obtained by heating at a high temperature.

(2) When a metal salt is used as a salt of molybdic acid and a metal compound of a metal other than molybdenum, the catalyst can be prepared, for example, as follows. Is a mixed salt-containing liquid containing molybdic acid salts and metal salts in a predetermined ratio removed by evaporation of water using a rotary evaporator or the like to obtain a dry solid, and drying and firing to obtain a catalyst? Alternatively, if necessary, an acid such as hydrochloric acid and / or an alkali such as aqueous ammonia is added to the mixed salt-containing solution to form a precipitate, and then the solvent is removed by decantation or filtration. Excluding the above, it is possible to exemplify a method of obtaining a catalyst by washing, drying and calcining if necessary. The mixed salt-containing liquid described above may be prepared by mixing an aqueous solution of a salt of molybdic acid and an aqueous solution of a metal salt or by adding water to a mixture of a salt of molybdic acid and a metal salt, if necessary. Can be used. As the metal salt used in the method of the present invention, for example, in the case of aluminum, aluminum nitrate, aluminum chloride, aluminum bromide, aluminum oxalate, aluminum acetate and aluminum isopropoxide can be shown. Taking the case of titanium as an example, titanium trichloride, titanium tetrachloride,
Titanium nitrate, titanium oxalate, and titanium tetraalkoxide can be used.

(3) When a hydroxide is used as a metal compound of molybdic acid or molybdenum oxide and a metal other than molybdenum, for example, the catalyst is prepared as follows. The catalyst of the present invention can be prepared by solid-phase reaction by calcining a uniform mixture containing molybdic acid or molybdenum oxide and the hydroxide in a predetermined amount at a predetermined temperature. In this case, a solvent such as water or / and an organic substance such as stearic acid may be added to the mixture, if necessary, prior to firing, and in this case, drying may be performed prior to firing as necessary. Be seen.

(4) When using a metal salt as molybdic acid or molybdenum oxide and a metal compound other than molybdenum,
The catalyst is prepared, for example, as follows. A method in which molybdic acid or molybdenum oxide is impregnated with an aqueous solution of a metal salt and then dried, or a method of firing, or a mixture of molybdic acid or molybdenum oxide added to an aqueous solution of a metal salt is evaporated to dryness using a rotary evaporator or the like, A method of baking after drying, or by adding an appropriate amount of an aqueous alkali solution such as ammonium water, potassium hydroxide, ammonium carbonate or sodium carbonate to the mixture under uniform stirring to convert the metal salt into a hydroxide, A catalyst can be prepared by a method in which a mixture of an oxide and molybdic acids or molybdenum oxide is obtained, and the mixture is filtered (washed if necessary) or evaporated to dryness, and then dried and calcined.

In the preparation of the catalyst of the present invention, the above (1) to (4)
It can be appropriately selected and used from among the various preparation methods described in 1 above.

Salts of molybdic acids, molybdic acids or molybdenum oxides and hydroxides or metal salts of metals other than molybdenum used in preparing the catalyst of the present invention (hereinafter, the metal component in these compounds is the second component, etc. It may be abbreviated as “)”, and it is usually desirable to set the usage ratio as follows. That is, a molybdenum atom in the composition of the catalyst of the present invention and a metal atom such as a second component such as an aluminum atom (hereinafter, this may be represented by the symbol M).
The use ratio of molybdic acid salts, molybdic acid or molybdenum oxide and the second component etc. is set so that the ratio of the number of atoms (M / Mo) is usually 0.1 to 50, preferably 0.2 to 20. To be done. In the method of the present invention,
The metal atom of the second component and the like includes the case where a mixture of at least two metals selected from the group of the above-mentioned metals is used, and the ratio of the number of atoms in this case (as the second component, etc. The total amount of metal atoms other than molybdenum / the number of molybdenum atoms) is adjusted so that the catalyst is set to fall within the above M / Mo range. The drying treatment carried out in the preparation of the catalysts described in (1) to (4) above is usually performed at room temperature to 150 ° C. for 2 to 24 hours and then calcined. In the calcination treatment of the catalyst of the present invention, it is usually desirable to set the calcination temperature to 200 to 800 ° C, preferably 300 to 700 ° C, and the calcination time is usually 3 hours.
As described above, it is desirable that the time is 5 hours or more. The catalyst is usually calcined in an oxygen-containing gas atmosphere, but it may be calcined in a titanium atmosphere if necessary.

In the method of the present invention, aminophenols, which are the objectives of reacting a divalent phenol with ammonia, a primary amine or a secondary amine by a liquid phase method, using the molybdenum-containing metal oxide prepared by the above method as a catalyst. Is obtained. Further, in this case, if necessary, phenylenediamines can be obtained. The amount of the catalyst used in this case is usually 0.001 to 1 as the amount of molybdenum atoms in the catalyst relative to 1 mol of the divalent phenol (a).
It is in the range of 0 g-atoms, preferably 0.01 to 1 g-atoms.

The reaction of the present invention can be carried out in a liquid phase or a gas phase, but in the method of the present invention, it is preferably carried out in a liquid phase, in which case it can also be carried out in the absence of a solvent. It can also be carried out in the presence of a solvent. Examples of the solvent when the reaction solvent is used include water, monovalent phenols, benzene, toluene, and the like, and also divalent phenols that are reaction substrates, or ammonia,
It is also possible to use solvent amounts of primary or secondary amines. Specific examples of monovalent phenols used as a reaction solvent include phenol and cresol (o-, m-,
p-form), ethylphenol (o-, m-, p-form),
Isopropylphenol (m-, p-form), 2,6-xylenol, 2,3-xylenol, 2,4-xylenol, 2,
5-xylenol, methoxyphenol (o-, m-, p
-Body), etc., but it is preferable to use phenol in the method of the present invention. In the method of the present invention, two or more kinds of these solvents may be mixed and used, if necessary.

The amount of the reaction solvent used in the method of the present invention is usually 1 to 100 parts by weight, preferably 2 to 20 parts by weight, based on 1 part by weight of the divalent phenol (a).

In 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 an inert gas such as argon or helium under the reaction conditions.

In the method of the present invention, the reaction proceeds by heating a mixture of the divalent phenol (a), ammonia, the primary amine or secondary amine (b), the catalyst and, if necessary, the solvent with stirring. The temperature during the reaction varies greatly depending on the reaction substrate, its concentration, the type of catalyst and its concentration, but it is usually 150 to 350 ° C, preferably 18
It is in the range of 0 to 300 ° C. The method of the present invention can be carried out by any of a batch method, a semi-continuous method and a continuous method.

In the method of the present invention, the aminophenols can be produced almost selectively by appropriately selecting the reaction conditions, the aminophenols and the phenylenediamines can be simultaneously produced, and the phenol It is also possible to improve the selection of cormorant for nylene diamine. For example, in general, ammonia for divalent phenols (a),
When the molar ratio of the primary amine or secondary amine (b) is lowered and the reaction is carried out under a relatively low temperature condition, the selectivity to aminophenols is improved, and the molar ratio is increased to a relatively high temperature. When the reaction is carried out under the conditions, the selectivity to phenyldiamines is improved.

In the method of the present invention, the catalyst can be separated from the mixture obtained by removing the aminating agent from the reaction mixture after completion of the reaction by a simple operation such as filtration. Further, molybdenum, which is a constituent element of the catalyst, is recovered with almost no dissolution in the reaction solution, and even if the recovered catalyst is repeatedly used in the amination reaction, almost no decrease in activity is observed. The reaction product after separation of the catalyst is treated according to a conventional method such as a crystallization method to obtain the desired product.

When the catalyst of the present invention is used, aminophenols can be obtained from divalent phenols with high selectivity, and after completion of the reaction, the catalyst can be separated and recovered by an extremely simple method such as filtration. From this point, it becomes possible to industrially produce aminophenols and the like.

Next, the method of the present invention will be specifically described with reference to examples.

Example 1 42.7 g of ammonium paramolybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄ 4H ₂ O) was dissolved in 150 ml of distilled water, and 25.9 g of aluminum nitrate / 9-hydrate prepared separately was distilled water. A solution dissolved in 80 ml was added to prepare a mixed solution, and water was removed from the mixed solution at about 60 ° C. by using a rotary evaporator to obtain a solid. 100 of the solid
After drying at 24 ° C. for 24 hours and then calcination in air at 500 ° C. for 5 hours, 38 g of a molybdenum-containing mixed metal oxide which is the catalyst of the present invention was obtained. The ratio of Al atoms to Mo atoms of the catalyst was Al / Mo = 2/7 as a result of atomic absorption spectrometry, and the molybdenum content was 65.
% By weight.

Resorcin 11 in an autoclave made of SUS with an internal volume of 50 ml.
0 g, 4.00 g of phenol and 0.83 g of the above-prepared catalyst were charged, the autoclave was replaced with nitrogen gas, and then ammonia gas was introduced into the autoclave and charged with 085 g, and the reaction was carried out at 210 ° C. for 6 hours. After completion of the reaction, the autoclave was cooled to room temperature and then deammonified, and then the catalyst was separated from the reaction mixture by filtration while the content was being washed out with ethanol using a No. 2 filter paper to obtain a filtrate. The results of analyzing the filtrate by gas chromatography are shown in Table 1.

Example 2 The reaction and operation were carried out under the same conditions as in Example 1, except that 0.83 g of the catalyst obtained by calcining the recovered catalyst in air at 500 ° C. for 5 hours after being used in the reaction in Example 1 was used. The results are shown in Table 1.

Example 3 In Example 1, the reaction solvent was changed from phenol to water, and the catalyst prepared in Example 1 was reduced to 0.33 g.
Table 1 shows the results obtained in the same manner as in Example 1 except that the reaction was performed at 10 ° C. for 4.5 hours.

Example 4 2 g of paramolybdic acid was dissolved in 6 ml of distilled water,
Separately, a solution of 15 g of aluminum nitrate nonahydrate dissolved in 40 ml of distilled water was added to form a mixture, and further ammonia water was added to prepare pH7. The precipitate obtained at this time was filtered off, dried at 100 ° C for 24 hours, and then dried in air at 500 ° C.
It was calcined for 5 hours to obtain a catalyst. The Al / Mo atomic ratio of the catalyst is
It was 10/1 and the molybdenum content was 14.6% by weight.

Table 1 shows the results of the same procedure as in Example 1 except that 0.50 g of the catalyst was used and the reaction was performed at 220 ° C. for 4 hours.

Example 5 To a solution of 10.9 g of ammonium paramolybdate dissolved in 40 ml of distilled water was added 200 g of a 20% by weight aqueous solution of titanium trichloride with stirring at room temperature to form a mixed solution, which was neutralized with aqueous ammonia. The solvent was removed with a rotary evaporator to obtain a solid, which was dried at 100 ° C. for 24 hours and then calcined in air at 700 ° C. for 3 hours to obtain a catalyst. Ti / Mo of the catalyst
Had an atomic ratio of 4.2, and the molybde content was 20% by weight.

Table 1 shows the results obtained in the same manner as in Example 1 except that 0.50 g of the catalyst was used and the reaction was performed at 220 ° C. for 4 hours.

Comparative Example 1 As a catalyst, α-alumina obtained by calcining at 1000 ° C. for 3 hours was used.
Table 1 shows the results of the same procedure as in Example 1 except that 45 g was used and the reaction was carried out at 220 ° C. for 4 hours.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C07C 209/18 213/02 215/76 7457-4H (56) Reference JP-A-55-53250 ( JP, A) JP 55-108841 (JP, A) JP 48-28429 (JP, A) JP 52-100427 (JP, A) JP 52-42829 (JP, A) JP Sho 52-100428 (JP, A)

Claims (1)

[Claims] 1. A molybdic acid salt, a molybdenum compound (A) selected from molybdic acids and molybdenum oxide, and copper, magnesium, zinc, cadmium, aluminum, gallium, titanium, zirconium, tin, chromium,
The above metal other than molybdenum / molybdenum obtained by heating and reacting a mixture of a hydroxide or metal salt (B) of a metal other than molybdenum selected from the group consisting of tungsten, iron, cobalt and nickel at a high temperature of 300 ° C. or higher. Using a mixed metal oxide having an atomic ratio of 0.1 to 50 as a catalyst in the presence of the catalyst to react the dihydric phenol (a) with ammonia, primary amine or secondary amine (b). A method for aminating dihydric phenols.