JP2003073342A - Method for producing halogenated aromatic methylamine compounds - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for profitably producing a halogenated aromatic methylamine compound of formula (2) [X is chlorine atom or fluorine atom; (m) is an integer of 1 to 5; (n) is an integer of 1 to 5; (m)+(n)<=6; when (n) is >=2, X groups may be the same or different each other; (a) is an integer of >=1] especially useful for producing pyrethroid insecticides in a high yield, and to provide an intermediate raw material for producing agrochemicals, medicines or the like, especially the pyrethroid insecticides. SOLUTION: This method for producing the halogenated aromatic methylamine compound comprises reducing a halogenated aromatic nitrile compound with hydrogen in the presence of an organic acid and a hydrogenation catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel method for producing halogenated aromatic methylamines useful as an intermediate for producing agricultural chemicals, pharmaceuticals and the like. In particular 2,3,5,6-tetrafluoroxylylenediamine and 2,3,4,6-
Tetrafluoroxylylenediamine is useful as an intermediate for producing cyclopropanecarboxylic acid esters having an excellent insecticidal action.

[0002]

2. Description of the Related Art There are many known methods for producing aromatic methylamines by hydrogenating aromatic nitriles. For example, British Patent Nos. 810530, 852972 and 1149251 disclose a method of hydrogenating terephthalonitrile in the presence of ammonia to produce xylylenediamine. However, although such a condition can prevent the secondary amine by-product to some extent, it produces a compound such as a halogenated aromatic methylamine in which a nucleophilic substitution reaction of a halogen atom with an amino group occurs as a side reaction. Not suitable for.

As a method for producing halogenated aromatic methylamines, for example, Japanese Examined Patent Publication No. 4-14096 discloses a halogenated xylylenediene in which halogenated terephthalonitrile is reacted in the presence of a hydrogenation catalyst under inorganic acidic conditions. A method for making amines is described. However, in this method, since the acid used is a strong acid such as sulfuric acid, a metal such as nickel or cobalt, which is easily dissolved under acidic conditions, cannot be used as a catalyst, and expensive palladium is used.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a means for industrially producing a halogenated aromatic methylamine useful as an intermediate for the production of agricultural chemicals, pharmaceuticals and the like.

[0005]

The present inventors have found that the equation (1)
By reducing a halogenated aromatic nitrile represented by in the presence of an organic acid in a solvent,

[Chemical 6] (In the formula, X represents a chlorine atom or a fluorine atom, and m is 1
Is an integer of 1 to 5, n is an integer of 1 to 5, and m + n ≦
6 and when n is 2 or more, X may be the same or different. ) It was found that the halogenated aromatic methylamines represented by the formula (2) can be produced in high yield, and the present invention has been completed.

[Chemical 7] (In the formula, X and m, n are as defined above, and a represents an integer of 1 or more and m or less.)

By using an organic acid, it has become possible to use a metal such as nickel or cobalt which is easily dissolved in a strong acid as a catalyst. In addition, by using an organic acid salt for the amino group of the amines produced by this reaction, it is possible to suppress side reactions such as an addition reaction of the amino group with a nitrile group and a substitution reaction with halogen.

The present invention relates to the following items.

[1] Expression (1)

[Chemical 8] (In the formula, X represents a chlorine atom or a fluorine atom, and m is 1
Is an integer of 1 to 5, n is an integer of 1 to 5, and m + n ≦
6 and when n is 2 or more, X may be the same or different. ), Halogenated aromatic nitriles are hydrogen-reduced using a hydrogenation catalyst in the presence of an organic acid in a solvent, the formula (2)

[Chemical 9] (In the formula, X and m and n are as defined above, and a is an integer of 1 or more and m or less.) A method for producing a halogenated aromatic methylamine.

[2] The halogenated aromatic nitriles represented by the above formula (1) are tetrafluoroterephthalonitrile or tetrafluoroisophthalonitrile, and the halogenated aromatic methylamines represented by the formula (2). But,
2,3,5,6-tetrafluoroxylylenediamine or 2,3,4,6-tetrafluoroxylylenediamine, the method for producing a halogenated aromatic methylamine according to [1]. .

[3] The solvent is a single or mixed solvent containing at least one selected from aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, esters and water [1] or The method for producing a halogenated aromatic methylamine according to [2].

[4] The solvent is a single solvent or a mixed solvent containing at least one selected from benzene, toluene, xylene, ethylbenzene, hexane, cyclohexane, methanol, ethanol, propanol, tetrahydrofuran, dioxane, dioxolane, ethyl acetate and water. The method for producing a halogenated aromatic methylamine according to [1] or [2], characterized in that

[5] Production of halogenated aromatic methylamines according to [3] or [4], characterized in that the solvent is water and a mixed solvent of water and an organic solvent which is insoluble at an arbitrary ratio. Method.

[6] The method for producing a halogenated aromatic methylamine according to [5], wherein the organic solvent which is insoluble in water at an arbitrary ratio is an aromatic hydrocarbon.

[7] The method for producing a halogenated aromatic methylamine according to [6], wherein the aromatic hydrocarbon is toluene, xylene, or ethylbenzene.

[8] The method for producing a halogenated aromatic methylamine according to [1] or [2], wherein the solvent is water.

[9] Production of halogenated aromatic methylamines according to any one of [1] to [8], wherein the organic acid is at least one selected from formic acid, acetic acid and propionic acid. Method.

[10] The catalyst is nickel, palladium,
The method for producing a halogenated aromatic methylamine according to any one of [1] to [9], which comprises at least one metal selected from platinum, ruthenium, cobalt and copper.

[11] The method for producing a halogenated aromatic methylamine according to any one of [1] to [9], wherein the catalyst is sponge nickel or sponge cobalt.

[12] The method for producing a halogenated aromatic methylamine according to [11], wherein the catalyst is sponge nickel.

[13] The method for producing a halogenated aromatic methylamine according to [12], wherein the contact is sponge nickel to which molybdenum is added as a different metal.

[14] The halogenated aromatic methylamine according to any one of [1] to [13], which is used after pretreating the catalyst in a solvent in an atmosphere of hydrogen gas at 40 ° C. or lower. Manufacturing method.

[15] The method for producing a halogenated aromatic methylamine according to any one of [1] to [9], wherein the catalyst is supported palladium.

[16] The halogenated aromatic methylamine according to any one of [1] to [15], wherein the amount of the solvent used is 1 to 20 times by mass that of the halogenated aromatic nitrile. Manufacturing method.

[17] The amount of the organic acid used is 50 to 500 mol% with respect to the nitrile group of the halogenated aromatic nitrile.
The method for producing a halogenated aromatic methylamine according to any one of [1] to [16], wherein

[18] The halogenated aroma according to any one of [1] to [17], characterized in that the amount of the catalyst used is 0.01 to 1 times the mass of the halogenated aromatic nitrile. Of producing group methylamines.

[19] Reduction of hydrogen with a reaction temperature of room temperature to 1
The method for producing a halogenated aromatic methylamine according to any one of [1] to [17], which is performed at 00 ° C. and a hydrogen partial pressure of 0.1 to 5 MPa. [20] Formula (2) obtained by the manufacturing method according to any one of [1] to [19]

[Chemical 10] (In the formula, X represents a chlorine atom or a fluorine atom, and m is 1
Is an integer of 1 to 5, n is an integer of 1 to 5, and m + n ≦
6 and when n is 2 or more, X may be the same or different. a represents an integer of 1 or more and m or less)
Halogenated aromatic methylamines represented by. [21] Formula (1)

[Chemical 11] (In the formula, X represents a chlorine atom or a fluorine atom, and m is 1
Is an integer of 1 to 5, n is an integer of 1 to 5, and m + n ≦
6 and when n is 2 or more, X may be the same or different. From the halogenated aromatic nitriles represented by the formula (2)

[Chemical 12] (In the formula, X and m and n are as defined above, and a represents an integer of 1 or more and m or less.) A catalyst used for producing a halogenated aromatic methylamine.

[0027]

The present invention will be further described in detail.
The halogenated aromatic nitriles used as the raw material of the present invention are commercially available and easily available. Formula (1)
In the above, the number and position of the nitrile group and the halogen are not limited. Examples of halogen types include chlorine and fluorine.

[Chemical 13] (In the formula, X represents a chlorine atom or a fluorine atom, and m is 1
Is an integer of 1 to 5, n is an integer of 1 to 5, and m + n ≦
6 and when n is 2 or more, X may be the same or different. )

[Chemical 14] (In the formula, X and m, n are as defined above, and a represents an integer of 1 or more and m or less.)

Specific examples of the halogenated aromatic nitrile represented by the formula (1) include, for example, tetrafluorophthalonitrile, tetrafluoroisophthalonitrile, tetrafluoroterephthalonitrile, pentafluorobenzonitrile, 2,3,3. 5,6-tetrafluorobenzonitrile, 2,3,4,6-tetrafluorobenzonitrile, 2,3,4,5-tetrafluorobenzonitrile,
2,4,6-trifluoro-5-chloroisophthalonitrile, tetrachlorophthalonitrile, tetrachloroisophthalonitrile, tetrachloroterephthalonitrile and the like can be mentioned.

In the present invention, the halogenated aromatic nitrile represented by the formula (1) is reduced by using a hydrogenation catalyst in the presence of an organic acid in a solvent to give the halogenated aromatic nitrile represented by the formula (2). Group methylamines are obtained.

[Chemical 15] (In the formula, X represents a chlorine atom or a fluorine atom, and m is 1
Is an integer of 1 to 5, n is an integer of 1 to 5, and m + n ≦
6 and when n is 2 or more, X may be the same or different. a represents an integer of 1 or more and m or less)

The organic acid used in the present invention is a carboxylic acid, and examples thereof include formic acid, acetic acid, propionic acid, oxalic acid, citric acid, glycolic acid, benzoic acid and the like.
Particularly preferred are formic acid, acetic acid, and propionic acid. These organic acids may be used alone or in combination of two or more. The amount of the organic acid used is 50 to 500 mol%, particularly preferably 100 to 300 mol%, based on the nitrile group of the halogenated aromatic nitrile represented by the formula (1). The organic acid may be added all at once at the start of the reaction, or may be added continuously or intermittently as the reaction progresses.

The catalyst used in the present invention is a metal catalyst containing at least one of cobalt, iron, nickel, platinum and palladium. Even if the catalyst is metal,
It can also be used in the form of supported catalysts. Activated carbon, silica, alumina or the like can be used as a carrier for carrying. Examples of preferable catalysts include sponge nickel and sponge cobalt. Further, in the present invention, a modified sponge catalyst in which nickel or cobalt is modified by the presence of a metal or a metal oxide other than nickel or cobalt can also be used. For example, a modified sponge nickel catalyst modified with molybdenum may be mentioned.

The amount of the catalyst used is 0.01 to 1 times by mass, particularly preferably 0.02 to 0.5 times by mass with respect to the halogenated aromatic nitrile represented by the formula (1).

By pretreating the catalyst in a solvent in a hydrogen gas atmosphere, the activity of the catalyst can be improved. The temperature during the pretreatment is 100 ° C. or lower, preferably 40 ° C. or lower. The hydrogen partial pressure is 0.1 MPa to 5 MPa, preferably 0.2 MPa to 3 MPa.

The solvent used in the present invention is not particularly limited as long as it does not affect the reduction reaction. For example,
Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, aliphatic hydrocarbons such as hexane and cyclohexane, methanol, ethanol and propanol,
Alone or at least one selected from alcohols such as butanol, ethylene glycol, propylene glycol, glycerin and ethylene glycol methyl ether, ethers such as tetrahydrofuran, dioxane and dioxolane, esters such as ethyl acetate and butyl acetate, and water. It is a mixed solvent. In particular, water alone or a mixed solvent of water and a solvent insoluble in water at an arbitrary ratio is preferably used. A solvent that does not dissolve in water at an arbitrary ratio is a solvent that separates into two layers when mixed with water at least at a certain ratio, and examples thereof include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, and ethyl acetate as esters. Butyl acetate is an example. In such a mixed solvent system, when the solubility of the reaction substrate in water is low, it is expected that the substrate is dissolved in the organic solvent side by the organic solvent and the reaction rate is increased. In addition, at the same time, by using water at the same time, the amines of the product are transferred as an organic acid salt to the aqueous layer to cause a side reaction (a reaction between amine and nitrile to polymerize. A substitution reaction between amine and halogen. ) Can be expected to be effective.

Although the amount of the solvent used is not particularly limited, it is preferably 2 to 20 times by mass the amount of the halogenated aromatic nitrile represented by the formula (1).

The reaction temperature in the present invention is room temperature to 100.
C., preferably room temperature to 60.degree. The hydrogen partial pressure is 0.1 to 5 MPa, preferably 0.2 to 3 MPa. The hydrogen gas used in this reaction does not necessarily have to be highly pure, and may contain an inert gas that does not particularly affect the reduction reaction.

The reaction system is not particularly limited, but may be a catalyst suspension flow system, a fixed bed flow system, a trickle head,
Alternatively, a batch method or the like is adopted.

Formula (2) obtained by the manufacturing method of the present invention
The halogenated aromatic methylamines represented by can be isolated from the liquid after the reaction by separating the catalyst by filtration or the like, and after neutralization, can be isolated by a usual isolation method such as concentration, extraction or distillation.

[0039]

EXAMPLES The present invention will be described below with reference to examples.

The analysis conditions of gas chromatography used in the analysis of this example are as follows. <Gas chromatography analysis conditions> Apparatus HP 6850 column DB1701 manufactured by Hewlett-Packard Co. 0.32 mm × 30 m Film thickness 0.25 μm Carrier gas He Flow rate 1.2 ml / min. (Constant flow) Split ratio 50 Detector FID inj. temp. 300 ° C. det. temp. 300 ℃ Analysis temperature 100 ℃ (5min.)-10 ℃ / min. → 15
0 ℃ (10min.)-15 ℃ / min. → 280 ℃ (5min.) Internal standard 1,4-butanediol

Example 1 An autoclave having a volume of 100 cc was charged with 20 g of water, 10 g of toluene, 2.0 g of sponge nickel catalyst, 3.0 g of acetic acid and 4.0 g of tetrafluoroterephthalonitrile, and after purging with nitrogen, hydrogen gas was used. It was sufficiently replaced and pressurized to 0.85 MPa (gauge pressure). The stirring and heating of the autoclave were started and the pressure was reduced to 0.
Hydrogen supply was continued while maintaining the pressure at 85 Mpa, and stirring was continued at 40 ° C. The amount of absorbed hydrogen was monitored by a mass flow meter, and the reaction was terminated when the absorption of hydrogen was stopped. When the reaction solution was analyzed by gas chromatography internal standard method, the conversion rate of tetrafluoroterephthalonitrile was 99% or more, and the yield of 2,3,5,6-tetrafluoroxylylenediamine was 83%. It was The product was confirmed by gas chromatography-mass spectrometry.

<Example 2> The same operation as in Example 1 was performed except that toluene was changed to xylene. When the reaction solution was analyzed by gas chromatography internal standard method, the conversion rate of tetrafluoroterephthalonitrile was 99% or more, and the yield of 2,3,5,6-tetrafluoroxylylenediamine was 80%. It was

Example 3 In an autoclave having a volume of 100 cc, 30 g of water, 2.0 g of sponge nickel catalyst, 3.0 g of acetic acid, 4.0 g of tetrafluoroterephthalonitrile.
The same operation as in Example 1 was carried out except that was charged. When the reaction solution was analyzed by gas chromatography internal standard method, the conversion rate of tetrafluoroterephthalonitrile was 99.
%, And the yield of 2,3,5,6-tetrafluoroxylylenediamine was 90%.

Example 4 In an autoclave having a volume of 500 cc, 200 g of water, 12.5 g of sponge nickel catalyst,
Acetic acid 37.5 g, tetrafluoroterephthalonitrile 5
The same operation as in Example 1 was performed except that 0.0g was charged. When the reaction solution was analyzed by gas chromatography internal standard method, the conversion rate of tetrafluoroterephthalonitrile was 99% or more, and the yield of 2,3,5,6-tetrafluoroxylylenediamine was 95%. It was A 30 wt% sodium hydroxide aqueous solution was added to the reaction solution to adjust the pH to 12.3. After filtering off the insoluble matter, toluene 3
The aqueous layer was washed with 0 g. After separating the toluene layer, the water tank was extracted three times with 300 g of ethyl acetate. The ethyl acetate layers were collected and distilled under reduced pressure to obtain 42.8 g of TFXDA as a fraction at 120 ° C. at 5 mmHg. The recovery rate was 86.8%.

Example 5 In an autoclave having a volume of 500 cc, 100 cc of water and 10.0 g of sponge nickel catalyst were charged, and the hydrogen pressure was set to 0.5 MPa at 15 ° C. The stirring of the autoclave was started, the temperature was kept at 15 ° C., and the stirring was continued for 1 hour. Water 100c in the autoclave
c, 37.5 g of acetic acid and 50.0 g of tetrafluoroterephthalonitrile were charged and the same operation as in Example 1 was performed.
When the reaction solution was analyzed by gas chromatography internal standard method, the conversion rate of tetrafluoroterephthalonitrile was 99% or more, and the yield of 2,3,5,6-tetrafluoroxylylenediamine was 94%. It was When the same isolation procedure as in Example 4 was carried out, 42.4 g of TFXDA was used.
Got The recovery rate was 86.9%.

Example 6 The same operation as in Example 4 was carried out except that 12.5 g of sponge nickel catalyst containing molybdenum was used as the catalyst. When the reaction solution was analyzed by gas chromatography internal standard method, the conversion rate of tetrafluoroterephthalonitrile was 99% or more,
The yield of 2,3,5,6-tetrafluoroxylylenediamine was 96%. When isolated in the same manner as in Example 4, 43.4 g of TFXDA was obtained. Recovery rate is 87.0%
Met.

Comparative Example 37.5 g of sulfuric acid instead of acetic acid
The same operation as in Example 4 was performed except that was used. When the reaction solution was analyzed by gas chromatography internal standard method, the conversion rate of tetrafluoroterephthalonitrile was 23.
%, And the yield of 2,3,5,6-tetrafluoroxylylenediamine was 12%.

[0048]

INDUSTRIAL APPLICABILITY According to the present invention, the halogenated aromatic methylamines of the formula (2) can be produced in a high yield by an industrially advantageous method.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kohei Morikawa             Akira 5-1, Ogimachi, Kawasaki-ku, Kawasaki-shi, Kanagawa             Kawasaki Research Co., Ltd.             Indoor F-term (reference) 4G069 AA02 AA03 AA08 BB02A                       BB02B BC31A BC59A BC59B                       BC66A BC66B BC67A BC70A                       BC72A BC75A CB06 DA05                       EB11 FB13 FB44 FC07                 4H006 AA02 AC52 BA14 BA20 BA21                       BA23 BA25 BA26 BA81 BB11                       BB14 BB17 BB31 BC10 BC11                       BC34 BC35 BC40                 4H039 CA71 CB30 CF40

Claims (21)

[Claims] 1. Formula (1): (In the formula, X represents a chlorine atom or a fluorine atom, and m is 1
Is an integer of 1 to 5, n is an integer of 1 to 5, and m + n ≦
6 and when n is 2 or more, X may be the same or different. ), Halogenated aromatic nitriles are hydrogenated using a hydrogenation catalyst in the presence of an organic acid in a solvent, represented by the formula (2): (In the formula, X and m and n are as defined above, and a is an integer of 1 or more and m or less.) A method for producing a halogenated aromatic methylamine. 2. The halogenated aromatic nitrile represented by the formula (1) is tetrafluoroterephthalonitrile or tetrafluoroisophthalonitrile, and the halogenated aromatic methylamine represented by the formula (2) is ,
The method for producing a halogenated aromatic methylamine according to claim 1, which is 2,3,5,6-tetrafluoroxylylenediamine or 2,3,4,6-tetrafluoroxylylenediamine. . 3. The solvent according to claim 1, wherein the solvent is a single solvent or a mixed solvent containing at least one selected from aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, esters and water. The method for producing a halogenated aromatic methylamine according to 1. 4. The solvent is benzene, toluene, xylene,
Ethylbenzene, hexane, cyclohexane, methanol, ethanol, propanol, tetrahydrofuran,
The method for producing halogenated aromatic methylamines according to claim 1 or 2, which is a single solvent or a mixed solvent containing at least one selected from dioxane, dioxolane, ethyl acetate and water. 5. The method for producing a halogenated aromatic methylamine according to claim 3, wherein the solvent is water and a mixed solvent of water and an organic solvent which is insoluble at an arbitrary ratio. 6. The method for producing halogenated aromatic methylamines according to claim 5, wherein the organic solvent which is insoluble in water at an arbitrary ratio is an aromatic hydrocarbon. 7. The aromatic hydrocarbon is toluene, xylene,
It is ethylbenzene, The manufacturing method of the halogenated aromatic methylamines of Claim 6 characterized by the above-mentioned. 8. The method for producing halogenated aromatic methylamines according to claim 1, wherein the solvent is water. 9. The method for producing a halogenated aromatic methylamine according to claim 1, wherein the organic acid is at least one selected from formic acid, acetic acid and propionic acid. 10. The halogenated aromatic methyl according to claim 1, wherein the catalyst contains at least one metal selected from nickel, palladium, platinum, ruthenium, cobalt and copper. Method for producing amines. 11. The method for producing halogenated aromatic methylamines according to claim 1, wherein the catalyst is sponge nickel or sponge cobalt. 12. The method for producing halogenated aromatic methylamines according to claim 11, wherein the catalyst is sponge nickel. 13. The method for producing halogenated aromatic methylamines according to claim 12, wherein the catalyst is sponge nickel to which molybdenum is added as a different metal. 14. The catalyst in a solvent under an atmosphere of hydrogen gas 4
The method for producing a halogenated aromatic methylamine according to any one of claims 1 to 13, which is used after pretreatment at 0 ° C or lower. 15. The method for producing halogenated aromatic methylamines according to claim 1, wherein the catalyst is supported palladium. 16. The production of halogenated aromatic methylamines according to claim 1, wherein the amount of the solvent used is 1 to 20 times by mass that of the halogenated aromatic nitriles. Method. 17. The halogenated aromatic compound according to claim 1, wherein the amount of the organic acid used is 50 to 500 mol% with respect to the nitrile group of the halogenated aromatic nitriles. Method for producing methylamines. 18. The halogenated aromatic methylamine according to claim 1, wherein the amount of the catalyst used is 0.01 to 1 times the mass of the halogenated aromatic nitriles. Manufacturing method. 19. Hydrogen reduction is carried out at a reaction temperature of room temperature to 100.
The method for producing a halogenated aromatic methylamine according to any one of claims 1 to 17, wherein the hydrogen partial pressure is 0.1 to 5 MPa at 0 ° C. 20. The formula (2) obtained by the production method according to claim 1. (In the formula, X represents a chlorine atom or a fluorine atom, and m is 1
Is an integer of 1 to 5, n is an integer of 1 to 5, and m + n ≦
6 and when n is 2 or more, X may be the same or different. a represents an integer of 1 or more and m or less)
Halogenated aromatic methylamines represented by. 21. Formula (1): (In the formula, X represents a chlorine atom or a fluorine atom, and m is 1
Is an integer of 1 to 5, n is an integer of 1 to 5, and m + n ≦
6 and when n is 2 or more, X may be the same or different. From the halogenated aromatic nitriles represented by the formula (2) (In the formula, X and m and n are as defined above, and a represents an integer of 1 or more and m or less.) A catalyst used for producing a halogenated aromatic methylamine.