JPH07188146A - Production of phenoxybenzoylnitrile compound - Google Patents

Abstract

PURPOSE:To provide an industrially highly valuable method for producing a phenoxybenzoylnitrile compound useful as a production intermediate for agrochemicals, medicines, dyestuffs, etc. CONSTITUTION:A phenoxybenzoyl halide compound as a raw material is reacted with sodium cyanide or potassium cyanide as a cyanidation agent in the presence of a catalytic amount of a pyridine compound or a quinoline compound and a cupric halide catalyst in a nitrile solvent such as acetonitrile under a mild temperature condition to efficiently obtain the corresponding phenoxybenzoylnitrile compound in a high yield.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing phenoxybenzoyl nitriles useful as an intermediate for producing agricultural drugs, dyes and the like. More particularly, it relates to an improved process for making phenoxybenzoyl nitriles, which comprises reacting phenoxybenzoyl halides with an alkali metal cyanide in the presence of pyridines or quinolines and copper halides.

[0002]

2. Description of the Related Art Conventionally, as a method for producing benzoyl nitriles using benzoyl halides, a two-phase reaction using a phase transfer catalyst [Tetrahedron lett., No. 26, pp 2
275-2278 (1974)] is known. However, it is well known that in this method, dimerization of benzoyl nitrile is likely to proceed. In addition, a method of reacting benzoyl chloride with silver cyanide or cuprous cyanide [Org. Synth., Col.
l.3, p112 (1955)], but silver cyanide used in this method has a problem in terms of price. On the other hand, cuprous cyanide has a problem in treating wastewater containing a copper salt generated after the reaction,
It is not an industrial manufacturing method. As described above, in the conventionally known method for producing benzoylnitriles, problems such as a by-product of a dimer of benzoylnitrile, use of an expensive cyan compound, and wastewater treatment are problems to be avoided.

There are also a few known methods for producing benzoyl nitrites using an alkali metal cyanide. For example, in reacting an acid halide with an alkali metal cyanide, a method of reacting in a solvent containing nitrile [JP-A-57-77661] and a method of reacting in the presence of an inactive carboxylic acid nitrile [JP-A-Sho] 5
3-105425, JP-A-53-105426], and a method of allowing a compound containing an alkylene oxide group to coexist [JP-A-3-5448 and JP-A-3-5].
No. 449] and the like are disclosed. However, these methods require a temperature condition of 80 ° C. or higher in order to efficiently carry out the nitration reaction. When these methods are applied to the phenoxybenzoyl halides of the present application, the target nitrile compound is hardly obtained, and the intramolecularly cyclized xanthone compound becomes the main product. Therefore, it was found that these methods are not preferable methods for producing phenoxybenzoylnitriles.

[0004]

The object of the present invention is to solve the above problems of the prior art and to improve the phenoxybenzoyl nitriles useful as intermediates for the production of agricultural drugs, dyes, etc. To provide a simple manufacturing method.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors in order to solve the problems of the prior art, sodium cyanide was used in a nitrile solvent such as acetonitrile in the presence of a copper halide catalyst. Alternatively, they have found that by using potassium cyanide as a cyanating agent, phenoxybenzoyl halides can be efficiently converted to phenoxybenzoylnitriles without producing xanthone or the like as a by-product. Furthermore, by adding a catalytic amount of pyridines or quinolines, it is possible to obtain the desired phenoxybenzoylnitriles with high yield and high selectivity while suppressing by-products such as benzoylnitrile dimers. And completed the present invention.

That is, the present invention is a process for producing phenoxybenzoyl nitriles, which comprises reacting a phenoxybenzoyl halide with an alkali metal cyanide in the presence of pyridines or quinolines and copper halide. According to the method of the present invention, it is possible to obtain phenoxybenzoylnitriles in a high yield and a high selectivity under relatively mild conditions. The desired product after the reaction may be isolated by a simple operation in which water is added to the reaction mixture to dissolve the inorganic salt, phenoxybenzoylnitriles are extracted with an inert organic solvent, and the solvent is distilled off. Therefore, the method of the present invention is an industrially applicable excellent method, and the phenoxybenzoylnitriles obtained by the present invention have a quality that can be sufficiently used as a production intermediate useful for agricultural drugs, dyes and the like. .

The method of the present invention will be described below. The phenoxybenzoyl halides used in the method of the present invention are a benzoyl halide substituted by an phenoxy group substituted by an alkyl group, an alkoxy group or a halogen, or an unsubstituted phenoxybenzoyl halide, specifically, 2- Phenoxybenzoyl chloride, 2-phenoxybenzoyl bromide, 2- (4-
Methylphenoxy) benzoyl chloride, 2- (4-methylphenoxy) benzoyl bromide, 2- (3-methylphenoxy) benzoyl chloride, 2- (3-methylphenoxy) benzoyl bromide, 2- (3,4-dimethylphenoxy) benzoyl Chloride, 2- (3,4-
Dimethylphenoxy) benzoyl bromide, 2- (4-
Ethylphenoxy) benzoyl chloride, 2- (4-ethylphenoxy) benzoyl bromide, 2- (3-ethylphenoxy) benzoyl chloride, 2- (3-ethylphenoxy) benzoyl bromide, 2- (3,4-diethylphenoxy) benzoyl Chloride,

2- (3,4-diethylphenoxy) benzoyl bromide, 2- (4-methoxyphenoxy) benzoyl chloride, 2- (4-methoxyphenoxy) benzoyl bromide, 2- (3-methoxyphenoxy) benzoyl chloride, 2 -(3-Methoxyphenoxy) benzoyl bromide, 2- (3,4-dimethoxyphenoxy) benzoyl chloride, 2- (3,4-dimethoxyphenoxy) benzoyl bromide, 2- (4-chlorophenoxy) benzoyl chloride, 2- ( 4-bromophenoxy) benzoyl chloride, 2- (3-chlorophenoxy) benzoyl chloride, 2- (3-chlorophenoxy) benzoyl bromide, 2- (3,4-dichlorophenoxy) benzoyl chloride, 2- (3,4 -Dichlorophenoxy) benzoi Lubromid and the like can be mentioned. However, the phenoxybenzoyl halides are not limited by the compounds listed here.

As an alkali metal cyanide used as a cyanating agent for phenoxybenzoyl halides, industrially inexpensive sodium cyanide and potassium cyanide are often used. Of course, the amount of alkali metal cyanide used is less than the theoretical amount, but it is usually used in excess of the theoretical amount in consideration of the conversion rate of the raw material phenoxybenzoyl halides and the yield of the desired phenoxybenzoylnitriles. It is appropriate to do. From the economical point of view, the upper limit of the amount used is preferably not more than 2 times the mole of the phenoxybenzoyl halide as the raw material.

The type of copper halide used in the reaction is not particularly limited as long as it is a copper halide, but the halogen of the copper halide is chlorine, bromine or iodine, cuprous chloride,
Examples thereof include cupric chloride, cuprous bromide, cupric bromide, cuprous iodide and cupric iodide. Preferred is cuprous chloride or cuprous bromide. The amount of copper halide used is
0.1 to 0.1% of the raw material phenoxybenzoyl halides
It is preferably 50% by weight, more preferably 0.5 to 10% by weight. The use of other metal halides, particularly metal halides having Lewis acidity, is not preferable because xanthones, which are cyclized phenoxybenzoyl halides, are easily produced.

Also, the use of pyridines or quinolines has the effect of promoting the reaction rate. The type of pyridines or quinolines to be used is not particularly limited, but may be unsubstituted pyridine or pyridine substituted with an alkyl group (eg:
Picolines, N, N-dimethyl-4-aminopyridine, etc.) or unsubstituted quinoline, quinoline substituted with an alkyl group, etc. can be used alone or as a mixture. Further, these pyridines or quinolines may be used as salts, and hydrochlorides, hydrobromides, etc. of pyridines or quinolines can also be used. The amount of pyridines or quinolines used is not particularly limited, but if pyridines or quinolines are used in excess, phenoxybenzoylnitrile dimer and other by-products increase. On the other hand, if the amount is too small, the reaction rate becomes slow, which is industrially undesirable. Therefore, the amount of pyridines or quinolines used is preferably 0.01 to 1% by weight, and more preferably 0.01 to 0.5% by weight, based on the phenoxybenzoyl halides as a raw material.

The reaction solvent is not particularly limited as long as it is a solvent in which a trace amount of the alkali metal cyanide used or copper cyanide formed in the system is dissolved, but for example, ether or an ether solvent such as tetrahydrofuran, ethyl acetate or It is an ester solvent such as butyl acetate or a nitrile solvent such as acetonitrile. Among them, a nitrile solvent is preferable, and specifically, acetonitrile, isobutyric acid nitrile or the like is preferable. The reaction temperature is not particularly limited as long as it is a temperature at which the phenoxybenzoyl halides which are the starting materials or the phenoxybenzoylnitriles which are the target compounds do not form xanthones which are cyclized products, and in the method of the present invention, a mild temperature of 80 ° C. or lower is used. The desired phenoxybenzoyl nitriles can be efficiently obtained under various temperature conditions. The reaction time is not uniquely determined by the raw material concentration and the reaction temperature, but usually the reaction is completed within 8 hours, and phenoxybenzoylnitriles can be obtained in high yield and high quality.

A specific embodiment of the method of the present invention is as follows. A predetermined amount of an alkali metal cyanide, a predetermined amount of copper halide, and a predetermined amount of pyridines or quinolines were charged into a predetermined amount of a nitrile solvent, heated and dissolved in a predetermined amount of a nitrile solvent with stirring. A predetermined amount of phenoxybenzoyl halides is dropped to react. The order of charging the raw materials, the catalyst and the solvent is not limited to the above method. As for the reaction method, various methods such as a method of charging all the raw materials, the catalyst and the solvent to heat them, a method of charging the alkali metal cyanide in portions, a method of charging the phenoxybenzoyl halide in portions, etc. Methods are available. Among them, the method of dropping the raw material phenoxybenzoyl halide at the end and reacting it is preferable for the purpose of suppressing by-products. In the present invention, the progress of the reaction can be known using an analytical means such as high performance liquid chromatography.

As a method for isolating the phenoxybenzoyl nitrites produced by the above nitration reaction, the reaction mixture may be cooled after the reaction, if necessary, and then dissolved in an amount such that the by-produced metal chloride and the residual alkali metal cyanide are dissolved. Water is added for liquid separation, or hexane, toluene, the organic solution obtained by liquid separation extraction using a solvent inert to phenoxybenzoylnitriles such as ethyl acetate is washed with water, and then dried with a desiccant, It can be isolated by a simple operation of distilling off the solvent under reduced pressure. In order to obtain phenoxybenzoyl nitriles of higher purity, the phenoxybenzoyl nitriles obtained by the above method are purified by distillation under reduced pressure or at a temperature condition at which phenoxybenzoyl nitrites are not decomposed or phenoxybenzoyl nitriles. Depending on the nature of the above, a method of crystallizing and purifying using a suitable solvent can be mentioned. The phenoxybenzoyl nitriles obtained by the method of the present invention have a quality that can be sufficiently utilized as a production intermediate useful for agricultural medicine, dyes and the like.

[0015]

EXAMPLES The present invention will be specifically illustrated by the following examples. Example 1 200 ml of acetonitrile, 13 g (0.24 mol) of 90% sodium cyanide, 2.0 g (0.02 mol) of cuprous chloride and 0.13 g (1.6 mmol) of pyridine were added to a 500 ml round bottom flask equipped with a cooling condenser. , Reaction solution 60
The mixture was heated to ℃ and stirred. 2-phenoxybenzoyl chloride (46.4 g, 0.2 mol) of acetonitrile was added to the reaction solution.
The 0 ml solution was added dropwise over 3 hours. 1 more after the dropping
The reaction was carried out at 60 ° C. for an hour. After cooling the reaction solution to room temperature, 300 ml of toluene was added to the reaction solution. Water in this solution 30
The organic layer obtained by adding 0 ml and separating the solution was saturated with sodium bicarbonate water (300 m).
After washing with l, it was washed again with 300 ml of water. The obtained organic layer was dehydrated with anhydrous sodium sulfate. This solution was concentrated under reduced pressure to obtain 43 g of crude 2-phenoxybenzoylnitrile. As a result of analyzing this crude 2-phenoxybenzoyl nitrile by high performance liquid chromatography, the composition of the crude 2-phenoxybenzoyl nitrile was 96% of 2-phenoxybenzoyl nitrile, 1% of dimer of 2-phenoxybenzoyl nitrile, and by-product 3 %Met. No xanthone by-product was observed. ^{Yield: 93%, IR: 2230cm -1} , 1660cm -1

Examples 2 to 3 Pyridines or quinolines were examined in Examples 2 to 3. The other conditions were the same as in Example 1. The results are shown in Table 1.

[0017]

[Table 1] ((w%) ^* :% by weight based on the raw material 2-phenoxybenzoyl chloride)

Example 4 In Example 4, the type of alkali metal cyanide was examined. The conditions were the same as in Example 1 except that the alkali metal cyanide compound was changed. The results are shown in Table 2.

[0019]

[Table 2]

[Comparative Examples 1 and 2] In Comparative Example 1, pyridine and cuprous chloride were not added, and in Comparative Example 2, pyridine was not added. The other conditions were the same as in Example 1. The results are shown in Table 3.

[0021]

[Table 3] ((W%) ^* :% by weight based on the raw material 2-phenoxybenzoyl chloride)

[Examples 5-8] The types of phenoxybenzoyl halides used in the reaction in Examples 5-8 were examined. The other conditions were the same as in Example 1. The production rate was measured by analyzing a part of the reaction solution by high performance liquid chromatography. The results are shown in Table 4.

[0023]

[Table 4]

[0024]

According to the present invention, when converting phenoxybenzoyl halides to phenoxybenzoylnitriles, cyanide is used in the presence of a catalytic amount of pyridines or quinolines and a copper halide catalyst in a nitrile solvent such as acetonitrile. Phenoxybenzoyl nitrites can be obtained by using sodium chloride or potassium cyanide as a cyanating agent and reacting under milder conditions. The method of the present invention is an industrially applicable excellent method. According to the method of the present invention, it is possible to obtain phenoxybenzoylnitriles in a high yield and a high selectivity under relatively mild conditions. Furthermore, the method of isolating the desired product after the reaction is also a simple method in which the reaction mixture is washed with water and the organic layer obtained by extraction and separation with an inert organic solvent that does not react with the phenoxybenzoylnitriles, and then the solvent is distilled off. It can be isolated by operation. Therefore, the present invention is an industrially valuable method for producing phenoxybenzoylnitriles, which are useful intermediates for agricultural medicines, dyes and the like.

Continuation of the front page (72) Inventor Ryuichi Mita 30 Asamu-cho, Omuta-shi, Fukuoka Mitsui Toatsu Chemical Co., Ltd.

Claims (5)

[Claims] 1. A process for producing phenoxybenzoyl nitriles, which comprises reacting a phenoxybenzoyl halide with an alkali metal cyanide in the presence of pyridines or quinolines and copper halide. 2. The phenoxybenzoyl halide is a benzoyl halide substituted by an alkyl group, an alkoxy group or a phenoxy group substituted by a halogen, or an unsubstituted phenoxybenzoyl halide, and the halide is chlorine or bromine. The method described in 1. 3. The method according to claim 1, wherein the pyridines or quinolines are pyridines unsubstituted or substituted with an alkyl group or quinolines unsubstituted or substituted with an alkyl group. 4. The method according to claim 1, wherein the halogen of the copper halide is chlorine, bromine or iodine. 5. The method according to claim 1, wherein the alkali metal cyanide is sodium cyanide or potassium cyanide.