JP2005200410A - Method for producing tetraarylphosphonium halide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tetraarylphosphonium halide in high yield under a mild condition from triarylphosphine and an aryl halide. <P>SOLUTION: The tetraarylphosphonium halide is produced by reacting the triarylphosphine with the aryl halide by using a metal halide such as nickel chloride as a catalyst and N, N-dimethylformamide as a reaction solvent, preferably at a temperature of 130°C or more to less than 150°C. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for industrially advantageously producing a tetraarylphosphonium halide useful as a catalyst for various reactions.

  A tetraarylphosphonium halide useful as a halogen exchange reaction catalyst, a phase transfer catalyst, a polymerization catalyst, or the like can be produced by a reaction of a triarylphosphine and an aryl halide. In general, the reaction is carried out in the presence of a metal halide catalyst, and various reaction solvents have been proposed. For example, a method using a methanol solvent (Non-Patent Documents 1 and 2), a method using a benzonitrile solvent (Non-Patent Document 3), an aliphatic polyhydric alcohol, an aliphatic polyhydric alcohol monoether, a phenol, a carbon number A method using a water-soluble high-boiling solvent such as an aliphatic carboxylic acid having 5 to 6 (Patent Document 1) is known. Among these, the method of Patent Document 1 has been proposed as an improvement of the disadvantages of the method using a methanol solvent or a benzonitrile solvent.

  That is, according to Patent Document 1, in the method using the methanol solvent, a pressure vessel is necessary because the reaction is performed under high temperature and high pressure, and when methanol is distilled off after the reaction, the reaction product is solidified and The problem is that the handling and separation of the object are complicated. In the method using the benzonitrile solvent, it is pointed out that it is necessary to use a large amount of a metal halide catalyst, and there are various problems in separating the target product from the reaction mixture. On the other hand, the method of Patent Document 1 using the above-mentioned water-soluble high boiling point solvent improves these drawbacks, and it is said that the reaction can be carried out under mild conditions at normal pressure.

  However, even in this improved method, although the conditions are mild, the reaction temperature is recommended to be 150 ° C. or higher, particularly 160 ° C. or higher. In a specific example, the reaction is performed at a temperature exceeding 170 ° C. .

JP 9-328492 A Bull. Chem. Soc. Jpn. , 30, 667 (1957) The Nippon Chemical Journal, Volume 86, 112 (1965) Chem. Ber. 99, 2782 (1966)

  Accordingly, an object of the present invention is to provide a method for producing a tetraarylphosphonium halide which can be reacted with high selectivity at a lower temperature and at normal pressure or without so high pressure, and the target product can be easily separated. Is to provide.

  That is, according to the present invention, there is provided a process for producing a tetraarylphosphonium halide, characterized by reacting a triarylphosphine and an aryl halide in the presence of a metal halide catalyst and N, N-dimethylformamide.

  According to the present invention, a tetraarylphosphonium halide can be produced at a temperature of less than 150 ° C. at normal pressure or in a slightly pressurized state with a high yield. Further, when tetraarylphosphonium halide is isolated from the reaction mixture, it can be carried out without requiring a complicated operation.

（式中、Ａｒ^１、Ａｒ^２、Ａｒ^３は、アリール基）で示されるものである。上記式（１）において、Ａｒ^１、Ａｒ^２、Ａｒ^３は、それぞれ同一又は異なるアリール基であり、これらの二つは互いに結合していてもよい。またこれらは、芳香環に置換基を有するものでも有しないものでもよい。具体的には、置換基を有する又は有しないフェニル基、置換基を有する又は有しないナフチル基などである。ここに置換基としては、メチル基、エチル基、フェニル基などの炭化水素基、メトキシ基、エトキシ基、フェノキシ基などのアルコキシ基又はアリーロキシ基、トリフルオロメチル基のようなハロゲン化炭化水素基、フッ素、塩素、臭素、沃素などのハロゲンなどを例示することができる。これら置換基は２以上有していてもよい。 The triarylphosphine used in the present invention has the following formula (1)

(Wherein Ar ¹ , Ar ² , and Ar ³ are aryl groups). In the above formula (1), Ar ¹ , Ar ² , and Ar ³ are the same or different aryl groups, and these two may be bonded to each other. These may or may not have a substituent on the aromatic ring. Specific examples include a phenyl group having or not having a substituent, a naphthyl group having or not having a substituent. Examples of the substituent include a hydrocarbon group such as a methyl group, an ethyl group, and a phenyl group, an alkoxy group such as a methoxy group, an ethoxy group, and a phenoxy group, or an aryloxy group, a halogenated hydrocarbon group such as a trifluoromethyl group, Illustrative are halogens such as fluorine, chlorine, bromine and iodine. These substituents may have two or more.

  More specifically, as triarylphosphine, triphenylphosphine, tris (2-methylphenyl) phosphine, tris (3-methylphenyl) phosphine, tris (4-methylphenyl) phosphine, tris (2-ethylphenyl) phosphine, Tris (3-ethylphenyl) phosphine, tris (4-ethylphenyl) phosphine, tris (2,3-dimethylphenyl) phosphine, tris (2,4-dimethylphenyl) phosphine, tris (2,4,6-trimethylphenyl) ) Phosphine, diphenyl (2-methylphenyl) phosphine, diphenyl (3-methylphenyl) phosphine, diphenyl (4-methylphenyl) phosphine, tris (2-trifluoromethylphenyl) phosphine, tris (3-methoxyphenyl) Sphin, tris (2,4,6-trimethoxyphenyl) phosphine, tris (2-chlorophenyl) phosphine, tris (3-chlorophenyl) phosphine, tris (4-fluorophenyl) phosphine, tri (1-naphthyl) phosphine, tri And (2-naphthyl) phosphine.

（式中、Ａｒ^４はアリール基、Ｘはハロゲン）で示される芳香族化合物であって、Ａｒ^４は、Ａｒ^１等と同様に、芳香環に置換基を有するものでも有しないものでもよい。置換基を有する場合には、置換基としてメチル基、エチル基、フェニル基などの炭化水素基、メトキシ基、エトキシ基、フェノキシ基などのアルコキシ基又はアリーロキシ基、トリフルオロメチル基のようなハロゲン化炭化水素基、フッ素、塩素、臭素、沃素などのハロゲンなどを例示することができる。これら置換基は２以上有していてもよい。 The aryl halide used in the present invention has the following formula (2)

(In the formula, Ar ⁴ is an aryl group, and X is a halogen), and Ar ⁴ may or may not have a substituent on the aromatic ring, similarly to Ar ¹ and the like. When having a substituent, a halogenated group such as a hydrocarbon group such as a methyl group, an ethyl group or a phenyl group, an alkoxy group such as a methoxy group, an ethoxy group or a phenoxy group, an aryloxy group or a trifluoromethyl group. Examples include hydrocarbon groups, halogens such as fluorine, chlorine, bromine and iodine. These substituents may have two or more.

  More specifically, as the aryl halide, bromobenzene, iodobenzene, 1-chloronaphthalene, 1-bromonaphthalene, 1-iodonaphthalene, 2-chloronaphthalene, 2-bromonaphthalene, 2-iodonaphthalene, 2-bromotoluene 3-bromotoluene, 4-bromotoluene, 2-iodotoluene, 3-iodotoluene, 4-iodotoluene, 2-bromoethylbenzene, 4-bromoethylbenzene, 2-iodoethylbenzene, 4-iodoethylbenzene, 2,3- Dimethylchlorobenzene, 2,4-dimethylchlorobenzene, 3,4-dimethylchlorobenzene, 2,5-dimethylchlorobenzene, 2,3-dimethylbromobenzene, 2,4-dimethylbromobenzene, 3,4-dimethylbromobenzene, 2, 5-Dimethyl Bromobenzene, 3-chloroanisole, 3-bromoanisole, 3-iodoanisole, 2-bromobiphenyl, 4-bromobiphenyl, 2-iodobiphenyl, 4-iodobiphenyl, 4,4′-dibromobiphenyl, 4-bromodiphenyl ether 1,2-dichlorobenzene, 1,4-dichlorobenzene, 1,2-dibromobenzene, 1,4-dibromobenzene, 1,4-diiodobenzene, 4-chlorobromobenzene, 4-chloroiodobenzene, etc. Can be mentioned.

（式中、Ａｒ^１、Ａｒ^２、Ａｒ^３、Ａｒ^４、Ｘは、上記式（１）又は（２）のものと同じ）で示されるテトラアリールホスホニウムハライドを得るものである。反応に際しては、触媒として金属ハロゲン化物触媒、また反応溶媒としてＮ，Ｎ−ジメチルホルムアミドがそれぞれ使用される。金属ハロゲン化物触媒としては、周期律表７〜１２族金属のハロゲン化物の使用が好ましい。具体的には、７族金属のハロゲン化物としては、塩化マンガン、臭化マンガン、沃化マンガンなどのマンガンハロゲン化物、８族金属のハロゲン化物としては、塩化鉄、臭化鉄、沃化鉄などの鉄ハロゲン化物、９族金属のハロゲン化物としては、塩化コバルト、臭化コバルト、沃化コバルトなどのコバルトハロゲン化物、１０族金属のハロゲン化物としては、塩化ニッケル、臭化ニッケル、沃化ニッケルなどのニッケルハロゲン化物、１１族金属のハロゲン化物としては、塩化銅、臭化銅、沃化銅などの銅ハロゲン化物、１２族金属のハロゲン化物としては、塩化亜鉛、臭化亜鉛、沃化亜鉛などの亜鉛ハロゲン化物などを挙げることができる。これら金属ハロゲン化物の中では、周期律表９〜１２族金属のハロゲン化物、とくに塩化物又は臭化物の使用が好ましい。すなわちニッケル、コバルト、銅又は亜鉛のハロゲン化物、とくに塩化物又は臭化物が好ましく、とりわけニッケルのハロゲン化物、とくに塩化物又は臭化物の使用が最も好ましい。これら金属ハロゲン化物は、無水のものでも水和物でも使用することができる。一般には微量の水の存在により、反応が促進される一方で、過剰の水の存在は反応に悪影響を及ぼすことがあるので、水和物の使用及び／又は微量の水の添加により水分量を調整することが望ましい。例えば上記金属ハロゲン化物１モルに対し、結晶水と別途添加する水の合計量が、４０モル以下、好ましくは５〜３５モル、一層好ましくは１０〜３０モルとなるように調整するのが望ましい。 In the present invention, by reacting the above triarylphosphine with an aryl halide, the following formula (3)

(In the formula, Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , X are the same as those in the above formula (1) or (2)) to obtain a tetraarylphosphonium halide. In the reaction, a metal halide catalyst is used as a catalyst, and N, N-dimethylformamide is used as a reaction solvent. As the metal halide catalyst, it is preferable to use a halide of a metal in groups 7 to 12 of the periodic table. Specifically, group 7 metal halides include manganese halides such as manganese chloride, manganese bromide and manganese iodide, and group 8 metal halides include iron chloride, iron bromide and iron iodide. As iron halides of Group 9, and halides of Group 9 metals, cobalt halides such as cobalt chloride, cobalt bromide and cobalt iodide, and as halides of Group 10 metals, nickel chloride, nickel bromide and nickel iodide, etc. Nickel halides of Group 11, metal halides such as copper chloride, copper bromide, copper iodide, etc., and group 12 metal halides such as zinc chloride, zinc bromide, zinc iodide, etc. And zinc halides. Among these metal halides, the use of halides of group 9-12 metals in the periodic table, particularly chlorides or bromides is preferred. That is, nickel, cobalt, copper or zinc halides, particularly chlorides or bromides are preferred, and nickel halides, especially chlorides or bromides are most preferred. These metal halides can be used either anhydrous or hydrated. In general, the reaction is promoted by the presence of a trace amount of water, but the presence of excess water may adversely affect the reaction. Therefore, the amount of water can be reduced by using a hydrate and / or adding a trace amount of water. It is desirable to adjust. For example, it is desirable to adjust the total amount of water added separately from crystallization water to 40 mol or less, preferably 5 to 35 mol, and more preferably 10 to 30 mol per 1 mol of the metal halide.

  In the reaction of the present invention, N, N-dimethylformamide is used as a reaction solvent. Thus, tetraarylphosphonium halide can be produced in good yield at a temperature of less than 150 ° C. under normal pressure or a slight pressure of the reaction mixture's self-generated pressure in a closed system.

  In the reaction of the present invention, the aryl halide is usually 0.8 to 2 times mol, preferably 0.9 to 1.5 times mol, more preferably 1.0 to 1.3 mol, relative to triarylphosphine. Used in a molar ratio. Moreover, the usage-amount of a metal halide is 0.1-40 mol% normally with respect to a triaryl phosphine, Preferably it is about 1-30 mol%. Further, the amount of N, N-dimethylformamide used as a reaction solvent is usually about 0.1 to 10 times by weight, particularly about 0.2 to 5 times by weight with respect to triarylphosphine in consideration of yield and post-treatment operation. It is good to make the ratio.

  The reaction of the present invention is carried out by charging the above raw material, catalyst and solvent into a reaction vessel. The reaction temperature is preferably 130 ° C or higher, more preferably 130 ° C or higher and lower than 150 ° C. The reaction vessel may be an open system or a closed system, but it is preferably carried out in a closed container that forms a slight pressure system due to the autogenous pressure of the reaction mixture. The reaction pressure is affected by the amount of water in the system, but the reaction is usually carried out in a slightly pressurized state of atmospheric pressure or higher and 0.5 MPa or lower, preferably 0.3 MPa or lower. The reaction time is usually about 0.5 to 30 hours, although it varies depending on the type of raw material compound and catalyst, the amount used, the reaction temperature, and the like.

  After completion of the reaction, unreacted aryl halide, N, N-dimethylformamide and the like are distilled off from the reaction mixture and concentrated, and water and a water-insoluble solvent such as a hydrocarbon solvent such as toluene are added to the concentrate and heated. Then, if the two layers are separated and the aqueous layer is cooled, the target tetraarylphosphonium halide crystallizes out, which can be separated. The purity of the tetraarylphosphonium halide thus obtained can be increased by washing, recrystallization or the like, if necessary.

Hereinafter, the present invention will be described in more detail with reference to examples.
[Example 1]
A 100 ml eggplant type flask is charged with 10 g of triphenylphosphine, 10.2 g of bromobenzene, 1.7 g of nickel chloride hexahydrate and 25 g of N, N-dimethylformamide, and at a solution temperature of 138 ° C. for 16 hours under normal pressure conditions. The reaction was carried out with stirring. After completion of the reaction, unreacted bromobenzene, N, N-dimethylformamide and water were distilled off under reduced pressure (21.0 g). After the distillation residue was cooled to room temperature, 14.3 g of toluene and 35.7 g of water were added, heated to 80 ° C., dissolved, allowed to stand, separated into two layers, and then the aqueous layer was separated. The separated aqueous layer was cooled to room temperature to precipitate crystals, which were collected by suction filtration. The obtained crystal was washed with 10 g of water and then dried under reduced pressure at 100 ° C. for 5 hours to obtain 13.31 g of tetraphenylphosphonium bromide (purity 98.9%) (triphenylphosphine reference yield 82.4%). ).

[Example 2]
After adding 10 g of triphenylphosphine, 10.2 g of bromobenzene, 0.9 g of nickel chloride and 25 g of N, N-dimethylformamide to a 300 ml pressure-resistant glass container, the container is sealed and sealed at a temperature of 140 ° C. and a reaction pressure of 0.2 MPa. The reaction was carried out with stirring for a time. After completion of the reaction, unreacted bromobenzene and N, N-dimethylformamide were distilled off under reduced pressure (24.5 g). After the distillation residue was cooled to room temperature, 14.3 g of toluene and 30.7 g of water were added, heated to 80 ° C., dissolved, allowed to stand, separated into two layers, and then the aqueous layer was separated. The separated aqueous layer was cooled to room temperature to precipitate crystals, which were collected by suction filtration. The obtained crystals were washed with 10 g of water, and then dried under reduced pressure at 100 ° C. for 5 hours to obtain 14.63 g of tetraphenylphosphonium bromide (purity 90.4%) (triphenylphosphine reference yield 82.7%). ).

[Example 3]
To a 1000 ml pressure-resistant glass container, 100.0 g of triphenylphosphine, 83.8 g of bromobenzene, 17.2 g of nickel chloride hexahydrate, 150 g of N, N-dimethylformamide and 11.0 g of water were added and sealed. The reaction was conducted with stirring at a temperature of 140 ° C. and a reaction pressure of 0.3 MPa for 5 hours. After completion of the reaction, unreacted bromobenzene and N, N-dimethylformamide were distilled off under reduced pressure (119.4 g). After the distillation residue was cooled to room temperature, 110.0 g of toluene and 310.0 g of water were added, heated to 80 ° C., dissolved and allowed to stand. After separating into two layers, the aqueous layer was separated. The separated aqueous layer was cooled to room temperature to precipitate crystals, which were collected by suction filtration. The obtained crystals were washed with 150 g of water and then dried under reduced pressure at 110 ° C. for 3 hours to obtain 95.0 g of tetraphenylphosphonium bromide (purity 99.7%) (triphenylphosphine reference yield 94.6%). ).

[Example 4]
After adding 100.0 g of triphenylphosphine, 83.8 g of bromobenzene, 17.2 g of nickel chloride hexahydrate, 100 g of N, N-dimethylformamide and 11.0 g of water to a 1000 ml pressure-resistant glass container, the container was sealed, The reaction was conducted with stirring at a temperature of 140 ° C. and a reaction pressure of 0.3 MPa for 5 hours. After completion of the reaction, unreacted bromobenzene and N, N-dimethylformamide were distilled off under reduced pressure (117.3 g). After the distillation residue was cooled to room temperature, 110.0 g of toluene and 310.0 g of water were added, heated to 80 ° C., dissolved and allowed to stand. After separating into two layers, the aqueous layer was separated. The separated aqueous layer was cooled to room temperature to precipitate crystals, which were collected by suction filtration. The obtained crystals were washed with 150 g of water and then dried under reduced pressure at 110 ° C. for 3 hours to obtain 94.2 g of tetraphenylphosphonium bromide (purity 98.1%) (triphenylphosphine reference yield 92.4%). ).

[Example 5]
After adding 100.0 g of triphenylphosphine, 83.8 g of bromobenzene, 17.2 g of nickel chloride hexahydrate, 50 g of N, N-dimethylformamide and 11.0 g of water to a 1000 ml pressure-resistant glass container, the container was sealed, The reaction was conducted with stirring at a temperature of 140 ° C. and a reaction pressure of 0.3 MPa for 9 hours. After completion of the reaction, unreacted bromobenzene and N, N-dimethylformamide were distilled off under reduced pressure (116.9 g). After the distillation residue was cooled to room temperature, 110.0 g of toluene and 310.0 g of water were added, heated to 80 ° C., dissolved and allowed to stand. After separating into two layers, the aqueous layer was separated. The separated aqueous layer was cooled to room temperature to precipitate crystals, which were collected by suction filtration. The obtained crystals were washed with 150 g of water and then dried under reduced pressure at 110 ° C. for 3 hours to obtain 94.1 g of tetraphenylphosphonium bromide (purity 99.4%) (triphenylphosphine reference yield 95.0%). ).

[Example 6]
After adding 100.0 g of triphenylphosphine, 83.8 g of bromobenzene, 17.2 g of nickel chloride hexahydrate, 50 g of N, N-dimethylformamide and 18.2 g of water to a 1000 ml pressure-resistant glass container, the container was sealed. The reaction was conducted with stirring at a temperature of 140 ° C. and a reaction pressure of 0.3 MPa for 5 hours. After completion of the reaction, unreacted bromobenzene and N, N-dimethylformamide were distilled off under reduced pressure (118.4 g). After the distillation residue was cooled to room temperature, 110.0 g of toluene and 310.0 g of water were added, heated to 80 ° C., dissolved and allowed to stand. After separating into two layers, the aqueous layer was separated. The separated aqueous layer was cooled to room temperature to precipitate crystals, which were collected by suction filtration. The obtained crystals were washed with 150 g of water and then dried under reduced pressure at 110 ° C. for 3 hours to obtain 94.8 g of tetraphenylphosphonium bromide (purity 98.6%) (triphenylphosphine reference yield 93.5%). ).

[Example 7]
After adding 100.0 g of triphenylphosphine, 83.8 g of bromobenzene, 17.2 g of nickel chloride hexahydrate, 50 g of N, N-dimethylformamide and 31.2 g of water to a 1000 ml pressure-resistant glass container, the container was sealed, The reaction was conducted with stirring at a temperature of 140 ° C. and a reaction pressure of 0.3 MPa for 5 hours. After completion of the reaction, unreacted bromobenzene and N, N-dimethylformamide were distilled off under reduced pressure (119.9 g). After the distillation residue was cooled to room temperature, 110.0 g of toluene and 310.0 g of water were added, heated to 80 ° C., dissolved and allowed to stand. After separating into two layers, the aqueous layer was separated. The separated aqueous layer was cooled to room temperature to precipitate crystals, which were collected by suction filtration. The obtained crystals were washed with 150 g of water and then dried under reduced pressure at 110 ° C. for 3 hours to obtain 91.8 g of tetraphenylphosphonium bromide (purity 99.0%) (triphenylphosphine reference yield 90.9%). ).

Claims (3)

  A process for producing a tetraarylphosphonium halide, comprising reacting a triarylphosphine with an aryl halide in the presence of a metal halide catalyst and N, N-dimethylformamide.   The method for producing a tetraarylphosphonium halide according to claim 1, wherein the reaction is carried out in the presence of 40 mol or less of water with respect to 1 mol of the metal halide.   The method for producing a tetraarylphosphonium halide according to claim 1 or 2, wherein the reaction is performed at a temperature of 130 ° C or higher and lower than 150 ° C.