JP2003171332A - Method for producing bisbenzyl compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a solution to a problem occurring in industrialization of production of a bisbenzyl compound. <P>SOLUTION: The bisbenzyl compound can be produced in a high yield in high productivity by reacting a bis(phenylacetyl)benzene compound with a sulfoxide compound and a halogenide in the presence of an acid and an organic solvent. A sulfide compound produced in the reaction is returned to the sulfoxide compound by oxidation and can be recovered. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a bisbenzyl compound. Bisbenzyl compounds are important intermediates for electronic materials and functional polymer monomers.

[0002]

2. Description of the Related Art A method for producing a bisbenzyl compound starting from a bis (phenylacetyl) benzene compound is known. According to US Pat. No. 4,082,806, the synthesis of bisbenzyl compounds is carried out by bis (phenylacetyl) benzene compounds in the presence of cupric halide or in the presence of cupric halide and hydrogen bromide in a dimethylsulfoxide solvent. It is carried out. Also, J. Org. Chem. U
SSR. , 22p753 (1989), bisbenzyl is synthesized with dimethyl sulfoxide in the presence of hydrogen bromide without using cupric halide. The produced bisbenzyl compound is purified by adding the reaction solution to a large amount of water, filtering the precipitated bisbenzyl compound, and recrystallizing it using an alcohol solvent. The solubility of bisbenzyls in alcohols is low, and the solid concentration is about 5%.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object thereof is to provide a solution to a problem that occurs during industrialization of the production of bisbenzyl compounds. That is, the methods described in US patents and Russian documents have the following problems in industrialization.
That is, in the known method, it is necessary to react with a high boiling point dimethyl sulfoxide as a solvent under a high dilution condition for a long time, and it is an object to improve the complexity of isolation and purification, the low productivity and the like. Let's do it. In addition, one of the challenges is to control the malodor of dimethyl sulfide, which is a malodorous substance produced as a byproduct during the reaction.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have found that the above object can be achieved by reacting a bis (phenylacetyl) benzene compound with a sulfoxide compound and a halide in the presence of an acid and an organic solvent. Has been completed. Further, they have found that the sulfide compound generated at that time can be returned to sulfoxide by oxidation and recovered, and thus completed the present invention.

That is, the present invention relates to the following inventions, for example.

[1] Formula (1)

[Chemical 3] (In the formula, R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a monocyclic aryl group, and an alkyl group having 1 to 4 carbon atoms.
4 alkyl group and a dialkylamino group, a nitro group, R ₅ to R ₁₄ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, mono- Aryl group and alkyl group of 1 to 1 carbon atoms
4 represents a dialkylamino group or a nitro group, which are alkyl groups. ), A bis (phenylacetyl) benzene compound represented by the formula (2) is reacted with a sulfoxide compound and hydrogen halide in the presence of an organic solvent.

[Chemical 4] (In the formula, R _{1 to} R ₁₄ are the same as above, and the positional relationship of the substituents corresponds to the formula (1).) The method for producing a bisbenzyl compound represented by the formula.

[2] The method for producing a bisbenzyl compound according to [1], wherein R _{1 to} R ₁₄ are each independently a hydrogen atom or a halogen atom.

[3] The bis (phenylacetyl) benzene compound is 1,4-bis (phenylacetyl) benzene and the bisbenzyl compound is the corresponding 1,4-bisbenzyl. [1] 1. And a method for producing the bisbenzyl compound.

[4] The method for producing a bisbenzyl compound according to any one of [1] to [3], wherein the organic solvent is an aliphatic carboxylic acid.

[5] The bisbenzyl according to any one of [1] to [4], wherein the sulfoxide compound is a dialkyl sulfoxide compound having an alkyl group of 1 to 4 carbon atoms and / or tetramethylene sulfoxide. Method for producing compound.

[6] The hydrogen halide is hydrogen bromide and / or hydrogen iodide [1] to
The method for producing the bisbenzyl compound according to any one of [5].

[7] The method for producing a bisbenzyl compound according to any one of [1] to [6], wherein the organic solvent is acetic acid.

[8] The method for producing a bisbenzyl compound according to any one of [1] to [7], wherein the sulfoxide compound is dimethyl sulfoxide.

[9] The method for producing a bisbenzyl compound according to [8], wherein the dimethyl sulfide produced in the reaction is oxidized to form dimethyl sulfoxide and reused.

[10] The method for producing a bisbenzyl compound according to [9], characterized in that dimethyl sulfide produced in the reaction is distilled off, treated with oxygen to obtain dimethyl sulfoxide, and reused.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The present invention is not limited to this.

The reaction method in the present invention is carried out by mixing a bis (phenylacetyl) benzene compound with a hydrogen halide or sulfoxide compound in an organic solvent and stirring the mixture at a predetermined temperature for a predetermined time. After completion of stirring, the produced bisbenzyl compound is obtained.

The charging of the reaction raw materials and the reaction can be carried out under atmospheric pressure. A glass container is suitable as the reactor.

Although the reaction mechanism of the reaction of the present invention has not been clarified, experimental results and known literature (J. Or.
g. Chem. , 40p1990 (1975), J.O.
rg. Chem. , 50p5022 (1985)), it is estimated that the process proceeds as shown below.

From 1,4-bis (phenylacetyl) benzene to 1,4-bisbenzyl in the presence of hydrogen bromide as a hydrogen halide and dimethylsulfoxide as a sulfoxide compound in an organic solvent (in the formula (2), R ₁ , R ₂ ,
R ₃ , R ₄ , R ₅ , and R ₆ are all hydrogen and refer to a compound in which the position of the substituent is the para position. ) Will be described as an example.

First, a redox reaction occurs between dimethyl sulfoxide and hydrogen bromide. Dimethyl sulfoxide is reduced to dimethyl sulfide and hydrogen bromide is oxidized to bromine (equation (3)). 2HBr + Me ₂ SO-→ Br ₂ + Me ₂ S + H ₂ O (3)

Bromine reacts with bis (phenylacetyl) benzene to form an α-dibromo compound (formula (4)). Here, in order to simplify the explanation and to clarify the essence of the reaction, it is assumed that a dibromo compound is generated for convenience.

[Chemical 5] At this time, hydrogen bromide is released, and the hydrogen bromide is again oxidized by dimethyl sulfoxide to be bromine.

The α-dibromo compound reacts with dimethyl sulfoxide to give 1,4-bisbenzyl (formula (5)). It is presumed that this is a reaction mechanism similar to the general dimethyl sulfoxide oxidation of α-haloketones.

[Chemical 6] At this time, dimethyl sulfoxide and hydrogen bromide are released.
Hydrogen bromide is again oxidized to bromine by dimethyl sulfoxide.

Therefore, it is considered that dimethyl sulfide is produced in accordance with the reaction and hydrogen bromide acts catalytically.

The actual operation of the present invention will be described.

The reaction temperature is 40 ° C to 180 ° C, preferably 60 to 120 ° C. The reaction time is 0.5 to 2
0 hours is preferred.

An organic solvent is used in the reaction of the present invention. The organic solvent that can be used is a solvent inert to halogen molecules such as bromine and iodine generated during the reaction. Acetic acid, aliphatic carboxylic acids such as propionic acid, polar amides such as formamide and dimethylformamide, sulfolane-containing sulfolanes, imidazolidones such as 1,3-dimethyl-2-imidazolidione, dioxane, 1,2- Ethers such as dimethoxyethane and diglyme are used. Of these, aliphatic lower carboxylic acids are preferred, and acetic acid is particularly suitable.
These organic solvents may be used alone or as a mixture. The solvent is used in an amount of 2 to 20 times by mass, preferably 4 to 8 times by mass that of bis (phenylacetyl) benzene.

Hydrogen halide is required in the reaction of the present invention. Hydrogen bromide and hydrogen iodide are preferably used as the hydrogen halide. The hydrogen halide is used in an amount of 0.1 to 2.0 times, and preferably 0.5 to 1.5 times the molar amount of the bis (phenylacetyl) benzene compound.
The hydrogen halide can be used in any form such as an aqueous solution, gas or solution. It may be added all at once when the reaction is charged, or may be added dropwise in the required amount.

The reaction of the present invention requires a sulfoxide compound. Aliphatic sulfoxide compounds such as dimethyl sulfoxide and aromatic sulfoxide compounds such as diphenyl sulfoxide are used, and the alkyl group has 1 to 4 carbon atoms.
Of dialkyl sulfoxide or tetramethylene sulfoxide having a cyclic structure is preferable, and dimethyl sulfoxide is particularly preferable. The sulfoxide compound is 4 to 20 relative to the bis (phenylacetyl) benzene compound.
It is used in a double molar amount, preferably a 6 to 10-fold molar amount.

When dimethyl sulfoxide is used as the sulfoxide compound, dimethyl sulfide is produced as the reaction progresses. Although the reaction can be carried out without distilling dimethyl sulfide, the reaction rate is slower than in the case of distilling dimethyl sulfide, so it is desirable to carry out the reaction while distilling dimethyl sulfide. Dimethyl sulfide distilled from the reactor can be recovered, dimethyl sulfide can be oxidized to dimethyl sulfoxide with an oxidizing agent such as hydrogen peroxide, and the dimethyl sulfoxide can be used again in the reaction.

The isolation and purification of the product will be described. The reaction of 1,4-bis (phenylacetyl) benzene with 1,4-bisbenzyl in the presence of hydrogen bromide, sulfoxide or dimethyl sulfoxide in an acetic acid solvent will be described as an example.
After completion of the reaction, the solution is uniform under heating at about 70 ° C. or higher. When acetic acid is added so that the concentration of 1,4-bisbenzyl is about 5% and the mixture is cooled in the order, 1,4-bisbenzyl crystals are precipitated. 1,4-bisbenzyl is filtered, washed with water and isolated. Although this method is simple, there are many losses in the mother liquor. In order to increase the recovery rate, the reaction solution is heated at 90 to 100 ° C.
Keep the same amount of water and add the same weight of acetic acid as it is added to 1,4-
Precipitate bisbenzyl. If you add water and cool it down 1,
Almost all 4-bisbenzyl is precipitated. 1,4-bisbenzyl is obtained by filtration, washing with water and drying. The 1,4-bisbenzyl thus obtained has a sufficient purity as a raw material for electronic materials and functional polymer monomers.

[0032]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

High-performance liquid chromatographic bluff analysis conditions (same below) Column: Kanto Kagaku RP-18 (ODS) Feldcap treatment Eluent: Water / acetonitrile = 35/65 (volume)
e) Condition: Flow rate 1.5 ml / min UV 265 nm Column oven: 40 ° C.

Example 1 1,4-bis (phenylacetyl) benzene 31.4
g, 62.5 g of dimethyl sulfoxide, and 157 g of acetic acid were mixed at room temperature, and then 17.21 g of 47% HBr aqueous solution was added at room temperature.
Was added. The reaction was carried out for 3 hours while keeping the internal temperature at 95 to 105 ° C. and distilling dimethylflufide. Acetic acid 157g
Was added and cooled to room temperature over 8 hours. The precipitated crystals were filtered, washed with water and dried to give 1,4-bisbenzyl 24.
1 g (isolated yield 70%) was obtained. The purity of 1,4-bisbenzyl obtained by high performance liquid chromatography analysis was 99% or more.

Example 2 1,4-bis (phenylacetyl) benzene 31.4
g, 62.5 g of dimethyl sulfoxide, and 157 g of acetic acid were mixed at room temperature, and then 17.21 g of 47% HBr aqueous solution was added at room temperature.
Was added. The reaction was carried out for 3 hours while keeping the internal temperature at 95 to 105 ° C. and distilling dimethylflufide. 157 g of water was added over 3 hours while keeping the internal temperature at 90 to 100 ° C., and cooled to room temperature over 8 hours. The precipitated solid is filtered, washed with water,
After being dried, 33.9 g of 1,4-bisbenzyl (isolated yield: 9
9%) was obtained. The purity of 1,4-bisbenzyl obtained by high performance liquid chromatography analysis was 99% or more.

Example 3 1,4-bis (phenylacetyl) benzene 31.4
g, dimethyl sulfoxide 62.5 g, and acetic acid 157 g were mixed at room temperature. 30% HBr / acetic acid solution at room temperature 27.
0 g was added. The internal temperature was kept at 55 to 60 ° C., and the reaction was carried out for 8 hours without distilling dimethylflufide. When a part of the reaction solution was sampled and analyzed by high performance liquid chromatography, the yield of 1,4-bisbenzyl was 84%.

Example 4 1,4-bis (phenylacetyl) benzene 31.4
g, dimethyl sulfoxide 62.5 g, and acetic acid 157 g were mixed at room temperature. 30% HBr / acetic acid solution at room temperature 27.
0 g was added. The reaction was carried out for 3 hours while keeping the internal temperature at 95 to 105 ° C. and distilling dimethylflufide. When a part of the reaction solution was sampled and analyzed by high performance liquid chromatography, the yield of 1,4-bisbenzyl was 101% (quantification error).

Example 5 1,4-bis (phenylacetyl) benzene 31.4
g, dimethyl sulfoxide 62.5 g, and acetic acid 157 g were mixed at room temperature. HBr gas at room temperature to 50 ° C. or lower 8.
3 g was introduced. After introducing HBr gas, the internal temperature is adjusted to 95 to 10
The reaction was carried out for 3 hours while keeping the temperature at 5 ° C. and distilling dimethylflufide. When a part of the reaction solution was sampled and analyzed by high performance liquid chromatography, the yield of 1,4-bisbenzyl was 99%.

Example 6 (manufacturing on a large scale) 80 g of 1,4-bis (phenylacetyl) benzene, 160 kg of dimethyl sulfoxide and 400 kg of acetic acid were mixed at room temperature in a 1 m ³ glass reaction kettle at room temperature and then 47 at room temperature. 44 kg of a% HBr aqueous solution was added. Inner temperature is 95 ~
The reaction was carried out for 6 hours while keeping the temperature at 105 ° C. and distilling dimethylflufide. 400 kg of water was added over 6 hours while maintaining the internal temperature at 90 to 100 ° C., and cooled to room temperature over 12 hours. The deposited solid is deliquored with a centrifuge and water 200 k
g, and washed with 200 kg of methanol. It was dried under reduced pressure to obtain 84 kg of 1,4-bisbenzyl (purity 98%, yield 96%).

Example 7 (Recovery and reuse of dimethyl sulfide) 1,4-bis (phenylacetyl) benzene 31.4
g, 62.5 g of dimethyl sulfoxide, and 157 g of acetic acid were mixed at room temperature, and then 17.21 g of 47% HBr aqueous solution was added at room temperature.
Was added. The reaction was carried out for 4 hours while keeping the internal temperature at 95 to 105 ° C and distilling dimethylflufide. Isolation of 1,4-bisbenzyl was carried out according to Example 2 and 33.5 g (yield 9
8%).

48 g of dimethyl sulfide produced by the reaction was recovered (theoretical amount: 49.7 g). 48 g of dimethyl sulfide was added dropwise to 100 g of 30% hydrogen peroxide under ice cooling so that the internal temperature did not exceed 40 ° C. A 5% aqueous solution of sodium bisulfite is added until the iodine starch test paper no longer develops color. The water was distilled off under reduced pressure, and further rectification under reduced pressure (theoretical plate number 5: 83 ° C./17 mmHg) to obtain 45 g of dimethyl sulfoxide (recovery rate 75%).

2,4-bis (phenylacetyl) benzene 22.6 g, dimethyl sulfoxide 45 g, acetic acid 11
After mixing 0 g at room temperature, 47% HBr aqueous solution at room temperature 12.
4 was added. The reaction was carried out for 4 hours while keeping the internal temperature at 95 to 105 ° C and distilling dimethylflufide. When a part of the reaction solution was sampled and analyzed by high performance liquid chromatography, the yield of 1,4-bisbenzyl was 99%.

[0043]

EFFECTS OF THE INVENTION According to the present invention, a bisbenzyl compound, which is an important intermediate for electronic materials, functional polymer monomers, etc., can be simply and highly purified.

Claims (10)

[Claims] 1. Formula (1): (In the formula, R _{1 to} R ₄ are each independently a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a monocyclic aryl group, and an alkyl group having 1 to 4 carbon atoms.
4 alkyl group and a dialkylamino group, a nitro group, R ₅ to R ₁₄ each independently represent a hydrogen atom, a halogen atom, an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 4 carbon atoms, mono- Aryl group and alkyl group of 1 to 1 carbon atoms
4 represents a dialkylamino group or a nitro group, which are alkyl groups. ) A bis (phenylacetyl) benzene compound represented by the formula (2) is reacted with a sulfoxide compound and hydrogen halide in the presence of an organic solvent. (In the formula, R _{1 to} R ₁₄ are the same as above, and the positional relationship of the substituents corresponds to the formula (1).) The method for producing a bisbenzyl compound represented by the formula. 2. The method for producing a bisbenzyl compound according to claim 1, wherein R _{1 to} R ₁₄ are each independently a hydrogen atom or a halogen atom. 3. The bisbenzyl according to claim 1, wherein the bis (phenylacetyl) benzene compound is 1,4-bis (phenylacetyl) benzene and the bisbenzyl compound is the corresponding 1,4-bisbenzyl. Method for producing compound. 4. The method for producing a bisbenzyl compound according to claim 1, wherein the organic solvent is an aliphatic carboxylic acid. 5. The production of the bisbenzyl compound according to claim 1, wherein the sulfoxide compound is a dialkyl sulfoxide compound having an alkyl group of 1 to 4 carbon atoms and / or tetramethylene sulfoxide. Method. 6. The method for producing a bisbenzyl compound according to claim 1, wherein the hydrogen halide is hydrogen bromide and / or hydrogen iodide. 7. The method for producing a bisbenzyl compound according to claim 1, wherein the organic solvent is acetic acid. 8. The method for producing a bisbenzyl compound according to claim 1, wherein the sulfoxide compound is dimethyl sulfoxide. 9. The method for producing a bisbenzyl compound according to claim 8, wherein the dimethyl sulfide produced in the reaction is oxidized to form dimethyl sulfoxide and reused. 10. The method for producing a bisbenzyl compound according to claim 9, wherein dimethyl sulfide produced in the reaction is distilled out, subjected to oxygen oxidation treatment to obtain dimethyl sulfoxide, and reused.