JP2003238476A - Method for producing bisbenzoin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for simply producing a high-purity bisbenzoin compound being an important intermediate for a monomer for an electronic material, a functional polymer, etc., namely a method for producing the bisbenzoin compound, with which problems occurring in industrialization of compound production are solved and especially a prussic acid compound is not used. <P>SOLUTION: A phthalaldehyde compound containing two aldehyde groups in the benzene ring is reacted with a benzaldehyde compound containing one aldehyde group in the benzene ring in the presence of a base and an imidazolium salt compound optionally by adding an organic solvent to give the objective high-purity bisbenzoin compound in a high yield. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art A method for producing a bisbenzoin compound by cross-benzoin condensation of phthalaldehyde and benzaldehyde is known. J. Org. Chem. , 41p
2230 (1976), a bisulfite adduct is synthesized by reacting terephthalaldehyde with sodium bisulfite, and the biscyanohydrin derivative is induced with potassium cyanide. The selectivity of cross-benzoin condensation is ensured by reacting biscyanohydrin with benzaldehyde. Further, according to JP-A-55-157533, bisbenzoin is synthesized by carrying out cross-benzoin condensation of p- or m-phthalaldehyde and benzaldehyde using a catalytic amount of potassium bromide.

However, J. Org. Chem. , 41p
In the method of 2230 (1976), highly toxic potassium cyanide is used in a stoichiometric amount or more, and hydrocyanic acid is released after the reaction, and in JP-A-55-157533, the highly toxic potassium cyanide remains without being consumed by the reaction. To do. With either method, a highly toxic bromide remains, so industrially it is necessary to take measures to ensure safety.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and an object thereof is to provide a method for safely and inexpensively producing a bisbenzoin compound in a high yield.

[0005]

Means for Solving the Problems The present inventors have found that the above object can be achieved by reacting a phthalaldehyde compound and a benzaldehyde compound in the presence of a base and an imidazolium salt compound, and have completed the present invention. .
That is, the present invention comprises the following items, for example.

[1] A method for producing a bisbenzoin compound in which a phthalaldehyde compound and a benzaldehyde compound are reacted in the presence of a base and an imidazolium salt compound.

[2] Formula (1)

[Chemical 9] (In the formula, X ^{1 to} X ⁴ each independently represent a hydrogen atom, a chlorine atom, or a fluorine atom.) And a phthalaldehyde compound represented by the formula (2).

[Chemical 10] (In the formula, Y ^{1 to} Y ⁴ each independently represent a hydrogen atom, a chlorine atom, or a fluorine atom, R represents a hydrogen atom, an optionally branched alkyl group having 1 to 8 carbon atoms, a monocyclic aryl group, A benzaldehyde compound represented by C7 to C9 aralkyl group) is reacted in the presence of a base and an imidazolium salt compound to obtain a compound of formula (3),

[Chemical 11] Formula (4)

[Chemical 12] Formula (5)

[Chemical 13] And equation (6)

[Chemical 14] (In the formula, X ^{1 to} X ⁴ , Y ^{1 to} Y ⁴ , and R have the same meanings as described above.) A method for producing a bisbenzoin compound containing at least one isomer.

[3] The imidazolium salt compound has the formula (7)
Or / and formula (8)

[Chemical 15]

[Chemical 16] (In the formula, R ¹ , R ² , R ⁵ , and R ⁶ represent an alkyl group having 1 to 8 carbon atoms which may be branched, a monocyclic aryl group, an aralkyl group having 7 to 9 carbon atoms, and R ³ , R ⁴ has 1 to 1 carbon atoms
8 optionally branched alkyl group, monocyclic aryl group, C 7-9 aralkyl group, optionally branched C 1-8 alkoxy group, hydroxymethyl group, cyano group, nitro group , Carboxyl group, ester group,
An amide group, a ketone group, a sulfide group, a sulfoxide group, a sulfonyl group, a halogen atom, Z is a halogen atom,
_{CH 3 SO 3, CF 3 SO} 3, showing a _{ClO 4, BF 4, PF 6} . [3] The method for producing a bisbenzoin compound according to [1] or [2], which comprises reacting in the presence of an imidazolium salt compound.

[4] The method for producing a bisbenzoin compound according to any one of [1] to [3], wherein the base is a tertiary amine.

[5] The bisbenzoin compound described in [4], wherein the tertiary amine is at least one selected from diazabicycloundecene, diazabicyclononane and diazabicyclooctadecane. Method.

[6] The process for producing a bisbenzoin compound according to any one of [1] to [3], wherein the base is an inorganic base having a pH of 11 or more when it is used as a 1% by weight aqueous solution.

[7] The inorganic base is sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium oxide, potassium oxide, barium oxide, calcium oxide, sodium carbonate, potassium carbonate, barium carbonate, calcium carbonate, It is at least one selected from sodium acetate, potassium acetate, sodium hydride, potassium hydride, calcium hydride, sodium amide, potassium amide, sodium methoxide, sodium ethoxide, potassium butoxide, magnesium methoxide and magnesium ethoxide. [6] The method for producing a bisbenzoin compound according to [6].

[8] The method for producing a bisbenzoin compound according to any one of [1] to [7], wherein the reaction is carried out in the presence of an organic solvent.

[9] In any one of [1] to [8], wherein the phthalaldehyde compound is terephthalaldehyde, the benzaldehyde compound is benzaldehyde, and the bisbenzoin compound is 1,4-bisbenzoin. The manufacturing method described.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The reaction method of the present invention is carried out by mixing a phthalaldehyde compound, a benzaldehyde compound, a base and an imidazolium salt compound in an organic solvent and stirring the mixture at a predetermined temperature for a predetermined time. After the stirring is completed, the produced bisbenzoin compound is obtained.

The order of mixing the phthalaldehyde compound, the benzaldehyde compound, the base and the imidazolium salt compound is not particularly limited.

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

The reaction temperature is -20 to 150 ° C, preferably 0 to 80 ° C. The reaction time is 0.1 to 20.
Time is preferred.

The phthalaldehyde compound which is one of the raw material compounds of the present invention is a compound in which two aldehyde groups are substituted on the benzene ring, but other substituents are not particularly limited. Preferably, the formula (1)

[Chemical 17] (In the formula, X ^{1 to} X ⁴ each independently represent a hydrogen atom, a chlorine atom, or a fluorine atom).

For example, isophthalaldehyde, terephthalaldehyde, tetrachloroisophthalaldehyde, tetrachloroterephthalaldehyde, tetrafluoroisophthalaldehyde, tetrafluoroterephthalaldehyde, 2-chloroisophthalaldehyde, 3-chloroisophthalaldehyde, 4-chloroisophthalaldehyde,
2-chloroterephthalaldehyde, 2-fluoroisophthalaldehyde, 3-fluoroisophthalaldehyde,
Examples include 4-fluoroisophthalaldehyde, 2-fluoroterephthalaldehyde, 2,5-dichloroterephthalaldehyde, and 2,5-difluoroterephthalaldehyde. Especially preferred is terephthalaldehyde.

The other starting material, benzaldehyde, is not particularly limited as long as it is a compound in which one aldehyde group is substituted on the benzene ring, but the preferred one is represented by formula (2).

[Chemical 18] (In the formula, Y ^{1 to} Y ⁴ each independently represent a hydrogen atom, a chlorine atom, or a fluorine atom, R represents a hydrogen atom, an optionally branched alkyl group having 1 to 8 carbon atoms, a monocyclic aryl group, It is a benzaldehyde compound represented by a C7-C9 aralkyl group.).

For example, benzaldehyde, m-tolualdehyde, p-tolualdehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, m-fluorobenzaldehyde, p-fluorobenzaldehyde, 2,4
-Dichlorobenzaldehyde, 3,4-dichlorobenzaldehyde, 2,3-difluorobenzaldehyde,
3,4-difluorobenzaldehyde may be mentioned. Particularly preferred is benzaldehyde.

The benzaldehyde compound is usually used in an amount about 2 times the molar amount of the phthalaldehyde compound. It is possible to use one of them in excess, but if they are used in excess, the amount of by-products resulting from self-condensation of extra raw materials increases.

The benzoin compound obtained by this reaction is represented by the formulas (3), (4), (5) and (if the compounds represented by the formulas (1) and (2) are used as raw materials. 6)

[Chemical 19]

[Chemical 20]

[Chemical 21]

[Chemical formula 22] (In the formula, X ^{1 to} X ⁴ , Y ^{1 to} Y ⁴ , and R are formula (1) and formula (2)
Has the same meaning as. 4) tautomers represented by) are considered, and the production ratio thereof is considered to be different depending on the position and type of the substituents of the benzaldehyde compound and the phthalaldehyde compound as raw materials, the reaction conditions and the like. The product benzoin compound has the formula (3), (4), (5) and (6)
However, it is difficult to determine the production ratio clearly.

In the reaction of the present invention, an imidazolium salt compound is used as a catalyst precursor. The imidazolium salt compound is synthesized by quaternizing the nitrogen atom at the 3-position of the imidazole compound with a carbon electrophilic species. The exchange of counter anion is carried out by a salt exchange reaction.

The imidazolium salt compound that can be used is represented by the formula (7) or (8)

[Chemical formula 23]

[Chemical formula 24] (In the formula, R ¹ , R ² , R ⁵ , and R ⁶ represent an alkyl group having 1 to 8 carbon atoms which may be branched, a monocyclic aryl group, an aralkyl group having 7 to 9 carbon atoms, and R ³ , R ⁴ has 1 to 1 carbon atoms
8 optionally branched alkyl group, monocyclic aryl group, C 7-9 aralkyl group, optionally branched C 1-8 alkoxy group, hydroxymethyl group, cyano group, nitro group , Carboxyl group, ester group,
An amide group, a ketone group, a sulfide group, a sulfoxide group, a sulfonyl group, a halogen atom, Z is a halogen atom,
_{CH 3 SO 3, CF 3 SO} 3, showing a _{ClO 4, BF 4, PF 6} . ) The imidazolium salt compound represented by

By way of example of the imidazolium salt compound,
1,3-Dimethyl-imidazolium chlorine salt, 1,3-dimethyl-imidazolium bromine salt, 1,3-dimethyl-imidazolium iodine salt, 1,3-dimethyl-imidazolium perchlorate salt, 1,3- Lower alkylated products such as dimethyl-imidazolium trifluoromethanesulfonate,
1-phenyl-3-methyl-imidazolium chloride salt, 1-
Phenyl-3-methyl-imidazolium bromine salt, 1-phenyl-3-methyl-imidazolium iodine salt, 1-phenyl-3-methyl-imidazolium perchlorate salt, 1-
Phenyl-3-methyl-imidazolium trifluoromethanesulfonate, 1-methyl-3-phenyl-imidazolium chloride, 1-methyl-3-phenyl-imidazolium bromine salt, 1-methyl-3-phenyl-imidazo Arylated products such as lithium iodine salt, 1-methyl-3-phenyl-imidazolium perchlorate, 1-methyl-3-phenyl-imidazolium tofluoromethanesulfonate, and the like.
1-benzyl-3-methyl-imidazolium chloride, 1-
Benzyl-3-methyl-imidazolium bromine salt, 1-benzyl-3-methyl-imidazolium iodine salt, 1-benzyl-3-methyl-imidazolium perchlorate salt, 1-
Benzyl-3-methyl-imidazolium trifluoromethanesulfonate, 1-methyl-3-benzyl-imidazolium chloride, 1-methyl-3-benzyl-imidazolium bromine salt, 1-methyl-3-benzyl-imidazo Benzylated products such as lithium iodide, 1-methyl-3-benzyl-imidazolium perchlorate, 1-methyl-3-benzyl-imidazolium tofluoromethanesulfonate,
1,3,4-trimethyl-imidazolium bromine salt, 1,
3-dimethyl-4-phenyl-imidazolium bromine salt,
1,3,5-trimethyl-imidazolium bromine salt, 1,
3-dimethyl-5-phenyl-imidazolium bromine salt,
1,3,4,5-Tetra-methyl-imidazolium bromine salt is mentioned as the derivative of the formula (7), 1,3-dimethyl-benzimidazolium bromine salt, 1,3-dimethyl-benzimidazolium bromine salt, 1,3-Dimethyl-benzimidazolium iodine salt, 1,3-dimethyl-benzimidazolium perchlorate, and 1,3-dimethyl-benzimidazolium trifluoromethanesulfonate are mentioned as the formula (8) derivative.

These imidazolium compounds may be used alone or in combination of two or more.

The imidazolium salt compound is used in an amount of 0.001 to 0.9 mol based on the phthalaldehyde compound,
The amount is preferably 0.05 mol to 0.5 mol, and more preferably 0.01 mol to 0.2 mol.

In the present invention, a base is required to generate a catalyst species from an imidazolium salt compound which is a catalyst precursor. Both organic and inorganic bases can be used as the base, but a base that can deprotonate the hydrogen at the 2-position of the imidazolium salt compound is selected.

As the organic base that can be used, amines are used, and tertiary amines are particularly preferable.
Examples include diazabicycloundecene, diazabicyclononane, and diazabicyclooctadecane.

As the inorganic base that can be used, a base stronger than that showing a pH of 11 or more when a 1% by mass solution is used is required.

Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, and alkali metal hydroxides such as sodium oxide and potassium oxide. Oxides, barium oxide, alkaline earth metal oxides such as calcium oxide, sodium carbonate, potassium carbonate,
Alkali and alkaline earth metal carbonates such as barium carbonate and calcium carbonate, carboxylic acid alkali metal salts such as sodium acetate and potassium acetate, alkali metal hydrides such as sodium hydride and potassium hydride, calcium hydride and the like Alkaline earth metal hydrides, amides such as sodium amide and potassium amide, alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium butoxide, alkaline earth metal alkoxides such as magnesium methoxide and magnesium ethoxide, etc. Can be given.

These bases may be used alone or
You may use it in mixture of 2 or more types.

The base is used in an amount of at least 1 mol, preferably 1.05 mol to 1.5 mol, based on the imidazolium salt compound of the catalyst precursor.

In the present invention, an organic solvent can be used. Although water may be used, it is preferable to use an organic solvent because the solubility of the raw material aromatic aldehyde or the product bisbenzyl compound in water is low in many cases. Examples of the organic solvent that can be used include ether solvents such as tetrahydrofuran, dioxane, dimethoxymethane and diglyme, and alcohol solvents such as methanol, ethanol, propanol and butanol.
These organic solvents may be used alone or in combination of two or more.

[0037]

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.

The conditions of the liquid chromatograph used for the analysis are as follows.

[0039] <High performance liquid chromatograph analysis conditions>     Column: Kanto Chemical RP-18 (ODS) Feld cap treatment     Eluent: water / acetonitrile = 35/65 (volume)     Conditions: Flow rate 1.5 ml / min             Detection wavelength UV 265nm             Pressure 70kg / cm             Column temperature 40 ℃

Example 1 Methanol 20 ml, terephthalaldehyde 1.34
g, benzaldehyde 2.33 g, 1,3-dimethyl-
0.18 g of imidazolium bromine salt and 0.04 g of sodium hydroxide were mixed and stirred at room temperature. The reaction was carried out at 40 ° C for 6 hours. When a part of the reaction solution was sampled and analyzed by high performance liquid chromatography, the yield of 1,4-bisbenzoin (an isomer corresponding to the formula (3) as the formula (9) is exemplified) was 51%. It was

[0041]

[Chemical 25]

Example 2 20 ml of tetrahydrofuran, 1.34 g of terephthalaldehyde, 2.33 g of benzaldehyde, 0.25 g of 1-methyl-3-benzyl-imidazolium bromine salt and 0.024 g of sodium hydride were mixed and stirred at room temperature.
The reaction was carried out at 50 ° C for 3 hours. A part of the reaction solution was sampled and analyzed by high performance liquid chromatography.
The yield of -bisbenzoin was 54%.

Example 3 20 ml of methanol, isophthalphthalaldehyde 1.
34 g, benzaldehyde 2.33 g, 1,3-dimethyl-benzimidazolium bromine salt 0.23 g, and diazabicycloundecene 0.07 g were mixed and stirred at room temperature.
The reaction was carried out at 40 ° C for 6 hours. A part of the reaction solution was sampled and analyzed by high performance liquid chromatography.
The yield of -bisbenzoin (the isomer corresponding to the formula (3) as the formula (10) is exemplified) was 61%.

[0044]

[Chemical formula 26]

Example 4 20 ml of tetrahydrofuran, 1.34 g of terephthalaldehyde, 2.33 g of benzaldehyde, 1-methyl-3-benzyl-benzimidazolium bromine salt 0.3
and 0.05 g of diazabicycloundecene were mixed and stirred at room temperature. The reaction was carried out at 50 ° C for 3 hours. When a part of the reaction solution was sampled and analyzed by high performance liquid chromatography, the yield of 1,4-bisbenzoin was 64%.

[0046]

EFFECTS OF THE INVENTION According to the present invention, a bisbenzoin compound, which is an important intermediate for electronic materials, functional polymer monomers, etc., can be easily produced with high purity.

Claims (9)

[Claims] 1. A method for producing a bisbenzoin compound, which comprises reacting a phthalaldehyde compound and a benzaldehyde compound in the presence of a base and an imidazolium salt compound. 2. Formula (1): (In the formula, X ^{1 to} X ⁴ each independently represent a hydrogen atom, a chlorine atom, or a fluorine atom.) And a phthalaldehyde compound represented by the formula (2): (In the formula, Y ^{1 to} Y ⁴ each independently represent a hydrogen atom, a chlorine atom, or a fluorine atom, R represents a hydrogen atom, an optionally branched alkyl group having 1 to 8 carbon atoms, a monocyclic aryl group, A benzaldehyde compound represented by a C7-C9 aralkyl group) is reacted in the presence of a base and an imidazolium salt compound. Formula (4) Formula (5) And the formula (6) (In the formula, X ^{1 to} X ⁴ , Y ^{1 to} Y ⁴ , and R have the same meanings as described above.) A method for producing a bisbenzoin compound containing at least one isomer. 3. The imidazolium salt compound is represented by the formula (7) or / and the formula (8): [Chemical 8] (In the formula, R ¹ , R ² , R ⁵ , and R ⁶ represent an alkyl group having 1 to 8 carbon atoms which may be branched, a monocyclic aryl group, an aralkyl group having 7 to 9 carbon atoms, and R ³ , R ⁴ has 1 to 1 carbon atoms
8 optionally branched alkyl group, monocyclic aryl group, C 7-9 aralkyl group, optionally branched C 1-8 alkoxy group, hydroxymethyl group, cyano group, nitro group , Carboxyl group, ester group,
An amide group, a ketone group, a sulfide group, a sulfoxide group, a sulfonyl group, a halogen atom, Z is a halogen atom,
_{CH 3 SO 3, CF 3 SO} 3, showing a _{ClO 4, BF 4, PF 6} . The reaction is carried out in the presence of an imidazolium salt compound represented by the formula (1). 4. The method for producing a bisbenzoin compound according to claim 1, wherein the base is a tertiary amine. 5. The method for producing a bisbenzoin compound according to claim 4, wherein the tertiary amine is at least one selected from diazabicycloundecene, diazabicyclononane and diazabicyclooctadecane. . 6. The base sometimes has a pH as a 1% by weight aqueous solution.
Is an inorganic base having 11 or more. 4. The method for producing a bisbenzoin compound according to claim 1, wherein 7. The inorganic base is sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium oxide, potassium oxide, barium oxide, calcium oxide, sodium carbonate, potassium carbonate, barium carbonate, calcium carbonate, acetic acid. Sodium, potassium acetate,
Sodium hydride, potassium hydride, calcium hydride, sodium amide, potassium amide, sodium methoxide, sodium ethoxide, potassium butoxide,
It is at least 1 sort (s) chosen from magnesium methoxide and magnesium ethoxide, The manufacturing method of the bisbenzoin compound of Claim 6 characterized by the above-mentioned. 8. The method for producing a bisbenzoin compound according to claim 1, wherein the reaction is carried out in the presence of an organic solvent. 9. The method according to claim 1, wherein the phthalaldehyde compound is terephthalaldehyde, the benzaldehyde compound is benzaldehyde, and the bisbenzoin compound is 1,4-bisbenzoin. Method.