JP5151180B2 - 3,3 ', 4,4'-cyclohexenylphenyltetracarboxylic acid compound group and method for producing 3,3', 4,4'-biphenyltetracarboxylic acid compound - Google Patents

Description

  The present invention relates to a 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound group and a method for producing a 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound. 3,3 ′, 4,4′-biphenyltetracarboxylic acid compounds are widely known to be useful compounds as raw materials for polyimide and the like. On the other hand, the 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound group can be derived into a 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound by dehydrogenation, for example. It is a useful compound that can be used.

Conventionally, the 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound group and the production method thereof have not been known. On the other hand, as a method for producing 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound, for example, 4-chlorophthalic acid is dimerized in an aqueous solvent in the presence of a palladium catalyst, and selected. A method for producing biphenyltetracarboxylic acid at a rate of 85% is disclosed (for example, see Non-Patent Document 1). However, in this method, in order to obtain the target product with high selectivity, activation treatment of the palladium catalyst with hydrochloric acid is indispensable, and there is a problem as an industrial production method.
Journal of Synthetic Organic Chemistry, Vol. 57, No. 5, p. 435, 1999

  The problem to be solved by the present invention is to solve the above-mentioned problems, and in a simple manner, 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound group and 3,3 ′, 4,4′- An industrially suitable 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound group and 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound production method for obtaining a biphenyltetracarboxylic acid compound It is to provide.

  The subject of this invention is general formula (1a) to (1c).

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
This is solved by a group of 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compounds represented by:

  The subject of the present invention is also a palladium compound and a phosphine ligand, or a palladium complex obtained by a reaction of a palladium compound and a phosphine ligand, and a base in the presence of the general formula (1).

(In the formula, R is as defined above, and X represents a halogen atom.)
4-halogeno-o-phthalic acid compound represented by the general formula (2)

（式中、Ｒは、前記と同義である。）
で示される4-シクロヘキセニルジカルボン酸化合物とを反応させることを特徴とする、一般式（１ａ）から（１ｃ）

(In the formula, R is as defined above.)
And a 4-cyclohexenyl dicarboxylic acid compound represented by the general formula (1a) to (1c):

(In the formula, R is as defined above.)
3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compounds represented by the general formula (4)

(In the formula, R is as defined above.)
It can also be solved by a method for producing a 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound represented by

  According to the present invention, 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound group and 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound are obtained industrially by a simple method. A suitable 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound group and a method for producing a 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound can be provided.

  The 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound group of the present invention is represented by the above general formulas (1a) to (1d). In the general formulas (1a) to (1d), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. It is done. These groups include various isomers, and the hydrogen atom of the alkyl group may be substituted with a group that does not participate in the reaction. The 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound group is a positional isomer having different double bond positions as shown in (1a) to (1d), and is described later in the present invention. It is considered that (1a) produced in the reaction of (1a) isomerizes to produce (1b) to (1d). All of these compound groups are active ingredients as raw materials for 3,3 ′, 4,4′-biphenyltetracarboxylic acid compounds.

  The 4-halogeno-o-phthalic acid compound used in the reaction of the present invention is represented by the general formula (2). In the general formula (2), R is as defined in the general formula (1), X is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The 4-cyclohexenyl dicarboxylic acid compound used in the reaction of the present invention is represented by the general formula (3). In the general formula (3), R has the same definition as that defined in the general formula (1).

  The amount of the 4-cyclohexenyl dicarboxylic acid compound to be used is preferably 1 to 100 mol, more preferably 1 to 10 mol, per 1 mol of the 4-halogeno-o-phthalic acid compound.

  Examples of the palladium compound used in the reaction of the present invention include palladium salts such as palladium acetate; palladium complexes such as tris (dibenzylideneacetone) dipalladium; palladium-supported catalysts such as palladium / carbon, preferably Palladium complexes, more preferably tris (dibenzylideneacetone) dipalladium are used. In addition, you may use these palladium compounds individually or in mixture of 2 or more types.

  The amount of the palladium compound used is preferably 0.1 mol% to 100 mol%, more preferably 0.1 mol% to 10 mol%, based on 1 mol of the 4-halogeno-o-phthalic acid compound.

  Examples of the phosphine ligand used in the reaction of the present invention include trialkylphosphines such as tri-n-butylphosphine, tri-t-butylphosphine and tricyclohexylphosphine; triphenylphosphine, tri-o-tolylphosphine and the like. The triarylphosphine is preferably trialkylphosphine, more preferably tri-t-butylphosphine. In addition, you may use these phosphine ligands individually or in mixture of 2 or more types.

  The amount of the phosphine ligand to be used is preferably 1 to 100 mol, more preferably 1 to 10 mol, per 1 mol of the palladium atom of the palladium compound.

  Examples of the base used in the reaction of the present invention include organic amines such as triethylamine and dicyclohexylmethyl; pyridines such as pyridine and methylpyridine; alkali metal phosphates such as trisodium phosphate and tripotassium phosphate; phosphorus Alkali metal hydrogen phosphates such as dipotassium acid monohydrogen; Alkali metal acetates such as sodium acetate and potassium acetate; Alkali metal carbonates such as sodium carbonate and potassium carbonate; Alkali metal carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate Hydrogen salt; Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; Alkali metal alkoxides such as sodium methoxide and potassium methoxide can be mentioned, preferably alkali metal carbonates, organic amines, more preferably organic Amines are used. In addition, you may use these bases individually or in mixture of 2 or more types.

  The amount of the base used is preferably 1 to 100 mol, more preferably 1 to 10 mol, per 1 mol of the 4-halogeno-o-phthalic acid compound.

  The reaction of the present invention is desirably carried out in an organic solvent, and the organic solvent used is not particularly limited as long as it does not inhibit the reaction. For example, nitriles such as acetonitrile and propionitrile; N-methylpyrrolidinone, Amides such as N, N-dimethylacetamide and N, N-dimethylformamide; Aromatic hydrocarbons such as toluene and xylene; and ethers such as tetrahydrofuran and dioxane are preferable, but amides, imides and ethers are preferable. More preferably, N, N′-dimethylimidazolidinone, dioxane is used. In addition, you may use these organic solvents individually or in mixture of 2 or more types.

  The amount of the organic solvent to be used is preferably 1 to 100 mol, more preferably 1 to 20 mol, per 1 mol of the 4-halogeno-o-phthalic acid compound.

  In the reaction of the present invention, for example, a 4-halogeno-o-phthalic acid compound, a 4-cyclohexenyl dicarboxylic acid compound, a palladium compound, a phosphine ligand, a base and an organic solvent are mixed (in advance, a palladium compound and a phosphine compound are mixed). This may be carried out by a method of reacting with a ligand to form a palladium complex, which may be used without isolation or isolation), and a reaction with stirring. The reaction temperature at that time is preferably 0 to 200 ° C., more preferably 20 to 150 ° C., and the reaction pressure is not particularly limited.

  According to the present invention, 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound group and 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound are obtained. It can be isolated and purified by general methods such as extraction, filtration, concentration, distillation, recrystallization, column chromatography and the like.

  Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.

Example 1 ([R = methyl group]; synthesis of methyl 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylate group and methyl 3,3 ′, 4,4′-biphenyltetracarboxylate)
Tris (dibenzylidene) dipalladium 0.30 g (0.33 mmol), 10 wt% tri-t-butylphosphine hexane solution 0.26 g (0.13 mmol) was added to a 100 ml internal flask equipped with a stirrer, thermometer and reflux condenser. ), 4.10 g (22.32 mol) of dimethyl 4-chloro-o-phthalate, 8.76 g (44.1 mmol) of methyl 3,4-cyclohexylene dicarboxylate, 4.74 g (24.27 mmol) of dicyclohexylmethylamine and N, N′-dimethylimidazo After adding 36 ml of ridinone, the mixture was reacted at 140 ° C. for 3 hours with stirring. After completion of the reaction, 200 ml of toluene was added to the reaction solution, followed by washing 10 times with 100 ml of a saturated sodium chloride aqueous solution, and the toluene layer was dried over magnesium sulfate. After filtration, the filtrate was concentrated under source pressure, and the concentrate was purified by flash column chromatography (hexane / ethyl acetate = 9/1 (volume ratio)) to obtain 2.94 g as a yellow oil. When this was analyzed by gas chromatography, the tetramethyl group of 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylate and the tetramethyl 3,3 ′, 4,4′-biphenyltetracarboxylate were 7: 3 mixture.
The spectrum data of the gas chromatography-mass spectrometry (GC-MS) is shown in FIG.

  In addition, 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid tetramethyl group (that is, methyl 3,3 ′, 4,4 ′-(6-cyclohexenylphenyl) tetracarboxylate, 3,3 ′ , 4,4 '-(1-Cyclohexenyl) phenyl tetracarboxylate, 3,3', 4,4 '-(5-cyclohexenyl) phenyl tetracarboxylate and 3,3', 4,4'- (Mixture of (5-cyclohexenyl) phenyl tetracarboxylate) is a novel compound represented by the following physical property values.

¹ H-NMR (CDCl ₃ , δ (ppm));
[Tetramethyl group of 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid]
Peaks attributable to hydrogen on the benzene ring; 7.72 (1H), 7.52 (1H), 7.39 (1H)
Peaks attributable to hydrogen of methyl group; 3.91 (3H), 3.90 (3H), 3.77 (3H), 3.73 (3H)
Peaks attributable to hydrogen of methine group and methylene group; 7.20 to 7.24 (1H), 2.90 to 3.00 (1H), 2.57 to 2.67 (1H), 2.30 to 2.35 (2H), 1.91 to 2.06 (2H)
CI-MS (m / e); 391 (M + 1)

[Tetramethyl 3,3 ', 4,4'-biphenyltetracarboxylic acid]
Peaks attributed to hydrogen on the biphenyl group; 7.94 (2H), 7.87 (2H), 7.77 (2H)
Peaks attributable to hydrogen of methyl group; 3.95 (6H), 3.94 (6H)
CI-MS (m / e); 387 (M + 1)

Example 2 ([R = methyl group]; synthesis of methyl 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylate group and methyl 3,3 ′, 4,4′-biphenyltetracarboxylate)
Tris (dibenzylidene) dipalladium 0.300 g (0.33 mmol), 10 wt% tri-t-butylphosphine hexane 0.57 g (0.26 mmol) was added to a 25-ml three-neck flask equipped with a stirrer, thermometer and reflux condenser , 4-chloro-o-phthalate dimethyl 1.00 g (4.37 mmol), methyl 3,4-cyclohexylene dicarboxylate 1.73 g (8.74 mmol), dicyclohexylmethylamine 0.94 g (4.81 mmol) and dioxane 10 ml were added and stirred. The reaction was carried out at 100 ° C. for 6 hours. After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). As a result, the tetramethyl group of 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylate was 26.3%, 3,3 ′, 4, 23.2% tetramethyl 4′-biphenyltetracarboxylate was produced.

Example 3 ([R = methyl group]; synthesis of methyl 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylate group and methyl 3,3 ′, 4,4′-biphenyltetracarboxylate)
Tris (dibenzylidene) dipalladium 0.051 g (0.056 mmol), 10 wt% tri-t-butylphosphine hexane 0.57 g (0.26 mmol) were added to a 25-ml three-neck flask equipped with a stirrer, thermometer and reflux condenser , Dimethyl 4-bromo-o-phthalate (1.00 g, 3.68 mmol), methyl 3,4-cyclohexylene dicarboxylate (3.64 g, 18.4 mmol), dicyclohexylmethylamine (0.79 g, 4.04 mmol) and dioxane (10 ml) were added and stirred. The reaction was carried out at 100 ° C. for 6 hours. After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). As a result, the tetramethyl group of 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylate was 58.9%, 3,3 ′, 4, 11.8% of tetramethyl 4′-biphenyltetracarboxylate was produced.

Example 4 ([R = methyl group]; synthesis of methyl 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylate group and methyl 3,3 ′, 4,4′-biphenyltetracarboxylate)
Tris (dibenzylidene) dipalladium 0.043g (0.047mmol), 10wt% tri-t-butylphosphinehexane Then, dimethyl 4-iodo-o-phthalate 1.00 g (3.12 mmol), methyl 3,4-cyclohexenedicarboxylate 1.24 g (6.26 mmol), tributylamine 0.82 ml (3.44 mmol) and dioxane 10 ml were added and stirred. The reaction was carried out at 100 ° C. for 6 hours. After completion of the reaction, the reaction solution was analyzed by gas chromatography (internal standard method). As a result, the tetramethyl group of 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylate was 12.3%, 3,3 ′, 4, 38.7% of tetramethyl 4′-biphenyltetracarboxylate was produced.

  The present invention relates to a 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound group and a method for producing a 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound. 3,3 ′, 4,4′-biphenyltetracarboxylic acid compounds are widely known to be useful compounds as raw materials for polyimide and the like. On the other hand, the 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound group can be derived into a 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound by dehydrogenation, for example. It is a useful compound that can be used.

2 is spectrum data of gas chromatography-mass spectrometry (GC-MS) of the reaction solution of Example 1.

Claims (7)

From general formulas (1a) to (1d)

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
A mixture containing all of the 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound represented by the formula: In the presence of a palladium compound and a phosphine ligand, or a palladium complex obtained by a reaction between a palladium compound and a phosphine ligand, and a base, the compound represented by the general formula (1)

(In the formula, R is as defined above, and X represents a halogen atom.)
4-halogeno-o-phthalic acid compound represented by the general formula (2)

(In the formula, R is as defined above.)
And a 4-cyclohexenyl dicarboxylic acid compound represented by the general formula (1a) to (1d):

(In the formula, R is as defined above.)
And a mixture containing all the 3,3 ′, 4,4′-cyclohexenylphenyltetracarboxylic acid compound represented by the formula (4)

(In the formula, R is as defined above.)
A method for producing a 3,3 ′, 4,4′-biphenyltetracarboxylic acid compound represented by the formula:   The process according to claim 2, wherein the reaction is carried out in an organic solvent.   The method according to claim 2, wherein the palladium compound is tris (dibenzylidene) dipalladium (II).   The process according to claim 2, wherein the phosphine ligand is trialkylphosphine.   The process according to claim 2, wherein the base is an organic amine.   The method according to claim 3, wherein the organic solvent is an amide, an imide, an ether, or a mixed solvent thereof.

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