JP4961773B2 - Aromatic carboxylic acids and acid halides thereof - Google Patents

Description

  The present invention relates to aromatic carboxylic acids and acid halides thereof.

Aromatic carboxylic acids having two carboxyl groups per molecule and acid halides thereof are used as raw materials for aromatic polyamide resins, polyarylate resins, polybenzoxazole resins and polybenzothiazole resins. For these resins, resins having various structures are synthesized according to the use, and various structures corresponding to the resin structure are selected and used for aromatic carboxylic acids and acid halides thereof.
On the other hand, since these resins are generally thermoplastic polymers and have high heat resistance, they are often used for applications exposed to high-temperature environments. In addition, in these resins, as a means for increasing heat resistance, attempts have been made to introduce thermosetting substituents, and aromatics having two carboxyl groups in one molecule into which thermosetting substituents are introduced. Although technical examples of carboxylic acids and acid halides thereof are disclosed (for example, see Non-Patent Document 1), further improvements in low dielectric properties and mechanical strength, which are characteristics of resins using these, are further desired. It is rare.
B. J. et al. Jensen and P.M. M.M. Hergenroter, Journal of Polymer Science: Polymer Chemistry Edition, Vol. 23, 2233-2246, 1985

  An object of the present invention is to provide an aromatic carboxylic acid and an acid halide thereof that are suitable for the above-mentioned use and are a raw material for a resin having excellent heat resistance.

  The present invention is achieved by the following items (1) to (4).

(1) An aromatic carboxylic acid represented by the general formula (1).

（式（１）中、Ｙは、水素原子、アルキル基、又は芳香族基を示し、Ａｒは芳香族基を示し、式（１）で表される芳香族カルボン酸構造中の水素原子は、アダマンタン構造を含む基で置換されていても良い。前記アダマンタン構造を含む基は、炭素数１以上２０以下のアルキル基を有していても良い。ｎは１〜５の整数である。ｍは１〜４の整数である。）

(In formula (1), Y represents a hydrogen atom, an alkyl group, or an aromatic group, Ar represents an aromatic group, and the hydrogen atom in the aromatic carboxylic acid structure represented by formula (1) is The group containing an adamantane structure may be substituted, the group containing an adamantane structure may have an alkyl group having 1 to 20 carbon atoms, n is an integer of 1 to 5. m is It is an integer of 1 to 4.)

(2) The aromatic carboxylic acid according to item (1), wherein the aromatic carboxylic acid contains an aromatic group as Y in the general formula (1).
(3) The aromatic carboxylic acid according to (1) or (2), wherein the aromatic carboxylic acid has a phenyl group as the aromatic group.
(4) An aromatic halide of an aromatic carboxylic acid having a structure in which the carboxyl group is substituted with a carbonyl halide group in the aromatic carboxylic acid described in any one of the items (1) to (3) .

  According to the present invention, an aromatic carboxylic acid represented by the general formula (1) and an acid halide of the aromatic carboxylic acid can be obtained, and these are useful as raw materials for polymers, particularly condensed polymers. . When used in a polymer, the aromatic monocarboxylic acid compound in which n is 1 in the general formula (1) can be introduced into the side chain and terminal of the polymer, and the aromatic dicarboxylic acid compound in which n is 2 is Aromatic carboxylic acid compounds having n of 3 to 5 can be directly introduced into the main chain of the polymer, and can be directly introduced into the main chain of the branched polymer to improve the properties of the polymer. Useful.

  The present invention is an aromatic carboxylic acid represented by the general formula (1). In the aromatic carboxylic acid represented by the general formula (1), Y represents a hydrogen atom, an alkyl group, or an aromatic group, and Ar represents an aromatic group. Examples of the alkyl group include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group. Absent. With these, a resin having solubility can be obtained. Examples of the aromatic group include, but are not limited to, a phenyl group, a naphthalene group, an anthracene group, and a phenanthrene group. Of these, a phenyl group is particularly preferred because of its excellent resin solubility. When Y is an aromatic group, Y and Ar may be the same as or different from each other. Examples where the aromatic group is a phenyl group include the following formula (2), formula (3) and formula (4).

（式（２）中、Ｙ、ｎ及びｍは、上記一般式（１）におけるＹ、ｎ及びｍと同じである。）

(In the formula (2), Y, n and m are the same as Y, n and m in the general formula (1).)

（式（３）中、ｎ及びｍは、上記一般式（１）におけるｎ及びｍと同じである。）

(In formula (3), n and m are the same as n and m in the general formula (1).)

（式（４）中、ｎは、上記一般式（１）におけるｎと同じである。）

(In formula (4), n is the same as n in the general formula (1)).

  The hydrogen atom on the aromatic carboxylic acid in the present invention may be substituted with a group containing an adamantane structure. However, hydrogen in at least one carboxyl group is not substituted. The group containing an adamantane structure may have an alkyl group having 1 to 20 carbon atoms. In any of the above formulas, n is an integer of 1 to 5. m is an integer of 1-4.

  The aromatic carboxylic acid of the present invention can be used as a raw material for a polymer such as a condensation polymer. In that case, for example, in the general formula (1), an aromatic monocarboxylic acid compound in which n is 1 is high. An aromatic dicarboxylic acid compound in which n is 2 can be introduced directly into the main chain of the polymer, and an aromatic carboxylic acid compound in which n is 3-5 is The polymer can be directly introduced into the main chain of the branched polymer, and the properties of the polymer can be improved.

  Examples of the group containing an adamantane structure include a group having a diamondoid structure having an adamantane structure as a basic unit and a group having a polyadamantane structure in which two or more adamantanes are bonded. Examples of the group having the diamondoid structure include an adamantyl group, a diamantyl group, a triamantyl group, a tetramantyl group, a pentamantyl group, a hexamantyl group, a heptamantyl group, an octamantyl group, a nonamantyl group, a decamantyl group, an undecamantyl group, and an adamantylphenyl group. , Diamantylphenyl group, triamantylphenyl group, tetramantylphenyl group, pentamantylphenyl group, hexamantylphenyl group, heptamantylphenyl group, octamantylphenyl group, nonamantylphenyl group, decaman Tilphenyl group, undecamantylphenyl group, adamantylphenoxyphenyl group, diamantylphenoxyphenyl group, triamantylphenoxyphenyl group, tetramantylphenoxyphenyl group, Examples include tamantylphenoxyphenyl group, hexamantylphenoxyphenyl group, heptamantylphenoxyphenyl group, octamantylphenoxyphenyl group, nonamantylphenoxyphenyl group, decamantylphenoxyphenyl group, and undecamantylphenoxyphenyl group. Examples of the group having the polyadamantane structure include 1,1′-biadamantyl groups and 2,2′-biadamantyl groups, such as biadamantyl groups, 1,1 ′, 1 ″ -triadamantyl groups, and 2,2 Triadamantyl groups such as', 2 ″ -triadamantyl group, 1,1 ′, 1 ″, 1 ′ ″-tetraadamantyl group and 2,2 ′, 2 ″, 2 ′ ″-tetraadamantyl group Tetraadamantyl groups such as 1,1 ′, 1 ″, 1 ′ ″, 1 ″ ″-pentaada 1,2 ′, 2 ″, 2 ′ ″, 2 ″ ″-pentaadamantyl groups such as pentaadamantyl group, 1,1 ′, 1 ″, 1 ′ ″, 1 ′ ″ ', 1' '' ''-hexaadamantyl group and 2,2 ', 2' ', 2' '', 2 '' '', 2 '' '' ''-hexaadamantyl group such as hexaadamantyl group, hepta Adamantyl group, octaadamantyl group, nonaadamantyl group, decaadamantyl group, undecaadamantyl group, biadamantylphenyl group, triadamantylphenyl group, tetraadamantylphenyl group, pentaadamantylphenyl group, hexaadamantylphenyl group, heptaadamantylphenyl group, Octaadamantylphenyl group, Nonaadamantylphenyl group, Decaadamantylphenyl group, Undecaadamanti Ruphenyl group, biadamantylphenoxyphenyl group, triadamantylphenoxyphenyl group, tetraadamantylphenoxyphenyl group, pentaadamantylphenoxyphenyl group, hexaadamantylphenoxyphenyl group, heptaadamantylphenoxyphenyl group, octaadamantylphenoxyphenyl group, nonadamantylphenoxyphenyl group , A decaadamantyl phenoxyphenyl group, an undecaadamantyl phenoxyphenyl group, and the like, but are not limited thereto. With these, a resin having heat resistance can be obtained.

  The group containing an adamantane structure may have an alkyl group having 1 to 20 carbon atoms. Examples of the alkyl group include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group. Absent. By these, the resin which has solubility and heat resistance can be obtained.

As the aromatic carboxylic acid of the present invention, for example, as dicarboxylic acid,
3- (1,3-butadiynyl) phthalic acid, 4- (1,3-butadiynyl) phthalic acid, 3- (4- (n-hexyl) -1,3-butadiynyl) phthalic acid, 4- (4- ( n-hexyl) -1,3-butadiynyl) phthalic acid, 3- (4-phenyl-1,3-butadiynyl) phthalic acid, 4- (4-phenyl-1,3-butadiynyl) phthalic acid, 3- (4 -(4- (1-adamantyl) phenyl) -1,3-butadiynyl) phthalic acid, 3- (4- (4- (2-adamantyl) phenyl) -1,3-butadiynyl) phthalic acid, 4- (4 -(4- (1-adamantyl) phenyl) -1,3-butadiynyl) phthalic acid, 4- (4- (4- (2-adamantyl) phenyl) -1,3-butadiynyl) phthalic acid, 3- (4 -(4- (1- (3,5-dimethyladam Til)) phenyl) -1,3-butadiynyl) phthalic acid, 3- (4- (4- (2- (1,3-dimethyladamantyl)) phenyl) -1,3-butadiynyl) phthalic acid, 4- ( 4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) phthalic acid, 4- (4- (4- (2- (1,3-dimethyladamantyl)) phenyl ) -1,3-butadiynyl) phthalic acid, 3- (4- (4- (1-diamantyl) phenyl) -1,3-butadiynyl) phthalic acid, 3- (4- (4- (2-diamantyl) phenyl) ) -1,3-butadiynyl) phthalic acid, 4- (4- (4- (1-diamantyl) phenyl) -1,3-butadiynyl) phthalic acid, 4- (4- (4- (2-diamantyl) phenyl) ) -1,3-Butadiynyl) Phosphoric acid, 3- (4- (4- (1-tetramantyl) phenyl) -1,3-butadiynyl) phthalic acid, 3- (4- (4- (2-tetramantyl) phenyl) -1,3-butadiynyl) Phthalic acid, 4- (4- (4- (1-tetramantyl) phenyl) -1,3-butadiynyl) phthalic acid, 4- (4- (4- (2-tetramantyl) phenyl) -1,3-butadiynyl) Phthalic acid, 3- (4- (4- (3- (1,1′-biadamantyl)) phenyl) -1,3-butadiynyl) phthalic acid, 3- (4- (4- (2- (1, 1'-biadamantyl)) phenyl) -1,3-butadiynyl) phthalic acid, 4- (4- (4- (3- (1,1'-biadamantyl)) phenyl) -1,3-butadiynyl) phthalate Acid, 4- (4- (4- (2- (1,1′-biadamantyl) ) Phenyl) -1,3-butadiynyl) phthalic acid, 3- (4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) phthalic acid, 3- (4- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) -1, 3-butadiynyl) phthalic acid, 4- (4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl ) Phthalic acid, 4- (4- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) phthalic acid 3,4-bis (4-phenyl-1,3-butadiynyl) phthalic acid, 3,5-bis (4-phenyl-1,3-butadiynyl) ) Phthalic acid, phthalic acid, etc.
4- (1,3-butadiynyl) isophthalic acid, 5- (1,3-butadiynyl) isophthalic acid, 4- (4- (n-hexyl) -1,3-butadiynyl) isophthalic acid, 5- (4- ( n-hexyl) -1,3-butadiynyl) isophthalic acid, 4- (4-phenyl-1,3-butadiynyl) isophthalic acid, 5- (4-phenyl-1,3-butadiynyl) isophthalic acid, 4- (4 -(4- (1-adamantyl) phenyl) -1,3-butadiynyl) isophthalic acid, 4- (4- (4- (2-adamantyl) phenyl) -1,3-butadiynyl) isophthalic acid, 5- (4 -(4- (1-adamantyl) phenyl) -1,3-butadiynyl) isophthalic acid, 5- (4- (4- (2-adamantyl) phenyl) -1,3-butadiynyl) isophthalic acid, 4- ( -(4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid, 4- (4- (4- (2- (1,3-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid, 5- (4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid, 5- (4- (4- (2- (1,3-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid, 4- (4- (4- (1-diamantyl) phenyl) -1,3-butadiynyl) isophthalic acid, 4 -(4- (4- (2-diamantyl) phenyl) -1,3-butadiynyl) isophthalic acid, 5- (4- (4- (1-diamantyl) phenyl) -1,3-butadiynyl) isophthalic acid, 5 − 4- (4- (2-diamantyl) phenyl) -1,3-butadiynyl) isophthalic acid, 4- (4- (4- (1-tetramantyl) phenyl) -1,3-butadiynyl) isophthalic acid, 4- ( 4- (4- (2-tetramantyl) phenyl) -1,3-butadiynyl) isophthalic acid, 5- (4- (4- (1-tetramantyl) phenyl) -1,3-butadiynyl) isophthalic acid, 5- ( 4- (4- (2-tetramantyl) phenyl) -1,3-butadiynyl) isophthalic acid, 4- (4- (4- (3- (1,1′-biadamantyl)) phenyl) -1,3- Butadiynyl) isophthalic acid, 4- (4- (4- (2- (1,1′-biadamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid, 5- (4- (4- (3- ( 1,1'-biadamantyl )) Phenyl) -1,3-butadiynyl) isophthalic acid, 5- (4- (4- (2- (1,1′-biadamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid, 4- ( 4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) isophthalic acid, 4- (4- ( 4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) isophthalic acid, 5- (4- (4- ( 7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) isophthalic acid, 5- (4- (4- (2- (2- ( 1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) Isophthalic acid such as sophthalic acid, 4,5-bis (4-phenyl-1,3-butadiynyl) isophthalic acid, 4,6-bis (4-phenyl-1,3-butadiynyl) isophthalic acid,
2- (1,3-butadiynyl) terephthalic acid, 2- (4- (n-hexyl) -1,3-butadiynyl) terephthalic acid, 2- (4-phenyl-1,3-butadiynyl) terephthalic acid, 2- (4- (4- (1-adamantyl) phenyl) -1,3-butadiynyl) terephthalic acid, 2- (4- (4- (2-adamantyl) phenyl) -1,3-butadiynyl) terephthalic acid, 2- (4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) terephthalic acid, 2- (4- (4- (2- (1,3-dimethyladamantyl))) Phenyl) -1,3-butadiynyl) terephthalic acid, 2- (4- (4- (1-diamantyl) phenyl) -1,3-butadiynyl) terephthalic acid, 2- (4- (4- (2-diamantyl)) Phenyl -1,3-butadiynyl) terephthalic acid, 2- (4- (4- (1-tetramantyl) phenyl) -1,3-butadiynyl) terephthalic acid, 2- (4- (4- (2-tetramantyl) phenyl) -1,3-butadiynyl) terephthalic acid, 2- (4- (4- (3- (1,1′-biadamantyl)) phenyl) -1,3-butadiynyl) terephthalic acid, 2- (4- (4 -(2- (1,1'-biadamantyl)) phenyl) -1,3-butadiynyl) terephthalic acid, 2- (4- (4- (7- (1,1 '-(3,5,3')) , 5′-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) terephthalic acid, 2- (4- (4- (2- (1,1 ′-(3,5,3 ′, 5 ′) -Tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) terephthal Terephthalic acid such as phosphoric acid, 2,3-bis (4-phenyl-1,3-butadiynyl) terephthalic acid, 2,5-bis (4-phenyl-1,3-butadiynyl) terephthalic acid, etc.
As monocarboxylic acid,
2- (1,3-butadiynyl) benzoic acid, 3- (1,3-butadiynyl) benzoic acid, 4- (1,3-butadiynyl) benzoic acid, 2- (4- (n-hexyl) -1,3 -Butadiynyl) benzoic acid, 3- (4- (n-hexyl) -1,3-butadiynyl) benzoic acid, 4- (4- (n-hexyl) -1,3-butadiynyl) benzoic acid, 2- (4 -Phenyl-1,3-butadiynyl) benzoic acid, 3- (4-phenyl-1,3-butadiynyl) benzoic acid, 4- (4-phenyl-1,3-butadiynyl) benzoic acid, 2- (4- ( 4- (1-adamantyl) phenyl) -1,3-butadiynyl) benzoic acid, 2- (4- (4- (2-adamantyl) phenyl) -1,3-butadiynyl) benzoic acid, 3- (4- ( 4- (1-adamantyl) phenyl) -1,3- Tadiynyl) benzoic acid, 3- (4- (4- (2-adamantyl) phenyl) -1,3-butadiynyl) benzoic acid, 4- (4- (4- (1-adamantyl) phenyl) -1,3- Butadiynyl) benzoic acid, 4- (4- (4- (2-adamantyl) phenyl) -1,3-butadiynyl) benzoic acid, 2- (4- (4- (1- (3,5-dimethyladamantyl)) Phenyl) -1,3-butadiynyl) benzoic acid, 2- (4- (4- (2- (1,3-dimethyladamantyl)) phenyl) -1,3-butadiynyl) benzoic acid, 3- (4- ( 4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) benzoic acid, 3- (4- (4- (2- (1,3-dimethyladamantyl)) phenyl) -1 , 3-Butadiynyl) benzoic acid, 4 (4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) benzoic acid, 4- (4- (4- (2- (1,3-dimethyladamantyl)) Phenyl) -1,3-butadiynyl) benzoic acid, 2- (4- (4- (1-diamantyl) phenyl) -1,3-butadiynyl) benzoic acid, 2- (4- (4- (2-diamantyl)) Phenyl) -1,3-butadiynyl) benzoic acid, 3- (4- (4- (1-diamantyl) phenyl) -1,3-butadiynyl) benzoic acid, 3- (4- (4- (2-diamantyl)) Phenyl) -1,3-butadiynyl) benzoic acid, 4- (4- (4- (1-diamantyl) phenyl) -1,3-butadiynyl) benzoic acid, 4- (4- (4- (2-diamantyl)) Phenyl) -1,3-butadiynyl) Benzoic acid, 2- (4- (4- (1-tetramantyl) phenyl) -1,3-butadiynyl) benzoic acid, 2- (4- (4- (2-tetramantyl) phenyl) -1,3-butadiynyl) Benzoic acid, 3- (4- (4- (1-tetramantyl) phenyl) -1,3-butadiynyl) benzoic acid, 3- (4- (4- (2-tetramantyl) phenyl) -1,3-butadiynyl) Benzoic acid, 4- (4- (4- (1-tetramantyl) phenyl) -1,3-butadiynyl) benzoic acid, 4- (4- (4- (2-tetramantyl) phenyl) -1,3-butadiynyl) Benzoic acid, 2- (4- (4- (3- (1,1′-biadamantyl)) phenyl) -1,3-butadiynyl) benzoic acid, 2- (4- (4- (2- (1, 1'-biadamantyl)) phenyl) -1,3 Butadiynyl) benzoic acid, 3- (4- (4- (3- (1,1′-biadamantyl)) phenyl) -1,3-butadiynyl) benzoic acid, 3- (4- (4- (2- ( 1,1′-biadamantyl)) phenyl) -1,3-butadiynyl) benzoic acid, 4- (4- (4- (3- (1,1′-biadamantyl)) phenyl) -1,3-butadiynyl ) Benzoic acid, 4- (4- (4- (2- (1,1′-biadamantyl)) phenyl) -1,3-butadiynyl) benzoic acid, 2- (4- (4- (7- (1 , 1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) benzoic acid, 2- (4- (4- (2- (1,1 ′) -(3,5,3 ', 5'-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) benzoic acid, 3- ( -(4- (7- (1,1 '-(3,5,3', 5'-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) benzoic acid, 3- (4- (4 -(2- (1,1 '-(3,5,3', 5'-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) benzoic acid, 4- (4- (4- (7 -(1,1 '-(3,5,3', 5'-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) benzoic acid, 4- (4- (4- (2- (1 , 1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) -1,3-butadiynyl) benzoic acid, 3,4-bis (4-phenyl-1,3-butadiynyl) Benzoic acid such as benzoic acid, 3,5-bis (4-phenyl-1,3-butadiynyl) benzoic acid, and the like,
As tricarboxylic acid,
5- (1,3-butadiynyl) -1,2,3-benzenetricarboxylic acid, 5- (4- (n-hexyl) -1,3-butadiynyl) -1,2,3-benzenetricarboxylic acid, 5- (4-Phenyl-1,3-butadiynyl) -1,2,3-benzenetricarboxylic acid, 5- (4- (4- (1-adamantyl) phenyl) -1,3-butadiynyl) -1,2,3 -Benzenetricarboxylic acid, 5- (4- (4- (2-adamantyl) phenyl) -1,3-butadiynyl) -1,2,3-benzenetricarboxylic acid, 5- (4- (4- (1- ( 3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) -1,2,3-benzenetricarboxylic acid, 5- (4- (4- (2- (1,3-dimethyladamantyl)) phenyl) -1,3-butadiynyl -1,2,3-benzenetricarboxylic acid, 5- (4- (4- (1-diamantyl) phenyl) -1,3-butadiynyl) -1,2,3-benzenetricarboxylic acid, 5- (4- ( 4- (2-diamantyl) phenyl) -1,3-butadiynyl) -1,2,3-benzenetricarboxylic acid, 5- (4- (4- (1-tetramantyl) phenyl) -1,3-butadiynyl)- 1,2,3-benzenetricarboxylic acid, 5- (4- (4- (2-tetramantyl) phenyl) -1,3-butadiynyl) -1,2,3-benzenetricarboxylic acid, 5- (4- (4 -(3- (1,1'-biadamantyl)) phenyl) -1,3-butadiynyl) -1,2,3-benzenetricarboxylic acid, 5- (4- (4- (2- (1,1 ') -Biadamantyl)) phenyl) -1,3 -Butadiynyl) -1,2,3-benzenetricarboxylic acid, 5- (4- (4- (7- (1,1 '-(3,5,3', 5'-tetramethylbiadamantyl))) phenyl ) -1,3-butadiynyl) -1,2,3-benzenetricarboxylic acid, 5- (4- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbi)) Examples include, but are not limited to, 1,2,3-benzenetricarboxylic acid such as adamantyl))) phenyl) -1,3-butadiynyl) -1,2,3-benzenetricarboxylic acid.

  Further, in the aromatic carboxylic acid represented by the general formula (1) of the present invention, the acid halide in which the carboxyl group is substituted with a carbonyl halide group includes hydroxy group contained in the carboxyl group in the aromatic carboxylic acid. A compound in which a group is substituted with a halogen atom such as fluorine, chlorine and bromine.

  The method for producing the aromatic carboxylic acid represented by the general formula (1) of the present invention can be obtained, for example, by subjecting an aromatic carboxylic acid having an ethynyl group and a compound having an ethynyl group to a coupling reaction. Furthermore, the acid halide can be obtained by treating this with a halogenating agent. As one representative example, in the case of the aromatic carboxylic acid represented by the general formula (2), for example, it can be synthesized by the following route.

式（７）及び式（８）中、Ｙ₁は、トリメチルシリル基、ヒドロキシプロピル基、アルキル基、又は芳香族基を示し、式（２）及び式（５）中、Ｙは、水素原子、アルキル基、又は芳香族基を示す。式（２）、式（５）、式（６）、式（７）、及び式（８）中、水素原子は、アダマンタン構造を含む基で置換されていても良い。前記アダマンタン構造を含む基は、炭素数１以上２０以下のアルキル基を有していても良い。ｎは１〜５の整数である。ｍは１〜４の整数である。式（５）中のＸはハロゲン原子を表す。

In Formula (7) and Formula (8), Y ₁ represents a trimethylsilyl group, a hydroxypropyl group, an alkyl group, or an aromatic group. In Formula (2) and Formula (5), Y represents a hydrogen atom or an alkyl group. A group or an aromatic group; In Formula (2), Formula (5), Formula (6), Formula (7), and Formula (8), the hydrogen atom may be substituted with a group containing an adamantane structure. The group containing an adamantane structure may have an alkyl group having 1 to 20 carbon atoms. n is an integer of 1-5. m is an integer of 1-4. X in Formula (5) represents a halogen atom.

  The aromatic carboxylic acid compound having an ethynyl group (general formula (6)) used as the starting material can be synthesized according to the method described in the patent literature (Japanese Patent Application Laid-Open No. 2002-201158, p1-p10). it can.

In the compound having an ethynyl group represented by the general formula (7), examples of the substituent Y ₁ include a group that acts as a protective group. In this case, a trimethylsilyl group, a hydroxypropyl group, and the like are preferable. Further, examples of the substituent Y ₁ include an alkyl group and an aromatic group. Examples of the alkyl group include, but are not limited to, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group. Absent. With these, a resin having solubility can be obtained. Examples of the aromatic group include, but are not limited to, a phenyl group, a naphthalene group, an anthracene group, and a phenanthrene group. Among these, a phenyl group is particularly preferable because of excellent solubility of the resin.
Examples of the compound having an ethynyl group represented by the general formula (7) wherein the substituent Y ₁ is a trimethylsilyl group include trimethylsilylacetylene and the like, and the example where the substituent Y ₁ is a hydroxypropyl group Examples include 2-methyl-3-butyn-2-ol.

Examples of the compound having an ethynyl group represented by the general formula (7), in which the substituent Y ₁ is a phenyl group, include ethynylbenzene, 4- (1-adamantyl) -1-ethynylbenzene, 4- (2-adamantyl) -1-ethynylbenzene, 4- (1- (3,5-dimethyladamantyl))-1-ethynylbenzene, 4- (2- (1,3-dimethyladamantyl))-1-ethynylbenzene 4- (1-diamantyl) -1-ethynylbenzene, 4- (2-diamantyl) -1-ethynylbenzene, 4- (1-tetramantyl) -1-ethynylbenzene, 4- (2-tetramantyl) -1- Ethynylbenzene, 4- (3- (1,1′-biadamantyl))-1-ethynylbenzene, 4- (2- (1,1′-biadamantyl))-1-ethynylben Zen, 4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl)))-1-ethynylbenzene, and 4- (2- (1,1 ′-( 3,5,3 ′, 5′-tetramethylbiadamantyl)))-1-ethynylbenzene, and the like.

  First, an aromatic carboxylic acid compound having an ethynyl group represented by the general formula (6) and a compound having an ethynyl group represented by the general formula (7) are subjected to a coupling reaction, thereby obtaining the general formula (8). The aromatic carboxylic acid compound represented by this is obtained. In the coupling reaction, a catalyst may be used, and examples thereof include a transition metal catalyst such as copper.

Next, in the aromatic carboxylic acid compound represented by the general formula (8) obtained above, when the substituent Y ₁ is a group that acts as a protective group, by treating with a deprotecting agent, the general formula (2) The aromatic carboxylic acid compound represented by this is obtained. On the other hand, when the substituent Y ₁ is an alkyl group or an aromatic group, the general formula (8) and the general formula (2) are the same compound.

  Next, by treating the aromatic carboxylic acid compound represented by the general formula (2) obtained above with a halogenating agent, an acid halide represented by the general formula (5) can be obtained.

Hereinafter, the example of a manufacturing method is demonstrated more concretely.
As a method for obtaining the aromatic carboxylic acid compound represented by the general formula (8), an aromatic carboxylic acid compound having an ethynyl group represented by the general formula (6) and an acetylene represented by the general formula (7) And a compound in which one side is substituted with a protecting group Y ₁ , an alkyl group or an aromatic group Y ₁ in the presence of a catalyst in an inert gas atmosphere such as nitrogen, argon and helium, in a temperature range of 0 to 150 ° C. A reaction product can be obtained by coupling reaction. At this time, the reaction time is not particularly limited. By subjecting the reaction product thus obtained to a separation operation such as concentration and reprecipitation, a compound represented by the general formula (8) can be obtained. It can be purified by column chromatography, recrystallization and the like.

The compound in which _one side of the acetylene represented by the general formula (7) is protected with a protecting group Y ₁ is not limited as long as the protecting group Y ₁ can be deprotected with an alkali metal hydroxide, Trimethylsilylacetylene in which the protective group Y ₁ is a trimethylsilyl group and 3-methyl-1-butyn-3-ol in which the hydroxypropyl group is suitable are preferred.
The compound represented by the general formula (7) is theoretically equivalent to 1 equivalent to the m ethynyl groups of the compound represented by the general formula (6), but the reaction proceeds completely. In order to achieve this, the amount added should be adjusted in the range of 1 to 20 equivalents.

  As the catalyst system, any catalyst system capable of forming a carbon-carbon bond can be used without particular limitation. For example, it is desirable to use copper (II) acetate monohydrate. The amount of copper (II) acetate monohydrate added is not particularly limited, but is between 1 and 30 equivalents with respect to m ethynyl groups of the compound represented by the general formula (6). It is preferable.

  As the solvent used in this reaction, it is preferable to use a mixed solvent of an amine solvent and an alcohol solvent in order to promote the catalytic reaction. Examples of the amine solvent include tertiary amines such as diethylamine, triethylamine, butylamine and tributylamine, and cyclic amines such as pyridine and piperidine. Of these, pyridine is preferred. Examples of the alcohol solvent include methanol, ethanol, butanol, and isopropanol. Of these, methanol is preferred. As a mixing ratio of the amine solvent and the alcohol solvent, the alcohol solvent is preferably 0.1 to 10 times by volume with respect to the amine solvent. The amount used is not particularly specified, but it is preferably 2 to 50 times by weight based on the raw materials used for the synthesis. These solvents are preferably distilled in advance in order to prevent side reactions and catalyst deactivation.

Next, as a method of obtaining the aromatic carboxylic acid compound represented by the general formula (2), by treating the compound represented by the general formula (8) in a solvent in the presence of an alkali metal hydroxide, When the substituent Y ₁ is a protective group such as a trimethylsilyl group or a hydroxypropyl group, a reaction product is obtained by performing deprotection. At this time, the reaction temperature and reaction time are not particularly limited, but the reaction temperature may be in the range of room temperature to the reflux temperature of the solvent. The obtained reaction product is separated from the crystals precipitated by cooling, washed with an alcohol solvent such as methanol, ethanol, butanol and isopropanol, and then dried to obtain an aroma represented by the general formula (2). A group carboxylic acid compound can be obtained. On the other hand, when the substituent Y ₁ is an alkyl group or an aromatic group, the general formula (8) and the general formula (2) are the same compound.

  As the alkali metal hydroxide, potassium hydroxide and sodium hydroxide are preferable, and the addition amount is 3 equivalents or more with respect to the compound represented by the general formula (8), and may be more than this. .

  The reaction solvent is not particularly limited as long as it is other than esters that can react with an alkali metal hydroxide, but alcohol-based solvents such as methanol, ethanol, butanol, and isopropanol, which have high alkali metal hydroxide solubility. Is preferred. The amount of the solvent is not particularly limited, but it is preferable to use 5 to 50 times by weight with respect to the compound represented by the general formula (8) from the viewpoint of operability.

  Of the acid halides of the aromatic carboxylic acid represented by the general formula (5) of the present invention, the acid chloride, the acid bromide and the acid fluoride are the fragrance represented by the general formula (2) obtained above. After reacting the group carboxylic acid in a solvent or an excess amount of a halogenating agent as a solvent in a temperature range of 0 to 150 ° C., the solvent is distilled off, and the resulting solid is washed with a solvent, Further, it can be obtained by recrystallization.

As the halogenating agent in the synthesis of the acid halide represented by the general formula (5), thionyl chloride as a chlorinating agent, phosphorus tribromide as a brominating agent, fluorinated sulfonic acid as a fluorinating agent, etc. It is preferable to use it. The amount of the halogenating agent used is preferably 2 equivalents or more with respect to the aromatic carboxylic acid represented by the general formula (2), and there is no particular upper limit, and when no solvent is used, it is 10 equivalents or more. It can be used in large excess. In the acid halide, the acid iodide can be obtained by allowing an iodinating agent such as phosphorus iodide to act after obtaining the acid chloride.
The solvent is not particularly limited. For example, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane and cyclohexane, dichloromethane, chloroform, carbon tetrachloride, 1, Examples include chlorinated solvents such as 2-dichloroethane and chlorobenzene. These can use arbitrary quantity with respect to the aromatic carboxylic acid represented by General formula (2).

Furthermore, a base such as N, N-dimethylformamide and pyridine may be added in order to accelerate the synthesis reaction of the acid halide represented by the general formula (5).
Further, in order to suppress polymerization at the ethynyl moiety, a polymerization inhibitor such as hydroquinone and hydroquinone monomethyl ether may be added.

  The aromatic carboxylic acid halide represented by the general formula (5) of the present invention is synthesized by organic synthetic chemistry, Vol. 39, No. 4, p. 312-p. 321 (1981) can be used as a polymer raw material by active esterification with 1-hydroxybenzotriazole, 1-hydroxysuccinimide, 2-hydroxypyridine, or the like.

The aromatic carboxylic acid and its acid halide obtained above are converted into a polyamide resin, a polyimide resin precursor, a polybenzoxazole resin precursor, etc. by a condensation reaction with a diamine compound and a bisaminophenol compound. Can do.
Examples of the diamine compound include benzenediamine and naphthalenediamine, and examples of the bisaminophenol compound include dihydroxydiaminobenzene and dihydroxydiaminobiphenyl, but are not limited thereto.

Examples are given below to illustrate the present invention, but the present invention is not limited thereby.
The obtained compound was subjected to mass spectrometry, elemental analysis, ¹ H-NMR measurement, and melting point measurement for property evaluation. The measurement conditions for each characteristic were as follows.

Test method (1) Mass spectrometry (MS): Measured by a field desorption (FD) method using a JMS-700 type manufactured by JEOL Ltd.
(2) Elemental analysis: Carbon and hydrogen were measured by PERKIN ELMER type 2400, and chlorine was measured by a flask combustion titration method.
(3) ¹ H-NMR measurement: Measured at a resonance frequency of 400 MHz using a JNM-GSX400 type manufactured by JEOL.
(4) Melting point measurement: Using a DSC-200 type differential scanning calorimeter (DSC) manufactured by Seiko Electronics, 10 ° C./min. It measured with the temperature increase rate of.

Example 1
(1) [Synthesis of 5-ethynylisophthalic acid]
5-Ethynylisophthalic acid was synthesized according to the method described in the patent literature (Japanese Patent Laid-Open No. 2002-201158, p1-p10).

(2) [Synthesis of 5- (4-phenyl-1,3-butadiynyl) isophthalic acid from 5-ethynylisophthalic acid]
A 4-neck 1-liter flask equipped with a thermometer, a nitrogen inlet tube and a stirrer was charged with 89.6 g (0.449 mol) of copper (II) acetate monohydrate, 250 ml of pyridine and 250 ml of methanol, and nitrogen was added to the flask. And stirred while cooling the flask in an ice bath to obtain a suspension. After 30 minutes, 3.90 g (0.0205 mol) of 5-ethynylisophthalic acid and 5.01 g (0.0491 mol) of ethynylbenzene were added and reacted for 6 hours while cooling in an ice bath and further for 1 hour at room temperature. Thereafter, the reaction solution was poured into 3500 ml of water, the precipitated solid was collected by filtration, and this solid was dried under reduced pressure at 50 ° C. to give 5.12 g of 5- (4-phenyl-1,3-butadiynyl). Isophthalic acid was obtained (yield 86%).

(3) [Synthesis of 5- (4-phenyl-1,3-butadiynyl) isophthalic acid dichloride from 5- (4-phenyl-1,3-butadiynyl) isophthalic acid]
5- (4-Phenyl-1,3-butadiynyl) isophthalic acid 69.7 g (0.24 mol) obtained by repeating the above operation in a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer And 400 ml of 1,2-dichloroethane were charged and cooled to 0 ° C. To this, 391 g (4.5 mol) of thionyl chloride was added dropwise over 1 hour in an atmosphere of 5 ° C. or lower. Thereafter, 4 ml of dimethylformamide and 4 g of hydroquinone were added, followed by stirring at 45 to 50 ° C. for 3 hours. After cooling, the crystals formed upon cooling were removed by filtration, and the crystals were washed with 150 ml of chloroform. The filtrate and the washing solution were combined and concentrated under reduced pressure at 40 ° C. or lower, and the resulting residue was extracted and filtered twice with 200 ml of diethyl ether. Diethyl ether was distilled off from the extract under reduced pressure to obtain a semisolid crude product. This was washed with dry n-hexane and then recrystallized with diethyl ether to obtain 14.9 g of 5- (4-phenyl-1,3-butadiynyl) isophthalic acid dichloride ( Yield 19%).

  The spectral data of 5- (4-phenyl-1,3-butadiynyl) isophthalic acid and 5- (4-phenyl-1,3-butadiynyl) isophthalic acid dichloride obtained above are shown below. These data indicate that the obtained compound is the target product.

[5- (4-Phenyl-1,3-butadiynyl) isophthalic acid (C ₁₈ H ₁₀ O ₄ )]
Appearance: White powder MS (FD) (m / z): 290 (M ⁺ )
Elemental analysis: Theoretical value C: 74.48% H: 3.47%
Measured value C: 74.12% H: 3.14%
¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 7.5 (m, 3H), 7.6 (m, 2H), 8.2 (d, 2H), 8.5 (t, 1H)

[5- (4-Phenyl-1,3-butadiynyl) isophthalic acid dichloride (C ₁₈ H ₈ Cl ₂ O ₂ )]
Appearance: White powder MS (FD) (m / z): 326 (M ⁺ )
Elemental analysis: Theoretical value C: 66.08% H: 2.46% Cl: 21.67%
Actual value C: 66.41% H: 2.08% Cl: 21.70%
¹ H-NMR (400 MHz, CDCl ₃ ): δ 7.4 (m, 3H), 7.5 (m, 2H), 8.5 (d, 2H), 8.7 (t, 1H)
Melting point: 104 ° C. (DSC, 10 ° C./min.)

(Example 2)
(1) [Synthesis of 4- (1- (3,5-dimethyladamantyl)) phenol]
In a 2 liter flask equipped with a thermometer, a Dimroth condenser, a nitrogen inlet, and a stirrer, 77.4 g (0.822 mol) of phenol and 20.0 g (0.0822 mol) of 1-bromo-3,5-dimethyladamantane were added. The mixture was charged, nitrogen was passed through the flask, and the mixture was heated to reflux for 30 minutes while adjusting the temperature to 140 ° C. with an oil bath. Thereafter, 800 mL of water was added, and the mixture was heated to reflux in an oil bath for 10 minutes to obtain a solution separated into two layers. By cooling the solution in an ice bath, the lower orange solution is turned into a white solid, and the white solid is taken out by decantation. The solution is stirred twice in 500 mL of 2% aqueous sodium hydroxide solution and twice in 500 mL of water, filtered. As a result, 7.8 g of 4- (1- (3,5-dimethyladamantyl)) phenol was obtained (yield 37%).

(2) [Synthesis of 1- (1- (3,5-dimethyladamantyl))-4-trifluoromethanesulfonyloxybenzene]
In a 4-neck 100 ml flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, 4.0 g (0.0157 mol) of 4- (1- (3,5-dimethyladamantyl)) phenol obtained above and pyridine were obtained. 20 mL was charged, and nitrogen was passed through the flask to dissolve with stirring. Then, it was made -15 degreeC by cooling with an ice / methanol bath, trifluoromethanesulfonic anhydride was dripped using the dropping funnel, and it stirred at room temperature for 2 hours after completion | finish of dripping. Ethyl acetate 100mL and saturated sodium chloride aqueous solution 100mL were added to the reaction solution, and it moved to the separating funnel. The ethyl acetate layer was taken out and washed twice with 100 mL of saturated aqueous sodium chloride solution. Thereafter, ethyl acetate was distilled off under reduced pressure by a rotary evaporator to obtain 5.4 g of 1- (1- (3,5-dimethyladamantyl))-4-trifluoromethanesulfonoxybenzene (yield 88%).

(3) [Synthesis of 1- (1- (3,5-dimethyladamantyl))-4- (3-hydroxy-3-methyl- (1-butynyl)) benzene]
1- (1- (3,5-dimethyladamantyl))-4-trifluoromethanesulfonyloxy obtained above was added to a four-necked 100 ml flask equipped with a thermometer, a Dimroth condenser, a nitrogen inlet tube and a stirrer. Benzene 2.0 g (0.0051 mol), triphenylphosphine 0.4 g (0.0015 mol), copper iodide 0.2 g (0.0010 mol) and 2-methyl-3-butyn-2-ol 1.1 g (0 0.134 mol) was charged and nitrogen was allowed to flow through the flask. Subsequently, 10 ml of dehydrated triethylamine and 10 ml of dehydrated pyridine were added and dissolved by stirring. After continuously flowing nitrogen for 1 hour, 0.2 g (0.0003 mol) of dichlorobis (triphenylphosphine) palladium was quickly added, and the mixture was heated to reflux for 1 hour while adjusting the temperature to 110 ° C. with an oil bath. Thereafter, triethylamine and pyridine were distilled off under reduced pressure to obtain a viscous brown solution. This was poured into 500 ml of water, and the precipitated solid was collected by filtration, and further washed twice with 500 ml of water, 500 ml of 5 mol / L hydrochloric acid, and 500 ml of water. The solid was dried at 50 ° C. under reduced pressure to give 1.5 g of 1- (1- (3,5-dimethyladamantyl))-4- (3-hydroxy-3-methyl- (1-butynyl)) benzene. (Yield 91%) was obtained.

(4) [Synthesis of 4- (1- (3,5-dimethyladamantyl))-1-ethynylbenzene]
3 L of n-butanol and 226 g (2.72 mol) of potassium hydroxide (85%) were charged in a 5 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, and dissolved by heating under reflux. To this, 110.0 g of 1- (1- (3,5-dimethyladamantyl))-4- (3-hydroxy-3-methyl- (1-butynyl)) benzene obtained by repeating the above-described operation was added. 341 mol) was added and heated to reflux for 30 minutes. This was cooled in an ice bath, and the precipitated crystals were collected by filtration. The crystals were washed twice with 1 liter of ethanol and dried under reduced pressure at 60 ° C. to obtain 81.1 g of 1- (4-ethynylphenyl) -3,5-dimethyladamantane (90%).

(5) [Synthesis of 5-ethynylisophthalic acid]
5-Ethynylisophthalic acid was synthesized according to the method described in Example 1 (1).

(6) [Synthesis of 5- (4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid from 5-ethynylisophthalic acid]
4- (1- (3,5-dimethyladamantyl))-1-ethynylbenzene obtained in Example 2 (4) instead of 5.01 g (0.0491 mol) of ethynylbenzene in Example 1 (2) Similarly, except that 12.98 g (0.0491 mol) was used, 7.98 g of 5- (4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl ) Isophthalic acid was obtained (yield 86%).

(7) From [5- (4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid to 5- (4- (4- (1- (3 Synthesis of 5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid dichloride]
In Example 1 (3), instead of 69.7 g (0.24 mol) of 5- (4-phenyl-1,3-butadiynyl) isophthalic acid, the procedure of Example 2 (6) was repeated. 22.32 g in the same manner except that 108.61 g (0.24 mol) of (4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid was used. Of 5- (4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid dichloride was obtained (yield 19%).

  5- (4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid and 5- (4- (4- (1- (3 The spectral data of 5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid dichloride are shown below. These data indicate that the obtained compound is the target product.

[5- (4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid (C ₃₀ H ₂₈ O ₄ )]
Appearance: White powder MS (FD) (m / z): 452 (M ⁺ )
Elemental analysis: Theoretical value C: 79.62% H: 6.24%
Measured value C: 79.12% H: 6.14%

[5- (4- (4- (1- (3,5-dimethyladamantyl)) phenyl) -1,3-butadiynyl) isophthalic acid dichloride (C ₃₀ H ₂₆ Cl ₂ O ₂ )]
Appearance: White powder MS (FD) (m / z): 488 (M ⁺ )
Elemental analysis: Theoretical value C: 73.62% H: 5.35% Cl: 14.49%
Actual value C: 73.41% H: 5.08% Cl: 14.70%

(Example 3)
(1) [Synthesis of 4-ethynylbenzoic acid]
4-Ethynylbenzoic acid was synthesized according to the method described in the patent document (Japanese Patent Laid-Open No. 2002-201158, p1-p10).

(2) [Synthesis of 4- (4-phenyl-1,3-butadiynyl) benzoic acid from 4-ethynylbenzoic acid]
Instead of 3.90 g (0.0205 mol) of 5-ethynylisophthalic acid in Example 1 (2), 3.00 g (0.0205 mol) of 4-ethynylbenzoic acid obtained by repeating the operation of Example 3 (1) ) Was used in a similar manner to obtain 4.34 g of 4- (4-phenyl-1,3-butadiynyl) benzoic acid (yield 86%).

(3) [Synthesis of 4- (4-phenyl-1,3-butadiynyl) benzoic acid monochloride from 4- (4-phenyl-1,3-butadiynyl) benzoic acid]
In Example 1 (3), instead of 69.7 g (0.24 mol) of 5- (4-phenyl-1,3-butadiynyl) isophthalic acid, the procedure of Example 3 (2) was repeated. 4- (4-Phenyl-1,3-butadiynyl) benzoic acid monochloride 12 except that 59.10 g (0.24 mol) of (4-phenyl-1,3-butadiynyl) benzoic acid was used. 0.07 g was obtained (19% yield).

  The spectral data of 4- (4-phenyl-1,3-butadiynyl) benzoic acid and 4- (4-phenyl-1,3-butadiynyl) benzoic acid monochloride obtained above are shown below. These data indicate that the obtained compound is the target product.

[4- (4-Phenyl-1,3-butadiynyl) benzoic acid (C ₁₇ H ₁₀ O ₂ )]
Appearance: White powder MS (FD) (m / z): 246 (M ⁺ )
Elemental analysis: Theoretical value C: 82.91% H: 4.09%
Measured value C: 82.12% H: 4.14%

[4- (4-Phenyl-1,3-butadiynyl) benzoic acid monochloride (C ₁₇ H ₉ Cl ₁ O ₁ )]
Appearance: White powder MS (FD) (m / z): 264 (M ⁺ )
Elemental analysis: Theoretical value C: 77.14% H: 3.43% Cl: 13.39%
Actual value C: 77.12% H: 3.14% Cl: 14.39%

Example 4
(1) [Synthesis of 5-ethynylisophthalic acid]
5-Ethynylisophthalic acid was synthesized according to the method described in the patent literature (Japanese Patent Laid-Open No. 2002-201158, p1-p10).

(2) [Synthesis of 5- (5-hydroxy-5-methyl-1,3-hexadiynyl) isophthalic acid from 5-ethynylisophthalic acid]
In Example 1 (2), the same procedure was repeated except that 4.13 g (0.0491 mol) of 2-methyl-3-butyn-2-ol was used instead of 5.01 g (0.0491 mol) of ethynylbenzene. 80 g of 5- (5-hydroxy-5-methyl-1,3-hexadiynyl) isophthalic acid was obtained (yield 86%).

(3) [Synthesis of 5- (1,3-butadiynyl) isophthalic acid from 5- (5-hydroxy-5-methyl-1,3-hexadiynyl) isophthalic acid]
A 4-neck flask equipped with a thermometer, a Dimroth condenser, and a stirrer was charged with 3 L of n-butanol and 182.00 g (2.76 mol) of potassium hydroxide (85%) and dissolved by heating and stirring. To this was added 92.57 g (0.34 mol) of 5- (5-hydroxy-5-methyl-1,3-hexadiynyl) isophthalic acid obtained by repeating the procedure of Example 4 (2), and the mixture was heated to reflux for 30 minutes. This was cooled in an ice bath, and the precipitated crystals were collected by filtration. The crystals were washed twice with 1 liter of ethanol and dried under reduced pressure at 60 ° C. to obtain a solid. This solid was dissolved in 20 mL of ion-exchanged water and filtered through 5C filter paper to remove insoluble matters. To this filtrate, 5 mol / L hydrochloric acid was added with stirring until the pH reached 1. The precipitated solid was collected by filtration, and further washed with ion-exchanged water and filtered twice. The obtained solid was dried under reduced pressure at 50 ° C. to obtain 70.63 g of 5- (1,3-butadiynyl) isophthalic acid (yield 97%).
(4) [Synthesis of 5- (1,3-butadiynyl) isophthalic acid dichloride from 5- (1,3-butadiynyl) isophthalic acid]
In Example 1 (3), instead of 69.7 g (0.24 mol) of 5- (4-phenyl-1,3-butadiynyl) isophthalic acid, the procedure of Example 4 (3) was repeated. 11.45 g of 5- (1,3-butadiynyl) isophthalic acid dichloride was obtained in the same manner except that 51.40 g (0.24 mol) of (1,3-butadiynyl) isophthalic acid was used. (Rate 19%).

  The spectral data of 5- (1,3-butadiynyl) isophthalic acid and 5- (1,3-butadiynyl) isophthalic acid dichloride obtained above are shown below. These data indicate that the obtained compound is the target product.

[5- (1,3-butadiynyl) isophthalic acid _{(C 12 H 6 O 4)} ]
Appearance: White powder MS (FD) (m / z): 214 (M ⁺ )
Elemental analysis: Theoretical value C: 67.30% H: 2.82%
Measured value C: 67.12% H: 2.14%

[5- (1,3-butadiynyl) isophthalic acid dichloride (C ₁₂ H ₄ Cl ₂ O ₂ )]
Appearance: White powder MS (FD) (m / z): 250 (M ⁺ )
Elemental analysis: Theoretical value C: 57.41% H: 1.61% Cl: 28.24%
Actual value C: 57.12% H: 1.14% Cl: 28.39%

(Example 5)
(1) [Synthesis of 3,5-diethynylbenzoic acid]
3,5-diethynylbenzoic acid was synthesized with reference to a method described in a patent document (Japanese Patent Application Laid-Open No. 2002-201158, p1-p10).

(2) [Synthesis of 3,5-bis (4-phenyl-1,3-butadiynyl) benzoic acid from 3,5-diethynylbenzoic acid]
Instead of 3.90 g (0.0205 mol) of 5-ethynylisophthalic acid in Example 1 (2), 1.75 g (0 of 3,5-diethynylbenzoic acid obtained by repeating the operation of Example 5 (1) 0.028 mol) was used in the same manner to obtain 3.28 g of 3,5-bis (4-phenyl-1,3-butadiynyl) benzoic acid (yield 86%).

(3) [Synthesis of 3,5-bis (4-phenyl-1,3-butadiynyl) benzoic acid monochloride from 3,5-bis (4-phenyl-1,3-butadiynyl) benzoic acid]
In Example 1 (3), instead of 69.7 g (0.24 mol) of 5- (4-phenyl-1,3-butadiynyl) isophthalic acid, the procedure of Example 5 (2) was repeated. In the same manner except that 88.90 g (0.24 mol) of 5-bis (4-phenyl-1,3-butadiynyl) benzoic acid was used, 3,5-bis (4-phenyl-1,3-butadiynyl) 17.73 g of benzoic acid monochloride was obtained (19% yield).

  The spectral data of 3,5-bis (4-phenyl-1,3-butadiynyl) benzoic acid and 3,5-bis (4-phenyl-1,3-butadiynyl) benzoic acid monochloride obtained above are shown below. Show. These data indicate that the obtained compound is the target product.

[3,5-bis (4-phenyl-1,3-butadiynyl) benzoic acid (C ₂₇ H ₁₄ O ₂ )]
Appearance: White powder MS (FD) (m / z): 370 (M ⁺ )
Elemental analysis: Theoretical value C: 87.55% H: 3.81%
Measured value C: 87.12% H: 3.14%

[3,5-bis (4-phenyl-1,3-butadiynyl) benzoic acid monochloride (C ₂₇ H ₁₃ Cl ₁ O ₁ )]
Appearance: White powder MS (FD) (m / z): 389 (M ⁺ )
Elemental analysis: Theoretical value C: 83.40% H: 3.37% Cl: 9.12%
Actual value C: 83.12% H: 3.14% Cl: 9.39%

  The aromatic carboxylic acid represented by the general formula (1) obtained by the present invention and its acid halide can be active esterified, and the resin obtained therefrom can improve dielectric properties and mechanical properties. Therefore, these are useful as raw materials for polymers, particularly condensation polymers.

Claims (3)

An acid halide of an aromatic carboxylic acid having a structure in which a carboxyl group is substituted with a carbonyl halide group in the aromatic carboxylic acid represented by the general formula (1).

(In formula (1), Y represents a hydrogen atom, an alkyl group, or an aromatic group, Ar represents an aromatic group, and the hydrogen atom in the aromatic carboxylic acid structure represented by formula (1) is The group containing an adamantane structure may be substituted, the group containing an adamantane structure may have an alkyl group having 1 to 20 carbon atoms, n is an integer of 1 to 5. m is It is an integer of 1 to 4.) The acid halide of an aromatic carboxylic acid according to claim 1, wherein the acid halide of the aromatic carboxylic acid contains an aromatic group as Y in the general formula (1). Acid halides of the aromatic carboxylic acids, acid halides of an aromatic carboxylic acid according to claim 1 or 2 are those having a phenyl group as the aromatic group.