JP2005281297A - Aromatic carboxylic acid, its acid halide and their synthetic methods - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new aromatic carboxylic acid which is useful as a raw material for a condensed polymer with a high heat resistance, and an acid halide thereof. <P>SOLUTION: In the aromatic carboxylic acid of formula (1) (wherein R is a substituent containing an adamantane structure; and n is an integer of 1 or 2), the substituent containing an adamantane structure is bonded to an ethynyl group. The acid halide of the compound is also provided. The compound of formula (1) is synthesized from an acetylene containing the adamantane structure and an aromatic polycarboxylate. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to aromatic carboxylic acids and their acid halides, and methods for their synthesis.

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 application, 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 improving 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 them, 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 suitable for the above-mentioned use, and a synthesis method thereof.

  That is, the present invention provides an aromatic carboxylic acid represented by the general formula (1), wherein a substituent containing an adamantane structure is bonded to an ethynyl group, and the substituent containing an adamantane structure is an ethynyl group. It is an acid halide of the carboxylic acid represented by the general formula (2), which has a bonded group.

（式中、Ｒは、アダマンタン構造を含む置換基を表す。また、式中のｎは１または２の整数である。）

(In the formula, R represents a substituent having an adamantane structure. In the formula, n is an integer of 1 or 2.)

（式中、Ｒは、アダマンタン構造を含む置換基を、Ｘはハロゲン原子を表す。また、式中のｎは１または２の整数である。）

(In the formula, R represents a substituent containing an adamantane structure, X represents a halogen atom, and n in the formula is an integer of 1 or 2.)

  In the present invention, the substituent containing the adamantane structure is 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, a biadamantyl group. Group, triadamantyl group, tetraadamantyl group, pentaadamantyl group, hexaadamantyl group, heptaadamantyl group, octaadamantyl group, nonaadamantyl group, decaadamantyl group, undecaadamantyl group, adamantylphenyl group, diamantylphenyl group, tria Mantylphenyl group, tetramantylphenyl group, pentamantylphenyl group, hexamantylphenyl group, heptamantylphenyl group, octamantylphenyl group, nonamantyl Enyl group, decamantylphenyl group, undecamantylphenyl group, biadamantylphenyl group, triadamantylphenyl group, tetraadamantylphenyl group, pentaadamantylphenyl group, hexaadamantylphenyl group, heptaadamantylphenyl group, octaadamantylphenyl group, nona Adamantylphenyl group, decaadamantylphenyl group, undecaadamantylphenyl group, adamantylphenoxyphenyl group, diamantylphenoxyphenyl group, triamantylphenoxyphenyl group, tetramantylphenoxyphenyl group, pentamantylphenoxyphenyl group, hexaman Tylphenoxyphenyl group, heptamantylphenoxyphenyl group, octamantylphenoxyphenyl group, nonamantylphenoxyphene Group, decamantylphenoxyphenyl group, undecamantylphenoxyphenyl group, biadamantylphenoxyphenyl group, triadamantylphenoxyphenyl group, tetraadamantylphenoxyphenyl group, pentaadamantylphenoxyphenyl group, hexaadamantylphenoxyphenyl group, heptaadamantylphenoxyphenyl Group, octaadamantylphenoxyphenyl group, nonaadamantylphenoxyphenyl group, decaadamantylphenoxyphenyl group and undecaadamantylphenoxyphenyl group, at least one selected from the aromatic carboxylic acids and halides of the aromatic carboxylic acids It is.

  The present invention also provides the aromatic carboxylic acid and the aromatic carboxylic acid halide, wherein the substituent containing the adamantane structure has an alkyl group having 1 to 20 carbon atoms.

  Furthermore, the present invention provides a compound represented by the general formula (5) obtained by reacting a compound represented by the general formula (3) and a compound represented by the general formula (4) with an alkali metal water. An aromatic carboxylic acid represented by the general formula (1), wherein the compound represented by the general formula (6) is produced by treatment in the presence of an oxide, and the product is further acid-treated. Preferably, a transition metal catalyst is used in the reaction between the compound represented by the general formula (3) and the compound represented by the general formula (4).

（式中、Ｙは脱離基を表す。また、式中のｎは１または２の整数である。）

(In the formula, Y represents a leaving group. In the formula, n is an integer of 1 or 2.)

（式中、Ｒは、アダマンタン構造を含む置換基を表す。）

(In the formula, R represents a substituent containing an adamantane structure.)

（式中、Ｒは、アダマンタン構造を含む置換基を表す。また、式中のｎは１または２の整数である。）

(In the formula, R represents a substituent having an adamantane structure. In the formula, n is an integer of 1 or 2.)

（式中、Ｒは、アダマンタン構造を含む置換基を表し、Ｍはアルカリ金属を表す。また、式中のｎは１または２の整数である。）

(In the formula, R represents a substituent containing an adamantane structure, M represents an alkali metal, and n in the formula is an integer of 1 or 2.)

  Furthermore, the present invention is characterized in that the compound represented by the general formula (6) or the compound represented by the general formula (1) obtained by the synthesis method is treated with a halogenating agent. This is a method for synthesizing an acid halide of an aromatic carboxylic acid represented by formula (2).

  According to the present invention, an aromatic carboxylic acid represented by the general formula (1) and a compound represented by the general formula (2) which is an acid halide of the aromatic carboxylic acid can be obtained. It is particularly useful as a raw material for condensation polymers. As a specific example, in general formulas (1) and (2), a dicarboxylic acid compound in which n is 2 can be directly introduced into the main chain of the polymer, and a monocarboxylic acid compound in which n is 1 is high. It can be introduced into the side chain and terminal of the molecule and is useful for improving the properties of the polymer.

The present invention is an aromatic carboxylic acid characterized in that a substituent containing an adamantane structure represented by the general formula (1) has a group bonded to an ethynyl group, and the substituent containing an adamantane structure includes: Examples thereof include a group having a diamondoid structure having a 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 a 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, Tamantyl phenoxyphenyl group, hexamantyl phenoxyphenyl group, heptamantyl phenoxyphenyl group, octamantyl phenoxyphenyl group, nonamantyl phenoxyphenyl group, decamantyl phenoxyphenyl group, and undecamantylphenyl group, etc. Examples of the group having a polyadamantane structure include 1,1′-biadamantyl groups and 2,2′-biadamantyl groups, such as biadamantyl groups, 1,1 ′, 1 ″ -triadamantyl groups, and 2,2 ′. , 2 ″ -triadamantyl groups such as 1,1 ′, 1 ″, 1 ′ ″-tetraadamantyl groups and 2,2 ′, 2 ″, 2 ′ ″-tetraadamantyl groups Tetraadamantyl group, 1,1 ′, 1 ″, 1 ′ ″, 1 ″ ″-pentaadamantyl group and 2,2 ′, 2 ″, 2 ′ ″, 2 ″ ″- Pentaadamantyl group such as tantaladamantyl group, 1,1 ′, 1 ″, 1 ′ ″, 1 ″ ″, 1 ′ ″ ″-heptaadamantyl group and 2,2 ′, 2 ″, 2 ''',2'''',2'''''-heptaadamantyl group such as heptaadamantyl group, hexaadamantyl 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, undecaadamantylphenyl group, biadamantyl Phenoxyphenyl group, triadamantylphenoxyphenyl group, te Laadamantylphenoxyphenyl group, pentaadamantylphenoxyphenyl group, hexaadamantylphenoxyphenyl group, heptaadamantylphenoxyphenyl group, octaadamantylphenoxyphenyl group, nonaadamantylphenoxyphenyl group, decaadamantylphenoxyphenyl group, and undecaadamantylphenoxyphenyl group Although it is mentioned, it is not limited to these. As a result, a resin having a low relative dielectric constant can be obtained.

  The substituent containing the adamantane structure may have an alkyl group having 1 to 20 carbon atoms. Examples of the alkyl group include, but are not limited to, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a 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,
3- (2- (1-adamantyl) ethynyl) phthalic acid, 3- (2- (2-adamantyl) ethynyl) phthalic acid, 4- (2- (1-adamantyl) ethynyl) phthalic acid, 4- (2- (2-adamantyl) ethynyl) phthalic acid,
3- (2- (1- (3,5-dimethyladamantyl)) ethynyl) phthalic acid, 3- (2- (2- (1,3-dimethyladamantyl)) ethynyl) phthalic acid, 4- (2- ( 1- (3,5-dimethyladamantyl)) ethynyl) phthalic acid, 4- (2- (2- (1,3-dimethyladamantyl)) ethynyl) phthalic acid,
4- (2- (1-adamantyl) ethynyl) isophthalic acid, 4- (2- (2-adamantyl) ethynyl) isophthalic acid, 5- (2- (1-adamantyl) ethynyl) isophthalic acid, 5- (2- (2-adamantyl) ethynyl) isophthalic acid,
4- (2- (1- (3,5-dimethyladamantyl)) ethynyl) isophthalic acid, 4- (2- (2- (1,3-dimethyladamantyl)) ethynyl) isophthalic acid, 5- (2- ( 1- (3,5-dimethyladamantyl)) ethynyl) isophthalic acid, 5- (2- (2- (1,3-dimethyladamantyl)) ethynyl) isophthalic acid,
5- (2- (1-adamantyl) ethynyl) terephthalic acid, 5- (2- (2-adamantyl) ethynyl) terephthalic acid,
5- (2- (1- (3,5-dimethyladamantyl)) ethynyl) terephthalic acid, 5- (2- (2- (1,3-dimethyladamantyl)) ethynyl) terephthalic acid,
3- (2- (1-diamantyl) ethynyl) phthalic acid, 3- (2- (2-diamantyl) ethynyl) phthalic acid, 4- (2- (1-diamantyl) ethynyl) phthalic acid, 4- (2- (2-diamantyl) ethynyl) phthalic acid,
4- (2- (1-diamantyl) ethynyl) isophthalic acid, 4- (2- (2-diamantyl) ethynyl) isophthalic acid, 5- (2- (1-diamantyl) ethynyl) isophthalic acid, 5- (2- (2-diamantyl) ethynyl) isophthalic acid,
5- (2- (1-diamantyl) ethynyl) terephthalic acid, 5- (2- (2-diamantyl) ethynyl) terephthalic acid,
3- (2- (1-tetramantyl) ethynyl) phthalic acid, 3- (2- (2-tetramantyl) ethynyl) phthalic acid, 4- (2- (1-tetramantyl) ethynyl) phthalic acid, 4- (2- (2-tetraamantyl) ethynyl) phthalic acid,
4- (2- (1-tetramantyl) ethynyl) isophthalic acid, 4- (2- (2-tetramantyl) ethynyl) isophthalic acid, 5- (2- (1-tetramantyl) ethynyl) isophthalic acid, 5- (2- (2-tetramantyl) ethynyl) isophthalic acid,
5- (2- (1-tetramantyl) ethynyl) terephthalic acid, 5- (2- (2-tetramantyl) ethynyl) terephthalic acid,
3- (2- (3- (1,1′-biadamantyl)) ethynyl) phthalic acid, 3- (2- (2- (1,1′-biadamantyl)) ethynyl) phthalic acid, 4- (2 -(3- (1,1'-biadamantyl)) ethynyl) phthalic acid, 4- (2- (2- (1,1'-biadamantyl)) ethynyl) phthalic acid,
3- (2- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) ethynyl) phthalic acid, 3- (2- (2- (1,1 ′ -(3,5,3 ', 5'-tetramethylbiadamantyl))) ethynyl) phthalic acid, 4- (2- (7- (1,1'-(3,5,3 ', 5'-tetra) Methylbiadamantyl))) ethynyl) phthalic acid, 4- (2- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) ethynyl) phthalic acid,
4- (2- (3- (1,1′-biadamantyl)) ethynyl) isophthalic acid, 4- (2- (2- (1,1′-biadamantyl)) ethynyl) isophthalic acid, 5- (2 -(3- (1,1'-biadamantyl)) ethynyl) isophthalic acid, 5- (2- (2- (1,1'-biadamantyl)) ethynyl) isophthalic acid,
4- (2- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) ethynyl) isophthalic acid, 4- (2- (2- (1,1 ′ -(3,5,3 ', 5'-tetramethylbiadamantyl))) ethynyl) isophthalic acid, 5- (2- (7- (1,1'-(3,5,3 ', 5'-tetra) Methylbiadamantyl))) ethynyl) isophthalic acid, 5- (2- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) ethynyl) isophthalic acid,
5- (2- (3- (1,1′-biadamantyl)) ethynyl) terephthalic acid, 5- (2- (2- (1,1′-biadamantyl)) ethynyl) terephthalic acid,
5- (2- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) ethynyl) terephthalic acid, 5- (2- (2- (1,1 ′ -(3,5,3 ', 5'-tetramethylbiadamantyl))) ethynyl) terephthalic acid,
4- (2- (1-adamantyl) ethynyl) benzoic acid, 3- (2- (1-adamantyl) ethynyl) benzoic acid, 2- (2- (1-adamantyl) ethynyl) benzoic acid,
4- (2- (1- (3,5-dimethyladamantyl)) ethynyl) benzoic acid, 3- (2- (1- (3,5-dimethyladamantyl)) ethynyl) benzoic acid, 2- (2- ( 1- (3,5-dimethyladamantyl)) ethynyl) benzoic acid,
4- (2- (2-adamantyl) ethynyl) benzoic acid, 3- (2- (2-adamantyl) ethynyl) benzoic acid, 2- (2- (2-adamantyl) ethynyl) benzoic acid,
4- (2- (2- (1,3-dimethyladamantyl)) ethynyl) benzoic acid, 3- (2- (2- (1,3-dimethyladamantyl)) ethynyl) benzoic acid, 2- (2- ( 2- (1,3-dimethyladamantyl)) ethynyl) benzoic acid,
4- (2- (1-tetramantyl) ethynyl) benzoic acid, 3- (2- (1-tetramantyl) ethynyl) benzoic acid, 2- (2- (1-tetramantyl) ethynyl) benzoic acid, 4- (2- (2-tetramantyl) ethynyl) benzoic acid, 3- (2- (2-tetramantyl) ethynyl) benzoic acid, 2- (2- (2-tetramantyl) ethynyl) benzoic acid,
4- (2- (3- (1,1′-biadamantyl)) ethynyl) benzoic acid, 3- (2- (3- (1,1′-biadamantyl)) ethynyl) benzoic acid, 2- (2 -(3- (1,1'-biadamantyl)) ethynyl) benzoic acid,
4- (2- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) ethynyl) benzoic acid, 3- (2- (7- (1,1 ′ -(3,5,3 ', 5'-tetramethylbiadamantyl))) ethynyl) benzoic acid, 2- (2- (7- (1,1'-(3,5,3 ', 5'-tetra) Methylbiadamantyl))) ethynyl) benzoic acid,
4- (2- (2- (1,1′-biadamantyl)) ethynyl) benzoic acid, 3- (2- (2- (1,1′-biadamantyl)) ethynyl) benzoic acid, 2- (2 -(2- (1,1'-biadamantyl)) ethynyl) benzoic acid,
4- (2- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) ethynyl) benzoic acid, 3- (2- (2- (1,1 ′ -(3,5,3 ', 5'-tetramethylbiadamantyl))) ethynyl) benzoic acid, 2- (2- (2- (1,1'-(3,5,3 ', 5'-tetra) Methylbiadamantyl))) ethynyl) benzoic acid,
3- (2- (4- (1-adamantyl) phenyl) ethynyl) phthalic acid, 3- (2- (4- (2-adamantyl) phenyl) ethynyl) phthalic acid, 4- (2- (4- (1 -Adamantyl) phenyl) ethynyl) phthalic acid, 4- (2- (4- (2-adamantyl) phenyl) ethynyl) phthalic acid,
3- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) phthalic acid, 3- (2- (4- (2- (1,3-dimethyladamantyl)) phenyl) ethynyl ) Phthalic acid, 4- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) phthalic acid, 4- (2- (4- (2- (1,3-dimethyladamantyl)) ) Phenyl) ethynyl) phthalic acid,
4- (2- (4- (1-adamantyl) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (2-adamantyl) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (1 -Adamantyl) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (2-adamantyl) phenyl) ethynyl) isophthalic acid,
4- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (2- (1,3-dimethyladamantyl)) phenyl) ethynyl ) Isophthalic acid, 5- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (2- (1,3-dimethyladamantyl)) ) Phenyl) ethynyl) isophthalic acid,
5- (2- (4- (1-adamantyl) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (2-adamantyl) phenyl) ethynyl) terephthalic acid,
5- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (2- (1,3-dimethyladamantyl)) phenyl) ethynyl )Terephthalic acid,
3- (2- (4- (1-diamantyl) phenyl) ethynyl) phthalic acid, 3- (2- (4- (2-diamantyl) phenyl) ethynyl) phthalic acid, 4- (2- (4- (1 -Diamantyl) phenyl) ethynyl) phthalic acid, 4- (2- (4- (2-diamantyl) phenyl) ethynyl) phthalic acid,
4- (2- (4- (1-diamantyl) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (2-diamantyl) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (1 -Diamantyl) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (2-diamantyl) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (1-diamantyl) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (2-diamantyl) phenyl) ethynyl) terephthalic acid,
3- (2- (4- (1-tetramantyl) phenyl) ethynyl) phthalic acid, 3- (2- (4- (2-tetramantyl) phenyl) ethynyl) phthalic acid, 4- (2- (4- (1 -Tetramantyl) phenyl) ethynyl) phthalic acid, 4- (2- (4- (2-tetramantyl) phenyl) ethynyl) phthalic acid,
4- (2- (4- (1-tetramantyl) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (2-tetramantyl) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (1 -Tetramantyl) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (2-tetramantyl) phenyl) ethynyl) isophthalic acid,
5- (2- (4- (1-tetramantyl) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (2-tetramantyl) phenyl) ethynyl) terephthalic acid,
3- (2- (4- (3- (1,1′-biadamantyl)) phenyl) ethynyl) phthalic acid, 3- (2- (4- (2- (1,1′-biadamantyl)) phenyl ) Ethynyl) phthalic acid, 4- (2- (4- (3- (1,1′-biadamantyl)) phenyl) ethynyl) phthalic acid, 4- (2- (4- (2- (1,1 ′) -Biadamantyl)) phenyl) ethynyl) phthalic acid,
3- (2- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) phthalic acid, 3- (2- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) phthalic acid, 4- (2- (4- (7- (1,1 ′ -(3,5,3 ', 5'-tetramethylbiadamantyl))) phenyl) ethynyl) phthalic acid, 4- (2- (4- (2- (1,1'-(3,5,3 ') , 5'-tetramethylbiadamantyl))) phenyl) ethynyl) phthalic acid,
4- (2- (4- (3- (1,1′-biadamantyl)) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (2- (1,1′-biadamantyl)) phenyl ) Ethynyl) isophthalic acid, 5- (2- (4- (3- (1,1′-biadamantyl)) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (2- (1,1 ′) -Biadamantyl)) phenyl) ethynyl) isophthalic acid,
4- (2- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (7- (1,1 ′ -(3,5,3 ', 5'-tetramethylbiadamantyl))) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (2- (1,1'-(3,5,3 ') , 5'-tetramethylbiadamantyl))) phenyl) ethynyl) isophthalic acid,
5- (2- (4- (3- (1,1′-biadamantyl)) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (2- (1,1′-biadamantyl)) phenyl ) Ethynyl) terephthalic acid,
5- (2- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) terephthalic acid,
4- (2- (4- (1-adamantyl) phenyl) ethynyl) benzoic acid, 3- (2- (4- (1-adamantyl) phenyl) ethynyl) benzoic acid, 2- (2- (4- (1 -Adamantyl) phenyl) ethynyl) benzoic acid,
4- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) benzoic acid, 3- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl ) Benzoic acid, 2- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) benzoic acid,
4- (2- (4- (2-adamantyl) phenyl) ethynyl) benzoic acid, 3- (2- (4- (2-adamantyl) phenyl) ethynyl) benzoic acid, 2- (2- (4- (2 -Adamantyl) phenyl) ethynyl) benzoic acid,
4- (2- (4- (2- (1,3-dimethyladamantyl)) phenyl) ethynyl) benzoic acid, 3- (2- (4- (2- (1,3-dimethyladamantyl)) phenyl) ethynyl ) Benzoic acid, 2- (2- (4- (2- (1,3-dimethyladamantyl)) phenyl) ethynyl) benzoic acid,
4- (2- (4- (1-tetramantyl) phenyl) ethynyl) benzoic acid, 3- (2- (4- (1-tetramantyl) phenyl) ethynyl) benzoic acid, 2- (2- (4- (1 -Tetramantyl) phenyl) ethynyl) benzoic acid, 4- (2- (4- (2-tetramantyl) phenyl) ethynyl) benzoic acid, 3- (2- (4- (2-tetramantyl) phenyl) ethynyl) benzoic acid, 2- (2- (4- (2-tetramantyl) phenyl) ethynyl) benzoic acid,
4- (2- (4- (3- (1,1′-biadamantyl)) phenyl) ethynyl) benzoic acid, 3- (2- (4- (3- (1,1′-biadamantyl)) phenyl ) Ethynyl) benzoic acid, 2- (2- (4- (3- (1,1′-biadamantyl)) phenyl) ethynyl) benzoic acid,
4- (2- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) benzoic acid, 3- (2- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) benzoic acid, 2- (2- (4- (7- (1,1 ′ -(3,5,3 ', 5'-tetramethylbiadamantyl))) phenyl) ethynyl) benzoic acid,
4- (2- (4- (2- (1,1′-biadamantyl)) phenyl) ethynyl) benzoic acid, 3- (2- (4- (2- (1,1′-biadamantyl)) phenyl ) Ethynyl) benzoic acid, 2- (2- (4- (2- (1,1′-biadamantyl)) phenyl) ethynyl) benzoic acid,
4- (2- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) benzoic acid, 3- (2- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenyl) ethynyl) benzoic acid, 2- (2- (4- (2- (1,1 ′ -(3,5,3 ', 5'-tetramethylbiadamantyl))) phenyl) ethynyl) benzoic acid,
3- (2- (4- (4- (1-adamantyl) phenoxy) phenyl) ethynyl) phthalic acid, 3- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (1-adamantyl) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) phthalic acid,
3- (2- (4- (4- (1- (3,5-dimethyladamantyl)) phenoxy) phenyl) ethynyl) phthalic acid, 3- (2- (4- (4- (2- (1,3 -Dimethyladamantyl)) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (1- (3,5-dimethyladamantyl)) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2 -(4- (4- (2- (1,3-dimethyladamantyl)) phenoxy) phenyl) ethynyl) phthalic acid,
4- (2- (4- (4- (1-adamantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (1-adamantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) isophthalic acid,
4- (2- (4- (4- (1- (3,5-dimethyladamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (4- (2- (1,3 -Dimethyladamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (1- (3,5-dimethyladamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2 -(4- (4- (2- (1,3-dimethyladamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid,
5- (2- (4- (4- (1-adamantyl) phenoxy) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) terephthalic acid,
5- (2- (4- (4- (1- (3,5-dimethyladamantyl)) phenoxy) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (2- (1,3 -Dimethyladamantyl)) phenoxy) phenyl) ethynyl) terephthalic acid,
3- (2- (4- (4- (1-diamantyl) phenoxy) phenyl) ethynyl) phthalic acid, 3- (2- (4- (4- (2-diamantyl) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (1-diamantyl) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (2-diamantyl) phenoxy) phenyl) ethynyl) phthalic acid,
4- (2- (4- (4- (1-diamantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (4- (2-diamantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (1-diamantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (2-diamantyl) phenoxy) phenyl) ethynyl) isophthalic acid,
5- (2- (4- (4- (1-diamantyl) phenoxy) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (2-diamantyl) phenoxy) phenyl) ethynyl) terephthalic acid,
3- (2- (4- (4- (1-tetramantyl) phenoxy) phenyl) ethynyl) phthalic acid, 3- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (1-tetramantyl) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl) phthalic acid,
4- (2- (4- (4- (1-tetramantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (1-tetramantyl) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl) isophthalic acid,
5- (2- (4- (4- (1-tetramantyl) phenoxy) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl) terephthalic acid,
3- (2- (4- (4- (3- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) phthalic acid, 3- (2- (4- (4- (2- (1, 1′-biadamantyl)) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- (4- (3- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) phthalic acid, 4 -(2- (4- (4- (2- (1,1'-biadamantyl)) phenoxy) phenyl) ethynyl) phthalic acid,
3- (2- (4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) phthalic acid, 3- ( 2- (4- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- ( 4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) phthalic acid, 4- (2- (4- ( 4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) phthalic acid,
4- (2- (4- (4- (3- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid, 4- (2- (4- (4- (2- (1, 1'-biadamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- (4- (3- (1,1'-biadamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid, 5 -(2- (4- (4- (2- (1,1'-biadamantyl)) phenoxy) phenyl) ethynyl) isophthalic acid,
4- (2- (4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) isophthalic acid, 4- ( 2- (4- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- ( 4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) isophthalic acid, 5- (2- (4- ( 4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) isophthalic acid,
5- (2- (4- (4- (3- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) terephthalic acid, 5- (2- (4- (4- (2- (1, 1′-biadamantyl)) phenoxy) phenyl) ethynyl) terephthalic acid,
5- (2- (4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) terephthalic acid, 5- ( 2- (4- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) terephthalic acid,
4- (2- (4- (4- (1-adamantyl) phenoxy) phenyl) ethynyl) benzoic acid, 3- (2- (4- (4- (1-adamantyl) phenoxy) phenyl) ethynyl) benzoic acid, 2- (2- (4- (4- (1-adamantyl) phenoxy) phenyl) ethynyl) benzoic acid,
4- (2- (4- (4- (1- (3,5-dimethyladamantyl)) phenoxy) phenyl) ethynyl) benzoic acid, 3- (2- (4- (4- (1- (3,5 -Dimethyladamantyl)) phenoxy) phenyl) ethynyl) benzoic acid, 2- (2- (4- (4- (1- (3,5-dimethyladamantyl)) phenoxy) phenyl) ethynyl) benzoic acid,
4- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) benzoic acid, 3- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) benzoic acid, 2- (2- (4- (4- (2-adamantyl) phenoxy) phenyl) ethynyl) benzoic acid,
4- (2- (4- (4- (2- (1,3-dimethyladamantyl)) phenoxy) phenyl) ethynyl) benzoic acid, 3- (2- (4- (4- (2- (1,3 -Dimethyladamantyl)) phenoxy) phenyl) ethynyl) benzoic acid, 2- (2- (4- (4- (2- (1,3-dimethyladamantyl)) phenoxy) phenyl) ethynyl) benzoic acid,
4- (2- (4- (4- (1-tetramantyl) phenoxy) phenyl) ethynyl) benzoic acid, 3- (2- (4- (4- (1-tetramantyl) phenoxy) phenyl) ethynyl) benzoic acid, 2- (2- (4- (4- (1-tetramantyl) phenoxy) phenyl) ethynyl) benzoic acid, 4- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl) benzoic acid, 3- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl) benzoic acid, 2- (2- (4- (4- (2-tetramantyl) phenoxy) phenyl) ethynyl) benzoic acid,
4- (2- (4- (4- (3- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) benzoic acid, 3- (2- (4- (4- (3- (1, 1′-biadamantyl)) phenoxy) phenyl) ethynyl) benzoic acid, 2- (2- (4- (4- (3- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) benzoic acid,
4- (2- (4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) benzoic acid, 3- ( 2- (4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) benzoic acid, 2- (2- ( 4- (4- (7- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) benzoic acid,
4- (2- (4- (4- (2- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) benzoic acid, 3- (2- (4- (4- (2- (1, 1′-biadamantyl)) phenoxy) phenyl) ethynyl) benzoic acid, 2- (2- (4- (4- (2- (1,1′-biadamantyl)) phenoxy) phenyl) ethynyl) benzoic acid,
4- (2- (4- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) benzoic acid, 3- ( 2- (4- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) benzoic acid, 2- (2- ( 4- (4- (2- (1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantyl))) phenoxy) phenyl) ethynyl) benzoic acid,
However, it is not limited to these.

  Moreover, as the acid halide of the aromatic carboxylic acid represented by the general formula (2) of the present invention, in the aromatic carboxylic acid, the hydroxy group contained in the carboxyl group is a halogen atom such as fluorine, chlorine and bromine. It is a substituted compound.

  The aromatic carboxylic acid represented by the general formula (1) and the acid halide represented by the general formula (2) of the present invention can be synthesized, for example, by the following route.

式（１）、（２）、（４）、（５）および（６）中のＲは、アダマンタン構造を含む置換基を、式（２）中のＸはハロゲン原子を、式（３）中のＹは脱離基を、式（６）中のＭはアルカリ金属を表す。また、式中のｎは１または２の整数である。

R in the formulas (1), (2), (4), (5) and (6) is a substituent containing an adamantane structure, X in the formula (2) is a halogen atom, in the formula (3) Y in the formula represents a leaving group, and M in the formula (6) represents an alkali metal. N in the formula is an integer of 1 or 2.

  The compound (general formula (4)) in which one side of acetylene used as the starting material is substituted with a substituent having an adamantane structure (general formula (4)) is a literature (Y. Okano, T. Masuda and T. Higasura, Journal of Polymer Science: Polymer). Chemistry Edition, Vol. 23, 2527-2537, 1985) can be synthesized from a compound having a substituent containing the adamantane structure and a bromo group.

Examples of the compound having a substituent and a bromo group containing the adamantane structure include 1-bromoadamantane,
2-bromoadamantane, 1-bromo-3,5-dimethyladamantane, 2-bromo-1,3-dimethyladamantane, 1-bromodiamantane, 2-bromodiamantane, 1-bromotriamantane, 2-bromotriamantane 1-bromotetramantane, 2-bromotetramantane, 1-bromopentamantane, 2-bromopentamantane, 1-bromohexamantane, 2-bromohexamantane, 1-bromoheptamantane, 2-bromoheptamantane, 1 -Bromooctamantane, 2-bromooctamantane, 1-bromononamantane, 2-bromononamantane, 1-bromodecamantane, 2-bromodecamantane, 1-bromoundecamantane, 2-bromoundecamantane, 2 -Bromo-1,1'-biadamantane, 3-bromo -1,1'-biadamantane, 2-bromo-1,1 '-(3,5,3', 5'-tetramethylbiadamantane), 7-bromo-1,1 '-(3,5,3 ', 5'-tetramethylbiadamantane), 2-bromo-1,1', 1 ''-triadamantane, 3-bromo-1,1 ', 1''-triadamantane, 2-bromo-1,1 ', 1 ″, 1 ′ ″-tetraadamantane, 3-bromo-1,1 ′, 1 ″, 1 ′ ″-tetraadamantane, 1- (4-bromophenyl) adamantane, 2- (4- Bromophenyl) adamantane, 1- (4-bromophenyl) -3,5-dimethyladamantane, 2- (4-bromophenyl) -1,3-dimethyladamantane, 1- (4-bromophenyl) diamantane, 2- ( 4-Bromophenyl) diamantane, 1- (4-bromophenyl) tria Mantan, 2- (4-bromophenyl) triamantane, 1- (4-bromophenyl) tetramantane, 2- (4-bromophenyl) tetramantane, 1- (4-bromophenyl) pentamantane, 2- (4 -Bromophenyl) pentamantane, 1- (4-bromophenyl) hexamantane, 2- (4-bromophenyl) hexamantane, 1- (4-bromophenyl) heptamantane, 2- (4-bromophenyl) heptamantane, 1 -(4-Bromophenyl) octamantane, 2- (4-bromophenyl) octamantane, 1- (4-bromophenyl) nonamantane, 2- (4-bromophenyl) nonamantane, 1- (4-bromophenyl) decamantane 2- (4-bromophenyl) decamantane, 1- (4-bromophenyl) undeca 2- (4-bromophenyl) undecamantane, 2- (4-bromophenyl) -1,1′-biadamantane, 3- (4-bromophenyl) -1,1′-biadamantane, 2- (4-Bromophenyl) -1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantane), 7- (4-Bromophenyl) -1,1 ′-(3,5,3 ′ , 5′-tetramethylbiadamantane), 2- (4-bromophenyl) -1,1 ′, 1 ″ -triadamantane, 3- (4-bromophenyl) -1,1 ′, 1 ″ -tri Adamantane, 2- (4-bromophenyl) -1,1 ′, 1 ″, 1 ′ ″-tetraadamantane, 3- (4-bromophenyl) -1,1 ′, 1 ″, 1 ′ ″ -Tetraadamantane, 1- (4- (4-bromophenoxy) phenyl) adamantane, 2- (4- (4-bromo) Phenoxy) phenyl) adamantane, 1- (4- (4-bromophenoxy) phenyl) -3,5-dimethyladamantane, 2- (4- (4-bromophenoxy) phenyl) -1,3-dimethyladamantane, 1- (4- (4-bromophenoxy) phenyl) diamantane, 2- (4- (4-bromophenoxy) phenyl) diamantane, 1- (4- (4-bromophenoxy) phenyl) triamantane, 2- (4- ( 4-bromophenoxy) phenyl) triamantane, 1- (4- (4-bromophenoxy) phenyl) tetramantane, 2- (4- (4-bromophenoxy) phenyl) tetramantane,
1- (4- (4-bromophenoxy) phenyl) pentamantane, 2- (4- (4-bromophenoxy) phenyl) pentamantane, 1- (4- (4-bromophenoxy) phenyl) hexamantane, 2- (4- (4-Bromophenoxy) phenyl) hexamantane, 1- (4- (4-bromophenoxy) phenyl) heptamantane, 2- (4- (4-bromophenoxy) phenyl) heptamantane, 1- (4- ( 4-bromophenoxy) phenyl) octamantane, 2- (4- (4-bromophenoxy) phenyl) octamantane, 1- (4- (4-bromophenoxy) phenyl) nonamantane, 2- (4- (4-bromo Phenoxy) phenyl) nonamantane, 1- (4- (4-bromophenoxy) phenyl) decamantane, 2- (4- ( -Bromophenoxy) phenyl) decamantane, 1- (4- (4-bromophenoxy) phenyl) undecamantane, 2- (4- (4-bromophenoxy) phenyl) undecamantane, 2- (4- (4- Bromophenoxy) phenyl) -1,1'-biadamantane, 3- (4- (4-bromophenoxy) phenyl) -1,1'-biadamantane, 2- (4- (4-bromophenoxy) phenyl)- 1,1 ′-(3,5,3 ′, 5′-tetramethylbiadamantane), 7- (4- (4-bromophenoxy) phenyl) -1,1 ′-(3,5,3 ′, 5 '-Tetramethylbiadamantane), 2- (4- (4-bromophenoxy) phenyl) -1,1', 1 ''-triadamantane, 3- (4- (4-bromophenoxy) phenyl) -1, 1 ', 1''-Triadama Nthane, 2- (4- (4-bromophenoxy) phenyl) -1,1 ′, 1 ″, 1 ′ ″-tetraadamantane and 3- (4- (4-bromophenoxy) phenyl) -1,1 ', 1'',1'''-tetraadamantane and the like.

  First, a methyl ester compound of an aromatic carboxylic acid represented by the general formula (3) in which one hydrogen atom on the benzene ring is substituted with a leaving group Y, and a compound represented by the general formula (4) A compound represented by the general formula (5) is obtained by a coupling reaction. In the coupling reaction, a catalyst may be used. For example, a transition metal catalyst such as palladium is used. However, at this time, the leaving group Y is preferably a group that can be easily eliminated from an alkyl group or an aromatic group by a coupling reaction under a catalyst, for example, a halogen atom such as fluorine, chlorine, bromine and iodine, Preferred examples include a trifluoromethanesulfonoxy group.

  Next, the compound represented by the general formula (5) obtained above is subjected to a demethylation reaction from a methyl ester group using a basic alkali metal hydroxide, and the aromatic represented by the general formula (6). An alkali metal salt of a carboxylic acid derivative is obtained.

  Furthermore, by treating the alkali metal salt of the aromatic carboxylic acid derivative represented by the general formula (6) obtained above with an acid, the aromatic carboxylic acid represented by the general formula (1) By treating with an agent, an acid halide represented by the general formula (2) can be obtained.

  As an aromatic carboxylic acid in which one hydrogen atom on the benzene ring represented by the general formula (3) is substituted with Y, when the leaving group Y is a trifluoromethanesulfonyloxy group, for example, the formula (7 Esterification of a dimethyl aromatic carboxylate in which one hydrogen atom on the benzene ring represented by formula (II) is substituted with a hydroxy group with trifluoromethanesulfonic anhydride (formula (8)) gives a formula (3 ′) Thus, it is possible to obtain a dimethyl aromatic carboxylate in which one hydrogen atom on the benzene ring represented by the above formula is substituted with a trifluoromethanesulfonyloxy group.

（式中、ｎは１または２の整数を表す。）

(In the formula, n represents an integer of 1 or 2.)

  However, since trifluoromethanesulfonic anhydride (formula (8)) is expensive and requires careful handling such as use under water-free conditions, the following method is given as another method. be able to. First, Sandmeyer that proceeds via a diazonium salt (general formula (10)) using, as a raw material, an aromatic carboxylic acid in which one hydrogen atom on the benzene ring represented by formula (9) is substituted with an amino group. By carrying out the reaction, an aromatic carboxylic acid in which the leaving group Y represented by the general formula (11) is a halogen atom is synthesized, and then the aromatic carboxylic acid is methyl esterified with methanol. Dimethyl aromatic carboxylate in which the leaving group Y represented by the general formula (3) is a halogen atom such as fluorine, chlorine and bromine can be obtained inexpensively and easily.

（式中、Ｙはフッ素、塩素、臭素またはヨウ素を示し、ｎは１または２の整数を表す。）

(In the formula, Y represents fluorine, chlorine, bromine or iodine, and n represents an integer of 1 or 2.)

Hereinafter, an example of the manufacturing method will be described.
When dimethyl 5-bromoisophthalate (Y = Br in formula (3)) is used as the methyl ester compound of the aromatic carboxylic acid represented by the general formula (3), first, 5-aminoisophthalic acid (formula ( 9)) is reacted with hydrobromic acid and sodium nitrite to obtain a diazonium bromoacid salt (general formula (10)). By reacting this with cuprous bromide, nitrogen gas is generated and 5-bromoisophthalic acid (general formula (11)) is obtained. Subsequently, in the presence of an inert gas such as nitrogen, argon and helium, an acidic catalyst such as sulfuric acid is present, and methanol is added to reflux to cause esterification of methanol and carboxylic acid, resulting in dimethyl 5-bromoisophthalate. Is obtained. At this time, it is desirable to use a large excess of methanol in order to move the equilibrium of the reaction to the product side. In order to reduce the amount of water in the system, it is better to distill methanol in advance.

In the case of using dimethyl 5-trifluoromethanesulfonyloxyisophthalate (Y = trifluoromethanesulfonyloxy group in the general formula (3)) as the aromatic carboxylic acid represented by the general formula (3), To a solution obtained by dissolving dimethyl 5-hydroxyisophthalate (formula (7)) and a base in a solvent and cooling to −78 ° C. to 10 ° C., trifluoromethanesulfonic anhydride is added, and 0 ° C. to the boiling point of the solvent or less. To obtain the product. At this time, the reaction time is not particularly limited. Moreover, in the said reaction, it can suppress that reaction advances rapidly by the heat_generation | fever in reaction and the occurrence of bumping of a solvent, etc. by performing cooling before addition of trifluoromethanesulfonic acid anhydride.
By subjecting the reaction product thus obtained to conventional separation means such as extraction, liquid separation and concentration, dimethyl 5-trifluoromethanesulfonyloxyisophthalate can be obtained.
Further, it can be purified by recrystallization, column chromatography or the like, if necessary.

The amount of trifluoromethanesulfonic anhydride used in the synthesis of dimethyl 5-trifluoromethanesulfonyloxyisophthalate is preferably 1 to 1.5 equivalents with respect to dimethyl 5-hydroxyisophthalate.
The base is preferably a tertiary amine which does not have active hydrogen, and examples thereof include pyridines such as pyridine and methylpyridine, and trialkylamines such as triethylamine and tributylamine. The amount is preferably 1 to 1.5 equivalents with respect to the total amount of dimethyl 5-hydroxyisophthalate and trifluoromethanesulfonic anhydride.
The solvent may be an inert solvent in the synthesis, for example, aromatic hydrocarbons such as benzene and toluene, aliphatic hydrocarbons such as n-hexane and cyclohexane, dichloromethane, 1,2-dichloromethane. And halogenated hydrocarbons such as chloroform, ethers such as ethyl ether and tetrahydrofuran, and the like. These may be used alone or in combination, and the amount used is not particularly limited.
In addition, if water exists in the solvent, a side reaction occurs with the reaction reagent trifluoromethanesulfonic acid anhydride, and the actual reaction equivalent ratio changes, so an anhydrous solvent is used or the amount of water contained in advance is set. It is desirable to grasp and adjust the amount used to charge more than the theoretical equivalent.

  Next, as a method of obtaining the compound represented by the general formula (5), the dimethyl 5-bromoisophthalate or the dimethyl 5-trifluoromethanesulfonyloxy (general formula (3)) obtained above, A compound in which one side of acetylene represented by the formula (4) is substituted with a substituent containing an adamantane structure is 20 to 150 ° C. in an inert gas atmosphere such as nitrogen, argon and helium in the presence of a catalyst. A reaction product is obtained by performing a coupling reaction in the temperature range. 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 (5) can be obtained. It can be purified by column chromatography, recrystallization and the like.

In the synthesis of the compound represented by the general formula (5), it is theoretically sufficient that the compound represented by the general formula (4) is 1 equivalent times the compound represented by the general formula (3). However, the amount of addition should be adjusted in the range of 1 to 2 equivalents in order to allow the reaction to proceed completely.
As the catalyst system, any catalyst system that can form a carbon-carbon bond can be used without particular limitation. For example, a catalyst system comprising dichlorobis (triphenylphosphine) palladium, copper iodide, and triphenylphosphine. It is desirable to use In this catalyst system, the amount of dichlorobis (triphenylphosphine) palladium added is not particularly limited, but is preferably 0.1 to 1 mol% with respect to the compound represented by the general formula (5). The addition amount is preferably 1 to 20 equivalents to dichlorobis (triphenylphosphine) palladium, and the addition amount of copper iodide is between 1 to 5 equivalents to dichlorobis (triphenylphosphine) palladium. It is preferable.
As a solvent used in this reaction, it is preferable to use an amine-based solvent in order to capture the generated acid and promote the catalytic reaction. Examples of such solvents include tertiary amines such as diethylamine, triethylamine, butylamine and tributylamine, and cyclic amines such as pyridine and piperidine. These solvents can be used alone or in combination of two or more. 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 for obtaining the alkali metal salt of the aromatic carboxylic acid derivative represented by the general formula (6), the compound represented by the general formula (5) is treated in a solvent in the presence of an alkali metal hydroxide. As a result, a methyl ester group is demethylated to obtain a reaction product. 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.
Furthermore, the reaction product obtained here is separated from the crystals precipitated by cooling, washed with an alcohol-based solvent such as methanol, ethanol, butanol and isopropanol, and then dried to give a general formula (6) The alkali metal salt of the aromatic carboxylic acid derivative represented can be obtained.

As the alkali metal hydroxide in the synthesis of the alkali metal salt of the aromatic carboxylic acid derivative represented by the general formula (6), potassium hydroxide, sodium hydroxide and the like are preferable. 3 equivalent times or more is preferable with respect to the compound represented by (5), and there may be more than this.
The reaction solvent is not particularly limited as long as it is an ester other than an ester that can react with an alkali metal hydroxide, but alcohol-based alcohols such as methanol, ethanol, butanol and isopropanol have high solubility of alkali metal hydroxide. A solvent is preferred. The amount of the solvent is not particularly limited, but is preferably 5 to 50 times by weight with respect to isophthalic acid dimethyl ester from the viewpoint of ease of operation.

  Next, the alkali metal salt (general formula (6)) of the aromatic carboxylic acid derivative obtained above is dissolved in water and acidified with an acid such as hydrochloric acid, sulfuric acid and nitric acid, preferably until pH 1 is reached. Thus, a precipitate is obtained, which is collected by filtration, washed, and dried, whereby the aromatic carboxylic acid represented by the general formula (1) of the present invention can be obtained. In this case, if exposed to strong acid for a long time, the ethynyl moiety in the aromatic carboxylic acid may undergo a side reaction such as addition reaction or polymerization.

  Of the acid halides of the aromatic carboxylic acids represented by the general formula (2) of the present invention, acid chlorides, acid bromides and acid fluorides are alkali metal salts of the aromatic carboxylic acid derivatives obtained above ( The general formula (6)) is reacted in a solvent or in an excessive amount of a halogenating agent as a solvent in a temperature range of 0 to 150 ° C., and then the solvent is distilled off. It can be obtained by washing and further recrystallization. Moreover, you may use the aromatic carboxylic acid represented by General formula (1) instead of the aromatic carboxylic acid derivative alkali metal salt represented by General formula (6).

As the halogenating agent in the synthesis of the acid halide represented by the general formula (2), chlorinating agent such as thionyl chloride, brominating agent such as phosphorus tribromide, fluorinating agent such as fluorinated sulfonic acid, etc. It is preferable to use it. The amount of the halogenating agent used is preferably 2 equivalents or more with respect to the alkali metal salt of the aromatic carboxylic acid derivative represented by the general formula (6). There is no particular upper limit, and when no solvent is used, It may be used in a large excess of 10 equivalents or more. The acid iodide can be obtained by allowing an iodinating agent such as phosphorus iodide to act on 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 alkali metal salt of the aromatic carboxylic acid derivative represented by General formula (6).

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 (2).
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 (2) of the present invention can be synthesized by using 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 infrared spectroscopic analysis, mass spectrometry, elemental analysis, and relative permittivity measurement for property evaluation. The measurement conditions for each characteristic were as follows.

Test method (1) Infrared spectroscopic analysis (IR): JIR-5500 type manufactured by JEOL Ltd. was used for measurement by the KBr tablet method.
(2) Mass spectrometry (MS): Measured by a field desorption (FD) method using a JMS-700 type manufactured by JEOL Ltd.
(3) Elemental analysis: Carbon and hydrogen were measured using a model 2400 manufactured by PERKIN ELMER, and chlorine was measured by a flask combustion titration method.
(4) Dielectric constant: Using an automatic mercury probe CV measuring device SSM495 manufactured by Nippon SSM Co., Ltd., heat the measurement sample obtained below in an atmosphere of 22 ° C. and 45% humidity. The relative dielectric constant of the cured film (film thickness: 1 μm) was measured.
Regarding the aromatic dicarboxylic acid dichloride obtained in Examples 1 to 4, 8 and Comparative Example 1, first, 0.65 g (3 mmol) of 3,3′-diamino-4,4′-dihydroxybiphenyl was added to a 100 mL flask. ) And 20 mL of N-methylpyrrolidone were added, and the aromatic dicarboxylic acid dichloride (3 mmol) was added while stirring at 10 ° C. in a nitrogen stream, and then the reaction solution was stirred at 20 ° C. for 24 hours. The reaction solution was added to 500 mL of ion exchange water, and the solid recovered by filtration was further washed with stirring in 500 mL of ion exchange water for 1 hour. Further, a sample obtained by drying under reduced pressure at 60 ° C. for 2 days was used as a measurement sample.
Next, the coating varnish composed of the measurement sample obtained above and N-methylpyrrolidone was applied onto a silicon wafer by a spin coating method to obtain a uniform film thickness, and then heated and dried at 150 ° C. for 10 minutes. Furthermore, using an oven in which nitrogen was introduced and the oxygen concentration was controlled to 100 ppm or less, heating was performed at 350 ° C. for 60 minutes to obtain a coating film for measurement.
In addition, the aromatic monocarboxylic acid monochloride obtained in Example 5 was the same as Example 1 except that 1 mmol of the aromatic dicarboxylic acid dichloride (3 mmol) was added in Example 1 and then 1 mmol was added. To obtain a measurement sample.
Further, the aromatic monocarboxylic acid monochloride obtained in Example 6 was the same as Example 3 except that 1 mmol of the aromatic dicarboxylic acid dichloride (3 mmol) was added in Example 3 and then 1 mol was added. To obtain a measurement sample.
Further, the aromatic monocarboxylic acid monochloride obtained in Example 7 was the same as Example 3 except that 1 mmol of the aromatic dicarboxylic acid dichloride (3 mmol) was added in Example 4 and then 1 mol was added. To obtain a measurement sample.

(Example 1)
(1) [Synthesis of 1-ethynyladamantane]
According to the method described in the literature (Y. Okano, T. Masuda and T. Higashira, Journal of Polymer Science: Polymer Chemistry Edition, Vol. 23, 2527-2537, 1985) Synthesized.

(2) [Synthesis of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne from dimethyl 5-bromo-isophthalate]
In a four-neck 1 liter flask equipped with a thermometer, a Dimroth condenser, a nitrogen inlet and a stirrer, 125 g (0.458 mol) of dimethyl 5-bromo-isophthalate, 1.1 g (0.00419 mol) of triphenylphosphine, 0.275 g (0.00144 mol) of copper iodide and 64.26 g (0.401 mol) of 1-ethynyladamantane obtained above were charged, and nitrogen was allowed to flow into the flask. Subsequently, 375 ml of dehydrated triethylamine and 200 ml of dehydrated pyridine were added and dissolved by stirring. After continuing to flow nitrogen for 1 hour, 0.3 g (0.000427 mol) of dichlorobis (triphenylphosphine) palladium was quickly added and heated to reflux for 1 hour in 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 under reduced pressure at 50 ° C. to obtain 121.5 g of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne (yield 86%).

(3) [Synthesis of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt from 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne]
In a 5 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, 3 liters of n-butanol and 226 g (2.72 mol) of potassium hydroxide (85%) were charged and dissolved by heating under reflux. To this, 120 g (0.341 mol) of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne obtained above 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 132.49 g of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt (97%).

(4) [Synthesis of 5- (2- (1-adamantyl) ethynyl) isophthalic acid from 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt]
Insoluble matter was obtained by dissolving 7.6 g (0.019 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt obtained above in 20 ml of ion-exchanged water and filtering with 5C filter paper. Removed. 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 6.1 g of 5- (2- (1-adamantyl) ethynyl) isophthalic acid (yield 99.5%).

(5) [Synthesis of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dichloride from 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt]
To a 2 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, 96.1 g (0.24 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt obtained above and 1 , 2-dichloroethane 400 ml was charged and cooled to 0 ° C. To this, 391 g (4.5 mol) of thionyl chloride was added dropwise at 5 ° C. or less over 1 hour. Thereafter, 4 ml of dimethylformamide and 4 g of hydroquinone were added, and the mixture was stirred 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 m 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 16.5 g of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dichloride (yield) 19%).

  The spectral data of 5- (2- (1-adamantyl) ethynyl) isophthalic acid and 5- (2- (1-adamantyl) ethynyl) isophthalic acid dichloride obtained above are shown below. These data indicate that the obtained compound is the target product.

[5- (2- (1-adamantyl) ethynyl) isophthalic acid _{(C 20 H 20 O 4)} ]
Appearance: White powder IR: 1710-1680 cm ⁻¹ (carboxylic acid), 2260-2190 cm ⁻¹ (ethynyl group)
Elemental analysis: Theoretical value C: 74.06% H: 6.21% O: 19.73%
Measured value C: 74.12% H: 6.14% O: 19.74%

[5- (2- (1-adamantyl) ethynyl) isophthalic acid dichloride (C ₂₀ H ₁₈ Cl ₂ O ₂ )]
Appearance: White powder IR: 1800-1770 cm ⁻¹ (carboxylic acid chloride), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 290 (M ⁺ -2Cl)
Elemental analysis: Theoretical value C: 66.49% H: 5.02% Cl: 19.63 O: 8.86%
Actual value C: 66.41% H: 5.08% Cl: 19.70 O: 8.81%
The measurement results of relative permittivity are shown below.
Dielectric constant: 2.7

(Example 2)
(1) [Synthesis of 2-ethynyladamantane]
2-Ethynyladamantane was synthesized in the same manner as in Example 1 (1) except that 1-bromoadamantane was changed to 2-bromoadamantane.
(2) [Synthesis of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (2-adamantyl) ethyne from dimethyl 5-bromo-isophthalate]
In the synthesis of Example 1 (2), 111.8 g was similarly obtained except that 64.26 g (0.401 mol) of 1-ethynyladamantane was changed to 64.26 g (0.401 mol) of 2-ethynyladamantane obtained above. Of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (2-adamantyl) ethyne was obtained (yield 79%).

(3) [Synthesis of 5- (2- (2-adamantyl) ethynyl] isophthalic acid dipotassium salt from 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (2-adamantyl) ethyne]
In the synthesis of Example 1 (3), 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne (120 g, 0.341 mol) was obtained as described above. 119.1 g of 5- (2- (2-adamantyl) ethynyl) isophthalic acid dibenzoate in the same manner except for 110 g (0.313 mol) of -bis (methoxycarbonyl) phenyl) -2- (2-adamantyl) ethyne The potassium salt was obtained (yield 95%).

(4) [Synthesis of 5- (2- (2-adamantyl) ethynyl) isophthalic acid from 5- (2- (2-adamantyl) ethynyl) isophthalic acid dipotassium salt]
In the synthesis of Example 1 (4), 7.6 g (0.019 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained above. 5- (2- (2-adamantyl) Except for changing to 7.6 g (0.019 mol) of ethynyl) isophthalic acid dipotassium salt, 6.0 g of 5- (2- (2-adamantyl) ethynyl) isophthalic acid was obtained (yield 99%).

(5) [Synthesis of 5- (2- (2-adamantyl) ethynyl) isophthalic acid dichloride from 5- (2- (2-adamantyl) ethynyl) isophthalic acid dipotassium salt]
In Example 1 (5), 96.1 g (0.24 mol) of (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained as described above. (2- (2-adamantyl) ethynyl) isophthalic acid dipotassium 19.9 g of 5- (2- (2-adamantyl) ethynyl) isophthalic acid dichloride was obtained in the same manner except that the salt was 96.1 g (0.24 mol) (yield 23%).

  The spectral data of 5- (2- (2-adamantyl) ethynyl) isophthalic acid and 5- (2- (2-adamantyl) ethynyl) isophthalic acid dichloride obtained above are shown below. These data indicate that the obtained compound is the target product.

[5- (2- (2-adamantyl) ethynyl) isophthalic acid _{(C 20 H 20 O 4)} ]
Appearance: White powder MS (FD) (m / z): 324 (M ⁺ )
IR: 1710-1680 cm ⁻¹ (carboxylic acid), 2260-2190 cm ⁻¹ (ethynyl group)
Elemental analysis: Theoretical value C: 74.06% H: 6.21% O: 19.73%
Actual value C: 74.40% H: 6.27% O: 19.33%

[5- (2- (2-adamantyl) ethynyl) isophthalic acid dichloride (C ₂₀ H ₁₈ Cl ₂ O ₂ )]
Appearance: White powder IR: 1800-1770 cm ⁻¹ (carboxylic acid chloride), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 290 (M ⁺ -2Cl)
Elemental analysis: Theoretical value C: 66.49% H: 5.02% Cl: 19.63 O: 8.86%
Actual value C: 66.56% H: 5.11% Cl: 19.51 O: 8.82%
The measurement results of relative permittivity are shown below.
Dielectric constant: 2.7

(Example 3)
(1) [Synthesis of tetramantane]
Tetramantane was synthesized according to the method described in the literature (W. Burns et al., Journal of Chemical Society, Chemical Communication, 1976, 893 (1976)).

(2) [Synthesis of 1-bromotetramantane]
Into a four-necked 5 L flask equipped with a thermometer, a stirrer, and a reflux tube, 1.6 L of carbon tetrachloride and 40 g (0.250 mol) of bromine were added, and 132.8 g (0 .455 mol) was added in small portions. During the addition, the internal temperature was kept at 20 ° C to 30 ° C. When the temperature did not rise after completion of the addition, the reaction was continued for 1 hour. Thereafter, it was poured into about 4 L of cold water, and the crude product was filtered off, washed with pure water and dried. The crude product was recrystallized from hot ethanol. The obtained recrystallized product was dried under reduced pressure to obtain 160.0 g of 1-bromotetramantane (yield 98%). IR measurement showed that the absorption of the bromo group was 690 to 515 cm ⁻¹ , the molecular weight was 371, and the results of mass spectrometry showed that the product was 1-bromotetramantane.

(3) [Synthesis of 1-ethynyltetramantane]
128.1 g of 1-ethynyltetramantane was synthesized in the same manner as in Example 1 (1) except that 1-bromoadamantane was changed to the 1-bromotetramantane obtained above.

(4) [Synthesis of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-tetramantyl) ethyne from dimethyl 5-bromo-isophthalate]
160. In the synthesis of Example 1 (2), except that 64.26 g (0.401 mol) of 1-ethynyladamantane was changed to 126.9 g (0.401 mol) of 1-ethynyltetramantane obtained above, 160. 0 g of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-tetramantyl) ethyne was obtained (yield 78%).

(5) [Synthesis of 5- (2- (1-tetramantyl) ethynyl) isophthalic acid dipotassium salt from 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-tetramantyl) ethyne]
In the synthesis of Example 1 (3), 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne (120 g, 0.341 mol) was obtained as described above. 151.6 g of 5- (2- (1-tetramantyl) ethynyl) isophthalate in the same manner except that 159.2 g (0.313 mol) of bis (methoxycarbonyl) phenyl) -2- (1-tetramantyl) ethyne The acid dipotassium salt was obtained (yield 87%).

(6) [Synthesis of 5- (2- (1-tetramantyl) ethynyl) isophthalic acid from 5- (2- (1-tetramantyl) ethynyl) isophthalic acid dipotassium salt]
In the synthesis of Example 1 (4), 7.6 g (0.019 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained above. 5- (2- (1-tetramantyl) 8.4 g of 5- (2- (1-tetramantyl) ethynyl) isophthalic acid was obtained in the same manner except that 10.6 g (0.019 mol) of ethynyl) isophthalic acid dipotassium salt (yield 92%).

(7) [Synthesis of 5- (2- (1-tetramantyl) ethynyl) isophthalic acid dichloride from 5- (2- (1-tetramantyl) ethynyl) isophthalic acid dipotassium salt]
In Example 1 (5), 96.1 g (0.24 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained above. 5- (2- (1-tetramantyl) ethynyl) Except for using 133.6 g (0.24 mol) of isophthalic acid dipotassium salt, 26.1 g of 5- (2- (1-tetramantyl) ethynyl) isophthalic acid dichloride was obtained (yield 21%). ).

  The spectral data of 5- (2- (1-tetramantyl) ethynyl) isophthalic acid and 5- (2- (1-tetramantyl) ethynyl) isophthalic acid dichloride obtained above are shown below. These data indicate that the obtained compound is the target product.

[5- (2- (1-tetramantyl) ethynyl) isophthalic acid (C ₃₂ H ₃₂ O ₄ )]
Appearance: White powder IR: 1710-1680 cm ⁻¹ (carboxylic acid), 2260-2190 cm ⁻¹ (ethynyl group)
Elemental analysis: Theoretical value C: 79.97% H: 6.71% O: 13.32%
Actual value C: 79.74% H: 6.52% O: 13.74%

[5- (2- (1-tetramantyl) ethynyl) isophthalic acid dichloride (C ₃₂ H ₃₀ Cl ₂ O ₂ )]
Appearance: White powder IR: 1800-1770 cm ⁻¹ (carboxylic acid chloride), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 447 (M ⁺ -2Cl)
Elemental analysis: Theoretical value C: 74.28% H: 5.84% Cl: 13.70% O: 6.18%
Actual value C: 74.02% H: 5.88% Cl: 13.59% O: 6.51%
The measurement results of relative permittivity are shown below.
Relative permittivity: 2.6

Example 4
(1) [Synthesis of 1,1′-biadamantane]
1,1′-biadamantane was synthesized from 1-bromoadamantane according to the method described in the literature (Reinhardt, HF Journal of Organic Chemistry 1962, 27, 3258).

(2) [Synthesis of 3-bromo-1,1′-biadamantane]
In Example 3 (2), 3-bromo-1 was similarly prepared except that 132.8 g (0.455 mol) of tetramantane was changed to 123.1 g (0.455 mol) of 1,1′-biadamantane obtained above. , 1'-biadamantane was obtained (yield 96%).

(3) [Synthesis of 3-ethynyl-1,1′-biadamantane]
12eth g of 3-ethynyl-1,1′-biadamantane was synthesized in the same manner as in Example 1 (1) except that 1-bromoadamantane was changed to 3-bromo-1,1′-biadamantane obtained above. did.

(4) [Synthesis of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (3- (1,1′-biadamantyl)) ethyne from dimethyl 5-bromo-isophthalate]
In the synthesis of Example 1 (2), except that 64.26 g (0.401 mol) of 1-ethynyladamantane was changed to 118.0 g (0.401 mol) of 3-ethynyl-1,1′-biadamantane obtained above. Similarly, 155.0 g of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (3- (1,1′-biadamantyl)) ethyne was obtained (yield 79%).

(5) From [1- (3,5-bis (methoxycarbonyl) phenyl) -2- (3- (1,1′-biadamantyl)) ethyne to 5- (2- (3- (1,1′-) Biadamantyl)) ethynyl) isophthalic acid dipotassium salt]
In the synthesis of Example 1 (3), 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne (120 g, 0.341 mol) was obtained as described above. -Bis (methoxycarbonyl) phenyl) -2- (3- (1,1′-biadamantyl)) ethyne 139.3 g of 5- (2- (3- (1,1′-biadamantyl)) ethynyl) isophthalic acid dipotassium salt was obtained (yield 83%).

(6) [5- (2- (3- (1,1′-biadamantyl)) ethynyl) isophthalic acid dipotassium salt to 5- (2- (3- (1,1′-biadamantyl)) ethynyl) Synthesis of isophthalic acid]
In the synthesis of Example 1 (4), 7.6 g (0.019 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained above. 5- (2- (3- (1 , 1′-Biadamantyl)) ethynyl) isophthalic acid dipotassium salt In the same manner as in 10.2 g (0.019 mol), 5- (2- (3- (1,1′-biadamantyl)) ethynyl ) 7.8 g of isophthalic acid was obtained (yield 89%).

(7) [5- (2- (3- (1,1′-biadamantyl)) ethynyl) isophthalic acid dipotassium salt to 5- (2- (3- (1,1′-biadamantyl)) ethynyl) Synthesis of isophthalic acid dichloride]
In Example 1 (5), 96.1 g (0.24 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained above. 5- (2- (3- (1,1 '-Biadamantyl)) ethynyl) isophthalic acid dipotassium salt 128.3 g (0.24 mol) in the same manner, 36.9 g of 5- (2- (3- (1,1'-biadamantyl)) ) Ethynyl) isophthalic acid dichloride was obtained (yield 31%).

  5- (2- (3- (1,1′-biadamantyl)) ethynyl) isophthalic acid and 5- (2- (3- (1,1′-biadamantyl)) ethynyl) isophthalic acid The spectrum data of chloride is shown below. These data indicate that the obtained compound is the target product.

[5- (2- (3- (1,1′-biadamantyl)) ethynyl) isophthalic acid (C ₃₀ H ₃₄ O ₄ )]
Appearance: White powder IR: 1710-1680 cm ⁻¹ (carboxylic acid), 2260-2190 cm ⁻¹ (ethynyl group)
Elemental analysis: Theoretical value C: 78.57% H: 7.47% O: 13.96%
Actual value C: 78.34% H: 7.52% O: 14.14%

[5- (2- (3- (1,1′-biadamantyl)) ethynyl) isophthalic acid dichloride (C ₃₀ H ₃₂ Cl ₂ O ₂ )]
Appearance: White powder IR: 1800-1770 cm ⁻¹ (carboxylic acid chloride), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 424 (M ⁺ -2Cl)
Elemental analysis: Theoretical value C: 72.72% H: 6.51% Cl: 14.31% O: 6.46%
Actual measurement C: 72.66% H: 6.59% Cl: 14.59% O: 6.16%
The measurement results of relative permittivity are shown below.
Relative permittivity: 2.6

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

(2) [Synthesis of 1- (4-methoxycarbonylphenyl) -2- (1-adamantyl) ethyne from dimethyl 4-bromo-benzoate]
In the same manner as in Example 1 (2), except that 125 g (0.458 mol) of dimethyl 5-bromo-isophthalate was changed to 96.9 g (0.451 mol) of dimethyl 4-bromo-benzoate, 96.80 g of 1 -(4-Methoxycarbonylphenyl) -2- (1-adamantyl) ethyne was synthesized (yield 82%).

(3) [Synthesis of 4- (2- (1-adamantyl) ethynyl) benzoic acid potassium salt from 1- (4-methoxycarbonylphenyl) -2- (1-adamantyl) ethyne]
In Example 1 (3), 1- (4-methoxycarbonylphenyl) was obtained as described above in an amount of 120 g (0.341 mol) of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne. 90.3 g of 4- (2- (1-adamantyl) ethynyl) benzoic acid potassium salt was synthesized in the same manner except that 96.8 g (0.329 mol) of) -2- (1-adamantyl) ethyne was used ( Yield 98%).

(4) [Synthesis of 4- (2- (1-adamantyl) ethynyl) benzoic acid from 4- (2- (1-adamantyl) ethynyl) benzoic acid potassium salt]
In Example 1 (4), 7.6 g (0.019 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt obtained above (4- (2- (1-adamantyl) ethynyl)) 5.17 g of 4- (2- (1-adamantyl) ethynyl) benzoic acid was synthesized in the same manner except that 6.1 g (0.019 mol) of potassium benzoate was used (yield 97%).

(5) [Synthesis of 4- (2- (1-adamantyl) ethynyl) benzoic acid chloride from 4- (2- (1-adamantyl) ethynyl) benzoic acid potassium salt]
In Example 1 (5), 96.1 g (0.24 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained above. 4- (2- (1-adamantyl) ethynyl) 33.0 g of 4- (2- (1-adamantyl) ethynyl) benzoic acid chloride was synthesized in the same manner except that 76.43 g (0.24 mol) of potassium benzoate was used (yield 46%).

The spectral data of 4- (2- (1-adamantyl) ethynyl) benzoic acid and 4- (2- (1-adamantyl) ethynyl) benzoic acid chloride obtained above are shown below. These data indicate that the obtained compound is the target product.

[4- (2- (1-adamantyl) ethynyl) benzoic acid (C ₁₉ H ₂₀ O ₂ )]
Appearance: White powder IR: 1710-1680 cm ⁻¹ (carboxylic acid), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 280 (M ^<+> )
Elemental analysis: Theoretical value C: 81.40% H: 7.19% O: 11.41%
Actual measurement C: 81.32% H: 7.21% O: 11.47%

[4- (2- (1-adamantyl) ethynyl) benzoic acid chloride (C ₁₉ H ₁₉ ClO)]
Appearance: White powder IR: 1800-1770 cm ⁻¹ (carboxylic acid chloride), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 263 (M ^<+> -Cl)
Elemental analysis: Theoretical value C: 76.37% H: 6.41% Cl: 11.86 O: 5.35%
Found C: 76.45% H: 6.48% Cl: 11.92 O: 5.15%
The measurement results of relative permittivity are shown below.
Dielectric constant: 2.7

(Example 6)
(1) [Synthesis of tetramantane]
Tetramantane was synthesized according to the method described in Example 3 (1).

(2) [Synthesis of 1-bromotetramantane]
According to the method described in Example 3 (2), 1-bromotetramantane was synthesized from the tetramantane obtained above.

(3) [Synthesis of 1-ethynyltetramantane]
According to the method described in Example 3 (3), 128.1 g of 1-ethynyltetramantane was synthesized.

(4) [Synthesis of 1- (4-methoxycarbonylphenyl) -2- (1-tetramantyl) ethyne from methyl 4-bromo-benzoate]
In Example 1 (2), 125 g (0.458 mol) of dimethyl 5-bromo-isophthalate was changed to 96.9 g (0.451 mol) of dimethyl 4-bromo-benzoate and 64.26 g (0.401 mol) of 1-ethynyladamantane. ) In the same manner except that 126.9 g (0.401 mol) of 1-ethynyltetramantane obtained above was obtained, 139.7 g of 1- (4-methoxycarbonylphenyl) -2- (1-tetramantyl) ethyne was obtained. Synthesized (yield 77%).

(5) [Synthesis of 4- (2- (1-tetramantyl) ethynyl) benzoic acid potassium salt from 1- (4-methoxycarbonylphenyl) -2- (1-tetramantyl) ethyne]
In the synthesis of Example 1 (3), 120 g (0.341 mol) of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne was obtained as described above. 132.4 g of 4- (2- (1-tetramantyl) ethynyl) benzoic acid potassium salt is obtained in the same manner except that 139.7 g (0.310 mol) of carbonylphenyl) -2- (1-tetramantyl) ethyne is obtained. (Yield 90%).

(6) [Synthesis of 4- (2- (1-tetramantyl) ethynyl) benzoic acid from 4- (2- (1-tetramantyl) ethynyl) benzoic acid potassium salt]
In the synthesis of Example 1 (4), 7.6 g (0.019 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained above. 4- (2- (1-tetramantyl) Ethinyl) benzoic acid potassium salt 8.0 g of 4- (2- (1-tetramantyl) ethynyl) benzoic acid was obtained in the same manner except that 9.0 g (0.019 mol) was obtained (yield 96%).

(7) [Synthesis of 4- (2- (1-tetramantyl) ethynyl) benzoic acid chloride from 4- (2- (1-tetramantyl) ethynyl) benzoic acid potassium salt]
In Example 1 (5), 96.1 g (0.24 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained as above (4- (2- (1-tetramantyl) ethynyl)) Except for using 113.9 g (0.24 mol) of benzoic acid potassium salt, 28.4 g of 4- (2- (1-tetramantyl) ethynyl) benzoic acid chloride was obtained in the same manner (yield 26%).

  The spectral data of 4- (2- (1-tetramantyl) ethynyl) benzoic acid and 4- (2- (1-tetramantyl) ethynyl) benzoic acid chloride obtained above are shown below. These data indicate that the obtained compound is the target product.

[4- (2- (1-tetramantyl) ethynyl) benzoic acid (C ₃₁ H ₃₂ O ₂ )]
Appearance: White powder IR: 1710-1680 cm ⁻¹ (carboxylic acid), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 436 (M ^<+> )
Elemental analysis: Theoretical value C: 85.27% H: 7.39% O: 7.34%
Actual measurement C: 85.32% H: 7.21% O: 7.47%

[4- (2- (1-tetramantyl) ethynyl) benzoic acid chloride (C ₃₁ H ₃₁ ClO)]
Appearance: White powder IR: 1800-1770 cm ⁻¹ (carboxylic acid chloride), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 419 (M ^<+> -Cl)
Elemental analysis: Theoretical value C: 81.83% H: 6.87% Cl: 7.79 O: 3.51%
Actual value C: 81.65% H: 6.78% Cl: 7.92 O: 3.65%
The measurement results of relative permittivity are shown below.
Relative permittivity: 2.6

(Example 7)
(1) [Synthesis of 1,1′-biadamantane]
According to the method described in Example 4 (1), 1,1′-biadamantane was synthesized.

(2) [Synthesis of 3-bromo-1,1′-biadamantane]
According to the method described in Example 4 (2), 3-bromo-1,1′-biadamantane was synthesized from the 1,1′-biadamantane obtained above.

(3) [Synthesis of 3-ethynyl-1,1′-biadamantane]
According to the method described in Example 4 (3), 3-ethynyl-1,1′-biadamantane was synthesized from 3-bromo-1,1′-biadamantane obtained above.

(4) [Synthesis of 1- (4-methoxycarbonylphenyl) -2- (3- (1,1′-biadamantane)) ethyne from methyl 4-bromo-benzoate]
In Example 1 (2), 125 g (0.458 mol) of dimethyl 5-bromo-isophthalate was changed to 96.9 g (0.451 mol) of dimethyl 4-bromo-benzoate, and 64.26 g (0.401 mol) of 1-ethynyladamantane was obtained. ) In the same manner except that 118.1 g (0.401 mol) of 3-ethynyl-1,1′-biadamantane obtained above was obtained, 128.9 g of 1- (4-methoxycarbonylphenyl) -2- ( 3- (1,1′-biadamantane)) ethyne was synthesized (yield 75%).

(5) [1- (4-Methoxycarbonylphenyl) -2- (3- (1,1′-biadamantane)) ethyne to 4- (2- (3- (1,1′-biadamantane)) ethynyl ) Synthesis of potassium benzoate]
In the synthesis of Example 1 (3), 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne (120 g, 0.341 mol) was obtained as described above. 124.7 g of 4- (2- (3- (1) are similarly obtained except that 128.9 g (0.301 mol) of carbonylphenyl) -2- (3- (1,1′-biadamantane)) ethyne. , 1'-biadamantane)) ethynyl) benzoic acid potassium salt was obtained (yield 94%).

(6) [4- (2- (3- (1,1′-biadamantane)) ethynyl) benzoic acid potassium salt to 4- (2- (3- (1,1′-biadamantane)) ethynyl) benzoic acid Synthesis of acid]
In the synthesis of Example 1 (4), 7.6 g (0.019 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained above. 4- (2- (3- (1 , 1′-biadamantane)) ethynyl) benzoic acid potassium salt, except that 8.4 g (0.019 mol), 4- (2- (3- (1,1′-biadamantane)) ethynyl) 7.7 g of benzoic acid was obtained (yield 98%).

(7) [4- (2- (3- (1,1′-biadamantane)) ethynyl) benzoic acid potassium salt to 4- (2- (3- (1,1′-biadamantane)) ethynyl) benzoic acid Synthesis of acid chloride]
In Example 1 (5), 96.1 g (0.24 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained in the above manner as 4- (2- (3- (1,1 '-Biadamantane)) ethynyl) benzoic acid potassium salt 105.3 g (0.24 mol) in the same manner, 35.3 g of 4- (2- (3- (1,1′-biadamantane)) Ethynyl) benzoic acid chloride was obtained (yield 34%).

  4- (2- (3- (1,1′-biadamantane)) ethynyl) benzoic acid and 4- (2- (3- (1,1′-biadamantane)) ethynyl) benzoic acid chloride obtained above The spectral data of the product is shown below. These data indicate that the obtained compound is the target product.

[4- (2- (3- (1,1′-biadamantyl)) ethynyl) benzoic acid (C ₂₉ H ₃₄ O ₂ )]
Appearance: White powder IR: 1710-1680 cm ⁻¹ (carboxylic acid), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 414 (M ^<+> )
Elemental analysis: Theoretical value C: 84.02% H: 8.27% O: 7.72%
Measured value C: 83.96% H: 8.21% O: 7.83%

[4- (2- (3- (1,1′-biadamantyl)) ethynyl) benzoic acid chloride (C ₂₉ H ₃₃ ClO)]
Appearance: White powder IR: 1800-1770 cm ⁻¹ (carboxylic acid chloride), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 397 (M ^<+> -Cl)
Elemental analysis: Theoretical value C: 80.44% H: 7.68% Cl: 8.19 O: 3.69%
Actual value C: 80.25% H: 7.78% Cl: 8.02 O: 3.95%
The measurement results of relative permittivity are shown below.
Relative permittivity: 2.6

(Example 8)
(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 flask was charged with nitrogen, and heated to reflux for 30 minutes in 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 four-necked 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 poured into the flask to dissolve with stirring. Then, it was made -15 degreeC by cooling with an ice / methanol bath, the 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. Then, 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]
In a 4-neck 100 ml flask equipped with a thermometer, a Dimroth condenser, a nitrogen inlet tube and a stirrer, 1- (1- (3,5-dimethyladamantyl))-4-trifluoromethanesulfonyloxy obtained above was added. 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 in 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. This 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 1- (4-ethynylphenyl) -3,5-dimethyladamantane]
In a 5 L four-necked flask equipped with a thermometer, a Dimroth condenser and a stirrer, 3 liters of n-butanol and 226 g (2.72 mol) of potassium hydroxide (85%) were charged and dissolved by heating under reflux. To this was added 110.0 g (0.341 mol) of 1- (1- (3,5-dimethyladamantyl))-4- (3-hydroxy-3-methyl- (1-butynyl)) benzene obtained above. And refluxed 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 dimethyl 5- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalate from dimethyl 5-bromo-isophthalate]
In Example 1 (2), 64.26 g (0.401 mol) of 1-ethynyladamantane is converted to 106.0 g (0.401 mol) of 1- (4-ethynylphenyl) -3,5-dimethyladamantane obtained above. In the same manner, 137.3 g of dimethyl 5- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalate was synthesized (yield 75%).

(6) [5- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalate dimethyl to 5- (2- (4- (1- (3,5-dimethyladamantyl) )) Synthesis of phenyl) ethynyl) isophthalic acid dipotassium salt]
In the synthesis of Example 1 (3), 120 g (0.341 mol) of 1- (3,5-bis (methoxycarbonyl) phenyl) -2- (1-adamantyl) ethyne was obtained above. 142.8 g of 5- (2- (4- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid except that 137.3 g (0.301 mol) was used. 1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid dipotassium salt was obtained (yield 94%).

(7) From [5- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid dipotassium salt, 5- (2- (4- (1- (3,5- Synthesis of dimethyladamantyl)) phenyl) ethynyl) isophthalic acid]
In the synthesis of Example 1 (4), 7.6 g (0.019 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained above. 5- (2- (4- (1 -(3,5-Dimethyladamantyl)) phenyl) ethynyl) isophthalic acid dipotassium salt 9.6 g (0.019 mol) in the same manner as in 5- (2- (4- (1- (3,5 -8.0 g of dimethyladamantyl)) phenyl) ethynyl) isophthalic acid were obtained (yield 98%).

(8) From [5- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid dipotassium salt, 5- (2- (4- (1- (3,5- Synthesis of dimethyladamantyl)) phenyl) ethynyl) isophthalic acid dichloride]
In Example 1 (5), 96.1 g (0.24 mol) of 5- (2- (1-adamantyl) ethynyl) isophthalic acid dipotassium salt was obtained above. 3,8.0 g of 5- (2- (4- (1- (3)) in the same manner except that 121.1 g (0.24 mol) of 3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid dipotassium salt. , 5-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid dichloride was obtained (yield 34%).

  5- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid and 5- (2- (4- (1- (3,5-dimethyladamantyl)) obtained above The spectral data of) phenyl) ethynyl) isophthalic acid dichloride are shown below. These data indicate that the obtained compound is the target product.

[5- (2- (4- (1- (3,5-dimethyl adamantyl)) phenyl) ethynyl) isophthalic acid _{(C 28 H 28 O 4)} ]
Appearance: White powder IR: 1710-1680 cm ⁻¹ (carboxylic acid), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 428 (M ^<+> )
Elemental analysis: Theoretical value C: 78.48% H: 6.59% O: 14.93%
Actual value C: 78.12% H: 6.14% O: 14.74%

[5- (2- (4- (1- (3,5-dimethyladamantyl)) phenyl) ethynyl) isophthalic acid dichloride (C ₂₈ H ₂₆ Cl ₂ O ₂ )]
Appearance: White powder IR: 1800-1770 cm ⁻¹ (carboxylic acid chloride), 2260-2190 cm ⁻¹ (ethynyl group)
MS (FD) (m / z): 394 (M ^<+ > ^- 2Cl)
Elemental analysis: Theoretical value C: 72.26% H: 5.63% Cl: 15.24 O: 6.88%
Actual value C: 72.41% H: 5.08% Cl: 15.70 O: 6.81%
The measurement results of relative permittivity are shown below.
Dielectric constant: 2.7

(Comparative Example 1)
(1) [Synthesis of 5- (4-ethynylphenoxy) isophthalic acid dichloride]
5- (4-Ethynylphenoxy) isophthalic acid according to the method described in the literature (B. J. Jensen and PM Hergenroter, Journal of Polymer Science: Polymer Chemistry Edition, Vol. 23, 2233-2246, 1985). Dichloride was synthesized.
The measurement results of relative permittivity are shown below.
Relative dielectric constant: 3.7

  As is clear from the above, it was shown that the aromatic carboxylic acid and its acid halide provided by the present invention can be suitably used as a raw material for a polymer having a low relative dielectric constant.

  The aromatic carboxylic acid represented by the general formula (1) obtained by the present invention and the acid halide represented by the general formula (2) (1) can be active esterified, and the resin obtained therefrom is Since dielectric properties and mechanical properties can be improved, they are useful as raw materials for polymers, particularly condensation polymers.

Claims (9)

An aromatic carboxylic acid having a group represented by the general formula (1) having a substituent having an adamantane structure bonded to an ethynyl group.

(In the formula, R represents a substituent having an adamantane structure. In the formula, n is an integer of 1 or 2.)   The substituent containing the adamantane structure is 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, a biadamantyl group, or a triadamantyl group. Group, tetraadamantyl group, pentaadamantyl group, hexaadamantyl group, heptaadamantyl group, octaadamantyl group, nonaadamantyl group, decaadamantyl group, undecaadamantyl group, adamantylphenyl group, diamantylphenyl group, triamantylphenyl group , Tetramantylphenyl group, pentamantylphenyl group, hexamantylphenyl group, heptamantylphenyl group, octamantylphenyl group, nonamantylphenyl group Decamantylphenyl group, undecamantylphenyl group, biadamantylphenyl group, triadamantylphenyl group, tetraadamantylphenyl group, pentaadamantylphenyl group, hexaadamantylphenyl group, heptaadamantylphenyl group, octaadamantylphenyl group, nonaadamantylphenyl group , Decaadamantylphenyl group, undecaadamantylphenyl group, adamantylphenoxyphenyl group, diamantylphenoxyphenyl group, triamantylphenoxyphenyl group, tetramantylphenoxyphenyl group, pentamantylphenoxyphenyl group, hexamantylphenoxyphenyl Group, heptamantylphenoxyphenyl group, octamantylphenoxyphenyl group, nonamantylphenoxyphenyl group, Mantylphenoxyphenyl group, undecamantylphenoxyphenyl group, biadamantylphenoxyphenyl group, triadamantylphenoxyphenyl group, tetraadamantylphenoxyphenyl group, pentaadamantylphenoxyphenyl group, hexaadamantylphenoxyphenyl group, heptaadamantylphenoxyphenyl group, octa The aromatic carboxylic acid according to claim 1, which is at least one selected from an adamantylphenoxyphenyl group, a nonaadamantylphenoxyphenyl group, a decaadamantylphenoxyphenyl group, and an undecaadamantylphenoxyphenyl group.   The aromatic carboxylic acid according to claim 1 or 2, wherein the substituent containing the adamantane structure has an alkyl group having 1 to 20 carbon atoms. An acid halide of an aromatic carboxylic acid represented by the general formula (2), wherein the substituent having an adamantane structure has a group bonded to an ethynyl group.

(In the formula, R represents a substituent containing an adamantane structure, X represents a halogen atom, and n in the formula is an integer of 1 or 2.)   The substituent containing the adamantane structure is 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, a biadamantyl group, or a triadamantyl group. Group, tetraadamantyl group, pentaadamantyl group, hexaadamantyl group, heptaadamantyl group, octaadamantyl group, nonaadamantyl group, decaadamantyl group, undecaadamantyl group, adamantylphenyl group, diamantylphenyl group, triamantylphenyl group , Tetramantylphenyl group, pentamantylphenyl group, hexamantylphenyl group, heptamantylphenyl group, octamantylphenyl group, nonamantylphenyl group Decamantylphenyl group, undecamantylphenyl group, biadamantylphenyl group, triadamantylphenyl group, tetraadamantylphenyl group, pentaadamantylphenyl group, hexaadamantylphenyl group, heptaadamantylphenyl group, octaadamantylphenyl group, nonaadamantylphenyl group , Decaadamantylphenyl group, undecaadamantylphenyl group, adamantylphenoxyphenyl group, diamantylphenoxyphenyl group, triamantylphenoxyphenyl group, tetramantylphenoxyphenyl group, pentamantylphenoxyphenyl group, hexamantylphenoxyphenyl Group, heptamantylphenoxyphenyl group, octamantylphenoxyphenyl group, nonamantylphenoxyphenyl group, Mantylphenoxyphenyl group, undecamantylphenoxyphenyl group, biadamantylphenoxyphenyl group, triadamantylphenoxyphenyl group, tetraadamantylphenoxyphenyl group, pentaadamantylphenoxyphenyl group, hexaadamantylphenoxyphenyl group, heptaadamantylphenoxyphenyl group, octa The halide of the aromatic carboxylic acid according to claim 4, which is at least one selected from the group consisting of adamantylphenoxyphenyl group, nonaadamantylphenoxyphenyl group, decaadamantylphenoxyphenyl group and undecaadamantylphenoxyphenyl group.   The aromatic carboxylic acid and the aromatic carboxylic acid halide according to claim 4 or 5, wherein the substituent containing the adamantane structure has an alkyl group having 1 to 20 carbon atoms. The compound represented by general formula (5) obtained by reacting the compound represented by general formula (3) with the compound represented by general formula (4) is treated in the presence of an alkali metal hydroxide. A method for synthesizing the aromatic carboxylic acid represented by the general formula (1), wherein the compound represented by the general formula (6) is produced, and the product is further acid-treated.

(In the formula, R represents a substituent having an adamantane structure. In the formula, n is an integer of 1 or 2.)

(In the formula, Y represents a leaving group. In the formula, n is an integer of 1 or 2.)

(In the formula, R represents a substituent containing an adamantane structure.)

(In the formula, R represents a substituent having an adamantane structure. In the formula, n is an integer of 1 or 2.)

(In the formula, R represents a substituent containing an adamantane structure, M represents an alkali metal, and n in the formula is an integer of 1 or 2.)   A transition metal catalyst is used in the reaction between the compound represented by the general formula (3) and the compound represented by the general formula (4), and represented by the general formula (1) according to claim 7. A method for synthesizing aromatic carboxylic acids. A compound represented by the general formula (6) or a compound represented by the general formula (1) obtained by the synthesis method according to claim 7 or 8 is treated with a halogenating agent. A method for synthesizing an acid halide of an aromatic carboxylic acid represented by (2).

(In the formula, R represents a substituent having an adamantane structure. In the formula, n is an integer of 1 or 2.)

(In the formula, R represents a substituent containing an adamantane structure, X represents a halogen atom, and n in the formula is an integer of 1 or 2.)

(In the formula, R represents a substituent containing an adamantane structure, M represents an alkali metal, and n in the formula is an integer of 1 or 2.)