JP2008056615A - Vinylethynylaryl carboxylic acid, method for producing the same, and method for producing heat cross-linking compound by using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new vinylethynylaryl carboxylic acid compound useful as an intermediate for pharmaceuticals, agrochemicals, raw materials for functional materials such as liquid crystals, electronic materials, a highly durable resin, etc., and to provide a method for stably producing the same with high purity, and to provide a heat cross-linking compound using the vinylethynylaryl carboxylic acid as raw material. <P>SOLUTION: The invention relates to the compound represented by general formula (I). In the general formula (I), Q<SP>1</SP>is a phenylene group, a 1-naphthylene group, etc., n is 1 to 4. R<SP>1</SP>is a monovalent substituent selected from a carboxy group, alkoxycarbonyl group, etc., R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>are each H, Cl, an alkoxy group, an amino group, etc. Wherein the sum of atomic weights constituting the groups R<SP>2</SP>, R<SP>3</SP>, R<SP>4</SP>is greater than 55. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to novel vinylethynyl aromatic carboxylic acids useful as functional materials such as pharmaceutical and agrochemical intermediates, liquid crystals, electronic materials, and highly durable resins, a method for producing the same, and a method for producing a heat-crosslinkable compound using the same. .

Aryl ethynyl phthalate derivatives are important compounds as raw materials for functional materials such as intermediates for pharmaceuticals and agricultural chemicals, liquid crystals, electronic materials, and high durability resins, and in recent years, the carbon-carbon triple bond structure present in the molecule is utilized. It has been attracting attention as a research object for various functional materials. For example, phenyl ethynyl phthalic anhydride is used as a terminal blocker raw material that imparts thermosetting properties to a polyimide oligomer (see, for example, Patent Document 1 and Non-Patent Documents 1 to 3). The carbon-carbon triple bond bonded to the aryl group is stable at room temperature and exhibits a thermal crosslinking action when entering a certain temperature range, so that it is useful as a means for improving the moldability of the heat-resistant resin. It is known (for example, Non-Patent Document 4).
On the other hand, examples of using 3-ethynylaniline or 3-phenylethynylaniline as the end-capping material that imparts thermosetting properties are described in Non-Patent Document 5, but the curing temperatures of both differ by 100 ° C. or more. Therefore, for example, an ethynyl compound having a terminal hydrogen such as 3-ethynylaniline is susceptible to crosslinking in the temperature region of the dehydration ring-closing step in the synthesis of thermosetting resins such as polyimide and polybenzoxazole, Diarylethynylene compounds such as 3-phenylethynylaniline have a curing temperature that is too high, and this has adverse effects such as oxidation on the copper foil used in the field of electronic materials in combination with polyimide and polybenzoxazole. In order to obtain a crosslinking temperature corresponding to the middle of both, There ene - use of certain aniline compounds having the in-structure has been proposed.

However, on such an aromatic ring to which an electron-withdrawing group such as phthalic acid or benzoic acid is bonded, which is higher in crystallinity than general anilines and easy to handle in terms of excellent oxidation resistance, Substances to which vinylethynyl groups are bonded, examples of which are described in Non-Patent Document 6 or Non-Patent Document 7, but these specific aniline compounds are highly harmful tin compounds in terms of synthesis methods In addition, it is necessary to use an organic compound of zinc chloride having an expensive trimethylsilyl protecting group, and there is a problem that it is difficult to manufacture and high in cost, so that it is not practical, a raw material for end-capping agent that imparts thermosetting properties, etc. Therefore, a new compound having an ethynylaryl structure that is useful for the preparation and easy to produce has been desired.
US Pat. No. 5,567,800 “Polymer”, 1994, Vol. 35, p. 4874-4880 “Polymer”, 1994, Vol. 35, p. 4857-4864 “Functional Materials”, 2000, Vol. 20, No. 12, p. 33-40 “Polymer”, 2005, Vol. 18, p. 6968-6975 “Polymer Preprints”, 1984, Vol. 25, p. 110-111 “Journal of Organic Chemistry”, 1999, Vol. 64, p. 8873-8879 “Tetrahedron”, 2000, Vol. 56, p. 2533-2545

An object of the present invention is to provide vinylethynyl arylcarboxylic acids useful as raw materials for functional materials such as intermediates for medicines and agricultural chemicals, liquid crystals, electronic materials, and highly durable resins.
A further object of the present invention is to provide a method for producing the compound capable of obtaining vinylethynylarylcarboxylic acids having a stable and high purity, which can be carried out on an industrial scale, and thermal crosslinking using vinylethynylarylcarboxylic acids as raw materials. It is in providing the manufacturing method of an ionic compound.

  As a result of intensive studies by the present inventors, an electron-withdrawing group is used as a substituent by reacting an aryl halide bonded to a carbonyl structure with a 1-in-3-ol compound that can be produced at low cost in the presence of a catalyst. It was found that the aryl ethynyl vinyl compound having the above could be easily obtained, and the model oligomer made using the same was sufficiently separated from the diaryl ethynylene structure and the thermosetting temperature derived from the ethynyl aryl structure under the same conditions. The present invention was completed by finding an intermediate thermosetting temperature.

That is, the present invention is as follows.
<1> A compound represented by the following general formula (I).

In the general formula (I), Q ¹ represents a phenylene group, 1-naphthylene group, 2-naphthylene group, pyridinylene group, imidazolylene group, pyrazolylene group, or triazinylene group, and n is 1 to 4.
R ¹ is a monovalent substituent selected from a carboxyl group, an alkoxycarbonyl group, an aminocarbonyl group, and a 2-benzoxazolyl group. When n is 2 or more, a plurality of R ¹ may be the same as each other May be different. Here, when n is 2 or more, a plurality of R ¹ may be connected to form a ring, and the formed ring structure includes an acid anhydride and an imidodicarbonyl group. R ¹ may further have a substituent, and the terminal carboxyl group may have a salt structure.
R ² , R ³ and R ⁴ are each independently a hydrogen atom, chlorine atom, alkoxyl group, amino group, alkylamino group, dialkylamino group, diacylimino group, sulfonyl group, carboxyl group, alkoxycarbonyl group, hydroxyl group, mercapto Represents a group, an alkyl group, an aryl group, an alkynyl group, or an alkenyl group. Two or more of R ² , R ³ and R ⁴ may be connected to each other to form a ring, but the formed ring structure does not include an aromatic hydrocarbon ring. Here, the sum of the atomic weights constituting R ² , R ³ , and R ⁴ is greater than 55.

<2> In the general formula (I), n is 1 and R ¹ represents a carboxylic acid, or n is 2 and two R ¹ form a carboxylic acid anhydride, and , Q ¹ represents a phenylene group or a 2-naphthylene group, The compound according to <1>.
<3> The compound according to <1> or <2>, wherein the compound represented by the general formula (I) is a compound represented by the following formulas (1) to (12) or a salt thereof: . That is, the part of the carboxy group in the following formulas (1) to (12) may have a structure such as a sodium salt, a lithium salt, or a tetramethylammonium salt.

<4> Any one of <1> to <3>, comprising a step of reacting a compound represented by the following general formula (II) with a compound represented by the general formula (III) A method for producing the compound described in 1.

In the general formula (II), R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a chlorine atom, an alkoxyl group, an amino group, an alkylamino group, a dialkylamino group, a diacylimino group, a sulfonyl group, or a carboxyl group. Represents an alkoxycarbonyl group, a hydroxyl group, a mercapto group, an alkyl group, an aryl group, an alkynyl group, or an alkenyl group. Two or more of R ² , R ³ and R ⁴ may be connected to each other to form a ring, but the formed ring structure does not include an aromatic hydrocarbon ring. Here, the sum of the atomic weights constituting R ² , R ³ , and R ⁴ is greater than 55.

In the general formula (III), Q ¹ represents a phenylene group, 1-naphthylene group, 2-naphthylene group, pyridinylene group, imidazolylene group, pyrazolylene group, or triazinylene group, and n is 1 to 4.
R ¹ is a monovalent substituent selected from a carboxyl group, an alkoxycarbonyl group, an aminocarbonyl group, and a 2-benzoxazolyl group. When n is 2 or more, a plurality of R ¹ may be the same as each other May be different. Here, when n is 2 or more, a plurality of R ¹ may be connected to form a ring, and the formed ring structure includes an acid anhydride and an imidodicarbonyl group.
X represents a chlorine atom, a bromine atom, or an iodine atom.

<5> The method according to <4>, wherein one or more types of catalysts are used in the step of reacting the compound represented by the general formula (II) with the compound represented by the general formula (III). Manufacturing method.
<6> A method for producing a thermally crosslinkable compound, comprising using the compound according to any one of claims 1 to 3 as a raw material for a reactive crosslinking group.

Conventionally, in a method of introducing an ethynyl group into an aryl group, a 1-in-3-ol compound obtained by adding acetylene to a ketone, for example, a so-called acetylene alcohol such as 1-ethynyl-1-cyclohexanol is used. It is disclosed in “Journal of Organic Chemistry” (1983, Vol. 48, No. 25, pages 5135-5138) that it can be synthesized under reaction conditions using an aryl halide as a raw material and a catalyst. The acetylene alcohols are acidic except for special cases such as propargyl alcohol obtained by adding acetylene to formaldehyde and 1-phenyl-2-propyn-1-ol obtained by adding acetylene to benzaldehyde. Atmosphere It is known that a terminal ethynyl vinyl compound can be easily obtained by performing a dehydration reaction of a gas, “Bulletin of the Academy of Sciences of the USSR” (1958, 315-318). Page].
In the present invention, an aryl halide bonded to a carbonyl structure is selected, and this is reacted with a 1-in-3-ol compound in the presence of a catalyst. Therefore, an arylethynyl vinyl compound having an electron-withdrawing group as a substituent is obtained. High purity, stability, and reproducibility could be obtained.
Since the novel compound obtained here has a reactive cross-linked structure in a stable form, it is useful in a method for producing a heat cross-linkable compound.

  INDUSTRIAL APPLICABILITY According to the present invention, vinylethynyl arylcarboxylic acids useful as raw materials for functional materials such as intermediates for medicines and agricultural chemicals, liquid crystals, electronic materials, and highly durable resins, and methods for producing the same can be provided. Further, by using the vinyl ethynyl aryl carboxylic acids, a new crosslinking reactive molecule can be provided.

Hereinafter, the present invention will be described in detail.
First, the novel vinylethynyl arylcarboxylic acids represented by the following general formula (I) will be described.

In the general formula (I), Q ¹ represents a phenylene group, 1-naphthylene group, 2-naphthylene group, pyridinylene group, imidazolylene group, pyrazolylene group, or triazinylene group, and preferably phenylene group, 1-naphthylene group, imidazolylene. Group or a triazinylene group, more preferably a phenylene group or a 1-naphthylene group.
n is 1 to 4, preferably 1, 2, or 4, more preferably 1 or 2.

R ¹ is a monovalent substituent selected from a carboxyl group, an alkoxycarbonyl group, an aminocarbonyl group, and a 2-benzoxazolyl group. When n is 2 or more, a plurality of R ¹ may be the same as each other May be different. Here, when n is 2 or more, a plurality of R ¹ may be connected to form a ring, and the formed ring structure includes an acid anhydride and an imidodicarbonyl group.
R ¹ may have one or more substituents, and examples of the substituents that can be introduced include alkyl groups, aryl groups, alkoxy groups, amino groups, hydroxy groups, halogen atoms, carboxyl groups, alkoxycarbonyl groups, and sulfo groups. , An aminosulfonyl group, or a nitro group.
Specific examples when R ¹ is an alkoxycarbonyl group include a methoxycarbonyl, ethoxycarbonyl, 2-propoxycarbonyl, 1-propoxycarbonyl, 1-butoxycarbonyl, phenoxycarbonyl, or benzyloxycarbonyl group. Substituents whose crystallinity is improved by an alkoxyl group in that a high-purity compound can be easily synthesized, such as a benzyloxycarbonyl group, a succinylimino-N-oxycarbonyl group, and a phthaloilimino-N-oxycarbonyl group From the viewpoint that it can be synthesized at a low cost, a methoxycarbonyl group, an ethoxycarbonyl group, a 1-butoxycarbonyl group, and a phenoxycarbonyl group are preferable, and among them, a methoxycarbonyl group or an ethoxycarbonyl group is preferable.

Specific examples when R ¹ is an optionally substituted aminocarbonyl group include, for example, aminocarbonyl group, dimethylaminocarbonyl group, diethylaminocarbonyl group, butylaminocarbonyl group, morpholinocarbonyl group, phenylamino Examples include a carbonyl group, a benzylaminocarbonyl group, a phthalominocarbonyl group, a hydrazoiminocarbonyl group, or an octylaminocarbonyl group, among which an aminocarbonyl group, a diethylaminocarbonyl group, a butylaminocarbonyl group, a morpholinocarbonyl group, or A phenylaminocarbonyl group is preferable, and an aminocarbonyl group and a phenylaminocarbonyl group are more preferable.

Specific examples when R ¹ is an optionally substituted 2-benzoxazolyl group include an unsubstituted benzoxazolyl group, a 2- (5-amino) benzoxazolyl group, 2- (5-hydroxy) benzoxazolyl group, 2- (6-amino-5-hydroxy) benzoxazolyl group, 2- (5-chloro) benzoxazolyl group, or 2- (5-bromo ) Benzoxazolyl group, among them, unsubstituted benzoxazolyl group, 2- (5-amino) benzoxazolyl group, 2- (5-hydroxy) benzoxazolyl group, or 2 A-(6-amino-5-hydroxy) benzoxazolyl group is preferable, and a 2- (5-amino) benzoxazolyl group or a 2- (5-hydroxy) benzoxazolyl group is more preferable.

In the general formula (I), when n is 2 or more, a plurality of R ¹ may be connected to each other to form a ring. Examples of the formed ring structure include an acid anhydride structure, N— Examples include phenylimide structure, N-methylimide structure, N-pentafluoroethylimide structure, N- (4′-amino) phenylimide structure, N- (3′-amino) phenylimide structure, etc. An acid anhydride structure, an N-phenylimide structure, an N- (4′-amino) phenylimide structure, or an N- (3′-amino) phenylimide structure is preferable, and an acid anhydride structure or N- (3′- An amino) phenylimide structure is more preferred.

In the general formula (I), as a preferred embodiment, n is 1, R ¹ represents a carboxylic acid, Q ¹ represents a phenylene group or a 2-naphthylene group, and n is 2. there are forms two R ¹ is a carboxylic acid anhydride bonded together, and, Q ¹ can be mentioned a compound represents a phenylene group or a 2-naphthylene group.

R ² , R ³ and R ⁴ are each independently a hydrogen atom, chlorine atom, alkoxyl group, amino group, alkylamino group, dialkylamino group, diacylimino group, sulfonyl group, carboxyl group, alkoxycarbonyl group, hydroxyl group, mercapto Represents a group, an alkyl group, an aryl group, an alkynyl group, or an alkenyl group. Two or more of R ² , R ³ and R ⁴ may be connected to each other to form a ring, but the formed ring structure does not include an aromatic hydrocarbon ring. Here, the sum of the atomic weights constituting R ² , R ³ , and R ⁴ is greater than 55.
R ² , R ³ , and R ⁴ may each have a substituent, and examples of the substituent that can be introduced include an alkyl group, an aryl group, an alkoxy group, a dialkylamino group, a hydroxy group, and a fluorine atom. Is mentioned.

R ² , R ³ , and R ⁴ are preferably an alkoxyl group, a dialkylamino group, a diacylimino group, a sulfonyl group, an alkoxycarbonyl group, a hydroxyl group, a mercapto group, an alkyl group, and an alkynyl group, and an alkoxyl group, an alkoxycarbonyl group, More preferred are a hydroxyl group, a mercapto group, and an alkyl group.
More specific examples of R ² , R ³ , and R ⁴ include a methoxy group, an ethoxy group, a 2-propoxyl group, a butylamino group, a diethylamino group, a maleino group, a phthalimino group, a methoxycarbonyl group, and an ethoxycarbonyl group. Methyl group, ethyl group, 1-propyl group, 2-propyl group, n-butyl group, tert-butyl group, or ethynyl group.

  Among them, methoxy group, ethoxy group, 2-propoxyl group, diethylamino group, maleino group, phthalimino group, methoxycarbonyl group, ethoxycarbonyl group, methyl group, ethyl group, 1-propyl group, 2-propyl group, n- A butyl group, a tert-butyl group, or an ethynyl group is preferable, and a hydrogen atom, an amino group, a sulfonyl group, a hydroxyl group, and a mercapto group are also preferable, and a methoxy group, an ethoxy group, and a 2-propoxyl group are more preferable. , A methoxycarbonyl group, an ethoxycarbonyl group, a methyl group, an ethyl group, a 2-propyl group, a tert-butyl group, a hydroxyl group, or a mercapto group.

Further, a specific embodiment in which two or more of R ² , R ³ and R ⁴ are linked to each other to form a ring structure and the ring structure is not an aromatic hydrocarbon ring, Structures such as cyclohexenyl, 2,6-dimethylcyclohex-1-yl, 1-thiophenyl, 2-thiophenyl, 1- (3,4-dihydro) naphthyl ring including vinyl group in formula (I) are mentioned. Preferably, it is a cyclohexenyl, 1-thiophenyl, or 1- (3,4-dihydro) naphthyl ring, and more preferably cyclohexenyl or 1-thiophenyl.

In the general formula (I), the sum of the atomic weights of R ² , R ³ , and R ⁴ is 55 or more. Under certain conditions, the raw material compound having a vinyl ethynyl group may evaporate and the reaction may not proceed sufficiently, resulting in a problem that it is not suitable for synthesis on a production scale.
The sum of R ^{2, R 3,} and atomic weight of ^{R 4 is,} all atoms constituting R 2, ^{R 3,} and ^{R 4,} i.e., in those having a substituent, in sum atomic weight, including also the substituent Yes, about 55-161 is preferable, and the range of 65-104 is more preferable.
Even when any of R ² , R ³ , and R ⁴ is a low molecular weight substituent such as a methyl group or an ethyl group, the effects of the present invention can be obtained if the sum of the atomic weights of these three functional groups is 55 or more. It can be said that he can play.

In the general formula (I) in the present invention, as a preferred embodiment, a compound in which n is 1, R ¹ represents a carboxyl group, and Q ¹ represents a phenylene group or a 2-naphthylene group, and n there forms a carboxylic acid anhydride two R ¹ a 2 are bonded to each other, and, Q ¹ represents a phenylene group or a 2-naphthylene group, and, R ^{2, R 3,} and R ⁴ are each a hydrogen atom, a methyl group, an ethyl group, 2-propyl, t- butyl group or compound represents a phenyl group, and the like. From such a viewpoint, the exemplary compounds (1) to (12) are preferable, and exemplary compounds (1), (2), (9), and (10) are particularly preferable.
These compounds may have a salt structure, in which case the carboxylic acid moiety may have a structure such as a sodium salt, a lithium salt, or a tetramethylammonium salt.

  Next, the suitable manufacturing method of vinylethynyl aryl carboxylic acid which is a compound represented by the said general formula (I) of this invention is demonstrated.

The vinyl ethynyl aryl carboxylic acids represented by the general formula (I) of the present invention include, for example, a copper iodide and a phosphine in a basic condition by using a substituted or unsubstituted aryl acetylene compound and a phthalic acid diester having a halogen substituent. The synthesis can be performed with reference to a synthesis method in which a palladium (II) complex having a ligand is used as a catalyst, for example, a synthesis method such as JP-A-2006-76991. According to this method, the vinylethynylarylcarboxylic acids represented by the general formula (I) of the present invention can be synthesized with good yield, which is one of the preferred methods.
Specifically, a vinyl ethynyl compound represented by the following general formula (II) is used as a compound having an ethynyl group, and this is reacted with a halogenated arylcarboxylic acid represented by the general formula (III) described later. Thus, an intermediate for synthesizing the compound represented by the general formula (I) and the compound represented by the general formula (I) with high purity can be synthesized.

In the general formula (II), n, R ² , R ³ , and R ⁴ have the same meanings as in the general formula (I).

In the general formula (III), Q ¹ , R ¹ and n have the same meanings as in the general formula (I). X represents a chlorine atom, a bromine atom, or an iodine atom.

  Next, the compound represented by the general formula (II) and the general formula (III) is reacted to give the compound represented by the general formula (I) or a derivative thereof, for example, an intermediate used for the synthesis of the compound Explain how to lead.

The reaction conditions for synthesizing the compound represented by the general formula (I) or the derivative thereof by reacting the compounds represented by the general formula (II) and the general formula (III) include the presence of a catalyst under basic conditions. Under the conditions, room temperature or heating is preferably performed so that hydrogen halide is eliminated. Specifically, the coupling reaction of each of the above compounds is preferably performed in an organic solvent in the presence of a base and a catalyst.
The base that can be used in this reaction may be either an inorganic base or an organic base, but is preferably weakly basic. In addition, in the case of an organic base, particularly an amine compound, the compound represented by the above general formula (III) is used. From the viewpoint of little influence, a secondary amine or a tertiary amine is preferable to a primary amine.

Specific examples of the base used in this reaction include carbonates such as sodium carbonate, lithium carbonate, potassium carbonate, calcium carbonate and magnesium carbonate, bicarbonates such as sodium bicarbonate and potassium bicarbonate, triethylamine and diisopropylamine. Organic bases such as diisopropylethylamine, tributylamine, morpholine, N-methylmorpholine, triethanolamine, piperazine, piperidine, dimethylaniline, diethylaniline, pyrrolidine, imidazole, pyrazole, among others, sodium carbonate, potassium carbonate, Sodium bicarbonate, triethylamine, diisopropylamine, tributylamine, N-methylmorpholine, and dimethylaniline are preferred, and triethylamine, diisopropylamine, dimethylaniline are preferred. Ruanirin is more preferable.
When the base itself is used as a reaction solvent, the base may be used in an amount of about 10 to 20 equivalents. When another solvent is used in combination, the base is used in an amount of 1 to 8 equivalents. Is preferred, 1.5 to 5 equivalents are more preferred, and most preferably 2 to 4 equivalents.

The central metal of the catalyst used in the coupling reaction for synthesizing the compound represented by the general formula (I) by reacting the compound represented by the general formula (II) with the compound represented by the general formula (III) Examples thereof include palladium, nickel, rhodium, cobalt and the like, and the metal may contain a plurality of types. Palladium or rhodium is preferable, and palladium is more preferable. The central metal may be zero-valent or cation.
The catalyst may be bonded to a ligand to show its activity, a complex with a diketone compound, a complex with a phosphine ligand, a metal adsorbed with activated carbon instead of the ligand, such as palladium carbon Is preferable as a catalyst, but an embodiment in which coordination with phosphine is performed or an adsorption mode with activated carbon is preferable. Specific examples of the ligand include dibenzylacetone, acetylacetone, triphenylphosphine, tri (o-toluyl) phosphine, tri-n-butylphosphine, tricyclohexylphosphine, and tritert-butylphosphine. However, dibenzylacetone, triphenylphosphine, tri (o-toluyl) phosphine, tri-n-butylphosphine, or tricyclohexylphosphine is preferable, and triphenylphosphine or tri (o-toluyl) phosphine is more preferable. This ligand may be generated in a reaction vessel for synthesizing the compound represented by the general formula (I) or may be present in advance in a reaction solvent.
The addition amount of the catalyst is usually preferably about 1.0 × 10 ^{−7 to} 1.0 × 10 ⁻² in terms of molar ratio with respect to 1 mol of the compound represented by the general formula (III). However, the amount of the catalyst may be an amount exceeding the number of ligands that can be bound.

In synthesizing the compound represented by the general formula (I) by reacting the compound represented by the general formula (II) and the compound represented by the general formula (III), a cocatalyst is used together with the above-mentioned base and catalyst. A co-catalyst that may be used in the present invention includes a copper compound or an onium salt, and these may be added.
Copper compounds as promoters include copper (I) iodide, copper (II) tartrate, copper (II) acetate, copper (I) acetate, copper (I) bromide, copper (I) chloride, or copper oxide (I) can be mentioned, among which copper (I) iodide, copper (I) acetate, copper (I) bromide, copper (I) chloride or copper (I) oxide which is monovalent copper Preferably, copper (I) iodide or copper (I) acetate is more preferable.

Examples of the onium salt as a co-catalyst include halogenated tetraphenylantimony, halogenated tetraphenylphosphonium, halogenated tetraalkylammonium, tetraalkylammonium hydrogensulfate, and tetraalkylammonium alkylsulfonium salts. Preferred examples include tetraphenylphosphonium chloride, tetraphenylphosphinium bromide, tetrabutylammonium iodide, tetrabutylammonium bromide, tetraethylammonium chloride, and tetraethylammonium methanesulfonate. More preferred are phenylphosphinium, tetrabutylammonium iodide, tetrabutylammonium bromide, or tetraethylammonium methanesulfonate.
It is preferable that the usage-amount of these promoters is the range of 1.0 * 10 < ^-6 > -5.0 * 10 ^<-2 > mol with respect to 1 mol of compounds represented by general formula (III).

  The solvent used in the reaction for synthesizing the compound represented by the general formula (I) by reacting the compound represented by the general formula (II) and the compound represented by the general formula (III) is used in the same reaction. When the base is a liquid organic base, it may also serve as a solvent. Examples of the solvent that can be used in the production method of the present invention other than the organic base include aromatic hydrocarbons such as toluene and xylene, ester solvents such as ethyl acetate and butyl acetate, diisopropyl ether, tert-butyl methyl ether, Ether solvents such as tetrahydrofuran and diethylene glycol dimethyl ether; alcohol solvents such as 1-methoxy-2-propanol, diethylene glycol and n-butanol; N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethyl-2-imidazo Amide solvents such as linone; among others, toluene, xylene, butyl acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, n-butanol, or 4-methyl-2-pentano And alcohol solvents such as N, methyl-2-pyrrolidone, N, N-dimethylacetamide, etc. are preferred, more preferably toluene, xylene, butyl acetate, 1-methoxy-2-propanol, or 4-methyl-2-pen Tanol or N, N-dimethylacetamide.

The initial method of the reaction is to disperse the compound represented by the general formula (III) in a solvent, add an appropriate amount of the catalyst, and then add or drop the compound represented by the general formula (II). .
The reaction is carried out at an internal temperature of about 50 ° C. to 150 ° C. Among them, it is preferably carried out at 60 to 140 ° C., more preferably 70 to 130 ° C.

When the compound represented by the general formula (II) and the compound represented by the general formula (III) are reacted to synthesize the compound represented by the general formula (I) or a derivative thereof by the above or similar method, In the compound represented by the general formula (III), R ¹ is preferably not a carboxyl group from the viewpoint of reactivity, and is preferably a carboxylic acid derivative such as a carboxylic acid ester group. Preferable more specific examples of R ¹ include an alkoxycarbonyl group, an aminocarbonyl group, or a 2-benzoxazolyl group. Specific examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, 2-propoxycarbonyl, 1-propoxycarbonyl, 1-butoxycarbonyl, phenoxycarbonyl, or benzyloxycarbonyl group, in that high purity can be easily achieved. A substituent whose crystallinity is improved by an alkoxyl group is preferable, and a methoxycarbonyl group, an ethoxycarbonyl group, a 1-butoxycarbonyl group, or a phenoxycarbonyl group is preferable from the viewpoint that it can be synthesized at a low cost. A carbonyl group is preferred.

Specific examples when R ¹ is an optionally substituted aminocarbonyl group include an aminocarbonyl group, a dimethylaminocarbonyl group, a diethylaminocarbonyl group, a butylaminocarbonyl group, a morpholinocarbonyl group, a phenylaminocarbonyl group, Examples include benzylaminocarbonyl group, phthalominocarbonyl group, hydrazoiminocarbonyl group, and octylaminocarbonyl group. Among them, aminocarbonyl group, diethylaminocarbonyl group, butylaminocarbonyl group, morpholinocarbonyl group, or phenylamino A carbonyl group is preferable, and an aminocarbonyl group and a phenylaminocarbonyl group are more preferable. Specific examples when R ¹ is an optionally substituted 2-benzoxazolyl group include an unsubstituted benzoxazolyl group, a 2- (5-amino) benzoxazolyl group, 2- (5-hydroxy) benzoxazolyl group, 2- (6-amino-5-hydroxy) benzoxazolyl group, 2- (5-chloro) benzoxazolyl group, or 2- (5-bromo ) Benzoxazolyl group, among them, unsubstituted benzoxazolyl group, 2- (5-amino) benzoxazolyl group, 2- (5-hydroxy) benzoxazolyl group, or A 2- (6-amino-5-hydroxy) benzoxazolyl group is preferable, and a 2- (5-amino) benzoxazolyl group or a 2- (5-hydroxy) benzoxazolyl group is more preferable.

When n is 2 or more in the general formula (I), R ¹ may be linked to each other to form a ring, in which case an acid anhydride structure, N-phenylimide structure, N-methylimide structure, N-pentafluoro Examples thereof include an ethylimide structure, an N- (4′-amino) phenylimide structure, and an N- (3′-amino) phenylimide structure. Among these, an acid anhydride structure, an N-phenylimide structure, an N— A (4′-amino) phenylimide structure or an N- (3′-amino) phenylimide structure is preferable, and an acid anhydride structure or an N- (3′-amino) phenylimide structure is more preferable.

Examples of the method for isolating the vinylethynylarylcarboxylic acid, which is the target substance of the present invention, from the reaction mixture include a method of applying separation and purification techniques such as chromatography, crystallization or recrystallization after extraction with an organic solvent. be able to.
The vinyl ethynyl arylcarboxylic acids, which are compounds represented by the general formula (I) of the present invention, are preferably isolated by crystallization from the viewpoint of reaction by-product removability. When vinylethynylarylcarboxylic acids are precipitated by cooling the solution extracted with an organic solvent, the arylethynylphthaldiester compound can be isolated by ordinary solid-liquid separation. Alternatively, vinylethynylarylcarboxylic acids can be crystallized from an appropriate solvent system and isolated by solid-liquid separation.

As an organic solvent for extraction used when the vinylethynylarylcarboxylic acid is an ester or carboxylic acid, an ether solvent such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, methoxybenzene, etc. from the viewpoint of compatibility, Examples include ester solvents such as ethyl acetate and n-butyl acetate, and aromatic hydrocarbon solvents such as methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone. From the viewpoint of mass production suitability and availability on an industrial scale, etc. A solvent based on a solvent and a ketone solvent are preferred.
Specific examples of the organic solvent preferably used in the extraction and purification step include ethyl acetate, n-butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like. Among these, ethyl acetate, methyl ethyl ketone, methyl isobutyl, etc. Ketones are the more preferred solvent.

  Examples of the solvent system for crystallization when the vinylethynylarylcarboxylic acid is an ester or carboxylic acid include a mixed system of the organic solvent described above and another organic solvent. Other organic solvents to be mixed include lower alcohols having 1 to 4 carbon atoms, acetonitrile, propionitrile, etc., but preferably used solvents are lower alcohols having 1 to 4 carbon atoms, acetonitrile, and aromatic carbonization. A solvent selected from hydrogen and saturated hydrocarbons, more preferably methanol, 2-propanol, acetonitrile, toluene, hexane, or heptane. Examples of preferred crystallization solvents include toluene alone, hexane alone, toluene / 2-propanol mixed system, hexane / 2-propanol mixed system, heptane / 2-propanol mixed system, hexane / acetonitrile mixed system, and the like. By the above method, impurities and coloring components derived from the reaction step can be effectively removed, and high purity vinylethynyl arylcarboxylic acids can be obtained.

Next, the manufacturing method of vinyl ethynyl aryl carboxylic acid anhydrides included in the compound represented by the general formula (I) of the present invention will be described.
In order to produce such an anhydride, the vinylethynylarylcarboxylic acid diester represented by the general formula (I) of the present invention (that is, two R ¹ linked to Q ¹ in the general formula (I) are cyclic anhydrides). A compound having no physical structure, for example, the exemplified compound (3)) may be hydrolyzed to be converted into a vinylethynylaryl (mono, di, tri, or tetra) carboxylic acid compound, which may be cyclized. Thus, a vinyl ethynyl aryl carboxylic acid anhydride like exemplary compound (1) can be manufactured.
Here, as a method of hydrolyzing an ester compound such as vinylethynylarylcarboxylic acid diester, alkaline hydrolysis is preferred in the present invention.

Examples of the base used for the alkali hydrolysis include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides, organic bases, and the like. Preferred bases are alkali metal hydroxides. More specifically, examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, and cesium hydroxide. Sodium hydroxide or potassium hydroxide is preferably used. The base used here may be in the form of flakes or pellets, or may be used as a solution of any concentration (for example, a 25 mass% sodium hydroxide aqueous solution, a 48 mass% potassium hydroxide aqueous solution). Good. Considering production on an industrial scale, it is easy to use in a solution state.
The amount of alkali metal hydroxide used in the hydrolysis step is 1.0 with respect to one carboxyl group in the vinylethynylarylcarboxylic acid such as compound (3) used as a starting material in the production method of the present invention. The range of -5.0 times mole is preferable, More preferably, it is 1.0-2.5 times mole, More preferably, it is 1.05-1.5 times mole.

  The reaction solvent that can be used in the hydrolysis step is not particularly limited as long as it does not cause problems in the process operation, does not disturb the progress of the reaction, and does not adversely affect the reaction by decomposition in the alkaline hydrolysis step of the present invention. However, water or a mixed system composed of water and an organic solvent is preferably selected. Here, examples of the organic solvent that may be used in combination with water include alcohol solvents such as methanol, ethanol, 2-propanol, and 1-butanol; N-methylpyrrolidone, sulfolane, acetonitrile, N, N-dimethylimidazolidinone, and the like. And aprotic polar solvents; ether solvents such as 1,2-dimethoxyethane and tetrahydrofuran; nitrogen-containing heteroaromatic solvents such as pyridine; and the like. It is also possible to use a plurality of solvents selected from these. Among these, alcohol solvents, aprotic polar solvents, and pyridine are preferably used. Specific solvents include methanol, ethanol, 2-propanol, 1-butanol, N-methylpyrrolidone, acetonitrile, N, N -The use of dimethylimidazolidinone is more preferred, and the most preferred solvent is water or water and methanol, ethanol, 1-butanol, N-methylpyrrolidone, acetonitrile or a few selected from these. It is a combined system of solvents.

Although the reaction temperature in a hydrolysis process has the preferable range of 0-200 degreeC, More preferably, it is 20-100 degreeC, More preferably, it is 20-80 degreeC.
Although reaction time changes with preparation amounts and reaction temperature, the range of 0.5 to 12 hours is preferable, and the range of 1 to 6 hours is more preferable. As the reaction proceeds, vinylethynylaryl (mono, di, tri, or tetra) carboxylic acid dissolves. In the hydrolysis step, an inert atmosphere is not particularly required, but the reaction may be performed under an argon or nitrogen stream.

  A preferable treatment method as a post-treatment of the reaction mixture after completion of hydrolysis is a method of treating with an adsorbent. Examples of the adsorbent include silica gel, magnesium oxide, aluminum oxide, or a commercially available adsorbent made of a mixed system of these metal oxides, and clay minerals such as activated carbon, zeolite, and montmorillonite, preferably a mixed system of silica gel and metal oxide. It is also possible to use a plurality of these adsorbents or activated carbons. The most preferred adsorbent in the present invention is activated carbon.

The amount of adsorbent used is preferably in the range of 0.1 to 200% by weight, more preferably 0.5 to 50% by weight, based on the vinylethynyl (mono, di, tri, or tetra) arylcarboxylic acid used as a raw material. More preferably, it is 1-20 mass%.
The temperature of the adsorbent treatment is preferably in the range of 0 to 80 ° C, more preferably 10 to 60 ° C, still more preferably 20 to 40 ° C.
The adsorbent treatment time varies depending on the amount charged and the treatment temperature, but generally it is preferably in the range of 0.5 to 12 hours.
It can also be left overnight in the adsorbent treatment process. The used adsorbent can be easily removed by ordinary solid-liquid separation. At this time, a filter aid such as celite, radiolite, and powdered cellulose may be used.

In the production method of the present invention, after the above adsorbent treatment, an acid is subsequently added to convert the vinyl ethynyl (mono, di, tri, or tetra) aryl carboxylic acid salt into an acid, Conversion to a vinylethynyl (mono, di, tri, or tetra) aryl carboxylic acid compound is particularly preferred.
Conversion of vinyl ethynyl (mono, di, tri, or tetra) aryl carboxylate present in the reaction mixture to a vinyl ethynyl (mono, di, tri, or tetra) aryl carboxylic acid compound by conversion from salt to acid is It is preferably carried out by allowing an acid to act on the reaction solution after the adsorbent treatment.

As for the usage-amount of an acid, 1 equivalent or more is preferable with respect to one carboxyl group, More preferably, it is 1-1.5 equivalent.
The acid type is preferably an acid having a pKa in the aqueous solution of 4 or less, and more preferably 2.5 or less. Examples of such acids include organic acids (organic sulfonic acids such as methanesulfonic acid, carboxylic acids such as formic acid, acetic acid, trichloroacetic acid, citric acid), mineral acids (that is, inorganic acids such as hydrohalic acid, sulfuric acid). , Nitric acid, phosphoric acid, etc.). Of these, mineral acids are preferred. Specifically preferred acids are hydrochloric acid, sulfuric acid, methanesulfonic acid, acetic acid, citric acid or formic acid, more preferred are hydrochloric acid, sulfuric acid or methanesulfonic acid, and even more preferred are hydrochloric acid or sulfuric acid.
The vinyl ethynyl (mono, di, tri, or tetra) aryl carboxylic acid compound as shown in compound (3) is precipitated by conversion from salt to acid, so the target product is isolated by ordinary solid-liquid separation. can do.

  In the conversion to a vinylethynyl (mono, di, tri, or tetra) arylcarboxylic acid compound by conversion from a salt to an acid, water and an organic solvent that separates into two layers may coexist, and a preferred embodiment of the present invention It is one of. Examples of the organic solvent that separates into two layers from water include ether solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, methoxybenzene, and ethoxybenzene, ester solvents such as ethyl acetate and n-butyl acetate, methyl ethyl ketone, methyl Examples thereof include ketone solvents such as isobutyl ketone and cyclohexanone, aliphatic hydrocarbon solvents represented by hexane and heptane, and aromatic hydrocarbon solvents.

  Specific examples of the organic solvent that is preferably used from the viewpoint of mass production suitability and availability on an industrial scale include methyl-t-butyl ether, toluene, xylene (o-isomer, m-isomer, p-isomer). Or any mixture of these in any ratio), mesitylene, ethylbenzene, t-butylbenzene, isopropylbenzene (cumene), chlorobenzene, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl ethyl ketone, methyl Isobutyl ketone, cyclohexanone, and the like can be mentioned. Among these, methyl-t-butyl ether, toluene, xylene, ethylbenzene, ethyl acetate, n-butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone are more preferable, methyl-t-butyl ether, Toluene, xylene, acetic acid Chill, methyl ethyl ketone is more preferable solvent. A plurality of these can be used in combination. By making the organic solvent coexist, the aryl ethynyl phthalic acid compound produced by the conversion from salt to acid can be effectively extracted into the organic layer. On the other hand, inorganic salts and the like are transferred to and removed from the aqueous layer. The organic layer containing the arylethynylphthalic acid compound separated from the reaction mixture separated into two layers can proceed to the next ring closing step as it is, and is an industrially superior advantage.

  Ring closure of vinylethynyl (mono, di, tri, or tetra) arylcarboxylic acid compound such as compound (3), preferably chemical or thermal ring closure, leads to arylethynylphthalic anhydride such as compound (1) The method to do is not specifically limited. For example, the ring can be easily closed by heating with acetic anhydride in the presence of a solvent. Alternatively, it is possible to close the ring by heating to 110 ° C. to 150 ° C. In this case, it is preferable to use a solvent having a property of removing water by azeotropic distillation such as toluene.

Hereinafter, the ring closing method will be described in detail.
Reagents are used for chemical ring closure.
Examples of the reactant include acetic anhydride, succinic anhydride, acetyl chloride, chlorosulfonic acid, thionyl chloride, phosphorus oxychloride, and propenyl acetate. Of these, acetic anhydride, acetyl chloride, chlorosulfonic acid, and phosphorus oxychloride are preferable, and acetic anhydride and phosphorus oxychloride are more preferable.

  The reaction solvent is not particularly limited as long as it does not generate an ester or an acid amide by reacting with an acid anhydride such as alcohol or amine, but it is a hydrocarbon solvent (including aromatic and aliphatic). ), Halogen solvents (including aromatic and aliphatic), amide solvents, ester solvents, ketone solvents, nitrile solvents, ether solvents, among others, aromatic hydrocarbon solvents, esters A solvent, a ketone solvent, a nitrile solvent, and an ether solvent are preferable, and an aromatic hydrocarbon solvent, an ester solvent, and a ketone solvent are more preferable.

  Specific examples of these include decane, toluene, xylene, chlorobenzene, dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, ethyl acetate, butyl acetate, diethyl carbonate, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, Acetonitrile, propionitrile, anisole, t-butyl methyl ether, diisopropyl ether and the like can be mentioned. Among these, toluene, xylene, ethyl acetate, butyl acetate, diethyl carbonate, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetonitrile, propionitrile, anisole, t-butyl methyl ether, diisopropyl ether are preferable, and toluene, Examples include xylene, ethyl acetate, butyl acetate, diethyl carbonate, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, and acetone.

On the other hand, in order to thermally close the ring, there is a method of using a solvent having a property of azeotropically irrigating water in order to remove water generated at the time of cyclization without solvent sublimation. A method using a solvent having the following is preferable.
Examples of such solvents include hydrocarbon solvents (including aromatic and aliphatic), halogen solvents (including aromatic and aliphatic), ester solvents, ketone solvents, ether solvents, and the like. Of these, aromatic hydrocarbon solvents, ester solvents, and ether solvents are preferable, and aromatic hydrocarbon solvents and ester solvents are more preferable.
Specific examples thereof include decane, toluene, xylene, chlorobenzene, butyl acetate, diethyl carbonate, cyclohexanone, methyl isobutyl ketone, anisole, and 1,2-dimethoxyethane, among which toluene, xylene, acetic acid, and the like. Butyl, diethyl carbonate, anisole, and 1,2-dimethoxyethane are preferable, and toluene, xylene, butyl acetate, and diethyl carbonate are more preferable.

  In many cases, the arylethynylphthalic anhydride represented by the exemplified compound (1) is precipitated as crystals by cooling the reaction solution after completion of the reaction, so that the target product is isolated by ordinary solid-liquid separation. can do. Or it can also take out by crystallization using a poor solvent together. It is also possible to do.

Examples of the solvent system for crystallization when the vinyl ethynyl arylcarboxylic acid is an acid anhydride include a mixed system of an organic solvent having no hydroxyl group and another organic solvent. Other organic solvents to be mixed include acetone, methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, propionitrile, hexane, heptane, cyclohexane, diisopropyl ether, etc., but preferably used solvents are methyl ethyl ketone, methyl isobutyl ketone, acetonitrile, A solvent selected from hexane, heptane and diisopropyl ether, more preferably methyl ethyl ketone, acetonitrile, hexane and heptane. Examples of preferred crystallization solvents include toluene alone, hexane alone, toluene / acetonitrile mixed system, hexane / toluene mixed system, heptane / methyl isobutyl ketone mixed system, hexane / acetonitrile mixed system, and the like. By the above method, impurities and coloring components derived from the reaction step can be effectively removed, and high purity vinylethynyl arylcarboxylic acids can be obtained.
The vinyl ethynyl aryl carboxylic acid anhydrides obtained by such a method have extremely high purity and can be suitably used as an end-capping material such as a polyimide resin.

Specific examples [compound (1) to compound (12)] of novel vinylethynylarylcarboxylic acids which are preferably produced by the production method of the present invention and are included in the compound represented by the general formula (I) are shown below. However, the present invention is not limited to these.
In addition, the carboxy group part in the following compounds (1) to (12) may have a salt structure such as a sodium salt, a lithium salt, or a tetramethylammonium salt.

Since these compounds have a stable double bond in the molecule, the compound represented by the general formula (I) is used as a raw material for the reactive crosslinking group to produce a thermally crosslinkable compound. Can do.
For example, 1,3-bis (3-aminophenoxy) benzene and the exemplified compound (1) included in the compound represented by the general formula (I): 4- (2- (1- (1- By adding cyclohexenyl) ethynyl) phthalic anhydride in order and reacting them, a bisimide compound that is a thermally crosslinkable compound can be obtained in high yield.

  The novel vinyl ethynyl aryl carboxylic acids of the present invention can be easily obtained with a high-purity compound by the production method of the present invention, a terminal sealing material such as a polyimide resin, a material having a reactive crosslinking group, a highly durable resin, It is useful as a raw material for functional materials such as pharmaceutical and agrochemical intermediates, liquid crystals, electronic materials, adhesives, and insulators.

  Hereinafter, the present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited thereto.

[Example 1]
<Synthesis of 4- (2- (1-cyclohexenyl) ethynyl) phthalic acid [compound (3)]>
[1-1. ] Synthesis of 4- (2- (1-cyclohexenyl) ethynyl) phthalic acid dimethyl ester In a three-necked flask containing 100 ml, under a nitrogen stream, 25 ml of toluene, 13.65 g of 4-bromophthalic acid dimethyl ester, 1-ethynylcyclohexene (Aldrich, containing 0.2% 2,6-ditert-butyl-4-methylphenol) 6.37 g, triphenylphosphine 33 mg, trans-dichlorobis (triphenylphosphine) palladium (II) 8.8 mg, and Then, 85.7 mg of cuprous iodide was added, and 15 ml of triethylamine was added while stirring.
The reaction mixture was placed in an external 125 ° C. heat bath and heated to reflux for 8 hours while being heated. After cooling to room temperature, the reaction solution was filtered to remove the generated salt and catalyst, and washed with 30 ml of toluene. The filtrate and the washing solution were combined, concentrated, and separated by silica gel column chromatography to obtain 5.70 g of liquid 4- (2- (1-cyclohexenyl) ethynyl) phthalic acid dimethyl ester. The yield was 38.5%.
The structure of the obtained compound was confirmed by NMR. The data is as follows.
¹ H-NMR δ (TMS: CDCl ₃ ): 1.59-1.71 ppm (m, 4H), 2.13 to 2.23 ppm (m, 4H), 3.92 ppm (s, 3H), 3.94 ppm (S, 3H), 6.26 ppm (m, 1H), 7.53 ppm (dd, 1H), 7.69 ppm (d, 1H), 7.70 ppm (dd, 1H)
IR νmax (KBr): 820 (w), 849 (w), 887 (w), 1126 (m), 1294 (s), 1435 (m), 1732 (vs), 2361 (w), 2943 (w) cm ^-1

[1-2. ] Synthesis of 4- (2- (1-cyclohexenyl) ethynyl) phthalic acid [Compound (3)] 4- (2- (1-Cyclohexenyl) ethynyl) phthalic acid dimethyl ester obtained in (1-1) 4.47 g was suspended in a mixture consisting of 30 ml of water, 15 ml of acetonitrile, and 3.5 g of 25% aqueous sodium hydroxide, and stirred in a water bath for 1 hour at an internal temperature of 80 ° C. to confirm the decomposition of the ester. . This liquid was cooled to an internal temperature of 45 ° C., 0.5 g of activated carbon was added, and the mixture was stirred at the same temperature for 30 minutes. Activated carbon was removed by filtration using diatomaceous earth as a filtering agent, and after washing with water, the filtrate and the washing solution were combined. To this aqueous solution containing sodium salt, 3.7 g of 36% concentrated hydrochloric acid was added, 15 ml of methyl ethyl ketone was added for extraction, the organic layer was taken out, concentrated to dryness, redissolved with 2-propanol and added with water. The precipitated crystals were taken out by suction filtration and dried overnight to obtain 3.33 g of 4- (2- (1-cyclohexenyl) ethynyl) phthalic acid [compound (3)]. The yield was 82.2%.

The structure of the obtained compound was confirmed by NMR. The data is as follows.
¹ H-NMR δ (TMS: dimethyl sulfoxide): 1.57 ppm (m, 2H), 1.62 ppm (dd, 2H), 2.13-2.17 ppm (m, 4H), 6.28 ppm (t, 1H) ), 7.58 ppm (dd, 1H), 7.62 ppm (d, 1H), 7.68 ppm (dd, 1H)
IR νmax (KBr): 918 (w), 1234 (s), 1473 (s), 1684 (m), 1907 (w, br), 2937 (w) cm ⁻¹

[Example 2]
[2-1. Synthesis of 4- (2- (1-cyclohexenyl) ethynyl) phthalic anhydride [Compound (1)] 4- (2- (1-Cyclohexenyl) ethynyl) phthalic acid [Compound] obtained in Example 1 (3)] 2.7 g was suspended in 10 ml of toluene, 1.5 g of acetic anhydride was added, and the mixture was heated to reflux at 107 to 110 ° C. for 1.5 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure to 2.0 g, and cooled in an ice-water bath to precipitate 4- (2- (1-cyclohexenyl) ethynyl) phthalic anhydride crystals. . This was filtered, washed and dried to obtain 1.8 g of 4-phenylethynylphthalic anhydride [compound (1)] as pale yellowish green crystals. The yield was 71%.

The structure of the obtained compound was confirmed by NMR. The data is as follows.
¹ H-NMR δ (TMS: dimethyl sulfoxide): 1.58 ppm (m, 2H), 1.63 ppm (m, 2H), 2.14-2.20 ppm (m, 4H), 6.37 ppm (t, 1H) ), 7.96 ppm (dd, 1H), 8.04 ppm (d, 1H), 8.06 ppm (s, 1H)
IR νmax (KBr): 737 (s), 922 (m), 1607 (s), 1774 (vs), 1852 (s), 2931 (w) cm ⁻¹

Example 3
<Synthesis of Bisimide Compound Using Compound (1): Synthesis of 1,3-bis (3- (4- (2- (1-cyclohexenyl) ethynyl) phthalimino) phenoxy) benzene>
0.12 g of 1,3-bis (3-aminophenoxy) benzene and 4- (2- (1-cyclohexenyl) ethynyl) phthalic anhydride [compound (1) obtained in Example 2] in 4 g of glacial acetic acid 0.25 g was added in order, and after stirring at room temperature for 2 hours, the mixture was heated in an oil bath at 120 ° C. and reacted for 4 hours. After cooling the reaction solution, an additional 10 g of glacial acetic acid was added and stirred at room temperature for 30 minutes.
The precipitated crystals were filtered and dried at 50 ° C. for 2 days, and the target substance 1,3-bis (3- (4- (2- (1-cyclohexenyl) ethynyl) phthalimino) phenoxy) benzene 0.30 g Got. The yield was 96%.

The structure of the obtained compound was confirmed by NMR. The data is as follows.
¹ H-NMR δ (TMS: dimethyl sulfoxide): 1.59 ppm (m, 4H), 1.63 ppm (m, 4H), 2.15 to 2.21 ppm (m, 8H), 3.65 ppm (m, 2H) ), 6.72 ppm (t, 1H), 6.89 ppm (dd, 2H), 7.15 ppm (dd, 1H), 7.17 (m, 3H), 7.24 (dd, 2H), 7.45. (T, 1H), 7.54 (t, 2H), 7.82-7.88 ppm (m, 6H)
IR νmax (KBr): 675 (w), 743 (m), 773 (w), 846 (w), 1072 (w), 1234 (s), 1719 (vs), 1776 (m), 2930 (w) cm ^-1

[Comparative Example 1]
(Compound obtained in Example 3: 1,3-bis (3- (4- (2- (1-cyclohexenyl) ethynyl) phthalimino) phenoxy) Synthesis of benzene and comparative substance: 1,3-bis Synthesis of (3- (4-ethynylphthalimino) phenoxy) benzene>
In Example 3, except that 4- (2- (1-cyclohexenyl) ethynyl) phthalic anhydride [Compound (1) of the present invention] was used instead of 4-ethynylphthalic anhydride The reaction was conducted in the same manner as in 3.
Specifically, 2.92 g of 1,3-bis (3-aminophenoxy) benzene and 3.44 g of 4-ethynylphthalic anhydride were sequentially added to 10 g of glacial acetic acid, and the mixture was stirred at room temperature for 4 hours. The mixture was heated in an oil bath and allowed to react for 3 hours. The reaction mixture was cooled and stirred at room temperature for 30 minutes. The precipitated crystals were filtered and dried at 50 ° C. for 2 days to obtain 5.42 g of 1,3-bis (3- (4-ethynylphthalimino) phenoxy) benzene. The yield was 90%.

[Comparative Example 2]
<Compound obtained in Example 3: Synthesis of 1,3-bis (3- (4- (2- (1-cyclohexenyl) ethynyl) phthalimino) phenoxy) benzene and a substance as a comparative control: 1,3-bis Synthesis of (3- (4-phenylethynylphthalimino) phenoxy) benzene>
Example 3 was carried out except that 4- (2- (1-cyclohexenyl) ethynyl) phthalic anhydride [Compound (1) of the present invention] was used instead of 4-phenylethynylphthalic anhydride. The reaction was carried out in the same manner as in Example 3.
Specifically, 1.92 g of 1,3-bis (3-aminophenoxy) benzene and 4.96 g of 4-ethynylphthalic anhydride were sequentially added to 30 g of glacial acetic acid, and the mixture was stirred at room temperature for 4 hours. The mixture was placed in an oil bath and the temperature was raised and reacted for 2 hours. After cooling the reaction solution, it is allowed to stand overnight at room temperature, and 50 ml of toluene is added to make a slurry, and then the crystals are taken out by suction filtration, washed and dried to obtain 6.96 g of 1,3-bis (3- (4 -Phenylethynylphthalimino) phenoxy) benzene was obtained. The yield was 91%.

(Evaluation of compounds)
<Comparison of thermal reaction temperature>
Crystals of 1,3-bis (3- (4-ethynylphthalimino) phenoxy) benzene obtained in Example 3, 1,3-bis (3- (4-ethynylphthalimino) phenoxy) obtained in Comparative Example 1 The behavior of the compound was investigated by heating the benzene crystal and the 1,3-bis (3- (4-phenylethynylphthalimino) phenoxy) benzene crystal obtained in Comparative Example 2. Specifically, a differential calorimetry (DSC) measurement was performed in which about 10 mg of each crystal was heated to 500 ° C. at a rate of 5 ° C. per minute in a helium atmosphere of 50 ml per minute. The results are shown in Table 1 below.

  As is apparent from Table 1, 1,3-bis (3- (4-ethynylphthalimino) phenoxy) benzene obtained by using the novel compound of the present invention has a temperature range for thermosetting more than that of Comparative Example 1. On the other hand, since it is a lower temperature range than Comparative Example 2, it exhibits a thermal behavior suitable for use as an electronic material for heat-resistant resins such as polyimide and polybenzoxazole, and the novel compound of the present invention is thus It can be seen that it is useful as a material for such heat-crosslinkable compounds.

Claims (6)

The compound represented by the following general formula (I).

In the general formula (I), Q ¹ represents a phenylene group, 1-naphthylene group, 2-naphthylene group, pyridinylene group, imidazolylene group, pyrazolylene group, or triazinylene group, and n is 1 to 4.
R ¹ is a monovalent substituent selected from a carboxyl group, an alkoxycarbonyl group, an aminocarbonyl group, and a 2-benzoxazolyl group. When n is 2 or more, a plurality of R ¹ may be the same as each other May be different. Here, when n is 2 or more, a plurality of R ¹ may be connected to form a ring, and the formed ring structure includes an acid anhydride and an imidodicarbonyl group.
R ² , R ³ and R ⁴ are each independently a hydrogen atom, chlorine atom, alkoxyl group, amino group, alkylamino group, dialkylamino group, diacylimino group, sulfonyl group, carboxyl group, alkoxycarbonyl group, hydroxyl group, mercapto Represents a group, an alkyl group, an aryl group, an alkynyl group, or an alkenyl group. Two or more of R ² , R ³ and R ⁴ may be connected to each other to form a ring, but the formed ring structure does not include an aromatic hydrocarbon ring. Here, the sum of the atomic weights constituting R ² , R ³ , and R ⁴ is greater than 55. In the general formula (I), n is 1 and R ¹ represents a carboxylic acid, or n is 2 and two R ¹ form a carboxylic acid anhydride, and Q ¹ Represents a phenylene group or a 2-naphthylene group, The compound according to claim 1. The compound represented by the general formula (I) is a compound represented by the following formulas (1) to (12) or a salt thereof.

4. The method according to claim 1, comprising a step of reacting a compound represented by the following general formula (II) with a compound represented by the general formula (III). 5. A method for producing the compound.

In the general formula (II), R ² , R ³ , and R ⁴ are each independently a hydrogen atom, a chlorine atom, an alkoxyl group, an amino group, an alkylamino group, a dialkylamino group, a diacylimino group, a sulfonyl group, or a carboxyl group. Represents an alkoxycarbonyl group, a hydroxyl group, a mercapto group, an alkyl group, an aryl group, an alkynyl group, or an alkenyl group. Two or more of R ² , R ³ and R ⁴ may be connected to each other to form a ring, but the formed ring structure does not include an aromatic hydrocarbon ring. Here, the sum of the atomic weights constituting R ² , R ³ , and R ⁴ is greater than 55.

In the general formula (III), Q ¹ represents a phenylene group, 1-naphthylene group, 2-naphthylene group, pyridinylene group, imidazolylene group, pyrazolylene group, or triazinylene group, and n is 1 to 4.
R ¹ is a monovalent substituent selected from a carboxyl group, an alkoxycarbonyl group, an aminocarbonyl group, and a 2-benzoxazolyl group. When n is 2 or more, a plurality of R ¹ may be the same as each other May be different. Here, when n is 2 or more, a plurality of R ¹ may be connected to form a ring, and the formed ring structure includes an acid anhydride and an imidodicarbonyl group.
X represents a chlorine atom, a bromine atom, or an iodine atom.   5. The production method according to claim 4, wherein at least one kind of catalyst is used in the step of reacting the compound represented by the general formula (II) with the compound represented by the general formula (III). .   A method for producing a thermally crosslinkable compound, wherein the compound according to any one of claims 1 to 3 is used as a raw material for a reactive crosslinking group.