JP2009091347A - Novel acetylene compound and salt thereof, method for producing the novel acetylene compound and salt thereof, and amide, imide and benzimidazole compounds and oligomer or polymer having the acetylene compound residue on its partial moiety - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel acetylene compound that is useful as a raw material for high heat-resistant condensation polymer. <P>SOLUTION: The acetylene compound represented by general formula (1) (wherein X is -OCO-, -NRCO- or the like, Ar is an aryl or hetero aryl group; R, R', R'', R''' are individually H, a hydrocarbon group or a hetero ring group; R<SP>1</SP>is H or an alkyl group or the like; A is a hydrocarbon group or hetero ring group; and m, n, and a are each an integer). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention is useful as a raw material for liquid crystal materials, nonlinear optical materials, electronic materials, adhesive materials, sliding agent materials, photographic additives, gas separation membrane materials and other functional materials, and pharmaceutical and agrochemical intermediates. The present invention relates to a novel acetylene compound having two or more amino groups in the molecule, a process for producing the same, a derivative, a polymer and an oligomer containing the same as a constituent unit.

Aromatic compounds having an ethynyl group are useful as raw materials for functional materials such as pharmaceutical and agrochemical intermediates, liquid crystals, and electronic materials, and in recent years, various compounds utilizing the carbon-carbon triple bond structure existing in the molecule. It is attracting attention as a research object related to functional materials. For example, it is used as a terminal sealing material that imparts heat resistance and oxidation resistance to thermosetting properties to polyimide oligomers (for example, Patent Document 1 and Non-Patent Documents 1 to 3). However, acetylene compounds having two or more amino groups that can be introduced into the main chain of the polymer are those in which the acetylene terminal is a phenyl group (Patent Documents 2 and 3) and two or more aminophenol derivatives are linked in a cyclic manner. Only those having a different structure (Patent Document 4) have been reported, and these compounds have problems such as requiring a high temperature for thermosetting.

  In addition, examples of methods for synthesizing the above compounds include synthesis by reducing the nitro group after condensation reaction with the corresponding nitro compound, and finally introducing an ethynyl group into the molecule by a coupling reaction in the synthesis process of the synthesized product. The route to do was only known.

  The method of reducing the nitro group has a problem of going through an explosive nitrophenylacetylene compound. In addition, when an ethynyl group is introduced into a molecule by a coupling reaction, the synthesis of a terminal ethynyl type compound requires protection of the ethynyl group, but the target product is hydrolyzed during the deprotection reaction, which is satisfactory. There was a problem that it could not be obtained in a yield.

  Furthermore, when synthesizing these compounds, the compounds were isolated and synthesized in each step, and there was no method of synthesizing them consistently.

US Pat. No. 5,567,800 JP 2005-320417 A JP 2001-056469 A JP 2005-272352 A “Polymer”, 1994, Vol. 35, p. 4874-4880 “Polymer”, 1994, Vol. 35, p. 4857-4864 “Functional Materials”, 2000, Vol. 20, No. 12, p. 33-40

  An object of the present invention is to provide a novel acetylene compound having two or more amino groups that can be introduced into a condensation polymer. Another object of the present invention is to provide a derivative compound, a polymer and an oligomer containing the same as a constituent unit, and further to provide a method for producing the above compound safely and with high efficiency.

  As a result of intensive studies in view of the above circumstances, the present inventors have found a novel acetylene compound having two or more amino groups in the molecule, and further, an amine or phenol having an ethynyl group and an amino group in the same molecule. The present inventors have found a method for producing the above-described compound by reacting a carboxylic acid and a derivative thereof or a carbamic acid ester, and have arrived at the present invention. That is, the above-mentioned subject of the present invention was specifically achieved by the following means.

<1> An acetylene compound represented by the following general formula (1) and a salt thereof.

(Wherein X represents —OCO—, —NRCO—, —NRCONR—, —NRCOO—, —OCONR—, —OCOO—, —OCS—, —NRCS—, —NRCSNR—, —OCSO—, —S—, Represents —O—, —SO—, —SO ₂ —, —NR—, —CO—, —CS—, —CRR′—, —CRR′—CR ″ R ′ ″ —, and a single bond, Ar Represents an aryl group or a heteroaryl group, R, R ′, R ″, and R ′ ″ each represent a hydrogen atom, a hydrocarbon group, or a heterocyclic group. R ¹ represents a hydrogen atom, an alkyl group, or an alkenyl. A group, a heterocyclic group, or an alkylsilyl group, A represents a hydrocarbon group or a heterocyclic group, m represents an integer of 1 or more, n represents an integer of 2 or more, and a represents 1 or more and 5 or less. Represents an integer.)

<2> The acetylene compound and salt thereof according to <1>, wherein the acetylene compound represented by the general formula (1) and a salt thereof are represented by the following general formula (2).

(In the formula, R ² and R ³ each independently represent a hydrogen atom or a group that can be substituted on a benzene ring. X represents —OCO—, —NRCO—, —NRCONR—, —NRCOO—, and b represents 0 or more. 4 represents an integer of 4 or less, c represents an integer of 0 to 3, m represents an integer of 1 to 4, and n represents an integer of 2 to 5. R, R ¹ , X, and a are each It is synonymous with R, R ¹ , X, and a in the general formula (1).

<3> The acetylene compound and the salt thereof according to <2>, wherein X in the general formula (2) is —OCO— or —NHCO—.
<4> The acetylene compound and the salt thereof according to <3>, wherein m is 1 in the general formula (2).
<5> The acetylene compound and the salt thereof according to <4>, wherein a is 1 in the general formula (2).
<6> The acetylene compound and the salt thereof according to <5>, wherein n is 2 in the general formula (2).
<7> The acetylene compound and the salt thereof according to <6>, wherein the substituent of the ethynyl group in the general formula (2) is a meta position or a para position with respect to X.

<8> The acetylene compound represented by the general formula (1), and a —COOH group, —COOR ⁰ group, —CSOH group, —COSH group, —CSSH group, —OCOL ′ group, —NRCOL ′ group in the molecule An amide compound having a partial structure of an acetylene compound residue according to <1>, which is prepared and prepared from a compound having any one of -OCSL 'group, -NCO, and -NSO groups, An imide compound and a benzimidazole compound. Here, L represents a monovalent leaving group, and R ⁰ represents a hydrocarbon group. R has the same meaning as R in the general formula (1).

<9> At least selected from the group consisting of the acetylene compound according to any one of <1> to <7> above, an amine compound, a carboxylic acid compound, a carboxylic acid anhydride, a polyol compound, and an aldehyde compound. An oligomer or polymer comprising one or more monomer units as a constituent element.
<10> The oligomer or polymer according to <9>, wherein the oligomer or polymer has a structure obtained by block copolymerization of two or more types.
<11> Protected from the amino group of the acetylene compound represented by the following general formula (3) and then represented by the general formula (5) having an ethynyl group via the compound represented by the general formula (4) The method for producing a compound according to <3>, wherein the compound is subjected to a condensation reaction to produce the acetylene compound represented by the general formula (2).

(In the general formula ^{(3), R 3, c} , m, n are .R ⁴ is substitutable hydrogen atom or an amino group in R ^3, c, respectively, in the general formula (2), m, and n synonymous Represents a group)

(In General Formula (4), L represents a monovalent leaving group, R ⁵ represents a functional group that can be used as a protective group for an amino group, and R ³ , c, and m each represent General Formula (2). in a ^R 3, c, synonymous with m .R ⁴ has the same meaning as ^{R 4} in the general formula (3).).

(In the general formula ^(5), R ^1, R 2, a, b are respectively a ^{R 1,} R 2, a, the same meaning as b in the general formula (2) .Z is -OH or _-NH 2, - NHR and R are the same as R in the general formula (1). ).

<12> The production method according to <11>, wherein the substituent L in the general formula (4) is a halogen atom, a methanesulfonyl group, or a phenoxycarbonyl group.
<13> The production method according to <12>, wherein (I) a step of protecting the amino group of the acetylene compound represented by the general formula (3), (II) a protected compound represented by the general formula (4) It is carried out without isolating the compound in each of the step of reacting with the acetylene compound represented by the general formula (5) after conversion to the compound represented by formula (5) and the step of (III) deprotecting the amino group. It is a manufacturing method as described in <12>.

    According to the present invention, it is possible to provide an acetylene compound having two or more amino groups that can be introduced into a condensation polymer. Moreover, the derivative compound, polymer, and oligomer which contain it as a structural unit can be provided. Furthermore, the method of manufacturing the said compound safely and highly efficiently can be provided. The polymer in which the acetylene compound is introduced into the main chain or side chain of the polymer can provide a crosslinked polymer having a higher crosslinking density by performing a thermal crosslinking treatment.

The present invention is described in detail below. One embodiment of the present invention is a compound represented by the following general formula (1).

  In General Formula (1), Ar represents an (a + 1) -valent aryl group or heteroaryl group. Ar may be optionally substituted. Examples of the unsubstituted aryl include benzene, naphthalene, fluorene, anthracene, indene, indane, biphenyl and the like. Examples of the unsubstituted heteroaryl include furan, thiophene, pyridine, imidazole, pyrazole, triazole, oxazole, carbazole, indole, chromene, chroman, quinoline, dibenzofuran and the like.

  The optionally substituted (a + 1) -valent aryl group or heteroaryl group includes a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) relative to the unsubstituted aryl group or heteroaryl group. Atom), cyano group, nitro group, sulfonyl group, amide group, C1-C20 alkoxy group (for example, methoxy, butoxy, dodecyloxy), aryl group (for example, phenyl, naphthyl), hydroxyl group, silyl group, etc. And a hydrocarbon group having a structure substituted at the position. Among them, Ar is preferably an (a + 1) -valent phenyl group, an aryl group such as naphthyl, and more preferably an (a + 1) -valent phenyl group.

X is -OCO-, -NRCO-, -NRCONR'-, -NRCOO-, -OCONR-, -OCOO-, -OCS-, -NRCS-, -NRCSNR'-, -OCSO-, -S-, -O —, —SO—, —SO ₂ —, —NR—, —CO—, —CS—, —CRR′—, —CRR′—CR ″ R ′ ″ —, and a single bond are represented. Here, R, R ′, R ″, and R ′ ″ each represent a hydrogen atom, a hydrocarbon group, or a heterocyclic group. This hydrocarbon group or heterocyclic group may be optionally substituted. R or R ′ and Ar or A, R and R ′, R ′ and R ″, or R ″ and R ′ ″ may be connected to each other to form a ring.

  Examples of the unsubstituted hydrocarbon group include a linear or branched aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic ring group having 6 to 20 carbon atoms. Examples of the linear or branched aliphatic group include an alkyl group (for example, methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, neopentyl, hexyl, 2-ethylhexyl, octyl, dodecyl, etc.), An alkenyl group (for example, propenyl, butenyl, etc.) and the like, and an alicyclic group include a cycloalkyl group (for example, cyclopentyl, cyclohexyl, menthyl, etc.), a cycloalkenyl group (for example, cyclohexenyl, etc.), an alicyclic polycyclic group ( For example, bornyl, norbornyl, decalinyl, adamantyl, diamantyl, etc.), spiro ring (for example, spiro [3.4] octane, spiro [4.4] nonane, spiro [5.5] undecane and the like can be mentioned.

  Examples of the aromatic ring include benzene, naphthalene, fluorene, anthracene, indene, indane, biphenyl and the like. Examples of the heterocycle include heteroaromatic rings and heteroalicyclic compounds. Examples of the heteroaromatic ring include furan, thiophene, pyridine, imidazole, pyrazole, triazole, oxazole, carbazole, indole, chromene, chroman, quinoline, dibenzofuran, and the like, and examples of the heteroalicyclic compound include oxetane, thietane, oxolane, Examples include thiolane, pyrroline, pyrrolidine, pyrazoline, imidazoline, oxane, thiane, piperidine, pyrrolidone and the like.

  As the optionally substituted hydrocarbon group or heterocycle, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) with respect to the unsubstituted hydrocarbon group or heterocycle exemplified above, A cyano group, a nitro group, a sulfonyl group, an acylamino group having 1 to 20 carbon atoms (for example, formylamino, acetylamino, propanoylamino, octanoylamino, benzoylamino, naphthoylamino, etc.), an alkoxy group having 1 to 20 carbon atoms (For example, methoxy, butoxy, dodecyloxy), a hydrocarbon group having a structure in which an aryl group (for example, phenyl, naphthyl), a hydroxyl group, a silyl group or the like is substituted at an arbitrary position, or a heterocyclic ring can be mentioned. Among these, R, R ′, R ″, and R ″ ″ each preferably represent a hydrogen atom, an unsubstituted or optionally substituted alkyl group, or a heterocyclic group. More preferred are a hydrogen atom, an unsubstituted or optionally substituted alkyl group having 1 to 8 carbon atoms, and particularly preferred is a hydrogen atom.

  In X, -OCO-, -NRCO-, -NRCONR'-, -NRCOO-, -OCONR-, and -OCOO- are preferable, and -OCO- and -NRCO- are particularly preferable.

R ¹ represents a hydrogen atom or an alkyl group, an alkenyl group, a heterocyclic group, or an alkylsilyl group. R ¹ other than a hydrogen atom may be optionally substituted. As an unsubstituted alkyl group, an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, neopentyl, hexyl, 2-ethylhexyl, octyl, dodecyl, etc.) , Cycloalkyl groups (eg cyclopentyl, cyclohexyl, menthyl etc.), cycloalkylene groups (eg cyclohexene), heterocycles (eg furan, thiophene, pyridine, imidazole, indole), condensed polycycles (eg adamantane, diamantane) Alicyclic polycyclic groups (for example, bornyl, norbornyl, decalinyl, adamantyl, diamantyl, etc.), spirocyclic groups (for example, spiro [3.4] octane, spiro [4.4] nonane, spiro [5.5] undecane, etc.) Can be mentioned.

Examples of the optionally substituted alkyl group, heterocyclic group, and alkylsilyl group include a halogen atom (for example, a fluorine atom, a chlorine atom, an unsubstituted alkyl group, a heterocyclic group, and an alkylsilyl group exemplified above). Bromine atom, iodine atom), cyano group, nitro group, sulfonyl group, C1-C20 acylamino group (for example, formylamino, acetylamino, propanoylamino, octanoylamino, benzoylamino, naphthoylamino, etc.), carbon An alkyl group having a structure in which an alkoxy group (for example, methoxy, butoxy, dodecyloxy), an aryl group (for example, phenyl, naphthyl), a hydroxyl group, a silyl group, etc. is substituted at any position, a heterocyclic group, Represents an alkylsilyl group. Examples of alkylsilyl groups include trimethylsilyl, triethylsilyl, diisopropylmethylsilyl and the like. Among them, R ¹ is preferably a hydrogen atom, an optionally substituted alkyl group, an unsubstituted heterocyclic group, or an alkylsilyl group, more preferably an unsubstituted or hydroxyl group, a halogen atom (for example, a fluorine atom, a chlorine atom). ), An alkyl group having 1 to 6 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, an alkylsilyl group having 1 to 6 carbon atoms, or a hydrogen atom. More preferably, they are an unsubstituted C1-C6 alkyl group, a C1-C6 alkylsilyl group, or a hydrogen atom, and especially a hydrogen atom is preferable.

  A represents a (m + 1) -valent hydrocarbon group or a heterocyclic group. A may be optionally substituted. Examples of the unsubstituted hydrocarbon group include a linear or branched aliphatic group having 1 to 20 carbon atoms, an alicyclic group having 3 to 20 carbon atoms, and an aromatic ring group having 6 to 20 carbon atoms. Examples of the linear or branched aliphatic group include an alkyl group (for example, methyl, ethyl, propyl, i-propyl, butyl, sec-butyl, t-butyl, neopentyl, hexyl, 2-ethylhexyl, octyl, dodecyl, etc.), An alkenyl group (eg, propenyl, butenyl, etc.) and the like, and an alicyclic group include a cycloalkyl group (eg, cyclopentyl, cyclohexyl, menthyl, etc.), a cycloalkenyl group (eg, cyclohexenyl, etc.), an alicyclic polycyclic group ( For example, bornyl, norbornyl, decalinyl, adamantyl, diamantyl, etc.), spiro ring (for example, spiro [3.4] octane, spiro [4.4] nonane, spiro [5.5] undecane and the like can be mentioned.

  Examples of the aromatic ring group include benzene, naphthalene, fluorene, anthracene, indene, indane, biphenyl and the like. Examples of the heterocycle include heteroaromatic rings and heteroalicyclic compounds. Examples of the heteroaromatic ring include furan, thiophene, pyridine, imidazole, pyrazole, triazole, oxazole, carbazole, indole, chromene, chroman, quinoline, dibenzofuran, and the like, and examples of the heteroalicyclic compound include oxetane, thietane, oxolane, Examples include thiolane, pyrroline, pyrrolidine, pyrazoline, imidazoline, oxane, thiane, piperidine, pyrrolidone and the like.

  As the optionally substituted hydrocarbon group or heterocycle, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) with respect to the unsubstituted hydrocarbon group or heterocycle exemplified above, A cyano group, a nitro group, a sulfonyl group, an acylamino group having 1 to 20 carbon atoms (for example, formylamino, acetylamino, propanoylamino, octanoylamino, benzoylamino, naphthoylamino, etc.), an alkoxy group having 1 to 20 carbon atoms (For example, methoxy, butoxy, dodecyloxy), a hydrocarbon group having a structure in which an aryl group (for example, phenyl, naphthyl), a hydroxyl group, a silyl group or the like is substituted at an arbitrary position, or a heterocyclic ring can be mentioned. Among them, A is preferably an (m + 1) -valent unsubstituted or optionally substituted benzene ring group, and more preferably an (m + 1) -valent unsubstituted benzene ring group.

a represents an integer of 1 or more and 5 or less, preferably 1 to 3, particularly preferably 1. m represents an integer of 1 or more, preferably 1 to 3, and particularly preferably 1. n represents an integer of 2 or more, and is preferably 2. When a and m are 2 or more, a plurality of R ₁ and ethynylaryl-containing residues in brackets may be the same as or different from each other. ).

  The salt of the compound represented by the general formula (1) is a salt of an amino group and an acid capable of forming a salt, and examples of the acid include inorganic acids and organic acids. Examples of inorganic acids include hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, carbonic acid, bicarbonate, hydrofluoric acid, bromic acid, phosphoric acid, phosphorous acid, silicic acid, and boric acid. Organic acids include sulfone. Acids, sulfinic acids, alkyl sulfates, phosphonic acids, carboxylic acids, phosphate esters, phenols, and the like, and organic compounds described in JP-A-60-88942, JP-A-2-96755, etc. Examples include acids. Specific organic acids include methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, p-toluenesulfinic acid, ethyl acid, phenylphosphonic acid, phenylphosphinic acid, phenyl phosphate, Diphenyl phosphate, formic acid, acetic acid, propionic acid, butyric acid, glycolic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, trifluoroacetic acid, bromoacetic acid, methoxyacetic acid, oxaloacetic acid, citric acid, oxalic acid, succinic acid, apple Acid, tartaric acid, fumaric acid, maleic acid, malonic acid, ascorbic acid, benzoic acid, substituted benzoic acids such as 3,4-dimethoxybenzoic acid, phenoxyacetic acid, phthalic acid, picric acid, nicotinic acid, picolinic acid, dipicolinic acid , Adipic acid, p-toluic acid, terephthalic acid, 1, - cyclohexene-2,2-dicarboxylic acid, erucic acid, lauric acid, n- undecanoic acid, ascorbic acid, phenol, etc. p- chlorophenol and the like. Among them, inorganic acids, sulfonic acids, and carboxylic acids are preferable, hydrochloric acid, sulfuric acid, sulfurous acid, nitric acid, carbonic acid, phosphoric acid, sulfonic acids, phosphonic acids, and carboxylic acids are more preferable, and hydrochloric acid, sulfuric acid, nitric acid are more preferable. Methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, phenylphosphonic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, fluoroacetic acid, trifluoroacetic acid, formic acid, and oxalic acid. In particular, hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, chloroacetic acid, fluoroacetic acid, trifluoroacetic acid, and oxalic acid are preferable.

Another embodiment of the present invention is a compound represented by the following general formula (2).

X represents any of —OCO—, —NRCO—, —NRCONR—, and —NRCOO—. R ² and R ³ each independently represent a hydrogen atom or a functional group that can be substituted on the benzene ring, specifically a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group Group, C1-C20 alkoxy group (for example, methoxy, butoxy, dodecyloxy, trimethylsilyloxy), C1-C20 alkyl group (for example, methyl, butyl, octyl, hexadecyl), aryl groups such as phenyl, naphthyl, etc. Represents. Among them, a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, an acylamino group having 1 to 20 carbon atoms (for example, formylamino, acetylamino, propanoylamino, octanoylamino, benzoylamino, naphthoylamino, etc.), 1 to carbon atoms 20 alkyl groups and alkoxy groups are preferred, more preferably hydrogen atoms, halogen atoms, alkyl groups having 1 to 8 carbon atoms, and alkoxy groups having 1 to 8 carbon atoms, still more preferably hydrogen atoms, chlorine atoms, A fluorine atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, and a hydrogen atom is particularly preferable.

R ^1, a is the same meaning as ^R 1, a in the general formula (1), and preferred ranges are also the same. b represents an integer of 0 or more and 4 or less, and is preferably 4. c represents an integer of 0 or more and 3 or less, and is preferably 3. m represents an integer of 1 or more and 4 or less, and is preferably 1. n represents an integer of 2 or more and 5 or less, and is preferably 2. The sum of a and b is 5, and the sum of c, m, and n is 6. As an acid for salt formation, it is synonymous with the acid in General formula (1), and its preferable range is also the same.

  In another embodiment of the present invention, the amino group of the acetylene compound represented by the following general formula (3) is protected and then the general formula (4) having an ethynyl group via the compound represented by the general formula (4). 5) A method for producing an acetylene compound, which comprises a condensation reaction with a compound represented by 5) to produce an acetylene compound represented by the general formula (2).

In the general formula (3), R ^3, c, m, n is an R ³ in the general formula (2), respectively, c, m, and n synonymous. R ⁴ represents a hydrogen atom or a group that can be substituted with an amino group. Examples of the group capable of substituting an amino group include the hydrocarbon groups mentioned for R in the general formula (1), and acyl groups having 1 to 20 carbon atoms (for example, formyl, acetyl, propanoyl, octanoyl, benzoyl, Examples thereof include naphthoyl, cinnamoyl, etc. Among these, R ⁴ is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. More preferred are a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom is particularly preferred.

  Examples of the compound represented by the general formula (3) include diaminobenzoic acids (for example, 3,5-diaminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-bis (N-methylamino) benzoic acid, 3, 4-bis (N-methylamino) benzoic acid 3,5-diaminobenzoic acid-2 hydrate, 3,4-diaminobenzoic acid-2-hydrate, 2-methyl-3,5-diaminobenzoic acid, 2,6-dimethyl-3,5-diaminobenzoic acid, 2,6-dimethyl-3,5-bis (N-methylamino) benzoic acid, 2-phenyl-3,5-diaminobenzoic acid, 4-fluoro- 3,5-diaminobenzoic acid, 3,5-diaminobenzoic acid hydrochloride, 3,4-diaminobenzoic acid hydrochloride, 2-methyl-3,5-diaminobenzoic acid methanesulfonate, 2,6-dimethyl-3 , 5-Diaminobenzoic acid oxalate, 2 Phenyl-3,5-diaminobenzoic acid sulfate, etc.), triaminobenzoic acid (eg, 2,4,6-triaminobenzoic acid, etc.), tetraaminobenzoic acid (eg, 2,3,5,6, tetraaminobenzoic acid) And diaminophthalic acids (for example, 4,5-diaminophthalic acid and the like). Among these, 3,5-diaminobenzoic acid and 3,4-diaminobenzoic acid are preferable from the viewpoint of availability of raw materials, and 3,5-diaminobenzoic acid is more preferable.

The compound represented by the general formula (4) is a compound derived from Formula ^(3), R 3, c, m are each is ^R 3, c, m synonymous in the general formula (2) . R ⁴ has the same meaning as ^{R 4} in the general formula (3).

R ⁵ represents a functional group that can be used as a protecting group for an amino group. Specifically, any compound described as a protecting group for an amino group in Non-Patent Document 4 (PROTECTIVE GROUPS in ORGANIC SYNTHESIS) may be used. Specifically, an acetyl group, a benzyloxycarbonyl (BOM) group may be used. 2- (trimethylsilyl) ethoxycarbonyl (TEOC) group, t-butoxycarbonyl (Boc) group, allyloxycarbonyl (AOC) group, 2,2,2-trichloroethoxycarbonyl (Troc) group, 9-fluorenylmethoxy A carbonyl (FMOC) group, a tosyl (Ts) group, a mesyl (Ms) group, etc. are mentioned. Among these, t-butoxycarbonyl group, methoxycarbonyl group, and acetyl group are preferable.

  L is a monovalent leaving group and may be anything as long as it can replace a nitrogen atom or an oxygen atom by reaction with an amino group or a hydroxyl group, and preferably a halogen atom (for example, fluorine, chlorine, bromine, iodine). ), Sulfonate groups (eg, mesylate, tosylate, triflate), methanesulfonyl groups, alkoxycarbonyl groups, phenoxycarbonyl groups, diazonium groups, trialkylammonium groups (eg, trimethylammonium), and the like. A halogen atom, a methanesulfonyl group, a sulfonate group, and an alkoxycarbonyl group are more preferable, and a halogen atom or a methanesulfonyl group is still more preferable.

In general formula (5), R1, R2, a, and b have the same meanings as R1, R2, a, and b in general formula (2), respectively. Z represents —NH ₂ (—NHR, R is the same as R in the general formula (1)), —OH.

  Examples of the compound represented by the general formula (5) include anilines (for example, m-ethynylaniline, p-ethynylaniline, o-ethynylaniline, 5-ethynyl-2-methylaniline, 3-ethynyl-4-methylaniline). 5-ethynyl-3-fluoroaniline, 3-ethynyl-4-fluoroaniline, 3-ethynyl-4-methoxyaniline, 3-ethynyl-4-ethoxyaniline, 2,6-dimethyl-4-ethynylaniline, 2, 3-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 3,6-diethynylaniline, 2,4,6-triethynylaniline, m-propynylaniline, m-butynylaniline M-hexynylaniline, m-dodecylethynylaniline, mt-butylethynylaniline, m-cyclohexene Silethynylaniline, m-3-pyridylethynylaniline, m-2-pyridylethynylaniline, m-naphthylethynylaniline, m-quinolinylethynylaniline, m- (3-hydroxy-3-methyl-1-butynyl) aniline 3- (3-hydroxy-3-methyl-1-butynyl) -5-methylaniline, m-trimethylsilylethynylaniline, m-ethynyltoluidine, p-ethynyltoluidine, o-ethynyl-p-chloraniline, 2,3 -Diethynyl-5-methylaniline, 3,4-diethynyl toluidine, 3,5-diethynyl toluidine, 4-chloro-3,6-diethynylaniline, m-propynyl toluidine, m-butynyl toluidine, m-hex Sinyltoluidine, 3-dodecylethynyl-5-methoxyaniline, 3- -Butylethynyl-5-chloroaniline, 3-cyclohexylethynyl-5-chloroaniline, m- (2-hydroxypropyl-2-ethynyl) toluidine, m-trimethylsilylethynyltoluidine, N-methyl-m-ethynylaniline, N- Methyl-p-ethynylaniline, N-methyl-5-ethynyl-2-methylaniline, N-methyl-5-ethynyl-3-fluoroaniline, N-methyl-3-ethynyl-4-methoxyaniline, N-ethyl- 3-ethynyl-4-ethoxyaniline, N-methyl-2,6-dimethyl-4-ethynylaniline, N-methyl-3,5-diethynylaniline, N-methyl-2,4,6-triethynylaniline, N-methyl-m-propynylaniline, N-methyl-m-butynylaniline, N-methyl-mt Butylethynylaniline, N-methyl-m-cyclohexylethynylaniline, N-methyl-m-3-pyridylethynylaniline, m- (3-hydroxy-3-methyl-1-butynyl) -N-methyl-aniline, N- Methyl-m-trimethylsilylethynylaniline, N-methyl-m-ethynyltoluidine, N-methyl-2,3-diethynyl-5-methylaniline, N-methyl-3,5-diethynyltoluidine, N-methyl-m- Butynyl toluidine, N-methyl-m- (2-hydroxypropyl-2-ethynyl) toluidine, N-methyl-m-trimethylsilylethynyl toluidine, etc.),

Phenols (for example, m-ethynylphenol, p-ethynylphenol, o-ethynylphenol, 5-ethynyl-2-methylphenol, 3-ethynyl-5-fluorophenol, 2,3-diethynylphenol, 3,4- Diethynylphenol, 3,5-diethynylphenol, 3,6-diethynylphenol, 2,4,6-triethynylphenol, m-propynylphenol, m-butynylphenol, m-hexynylphenol, m-dodecyl Ethynylphenol, mt-butylethynylphenol, m-cyclohexylethynylphenol, m-3-pyridylethynylphenol, m-2-pyridylethynylphenol, m-naphthylethynylphenol, m-quinolinylethynylphenol, m- ( 2-hydroxypro Ru-2-ethynyl) phenol, m-trimethylsilylethynylphenol, m-ethynylcresol, p-ethynylcresol, o-ethynyl-p-chlorophenol, 3-ethynyl-4-methylphenol, 3-ethynyl-4-methoxyphenol 3-ethynyl-4-ethoxyphenol, 3-ethynyl-4-fluorophenol, 4-ethynyl-2,6-dimethylphenol, 2,3-diethynyl-5-methylphenol, 3,4-diethynylphenol, 3 , 5-diethynylphenol, 4-chloro-3,6-diethynylphenol, m-propynylcresol, m-butynylcresol, m-hexynylcresol, 3-dodecylethynyl-5-methoxyphenol, 3-t- Butylethynyl-5-chlorophenol, 3-chloro Rohexylethynyl-5-chlorophenol, m- (2-hydroxypropyl-2-ethynyl) cresol, m-trimethylsilylethynylcresol, m- (3-hydroxy-3-methyl-1-butynyl) phenol, etc.) It is done.

Among these, from the viewpoint of availability of raw materials and reactivity, m-ethynylaniline, p-ethynylaniline, o-ethynylaniline, 2,3-diethynylaniline, 3,4-diethynylaniline, 3,5-di Ethynylaniline, 3,6-diethynylaniline, m-propynylaniline, m-hexynylaniline, mt-butylethynylaniline, m-cyclohexylethynylaniline, m-3-pyridylethynylaniline, m-trimethylsilylethynylaniline, m-ethynyltoluidine, m- (3-hydroxy-3-methyl-1-butynyl) aniline, m-ethynylphenol, p-ethynylphenol, o-ethynylphenol, 2,3-diethynylphenol, 3,4-di Ethynylphenol, 3,5-diethynylphenol, 3,6-di Tinylphenol, m-propynylphenol, m-hexynylphenol, m-t-butylethynylphenol, m-cyclohexylethynylphenol, m-3-pyridylethynylphenol, m-trimethylsilylethynylphenol, m-ethynylcresol, m- (3-hydroxy-3-methyl-1-butynyl) phenol and the like are preferable, and in particular, m-ethynylaniline, p-ethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, m-propynylaniline, m-cyclohexylethynylaniline, m- (3-hydroxy-3-methyl-1-butynyl) aniline, m-ethynylphenol, p-ethynylphenol, 3,4-diethynylphenol, 3,5-diethynylphenol, m -Propynylpheno Le, m- cyclohexyl ethynyl phenol, the m-(3- hydroxy-3-methyl-1-butynyl) phenol preferred.

<Compounds derived from acetylene compounds>
Another aspect of the present invention is an acetylene compound represented by the general formula (1), and a —CHO group, —COOH group, —COOR ⁰ group, —CSOH group, —COSH group, —CSSH group in the molecule. The acetylene compound residue according to the general formula (1), which is prepared and prepared from a compound having any one of-, -OCOL 'group, -NRCOL' group, -OCSL 'group, -NCO, and -NSO group Is a derivative compound having a partial structure. Here, L ′ represents a monovalent leaving group, and R ⁰ represents a hydrocarbon group. Examples of the hydrocarbon group as R ⁰ here include the same hydrocarbon groups as those for R in the general formula (1). Among them, R ⁰ is preferably unsubstituted or halogen-substituted, alkoxy-substituted alkyl group, cycloalkyl group, alicyclic polycyclic group or aromatic ring group, and is unsubstituted or halogen-substituted or alkoxy-substituted having 1 to 10 carbon atoms. More preferably an alkyl group, a cycloalkyl group, or a phenyl group, more preferably an unsubstituted or halogen-substituted, alkoxy-substituted alkyl group, a cycloalkyl group, or a phenyl group having 1 to 6 carbon atoms. -4 unsubstituted or halogen-substituted, alkoxy-substituted alkyl groups, or phenyl groups are preferred.
R has the same meaning as R in the general formula (1).

-CHO group, -COOH group, -COOR ⁰ group, -CSOH group, -CASH group, -CSHSH group, -OCOL 'group, -NRCOL' group, -OCSL 'group, -NCO group, -NSO group in the molecule Examples of the compound having any one of aldehydes (eg, benzaldehyde, 3-fluorobenzaldehyde, etc.), carboxylic acids (eg, aliphatic carboxylic acids such as acetic acid, propionic acid, pivaloyl acid, cyclohexanecarboxylic acid, benzoic acid, 4 -Aromatic carboxylic acids such as fluorobenzoic acid, 3,5-dimethylbenzoic acid, naphthalenecarboxylic acid, and complex such as 3-furancarboxylic acid, 2-thiophenecarboxylic acid, pyridine-3-carboxylic acid, pyrrole-1-carboxylic acid Ring carboxylic acids), esters (eg ethyl acetate, methyl benzoate, etc.), thiocarbo Acids (eg, hexanethio-S-acid, thio-O-acetic acid, cyclohexanecarbothio-O-acid, heptanedithioic acid, etc.), carbamates (eg, N-phenoxycarbonylaniline, Np-nitrophenoxycarbonylaniline, N- Methoxycarbonylaniline, N-isopropoxycarbonylaniline, Nt-butoxycarbonylaniline, N-phenoxycarbonylcyclohexylamine, etc.)
Acid halides (eg phosgene, phenyl chlorocarbonate, methyl chloroformate, phenyl bromocarbonate etc.), thiocarbamates (eg N-phenoxythiocarbonylaniline, Np-nitrophenoxythiocarbonylaniline, N-methoxythiocarbonyl) Aniline, Nt-butoxythiocarbonylaniline, N-phenoxythiocarbonylcyclohexylamine, etc.), isocyanates (eg phenyl isocyanate, pentyl isocyanate, 4-methylphenyl isocyanate, 4-fluoroisocyanate, cyclohexyl isocyanate, etc.), thioisocyanates (For example, phenylthioisocyanate, butylthioisocyanate, p-toluyl isothiocyanate, cyclohexyl isothiocyanate, 2,4,6-teto Lamethyl isothiocyanate, etc.).

  Among these, carboxylic acids, acid halides, thiocarbamates, isocyanates, and thioisocyanates are preferable from the viewpoint of reactivity with amino groups and availability of raw materials, and carboxylic acids are more preferable.

  L ′ represents a monovalent leaving group and may be anything as long as it can replace a nitrogen atom or an oxygen atom by reaction with an amino group or a hydroxyl group, and preferably a halogen atom (for example, fluorine, chlorine, bromine, Iodine), sulfonate groups (for example, mesylate, tosylate, triflate), methanesulfonyl group, alkoxyl group, alkoxycarbonyl group, diazonium group, trialkylammonium group (for example, trimethylammonium) and the like. More preferred are a halogen atom, a methanesulfonyl group, a sulfonate group, an alkoxyl group and an alkoxycarbonyl group, and further preferred are a halogen atom, an alkoxyl group and an alkoxycarbonyl group.

In the molecule and the acetylene compound represented by the general formula (1), -CHO group, -COOH group, -COOR ⁰ group, -CSOH group, -COSH group, -CSSH group, -OCOL 'group, -NRCOL' group,- From a compound having any one of OCSL ′ group, —NCO group, and —NSO group (as a method for preparing and inducing a derivative compound having an acetylene compound residue described in the general formula (1) in a partial structure When an acetylene compound represented by the general formula (1) is reacted with a compound having —COOH group, —CSOH group, —COSH group, or —CSSH group in the molecule, these compounds are active against the condensation reaction. And a method of reacting with the compound represented by the general formula (1) and a method of directly condensing in the presence of a catalyst.

  Among these, the compounds represented by the general formula (1) after changing these compounds to intermediates having high activity for the condensation reaction from the viewpoint of reactivity and prevention of decomposition and reaction of the target ethynyl group The method of making it react with is preferable.

An acetylene compound represented by the general formula (1) and a compound having one of -CHO group, -OCOL 'group, -NRCOL' group, -OCSL 'group, -NCO group, and -NSO group in the molecule. What is necessary is just to make these compounds and the compound represented by General formula (1) react directly when making it react.

<Polymer derived from acetylene compound>
In another aspect of the present invention, at least the acetylene compound according to any one of <1> to <7> above, an amine compound, a carboxylic acid compound, a carboxylic acid anhydride, a polyol compound, an aldehyde compound, and a thiocarboxylic acid It is an oligomer or polymer containing one or more monomer units selected from the group consisting of compounds, thiocarboxylic acid anhydrides, and polythiol compounds as constituent elements.

Examples of the polymer containing at least the acetylene compound according to any one of <1> to <7> as a constituent unit include polyamine, polyimide, polyisoimide, polyesterimide, polyetherimide, polyamideimide, and polyamide. Examples include acids, polyamic acid esters, polyamides, polythioamides, polyurethanes, polyureas, polyazomethines, preferably polyimides, polyisoimides, polyester imides, polyether imides, polyamide imides, polyamic acids, polyamic acid esters, polyamides, and more preferably. Are polyimide, polyisoimide, polyesterimide, polyetherimide, polyamideimide, and polyamic acid.
The polymer may be a single copolymer or a block copolymer. The backbone skeleton may be aromatic or aliphatic, and may contain silicone, fluorene, or the like in the main chain or side chain, but is preferably aromatic.

As the polymer containing the acetylene compound as a structural unit, any one of the acetylene compounds represented by the general formula (1) and a —CHO group, a —COOH group, a —COOR ⁰ group, a —CSOH group in the molecule, -COSH group, -CSH group, -NCO group, compound having two of -NSO groups, acid anhydride, and substituted or unsubstituted hydrocarbon compound having two or more amino groups in the molecule (amine compound) ) And / or a polyol compound can be adjusted by reacting with an aldehyde compound as necessary.

Examples of the compound having two of -CHO group, -COOH group, -COOR ⁰ group, -CSOH group, -COSH group, -CSSH group, -NCO group, and -NSO group in the molecule include dialdehydes ( For example, terephthalaldehyde, isophthalaldehyde, phthalaldehyde, 4-methylphthalaldehyde, 4-methylisophthalaldehyde, 2,5-dimethylterephthalaldehyde, 1,4-cyclohexanedialdehyde, 2-fluoro-1,4-benzenedialdehyde, 3-methoxy-1,4-benzenedialdehyde, 1,6-hexanedialdehyde, 4,4′-dialdehydebiphenyl, 2,2-bis (4-aldehydephenyl) propane, 1,3-diacetylbenzene, 1 , 4-diacetylcyclohexane), dicarboxylic acids (eg terephthalate) Acid, isophthalic acid, phthalic acid, 4-methylphthalic acid, 4-methylisophthalic acid, 2,5-dimethylterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 2-fluoro-1,4-benzenedicarboxylic acid, 3-methoxy -1,4-benzenedicarboxylic acid, 1,6-hexanedicarboxylic acid, 4,4′-dicarboxybiphenyl, 2,2-bis (4-carboxyphenyl) propane, bis (4-carboxyphenyl) sulfone, 4, 4′-dicarboxybenzophenone, 4,4′-dicarboxybiphenyl ether, 3,3′-dicarboxybiphenyl, 2,2-bis (3-carboxyphenyl) propane, bis (3-carboxyphenyl) sulfone, 3, 3'-dicarboxybenzophenone, 4,4'-dicarboxy-3,3'-dimethylbiphenyl ether 4,4′-dicarboxy-3,3′-dimethylbiphenyl, 2,2-bis (4-carboxy-3-methylphenyl) propane, bis (4-carboxy-3-methylphenyl) sulfone, 4, 4′-dicarboxy-3,3′-dimethylbenzophenone, 4,4′-dicarboxy-3,3′-dichlorobiphenyl, 2,2-bis (4-carboxy-3-chlorophenyl) propane, bis ( 4-carboxy-3-chlorophenyl) sulfone, 4,4′-dicarboxy-3,3′-dichlorobenzophenone)

, Diesters (for example, isophthalic acid methyl ester, terephthalic acid dimethyl ester), dithiocarboxylic acids (for example, hexanedithio-s-acid, hexanedithiodicarboxylic acid), dicarbamates (for example, N-Fe xy), thiocarbamine sun diester (For example), diisocyanates (for example, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate), dithioisocyanates (for example, 1,4-phenylene dithioisocyanate, 1,3-phenylene dithioisocyanate, 1,4-cyclohexyl diisothiocyanate) , 5-methyl-1,3-phenylenedithioisocyanate) alone or in combination of two or more.

  The amine compound that can be used in the polymer of the present invention is not particularly limited, but a diamine compound is desirable from the viewpoint of obtaining a high tensile elastic modulus and high heat resistance (glass transition temperature). Specifically, the following diamine compounds are exemplified. p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,4-diamino-2-methylbenzene, 1,3-diamino-4-methyl-benzene, 1,3-diamino-4-chloro-benzene, 1,3-diamino-4-acetylamino-benzene, 1,3-bisaminoethyl-benzene, hexamethylenediamine,

3,3′-diaminobiphenyl, 4,4′-diamino-3,3′-dimethylbiphenyl, 4,4′-diamino-3,3′-dichlorobiphenyl, 2, 2′-difluoro-4, 4 ′ -Diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,2'-difluoro-5,5'-diaminobiphenyl, 3,3'-difluoro-5,5'-diaminobiphenyl, 2 2,2'-dichloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 2,2'-dichloro-5,5'-diaminobiphenyl, 3,3'-dichloro -5,5'-diaminobiphenyl, 2,2'-dibromo-4,4'-diaminobiphenyl, 3,3'-dibromo-4,4 ' -Diaminobiphenyl, 2,2'-dibromo-5,5'-diaminobiphenyl, 3,3'-dibromo-5,5'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4 ' -Diaminebiphenyl, 3,3'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -5,5'-diaminobiphenyl, 3,3'-bis (Trifluoromethyl) -5,5′-diaminobiphenyl, 2,2′-bis (trichloromethyl) -4,4′-diaminebiphenyl, 3,3′-bis (trichloromethyl) -4,4′-diamino Biphenyl, 2,2'-bis (trichloromethyl) -5,5'-diaminobiphenyl, 3,3'- Bis (trichloromethyl) -5,5'-diaminobiphenyl, 2,2'-bis (tribromomethyl) -4,4'-diaminebiphenyl, 3,3'-bis (tribromomethyl) -4,4 ' -Diaminobiphenyl, 2,2'-bis (tribromomethyl) -5,5'-diaminobiphenyl, 3,3'-bis (tribromomethyl) -5,5'-diaminobiphenyl, 3,3'-diamino Diphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 4,4′-diamino-3,3′-dimethylbiphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl Sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-di Aminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, bis (4-amino-3-methylphenyl) sulfone, bis (4-amino-3-chlorophenyl) sulfone, bis ( 4-aminophenyl) sulfone, bis (3-aminophenyl) sulfone, bis (5-fluoro-4-aminophenyl) sulfone, bis (5-fluoro-3-aminophenyl) sulfone, bis (5-chloro-4- Aminophenyl) sulfone, bis (5-chloro-3-aminophenyl) sulfone, bis (5-bromo-4-aminophenyl) sulfone, bis (5-bromo-3-aminophenyl) sulfone, bis (5-trifluoro) Methyl-4-aminophenyl) sulfone, bis 5-trifluoromethyl-3-aminophenyl) sulfone, bis (5-trichloromethyl-4-aminophenyl) sulfone, bis (5-trichloromethyl-3-aminophenyl) sulfone, bis (5-tribromomomethyl-4 -Aminophenyl) sulfone, bis (5-tribromomethyl-3-aminophenyl) sulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'- Diamino-3,3′-dimethylbenzophenone, 4,4′-diamino-3,3′-dichlorobenzophenone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 2,2-di (3-aminopheny Propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-di (3-aminophenyl) -1, 1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-Aminophenyl) -1,1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-amino-3-methylphenyl) propane, 2,2-bis (4 -Amino-3-chlorophenyl) propane,

1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) ) -1-phenylethane, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4- Bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1, 4-Bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α-dimethyl Benzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4- Amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) ) Benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6-bis (3-Aminophenoxy) benzonitrile, 2,6-bis (
3-aminophenoxy) pyridine,

  4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-amino Phenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [ 4- (3-aminophenoxy) phenyl] sulfone, bis [4- (5-fluoro-4-aminophenoxy) phenyl] sulfone, bis [4- (5-fluoro-3-aminophenoxy) phenyl] sulfone, bis [ 4- (5-Chloro-4-aminophenoxy) Enyl] sulfone, bis [4- (5-chloro-3-aminophenoxy) phenyl] sulfone, bis [4- (5-bromo-4-aminophenoxy) phenyl] sulfone, bis [4- (5-bromo-3 -Aminophenoxy) phenyl] sulfone, bis [4- (5-trifluoromethyl-4-aminophenoxy) phenyl] sulfone, bis [4- (5-trifluoromethyl-3-aminophenoxy) phenyl] sulfone, bis [ 4- (5-trichloromethyl-4-aminophenoxy) phenyl] sulfone, bis [4- (5-trichloromethyl-3-aminophenoxy) phenyl] sulfone, bis [4- (5-tribromomethyl-4-amino Phenoxy) phenyl] sulfone, bis [4- (5- Ribromomethyl-3-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl ] Methane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3- Aminophenoxy) phenyl] -1,1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3 -Hexafluoropropane,

  1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) Benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3- Bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [ 4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene,

  4,4′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [ 4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3′-diamino-4,4′- Diphenoxybenzophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone,

  6,6'-bis (3-aminophenoxy) 3,3,3, '3,'-tetramethyl-1,1'-spirobiindane, 6,6'-bis (4-aminophenoxy) 3,3,3 , '3,'-tetramethyl-1,1'-spirobiindane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (3-aminobutyl) polydimethylsiloxane, diaminopolysiloxane, and the like can be used alone or in combination of two or more.

The amine compounds exemplified above can be used alone or in combination as appropriate. In the amine compound, a part or all of the hydrogen atoms on the aromatic ring of the amine compound are substituted with a substituent selected from a fluorine atom, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group. Diamine may be used. For the purpose of introducing branching, a part of the amine compound may be replaced with a triamine compound or a tetraamine compound. Specific examples of such triamine compounds include, for example, pararose aniline.

  Although it does not specifically limit as an acid anhydride which can be used for the polymer of this invention, Specifically, the following are mentioned. Pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, 3-chloropyromellitic dianhydride, 3-bromopyromellitic dianhydride, 3-trifluoromethylpyromellitic dianhydride, 3 -Trichloromethyl pyromellitic dianhydride, 3- Tribromomethyl pyromellitic dianhydride, 3, 6-Difluoropyromellitic dianhydride, 3, 6-Dichloropyromellitic dianhydride, 3, 6- Dibromopyromellitic dianhydride, 3,6-bistrifluoromethylpyromellitic dianhydride, 3,6-bistrichloromethylpyromellitic dianhydride, 3,6-bistribromomethylpyromellitic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenylte Lacarboxylic acid dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, bis (2,3-dicarboxyl Phenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) sulfide dianhydride, bis (3,4-dicarboxyphenyl) sulfide dianhydride Bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2, 3-dicarboxyphenyl) -1, 1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3 , 3-hexafluoropropane dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1, 4-bis (2,3-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) ) Biphenyl dianhydride, 2,2-bis [(3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 9, 9-bi (3,4-Dicarboxyphenyl) fluorenic dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorenic dianhydride, 4,4'-biphenylenebis (trimerit Acid monoester acid anhydride), p-phenylenebis (trimellitic acid monoester acid anhydride), p-methylphenylenebis (trimellitic acid monoester acid anhydride), p- (2,3-dimethylphenylene) bis (Trimellitic acid monoester acid anhydride) 1,4-naphthalenebis (trimellitic acid monoester acid anhydride) 2,6-naphthalenebis (trimellitic acid monoester acid anhydride) 2,2,2-bis [ 4- (trimellitic acid monoester anhydride) phenyl] propane, 2,2-bis [4 (Trimellitic acid monoester anhydride) phenyl] hexafluoropropane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3, 4,9,10-perylenetetracarboxylic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,1,3,3-tetramethyldisiloxane dianhydride, 1- (2 , 3-Dicarboxyphenyl) -3- (3,4-dicarboxyphenyl) -1,1,1,3,3-tetramethyldisiloxane dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride , Ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, a cyclopentane tetracarboxylic acid dianhydride alone or can be used in combination of two or more.

The acid anhydrides exemplified above can be used alone or in combination as appropriate. In addition, any of the above tetracarboxylic dianhydrides may be selected from a fluorine atom, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group, with some or all of the hydrogen atoms on the aromatic ring. It can also be used after being substituted with a substituent.
Further, a part of the acid anhydride may be replaced with hexacarboxylic dianhydrides and octacarboxylic dianhydrides.

  Although it does not specifically limit as a polyol compound which can be used when using a polyol for the polymer of this invention, Specifically, the following are mentioned. For example, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) -1-phenylpropane, bis (4-hydroxyphenyl) sulfone, 4 , 4′-dihydroxybenzophenone, 4,4′-dihydroxybiphenyl ether, 3,3′-dihydroxybiphenyl, 2,2-bis (3-hydroxyphenyl) propane, bis (3-hydroxyphenyl) sulfone, 3,3 ′ -Dihydroxybenzophenone, 4,4'-dihydroxy-3,3'-dimethylbiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 2,2-bis (4-hydroxy-3-methylphenyl) Propane, bis (4-hydroxy-3-methylphenyl) sulfone, 4,4 -Dihydroxy-3,3'-dimethylbenzophenone, 4,4'-dihydroxy-3,3'-dichlorobiphenyl, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-amino- 3-chlorophenyl) sulfone, 4,4′-diamino-3,3′-dichlorobenzophenone, 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxy-2-methylbenzene, 1, 3-dihydroxy-4-methyl-benzene, 1,3-dihydroxy-4-chloro-benzene, 1,3-dihydroxy-4-acetoxy-benzene, 1,3-bishydroxyethyl-benzene, ethylene glycol, diethylene glycol, propylene Glycol, dipropylene glycol, butane polyol, hexane polio Le, cyclohexane polyol, 1,6-bis hydroxymethyl cyclohexane, but neopentyl glycol, but is not limited thereto. These can be used alone or in combination of two or more.

  Although it does not specifically limit as an aldehyde compound which can be used when using an aldehyde compound for the polymer of this invention, Specifically, the following are mentioned, for example. Examples include formaldehyde, acetaldehyde, trioxane, propionaldehyde, and benzaldehyde. These can be used alone or in combination of two or more. Among these, formaldehyde and acetaldehyde are preferable.

The polymer of the present invention can also contain dicarboxylic acids, diesters, diureas, diisocyanates and the like as other structural units.

Although it does not restrict | limit especially as a manufacturing method of the polymer of this invention, The polymer of this invention can be prepared by using the said acetylene compound and said monomer or monomer mixture.
For example, as a method for producing a polyimide polymer according to the present invention, a method of ring-closing and imidizing after passing through a polyamic acid, a method of passing through a polyisoimide, a part of which is imidized and further passing through a polyamic acid However, there is no particular limitation on the production of the polyimide polymer included in the present invention. A method in which an acid anhydride is dispersed in an organic solvent in which an amine compound such as diamine is dissolved, and is completely dissolved and polymerized by stirring. After the acid anhydride is dissolved and / or dispersed in an organic solvent, the amine is dissolved. Known polymerization methods such as a method of polymerizing using a compound and a method of polymerizing by reacting a mixture of an acid anhydride and an amine compound in an organic solvent can be used.
In imidization, water is generated by cyclization of polyamic acid, and this water can be azeotroped with benzene, toluene, xylene, tetralin, etc. and removed from the reaction system to promote imidization. Preferably, if a dehydrating agent such as an aliphatic acid anhydride such as acetic anhydride or an aromatic acid anhydride is used, the imidization reaction easily proceeds.

  Further, if necessary, a polycondensation accelerator can be added to the reaction system to complete the reaction quickly. Examples of such polycondensation accelerators include basic polycondensation accelerators and acidic polycondensation accelerators. Both can be used together. Examples of the basic polycondensation accelerator include N, N-dimethylaniline, N, N-diethylaniline, pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline, 2,4-lutidine, and triethylamine. , Tributylamine, tripentylamine, N-methylmorpholine, diazabicycloundecene, diazabicyclononene and the like. Examples of acidic polycondensation accelerators include benzoic acid, o-hydroxybenzoic acid, m- Hydroxybenzoic acid, p-hydroxybenzoic acid, 2,4-dihydroxybenzoic acid, p-hydroxyphenylacetic acid, 4-hydroxyphenylpropionic acid, phosphoric acid, p-phenolsulfonic acid, p-toluenesulfonic acid, crotonic acid, etc. Can be mentioned.

The polycondensation accelerator is used in an amount of 1 to 50 mol%, preferably 5 to 35 mol%, based on the diamine or diamine component. By using these polycondensation accelerators, the reaction temperature is lowered. Since it can be set, not only side reactions caused by heating, which is often caused by coloring, can be prevented, but the reaction time can be greatly shortened, which is economical.
The polymerization temperature of the polyamic acid is preferably 60 ° C. or lower, and more preferably 40 ° C. or lower because the reaction is efficient and the viscosity of the polyamic acid is likely to increase.
Examples of the solvent that can be used in the production of the polymer include ureas such as tetramethylurea, N, N-dimethylethylurea, sulfoxides or sulfones such as dimethylsulfoxide, diphenylsulfone, and tetramethylsulfone, N, Such as N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), N, N′-diethylacetamide, N-methyl-2-pyrrolidone (NMP), γ-butyllactone, hexamethylphosphoric triamide Amide or aprotic solvent of phosphorylamide, alkyl halides such as chloroform and methylene chloride, aromatic hydrocarbons such as benzene and toluene, phenols such as phenol and cresol, dimethyl ether, diethyl ether, p- Cresol Ethers such as such Chirueteru the like. Usually, these solvents are used alone, but two or more kinds may be used in appropriate combination as required. Of these, amides such as DMF, DMAc and NMP are preferably used.

  Another aspect of the present invention is a composition comprising a polymer containing at least one acetylene compound of the acetylene compound represented by the general formula (1) as a structural unit. Examples of the composition used include a polymer solution, a mixture of the polymer solution and particles such as filler, a mixture of polymer solid and filler particles, and the polymer solution immersed in fibers. And the like. From the viewpoint of easy curing, a polymer solution is preferred.

  The solvent used in the polymer solution is not particularly limited. For example, amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane) are used. ) Sulfoxide solvents (eg dimethyl sulfoxide), ureido solvents (eg tetramethyl urea), ether solvents (eg dioxane, cyclopentyl methyl ether), ketone solvents (eg acetone, cyclohexanone), hydrocarbon solvents (eg toluene, Xylene, n-decane), halogen solvents (eg, tetrachloroethane, chlorobenzene, methylene chloride, chloroform), pyridine solvents (eg, pyridine, γ-picoline, 2,6-lutidine), ester solvents (eg, ethyl acetate, acetic acid) The Le), and nitrile-based solvents (e.g., acetonitrile) is used alone or in combination. Of these, from the viewpoint of good solubility of the polymer, preferably an amide solvent, a sulfone solvent, a sulfoxide solvent, a ureido solvent, an ether solvent, a halogen solvent, a pyridine solvent, and a nitrile solvent. More preferred are amide solvents, ether solvents, halogen solvents, and nitrile solvents, and more preferred are amide solvents and nitrile solvents. These solvents may be used alone or in combination of two or more.

Another aspect of the present invention is obtained by curing a polymer containing at least one acetylene compound of any one of the acetylene compounds represented by the general formula (1) as a constituent unit or a composition containing the polymer. It is a cured product.
The obtained polymer of the present invention contains an acetylene group as a constituent component, and by further polymerizing this acetylene group, a cured product having more excellent mechanical properties and heat resistance can be obtained. (Here, the product produced by the reaction of acetylene in the polymer is referred to as “cured product”). Although it does not specifically limit as a reaction method of an acetylene group, Reaction of acetylene groups, what is called a polymerization reaction can be advanced by irradiation of a heat | fever, light, and a radiation. By the polymerization reaction of the acetylene group, the obtained target product (cured product) has a branched or three-dimensional crosslinked structure, and it becomes possible to obtain a molded product excellent in tensile elastic modulus and heat resistance (glass transition temperature). .

  A preferable curing method of the acetylene group is a method of applying temperature to the polymer of the present invention, and the preferable curing temperature is 100 to 500 ° C, more preferably 150 to 450 ° C, and further preferably 200 to 400 ° C. In addition, the time required for curing varies depending on the temperature and thus cannot be generally described. However, it is 1 minute to 24 hours, preferably 10 minutes to 10 hours, and more preferably 30 minutes to 5 hours. When it is in these ranges, a cured product having excellent mechanical properties and heat resistance can be obtained.

Specific examples of the acetylene compound of the present invention are shown below, but the present invention is not limited thereby.

In the formula, each of x, y, and z is an integer of 1 or more.

VIII. Description of Manufacturing Method Next, the manufacturing method of the present invention will be described. The method for producing an acetylene compound having two or more amino groups according to the present invention has a carboxylic acid group, a carboxylic acid ester group, a carbamic acid ester group, a thiocarboxylic acid group, a thiocarboxylic acid ester group in the molecule, and two amino groups. In this method, a compound having at least one compound and a compound having at least one ethynyl group having an amino group, a hydroxyl group or a thiol group in the molecule are subjected to a condensation reaction.

  Two methods can be considered as the above method. One method is 1) first protecting the amino group of a compound having two or more amino groups, and then directly reacting the compound having one or more ethynyl groups, and another method is 2) In this method, the amino group of a compound having two or more compounds is first protected, the carboxyl group to be reacted is changed to a more active intermediate, and then the compound having one or more ethynyl groups is reacted. These methods will be described in order.

  1) Description of a method of first protecting an amino group of a compound having two or more amino groups, and then directly reacting a compound having one or more ethynyl groups.

  A method for producing the acetylene compound represented by the general formula (2), which comprises reacting the acetylene compound represented by the general formula (3) with the compound represented by the general formula (5), will be described.

  When the compound represented by the general formula (3) is reacted with the compound represented by the general formula (5), the compound represented by the general formula (3) may be reacted as it is. It is preferable that the amino group of the compound represented by 3) is first protected and then reacted with the compound represented by the general formula (5).

  Any protecting group for the amino group of the general formula (3) can be used without any problem as long as it is described as “protecting group for amino group” in “PROTECTIVE GROUPS in ORGANIC SYNTHESIS”. Specific examples of preferred protective groups include acetyl, benzyloxycarbonyl (BOM), 2- (trimethylsilyl) ethoxycarbonyl (TEOC), t-butoxycarbonyl (Boc), allyloxycarbonyl (AOC), Examples include 2,2-trichloroethoxycarbonyl (Troc) group, 9-fluorenylmethoxycarbonyl (FMOC) group, tosyl (Ts) group, mesyl (Ms) group, and the like. Among these, a t-butoxycarbonyl group, a methoxycarbonyl group, and an acetyl group are preferable.

  The reaction conditions for protecting the amino group can be applied without problems as long as they are the methods described in the above documents. A compound in which an amino group is protected can be isolated and purified by means of reprecipitation, crystallization or the like, but can also be used in the next reaction as it is.

  When reacting the compound represented by the general formula (3) and the compound represented by the general formula (5), a catalyst may be added to the reaction system as necessary. It is preferable to carry out in the presence. Specifically, inorganic acids such as hydrogen chloride, hydrogen bromide, sulfuric acid and phosphoric acid, organic acids such as p-toluenesulfonic acid and camphor-10-sulfonic acid, acidic ion exchange resins such as amberlite and amberlist, etc. Alternatively, the reaction may be performed by a method using a condensing agent such as diacid carbodiimide or 1-ethyl-3- (3-dimethylaminopyrrolyl) -carbodiimide.

The use amount of the acetylene compound represented by the general formula (5) with respect to the carboxylic acid represented by the general formula (3) or a derivative compound thereof is preferably in the range of 0.5 to 10-fold mol, more preferably 0.8 to 2.0. Double mole, more preferably 0.9 to 1.2 mole. If it is less than 0.5 mol, the yield after the reaction is lowered, and it is not preferable. If it exceeds 10 mol, it does not cause a large obstacle to the reaction, but it is not preferable in terms of production cost because an excessive raw material is used. .

  As a solvent that can be used for the reaction, 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 amidation, esterification, or thioesterification process of the present invention. Although there is no particular limitation, for example, amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane) sulfoxide solvents (for example, dimethyl sulfoxide), Ureide solvents (eg tetramethylurea), ether solvents (eg dioxane, cyclopentylmethyl ether), ketone solvents (eg acetone, cyclohexanone), hydrocarbon solvents (eg toluene, xylene, n-decane), halogen solvents (For example, tetrachloroethane, chlorobenze , Methylene chloride, chloroform), pyridine solvents (eg, pyridine, γ-picoline, 2,6-lutidine), ester solvents (eg, ethyl acetate, butyl acetate), and nitrile solvents (eg, acetonitrile) alone or in combination. Use. Of these, amide solvents, sulfone solvents, sulfoxide solvents, ureido solvents, ether solvents, halogen solvents, pyridine solvents, and nitrile solvents, more preferably amide solvents, ether solvents, Halogen solvents and nitrile solvents, more preferably amide solvents and nitrile solvents. These solvents may be used alone or in combination of two or more.

  The reaction temperature is preferably in the range of -30 ° C to 300 ° C, more preferably 0 ° C to 200 ° C, still more preferably 20 ° C to 150 ° C. The reaction time varies depending on the amount charged and the reaction temperature, but is preferably in the range of 0.5 to 12 hours, more preferably in the range of 0.5 to 6 hours.

  The atmosphere in the reaction is preferably a sufficiently dried inert gas atmosphere. Since the presence of moisture reduces the reaction rate, it is preferably reduced as much as possible. As specific examples of the inert gas, rare gases such as nitrogen and argon can be suitably used.

  Examples of the method for isolating the acetylene compound of the present invention from the reaction mixture include separation and purification methods such as chromatography, crystallization or recrystallization after extraction with an organic solvent. When the acetylene compound is precipitated by cooling the solvent extracted with an organic solvent, the acetylene compound can be isolated by ordinary solid-liquid separation. Alternatively, it is also possible to crystallize the acetylene compound from an appropriate solvent system and isolate it by solid-liquid separation.

  Organic solvents for extracting acetylene compounds include ether solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether and methoxybenzene, ester solvents such as ethyl acetate and n-butyl acetate, and fats such as hexane, heptane and cyclohexane. Aromatic hydrocarbon solvents such as toluene and xylene, halogen solvents such as chloroform and methylene chloride, etc. from the viewpoint of mass production suitability, safety, availability, etc. on an industrial scale To ester solvents, aliphatic hydrocarbon solvents, and aromatic hydrocarbon solvents are preferred. Specific examples of the organic solvent preferably used include toluene, xylene (may be any of o-form, m-form, p-form, or a mixture of these in any proportion), mesitylene, ethylbenzene, isopropylbenzene. (Cumene), chlorobenzene, hexane, heptane, ethyl acetate, n-butyl acetate, etc., among which toluene, xylene, ethylbenzene, hexane, heptane, ethyl acetate, n-butyl acetate are more preferable, and toluene, hexane Further preferred solvents are heptane and ethyl acetate. The above solvents may be used alone or in combination of two or more.

  Examples of the organic solvent for crystallizing the acetylene compound include a mixed system of the organic solvent described above and another organic solvent. Other organic solvents to be mixed include ether solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, methoxybenzene, nitrile solvents such as acetonitrile, aliphatic hydrocarbon solvents such as hexane, heptane, cyclohexane, etc. , Aromatic hydrocarbon solvents such as toluene and xylene, and alcohol solvents such as 2-propanol and t-butanol. From the viewpoints of suitability for mass production on an industrial scale, safety, availability, etc. Ester solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents and water are preferred. Specific examples of the organic solvent preferably used include toluene, xylene (which may be o-isomer, m-isomer, p-isomer, or a mixture of these in any proportion), 2-propanol, t- Butanol, mesitylene, ethylbenzene, isopropylbenzene (cumene), hexane, heptane, acetonitrile, propionitrile, diisopropyl ether, methyl-t-butyl ether, methoxybenzene are more preferred, toluene, acetonitrile, diisopropyl ether, methyl-t-butyl ether, water Is more preferable. The above solvents may be used alone or in combination of two or more.

  The conditions for deprotecting the protecting group of the amino group can be used without any particular problems under the conditions listed as the protecting group deprotecting method corresponding to “PROTECTING GROUPS in ORGANIC SYNTHESIS”.

  Examples of the method for isolating the acetylene compound of the present invention from the reaction mixture include separation and purification methods such as chromatography, crystallization or recrystallization after extraction with an organic solvent. When the acetylene compound is precipitated by cooling the solvent extracted with the organic solvent, the acetylene compound can be isolated by ordinary solid-liquid separation. Alternatively, it is also possible to crystallize the acetylene compound from an appropriate solvent system and isolate it by solid-liquid separation.

  Organic solvents for extracting acetylene compounds include ether solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether and methoxybenzene, ester solvents such as ethyl acetate and n-butyl acetate, and fats such as hexane, heptane and cyclohexane. Aromatic hydrocarbon solvents such as toluene and xylene, halogen solvents such as chloroform and methylene chloride, etc. from the viewpoint of mass production suitability, safety, availability, etc. on an industrial scale To ester solvents, aliphatic hydrocarbon solvents, and aromatic hydrocarbon solvents are preferred. Specific examples of the organic solvent preferably used include toluene, xylene (may be any of o-form, m-form, p-form, or a mixture of these in any proportion), mesitylene, ethylbenzene, isopropylbenzene. (Cumene), chlorobenzene, hexane, heptane, ethyl acetate, n-butyl acetate, diethyl ether, diisopropyl ether, methyl-t-butyl ether, etc., among which toluene, xylene, ethylbenzene, hexane, heptane, ethyl acetate, N-butyl acetate and diethyl ether are more preferable, and toluene and ethyl acetate are more preferable solvents. The above solvents may be used alone or in combination of two or more.

  Examples of the organic solvent for crystallizing the acetylene compound include a mixed system of the organic solvent described above and another organic solvent. Other organic solvents to be mixed include ether solvents such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, methoxybenzene, nitrile solvents such as acetonitrile, aliphatic hydrocarbon solvents such as hexane, heptane, cyclohexane, etc. , Aromatic hydrocarbon solvents such as toluene and xylene, and alcohol solvents such as 2-propanol and t-butanol. From the viewpoints of suitability for mass production on an industrial scale, safety, availability, etc. Ester solvents, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents and water are preferred. Specific examples of the organic solvent preferably used include toluene, xylene (which may be o-isomer, m-isomer, p-isomer, or a mixture of these in any proportion), 2-propanol, t- Butanol, mesitylene, ethylbenzene, isopropylbenzene (cumene), hexane, heptane, acetonitrile, propionitrile, diisopropyl ether, methyl-t-butyl ether, methoxybenzene are more preferred, toluene, acetonitrile, diisopropyl ether, methyl-t-butyl ether, water Is more preferable. The above solvents may be used alone or in combination of two or more.

  Moreover, it is also possible to isolate as a corresponding salt by adding a suitable acid to the reaction liquid after completion | finish of reaction or after extraction. As the acid, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids such as oxalic acid, methanesulfonic acid and acetic acid can be used. The compound isolated as a salt can be taken out as an amino group by crystallization with a poor solvent after neutralization by adding an inorganic base or an organic base.

  2) Regarding a method of first protecting an amino group of a compound having two or more amino groups, then changing a carboxyl group to be reacted to a more active intermediate, and then reacting a compound having one or more ethynyl groups. Explanation.

  In this method, the compound represented by the general formula (3) is reacted with the compound represented by the general formula (5) after protecting the compound represented by the general formula (3). It is a method of converting into an active intermediate represented by

  The method for protecting the amino group of the compound represented by the general formula (3) is the same as the method for protecting the amino group described in 1).

As a method of synthesizing the compound represented by the general formula (4), a method of synthesizing by reacting an activator after protecting the compound represented by the general formula (3) is preferable.

  As an activator, when L in the general formula (4) is chlorine, chlorine, thionyl chloride, oxalyl chloride, phosphorus pentachloride, N-chlorosuccinimide, carbon tetrachloride, etc., when L is bromine Is bromine, N-bromosuccinimide, carbon tetrabromide, etc., when L is a sulfonyl derivative, methanesulfonyl chloride, -p-toluenesulfonyl chloride, etc., when it is an acid anhydride, methyl chlorocarbonate, Examples thereof include alkyl chlorocarbonates such as ethyl chlorocarbonate and isopropyl chlorocarbonate. Among these, the method using thionyl chloride, oxalyl chloride, and methanesulfonyl chloride is preferable.

  The activator can be added to the reaction system from the start of the reaction, but a method of dropping it into the reaction system is more preferable.

  When the compound represented by the general formula (4) is synthesized from the compound in which the amino group of the compound represented by the general formula (3) is protected, a base may be added to the reaction system as necessary. The base that can be used is not particularly limited, and both organic bases and inorganic bases can be used.

  The amount of the activator used when synthesizing the compound represented by the general formula (4) is preferably in the range of 1.0 to 20 times mol, more preferably 1.0 to 3.0 times mol, More preferably, it is 1.0 to 1.2 times mole. If it is less than 1.0-fold mol, unreacted (3) is always generated, which leads to a decrease in yield, and if it exceeds 20-fold mol, there is no significant hindrance to the reaction. Since raw materials are used, it is not preferable in terms of production cost.

  The solvent that can be used for the reaction is not particularly limited as long as it does not cause problems in the process operation, does not hinder the progress of the reaction, and does not adversely affect the reaction in the halogenation, acid anhydride formation, and sulfonyl derivatization processes of the present invention. Although there is no limitation, for example, amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone solvents (for example, sulfolane) sulfoxide solvents (for example, dimethyl sulfoxide), ureido Solvents (eg tetramethylurea), ether solvents (eg dioxane, cyclopentylmethyl ether), ketone solvents (eg acetone, 2-butanone, cyclohexanone), hydrocarbon solvents (eg toluene, xylene, n-decane), Halogenated solvents (eg tetrachloroethane, Olobenzene, methylene chloride, chloroform), pyridine solvents (eg, pyridine, γ-picoline, 2,6-lutidine), ester solvents (eg, ethyl acetate, butyl acetate), and nitrile solvents (eg, acetonitrile) alone or in combination And use. Of these, amide solvents, sulfone solvents, sulfoxide solvents, ureido solvents, ether solvents, halogen solvents, pyridine solvents, and nitrile solvents, more preferably amide solvents, ether solvents, Halogen solvents and nitrile solvents, more preferably amide solvents and nitrile solvents. These solvents may be used alone or in combination of two or more.

  The reaction temperature is preferably in the range of -30 ° C to 80 ° C, more preferably -20 ° C to 50 ° C, still more preferably -10 ° C to 30 ° C. The reaction time varies depending on the charged amount and the reaction temperature, but is preferably in the range of 0.5 to 12 hours, and more preferably in the range of 0.5 to 3 hours.

  The atmosphere in the reaction is preferably a sufficiently dried inert gas atmosphere. Since the presence of moisture leads to decomposition of the compound represented by the general formula (4), it is preferable to reduce it as much as possible. As specific examples of the inert gas, rare gases such as nitrogen and argon can be suitably used.

  The active intermediate represented by the general formula (4) synthesized by the above method can be taken out, but it is generated in the reaction system and directly reacted with the compound represented by the following general formula (5). May be used.

  Next, the reaction between the compound represented by the general formula (4) and the compound represented by the general formula (5) will be described. The use amount of the acetylene compound represented by the general formula (5) with respect to the compound represented by the general formula (4) is preferably in the range of 0.5 to 10 times mol, more preferably 0.8 to 2.0 times mol, More preferably, it is 0.9 to 1.2 times mol. If it is less than 0.5-fold mol, it is not preferable because the yield after the reaction is lowered, and it is not preferable. If it exceeds 10-fold mol, the reaction will not be greatly hindered. Not preferable.

There is no particular limitation on the method of adding the compound in the reaction of the compound represented by the general formula (4) with the compound represented by the general formula (5). The method of dripping the other compound in the solution of the compound represented by (4) or General formula (5) is more preferable.

  As a solvent that can be used for the reaction, when the compound represented by the general formula (4) is used as it is without being isolated, the solvent used when the compound represented by the general formula (4) is synthesized is used as it is. I do not care. As a solvent in the case where the compound represented by the general formula (4) is once isolated and newly charged, it does not cause problems in process operation, does not disturb the progress of the reaction, and amidation and esterification of the present invention. The thioesterification step is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include amide solvents (for example, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone), sulfone Solvents (eg sulfolane) sulfoxide solvents (eg dimethyl sulfoxide), ureido solvents (eg tetramethylurea), ether solvents (eg dioxane, cyclopentylmethyl ether), ketone solvents (eg acetone, cyclohexanone), hydrocarbons Solvent (for example, toluene, xylene, n-decane), halogen type Vehicle (for example, tetrachloroethane, chlorobenzene, methylene chloride, chloroform), pyridine-based solvent (for example, pyridine, γ-picoline, 2,6-lutidine), ester-based solvent (for example, ethyl acetate, butyl acetate), and nitrile-based solvent (for example, Acetonitrile) is used alone or in combination. Of these, amide solvents, sulfone solvents, sulfoxide solvents, ureido solvents, ether solvents, halogen solvents, pyridine solvents, and nitrile solvents, more preferably amide solvents, ether solvents, Halogen solvents and nitrile solvents, more preferably amide solvents and nitrile solvents. These solvents may be used alone or in combination of two or more.

  The reaction temperature is preferably in the range of −30 ° C. to 200 ° C., more preferably −10 ° C. to 100 ° C., still more preferably 0 ° C. to 50 ° C. The reaction time varies depending on the amount charged and the reaction temperature, but is preferably in the range of 0.5 to 12 hours, more preferably in the range of 0.5 to 6 hours.

  The atmosphere in the reaction is preferably a sufficiently dried inert gas atmosphere. Since the presence of moisture leads to decomposition of the compound represented by the general formula (4), it is preferable to reduce it as much as possible. As specific examples of the inert gas, rare gases such as nitrogen and argon can be suitably used.

The conditions for taking out the acetylene compound after completion of the reaction are the same as those for taking out the acetylene compound after completion of the reaction described in 1). The conditions for deprotecting the amino-protecting group are the same as the reaction conditions described in 1).

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. The obtained compound was subjected to measurement of various spectra of H-NMR and MS for property evaluation. The measurement conditions for each characteristic were as follows:

<Test method>
(1) Nuclear magnetic resonance spectrum analysis ( ¹ H-NMR): Measured at a resonance frequency of 400 MHz using AV400M manufactured by BRUKER. As a measurement solvent, deuterated dimethyl sulfoxide DMSO-d ₆ which is a deuterated solvent was used.
(2) Mass spectrometry (MS): Measured by ESI method using APIQSTAR Pulsar i manufactured by Applied Biosystems.

[Example 1]
Intermediate compound 1 was synthesized based on the following formula.

  In a 300 ml three-necked flask, under a nitrogen stream, 10.0 g (28.4 mmol) of compound 3,5- (di-t-butylcarboxy) diaminobenzoic acid, 100 ml of acetonitrile, 2.87 g (28.4 mmol) of triethylamine were put in this order. Stir. Under ice cooling, 3.25 g (28.4 mmol) of methanesulfonyl chloride was added dropwise, and the mixture was stirred for 30 minutes under ice cooling. A solution prepared by mixing 3.32 g (28.4 mmol) of 3-ethynylaniline and 2.87 g (28.4 mmol) of triethylamine in 5 ml of acetonitrile was added dropwise to the reaction solution. After confirming disappearance of the raw material by HPLC, 250 ml of water and 250 ml of ethyl acetate were added to separate the layers. A 1N aqueous hydrochloric acid solution was added to the obtained ethyl acetate layer for liquid separation, and the mixture was neutralized with an aqueous sodium bicarbonate solution and washed with distilled water. The obtained ethyl acetate layer was dried over anhydrous magnesium sulfate and concentrated by a rotary evaporator. 9.6 g of a brown solid was obtained.

  80 ml of methanol was added to 9.6 g of a brown solid and heated to reflux with stirring. After confirming complete dissolution, the mixture was ice-cooled for 2 hours, and the resulting crystals were filtered to obtain 5.3 g (11.7 mmol) of the desired intermediate compound 1 (yield 41%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.40 (s, 1H), 9.86 (s, 2H) 8.27 (s, 1H), 7.87 (s, 2H), 7. 81 (s, 1H), 7.62 (d, 1H), 7.29 (s, 1H), 7.14 (d, 1H), 4.10 (s, 1H), 1.49 (s, 18H) )
MS: M ⁺ = 451.21

[Example 2]
Exemplified compound (1) -43 was synthesized based on the following formula.

  Intermediate compound 1 (3.0 g, 6.64 mmol), acetonitrile (60 ml), and distilled water (10 ml) were added to a 200 ml three-necked flask, and the mixture was stirred at room temperature. To this solution, 17 ml of concentrated hydrochloric acid was added and stirred for 4 hours. 60 ml of acetonitrile was added, and the precipitated solid was filtered to obtain 1.29 g of the target compound (1) -43 (yield 61%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.04 (s, 1H), 7.92 (s, 1H), 7.76 (d, 1H), 7.36 (t, 1H), 7 .22 (d, 1H), 6.96 (s, 1H), 6.68 (s, 1H), 4.19 (s, 1H)
MS: M ⁺ = 323.06

[Example 3]
Exemplified compound (1) -1 was synthesized based on the following formula.

  1.0 g (3.08 mmol) of Compound (1) -43 and 45 ml of distilled water were added and stirred. Sodium bicarbonate was added to this solution until pH = 7. The precipitated solid was separated by filtration to obtain 0.77 g of the target compound (1) -1 (yield 99.4%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.03 (s, 1H), 7.92 (s, 1H), 7.77 (d, 1H), 7.32 (t, 1H), 7 .14 (d, 1H), 6.28 (s, 1H), 6.00 (s, 1H), 4.95 (s, 4H), 4.16 (s, 1H)
MS: M ⁺ = 251.11

[Example 4]
Exemplified intermediate compound 2 was synthesized based on the following formula.

  The intermediate shown in the following formula in the same manner as the synthesis of intermediate compound 1 except that 4-ethynylaniline (28.4 mmol) was used instead of 3-ethynylaniline (28.4 mmol) in the synthesis of intermediate compound 1. 8.3 g of compound 2 was obtained (yield 65%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.40 (s, 1H), 9.51 (s, 2H) 7.81 (s, 1H), 7.75 (d, 2H), 7. 52 (s, 2H), 7.44 (d, 2H), 4.10 (s, 1H), 1.48 (s, 18H)
MS: M ⁺ = 451.21

[Example 5]
Exemplified compound (1) -2 was synthesized based on the following formula.

Intermediate compound 2 (3.0 g, 6.64 mmol), toluene (100 ml) and acetonitrile (150 ml) were added to a 500 ml three-necked flask, and the mixture was stirred at room temperature. To this solution, 1.2 g of methanesulfonic acid was added and stirred for 4 hours. The reaction mixture was added to an aqueous sodium bicarbonate solution, ethyl acetate was added, and the mixture was separated and washed with distilled water. The obtained ethyl acetate layer was dried over anhydrous magnesium sulfate and concentrated by a rotary evaporator. The precipitated solid was filtered to obtain 0.74 g of the target compound (1) -2 (yield 44%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.12 (s, 1H), 7.77 (d, 2H), 7.42 (d, 2H), 6.27 (s, 1H), 5 .99 (s, 1H), 4.96 (s, 4H), 4.08 (s, 1H)
MS: M ⁺ = 251.11

[Example 6]
Example intermediate compound 3 was synthesized based on the following formula.

  In the synthesis of intermediate compound 1, intermediate compound 3 was prepared in the same manner as in the synthesis of intermediate compound 1 except that 3-ethynylphenol (28.4 mmol) was used instead of 3-ethynylaniline (28.4 mmol). .35 g was obtained (yield 65%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 9.86 (s, 2H) 8.27 (s, 1H), 8.12 (s, 2H), 7.32 (d, 1H), 7. 31 (t, 1H), 7.29 (s, 1H), 7.13 (d, 1H), 3.06 (s, 1H), 1.49 (s, 18H)
MS: M ⁺ = 45.19

[Example 7]
Exemplified compound (1) -3 was synthesized based on the following formula.

Intermediate compound 3 (2.5 g, 5.52 mmol), acetonitrile (50 ml), and distilled water (10 ml) were added to a 500 ml three-necked flask and stirred. To this solution, 14 ml of concentrated hydrochloric acid was added and stirred for 4 hours. A sodium bicarbonate aqueous solution was added to the reaction solution, ethyl acetate was added thereto, and the mixture was separated and washed with distilled water. The obtained ethyl acetate layer was dried over anhydrous magnesium sulfate and concentrated by a rotary evaporator. The precipitated solid was filtered to obtain 1.15 g of the target compound (1) -3 (yield 82%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 7.32 (d, 1H), 7.31 (s, 1H), 7.30 (t, 1H), 7.13 (d, 1H), 6 .70 (s, 2H), 5.91 (s, 1H), 5.85 (s, 4H), 3.06 (s, 1H)
MS: M ⁺ = 252.09

[Example 8]
Exemplified intermediate compound 4 was synthesized based on the following formula.

In the synthesis of Intermediate Compound 1, 4- (3-aminophenyl) -2-methyl-3-butyn-2-ol (28.4 mmol) was used instead of 3-ethynylaniline (28.4 mmol). In the same manner as in the synthesis of Intermediate Compound 1, 6.51 g of Intermediate Compound 4 was obtained (45% yield). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.40 (s, 1H), 9.86 (s, 2H), 8.27 (s, 1H), 7.87 (s, 2H), 7 .81 (s, 1H), 7.62 (d, 1H), 7.29 (t, 1H), 7.16 (d, 1H), 5.45 (s, 1H), 1.49 (s, 18H), 1.47 (s, 6H)
MS: M ⁺ = 509.59

[Example 9]
Exemplified compound (1) -16 was synthesized based on the following formula.

Except that intermediate compound 4 (5.52 mmol) was used instead of intermediate compound 3 (5.52 mmol) in the synthesis of exemplary compound (1) -3, an experiment was conducted in the same manner as in the synthesis of (1) -3 to obtain a compound. 1.21 g of (1) -16 was obtained (yield 71%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.40 (s, 1H), 7.81 (s, 1H), 7.62 (d, 1H), 7.29 (t, 1H), 7 .16 (d, 1H), 6.51 (s, 2H), 5.91 (s, 1H), 5.85 (s, 4H), 5.45 (s, 1H), 1.47 (s, 6H)
MS: M ⁺ = 309.15

[Example 10]
Synthesis by (1) -1 consistent method To a 1000 ml three-necked flask, 10 g (65.7 mmol) of 3,5-diaminobenzoic acid, 150 ml of t-butanol, and 150 ml of 1N NaOH aqueous solution were added and stirred to confirm dissolution. While cooling with ice, 29.4 g (134.7 mmol) of di-t-butyl dicarbonate was added dropwise and stirred. After confirming the disappearance of the raw materials by HPLC, 300 ml of toluene was added, and hydrochloric acid was added for neutralization and liquid separation was performed. After 200 ml of water was added for liquid separation, 6.7 g (65.7 mmol) of triethylamine was added to the oil layer, and the mixture was stirred under a nitrogen atmosphere. To this reaction solution, 7.5 g (65.7 mmol) of methanesulfonyl chloride was added dropwise under ice cooling, and the mixture was stirred for 30 minutes under ice cooling. To this reaction solution, a solution prepared by mixing 7.7 g (65.7 mmol) of 3-ethynylaniline and 6.7 g (65.7 mmol) of triethylamine in 10 ml of toluene was dropped. After confirming disappearance of the raw material by HPLC, 200 ml of water was added to separate the layers. To the obtained toluene layer, 22.1 g (230 mmol) of methanesulfonic acid was stirred at room temperature. After confirming disappearance of the raw material by HPLC, the solution was neutralized with an aqueous sodium bicarbonate solution and washed with distilled water. The obtained organic layer was concentrated by an evaporator to obtain 7.74 g of (1) -1 (yield 47%). The physical property values of the obtained compound were the same as those of the compound obtained in Example 3.

[Example 11]
Compound (1) -11 was synthesized based on Example 10 except that 3,5-diethynylaniline was used instead of 3-ethynylaniline in Example 10.

[Example 12]
Compound (1) -11 was synthesized based on Example 10 except that 3,5-diethynylaniline was used instead of 3-ethynylaniline in Example 10.

[Example 13]
(1) Synthesis of -30 Amidol dihydrochloride 10 g (0.050 mol), water 200 ml, and potassium carbonate 21.0 g (0.15 mol) were added in this order to a 500 ml three-necked flask and dissolved by stirring. Under ice-cooling, 22.3 g (0.10 mol) of di-t-butyl dicarbonate was added dropwise over 1.5 hours. After completion of the dropwise addition, the reaction mixture was returned to room temperature and reacted. After confirming disappearance of the raw material by HPLC, neutralization and acid precipitation were performed with HCl, and intermediate 1 was obtained after filtration. The obtained intermediate 1 was dissolved in NMP, and 19.8 g (0.15 mol) of pyridine was added. Under ice-cooling, phenyl chlorocarbonate was added dropwise, and after completion of the addition, the mixture was returned to room temperature and reacted. After confirming disappearance of the raw material by HPLC, 11.8 g (0.10 mol) of 3-ethynylphenol was added and heated to 50 ° C. After confirming disappearance of 3-ethynylphenol by HPLC, 96.1 g (1.0 mol) of methanesulfonic acid was added under ice-cooling, and the reaction was carried out. The resulting reaction solution was neutralized with multilayer water and crystallized with toluene to obtain 6.0 g of (1) -30 (yield 45%).
The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 7.24 (s, 1H), 7.23 (d, 2H), 7.20 (t, 1H), 7.05 (d, 1H), 6 .57 (d, 2H), 5.79 (d, 1H), 5.63 (s, 1H), 5.85 (s, 4H), 3.06 (s, 1H)
MS: M ⁺ = 268.08

[Example 14]
Compound (1) -35 was synthesized based on Example 10 except that 3-ethynyl-4-fluoroaniline was used instead of 3-ethynylaniline in Example 10.

[Example 15]
Compound (1) -59 was synthesized based on Example 10 except that 3,5-diaminocyclohexanecarboxylic acid was used in place of 3,5-diaminobenzoic acid in Example 10.

[Example 16]
Compound (2) -1 was synthesized according to the following method.

A 100 ml four-necked flask was charged with 3.0 g (11.9 mmol) of (1) -1 synthesized by the method of Example 3 and 20 g of NMP, and dissolved in a nitrogen stream. 4-Ethynylphthalic anhydride (4.11 g, 23.9 mmol) was added in portions and stirred at room temperature for 4 hours to synthesize an amic acid solution. Subsequently, 0.19 g (2.39 mmol) of pyridine and 7.32 g (71.6 mmol) of acetic anhydride were added dropwise. The mixture was stirred at room temperature for several hours, and the precipitated crystals were filtered and dried to obtain 5.01 g of (1) -30 (yield 75%). The physical properties of the obtained compound were as follows.

¹ H-NMR (400 MHz, DMSO-d ₆ ): δ 10.40 (s, 1H), 8.29 (s, 2H), 8.27 (s, 1H), 8.10 (d, 2H), 8 .07 (s, 2H), 7.85 (d, 2H), 7.81 (s, 1H), 7.62 (d, 1H), 7.29 (t, 1H), 7.14 (d, 1H), 4.08 (s, 1H), 3.06 (s, 2H)
MS: M ⁺ = 559.12

[Example 17]
(3) -5 Synthesis According to the method described in Non-Patent Document 2, (1) -1,4-phenylethynylphthalic anhydride, 4,4′-oxydianiline, and 4,4′-oxydiphthalic anhydride From an N-methylpyrrolidone (hereinafter abbreviated as NMP) solution of the product, an amic acid oligomer solution having an average molecular weight of about 9,000 was prepared, and the resulting amic acid oligomer was centrifuged, and then coated, dried, and sequentially 100 ° C. A film of crosslinked imide oligomer was obtained through a process of heat treatment at 250 ° C. and 350 ° C. for 1 hour each. On the other hand, toluene was added to the NMP solution of the amic acid oligomer, and the imide oligomer was isolated through an azeotropic dehydration step, cooling, filtration, washing with water / methanol in order, and a drying step.

  The mechanical properties at 23 ° C. of the film prepared by the method described above were measured by the method of American Society for Testing and Materials (ASTM) D882. The results are shown in Table 1.

[Example 18]
In Example 17, an experiment was performed in the same manner as in Example 17 except that (1) -35 was used instead of (1) -1, and an imide oligomer was obtained.
The physical property measurement results of the obtained polymer are shown in Table 1.

[Example 19]
In Example 17, an experiment was performed in the same manner as in Example 17 except that (1) -59 was used instead of (1) -1, and an imide oligomer was obtained.
The physical property measurement results of the obtained polymer are shown in Table 1.

[Example 20]
In a 200 mL three-necked flask substituted with an inert gas, 0.018 mol of bis (4-aminophenyl) ether, 0.005 mol of compound (1) -1 and 0.004 mol of aniline are taken and dissolved by adding 110 mL of NMP. To do. While stirring this reaction solution at room temperature, 0.025 mol of 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride was added as a solid and stirred at room temperature for 2 hours. Thereafter, 0.05 mol of acetic anhydride and 0.005 mol of pyridine were added and stirred at room temperature for 1 hour, then heated to 60 ° C. and stirred for 3 hours to obtain a polyimide solution.

The obtained solution was dropped into 300 mL of acetonitrile, and the resulting precipitate was filtered and dried to obtain a polyimide powder having (1) -1 at both ends. 10 g of this powder was dissolved in 50 mL of N-methyl-2-pyrrolidone to obtain a polyimide solution having (1) -1.
After applying this solution on a quartz glass plate using a blade, drying, and thermosetting at 250 ° C., the polyimide film obtained on this quartz glass plate has a mechanical property at 23 ° C. It was measured by the method of Test Association (ASTM) D882. The results are shown in Table 1.

[Example 21]
In Example 20, an experiment was performed in the same manner as in Example 20 except that (1) -35 was used instead of (1) -1, and an imide oligomer was obtained.

The mechanical properties at 23 ° C. of the film prepared by the method described above were measured by the method of American Society for Testing and Materials (ASTM) D882. The results are shown in Table 1.

[Example 22]
Compound (1) -1 (0.018 mol) and triethylamine (0.090 mol) are added to a 200 mL three-necked flask replaced with an inert gas, and 110 mL of NMP is added and dissolved. The reaction mixture was ice-cooled, 4-nitrophenol (0.020 mol) was added dropwise, and the mixture was stirred at the same temperature for 30 min. To this solution, 3,4 '-(diaminodiphenyl ether (0.018 mol) dissolved in 20 ml of NMP was gradually added, and after completion of the dropwise addition, the temperature was returned to room temperature and stirred for 2 hours.
After applying this solution on a quartz glass plate using a blade, drying, and thermosetting at 250 ° C., the polyimide film obtained on this quartz glass plate has a mechanical property at 23 ° C. It was measured by the method of Test Association (ASTM) D882. The results are shown in Table 1.

[Example 23]
Compound (1) -1 (0.018 mol) and triethylamine (0.090 mol) are added to a 200 mL three-necked flask replaced with an inert gas, and 110 mL of NMP is added and dissolved. The reaction mixture was ice-cooled, 4-nitrophenol (0.020 mol) was added dropwise, and the mixture was stirred at the same temperature for 30 min. To this solution, 4,4 ′-(dihydroxydiphenylmethane (0.018 mol) dissolved in 20 ml of NMP was gradually added. After completion of the dropwise addition, the solution was returned to room temperature and stirred for 2 hours.
After applying this solution on a quartz glass plate using a blade, drying, and thermosetting at 250 ° C., the polyimide film obtained on this quartz glass plate has a mechanical property at 23 ° C. It was measured by the method of Test Association (ASTM) D882. The results are shown in Table 1.

[Example 24]
Compound (1) -1 (0.018 mol), aniline (0.004 mol) and triethylamine (0.090 mol) are added to a 200 mL three-necked flask substituted with an inert gas, and NMP 110 mL is added and dissolved. While stirring this reaction solution at room temperature, 0.018 mol of 3,3 ′-(naphthalenedicarboxylic acid dichloride was gradually added as a solid and stirred at room temperature for 2 hours.
After applying this solution on a quartz glass plate using a blade, drying, and thermosetting at 250 ° C., the polyimide film obtained on this quartz glass plate has a mechanical property at 23 ° C. It was measured by the method of Test Association (ASTM) D882. The results are shown in Table 1.

[Comparative Example 1]
According to the method described in Non-Patent Document 2, from an N-methylpyrrolidone solution of 4-phenylethynylphthalic anhydride, 3,4'-oxydianiline, and 4,4'-oxydiphthalic anhydride, an average molecular weight of about 9 After the amide oligomer oligomer solution was prepared by centrifugation, the resulting amic acid oligomer was centrifuged, coated, dried, and sequentially subjected to heat treatment at 100 ° C, 250 ° C, and 350 ° C for 1 hour each to crosslink the imide oligomer. A product film was obtained. On the other hand, toluene was added to the N-methylpyrrolidone solution of the amic acid oligomer, and the imide oligomer was isolated through an azeotropic dehydration step, cooling, filtration, washing with water and methanol in this order, and a drying step.
This powder was dissolved in NMP to obtain a solution, which was applied onto a quartz glass plate using a blade, dried and heat-cured at 250 ° C. in the same manner as in Example 17, and then obtained on this quartz glass plate. The mechanical properties of the polyimide film at 23 ° C. were measured by the method of American Society for Testing and Materials (ASTM) D882. The results are shown in Table 1.

[Comparative Example 2]
The experiment was performed in the same manner as in Example 22 except that 3,5-dimethylaniline was used instead of (1) -1. Table 1 shows measured values of physical properties of the obtained film.

[Comparative Example 3]
The experiment was performed in the same manner as in Example 23 except that 3,5-dimethylaniline was used instead of (1) -2. Table 1 shows measured values of physical properties of the obtained film.

[Comparative Example 4]
In Example 24, it was the same as Example 24 except that 3,4'-diaminodiphenyl ether was used instead of (1) -1 and 4-phenylethynylphthalic anhydride (0.004 mol) was added instead of aniline. The experiment was conducted. Table 1 shows measured values of physical properties of the obtained film.

[Comparative Example 5]
In Example 16, the experiment was performed in the same manner as in Example 16 except that aniline was used instead of (1) -1. Table 1 shows measured values of physical properties of the obtained film.

  The mechanical properties at 23 ° C. of the film prepared by the method described above were measured by the method of American Society for Testing and Materials (ASTM) D882. The results are shown in Table 1.

  As apparent from Table 1 above, the film prepared from the polymer obtained by introducing the acetylene compound into the main chain according to the present invention has higher tensile strength and elastic modulus than the conventionally known polymer having the acetylene compound introduced into the terminal. It turns out that it is excellent.

  The acetylene compound provided by the present invention can be introduced into a polymer and subjected to a curing treatment to obtain a thermosetting polymer or oligomer that can improve mechanical strength, heat resistance, and chemical resistance.

Claims (13)

An acetylene compound represented by the following general formula (1) and a salt thereof.

(Wherein X represents —OCO—, —NRCO—, —NRCONR′—, —NRCOO—, —OCONR—, —OCOO—, —OCS—, —NRCS—, —NRCSNR′—, —OCSO—, —S —, —O—, —SO—, —SO ₂ —, —NR—, —CO—, —CS—, —CRR′—, —CRR′—CR ″ R ′ ″ —, and a single bond are represented. , Ar represents an aryl group or a heteroaryl group, R, R ′, R ″, R ′ ″ represent a hydrogen atom hydrocarbon group or a heterocyclic group, respectively, R ¹ represents a hydrogen atom or an alkyl group, Represents an alkenyl group, a heterocyclic group, or an alkylsilyl group, A represents a hydrocarbon group or a heterocyclic group, m represents an integer of 1 or more, n represents an integer of 2 or more, and a represents 1 or more and 5 or less. Represents an integer). The acetylene compound and the salt thereof according to claim 1, wherein the acetylene compound represented by the general formula (1) and a salt thereof are represented by the following general formula (2).

(In the formula, R ² and R ³ each independently represent a hydrogen atom or a group that can be substituted on a benzene ring. X represents —OCO—, —NRCO—, —NRCONR—, —NRCOO—, and b represents 0 or more. 4 represents an integer of 4 or less, c represents an integer of 0 to 3, m represents an integer of 1 to 4, and n represents an integer of 2 to 5. R, R ¹ , X, and a are each And has the same meaning as R, R ¹ , X, and a in formula (1)).   The acetylene compound and the salt thereof according to claim 2, wherein X in the general formula (2) is -OCO- or -NHCO-.   The acetylene compound and the salt thereof according to claim 3, wherein m is 1 in the general formula (2).   In the said General formula (2), a is 1, The acetylene compound and its salt of Claim 4 characterized by the above-mentioned.   In the said General formula (2), n is 2, The acetylene compound and its salt of Claim 5 characterized by the above-mentioned.   In the said General formula (2), the position of the substituent of an ethynyl group is a meta position or a para position with respect to X, The acetylene compound and its salt of Claim 6 characterized by the above-mentioned. The acetylene compound represented by the general formula (1), and -COOH group, -COOR ⁰ group, -CSOH group, -COSH group, -CSSH group, -OCOL 'group, -NRCOL' group, -OCSL in the molecule An amide compound, an imide compound having a partial structure of an acetylene compound residue according to claim 1, wherein the amide compound residue is adjusted and derived from a compound having one of a group, -NCO, and -NSO group, And benzimidazole compounds. Here, L ′ represents a monovalent leaving group, and R ⁰ represents a hydrocarbon group. R has the same meaning as R in the general formula (1).   At least one monomer selected from the group consisting of at least the acetylene compound according to any one of claims 1 to 7, an amine compound, a carboxylic acid compound, a carboxylic acid anhydride, a polyol compound, and an aldehyde compound. An oligomer or polymer comprising a unit as a constituent element.   The oligomer or polymer according to claim 9, wherein the oligomer or polymer has a structure obtained by block copolymerization of two or more kinds. The amino group of the acetylene compound represented by the following general formula (3) is protected and then condensed with the compound represented by the general formula (5) having an ethynyl group via the compound represented by the general formula (4). The method for producing an acetylene compound and a salt thereof according to claim 3, wherein the acetylene compound represented by the general formula (2) is produced by reaction.

(In the general formula ^{(3), R 3, c} , m, n are .R ⁴ is substitutable hydrogen atom or an amino group in ^R 3, c, respectively, in the general formula (2), m, and n synonymous Represents a group).

(In General Formula (4), L represents a monovalent leaving group, R ⁵ represents a functional group that can be used as a protective group for an amino group, and R ³ , c, and m each represent General Formula (2). in a ^R 3, c, synonymous with m .R ⁴ has the same meaning as ^{R 4} in the general formula (3).).

(In the general formula ^(5), R ^1, R 2, a, b are respectively a ^{R 1,} R 2, a, the same meaning as b in the general formula (2) .Z is -OH or _-NH 2, - NHR and R are the same as R in the general formula (1). ).   The method for producing an acetylene compound and a salt thereof according to claim 11, wherein the substituent L of the general formula (4) is a halogen atom, a methanesulfonyl group, or a phenoxycarbonyl group.   It is a manufacturing method of Claim 12, Comprising: (I) The process of protecting the amino group of the acetylene compound represented by General formula (3), (II) The compound shown by General formula (4) in the protected compound The compound is converted without being isolated in each of the step of reacting with the acetylene compound represented by the general formula (5) and the step of (III) deprotecting the amino group. 12. A process for producing an acetylene compound and a salt thereof according to 12.