WO2010013620A1 - Process for producing phthalic anhydride derivative - Google Patents

Process for producing phthalic anhydride derivative Download PDF

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Publication number
WO2010013620A1
WO2010013620A1 PCT/JP2009/063080 JP2009063080W WO2010013620A1 WO 2010013620 A1 WO2010013620 A1 WO 2010013620A1 JP 2009063080 W JP2009063080 W JP 2009063080W WO 2010013620 A1 WO2010013620 A1 WO 2010013620A1
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phthalic anhydride
represented
organic
general formula
acid
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PCT/JP2009/063080
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French (fr)
Japanese (ja)
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進介 井上
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マナック株式会社
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Priority to CN2009801284455A priority Critical patent/CN102099349A/en
Priority to JP2010522682A priority patent/JP5485890B2/en
Publication of WO2010013620A1 publication Critical patent/WO2010013620A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3

Definitions

  • the present invention is a phthalic anhydride derivative useful as a raw material of a heat-resistant resin such as a polyesterimide resin or polyimide, a curing agent such as an epoxy resin, or a resin modifier, particularly an ester group-containing phthalic anhydride derivative or an ethynyl group
  • a heat-resistant resin such as a polyesterimide resin or polyimide
  • a curing agent such as an epoxy resin
  • a resin modifier particularly an ester group-containing phthalic anhydride derivative or an ethynyl group
  • the present invention relates to a method for producing a phthalic anhydride derivative.
  • the present invention also relates to a method for purifying a phthalic anhydride derivative.
  • An ester group-containing phthalic anhydride derivative is useful as a raw material for heat-resistant resins such as a polyesterimide resin, a curing agent such as an epoxy resin, or a resin modifier.
  • a method for producing it for example, (1) benzene, Method by reaction of trimellitic anhydride chloride with phenols or diols in an organic solvent such as toluene (see, for example, Patent Document 1), (2) Heating trimellitic anhydride and phenols at 250 to 300 ° C (3) transesterification of trimellitic anhydride with a lower alkanoic acid ester of a phenol in the presence of an inorganic compound such as a silica / alumina compound as a catalyst. (For example, see Patent Document 2) or a method performed in the presence of a specific solvent (for example, see Patent Document 3) Such as are known.
  • the ethynyl group-containing phthalic anhydride derivative is extremely useful as a raw material for providing a material having adhesiveness, heat resistance and mechanical strength required in the polyimide field.
  • a method for producing an ethynyl group-containing phthalic anhydride derivative for example, phenylethynyl phthalic anhydride, a method is known in which ethynylbenzene and bromophthalic anhydride are reacted in the presence of a large excess of a basic organic substance. (For example, refer nonpatent literature 2). JP 2005-298623 A JP-A-7-41472 Japanese Patent Laid-Open No. 10-147582 J. Polym. Sci., Vol 4, 1531-41, Part A, (1966) Highperform. Polym. Vol. 6, 423 (1994)
  • Patent Document 1 In the method disclosed in Patent Document 1 cited in the background art, after the reaction of trimellitic anhydride chloride and phenols in the presence of a basic substance, the hydrohalide salt of the basic substance produced as a by-product is treated with water. Is removed. At this time, since a part of the phthalic anhydride skeleton of the reaction product undergoes hydrolysis and ring-opening, reclosing with acetic anhydride is necessary.
  • the method disclosed in Patent Document 2 using an inorganic catalyst has a problem that it is difficult to remove the inorganic catalyst to be used, and the resulting ester group-containing phthalic anhydride derivative is likely to be an impurity.
  • Non-Patent Document 2 is a method in which ethynylbenzene and bromophthalic anhydride are reacted in the presence of a large excess of a basic organic substance, and then by-produced hydrobromic acid. The salt is removed and the resulting reaction product is crystallized in water. At this time, as described above, a part of the phthalic anhydride skeleton undergoes hydrolysis to open a ring, and thus re-ring closure by heat is necessary.
  • the present invention provides a method for efficiently producing a phthalic anhydride derivative without opening the phthalic anhydride skeleton. Similarly, a method for efficiently purifying a phthalic anhydride derivative without opening the phthalic anhydride skeleton is also provided.
  • the present inventor has conducted various studies to solve the above problems, and in the presence of a basic substance, an organic halide containing a phthalic anhydride skeleton and an organic proton donor are reacted to produce phthalic anhydride.
  • an organic halide containing a phthalic anhydride skeleton and an organic proton donor are reacted to produce phthalic anhydride.
  • a hydrohalic acid salt of a basic substance as a by-product with an organic acid
  • phthalic anhydride is obtained without ring-opening the phthalic anhydride skeleton of the obtained product. It has been found that derivatives can be produced efficiently.
  • the present inventor is a method for purifying a phthalic anhydride derivative obtained by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, comprising: It was found that the phthalic anhydride derivative can be efficiently purified without dissolving the phthalic anhydride skeleton of the product by dissolving and removing the resulting hydrohalic acid salt of the basic substance with an organic acid.
  • the phthalic anhydride derivatives of the present invention are raw materials for heat-resistant resins such as polyesterimide resins, curing agents such as epoxy resins, or resin modifiers.
  • used as The method for producing a phthalic anhydride derivative according to the present invention does not have the problem of requiring ring opening by hydrolysis of the phthalic anhydride skeleton and the need for a re-ring closing step as in the prior art, and requires a special solvent or catalyst. It is useful because it can be efficiently produced by a simple method.
  • the present invention is a method for producing a phthalic anhydride derivative by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, wherein
  • the present invention relates to a method comprising dissolving and removing a hydrohalide salt of a substance with an organic acid.
  • a typical first aspect of the present invention is an organic proton donor represented by the general formula (1):
  • Ar 1 represents the following formula (2):
  • a divalent aromatic group selected from the group consisting of R 1 and R 2 are the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms)
  • trimellitic anhydride represented by general formula (4) in the presence of a basic substance:
  • a typical second embodiment of the present invention is an organic proton donor, represented by the general formula (5):
  • Ar 2 represents the following formula (6):
  • General formula (7) which is an organic halide containing a phthalic anhydride skeleton:
  • the ethynyl group-containing phthalic anhydride derivative represented by the formula (1) is a method comprising the step of dissolving and removing a by-product basic hydrohalide salt with an organic acid.
  • the organic acid is preferably selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, and mixtures thereof.
  • the basic substance is a trialkylamine and / or a pyridine derivative.
  • the present invention is also a method for purifying a phthalic anhydride derivative obtained by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, which comprises a by-product base.
  • the present invention relates to a method comprising the step of dissolving and removing a hydrohalic acid salt of an organic substance with an organic acid.
  • the method of the present invention is a method for producing a phthalic anhydride derivative.
  • a basic hydrohalide salt is by-produced and a derivative containing a phthalic anhydride skeleton (ie, a phthalic anhydride derivative) is obtained as a final product.
  • a derivative containing a phthalic anhydride skeleton ie, a phthalic anhydride derivative
  • the organic halide containing a phthalic anhydride skeleton represented by the general formula (II) includes a halogenated phthalic anhydride in which Y 1 is a direct bond; or Y 1 is — And trimellitic anhydride halide which is O-.
  • the trimellitic anhydride halide represented by the general formula (3) or the halogenated phthalic anhydride represented by the general formula (7) is preferable.
  • trimellitic anhydride halide represented by the general formula (3) examples include trimellitic anhydride chloride, trimellitic anhydride bromide, trimellitic anhydride iodide and the like, but trimellitic anhydride chloride is preferable.
  • halogenated phthalic anhydride represented by the general formula (7) examples include chlorophthalic anhydride, bromophthalic anhydride, and iodophthalic anhydride, and bromophthalic anhydride is preferable.
  • the organic proton donor represented by the general formula (III) is an aromatic hydroxy compound in which n is 1 and Y 2 is —O—;
  • An aromatic alkenylene or alkynylene compound wherein Y 2 is an alkenylene or alkynylene having 2 to 4 carbon atoms eg ethenylene, propenylene or 1- or 2-butenylene, or ethynylene, propynylene or 1- or 2-butynylene
  • Y 1 is —C (O) —
  • Y 2 is —O—.
  • the organic proton donor represented by the general formula (III) is an aromatic hydroxy compound or aromatic Means a group diol compound.
  • the organic proton donor represented by the general formula (III) is preferably an aromatic diol compound represented by the general formula (1) or an aromatic ethynyl compound represented by the general formula (5).
  • R 1 and R 2 are hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl , Ethyl, propyl, isopropyl, butyl, t-butyl.
  • Preferred aromatic diol compounds include hydroquinone, resorcinol, pyrocatechol, 4,4′-biphenyldiol, 2,2′-biphenyldiol, 3,4′-biphenyldiol, R 1 and R 2 are hydrogen, , 4′-dihydroxydiphenyl ether, 2,2′-dihydroxydiphenyl ether, and the like.
  • R 1 and R 2 are hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl, Those which are ethyl, propyl, isopropyl, butyl, t-butyl.
  • ethynyl benzene, ethynyl biphenyl, ethynyl biphenyl ether, ethynyl phthalic anhydride, etc., in which R 1 and R 2 are hydrogen are exemplified.
  • the production of the phthalic anhydride derivative of the present invention is carried out by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance.
  • the reaction conditions may be appropriately set according to the ordinary knowledge of those skilled in the art depending on the starting materials and basic materials used.
  • the reaction conditions in representative embodiments of the present invention are outlined below, but the present invention is not limited to these.
  • the ester group-containing phthalic anhydride derivative represented by the general formula (4) is produced in the presence of a basic substance with respect to 2 moles of trimellitic anhydride.
  • the reaction is carried out by reacting an aromatic diol compound in an amount of 0.95 to 1.50 mol.
  • Such a reaction is preferably carried out in a solvent, particularly in a non-aqueous solvent.
  • Solvents that can be used are not particularly limited, but acetonitrile, tetrahydrofuran, 1,4-dioxane, picoline, pyridine, chloroform, toluene, xylene, dichloromethane, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N , N-dimethylacetamide, N, N-diethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, and the like. These solvents may be used alone or in combination of two or more.
  • Such a reaction is usually performed at ⁇ 10 to 50 ° C., preferably 0 to 30 ° C.
  • the reaction temperature is higher than 50 ° C., a side reaction occurs partially, which causes a decrease in yield, which is not preferable.
  • the basic substance used in such a reaction is not particularly limited, but tri (C 1-6 -alkyl) amine such as trimethylamine, triethylamine, diisopropylmethylamine, or pyridine, methylpyridine, N, N-dimethylamino- Examples include pyridine derivatives such as 4-pyridine.
  • the basic substances may be used alone or in combination of two or more.
  • the amount used is equimolar or more, preferably 1.1 to 3.0 times the molar amount of trimellitic anhydride, so that the ester group-containing phthalic anhydride derivative represented by the general formula (4) can be obtained. Obtained with high purity.
  • the organic acid that dissolves and removes the basic hydrohalide salt as a by-product is a linear or branched alkanoic acid having 1 to 4 carbon atoms, preferably formic acid, acetic acid, Although propionic acid, butyric acid or isobutyric acid can be mentioned, it is preferable to use acetic acid for economic reasons.
  • the amount used is equimolar or more, preferably 1.0 to 2.0 times the molar amount of the basic substance.
  • the method for dissolving and removing may be selected by those skilled in the art depending on the properties of the starting material, reaction product, and by-product basic material such as hydrohalide.
  • by-product basic material such as hydrohalide.
  • the organic acid is added directly to the reaction system, or the precipitate is filtered off, By washing this with an organic acid, only the basic substance can be dissolved and removed, and the target product can be isolated.
  • “by-product basic hydrohalide is dissolved and removed with an organic acid” means about 90 of the theoretical amount (weight) of by-product basic hydrohalide.
  • phthalic anhydride derivatives particularly ester group-containing phthalic anhydride derivatives represented by the general formula (4) of the present invention are hardly soluble or substantially insoluble in organic acids. Therefore, this allows the ester group-containing phthalic anhydride derivative represented by the general formula (4) of the present invention to be about 90% or more, preferably 95% or more, more preferably 99% without opening the phthalic anhydride skeleton. % Or higher purity.
  • an ethynyl group-containing phthalic anhydride derivative represented by the general formula (8) of the present invention is generally performed with an aromatic ethynyl compound represented by the general formula (5).
  • the halogenated phthalic anhydride represented by the formula (7) is preferably reacted in the presence of a basic substance at 50 to 130 ° C., preferably around 60 to 100 ° C.
  • the basic substance used in such a reaction is not particularly limited, but tri (C 1-6 -alkyl) amine such as trimethylamine, triethylamine, diisopropylmethylamine, or pyridine, methylpyridine, N, N-dimethylamino- Examples include pyridine derivatives such as 4-pyridine.
  • the basic substances may be used alone or in combination of two or more.
  • the amount used is equimolar or more, preferably 1.1 to 3.0 times the molar amount of the halogenated phthalic anhydride.
  • Such a reaction is preferably carried out in a solvent, particularly in a non-aqueous solvent.
  • Solvents that can be used are not particularly limited, but acetonitrile, tetrahydrofuran, 1,4-dioxane, picoline, pyridine, chloroform, toluene, xylene, dichloromethane, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N , N-dimethylacetamide, N, N-diethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, and the like. These solvents may be used alone or in combination of two or more.
  • Such a reaction is preferably carried out in the presence of a catalyst.
  • the catalyst used is, for example, a divalent or zero-valent palladium complex, and a suitable one is represented by general formula (9) or general formula (10).
  • Y includes, for example, chlorine, bromine or iodine atom, or R 3 COO—.
  • R 3 is a linear or branched alkyl group having 1 to 4 carbon atoms.
  • L include a ligand containing each atom of P, As, and Sb. Specific examples include (R 4 ) 3 P.
  • R 4 is aryl optionally substituted with an alkyl group having 1 to 8 carbon atoms. Examples include bis (triphenylphosphine) dichloropalladium (II), tetrakis (triphenylphosphine) palladium (0), and the like.
  • the compound which substituted P atom by As atom and Sb atom can also be mentioned.
  • the palladium complex represented by the general formula (9) a mixture of the compound represented by PdY 2 and the ligand L may be used.
  • copper halide can also be used as a co-catalyst. When used, the reaction can proceed smoothly. However, when these are used with an ethynyl compound, it may react with copper to form an explosive unstable compound, copper acetylide. Care must be taken when using copper chloride. Examples of the copper halide include copper chloride, copper bromide, and copper iodide, with copper iodide being preferred.
  • the by-product basic hydrohalide salt is dissolved and removed using an organic acid in the same manner as in the production of the ester group-containing phthalic anhydride derivative represented by the general formula (4).
  • the organic acid include linear or branched alkanoic acids having 1 to 4 carbon atoms, preferably formic acid, acetic acid, propionic acid, butyric acid or isobutyric acid.
  • acetic acid is used. It is preferred to use.
  • the amount used is equimolar or more, preferably 1.0 to 2.0 times the molar amount of the basic substance.
  • the method for dissolving and removing may be selected by those skilled in the art depending on the properties of the starting material, reaction product, and by-product basic substance hydrohalide.
  • the organic acid is added directly to the reaction system, or the precipitate is filtered off, By washing this with an organic acid, only the basic substance can be dissolved and removed, and the target product can be isolated.
  • “by-product basic hydrohalide is dissolved and removed with an organic acid” means about 90 of the theoretical amount (weight) of by-product basic hydrohalide. % Or more, preferably 95% or more, more preferably 99% or more is dissolved in an organic acid by the method as described above and removed.
  • phthalic anhydride derivatives particularly ethynyl group-containing phthalic anhydride derivatives represented by the general formula (8) of the present invention are hardly soluble or substantially insoluble in organic acids. Therefore, this allows the ethynyl group-containing phthalic anhydride derivative represented by the general formula (8) of the present invention to be about 90% or more, preferably 95% or more, more preferably 99% without opening the phthalic anhydride skeleton. % Or higher purity.
  • the present invention is a method of purifying a phthalic anhydride derivative obtained by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, It can be said that the method includes a step of dissolving and removing the hydrohalic acid salt of the basic substance by-produced with an organic acid.
  • Examples of such “basic substances”, “organic halides containing a phthalic anhydride skeleton”, “organic proton donors”, and “phthalic anhydride derivatives” in this method, and preferred implementation conditions are as described above. .
  • Example 1 In a 500 mL four-necked flask equipped with a stirrer, thermometer, upward reflux tube, and nitrogen gas introduction tube, hydroquinone 22.0 g (0.20 mol), pyridine 47.5 g (0.60 mol), N, N -100 g of dimethylformamide was charged and dissolved in a nitrogen atmosphere with stirring. After cooling to 0 ° C., a solution prepared by dissolving 84.2 g (0.40 mol) of trimellitic anhydride chloride in 200 g of N, N-dimethylformamide was reacted while dropping dropwise at 0 to 10 ° C. in a nitrogen atmosphere. .
  • Example 2 Using 37.2 g (0.20 mol) of 4,4′-biphenol in place of hydroquinone, the same operation as in Example 1 was carried out, and it was confirmed that no pyridine derived from pyridine hydrochloride was contained in the product. This was confirmed by liquid chromatography measurement. The purity of the target product, 4,4′-bis (trimellitic acid ester anhydride) biphenyl, was 96.2%.
  • Example 3 In a 500 mL four-necked flask equipped with a stirrer, thermometer, upward reflux tube and nitrogen gas introduction tube, 68.1 g (0.30 mol) of 4-bromophthalic anhydride, 100 g of toluene, 36.4 g of triethylamine (0 .36 mol) and 0.31 g (0.45 ⁇ 10 ⁇ 3 mol) of bistriphenylphosphine dichloropalladium were charged and heated to 80 ° C. Next, 30.6 g (0.30 mol) of phenylacetylene was reacted while being dropped. After dropping, the mixture was aged for 15 hours.
  • the precipitated phenylethynylphthalic anhydride and triethylamine hydrochloride were solid-liquid separated and washed with 40 g of propionic acid to dissolve and remove the triethylamine hydrochloride. It was confirmed by NMR measurement that the product did not contain triethylamine derived from triethylamine hydrochloride. The purity of the target phenylethynyl phthalic anhydride was 97.8%.
  • the phthalic anhydride derivative obtained by the production method of the present invention in particular, an ester group-containing phthalic anhydride derivative, an ethynyl group-containing phthalic anhydride derivative, can be used as a curing agent, a modifier, such as a polyesterimide resin raw material, an epoxy resin, It is particularly useful as a low water absorption polyesterimide raw material and heat resistant material.
  • a modifier such as a polyesterimide resin raw material, an epoxy resin
  • the present invention provides a very useful production method that can efficiently remove by-products without ring-opening the phthalic anhydride skeleton. It is to provide.

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Abstract

Disclosed is a novel process for producing a phthalic anhydride derivative, particularly a process for producing a phthalic anhydride derivative efficiently without the need of opening a ring contained in a phthalic anhydride skeleton. Specifically disclosed is a process for producing a phthalic anhydride derivative by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance.  The process is characterized by involving a step of dissolving a hydrohalide salt of the basic substance, which is a substance produced as a by-product, in an organic acid to remove the hydrohalide salt.

Description

無水フタル酸誘導体の製造方法Method for producing phthalic anhydride derivative
　本発明は、ポリエステルイミド樹脂もしくはポリイミド等の耐熱樹脂の原料、エポキシ樹脂等の硬化剤、または樹脂改質剤として有用な無水フタル酸誘導体、特には、エステル基含有無水フタル酸誘導体またはエチニル基含有無水フタル酸誘導体の製造方法に関する。また本発明は、無水フタル酸誘導体を精製する方法にも関する。 The present invention is a phthalic anhydride derivative useful as a raw material of a heat-resistant resin such as a polyesterimide resin or polyimide, a curing agent such as an epoxy resin, or a resin modifier, particularly an ester group-containing phthalic anhydride derivative or an ethynyl group The present invention relates to a method for producing a phthalic anhydride derivative. The present invention also relates to a method for purifying a phthalic anhydride derivative.
　エステル基含有無水フタル酸誘導体は、ポリエステルイミド樹脂等の耐熱樹脂の原料、エポキシ樹脂等の硬化剤、または樹脂改質剤として有用であり、それを製造する方法として、例えば、（１）ベンゼン、トルエン等の有機溶媒中、無水トリメリット酸クロリドとフェノール類またはジオール類との反応による方法（例えば、特許文献１参照）、（２）無水トリメリット酸とフェノール類とを２５０～３００℃で加熱することによる方法（例えば、非特許文献１参照）、（３）無水トリメリット酸とフェノール類の低級アルカン酸エステルとのエステル交換反応を、触媒としてシリカ・アルミナ系化合物などの無機化合物の存在下に行う方法（例えば、特許文献２参照）、または特定の溶媒の存在下に行う方法（例えば、特許文献３参照）などが知られている。 An ester group-containing phthalic anhydride derivative is useful as a raw material for heat-resistant resins such as a polyesterimide resin, a curing agent such as an epoxy resin, or a resin modifier. As a method for producing it, for example, (1) benzene, Method by reaction of trimellitic anhydride chloride with phenols or diols in an organic solvent such as toluene (see, for example, Patent Document 1), (2) Heating trimellitic anhydride and phenols at 250 to 300 ° C (3) transesterification of trimellitic anhydride with a lower alkanoic acid ester of a phenol in the presence of an inorganic compound such as a silica / alumina compound as a catalyst. (For example, see Patent Document 2) or a method performed in the presence of a specific solvent (for example, see Patent Document 3) Such as are known.
　エチニル基含有無水フタル酸誘導体は、ポリイミド分野で必要とされている接着性、耐熱性、機械強度を兼ね備えた材料を提供する原料として、極めて利用価値が高い。エチニル基含有無水フタル酸誘導体、例えば、フェニルエチニル無水フタル酸を製造する方法としては、エチニルベンゼンとブロモ無水フタル酸とを大過剰の塩基性有機物質の存在下、反応させる方法が知られている（例えば、非特許文献２参照）。
特開２００５－２９８６２３号公報 特開平７－４１４７２号公報 特開平１０－１４７５８２号公報 J. Polym. Sci., vol 4, 1531-41, Part A, (1966) Highperform. Polym. 6巻，423 (1994) The ethynyl group-containing phthalic anhydride derivative is extremely useful as a raw material for providing a material having adhesiveness, heat resistance and mechanical strength required in the polyimide field. As a method for producing an ethynyl group-containing phthalic anhydride derivative, for example, phenylethynyl phthalic anhydride, a method is known in which ethynylbenzene and bromophthalic anhydride are reacted in the presence of a large excess of a basic organic substance. (For example, refer nonpatent literature 2).
JP 2005-298623 A JP-A-7-41472 Japanese Patent Laid-Open No. 10-147582 J. Polym. Sci., Vol 4, 1531-41, Part A, (1966) Highperform. Polym. Vol. 6, 423 (1994)
　前記背景技術で挙げた、特許文献１に開示される方法は、無水トリメリット酸クロリドとフェノール類を塩基性物質の存在下で反応後、副生する塩基性物質のハロゲン化水素酸塩を水で除去している。このとき、反応生成物の無水フタル酸骨格の一部が加水分解を受け開環するため、無水酢酸による再閉環が必要となる。また、無機触媒を利用する特許文献２に開示される方法では、使用する無機触媒を除去し難く、得られるエステル基含有無水フタル酸誘導体の不純物となりなりやすいといった問題がある。 In the method disclosed in Patent Document 1 cited in the background art, after the reaction of trimellitic anhydride chloride and phenols in the presence of a basic substance, the hydrohalide salt of the basic substance produced as a by-product is treated with water. Is removed. At this time, since a part of the phthalic anhydride skeleton of the reaction product undergoes hydrolysis and ring-opening, reclosing with acetic anhydride is necessary. In addition, the method disclosed in Patent Document 2 using an inorganic catalyst has a problem that it is difficult to remove the inorganic catalyst to be used, and the resulting ester group-containing phthalic anhydride derivative is likely to be an impurity.
　また、前記背景技術で挙げた、非特許文献２に開示される方法は、エチニルベンゼンとブロモ無水フタル酸を、大過剰の塩基性有機物質の存在下で反応後、副生する臭化水素酸塩を除去し、得られた反応生成物を水中で晶析する。このとき、上記と同様に無水フタル酸骨格の一部が加水分解を受け開環するため、熱による再閉環が必要となる。 In addition, the method disclosed in Non-Patent Document 2 mentioned in the background art is a method in which ethynylbenzene and bromophthalic anhydride are reacted in the presence of a large excess of a basic organic substance, and then by-produced hydrobromic acid. The salt is removed and the resulting reaction product is crystallized in water. At this time, as described above, a part of the phthalic anhydride skeleton undergoes hydrolysis to open a ring, and thus re-ring closure by heat is necessary.
　本発明は、無水フタル酸骨格を開環させることなく、効率よく無水フタル酸誘導体を製造する方法を提供するものである。同様に、無水フタル酸骨格を開環させることなく、効率よく無水フタル酸誘導体を精製する方法も提供する。 The present invention provides a method for efficiently producing a phthalic anhydride derivative without opening the phthalic anhydride skeleton. Similarly, a method for efficiently purifying a phthalic anhydride derivative without opening the phthalic anhydride skeleton is also provided.
　本発明者は、上記のような問題点を解決するために種々研究を行い、塩基性物質の存在下、無水フタル酸骨格を含む有機ハロゲン化物と有機プロトン供与体とを反応させて、無水フタル酸誘導体を製造する方法において、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去することにより、得られた生成物の無水フタル酸骨格を開環させることなく、無水フタル酸誘導体を効率よく製造し得ることを見出した。 The present inventor has conducted various studies to solve the above problems, and in the presence of a basic substance, an organic halide containing a phthalic anhydride skeleton and an organic proton donor are reacted to produce phthalic anhydride. In the method of producing an acid derivative, by dissolving and removing a hydrohalic acid salt of a basic substance as a by-product with an organic acid, phthalic anhydride is obtained without ring-opening the phthalic anhydride skeleton of the obtained product. It has been found that derivatives can be produced efficiently.
　同様に、本発明者は、塩基性物質の存在下、無水フタル酸骨格を含む有機ハロゲン化物と有機プロトン供与体とを反応させることにより得られる無水フタル酸誘導体を精製する方法であって、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去することにより、生成物の無水フタル酸骨格を開環させることなく、無水フタル酸誘導体を効率よく精製し得ることを見出した。 Similarly, the present inventor is a method for purifying a phthalic anhydride derivative obtained by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, comprising: It was found that the phthalic anhydride derivative can be efficiently purified without dissolving the phthalic anhydride skeleton of the product by dissolving and removing the resulting hydrohalic acid salt of the basic substance with an organic acid.
　本発明の無水フタル酸誘導体、特には、エステル基含有無水フタル酸誘導体またはエチニル基含有無水フタル酸誘導体は、ポリエステルイミド樹脂等の耐熱樹脂の原料、エポキシ樹脂等の硬化剤、または樹脂改質剤として利用される。本発明の無水フタル酸誘導体の製造方法は、従来技術にみられる、無水フタル酸骨格の加水分解による開環や、それに伴い再閉環工程を要するといった課題もなく、かつ特別な溶媒や触媒を必要としない簡便な方法で、効率的に製造できる点から有用である。 The phthalic anhydride derivatives of the present invention, in particular, ester group-containing phthalic anhydride derivatives or ethynyl group-containing phthalic anhydride derivatives are raw materials for heat-resistant resins such as polyesterimide resins, curing agents such as epoxy resins, or resin modifiers. Used as The method for producing a phthalic anhydride derivative according to the present invention does not have the problem of requiring ring opening by hydrolysis of the phthalic anhydride skeleton and the need for a re-ring closing step as in the prior art, and requires a special solvent or catalyst. It is useful because it can be efficiently produced by a simple method.
　すなわち、本発明は、塩基性物質の存在下、無水フタル酸骨格を含む有機ハロゲン化物と有機プロトン供与体とを反応させて、無水フタル酸誘導体を製造する方法であって、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する工程を含むことを特徴とする方法に関する。 That is, the present invention is a method for producing a phthalic anhydride derivative by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, wherein The present invention relates to a method comprising dissolving and removing a hydrohalide salt of a substance with an organic acid.
　本発明のより具体的な態様は、塩基性物質Ｂの存在下、下記一般式（II）：
Figure JPOXMLDOC01-appb-C000014
 （式中、Ｘは、塩素、臭素、またはヨウ素であり、Ｙ1は、直接結合、または－Ｃ（Ｏ）－である）
で表される無水フタル酸骨格を含む有機ハロゲン化物と、下記一般式（III）：
Figure JPOXMLDOC01-appb-C000015
 〔式中、ｎは、１または２であり；
ｎが１である場合、
Ａｒは、下記式：
Figure JPOXMLDOC01-appb-C000016
 （ここで、Ｒ1およびＲ2は、同一または異なって、水素または炭素数１～４のアルキル基である）よりなる群から選ばれる１価の芳香族基であり、Ｙ2は、－Ｏ－、または炭素数２～４のアルケニレンもしくはアルキニレン基であり；
ｎが２である場合、
Ａｒは、下記式：
Figure JPOXMLDOC01-appb-C000017
 （ここで、Ｒ1およびＲ2は、同一または異なって、水素または炭素数１～４のアルキル基である）よりなる群から選ばれる２価の芳香族基であり、Ｙ2は、－Ｏ－である；
ただし、Ｙ1が－Ｃ（Ｏ）－である場合、Ｙ2は、－Ｏ－である〕
で表される有機プロトン供与体とを反応させて、下記一般式（Ｉ）：
Figure JPOXMLDOC01-appb-C000018
 〔式中、Ａｒ、Ｙ1、Ｙ2およびｎは、上記と同義である〕
で表される無水フタル酸誘導体を製造する方法であって、副生する塩基性物質のハロゲン化水素酸塩：Ｂ・ＨＸを有機酸で溶解除去する工程を含むことを特徴とする方法に関する。 In a more specific embodiment of the present invention, in the presence of the basic substance B, the following general formula (II):
Figure JPOXMLDOC01-appb-C000014
 (Wherein X is chlorine, bromine, or iodine, and Y 1 is a direct bond or —C (O) —)
An organic halide containing a phthalic anhydride skeleton represented by the following general formula (III):
Figure JPOXMLDOC01-appb-C000015
 [Wherein n is 1 or 2;
When n is 1,
Ar is represented by the following formula:
Figure JPOXMLDOC01-appb-C000016
 (Wherein R 1 and R 2 are the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms), and Y 2 is —O -Or an alkenylene or alkynylene group having 2 to 4 carbon atoms;
If n is 2,
Ar is represented by the following formula:
Figure JPOXMLDOC01-appb-C000017
 Wherein R 1 and R 2 are the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms, and Y 2 is —O -Is;
However, when Y 1 is —C (O) —, Y 2 is —O—.]
Is reacted with an organic proton donor represented by the following general formula (I):
Figure JPOXMLDOC01-appb-C000018
 [Wherein Ar, Y 1 , Y 2 and n are as defined above]
The method further comprises a step of dissolving and removing a hydrohalic acid salt B: HX as a by-product basic substance with an organic acid.
　本発明の代表的な第一の態様は、有機プロトン供与体である一般式（１）： A typical first aspect of the present invention is an organic proton donor represented by the general formula (1):
Figure JPOXMLDOC01-appb-C000019
 （式中、Ａｒ1は、下記式（２）：
Figure JPOXMLDOC01-appb-C000019
 (In the formula, Ar 1 represents the following formula (2):
Figure JPOXMLDOC01-appb-C000020
 よりなる群から選ばれる２価の芳香族基であり、Ｒ1およびＲ2は、同一または異なって、水素または炭素数１～４のアルキル基である）
で表される芳香族ジオール化合物と、無水フタル酸骨格を含む有機ハロゲン化物である一般式（３）：
Figure JPOXMLDOC01-appb-C000020
 A divalent aromatic group selected from the group consisting of R 1 and R 2 are the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms)
And an organic halide containing a phthalic anhydride skeleton represented by the general formula (3):
Figure JPOXMLDOC01-appb-C000021
 （式中、Ｘは、塩素、臭素、またはヨウ素である）
で表される無水トリメリット酸ハライドとを塩基性物質の存在下に反応させて、一般式（４）：
Figure JPOXMLDOC01-appb-C000021
 (Wherein X is chlorine, bromine or iodine)
Is reacted with trimellitic anhydride represented by general formula (4) in the presence of a basic substance:
Figure JPOXMLDOC01-appb-C000022
 （式中、Ａｒ1は、上記と同義である）
で示されるエステル基含有無水フタル酸誘導体を製造する方法であって、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する工程を含む方法に関する。
Figure JPOXMLDOC01-appb-C000022
 (Wherein Ar 1 has the same meaning as above)
It is related with the method of manufacturing the ester group containing phthalic anhydride derivative shown by these, Comprising: Dissolving and removing the hydrohalic acid salt of the basic substance byproduced with an organic acid.
　更に、本発明の代表的な第二の態様は、有機プロトン供与体である、一般式（５）： Furthermore, a typical second embodiment of the present invention is an organic proton donor, represented by the general formula (5):
Figure JPOXMLDOC01-appb-C000023
 （式中、Ａｒ2は、下記式（６）：
Figure JPOXMLDOC01-appb-C000023
 (In the formula, Ar 2 represents the following formula (6):
Figure JPOXMLDOC01-appb-C000024
 よりなる群から選ばれる１価の芳香族基であり、Ｒ1およびＲ2は、同一または異なって、水素または炭素数１～４のアルキル基である）で表される芳香族エチニル化合物と、無水フタル酸骨格を含む有機ハロゲン化物である一般式（７）：
Figure JPOXMLDOC01-appb-C000024
 An aromatic ethynyl compound represented by the following formula: a monovalent aromatic group selected from the group consisting of: R 1 and R 2 being the same or different and being hydrogen or an alkyl group having 1 to 4 carbon atoms; General formula (7) which is an organic halide containing a phthalic anhydride skeleton:
Figure JPOXMLDOC01-appb-C000025
 （式中、Ｘは、塩素、臭素、またはヨウ素である）
で表されるハロゲン化無水フタル酸とを塩基性物質の存在下に反応させて、一般式（８）：
Figure JPOXMLDOC01-appb-C000025
 (Wherein X is chlorine, bromine or iodine)
Is reacted with a halogenated phthalic anhydride represented by the general formula (8):
Figure JPOXMLDOC01-appb-C000026
 （式中、Ａｒ2は、上記と同義である）
で示されるエチニル基含有無水フタル酸誘導体を製造する方法であって、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する工程を含む方法に関する。
Figure JPOXMLDOC01-appb-C000026
 (Wherein Ar 2 has the same meaning as above)
The ethynyl group-containing phthalic anhydride derivative represented by the formula (1) is a method comprising the step of dissolving and removing a by-product basic hydrohalide salt with an organic acid.
　本発明の方法において、好適には、有機酸は、ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸およびこれらの混合物よりなる群から選ばれる。 In the method of the present invention, the organic acid is preferably selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, and mixtures thereof.
　本発明の方法において、好適には、塩基性物質は、トリアルキルアミンおよび／またはピリジン誘導体である。 In the method of the present invention, preferably, the basic substance is a trialkylamine and / or a pyridine derivative.
　本発明はまた、塩基性物質の存在下、無水フタル酸骨格を含む有機ハロゲン化物と有機プロトン供与体とを反応させることにより得られる無水フタル酸誘導体を精製する方法であって、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する工程を含むことを特徴とする方法に関する。 The present invention is also a method for purifying a phthalic anhydride derivative obtained by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, which comprises a by-product base. The present invention relates to a method comprising the step of dissolving and removing a hydrohalic acid salt of an organic substance with an organic acid.
　本発明の方法は、無水フタル酸誘導体を製造する方法において、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去するため、無水フタル酸骨格の加水分解による開環や、それに伴う再閉環工程が不要であることを特徴とする。したがって、塩基性物質のハロゲン化水素酸塩が副生し、かつ無水フタル酸骨格を含む誘導体（すなわち、無水フタル酸誘導体）が最終生成物として得られる製造方法であれば、本発明の方法を適用することができる。 The method of the present invention is a method for producing a phthalic anhydride derivative. In order to dissolve and remove the hydrohalic acid salt of a basic product by-product with an organic acid, ring opening by hydrolysis of the phthalic anhydride skeleton, The accompanying re-ringing step is unnecessary. Accordingly, the method of the present invention can be used as long as it is a production method in which a basic hydrohalide salt is by-produced and a derivative containing a phthalic anhydride skeleton (ie, a phthalic anhydride derivative) is obtained as a final product. Can be applied.
　本発明のより具体的な態様で、一般式（II）で表される無水フタル酸骨格を含む有機ハロゲン化物としては、Ｙ1が直接結合である、ハロゲン化無水フタル酸；またはＹ1が－Ｏ－である、無水トリメリット酸ハライドが挙げられる。一般式（３）で表される無水トリメリット酸ハライドまたは一般式（７）で表されるハロゲン化無水フタル酸が好ましい。 In a more specific embodiment of the present invention, the organic halide containing a phthalic anhydride skeleton represented by the general formula (II) includes a halogenated phthalic anhydride in which Y 1 is a direct bond; or Y 1 is — And trimellitic anhydride halide which is O-. The trimellitic anhydride halide represented by the general formula (3) or the halogenated phthalic anhydride represented by the general formula (7) is preferable.
　一般式（３）で表される無水トリメリット酸ハライドとしては、無水トリメリット酸クロリド、無水トリメリット酸ブロミド、無水トリメリット酸ヨージドなどが挙げられるが、無水トリメリット酸クロリドが好ましい。 Examples of the trimellitic anhydride halide represented by the general formula (3) include trimellitic anhydride chloride, trimellitic anhydride bromide, trimellitic anhydride iodide and the like, but trimellitic anhydride chloride is preferable.
　一般式（７）で表わされるハロゲン化無水フタル酸としては、クロロ無水フタル酸、ブロモ無水フタル酸、ヨード無水フタル酸が挙げられるが、ブロモ無水フタル酸が好ましい。 Examples of the halogenated phthalic anhydride represented by the general formula (7) include chlorophthalic anhydride, bromophthalic anhydride, and iodophthalic anhydride, and bromophthalic anhydride is preferable.
　本発明のより具体的な態様で、一般式（III）で表される有機プロトン供与体としては、ｎが１であり、Ｙ2が－Ｏ－である、芳香族ヒドロキシ化合物；ｎが１であり、Ｙ2が炭素数２～４のアルケニレンもしくはアルキニレン（例えばエテニレン、プロペニレンまたは１－もしくは２－ブテニレン、あるいはエチニレン、プロピニレンまたは１－もしくは２－ブチニレン）である芳香族アルケニレンもしくはアルキニレン化合物；またはｎが２であり、Ｙ2が－Ｏ－である、芳香族ジオール化合物が挙げられる。ただし、Ｙ1が－Ｃ（Ｏ）－である場合、Ｙ2は、－Ｏ－である。すなわち一般式（II）で表される無水フタル酸骨格を含む有機ハロゲン化物が無水トリメリット酸ハライドである場合、一般式（III）で表される有機プロトン供与体は、芳香族ヒドロキシ化合物または芳香族ジオール化合物であることを意味する。一般式（III）で表される有機プロトン供与体としては、一般式（１）で表される芳香族ジオール化合物または一般式（５）で表される芳香族エチニル化合物が好ましい。 In a more specific embodiment of the present invention, the organic proton donor represented by the general formula (III) is an aromatic hydroxy compound in which n is 1 and Y 2 is —O—; An aromatic alkenylene or alkynylene compound wherein Y 2 is an alkenylene or alkynylene having 2 to 4 carbon atoms (eg ethenylene, propenylene or 1- or 2-butenylene, or ethynylene, propynylene or 1- or 2-butynylene); or n And aromatic diol compounds in which Y 2 is —O—. However, when Y 1 is —C (O) —, Y 2 is —O—. That is, when the organic halide containing a phthalic anhydride skeleton represented by the general formula (II) is trimellitic anhydride halide, the organic proton donor represented by the general formula (III) is an aromatic hydroxy compound or aromatic Means a group diol compound. The organic proton donor represented by the general formula (III) is preferably an aromatic diol compound represented by the general formula (1) or an aromatic ethynyl compound represented by the general formula (5).
　一般式（１）で表される芳香族ジオール化合物としては、式（２）において、Ｒ1およびＲ2が水素または炭素数１～４の直鎖状もしくは分岐鎖状のアルキル基、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、ｔ－ブチルであるものが挙げられる。好ましい芳香族ジオール化合物としては、Ｒ1およびＲ2が水素である、ヒドロキノン、レゾルシノール、ピロカテコール、４，４’－ビフェニルジオール、２，２’－ビフェニルジオール、３，４’－ビフェニルジオール、４，４’－ジヒドロキシジフェニルエーテル、２，２’－ジヒドロキシジフェニルエーテルなどが挙げられる。 As the aromatic diol compound represented by the general formula (1), in the formula (2), R 1 and R 2 are hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl , Ethyl, propyl, isopropyl, butyl, t-butyl. Preferred aromatic diol compounds include hydroquinone, resorcinol, pyrocatechol, 4,4′-biphenyldiol, 2,2′-biphenyldiol, 3,4′-biphenyldiol, R 1 and R 2 are hydrogen, , 4′-dihydroxydiphenyl ether, 2,2′-dihydroxydiphenyl ether, and the like.
　一般式（５）で表わされる芳香族エチニル化合物としては、式（６）において、Ｒ1およびＲ2が水素または炭素数１～４の直鎖状もしくは分岐鎖状のアルキル基、例えば、メチル、エチル、プロピル、イソプロピル、ブチル、ｔ－ブチルであるものが挙げられる。好ましくは、Ｒ1およびＲ2が水素である、エチニルベンゼン、エチニルビフェニル、エチニルビフェニルエーテル、エチニル無水フタル酸などが挙げられる。 As the aromatic ethynyl compound represented by the general formula (5), in the formula (6), R 1 and R 2 are hydrogen or a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl, Those which are ethyl, propyl, isopropyl, butyl, t-butyl. Preferably, ethynyl benzene, ethynyl biphenyl, ethynyl biphenyl ether, ethynyl phthalic anhydride, etc., in which R 1 and R 2 are hydrogen are exemplified.
　本発明の無水フタル酸誘導体の製造は、塩基性物質の存在下、無水フタル酸骨格を含む有機ハロゲン化物と有機プロトン供与体とを反応させることにより実施される。反応条件は、使用される出発物質や塩基性物質に応じて、当業者の通常の知識に従って、適宜設定すればよい。以下に本発明の代表的な実施態様における反応条件について概説するが、本発明はこれらに限定されるものではない。 The production of the phthalic anhydride derivative of the present invention is carried out by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance. The reaction conditions may be appropriately set according to the ordinary knowledge of those skilled in the art depending on the starting materials and basic materials used. The reaction conditions in representative embodiments of the present invention are outlined below, but the present invention is not limited to these.
　例えば、本発明の代表的な第一の態様で、一般式（４）で表されるエステル基含有無水フタル酸誘導体の製造は、塩基性物質の存在下、無水トリメリット酸ハライド２モルに対し、好適には、芳香族ジオール化合物を０.９５～１．５０モル反応させることにより実施される。 For example, in the typical first aspect of the present invention, the ester group-containing phthalic anhydride derivative represented by the general formula (4) is produced in the presence of a basic substance with respect to 2 moles of trimellitic anhydride. Preferably, the reaction is carried out by reacting an aromatic diol compound in an amount of 0.95 to 1.50 mol.
　かかる反応は、好適には、溶媒中、特に非水溶媒中で行なわれる。使用可能な溶媒としては、特に限定されないが、アセトニトリル、テトラヒドロフラン、１，４－ジオキサン、ピコリン、ピリジン、クロロホルム、トルエン、キシレン、ジクロロメタン、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、ジメチルスルホキシド、γ－ブチロラクトンなどの非プロトン性溶媒が挙げられる。また、これらの溶媒を単独でも、２種以上混合して用いてもよい。 Such a reaction is preferably carried out in a solvent, particularly in a non-aqueous solvent. Solvents that can be used are not particularly limited, but acetonitrile, tetrahydrofuran, 1,4-dioxane, picoline, pyridine, chloroform, toluene, xylene, dichloromethane, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N , N-dimethylacetamide, N, N-diethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and the like. These solvents may be used alone or in combination of two or more.
　かかる反応は、通常、－１０～５０℃で、好ましくは０～３０℃で行われる。反応温度が５０℃より高いと一部副反応が起こり、収率低下の原因となり、好ましくない。 Such a reaction is usually performed at −10 to 50 ° C., preferably 0 to 30 ° C. When the reaction temperature is higher than 50 ° C., a side reaction occurs partially, which causes a decrease in yield, which is not preferable.
　かかる反応に使用する塩基性物質としては、特に限定されないが、トリメチルアミン、トリエチルアミン、ジイソプロピルメチルアミンのようなトリ（Ｃ1-6－アルキル）アミン、またはピリジン、メチルピリジン、Ｎ，Ｎ－ジメチルアミノ－４－ピリジンのようなピリジン誘導体等が挙げられる。塩基性物質は、単独でも２種以上を組み合わせて使用してもよい。その使用量は、無水トリメリット酸ハライドと等モル量以上、好ましくは、１．１から３．０倍モル量を使用することで一般式（４）で表わされるエステル基含有無水フタル酸誘導体が高純度で得られる。 The basic substance used in such a reaction is not particularly limited, but tri (C 1-6 -alkyl) amine such as trimethylamine, triethylamine, diisopropylmethylamine, or pyridine, methylpyridine, N, N-dimethylamino- Examples include pyridine derivatives such as 4-pyridine. The basic substances may be used alone or in combination of two or more. The amount used is equimolar or more, preferably 1.1 to 3.0 times the molar amount of trimellitic anhydride, so that the ester group-containing phthalic anhydride derivative represented by the general formula (4) can be obtained. Obtained with high purity.
　反応後、副生する塩基性物質のハロゲン化水素酸塩を溶解除去する有機酸としては、炭素数１～４個の直鎖状または分岐鎖状のアルカン酸、好適には、ギ酸、酢酸、プロピオン酸、酪酸またはイソ酪酸が挙げられるが、経済的な理由から酢酸を使用するのが好ましい。その使用量は、塩基性物質と等モル量以上、好ましくは、１．０から２．０倍モル量である。 After the reaction, the organic acid that dissolves and removes the basic hydrohalide salt as a by-product is a linear or branched alkanoic acid having 1 to 4 carbon atoms, preferably formic acid, acetic acid, Although propionic acid, butyric acid or isobutyric acid can be mentioned, it is preferable to use acetic acid for economic reasons. The amount used is equimolar or more, preferably 1.0 to 2.0 times the molar amount of the basic substance.
　溶解除去する方法は、出発物質、反応生成物および副生する塩基性物質のハロゲン化水素酸塩等の性質に応じて、当業者が適切な方法を選択すればよい。例えば、反応終了後の反応系において反応生成物と塩基性物質のハロゲン化水素酸塩とが沈殿するのであれば、反応系に有機酸を直接添加することにより、または沈殿物を濾別し、これを有機酸で洗浄することにより、実質的に塩基性物質のみを溶解除去して、目的生成物の単離を行なえばよい。なお、本発明において「副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する」とは、副生する塩基性物質のハロゲン化水素酸塩の理論量（重量）の約９０％以上、好ましくは９５％以上、より好ましくは９９％以上を、前述のような方法により有機酸に溶解させ、除去することを意味する。一方、無水フタル酸誘導体、特に本発明の一般式（４）で表わされるエステル基含有無水フタル酸誘導体は、有機酸に溶けにくい、ないしは実質的に不溶である。したがって、これにより、無水フタル酸骨格を開環することなく、本発明の一般式（４）で表わされるエステル基含有無水フタル酸誘導体を約９０％以上、好ましくは９５％以上、より好ましくは９９％以上の純度で製造することができる。 The method for dissolving and removing may be selected by those skilled in the art depending on the properties of the starting material, reaction product, and by-product basic material such as hydrohalide. For example, if the reaction product and the basic hydrohalide salt precipitate in the reaction system after completion of the reaction, the organic acid is added directly to the reaction system, or the precipitate is filtered off, By washing this with an organic acid, only the basic substance can be dissolved and removed, and the target product can be isolated. In the present invention, “by-product basic hydrohalide is dissolved and removed with an organic acid” means about 90 of the theoretical amount (weight) of by-product basic hydrohalide. % Or more, preferably 95% or more, more preferably 99% or more is dissolved in an organic acid by the method as described above and removed. On the other hand, phthalic anhydride derivatives, particularly ester group-containing phthalic anhydride derivatives represented by the general formula (4) of the present invention are hardly soluble or substantially insoluble in organic acids. Therefore, this allows the ester group-containing phthalic anhydride derivative represented by the general formula (4) of the present invention to be about 90% or more, preferably 95% or more, more preferably 99% without opening the phthalic anhydride skeleton. % Or higher purity.
　例えば、本発明の代表的な第二の態様で、本発明の一般式（８）で表わされるエチニル基含有無水フタル酸誘導体の製造は、一般式（５）で表わされる芳香族エチニル化合物と一般式（７）で表わされるハロゲン化無水フタル酸とを、塩基性物質の存在下、５０～１３０℃で、好ましくは６０～１００℃付近で反応させるのが好適である。 For example, in a typical second embodiment of the present invention, the preparation of an ethynyl group-containing phthalic anhydride derivative represented by the general formula (8) of the present invention is generally performed with an aromatic ethynyl compound represented by the general formula (5). The halogenated phthalic anhydride represented by the formula (7) is preferably reacted in the presence of a basic substance at 50 to 130 ° C., preferably around 60 to 100 ° C.
　かかる反応に使用する塩基性物質としては、特に限定されないが、トリメチルアミン、トリエチルアミン、ジイソプロピルメチルアミンのようなトリ（Ｃ1-6－アルキル）アミン、またはピリジン、メチルピリジン、Ｎ，Ｎ－ジメチルアミノ－４－ピリジンのようなピリジン誘導体等が挙げられる。塩基性物質は、単独でも２種以上を組み合わせて使用してもよい。その使用量は、ハロゲン化無水フタル酸と等モル量以上、好ましくは、１．１から３．０倍モル量を使用することが好適である。 The basic substance used in such a reaction is not particularly limited, but tri (C 1-6 -alkyl) amine such as trimethylamine, triethylamine, diisopropylmethylamine, or pyridine, methylpyridine, N, N-dimethylamino- Examples include pyridine derivatives such as 4-pyridine. The basic substances may be used alone or in combination of two or more. The amount used is equimolar or more, preferably 1.1 to 3.0 times the molar amount of the halogenated phthalic anhydride.
　かかる反応は、好適には、溶媒中、特に非水溶媒中で行なわれる。使用可能な溶媒としては、特に限定されないが、アセトニトリル、テトラヒドロフラン、１，４－ジオキサン、ピコリン、ピリジン、クロロホルム、トルエン、キシレン、ジクロロメタン、Ｎ－メチル－２－ピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジエチルアセトアミド、ジメチルスルホキシド、γ－ブチロラクトンなどの非プロトン性溶媒が挙げられる。また、これらの溶媒を単独でも、２種以上混合して用いてもよい。 Such a reaction is preferably carried out in a solvent, particularly in a non-aqueous solvent. Solvents that can be used are not particularly limited, but acetonitrile, tetrahydrofuran, 1,4-dioxane, picoline, pyridine, chloroform, toluene, xylene, dichloromethane, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N , N-dimethylacetamide, N, N-diethylacetamide, dimethyl sulfoxide, γ-butyrolactone, and the like. These solvents may be used alone or in combination of two or more.
　かかる反応は、好適には、触媒の存在下で行なわれる。使用される触媒は、例えば、２価又は０価のパラジウム錯体であり、好適なものを一般式（９）又は一般式（１０）に示す。 Such a reaction is preferably carried out in the presence of a catalyst. The catalyst used is, for example, a divalent or zero-valent palladium complex, and a suitable one is represented by general formula (9) or general formula (10).
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　ここでＹとしては、例えば、塩素、臭素又はヨウ素原子、或いは、Ｒ3ＣＯＯ－、などが挙げられる。ここでＲ3は、炭素数１～４の直鎖状もしくは分岐鎖状のアルキル基である。Ｌとしては、例えば、Ｐ、Ａｓ、Ｓｂの各原子を含む配位子が挙げらえる。具体例としては、（Ｒ4）3Ｐが挙げられる。ここでＲ4は、場合により炭素数１～８のアルキル基で置換されたアリールである。例としては、ビス（トリフェニルホスフィン）ジクロロパラジウム（ＩＩ）、テトラキス（トリフェニルホスフィン）パラジウム（０）等が挙げられる。更に、Ｐ原子をＡｓ原子やＳｂ原子で置換した化合物も挙げる事ができる。一般式（９）で表わされるパラジウム錯体は、ＰｄＹ2で表わされる化合物と配位子Ｌとの混合物を使用してもよい。また、助触媒として、ハロゲン化銅を使用することもできる。使用することにより、反応をスムーズに進行させることができるが、これらをエチニル化合物と使用すると、銅と反応して、爆発性の不安定化合物である銅アセチリドを形成する可能性があるため、ハロゲン化銅の使用には注意を要する。ハロゲン化銅としては、塩化銅、臭化銅、ヨウ化銅が挙げられ、ヨウ化銅が好適である。 Here, Y includes, for example, chlorine, bromine or iodine atom, or R 3 COO—. Here, R 3 is a linear or branched alkyl group having 1 to 4 carbon atoms. Examples of L include a ligand containing each atom of P, As, and Sb. Specific examples include (R 4 ) 3 P. Here, R 4 is aryl optionally substituted with an alkyl group having 1 to 8 carbon atoms. Examples include bis (triphenylphosphine) dichloropalladium (II), tetrakis (triphenylphosphine) palladium (0), and the like. Furthermore, the compound which substituted P atom by As atom and Sb atom can also be mentioned. As the palladium complex represented by the general formula (9), a mixture of the compound represented by PdY 2 and the ligand L may be used. Moreover, copper halide can also be used as a co-catalyst. When used, the reaction can proceed smoothly. However, when these are used with an ethynyl compound, it may react with copper to form an explosive unstable compound, copper acetylide. Care must be taken when using copper chloride. Examples of the copper halide include copper chloride, copper bromide, and copper iodide, with copper iodide being preferred.
　反応後、副生する塩基性物質のハロゲン化水素酸塩は、上述した一般式（４）で表わされるエステル基含有無水フタル酸誘導体の製造と同様に、有機酸を利用して溶解除去することができる。有機酸としては、炭素数１～４個の直鎖状または分岐鎖状のアルカン酸、好適には、ギ酸、酢酸、プロピオン酸、酪酸またはイソ酪酸が挙げられるが、経済的な理由から酢酸を使用するのが好ましい。その使用量は、塩基性物質と等モル量以上、好ましくは、１．０から２．０倍モル量を使用する。 After the reaction, the by-product basic hydrohalide salt is dissolved and removed using an organic acid in the same manner as in the production of the ester group-containing phthalic anhydride derivative represented by the general formula (4). Can do. Examples of the organic acid include linear or branched alkanoic acids having 1 to 4 carbon atoms, preferably formic acid, acetic acid, propionic acid, butyric acid or isobutyric acid. For economic reasons, acetic acid is used. It is preferred to use. The amount used is equimolar or more, preferably 1.0 to 2.0 times the molar amount of the basic substance.
　溶解除去する方法は、出発物質、反応生成物および副生する塩基性物質のハロゲン化水素酸塩の性質に応じて、当業者が適切な方法を選択すればよい。例えば、反応終了後の反応系において反応生成物と塩基性物質のハロゲン化水素酸塩とが沈殿するのであれば、反応系に有機酸を直接添加することにより、または沈殿物を濾別し、これを有機酸で洗浄することにより、実質的に塩基性物質のみを溶解除去して、目的生成物の単離を行なえばよい。なお、本発明において「副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する」とは、副生する塩基性物質のハロゲン化水素酸塩の理論量（重量）の約９０％以上、好ましくは９５％以上、より好ましくは９９％以上を、前述のような方法により有機酸に溶解させ、除去することを意味する。一方、無水フタル酸誘導体、特に本発明の一般式（８）で表わされるエチニル基含有無水フタル酸誘導体は、有機酸に溶けにくい、ないしは実質的に不溶である。したがって、これにより、無水フタル酸骨格を開環することなく、本発明の一般式（８）で表わされるエチニル基含有無水フタル酸誘導体を約９０％以上、好ましくは９５％以上、より好ましくは９９％以上の純度で製造することができる。 The method for dissolving and removing may be selected by those skilled in the art depending on the properties of the starting material, reaction product, and by-product basic substance hydrohalide. For example, if the reaction product and the basic hydrohalide salt precipitate in the reaction system after completion of the reaction, the organic acid is added directly to the reaction system, or the precipitate is filtered off, By washing this with an organic acid, only the basic substance can be dissolved and removed, and the target product can be isolated. In the present invention, “by-product basic hydrohalide is dissolved and removed with an organic acid” means about 90 of the theoretical amount (weight) of by-product basic hydrohalide. % Or more, preferably 95% or more, more preferably 99% or more is dissolved in an organic acid by the method as described above and removed. On the other hand, phthalic anhydride derivatives, particularly ethynyl group-containing phthalic anhydride derivatives represented by the general formula (8) of the present invention are hardly soluble or substantially insoluble in organic acids. Therefore, this allows the ethynyl group-containing phthalic anhydride derivative represented by the general formula (8) of the present invention to be about 90% or more, preferably 95% or more, more preferably 99% without opening the phthalic anhydride skeleton. % Or higher purity.
　このように、本発明は、塩基性物質の存在下、無水フタル酸骨格を含む有機ハロゲン化物と有機プロトン供与体とを反応させることにより得られる無水フタル酸誘導体とを精製する方法であって、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する工程を含むことを特徴とする方法であるともいえる。かかる方法における、「塩基性物質」、「無水フタル酸骨格を含む有機ハロゲン化物」、「有機プロトン供与体」および「無水フタル酸誘導体」の例示や、好適な実施条件は、上述のとおりである。 Thus, the present invention is a method of purifying a phthalic anhydride derivative obtained by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, It can be said that the method includes a step of dissolving and removing the hydrohalic acid salt of the basic substance by-produced with an organic acid. Examples of such “basic substances”, “organic halides containing a phthalic anhydride skeleton”, “organic proton donors”, and “phthalic anhydride derivatives” in this method, and preferred implementation conditions are as described above. .
　以下に、本発明を具体的に実施例を示すが、本発明は実施例の内容に制限されるものではない。なお、実施例中の純度は、高速液体クロマトグラフィーにより測定した。
　塩基性物質のハロゲン化水素酸塩由来の残存塩基性物質は、高速液体クロマトグラフィー及びＮＭＲ測定により確認した。
　高速液体クロマトグラフィー測定
　機種：島津製作所製高速液体クロマトグラフィー　ＳＰＤ－１０Ａ
　カラム：ＯＤＳ－８０Ｔ　（３φ×１５０ｍｍ）　４０℃
　溶離液：アセトニトリル：水：燐酸＝４００：６００：０．５（容量比）
　検出波長：２５４ｎｍ
　ＮＭＲ測定
　機種：日本電子データム製　ＪＥＯＬ　ＦＴ－ＮＭＲ４００ Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the contents of the examples. In addition, the purity in an Example was measured by the high performance liquid chromatography.
The remaining basic substance derived from the basic hydrohalide was confirmed by high performance liquid chromatography and NMR measurement.
High-performance liquid chromatography measurement Model: High-performance liquid chromatography SPD-10A manufactured by Shimadzu Corporation
Column: ODS-80T (3φ × 150mm) 40 ° C
Eluent: acetonitrile: water: phosphoric acid = 400: 600: 0.5 (volume ratio)
Detection wavelength: 254 nm
NMR measurement Model: JEOL FT-NMR400 manufactured by JEOL Datum
　（例１）
　撹拌機、温度計、上向き還流管、窒素ガス導入管を付けた５００ｍＬの四つ口フラスコに、ハイドロキノン２２.０ｇ（０.２０モル）、ピリジン４７．５ｇ（０．６０モル）、Ｎ，Ｎ－ジメチルホルムアミド１００ｇを仕込み、攪拌しながら窒素雰囲気下で溶解させた。０℃に冷却後、Ｎ，Ｎ－ジメチルホルムアミド２００ｇ中に無水トリメリット酸クロリド８４．２ｇ（０．４０モル）を溶解させた溶液を、窒素雰囲気下０～１０℃で滴下しながら反応させた。反応後、析出した１，４－ビス（トリメリト酸エステル酸無水物）ベンゼン及びピリジン塩酸塩を固液分離し、酢酸５４ｇで洗浄して、ピリジン塩酸塩を溶解除去した。生成物中にピリジン塩酸塩由来のピリジンが含まれないことを、高速液体クロマトグラフィー測定で確認した。目的物である１，４－ビス（トリメリト酸エステル酸無水物）ベンゼンの純度は、９５.３％であった。 (Example 1)
In a 500 mL four-necked flask equipped with a stirrer, thermometer, upward reflux tube, and nitrogen gas introduction tube, hydroquinone 22.0 g (0.20 mol), pyridine 47.5 g (0.60 mol), N, N -100 g of dimethylformamide was charged and dissolved in a nitrogen atmosphere with stirring. After cooling to 0 ° C., a solution prepared by dissolving 84.2 g (0.40 mol) of trimellitic anhydride chloride in 200 g of N, N-dimethylformamide was reacted while dropping dropwise at 0 to 10 ° C. in a nitrogen atmosphere. . After the reaction, precipitated 1,4-bis (trimellitic acid ester anhydride) benzene and pyridine hydrochloride were separated into solid and liquid and washed with 54 g of acetic acid to dissolve and remove pyridine hydrochloride. It was confirmed by high performance liquid chromatography measurement that pyridine derived from pyridine hydrochloride was not contained in the product. The purity of 1,4-bis (trimellitic acid ester anhydride) benzene, which is the target product, was 95.3%.
　（例２）
　ハイドロキノンの代わりに４，４’－ビフェノール３７.２ｇ（０.２０モル）を使用し、例１と同様の操作を行い、生成物中にピリジン塩酸塩由来のピリジンが含まれないことを、高速液体クロマトグラフィー測定で確認した。目的物である４，４’－ビス（トリメリト酸エステル酸無水物）ビフェニルの純度は、９６.２％であった。 (Example 2)
Using 37.2 g (0.20 mol) of 4,4′-biphenol in place of hydroquinone, the same operation as in Example 1 was carried out, and it was confirmed that no pyridine derived from pyridine hydrochloride was contained in the product. This was confirmed by liquid chromatography measurement. The purity of the target product, 4,4′-bis (trimellitic acid ester anhydride) biphenyl, was 96.2%.
　（例３）
　撹拌機、温度計、上向き還流管、窒素ガス導入管を付けた５００ｍＬの四つ口フラスコに、４－ブロモ無水フタル酸６８.１ｇ（０.３０モル）、トルエン１００ｇ、トリエチルアミン３６．４ｇ（０．３６モル）、ビストリフェニルホスフィンジクロロパラジウム０．３１ｇ（０．４５×１０－３モル）を仕込み、８０℃に加熱した。次に、フェニルアセチレン３０．６ｇ（０．３０モル）を滴下しながら反応させた。滴下後、１５時間熟成させた。析出するフェニルエチニルフタル酸無水物及びトリエチルアミン塩酸塩を固液分離し、プロピオン酸４０ｇで洗浄して、トリエチルアミン塩酸塩を溶解除去した。生成物中にトリエチルアミン塩酸塩由来のトリエチルアミンが含まれないことを、ＮＭＲ測定で確認した。目的物であるフェニルエチニルフタル酸無水物の純度は、９７.８％であった。 (Example 3)
In a 500 mL four-necked flask equipped with a stirrer, thermometer, upward reflux tube and nitrogen gas introduction tube, 68.1 g (0.30 mol) of 4-bromophthalic anhydride, 100 g of toluene, 36.4 g of triethylamine (0 .36 mol) and 0.31 g (0.45 × 10 −3 mol) of bistriphenylphosphine dichloropalladium were charged and heated to 80 ° C. Next, 30.6 g (0.30 mol) of phenylacetylene was reacted while being dropped. After dropping, the mixture was aged for 15 hours. The precipitated phenylethynylphthalic anhydride and triethylamine hydrochloride were solid-liquid separated and washed with 40 g of propionic acid to dissolve and remove the triethylamine hydrochloride. It was confirmed by NMR measurement that the product did not contain triethylamine derived from triethylamine hydrochloride. The purity of the target phenylethynyl phthalic anhydride was 97.8%.
　本発明の製法で得られる無水フタル酸誘導体、特にはエステル基含有無水フタル酸誘導体、エチニル基含有無水フタル酸誘導体は、ポリエステルイミド樹脂原料、エポキシ樹脂等の硬化剤、改質剤として利用でき、特に低吸水率ポリエステルイミド原料、耐熱材料として有用である。本発明は、これらのエステル基含有無水フタル酸誘導体、エチニル基含有無水フタル酸誘導体の製造において、無水フタル酸骨格を開環させることなく、効率的に副生物を除去できる極めて有用な製造方法を提供するものである。 The phthalic anhydride derivative obtained by the production method of the present invention, in particular, an ester group-containing phthalic anhydride derivative, an ethynyl group-containing phthalic anhydride derivative, can be used as a curing agent, a modifier, such as a polyesterimide resin raw material, an epoxy resin, It is particularly useful as a low water absorption polyesterimide raw material and heat resistant material. In the production of these ester group-containing phthalic anhydride derivatives and ethynyl group-containing phthalic anhydride derivatives, the present invention provides a very useful production method that can efficiently remove by-products without ring-opening the phthalic anhydride skeleton. It is to provide.

Claims (7)

  1. 　塩基性物質の存在下、無水フタル酸骨格を含む有機ハロゲン化物と有機プロトン供与体とを反応させて、無水フタル酸誘導体を製造する方法において、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する工程を含むことを特徴とする、方法。 In a method for producing a phthalic anhydride derivative by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, A method comprising dissolving and removing with an organic acid.
  2. 　塩基性物質Ｂの存在下、下記一般式（II）：
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｘは、塩素、臭素、またはヨウ素であり、Ｙ1は、直接結合、または－Ｃ（Ｏ）－である）
    で表される無水フタル酸骨格を含む有機ハロゲン化物と、下記一般式（III）：
    Figure JPOXMLDOC01-appb-C000002
     〔式中、ｎは、１または２であり；
    ｎが１である場合、
    Ａｒは、下記式：
    Figure JPOXMLDOC01-appb-C000003
     （ここで、Ｒ1およびＲ2は、同一または異なって、水素または炭素数１～４のアルキル基である）よりなる群から選ばれる１価の芳香族基であり、Ｙ2は、－Ｏ－、または炭素数２～４のアルケニレンもしくはアルキニレン基であり；
    ｎが２である場合、
    Ａｒは、下記式：
    Figure JPOXMLDOC01-appb-C000004
     （ここで、Ｒ1およびＲ2は、同一または異なって、水素または炭素数１～４のアルキル基である）よりなる群から選ばれる２価の芳香族基であり、Ｙ2は、－Ｏ－である；
    ただし、Ｙ1が－Ｃ（Ｏ）－である場合、Ｙ2は、－Ｏ－である〕
    で表される有機プロトン供与体とを反応させて、下記一般式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000005
     〔式中、Ａｒ、Ｙ1、Ｙ2およびｎは、上記と同義である〕
    で表される無水フタル酸誘導体を製造する方法において、副生する塩基性物質のハロゲン化水素酸塩：Ｂ・ＨＸを有機酸で溶解除去する工程を含むことを特徴とする、方法。     In the presence of the basic substance B, the following general formula (II):
    Figure JPOXMLDOC01-appb-C000001
     (Wherein X is chlorine, bromine, or iodine, and Y 1 is a direct bond or —C (O) —)
    An organic halide containing a phthalic anhydride skeleton represented by the following general formula (III):
    Figure JPOXMLDOC01-appb-C000002
     [Wherein n is 1 or 2;
    When n is 1,
    Ar is represented by the following formula:
    Figure JPOXMLDOC01-appb-C000003
     (Wherein R 1 and R 2 are the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms), and Y 2 is —O -Or an alkenylene or alkynylene group having 2 to 4 carbon atoms;
    If n is 2,
    Ar is represented by the following formula:
    Figure JPOXMLDOC01-appb-C000004
     Wherein R 1 and R 2 are the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms, and Y 2 is —O -Is;
    However, when Y 1 is —C (O) —, Y 2 is —O—.]
    Is reacted with an organic proton donor represented by the following general formula (I):
    Figure JPOXMLDOC01-appb-C000005
     [Wherein Ar, Y 1 , Y 2 and n are as defined above]
    A method for producing a phthalic anhydride derivative represented by formula (1), comprising a step of dissolving and removing a hydrohalide salt of B: HX as a by-product with an organic acid.
  3. 　有機プロトン供与体が、一般式（１）：
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ａｒ1は、下記式（２）：
    Figure JPOXMLDOC01-appb-C000007
     よりなる群から選ばれる２価の芳香族基であり、Ｒ1およびＲ2は、同一または異なって、水素または炭素数１～４のアルキル基である）
    で表される芳香族ジオール化合物であり、無水フタル酸骨格を含む有機ハロゲン化物が、一般式（３）：
    Figure JPOXMLDOC01-appb-C000008
     （式中、Ｘは、塩素、臭素、またはヨウ素である）
    で表される無水トリメリット酸ハライドであり、そして得られる無水フタル酸誘導体が、一般式（４）：
    Figure JPOXMLDOC01-appb-C000009
     （式中、Ａｒ1は、上記と同義である）
    で表されるエステル基含有無水フタル酸誘導体である、請求項１または２に記載の方法。     The organic proton donor is represented by the general formula (1):
    Figure JPOXMLDOC01-appb-C000006
     (In the formula, Ar 1 represents the following formula (2):
    Figure JPOXMLDOC01-appb-C000007
     A divalent aromatic group selected from the group consisting of R 1 and R 2 are the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms)
    An organic halide having a phthalic anhydride skeleton represented by the general formula (3):
    Figure JPOXMLDOC01-appb-C000008
     (Wherein X is chlorine, bromine or iodine)
    And the resulting phthalic anhydride derivative is represented by the general formula (4):
    Figure JPOXMLDOC01-appb-C000009
     (Wherein Ar 1 has the same meaning as above)
    The method of Claim 1 or 2 which is an ester group containing phthalic anhydride derivative represented by these.
  4. 　有機プロトン供与体が、一般式（５）：
    Figure JPOXMLDOC01-appb-C000010
     （式中、Ａｒ2は、下記式（６）：
    Figure JPOXMLDOC01-appb-C000011
     よりなる群から選ばれる１価の芳香族基であり、Ｒ1およびＲ2は、同一または異なって、水素または炭素数１～４のアルキル基である）
    で表される芳香族エチニル化合物であり、無水フタル酸骨格を含む有機ハロゲン化物が、一般式（７）：
    Figure JPOXMLDOC01-appb-C000012
     （式中、Ｘは、塩素、臭素、またはヨウ素を表す）
    で表されるハロゲン化無水フタル酸であり、そして得られる無水フタル酸誘導体が、一般式（８）：
    Figure JPOXMLDOC01-appb-C000013
     （式中、Ａｒ2は、上記と同義である）
    で表されるエチニル基含有無水フタル酸誘導体である、請求項１または２に記載の方法。     The organic proton donor is represented by the general formula (5):
    Figure JPOXMLDOC01-appb-C000010
     (In the formula, Ar 2 represents the following formula (6):
    Figure JPOXMLDOC01-appb-C000011
     A monovalent aromatic group selected from the group consisting of: R 1 and R 2 are the same or different and are hydrogen or an alkyl group having 1 to 4 carbon atoms)
    And an organic halide containing a phthalic anhydride skeleton is represented by the general formula (7):
    Figure JPOXMLDOC01-appb-C000012
     (Wherein X represents chlorine, bromine, or iodine)
    And the resulting phthalic anhydride derivative is represented by the general formula (8):
    Figure JPOXMLDOC01-appb-C000013
     (Wherein Ar 2 has the same meaning as above)
    The method of Claim 1 or 2 which is an ethynyl group containing phthalic anhydride derivative represented by these.
  5. 　有機酸が、ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸およびこれらの混合物よりなる群から選ばれる、請求項１～４のいずれか１項に記載の方法。 The method according to any one of claims 1 to 4, wherein the organic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, and a mixture thereof.
  6. 　塩基性物質が、トリアルキルアミンおよび／またはピリジン誘導体である、請求項１～５のいずれか１項に記載の方法。 The method according to any one of claims 1 to 5, wherein the basic substance is a trialkylamine and / or a pyridine derivative.
  7. 　塩基性物質の存在下、無水フタル酸骨格を含む有機ハロゲン化物と有機プロトン供与体とを反応させることにより得られる無水フタル酸誘導体とを精製する方法であって、副生する塩基性物質のハロゲン化水素酸塩を有機酸で溶解除去する工程を含むことを特徴とする、方法。 A method for purifying a phthalic anhydride derivative obtained by reacting an organic halide containing a phthalic anhydride skeleton with an organic proton donor in the presence of a basic substance, wherein A method comprising dissolving and removing a hydride salt with an organic acid.
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