JPH11180970A - Production of dicarboxylic acid anhydride having carbon-carbon triple bond - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing, in a high yield, a pure dicarboxylic acid anhydride having carbon-carbon triple bond(s) useful as a raw material for polymer composite resin for airplane and spacecraft, by the reaction of an ethynylbenzene compound with a phthalic acid anhydride derivative, hydrolysis of the obtained product, acid precipitation, followed by cyclization of the obtained precipitates. SOLUTION: This method comprises the reaction of (A) a compound shown by formula I (R1 is a 1-4C alkyl, an alkoxy, phenyl, or phenoxy; (n) is 0-2) with (B) a compound shown by formula II (X1 is a halogen) in the presence of (C) a copper halide. (D) a Pd(II) or Pd(0) complex, and (E) a basic organic solvent, hydrolysis using (F) a basic aqueous solution, acid precipitation of the obtained aqueous layer using at least one equivalent of an acid per (G) the carboxylic acid of component B, followed by filtration to give a dicarboxylic acid, which is then chemically or thermally cyclized to give a compound shown by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a dicarboxylic anhydride having a carbon-carbon triple bond. The method of the present invention has made it possible to industrially produce a high-purity dicarboxylic anhydride having a carbon-carbon triple bond in high yield.

[0002]

2. Description of the Related Art Polymer composite materials are lightweight and excellent in strength. Among them, advanced composite materials typified by carbon fiber reinforced epoxy resin are used as structural materials mainly in the aviation and space fields such as civil aircraft. It is being used. However, the common use temperature of advanced composite materials represented by carbon fiber reinforced epoxy resin is 135 ° C or less,
In order to further reduce the weight of space equipment and achieve higher performance, it is essential to increase the continuous use temperature of advanced composite materials. In particular, a high-performance heat-resistant composite material is considered to be indispensable for the development of a subsonic aircraft development and the realization of a single-stage spacecraft, and high heat resistance of the matrix resin is strongly demanded.

As one of the methods, a group having a carbon-carbon triple bond such as a phenylethynyl group is introduced into a terminal or a side chain of a polyimide having a glass transition point of 300 ° C. or less or an oligomer thereof, and after polymerization, a temperature of 300 ° C. or more is obtained. Development of a thermosetting polyimide that is cured by heating to a temperature has been performed. This attempt aims to improve the creep resistance and heat resistance, which are the characteristics of thermosetting resins, while imparting toughness at the linear portion. Attention has been paid to a method for increasing the heat resistance of resins (Reinforced Plastics, Vol. 43, No. 9, 14-25).
page).

For example, NASA (National Ae)
ronautics and Space Admin
accommodation, U.S.A. S. A. Paul)
M. Hergenrother et al. Have developed thermoset polyimides in which dicarboxylic acid anhydrides containing phenylethynyl groups at the terminals of various types of polyimides have been introduced (US Pat. No. 5,567,800).

However, no industrial production method is known for the production of dicarboxylic anhydrides having a group containing a carbon-carbon triple bond such as a phenylethynyl group. G. FIG. Smith Jr. Et al., In Polymer Preprints, Vol. 35, No. 1, p. 353 (1995),
The yield is 62%, and the development of an industrially feasible method for producing a dicarboxylic anhydride having a high-purity carbon-carbon triple bond with a high yield has been demanded.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to overcome the above-mentioned problems and to realize a commercially available dicarboxylic anhydride having a carbon-carbon triple bond with high yield and high purity. An object of the present invention is to provide a production method and a dicarboxylic anhydride having a carbon-carbon triple bond obtained by the method.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, the general formula (1)
[Formula 4]

[0008]

Embedded image (In the formula, n is an integer of 0 to 2, and R 1 has 1 carbon atom.
When n is 2, each R1 in the formula may be the same or different from each other, wherein R1 is an alkyl group, an alkoxy group, a phenyl group, or a phenoxy group. ) Or an ethynylbenzene represented by the general formula (2)

[0009]

Embedded image (Wherein X 1 represents a halogen atom) and a phthalic anhydride derivative represented by the following general formula (3):

[0010]

Embedded image (In the formula, n is an integer of 0 to 2, and R 1 has 1 carbon atom.
When n is 2, each R1 in the formula may be the same or different from each other, wherein R1 is an alkyl group, an alkoxy group, a phenyl group, or a phenoxy group. Various studies were made on the reaction for obtaining the dicarboxylic anhydride represented by the formula (1), and the reaction conditions were optimized to complete the present invention. The present invention provides the following [1] to
It is specified by the items described in [2]. [1] General formula (1)

[0011]

Embedded image (In the formula, n is an integer of 0 to 2, and R 1 has 1 to 1 carbon atoms.
And when n is 2, each R1 in the formula may be the same or different. ) Or an ethynylbenzene represented by the general formula (2)

[0012]

Embedded image (Wherein X 1 represents a halogen atom) and a phthalic anhydride derivative represented by the following general formula (3):

[0013]

Embedded image (In the formula, n is an integer of 0 to 2, and R 1 has 1 carbon atom.
When n is 2, each R1 in the formula may be the same or different from each other, wherein R1 is an alkyl group, an alkoxy group, a phenyl group, or a phenoxy group. In obtaining a dicarboxylic anhydride represented by the formula (1), a copper halide, a divalent or zero-valent palladium complex and a basic organic solvent are used in the presence of a general formula (1)
After reacting the ethynylbenzene represented by the chemical formula 7 or a derivative thereof with the phthalic anhydride derivative represented by the general formula (2) [8], the reaction is hydrolyzed with a basic aqueous solution, and the aqueous layer thereof is formed. Is acid-precipitated with one or more equivalents of the carboxylic acid of the phthalic anhydride derivative used in the reaction, filtered to obtain a dicarboxylic acid, which is chemically or thermally ring-closed to give a compound of the general formula (3) ) A method for producing a dicarboxylic anhydride having a carbon-carbon triple bond, which comprises obtaining a dicarboxylic anhydride represented by the following chemical formula 9. [2] A dicarboxylic anhydride having a carbon-carbon triple bond produced by the production method according to [1].

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The production method of the present invention has the general formula (1)
[Formula 10]

[0015]

Embedded image (In the formula, n is an integer of 0 to 2, and R 1 has 1 to 4 carbon atoms.
And when n is 2, each R1 in the formula may be the same or different. ) Or an ethynylbenzene or a derivative thereof represented by the general formula (2):

[0016]

Embedded image (Wherein X 1 represents a halogen atom) and a phthalic anhydride derivative represented by the following general formula (3):

[0017]

Embedded image (In the formula, n is an integer of 0 to 2, and R 1 has 1 to 4 carbon atoms.
And when n is 2, each R1 in the formula may be the same or different. In the reaction to obtain the dicarboxylic anhydride represented by the general formula (1), the term “ethynylbenzene” or the derivative thereof represented by the general formula (1) refers to all of the general formula (1) represented by the general formula (1). Including, for example, specifically ethynylbenzene, 2-methylphenylacetylene, 3-methylphenylacetylene, 4-methylphenylacetylene, 2,4-dimethylphenylacetylene,
2-methoxyphenylacetylene, 4-methoxyphenylacetylene, 2-phenylphenylacetylene, 4-
Phenyl phenyl acetylene, 2-phenoxy phenyl acetylene, 4-phenoxy phenyl acetylene and the like are listed. The phthalic anhydride derivative represented by the general formula (2) [formula 11] is represented by the general formula (2) [formula 11]. It includes all the structures represented, and specifically includes, for example, 4-bromophthalic anhydride, 4-iodophthalic anhydride and the like. The amount ratio of the raw materials is not particularly limited, but the number of moles of ethynylbenzene or a derivative thereof represented by the general formula (1) [formula 10] is represented by the general formula (2) [formula 11] because of ease of purification. It is preferable that the amount of the phthalic anhydride derivative is excessive compared to the number of moles of the phthalic anhydride derivative, and it is more preferable that the general formula (1)
0] is 1.005 times or more and 2.000 times or less the number of moles of the phthalic anhydride derivative represented by the general formula (2) [Formula 11]. The dicarboxylic anhydride obtained from these raw materials is uniquely determined by the raw materials used, and specifically, 4-phenylethynylphthalic anhydride, 4- (2-methylphenylethynyl) phthalic anhydride, 4- (3-methylphenylethynyl) phthalic anhydride, 44-(-methylphenylethynyl) phthalic anhydride, 4- (2,4
-Dimethylphenylethynyl) phthalic anhydride, 4-
(2-methoxyphenylethynyl) phthalic anhydride, 4
-(4-methoxyphenylethynyl) phthalic anhydride,
4- (2-phenylphenylethynyl) phthalic anhydride, 4- (4-phenylphenylethynyl) phthalic anhydride, 4- (2-phenoxyphenylethynyl) phthalic anhydride, 4- (4-phenoxyphenylethynyl) ) Phthalic anhydride.

In the production method of the present invention, a basic organic solvent is used. As the basic organic solvent, for example, diethylamine, triethylamine, pyridine and the like are used, and preferably triethylamine. These can be used alone or as a mixture of two or more. Further, as the solvent, other ordinary organic solvents can be used in combination within a range not impairing the excellent method for producing a basic organic solvent of the present invention. Usual organic solvents used include:
Although not particularly limited, for example, o-cresol, m-cresol, p-cresol, m-cresylic acid, xylene, toluene, picoline, N-methyl-2
-Pyrrolidone, N, N-dimethylacetamide, N,
N-dimethylformamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, 1,3-dimethyl-2-imidazolidinone, N-methylcaprolactam, 1,2-dimethoxyethane, bis (2-methoxyethyl) Ether, 1,2-bis (2-methoxyethoxy) ethane, bis 2- (2-methoxyethoxy)
Ethyl ether, tetrahydrofuran, 1,3-
Dioxane, 1,4-dioxane, pyrroline, dimethyl sulfoxide, dimethyl sulfone, tetramethyl urea,
Selected from the group consisting of hexamethylphosphoramide, phenol, p-chlorophenol, anisole, benzene, water, acetone, methanol, ethanol, propyl alcohol, methyl ethyl ketone or a mixture of two or more of these solvents Organic solvents are mentioned. The amount of these solvents is not particularly limited, but it can be sufficiently carried out when the concentration of the raw material is in the range of 2 to 50% by weight based on the total amount of the reaction mass. In addition, by removing dissolved oxygen from the system by blowing nitrogen into the solvent before the reaction, side reactions of the reaction can be suppressed.

The copper halide used in the production method of the present invention is not limited, but copper chloride or copper iodide is used, and preferably copper iodide is used. Although the amount of the copper halide used is not limited, the number of moles is 0.0000001 times or more and 0.00.0 times or more the number of moles of the phthalic anhydride derivative represented by the general formula (2) [formula 11].
One time or less is sufficient. The divalent or zero-valent palladium complex used in the production method of the present invention has the following general formula (4) [formula 13] or general formula (5) [formula 14].

[0020]

Embedded image L2Pd (II) X'2 (4)

[0021]

L4Pd (0) (5) (where Pd (II) is divalent palladium and Pd (0)
Represents zero-valent palladium, L represents a ligand having one phosphorus atom, arsenic atom, or antimony atom in one molecule, and having two phosphorus atoms, arsenic atom, or antimony atom in one molecule The ligand can also be represented as L2.
In the formula, X ′ is a chlorine atom, a bromine atom, an iodine atom, or —OCOCH 3, —OCOC 2 H 5, —OCOC 3 H
7, -OCOC4H9, -OCCH3 (CHCOCH3) and the like). The palladium complex used is 2
In the case of valency, a part thereof is L (or L2) and / or Pd (I
I) It may be X'2. Specific examples of the ligand of the palladium complex to be used include, for example, [Formula 15] to [Formula 17].

[0022]

Embedded image (CH3) 3P, (C2H5) 3P, (CH2 = C
(HCH2) 3P, (C3H7) 3P, (C4H9) 3P, (C5
(H11) 3P, (C6H13) 3P, (C7H15) 3P, (C8H
17) 3P, (C6H5) 3P, (CH3C6H4) 3P, (Cl
(C6H4) 3P, (CH3OC6H4) P, (C6H5CH2) 3
P, (C4H9) 2 (C6H5) P, (C4H9) (C6H5) 2
P, (CH3OC6H4) (C6H5) 2P, (C6H5) 2P
CH2CH2P (C6H5) 2,

[0023]

Embedded image

[0024]

(C6H5) 2PCH2CH2OCH2CH2P
(C6H5) 2, (CH3O) 3P, (C2H5O) 3P, (C
3H7O) 3P, (C4H9O) 3P, (C5H11O) 3P,
(C6H13O) 3P, (C7H15O) 3P, (C8H17O) 3
P, (C6H5O) 3P, (CH3C6H4O) 3P, (C6H
5CH2O) 3P, (ClC6H4O) 3P, (CH3OC6H
(4O) 3P, (C4H9O) 2 (C6H5) P, (C4H9O)
(C6H5) 2P, (CH3C6H4O) (C6H5) 2P,
Phosphorus compounds such as (C4H9O) (C6H5O) 2P;
H3) 3As, (C2H5) 3As, (CH2 = CHCH2) 3
As, (C3H7) 3As, (C4H9) 3As, (C5H1
1) 3As, (C6H13) 3As, (C7H15) 3As, (C
8H17) 3As, (C6H5) 3As, (CH3C6H4) 3A
s, (ClC6H4) 3As, (CH3OC6H4) As,
(C6H5CH2) 3As, (C6H5) 2AsCH2CH2A
arsenic compounds such as s (C6H5) 2, (CH3) 3Sb,
(C2H5) 3Sb, (CH2 = CHCH2) 3Sb, (C3
H7) 3Sb, (C4H9) 3Sb, (C5H11) 3Sb,
(C6H13) 3Sb, (C7H15) 3Sb, (C8H17) 3S
b, (C6H5) 3Sb, (CH3C6H4) 3Sb, (Cl
(C6H4) 3Sb, (CH3OC6H4) Sb, (C6H5CH
2) 3Sb, (C6H5) 2SbCH2CH2Sb (C6H5)
2, antimony compounds such as. The amount of these palladium complexes to be used is not particularly limited, but the number of moles is 0.0000001 times or more and 0.01 times or less the number of moles of the phthalic anhydride derivative represented by the general formula (2) [Formula 11]. Is enough.

Although the reaction conditions of the production method of the present invention are not particularly limited, the reaction can be carried out sufficiently at normal pressure, and the reaction temperature varies from 0 ° C. to 200 ° C. depending on the type and amount and concentration of the reaction solvent and catalyst. The following is preferred. The reaction time varies depending on the type, amount, concentration and reaction temperature of the catalyst.
0 minutes to 24 hours is sufficient. In the production method of the present invention, after the reaction, the solution is hydrolyzed with a basic aqueous solution, and the aqueous layer is subjected to acid precipitation with one or more equivalents of acid relative to the carboxylic acid of the phthalic anhydride derivative used in the reaction, followed by filtration. It is characterized by obtaining a dicarboxylic acid.

The basic aqueous solution and the acid can be arbitrarily selected, but usually, an aqueous sodium hydroxide solution and hydrochloric acid are used. Although the amount of the basic aqueous solution is not limited,
It is preferably at least 1 equivalent, more preferably at least 1.05 equivalent, to the carboxylic acid of the phthalic anhydride derivative used. The amount of the acid used for the acid precipitation is 1 equivalent or more based on the carboxylic acid of the phthalic anhydride derivative used. Even if this amount is insufficient, the solution becomes acidic and may precipitate, but in this case, the amount of by-products of the reaction increases, and the yield decreases significantly. The amount of the acid used for the acid precipitation is preferably 1.05 to the carboxylic acid of the phthalic anhydride derivative used.
It is more than equivalent. In order to remove unreacted substances and the like contained in the aqueous layer before the acid precipitation, it is preferable to extract the unreacted substances and the like with a generally used organic solvent such as toluene. The dicarboxylic acid obtained by this method can be chemically or thermally ring-closed to obtain a dicarboxylic anhydride represented by the general formula (3) [Formula 12].

The method of ring closure is not limited. For example, the ring can be easily closed by reacting in acetic anhydride at 50 ° C. to 130 ° C. for 2 to 24 hours. In this case, it is of course possible to replace part of acetic anhydride with a commonly used organic solvent such as toluene. Further, as a ring closing method, it is also possible to adopt another method of thermally closing the ring. For example, by heating a dicarboxylic acid in nitrogen at 150 to 250 ° C. for 2 to 12 hours, the ring can be easily closed.

The obtained dicarboxylic anhydride represented by the general formula (3) [formula 12] can be purified by recrystallization with toluene / chloroform or the like. The resulting dicarboxylic anhydride represented by the general formula (3) [Formula 12] is obtained by substituting a part of tetracarboxylic anhydride used for a polymer or oligomer monomer such as polyimide with this, It can be introduced at the polymer end. It can also be introduced into the side chains of various polymers. A polymer or oligomer in which a dicarboxylic anhydride having a carbon-carbon triple bond is introduced into a polymer terminal and / or a side chain can improve mechanical strength, heat resistance, and chemical resistance by curing treatment.

[0029]

EXAMPLES Hereinafter, the production method of the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. [Example 1] In a container equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, 1.10 g of triphenylphosphine (0.
4 mmol) and 681.0 of 4-bromophthalic anhydride.
g (3.00 mol) of phenylacetylene in 321.
7 g (3.15 mol), 3.5 L of triethylamine
Charged and bubbled nitrogen for 30 minutes with vigorous stirring. Stop publishing and introduce nitrogen, here P
0.21 g (0.3 mm) of dCl2 [P (C6H5) 3] 2
ol) and the temperature was raised to 60 ° C. Further, 0.23 g (1.5 mmol) of copper iodide was charged, the temperature was slowly raised, and the reaction was performed at 85 to 90 ° C. for 4 hours. After the completion of the reaction, the mixture was cooled, 7.5 L of a 1 N aqueous solution of sodium hydroxide was charged, and the mixture was stirred for 2 hours. To remove the organic layer and remove unreacted raw materials and the like dissolved in the remaining aqueous layer, 2 L of toluene was added thereto and extracted with toluene three times, and 2N hydrochloric acid was added to the obtained uniform aqueous layer. 3.25 L of water was charged dropwise. The obtained precipitate was filtered, washed with 5 L of water, and dried at 110 ° C.
Dry under reduced pressure for 24 hours. The obtained 4-phenylethynylphthalic acid was an acetone-soluble white powder, having a purity of 99.4%, a yield of 784.4 g, and a yield of 98.2% as measured by high performance liquid chromatography. Further, 784.4 g of the obtained 4-phenylethynylphthalic acid, 730 g of acetic anhydride, and 730 g of toluene were charged into a vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube, and the mixture was stirred at 110 ° C under reflux for 4 hours. After cooling to 100 ° C., the mixture was filtered hot, cooled, and the obtained precipitate was filtered, washed with 500 g of a mixed solvent of acetic anhydride / toluene (mixing ratio: 5/5; weight ratio), and further mixed with a mixed solvent of toluene / hexane. (Mixing ratio 5 /
5; weight ratio) 500 g. This was dried at 140 ° C. under a reduced pressure and nitrogen stream for 12 hours. The obtained 4-phenylethynylphthalic anhydride was a toluene-soluble yellow-white powder, the yield was 689.0 g, and the total reaction yield was 92.5%. The melting point of the obtained 4-phenylethynylphthalic anhydride was 151.8 to 152.6 ° C., and the IR and NMR were as shown in FIG. 1 [FIG. 1] and FIG. 2 [FIG. 2].

Example 2 The procedure of Example 1 was repeated except that the amount of 2N hydrochloric acid used for acid precipitation was changed to 6.0 L.
-Phenylethynylphthalic anhydride was obtained. 4 obtained
-Phenylethynylphthalic anhydride was a yellow-white powder soluble in toluene, the yield was 685.8 g, and the total reaction yield was 92.3%. The melting point of the obtained 4-phenylethynylphthalic anhydride is 151.9 to 152.8 ° C.
Met.

[Comparative Example 1] Triphenylphosphine was placed in a vessel equipped with a stirrer, a reflux condenser and a nitrogen inlet tube.
10 g (0.4 mmol), 681.0 g (3.00 mol) of 4-bromophthalic anhydride, 321.7 g (3.15 mol) of phenylacetylene, 3.5 L of triethylamine, PdCl2 [P (C6H5) 3] 2 The reaction was carried out at 85 to 90 ° C. for 4 hours in the same manner as in Example 1 using 0.23 g (1.5 mmol) of copper iodide. After the completion of the reaction, the mixture was cooled, 7.5 L of a 1 N aqueous solution of sodium hydroxide was charged, and the mixture was stirred for 2 hours. To remove the organic layer and remove unreacted raw materials and the like dissolved in the remaining aqueous layer, 2 L of toluene was added thereto and extracted with toluene three times, and 2N hydrochloric acid was added to the obtained uniform aqueous layer. Water was added dropwise while paying attention to the pH of the solution until the solution became acidic. When the pH reached 5, the dropwise addition of hydrochloric acid was stopped, and the obtained precipitate was filtered, washed with 5 L of water, and dried at 110 ° C. under reduced pressure for 24 hours. The amount of aqueous hydrochloric acid used was 1.55 L, and the amount of carboxylic acid of the phthalic anhydride derivative used in the reaction was 0.5
One equivalent. The obtained white powder was almost insoluble in acetone. Using this, a ring-closing treatment was performed in the same manner as in Example 1. As a result, since the obtained yellow-white powder was partially insoluble in toluene, it was recrystallized from toluene to give 4-phenylethynylphthalic anhydride. I got Yield 388.0
g, the overall reaction yield was 52.1%. The melting point of the obtained 4-phenylethynylphthalic anhydride was 151.
3-152.9 ° C.

[Comparative Example 2] A reaction was carried out in the same manner as in Comparative Example 1, and 2N hydrochloric acid solution used for acid precipitation was added dropwise while paying attention to the pH of the solution until the solution became acidic. When the pH reached 2, the dropwise addition of hydrochloric acid was stopped, and the obtained precipitate was filtered, washed with 5 L of water, and dried at 110 ° C. under reduced pressure for 24 hours. The amount of hydrochloric acid water used was 1.59 L, and the amount of carboxylic acid of the phthalic anhydride derivative used in the reaction was 0.5
It was 3 equivalents. The obtained white powder was almost insoluble in acetone. Using this, a ring-closing treatment was performed in the same manner as in Example 1. As a result, since the obtained yellow-white powder was partially insoluble in toluene, it was recrystallized from toluene to give 4-phenylethynylphthalic anhydride. I got Yield 416.2
g, the total yield of the reaction was 55.8%. The melting point of the obtained 4-phenylethynylphthalic anhydride was 151.
5-152.9 ° C.

Comparative Example 3 The procedure of Comparative Example 1 was repeated except that the 2N hydrochloric acid solution used for the acid precipitation was changed to 2.2 L.
-Phenylethynylphthalic anhydride was obtained. 4 obtained
-The yield of phenylethynylphthalic anhydride is 70.2
%, Melting point: 151.5 to 152.8 ° C. From the above results, it is clear that when the conditions of the present invention are deviated, the yield and purity are greatly reduced.

[0034]

Industrial Applicability According to the present invention, it has become possible to industrially produce a dicarboxylic anhydride having a carbon-carbon triple bond with high purity in a high yield. Furthermore, the dicarboxylic anhydride having a carbon-carbon triple bond can be introduced into a polymer terminal and / or a side chain, so as not to impair the formability of the polymer and to have mechanical strength, heat resistance, and heat resistance by a curing treatment. A thermosetting polymer or oligomer capable of improving chemical properties can be used.

[Brief description of the drawings]

FIG. 1. IR of 4-phenylethynylphthalic anhydride
It is a figure showing a chart.

FIG. 2. NM of 4-phenylethynylphthalic anhydride
It is the figure which showed the R chart.

[Explanation of symbols]

Wavenumber [cm ^-1 ]; wave number per cm. % T; transmittance [%].

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takashi Kuroki 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Pref. (72) Inventor Yuichi Okawa 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Chemicals ( 72) Inventor Hideaki Oikawa 1190 Kasama-cho, Sakae-ku, Yokohama City, Kanagawa Prefecture Inside Mitsui Chemicals, Inc.

Claims (2)

[Claims] 1. A compound represented by the general formula (1): (In the formula, n is an integer of 0 to 2, and R 1 has 1 to 1 carbon atoms.
And when n is 2, each R1 in the formula may be the same or different. ) Or an ethynylbenzene or a derivative thereof represented by the general formula (2): (Wherein X 1 represents a halogen atom) and a phthalic anhydride derivative represented by the following general formula (3): (In the formula, n is an integer of 0 to 2, and R 1 has 1 carbon atom.
When n is 2, each R1 in the formula may be the same or different from each other, wherein R1 is an alkyl group, an alkoxy group, a phenyl group, or a phenoxy group. In obtaining a dicarboxylic anhydride represented by the formula (1), a copper halide, a divalent or zero-valent palladium complex and a basic organic solvent are used in the presence of a general formula (1)
After reacting ethynylbenzene or a derivative thereof represented by the chemical formula 1 with a phthalic anhydride derivative represented by the general formula (2) or [2], the reaction is hydrolyzed with a basic aqueous solution, and the aqueous layer is formed. Is acid-precipitated with one or more equivalents of the carboxylic acid of the phthalic anhydride derivative used in the reaction, filtered to obtain a dicarboxylic acid, which is chemically or thermally ring-closed to give a compound of the general formula (3) ) A method for producing a dicarboxylic anhydride having a carbon-carbon triple bond, which comprises obtaining a dicarboxylic anhydride represented by Chemical Formula 3. 2. A dicarboxylic anhydride having a carbon-carbon triple bond produced by the production method according to claim 1.