TW201100395A - Method for producing diepoxy compound - Google Patents

Abstract

Disclosed is a method for reacting a dihydroxy compound expressed by formula (1) (wherein, R1 represents a hydrogen atom, a C1-3 alkyl group, or a C1-3 alkoxy group, R2 represents a hydrogen atom, a C1-3 alkyl group, or a C1-3 alkoxy group, R3 represents a hydrogen atom, a C1-3 alkyl group, or a C1-3 alkoxy group, R4 represents a hydrogen atom, a C1-3 alkyl group, or a C1-3 alkoxy group, R5 represents a hydrogen atom, a methyl group, or a C1-3 alkoxy group, R6 represents a hydrogen atom, a methyl group, or a C1-3 alkoxy group, R7 represents a hydrogen atom, a methyl group, or a C1-3 alkoxy group, and R8 represents a hydrogen atom, a methyl group, or a C1-3 alkoxy group) with a compound expressed by formula (2) (wherein, X1 represents a halogen atom) in the presence of ammonium salt, an inorganic base, and an alcohol compound to produce a diepoxy compound expressed by formula (3); (wherein, R1, R2, R3, R4, R5, R6, R7, and R8 each represent the same meaning as in formula (1)).

Description

201100395 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing a diepoxide compound. [Prior Art] The epoxy cured product obtained by curing the diepoxide compound exhibits excellent properties in terms of mechanical properties and electrical properties in addition to excellent heat resistance and moisture resistance, and is industrially wide. For use. In Macromol. Chem. Phys. 1 9 9, 853-859 (1998), a cured product obtained by hardening a diepoxide compound represented by the formula (A) and a hardener is described.

In the method for producing a diepoxy compound represented by the formula (A), it is described that a compound represented by the formula (B) is reacted with epichlorohydrin in the presence of benzyltrimethylammonium bromide. And mixing the obtained reaction mixture with an aqueous sodium hydroxide solution

SUMMARY OF THE INVENTION The present invention provides the following, etc.: < 1 > A method for producing a diepoxide compound represented by the formula (3) -5- (3) 201100395 (3)

(wherein R1 represents a hydrogen atom, a hospital group having a carbon number of 1 to 3, or a oxy group having 1 to 3 carbon atoms; R2 represents a hydrogen atom; an alkyl group having 1 to 3 carbon atoms; or an alkoxy group having 1 to 3 carbon atoms; And R3 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, R4 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; R5 represents a hydrogen atom, a methyl group or an alkoxy group having 1 to 3 carbon atoms, R6 represents a hydrogen atom, a methyl group or a oxy group having 1 to 3 carbon atoms, R7 represents a hydrogen atom, a methyl group or a carbon number of 1 to 3 Alkoxy group, R8 represents a hydrogen atom, a methyl group or an alkoxy group having 1 to 3 carbon atoms, and the compound represented by the formula (1) is present in the presence of an ammonium salt, an inorganic base and an alcohol compound. Compound reaction represented by formula (2)

(wherein R1, R2, R3, R4, R5, r6, r7 and r8 each have the same meaning as described above)

X

(2) In the formula, the method of producing the alcohol compound is at least one selected from the group consisting of a secondary alcohol and a tertiary alcohol. -6 - 201100395 &lt;3&gt; The method of producing &lt;1&gt; or &lt;2&gt; by mixing the compound represented by the formula (1), the compound represented by the formula (2), the money salt and the alcohol The compound is subjected to a reaction, and the reaction is further carried out by mixing the obtained mixture with an inorganic test group, and the method of any one of <1> to <3>, wherein the method of any one of &lt;1&gt; The method of any one of <1> to <4>, wherein the ammonium salt is a tetrabasic halide; &lt;6&gt; a diepoxide compound of the formula (4),

(wherein R 2Q represents a hydrogen atom or a methyl group, R21 represents a hydrogen atom or a methyl group, R22 represents a hydrogen atom or a methyl group, R23 represents a hydrogen atom or a methyl group, r24 represents a hydrogen Q atom or a methyl group, R25 represents a hydrogen atom or Methyl, R20 represents a hydrogen atom or a methyl group, and R27 represents a hydrogen atom or a methyl group. However, the number of methyl groups bonded to the benzene ring is 2, 3 or 4) in total. [Embodiment] [Best Mode for Carrying Out the Invention] First, a compound represented by the formula (1) (hereinafter simply referred to as a compound (1)) is characterized by the presence of an ammonium salt, an inorganic base, and an alcohol compound. A method for producing a diepoxy compound represented by the formula (3) obtained by reacting a compound represented by the formula (2) (hereinafter referred to simply as the compound (2)) (hereinafter referred to as a bicyclo201100395 oxy compound (3)) will be described. .

(wherein R1 represents a hydrogen atom, a hospital group having a carbon number of 1 to 3, or a oxy group having 1 to 3 carbon atoms; R2 represents a hydrogen atom; an alkyl group having 1 to 3 carbon atoms; or an alkoxy group having 1 to 3 carbon atoms; And R3 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, R4 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; R5 represents a hydrogen atom, a methyl group or an alkoxy group having 1 to 3 carbon atoms, R6 represents a hydrogen atom 'methyl group or an alkoxy group having 1 to 3 carbon atoms, and R7 represents a hydrogen atom, a methyl group or a carbon number of 1 to 3. Alkoxy, R8 represents a hydrogen atom, a methyl group or an alkoxy group having 1 to 3 carbon atoms

(2) (wherein, X1 represents a halogen atom

(3) (wherein R1, R2, R3, R4, R5, and r6' are shown to have the same meanings as defined above.) Alkyl groups having 1 to 3 carbon atoms in R1, R2, R3 and R4 In terms of methyl group, ethyl 'propyl group and isopropyl group', a methyl group is preferred.

The alkoxy groups of R1, R2, R3, R4, R5, R6, and R7 and the carbon number i to 3 in the uldent 8 may, for example, be a methoxy group, an ethoxy group, a propoxy group or an isopropoxy group. 8- 201100395 and methoxy is preferred. R1, R2, R3, R4, R5, R6, R7 and R8 are each independently a hydrogen atom, a methyl group or a decyloxy group, and a hydrogen atom or a methyl group is more preferred. Examples of the compound (1) include 1,4-phenylene-bis(4-hydroxybenzoate) and 1,4-phenylene-bis(4-hydroxy-2-methylbenzoate). ), 1,4-phenylene-bis(4-hydroxy-3-methylbenzoate), 1,4-phenylene-bis(4-hydroxy-3,5-dimethylbenzate) Acid ester) 0, 1,4-phenylene-bis(4-hydroxy-2,6-dimethylbenzoate), 2-methyl-1,4-phenylene-bis(4-hydroxyl) Benzoate), 2-methoxy-1,4-phenylene-bis(4-hydroxybenzoate), 2-methyl-1,4-phenylene-bis(4-hydroxy-) 2-methylbenzoate), 2-methyl-1,4-phenylene-bis(4-hydroxy-3-methylbenzoate), 2-methyl-1,4-benzobenzene Base-bis(4-hydroxy-3,5-dimethylbenzoate), 2-methyl-1,4-phenylene-bis(4-hydroxy-2,6-dimethylbenzoic acid) Ester), 2,6-dimethyl-1,4-phenylene-bis(4-hydroxybenzoate), 2,6-dimethyl-I,4-phenylene-bis(4- Hydroxy-3-methylbenzate), 2,6-dimethyl-1,4-phenylene-bis(4-hydroxy-3,5-dimethylbenzoate), 2, 3,6-trimethyl-1,4-phenylene-bis(4-hydroxybenzoate), 2,3,6-trimethyl -1,4-phenylene-bis(4-hydroxy-2,6-dimethylbenzoate), 2,3,5,6-tetramethyl-1,4-phenylene-bis ( 4-hydroxybenzoate), 2,3,5,6-tetramethyl-1,4-phenylene-bis(4-hydroxy-3-methylbenzoate) and 2,3,5 , 6-tetramethyl-1,4-phenylene-bis(4-hydroxy-3,5-dimethylbenzoate). Among them are 1,4-phenylene-bis(4-hydroxybenzoate), 1,4-phenylene-bis(4-hydroxy-2-methylbenzoate), 2-methyl -1,4-phenylene--9 - 201100395 bis(4-hydroxybenzoate), 2·methoxy-1,4_phenylene-bis(4-hydroxybenzoate), 2 -methyl-1,4-phenylene-bis(4-hydroxy-2-methylbenzoate), 2-methyl-1,4-phenylene-bis(4-hydroxy-3-methyl) Benzoate), 2,6-dimethyl-1,4-phenylene-bis(4-hydroxybenzoate), 2.3.6-trimethyl-I,4·phenylene- Preferably, bis(hydroxybenzoate) and 2.3.5.6-tetramethyl-1,4-phenylene-bis(4-hydroxybenzoate) are preferred. The compound (1) can be used commercially, and can also be used as Macromol.

Manufacturers of known methods such as the methods described in Chem. Phys. 1 99, 8 5 3 - 8 5 9 (1 998). In the formula (2), the halogen atom represented by χ1 may, for example, be a chlorine atom or a bromine atom, and preferably a chlorine atom. Examples of the compound (2) include epichlorohydrin and epibromohydrin, and epichlorohydrin is preferred. The compound (2) is used in an amount of usually 2 to 200 moles, preferably 5 to 150 moles, per mole of the compound (1). Examples of the ammonium salt include tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, and benzoic acid. Tributylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, four a 4-grade ammonium halide such as methyl ammonium iodide, tetraethyl ammonium iodide, tetrabutyl ammonium iodide or benzyl tributyl ammonium iodide, and tetrabutylammonium bromide and benzyl three Ammonium methyl bromide is preferred. It is also possible to mix two or more kinds of ammonium salts. The amount of the saddle salt to be used is usually 0.000 1 to 1 mol, preferably 0.001 to 0.5 mol, per mol of the compound (1). -10- 201100395 Examples of inorganic bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate, and alkali metal hydroxides. Preferably, sodium hydroxide and potassium hydroxide are preferred. It is also possible to mix two or more inorganic bases. The amount of the inorganic base to be used is usually 0.1 to 20 moles, preferably 0.5 to 10 moles, per mole of the compound (1). An inorganic group in a solid form such as a granular form may be used, and an inorganic base in the form of an aqueous solution having a concentration of about 10 to about 60% by weight may also be used. In the case of the alcohol compound, a secondary alcohol and a tertiary alcohol are preferred, a tertiary alcohol is preferred, and a tertiary alcohol having a carbon number of 4 to 10 is particularly preferred. Specific examples thereof include 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 2-octyl alcohol, and 4-indole. Alcohol, 2-dodecanol, 3-methyl-2-butanol, 3,3-dimethyl-2-butanol, 3-methyl-2-pentanol, 5-methyl-2-hexanol Alcohol, 4-methyl_3_heptanol, 2-methyl-2-propanol, 2-methyl-2-butanol, 2,3-dimethyl-2-butanol, 2-methyl- 2-pentanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 2,3-dimethyl-Q 3-pentanol, 3-ethyl-2,2-dimethyl Base-3-pentanol, 2-methyl-2-hexanol and 3,7-dimethyl-3-octanol. The amount of the alcohol compound to be used is usually 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 1 to 50 parts by weight, per part by weight of the compound (1). It can be used by mixing two or more alcohol compounds. The reaction of the compound (1) with the compound (2) is usually carried out by mixing the compound (1), the compound (2), an alcohol compound, an ammonium salt and an inorganic base. Wherein the reaction is preferably carried out by mixing the compound (1), the compound -11 - 201100395 (2), an ammonium salt and an alcohol compound, and further reacting the mixture by mixing the obtained mixture with an inorganic base. It is better. The reaction can be carried out in the presence of a solvent, and examples of the solvent include a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, N,N-dimethylformamide, hydrazine, hydrazine-dimethyl methacrylate. Aprotic amine, Ν-methylpyrrolidone, acetonitrile, benzonitrile, dimethyl hydrazine and other aprotic polar solvents and diethyl ether, tert-butyl methyl ether, 1,2-dimethoxy An ether solvent such as ethane, 1,4-dioxane, tetrahydrofuran or anisole is preferred, and an aprotic polar solvent is preferred. Compound (2) can be used as a solvent. In the reaction temperature, when the alcohol compound is a liquid, the alcohol compound can be used as a solvent. The solvent can be used in an amount of two or more kinds of the hydrazine solvent, and is usually 0.01 to 100 parts by weight, preferably 0.1 to 50 parts by weight, per part by weight of the compound (1). The reaction can be carried out under normal pressure conditions, under pressurized conditions, or under reduced pressure. The reaction can also be carried out under an atmosphere of an inert gas such as nitrogen or argon. The reaction temperature is usually - 20 ° C to 150 ° C, preferably - l ° ° C to 120 °. (: The progress of the hydrazine reaction can be confirmed by a general analytical method such as liquid chromatography. The reaction time is usually 0.5 to 7 2 hours. When the compound (1), the compound (2), the ammonium salt and the alcohol are mixed by mixing The reaction is carried out by the compound, and when the reaction is further carried out by mixing the obtained mixture with an inorganic test group, the temperature system of the compound (1), the compound -12-201100395 (2), the ammonium salt and the alcohol compound is mixed. It is preferably -1 0 °C to 1 5 (TC is preferred, (TC~1 20t is more preferable. The temperature at which the obtained mixture is mixed with the inorganic base is preferably -2 0 °C to 1 2 0 °C, - 1 〇t~8 0 ° C is more preferable. After the reaction is finished, for example, the reaction mixture can be mixed with water and, if necessary, with a water-insoluble solvent, and after stirring, a bicyclic ring is obtained by liquid separation. The organic layer of the oxygen compound (3). After the obtained organic layer is washed with water, the insoluble component can be removed by filtration if necessary, and the diepoxide compound (3) can be taken out by concentration. The diepoxy compound (3) can be further purified by a general purification method such as recrystallization. One-step purification. In terms of the diepoxy compound (3), I, 4-phenylene-bis{4-(2,3·epoxypropoxy)benzoate}, I, 4- Phenyl-bis{4-(2,3-epoxypropoxy)-2-methylbenzoate}, 1,4-phenylene-bis{4- (2,3-epoxy) Propyloxy)-3-methylbenzoate}, 1,4-phenylene-bis{4-(2,3-epoxypropoxy)-3,5-dimethylbenzene Q Formate}, 1,4-phenylene-bis{4-(2,3-epoxypropoxy)-2,6-dimethylbenzoate}, 2-methyl-1, 4-phenyl-bis(4-(2,3-epoxypropoxy)benzoate}, 2-methoxy-1,4-phenylene-double {4-(2,3 -epoxypropoxy)benzoate}, 2-methyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)-2-methylbenzene Acid ester}, 2-methyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)-3-methylbenzoate}, 2-methyl-1 , 4-phenylene-bis{4_(2,3-epoxypropoxy)-3,5-dimethylbenzoate}, 2-methyl-1,4-phenylene-double {4-(2,3-Epoxypropoxy)-2,6-dimethylbenzoate}, 2,6-dimethyl-1,4-phenylene-double {4- ( 2,3-epoxy-13- 201100395 Benzoate}, 2,6-dimethyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)-3-methylbenzoate} 2,6-Dimethyl-I,4-phenylene-bis{4-(2,3-epoxypropoxy)-3,5-dimethylbenzoate}, 2,3 ,6-trimethyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)benzoate}, 2,3,6-trimethyl-1,4 -Phenyl-bis{4-(2,3-epoxypropoxy)-2,6-dimethylbenzoate}, 2,3,5,6-tetramethyl-1,4 -Phenyl-bis{4-(2,3-epoxypropoxy)benzoate}, 2,3,5,6-tetramethyl-1,4-phenylene-double {4 - (2,3-epoxypropoxy)-3-methylbenzoic acid f ester} and 2,3,5,6-tetramethyl-1,4-phenylene-double {4- ( 2 , 3-epoxypropoxy)-3,5-dimethylbenzoate}. Among them, 1,4-phenylene-bis{4-(2,3-epoxypropoxy)benzoate}' 1,4-phenylene-bis{4-(2,3- Epoxypropoxy)-2-methylbenzoate}, 2-methyl-1,4-phenylene-bis{4_(2,3-epoxypropoxy)benzoate }, 2-methoxy-1,4-phenylene-bis{4-(2,3-epoxypropoxy)benzoate}, 2-methyl-1,4-phenylene -Bis{4-(2,3-epoxypropoxy)_2-methylbenzoate}, 2-methyl-I,4-phenylene-bis{4-(2,3- | Epoxypropoxy)-3-methylbenzoate}, 2,6-dimethyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy) Benzoate}, 2,3,6-trimethyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)benzoate} and 2,3, 5,6-Tetramethyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)benzoate} is preferred. Further, among the diepoxy compound (3), the diepoxy compound represented by the formula (4) is a novel compound and is excellent in solubility to methyl isobutyl ketone. -14- 201100395

(wherein R 2° represents a hydrogen atom or a methyl group, R21 represents a hydrogen atom or a methyl group, R22 represents a hydrogen atom or a methyl group, R23 represents a hydrogen atom or a methyl group, R24 represents a hydrogen atom or a methyl group, R25 represents a hydrogen atom or Methyl, R26 represents a hydrogen atom or a methyl group, and R27 represents a hydrogen atom or a methyl group. However, the number of methyl groups bonded to the benzene ring is 2, 3 or 4 in total. [Examples] The invention is specifically described by way of examples and comparative examples, but the invention is not limited to the examples. [Example 1] In a reaction vessel with a cooling device, 2-methyl-1,4-phenylene-bis(4-hydroxybenzoate) 2.00 g, tetrabutylammonium bromide. 08 8g' 17.2mL of epichlorohydrin and 17.2mL of 2-methyl-2-propanol were mixed at about 25 °C. The resulting mixture was stirred at 7 ° C for 12 hours and then cooled to room temperature. To the resulting mixture, a 45% by weight aqueous sodium hydroxide solution of 4·40 g was slowly added. The resulting mixture was stirred at room temperature for 3 hours. After the resulting reaction mixture was cooled to 0 ° C, 10 mL of a 10% by weight aqueous solution of chlorinated solution was added. Further, 50 mL of ion-exchanged water was added. The resulting mixture was extracted with chloroform (1 mL) to give an organic layer and an aqueous layer. After the organic layer was washed three times with ion-exchanged water, the insoluble components in the obtained organic layer were removed by filtration to -15-201100395. The obtained filtrate was concentrated to give a crude product. To the obtained crude product, toluene and 2-propanol were added. The resulting mixture was cooled to room temperature and allowed to stand overnight. The precipitated solid was taken out by filtration and washed with 2-propanol and dried to give 2 _methyl-1,4-phenylene-bis{4 ·(2,3-epoxypropyl)benzene. Formate white crystal 丨· 8 8 g. The crystals were analyzed by liquid chromatography to have a purity (area percentage) of 9 5 · 9 %. The purity is assumed to be the content of 2-methyl-indole, 4-phenylene-bis{4-(2,3-epoxypropyl)benzoate} in the crystal, and the yield is calculated. Yield: 6.9 % (based on 2-methyl-1,4-phenylene-bis(4-hydroxybenzoate)). [Example 2] In a reaction vessel with a cooling device, 2-methyl-1,4-phenylphenyl-bis(4-hydroxybenzoate) 2.00 g, tetramethylammonium bromide. 42 g of hydrazine, 17.2 mL of epichlorohydrin and 17.2 mL of 2-methyl-2-propanol were mixed at about 25 °C. The resulting mixture was stirred at 70 ° C for 7 hours and then cooled to room temperature. To the resulting mixture, 4.40 g of a 15 wt% aqueous sodium hydroxide solution was slowly added. The resulting mixture was stirred at room temperature for 3 hours. The obtained reaction mixture was treated in the same manner as in Example 1 to obtain white of 2-methyl-1,4-phenylphenyl-bis{4-(2,3-epoxypropyl)benzoate}. Crystallized 1.68 g. The crystal was analyzed by liquid chromatography to obtain a purity (area percentage) of 94.9%. The purity is assumed to be the content of 2-methyl-1,4-phenylene-bis{heart (2,3-epoxypropyl)benzoate} in the crystal, and the yield is calculated. Yield: 60% (based on 2-methyl-1,4-phenylene-bis(4-hydroxybenzoic acid -16 - 201100395 ester)). [Example 3] 2-methyl-1,4-phenylene-bis(4-hydroxybenzoate) 2.00 g, benzyltrimethyl bromide was added to a reaction vessel equipped with a cooling device 0.063 g of ammonium, 17.2 mL of epichlorohydrin and 17.2 mL of 2-methyl-2-propanol were mixed at about 25 °C. The resulting mixture was stirred at 7 ° for 13 hours and then cooled to room temperature. To the resulting mixture, 4.40 g of a 15 wt% aqueous sodium hydroxide solution was slowly added. The resulting mixture was stirred at room temperature for 3 hours. The obtained reaction mixture was treated in the same manner as in Example 1 to obtain white of 2-methyl-1,4-phenylphenyl-bis{4-(2,3-epoxypropyl)benzoate}. Crystallization 1 · 5 1 g. The crystal was analyzed by liquid chromatography to obtain a purity (area percentage) of 9 5 · 6 %. The purity is assumed to be the content of 2-methyl-1,4-phenylphenyl-bis{4-(2,3-epoxypropyl)benzoate in the crystal, and the yield is calculated. Yield: 55% (based on 2-methyl-1,4-phenylene-bis(4-hydroxybenzate)). [Example 4] In a reaction vessel with a cooling device, 2-methyl-1,4-phenylene-bis(4-hydroxybenzoate) 2.00 g, tetrabutylammonium chloride. 〇76g, epichlorohydrin 17.2mL and 2-methyl-2-propanol 17.2mL were mixed at about 25 °C. The resulting mixture was stirred at 70 ° C for 7 hours and then cooled to room temperature. To the resulting mixture, 4.40 g of a 15 wt% aqueous sodium hydroxide solution was slowly added. The resulting mixture was stirred at room temperature for 3 hours. The obtained counter--17-201100395 mixture was treated in the same manner as in Example 1 to obtain 2-methyl-:I,4-phenylene-bis{4-(2,3-epoxypropyl)benzene. The white crystal of the formate) was 1. 7 8 g. The crystals were analyzed by liquid chromatography to obtain a purity (area percentage) of 97.5%. The purity is assumed to be the content of 2-methyl-oxime, phenyl-bis{4-(2,3-epoxypropyl)benzoate} in the crystal, and the yield is calculated. Yield: 68% (based on 2-methyl-I,4-phenylene-bis(4-hydroxybenzoate)). [Example 5] In a reaction vessel with a cooling device, 2-methyl-hydrazine, 4-phenylene-bis(4-hydroxybenzoate) 2.00 g, tetrabutylammonium iodide 0 .i 〇 lg, 17.2 mL of epichlorohydrin and 17.2 mL of 2-methyl-2-propanol were mixed at about 25 X: The resulting mixture was stirred at 70 T for 10 hours and then cooled to room temperature. To the resulting mixture was slowly added a 45% by weight aqueous sodium hydroxide solution of 4·40 g. The resulting mixture was stirred at room temperature for 3 hours. The obtained reaction mixture was treated in the same manner as in Example 1 to obtain white of 2-methyl-L.sup.-.sup.-succinyl-bis{4-(2,3-epoxypropyl)benzoate. Crystallization 1 · 7 5 g. The crystals were analyzed by liquid chromatography to obtain a purity (area percentage) of 9 7 _ 5 %. The purity is assumed to be the content of 2-methyl-oxime, 4-phenylene-bis{4-(2,3-epoxypropyl)benzoate} in the crystal, and the yield is calculated. Yield: 67% (based on 2-methyl-I,4-phenylene-bis(4-hydroxybenzoic acid vinegar)). [Example 6] -18- 201100395 In a reaction vessel with a cooling device, 2-methyl-1,4-phenylene-bis(4-hydroxybenzoate) 2.00 g 'tetrabutyl bromide Ammonium 〇. 〇 88 g, epichlorohydrin 17.2 mL, and 2-methyl-2-propanol 17.2 mL were mixed at about 25 °C. The resulting mixture was stirred at 70 ° C for 7 hours and then cooled to room temperature. To the resulting mixture, 4.40 g of a 15 wt% aqueous sodium hydroxide solution was slowly added. The resulting mixture was stirred at room temperature for 4 hours. The obtained reaction mixture was treated in the same manner as in Example 1 to obtain white of 2-methyl-1,4-de-Q-phenyl-bis{4_(2,3-epoxypropyl)benzoate}. Crystallized 1. 5 4 g. The crystal was analyzed by liquid chromatography to obtain a purity (area percentage) of 97.11%. The purity is assumed to be the content of 2-methyl-1,4-phenylene-bis{4-(2,3-epoxypropyl)benzoate in the crystal, and the yield is calculated. Yield: 59% (based on 2-methyl-1,4-phenylene-bis(4-hydroxybenzoate)). [Example 7] 2-methyl-1,4-phenylene-bis(4-hydroxybenzoate) 2.00 g of tetrabutylammonium bromide was added to a reaction vessel equipped with a cooling device. 8 8 g, epichlorohydrin 17.2 mL and 2-butanol 17.2 mL were mixed at about 25 °C. The resulting mixture was stirred at 70 ° C for 7 hours and then cooled to room temperature. To the resulting mixture, 4·40 g of a 15 wt% aqueous sodium hydroxide solution was slowly added. The resulting mixture was stirred at room temperature for 4 hours. The obtained reaction mixture was treated in the same manner as in Example 1 to obtain white of 2-methyl-1,4-phenylphenyl-bis{4-(2,3-epoxypropyl)benzoate}. Crystallization 1.44 g. The crystal was analyzed by liquid chromatography to obtain a purity (area percentage) of 97.8%. -19- 201100395 Assuming that the purity is the content of 2-methyl-1,4-phenylene-bis{4 epoxypropyl)benzoate in the crystal, the yield is calculated. Horse-producing (based on 2-methyl-1,4-phenylene-bis(4-hydroxybenzoate) [Comparative Example 1] 2-methyl- in a reaction vessel with a cooling device 1 base-bis(4-hydroxybenzoate) 2.00 g, tetrabutylammonium bromide, epichlorohydrin 1 7.2 m L was mixed at about 25 ° C. After stirring the resulting mixture for 12 hours, The mixture was cooled to room temperature, and 4.4 g of a 15 wt% aqueous sodium hydroxide solution was slowly added to the resulting mixture, and the resulting mixture was stirred at room temperature for 3 hours. The resulting reaction mixture was treated with Example 1 to give 2- The white crystal of methyl-1,4-phenylphenyl-bis{4-(2,3-cyclo)benzoate} was 0.86 g. By liquid chromatography, the purity (area percentage) was 90.8%. Assuming the content of 2-methyl-1,4-phenylene-bis{4-(2,3-epoxypropanecarboxylate) in the pure crystal, the yield was calculated. Yield: 33% (based on 2-methylphenyl-bis(4-hydroxybenzoate)) [Comparative Example 2] In a reaction vessel with a cooling device, 'addition at room temperature: I,4-extension Phenyl-bis(4-hydroxybenzoate) 2. 〇〇g, benzylammonium bromide 0.0 3 8 g And epichlorohydrin 8.6 m L. The resulting mixture was stirred under the conditions for 3 5 minutes. To the resulting mixture, 2.9 3 g of a 15 wt% aqueous sodium solution was added, and the mixture was further stirred for 35 minutes. 3-S: 5 5% quasi-), 4-extended benzene. 〇 42g and in 7〇 °C, the mild mixture is similarly oxypropylated to the degree of the base) phenyl-1,4-: _ Methyl-trimethyl reflux bar: % Hydrogen-oxygen mixture -20- 201100395 After cooling to room temperature, 25 mL of ion-exchanged water &amp; 25 mL of epichlorohydrin was added. After stirring the resulting mixture, the organic layer was separated. The organic layer was washed twice with water ion 2 5 m L, and then concentrated to obtain a crude product. The obtained crude product was recrystallized using toluene and 2-propanol to obtain 2-methyl-. 4-Phenyl-bis-{4_(2,3-epoxypropyl)benzoate} white crystals 1.1.3 g. By crystal analysis by liquid chromatography, purity (area percentage) was obtained. Q is 89.6%. It is assumed that the purity is the content of 2-methyl-1,4-phenylphenyl-bis{4-(2,3-epoxypropyl)benzoate in the crystal. The amount was calculated. Yield: 39% (based on 2-methyl-1,4-phenylene-bis(4-hydroxybenzoate)) [Reference Example 1] with Dean-Stark (Dean In the reaction vessel of the -Stark) apparatus, 39.22 g of 4-hydroxy-3-methylbenzoate, 16.00 g of methyl hydroquinone, cesium sulfate 63 g, and 1 1.6 mL of xylene were mixed at about 25 Torr. The resulting mixture was stirred under reflux for 1 hour and then cooled to room temperature. The water produced with the progress of the reaction was continuously removed from the reaction system using a Dean-stark apparatus. The solid precipitated in the reaction mixture was taken out by filtration, washed with methanol 300 mL, and then dried under reduced pressure at 5 ° C for 4 hours to give 2-methyl-1,4-phenylene-bis(4- Thin gray crystals of hydroxy-3-methylbenzoate 41.2 1 g. The crystal was analyzed by liquid chromatography to obtain a purity (area percentage) of 9 6.3%. The purity was assumed to be the content of 2-methyl-1,4-phenylene-bis-21 - 201100395 (4-hydroxy-3-methylbenzoate) in the crystal, and the yield was calculated. Yield · 78% (based on methyl hydroquinone). 'H-NMR (6: ppm, dimethyl hydrazine-d6) 1 〇 48 (br, 2H), 7.75-7.95 (c, 4H), 6.82-7.32 (c, 5H), 1.90-2.30 (c, 9H) [Example 8] In a reaction vessel with a cooling device, 2-methyl-154-phenylphenyl-bis(4-hydroxy-3-methylbenzoate) 2.00 g, tetramethyl 0.039 g of ammonium bromide, 15.9 mL of epichlorohydrin and 1 5 mL of 2-methyl-2-propanol were at about 25. (: Mixing. The resulting mixture was stirred at 70 ° C for 7 hours, and then cooled to room temperature. In the obtained mixture, slowly added: 7.5 wt% aqueous sodium hydroxide solution 4.07 g. Stir at room temperature The resulting mixture was stirred for 5 hours. After the addition of 15% by weight aqueous sodium hydroxide solution, 4 1 g of the obtained mixture was stirred for 2 hours. After the addition of 15% by weight aqueous sodium hydroxide solution (95 g) was further added to the obtained mixture. After stirring for 30 minutes, 0.41 g of a 15% by weight aqueous sodium hydroxide solution was further added to the resulting mixture, and the mixture was stirred for 30 minutes. After the obtained reaction mixture was cooled to 0 ° C, 1% by weight of ammonium chloride was added. The aqueous solution was extracted with chloroform (100 ml) to obtain an organic layer and an aqueous layer. After washing the organic layer three times with ion-exchanged water, the insoluble component was removed by filtration. Concentration to give a crude product containing 2-methyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)-3-methylbenzoate}. Toluene and 2-propanol are added to the crude product. -22- 201100395 The mixture was cooled to room temperature' and allowed to stand overnight. The precipitated solid was taken out by filtration, washed with 2-propanol, and dried to obtain 2-methyl-1,4-extension. White crystal of phenyl-bis{4_(2,3-epoxypropoxy)-3-methylbenzoate} 1. 8 8 g. The crystal was analyzed by liquid chromatography to obtain purity ( The area percentage) is 95.6 %. It is assumed that the purity is 2-methyl-1,4-phenylphenyl-bis{4-(2,3-epoxypropoxy)-3-methyl in the crystal. The content of benzoate} is 0. Yield: 73% (by 2-methyl-1,4-phenylene-bis(4-hydroxy-3-methylbenzoate) Benchmark) 1 H-NMR ( δ : ppm, CDC13 ) 7.92 - 8 . 1 9 ( c, 4 Η ) , 7.02-7.25 ( c, 3 Η ) , 6.8 0 - 7 · 0 0 ( c, 2 Η ) , 4 · 2 7-4 · 49 ( c, 2Η ), 3.95-4. 1 8 ( c, 2 Η ) , 3.3 5 - 3 · 5 5 ( c, 2 Η ) - 2.90- 3.09 ( c, 2H ) , 2.75 -2.8 7 ( c,2H ) , 2.32 ( s,6H ), 2.24 ( s,3H ) 〇 [Reference Example 2] In the reaction vessel with the Dean-Stark device, 4 _hydroxy-2-methylbenzoin 49.03g, 20.00 g of methyl hydroquinone, and 1 .58g sulfate 139.5mL be mixed xylenes at about 25 ° C. The resulting mixture was stirred under reflux for 6 hours and then cooled to room temperature. The water produced with the progress of the reaction was continuously removed from the reaction system using a Dean-Stark apparatus. The solid precipitated from the reaction mixture was taken out by filtration, washed with methanol 2600 mL, and then at 50. (: Drying under reduced pressure for 4 hours gave 2-methyl-1,4-phenylene-bis(4-hydroxy-2-methyl-23- 201100395 benzoate) as a white crystals of 3.7 g. The crystal was analyzed by liquid chromatography to obtain a purity (area percentage) of 99.0%. It is assumed that the purity is 2-methyl-1,4-phenylene-bis(4-hydroxy-2-methyl) in the crystal. The yield of the benzoic acid ester was calculated. Yield: 84% (based on methyl hydroquinone) W-NMRC 5 : ppm, dimethyl sub-grinding - d6) 10.37-10.42 ( c,2H ), 7.95-8. 13 ( c,2H ) ,7 _ 0 6 - 7.2 8 ( c,3 Η ) , 6.70- 6.82 (c,4H) - 2.53 ( s - 6H ) , 2.17(s, 3H) [Example 9] In a reaction vessel with a cooling device, 2-methyl-1,4-phenylene-bis(4-hydroxy-2-methylbenzoate) was 20.OOg, 0,822 g of tetrabutylammonium bromide, 159.5 mL of epichlorohydrin and 159.5 mL of 2-methyl-2-propanol were mixed at about 25 °C. The resulting mixture was stirred at 70 ° C for 7 hours and then cooled to 18 ° C. To the resulting mixture, 40.77 g of a 15 wt% aqueous sodium hydroxide solution was slowly added, and the resulting mixture was stirred at 18 ° C for 3 hours. After cooling the resulting reaction mixture to 〇 ° C, 300 mL of a 10% by weight aqueous solution of chlorinated solution was added. To the resulting mixture, 500 mL of ion-exchanged water was added, and extracted with chloroform (1 mL). After the obtained organic layer was washed three times with ion-exchanged water, the insoluble matter was removed by filtration. The obtained filtrate was concentrated to give a crude product containing 2-methyl-1,4-phenylphenyl-bis{4-(2,3-epoxypropoxy)-2-methylbenzoate}. . Toluene and 2-propanol were added to the obtained crude product. The resulting mixture was cooled to room temperature and allowed to stand overnight. The precipitated solid was taken out by filtration from -24 to 201100395, washed with 2-propanol, and then dried to obtain 2-methyl-1,4-phenylene-bis{4-(2,3-ring). White crystal 2 2.0 6 g of oxypropoxy)-2-methylbenzoate}. The crystal was analyzed by liquid chromatography to obtain a purity (area percentage) of 97.8%. It is assumed that the purity is the content of 2-methyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)-2-methylbenzoate} in the crystal. Calculate the yield. Yield: 85% (based on 2-methyl-I,4-phenylene-bis(4-hydroxy-2-methylbenzoate)). 'H-NMR ( &lt;5 : ppm, CDC13 ) 8_ 12-8.27 ( c, 2H ) &gt; 7.02-

7.22 ( c,3H) , 6.79-6.93 ( c,4H ), 4.28-4.41 ( c,2H ), 3.95-4.12 ( c,2H ) ,3 · 3 3 - 3 · 4 5 ( c,2 Η ) &gt 2.90- 2.98 (c,2Η) , 2.7 5 -2.85 ( c,2H ) , 2.66 ( s,6H ), 2.25 ( s,3H ) [Reference Example 3] 附 with Dean Stark (Dean In a reaction vessel of the -stark apparatus, 8.69 g of 4-hydroxy-2-methylbenzoic acid, 14.00 g of hydroquinone, 0.62 g of sulfuric acid and 97.7 mL of xylene were mixed at about 25 °C. The resulting mixture was stirred at reflux for 3 hours and then cooled to room temperature. The water produced along with the reaction was continuously removed from the reaction system using a Dean-Stark apparatus. The solid precipitated in the reaction mixture was taken out by filtration and washed with 300 mL of 2-propanol, and then dried at 5 (TC under reduced pressure for 4 hours) to obtain 1,4-phenyl-bis(4-hydroxy-2- 42.73g of thin gray crystal of methyl benzoate) -25- 201100395 The purity (area percentage) of the crystal obtained by liquid chromatography is 93.9%. It is assumed that the purity is 1,4- in the crystal. The content of phenyl-bis(4-hydroxy-2-methylbenzoate) was calculated as the yield. Yield: 83% (hydroquinone basis) H-NMRC (5: ppm, dimethyl基亚磨_d6) 10.34(br' 2H) ' 8.01 ( dd &gt; 2H ) , 7.29 (s' 4H ) ' 6.68-6.87 (c,4H), 2_52(s,6 Η ) [Example ίο] In the reaction vessel with a cooling device, 'I4-phenyl-bis(4-hydroxy-2-methylbenzoate) 2.00 g, tetrabutylammonium bromide, 85 g, epichlorohydrin 16.5 mL, and 16.5 mL of 2-methyl-2-propanol was mixed at about 25° C. The resulting mixture was stirred at 70 ° C for 7 hours and then cooled to room temperature. In the resulting mixture, 1 5 was slowly added. Weight. / 4. Sodium hydroxide aqueous solution 4.20g The mixture was stirred at room temperature for 3 hours, at 40 ° C for 2 hours, and further at 50 ° C for 3 hours. After the resulting reaction mixture was cooled to 0 ° C, 30 mL of a 1% by weight aqueous solution of ammonium chloride was added. After adding 50 mL of ion-exchanged water to the obtained mixture, the obtained mixture was extracted with 100 mL of chloroform. The obtained organic layer was washed three times with ion-exchanged water, and then the insoluble component was removed by filtration. A crude product containing 1,4 -phenyl-bis-{4_(2,3-epoxypropoxy)-2-methylbenzoic acid vinegar is obtained. Toluene is added to the obtained crude product. 2-propanol. The resulting mixture was cooled to room temperature and allowed to stand overnight. The precipitated solid was taken out by filtration through -26-201100395 and washed with 2-propanol to give white crystals. After adding toluene and 2·propanol, the obtained mixture was cooled to room temperature, and allowed to stand overnight. The precipitated solid was taken out by filtration, washed with 2-propanol, and then dried to obtain 1, White of 4-phenyl-bis(4-(2,3-epoxypropoxy)-2-methylbenzoate} Crystallization i91g. The crystal was analyzed by liquid chromatography to obtain a purity (area percentage) of 93.7%. Assuming that the purity is in the crystal, 4_phenylene-double {4-(0 2,3-ring) Yield of oxypropoxy)-2-methylbenzoate}, yield: 73% (by 1,4-phenylene-bis(4-hydroxy-2-methylbenzene) Formate)). 'H-NMR ( δ : ppm, CDC13 ) 8_ 12-8.25 ( c,2Η ) , 7.25 ( d,4H ) ' 6.76-6.90 ( c,4H ),4.23-4.40 ( c,2H ), 3.95 -4.08 ( c,2H) ,3.3 4-3.45 ( c,2H) , 2.83 -3.00 ( c ' 2H ) , 2.74-2.80 ( c,2H ), 2.66 ( s,6H ) 〇[Reference Example 4] with Dean - In the reaction vessel of the Dean-Stark device, '21.99 g of 4-hydroxybenzoic acid, 2,6-dimethylhydroquinone 丨uog, p-toluenesulfonic acid 1.5 1 g and xylene 1 9 9 m L was mixed at about 25 °C. The resulting mixture was stirred under reflux for 25 hours and then cooled to room temperature. The water produced as the reaction progressed was continuously removed from the reaction system using a Dean-Stark unit. The solid precipitated in the reaction mixture was taken out by filtration, washed with 1000 mL of methanol, and then dried at 5 ° (4 ° under reduced pressure to obtain 2,6-dimethyl-1,4-phenylene group). 15.84 g of a thin gray crystal of bis(4_经-27-201100395 benzoate). The crystal was analyzed by liquid chromatography to obtain a purity (area percentage) of 98.6 %. It is assumed that the purity is in the crystal. The content of 2,6-dimethyl-1,4-phenylene-bis(4-hydroxybenzoate) was calculated, and the yield was 52% (by 2,6-dimethyl pair). Hydroquinone as a reference) H-NMRC &lt;5: ppm, dimethyl hydrazine-d6) 10.53 (br, 2H), 8·00 ( dd, 4H ) , 7.04 ( s, 2H ) , 6.94 ( dd , 4H ) , 2.10 (s, 6H ) [Example 1 1] 2,6-Dimethyl-1,4-phenylene-bis(4-hydroxyphenyl) in a reaction vessel with a cooling device The acid ester) was 2.00 g, tetrabutylammonium bromide, ruthenium 85 g, epichlorohydrin 16.5 mL, and 2-methyl-2-propanol 16.5 mL were mixed at about 25 °C. The resulting mixture was stirred at 70 ° C for 7 hours and then cooled to room temperature. To the resulting mixture, 4.20 g of a 15 wt% aqueous sodium hydroxide solution was slowly added. The resulting mixture was stirred at room temperature for 4 hours and then at 50 ° C for 2 hours. After the obtained reaction mixture was cooled to 0 ° C, 30 mL of a 10% by weight aqueous ammonium chloride solution was added. After 5 mL of ion exchanged water was added to the obtained mixture, the resulting mixture was extracted with 100 mL of chloroform. After the obtained organic layer was washed three times with ion-exchanged water, the insoluble matter was removed by filtration. The obtained filtrate was concentrated to obtain a crude product containing 2,6-dimethyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)benzoate}. Toluene and 2-propanol were added to the obtained crude product. The resulting mixture was cooled to room temperature and allowed to stand overnight. The precipitated solid is taken out by filtration through -28 - 201100395 'washed with 2-propanol and dried to obtain 2,6-dimethyl-I,4-phenylene-bis(2,3-ring) The white crystal of oxypropoxy)benzoate} was 1.4 8 g. The crystal was analyzed by liquid chromatography to obtain a purity (area percentage) of 9 7 · 5 % ° assuming that the purity is 2,6 dimethyl-i,4-phenylene-double {4 in the crystal The content of -(2,3-epoxypropoxy)benzoate} was calculated, and the yield was calculated. Yield: 58% (based on 2,6-dimethyl", phenyl-bis(4-hydroxyl benzoate). !H-NMR ( 5 : ppm - CDC13 ) 8.17 ( dd , 4H), 6.82-7.16 (c '6H) ' 4.25-4.47 ( c, 2H ) , 3.95-4.13 ( c, 2H ), 3.3 2-3.49 ( c, 2H ) - 2.86-3.00 ( c &gt; 2H ) , 2.70-2.84 ( c , 2H ) , 2.20 ( s, 6H ) [Reference Example 5] In a reaction vessel with a Dean-Stark device, 将 '4-hydroxybenzoic acid 21.78g Further, trimethylhydroquinone I 2.00 g, P-toluenesulfonic acid 1-50 g, and xylene 197.1 mL were mixed at about 25 ° C. The resulting mixture was stirred under reflux for 24 hours, and then cooled to room temperature. The reaction was carried out and the resulting water system was continuously removed from the reaction system using a Dean Stark apparatus. The solids precipitated in the reaction mixture were filtered, taken out, and treated with methanol 100 mL. After washing, it was dried under reduced pressure at 50 °C for 4 hours to obtain 25.3 g of a thin gray crystal of 2,3,6-trimethyl-1,4-phenylene-bis(4-hydroxybenzoate). Purity can be obtained by analyzing the crystal by liquid chromatography Area percentage) -29- 201100395 is 98.2%. It is assumed that the purity is the content of 2,3,6-trimethyl-1,4-phenylene-bis(4-hydroxybenzoate) in the crystal. Yield: Yield: 8 1 % (based on trimethylhydroquinone). 'H-NMR ( δ : ppm, DMSO-d6 ) 1 0.54 ( br &gt; 2H ) &gt; 8.02 ( dd , 4H), 6.88-7.09 (c, 5H), 1.93-2.18 (c, 9H) [Example 12] 2,3,6-trimethyl-l,4 in a reaction vessel with a cooling device - phenyl-bis(4-hydroxybenzoate) 2.00 g, tetrabutylammonium bromide ruthenium 〇 82 g &gt; epichlorohydrin 15.9 mL and 2-methyl-2-propanol 15.9 mL at about 25 The mixture was stirred at ° C for 1 hour, and then cooled to room temperature. To the resulting mixture, 4.07 g of a 15% by weight aqueous sodium hydroxide solution was slowly added. The mixture was stirred at room temperature for 3 hours, and further stirred at 40 ° C for 2 hours. After the obtained reaction mixture was cooled to 0 ° C, 3 〇 mL of a 1% by weight aqueous ammonium chloride solution was added, and the resulting mixture was extracted with 10 mL of chloroform. . After the obtained organic layer was washed three times with ion-exchanged water, the insoluble matter was removed by filtration. The obtained filtrate was concentrated to give a crude product containing 2,3,6-trimethyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)benzoate}. Things. Toluene and 2-propanol were added to the obtained crude product. The resulting mixture was cooled to room temperature and allowed to stand overnight. The precipitated solid was taken out by filtration, washed with 2-propanol, and dried to obtain 2,3,6-trimethyl-I,4-phenylene-bis{4-(2,3- ring White crystal of 1.97 g of oxypropoxy)benzoate}. -30- 201100395 The crystal was analyzed by liquid chromatography to obtain a purity (area percentage) of 94.6%. The purity is assumed to be the content of 2,3,6-trimethyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)benzoate} in the crystal. Calculate the yield. Yield: 73% (based on 2,3,6-trimethyl-1,4-phenylene-bis(4-hydroxybenzoate)). 'H-NMR ( δ ppm, CDC13 ) 8 · 1 2 - 8 · 3 7 ( c,4 Η ) ' 6.9 5- 7.17(c,4H) , 6.91(s,1H) ,4.31-4.48 (c,2H ), 0 3.99-4.18 ( c,2H ) , 3.3 6-3.52 ( c,2H ) , 2.8 8-3.07 ( c ,2H) , 2.65-2.86 ( c,2H ) &gt; 2.05-2.35 ( c - 9H ) [Reference Example 6] In a reaction vessel equipped with a Dean-Stark apparatus, 8.31 g of 4-hydroxybenzoic acid, 5.00 g of tetramethylhydroquinone, and 0.57 of p-toluenesulfonic acid were used. 7 and 5 mL of g and xylene were mixed at about 25 °C. The resulting mixture was stirred under reflux for 46 hours and then cooled to room temperature. The water produced with the progress of the reaction was continuously removed outside the reaction system using a Dean-Stark apparatus. The solid precipitated in the reaction mixture was taken out by filtration, washed with methanol (1 mL), and then at 50. (: drying under reduced pressure for 4 hours to obtain 10.65 g of greenish-gray crystals of 2,3,5,6-tetramethyl-1,4-phenylene-bis(4-hydroxybenzoate). The crystals were analyzed and analyzed to obtain a purity (area percentage) of 96.8 %. It is assumed that the purity is 2,3,5,6-tetramethyl-1,4-phenylene-bis(4-hydroxyl) in the crystal. The yield of the benzoate) was calculated. Yield: 8 4% (based on tetramethylhydroquinone) -31 - 201100395 H-NMR (5: pPm, dimethyl hydrazine _ D6 ) ι〇·54 ( &amp;, π ), 8.04 ( d, 4H), 6.95 ( d, 4H), 2.01 ( s, 12H) [Example 1 3 ] In a reaction vessel with a cooling device, 2,3,5,6-tetramethyl-1.4-extension-benzo-bis(4-hydroxybenzoate) 2〇〇g, tetrabutylammonium bromide 0.079g, epichlorohydrin l5.4mL and 2 -Methyl-2-propanol 15.4 mL was mixed at about 25 ° C. The resulting mixture was stirred at 7 ° C for 7 hours and then cooled to i 8 ° C. In the resulting mixture, hydrazine was slowly added. 3.9 4 g of a 5 wt% aqueous sodium hydroxide solution. The resulting mixture was stirred at 8 7 for * hour and then stirred at 40 ° C for 3 hours. To the obtained mixture, 5.4 ml of dimethyl hydrazine was added, and the obtained mixture was stirred at 5 rc for 2 hours, stirred at 6 Torr for 2 hours, at 70 ° C for 3 hours, and then at 8 (rC stirred). After the reaction mixture was cooled to 〇 ° C, '1 〇 wt% aqueous ammonium chloride solution 30 mL was added. After adding 0.5 ml of ion-exchanged water to the obtained mixture, the resulting mixture was chloroform. 1 〇〇m L was extracted. The obtained organic layer was washed three times with ion-exchanged water, and the insoluble matter was removed by filtration. The obtained filtrate was concentrated to obtain 2,3,5,6-tetramethyl-1. , a crude product of 4-phenyl-bis(4-(2,3-epoxypropoxy)benzoate}. Toluene and 2-propanol were added to the obtained crude product. The mixture was cooled to room temperature and allowed to stand overnight. The precipitated solid was taken out by filtration, washed with 2-propanol, and dried to give 2,3,5,6-tetramethyl-1. White crystal of 4-phenyl-bis(4-(2,3-epoxypropoxy)benzoate} 1. 7 3 g. -32- 201100395 The crystal was analyzed by liquid chromatography. Purity (area The percentage) is 9 3 · 5 %. It is assumed that the purity is 2,3,5,6-tetramethyl-1,4-phenylene-bis{4-(2,3-epoxypropane) in the crystal. The yield of the oxy)benzoate} was calculated. Yield: 63% (2,3,5,6-tetramethyl-1,4-phenylene-bis(4-hydroxyphenyl) Acid ester) is the basis). 'H-NMR ( δ ppm - CDC13 ) 8.22 ( d &gt; 4H) , 7.04 ( d -

4H ) , 4.36 ( dd, 2H ) ' 4.04 ( dd, 2H ) , 3.40 ( m &gt; 2H 0 ) , 2.95 (m, 2H) , 2.80 (dd, 2H) &gt; 2.10 (s&gt; 12H) [Reference Example 7] In the reaction vessel with the Dean-Stark device, 21.68 g of 4-hydroxybenzoic acid, 1 l.OOg of methoxy hydroquinone, 1.49 g of p-toluenesulfonic acid 196.2 mL of xylene was mixed at about 25 °C. The resulting mixture was stirred under reflux for 24 hours and then cooled to room temperature. The water produced with the progress of the reaction was continuously removed outside the reaction system using a Dean-Stark apparatus. The solid precipitated from the reaction mixture was taken out by filtration, washed with 13 mL of cyclohexanone and 100 mL of methanol, and then dried under reduced pressure at 50 Torr for 4 hours to obtain 2-methoxy-1,4-benzene. The green-gray crystal of bis-(4-hydroxybenzoate) was 2.79 g. The crystals were analyzed by liquid chromatography to obtain a purity (area percentage) of 94.9%. The purity is assumed to be the yield of 2-methoxy-I,4-phenylene-bis(4-hydroxybenzoate) in the crystal. Yield: 9 % (based on methoxy hydroquinone) ° iH-NMRC &lt;5 : ppm, dimethyl sulfoxide - d6) l 〇.53 (br' 2H), -33- 201100395 7.82 -8.09 ( c &gt; 4H ) &gt; 7.24 ( d - 1 H ) , 7.1 〇 (d, lH), 6.78-7.00 ( c, 5H) , 3.74 ( s ' 3H) [Example 14] with cooling attached In the reaction vessel of the apparatus, 2-methoxy-1,4-phenylene-bis(4-hydroxybenzoate) 2.00 g, tetrabutylammonium bromide 0.08 5 g, epichlorohydrin 16_5 mL and 2 -Methyl-2-propanol 16.5 mL was mixed at about 25 °C. The resulting mixture was stirred at 70 ° C for 7 hours and then cooled to room temperature. To the resulting mixture, 4.20 g of a 15 wt% aqueous sodium hydroxide solution was slowly added. The resulting mixture was stirred at room temperature for 2 hours and 30 minutes. After the obtained reaction mixture was cooled to the end, 100 ml of a 1% by weight aqueous ammonium chloride solution was added. After the mixture was added with 50 ml of ion-exchanged water, the resulting mixture was extracted with 1 mL of chloroform. After the obtained organic layer was washed three times with ion-exchanged water, the insoluble matter was removed by filtration. The obtained filtrate was concentrated to give a crude product containing 2-methoxy-I,4-phenylene-bis{4-(2,3-epoxypropyloxy)benzoate. Toluene and 2-propanol were added to the obtained crude product. The resulting mixture was cooled to room temperature and allowed to stand overnight. The precipitated solid was taken out by filtration and washed with 2-propanol to give white crystals. Toluene and 2-propanol were added to the obtained white crystal. The resulting mixture was cooled to room temperature and allowed to stand overnight. The precipitated solid was taken out by filtration, washed with 2-propanol, and dried to obtain 2-methoxy-1,4-phenylene-bis{4-(2,3-epoxyoxypropoxyl). White crystal of benzoate} 1.15 g. The crystal was analyzed by liquid chromatography to obtain a purity (area percentage) of -34 to 201100395 of 95.7%. The purity is assumed to be the content of 2-methoxy-1,4-phenylene-bis{4-(2,3-epoxypropoxy)benzoate} in the crystal, and the yield is calculated. . Yield: 45% (based on 2-methoxy-1,4-phenylene-bis(4-hydroxybenzoate)). [H-NMR ( 5 : ppm, CDC13 ) 8.09- 8.2 8 ( c, 4H ) , 7.18 ( d, 1H) , 7.02 ( dd, 4H ) , 6 · 7 8 - 6.9 5 ( c, 2 H ) , 4.27 - 4.43 (c, 2H) &gt; 3.95-4. 1 2 ( c &gt; 2H ) , 3.81 (s, 3H), 2H ) , 2.75 -2.8 5 ( c 0 3.32-3.48 ( c, 2H) , 2.89- 3.03, 2H) &lt;Measurement of Solubility&gt; The 2-methyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)-2- obtained in Example 9 was obtained. Methyl benzoate} and 2-methyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)benzoate} at 4 ° C and 65 ° The solubility at the time of C is dissolved in methyl isobutyl ketone (diepoxide compound (g) χίοο / [dioxime epoxy compound (g) + methyl isobutyl ketone (g)], weight%). The results are shown in Table 1. As can be seen from Table 1, the solubility of 2-methyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)-2-methylbenzoate} is more than 2- The solubility of methyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)benzoate} is 11 times or more. -35- 201100395 [Table 1] Solubility (% by weight) 40 ° C 65 °C 2-Methyl-1,4-extension-based-double {4-(2,3- lysyloxypropoxy)_ 2-methylbenzoate} 12.12 28.59 2-methyl-1,4-phenylene-bis{4-(2,3-epoxypropoxy)benzoate} 1.10 2.00 Industrial Usability According to the present invention, a diepoxide compound represented by the formula (3) which is excellent in yield and purity can be produced. Further, the diepoxy compound represented by the formula (4) is excellent in solubility to methyl isobutyl ketone. -36-

Claims (1)

201100395 VII. Patent application scope: A method for manufacturing a diepoxide compound represented by formula (3) Ο 〇 R6 〇 R1 AM R4 R3 R8 R7 R3 R4 (3) (wherein R1 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; R2 represents a hydrogen atom; an alkyl group having 1 to 3 carbon atoms; or a carbon number of 1 to 3 Alkoxy group, R3 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and R4 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms. An oxy group, R5 represents a hydrogen atom, a methyl group or an alkoxy group having 1 to 3 carbon atoms, R6 represents a hydrogen atom, a methyl group or an alkoxy group having 1 to 3 carbon atoms, and R7 represents a hydrogen atom, a methyl group or a carbon number of 1 Alkoxy group of ～3, R 8 represents a hydrogen atom, a methyl group or an alkoxy group having 1 to 3 carbon atoms, and a compound represented by the ammonium salt, an inorganic base and an alcohol compound, and the formula (2) The compound shown is reacted to give formula (1) R6. FU2 R1 R5, R丨 (1) (wherein Ri, R2, R3, and R4 have the same meanings) (2) R7 and R8 each represent the former In the formula, X1 represents a halogen atom. -37-201100395 2 The production method of claim 1 wherein the alcohol compound is at least one selected from the group consisting of a secondary alcohol and a tertiary alcohol. 3. The production method according to claim 1, wherein the reaction is carried out by mixing the compound represented by the formula (1), the compound represented by the formula (2), an ammonium salt and an alcohol compound, and the obtained The mixture is mixed with the inorganic base, and the reaction is further carried out. 4. The production method according to claim 1, wherein the inorganic base is sodium hydroxide or potassium hydroxide. 5. The method of claim 1, wherein the ammonium salt is a 4- to ammonium halide 〇 6 - a diepoxide compound of the formula (4), r20 r21 R24 r25 r21 o20 R\ R/ QK\_/R Qr\_/R R2'3 , r22 R27 'R26 \23 (wherein R2() represents a hydrogen atom or a methyl group, R21 represents a hydrogen atom or a methyl group, and R22 represents a hydrogen atom. Or methyl, R23 represents a hydrogen atom or a methyl group, R24 represents a hydrogen atom or a methyl group, R25 represents a hydrogen atom or a methyl group, R26 represents a hydrogen atom or a methyl group, and R27 represents a hydrogen atom or a methyl group; however, it is bonded to benzene. The number of methyl groups in the ring is 2, 3 or 4) in total. -38- 201100395 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none