TW201130806A - Process for production of glycidyl ether compounds, and monoallyl monoglycidyl ether compound - Google Patents

Abstract

Provided are: a process by which a compound having an allyl ether linkage can be efficiently converted into the corresponding glycidyl ether compound under mild conditions using hydrogen peroxide as the oxidizing agent; and a novel monoallyl monoglycidyl ether compound having a biphenyl skeleton. Specifically provided are: a process for the production of glycidyl ether compounds which comprises reacting a compound having an allyl ether linkage with hydrogen peroxide to epoxidize the carbon-carbon double bond of the allyl group and thus form the corresponding glycidyl ether compound, characterized by using, as the reaction catalyst, a tungsten compound, a tertiary amine, and phenylphosphonic acid; and a monoallyl monoglycidyl ether compound having a biphenyl skeleton. The monoallyl monoglycidyl ether compound can be produced by the process.

Description

201130806 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a methacrylic propyl ether compound which is a epoxidized propyl ether compound. More specifically, the present invention uses a predetermined catalyst to oxidize a carbon-carbon double bond having an allyl ether-bonded compound with hydrogen peroxide, and is characterized by efficient epoxidation. The base ether compound is produced by subjecting the allyl group of the compound having an allyl ether bond to oxidation of hydrogen peroxide to form a monoallyl monoepoxypropane [previous art] as a raw material of the epoxy resin It is widely known to be produced on a large scale and is widely used in various fields. The conventionally known method for producing a glycidyl propyl ether is a method in which phenol is reacted with oxychloropropane under basic conditions in the presence or absence of a catalyst to obtain a glycidyl propyl ether. The organic chlorine compound is inevitably left to be present, and in some applications, for example, in motor applications, there is a disadvantage that the insulating property is lowered. Therefore, the direct epoxidation of the carbon-carbon double bond by the oxidizing agent for the allyl ether was also reviewed. The following patents are disclosed in Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Allyl ether, an organic method in toluene or the like, a monoethylene-based method in which the allylic substance is favorably carried out, and a ketone-carbon double bond-based hydroxy group compound are industrially corresponding alcohols, To make it with the ring, use this in the electrons of the allyl group 1 (曰本特开昭60-ether or phenolic solvent, make -5-201130806 with sodium tungstate and phosphate catalyst, at 4 The method of epoxidation by hydrogen peroxide in the presence of a per-ammonium salt. In this method, the amount of the tungsten compound used must be very large, and the epoxidation rate is not sufficient, and it cannot be implemented as an industrial production method. Patent Document 3 (U.S. Patent No. 5,663,391) discloses the use of an olefin in an organic solvent in the presence of a ruthenium oxide catalyst to cause oxidation with bismuth as an oxidant. a method of epoxidizing an olefin based on an alkyl group, but requiring a high-priced catalyst The oxidizing agent is not sufficient in the production of a phenyl propyl group. Patent Document 4 (Japanese Laid-Open Patent Publication No. Hei. No. 7-145221) and Patent Document 5 (Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei No. Hei. In the No. 8 publication, it is disclosed that the phenol novolak resin is subjected to allyl etherification by a halogenated allyl group, and then epoxidized by a peracid in an organic solvent, and it is necessary to use a high-risk peracid. Further, in the presence of a titanium-containing zeolite catalyst, a tertiary amine, a tertiary amine oxide or a mixture thereof, by the following Patent Document 6 (Japanese Patent Publication No. 2002-526483) A method of epoxidizing hydrogen peroxide. This method is useful when a olefin compound having a small molecular weight is used as a matrix. However, when a matrix having a large molecular weight like a phenyl ether has a poor catalyst efficiency, it is not applicable. [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 10-- No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. 5633391 [Patent Document 4] Japanese Patent Laid-Open No. 7_1 45 22 No. 1 [Patent Document 5] JP-A-58-173118 [Patent Document 6] Japanese Patent Publication No. 2〇〇2·526483 [Contents of the Invention]

[Problem to be Solved by the Invention] The problem to be solved by the present invention is to provide an epoxy propyl ether compound efficiently produced from a compound having an allyl ether bond under mild conditions using hydrogen peroxide as an oxidizing agent. method. At present, there is no report on the synthesis of a monoallyl monoepoxypropyl ether compound having a biphenyl skeleton. The monoallyl monoepoxypropyl ether compound can be hydrogenated by reacting with a compound having a Si-H group by having an allyl group. Further, a compound having various Si-H groups can be introduced into a biphenyl epoxy group. Propyl ether group. For example, in the case of synthesizing an epoxy resin used for a resist or a sealing material, it is considered to be capable of hydrogenation with a sulfonium compound having various Si-H groups, and is considered to be a one-step reaction. It is extremely useful to introduce a biphenyl skeleton having high heat resistance and high etching resistance and an epoxy group necessary for hardening. Therefore, the object of the present invention is to provide a novel monoallyl monoepoxypropyl ether compound having a biphenyl skeleton having high heat resistance and high etching resistance. [Means for Solving the Problem] The inventors of the present invention have found that the use of a tungsten compound, a tertiary organic amine, and a phenylphosphonic acid as a catalyst and a peroxidation by using the results of 201130806, which have been carefully studied and tested. The present invention can be completed by reacting an aqueous hydrogen solution with an allyl ether compound to efficiently produce a correspondingly epoxidized propyl ether compound. That is, the present invention is as follows: [1] A method for producing a glycidyl propyl ether compound by reacting a compound having an allyl ether bond with hydrogen peroxide by using the allyl group A method of producing a corresponding epoxy propyl ether compound by epoxidation of a carbon-carbon double bond is characterized in that a tungsten compound, a tertiary amine, and a phenylphosphonic acid are used as a reaction catalyst. [2] The method for producing a glycidyl propyl ether compound according to the above [1], wherein the tungsten compound is a partially neutralized salt of tungstic acid. [3] The method for producing a glycopropyl ether compound according to the above [1] or [2] wherein the tungsten compound is a mixture of sodium tungstate and tungstic acid, a mixture of sodium tungstate and mineral acid, or tungstic acid and a mixture of base compounds. [4] The method for producing a glycidyl ether compound according to any one of the above [1] to [3] wherein the tertiary amine is a trialkylamine, and the carbon number of the alkyl group bonded to the nitrogen atom thereof The total is 6 or more and 50 or less. [5] The method for producing a glycidyl ether compound according to any one of the above [1] to [4] wherein the compound having an allyl ether bond is a compound having a complex allyl ether bond . [6] The method for producing a glycidyl ether compound according to any one of the above [1] to [4] wherein the compound having an allyl ether bond is a compound having two propyl ether linkages And more has the step of separating the monoallyl monoepoxypropyl ether compound which is only epoxidized from the reaction product by only one -8 to 201130806. [7] The method for producing a glycidyl propyl ether compound according to any one of the above [1] to [6], wherein an organic solvent is not used as a reaction solvent. [8] The method for producing a glycidyl ether compound according to any one of the above [1] to [7] wherein the compound having an allyl ether bond has the following formula (1): 】

In the formula, R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms. Or, R1 and R2 together may form an alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms. 113, 114, 115, and 116 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms. And η represents a configuration represented by an integer of 0 or 1. [9] The method for producing a glycidyl ether compound according to any one of the above [1] to [8] wherein the compound having an allyl ether bond is selected from a diallyl group derived from bisphenol-indole At least one of a group of ether, bisphenol-F diallyl ether, and 3,3,5,5,-tetramethylbiphenyl-4,4,-diallyl ether. The method for producing a glycidyl ether compound according to any one of the above [1] to [7] wherein the compound having an allyl ether bond is selected from a carbon number of 2 to 20 α,ω-polyolefin diol diallyl ether, 1,4-cyclohexanedimethanol diallyl ether, and tricyclo[5.2.1. 02'6]decane dimethanol diallyl At least one of a group of ethers. [11] The method for producing a glycidyl ether compound according to any one of [1] to [7] wherein the compound having an allyl ether bond is a phenol-formaldehyde/allyl alcohol polycondensate or Cresol-formaldehyde-allyl alcohol polycondensate. [12] A monoallyl monoepoxypropyl ether compound having a biphenyl skeleton, which is a general formula (2) as follows:

(2) In the formula, 117, 118, 119, and R1() are each independently a hydrogen atom, an alkyl group having 1 to 1 ring of carbon, an alkenyl group having 2 to 10 carbon atoms, and a cycloalkane having 3 to 10 carbon atoms. The base or the aryl group having a carbon number of 6 to 10 is represented by. [13] The monoallyl monoglycidyl ether compound having a biphenyl skeleton according to the above [12], wherein R7, R8, R9, and R1Q in the formula are a methyl group. [Effects of the Invention] According to the method for producing a glycidyl ether compound of the present invention, hydrogen peroxide-10-201130806 and allyl ether are obtained by using a tungsten compound, a tertiary organic amine, and a phenylphosphonic acid as a catalyst. By reacting the compound, the corresponding epoxy propyl ether compound can be produced, and the organic chlorine-based impurities can be inhibited from being mixed as much as possible, and can be simultaneously manufactured in the field of electronic materials with ease and convenience in a simple operation, and at a low cost, or An epoxy resin which is widely used as a raw material for various polymers of a binder and a coating resin in various industrial fields, including the chemical industry. Therefore, the production method of the epoxypropyl ether compound of the present invention can produce a huge effect industrially. Further, since the monoallyl monoepoxypropyl ether compound of the present invention has an allyl group, it can be subjected to a hydrazine hydrogenation reaction with a compound having a Si-H group, since a compound having various Si-H groups can be introduced. It is a biphenyl epoxypropyl ether group which is extremely useful as an epoxy resin raw material used for a resist or a sealing material or the like. [Embodiment] Hereinafter, the present invention will be described in detail. In the method for producing a glycidyl ether compound of the present invention, hydrogen peroxide is used as the oxidizing agent. Hydrogen peroxide can be used as an aqueous hydrogen peroxide solution. The concentration of hydrogen peroxide is not particularly limited and is generally selected from the range of 1 to 80%, preferably 5 to 80%, more preferably 1 to 60%. From the viewpoint of industrial productivity, and from the viewpoint of energy costs at the time of separation, hydrogen peroxide is preferably at a high concentration, and on the other hand, from the viewpoint of economy, safety, etc., without using excessively high concentrations and/or Excess amount of hydrogen peroxide is preferred. If the concentration of hydrogen peroxide is less than 1%, the reactivity is low. The amount of hydrogen peroxide used is also not particularly limited to a carbon-carbon double bond of an allyl group having an allyl ether-bonded compound to be epoxidized, and is selected from 0.5 to 10 equivalents, preferably 0.8. -11 - 201130806 ~ 2 equivalent range. If it is outside this range, the raw materials of one of them become excessive and uneconomical. In the method for producing a glycidyl ether compound of the present invention, a tungsten compound used as a catalyst is preferably a compound which forms a tungstate anion in water, and examples thereof include tungstic acid, tungsten trisulfide, and tungsten trisulfide. Hexachlorochloride, phosphotungstic acid, ammonium tungstate, potassium tungstate dihydrate, sodium tungstate dihydrate, etc., and tungstic acid, tungsten trioxide, phosphotungstic acid, sodium tungstate dihydrate, etc. . These tungsten compounds may be used singly or in combination of two or more. The catalytic activity of such a compound which forms a tungstic anion in water is higher than that of the tungstic anion 1 · 以 in the presence of a relative cation of 0.2 to 0.8. For the preparation method of the tungsten composition, for example, an alkali metal salt of tungstic acid and tungstic acid can be mixed at the above ratio, and tungstic acid and an alkali compound (hydroxide, carbonate, etc. of an alkali metal or an alkaline earth metal) can be used. Mixing, or by combining an alkali metal salt or an alkaline earth metal salt of tungstic acid with a mineral acid-like acidic compound such as phosphoric acid or sulfuric acid, a partial neutralizing salt of tungstic acid can be formed by this preparation method. Preferred examples of such a compound include a mixture of sodium tungstate and tungstic acid, a mixture of sodium tungstate and mineral acid, or a mixture of tungstic acid and an alkali compound. The tungsten compound is used as a catalyst. The tungsten element is selected from 0.0001 to 20 mol% based on the number of carbon-carbon double bonds of the allyl group of the compound having an allyl ether bond. Good for 〇·〇ι~20% of the range. If less than 0.0001% by mole, the reactivity is low 'if more than 20% by mole, which is disadvantageous to cost." The tertiary amine used as a catalyst, the carbon number of the alkyl group bonded to the nitrogen atom thereof. The total of 6 or more organic acids (three-12-201130806 alkylamine) which is preferably 丨〇 or more is preferable because of the high activity of the epoxidation reaction. Examples of the tertiary organic amines include triethylamine 'tributylamine, tri-η-octylamine, tris-(2-ethylhexyl)amine, hydrazine, hydrazine-dimethyloctylamine, Ν,Ν·Dimethyl laurylamine, hydrazine, hydrazine-dimethyltetradecylamine, hydrazine, hydrazine-dimethylhexadecanylamine, hydrazine, hydrazine-dimethyloctadecylamine, hydrazine , Ν-dimethyl behenylamine, hydrazine, hydrazine-dimethyl cocoalkylamine, hydrazine, hydrazine-dimethyl tallow alkylamine, hydrazine, hydrazine, dimethyl hardened tallow alkylamine, hydrazine , Ν-dimethyloctadecylamine, hydrazine, hydrazine-diisopropyl-2-ethylhexylamine, hydrazine, hydrazine-dibutyl-2-ethylhexylamine, hydrazine-methyldioctyl Amine, hydrazine-methyl dimethyl decylamine, hydrazine-methyl dicocoalkylamine, N-methyl hardened tallow alkylamine, hydrazine-methyl octadecylamine, and the like. The total number of alkyl carbon atoms bonded to the nitrogen atom of the tertiary amine 'if it is considered to be the solubility of the compound having an allyl ether bond as a reaction substrate, preferably 5 or less, more preferably 3 0 the following. These tertiary amines may be used singly or in combination of two or more. The amount used is based on the number of carbon-carbon double bonds of the allyl ether-bonded compound of the matrix, and is selected from the group consisting of 〇.〇〇〇1~1〇mol% is better. Good for ο. ο 1~1 〇 Moer% range. If less than 〇 · 0 〇 〇 1 mol%, the reactivity is low. Right more than 1 〇 耳 耳 ear% is not conducive to cost. In the method for producing a glycopropyl ether compound of the present invention, phenylphosphonic acid is further used as a (helper) catalyst. The amount thereof is based on the number of carbon-carbon double bonds of the allyl group of the compound having an allyl ether bond in the matrix, and is preferably selected from the group consisting of 〇_〇〇〇1 to 10 mol%. 〇〇 1~10 Moh Q/. The scope. If the right is less than 0.00 0 1%, the reactivity is low, if more than 1 mole. /. It is not good for cost. In the method for producing a epoxidized propyl ether compound of the present invention, the epoxidized substrate is not particularly limited as long as it is a compound having an allyl ether bond, and the allyl ether contained in the compound is not particularly limited. The number of key knots may be one or two or more. a compound having a number of allyl ether linkages, which may be exemplified by phenyl allyl ether, hydrazine-, m-, p-cresol monoallyl ether, biphenyl-2-ol monoallyl ether And biphenyl-4-ol monoallyl ether, butyl allyl ether, cyclohexyl allyl ether, cyclohexane methanol monoallyl ether and the like. The compound having two groups of allyl ether linkages may, for example, 1,5-pentanediol diallyl ether, 1,6-hexanediol diallyl ether, 1,9-nonanediol II α,ω-alkylene glycol diallyl ether having a carbon number of 2 to 20, such as allyl ether, 1,1 fluorene-decanediol diallyl ether, neopentyl glycol diallyl ether α,ω-polyolefin diol diallyl ether, 1,4-cyclohexanedimethanol diallyl ether, tricyclo[5.2.1.0'6] decane II Methanol diallyl ether, or the following general formula (1): [Chemical 3]

In the formula, R1 and R2 are each independently a hydrogen atom, a carbon number of 1 to 6, a carbon number of 2 to 6 alkenyl groups, a cycloalkyl group having a carbon number of 3 to 12, or a carbon number of 6 to 10 Or, R1 and R2 may together form an alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms. 113, 1^4, 1^5, and 6 are each independently hydrogen-14-201130806 atom, carbon number 1~10 alkyl group, carbon number 2~10 alkenyl group, 12 ring hospital base or carbon number 6 An aryl group of ～10, and η represents a compound represented by 0 or }. Here, when η is 0, it means two bond bonds (biphenyl skeleton). Among these, it is more preferable that each of R1 to R6 is a single or a methyl group, and η is 1 or 0. Specific examples of the compound include diallyl ether of bisphenol-indene diene bisphenol-F, 2,6,2',6'-tetramethylbisphenol-octaether, 2,2' -Diallyl bisphenol-indole diallyl ether, 2,2'-diphenol-decadienyl ether, 4,4'-biphenol diallyl ether, 2,2'-biphenol Diallyl ether, 4,4'-ethylenebisguanidinium diisopropyl ether, hexyl bisphenol diallyl ether, 4,4'-(1-α-methylheptylene) bis-ether , 4,4'-(3,3,5-trimethylcyclohexylene) bisphenol diene 4,4'-(1-methyl-benzylidene) bisphenol diallyl ether, 3,3 ,, 5, ί biphenyl-4,4'-diallyl ether, and the like. Further, a compound having three or more allylic ether linkages is a phenol-formaldehyde/allyl alcohol polycondensate or cresol-formaldehyde. Allyl alcohol. These substrates may be subjected to an epoxidation reaction without using an organic solvent by mixing an aqueous hydrogen peroxide solution with the above-mentioned catalyst, without using an organic solvent, or by pulsing the hydrogen peroxide aqueous solution, and reducing the manufacturing equipment. For example, it is advantageous to omit the use of the explosion-proof equipment, the improvement of the work environment, and the improvement of the working environment, etc., and it is necessary to select it because the reaction rate is slow and the hydrolysis reaction is required depending on the solvent. An integer number of benzene rings having a carbon number of 3 to 1 is directly represented by hydrogen propyl ether, diallyl-t-butyl bisdiisopropyl 4,4'-cyclo arylene diallyl ether, tetramethyl The base may be exemplified by the fact that the polycondensate is produced by the organic solution oxidation reaction, and the solvent for disposal is not ideal. When the viscosity of the compound having the allyl ether bond as the substrate is too high, Or in the case of a solid, the minimum necessary organic solvent can be used. The organic solvent which can be used is preferably an aromatic hydrocarbon, an aliphatic hydrocarbon or an alicyclic hydrocarbon, and examples thereof include toluene, hydrazine, hexane, octane, and cyclohexane. The amount of use thereof is preferably from the viewpoint of the production cost and the like, and is preferably 50 parts by mass or less, more preferably 50 parts by mass or less, based on the production cost of the compound having an allyl ether bond. Use 30 parts by mass or less. When the amount of the organic solvent used is more than 50 parts by mass based on 100 parts by mass of the compound having an allyl ether bond, the substrate concentration is lowered and the reactivity is lowered. Further, as a method of performing epoxidation, in consideration of industrially stable production, the catalyst and the substrate can be placed in the reactor first, and the reaction temperature is kept at a fixed temperature as much as possible, and it is confirmed that hydrogen peroxide is reacted by the reaction. The situation of consumption, while slowly joining. According to this method, even if hydrogen peroxide is abnormally decomposed in the reactor to generate oxygen gas, the amount of hydrogen peroxide stored is small, and the pressure can be increased to a minimum. When the reaction temperature is too high, there are many side reactions, and hydrogen peroxide is also easily decomposed. When the temperature is too low, the consumption rate of hydrogen peroxide is slow and accumulated in the reaction system. It is preferably in the range of -10 to 120 ° C, more preferably in the range of 20 ° C to 10 ° C. After the completion of the reaction, there is almost no difference in the difference in specific gravity between the water layer and the organic layer. At this time, by mixing the aqueous layer with a saturated aqueous solution of the inorganic compound, the specific gravity difference is caused to the organic layer, even if the organic extraction solvent is not used. Two layers of separation are possible. In particular, since the specific gravity of the tungsten compound is heavy, in order to sink the water layer to the lower layer, it is also possible to use a tungsten compound which exceeds the amount of the above-mentioned -16-201130806 required for the original catalyst. At this time, it is preferable to further increase the efficiency of the tungsten compound by reusing the tungsten compound derived from the water layer. On the other hand, depending on the substrate, the specific gravity of the organic layer becomes close to 1.2. At this time, water is further added, and by making the specific gravity of the water layer close to 1, the upper layer may be the water layer and the lower layer. It is an organic layer. Further, the extraction of the reaction liquid may be carried out by using an organic solvent such as toluene, cyclohexane, hexane or dichloromethane, and the most suitable separation method may be selected depending on the conditions. After the organic layer separated from the aqueous layer is concentrated in this manner, the obtained epoxy propyl ether compound can be taken out by a usual method such as distillation, chromatography, recrystallization or sublimation. When the compound having an allyl ether bond is a compound having two allyl ether bonds, by performing the above separation and purification operation, only one of the allyl ether bonds can be epoxidized from the reaction product. The monoallyl monoepoxypropyl ether compound is isolated. For example, when a diallyl ether compound having a biphenyl skeleton is used as a substrate, the organic layer contains monoallyl monoepoxypropyl ether, diepoxypropyl ether, and unreacted diallyl ether. The compound can be purified by column chromatography as described in Example 16 to be described later, and the following general formula (2) can be obtained, for example.

In the formula, R7, R8, R9, and RIQ each independently represent a hydrogen atom, an alkyl group having a carbon number of 201130806, 1 to 10, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having a carbon number of 3 to fluorene, or a carbon number. Monoallyl monoepoxypropyl ether represented by 6 to 10 aryl}. R7, R8, R9, and R10 may also be a methyl group. [Examples] Hereinafter, the present invention will be more specifically described based on the examples, but the present invention is not limited by the following examples. [Example 1] A 300 mL three-necked beaker equipped with a dropping funnel and a Daicel condenser 0.95 0g (2.88mmol) of tungstate sodium (made by Nippon Inorganic Chemical Industry Co., Ltd.), 0.720g (2.88mmol) of tungstic acid (made by Nippon Inorganic Chemical Industry Co., Ltd.), and trioctylamine (Growong Chemical ( (manufactured by the company) 2.04 g (5-76 mmol), phenylphosphonic acid (manufactured by Nissan Chemical Co., Ltd.), 0.911 g (5-76 mmol), allyl phenyl ether 80 g (0.576 mol), stirred with a magnetic stirrer After the bath was warmed to 70 ° C, the reaction temperature was not more than 75 ° C and 84.0 g (0.864 mol) of a 35 % aqueous hydrogen peroxide solution was dropped. After the completion of the dropwise addition, stirring was continued for 2 hours, and the reaction liquid was allowed to cool to room temperature. Thereafter, 40 g of ethyl acetate was added, and the upper layer was an organic layer and the lower layer was an aqueous layer, and the organic layer was separated. As a result of analyzing the organic layer, the conversion of allyl phenyl ether was 55.8%, and the selectivity to p- propyl propyl ether was 66.3%. Further, the conversion rate and the selectivity are based on the results analyzed by gas chromatography, and are calculated based on the following calculation formula. -18- 201130806 Conversion rate (%) = (1 - residual raw material moles / used raw material moles) χ 1 〇〇 selectivity (%) = { (molar of the target compound / used raw materials Molar number) χ 10000} / conversion ratio (%) [Comparative Example 1] The reaction was carried out under the same conditions as in Example 1 except that phenylphosphonic acid was not added. As a result, the conversion ratio of the propyl phenyl acid was 3.6%, and only a very small amount of the epoxypropyl phenyl ether was detected by gas chromatography. [Comparative Example 2] The reaction was carried out under the same conditions as in Example 1 except that trioctylamine was not added. As a result, the conversion of allyl phenyl ether was 5.3 %, and only a very small amount of glycidyl phenyl acid was detected by gas chromatography. [Examples 2 to 10] The epoxidation reaction was carried out in the same manner as in Example 1 except that the catalyst components shown in Table 1 below were placed and the molar ratio was placed. The results are shown in Table 1 below. -19- 201130806 Epoxypropyl phenyl ether selectivity rate of 66.3% 54.8% 59.1% 59.9% 68. 4% 43. 5% 67. 2% 77. 1% 44. 2% 56. 7 % yield 37.0% 33. 9% 32. 8% 35. 9% 26.8% 17.6% 25.2% 36. 9% 21.7% 18.5% Conversion rate 55.8% 61. 9% 55. 6% 59. 9% 39. 1 % 40. 6% 37. 5% 47. 5% 49. 2% 32. 6% g ft « «VI rn S g SSSSS τ — SQ in Ο LO Other 0. 25 in CD 2: « r — Ο- τ τ—*— 1 11 τ—W CNJ LO Ο LO 〇ID d LO LO Ο LO Ο ir> ο in ci m CP LO d ΙΓ3 ir>c>c> LO o catalyst other 50% sulfuric acid NaOH ζ trioctyl Aminomethyldioctylaminemethyldioctylaminemethyldioctylaminemethyldioctylaminetriethylaminetributylaminetrihexylaminedimethylamine amide Kl§ niniru 〇u benzene Phosphonic acid (Nissan Chemical) phenylphosphonic acid phenylphosphonic acid phenylphosphonic acid phenylphosphonic acid phenylphosphonic acid decanoic acid 1 -phenylphosphonic acid --1 phenylphosphonic acid phenylphosphonic acid \ (曰Production Chemistry) .^ T Ps« h2wo4 H2W〇4 (St HjW04 NazW04-2H?0 Shape) 〇〇E Method One Na2W04 ·2Η20 Shapes) NazW 04 · 2Η20 Shapes) Na2W04-2H20 Shape) Naz W0, ·2ΗΖ0 涸 Shape) Na2W04.2H20 Shape) NazW04 ·2Η20 (Solid) o . <Si □CC?Draw 3= ^ CM CQ CVJ CO xr LT3卜GO σ) 〇-20- 201130806 [Synthesis Example 1]: Synthesis of diallyl ether of bisphenol-F In a 2000 ml eggplant type beaker, bisphenol-F-ST (manufactured by Mitsui Chemicals Co., Ltd.) 200 g (0.999mol), 50% aqueous 5%-Pd/C-STD type (NECHEMCAT), 2.13g (0.499mm〇l), triphenylphosphine (Beixing Chemical Co., Ltd.) 2.62g (9.99) Methyl), potassium carbonate (manufactured by Asahi Glass Co., Ltd.) 276 g (2.00 mol), allyl acetate (manufactured by Showa Denko Co., Ltd.) 220 g (2.20 mol), and isopropanol 200 g, in a nitrogen atmosphere '8 5 The reaction was carried out for 8 hours at °C. After the reaction, a part was sampled, diluted with ethyl acetate, and analyzed by gas chromatography to confirm that the ratio of bisphenol-F diallyl ether to monoallyl ether was changed to 99:1. Thereafter, 400 g of toluene was added to the reaction liquid, and Pd/C and the precipitated solid were removed by filtration, and isopropyl alcohol and toluene were distilled off by an evaporator. After repeating this reaction and the post-treatment operation four times, a distillate of 748 g (66% yield, bisphenol-F diallyl) was obtained by a molecular distillation apparatus (manufactured by Daikoku Co., Ltd.). The ether was 98.7%, the remainder was monoallyl ether), and the non-distillate was 3 68 g (bisphenol-F diallyl ether 8 8%). These analyses were carried out by gas chromatography. The viscosity of the distillate at 25 ° C was 25 mPa·s (determined by B-type viscosity meter (DRO-E (type: L V D V - E)). Further, the isomer ratio is 〇, 〇, -: o, p'-: p, p'- = 17: 52: 31 (analytical enthalpy obtained by gas chromatography). [Synthesis Example 2]: Synthesis of 3,3',5,5'-tetramethylbiphenyl-4,4'-diallyl ether For a 2000 ml eggplant type beaker, put in 3,3',5 , 5'-Tetramethyl·4,4'-biphenyldiol (China: Gansu Chemical Research Institute) 150g (0.619mol), 50% water 5%-Pd/C-STD type (NECHEMCAT (Stock)-21 - 201130806 ) 1.32g (0.310mmol), triphenylphosphine (Beixing Chemical Co., Ltd.) i.624g (6.19 mmol), potassium carbonate (made by Japan Soda Co., Ltd.) i71g (1.24mol) 136 g (1.36 mol) of allylic acetate (manufactured by Showa Denko Co., Ltd.) and 68.1 g of isopropyl alcohol were reacted at 85 ° C for 8 hours in a nitrogen atmosphere. After the reaction, a portion was sampled and diluted with ethyl acetate, and analyzed by gas chromatography to confirm 3,3',5,5'-tetramethylbiphenyl-4,4'-di The ratio of allyl ether to monoallyl ether was changed to 97:3. Thereafter, 200 g of toluene was added to the reaction liquid, and Pd/C and the precipitated solid were removed by filtration, and isopropyl alcohol and toluene were distilled off by an evaporator. After repeating this reaction and the post-treatment operation four times, 127.5 g of a distillate was obtained by a molecular distillation apparatus (manufactured by Daikoku Co., Ltd.) (the yield was 66%, the diallyl ether was 97.9%, and the balance was Monoallyl ether), non-distillate 31.7 g (diallyl ether 97.5%). These analyses were carried out by gas chromatography. The distillate had a melting point of 51.7 ° C and a viscosity at 60 ° C of 29 mPa·s (measured by B-type viscosity (DRO-E (type: LVDV-E)). [Synthesis Example 3]: Synthesis of 1,4-cyclohexanedimethanol diallyl ether In a 1000 ml beaker, 1,4-cyclohexanediol (manufactured by Eastman Chemicals) 100 g (0.693 mol), 50% hydrogen was placed. 110.9 g (1.39 mol) of an aqueous sodium oxide solution, 1.12 g (3.47 mmol) of tetrabutylammonium bromide (manufactured by LION AKZO Co., Ltd.), and 132.7 g (1.73 mol) of allyl chloride, were firstly flowed under a nitrogen stream. After heating at 4 ° C, the reaction temperature was gradually increased as the reaction progressed, and the temperature was raised to 70 ° C over 3 hours, and further reacted for 17 hours. The reaction solution was cooled to room temperature, and toluene (200 ml) was added to extract the mixture, and the organic layer was washed twice with pure water -22-201130806. After the toluene is distilled off by an evaporator, the initial fraction is removed by distillation under reduced pressure to obtain a boiling point of 8 〇. 4 t / 2 8 P a of 8 4 · 6 g (di-l-propyl ether) 94% 'remaining monoallyl ether'). These analyses were carried out by gas chromatography. Further, the viscosity in the 25 t of the distillate was 8.5 mPa·s (measured by a B-type viscometer (DV-E (type: LVDV-E) manufactured by BROOKFIELD). [Synthesis Example 4]: Synthesis of 1,6-hexanediol diallyl ether In a beaker of 1 000 ml, 16-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.) 100 g (0.846 mol), 50% hydrogen Aluminium oxide aqueous solution 1 3 5 · 4 g (1 · 6 9 m ο 1), tetrabutylammonium bromide (manufactured by LION AKZO Co., Ltd.) 1.36 g (4.23 mmol), allyl chloride 161.9 g (2.12 mol) The mixture was first heated at 40 T: under a nitrogen stream, and the reaction temperature was gradually increased as the reaction progressed. After the temperature was raised to 70 ° C over 2 hours, the reaction was further carried out for 10 hours. The reaction solution was cooled to room temperature, and 200 ml of toluene was added thereto to extract the reactant, and the organic layer was washed twice with pure water. After the toluene was distilled off by an evaporator, and the initial fraction was removed by distillation under reduced pressure, a distillation fraction of 82.6 ° C / 1 3 3 P a was obtained, 84.6 g (diallyl ether 97%). The remainder is monoallyl ether). These analyses were carried out by gas phase chromatography. Further, the viscosity of the distillate at 25 ° C was 2.3 mPa·s (measured by a B-type viscosity meter (DV-E (type: LVDV-E) manufactured by BROOKFIELD). [Example 1 1 to 1 5] An epoxidation reaction was carried out in the same manner as in Example 1 except that the allylphenyl ether of Example 1 was substituted with the compound shown in Table 2 below. The results are shown in Table 2 below.

-24-201130806 [Example 1 6] The product obtained in Example 13 was subjected to isolation from monoepoxypropyl monoallyl ether in the present example. The experimental sequence is as follows. For a 3〇〇niL three-neck beaker equipped with a drip funnel and a Daisy condenser, put sodium tungstate (made by Nippon Inorganic Chemical Industry Co., Ltd.) 0.95 0g (2.88mm〇1), tungstic acid (Japan Inorganic Chemical Industry) (stock) system: 0.720 § (2.88111111〇1), trioctylamine (manufactured by Kwong Wing Chemical Co., Ltd.) 2.04g (5.76mmol), phenylphosphonic acid (Nissan Chemical Co., Ltd.) 0.911g (5.76mmol) , 3,3',5,5,-tetramethylbiphenyl-4,4,-diallyl ether 92.9 g (0.288 mol), while stirring with a magnetic stirrer, warm in an oil bath until After 70 ° C, the reaction temperature was not more than 75 t and 35% aqueous hydrogen peroxide solution was added dropwise to 8 4 _ 0 g (〇. 8 6 4 m ο 1). After the completion of the dropwise addition, stirring was continued for 2 hours, and the reaction liquid was cooled to room temperature. Thereafter, 40 g of ethyl acetate was further added to make the upper layer an organic layer and the lower layer an aqueous layer, and the organic layer was separated. As a result of analysis of the organic layer, the conversion of 3,3 ',5,5 '-tetramethylbiphenyl-4,4'-diallyl ether was 54.2%, and the selectivity of the monoepoxide was selected. It was 64.9%, and the selectivity to the diepoxide was 15.5% (refer to Example 13, Table 2). Thereafter, the organic layer was washed with an aqueous solution of sodium sulfite, and the solvent of the organic layer was distilled off and dried using an evaporator and a vacuum pump to obtain a crude reactant, which was then purified by column chromatography (cerium oxide gel). 60N (spherical, neutral): manufactured by Kanto Chemical Co., Ltd.; hexane: ethyl acetate = 1 〇 -25 - 201130806 : 1~3 : 1), and 3,3', 5,5'-four Methylbiphenyl-4,4'-diepoxypropyl ether and 3,3',5,5'-tetramethylbiphenyl-4,4'-monoallyl monoepoxypropyl ether . From the results of NMRdH, 13C) and mass analysis (MS) of the obtained product, it was confirmed that the obtained product was 3,3',5,5'-tetramethylbiphenyl-4,4'-diepoxy. Propyl ether and 3,3',5,5'-tetramethylbiphenyl-4,4'-monoallyl monoepoxypropyl ether. The results of the measurement of the monoallyl monoepoxypropyl ether body are shown in Figs. The measurement conditions of MS are as follows:

Device: JEOL JMS-SX102A

Sample heating temperature: 80 ° C - [ 32 ° C / min] - 400 ° C Sample concentration: NMR measurement solution diluted 10 times with dichloromethane

Sample amount: 0.5 μl * Heated by 80 t by solvent evaporation and then introduced into MS. Ionization method: EI (electron ionization method) Sweeping cat range: m/z10 to 800 [Example 17] equipped with a reflux cooler, The monoallyl monoepoxypropyl ether body 0.18 (0.30111111〇1), 1,1,1,3,5,5,5 synthesized in Example 16 was added to a 50 ml three-neck beaker of a thermometer, a stirring device and a rubber cap. - Heptamethyltrioxane oxime. 7 7 g (0.35 mmol) and 1 ml of toluene were stirred at room temperature under a stream of argon. To the mixed solution, 0.002 g of a solution of 3% diethylenetetramethyldioxane platinum complex isopropanol (platinum amount: 6.0 M 0_5 g) was added, and the reaction solution was stirred at room temperature. After stirring at room temperature for 6 hours, the toluene solvent was removed under reduced pressure to give a crude material. Thereafter, it was purified by column chromatography -26-201130806 (cerium oxide gel 60N (spherical, neutral): manufactured by Kanto Chemical Co., Ltd.; toluene·ethyl acetate = 1 〇·· 1 ) And the following structural formula (3) is obtained: [Chemical 5]

0.13 g of monoepoxypropyl ether represented by H3C-Si-〇-Si-〇-Si-CH3 CH3 ch3 ch3. From the results of NMRdH, 13C, 29Si) and mass analysis (MS) of the obtained product, it was confirmed that the obtained product was a compound of the formula (3) (refer to Figs. 4 to 7). Namely, it shows that the monoallyl monoepoxypropyl ether compound synthesized in Example 16 can be reacted with a compound having a Si-H group by a hydrogenation reaction of hydrazine. The measurement conditions of MS are as follows =

Device: JEOL JMS-SX 1 02 A

Sample heating temperature: 80 ° C - [ 32 ° C / min] - 40 (TC sample concentration: N M R determination solution diluted 1 × times with dichloromethane

Sample amount: 0·5μ1 * Heated at 80 ° C by solvent evaporation and then introduced into MS. Ionization method: EI (electronic ionization method) Scanning range: m/zlO~800 [Industrial availability] - 27-201130806 The method for producing a glycidyl propyl ether compound according to the present invention can be produced by reacting hydrogen peroxide with an allyl ether compound by using a tungsten compound, a tertiary organic amine, and benzoic acid as a catalyst The corresponding epoxidized propyl ether compound is used in the field of electronic materials, which is safe and yield-efficient and low-cost, and can be easily produced at a low cost. An epoxy resin which is a useful material of a raw material of various polymers of an adhesive or a coating resin is widely used in the industrial field. Further, the monoallyl monoepoxypropyl ether compound of the present invention is subjected to a hydrazine hydrogenation reaction with a compound having a Si-H group, since a biphenyl ring can be introduced to a compound having various Si-H groups. An oxypropyl ether group is excellent in the synthesis of an epoxy resin used for a resist or a sealing material for high heat resistance and high etching resistance. [Simple description of the map]

Fig. 1 is a graph showing the results of 1H-NMR measurement of the product obtained in Example 16. Fig. 2 is a graph showing the results of 13C-NMR measurement of the product obtained in Example 16. [Fig. 3] Fig. 3 shows the results of measurement of mass analysis (MS) of the product obtained in Example 丨6. Fig. 4 is a graph showing the results of 1h-NMR measurement of the product obtained in Example 17.

Fig. 5 is a graph showing the results of 13C-NMR measurement of the product obtained in Example 17. -28-201130806 [Fig. 6] Fig. 6 shows the results of measurement of 29Si-NMR of the product obtained in Example 17. Fig. 7 is a graph showing the results of measurement of mass analysis (MS) of the product obtained in Example 17. -29-

Claims (1)

201130806 VII. Patent Application Range: 1. A method for producing a glycopropyl ether compound, which is a reaction of a compound having an allyl ether bond with hydrogen peroxide, by making the allyl carbon-carbon double The bond is epoxidized to produce a corresponding epoxy propyl ether compound characterized by using a tungsten compound, a tertiary amine, and a phenylphosphonic acid as a reaction catalyst, 2. The manufacture of the epoxy propyl ether compound of claim 1 The method wherein the tungsten compound is a partially neutralized salt of tungstic acid. 3. The method for producing a glycidyl ether compound according to claim 1 or 2, wherein the tungsten compound is a mixture of sodium tungstate and tungstic acid, a mixture of sodium tungstate and mineral acid, or a mixture of tungstic acid and an alkali compound. . 4. The process for producing a glycidyl propyl ether compound according to any one of claims 1 to 3, wherein the tertiary amine is a trialkylamine, and the total number of carbon atoms bonded to the alkyl group of the nitrogen atom is 6 Above 50 or less. 5. Process for producing a epoxidized propyl ether compound according to any one of claims 1 to 4, wherein the compound having the above allyl ether bond is a compound having a complex allyl ether bond. 6. The method for producing a glycidyl ether compound according to any one of claims 1 to 4, wherein the compound having an allyl ether bond is a compound having two allyl ether bonds, and further has The step of separating the one-only allyl ether bond from the mono-allyl monoepoxypropyl ether compound which is epoxidized from the reaction product. The method for producing a glycidyl propyl ether compound according to any one of claims 1 to 6, wherein an organic solvent is not used as a reaction solvent. 8. The method for producing a epoxidized propyl ether compound according to any one of claims 1 to 7, wherein the compound having an allyl ether bond has a formula (1): 1] In the formula, R1 and R2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a aryl group having 6 to 1 carbon atoms. Or, R1 and R2 together form an alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms; R3, R4, R5 and R6 are each independently a hydrogen atom and have a carbon number of 1 An alkyl group of ～10, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aryl group having a carbon number of 6 to 10' and 'η' represents a structure represented by an integer 0 of 0 or 1. The method for producing a glycidyl propyl ether compound according to any one of claims 1 to 8, wherein the compound having an allyl ether bond is selected from the group consisting of diallyl ether of bismuth-fluorene, bisphenol At least one of a group of -F diallyl ether and 3,3',5,5'-tetramethylbiphenyl-4,4'-diallyl ether. The method for producing a glycidyl ether compound according to any one of claims 1 to 7, wherein the compound having an allyl ether bond is selected from the group consisting of α,ω-polyolefin having a carbon number of 2 to 20. At least one of a group of diol diallyl ether, 1,4-cyclohexane dimethanol diallyl ether, and tricyclo [5.2.1. 02'6] decane dimethanol diallyl ether . The method for producing a glycidyl ether compound according to any one of claims 1 to 7, wherein the compound having an allyl ether bond is a phenol-formaldehyde-allyl alcohol polycondensate or Cresol-formaldehyde. Allyl alcohol polycondensate. 12. A monoallyl monoepoxypropyl ether compound having a biphenyl skeleton which is of the following general formula (2): In the formula, R7, R8' R9, and Rl<) each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and a carbon number of 3 to 10 or a carbon number. 6 to 10 of the aryl group represented by. 13. The mono-l-propyl monoglycidyl ether compound having a biphenyl skeleton according to claim 12, wherein R7, R8, r9 and R10 in the formula are a methyl group. -32-