JP5093771B2 - Process for producing multifunctional epoxy compounds by selective oxidation of triolefin compounds - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a novel process for safely and easily producing a polyfunctional epoxy compound by reaction of triolefins and a hydrogen peroxide aqueous solution under a mild condition without use of an organic solvent, and a method for controlling the stereoselectivity of the polyfunctional epoxy compound to be produced. <P>SOLUTION: According to the process, by reaction of triolefins and a hydrogen peroxide aqueous solution using a quaternary ammonium hydrogensulfate and a group VI metal compound as a phase transfer catalyst, a polyfunctional epoxy compound having an epoxy group and a double bond in a molecule is produced selectively with high yield, and the stereoselectivity of the polyfunctional epoxy compound to be produced can highly be controlled. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a method for epoxidizing triolefins so as to obtain a multifunctional epoxy compound containing an epoxy group and a double bond in the molecule. In particular, the present invention provides a novel polyfunctional epoxy compound that reacts triolefins with aqueous hydrogen peroxide in the presence of catalytic molybdenum or tungsten oxide to selectively epoxidize one double bond. It relates to the manufacturing method. The polyfunctional epoxy compound provided by the present invention is used as a raw material for resist materials (especially solder-resist materials) and as a raw material for various polymers such as intermediates of agricultural chemicals / pharmaceuticals, plasticizers, adhesives and paint resins. It is a useful substance that is widely used in various industrial fields.

The technology to selectively epoxidize one double bond of a compound (diolefin, triolefin, etc.) having two or more double bonds in the molecule is low productivity (low reactivity, low selectivity). Often limited to certain types of structures that are applicable.
Conventionally, a method using an organic peracid such as performic acid or peracetic acid as a selective epoxidizing agent for diolefins or triolefins is known (for example, Chem. Ber., 1985, 118, 1267-1270). , European Patent Publication No. 0033763, etc.), and there is a problem of corrosion of the apparatus because an equivalent amount of acid derived from an oxidizing agent is generated, and a diol is easily formed as a by-product in a substrate that is sensitive to acid.

  A selective epoxidation method of diolefins using oxone as an oxidant under a ketone catalyst (J. Org. Chem., 1998, 63, 2948-2953) is also known. In addition to the above, there is a need for a very large amount of catalyst ketone (20-30 mol% with respect to diolefins), and reaction such as pH in the solution and reaction temperature in order to suppress the decomposition of oxone during the reaction. There is a problem that it is necessary to strictly control the conditions.

  On the other hand, hydrogen peroxide solution is inexpensive and non-corrosive, has no by-product after the reaction or is water, and therefore has a low environmental load and is an excellent oxidizing agent for industrial use.

  As a method for producing an epoxy compound from an olefin using an aqueous hydrogen peroxide solution as an epoxidizing agent, (1) a method for epoxidation with hydrogen peroxide in the presence of quaternary ammonium chloride, phosphoric acids and tungsten metal salt 2003-192679), (2) a method of epoxidation with hydrogen peroxide using an organic rhenium oxide as a catalyst (JP 2001-25665), (3) a method of epoxidation with titanosilicate and hydrogen peroxide (J. Cat. 1993, 140, 71-83), and (4) a method of epoxidation with hydrogen peroxide in the presence of a fluoroalkyl ketone catalyst (Chem. Commun., 1999, 263-264). Basically relates to the epoxidation of monoolefins with only one double bond A.

For selective epoxidation of diolefins using hydrogen peroxide as an epoxidizing agent, (5) Formula Q ₃ XW ₄ O ₂₄ (wherein Q is a quaternary ammonium cation containing up to 70 carbon atoms) Wherein X represents P or As) in the presence of a catalyst represented by the formula (JP-A-4-275281), (6) quaternary ammonium chloride, phosphoric acid, There is a method of epoxidizing a diolefin having a methacrylic acid unit with hydrogen peroxide in the presence of a tungsten compound (Tetrahedron, 1992, 48 (24), 5099-5110). In (5), the amount of hydrogen peroxide Is less than 1 equivalent to 1 equivalent of diolefin, so the reaction yield is very poor (32 to 48% with respect to the diolefin used). Time to the manufacturing process, poor productivity costly. In addition, since the catalyst has surface activity, it requires a halogen-based hydrocarbon solvent such as methylene chloride for phase separation after completion of the reaction, so that the environmental load is large. The method (6) is limited to diolefins having methacrylic acid units. Furthermore, neither (5) nor (6) teaches selective epoxidation for triolefins.

  On the other hand, there are very few reports on selective epoxidation of triolefins using hydrogen peroxide as an epoxidizing agent, and most of them are monoepoxidation of macrocyclic aliphatic compounds having about 8 to 20 carbon atoms. It relates to the reaction. For example, (7) a method of monoepoxidizing 1,5,9-cyclododecatriene (CDT) in the presence of a tungsten compound and a quaternary pyridinium salt (Japanese Patent Laid-Open No. 2000-26441), (8) a polyhydride of tungsten and molybdenum A method of selectively monoepoxidizing a macrocyclic aliphatic compound with hydrogen peroxide in the presence of an oxometalate complex (Japanese Patent Laid-Open No. 2002-1555066). However, since the method (7) is less than 1 equivalent per 1 equivalent of triolefin, the conversion rate of the raw material is very bad. In the method (8), the monoepoxidation selectivity greatly decreases with time. There is a problem such as.

  Other examples of selective epoxidation of triolefins include (9) alkali metal, alkaline earth metal or ammonium water-soluble salts, phosphoric acid, sulfuric acid, p-toluenesulfonic acid and other acidic catalysts, and formic acid Examples thereof include a method of selectively epoxidizing diallyl tetrahydrophthalate with hydrogen peroxide to obtain diallyl 4,5-epoxycyclohexane-1,2-dicarboxylate (Japanese Patent Publication No. 50-39659). However, with the method (9), the yield was only about 65%, which was not satisfactory. Furthermore, the yield of stereoisomers of diallyl 4,5-epoxycyclohexane-1,2-dicarboxylate obtained by the method (9) is not disclosed.

Therefore, there is a strong demand for the development of a method for producing a polyfunctional epoxy compound selectively from triolefins safely in a simple operation without using an organic solvent under mild conditions in a high yield and at a low cost. ing. In addition, a method for producing an epoxy compound that can control the stereoselectivity of the resulting epoxy compound is strongly desired.
Chem. Ber. , 118, 1267-1270 (1985). J. et al. Org. Chem. 63, 2948-2953 (1998). J. et al. Cat. 140, 71-83 (1993) Chem. Commun. , 263-264 (1999) Tetrahedron, 48, 5099-5110 (1992) European Patent Publication No. 0033763 JP 2003-192679 A Japanese Patent Laid-Open No. 2001-25665 JP-A-4-275281 JP 2000-26441 A JP 2002-155066 A Japanese Patent Publication No.50-39659

  The present invention provides a novel process for producing a safe and easy polyfunctional epoxy compound by the reaction of triolefins and aqueous hydrogen peroxide without using an organic solvent under mild conditions, and the resulting polyfunctional epoxy The object is to control the stereoselectivity of the compound.

  As a result of intensive studies to solve the above problems, the present inventors have used triolefins by using, for example, quaternary ammonium hydrogen sulfate and a Group 6 metal compound as a phase transfer catalyst as a phase transfer catalyst without using an organic solvent. Reacts with an aqueous hydrogen peroxide solution to selectively produce a multifunctional epoxy compound containing an epoxy group and a double bond in the molecule in a high yield, and then stereoselection of the resulting multifunctional epoxy compound The present inventors have found that the sex is highly controlled and completed the present invention.

  That is, the present invention is characterized by reacting a triolefin with an aqueous hydrogen peroxide solution without using an organic solvent in the presence of quaternary ammonium hydrogen sulfate and a catalytic amount of a Group 6 metal compound. The present invention relates to a method for producing an epoxy compound.

(式中、Ｒ¹〜Ｒ⁶は、それぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜７のシクロアルキル基、アリール基、アラルキル基、アシル基、アシロキシ基、あるいは、Ｒ¹とＲ²、Ｒ¹とＲ³、Ｒ¹とＲ⁴、Ｒ¹とＲ⁵、Ｒ¹とＲ⁶、Ｒ²とＲ³、Ｒ²とＲ⁴、Ｒ²とＲ⁵、Ｒ²とＲ⁶、Ｒ³とＲ⁴、Ｒ³とＲ⁵、Ｒ³とＲ⁶、Ｒ⁴とＲ⁵、Ｒ⁴とＲ⁶又はＲ⁵とＲ⁶が炭素数１〜３の炭素鎖で架橋されたものを示し、これらは独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜７のシクロアルキル基、アリール基、アラルキル基、カルボキシル基、ハロゲン原子で置換されていてもよい。また、式中、Ｒ⁷〜Ｒ⁸は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ⁹〜Ｒ¹²は、それぞれ独立に、水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表す。)
で表される化合物を酸化して、下記一般式（２）：

(式中、Ｒ¹〜Ｒ⁶は、それぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜７のシクロアルキル基、アリール基、アラルキル基、アシル基、アシロキシ基、あるいは、Ｒ¹とＲ²、Ｒ¹とＲ³、Ｒ¹とＲ⁴、Ｒ¹とＲ⁵、Ｒ¹とＲ⁶、Ｒ²とＲ³、Ｒ²とＲ⁴、Ｒ²とＲ⁵、Ｒ²とＲ⁶、Ｒ³とＲ⁴、Ｒ³とＲ⁵、Ｒ³とＲ⁶、Ｒ⁴とＲ⁵、Ｒ⁴とＲ⁶又はＲ⁵とＲ⁶が炭素数１〜３の炭素鎖で架橋されたものを示し、これらは独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜７のシクロアルキル基、アリール基、アラルキル基、カルボキシル基、ハロゲン原子で置換されていてもよい。また、式中、Ｒ⁷〜Ｒ⁸は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ⁹〜Ｒ¹²は、それぞれ独立に、水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表す。)
で表されるエポキシ化合物を製造することを特徴とする当該エポキシ化合物の製造方法。 In more detail, this invention relates to the manufacturing method of the epoxy compound shown by the following [1]-[4].
[1] The following general formula (1) using an oxidizing agent in the presence of a phase transfer catalyst and a Group 6 metal compound:

Wherein R ^{1 to} R ⁶ are each independently a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cycloalkyl having 3 to 7 carbon atoms. Group, aryl group, aralkyl group, acyl group, acyloxy group, or R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ¹ and R ⁵ , R ¹ and R ⁶ , R ² and R ³ , R ² and R ⁴ , R ² and R ⁵ , R ² and R ⁶ , R ³ and R ⁴ , R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , R ⁴ and R ⁶ or R ⁵ and R ⁶ are cross-linked by a carbon chain having 1 to 3 carbon atoms, and these are independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 3 to 7 carbon atoms. cycloalkyl group, an aryl group, an aralkyl group, a carboxyl group, may be substituted with a halogen atom. in the above formula, R ⁷ to R ⁸ each independently represent a hydrogen atom or Represents an alkyl group of prime 1-4, R ⁹ to R ¹² each independently represent a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.)
The compound represented by the following formula (2) is oxidized:

Wherein R ^{1 to} R ⁶ are each independently a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cycloalkyl having 3 to 7 carbon atoms. Group, aryl group, aralkyl group, acyl group, acyloxy group, or R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ¹ and R ⁵ , R ¹ and R ⁶ , R ² and R ³ , R ² and R ⁴ , R ² and R ⁵ , R ² and R ⁶ , R ³ and R ⁴ , R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , R ⁴ and R ⁶ or R ⁵ and R ⁶ are cross-linked by a carbon chain having 1 to 3 carbon atoms, and these are independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 3 to 7 carbon atoms. cycloalkyl group, an aryl group, an aralkyl group, a carboxyl group, may be substituted with a halogen atom. in the above formula, R ⁷ to R ⁸ each independently represent a hydrogen atom or Represents an alkyl group of prime 1-4, R ⁹ to R ¹² each independently represent a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.)
The manufacturing method of the said epoxy compound characterized by manufacturing the epoxy compound represented by these.

[2] The method according to [1], wherein the phase transfer catalyst is a quaternary ammonium hydrogen sulfate compound.

[3] The method according to [1] or [2], wherein the group 6 metal compound is tungsten.

[4] The method according to any one of [1] to [3], wherein the oxidizing agent is an aqueous hydrogen peroxide solution.

  In addition, the group 6 metal compound described in this specification refers to a compound containing a metal belonging to group 6 based on the new International Pure and Applied Chemical Association (IUPAC) notation of the long-period periodic table. means.

  According to the method of the present invention, as a raw material for resist materials (particularly solder-resist materials) and as a raw material for various polymers such as intermediates of agricultural chemicals / pharmaceuticals, plasticizers, adhesives, and coating resins, A multifunctional epoxy compound, a useful substance widely used in the industrial field, can be produced safely from a reaction with the corresponding triolefins and hydrogen peroxide solution, safely in a good yield, at low cost, and with stereoselectivity. Can be controlled. Therefore, the present invention has a great industrial effect. Moreover, since this manufacturing method does not use an organic solvent, an acid, or a base, it also has an effect of reducing the burden on the environment.

(式中、Ｒ¹〜Ｒ⁶は、それぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜７のシクロアルキル基、アリール基、アラルキル基、アシル基、アシロキシ基、あるいは、Ｒ¹とＲ²、Ｒ¹とＲ³、Ｒ¹とＲ⁴、Ｒ¹とＲ⁵、Ｒ¹とＲ⁶、Ｒ²とＲ³、Ｒ²とＲ⁴、Ｒ²とＲ⁵、Ｒ²とＲ⁶、Ｒ³とＲ⁴、Ｒ³とＲ⁵、Ｒ³とＲ⁶、Ｒ⁴とＲ⁵、Ｒ⁴とＲ⁶又はＲ⁵とＲ⁶が炭素数１〜３の炭素鎖で架橋されたものを示し、これらは独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜７のシクロアルキル基、アリール基、アラルキル基、カルボキシル基、ハロゲン原子で置換されていてもよい。また、式中、Ｒ⁷〜Ｒ⁸は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ⁹〜Ｒ¹²は、それぞれ独立に、水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表す。)
一般式（２）

(式中、Ｒ¹〜Ｒ⁶は、それぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜７のシクロアルキル基、アリール基、アラルキル基、アシル基、アシロキシ基、あるいは、Ｒ¹とＲ²、Ｒ¹とＲ³、Ｒ¹とＲ⁴、Ｒ¹とＲ⁵、Ｒ¹とＲ⁶、Ｒ²とＲ³、Ｒ²とＲ⁴、Ｒ²とＲ⁵、Ｒ²とＲ⁶、Ｒ³とＲ⁴、Ｒ³とＲ⁵、Ｒ³とＲ⁶、Ｒ⁴とＲ⁵、Ｒ⁴とＲ⁶又はＲ⁵とＲ⁶が炭素数１〜３の炭素鎖で架橋されたものを示し、これらは独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜７のシクロアルキル基、アリール基、アラルキル基、カルボキシル基、ハロゲン原子で置換されていてもよい。また、式中、Ｒ⁷〜Ｒ⁸は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ⁹〜Ｒ¹²は、それぞれ独立に、水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表す。) Hereinafter, the present invention will be specifically described.
In the present invention, a compound represented by the following general formula (2) is produced by oxidizing a compound represented by the following general formula (1) using an oxidizing agent in the presence of a phase transfer catalyst and a group 6 metal compound. It is a manufacturing method of the epoxy compound characterized by the above-mentioned.
General formula (1)

Wherein R ^{1 to} R ⁶ are each independently a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cycloalkyl having 3 to 7 carbon atoms. Group, aryl group, aralkyl group, acyl group, acyloxy group, or R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ¹ and R ⁵ , R ¹ and R ⁶ , R ² and R ³ , R ² and R ⁴ , R ² and R ⁵ , R ² and R ⁶ , R ³ and R ⁴ , R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , R ⁴ and R ⁶ or R ⁵ and R ⁶ are cross-linked by a carbon chain having 1 to 3 carbon atoms, and these are independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 3 to 7 carbon atoms. cycloalkyl group, an aryl group, an aralkyl group, a carboxyl group, may be substituted with a halogen atom. in the above formula, R ⁷ to R ⁸ each independently represent a hydrogen atom or Represents an alkyl group of prime 1-4, R ⁹ to R ¹² each independently represent a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.)
General formula (2)

Wherein R ^{1 to} R ⁶ are each independently a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cycloalkyl having 3 to 7 carbon atoms. Group, aryl group, aralkyl group, acyl group, acyloxy group, or R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ¹ and R ⁵ , R ¹ and R ⁶ , R ² and R ³ , R ² and R ⁴ , R ² and R ⁵ , R ² and R ⁶ , R ³ and R ⁴ , R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , R ⁴ and R ⁶ or R ⁵ and R ⁶ are cross-linked by a carbon chain having 1 to 3 carbon atoms, and these are independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 3 to 7 carbon atoms. cycloalkyl group, an aryl group, an aralkyl group, a carboxyl group, may be substituted with a halogen atom. in the above formula, R ⁷ to R ⁸ each independently represent a hydrogen atom or Represents an alkyl group of prime 1-4, R ⁹ to R ¹² each independently represent a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.)

(式中、Ｒ¹〜Ｒ⁶は、それぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜７のシクロアルキル基、アリール基、アラルキル基、アシル基、アシロキシ基、あるいは、Ｒ¹とＲ²、Ｒ¹とＲ³、Ｒ¹とＲ⁴、Ｒ¹とＲ⁵、Ｒ¹とＲ⁶、Ｒ²とＲ³、Ｒ²とＲ⁴、Ｒ²とＲ⁵、Ｒ²とＲ⁶、Ｒ³とＲ⁴、Ｒ³とＲ⁵、Ｒ³とＲ⁶、Ｒ⁴とＲ⁵、Ｒ⁴とＲ⁶又はＲ⁵とＲ⁶が炭素数１〜３の炭素鎖で架橋されたものを示し、これらは独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜７のシクロアルキル基、アリール基、アラルキル基、カルボキシル基、ハロゲン原子で置換されていてもよい。また、式中、Ｒ⁷〜Ｒ⁸は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ⁹〜Ｒ¹²は、それぞれ独立に、水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表す。) First, the compound represented by general formula (1), which is a raw material component of the production method of the present invention, will be described.
The triolefin compound which is a raw material component of the production method of the present invention is a compound represented by the following general formula (1).
General formula (1)

Wherein R ^{1 to} R ⁶ are each independently a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cycloalkyl having 3 to 7 carbon atoms. Group, aryl group, aralkyl group, acyl group, acyloxy group, or R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ¹ and R ⁵ , R ¹ and R ⁶ , R ² and R ³ , R ² and R ⁴ , R ² and R ⁵ , R ² and R ⁶ , R ³ and R ⁴ , R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , R ⁴ and R ⁶ or R ⁵ and R ⁶ are cross-linked by a carbon chain having 1 to 3 carbon atoms, and these are independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 3 to 7 carbon atoms. cycloalkyl group, an aryl group, an aralkyl group, a carboxyl group, may be substituted with a halogen atom. in the above formula, R ⁷ to R ⁸ each independently represent a hydrogen atom or Represents an alkyl group of prime 1-4, R ⁹ to R ¹² each independently represent a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.)

In general formula (1), R ^{1 to} R ⁶ are each independently a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 3 to 7 carbon atoms. Cycloalkyl group, aryl group, aralkyl group, acyl group, acyloxy group, or R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ¹ and R ⁵ , R ¹ and R ⁶ , R ² and R ³ , R ² and R ⁴ , R ² and R ⁵ , R ² and R ⁶ , R ³ and R ⁴ , R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , R ⁴ and R ⁶ or R ⁵ and R ⁶ are cross-linked by a carbon chain having 1 to 3 carbon atoms, and these are independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 3 carbon atoms. May be substituted with a cycloalkyl group of ˜7, an aryl group, an aralkyl group, a carboxyl group, or a halogen atom. In the formula, R ^{7 to} R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{9 to} R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. An alkyl group or an alkoxy group having 1 to 4 carbon atoms is represented.

  Specific examples of the compound represented by the general formula (1) include compounds having the following structures.

Among these, the following compounds are preferable.

  There is no restriction | limiting in the density | concentration of the hydrogen-peroxide solution used in the manufacturing method of this invention, Although reaction to a triolefin compound occurs according to a density | concentration, Generally 1-80%, Preferably it is 20-80% Selected from a range.

  The amount of the hydrogen peroxide aqueous solution used is not limited, and the reaction to the triolefin compound occurs depending on the amount used, but is generally 0.8 to 10.0 equivalents, preferably 1. It is selected from the range of 0 to 3.0 equivalents.

As the phase transfer catalyst, for example, quaternary ammonium hydrogen sulfate can be suitably used.
Examples of the quaternary ammonium hydrogen sulfate include tetrahexylammonium hydrogen sulfate, tetraoctylammonium hydrogensulfate, methyltrioctylammonium hydrogensulfate, tetrabutylammonium hydrogensulfate, ethyltrioctylammonium hydrogensulfate, cetylpyridinium hydrogensulfate and the like. Examples thereof include tetrahexylammonium hydrogensulfate, tetraoctylammonium hydrogensulfate, and methyltrioctylammonium hydrogensulfate. These quaternary ammonium hydrogen sulfates may be used alone or in combination of two or more. The amount used is selected from the range of 0.0001 to 10 mol%, preferably 0.01 to 5 mol%, based on the triolefin as a substrate.

  In the case of molybdenum, the Group 6 metal compound is a compound that generates a molybdate anion in water. For example, molybdic acid, molybdenum trioxide, molybdenum trisulfide, molybdenum hexachloride, phosphomolybdic acid, ammonium molybdate, potassium molybdate Examples thereof include dihydrate and sodium molybdate dihydrate, but molybdic acid, molybdenum trioxide, and phosphomolybdic acid are preferable.

  In the case of tungsten, it is a compound that produces tungstate anions in water, such as tungstic acid, tungsten trioxide, tungsten trisulfide, tungsten hexachloride, phosphotungstic acid, ammonium tungstate, potassium tungstate dihydrate, tungstic acid Examples thereof include sodium dihydrate, and tungstic acid, tungsten trioxide, phosphotungstic acid, sodium tungstate dihydrate and the like are preferable. These Group 6 metal compounds may be used alone or in combination of two or more. The amount used is selected from the range of 0.0001 to 20 mol%, preferably 0.01 to 20 mol%, based on the triolefin as a substrate.

  It should be noted that this type of catalyst may be modified by using additives such as phosphoric acid, polyphosphoric acid, aminomethylphosphonic acid, and sodium phosphate, and is preferably added.

In the production method of the present invention, the reaction is usually performed in the range of 30 to 100 ° C, preferably in the range of 40 to 80 ° C.
The polyfunctional epoxy compound thus obtained is a compound represented by the general formula (2).

(式中、Ｒ¹〜Ｒ⁶は、それぞれ独立に、水素原子、ヒドロキシ基、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜７のシクロアルキル基、アリール基、アラルキル基、アシル基、アシロキシ基、あるいは、Ｒ¹とＲ²、Ｒ¹とＲ³、Ｒ¹とＲ⁴、Ｒ¹とＲ⁵、Ｒ¹とＲ⁶、Ｒ²とＲ³、Ｒ²とＲ⁴、Ｒ²とＲ⁵、Ｒ²とＲ⁶、Ｒ³とＲ⁴、Ｒ³とＲ⁵、Ｒ³とＲ⁶、Ｒ⁴とＲ⁵、Ｒ⁴とＲ⁶又はＲ⁵とＲ⁶が炭素数１〜３の炭素鎖で架橋されたものを示し、これらは独立に炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、炭素数３〜７のシクロアルキル基、アリール基、アラルキル基、カルボキシル基、ハロゲン原子で置換されていてもよい。また、式中、Ｒ⁷〜Ｒ⁸は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ⁹〜Ｒ¹²は、それぞれ独立に、水素原子、炭素数１〜４のアルキル基又は炭素数１〜４のアルコキシ基を表す。) General formula (2)

Wherein R ^{1 to} R ⁶ are each independently a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cycloalkyl having 3 to 7 carbon atoms. Group, aryl group, aralkyl group, acyl group, acyloxy group, or R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ¹ and R ⁵ , R ¹ and R ⁶ , R ² and R ³ , R ² and R ⁴ , R ² and R ⁵ , R ² and R ⁶ , R ³ and R ⁴ , R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , R ⁴ and R ⁶ or R ⁵ and R ⁶ are cross-linked by a carbon chain having 1 to 3 carbon atoms, and these are independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 3 to 7 carbon atoms. cycloalkyl group, an aryl group, an aralkyl group, a carboxyl group, may be substituted with a halogen atom. in the above formula, R ⁷ to R ⁸ each independently represent a hydrogen atom or Represents an alkyl group of prime 1-4, R ⁹ to R ¹² each independently represent a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.)

  Specific examples of the compound represented by the general formula (2) include compounds having the following structures.

  The target polyfunctional epoxy compound thus produced can be taken out by a usual method such as recrystallization, distillation or sublimation after concentrating the mixed solution after completion of the reaction.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.

The yields described herein are defined as follows:
Conversion rate (%) of the compound represented by the general formula (1) = [(mol number of the compound represented by the reacted general formula (1)) / (represented by the general formula (1) supplied to the reaction) Compound mol number)] × 100
Yield of compound represented by general formula (2) (%) = [(conversion rate of compound represented by general formula (1) (%)) × ((number of moles of polyfunctional epoxy compound produced)) / (Number of moles of the compound represented by the general formula (1) reacted)) × 100 (%))] / 100

Example 1
Na ₂ WO ₄ .2H ₂ O (790.6 mg, 2.40 mmol), 30% by mass aqueous hydrogen peroxide solution (14.96 g, 0.132 mol), methyl trioctylammonium hydrogen sulfate (559.2 mg, 1.20 mmol) , Aminomethylphosphonic acid (0.133 g, 1.20 mmol) and the following compound (1) (30.0 g, 0.120 mol) were mixed and reacted at 25 ° C. for 3 minutes, and then heated to 60 ° C. for 6 hours. Stir. After completion of the reaction, it was cooled to room temperature. After post-treatment with a saturated aqueous solution of sodium thiosulfate, the organic layer was taken out. When the obtained solution was measured by gas chromatography, the conversion rate of the raw material compound (1) was 96%, and the polyfunctional epoxy compound 4,5-epoxycyclohexane-1,2-dicarboxylic acid. It was confirmed that the yield of diallyl was 93%. As a result, no diepoxide or triepoxide was produced.

また、４, ５−エポキシシクロヘキサン−１，２−ジカルボン酸ジアリルには、下記化合物（２）及び下記化合物（３）に２種の異性体が存在するが、上記反応では、４, ５−エポキシシクロヘキサン−１，２−ジカルボン酸ジアリルのうち９６％が化合物（２）であり、４％が化合物（３）であることが、ガスクロマトグラフ(以下、ＧＣと記す。) 法により確認された。 Compound (1)

Further, diallyl 4,5-epoxycyclohexane-1,2-dicarboxylate has two isomers in the following compound (2) and the following compound (3), but in the above reaction, 4,5-epoxy It was confirmed by a gas chromatograph (hereinafter referred to as GC) method that 96% of cycloallyl-1,2-dicarboxylic acid diallyl was compound (2) and 4% was compound (3).

Compound (2)

なお、そのときのＧＣ法の分析条件は以下の通りである。
使用カラム：Ｊ＆Ｗ サイエンティフィック社製 ＨＰ−１
（長さ３０ｍ、内径０．３２ｍｍ、膜厚０．２５μｍ）
インジェクション温度：３００℃
検出器温度：３００℃
カラムの温度条件：スタート温度１３０℃で２分間ホールドし、その後２０℃／分の昇温速度で２８０℃まで昇温し、その後、６．５分間２８０℃でホールド Compound (3)

The analytical conditions of the GC method at that time are as follows.
Column used: HP-1 manufactured by J & W Scientific
(Length 30m, inner diameter 0.32mm, film thickness 0.25μm)
Injection temperature: 300 ° C
Detector temperature: 300 ° C
Column temperature condition: Hold at a start temperature of 130 ° C. for 2 minutes, then increase the temperature to 280 ° C. at a temperature increase rate of 20 ° C./min, and then hold at 280 ° C. for 6.5 minutes

Example 2
Na ₂ WO ₄ .2H ₂ O (790.6 mg, 2.40 mmol), 30% by mass aqueous hydrogen peroxide solution (14.96 g, 0.132 mmol), methyl trioctylammonium hydrogen sulfate (559.2 mg, 1.20 mmol) , Aminomethylphosphonic acid (0.133 g, 1.20 mmol) and the following compound (4) (31.7 g, 0.120 mol) were mixed and reacted at 25 ° C. for 3 minutes, and then heated to 60 ° C. for 6 hours. Stir. When the same operation as in Example 1 was performed, the conversion of the compound (4) as a raw material was 94%, and the polyfunctional epoxy compound 4-methyl-4,5-epoxycyclohexane-1,2- It was confirmed that the yield of diallyl dicarboxylate was 90%. As a result, no diepoxide or triepoxide was produced.

また、４−メチル−４, ５−エポキシシクロヘキサン−１，２−ジカルボン酸ジアリルには、下記化合物（５）及び下記化合物（６）に２種の異性体が存在するが、上記反応では、４−メチル−４, ５−エポキシシクロヘキサン−１，２−ジカルボン酸ジアリルのうち９６％が化合物（５）であり、４％が化合物（６）であることが、ＧＣ法により確認された。 Compound (4)

Further, 4-methyl-4,5-epoxycyclohexane-1,2-dicarboxylate diallyl has two isomers in the following compound (5) and the following compound (6). It was confirmed by the GC method that 96% of the diallyl-methyl-4,5-epoxycyclohexane-1,2-dicarboxylate was compound (5) and 4% was compound (6).

Compound (5)

なお、そのときのＧＣ法の分析条件は、実施例１で記載したのと同様の条件である。 Compound (6)

Note that the analysis conditions of the GC method at that time are the same as those described in Example 1.

Comparative Example 1
A 2-liter four-necked flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel is charged with 400 g of compound (1), 600 g of benzene, 41 g of 90% formic acid, 2 g of 40% phosphoric acid and 2 g of calcium chloride. While stirring the product, adjusting the temperature to 50 to 60 ° C., 132 g of a 50 mass% hydrogen peroxide aqueous solution was dropped from the dropping funnel over 30 minutes and reacted at 60 ° C. for 5 hours. Then, as a result of analyzing by GC method, the yield of diallyl 4,5-epoxycyclohexane-1,2-dicarboxylate was 65%.
Note that the analysis conditions of the GC method at that time are the same as those described in Example 1.

Claims (3)

The following general formula (1) using an aqueous hydrogen peroxide solution as an oxidizing agent in the presence of a phase transfer catalyst and a Group 6 metal compound without using an organic solvent :

Wherein R ^{1 to} R ⁶ are each independently a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cycloalkyl having 3 to 7 carbon atoms. Group, aryl group, aralkyl group, acyl group, acyloxy group, or R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ¹ and R ⁵ , R ¹ and R ⁶ , R ² and R ³ , R ² and R ⁴ , R ² and R ⁵ , R ² and R ⁶ , R ³ and R ⁴ , R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , R ⁴ and R ⁶ or R ⁵ and R ⁶ are cross-linked by a carbon chain having 1 to 3 carbon atoms, and these are independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 3 to 7 carbon atoms. cycloalkyl group, an aryl group, an aralkyl group, a carboxyl group, may be substituted with a halogen atom. in the above formula, R ⁷ to R ⁸ each independently represent a hydrogen atom or Represents an alkyl group of prime 1-4, R ⁹ to R ¹² each independently represent a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.)
The compound represented by the following formula (2) is oxidized:

Wherein R ^{1 to} R ⁶ are each independently a hydrogen atom, a hydroxy group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a cycloalkyl having 3 to 7 carbon atoms. Group, aryl group, aralkyl group, acyl group, acyloxy group, or R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R ¹ and R ⁵ , R ¹ and R ⁶ , R ² and R ³ , R ² and R ⁴ , R ² and R ⁵ , R ² and R ⁶ , R ³ and R ⁴ , R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , R ⁴ and R ⁶ or R ⁵ and R ⁶ are cross-linked by a carbon chain having 1 to 3 carbon atoms, and these are independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and 3 to 7 carbon atoms. cycloalkyl group, an aryl group, an aralkyl group, a carboxyl group, may be substituted with a halogen atom. in the above formula, R ⁷ to R ⁸ each independently represent a hydrogen atom or Represents an alkyl group of prime 1-4, R ⁹ to R ¹² each independently represent a hydrogen atom, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.)
The manufacturing method of the said epoxy compound characterized by manufacturing the epoxy compound represented by these.   The method of claim 1, wherein the phase transfer catalyst is a quaternary ammonium hydrogen sulfate compound.   The method according to claim 1, wherein the group 6 metal compound is tungsten.