JP2008106016A - Polyfunctional epoxy compounds by selective oxidation of polyolefin compounds - Google Patents

Abstract

The present invention provides a novel process for producing a safe and easy polyfunctional epoxy compound by reaction of polyolefins with an aqueous hydrogen peroxide solution under mild conditions.
A double bond site of a cycloolefin in a compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure is selected using hydrogen peroxide in the presence of a rhenium compound. The polyfunctional epoxy compound containing an epoxy group and a double bond in the molecule is selectively produced in a high yield by selectively oxidizing and producing a polyfunctional epoxy group-containing compound selectively in a high yield be able to.
[Selection figure] None

Description

  The present invention relates to a method for epoxidizing polyolefins so as to obtain a polyfunctional epoxy compound containing an epoxy group and a double bond in the molecule. In particular, the present invention relates to a novel process for producing a polyfunctional epoxy compound in which a triolefin and an aqueous hydrogen peroxide solution are reacted in the presence of a rhenium compound as a catalyst to selectively epoxidize one double bond. 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 compounds (polyolefins) having two or more double bonds in the molecule is low productivity (low reactivity, low selectivity) Are often restricted to certain types of structures.
Conventionally, a method using an organic peracid such as performic acid or peracetic acid as a selective epoxidizing agent for polyolefins is known (for example, Chem. Ber., 1985, 118, 1267-1270). European Patent Publication No. 0033763 (Patent Document 1) generates an equivalent amount of an oxidant-derived acid, which causes problems such as corrosion of the apparatus, and a diol is easily formed as a by-product in a substrate that easily reacts to an acid.

  A selective epoxidation method of diolefin using oxone as an oxidizing agent under a ketone catalyst (J. Org. Chem., 1998, 63, 2948-2953) is known. A very large amount of ketone is required (20-30 mol% with respect to diolefins), and the reaction conditions such as pH and reaction temperature in the solution must be strictly controlled to suppress the decomposition of oxone during the reaction. There is a problem that there is.

  On the other hand, hydrogen peroxide 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.

For selective epoxidation of diolefins using hydrogen peroxide as an epoxidizing agent, (1) Formula Q ₃ XW ₄ O ₂₄ , wherein Q is a quaternary ammonium cation containing up to 70 carbon atoms. And X represents P or As). A method of epoxidizing a diolefin with hydrogen peroxide in the presence of a catalyst represented by the formula (JP-A-4-275281 Patent Document 2), (2) quaternary ammonium chloride, phosphorus A method of epoxidizing a diolefin having a methacrylic acid unit with hydrogen peroxide in the presence of an acid or a tungsten compound (Tetrahedron, 1992, 48, 5099-5110 Non-Patent Document 3), (3) Tungsten compound and quaternary pyridinium salt Method for monoepoxidation of 1,5,9-cyclododecatriene (CDT) in the presence (JP 2000-2644 A) Patent Document 3), (4) A method of selectively monoepoxidizing a macrocyclic aliphatic compound with hydrogen peroxide in the presence of a polyoxometalate complex of tungsten and molybdenum (Japanese Patent Laid-Open No. 2002-155066). In (1), since the amount of hydrogen peroxide is less than 1 equivalent to 1 equivalent of diolefin, the reaction yield is very poor (32 to 48% with respect to the diolefin used).・ Production time is low and productivity is low. The method (2) is limited to diolefins having methacrylic acid units. Since the method (3) is less than 1 equivalent per 1 equivalent of triolefin, the conversion rate of the raw material is very bad. In the method (4), the monoepoxidation selectivity significantly decreases with time. There is a problem. Patent Document 2, Non-Patent Document 3, Patent Document 3 and Patent Document 4 are all about epoxidation of a compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure. We do not disclose anything.

  Examples of selective epoxidation of a compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure using hydrogen peroxide include (5) alkali metal, alkaline earth metal or ammonium In the presence of an acid catalyst such as a salt soluble in water, phosphoric acid, sulfuric acid, p-toluenesulfonic acid and formic acid, diallyl tetrahydrophthalate is selectively epoxidized with hydrogen peroxide, and 4,5-epoxycyclohexane-1 , 2-dicarboxylic acid diallyl method (Japanese Patent Publication No. 50-39659 Patent Document 5). However, with the method (5), the yield was only about 65%, which was not satisfactory.

  On the other hand, regarding the selective epoxidation of polyolefins using a rhenium compound as a catalyst and hydrogen peroxide as an epoxidizing agent, (6) a method of epoxidizing with hydrogen peroxide using an organic rhenium oxide as a catalyst 25665 Patent Document 6, CR Acad. Sci, Series IIC Chem., Vol. 3, 2000, 10, 793-801 Non-Patent Document 4, Tetrahedron, 2005, 61, 1069-1075 Non-Patent Document 5, etc.) Can be mentioned. However, Patent Document 6, Non-Patent Document 4, and Non-Patent Document 5 all disclose epoxidation of a compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure. Not.

Therefore, a polyfunctional epoxy compound can be selectively produced from a compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure with good yield and low yield under a mild condition and with a simple operation. There is a strong demand for the development of a manufacturing method at low cost.
Chem. Ber. , 118, 1267-1270 (1985). J. et al. Org. Chem. 63, 2948-2953 (1998). Tetrahedron, 48, 5099-5110 (1992) C. R. Acad. Sci. , Series IIC Chem. , Vol. 3, 10, 793-801 (2000) Tetrahedron, 61, 1069-1075 (2005) European Patent Publication No. 0033763 JP-A-4-275281 JP 2000-26441 A JP 2002-155066 A Japanese Patent Publication No.50-39659 Japanese Patent Laid-Open No. 2001-25665

  An object of the present invention is to provide a novel method for producing a safe and easy polyfunctional epoxy compound by a reaction between a polyolefin and an aqueous hydrogen peroxide solution under mild conditions.

  As a result of intensive studies to solve the above problems, the present inventors have found that at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure using hydrogen peroxide in the presence of a rhenium compound. It has been found that a double bond site of a cycloolefin in a compound having a hydrogen atom is selectively oxidized to selectively produce a polyfunctional epoxy group-containing compound in a high yield, and the present invention has been completed.

  That is, this invention relates to the manufacturing method of a polyfunctional epoxy compound in presence of the rhenium compound shown by the following [1]-[10].

[1] Oxidizing the double bond site of cycloolefin in a compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure using hydrogen peroxide in the presence of a rhenium compound. A method for producing a polyfunctional epoxy compound, comprising producing an epoxy group-containing compound.

[2] The method according to [1], wherein the cycloolefin structure is a carbon 6-8 membered ring.

（式中、Ｒ^１は水素又はメチル基を表し、Ｒ^２は炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^３〜Ｒ^１０はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ａは０〜３の整数を表し、そしてｂは０〜２の整数を表す。）
一般式（２）：

（式中、Ｒ^１１は水素又はメチル基を表し、Ｒ^１２は炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^１３〜Ｒ^２０はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｃは０〜３の整数を表し、そしてｄは０〜２の整数を表す。）
一般式（３）：

（式中、Ｒ^２１，Ｒ^２２はそれぞれ独立に水素又はメチル基を表し、Ｒ^２３，Ｒ^２４はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^２５〜Ｒ^３２はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｅ、ｇはそれぞれ独立に０〜３の整数を表し、そしてｆ、ｈはそれぞれ独立に０〜２の整数を表す。）
一般式（４）：

（式中、Ｒ^３３，Ｒ^３４はそれぞれ独立に水素又はメチル基を表し、Ｒ^３５，Ｒ^３６はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^３７〜Ｒ^４４はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｉ、ｋはそれぞれ独立に０〜３の整数を表し、そしてｊ、ｌはそれぞれ独立に０〜２の整数を表す。）
一般式（５）：

（式中、Ｒ^４５は水素又はメチル基を表し、Ｒ^４６〜Ｒ^５３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）
一般式（６）：

（式中、Ｒ^５４は水素又はメチル基を表し、Ｒ^５５〜Ｒ^６２はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）
一般式（７）：

（式中、Ｒ^６３，Ｒ^６４はそれぞれ独立に水素又はメチル基を表し、Ｒ^６５，Ｒ^６６はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^６７〜Ｒ^７３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｉ、ｋはそれぞれ独立に０〜３の整数を表し、そしてｊ、ｌはそれぞれ独立に０〜２の整数を表す。）
一般式（８）：

（式中、Ｒ^７４，Ｒ^７５はそれぞれ独立に水素又はメチル基を表し、Ｒ^７６，Ｒ^７７はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^７８〜Ｒ^８３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｉ、ｋはそれぞれ独立に０〜３の整数を表し、そしてｊ、ｌはそれぞれ独立に０〜２を表す。）
一般式（９）：

（式中、Ｒ^８４は水素又はメチル基を表し、Ｒ^８５〜Ｒ^９１はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）
一般式（１０）：

（式中、Ｒ^９２は水素又はメチル基を表し、Ｒ^９３〜Ｒ^９８はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）。 [3] The compound having the at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure is selected from the group consisting of the following general formulas (1) to (10): The method according to [1] or [2]:
General formula (1):

(In the formula, R ¹ represents hydrogen or a methyl group, R ² represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and R ^{3 to} R ¹⁰ represent Each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, a represents an integer of 0 to 3, and b represents an integer of 0 to 2).
General formula (2):

(In the formula, R ¹¹ represents hydrogen or a methyl group, R ¹² represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and R ^{13 to} R ²⁰ represent Each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, c represents an integer of 0 to 3, and d represents an integer of 0 to 2).
General formula (3):

(In the formula, R ²¹ and R ²² each independently represent hydrogen or a methyl group, and R ²³ and R ²⁴ each independently represents a divalent aliphatic, alicyclic or aromatic carbon selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{25 to} R ³² each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, e and g each independently represents an integer of 0 to 3, and f, h represents an integer of 0 to 2 independently.)
General formula (4):

(In the formula, R ³³ and R ³⁴ each independently represent hydrogen or a methyl group, and R ³⁵ and R ³⁶ are each independently a divalent aliphatic, alicyclic, or aromatic carbonization selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{37 to} R ⁴⁴ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, i, k each independently represents an integer of 0 to 3, and j, l represents each independently an integer of 0 to 2.)
General formula (5):

(In the formula, R ⁴⁵ represents hydrogen or a methyl group, and R ^{46 to} R ⁵³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (6):

(In the formula, R ⁵⁴ represents hydrogen or a methyl group, and R ^{55 to} R ⁶² each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (7):

(In the formula, R ⁶³ and R ⁶⁴ each independently represent hydrogen or a methyl group, and R ⁶⁵ and R ⁶⁶ each independently represents a divalent aliphatic, alicyclic or aromatic carbon selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{67 to} R ⁷³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine, i, k each independently represents an integer of 0 to 3, and j, l represents each independently an integer of 0 to 2.)
General formula (8):

(In the formula, R ⁷⁴ and R ⁷⁵ each independently represent hydrogen or a methyl group, and R ⁷⁶ and R ⁷⁷ each independently represents a divalent aliphatic, alicyclic, or aromatic carbonized group having 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{78 to} R ⁸³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, i, k each independently represents an integer of 0 to 3, and j, l represents 0-2 independently.)
General formula (9):

(Wherein R ⁸⁴ represents hydrogen or a methyl group, and R ^{85 to} R ⁹¹ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (10):

(Wherein R ⁹² represents hydrogen or a methyl group, and R ^{93 to} R ⁹⁸ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine).

(式中、Ｒ^９９は水素又はメチル基を表し、Ｒ^１００〜Ｒ^１０７はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、そしてｖは０〜２の整数を表す。）
一般式（１２）：

(式中、Ｒ^１０８は水素又はメチル基を表し、Ｒ^１０９〜Ｒ^１１６はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、そしてｗは０〜２の整数を表す。）。 [4] The compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure is a compound represented by the following general formula (11) or the following general formula (12): The method according to [1] or [2] above:
General formula (11):

(Wherein R ⁹⁹ represents hydrogen or a methyl group, R ^{100 to} R ¹⁰⁷ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine, and v represents an integer of 0 to 2) .)
General formula (12):

(Wherein R ¹⁰⁸ represents hydrogen or a methyl group, R ^{109 to} R ¹¹⁶ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, and w represents an integer of 0 to 2) .)

（式中、Ｒ^４５は水素又はメチル基を表し、Ｒ^４６〜Ｒ^５３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）
一般式（６）：

（式中、Ｒ^５４は水素又はメチル基を表し、Ｒ^５５〜Ｒ^６２はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）。 [5] The compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure is a compound represented by the following general formula (5) or the following general formula (6): The method according to [1] or [2] above:
General formula (5):

(In the formula, R ⁴⁵ represents hydrogen or a methyl group, and R ^{46 to} R ⁵³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (6):

(Wherein R ⁵⁴ represents hydrogen or a methyl group, and R ^{55 to} R ⁶² each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine).

（式中、Ｒ^１１７，Ｒ^１１８はそれぞれ独立に水素又はメチル基を表し、Ｒ^１１９〜Ｒ^１２６はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）
一般式（１４）：

（式中、Ｒ^１２７，Ｒ^１２８はそれぞれ独立に水素又はメチル基を表し、Ｒ^１２９〜Ｒ^１３６はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）。 [6] The compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure is a compound represented by the following general formula (13) or the following general formula (14): The method according to [1] or [2] above:
General formula (13):

(In the formula, R ¹¹⁷ and R ¹¹⁸ each independently represent hydrogen or a methyl group, and R ^{119 to} R ¹²⁶ each independently represent an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (14):

(Wherein R ¹²⁷ and R ¹²⁸ each independently represent hydrogen or a methyl group, and R ^{129 to} R ¹³⁶ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine).

[7] The method according to any one of [1] to [4], wherein the terminal vinyl or vinylidene structure is an allyl or methallyl structure.

[8] The method according to any one of [1] to [7], wherein the rhenium compound is methyltrioxorhenium.

[9] The method according to any one of [1] to [8], wherein an organic basic compound is used in an amount of 1 to 30 moles relative to the rhenium compound.

[10] Hydrogen peroxide is 0.8 to 0.8 with respect to the number of double bonds contained in the cycloolefin structure of the compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure. It contains 10.0 times, The method in any one of said [1]-[9] characterized by the above-mentioned.

  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 polyfunctional epoxy compound, a useful substance widely used in the industrial field, can be produced safely and easily in a simple operation from the reaction of the corresponding polyolefins and hydrogen peroxide solution. Bring.

The present invention will be specifically described below.
The present invention uses hydrogen peroxide in the presence of a rhenium compound to oxidize the double bond site of cycloolefin in a compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure. Then, it is a manufacturing method of the polyfunctional epoxy compound characterized by manufacturing an epoxy-group containing compound.

First, a compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure, which is a raw material component of the production method of the present invention, will be described.
The compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure, which is a raw material component of the production method of the present invention, has one or more cycloolefin structures and one or more compounds in the same molecule. As long as it is a compound having a terminal vinyl or vinylidene structure, there is no particular limitation.

  Among the cycloolefin structures, considering the ease of synthesis or availability, a preferred cycloolefin structure is a cycloolefin structure having a carbon 6-8 membered ring structure.

  Among the compounds having at least one or more cycloolefin structures and at least one or more terminal vinyl or vinylidene structures, the following general formulas (1) to (10) can be mentioned as preferable ones:

（式中、Ｒ^１は水素又はメチル基を表し、Ｒ^２は炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^３〜Ｒ^１０はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ａは０〜３の整数を表し、そしてｂは０〜２の整数を表す。）
一般式（２）：

（式中、Ｒ^１１は水素又はメチル基を表し、Ｒ^１２は炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^１３〜Ｒ^２０はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｃは０〜３の整数を表し、そしてｄは０〜２の整数を表す。）
一般式（３）：

（式中、Ｒ^２１，Ｒ^２２はそれぞれ独立に水素又はメチル基を表し、Ｒ^２３，Ｒ^２４はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^２５〜Ｒ^３２はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｅ、ｇはそれぞれ独立に０〜３の整数を表し、そしてｆ、ｈはそれぞれ独立に０〜２の整数を表す。）
一般式（４）：

（式中、Ｒ^３３，Ｒ^３４はそれぞれ独立に水素又はメチル基を表し、Ｒ^３５，Ｒ^３６はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^３７〜Ｒ^４４はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｉ、ｋはそれぞれ独立に０〜３の整数を表し、そしてｊ、ｌはそれぞれ独立に０〜２の整数を表す。）
一般式（５）：

（式中、Ｒ^４５は水素又はメチル基を表し、Ｒ^４６〜Ｒ^５３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）
一般式（６）：

（式中、Ｒ^５４は水素又はメチル基を表し、Ｒ^５５〜Ｒ^６２はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）
一般式（７）：

（式中、Ｒ^６３，Ｒ^６４はそれぞれ独立に水素又はメチル基を表し、Ｒ^６５，Ｒ^６６はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^６７〜Ｒ^７３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｍ、ｐはそれぞれ独立に０〜３の整数を表し、ｎ、ｑはそれぞれ独立に０〜２の整数を表す。）
一般式（８）：

（式中、Ｒ^７４，Ｒ^７５はそれぞれ独立に水素又はメチル基を表し、Ｒ^７６，Ｒ^７７はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^７８〜Ｒ^８３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｒ、ｔはそれぞれ独立に０〜３の整数を表し、そしてｓ、ｕはそれぞれ独立に０〜２を表す。）
一般式（９）：

（式中、Ｒ^８４は水素又はメチル基を表し、Ｒ^８５〜Ｒ^９１はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）
一般式（１０）：

（式中、Ｒ^９２は水素又はメチル基を表し、Ｒ^９３〜Ｒ^９８はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）。 General formula (1):

(In the formula, R ¹ represents hydrogen or a methyl group, R ² represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and R ^{3 to} R ¹⁰ represent Each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, a represents an integer of 0 to 3, and b represents an integer of 0 to 2).
General formula (2):

(In the formula, R ¹¹ represents hydrogen or a methyl group, R ¹² represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and R ^{13 to} R ²⁰ represent Each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, c represents an integer of 0 to 3, and d represents an integer of 0 to 2).
General formula (3):

(In the formula, R ²¹ and R ²² each independently represent hydrogen or a methyl group, and R ²³ and R ²⁴ each independently represents a divalent aliphatic, alicyclic or aromatic carbon selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{25 to} R ³² each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, e and g each independently represents an integer of 0 to 3, and f, h represents an integer of 0 to 2 independently.)
General formula (4):

(In the formula, R ³³ and R ³⁴ each independently represent hydrogen or a methyl group, and R ³⁵ and R ³⁶ are each independently a divalent aliphatic, alicyclic, or aromatic carbonization selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{37 to} R ⁴⁴ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, i, k each independently represents an integer of 0 to 3, and j, l represents each independently an integer of 0 to 2.)
General formula (5):

(In the formula, R ⁴⁵ represents hydrogen or a methyl group, and R ^{46 to} R ⁵³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (6):

(In the formula, R ⁵⁴ represents hydrogen or a methyl group, and R ^{55 to} R ⁶² each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (7):

(In the formula, R ⁶³ and R ⁶⁴ each independently represent hydrogen or a methyl group, and R ⁶⁵ and R ⁶⁶ each independently represents a divalent aliphatic, alicyclic or aromatic carbon selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{67 to} R ⁷³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine; m and p each independently represents an integer of 0 to 3; Each independently represents an integer of 0 to 2.)
General formula (8):

(In the formula, R ⁷⁴ and R ⁷⁵ each independently represent hydrogen or a methyl group, and R ⁷⁶ and R ⁷⁷ each independently represents a divalent aliphatic, alicyclic, or aromatic carbonized group having 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{78 to} R ⁸³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, r and t each independently represents an integer of 0 to 3, and s, u represents 0-2 independently.)
General formula (9):

(Wherein R ⁸⁴ represents hydrogen or a methyl group, and R ^{85 to} R ⁹¹ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (10):

(Wherein R ⁹² represents hydrogen or a methyl group, and R ^{93 to} R ⁹⁸ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine).

（式中、Ｒ^１は水素又はメチル基を表し、Ｒ^２は炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^３〜Ｒ^１０はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ａは０〜３の整数を表し、そしてｂは０〜２の整数を表す。）。 First, the compound represented by the general formula (1) will be described.
General formula (1):

(In the formula, R ¹ represents hydrogen or a methyl group, R ² represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and R ^{3 to} R ¹⁰ represent Each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, a represents an integer of 0 to 3, and b represents an integer of 0 to 2).

In general formula (1), R ¹ represents hydrogen or a methyl group. R ² represents a divalent aliphatic, alicyclic, or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and examples thereof include the following residues.

In general formula (1), R ^{3 to} R ¹⁰ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.
Moreover, although a represents the integer of 0-3, Preferably, it is 0 or 1, More preferably, it is 0. b is an integer of 0 to 2, but preferably b = 1.
R ^{3 to} R ¹⁰ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.

(式中、Ｒ^９９は水素又はメチル基を表し、Ｒ^１００〜Ｒ^１０７はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。また、ｖは０〜２の整数を表す。）。 When the compound represented by the general formula (1) is a = 0 in the formula, the compound is represented by the general formula (11):
General formula (11):

(In the formula, R ⁹⁹ represents hydrogen or a methyl group, R ^{100 to} R ¹⁰⁷ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine; and v represents an integer of 0 to 2) To express.).

In general formula (11), R ⁹⁹ represents hydrogen or a methyl group. R ^{100 to} R ¹⁰⁷ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine. Further, v is an integer of 0 to 2, but preferably v = 1.

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

（式中、Ｒ^１１は水素又はメチル基を表し、Ｒ^１２は炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^１３〜Ｒ^２０はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｃは０〜３の整数を表し、そしてｄは０〜２の整数を表す。）。 Next, the compound represented by the general formula (2) will be described:
General formula (2):

(In the formula, R ¹¹ represents hydrogen or a methyl group, R ¹² represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and R ^{13 to} R ²⁰ represent Each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, c represents an integer of 0 to 3, and d represents an integer of 0 to 2).

In the general formula (2), R ¹¹ represents hydrogen or a methyl group. R ¹² represents a divalent aliphatic, alicyclic, or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and examples thereof include the following residues.

(式中、Ｒ^１０８は水素又はメチル基を表し、Ｒ^１０９〜Ｒ^１１６はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｗは０〜２の整数を表す。）。 In General Formula (2), R ^{13 to} R ²⁰ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.
C represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0. d is an integer of 0 to 2, preferably d = 1.
R ^{13 to} R ²⁰ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.
In the compound represented by the general formula (2), c = 0 in the formula is a compound represented by the general formula (12):
Formula (12):

(Wherein R ¹⁰⁸ represents hydrogen or a methyl group, R ^{109 to} R ¹¹⁶ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine, and w represents an integer of 0 to 2. ).

In the general formula (12), R ¹⁰⁸ represents hydrogen or a methyl group. R ^{109 to} R ¹¹⁶ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, and w is an integer of 0 to 2, but preferably w = 1.

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

（式中、Ｒ^２１，Ｒ^２２はそれぞれ独立に水素又はメチル基を表す。Ｒ^２３，Ｒ^２４はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^２５〜Ｒ^３２はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｅ、ｇはそれぞれ独立に０〜３の整数を表し、そしてｆ、ｈはそれぞれ独立に０〜２の整数を表す。）。 Next, the compound represented by the general formula (3) will be described:
General formula (3):

(In the formula, R ²¹ and R ²² each independently represent hydrogen or a methyl group. R ²³ and R ²⁴ are each independently a divalent aliphatic, alicyclic or aromatic carbon selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{25 to} R ³² each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, e and g each independently represents an integer of 0 to 3, and f, h represents an integer of 0 to 2 each independently.

In general formula (3), R ²¹ and R ²² each independently represent hydrogen or a methyl group. R ²³ and R ²⁴ each independently represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and examples thereof include the following residues.

（式中、Ｒ^１１７，Ｒ^１１８はそれぞれ独立に水素又はメチル基を表し、Ｒ^１１９〜Ｒ^１２６はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）。 Formula ^{(3) R} 25 ^{~R 32} are each independently hydrogen, represents an atomic group selected from methyl group, ethyl group or chlorine.
E and g each independently represent an integer of 0 to 3, preferably 0 or 1 each independently. f and h each independently represent an integer of 0 to 2, but preferably both f and h are 1.
When the compound represented by the general formula (3) and e = g = 0 and f = h = 1 in the formula, the compound is represented by the general formula (13):
General formula (13):

(Wherein R ¹¹⁷ and R ¹¹⁸ each independently represent hydrogen or a methyl group, and R ^{119 to} R ¹²⁶ each independently represent an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine).

In the general formula (13), R ¹¹⁷ and R ¹¹⁸ each independently represent hydrogen or a methyl group. R ^{119 to} R ¹²⁶ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.

Specific examples of the compound represented by the general formula (3) include compounds having the following structures.

（式中、Ｒ^３３，Ｒ^３４はそれぞれ独立に水素又はメチル基を表し、Ｒ^３５，Ｒ^３６はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^３７〜Ｒ^４４はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｉ、ｋはそれぞれ独立に０〜３の整数を表し、そしてｊ、ｌはそれぞれ独立に０〜２の整数を表す。）。 Next, the compound represented by the general formula (4) will be described:
General formula (4):

(In the formula, R ³³ and R ³⁴ each independently represent hydrogen or a methyl group, and R ³⁵ and R ³⁶ are each independently a divalent aliphatic, alicyclic, or aromatic carbonization selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{37 to} R ⁴⁴ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, i, k each independently represents an integer of 0 to 3, and j, l independently represents an integer of 0 to 2).

In General Formula (4), R ³³ and R ³⁴ each independently represent hydrogen or a methyl group. R ³⁵ and R ³⁶ each independently represent a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and examples thereof include the following residues.

In the general formula (4), R ^{37 to} R ⁴⁴ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine. I and k each independently represent an integer of 0 to 3, preferably 0 or 1, each independently. j and l each independently represents an integer of 0 to 2, but preferably j and l are both 1.

（式中、Ｒ^１２７，Ｒ^１２８はそれぞれ独立に水素又はメチル基を表し、Ｒ^１２９〜Ｒ^１３６はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。） When i = k = 0 and j = 1 = 1 in the compound represented by the general formula (4), the compound is represented by the general formula (14):
General formula (14):

(Wherein R ¹²⁷ and R ¹²⁸ each independently represent hydrogen or a methyl group, and R ^{129 to} R ¹³⁶ each independently represent an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)

In General Formula (14), R ¹²⁷ and R ¹²⁸ each independently represent hydrogen or a methyl group. R ^{129 to} R ¹³⁶ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.

Specific examples of the compound represented by the general formula (4) include compounds having the following structures.

（式中、Ｒ^４５は水素又はメチル基を表し、Ｒ^４６〜Ｒ^５３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）。 Next, the compound represented by the general formula (5) will be described:
General formula (5):

(In the formula, R ⁴⁵ represents hydrogen or a methyl group, and R ^{46 to} R ⁵³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine).

In general formula (5), R ⁴⁵ represents hydrogen or a methyl group. R ^{46 to} R ⁵³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.

Specific examples of the compound represented by the general formula (5) include compounds having the following structures.

（式中、Ｒ^５４は水素又はメチル基を表し、Ｒ^５５〜Ｒ^６２はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）。 Next, the compound represented by the general formula (6) will be described:
General formula (6):

(Wherein R ⁵⁴ represents hydrogen or a methyl group, and R ^{55 to} R ⁶² each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine).

In the general formula (6), R ⁵⁴ represents hydrogen or a methyl group. R ⁵⁵ to R ⁶² represent each independently a hydrogen, an atom group selected from a methyl group, an ethyl group or chlorine.

Specific examples of the compound represented by the general formula (6) include compounds having the following structures.

（式中、Ｒ^６３，Ｒ^６４はそれぞれ独立に水素又はメチル基を表し、Ｒ^６５，Ｒ^６６はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^６７〜Ｒ^７３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｍ、ｐはそれぞれ独立に０〜３の整数を表し、そしてｎ、ｑはそれぞれ独立に０〜２の整数を表す。）。 Next, the compound represented by the general formula (7) will be described:
General formula (7):

(In the formula, R ⁶³ and R ⁶⁴ each independently represent hydrogen or a methyl group, and R ⁶⁵ and R ⁶⁶ each independently represents a divalent aliphatic, alicyclic or aromatic carbon selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{67 to} R ⁷³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine, m and p each independently represents an integer of 0 to 3, and n, q independently represents an integer of 0 to 2).

In General Formula (7), R ⁶³ and R ⁶⁴ each independently represent hydrogen or a methyl group. R ⁶⁵ and R ⁶⁶ each independently represent a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and examples thereof include the following residues.

In General Formula (7), R ^{67 to} R ⁷³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine. M and p each independently represent an integer of 0 to 3, preferably 0 or 1 each independently. n and q each independently represent an integer of 0 to 2, but preferably both n and q are 1.

Specific examples of the compound represented by the general formula (7) include compounds having the following structures.

（式中、Ｒ^７４，Ｒ^７５はそれぞれ独立に水素又はメチル基を表し、Ｒ^７６，Ｒ^７７はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^７８〜Ｒ^８３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｒ、ｔはそれぞれ独立に０〜３の整数を表し、そしてｓ、ｕはそれぞれ独立に０〜２を表す。）。 Next, the compound represented by the general formula (8) will be described:
General formula (8):

(In the formula, R ⁷⁴ and R ⁷⁵ each independently represent hydrogen or a methyl group, and R ⁷⁶ and R ⁷⁷ each independently represents a divalent aliphatic, alicyclic, or aromatic carbonized group having 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{78 to} R ⁸³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, r and t each independently represents an integer of 0 to 3, and s, u independently represents 0 to 2).

In the general formula (8), R ⁷⁴ and R ⁷⁵ each independently represent hydrogen or a methyl group. R ⁷⁶ and R ⁷⁷ each independently represent a divalent aliphatic, alicyclic, or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and examples thereof include the following residues.

In the general formula (8), R ^{78 to} R ⁸³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine. R and t each independently represent an integer of 0 to 3, preferably 0 or 1 each independently. s and u each independently represents an integer of 0 to 2, but preferably both s and u are 1.

Specific examples of the compound represented by the general formula (8) include compounds having the following structures.

（式中、Ｒ^８４は水素又はメチル基を表し、Ｒ^８５〜Ｒ^９１はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）。 Next, the compound represented by the general formula (9) will be described:
General formula (9):

(Wherein R ⁸⁴ represents hydrogen or a methyl group, and R ^{85 to} R ⁹¹ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine).

In the general formula (9), ^R84 represents hydrogen or a methyl group. R ^{85 to} R ⁹¹ each independently represent an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.
Specific examples of the compound represented by the general formula (9) include compounds having the following structures.

（式中、Ｒ^９２は水素又はメチル基を表し、Ｒ^９３〜Ｒ^９８はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）。 Next, the compound represented by the general formula (10) will be described:
General formula (10):

(Wherein R ⁹² represents hydrogen or a methyl group, and R ^{93 to} R ⁹⁸ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine).

In general formula (10), R ⁹² represents hydrogen or a methyl group. R ^{93 to} R ⁹⁸ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.

Specific examples of the compound represented by the general formula (10) include compounds having the following structures.

Next, hydrogen peroxide, which is an essential component of the method for producing a polyfunctional epoxy compound of the present invention, will be described.
The concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution used in the production method of the present invention is not particularly limited, and at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure depending on the concentration. Although the reaction to the olefin compound occurs, it is generally selected from the range of 1 to 80%, preferably 20 to 80%.

  The amount of hydrogen peroxide aqueous solution used is not particularly limited, and depending on the amount used, a reaction to a compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure occurs. In general, hydrogen peroxide is 0.8% relative to the number of double bonds contained in the cycloolefin structure of a compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure. It is preferable to contain -10.0 times, More preferably, it selects from the range of 1.0-3.0 times.

  Examples of the rhenium compound include methyl trioxorhenium, ethyl trioxo rhenium, n-propyl trioxo rhenium, cyclohexyl trioxo rhenium, n-butyl trioxo rhenium, benzyl trioxo rhenium, and the like. Is preferred. These rhenium compounds may be used alone or in combination of two or more. The amount used is preferably selected in the range of 0.0001 to 20 mol%, more preferably 0, based on the compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure. The range is 0.01 to 10 mol%.

  In addition, it is possible and preferable to use an organic basic compound together as a promoter.

  Organic basic compounds include pyridine, pyrazine, pyrazole, pyrimidine, piperidine, 2-cyanopyridine, 4-cyanopyridine, 2-propylpyridine, α-picoline, β-picoline, γ-picoline, 2,2′-bipyridine. 2-aminopyridine, 2- (methylamino) pyridine, pyrrolidine, o-methoxypyridine, p-methoxypyridine, aniline, 8-hydroxyquinoline, quinuclidine, 4,4′-dimethylaminopyridine, o-phenanthroline, 4- A nitrogen-containing organic basic compound such as piperidinopyridine can be given as a representative example.

  Although there is no restriction | limiting in particular as the usage-amount of this organic basic compound, It is preferable to use 0.1-100 times mole with respect to a rhenium compound, More preferably, it is 1-30 times mole.

  Although the reaction temperature in this manufacturing method is normally performed in the range of 0-100 degreeC, it is preferable that it is the range of 0-50 degreeC, More preferably, it is the range of 3-40 degreeC.

（式中、Ｒ^１は水素又はメチル基を表し、Ｒ^２は炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^３〜Ｒ^１０はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ａは０〜３の整数を表し、そしてｂは０〜２の整数を表す。）
一般式（１６）：

（式中、Ｒ^１１は水素又はメチル基を表し、Ｒ^１２は炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^１３〜Ｒ^２０はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｃは０〜３の整数を表し、そしてｄは０〜２の整数を表す。）
一般式（１７）：

（式中、Ｒ^２１，Ｒ^２２はそれぞれ独立に水素又はメチル基を表し、Ｒ^２３，Ｒ^２４はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^２５〜Ｒ^３２はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｅ、ｇはそれぞれ独立に０〜３の整数を表し、そしてｆ、ｈはそれぞれ独立に０〜２の整数を表す。）
一般式（１８）：

（式中、Ｒ^３３，Ｒ^３４はそれぞれ独立に水素又はメチル基を表し、Ｒ^３５，Ｒ^３６はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^３７〜Ｒ^４４はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｉ、ｋはそれぞれ独立に０〜３の整数を表し、そしてｊ、ｌはそれぞれ独立に０〜２の整数を表す。）
一般式（１９）：

（式中、Ｒ^４５は水素又はメチル基を表し、Ｒ^４６〜Ｒ^５３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）
一般式（２０）：

（式中、Ｒ^５４は水素又はメチル基を表し、Ｒ^５５〜Ｒ^６２はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）
一般式（２１）：

（式中、Ｒ^６３，Ｒ^６４はそれぞれ独立に水素又はメチル基を表し、Ｒ^６５，Ｒ^６６はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^６７〜Ｒ^７３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｍ、ｐはそれぞれ独立に０〜３の整数を表し、そしてｎ、ｑはそれぞれ独立に０〜２の整数を表す。）
一般式（２２）：

（式中、Ｒ^７４，Ｒ^７５はそれぞれ独立に水素又はメチル基を表し、Ｒ^７６，Ｒ^７７はそれぞれ独立に炭素数２〜８から選ばれる２価の脂肪族、脂環族、芳香族炭化水素残基を表し、Ｒ^７８〜Ｒ^８３はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表し、ｒ、ｔはそれぞれ独立に０〜３の整数を表し、そしてｓ、ｕはそれぞれ独立に０〜２を表す。）
一般式（２３）：

（式中、Ｒ^８４は水素又はメチル基を表し、Ｒ^８５〜Ｒ^９１はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。）
一般式（２４）：

（式中、Ｒ^９２は水素又はメチル基を表し、Ｒ^９３〜Ｒ^９８はそれぞれ独立に水素、メチル基、エチル基または塩素から選ばれる原子団を表す。） The polyfunctional epoxy compounds obtained from the compounds represented by the general formulas (1) to (10) are compounds represented by the following general formulas (15) to (24), respectively:
General formula (15):

(In the formula, R ¹ represents hydrogen or a methyl group, R ² represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and R ^{3 to} R ¹⁰ represent Each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, a represents an integer of 0 to 3, and b represents an integer of 0 to 2).
Formula (16):

(In the formula, R ¹¹ represents hydrogen or a methyl group, R ¹² represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and R ^{13 to} R ²⁰ represent Each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, c represents an integer of 0 to 3, and d represents an integer of 0 to 2).
Formula (17):

(In the formula, R ²¹ and R ²² each independently represent hydrogen or a methyl group, and R ²³ and R ²⁴ each independently represents a divalent aliphatic, alicyclic or aromatic carbon selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{25 to} R ³² each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, e and g each independently represents an integer of 0 to 3, and f, h represents an integer of 0 to 2 independently.)
Formula (18):

(In the formula, R ³³ and R ³⁴ each independently represent hydrogen or a methyl group, and R ³⁵ and R ³⁶ are each independently a divalent aliphatic, alicyclic, or aromatic carbonization selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{37 to} R ⁴⁴ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, i, k each independently represents an integer of 0 to 3, and j, l represents each independently an integer of 0 to 2.)
Formula (19):

(In the formula, R ⁴⁵ represents hydrogen or a methyl group, and R ^{46 to} R ⁵³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
Formula (20):

(In the formula, R ⁵⁴ represents hydrogen or a methyl group, and R ^{55 to} R ⁶² each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
Formula (21):

(In the formula, R ⁶³ and R ⁶⁴ each independently represent hydrogen or a methyl group, and R ⁶⁵ and R ⁶⁶ each independently represents a divalent aliphatic, alicyclic or aromatic carbon selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{67 to} R ⁷³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine, m and p each independently represents an integer of 0 to 3, and n, q independently represents an integer of 0 to 2.)
General formula (22):

(In the formula, R ⁷⁴ and R ⁷⁵ each independently represent hydrogen or a methyl group, and R ⁷⁶ and R ⁷⁷ each independently represents a divalent aliphatic, alicyclic, or aromatic carbonized group having 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{78 to} R ⁸³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, r and t each independently represents an integer of 0 to 3, and s, u represents 0-2 independently.)
Formula (23):

(Wherein R ⁸⁴ represents hydrogen or a methyl group, and R ^{85 to} R ⁹¹ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (24):

(In the formula, R ⁹² represents hydrogen or a methyl group, and R ^{93 to} R ⁹⁸ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)

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

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited by a following example.
Example 1
In a 50 ml three-necked round bottom flask equipped with a reflux condenser, 2.530 g (10.1 mmol) of the following compound (1), 24.9 mg (0.1 mmol) of methyltrioxorhenium, 80.3 mg (1.0 mmol) of pyrimidine And 5 mg of methylene chloride. Thereafter, 1.247 g (11.0 mmol) of 30% by mass hydrogen peroxide was added, a Stirling bar was added, and stirring was continued for 6 hours at room temperature using a magnetic stirrer. Thereafter, as a result of analysis by a gas chromatograph (hereinafter referred to as GC) method, the conversion rate of the compound (1) was 85%, and the yield of diallyl 4,5-epoxycyclohexane-1,2-dicarboxylate was 83%. %Met.

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の６８％が化合物（２）であり、３２％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 68% of the cycloallyl-1,2-dicarboxylic acid diallyl was compound (2) and 32% 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
The same operation as in Example 1 was carried out except that 1.673 g (10.1 mmol) of compound (4) was used instead of 2.530 g (10.1 mmol) of compound (1). As a result, the conversion rate of the compound (4) was 99.5%, and the yield of allyl 3,4-epoxycyclohexane-1-carboxylate was 80%.

また、３，４−エポキシシクロヘキサン−１−カルボン酸アリルには、化合物（５）及び化合物（６）に２種の異性体が存在するが、上記反応では、３，４−エポキシシクロヘキサン−１−カルボン酸アリルのうちの６１％が化合物（５）であり、３９％が化合物（６）であることが、ＧＣ法により確認された。 Compound (4):

Further, allyl 3,4-epoxycyclohexane-1-carboxylate has two isomers in compound (5) and compound (6). In the above reaction, 3,4-epoxycyclohexane-1- It was confirmed by GC method that 61% of allyl carboxylate was compound (5) and 39% was compound (6).

Compound (5):

なお、そのときのＧＣ法の分析条件は実施例１と同様であった。 Compound (6):

The GC analysis conditions at that time were the same as in Example 1.

Example 3
The same operation as in Example 1 was performed except that 1.917 g (10.0 mmol) of the compound (7) was used instead of 2.530 g (10.1 mmol) of the compound (1). As a result, the conversion rate of the compound (7) was 99.5%, and the yield of N-allyl-4,5-epoxycyclohexane-1,2-dicarboximide was 78%.

また、Ｎ−アリル−４, ５−エポキシシクロヘキサン−１，２−ジカルボキシイミドには、化合物（８）及び化合物（９）に２種の異性体が存在するが、上記反応では、Ｎ−アリル−４, ５−エポキシシクロヘキサン−１，２−ジカルボキシイミドのうちの１５％が化合物（８）であり、８５％が化合物（９）であることが、ＧＣ法により確認された。 Compound (7):

N-allyl-4,5-epoxycyclohexane-1,2-dicarboximide has two isomers in compound (8) and compound (9). In the above reaction, N-allyl It was confirmed by GC method that 15% of the -4,5-epoxycyclohexane-1,2-dicarboximide was the compound (8) and 85% was the compound (9).

Compound (8):

なお、そのときのＧＣ法の分析条件は実施例１と同様であった。 Compound (9):

The GC analysis conditions at that time were the same as in Example 1.

Example 4
Using a 50 ml glass container, to a mixture of compound (4) (2.0 g, 12.0 mmol), methyltrioxorhenium (10.0 mg, 0.042 mmol), pyrazole (82.0 mg, 1.2 mmol), Hydrogen peroxide solution (31%, 1.44 ml, 14.4 mmol) was added dropwise at room temperature with stirring. The reaction was allowed to stir at room temperature for 5 hours. After adding an aqueous sodium sulfite solution, organic substances were extracted with an organic solvent, washed with water, and dried over magnesium sulfate. The organic solvent was distilled off under reduced pressure, and the yield was calculated using ¹ H-NMR. As a result, all starting materials disappeared, and allyl 3,4-epoxycyclohexane-1-carboxylate was obtained at a yield of 85%. was gotten. Subsequently, allyl epoxycyclohexane-1-carboxylate with high purity was isolated by distillation under reduced pressure (5 mmHg, 135 ° C.).

Example 5
Using a 50 ml glass container, compound (4) (665 mg, 4.0 mmol), methyltrioxorhenium (5.0 mg, 0.021 mmol), pyrazole (29.0 mg, 0.42 mmol) were added to ethyl acetate (2 ml). Then, hydrogen peroxide solution (31%, 0.50 ml, 5.0 mmol) was added dropwise with stirring at room temperature. The reaction was allowed to stir at room temperature for 6 hours. After adding an aqueous sodium sulfite solution, organic substances were extracted with an organic solvent, washed with water, and dried over magnesium sulfate. The organic solvent was distilled off under reduced pressure, and the yield was calculated using ¹ H-NMR. As a result, all starting materials had disappeared, and allyl 4,5-epoxycyclohexane-1-carboxylate was obtained at a yield of 86%. was gotten.

Example 6
Using a 50 ml glass container, add a mixture of compound (4) (665 mg, 4.0 mmol), methyltrioxorhenium (4.5 mg, 0.019 mmol), pyridine (33.5 mg, 0.42 mmol) at room temperature. Then, hydrogen peroxide solution (31%, 0.45 ml, 4.5 mmol) was added dropwise with stirring. The reaction was allowed to stir at room temperature for 5 hours. After adding an aqueous sodium sulfite solution, organic substances were extracted with an organic solvent, washed with water, and dried over magnesium sulfate. The organic solvent was distilled off under reduced pressure, and the yield was calculated using ¹ H-NMR. As a result, all starting materials disappeared, and allyl 4,5-epoxycyclohexane-1-carboxylate was obtained in a yield of 88%. was gotten.

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 50 mass% hydrogen peroxide 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%.
The GC analysis conditions at that time were the same as in Example 1.
The conversion and yield described herein are defined as follows:

  Conversion of compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure (%) = [(reacted at least one cycloolefin structure and at least one terminal vinyl or Number of moles of compound having vinylidene structure) / (number of moles of compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure fed to the reaction)] × 100

  Yield of polyfunctional epoxy compound (%) = [(conversion rate of compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure) × ((mol of polyfunctional epoxy compound produced) Number) / (number of moles of reacted compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure)) × 100)] / 100

Claims (10)

  In the presence of a rhenium compound, hydrogen peroxide is used to oxidize the double bond site of the cycloolefin in the compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure, A method for producing a polyfunctional epoxy compound, comprising producing a group-containing compound.   The method according to claim 1, wherein the cycloolefin structure is a carbon 6-8 membered ring. The compounds having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure are represented by the following general formulas (1) to (10):
General formula (1):

(In the formula, R ¹ represents hydrogen or a methyl group, R ² represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and R ^{3 to} R ¹⁰ represent Each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, a represents an integer of 0 to 3, and b represents an integer of 0 to 2).
General formula (2):

(In the formula, R ¹¹ represents hydrogen or a methyl group, R ¹² represents a divalent aliphatic, alicyclic or aromatic hydrocarbon residue selected from 2 to 8 carbon atoms, and R ^{13 to} R ²⁰ represent Each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, c represents an integer of 0 to 3, and d represents an integer of 0 to 2).
General formula (3):

(In the formula, R ²¹ and R ²² each independently represent hydrogen or a methyl group, and R ²³ and R ²⁴ each independently represents a divalent aliphatic, alicyclic or aromatic carbon selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{25 to} R ³² each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, e and g each independently represents an integer of 0 to 3, and f, h represents an integer of 0 to 2 independently.)
General formula (4):

(In the formula, R ³³ and R ³⁴ each independently represent hydrogen or a methyl group, and R ³⁵ and R ³⁶ are each independently a divalent aliphatic, alicyclic, or aromatic carbonization selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{37 to} R ⁴⁴ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine; i and k each independently represents an integer of 0 to 3; l represents each independently an integer of 0 to 2.)
General formula (5):

(In the formula, R ⁴⁵ represents hydrogen or a methyl group, and R ^{46 to} R ⁵³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (6):

(In the formula, R ⁵⁴ represents hydrogen or a methyl group, and R ^{55 to} R ⁶² each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (7):

(In the formula, R ⁶³ and R ⁶⁴ each independently represent hydrogen or a methyl group, and R ⁶⁵ and R ⁶⁶ each independently represents a divalent aliphatic, alicyclic or aromatic carbon selected from 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{67 to} R ⁷³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine, m and p each independently represents an integer of 0 to 3, and n, q independently represents an integer of 0 to 2.)
General formula (8):

(In the formula, R ⁷⁴ and R ⁷⁵ each independently represent hydrogen or a methyl group, and R ⁷⁶ and R ⁷⁷ each independently represents a divalent aliphatic, alicyclic, or aromatic carbonized group having 2 to 8 carbon atoms. Represents a hydrogen residue, R ^{78 to} R ⁸³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, r and t each independently represents an integer of 0 to 3, and s, u represents 0-2 independently.)
General formula (9):

(Wherein R ⁸⁴ represents hydrogen or a methyl group, and R ^{85 to} R ⁹¹ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (10):

(In the formula, R ⁹² represents hydrogen or a methyl group, and R ^{93 to} R ⁹⁸ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
The method according to claim 1 or 2, characterized in that it is selected from the group consisting of: The compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure is represented by the following general formula (11) or general formula (12):
Formula (11)

(Wherein R ⁹⁹ represents hydrogen or a methyl group, R ^{100 to} R ¹⁰⁷ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine, and v represents an integer of 0 to 2) .)
General formula (12):

(Wherein R ¹⁰⁸ represents hydrogen or a methyl group, R ^{109 to} R ¹¹⁶ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group or chlorine, and w represents an integer of 0 to 2) The method according to claim 1, wherein the compound is represented by the following formula: The compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure is represented by the following general formula (5) or the following general formula (6):
General formula (5):

(In the formula, R ⁴⁵ represents hydrogen or a methyl group, and R ^{46 to} R ⁵³ each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (6):

(In the formula, R ⁵⁴ represents hydrogen or a methyl group, and R ^{55 to} R ⁶² each independently represents an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
The method according to claim 1, wherein the compound is represented by the formula: The compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure is represented by the following general formula (13) or the following general formula (14):
General formula (13):

(In the formula, R ¹¹⁷ and R ¹¹⁸ each independently represent hydrogen or a methyl group, and R ^{119 to} R ¹²⁶ each independently represent an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
General formula (14):

(Wherein R ¹²⁷ and R ¹²⁸ each independently represent hydrogen or a methyl group, and R ^{129 to} R ¹³⁶ each independently represent an atomic group selected from hydrogen, a methyl group, an ethyl group, or chlorine.)
The method according to claim 1, wherein the compound is represented by the formula:   The method according to claim 1, wherein the terminal vinyl or vinylidene structure is an allyl or methallyl structure.   The method according to claim 1, wherein the rhenium compound is methyltrioxorhenium.   The method according to any one of claims 1 to 8, wherein the organic basic compound is used in an amount of 1 to 30 moles relative to the rhenium compound.   Hydrogen peroxide is 0.8 to 10.0 with respect to the number of double bonds contained in the cycloolefin structure of the compound having at least one cycloolefin structure and at least one terminal vinyl or vinylidene structure. The method according to any one of claims 1 to 9, wherein the content is doubled.