JP2015166335A - Method for producing epoxy compound and catalyst composition for epoxidation reaction - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an epoxy compound without needing a cumbersome purification process and the like where, in production of the epoxy compound, a content of heavy metals such as tungsten is extremely small, further preferably a content of a nitrogen-containing compound derived from an onium salt is small, and further more preferably a content of chlorine is small.SOLUTION: Provided is a method for producing an epoxy compound comprising epoxidizing a carbon-carbon double bond of a compound having a carbon-carbon double bond by reacting the same with hydrogen peroxide in the presence of at least either of a tungsten compound and a molybdenum compound, and an onium salt. The onium salt has four or more acyloxy groups of 1 to 4 carbon atoms and a total carbon number of the onium salt is 20 or more.

Description

  The present invention relates to a method for producing an epoxy compound and a novel catalyst composition for epoxidation reaction used therefor.

Epoxy compounds are widely used as epoxy monomers as raw materials for epoxy resins and as raw materials for various chemical products.
In recent years, with the improvement in performance of electronic parts and optical parts, there has been a demand for higher purity of epoxy compounds such as epoxy resins and epoxy monomers used as raw materials thereof. In particular, in the use of electronic parts, since halogen compounds cause corrosion of wiring, it is required to reduce the halogen of epoxy compounds, particularly to reduce chlorination.

Conventionally, as a method for producing an epoxy compound, a method in which epichlorohydrin is allowed to act on an alcohol compound or a phenol compound corresponding to the target epoxy compound to form a glycidyl ether has been common.
However, the above method is not suitable for reducing the halogen content of epoxy compounds. The reason is as follows. A chlorine atom derived from epichlorohydrin becomes an organic chlorine compound chemically bonded to the obtained epoxy compound, and is mixed as an impurity in the epoxy compound. Therefore, the concentration of chlorine contained in the epoxy compound becomes high, and specifically, it is usually contained at about 1000 ppm or more. When an epoxy resin made from such an epoxy compound (epoxy monomer) with a high chlorine concentration is used as an IC encapsulant, for example, wiring corrosion and disconnection are likely to occur due to circuit miniaturization due to high integration. There was a problem of becoming.

Therefore, there is a need for an epoxidation method that does not use epichlorohydrin. As a production method thereof, a method has been proposed in which allyl alcohol is condensed with phenols using a metal catalyst such as a palladium catalyst to form an allyl ether, and then an epoxy compound is obtained using a peroxide (Patent Document 1). ).
In recent years, a method for producing allyl ethers having a low chlorine content, oxidizing the allyl ethers to convert them into epoxy compounds, and synthesizing a glycidyl ether having a low chlorine content has been developed. (For example, see Patent Documents 2 and 3)
In the epoxidation reaction used in these production methods, an onium salt such as an ammonium salt and at least one of a tungsten compound and a molybdenum compound coexist as a catalyst composition, and hydrogen peroxide is an oxidizing agent (epoxidizing agent). The method used as is known.

  This epoxidation reaction is a clean reaction with less waste compared to an epoxidation reaction with an organic peroxide typified by peracetic acid because the by-product is only water. Moreover, since 30-45 mass% hydrogen peroxide water is used, acquisition is easy and handling is simple. Furthermore, this epoxidation reaction can selectively oxidize an allyl group without oxidizing an aromatic group having an alkyl group or an alkoxyl group. In addition, since this epoxidation reaction can be applied to epoxidation of a compound (olefin compound) having a carbon-carbon double bond other than allyl ether, all epoxy compounds other than glycidyl ethers, that is, cyclic fat having an epoxy ring. This is a useful reaction suitable for the synthesis of group compounds, styrene oxides and the like.

However, in this epoxidation reaction, the onium salt that usually coexists as a catalyst uses an ammonium salt having a long chain alkyl group such as methyltrioctylammonium chloride or a pyridinium salt having a long chain alkyl group such as cetylpyridinium salt. Prepared. However, the onium salt having a long-chain alkyl group has a high distribution ratio to an organic solvent, and an epoxy compound dissolved in the organic phase after the reaction and a component derived from the catalyst composition, specifically tungsten or onium salt. However, there is a problem that separation and purification from an onium salt-derived nitrogen-containing compound is extremely difficult. Furthermore, when tungsten, nitrogen-containing compounds, and the like are removed by a method such as recrystallization or hanging washing, there is a problem that the purification yield (recovery rate) of the epoxy compound is low.

Therefore, heavy metal components derived from catalysts such as tungsten and molybdenum and ionic compounds such as onium salts remain in the resulting epoxy compound. These remained even when an epoxy resin was produced from an epoxy compound, and the product could be adversely affected.
Specifically, when heavy metals such as tungsten remain in an epoxy compound, it is reported that an epoxy resin produced using the epoxy compound is markedly colored when left under high temperature conditions (for example, , See Patent Document 4). In addition, when the epoxy resin is used as an electronic material, halogen such as chlorine remaining in the epoxy compound causes corrosion of the wiring, and residual metal and ionic compounds such as onium salts cause short circuit or corrosion of the wiring. Cause.

  As a method for solving this problem, several purification and removal methods have been reported (for example, Patent Documents 5 to 9).

Japanese National Patent Publication No. 10-511721 JP 2011-213716 A International Publication No. 2011/019061 JP 2009-185274 A JP 2010-70480 A JP 2010-235649 A JP 2002-69079 A Japanese Patent Laid-Open No. 2001-17863 JP 2013-1112639 A

However, it is difficult to produce an epoxy compound with a small amount of nitrogen-containing compounds derived from heavy metal components such as tungsten and onium salts by any of the conventional methods as described above.
In the production of an epoxy compound according to the present invention, the content of heavy metals such as tungsten is extremely small, preferably the content of nitrogen-containing compounds derived from onium salts (hereinafter simply referred to as nitrogen content), more preferably the content of chlorine. It is an object of the present invention to provide a method for producing an epoxy compound having a small amount without requiring a complicated purification step.

The inventor incorporated a new concept of introducing a structure that can be converted into a compound that can be easily removed into an onium salt that coexists as a catalyst, designed the compound, and used it in the epoxidation reaction.
Specifically, the reaction was carried out in the presence of an onium salt having at least one substituent in the molecule that can be converted into a functional group containing active hydrogen or a salt thereof. As a result, the desired epoxy compound was obtained and converted to a functional group containing active hydrogen or a salt thereof after the epoxidation reaction. As a result, the epoxy compound and the component derived from the epoxidizing agent were separated to obtain a highly pure epoxy compound. I found out that

The inventor has completed the invention and has filed a patent application as PCT / JP2013 / 059401. At this time, the process for preparing the onium salt is complicated, or a halogen compound is used for preparing the onium salt. In addition, after the epoxidation reaction, the onium salt is difficult to regenerate after being converted into a functional group containing active hydrogen or a salt thereof and separated.
However, as a result of further studies by the present inventor, by using a substituent having a specific structure as a substituent that can be converted into the functional group containing active hydrogen or a salt thereof, an onium can be efficiently obtained without using a halogen compound. The present inventors have found that a salt can be prepared and that the onium salt can be used repeatedly, thereby completing the present invention.

That is, the gist of the present invention is as follows.
[1] An epoxy compound that is epoxidized by reacting hydrogen peroxide with a carbon-carbon double bond of a compound having a carbon-carbon double bond in the presence of at least one of a tungsten compound and a molybdenum compound and an onium salt. A manufacturing method comprising:
An epoxy compound, wherein the onium salt has 4 or more acyloxy groups having 1 to 4 carbon atoms or one or more benzyloxy groups, and the onium salt has a total carbon number of 20 or more. Production method.
[2] The method for producing an epoxy compound according to the above [1], wherein the onium salt is a compound represented by any one of the following general formulas (1) to (3).

In the general formula (1),
R ^{1 to} R ⁴ each independently represents an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms, and some of the carbon atoms may be substituted with hetero atoms, Any two or more may be bonded to form a ring. At least one of R ^{1 to} R ⁴ has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms.

In the general formula (2), R ⁵ represents an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent and a part of carbon atoms may be substituted with a hetero atom.
R ^{6 to} R ¹⁰ may each independently have a substituent, and a part of carbon atoms may be substituted with a hetero atom, a C 1-25 aliphatic hydrocarbon group, a hydrogen atom , A halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group.

In addition, any one or more of R ^{5 to} R ¹⁰ may be bonded to form a ring, and at least one of them has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms as substituents. .
In the general formula (3), R ¹¹ and R ¹³ may each independently have a substituent, and a part of carbon atoms may be substituted with a hetero atom, and the fatty acid having 1 to 25 carbon atoms. Represents a hydrocarbon group.

R ¹² , R ¹⁴ , and R ¹⁵ may each independently have a substituent, and a C 1-25 aliphatic hydrocarbon in which some of the carbon atoms may be substituted with a hetero atom A group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group;
Any one or more of R ^{11 to} R ¹⁵ may be bonded to form a ring, and at least one group has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms as substituents. .

X ⁻ represents an anion.
[3] An epoxy compound that is epoxidized by reacting hydrogen peroxide with a carbon-carbon double bond of a compound having a carbon-carbon double bond in the presence of at least one of a tungsten compound and a molybdenum compound and an onium salt. A manufacturing method comprising:
The said onium salt is a compound represented by following General formula (4), The manufacturing method of the epoxy compound characterized by the above-mentioned.

In the general formula (4),
R ¹⁶ and R ¹⁷ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and some of the carbon atoms may be substituted with heteroatoms; In addition, each may be bonded to form a ring.
R ¹⁸ and R ²⁰ represent an optionally substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and some of the carbon atoms may be substituted with hetero atoms.

R ¹⁹ and R ²¹ represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
k and m each independently represent an integer of 1 to 5, and when k and m are each 2 or more, the plurality of R ¹⁹ and R ²¹ may be the same or different.
Y and Z each independently represent a halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group, and p is 0 ≦ p ≦ 5. -K represents an integer, and q represents an integer of 0 ≦ q ≦ 5-m. X ⁻ represents an anion.
[4] The method for producing an epoxy compound according to any one of [1] to [3], wherein the epoxidation is performed in the presence of at least one of phosphoric acids and phosphonic acids. [5] The epoxidation is performed in a two-phase solution comprising an aqueous phase containing at least one of the tungsten compound and molybdenum compound and an organic phase containing the compound having a carbon-carbon double bond. The method for producing an epoxy compound according to any one of the above [1] to [4].
[6] The method for producing an epoxy compound according to the above [5], wherein the pH of the aqueous phase is 2 or more and 6 or less.
[7] The method for producing an epoxy compound according to any one of the above [1] to [6], wherein the epoxidation is performed in the presence of a chelating agent,
[8] The compound according to any one of [1] to [7], wherein the compound having a carbon-carbon double bond is washed with an acidic aqueous solution before epoxidation. A method for producing an epoxy compound.
[9] Any of the above [1] to [8], wherein the compound having a carbon-carbon double bond is washed with a chelating agent before epoxidation. The manufacturing method of the epoxy compound of description.
[10] After the onium salt has 4 or more acyloxy groups having 1 to 4 carbon atoms and epoxidizes the compound having the carbon-carbon double bond, the onium salt is solvated with a basic compound. The method for producing an epoxy compound according to any one of the above [1], [2], and [4] to [9], further comprising a step of decomposing.
[11] The method for producing an epoxy compound according to the above [10], comprising a step of regenerating the solvated osmium salt after the solvolysis step.
[12] The onium salt further includes a step of catalytically hydrogenating the onium salt after epoxidizing the compound having one or more benzyloxy groups and having the carbon-carbon double bond. The method for producing an epoxy compound according to any one of [1], [2], and [4] to [9] above.
[13] The process according to any one of [3] to [9] above, further comprising a step of solvating the onium salt with a basic compound after epoxidizing the compound having a carbon-carbon double bond The manufacturing method of the epoxy compound in any one.
[14] A method for producing an epoxy resin by polymerizing an epoxy compound, the step of producing an epoxy compound by the method according to any one of the above [1] to [13], and the epoxy obtained in the step The manufacturing method of an epoxy resin characterized by including the process of superposing | polymerizing a compound.
[15] An onium salt represented by the following general formula (4).

In the general formula (4),
R ¹⁶ and R ¹⁷ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and some of the carbon atoms may be substituted with heteroatoms; In addition, each may be bonded to form a ring.
R ¹⁸ and R ²⁰ represent an optionally substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and some of the carbon atoms may be substituted with hetero atoms.

R ¹⁹ and R ²¹ represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
k and m each independently represent an integer of 1 to 5, and when k and m are each 2 or more, the plurality of R ¹⁹ and R ²¹ may be the same or different.
Y and Z each independently represent a halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group, and p is 0 ≦ p ≦ 5. -K represents an integer, and q represents an integer of 0 ≦ q ≦ 5-m.

X ⁻ represents an anion.
[16] In general formula (4), R ¹⁶ , R ¹⁷ , R ¹⁸ and R ²⁰ have a total carbon number of 14 or less, and R ¹⁹ and R ²¹ have a total carbon number of 6 or more. The onium salt according to [15], wherein
[17] A catalyst composition for epoxidation reaction comprising at least one of a tungsten compound and a molybdenum compound and at least one onium salt represented by the following general formulas (1) to (4).

In the general formula (1),
R ^{1 to} R ⁴ each independently represents an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms, and some of the carbon atoms may be substituted with hetero atoms, Any two or more may be bonded to form a ring. At least one of R ^{1 to} R ⁴ has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms.

In the general formula (2), R ⁵ represents an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent and a part of carbon atoms may be substituted with a hetero atom.
R ^{6 to} R ¹⁰ may each independently have a substituent, and a part of carbon atoms may be substituted with a hetero atom, a C 1-25 aliphatic hydrocarbon group, a hydrogen atom , A halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group.

In addition, any one or more of R ^{5 to} R ¹⁰ may be bonded to form a ring, and at least one of them has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms as substituents. .
In the general formula (3), R ¹¹ and R ¹³ may each independently have a substituent, and a part of carbon atoms may be substituted with a hetero atom, and the fatty acid having 1 to 25 carbon atoms. Represents a hydrocarbon group.

R ¹² , R ¹⁴ , and R ¹⁵ may each independently have a substituent, and a C 1-25 aliphatic hydrocarbon in which some of the carbon atoms may be substituted with a hetero atom A group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group;
Any one or more of R ^{11 to} R ¹⁵ may be bonded to form a ring, and at least one group has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms as substituents. .

In the general formula (4),
R ¹⁶ and R ¹⁷ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and some of the carbon atoms may be substituted with heteroatoms; In addition, each may be bonded to form a ring.
R ¹⁸ and R ²⁰ represent an optionally substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and some of the carbon atoms may be substituted with hetero atoms.

R ¹⁹ and R ²¹ represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
k and m each independently represent an integer of 1 to 5, and when k and m are each 2 or more, the plurality of R ¹⁹ and R ²¹ may be the same or different.
Y and Z each independently represent a halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group, and p is 0 ≦ p ≦ 5. -K represents an integer, and q represents an integer of 0 ≦ q ≦ 5-m.

X ⁻ represents an anion.

According to the production method of the present invention, an epoxy compound having a very small content of metal impurities such as tungsten can be obtained. In addition, it is possible to produce a high-purity epoxy compound having a very small content of nitrogen compound and chlorine derived from an onium salt by a simple method without requiring complicated steps such as purification.
Furthermore, it can be applied to the production of an epoxy compound that cannot be distilled or crystallized and is excellent in versatility. When the epoxy compound obtained by the method of the present invention is used as a raw material for electronic materials, optical materials, and medical and agricultural chemicals, problems due to impurities are reduced, and a product with high purity and high quality can be obtained.

And by using the onium salt which has a specific substituent, it becomes possible to collect | recover onium salt and to utilize repeatedly, and to improve manufacturing efficiency.
Further, by using the onium salt of the present invention, an epoxy compound having an extremely small content of metal impurities such as tungsten can be obtained. In addition, since a high-purity epoxy compound having an extremely small content of nitrogen compounds and chlorine derived from an onium salt can be obtained and regenerated and used, the production efficiency is high and the environmental load can be reduced.

  An onium salt having at least one functional group containing active hydrogen or a salt that can be converted to a salt thereof in the molecule is not limited to epoxidation reaction, and can be applied in various oxidation reactions. It is useful for the synthesis of aldehydes, carboxylic acids, sulfone compounds and the like.

Hereinafter, embodiments of the present invention will be described in more detail. However, the description of the constituent elements described below is an example of embodiments of the present invention, and the present invention is not limited to these contents. Various modifications can be made within the scope of the gist.
The first aspect of the method for producing an epoxy compound of the present invention is a compound having a carbon-carbon double bond (hereinafter sometimes referred to as “olefin compound”), and at least one of a tungsten compound and a molybdenum compound. Hydrogen peroxide in the presence of four or more acyloxy groups having 1 to 4 carbon atoms or one or more benzyloxy groups and the onium salt having a total carbon number of 20 or more. It is made to react.

In a second aspect, the olefin compound is reacted with hydrogen peroxide in the presence of at least one of a tungsten compound and a molybdenum compound and the onium salt described in the general formula (4).
In this specification, “at least one of tungsten compound and molybdenum compound” is sometimes referred to as “catalyst metal”, and “having four or more acyloxy groups having 1 to 4 carbon atoms or one or more benzyloxy groups. In addition, “onium salts containing 20 or more carbon atoms” and “compounds represented by the general formula (4)” are simply referred to as “onium salts”, and those containing the above “catalyst metals” and “onium salts” are referred to as “epoxidation” The catalyst composition for reaction is simply referred to as “catalyst composition” or simply “catalyst composition”, and the catalyst composition oxidized with hydrogen peroxide is sometimes referred to as “active catalyst”.

(Tungsten compounds and molybdenum compounds)
At least one of a tungsten compound and a molybdenum compound as a catalyst metal used in the present invention is a catalyst that is used when a carbon-carbon double bond of a compound having a carbon-carbon double bond is epoxidized with hydrogen peroxide. It is a metal species that acts as a catalyst by being present in the reaction system together with hydrogen oxide. Hereinafter, the tungsten compound and the molybdenum compound are also referred to as “catalyst metal”.

The tungsten compound is not particularly limited as long as it contains tungsten and has an effect as the above catalyst, but specifically, tungstic acid and its salts (hereinafter these are collectively referred to as “tungstic acids”). ) And the like.
Specific examples of the tungstic acids include tungstic acid; tungstates such as sodium tungstate, potassium tungstate, calcium tungstate, and ammonium tungstate; hydrates of the tungstates; 12-tungstophosphoric acid Phosphotungstic acid such as 18-tungstophosphoric acid; silicotungstic acid such as 12-tungstosilicic acid; 12-tungstoboric acid or metallic tungsten, etc. In this respect, tungstic acid, sodium tungstate, calcium tungstate, and 12-tungstophosphoric acid are more preferable.

The molybdenum compound is not particularly limited as long as it contains molybdenum and has an effect as the above-mentioned catalyst. Specifically, molybdic acid or a salt thereof (hereinafter collectively referred to as “molybdic acids”). ) And the like.
Examples of the molybdic acids include molybdic acid; molybdates such as sodium molybdate, potassium molybdate, and ammonium molybdate; and hydrates of the molybdates.

Among the tungsten compounds and molybdenum compounds, tungsten compounds are preferable in terms of availability, and tungstic acids, that is, sodium tungstate and its hydrate, calcium tungstate and its hydrate are more preferable.
The catalyst metals in the present invention can be used alone or in combination of two or more. The amount of the catalyst metal used can be appropriately adjusted depending on the properties of the olefin compound and the like to be used, and is not particularly limited, but is usually a mole of carbon-carbon double bonds contained in the olefin compound. Converted to catalytic metal atoms (for example, tungsten atoms when tungsten compounds are used) with respect to the number (the number of carbon-carbon double bonds contained in the olefin compound multiplied by the number of moles of one molecule of the olefin compound) And usually 0.001 mol or more, preferably 0.005 mol or more, more preferably 0.01 mol or more, and usually 1.0 mol or less, preferably 0.50 mol or less, more preferably 0.10. It is below the mole. This is because the reaction is likely to proceed and the economy is good by adjusting within the above range.

  When the catalyst metal is used, it may be used after being mixed with the olefin compound in the reaction system, or after being previously mixed with the olefin compound outside the reaction system. Hydrogen oxide may be mixed and mixed to activate the catalyst metal before use. Further, an onium salt, an organic solvent, and other additives, which will be described later, can be appropriately mixed and used.

(hydrogen peroxide)
As the hydrogen peroxide used in the present invention, a hydrogen peroxide solution is usually used.
When hydrogen peroxide water is used, its concentration is not particularly limited, but is usually 1% by weight or more, preferably 20% by weight or more and usually 60% by weight or less, and more preferably, availability, productivity, transportation Considering the cost and the like, it is 30% by mass or more and 45% by mass or less.

From the viewpoint of safety and productivity, it is more preferable to keep the hydrogen peroxide concentration in the system low during the reaction by adding water to the reaction system or sequentially adding hydrogen peroxide.
The amount of hydrogen peroxide used can be appropriately adjusted according to the reactivity of the olefin compound, and is not particularly limited. However, the number of moles of the olefin compound includes the number of carbon-carbon double bonds in one molecule of the olefin compound. The amount multiplied by the number is usually 0.5 times mol or more, preferably 1 time mol or more, usually 10 times mol or less, preferably 3 times mol or less. This is because if the amount used is within the above range, the epoxidation can be performed efficiently and efficiently.
The “use amount” here refers to the total amount of hydrogen peroxide used in producing an epoxy compound from the olefin compound.

(Onium salt)
The onium salt used in the present invention has four or more acyloxy groups having 1 to 4 carbon atoms or one or more benzyloxy groups, and has 20 or more carbon atoms (total carbon number of 20 or more). Onium salt of one embodiment) or a compound represented by the general formula (4) (onium salt of the second embodiment).
Since the onium salt contains 20 or more carbon atoms (total carbon number of 20 or more), it is liposoluble during the epoxidation reaction, soluble in the reaction solvent, and organic when separated into an aqueous phase and an organic phase. Distribute to the phase side. The onium salt is stable under epoxidation reaction conditions, or has a property that the catalytic ability is not significantly reduced even if the structure is changed during the epoxidation reaction.

It is considered that the onium salt forms an active epoxidation catalyst by mixing with the catalyst metal and hydrogen peroxide. Specifically, the onium salt forms a complex with the catalytic metal, and preferably forms a complex with at least one of phosphoric acids and phosphonic acids described later, and the complex is oxidized by hydrogen peroxide. By doing so, it is considered that an active epoxidation catalyst (active catalyst) with high reaction activity is obtained.
The active catalyst is fat-soluble, and normally dissolves together with the olefin compound in a solvent used as needed during the epoxidation reaction.

<Onium salt of the first aspect>
The onium salt of the first aspect has 4 or more acyloxy groups having 1 to 4 carbon atoms or one or more benzyloxy groups, and 20 or more carbon atoms (total carbon number is 20 or more). . These include a C1-C4 acyloxy group or benzyloxy group as a substituent which can be converted into a functional group containing active hydrogen or a salt thereof. Hereinafter, an onium salt containing an acyloxy group having 1 to 4 carbon atoms is abbreviated as “acylated onium salt”, and an onium salt containing a benzyloxy group is abbreviated as “benzylated onium salt”.

  Acyloxy group is solvated and decomposed easily by contact with a basic solution without decomposing the epoxy group, and can be removed by simple treatment such as washing with water. It can be decomposed into a group and a salt thereof, or a carboxylic acid ester, and the synthesis is also simple. Furthermore, an acyloxy group having 1 to 4 carbon atoms can be easily regenerated and reused by the action of an acid anhydride or the like.

Moreover, since fat solubility improves by having four or more C1-C4 acyloxy groups, it distributes efficiently to the organic phase containing an olefin compound.
On the other hand, a benzyloxy group has high fat solubility, and can be converted into a hydroxyl group and a salt thereof simply and without decomposition of an epoxy group by reduction, preferably catalytic hydrogenation. Moreover, since catalytic reduction is performed under neutral to acidic conditions, it is suitable for the production of an epoxy compound having an ester group that decomposes under basic conditions.

  Examples of the cationic species of the onium salt of the first embodiment (hereinafter simply referred to as “onium”) include ammonium, quaternary cations of nitrogen-containing heterocycles such as pyridinium and imidazolinium, and phosphonium. That is, examples of the onium salt include ammonium salts, pyridinium salts, imidazolinium salts, and phosphonium salts. Ammonium salts, pyridinium salts, and imidazolinium salts are preferably used because they are easily synthesized.

The anion species X ⁻ of the onium salt of the first embodiment is not particularly limited, but specifically, hydrogen sulfate ion, monomethyl sulfate ion, halide ion, nitrate ion, acetate ion, hydrogen carbonate ion, dihydrogen phosphate Examples include monovalent anions such as ions, sulfonate ions, carboxylate ions, and hydroxide ions, and divalent anions such as hydrogen phosphate ions and sulfate ions, and monovalent anions are preferred in terms of easy adjustment. . Of these, monomethyl sulfate ion, hydrogen sulfate ion from the point that the anion species is not added to the epoxy group of the epoxy compound that is the reaction product or the carbon-carbon double bond of the olefin compound that is the raw material compound, or because it is easy to prepare. Acetate ions, dihydrogen phosphate ions or hydroxide ions are preferred. The anionic species may be used alone or in combination of two or more.

  Specifically, the onium salt of the first aspect is preferably an onium salt represented by the following general formulas (1) to (3).

In the general formula ^(1), R 1 ~R ⁴ represent independently of carbon atoms 1 to 25 which may have a substituent aliphatic hydrocarbon group. The aliphatic hydrocarbon group having 1 to 25 carbon atoms may be linear, branched or cyclic. Specifically, a straight chain aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, an octyl group, a dodecanyl group, or a pentadecanyl group, and a branched chain in which an alkyl chain is further bonded thereto. Examples include aliphatic hydrocarbons and cyclic aliphatic hydrocarbon groups such as cyclohexyl.

Among these, a C1-C18 aliphatic hydrocarbon group is preferable.
Moreover, as for a C1-C25 aliphatic hydrocarbon group, the one part carbon atom may be substituted by the hetero atom. Specifically, the methylene group is —O—, —S—, —SO—, —SO ₂ —, —NH—, —NR ²⁷ — (R ²⁷ is a monovalent aliphatic hydrocarbon having 1 to 25 carbon atoms. Group, or a monovalent aromatic hydrocarbon group), —CONR ²⁸ — (R ²⁸ is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 25 carbon atoms, or a monovalent aromatic hydrocarbon group) ), —NHCONH—, —CONHCO—, —SO ₂ NR ²⁸ — (R ²⁸ has the same meaning as described above), and the like, may be substituted.

The aliphatic hydrocarbon group having 1 to 25 carbon atoms may have a substituent, but usually at least one of R ^{1 to} R ⁴ represents an acyloxy group or benzyloxy group having 1 to 4 carbon atoms. One or more substituents are included. One aliphatic hydrocarbon group having 1 to 25 carbon atoms may have only one or plural acyloxy groups or benzyloxy groups as a substituent.
Specifically, when an acyloxy group having 1 to 4 carbon atoms is used as a substituent, 1 to 4 or more acyloxy groups are contained in one aliphatic hydrocarbon group having 1 to 25 carbon atoms. Also good.

Furthermore, any one or more of R ^{1 to} R ⁴ may be bonded to form a ring such as a pyrrolidine ring or a piperidine ring.
When R ^{1 to} R ⁴ have an acyloxy group as a substituent, examples include an acetoxyethyl group, a 2,3-diacetoxypropyl group, and a 2,3-propionyloxypropyl group. A 2,3-diacetoxypropyl group that can be easily synthesized and regenerated is preferable.

When R ^{1 to} R ⁴ have a benzyloxy group as a substituent, examples thereof include a benzyloxyethyl group, a t-butylbenzyloxyethyl group, a triphenylmethyloxyethyl group, and the like. A benzyloxyethyl group from which an aromatic moiety can be easily removed by drying under reduced pressure is preferred.
Among R ^{1 to} R ^4, the substituent of a group that does not have an acyloxy group and a benzyloxy group as a substituent is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a dodecanyl group, A linear aliphatic hydrocarbon group such as a pentadecanyl group, a linear aliphatic hydrocarbon ether group such as a methoxyethyl group, an ethoxyethyl group, or a 2-ethoxyethoxyethyl group, or any two groups of R ^{1 to} R ⁴ are bonded. And pyrrolidine ring and piperidine ring.

In the above general formula (2), R ⁵ represents a C 1-25 aliphatic hydrocarbon group which may have a substituent and a part of carbon atoms may be substituted with a hetero atom. . R ⁵ has the same meaning as R ^{1 to} R ⁴ in the general formula (1).
R ^{6 to} R ¹⁰ may each independently have a substituent having the same meaning as R ^{1 to} R ^4, and some of the carbon atoms may have 1 to 25 carbon atoms optionally substituted with a heteroatom. Represents an aliphatic hydrocarbon group or at least one selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, and an N-alkylsulfamoyl group; .

In addition, any one or more of R ^{5 to} R ¹⁰ may be bonded to form a ring such as a quinoline ring.
Moreover, at least one of R ^{5 to} R ¹⁰ has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms as substituents.
When R ⁵ has an acyloxy group or a benzyloxy group as a substituent, it is the same as R ^{1 to} R ⁴ above. Moreover, when R < ⁶ > -R < ¹⁰ > has an acyloxy group or a benzyloxy group as a substituent, even if it has as a direct substituent in the pyridine ring of General formula (2), as a substituent with respect to substituents, such as an alkyl group, You may have, and in that case, you may have only one or more.

Among R ^{6 to} R ^10, the substituent of the group having no acyloxy group and benzyloxy group as a substituent is preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, or dodecanyl. Group, a linear aliphatic hydrocarbon group such as a pentadecanyl group.
In the general formula (3), R ¹¹ and R ¹³ may each independently have a substituent, and a part of carbon atoms may be substituted with a hetero atom, and the fatty acid having 1 to 25 carbon atoms. Represents a hydrocarbon group. R ¹¹ and R ¹³ have the same meanings as R ^{1 to} R ⁴ described above.

R ¹² , R ¹⁴ , and R ¹⁵ may each independently have a substituent, and a C 1-25 aliphatic hydrocarbon in which some of the carbon atoms may be substituted with a hetero atom Or at least one selected from a hydrogen atom, halogen atom, cyano group, nitro group, phenyl group, phenoxy group, benzyl group, N-alkylcarbamoyl group, and N-alkylsulfamoyl group, It is synonymous with R < ⁶ > -R < ¹⁰ > in (2).

Any one or more of R ^{11 to} R ¹⁵ may be bonded to form a ring.
Further, at least one group of R ^{11 to} R ¹⁵ has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms as a substituent.
When R ¹¹ and R ¹³ have an acyloxy group or a benzyloxy group as a substituent, they are the same as R ^{1 to} R ⁵ described above.

When R ¹² , R ¹⁴ , and R ¹⁵ have an acyloxy group or a benzyloxy group as a substituent, they are the same as R ^{6 to} R ¹⁰ in the general formula (2).
Among R ¹² , R ¹⁴ , and R ^15, a group that does not have an acyloxy group and a benzyloxy group as a substituent is the same as R ^{6 to} R ¹⁰ .
X ⁻ represents an anion of an onium salt. The anionic species is not particularly limited, but is usually 1
A valent anion, a divalent anion, and the like. Specifically, monovalent anions such as hydrogen sulfate ion, monomethyl sulfate ion, halide ion, nitrate ion, acetate ion, hydrogen carbonate ion, dihydrogen phosphate ion, sulfonate ion, carboxylate ion and hydroxide ion Divalent anions such as hydrogen phosphate ion and sulfate ion are preferred, and monovalent anions are preferred from the viewpoint of easy preparation. Among them, epoxy groups and raw material compounds of epoxy compounds whose anion species is a reaction product Monomethyl sulfate ion, hydrogen sulfate ion, acetate ion, dihydrogen phosphate ion or hydroxide ion is preferable from the viewpoint of not adding to the carbon-carbon double bond of the olefin compound and the ease of preparation.

  More preferred examples of the onium salt used in the present invention include the following general formulas (5) and (6).

In the above general formula (5), R ²⁹ and R ³⁰ each independently represent an alkyl group having 1 to 24 carbon atoms or a benzyl group in which some carbon atoms may be substituted with hetero atoms, and 1 carbon atom. ~ 24 alkyl groups are preferred. As specific substituents, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decanyl group, a dodecanyl group, a hexadecanyl group, an octadecanyl group, and the like are more preferable. Of these, the total number of carbon atoms of R ²⁹ and R ³⁰ is preferably 10 or more.

R ³¹ and R ³² each independently represents an alkylene group having 1 to 11 carbon atoms in which part of the carbon atoms may be substituted with a hetero atom, more preferably an alkylene group having 1 to 5 carbon atoms, and a methylene group being It is more preferable because it can be easily synthesized from readily available materials.
R ³³ and R ³⁴ represent an alkyl group having 1 to 4 carbon atoms, and a methyl group or an ethyl group is preferable. The acyloxy group having these substituents is separated from the epoxy compound by solvent addition, and then reacted with an inexpensive acid anhydride compound such as acetic anhydride or propionic anhydride to facilitate the onium before solvent addition. The salt can be regenerated, and the onium salt can be used repeatedly, which is more preferable from the economical viewpoint.

The total number of carbon atoms contained in the cation moiety in the formula is 20 or more.
X ⁻ represents an anion, preferably a monovalent anion, and more preferably monomethyl sulfate ion, hydrogen sulfate ion, dihydrogen phosphate ion or acetate ion.

In the general formula (6),
R ³⁵ and R ³⁶ are each independently an alkyl group which may be substituted with an aromatic ring, or which may have some carbon atoms substituted with heteroatoms. Specifically, a straight chain aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a dodecanyl group or a pentadecanyl group, an alkyl group such as a benzyl group or a t-butylbenzyl group. Examples thereof include a substituted benzyl group, and a benzyloxyalkyl group such as a benzyloxyethyl group and a t-butylbenzyloxyethyl group, and a t-butylbenzyl group and a benzyloxyethyl group are more preferable.

R ³⁷ represents an alkylene group having 2 to 11 carbon atoms in which part of the carbon may be substituted with a heteroatom, preferably an alkylene group having 1 to 5 carbon atoms, and can be easily synthesized from readily available materials. An ethylene group is more preferable.
R ³⁸ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, preferably a hydrogen atom, a methyl group, or a phenyl group, which can be synthesized using an inexpensive material, and after contact hydrogenation A hydrogen atom from which an aromatic moiety can be easily removed by drying under reduced pressure is more preferred.

a represents an integer of 0 to 2 and is preferably 0 or 1 because it can be easily synthesized from readily available materials.
R ³⁹ represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 25 carbon atoms in which some of the carbon atoms may be substituted with hetero atoms, a phenyl group, a phenoxy group, a benzyl group, an alkoxycarbonyl group. Group, an N-alkylcarbamoyl group or an N-alkylsulfamoyl group, preferably a hydrogen atom, an alkyl group having 3 to 25 carbon atoms, a phenyl group, a phenoxy group or an alkoxycarbonyl group, and a hydrogen atom which can be removed easily. preferable.

b represents an integer of 0 to 5 and is preferably 0 or 1 because it can be easily synthesized from readily available materials.
A plurality of R ³⁸ and R ³⁹ present in the same compound may be the same or different. The total number of carbon atoms contained in the cation moiety in the formula is 20 or more.
X ^- is an anion, monomethyl sulfate ion, hydrogen sulfate ion, dihydrogen phosphate ion, or an acetate ion.

<Onium salt of the second aspect>
The onium salt of the second embodiment is a compound represented by the following general formula (4), and has two benzoyloxy groups as substituents that can be converted into a functional group containing active hydrogen or a salt thereof. Hereinafter, the onium salt represented by the following general formula (4) is referred to as “benzoylated onium salt”.
In addition, the compound represented by the following general formula (4) and the general formula (8) described later is a novel compound suitable as the onium salt of the present invention.

In the general formula (4), R ¹⁶ and R ¹⁷ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 9 carbon atoms. In the alkyl group, the total number of carbon atoms of R ¹⁶ and R ¹⁷ is preferably 10 or less, and more preferably 8 or less. Some carbon atoms may be substituted with heteroatoms.
R ¹⁸ and R ²⁰ represent an optionally substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms, and more preferably ethylene. It is a group. This is because the onium salt produced by the solvation can be easily removed by washing with water, and the synthetic raw materials can be obtained at low cost.

In R ¹⁸ and R ²⁰ , some of the carbon atoms may be substituted with heteroatoms, or each may be bonded to form a ring.
R ¹⁹ and R ²¹ represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. From the viewpoint of ease of synthesis, R ¹⁹ and R ²¹ are preferably the same, and more preferably a t-butyl group from which a synthetic raw material can be obtained at low cost.

k and m each independently represent an integer of 1 to 5, and when k and m are each 2 or more, the plurality of R ¹⁹ and R ²¹ may be the same or different.
Y and Z each independently represent a halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group.

p is an integer of 0 ≦ p ≦ 5-k,
q is an integer of 0 ≦ q ≦ 5-m,
X ⁻ represents an anion. X is synonymous with the onium salt of the first aspect.
The ^{R 16,} R ^{17, R 18} and ^R total ^carbon number ²⁰ has is 14 or less, and is preferably the total number of carbon atoms of the ^{R 19} and ^{R 21} is 6 or more. Since the number of carbons in the onium salt is significantly different from before and after solvolysis, it has a high fat solubility during the reaction, so it is distributed to the organic phase and shows high activity. After solvolysis, it becomes a water-soluble compound and is removed by washing with water. It is because it is easy to do.

More preferably, R ¹⁶ , R ¹⁷ , R ¹⁸ and R ²⁰ have 9 to 12 carbon atoms in total, and R ¹⁹ and R ²¹ have 6 to 8 carbon atoms in total. When the total number of carbon atoms of R ¹⁹ and R ²¹ is within this range, both the lipophilicity during the reaction of the onium salt and the ease of removal of the substituted benzoic acid produced by solvolysis can be achieved. Furthermore, when the total number of carbon atoms of R ¹⁶ , R ¹⁷ , R ¹⁸ and R ²⁰ is within this range, both the lipophilicity during the reaction of the onium salt and the ease of removal of the onium salt after solvation are achieved. be able to.

From the viewpoint of ease of synthesis, R ¹⁹ and R ²¹ are preferably the same, and more preferably a t-butyl group from which a synthetic raw material can be obtained at low cost.
Specific examples of the compound described in the general formula (4) include a compound described in the following structural formula (8).

  The onium salt of the structural formula (8) can be obtained by solvating an onium salt in which the terminal structure is converted to a hydroxyl group and having 9 carbon atoms. This is preferable because it can be easily removed in the purification step. Further, since it is an ester of a primary hydroxyl group, it is characterized in that it is easier to synthesize and solvate than an ester of a secondary hydroxyl group. Moreover, it is preferable also from the point that it can synthesize | combine stably and with sufficient purity, and also a synthetic | combination raw material and reaction material are also preferable also at the point which is easy to acquire at low cost.

(Synthesis method of onium salt)
The method for synthesizing the onium salt used in the present invention is not particularly limited. For example, a nitrogen-containing heterocyclic compound having an acyloxy group or a benzyloxy group, such as a tertiary amine, a pyridine ring compound, or an imidazole ring compound, is synthesized. Examples thereof include an onium salt method and a method of introducing an acyloxy group or a benzyloxy group into an onium salt having a leaving group such as a hydroxyl group or halogen.

Examples of the method for introducing an acyloxy group include a dehydration condensation reaction between the corresponding alcohol and carboxylic acid, a condensation reaction using a corresponding alcohol and carboxylic acid condensing agent, a reaction between the corresponding alcohol and carboxylic acid chloride, and transesterification. A reaction, a method of reacting with an acid anhydride, a method of condensing a corresponding haloalkyl group and a carboxylate, and the like can be used.
Among these methods, industrially, a method using a dehydration condensation reaction is preferable from the viewpoint of cost and from the viewpoint of preventing mixing of halogen.

In addition, the method similar to said synthesis method is applicable to the regeneration method of onium salt after reaction after acyloxy group elimination | elimination.
When performing the said dehydration condensation reaction or transesterification, the method of making the corresponding alcohol react in presence of an acid catalyst is mentioned. At this time, it is preferable to carry out while removing water and alcohol produced by the reaction by a method such as distillation and adsorption.

The acid catalyst is not particularly limited. For example, mineral acids such as sulfuric acid, nitric acid and hydrochloric acid; phosphoric acids such as phosphinic acid, phosphonic acid and phosphoric acid; benzenesulfonic acid, toluenesulfonic acid, dimethylbenzenesulfonic acid, methane Organic acids such as sulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, trifluoroacetic acid, trichloroacetic acid and acetic acid; H ₃ PW ₁₂ O ₄₀ , H ₄ SiW ₁₂ O ₄₀ , H ₄ TiW ₁₂ O _{40 , H 5 CoW 12 O 40,} H 3 PMo 12 tungstate / molybdate acids _{O 40} and the like; hydrate or heteropoly acid of the tungstic acid / molybdenum acids; Amberlyst I
Cation exchange resin such as R120; H-type zeolite such as H-ZSM-5 can be used.

  Of these, organic acids are preferable because the reaction proceeds well without salt precipitation. Of these, toluenesulfonic acid, dimethylbenzenesulfonic acid, and methanesulfonic acid are separated into an organic phase and an aqueous phase by water washing after the reaction, and the aqueous phase is recovered and reused by azeotropic dehydration with toluene or the like. It is more preferable at the point which can do. Toluenesulfonic acid and dimethylbenzenesulfonic acid are more preferable in terms of cost because they can be prepared with toluene or xylene and sulfuric acid in the reaction system.

The amount of the acid catalyst used is 0.1 to 300% by mass, preferably 1 to 200% by mass, based on the substrate.
Can be used in a range of
The solvent used at the time of introducing the acyloxy group into the onium salt is not particularly limited as long as it does not participate in the reaction for introducing the acyloxy group, but aromatic hydrocarbons such as benzene, toluene, xylene, Aliphatic hydrocarbons such as hexane, heptane, octane, and dodecane are listed. Of these, toluene and xylene are preferred because they azeotrope with water and have a boiling point higher than the temperature required for the reaction.

Specifically, the method for introducing a benzyloxy group includes, for example, a condensation reaction using a condensing agent between the corresponding alcohol and benzyl alcohol, a condensation reaction between the corresponding alcohol and benzyl halide, and a condensation reaction between the haloalkyl group and benzyl alcohol. Can be used.
Among these methods, industrially, a condensation reaction between a corresponding alcohol and benzyl chloride is preferable from the viewpoint of cost.

  The solvent used at the time of introducing the benzyloxy group is not particularly limited as long as it does not participate in the reaction for introducing the benzyloxy group, but aromatic hydrocarbons such as benzene, toluene, xylene, hexane, Examples thereof include aliphatic hydrocarbons such as heptane, octane and dodecane, ethers such as diethyl ether, dibutyl ether and tetrahydrofuran, and nitrogen-containing aromatic hydrocarbons such as pyridine.

The amount of the solvent used for introducing the acyloxy group and benzyloxy group is not particularly limited, but it is preferably 0.5 to 10 times the amount of the substrate, and within this range, a sufficient reaction rate can be obtained and sufficient stirring is possible. It is.
In the present invention, the onium salts may be used alone or in combination of two or more.

  The amount of the onium salt used can be appropriately adjusted depending on the properties of the olefin compound to be used and is not particularly limited, but is usually 0.1 times mole or more in a molar ratio with respect to the catalyst metal used in the reaction, Preferably it is 0.2 times mol or more, more preferably 0.3 times mol or more, usually 5.0 times mol or less, preferably 2.0 times mol or less, more preferably 1.0 times mol or less. .

  The method for preparing the catalyst composition can be appropriately selected according to the olefin compound used in the reaction and the reactivity thereof, and is not particularly limited, but the catalyst metal and the onium salt are mixed in the reaction system. Either a method or a method of mixing the catalyst metal and the onium salt in advance outside the reaction system and then using them for the reaction may be used. Further, the method for adding phosphoric acids described later may be either a method of mixing in the reaction system or a method of previously mixing outside the reaction system.

When the catalyst metal and the onium salt are mixed in the reaction system, the mixing method and mixing order are not particularly limited, but specifically, the catalyst metal and the onium salt are usually included in the reaction system containing an olefin compound. It can be prepared by adding. The order of addition is not particularly limited, and either the catalyst metal or the onium salt may be added first, or may be added simultaneously.

  Alternatively, the catalyst metal and the onium salt can be mixed before use outside the reaction system. In this case, the mixing method, mixing order, and usage mode of the mixture are not particularly limited, but the catalyst metal and the onium salt produced in the catalyst composition can be used as they are by mixing the catalyst metal and the onium salt. You may isolate and use a complex with. Among them, it is convenient and preferable to mix the catalyst metal and the onium salt and use them as they are without isolation or activation.

(Phosphoric acids and phosphonic acids)
In the production method of the present invention, at least one of phosphoric acids and phosphonic acids can be used. In particular, when the epoxidation reaction is performed using the onium salt or the like using the catalytic metal as the active catalyst, it is preferable to use at least one of phosphoric acids and phosphonic acids from the viewpoint of improving the reactivity.

  Specific examples of phosphoric acids in the present invention include inorganic phosphoric acids such as phosphoric acid and phosphorous acid; phosphoric acid polymers such as polyphosphoric acid and pyrophosphoric acid; sodium phosphate, potassium phosphate, ammonium phosphate, phosphorus Inorganic phosphates such as sodium hydrogen phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate; monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, And phosphoric acid esters such as triethyl phosphoric acid and triphenyl phosphoric acid; Of these, phosphoric acid is preferred.

Examples of phosphonic acids include aminomethylphosphonic acid and phenylphosphonic acid.
Of these, in the present invention, it is preferable to use inexpensive phosphoric acid.
The amount of phosphoric acid and phosphonic acid used is not particularly limited, and the amount used can be appropriately adjusted depending on the type and the type of the catalyst metal, but preferably the aqueous phase of the two-phase reaction using the active catalyst. The amount used is adjusted so that the pH is in an appropriate range. The equivalent amount of phosphorus contained in any of the phosphoric acids and phosphonic acids is usually 0.1 times mol or more, preferably 0.2 times mol or more, in a molar ratio with respect to the metal in the catalyst metal used. Preferably it is 0.3 times mole or more, and is usually 5.0 times mole or less, preferably 2.0 times mole or less, more preferably 1.0 times mole or less.
At least one of phosphoric acids and phosphonic acids can be added so that the pH of the aqueous phase of the reaction solution is in an appropriate range, and other acids and bases are added as necessary to adjust the pH. You can also.

(Organic solvent)
In the present invention, an organic solvent can be used if necessary, and a reaction liquid containing an organic solvent is preferably used in terms of improving operability, such as when the olefin compound is a solid.
When an organic solvent is used in the epoxidation reaction of the present invention, the olefin compound may be dissolved or suspended in the organic solvent, but is usually dissolved in the organic solvent under the reaction temperature conditions. Is preferred.

The organic solvent used in the present invention is not particularly limited as long as it is inactive with respect to the olefin compound to be used and the active catalyst, but specifically, aromatic hydrocarbons such as benzene, toluene, xylene, etc .; hexane Aliphatic hydrocarbons such as methanol, ethanol, isopropanol, butanol, hexanol, cyclohexanol; halogen solvents such as chloroform, dichloromethane, dichloroethane; ethers such as tetrahydrofuran, dioxane; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; nitriles such as acetonitrile and butyronitrile; ester compounds such as ethyl acetate, butyl acetate and methyl formate; N, N-dimethylphenol Amides such as muamide, N, N-dimethylacetamide; ureas such as N, N′-dimethylimidazolidinone; and mixtures of these solvents, aromatic hydrocarbons, aliphatic hydrocarbons, and these A mixture of organic solvents is preferred.

Furthermore, aromatic hydrocarbons that are stable to the reaction are preferable, and toluene having a boiling point higher than the reaction temperature is more preferable. This is because when using the active catalyst having a particularly high reaction activity, it is preferable to carry out a two-phase reaction using an organic solvent that forms a two-phase system with water in terms of reaction efficiency and operation.
In addition, in order to perform the two-phase reaction smoothly, water may be added to the reaction solution as appropriate in addition to the organic solvent. The amount of water used is not particularly limited.

  The amount of the solvent used in the present invention can be appropriately adjusted depending on the solubility and various physical properties of the olefin compound, and is not particularly limited, but is usually the olefin compound used from the viewpoint of productivity and safety. The amount is 0.1 times or more and 10 times or less, preferably 5 times or less, more preferably 3 times or less.

(Chelating agent)
In the present invention, the epoxy compound may be produced in the presence of a chelating agent.
By allowing the chelating agent to coexist, it is considered that a chelate compound is formed with the metal impurities described later, and the epoxidation reaction can be performed safely without causing decomposition of hydrogen peroxide.
The chelating agent in the present invention refers to a compound having a multidentate ligand that binds to a metal ion to form a chelate compound.

  The chelating agent is not particularly limited, and specific examples include aminocarboxylic acids such as ethylenediaminetetraacetic acid and salts thereof, diethylenetriaminepentaacetic acid and salts thereof, triethylenetriaminehexaacetic acid and salts thereof, iminoacetic acid and salts thereof, and the like. Acids; oxycarboxylic acids such as citric acid, glycolic acid and their salts; organic phosphoric acids such as hydroxyethane diphosphones; condensed phosphates such as sodium pyrophosphate and sodium polyphosphate; amine compounds such as ethylenediamine and cyclene; bipyridine And nitrogen-containing heterocycles such as phenanthroline and porphyrin, and ether compounds such as crown ether. Of these, aminocarboxylic acids having an amino group and a carboxyl group in the molecule are preferred from the viewpoint that the effect obtained by the present invention is large, and particularly preferred because ethylenediaminetetraacetic acid and its salt are inexpensive and readily available. From the viewpoint of easy pH adjustment, ethylenediaminetetraacetic acid disodium salt is preferred. The number of substituents that can be coordinated by the chelating agent is more preferably coordinated to the metal more strongly, and is usually 2 or more, preferably 3 or more, and more preferably 4 or more.

The chelating agents may be used alone or in combination of two or more.
The amount of the chelating agent used in the present invention can be appropriately adjusted depending on the content of metal impurities described later, and is not particularly limited, but is usually equimolar or more with respect to the content of metal impurities. It is. Moreover, although an upper limit is also not restrict | limited, Usually, it is the quantity of the range which does not precipitate a chelating agent.

  Further, the concentration of the chelating agent in the reaction solution at the time of the epoxidation reaction is not particularly limited, but is usually the concentration in the reaction solution, particularly the concentration of the chelating agent in the aqueous phase in a two-phase reaction, Usually, it is 1 ppm or more, preferably 50 ppm or more, usually 10,000 ppm or less, preferably 5000 ppm, more preferably 2000 ppm or less.

(Compound having a carbon-carbon double bond)
The compound (olefin compound) having a carbon-carbon double bond used as a raw material in the present invention is not particularly limited as long as it is a compound having one or more carbon-carbon double bonds in the molecule.
Specific examples of the olefin compound include compounds described in JP2011-213716A. In particular, it is preferable to use an olefin compound represented by the following general formulas (9) to (14) as a raw material from the viewpoint that a highly purified, particularly low halogenated epoxy compound can be produced. Of these, the olefin compound represented by (10) is preferable, among which 3,3 ′, 5,5′-tetramethyl-4,4′-bis (2-propen-1-yloxy) -1,1′- Biphenyl (other name 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol diallyl ether) is preferred.

[Equation 1]
(R ²³ ) _n1- (A ¹ )-(OR) _m1 (9)

In General Formula (9), A ¹ represents any ^one of an aromatic hydrocarbon group, a group in which at least a part of the aromatic hydrocarbon group is reduced, and an aliphatic hydrocarbon group, and other than the OR group and R ²³ You may have the substituent of.
The aromatic hydrocarbon group for A ¹ is not particularly limited, and is a monocyclic aromatic hydrocarbon group such as a phenyl group, a condensed ring aromatic hydrocarbon group such as a naphthyl group, a heterocyclic aromatic hydrocarbon group, Or, the compound in which R in formula (9) is replaced with a hydrogen atom is a combination of a plurality of aromatics such as tris (4-hydroxyphenyl) -triazine, 1,1′-methylenebis-naphthalenediol, methylidenetrisphenol, etc. It may be what you did. Preferably, those having a plurality of aromatic hydrocarbon groups having 6 to 22 carbon atoms and aromatic hydrocarbon groups linked to each other can be mentioned.

Similarly, the group in which at least a part of the aromatic hydrocarbon group is reduced is not particularly limited, and examples thereof include a group in which at least a part of the aromatic hydrocarbon having 6 to 14 carbon atoms is reduced. Specific examples include a cyclohexyl group.
Similarly, the aliphatic group is not particularly limited, but a part of carbon atoms may be substituted with a heteroatom, and the aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. It is. Specific examples include C1-C25 linear aliphatic hydrocarbons and aliphatic hydrocarbons having an ether bond such as an ethyleneoxy group.

R represents an allyl group or a glycidyl group, which may have a substituent such as an alkyl group, a phenyl group, or an alkoxycarbonyl group, but is preferably an unsubstituted allyl group or a glycidyl group. In addition, when it has two or more OR groups, each OR group may be the same or different.
Examples of the substituent other than OR and R ²³ that A ¹ has include a glycidyl group, a phenyl group, a phenyloxy group, an alkyl group, an alkoxy group, and a halogen atom.

R ²³ represents an allyl group, which may have a substituent such as an alkyl group, a phenyl group, or an alkoxycarbonyl group, but is preferably an unsubstituted allyl group.
OR group is not particularly limited as substituents other than R ^23, a glycidyl group, a phenyl group, a phenyl group, an alkoxy group and a halogen atom.
m ¹ represents an integer of 1 or more and is not limited and varies depending on the number of substitutable hydrogen atoms on the substituent represented by A ¹ , but is preferably 2 or more and 4 or less.

When m ¹ is 2 or more, Rs may be the same or different.
n ¹ represents an integer of 0 or more, and the sum of m ¹ and n ¹ is 2 or more.
Specifically, the one represented by the general formula (9) is 1,6-bis (2-propene-1-
Yloxy) -naphthalene, 1,4-bis (2-propen-1-yloxy) -benzene, 1,4-bis (2-propen-1-yloxy) methyl] -cyclohexane, 1,1,1,1-tetra (Allyloxymethyl) methane, 1,1′-methylenebis-2,7-naphthalenediol tetraallyl ether, 2,4,6-tris [4- (2-allyloxy) phenyl] -1,3,5-triazine, Examples include 1,3-diallyl-2,4-diglycidyloxybenzene and 2-allyl-1,5-diglycidyloxynaphthalene.

In general formula (10), A ² and A ³ are each independently any of a divalent aromatic hydrocarbon group, a group in which at least a part of the aromatic hydrocarbon group is reduced, and an aliphatic hydrocarbon group. And may have a substituent other than the OR group, X ¹ and R ²³ . Except each valence is bivalent, the same meanings as in A ^1.
X ¹ represents a divalent linking group which may have a direct bond or a substituent.

As the divalent linking group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be substituted with a hetero element and may have a substituent, -O-, -S-, -SO _2- , -SO-, etc. are mentioned, and the linking group may have an unsaturated bond or a cyclic structure.
X ¹ is preferably a direct bond, a divalent alkylene group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon having 7 to 10 carbon atoms having a crosslinked condensed ring structure, and a direct bond or an alkylene group having 1 to 2 carbon atoms. Is more preferable.

In addition, adjacent A ² and A ³ connected via X ¹ may also form a ring in which a plurality of A ³ are further connected by substituents thereof. For example, a xanthene ring, a spirodibenzopyran ring, a spirobiindane ring and the like can be mentioned.
R, R ²³ , and n ¹ have the same meaning as in general formula (9).
Substituents other than OR and R ^{23 included in} A ² and A ³ are the same as those in General Formula (9).

m ² represents an integer of 1 or more, and varies depending on the number of substitutable hydrogen atoms on the substituent represented by A ² and is not limited, but is usually 4 or less, preferably 2 or less.
When m ² is 2 or more, Rs may be the same or different from each other. The sum of m ¹ and n ¹ is 2 or more, preferably the sum of m2 is 2, the sum of n1 is 0 or 2, and more preferably n1 is 0.

n represents 0 or an integer of 1 or more, and is usually 5 or less, preferably 3 or less, more preferably 0.
When n is 2 or more, A ³ may be the same as or different from each other.
Specifically, as represented by the general formula (10), 3,3 ′, 5,5′-tetramethyl-4,4′-bis (2-propen-1-yloxy) -1,1′-biphenyl ( Other names 3,3 ′, 5,5′-tetramethylbiphenol diallyl ether), 1,1 ′-(1-methylethylidene) bis [4- (2-propen-1-yloxy) -benzene] (other names bisphenol A diallyl ether), 1,1 ′-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [4- (2-propen-1-yloxy) -benzene], 1,1 ′. -Sulfonylbis [4- (2-propen-1-yloxy) -benzene], 4,4′-bis (2-propen-1-yloxy) -1,1′-biphenyl, 1,1 ′-(1- Methylethylidene) bis [4- (2- Propen-1-yloxy)]-cyclohexane], 3,3′-diallylbiphenyl-4,4′-diglycidyl ether (also known as 3,3′-diallyl-4,4′-diglycidyloxy-1,1 ′ -Biphenyl), 3,3′-diallylbiphenyl-4,4′-diallyl ether (alternative name 3,3′-diallyl-4,4′-diallyloxy-1,1′-biphenyl), 3,3′- Diallyl bisphenol A-diglycidyl ether (other name 2,2-bis (3-allyl-4-glycidyloxyphenyl) propane), 3,3′-diallyl bisphenol A-diallyl ether (other name 2,2-bis (3 -Allyl-4-allyloxyphenyl) propane) and the like.

[Equation 3]
_{^{H - [(R 23) n1}} - (A 2 (OR) m2) -X 2] i -H (11)

In General Formula (11), substituents other than A ² , m ² , n ¹ , and OR group have the same meaning as in General Formula (10).
R and R ²³ have the same meaning as in the general formula (9).
X ² represents a direct bond, an alkylene group which may have a substituent, or a phenylene group having two or more alkylene groups as a substituent. Carbon number of an alkylene group is 1-4 normally, Preferably it is a C1-C2 alkylene group.

i represents an integer of 2 or more and is usually 20 or less, preferably 10 or less.
Specific examples of the compound represented by the general formula (11) include 4- (2-propen-1-yloxy) benzoic acid-1,1 ′-(1,4-phenylene) ester, tris [4-allyloxy Phenyl) methane, polyallyl ether of cresol novolak, tris [3-allyl-4-glycidyloxyphenyl) methane, polyallyl ether of allyl cresol novolak, polyglycidyl ether of allyl cresol novolak, and the like.

  By applying the production method of the present invention to the compounds described in the general formulas (9) to (11), it is possible to produce an epoxy compound having a very small content of heavy metals such as tungsten and a low content of chlorine. it can.

In the above formula (12), m ⁴¹ and n ⁴¹ each independently represent an integer of 1 to 4, and A ^{41 to} A ⁴⁸ may each independently have a hydrogen atom, a halogen atom or a substituent. An alkyl group, an aromatic hydrocarbon group which may have a substituent, a nitro group, an alkoxyl group, an acyloxy group, a carbonyl group, a carboxyl group or a salt thereof is represented.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

As the alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a pentyl group, Linear or branched alkyl group such as hexyl group, heptyl group, octyl group, nonyl group, decyl group, cetyl group, stearyl group; cycloalkyl group such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, etc. Is mentioned. These alkyl groups may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group. Examples include alkoxyl groups such as nitro groups; carboxyl groups; alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups; acyloxy groups such as acetyloxy groups and propionyloxy groups.

Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
The aromatic hydrocarbon group may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom and bromine atom; methoxy group, ethoxy group, propoxy group, isopropoxy group, Alkoxy group such as butoxy group; nitro group; carboxyl group; alkoxycarbonyl group such as methoxycarbonyl group and ethoxycarbonyl group; acyl group such as acetyl group, propionyl group and benzoyl group; acyloxy group such as acetyloxy group and propionyloxy group Etc.

Examples of the alkoxyl group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, and a butoxy group.
Examples of the acyloxy group include an acetyloxy group, a propionyloxy group, and a benzoyloxy group.
Examples of the carbonyl group include alkoxycarbonyl, the carboxyl group or a salt thereof, carboxylic acid, and alkali metal salts such as sodium salt and potassium salt thereof.

In addition, any two or more of A ^{41 to} A ⁴⁸ may be bonded to each other to form a ring. The two molecules may be the same or single.
Examples of the bonding site include alkylene, ester, amide, urea bond and the like which may be substituted with a hetero atom.
Examples of the cyclic olefin represented by the general formula (12) include 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, 1,5-dimethyl-1,5-cyclo Examples thereof include cyclic non-conjugated olefins such as octadiene, dicyclopentadiene, and 2,5-norbornadiene, and 3-cyclohexen-1-carboxylic acid 3-cyclohexen-1-ylmethyl ester (celloxide precursor) having an ester bridge structure. .

  Another example of the compound having a carbon-carbon double bond used as a raw material in the present invention is a styrene compound represented by the following general formula (13).

In the above formula (13), A ^{51 to} A ⁵⁵ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 3 to 3 carbon atoms. 7 cycloalkyl group, aromatic hydrocarbon group, aralkyl group, acyl group, hydroxy group, halogen atom, carboxyl group or acyloxy group.
A ⁵⁶ is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, or a cycloalkyl having 3 to 7 carbon atoms. Group, aromatic hydrocarbon group, aralkyl group, acyl group, carboxyl group or acyloxy group. The linear or branched alkyl group having 1 to 8 carbon atoms may have a substituent, and examples of the substituent include 2-ethyl-1,3-indandione, trichloromethyl group, imidazolyl group, A triazolyl group and N-alkylsulfamoyl are mentioned. A ⁵⁷ and A ⁵⁸ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, carbon A cycloalkyl group, an aromatic hydrocarbon group, an aralkyl group, an acyl group, a carboxyl group, or an acyloxy group having a number of 3 to 7 is shown.

Note that any two or more of A ^{51 to} A ⁵⁸ may be bonded to each other to form a ring. )
Specific examples of the styrene represented by the general formula (13) include styrene, 4-methylstyrene, 4-fluorostyrene, 2,4-difluorostyrene, 3-chlorostyrene, 4-chlorostyrene, and 4-bromostyrene. 4-nitrostyrene, 4-vinylbenzoic acid, α-methylstyrene, β-methylstyrene, 1-phenyl-1-cyclohexene, indene, dihydronaphthalene, 2- [2- (3-chlorophenyl) -2-propene- 1-yl] -2-ethyl-1H-indene-1,3 (2H) -dione (indanophan precursor), 1,3-dichloro-5- (3,3,3-trichloro-1-methylenepropyl) -benzene ( Tandem precursor), 1- [2- (2,4-difluorophenyl) -2-propen-1-yl] -1H-1,2,4-triazole Etc.

In General Formula (14), A ⁶ represents an aromatic hydrocarbon group or an aliphatic hydrocarbon group, and may have a substituent other than X ³ .
Specific examples of A ⁶ include alkyl groups, alkenyl groups, phenyl groups, naphthyl groups, biphenyl groups, and biphenyl sulfones.
The substituent other than X ^{3 of} A ⁶ is not particularly limited, but specifically, an allyl group, glycidyl group, allyloxy group, glycidyloxy group, phenyl group, phenyloxy group, alkyl group, alkoxy group, halogen atom, etc. Is mentioned.

R is a substituent on the nitrogen atom and has the same meaning as in the general formula (9).
m ³ represents 1 or 2.
A ⁷ represents any one of a hydrogen atom, an aromatic hydrocarbon group, and an aliphatic hydrocarbon group, and preferably a hydrogen atom, an allyl group, a phenyl group, or an alkyl group.
n ³ represents 0 or 1, and m ³ + n ³ = 2.

X ³ _{is, -SO 2 -, - CO -} , - SO 2 NHCO -, - O-CO-, and represents a bond with -N-CO- or heteroatoms, preferably _-SO 2 -, -CO-.
m ⁴ represents an integer of 1 or more, and varies depending on the number of substitutable hydrogen atoms of A ⁶ and is not limited, but is preferably 2 or more and 4 or less.

When m ⁴ is 2 or more, the substituents X of A ⁶ may be the same or different, and the substituents R and A ⁷ on the nitrogen atom bonded to X may be the same or different.
Specific examples of the compound represented by the general formula (14) include N, N-diallylbenzenesulfonamide and N, N-diallyl-p-toluenesulfonamide.

(Method for producing epoxy compound)
The production method of the present invention is characterized in that the olefin compound is epoxidized in the presence of a catalyst metal, hydrogen peroxide and the onium salt. The specific reaction operation is not particularly limited, but the catalyst metal, hydrogen peroxide, and the onium salt are added to the olefin compound, and phosphoric acids and phosphonic acids as necessary, and further the organic solvent as necessary. Any of the chelating agents may be added.
In particular, in the case of a two-phase reaction, water may be further added as necessary.

(Pretreatment of olefin compounds)
The olefin compound in the present invention may be used after pretreatment if necessary when used in the epoxidation reaction of the present invention. By performing the pretreatment, the amount of metal impurities can be reduced. Therefore, in order to obtain the effects of the present invention remarkably, it is preferable to use after performing the following pretreatment.

Examples of the pretreatment method include a method of washing the olefin compound with an acidic aqueous solution and a method of washing with an aqueous chelating agent solution.
As a pretreatment method, an acidic aqueous solution or a chelating agent aqueous solution can be directly applied to the olefin compound for treatment, or the olefin compound can be dissolved in an organic solvent and then mixed and treated.

The type of acid used in the acidic aqueous solution is not particularly limited, and specific examples include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; and organic acids such as acetic acid and citric acid.
The pH of the acidic aqueous solution is not particularly limited, and varies depending on the stability of the olefin compound to be used. Usually, the pH is 1 or more, preferably 3 or more, usually 5 or less, preferably 4 or less. For the purpose of adjusting pH, various salts may be added. For example, sodium sulfate, sodium acetate, sodium phosphate, disodium hydrogen phosphate, sodium citrate and the like may be added.

Specifically, a mixed aqueous solution of acetic acid and sodium sulfate is preferable. For example, a pH = 4 aqueous solution containing 4% acetic acid and 1% sodium sulfate is more preferable. By performing the above washing treatment, the metal is solubilized in water and removed together with the aqueous phase.
The aqueous chelating agent solution is not particularly limited as long as it is an aqueous solution containing a compound capable of chelating with a metal, but an aqueous solution containing a so-called metal mask agent is preferable. The chelating agent used in the aqueous chelating agent solution is the same as the above-mentioned chelating agent, and ethylenediaminetetraacetic acid and pyrophosphoric acid are preferable in terms of operability and versatility.

The chelating agent used in the aqueous chelating agent solution may be the same as or different from the chelating agent that coexists in the reaction system.
The conditions for washing with an aqueous acid solution or an aqueous chelating agent solution are not particularly limited, but the washing time is usually from 30 minutes to 2 hours, and the washing temperature is usually from 10 ° C. to 30 ° C. By performing these treatments, the metal is solubilized in water and removed together with the aqueous phase.

(Reaction conditions)
The reaction temperature in the production method of the present invention is not particularly limited as long as the reaction is not inhibited, but is usually 10 ° C. or higher, preferably 35 ° C. or higher, more preferably 60 ° C. or higher, and usually 90 ° C. or lower, preferably 80 ° C. Below, more preferably 75 ° C. or less. This is because by reacting in the above temperature range, the reaction can proceed without lowering the reaction rate, and the reaction can proceed more safely.

The reaction time in the production method of the present invention can be appropriately selected depending on the reaction temperature, the amount of catalyst, the type of raw material and the like, and is not particularly limited, but is usually 1 hour or longer, preferably 3 hours or longer, more preferably 4 hours or longer. Usually, it is 48 hours or less, preferably 36 hours or less, more preferably 24 hours or less.
In the production method of the present invention, when hydrogen peroxide is reacted with the olefin compound, the amount of hydrogen peroxide contained in the reaction system is not particularly limited, but a smaller amount is preferable. It is 0.5 times mole or less normally with respect to the value which multiplied the number of moles of the compound which has the said carbon-carbon double bond to the number of double bonds contained, and 0.3 times mole or less is preferable. In particular, when the olefin raw material is consumed and the end of the reaction is reached, the consumption rate of hydrogen peroxide decreases, so 0.25-fold mol is more preferable.

  When the amount of hydrogen peroxide in the reaction system is large, when hydrogen peroxide is decomposed due to contamination with metal impurities, or when hydrogen peroxide is decomposed due to a rapid temperature increase, oxygen gas is rapidly generated or Ascending, foaming accompanying this occurs, which is not preferable for safety. When the amount of hydrogen peroxide present in the reaction system is less than the above amount, even when this hydrogen peroxide is instantly decomposed or reacted, the amount of heat generated is the water, solvent in the system, the olefin compound, etc. Therefore, the reaction can be carried out more safely.

At this time, although not limited, the reaction may be performed in a two-phase solution.
When the production method of the present invention is carried out by a two-phase reaction, the concentration of hydrogen peroxide in the aqueous phase is not particularly limited, but is preferably lower, preferably 5% by mass or less, more preferably 4% by mass or less, usually It is 0.1 mass% or more, and 0.3 mass% or more is preferable. This is because, within the above range, reoxidation of the catalytic metal occurs, and a reduction or stop of the reaction rate can be avoided.

Further, when the production method of the present invention is carried out with a two-phase solution, the amount of the aqueous phase and the organic phase is not particularly limited, but the mass of the aqueous phase is the amount of reaction heat or hydrogen peroxide relative to the mass of the olefin compound. In order to absorb the heat of decomposition by the specific heat or latent heat of water, and to reduce the concentration of hydrogen peroxide solution for the purpose of suppressing decomposition by metal impurities as described above, it is usually 1.5 times or more from the point that it is preferably diluted with water. It is more preferably 1.8 times or more, and more preferably 2.0 times or more. The upper limit is not limited as long as the reaction does not proceed because the concentration of hydrogen peroxide is too low, but it is usually 10 times or less, preferably 6 times or less in terms of productivity.

Further, the mass of the organic phase is not particularly limited, but is usually 5 times or less with respect to the mass of the olefin compound, and the reaction rate is lowered due to a decrease in the concentration of the substrate and the onium salt in the organic phase. Is preferably 2 times or less. Although a minimum is not specifically limited, Usually, it is 1.1 times or more.
In addition, a solvent, an olefin compound, and an onium salt are normally dissolved in the organic phase, and the weight of the organic phase represents the combined weight of all of these dissolved in the organic phase.

The total amount of the organic phase and the aqueous phase is not particularly limited, but in terms of safety, from the viewpoint of absorbing the heat of reaction and the heat of decomposition of hydrogen peroxide, it is usually more than twice the mass ratio to the substrate. In terms of productivity, it is 8 times or less.
Although the ratio of the organic phase / aqueous phase is not limited, it is usually 1 or less, preferably 0.5 or less. Although the reaction rate is affected by the concentration of the olefin compound and onium salt compound in the organic phase, it is not affected by the concentration of hydrogen peroxide, so it does not decrease the reaction rate and decomposes the heat of reaction and hydrogen peroxide. This is because a higher proportion of water is preferable from the viewpoint of absorbing heat.

The method for maintaining the hydrogen peroxide concentration in the aqueous phase of the two-phase reaction is not particularly limited, but it is preferable to add water before or during the addition of hydrogen peroxide. This is because by adding water, not only can the hydrogen peroxide concentration be kept low, but also the specific heat absorption and latent heat absorption of the reaction system increase, and the safety is further improved.
The total amount of water added is not particularly limited, but is usually 0.1 times or more, preferably 0.5 times or more, more preferably 1 time or more, in terms of mass ratio to the normal olefin compound. The amount is 5 times or less, preferably 3 times or less.

The pH during the reaction in the production method of the present invention can be appropriately adjusted depending on the structure and properties of the olefin compound to be subjected to the reaction and is not particularly limited, but the pH is usually 2 or more, preferably 2.5. As described above, it is usually 6 or less. When the onium salt is used for the reaction and the reaction is a two-phase reaction, the pH of the aqueous phase is preferably within the above range.
For example, when the olefin compound is a cyclic olefin, the reaction is preferably carried out at a pH close to neutrality because it tends to be epoxidized but the produced epoxy ring tends to be transferred or cleaved. On the other hand, when the olefin compound is allyl ether, it tends to be less epoxidized and less prone to cleavage than the cyclic olefin, so that the reaction tends to be more acidic, that is, at a lower pH than the cyclic olefin. . When the onium salt is used during the reaction, the pH changes depending on the amount of hydrogen peroxide in the aqueous phase of the two-phase reaction, and the epoxy produced in the latter half of the reaction is cleaved under acidic conditions. It is preferable to keep the pH within the optimum range by adding an acid or a base as appropriate according to the degree of progress.

  In the production method of the present invention, a buffer may be used as necessary. As the type of the buffer, any buffer that matches the target pH can be used as long as it does not inhibit the reaction. Examples of the buffer solution include citric acid and sodium citrate, acetic acid and sodium acetate, and the like as a combination of an aqueous phosphate solution, hydrogen phosphate, dihydrogen phosphate, or phenyl phosphate. In some cases, the above tungstic acids may be combined to form a buffer solution.

In the production method of the present invention, a co-oxidant can be used for the purpose of causing the reaction to proceed smoothly. Specifically, the catalyst composition may contain a carboxylic acid, preferably an aliphatic carboxylic acid having 1 to 10 carbon atoms. The cooxidant may be added to the composition. For example, in the case of an onium salt having an ester group, the ester group may be generated by receiving a solvent.

The reaction in the production method of the present invention is preferably performed under normal pressure and a nitrogen stream from the viewpoint of safety.
In the present invention, after the epoxidation reaction is completed, a reducing agent is added as necessary to quench excess hydrogen peroxide. When the onium salt is used in the reaction, it is preferable to perform the quenching treatment after discarding the aqueous phase of the two-phase reaction and washing the organic phase with water. Although it does not specifically limit as a reducing agent used for the said quench process, Sodium sulfite, sodium thiosulfate, hydrazine, an oxalic acid etc. are mentioned.

(Purification)
You may further refine | purify the epoxy compound obtained by said method as needed. In particular, the catalyst-derived metal used in the production method of the present invention, at least one of tungsten and molybdenum compounds, and the onium salt used as necessary are usually removed by purification. A specific purification method is not particularly limited, and a known method can be appropriately used. When the epoxy compound is a solid, crystallization, hanging washing, liquid separation, adsorption, sublimation and the like can be mentioned, and when the epoxy compound is a liquid, liquid separation, washing, adsorption and distillation can be mentioned.

  Purification by separation and washing may be performed by combining water and an organic solvent that is insoluble or hardly soluble in water, or combining a plurality of organic solvents that are not mixed with each other. Examples of the combination of water and an organic solvent insoluble or hardly soluble in water include a combination of an organic solvent such as ethyl acetate, toluene, diethyl ether, diisopropyl ether, n-hexane, and water. Examples of combinations of a plurality of organic solvents that are not mixed with each other include, for example, a combination of N, N′-dimethylformamide and n-heptane, n-hexane, n-pentane, diisopropyl ether, xylene, dimethyl sulfoxide and n -In combination with at least one of heptane, n-hexane, n-pentane, diisopropyl ether, diethyl ether, xylene, acetonitrile and n-heptane, n-hexane, n-pentane, cyclohexane, cyclopentane There is a combination with at least one and a combination with at least one of methanol and n-heptane, n-hexane and n-pentane.

For purification by crystallization, the solvent is distilled off under reduced pressure, or it is cooled and crystallized without distilling off, a solvent having a low solubility of the compound, a method of adding a so-called poor solvent to precipitate, and a compound having a high solubility. Any of a method of precipitation by combining a solvent, a so-called easy solvent and a poor solvent, a method of crystallization by adding water after completion of the reaction, and the like may be used. The solvent may be an organic solvent, water, a mixture thereof, a combination of organic solvents, or the like, and an appropriate one is selected depending on the solubility of the compound. Examples of the organic solvent include esters such as ethyl acetate, aliphatic hydrocarbons such as heptane, hexane, and cyclohexane, aromatic hydrocarbons such as benzene, toluene, and xylene, acetonitrile, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, and the like. Aprotic solvents, alcohols such as methanol, ethanol, 2-propanol and n-butanol, ketones such as acetone and methyl ethyl ketone, aprotic such as N, N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide A polar solvent.

For purification by hanging washing, a solvent having a low compound solubility, a so-called poor solvent is used. Although a preferable poor solvent changes with compounds, highly polar things, such as alcohols, such as methanol, and low polarity aliphatic hydrocarbons, such as a pentane, hexane, and a cyclohexane, are raised conversely.
Examples of the water-soluble solvent include tetrahydrofuran, 1,3-dioxolane, N, N-dimethylformamide, dimethyl sulfoxide and the like, and these can be used by mixing with water. When the amount of the solvent is too small, the purification effect is not sufficient, and when it is too large, the recovery rate is lowered. After completion of the hanging washing, the target product can be obtained by collecting the solid by filtration and drying.

Purification by adsorption includes activated carbon, activated clay, molecular sieves, alumina, zeolite, ion exchange resin and the like as chlorine-containing impurities and adsorbents.
Among the above purification methods, from the viewpoint of operation methods, a liquid separation method and an adsorption method are preferable regardless of the properties of the epoxy compound. When the epoxy compound is solid, the crystallization method is effective.

<Decomposition / removal process of onium salt>
After the epoxidation reaction, the onium salt is converted into an onium salt compound having a functional group containing active hydrogen or a salt thereof and separated from the epoxy compound. Since the onium salt having a functional group containing active hydrogen or a salt thereof is water-soluble, it can be easily removed by washing or the like. Along with this, the catalytic metal component forming a complex with the onium salt is also removed.
The method for converting to a functional group containing active hydrogen or a salt thereof is not particularly limited as long as it does not damage the epoxy compound, but the following methods are usually used.

(I) When the onium salt is an acylated onium salt or a benzoylated onium salt, it is preferable to perform solvolysis in the presence of a basic compound and remove the decomposition product by washing with water. Examples of the basic compound used in the solvolysis step include sodium hydroxide, lithium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate. Inorganic bases such as sodium hydroxide, potassium hydroxide, sodium phosphate and sodium hydrogen phosphate: organic bases such as ammonia, methylamine and ethylamine, of which sodium hydroxide, lithium hydroxide, potassium carbonate, carbonate Sodium, sodium hydrogen carbonate, potassium hydrogen carbonate, and potassium carbonate are preferable, and sodium hydroxide, lithium hydroxide, and potassium carbonate are particularly preferable. The solvent used in the solvolysis step is usually water or / and alcohol. As the alcohol, methanol, ethanol, propanol, and ethylene glycol are preferable, and methanol is particularly preferable.

The concentration, pH, and temperature of the basic solution are not particularly limited, but can be selected within a range where the epoxy compound does not decompose. Specifically, in the case of an aqueous solution, a basic aqueous solution having a concentration of usually 0.1 N to 5 N, preferably 0.3 N to 3 N, and more preferably 0.5 N to 2 N is used. The pH of the aqueous solution is usually 10-12. The temperature is usually 0 ° C. or higher, preferably 20 ° C. or higher, usually 60 ° C. or lower, preferably 45 ° C. or lower.
In the above step, the onium salt is decomposed into an onium salt compound having a functional group containing active hydrogen or a salt thereof and a compound derived from other structures. For example, in the case of acylated onium salts and benzoylated onium salts, a carboxylic acid is produced when the above treatment is carried out in water, and a carboxylic acid ester is produced when the reaction is carried out in an alcohol solvent. In the case of benzoylated onium salts, the corresponding aromatics are produced by reduction. For example, in the case of a benzoyl group, toluene is produced by catalytic hydrogenation. Separation of these products and the epoxy compound is not particularly limited as long as it is a method that does not impair the epoxy compound, but it is usually removed by washing with basic water, treatment with basic water or distillation under reduced pressure.

In the case where the onium salt is an acylated onium salt, the onium salt having a hydroxyl group produced by the elimination of the acyl group in the solvolysis step is a synthetic precursor of the acylated onium salt. It can be acylated again and used as an acylated onium salt. Therefore, a step of regenerating the solvated onium salt may be provided after the solvolysis step of the acylated onium salt.
(Ii) When the onium salt is a benzylated onium salt, it is preferable to perform reduction, preferably catalytic hydrogenation, and then remove the decomposed onium salt by washing with water.

(Epoxy compound)
The epoxy compound obtained by the production method of the present invention is preferably one in which the carbon-carbon double bond of the olefin compound is converted to an epoxy group, and all the carbon-carbon double bonds are epoxidized. .
An epoxy compound is obtained through the above epoxidation reaction, separation / removal step of the catalyst metal and onium salt used if necessary, and purification step as necessary.

In the epoxy compound obtained by the production method of the present invention, the content of the metal element derived from the catalyst metal is not particularly limited, but is usually 200 ppm or less, preferably 100 ppm or less, more preferably 10 ppm or less, More preferably, it is 1 ppm or less.
Similarly, in the epoxy compound obtained by the production method of the present invention, the nitrogen content derived from the onium salt is usually 500 ppm or less, preferably 200 ppm or less, more preferably 10 ppm or less, and further preferably 1 ppm or less.

The epoxy compound obtained by the production method of the present invention has a characteristic that the chlorine content is generally smaller than that of an epoxy compound synthesized using epichlorohydrin, although it depends on the chlorine content of the compound subjected to the reaction. .
Usually, the halogen atom content is low, and the content is usually 200 ppm or less, preferably 50 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less.

  The production method of the present invention can be used for the production of a pharmaceutical intermediate having an epoxy structure and a raw material for agricultural chemicals in addition to the epoxy resin described later. For example, production of an antifungal agent having a halogen-substituted styrene oxide structure, an intermediate of a diabetic drug, and the like can be raised. Since the epoxy compound obtained by the method of the present invention has few impurities, the concern about toxicity derived from the impurities is reduced.

(Epoxy resin)
The epoxy compound obtained by the production method of the present invention can produce an epoxy resin by polymerization. A known method can be applied to the polymerization reaction. Specifically, the polymerization reaction can be performed by a method described in JP-A-2007-246819.
The high-purity epoxy resin obtained by the method of the present invention can be used in electronic materials, optical materials, adhesives, construction fields and the like. Used as optical materials such as lighting sealants for wiring corrosion and short circuits caused by impurities when used as electronic component materials such as semiconductor encapsulants, printed wiring boards, build-up wiring boards, solder resists, etc. In this case, it is possible to reduce or avoid coloring and deterioration.

The onium salt used in the present invention is not limited to the epoxidation reaction described above, and can be applied to various oxidation reactions.
The inventor has filed a patent application as PCT / JP2013 / 059401, “an onium salt having one or more substituents that can be converted into a functional group containing active hydrogen or a salt thereof and containing 20 or more carbon atoms”, specifically, The onium salt of the invention can also be used in various oxidation reactions combined with hydrogen peroxide.

Specific usage methods include a method for producing an aldehyde and a carboxylic acid from a compound having a primary hydroxyl group, a method for producing a 1,2-diol from a compound having a carbon-carbon double bond, and a compound having a thioether bond. Used in a method for producing a sulfone compound.
Specifically, the aldehyde production method includes at least one of a tungsten compound and a molybdenum compound, and an onium having one or more substituents that have 20 or more carbon atoms and can be converted into a functional group containing active hydrogen or a salt thereof. An aldehyde can be obtained by reacting a compound having a primary hydroxyl group with hydrogen peroxide in the presence of a salt.

Specifically, the carboxylic acid production method has at least one of a tungsten compound and a molybdenum compound, and one or more substituents that have 20 or more carbon atoms and can be converted into a functional group containing active hydrogen or a salt thereof. Carboxylic acid can be obtained by reacting a compound having a primary hydroxyl group with hydrogen peroxide in the presence of an onium salt.
The production method of 1,2-diol includes at least one of a tungsten compound and a molybdenum compound, and an onium having one or more substituents having 20 or more carbon atoms and capable of being converted into a functional group containing active hydrogen or a salt thereof. Hydrogen peroxide can be reacted with a compound having a carbon-carbon double bond under acidic conditions in the presence of a salt to give 1,2-diol.

As a method for producing a sulfone compound, there is at least one of a tungsten compound and a molybdenum compound, and the presence of an onium salt having at least one substituent having at least 20 carbon atoms and having a functional group containing active hydrogen or a salt thereof. Then, a sulfone compound can be obtained by reacting a compound having a thioether bond with hydrogen peroxide.
In the various production methods described above, the onium salt of the present invention is preferred as the onium salt. The production conditions are not particularly limited, and can be appropriately adjusted according to the reactivity of the raw material and the target product.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by the following examples.
^<1 H-NMR analysis conditions>
Equipment: AVANCE400, 400MHz manufactured by BRUKER
Solvent: 0.03 volume% tetramethylsilane-containing deuterated chloroform Only Synthesis Example 4 was added with 0.005 volume% trifluoroacetic acid. Accumulation count: 16 times Data in the examples are in ¹ H-NMR (400 MHz, CDCl ₃ ). Represents the δ value.

<LC analysis conditions>
LC device: SPD-10Avp manufactured by Shimadzu Corporation
Temperature: 35 ° C
Column: Mightysil RP-18GP aqua 150-4.6 (5μ
m) (manufactured by Kanto Chemical)
(Hereinafter referred to as analysis condition 1)
Detector: UV 280nm
Eluent: Acetonitrile / 0.1% by volume trifluoroacetic acid aqueous solution = 90/10
(volume%)
Flow rate: 0.5 ml / min (hereinafter referred to as analysis condition 2)
Detector: UV 254nm
Eluent: acetonitrile / 0.1% by volume trifluoroacetic acid aqueous solution = 60/40
(Volume%) → 100/0 (volume%) in 20 minutes, then 100/0 (body
Held for 10 minutes at a flow rate of 0.5 ml / min.

<Mass analysis conditions>
LC device: Applied Biosystems Voyager-DE STR
Mass spectrometer
Ionization method: MALDI (+)

<GC analysis conditions>
Apparatus: GC-1700 manufactured by Shimadzu Corporation
Column: ZB-5 (30 m × 0.25 mmφ, particle diameter, manufactured by phenomenex)
0.25μm)
Detector: Hydrogen flame ion detector (FID)
Carrier gas (nitrogen flow rate): 28 ml / min Column temperature: Increased from 100 ° C to 300 ° C at 10 ° C / min INJ temperature: 250 ° C
DET temperature: 300 ° C

<Method for measuring nitrogen content>
The nitrogen content (weight ppm) was measured by the following method. A sample of 8 mg was combusted in an oxygen and argon atmosphere, and the generated decomposition gas was measured with a trace nitrogen analyzer (TN-10 model manufactured by Mitsubishi Chemical Analytech Co., Ltd.) using a combustion / reduced pressure chemiluminescence method. Further, aniline was dissolved in toluene and used as a standard sample.

<Conditions for detection of chlorine content>
The chlorine content (ppm by weight) was measured by the following method for the total amount of chlorine combined with inorganic and organic. The sample was burned and absorbed in the absorbing solution, and then measured with an ion chromatograph. AQF-100 manufactured by Mitsubishi Chemical Corporation was used as the combustion apparatus, and DX-500 manufactured by DIONEX was used as the ion chromatograph apparatus. The ion chromatograph used Ion Pac AS12A made from DIONEX for the column, and detected by electrical conductivity.

<ICP-MS analysis conditions>
Pretreatment method: dry ashing-acid dissolution method analyzer: ICP mass spectrometer 7500ce type manufactured by Agilent Technologies
In the following examples, “LC area” refers to the peak area of the analysis target compound obtained by liquid chromatography (LC) analysis, and “LC area%” refers to the target compound relative to the peak area of the total amount of the composition. The ratio of the peak area.

Similarly, “GC area” refers to the peak area of the target compound obtained by GC analysis, and “GC area%” refers to the ratio of the peak area of the target compound to the peak area of the total amount of the composition.
The “yield” in the examples was calculated by regarding the weight of the compound obtained by multiplying the purity by “LC area%” or “GC area%” as the yield.

  In the following examples, a diol compound whose epoxy ring was opened during the epoxidation reaction, an carboxylic acid compound oxidized after aldehyde isomerization with heat or acid, and the like are higher in polarity than the epoxy compound. A compound giving a faster retention time than the epoxy compound was by-produced. These compounds may be collectively referred to as “polar compounds” in the examples.

(Synthesis Example 1)
(Synthesis of epoxidation reaction raw materials)
3,3 ′, 5,5′-tetramethyl-4,4′-bis (2-propen-1-yloxy) -1,1′-biphenyl (alternative name: 3,3 ′, 5,5′-tetra Methyl bifunol diallyl ether) synthesized by a method according to Example 2 of JP 2011-213716 A was used. The metal content of about 60 elements in this compound was subjected to total qualitative and semi-quantitative measurement by the above ICP-MS analysis method (detection lower limit: about 1 ppm). Quantitative analysis was performed on chromium and cobalt that decompose hydrogen peroxide in a very small amount due to the possibility of contamination from the reactor (detection lower limit 0.01 ppm). As a result of the analysis, 2 ppm of iron and 0.02 ppm of chromium were contained. Cobalt was below the detection limit.

  10.0 g (31.0 mmol) of 3,3 ′, 5,5′-tetramethyl-4,4′-bis (2-propen-1-yloxy) -1,1′-biphenyl obtained above was dissolved in toluene. The solution dissolved in 10 ml was washed with 30 ml of an aqueous solution containing 1% by weight of anhydrous sodium sulfate and 1% by volume of acetic acid, 0.26 ml of 3% by weight sodium pyrophosphate aqueous solution, 0.12 ml of 10% by weight ethylenediaminetetraacetic acid solution, water Washed with 30 ml of mixture. After washing with 30 ml of water, it was concentrated to obtain crude crystals (sometimes simply referred to as “reaction raw material” in the following examples). The purity of the reaction raw material was 99.9% (LC area%, the above analysis condition 1). When the contents of iron and chromium in this compound were quantitatively analyzed by ICP-MS, iron was 0.3 ppm and chromium was below the detection limit (0.01 ppm).

(Synthesis Example 2)
(Synthesis of onium salt [1])
A mixed solution of 8-t-butylbenzoic acid 80.0 g (440 mmol), toluene 240 ml, and triethylamine 0.68 g (6.7 mmol) was heated to 75 ° C., and then 64.1 g (539 mmol) of thionyl chloride was added to 1.5. The mixture was added over time, and further reacted at 75 ° C. for 1.5 hours. After completion of the reaction, 100 ml of toluene was added at normal pressure, excess thionyl chloride was distilled off, 50 ml of toluene was further added under reduced pressure, and excess thionyl chloride was distilled off under reduced pressure to give 4-t-butylbenzoic acid. 90.8 g of acid chloride was obtained.

  To a mixed solution of 1.00 g (6.2 mmol) of N-butyldiethanolamine, 1.88 g (18.6 mmol) of triethylamine and 10 ml of toluene, 2.68 g (13.6 mmol) of 4-tert-butylbenzoic acid chloride obtained at room temperature. ) Was added dropwise. The mixture was stirred at 40 ° C. for 4.5 hours and then stirred at 60 ° C. for 10 hours. After completion of the reaction, the mixture was washed twice with 10 ml of water and concentrated. The obtained crude product was purified by column chromatography (silica 60N 150 g, developed by Kanto Chemical Co., Inc., developing solvent: hexane / ethyl acetate = 6/1), and N-butyl-N, N-di [2- (4-t -Butylbenzoyloxy) ethyl] amine 2.78 g was obtained. The purity was 99% (LC analysis condition 2), and the yield was 93%.

  To 0.20 g (0.42 mmol) of N-butyl-N, N-di [2- (4-t-butylbenzoyloxy) ethyl] amine obtained above, 0.6 ml of toluene was heated to 80 ° C., After adding 30 mg (2.5 mmol) of dimethyl sulfate and reacting for 2 hours, 30 mg (2.5 mmol) of dimethyl sulfate was further added and reacted for 3.5 hours. N-butyl-N, N-di [2- (4-t-butylbenzoyloxy) ethyl] -N-methylammonium monomethyl sulfate (with the above structural formula (8)) with an LC area of 97% (analysis condition 2) Formation of a compound whose counter ion is monomethyl sulfate (hereinafter referred to as onium salt [1]) was confirmed. This reaction solution was directly subjected to epoxidation reaction without purification.

The NMR data of each compound measured by the above measuring method was as follows.
N-butyl-N, N-di [2- (4-t-butylbenzoyloxy) ethyl] amine:
0.88 (3H, t, J = 7.3Hz), 1.32 (18H, s, t-Bu), 1.35-1.40 (2H, m, -CH 2 -), 1.40- 1.51 (2H, m, —CH ₂ —), 2.64 (2H, t, J = 5.3), 2.96 (4H, t, J = 6.0 Hz, N—CH ₂ —), 4.39 (4H, t, J = 6.0 Hz, O—CH ₂ −), 7.41 (4H, dd
d, J = 2.0, 3, 8, 8.6 Hz, Ar), 7.98 (4H, ddd, J = 2.0, 4.0, 8.8 Hz, Ar).
Onium salt [1]:
0.09 (3H, t, J = 7.3Hz, Me), 1.30-1.33 (2H, m, -CH 2 -), 1.32 (18H, s, t-Bu), 1. _{70-1.85 (2H, m, -CH 2} -), 3.45 (3H, s, N-Me), 3.50-3.60 (2H, m, N-CH 2 -C 3 H 7 _{) 3.66 (3H, s, MeSO} 2), 4.08-4.15 (4H, m, O-CH 2 -), 4.82-4.89 (4H, m, N-CH 2), 7.41 (4H, d, J = 8.6 Hz, Ar), 7.89 (4H, d, J = 8.6 Hz, Ar).

Example 1
Reaction material 2.50 g (7.8 mmol) obtained in Synthesis Example 1, sodium tungstate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 256 mg (0.78 mol), 8.5% (weight / volume) phosphoric acid A mixed solution of 0.98 ml (0.85 mmol) of the aqueous solution, 236 mg (0.39 mmol) of the onium salt [1], 2.5 ml of toluene and 1.5 ml of water was prepared.

This mixed solution was heated to 65 ° C. under a nitrogen stream, and 0.13 ml (1.77 mmol) of 42% by mass hydrogen peroxide was added at the start of the reaction and 30 minutes after the start of the reaction, and further for 1 hour from the start of the reaction. Thereafter, 0.25 ml (3.6 mmol) was added after 2 hours, 3 hours, 4 hours, and 6 hours, and reacted at 64-66 ° C. for a total of 7 hours. The mixed solution is a two-phase system, and the composition ratio of the organic phase is 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol diglycidyl ether (abbreviated as diepoxy) 76 in LC area%. .7%, and 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylbiphenyl monoallyl ether monoglycidyl ether (hereinafter abbreviated as monoepoxy compound) 10.6%, polar Compound 10.4%.

  After completion of the reaction, 10 ml of toluene was added, and the separated aqueous phase was discharged. The organic phase was washed with 5 ml of water and then washed with 5 ml of a 5 mass% aqueous sodium thiosulfate solution for reduction treatment. Subsequently, 10 ml of a 1N aqueous sodium hydroxide solution was added, the mixture was treated at 40 ° C. for 30 minutes, and the aqueous phase was discharged. The disappearance of the onium salt [1] in the organic phase was confirmed by LC analysis (Condition 2), and the same basic water treatment operation was further performed twice. After washing with 10 ml of water, the obtained organic phase was concentrated to obtain 2.45 g of the diepoxy compound as crude crystals. LC area 84.2% (LC analysis condition 2), yield 75%. The nitrogen content of the obtained diepoxy crude crystal was 49 ppm. The NMR data of the compound before and after the reaction were as follows.

3,3 ′, 5,5′-tetramethylbiphenol diallyl ether: 2.32 (12H, s, —CH ₃ ), 4.34 (4H, td, J = 1.5, 5.1 Hz, O—CH _2- ), 5.27 (2H, ddd, J = 2.3, 2.8, 10.6 Hz, -CH = CH ₂ ), 5.44 (2H, ddd, J = 1.5, 3.3). _{, 17.2Hz, -CH = CH 2)} , 6.06-6.19 (2H, m, - CH = CH 2), 7.18 (4H, s, -C 6 H 2 (Me) 2 -) .
3,3 ′, 5,5′-tetramethylbiphenol diglycidyl ether: 2.34 (12H, s, —CH ₃ ), 2.75 (2H, dd, J = 2.8, 4.9 Hz, —O _{-CH 2 -), 2.90 (2H} , dd, J = 4.3,4.9Hz, -O-CH 2 -), 3.36-3.41 (2H, m, -CH -), 3 .73 (2H, dd, J = 5.8, 11.0 Hz
, —O—CH ₂ —), 4.07 (2H, dd, J = 3.3, 11.0 Hz, —O—CH ₂ —), 7.18 (4H, s, —C ₆ H ₂ (Me ₂ ).

(Synthesis Example 3)
(Synthesis of onium salt [2])
A mixed solution of 4.0 g (36.2 mol) of 1-chloro-2,3-propanediol, 7.4 g (39.8 mmol) of tributylamine and 4 ml of acetonitrile was heated and stirred at 60 ° C. for 3.5 hours. Thereafter, 2.5 g (18.1 mol) of potassium carbonate was added and reacted at 80 ° C. for 8 hours. 10 ml of acetonitrile was added, and the deposited precipitate was filtered off and dried under reduced pressure to obtain 6.28 g of crude 2,3-dihydroxypropyltributylammonium chloride. Crude yield 67%.

  4-t- synthesized by the above method at room temperature into a mixture of 1.0 g of crude 2,3-dihydroxypropyltributylammonium chloride obtained by the above method, 20 ml of toluene and 1.17 g (11.5 mmol) of triethylamine. 1.66 g (8.4 mmol) of butylbenzoic acid chloride was added, and the reaction was performed at 60 ° C. for 12 hours. After allowing to cool, 10 ml of ethyl acetate was added, and after washing twice with 10 ml of water, the solvent was distilled off to obtain crude 2,3-di (4-t-butyl-phenyloxy) propyltributylammonium chloride.

  The crude 2,3-di (4-t-butyl-phenyloxy) propyltributylammonium chloride obtained above was purified with 100 ml of Diaion HP120 (manufactured by Mitsubishi Chemical Corporation) (developing solvent: ethanol) and concentrated. 0.15 g of the obtained residue was dissolved in 3 ml of toluene, washed twice with 3 ml of 10% (volume / volume) sulfuric acid and concentrated, and 2,3-di (4-tert-butyl-benzoyloxy) -N, 0.19 g of N, N-tributyl-1-propaneammonium hydrogen sulfate (hereinafter referred to as onium salt [2]) was obtained. The purity was 68% (LC analysis condition 2). The NMR data of the obtained onium salt [2] were as follows.

Onium salt [2]:
0.86 (9H, t, J = 8.0 Hz, n-Bu), 1.26 (6H, dd, J = 4.0, 8.0 Hz, n-Bu) 1.24 (9H, s, t -Bu), 1.34 (9H, s, t-Bu), 1.62-1.82 (6H, m, n-Bu), 3.26-3.5 (6H, m, n-Bu) _{, 4.24-4.55 (2H, m, -CH} 2 -O-CO), 4.60-4.80 (2H, m, -CH 2 -N), 5.94-5.98 (1H , M, -CH-), 7.35-7.52 (4H, m, -Ar), 7.90-8.09 (4H, m, -Ar)

(Example 2)
Reaction material 1.20 g (3.72 mmol) obtained in Synthesis Example 1, sodium tungstate dihydrate (manufactured by Wako Pure Chemical Industries) 123 mg (0.372 mmol), 8.5% (weight / volume) phosphoric acid aqueous solution A mixed solution of 0.47 ml (0.41 mmol), 126 mg (0.186 mmol) of the onium salt [2], 1.2 ml of toluene and 0.73 ml of water was prepared.

  The mixture was heated to 65 ° C. under a nitrogen stream, and 0.060 ml (0.86 mmol) of 42% by mass hydrogen peroxide was added at the start of the reaction and 30 minutes after the start of the reaction, respectively, and further for 1 hour from the start of the reaction. Thereafter, 0.12 ml (1.72 mmol) was added after 2 hours, 3 hours, and 4 hours, and reacted at 64-66 ° C. for a total of 8 hours. The reaction solution was a two-phase system, and the composition ratio of the organic phase was 85.1% diepoxy, 5.5% monoepoxy, and 6.8% polar compound in LC area%.

After completion of the reaction, 4.8 ml of toluene was added, and the separated aqueous phase was discharged. The organic phase was washed with 2.4 ml of water and then washed with 3 ml of a 5% by mass sodium thiosulfate aqueous solution for reduction treatment.
Subsequently, 4.8 ml of 1N aqueous sodium hydroxide solution was added, and an operation of treating at 40 ° C. for 30 minutes was performed. After confirming disappearance of the onium salt [2] by LC analysis (condition 2), the same operation was further performed twice. After washing with 4.8 ml of water, the obtained organic phase was concentrated to obtain 1.37 g of the diepoxy crude crystals. The purity was 85.2% (LC analysis condition 2) and the yield was 88%. The nitrogen content of the obtained crude crystal was 70 ppm.

(Synthesis Example 4)
(Synthesis of onium salt [3])
Stearylamine 5.0 g (18.6 mmol) and a toluene 5 ml solution were heated to 40 ° C., 3.02 g (40.8 mmol) of glycidol was added, reacted for 1 hour, heated to 70 ° C. and reacted for 7 hours, A toluene solution of N, N-bis (2,3-dihydroxypropyl) stearylamine was obtained.

To the above amine, 2.81 g (22.3 mmol) of dimethyl sulfate was added and heated to 50 ° C. During the heating, 5 ml of toluene was added and reacted for 1 hour to obtain a toluene solution of N, N-bis (2,3-dihydroxypropyl) -N-methylstearylammonium monomethyl sulfate.
11.4 g (111 mmol) of acetic anhydride was added to the toluene solution, heated to 60 ° C. and reacted for 4.5 hours. Excess toluene and acetic anhydride were distilled off under reduced pressure to obtain 6.87 g of di (2,3-diacetoxypropyl) methylstearylammonium monomethyl sulfate (hereinafter referred to as onium salt [3]). It contains 31% by mass of toluene, acetic acid and acetic anhydride, and the purity is estimated to be 61% (NMR). The yield was 41% (based on stearylamine).

The obtained onium salt [3] (diastereomer mixture) gave a peak at m / z 600.3 by LC-Mass. NMR data were as follows.
Onium salt [3]:
_{0.88 (3H, t, J =} 8.0Hz, -CH 3), 1.20-1.45 (32H, m, -C 16 H 32 -), 2.09-2.15 (12H, m _{, Ac), 3.15-3.30 (5H,} m, N-Me + N-CH 2 -), 3.78 (3H, s, MeSO 2), 3.70-4.590 (8H, m, O _{-CH 2 -, N-CH 2} -), 5.50-5.70 (2H, m, -CH (OAc) -).

(Example 3)
Reaction raw material 5.0 g (15.5 mmol) obtained in Synthesis Example 1, sodium tungstate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 512 mg (1.55 mmol), 8.5% (weight / volume) phosphoric acid A mixed solution of 1.25 ml (1.08 mmol) of an aqueous solution, 512 mg (0.776 mmol) of the onium salt [3], 2 ml of toluene and 1.5 ml of water was prepared.

  This mixed solution was heated to 65 ° C. under a nitrogen stream, and 0.25 ml (3.64 mmol) of 42% by mass hydrogen peroxide was added at the start of the reaction and 30 minutes after the start of the reaction, and further for 1 hour from the start of the reaction. Thereafter, 0.50 ml (7.28 mmol) was added after 2 hours, 3 hours, and 4 hours, and reacted at 64-70 ° C. for a total of 10 hours. The reaction liquid became a two-phase system, and the composition ratio of the organic phase was 66.8% diepoxy compound, 17.8% monoepoxy compound, and 11.0% polar compound in LC area%.

After completion of the reaction, 20 ml of toluene was added, and the separated aqueous phase was discharged. The organic phase was washed with 10 ml of water, and then washed with 12.5 ml of a 5% by mass aqueous sodium thiosulfate solution, followed by reduction treatment. Subsequently, 20 ml of a 1N sodium hydroxide aqueous solution was added, and an operation of treating at 40 ° C. for 30 minutes was performed three times. After confirming disappearance of the onium salt [3] by NMR analysis, it was washed with 20 ml of water, and the obtained organic phase was concentrated to obtain 5.00 g of diepoxy crude crystals. The purity was 60% (LC analysis condition 2), and the yield was 55%.
33 ml of methanol was added to 4.70 g of this diepoxy crude crystal, and the mixture was heated to 65 ° C. and washed for 2 hours. After cooling to 8 ° C., the precipitated crystals were collected by filtration to obtain 2.55 g. The purity was 87.4% (LC analysis condition 2), and the recovery rate was 79%.

(Synthesis Example 5)
(Synthesis of onium salt [4])
To a solution of 2.00 g (10.8 mmol) of triethanolamine hydrochloride and 40 ml of THF, 1.94 g (48.5 mmol) of 60% sodium hydride was added, and while cooling with ice water, 5.53 g (32.3 mmol) of benzyl bromide and A mixed solution of 2.0 ml of THF and 2.0 ml of DMF was added in portions over 1 hour while keeping the internal temperature at 20 ° C. or lower. After reacting at room temperature for 1 hour, it reacted at 60 ° C for 1 hour and at 70 ° C for 4 hours. After completion of the reaction, the reaction contents were poured into ice water with stirring, extracted with 100 ml of hexane, and further extracted twice with 50 ml of ethyl acetate, and the combined organic phases were washed with 20 ml of water and concentrated. The obtained oil was purified by silica gel chromatography (silica 60N 150 g, manufactured by Kanto Chemical Co., Ltd., developing solvent: hexane / ethyl acetate = 1/1), and 3 N, N, N-tri (2-benzyloxyethyl) amine was obtained. 0.0 g was obtained. The purity was 98% (LC area%, analysis condition 2), and the yield was 66%.

  0.36 g (0.86 mmol) of N, N, N-tri (2-benzyloxyethyl) amine, 0.72 ml of ethanol, 0.16 g (0.86 mmol) of t-butylbenzyl chloride, 28 mg of tetrabutylammonium bromide ( 0.086 mmol) was heated to 80 ° C. and reacted for 14 hours, ethanol was distilled off under reduced pressure, 5 ml of toluene and 5 ml of water were added for liquid separation, and the obtained organic phase was 1% (weight / weight). After washing with 5 ml of aqueous sulfuric acid and further with 5 ml of water, this was concentrated to obtain crude tri (2-benzyloxyethyl) -t-butylbenzylammonium hydrogen sulfate (hereinafter referred to as onium salt [4]). The purity was 52% (LC area%). It contains 27% of t-butylbenzyl ethyl ether (structure estimated from NMR) and 9.2% of unreacted t-butylbenzyl chloride (all LC area%). This was subjected to an oxidation reaction without purification.

The NMR data of the obtained onium salt [4] are as follows.
Onium salt [4]:
1.31 (9H, s, t- Bu), 3.80-3.84 (2H, m, O-CH 2 -), 4.02-4.06 (2H, m, N-CH 2 -) _{, 4.93 (2H, N-CH} 2 -Ph), 7.26-7.36 (15H, m, Ph), 7.40 (2H, d, J = 8.4Hz, Ar), 7.59 (2H, d, J = 8.4 Hz, Ar).

Example 4
1,5-cyclooctadiene 2.0 g (18.5 mmol; manufactured by Tokyo Chemical Industry Co., Ltd.), toluene 4 ml, sodium tungstate dihydrate 0.122 g (0.37 mmol), 8.5% (weight / volume) phosphorus 0.107 ml (0.092 mmol) of an aqueous acid solution, 0.1 m of water and 0.12 g (0.19 mmol) of the above onium salt [4] were added and stirred. After warming this mixture to 50 ° C., 0.30 ml (4.3 mmol) of 42% hydrogen peroxide was added 30 minutes after the start of the reaction under a nitrogen stream, and 0.50 ml (8.6 mmol) was added. 1 hour later, 2 hours later, 3 hours later, and 4 hours later, a total of 4 times was added. The reaction was conducted at an internal temperature of 50 to 51 ° C. for a total of 9 hours, and it was confirmed by the above GC analysis that 1,2,5,6-diepoxycyclooctane was produced at 76% (GC area%). In addition, 6.0% (GC area%) of a monoepoxy compound as a reaction intermediate was produced.

NMR data of the obtained 1,2,5,6-diepoxycyclooctane are as follows.
_{1.82-2.05 (8H, m, -CH 2} -), 3.08-3.90 (4H, m, -CH-O-)
The aqueous phase of the reaction solution was separated, 4 ml of ethyl acetate was added thereto for extraction, and this ethyl acetate solution was combined with the reaction organic phase. This was washed with 5 ml of 5% by mass aqueous sodium thiosulfate solution and then with 2 ml of water, and then concentrated to obtain 2.2 g of crude 1,2,5,6-diepoxycyclooctane having a purity of 76% (GC). Yield 64%.

  After adding 20 ml of ethanol to 0.5 g of crude 1,2,5,6-diepoxycyclooctane obtained by the above method, 34 mg of 5% Pd—C (PH) wet (manufactured by Kawaken Fine Chemical) was added thereto. Then, hydrogen was introduced into the reaction vessel and stirred for 6 hours. The disappearance of the onium salt [4] was confirmed by NMR analysis of the reaction solution.

(Comparative Example 1)
In the same manner as in Example 1, the reaction raw material 150.0 g (0.47 mol) obtained in Synthesis Example 1 was reacted with methyltrioctylammonium sulfate (23.5 mmol) as an ammonium salt. The composition ratio of the reaction product was 84% for the diepoxy compound (LC area%. After completion of the reaction, 147 g of crude crystals of the diepoxy compound were obtained in the same manner. Yield 76%. The purity was 91.2% (LC area%, LC analysis condition 2) The crude crystal contained methyltrioctylammonium salt, and 6 mol% from the proton integration ratio of terminal methyl of the octyl group by NMR analysis. (Represented by the ratio when the diepoxy compound is 100) The nitrogen and tungsten contents were measured by the above analysis method, and were found to be 142 ppm tungsten and 1600 ppm nitrogen.

(Comparative Example 2)
10.5 ml of methanol was added to 1.5 g of 3,3 ′, 5,5′-tetramethylbiphenol diglycidyl ether obtained by the method of Comparative Example 1, and after rinsing at 50 ° C. for 2 hours, cooling to 6 ° C. Then, 0.89 g of the washed crystal was collected by filtration. Recovery rate 62%. Purity 95.2% (LC area%, LC analysis condition 2). The hanging crystal contained a methyltrioctylammonium salt, and its content was 1.75 mol% (same NMR analysis as described above, corresponding to a residual nitrogen amount of 690 ppm).

(Synthesis Example 6)
(Synthesis of onium salt [1] without using a chlorine-containing compound)
47.2 g (0.25 mol) of p-toluenesulfonic acid monohydrate and 60 ml of toluene were charged into a 200 ml eggplant flask equipped with a Dane-Stark tube and heated at a jacket temperature of 120 ° C. to distill off water azeotropically. To this was added 44.2 g (0.25 mol) of 4-t-butylbenzoic acid and 20.0 g (0.12 mol) of N-butyldiethanolamine, and the reaction was carried out while distilling off the generated water at a jacket temperature of 135 ° C. for 10 hours. did. Furthermore, 30 ml of p-xylene was added, and the reaction was carried out while distilling off generated water at a jacket temperature of 140 ° C. for 7 hours while feeding nitrogen at a rate of 300 ml per minute near the reaction surface. The composition ratio of the reaction solution was LC area% (analysis condition 2), N-butyl-N, N-di [2- (4-t-butylbenzoyloxy) ethyl] amine 81.7%, N-butyl-N- It was a mixture of ethanol-N- [2- (4-t-butylbenzoyloxy) ethyl] amine 9.8% and 4-t-butylbenzoic acid 6.0%.

After completion of the reaction, 200 ml of toluene and 150 ml of saturated aqueous sodium hydrogen carbonate were added for neutralization, the aqueous phase was discharged, and further washed with 100 ml of saturated aqueous sodium hydrogen carbonate. The obtained organic phase was concentrated to obtain 60.0 g of crude N-butyl-N, N-di [2- (4-t-butylbenzoyloxy) ethyl] amine. The purity was 81% (LC analysis condition 2), and the yield was 81%.
The obtained crude N-butyl-N, N-di [2- (4-t-butylbenzoyloxy) ethyl] amine was subjected to column chromatography (300 g of silica 60N manufactured by Kanto Chemical Co., Inc., developing solvent: hexane / ethyl acetate = Purified in 4/1).

  5.13 g of the purified product thus obtained was methylated in the same manner as in Synthesis Example 2 above, and 30 ml of hexane was added to the resulting reaction solution to crystallize. This was filtered and dried to obtain crystals of onium salt [1]. 5.73 g was obtained. The purity was 92% (LC analysis condition 2) and the methylation step yield was 82%.

(Example 5)
3,3′-diallylbiphenyl-4,4′-diglycidyl ether (also known as 3,3′-diallyl-4,4′-glycidyloxy-1,1′-biphenyl) synthesized according to the method described in Japanese Patent No. 2539648 ) 0.50 g (1.32 mmol), sodium tungstate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) 52 mg (0.16 mol), 8.5% (weight / volume) phosphoric acid aqueous solution 0.15 ml (0.13 mmol) ), A mixed solution of 48 mg (0.079 mmol) of the onium salt [1] obtained in Synthesis Example 6 above, 2.0 ml of toluene, and 0.10 ml of water was prepared.

  This mixed solution was heated to 65 ° C. under a nitrogen stream, and 0.03 ml (0.44 mmol) of 42% by mass hydrogen peroxide was added at the start of the reaction and 30 minutes after the start of the reaction for 5 minutes to further react. After 45 minutes from the start, 0.05 ml (0.73 mmol) was added after 1.5 hours and 2 hours, respectively, and reacted at 63 to 66 ° C. for a total of 3 hours. The mixed solution is a two-phase system, and the composition ratio of the organic phase is LC area% (analysis condition 1), 3,3′-diglycidylbiphenol diglycidyl ether is 79.3%, 3-allyl-3′- Glycidyl biphenol diglycidyl ether was 8.4% and polar compound was 8.9%.

After completion of the reaction, 5 ml of toluene and 2 ml of water were added for liquid separation, and the separated aqueous phase was discharged. The organic phase was washed with 2 ml of 5% by mass aqueous sodium thiosulfate solution and subjected to reduction treatment. After discharging the aqueous phase, 2 ml of methanol and 90 mg of potassium carbonate were added, and the mixture was treated at room temperature for 30 minutes. Further, 2 ml of water was added to dissolve the inorganic salt, and the aqueous phase was discharged. The disappearance of the onium salt [1] in the organic phase was confirmed by LC analysis (Condition 2). The obtained organic phase was concentrated, and 3,3′-diglycidylbiphenol diglycidyl ether (another name 3,3′-glycidyl-4,4′-glycidyloxy-1,1′-biphenyl) was added as a white solid. .48 g was obtained. 83% purity (LC
Analysis condition 2), yield 73%.

The NMR data of 3,3′-diglycidyl biphenol diglycidyl ether was as follows.
2.58-2.64 (2H, m, C-glycidyl terminus), 2.77-2.82 (2H + 2H, m, C-glycidyl terminus, O-glycidyl terminus), 2.87-2.96 (2H + 2H) _{, m, C-C H 2} -CH-, O- glycidyl _{terminal), 2.97-3.06 (2H, m,} C-CH 2 -C H -), 3.25 (2H, m, C- _{CH 2 -C H -), 3.39} (2H, m, O-CH 2 -C H -), 3.95-4.05 (2H, m, O- CH 2 -CH), 4.27- _{4.34 (2H, m, O- CH} 2 -CH), 6.88-6.92 (2H, m, Ar) 7.37-7.41 (4H, m, Ar)

(Synthesis Example 7)
(Synthesis of epoxidation reaction raw materials)
Allyl bromide in a mixed solution of 5.00 g (16.2 mmol) of 2,2′-diallylbisphenol A (Aldrich), 20 ml of acetone, 10 m of N, N-dimethylformamide and 5.63 g (41 mmol) of potassium carbonate at room temperature 4.32 g (36 mmol) was added at room temperature over 4 hours. Thereafter, the mixture was heated to 60 ° C. and reacted for 3 hours. Furthermore, 1.43 g (12 mmol) of allyl bromide and 1.88 g (13 mmol) of potassium carbonate were added and reacted at an internal temperature of 65 ° C. for 1.5 hours and at an internal temperature of 70 ° C. for 6 hours.

After completion of the reaction, 20 ml of water was added to the reaction mixture to separate the free oily substance, and 30 ml of hexane was added to the aqueous phase for separation and extraction. The hexane phase was combined with the oil separated earlier, and this was washed with 3 ml of 1N aqueous sodium hydroxide solution and further washed twice with 4 ml of water. The resulting organic phase was concentrated to give 2,2-bis 5.80 g of (3-allyl-4-allyloxyphenyl) propane was obtained. LC purity 86% (analysis condition 2), yield 79%.

NMR data of the obtained 2,2-bis (3-allyl-4-allyloxyphenyl) propane are as follows.
_{1.62 (6H, s, -Me)} , 3.35-3.38 (4H, m, C-C H 2 -C =), 4.50-4.51 (4H, m, O- CH 2 _{-C =), 4.95-5.10 (4H,} m, C-CH 2 = C H 2), 5.24 (2H, dd, J = 1.6,10.6, O-CH 2 = C H ), 5.41 (2H, dd, J = 1.7, 17.2, O-CH ₂ = C H ), 5.90-6.12 (2H + 2H, m-CH ₂ =), 6. 72 (2H, d, J = 8.3, Ar), 6.95-7.15 (4H, m, Ar)

(Example 6)
4.00 g (10.3 mmol) of 2,2-bis (3-allyl-4-allyloxyphenyl) propane synthesized by the above method, sodium tungstate dihydrate (manufactured by Wako Pure Chemical Industries) 410 mg (1.24 mol) ), 154 mg (130 mmol) of 85% (weight / volume) phosphoric acid aqueous solution, 417 mg (0.62 mmol) of the onium salt [1] prepared by the method of Synthesis Example 6, 16 ml of toluene, and 2 ml of water were prepared.

This mixed solution was heated to 72 ° C. under a nitrogen stream, and 0.44 ml (0.60 mmol) of 42% by mass hydrogen peroxide was added at the start of the reaction, 30 minutes after the start of the reaction, 1 hour later, and 1.5 hours later. 2 hours later, 2.5 hours later, 3 hours later, 4 hours later, 4.5 hours later, 5 hours later, 6 hours later, the reaction was carried out at 72-73 ° C. for a total of 9 hours.
The reaction solution is a two-phase system, and the composition ratio of the organic phase is the compound 2,2-bis [4- (2,2) in which four allyl groups in one molecule are oxidized at LC area% (analysis condition 2). 3-epoxypropoxy) -3- (2,3-epoxypropyl) phenyl] -propane (hereinafter abbreviated as tetraepoxy compound) is 78.5%, 2- [4- (2,3-propenyloxy) -3- (2,3-epoxypropyl) phenyl] -2- [4- (2,3-epoxypropoxy) -3- (2,3-epoxypropyl) phenyl] -propane (hereinafter abbreviated as triepoxy compound 1) and 2 -[4- (2,3-epoxypropoxy) -3- (2,3-propenyl) phenyl] -2- [4- (2,3-epoxypropoxy) -3- (2,3-epoxypropyl) phenyl ] -Propane (hereinafter triepoxy) 2 abbreviated) is combined 10.0%, polar compound was 7.2%.

  After completion of the reaction, the aqueous phase was discharged, 8 ml of toluene and 4 ml of water were added to the organic phase, and after separation, the aqueous phase was discharged. The organic phase was washed with 8 ml of a 5% by weight aqueous sodium thiosulfate solution and subjected to reduction treatment. 4 ml of methanol and 1.42 g of potassium carbonate were added, and the mixture was treated at an internal temperature of 40 ° C. for 1 hour. Further, 4 ml of a 1N aqueous sodium hydroxide solution was added and treated at an internal temperature of 40 ° C. for 1 hour. After draining the aqueous phase, the organic phase was washed with 4 ml of water. After confirming disappearance of the onium salt [1] in the organic phase by LC analysis (condition 2), the obtained organic phase was concentrated to obtain 3.13 g of a liquid containing a tetraepoxy compound and a triepoxy compound.

In a similar manner 2,2-bis (3-allyl-4-allyloxyphenyl) propane 16.
A liquid containing a tetraepoxy compound and a triepoxy compound synthesized from 00 g was combined and purified on a silica gel column (silica gel 60N, manufactured by Kanto Chemical Co., Ltd., developing solvent: hexane / ethyl acetate = 2/1 → 1/1). 9.34 g (purity 98.1%, LC analysis condition 2) and 1.07 g of triepoxy compound (purity 96.1%, LC analysis condition 2) were obtained with a yield of 44% and 4.6%, respectively. The triepoxy compound is a mixture of the triepoxy compound 1 and the triepoxy compound 2, and is approximately 87:13 of the triepoxy compound 1 and the triepoxy compound 2 from the integral ratio of the proton peaks of the O-allyl group and the C-allyl group in NMR. It was found to be a mixture of

NMR data of the resulting tetraepoxy compound is as follows.
1.63 (6H, s, Me), 2.52-2.56 (2H, m, C-glycidyl terminus), 2.72-2.83 (2H + 2H + 2H, m, C-glycidyl terminus, O-glycidyl terminus) _{, C-C H 2 -CH)} , 2.86-2.94 (4H, m, O- glycidyl _{terminal, C-C H 2 -CH)} , 3.13-3.20 (2H, m, C- _{CH 2 -C H -), 3.32-3.38} (2H, m, O-CH 2 -C H -), 3.90-3.98 (2H, m, O-C H 2 -CH- _{), 4.19-4.26 (2H, m,} O-C H 2 -CH -), 6.72-6.76 (2H, m, Ar), 7.00-7.08 (4H, m , Ar)

The NMR data of the resulting triepoxy compound 1 are as follows.
1.63 (6H, s, Me), 2.50-2.56 (2H, m, C-glycidyl terminal), 2.70-2.80 (2H + 2H + 1H, m, C-glycidyl terminal, C-C H ₂ -CH, O-glycidyl-terminated), 2.88-2.96 (2H + 1H, m, C-C H 2 -CH, O- glycidyl terminal), 3.11-3.22 (2H, m, C- _{CH 2 -C H -) 3.31-3.37 (} 1H, m, O-CH 2 -C H -), 3.92-4.00 (1H, m, O-C H 2 -CH-) 4.18-4.25 (1H, m, O—C H ₂ —CH—), 4.52 (2H, d, J = 0.5, —O—C H ₂ —CH═CH ₂ ), _{5.22-5.29 (1H, m, CH =} C H 2), 5.36-5.44 (1H, m, CH = C H 2), 5.96-6.09 (1H, m _{, -C H = CH 2),} 6.70-6.77 (2H, m, Ar), 7.00-7.15 (4H, m, Ar)

(Example 7)
4.0 g (12.4 mmol) of the reaction raw material obtained in Synthesis Example 1, 205 mg (0.62 mol) of sodium tungstate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.), 0.102 g (0.002 mol) of 85% aqueous phosphoric acid solution. 87 mmol), 201 mg (0.31 mmol) of the onium salt [1] prepared by the method of Synthesis Example 6, a mixed solution of 4 ml of toluene and 8 ml of water was prepared.

  This mixed solution was heated to 72 ° C. under a nitrogen stream, and 0.27 ml (3.1 mmol) of 35% by mass hydrogen peroxide was added at the start of the reaction, 30 minutes after the start of the reaction, 1 hour later, 1.5 hours later. Thereafter, 2 hours later, 2.5 hours later, 3 hours later, 4 hours later, 5 hours later, 6.5 hours later, 8 hours later while adding in 5 minutes, the inner temperature is 71.5 to 74 ° C. For a total of 10 hours. The mixed solution is a two-phase system, and the composition ratio of the organic phase is 3,3 ′, 5,5′-tetramethylbiphenol diglycidyl ether (abbreviated as diepoxy) in LC area% (analysis condition 1). 5%, monoepoxy compound 12.5%, polar compound 9.3%.

The reaction liquid prepared from 6.0 g of the reaction raw materials was combined in the same manner, the aqueous phase was discharged, 20 ml of toluene and 10 ml of water were added to the organic phase, and after separation, the aqueous phase was discharged. It was washed with 10 ml of an aqueous sodium sulfate solution and subjected to a reduction treatment. To the obtained organic phase, 10 ml of methanol and 2.0 g of potassium carbonate were added and treated at an internal temperature of 40 ° C. for 2 hours. After adding 10 ml of water and washing, 5 ml of 1N aqueous sodium hydroxide solution was added and treated at an internal temperature of 40 ° C. for 1 hour, and then the organic phase was washed with 10 ml of water. After confirming disappearance of the onium salt [1] in the organic phase by LC analysis (condition 2), the obtained organic phase was concentrated to obtain 9.9 g of crude crystals of diepoxy compound. Purity 79% (LC analysis condition 2), yield 71%.

To this crude crystal, 10 ml of toluene and 50 ml of methanol were added for dissolution, and then 20 ml of methanol was added thereto and cooled to an internal temperature of 2 ° C. to precipitate crystals. This was collected by filtration to obtain 5.3 g of diepoxy crystals. Purity 91.8% (LC analysis condition 2), recovery 80%. The chlorine content of the obtained diepoxy compound was below the detection limit (10 ppm).
In Examples 1 to 7, decomposition of the onium salt was confirmed. In Examples 1 and 2, an epoxy compound with a small residual amount of nitrogen was obtained. In Example 7, an epoxy compound with little residual chlorine was obtained.

On the other hand, when the conventional onium salt obtained in Comparative Example 1 is used, these impurities remain, and even if crystallization purification is performed in Comparative Example 2, the loss due to crystallization is large, but a sufficient reduction effect Was not obtained.
With the onium salt used in the present invention, it is possible to obtain an epoxy compound with a low chlorine content, in which impurities such as metals such as tungsten and impurities such as nitrogen compounds are sufficiently reduced.

By the method for producing an epoxy compound of the present invention, an epoxy compound having a very small content of heavy metal impurities such as tungsten can be obtained. In addition, it is possible to produce a high-purity epoxy compound having a very small content of nitrogen compound and chlorine derived from an onium salt by a simple method without requiring complicated steps such as purification.
Furthermore, it can be applied to the production of epoxy compounds that cannot be distilled or crystallized and is excellent in versatility.

Moreover, since a chlorine-containing compound is not used, it can be applied to the production of an epoxy compound having a low chlorine content.
When the epoxy compound obtained by the method of the present invention is used as a raw material for electronic materials, optical materials, and medical and agricultural chemicals, problems due to impurities are reduced, and a product with high purity and high quality can be obtained.

  And by using the onium salt which has a specific substituent, it becomes possible to collect | recover onium salt and to utilize repeatedly, and to improve manufacturing efficiency.

Claims (17)

In a method for producing an epoxy compound, hydrogen peroxide is reacted with a carbon-carbon double bond of a compound having a carbon-carbon double bond in the presence of at least one of a tungsten compound and a molybdenum compound and an onium salt. There,
An epoxy compound, wherein the onium salt has 4 or more acyloxy groups having 1 to 4 carbon atoms or one or more benzyloxy groups, and the onium salt has a total carbon number of 20 or more. Production method. The said onium salt is a compound represented by either of following General formula (1)-(3), The manufacturing method of the epoxy compound of Claim 1 characterized by the above-mentioned.

(In the above general formula (1),
R ^{1 to} R ⁴ each independently represents an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms, and some of the carbon atoms may be substituted with hetero atoms, Any two or more may be bonded to form a ring. At least one of R ^{1 to} R ⁴ has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms.
In the general formula (2), R ⁵ represents an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent and a part of carbon atoms may be substituted with a hetero atom.
R ^{6 to} R ¹⁰ may each independently have a substituent, and a part of carbon atoms may be substituted with a hetero atom, a C 1-25 aliphatic hydrocarbon group, a hydrogen atom , A halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group.
In addition, any one or more of R ^{5 to} R ¹⁰ may be bonded to form a ring, and at least one of them has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms as substituents. .
In the general formula (3), R ¹¹ and R ¹³ may each independently have a substituent, and a part of carbon atoms may be substituted with a hetero atom, and the fatty acid having 1 to 25 carbon atoms. Represents a hydrocarbon group.
R ¹² , R ¹⁴ , and R ¹⁵ may each independently have a substituent, and a C 1-25 aliphatic hydrocarbon in which some of the carbon atoms may be substituted with a hetero atom A group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group;
Any one or more of R ^{11 to} R ¹⁵ may be bonded to form a ring, and at least one group has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms as substituents. .
X ⁻ represents an anion. ) In a method for producing an epoxy compound, hydrogen peroxide is reacted with a carbon-carbon double bond of a compound having a carbon-carbon double bond in the presence of at least one of a tungsten compound and a molybdenum compound and an onium salt. There,
The said onium salt is a compound represented by following General formula (4), The manufacturing method of the epoxy compound characterized by the above-mentioned.

In the general formula (4),
R ¹⁶ and R ¹⁷ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and some of the carbon atoms may be substituted with heteroatoms; In addition, each may be bonded to form a ring.
R ¹⁸ and R ²⁰ represent an optionally substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and some of the carbon atoms may be substituted with hetero atoms.
R ¹⁹ and R ²¹ represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
k and m each independently represent an integer of 1 to 5, and when k and m are each 2 or more, the plurality of R ¹⁹ and R ²¹ may be the same or different.
Y and Z each independently represent a halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group, and p is 0 ≦ p ≦ 5. -K represents an integer, and q represents an integer of 0 ≦ q ≦ 5-m.
X ⁻ represents an anion. )   The method for producing an epoxy compound according to any one of claims 1 to 3, wherein the epoxidation is performed in the presence of at least one of phosphoric acids and phosphonic acids.   The epoxidation is performed in a two-phase solution comprising an aqueous phase containing at least one of the tungsten compound and a molybdenum compound and an organic phase containing the compound having a carbon-carbon double bond. Item 5. The method for producing an epoxy compound according to any one of Items 1 to 4.   The method for producing an epoxy compound according to claim 5, wherein the pH of the aqueous phase is 2 or more and 6 or less.   The method for producing an epoxy compound according to any one of claims 1 to 6, wherein the epoxidation is carried out in the presence of a chelating agent.   The method for producing an epoxy compound according to any one of claims 1 to 7, wherein the compound having a carbon-carbon double bond is washed with an acidic aqueous solution.   The method for producing an epoxy compound according to claim 1, wherein the compound having a carbon-carbon double bond is washed with a chelating agent.   A step of solvating the onium salt with a basic compound after the onium salt has four or more acyloxy groups having 1 to 4 carbon atoms and epoxidizes the compound having the carbon-carbon double bond. The method for producing an epoxy compound according to any one of claims 1, 2, 4 to 9, further comprising:   The method for producing an epoxy compound according to claim 10, further comprising a step of regenerating the solvated onium salt after the hydrolysis step.   The onium salt further comprises a step of catalytically hydrogenating the onium salt after epoxidizing the compound having one or more benzyloxy groups and having the carbon-carbon double bond, The manufacturing method of the epoxy compound of any one of Claims 1, 2, 4-9. 10. The method according to claim 3, further comprising a step of solvating the onium salt with a basic compound after epoxidizing the compound having a carbon-carbon double bond. 11. A method for producing an epoxy compound.   A method for producing an epoxy resin by polymerizing an epoxy compound, the step of producing an epoxy compound by the production method according to any one of claims 1 to 13, and the polymerization of the epoxy compound obtained in the step And a method for producing an epoxy resin, comprising the step of producing an epoxy resin. An onium salt represented by the following general formula (4).

In the general formula (4),
R ¹⁶ and R ¹⁷ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and some of the carbon atoms may be substituted with heteroatoms; In addition, each may be bonded to form a ring.
R ¹⁸ and R ²⁰ represent an optionally substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and some of the carbon atoms may be substituted with hetero atoms.
R ¹⁹ and R ²¹ represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
k and m each independently represent an integer of 1 to 5, and when k and m are each 2 or more, the plurality of R ¹⁹ and R ²¹ may be the same or different.
Y and Z each independently represent a halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group, and p is 0 ≦ p ≦ 5. -K represents an integer, and q represents an integer of 0 ≦ q ≦ 5-m.
X ⁻ represents an anion. ) In the general formula (4), R ¹⁶ , R ¹⁷ , R ¹⁸ and R ²⁰ have a total carbon number of 14 or less, and R ¹⁹ and R ²¹ have a total carbon number of 6 or more. The onium salt according to claim 15. A catalyst composition for epoxidation reaction comprising at least one of a tungsten compound and a molybdenum compound and at least one onium salt represented by the following general formulas (1) to (4).

(In the above general formula (1),
R ^{1 to} R ⁴ each independently represents an optionally substituted aliphatic hydrocarbon group having 1 to 25 carbon atoms, and some of the carbon atoms may be substituted with hetero atoms, Any two or more may be bonded to form a ring. At least one of R ^{1 to} R ⁴ has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms.
In the general formula (2), R ⁵ represents an aliphatic hydrocarbon group having 1 to 25 carbon atoms which may have a substituent and a part of carbon atoms may be substituted with a hetero atom.
R ^{6 to} R ¹⁰ may each independently have a substituent, and a part of carbon atoms may be substituted with a hetero atom, a C 1-25 aliphatic hydrocarbon group, a hydrogen atom , A halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group.
In addition, any one or more of R ^{5 to} R ¹⁰ may be bonded to form a ring, and at least one of them has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms as substituents. .
In the general formula (3), R ¹¹ and R ¹³ may each independently have a substituent, and a part of carbon atoms may be substituted with a hetero atom, and the fatty acid having 1 to 25 carbon atoms. Represents a hydrocarbon group.
R ¹² , R ¹⁴ , and R ¹⁵ may each independently have a substituent, and a C 1-25 aliphatic hydrocarbon in which some of the carbon atoms may be substituted with a hetero atom A group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group;
Any one or more of R ^{11 to} R ¹⁵ may be bonded to form a ring, and at least one group has one or more acyloxy groups or benzyloxy groups having 1 to 4 carbon atoms as substituents. .
In the general formula (4),
R ¹⁶ and R ¹⁷ each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 20 carbon atoms, and some of the carbon atoms may be substituted with heteroatoms; In addition, each may be bonded to form a ring.
R ¹⁸ and R ²⁰ represent an optionally substituted divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and some of the carbon atoms may be substituted with hetero atoms.
R ¹⁹ and R ²¹ represent an aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
k and m each independently represent an integer of 1 to 5, and when k and m are each 2 or more, the plurality of R ¹⁹ and R ²¹ may be the same or different.
Y and Z each independently represent a halogen atom, a cyano group, a nitro group, a phenyl group, a phenoxy group, a benzyl group, an N-alkylcarbamoyl group, or an N-alkylsulfamoyl group, and p is 0 ≦ p ≦ 5. -K represents an integer, and q represents an integer of 0 ≦ q ≦ 5-m.
X ⁻ represents an anion. )