JP2015091788A - Method for producing epoxy compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently and safely produce an epoxy compound by suppressing decomposition of hydrogen peroxide in a method for producing an epoxy compound, in which a compound having a carbon-carbon double bond is reacted with hydrogen peroxide in the presence of a catalytic metal such as a tungsten compound and an onium salt.SOLUTION: The method for producing an epoxy compound, which produces an epoxy compound by reacting a compound having a carbon-carbon double bond with hydrogen peroxide to perform an epoxidation reaction, is characterized by: performing the epoxidation reaction in a two-phase solution comprising an aqueous phase containing at least one of a tungsten compound and a molybdenum compound, and an organic phase containing a compound having a carbon-carbon double bond, in the presence of an onium salt; and adding the hydrogen peroxide to the two-phase solution so that the hydrogen peroxide concentration in the aqueous phase is 7 mass% or less.

Description

  The present invention relates to a method for producing an epoxy compound by epoxidizing a carbon-carbon double bond of a compound having a carbon-carbon double bond.

Epoxy compounds are widely used as epoxy monomers as raw materials for epoxy resins, various chemical products such as agricultural chemicals and pharmaceutical intermediates, and intermediates and raw materials thereof.
In recent years, a method of reacting hydrogen peroxide in the presence of tungstic acid, phosphoric acid, and onium salt has been developed (for example, Non-Patent Document 1). In this method, it is not necessary to prepare a peroxide, and the reaction can be carried out with an easily available hydrogen peroxide solution. Further, it can be used for a compound having an aromatic ring that is easily oxidized with a peroxide, and is a highly versatile production method.

However, Patent Document 1 also reports that oxygen is generated by contact between tungstic acids and hydrogen peroxide during catalyst preparation.
On the other hand, when manufacturing a compound having a carbon-carbon double bond used as a raw material when manufacturing an epoxy compound, a metal catalyst such as palladium, ruthenium, or copper may be used (for example, Patent Documents 2 and 3). . Such raw materials may contain metal impurities derived from these metal catalysts. In addition to the raw materials used, metals such as cobalt, nickel, and iron may be eluted from the apparatus and storage container, and these may be mixed into the reaction system as metal impurities.

JP 2010-229065 A Japanese National Patent Publication No. 10-511721 JP 2012-116782 A

Bull. Chem. Soc. Jpn, 70, 905 (1997)

  When epoxidizing a compound having a carbon-carbon double bond, the method of reacting hydrogen peroxide in the presence of the tungstic acid and the onium salt is a highly versatile production method. Decomposes by heating to generate oxygen. In particular, when the metal impurities are mixed during the epoxidation reaction, the decomposition of hydrogen peroxide is further accelerated, and the generation of oxygen and heat generation associated with the decomposition become a major safety issue, so the safety is further improved. A high production method is demanded.

  The present invention has been made in view of the above situation, and a method for producing an epoxy compound in which hydrogen peroxide is reacted with a compound having a carbon-carbon double bond in the presence of a catalytic metal such as a tungsten compound and an onium salt. In the present invention, it is an object to suppress the decomposition of hydrogen peroxide and to manufacture efficiently and safely.

The inventor has disclosed a method for producing an epoxy compound in which a compound having a carbon-carbon double bond is reacted with hydrogen peroxide in the presence of an onium salt and at least one of a tungsten compound and a molybdenum compound. We found that by keeping the hydrogen concentration low or the amount of hydrogen peroxide in the aqueous phase small, the decomposition of hydrogen peroxide can be suppressed and the epoxidation can be performed safely without reducing the reaction rate. The present invention has been completed.

That is, the gist of the present invention is as follows.
[1] A method for producing an epoxy compound by reacting hydrogen peroxide with a compound having a carbon-carbon double bond and epoxidizing the epoxidation reaction in the presence of an onium salt, a tungsten compound and molybdenum. It is carried out in a two-phase system solution comprising an aqueous phase containing at least one of the compounds and an organic phase containing a compound having a carbon-carbon double bond, and the hydrogen peroxide concentration in the aqueous phase is 7% by mass or less The method according to claim 1, wherein the hydrogen peroxide is added to the two-phase solution.
[2] A method for producing an epoxy compound by reacting hydrogen peroxide with a compound having a carbon-carbon double bond and performing an epoxidation reaction, wherein the epoxidation reaction is performed using at least one of a tungsten compound and a molybdenum compound and onium. In the presence of a salt, and the content of the hydrogen peroxide is the number of double bonds contained in the compound having a carbon-carbon double bond in terms of the number of moles of the compound having the carbon-carbon double bond. The manufacturing method of the epoxy compound characterized by making it 0.5 times or less by molar ratio with respect to the quantity which multiplied the number.
[3] The epoxidation reaction is carried out 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 as described in [2] above,
[4] The mass of the water phase is 1.5 times or more of the mass of the compound having a carbon-carbon double bond, and the mass of the organic phase is the compound having a carbon-carbon double bond. It is 5 times or less of mass, The manufacturing method of the epoxy compound as described in said [1] or [3] characterized by the above-mentioned. [5] Having a carbon-carbon double bond before or during the addition of hydrogen peroxide to a mixture containing at least one of a compound having a carbon-carbon double bond, a tungsten and molybdenum compound, and an onium salt The method for producing an epoxy compound according to any one of the above [1] to [4], wherein water having a mass ratio of 0.1 to 5 times is added to the content of the compound.
[6] The method for producing an epoxy compound according to any one of the above [1] to [5], wherein the molecular weight of the epoxy compound with respect to the number of epoxy groups in one molecule of the epoxy compound is 100 or more.
[7] The method for producing an epoxy compound according to any one of [1] to [6], wherein the epoxidation reaction is performed at 50 to 75 ° C.
[8] The method for producing an epoxy compound according to any one of [1] to [7], wherein the compound having a carbon-carbon double bond contains a metal impurity in a mass ratio of 500 ppm or less.

  According to the production method of the present invention, in the production method of an epoxy compound in which hydrogen peroxide is reacted with a compound having a carbon-carbon double bond in the presence of a catalytic metal such as a tungsten compound and an onium salt, the decomposition of hydrogen peroxide is performed. Thus, the epoxy compound can be efficiently and safely produced even when metal impurities are mixed from the raw material.

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.
In the first aspect of the method for producing an epoxy compound of the present invention, a compound having a carbon-carbon double bond (hereinafter sometimes referred to as “olefin compound”) is reacted with hydrogen peroxide for epoxidation. And a two-phase solution comprising an aqueous phase containing at least one of a tungsten compound and a molybdenum compound, and an organic phase containing the olefin compound, in which at least one of a tungsten compound and a molybdenum compound as an catalytic metal and an onium salt are present. Among them, the epoxidation reaction is performed, and hydrogen peroxide is added to the two-phase solution so that the hydrogen peroxide concentration in the aqueous phase is 7% by mass or less.

  A second aspect of the method for producing an epoxy compound according to the present invention is a method for producing an epoxidized compound by epoxidation reaction by reacting a compound having a carbon-carbon double bond with hydrogen peroxide. In the presence of at least one of the compounds and the onium salt, the content of hydrogen peroxide is obtained by multiplying the number of double bonds contained in the olefin compound by the number of moles of the compound having a carbon-carbon double bond. On the other hand, it is characterized by being 0.5 mol or less.

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

The tungsten compound in the present invention is not particularly limited as long as it contains tungsten and has an effect as the above catalyst. Specific examples of the tungsten compound include tungstic acid and salts thereof (hereinafter collectively referred to as “tungstic acids”).
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. Tungstic acid, tungstate, and phosphotungstic acid are preferable, and tungstic acid, sodium tungstate, calcium tungstate, and 12-tungstophosphoric acid are more preferable from the viewpoint of availability.

The molybdenum compound in the present invention is not particularly limited as long as it contains molybdenum and has the above-mentioned action as a catalyst. Specifically, molybdic acid or a salt thereof (hereinafter these are 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 above tungsten compounds and molybdenum compounds, tungsten compounds are preferable in terms of availability, and tungstic acids, specifically, tungstic acid, or sodium tungstate and hydrates thereof, calcium tungstate and hydration thereof. More preferred.
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 1 mol of a carbon-carbon double bond contained in the olefin compound. Usually converted to a catalytic metal atom (for example, a tungsten atom when using a tungsten compound) with respect to (the number of carbon-carbon double bonds contained in the olefin compound multiplied by the molecular weight of the olefin compound) 0.001 mol or more, preferably 0.005 mol or more, more preferably 0.01 mol or more, usually 1.0 mol or less, preferably 0.50 mol or less, more preferably 0.10 mol or less. . 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 may be used after being mixed with the olefin compound outside the reaction system in advance. It can also be used after hydrogen is mixed together and the catalytic metal is activated. Further, an onium salt, an organic solvent, and other additives, which will be described later, can be appropriately mixed and used.

(hydrogen peroxide)
In the case of using hydrogen peroxide solution, the concentration is not particularly limited, but is usually 1% by mass or more, preferably 20% by mass or more and usually 60% by mass 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.

The amount of hydrogen peroxide used can be appropriately adjusted according to the reactivity of the olefin compound and the like, and is not particularly limited. However, the carbon-carbon duplex contained in one molecule of the olefin compound is the number of moles of the olefin compound. The amount multiplied by the number of bonds 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 production method of the present invention can carry out an epoxidation reaction in the presence of an onium salt. The onium salt is considered to form an active epoxidation catalyst when used in combination with the catalyst metal and hydrogen peroxide, and the reaction activity becomes high. Therefore, the onium salt is preferably used in the production method of the present invention. Specifically, the onium salt forms a complex with the catalytic metal, and the complex is further oxidized by hydrogen peroxide, whereby an active epoxidation catalyst (hereinafter referred to as “active catalyst”) having high reaction activity. ").

The active catalyst is preferably fat-soluble during the epoxidation reaction, and normally soluble in the solvent used as needed together with the olefin compound. Therefore, it is preferable that the active catalyst has high fat solubility in order to stably distribute it in a solvent.
In the present invention, since the onium salt preferably has a high fat solubility such that the catalyst metal becomes fat-soluble, it is preferable to use an onium salt having a higher fat solubility. One measure of the fat solubility of the onium salt is the number of carbons of the onium salt, and (carbon number / number of onium salts in one molecule) is 20 or more, more preferably 25 or more. More preferably, a cationic onium salt having 20 or more carbon atoms in its structure is more preferable.

Examples of the onium salt include ammonium salts such as methyltrioctylammonium salt, tetrahexylammonium salt, dilauryldimethylammonium salt, benzyltributylammonium salt, pyridinium salts such as cesylpyridinium salt, and phosphonium salts such as tetrahexylphosphonium salt. It is done.
As the onium salt, an onium salt invented by the present inventors and disclosed in PCT / JP2013 / 059461 can also be used. Specifically, it is preferable to use an onium salt having at least one substituent that can be converted into a functional group containing active hydrogen or a salt thereof and containing 20 or more carbon atoms.
These onium salts exhibit fat solubility during the epoxy reaction, but can be converted into a water-soluble substance by simple post-treatment such as hydrolysis after completion of the epoxidation reaction. This is preferable in that it can be efficiently dissolved and separated in the aqueous phase.

In the present invention, onium salts may be used alone or in combination of two or more.
The anion species of the onium salt used in the present invention is not particularly limited, but specifically, hydrogen sulfate ion, monomethyl sulfate ion, halide ion, nitrate ion, acetate ion, hydrogen carbonate ion, dihydrogen phosphate ion, Examples include monovalent anions such as sulfonate ions, carboxylate ions, and hydroxide ions, and divalent anions such as hydrogen phosphate ions and sulfate ions. Monovalent anions are preferred from the viewpoint of easy adjustment. Among them, monomethyl sulfate ion, hydrogen sulfate ion, acetate ion, phosphorus ion because the anion species is not added to the epoxy group of the epoxy compound that is the reaction product, the carbon-carbon double bond of the substrate, or the preparation is easy. Acid dihydrogen ions or hydroxide ions are preferred. The anionic species may be used alone or in combination of two or more.

  When using onium salt in this invention, although it does not specifically limit, It is preferable to use in the two-phase system reaction solution which consists of an organic phase and an aqueous phase. This is because the olefin compound having normal fat solubility reacts with the active catalyst imparted with fat solubility in the organic phase, so that side reactions are unlikely to occur.

  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, preferably in a molar ratio with respect to the catalyst metal used in the reaction. 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.

(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.

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

(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 preferably used as the phosphoric acid.

Examples of phosphonic acids in the present invention 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 can be added as necessary to adjust the pH. You can also.

(Chelating agent)
In the present invention, the epoxy compound can 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 thereof 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 salts thereof; 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 of great effects obtained in the present invention, and particularly preferred because ethylenediaminetetraacetic acid and its salts 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 content of the chelating agent in the reaction solution at the time of the epoxidation reaction is not particularly limited, but the chelating agent in the aqueous phase is usually in the reaction solution, particularly in a two-phase solution composed of an organic phase and an aqueous phase. The content is usually 1 ppm (μg / g) or more, preferably 50 ppm or more, usually 10,000 ppm or less, preferably 5000 ppm or less, and 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.
As said olefin compound used in this invention, a thing with high fat solubility is preferable. This is because a compound having high fat solubility has a low distribution to the aqueous phase, and even when water is added to the system, hydrolysis of the epoxy compound in the aqueous phase hardly occurs.
As a measure of fat solubility, the number of epoxy groups possessed when all the carbon-carbon double bonds in the molecule of the olefin compound are epoxidized to become epoxy groups (molecular weight / in one molecule) The number of epoxy groups is preferably 100 or more, more preferably 120 or more, and usually 1000 or less, preferably 500 or less.

  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 (1) to (5) as a raw material in that a highly purified, particularly low halogenated epoxy compound can be produced. Among these, the olefin compound represented by (2) is preferable, and among them, 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 (1)

In the general formula (1), 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 the formula (1) is replaced with a hydrogen atom is a plurality of linked 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.
Specific examples of the compound represented by the general formula (1) include 1,6-bis (2-propen-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, 1,3-diallyl-2,4-diglycidyloxybenzene, 2-allyl-1,5- And diglycidyloxynaphthalene.

一般式（２）中、Ａ^２、Ａ^３はそれぞれ独立に、２価の芳香族炭化水素基、芳香族炭化水素基の少なくともその一部が還元された基、及び脂肪族炭化水素基のいずれかを表し、ＯＲ基、Ｘ^１、Ｒ^２３以外の置換基を有していてもよい。それぞれの価数が２価である以外は、上記Ａ^１と同義である。

In general formula (2), A ² and A ³ are each independently a divalent aromatic hydrocarbon group, a group in which at least a part of the aromatic hydrocarbon group is reduced, or 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 (1).
Substituents other than OR and R ^{23 included in} A ² and A ³ are the same as those in General Formula (1).

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 (2), 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] (also known as 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'-diallyl Biphenyl-4,4′-diglycidyl ether (other name 3,3′-diallyl-4,4′-diglycidyloxy-1,1′-biphenyl), 3,3′-diallylbiphenyl-4,4′- Giant Ether (alternative name 3,3′-diallyl-4,4′-diallyloxy-1,1′-biphenyl), 3,3′-diallylbisphenol A-diglycidyl ether (alternative name 2,2-bis (3- Allyl-4-glycidyloxyphenyl) propane), 3,3′-diallylbisphenol 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 (3)

In General Formula (3), substituents other than A ² , m ² , n ¹ , and OR group have the same meaning as in General Formula (2).
R and R ²³ have the same meaning as in general formula (1).
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 (3) 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 (1) to (3), 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 (4), 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 (4) 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 includes a styrene compound represented by the following general formula (5).

(In the above formula ^{(5), A} 51 ^{~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, 3 carbon atoms -7, a cycloalkyl group, an aromatic hydrocarbon group, an aralkyl group, an acyl group, a hydroxy group, a halogen atom, a carboxyl group or an 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 (5) 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] -1
H-1,2,4-triazole]-and the like.

(Metal impurities)
The metal impurities in the present invention are metals other than the olefin compound, catalyst metal, and other reactants contained in the solution (reaction solution) used in the epoxidation containing the metal and the olefin compound. Says metal. In addition to metal ions, the metal impurity may be a simple metal or a metal compound.

Since the chelating agent is known to coordinate with metal ions and exhibit an effect, metal ions are important among metal impurities.
Furthermore, since the above chelating agent is usually coordinated by donating an unshared electron pair in the coordination site to the vacant orbital of the metal ion, it has a vacant orbital or has a replaceable ligand. The metal ions are particularly important.

  The metal species of the metal impurity is not particularly limited, but is usually a metal species that can contribute to the decomposition of hydrogen peroxide. The metal species may be classified as a so-called semi-metal, and is not particularly limited. However, it is an element belonging to Groups 3 to 16 of the periodic table showing normal orbital interaction. , Manganese, iron, ruthenium, cobalt, iridium, nickel, palladium, boron, silicon, tellurium and the like.

  Among these, from the point of high resolution of peroxide, metal impurities include metal elements belonging to Group 8 to Group 11 of the periodic table. Specifically, ruthenium, cobalt, iridium, nickel, palladium, iron , Copper and the like. In particular, metal impurities including cobalt, nickel, palladium, and ruthenium should be considered in terms of their concentration because hydrogen peroxide is decomposed even when its content is small.

  Although the origin of the metal impurities is not particularly limited, for example, those derived from a metal compound used as a reactant or a metal catalyst in the production process of the olefin compound; a reaction vessel used in the production process or epoxidation reaction of the olefin compound And those derived from production equipment such as pipes and the like; and those derived from containers, packaging materials, etc. at the time of purchase of the raw materials for producing olefin compounds, the organic solvents, or various reaction aids, and the like. The thing that is highly likely to be contained in the olefin compound is derived from a metal compound used as a reactant or a metal catalyst in the production process, and in particular, a metal catalyst used in the production of the olefin compound. Since those that are derived from the above, such as palladium and ruthenium, are highly likely to be contained, their concentration should be considered. Others that are likely to be contained in the olefin compound include those derived from contact with a reaction vessel or a storage vessel, and examples thereof include iron, cobalt, chromium, and nickel.

  The magnitude of the influence of metal impurities varies depending on the concentration of hydrogen peroxide, the reaction conditions, and the type of metal impurities, and the influence becomes significant when the concentration of hydrogen peroxide is high or when the reaction temperature is high. Therefore, the content of metal impurities in the olefin compound is usually 500 ppm (μg / g) or less, preferably 200 ppm or less, in terms of the weight ratio with respect to the amount of the olefin compound. Further, the lower limit of the metal impurity is preferably 1 ppm (μg / g) or more, more preferably 0.1 ppm (μg / g) or more, and more preferably 0 ppm or more when no metal impurity is contained. This is because when the metal impurity content is within the above range, the effect of the present invention is sufficiently obtained.

Less metal impurities are preferred. When epoxidation is performed in the presence of the chelating agent, the reaction solution of the metal impurity, that is, the compound having a carbon-carbon double bond, the catalyst metal, the hydrogen peroxide, and the chelate. The content contained in the solution containing the agent is usually 500 ppm (μg / g) or less, preferably 200 ppm (μg / g) or less. Further, the lower limit of the content of metal impurities in the reaction solution is preferably 1 ppm (μg / g) or more, more preferably 0.1 ppm (μg / g) or more, and further preferably 0.05 ppm. This is because when the metal impurity content is within the above range, the effect of the chelating agent is sufficiently obtained.

(Method for producing epoxy compound)
In the production method of the present invention, when the olefin compound is epoxidized in the presence of the catalyst metal, onium salt and hydrogen peroxide, the concentration of hydrogen peroxide or the amount of hydrogen peroxide relative to the olefin compound is specified. It is characterized by a range.

The first aspect of the present invention is a compound having an aqueous phase containing at least one of a tungsten compound and a molybdenum compound in the presence of an onium salt and a carbon-carbon double bond when hydrogen peroxide is reacted with the olefin compound. A two-phase solution comprising an organic phase containing is formed, and the hydrogen peroxide is added to the two-phase solution so that the hydrogen peroxide concentration in the aqueous phase is 7% by mass or less.
This is because when the hydrogen peroxide concentration is higher than the above concentration, decomposition due to heating is likely to occur, and when there is contamination of foreign substances such as metal, it is further accelerated. If the hydrogen peroxide concentration is lower than the above concentration, even if hydrogen peroxide is instantly decomposed, the calorific value is in a concentration range that can be sufficiently absorbed by the latent heat of water, causing problems such as the cooling device not working. Even if it is, the epoxy compound can be produced safely.

In the two-phase solution, the hydrogen peroxide concentration in the aqueous phase is preferably lower from the viewpoint of safety, preferably 5% by mass or less, and more preferably 4% by mass or less. The lower limit is not particularly limited, but is usually 0.1% by mass or more in order for the activation of the catalyst by hydrogen peroxide to constantly proceed and the substrate oxidation reaction to proceed efficiently. 3 mass% or more is preferable and 1.0% or more is more preferable.
In the second aspect of the present invention, when hydrogen peroxide is reacted with at least one of a tungsten compound and a molybdenum compound and the olefin compound in the presence of an onium salt, the amount of hydrogen peroxide contained in the reaction system is The value is 0.5 times or less the value obtained by multiplying the number of double bonds contained in the compound having carbon-carbon double bonds by the number of moles of the compound having carbon-carbon double bonds.

The amount of hydrogen peroxide is preferably small, and is preferably 0.3 times mol or less. In particular, when the olefin raw material is consumed and the end of the reaction is reached, the consumption rate of hydrogen peroxide is reduced, and therefore 0.25 times mol or less 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.

  In the first and second embodiments, when the reaction is performed in a two-phase solution, the amounts of the aqueous phase and the organic phase are not particularly limited, but the mass of the aqueous phase is usually 1 with respect to the mass of the olefin compound. 0.5 times or more, 1.8 times or more, and more preferably 2.0 times or more. In this range, the heat of reaction and the decomposition heat of hydrogen peroxide are easily absorbed by the specific heat and latent heat of water, and diluted with water to reduce the concentration of hydrogen peroxide to reduce the decomposition of hydrogen peroxide by metal impurities. This is because it is preferable. The upper limit is not particularly limited as long as the hydrogen peroxide concentration is within the appropriate range, but is usually 10 times or less, preferably 6 times or less in terms of productivity.

Further, the mass of the organic phase is usually 5 times or less with respect to the mass of the olefin compound, and the reaction rate decreases due to a decrease in the concentration of the substrate and the onium salt in the organic phase, preferably 3 times or less. A ratio of 2 times or less is more preferable. 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 dissolved in the organic phase, and the weight of the organic phase represents a total weight 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.

In the first and second embodiments, the method for keeping the hydrogen peroxide concentration in the aqueous phase of the two-phase solution low is not particularly limited, but water is added before or during the addition of hydrogen peroxide. Is preferred. 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. Another method for lowering the hydrogen peroxide concentration is to add hydrogen peroxide having a low concentration, but in this case, the amount of aqueous phase at the end of the reaction is larger than that in the initial reaction, and the production efficiency is increased. Since the hydrogen peroxide concentration in the system is further lowered by the water produced by the reaction and may fall below the appropriate range of the above-mentioned hydrogen peroxide concentration, the method of adding water Is preferred.
The total amount of water added is not particularly limited as long as it is within the appropriate range of the hydrogen peroxide concentration, but is usually 0.1 times or more, preferably 0.5 times the mass of the olefin compound. As described above, it is more preferably 1 time or more, usually 5 times or less, preferably 3 times or less.

  In the first and second embodiments, the addition method and order of hydrogen peroxide and the substrate and other reaction materials are not particularly limited, but from the viewpoint of keeping the hydrogen peroxide concentration and amount low, the epoxidation reaction and Since heat generation occurs during the decomposition of hydrogen peroxide, from the viewpoint of controlling the progress of the reaction and heat generation, hydrogen peroxide is added after adding the catalyst metal and onium salt, water or solvent added as necessary. A method of adding gradually, or a method of adding hydrogen peroxide in an amount necessary for oxidizing the catalyst metal in advance and activating the catalyst metal, and then gradually adding the remaining hydrogen peroxide.

  Further, as a method of gradually adding hydrogen peroxide, it may be added in divided portions or continuously and gradually. From the viewpoint of safety, it is preferable to add it according to the progress of the reaction so that unreacted hydrogen peroxide does not stay in the reaction system. It is preferable to slow down the addition rate compared to the initial stage.

(Reaction conditions)
The reaction temperature in the production method of the present invention is not particularly limited as long as the reaction proceeds, but is usually 10 ° C or higher, preferably 35 ° C or higher, more preferably 50 ° C or higher, and usually 90 ° C or lower, preferably 80 ° C. or lower, more preferably 75 ° C. or lower. 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. From the viewpoint of suppressing the production of a decomposition product of the epoxy compound of the product, it is usually 48 hours or shorter, preferably 36 hours or shorter, more preferably 24 hours or shorter.
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 co-oxidant may be added to the composition. For example, in the case of an onium salt having an ester group, the co-oxidant may be generated by hydrolysis of the ester group.

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.

(Pretreatment of olefin compounds)
The olefin compound in the present invention may be pretreated as necessary when used in the epoxidation reaction of the present invention. Since the amount of metal impurities can be reduced by performing the pretreatment, the following pretreatment is preferably performed in order to obtain the effects of the present invention remarkably.
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, if an acidic aqueous solution or a chelating agent aqueous solution can be directly applied to the olefin compound for treatment, the olefin compound is dissolved in an organic solvent and then mixed, and the acidic aqueous solution or chelating agent is mixed. It can also be treated with an aqueous solution.

Although the kind of acid used for acidic aqueous solution is not specifically limited, Specifically, inorganic acids, such as hydrochloric acid, a sulfuric acid, nitric acid, and phosphoric acid; Organic acids, such as an acetic acid and a citric acid, are mentioned.
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.

(Purification)
The epoxy compound obtained by the above method can be further purified as necessary. 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 at least one of n-heptane, n-hexane, n-pentane, diisopropyl ether, and 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.

Examples of purification by adsorption include activated carbon, activated clay, molecular sieves, alumina, zeolite, and ion exchange resin.
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.

(Epoxy compound)
The epoxy compound obtained by the production method of the present invention is obtained by converting the carbon-carbon double bond of the olefin compound to an epoxy group. When the epoxy compound is an epoxy monomer, two or more carbon- Those in which the carbon double bond is epoxidized are preferred. 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.
In the production method of the present invention, when an onium salt is prepared by a method that does not use a chlorine compound, a chlorine-containing compound is not produced during the reaction. Therefore, an epoxy compound obtained by this method using a reaction raw material having a low chlorine content generally has a characteristic that the chlorine content is lower than that of an epoxy compound synthesized using epichlorohydrin.

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 using the epoxy compound obtained in 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.

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>
Apparatus: AVANCE400, 400MHz made by BRUKER
Solvent: 0.03 vol% tetramethylsilane-containing deuterated chloroform Data in the examples represent δ values in ¹ H-NMR (400 MHz, CDCl ₃ ).

<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)
(Hereafter, it was set as analysis condition 1, and unless otherwise indicated, LC analysis was performed under this condition.)
Detector: UV 280nm
Eluent: acetonitrile / 0.1% 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 volume% trifluoroacetic acid aqueous solution 60/40 → 20 minutes
Held at 100/0 (vol%) for 10 minutes, and then at 100/0 (vol%) for 10 minutes.

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.
The “yield” in the examples was calculated by considering the weight of the compound obtained by multiplying the purity by “LC area%” as the yield.

<Redox titration conditions>
Titration device: manufactured by Mitsubishi Chemical Corporation Detection electrode: platinum (composite type)
Titration method: After diluting the aqueous phase with 7% by mass sulfuric acid aqueous solution, an excess amount of 10% by mass potassium iodide aqueous solution
Add the free iodine to 0.1N sodium thiosulfate aqueous solution to form peroxide.
Reduced titration. The amount of peroxide was expressed in terms of hydrogen peroxide weight percent.

<ICP-MS analysis conditions>
Pretreatment method: dry ashing-acid dissolution method Analytical device: ICP mass spectrometer manufactured by Agilent Technologies
7500ce type

In the following examples, a diol compound in which an epoxy ring was opened during an epoxidation reaction, and also an epoxy ring having higher polarity than an epoxy compound, such as an oxidized carboxylic acid after aldehyde isomerization with heat or acid, the LC A compound giving a faster retention time than the epoxy compound under the analysis conditions was by-produced. These compounds are sometimes collectively referred to as “polar compounds”.

In the following examples, “conversion rate” refers to the percentage of epoxidized carbon-carbon double bonds among the carbon-carbon double bonds contained in the olefin compound used as a reaction raw material. Yes, specifically, for example, when the number of olefins in one molecule of the olefin compound is 2, the value calculated by the following formula is represented.
(Conversion) = 100− [Raw material LC area% + (Intermediate LC area% / 2)] (%)

(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 biphenol 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 of 3,3 ′, 5,5′-tetramethyl-4,4′-bis (2-propen-1-yloxy) -1,1′-biphenyl obtained above was dissolved in 10 ml of toluene. The solution was washed with 30 ml of an aqueous solution containing 1% by weight of anhydrous sodium sulfate and 1% by volume of acetic acid, and then a mixed solution of 0.26 ml of 3% by weight sodium pyrophosphate aqueous solution, 0.12 ml of 10% by weight ethylenediaminetetraacetic acid solution and 30 ml of water. Washed with. This was washed with 30 ml of water and then concentrated, and the resulting crude crystals were subjected to the reaction. Hereinafter, this is referred to as reaction raw material A. The purity of the reaction raw material A 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)
2- [2- (3-Chlorophenyl) -2-propen-1-yl] -2-ethyl-1H-indene-1,3 (2H) -dione was synthesized from the Society of Organic Synthesis (2001), 59 (9). , 845-854. Hereinafter, this is referred to as reaction raw material B. The purity of the reaction raw material B was 96.6% (LC area%, the above analysis condition 2).

  The conversion rate in the following examples indicates the percentage of epoxidized olefin, and in the case of a compound having two olefins in the molecule, 100- [raw material LC area% + (intermediate LC area% / 2) ]] (%). The raw material represents an olefin compound, and the intermediate represents a compound obtained by epoxidizing one of the olefins. In the case of a compound having one olefin in the molecule, it was calculated as 100-raw material LC area% (%).

In the following examples, “hydrogen peroxide decomposition rate” represents the proportion of hydrogen peroxide consumed by decomposition in the hydrogen peroxide added to the reaction solution. Specifically, the value calculated by the following formula is represented.
The theoretical conversion rate is the conversion rate when all of the added hydrogen peroxide has reacted, and the conversion rate means the conversion rate obtained as a result of the actual reaction.
(Hydrogen peroxide decomposition rate) = [theoretical conversion rate (%) − conversion rate (%)] / theoretical conversion rate (%)

The approximate value of the amount and concentration of hydrogen peroxide in the aqueous phase during the reaction is determined by the following method by calculating the above conversion rate by LC analysis, thereby calculating the number of moles of hydrogen peroxide consumed in the reaction. It was. However, the actual amount and concentration of hydrogen peroxide are lost by decomposition as shown in Table 1 in addition to the consumption of hydrogen peroxide in the reaction. Therefore, the actual amount and concentration of hydrogen peroxide in the system are lower than approximate values.
(Approximate number of moles of hydrogen peroxide in the aqueous phase) = (number of moles of hydrogen peroxide added)-(number of moles of hydrogen peroxide consumed in the reaction)
(Approximate value of the concentration of hydrogen peroxide in the aqueous phase) = (number of moles of hydrogen peroxide added) − (number of moles of hydrogen peroxide consumed in the reaction) × 34 / amount of water phase (ml) × 100

Hereinafter, in Examples 1 and 2 and Comparative Examples 1 and 2, 1.4 times moles of hydrogen peroxide was dividedly added to the olefin compound as a reaction raw material, and the amount and decomposition of hydrogen peroxide consumed by the reaction. The amount of hydrogen peroxide consumed was calculated.
Hereinafter, in Example 3 and Comparative Examples 3 and 4, the influence of the amount of water and toluene on the reaction rate was examined.
Hereinafter, in Examples 4 to 6, the reaction was performed while controlling the amount and concentration of hydrogen peroxide in the reaction system by adding hydrogen peroxide in accordance with the progress of the reaction, that is, consumption of hydrogen peroxide. . In Example 6, the chlorine content of the obtained compound was measured.

Example 1
Reaction raw material A2.0 g (6.2 mmol) obtained in Synthesis Example 1, sodium tungstate dihydrate (manufactured by Wako Pure Chemical Industries) 205 mg (0.62 mmol), 8.5% (weight / volume) phosphoric acid aqueous solution A mixed solution of 0.64 ml (0.56 mmol), methyltrioctylammonium hydrogen sulfate (manufactured by Tokyo Chemical Industry) 145 mg (0.31 mmol), and toluene 2.0 ml was prepared. To this was added 3.3 ml of water. The total amount of water contained in this mixture was 4.0 ml.

This mixture was heated to 65 ° C. under a nitrogen stream, and 0.10 ml (1.5 mmol) of 42% by mass hydrogen peroxide was added at the start of the reaction and 30 minutes after the start of the reaction. After 2 hours later, 0.20 ml (0.30 mmol) was added, followed by reaction at 64-66 ° C. for a total of 5 hours. During the reaction, the organic phase was analyzed every hour under the above LC analysis condition 1. The reaction stopped 4 hours after the start of the reaction, and the composition ratio of the organic phase 5 hours after the start of the reaction was 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol diglycidyl ether in LC area%. (Hereinafter abbreviated as diepoxy) 42.2%, 4,4'-dihydroxy-3,3 ', 5
, 5′-tetramethylbiphenyl monoallyl ether monoglycidyl ether (hereinafter abbreviated as monoepoxy compound) 40.3%, reaction raw material A 10.9%, polar compound 6.1%, and conversion rate of allyl group is 69 %Met.
After the reaction, the aqueous phase was subjected to oxidation-reduction titration under the above titration conditions. The peroxide concentration was 0.1% by mass in terms of hydrogen peroxide concentration.

(Comparative Example 1)
A mixture of reaction raw material A, sodium tungstate dihydrate, 8.5% (weight / volume) phosphoric acid aqueous solution, methyltrioctylammonium hydrogensulfate and toluene was prepared in the same manner as in Example 1 above. Further, 0.55 ml of water was added thereto, so that the total amount of water contained in the mixed solution was 1.2 ml.

The reaction was conducted in the same manner as in Example 1. The composition ratio of the organic phase at 5 hours after the start of the reaction was LC area%, diepoxy 39.8%, monoepoxy 43.6%, reaction raw material A 13.2%, polar The compound was 3.2%. The conversion rate of allyl group was 65%.
After the reaction, the aqueous phase was subjected to oxidation-reduction titration under the above titration conditions. The hydrogen peroxide concentration was 0.1% by mass in terms of hydrogen peroxide concentration.

(Comparative Example 2)
A mixture of reaction raw material A, sodium tungstate dihydrate, 8.5% (weight / volume) phosphoric acid aqueous solution, methyltrioctylammonium hydrogensulfate and toluene was prepared in the same manner as in Example 1 above. 0.42 ml of 0.01% (weight / volume) palladium acetate aqueous solution and 0.13 ml of water were added to make the total amount of water contained in the mixed solution 1.2 ml.
The reaction was carried out under the same reaction conditions as in Example 1. The reaction stopped after 4 hours from the start of the reaction, and the composition ratio of the organic phase at 5 hours after the start of the reaction was LC area%, 23.9% diepoxy, monoepoxy Body 46.8%, reaction raw material A 27.2%, polar compound 2.0%, allyl group conversion was 49%.

(Example 2)
A mixture of reaction raw material A, sodium tungstate dihydrate, 8.5% (weight / volume) phosphoric acid aqueous solution, methyltrioctylammonium hydrogensulfate and toluene was prepared in the same manner as in Example 1 above. 0.42 ml of 0.01% (weight / volume) palladium acetate aqueous solution and 2.9 ml of water were added to make the total amount of water contained in the mixed solution 4.0 ml.
The reaction was carried out under the same reaction conditions as in Example 1. The reaction stopped after 4 hours from the start of the reaction, and the composition ratio of the organic phase at the 5th hour was LC area%, diepoxy compound 34.2%, monoepoxy compound 45 0.7%, reaction raw material A 17.2%, polar compound 0.2%, and the conversion rate of allyl group was 60%.

(Comparative Example 3)
Reaction raw material A 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 1.6 ml (1.40 mmol) of an aqueous solution, 361 mg (0.78 mmol) of methyltrioctylammonium hydrogen sulfate (manufactured by Tokyo Chemical Industry) and 5 ml of toluene was prepared.

The mixture was heated to 65 ° C. under a nitrogen stream, and 0.26 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. Thereafter, 0.20 ml (7.28 mmol) was added after 2 hours, 3 hours, and 5 hours, and reacted at 64-66 ° C for a total of 9 hours. During the reaction, the organic phase was analyzed every hour under the above LC analysis condition 1. The composition ratio of the organic phase at 9 hours was LC area%: diepoxy compound 86.1%, monoepoxy compound 5.4%, reaction raw material A 0.1%, polar compound 8.0%, allyl group conversion Was 97%.
When the concentration of hydrogen peroxide during the reaction was determined by the above method, the maximum value was estimated to be 19%.

(Example 3)
A mixture of reaction raw material A, sodium tungstate dihydrate, 8.5% (weight / volume) phosphoric acid aqueous solution, methyltrioctylammonium hydrogensulfate and toluene was prepared in the same manner as in Comparative Example 3 above. . 8.4 ml of water was added thereto, and the total amount of water contained in the mixed solution was made 10 ml.
In the same manner as in Comparative Example 3 above, the reaction was carried out by adding hydrogen peroxide water, and the composition ratio of the organic phase 9 hours after the start of the reaction was LC area% of 84.0% diepoxy compound, 2.9% monoepoxy compound, The reaction raw material A was 0.1%, the polar compound was 12.7%, and the conversion rate of the allyl group was 99%.
When the concentration of hydrogen peroxide during the reaction was determined by the above method, the maximum value was estimated to be 4.5%.

(Comparative Example 4)
In the same manner as in Comparative Example 3, the reaction raw material A, sodium tungstate dihydrate, 8.
A mixture of 5% (weight / volume) phosphoric acid aqueous solution, methyl trioctyl ammonium hydrogen sulfate and toluene was prepared, and 5 ml of toluene was further added thereto.
In the same manner as in Example 5 above, the reaction was carried out by adding aqueous hydrogen peroxide, and the composition ratio of the organic phase 9 hours after the start of the reaction was 74.2% diepoxy, 20.7% monoepoxy, LC area%, The reaction raw material A was 1.4%, the polar compound was 3.1%, and the conversion rate of the allyl group was 88%.
When the concentration of hydrogen peroxide during the reaction was determined by the above method, the maximum value was estimated to be 19%.

Example 4
Reaction raw material B 2.0 g (6.2 mmol) obtained in Synthesis Example 2, sodium tungstate dihydrate (manufactured by Wako Pure Chemical Industries) 203 mg (0.62 mol), 8.5% (weight / volume) phosphoric acid An aqueous solution 0.63 ml (0.55 mmol), methyltrioctylammonium hydrogensulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) 361 mg (0.31 mmol), and toluene 2.0 ml were mixed with this mixture at 65 ° C. under a nitrogen stream. After heating, 0.10 ml (1.4 mmol) of 42% by mass hydrogen peroxide was added at the start of the reaction, 30 minutes, 1 hour, 2 hours, 3 hours, and 8 hours after the start of the reaction. The reaction was carried out at ~ 66 ° C for a total of 7 hours. During the reaction, the organic phase was analyzed every hour under the above LC analysis condition 1. The composition ratio of the organic phase at 9 hours was LC area%, 2-[[2- (3-chlorophenyl) -2-oxiranyl] methyl] -2-ethyl-1H-indene-1,3 (2H) -dione ( (Hereinafter abbreviated as indanophan) 96.4%, reaction raw material B 2.2%, and the conversion rate of allyl group was 98%.
When the amount of hydrogen peroxide in the aqueous phase during the reaction was estimated by the above calculation, it was always 6.5 mmol or less, which was 0.42 times the number of moles of the reaction raw material B charged.

(Synthesis Example 3)
(Synthesis of onium salt [1])
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).

To 5.13 g (10.6 mmol) of the obtained purified product, 15 ml of toluene was added and heated to 80 ° C., 0.61 ml (6.4 mmol) of dimethyl sulfate was added and reacted for 1.5 hours. 61 ml (6.4 mmol) was added and reacted for 1.5 hours. To this was added 30 ml of hexane for crystallization, and this was collected by filtration, dried, and N-butyl-N, N-di [2- (4-t-butylbenzoyloxy) ethyl-N-methylammonium monomethyl sulfate (hereinafter referred to as onium). 5.73 g of crystals of salt [1] were 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′-diglycidyloxy-1,1′-) synthesized by the method described in Japanese Patent No. 2539648 Biphenyl, hereinafter referred to as reaction raw material C) 0.50 g (1.32 mm)
ol), 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), in Synthesis Example 3 above A mixed solution of 48 mg (0.079 mmol) of the obtained onium salt [1], 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 (also known as 3,3′-diglycidyl-4,4′-diglycidyloxy-1,1′-biphenyl) as a white solid 0.48 g was obtained. 83% purity (
LC analysis condition 2), 73% yield.
When the concentration of hydrogen peroxide during the reaction was determined by the above method, the maximum value was estimated to be 6.5%. The amount of hydrogen peroxide was estimated to be 0.27 times at the maximum with respect to the number of moles of olefin of the reaction raw material C.

(Example 6)
4.0 g (12.4 mmol) of the reaction raw material A 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), a mixed solution of 201 mg (0.31 mmol) of the onium salt [1] prepared by the method of Synthesis Example 3, 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 76.5% of 3,3 ′, 5,5′-tetramethylbiphenol diglycidyl ether (abbreviated as a diepoxy compound) in LC area%, monoepoxy The body was 12.1% and the polar compound was 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 and 9.9 g of 3,3 ′, 5,5′-tetramethyl-4 4,4'-biphenol Diglycidyl ether (diepoxy compound) crude crystals were obtained. Purity 79% (LC analysis condition 2), yield 71%.

The concentration and amount of hydrogen peroxide during the reaction were determined by the above method. The maximum value of the hydrogen peroxide concentration was 3.4%, and the hydrogen peroxide amount was the maximum with respect to the number of moles of olefin of the reaction raw material A. It was estimated to be 0.36 times.
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).
For comparison, the results of Example 1, Example 2, Comparative Example 1, Comparative Example 2, Example 3, Comparative Example 3, and Comparative Example 4 are shown in Tables 1 and 2.

Hydrogen peroxide decomposes about 7% of the amount added during the reaction (Comparative Example 1), but when water is added and the concentration of hydrogen peroxide in the aqueous phase is constantly reduced to 5.4% by weight or less Degradation was significantly reduced to about 1% (Example 1).
Palladium promotes the decomposition of hydrogen peroxide, and about 30% of the amount added is decomposed (Comparative Example 2). However, the concentration of hydrogen peroxide in the aqueous phase is always 5.4% by mass or less by adding water. When thinned, the degradation was reduced to 14% (Example 2).

  The amount of water had little influence on the reaction rate, and the change with time of the reaction was almost the same. (Comparative Example 3, Example 3) When the amount of water added was large, the concentration of hydrogen peroxide in the system could always be kept low at 4.5% by mass or less. As the amount of toluene increased, the reaction rate decreased. (Comparative Example 3, Comparative Example 4)

  When the reaction solution forms a two-phase system of an organic phase and an aqueous phase, when the olefin compound or onium salt used in the reaction is a fat-soluble compound, the distribution to the aqueous phase is small, and the degree varies depending on the type of solvent used Is mainly present in the organic phase. As shown in Examples 5 to 7 below, the reaction rate is affected by the concentration of the olefin compound and the onium salt in the organic phase, but not by the concentration of hydrogen peroxide. Therefore, the reaction rate does not decrease even when water is added, but the reaction rate decreases when a large amount of organic solvent is used. Moreover, when the epoxy compound to be produced is also fat-soluble, the epoxy ring is rarely opened in an acidic aqueous phase, and there is little concern about a decrease in yield due to the addition of water.

The NMR data of the compound before and after the reaction were as follows.
¹ H-NMR (400 MHz, CDCl ₃ ) δ value [3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diallyl ether]:
_{2.32 (12H, s, -CH 3} ), 4.34 (4H, dt, J = 1.5,5.1Hz, O-CH 2 -), 5.27 (2H, ddd, J = 2. _{3,2.8,10.6Hz, -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 = 2.8,4.9Hz, -O-CH 2 -), 2.90 (2H, dd, J = 4 .3, 4.9 Hz, —O—CH ₂ —), 3.36-3.41 (2H, m, —CH—), 3.73 (2H, dd, J = 5.8, 1
1.0 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 −)

[2- [2- (3-Chlorophenyl) -2-propen-1-yl] -2-ethyl-1
H-indene-1,3 (2H) -dione]:
_{0.66 (3H, t, J =} 8.0Hz, -CH 3), 1.92 (4H, dd, J = 0.8,12.0Hz, - C 2 H 2 -CH 3), 3.03 _{(2H, s, -CH 2 -} ), 7.66-7.71 (1H, m, C = CH 2), 6.58 (1H, dd, J = 2.0,2.0Hz, Ph), 6.81 (1H, dd, J = 2.0, 8.0 Hz, Ph) 7.06 (1H, dd, J = 8.0, 8, 0 Hz, Ph), 7.09 (1H, ddd, J = 0.8, 0.8, 7.8 Hz, Ph), 7.67-7.74 (4H, m, Indition)

[Indanofan]:
_{0.63 (3H, t, J =} 7.6Hz, -CH 3), 1.92 (4H, dd, J = 7.3,14.6Hz, -C 2 H 2 -CH 3), 2.47 _{(1H, d, J = 5.2Hz} , -CH 2 -), 2.58 (1H, d, 14.4Hz, O-CH 2 -), 2.76 (1H, d, J = 14.4Hz, _{O-CH 2 -), 2.83} (1H, d, J = 5.2Hz, -CH 2 -), 6.81 (1H, dd, J = 0.5,1.8Hz, Ph), 6. 96-7.01 (1H, m, Ph), 7.07-7.15 (2H, m, Ph), 7.72-7.84 (3H, m, Ind.), 7.90-7.94. (1H, m, Indition)

[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)

[3,3′-diglycidyl biphenol diglycidyl ether]:
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)

The molecular weight of the epoxy compound relative to the number of epoxy groups in one molecule of epoxy compound (molecular weight of epoxy compound / number of epoxy groups in one molecule of epoxy compound) is as follows.
3,3 ′, 5,5′-tetramethylbiphenol diglycidyl ether: 177
Indanofan: 341
3,3′-diglycidyl biphenol diglycidyl ether: 105

  According to the production method of the present invention, in the production method of an epoxy compound in which hydrogen peroxide is reacted in the presence of a catalytic metal such as a tungsten compound and an onium salt, the decomposition of hydrogen peroxide is suppressed, and metal impurities, etc. Even in the case of mixing, it is possible to manufacture efficiently and safely.

Claims (8)

A method for producing an epoxy compound by epoxidation reaction by reacting a compound having a carbon-carbon double bond with hydrogen peroxide,
The epoxidation reaction is performed in a two-phase system solution comprising an aqueous phase containing at least one of a tungsten compound and a molybdenum compound and an organic phase containing a compound having a carbon-carbon double bond in the presence of an onium salt. And the said hydrogen peroxide is added to the said two-phase system solution so that the hydrogen peroxide concentration in the said water phase may be 7 mass% or less, The manufacturing method of the epoxy compound characterized by the above-mentioned. A method for producing an epoxy compound by epoxidation reaction by reacting a compound having a carbon-carbon double bond with hydrogen peroxide,
The epoxidation reaction is performed in the presence of at least one of a tungsten compound and a molybdenum compound and an onium salt, and the content of the hydrogen peroxide is doubled in the compound having a carbon-carbon double bond. The method for producing an epoxy compound, wherein the number is 0.5 times or less of a value obtained by multiplying the number of bonds by the number of moles of the compound having a carbon-carbon double bond.   The epoxidation reaction is performed in a two-phase solution including 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. The manufacturing method of the epoxy compound of Claim 2.   The mass of the water phase is 1.5 times or more of the mass of the compound having a carbon-carbon double bond, and the mass of the organic phase is 5 of the mass of the compound having the carbon-carbon double bond. It is below 2 times, The manufacturing method of the epoxy compound of Claim 1 or 3 characterized by the above-mentioned.   Inclusion of a compound having a carbon-carbon double bond before or during the addition of hydrogen peroxide to a mixture containing at least one of a compound having a carbon-carbon double bond, a tungsten and molybdenum compound, and an onium salt The method for producing an epoxy compound according to any one of claims 1 to 4, wherein water having a mass ratio of 0.1 to 5 times is added to the amount.   The method for producing an epoxy compound according to any one of claims 1 to 5, wherein the molecular weight of the epoxy compound with respect to the number of epoxy groups in one molecule of the epoxy compound is 100 or more.   The said epoxidation reaction is performed at 50-75 degreeC, The manufacturing method of the epoxy compound in any one of Claims 1-6 characterized by the above-mentioned.   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 contains a metal impurity in a mass ratio of 500 ppm or less.