JP2013112639A - Quaternary ammonium salt, catalyst for oxidation reaction containing the same, method for producing epoxy compound, and method for separating the catalyst for oxidation reaction - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a quaternary ammonium salt capable of separating simply and easily a catalyst for oxidation reaction from a product in a reaction solution after reaction, in a method for producing the oxidized product by oxidizing an organic compound with hydrogen peroxide in the presence of the catalyst for the oxidation reaction.SOLUTION: There is disclosed a quaternary ammonium salt expressed by formula (1), wherein R, R, Reach independently represents a hydrocarbon group which may have a substituent; R4 represents a hydrogen atom or a hydrocarbon group which may have a substituent; Xrepresents a counter anion; and n is an integer of 1-20.

Description

  The present invention relates to a quaternary ammonium salt, an oxidation reaction catalyst containing the quaternary ammonium salt, a method for producing an epoxy compound, and a method for separating the oxidation reaction catalyst. More specifically, in an oxidation reaction in which an organic compound is oxidized with hydrogen peroxide in the presence of an oxidation reaction catalyst, a quaternary capable of easily and easily separating the oxidation reaction catalyst from the oxidized product. The present invention relates to an ammonium salt and an oxidation reaction catalyst containing the ammonium salt. The present invention also relates to a method for producing an epoxy compound in which an olefin carbon-carbon double bond is epoxidized with hydrogen peroxide in the presence of the oxidation reaction catalyst. Further, the present invention relates to a simple and easy separation method of the oxidation reaction catalyst.

  Oxidation reactions using oxidants are used in various applications. For example, production of aldehydes and carboxylic acids by oxidation of primary alcohols, production of ketones by oxidation of secondary alcohols, oxidation of unsaturated compounds. It is used for the production of various organic compounds such as the production of epoxy compounds and diols. Above all, the oxidation reaction using hydrogen peroxide as an oxidant attracts attention from the viewpoint of reducing environmental impact because hydrogen peroxide is inexpensive, does not show corrosivity, and the by-product is water. Yes.

  Conventionally, for example, in a reaction in which an unsaturated compound having at least one double bond is epoxidized with hydrogen peroxide, a metal compound (for example, a compound containing a Group 6 element of the periodic table such as tungsten, rhenium, etc.) is used as a catalyst. A compound containing a group 7 element of the periodic table, a compound containing a group 8 element of the periodic table such as osmium), and industrially, a compound containing a group 6 element of the periodic table from the viewpoint of low cost ( In particular, tungsten compounds are widely used.

  Patent Document 1 discloses a method for producing an epoxy compound from an organic compound having one or more C═C bonds in a molecule with an oxidation catalyst that is inexpensive, versatile, and can maintain high catalytic activity. An organic phase composed of an organic compound having one or more C═C double bonds in the molecule and an onium salt with respect to an aqueous phase containing a tungsten compound, ammonium phosphate, and hydrogen peroxide. A method of adding and reacting is disclosed.

  In Patent Document 2, the above double bond is epoxidized with high efficiency by a reaction between an organic compound (olefin) having a double bond and an aqueous hydrogen peroxide solution under mild conditions without using an organic solvent. As a method for producing an epoxy compound in a highly active catalyst system, a method using a tungsten compound and a tertiary amine having a specific structure and / or a quaternary ammonium salt having a specific structure as a catalyst is disclosed.

JP 2010-106010 A JP 2010-155805 A

  However, in the method for producing an epoxy compound disclosed in Patent Documents 1 and 2, there has been a problem that it is difficult to separate the tungsten compound used as a catalyst from the epoxy compound obtained as a product. More specifically, in the method for producing an epoxy compound disclosed in Patent Documents 1 and 2, since a tungsten compound exists in both the aqueous phase and the organic phase in the reaction solution after the reaction, the product in the organic phase It was difficult to separate the tungsten compound.

  For this reason, an organic compound (for example, an organic compound having an ethylenically unsaturated double bond) is oxidized with hydrogen peroxide in the presence of an oxidation reaction catalyst, and a corresponding oxidized product (("oxidized compound" and For example, in the method for producing the epoxy compound), it is currently required that the oxidation reaction catalyst can be easily and easily separated from the oxidation compound.

Accordingly, an object of the present invention is to oxidize an organic compound with hydrogen peroxide in the presence of an oxidation reaction catalyst to produce an oxidized product (particularly an epoxy compound). An object of the present invention is to provide a quaternary ammonium salt that enables easy and easy separation of an oxidation reaction catalyst from a product.
Another object of the present invention is to oxidize an organic compound with hydrogen peroxide to produce an oxidized product, which can be easily and easily separated from the product in the reaction solution after the reaction. Another object of the present invention is to provide a catalyst for oxidation reaction of organic compounds.
Furthermore, another object of the present invention is a method for producing an epoxy compound by epoxidizing a double bond of an organic compound (olefin) having an ethylenically unsaturated double bond with hydrogen peroxide in the presence of an oxidation reaction catalyst. In other words, it is an object of the present invention to provide a method for producing an epoxy compound capable of easily and easily separating an oxidation reaction catalyst from an epoxy compound in a reaction solution after the reaction.
Furthermore, another object of the present invention is to oxidize an organic compound with hydrogen peroxide in the presence of an oxidation reaction catalyst to produce an oxidized product, and from the product in the reaction solution, An object of the present invention is to provide a method for separating an oxidation reaction catalyst, which can easily and easily separate the oxidation reaction catalyst.

  As a result of diligent studies to solve the above problems, the present inventors have determined that an oxidation reaction catalyst containing a quaternary ammonium salt having a specific structure as a phase transfer catalyst is an oxidation reaction of an oxidation reaction of an organic compound with hydrogen peroxide. It was found that the catalyst for oxidation reaction could be easily and easily separated from the product (oxidized compound) in the reaction solution after the reaction when used as a catalyst for reaction, and the present invention was completed.

［式（１）中、Ｒ¹、Ｒ²、Ｒ³は、それぞれ独立に、置換基を有していてもよい炭化水素基を表す。Ｒ⁴は、水素原子又は置換基を有していてもよい炭化水素基を表す。Ｘ^-は、カウンターアニオンを表す。ｎは１〜２０の整数である。］
で表される第四級アンモニウム塩を提供する。 That is, the present invention provides the following formula (1):

[In formula (1), R ¹ , R ² and R ³ each independently represents a hydrocarbon group which may have a substituent. R ⁴ represents a hydrogen atom or a hydrocarbon group which may have a substituent. X ⁻ represents a counter anion. n is an integer of 1-20. ]
The quaternary ammonium salt represented by these is provided.

  The present invention also provides an organic compound oxidation reaction catalyst comprising the quaternary ammonium salt as a phase transfer catalyst.

  Furthermore, the above-mentioned catalyst for oxidation reaction comprising a heteropolyacid or a salt thereof or a precursor compound thereof is provided.

  Furthermore, the heteropolyacid or salt thereof is a heteropolyacid or salt thereof containing a phosphorus atom and at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium. A catalyst is provided.

  Further, the precursor compound includes an inorganic acid or a salt thereof containing at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium, and a phosphorus atom-containing oxo acid or a salt thereof. An oxidation reaction catalyst is provided.

  Further, the present invention provides the oxidation reaction catalyst, wherein the oxidation reaction of the organic compound is an olefin epoxidation reaction with hydrogen peroxide.

  The present invention also includes a process for producing an epoxy compound, comprising the step of epoxidizing a carbon-carbon double bond of an olefin with hydrogen peroxide to form an epoxy compound in the presence of the oxidation reaction catalyst. I will provide a.

  Further, the present invention separates the oxidation reaction catalyst from the oxidation compound in the reaction solution after oxidizing the organic compound with hydrogen peroxide in the presence of the oxidation reaction catalyst to form an oxidation compound. A step of selectively distributing the oxidation reaction catalyst to the aqueous phase by controlling the temperature of the reaction solution, and then separating the organic phase and the aqueous phase of the reaction solution by a liquid separation operation. And a method for separating the catalyst for oxidation reaction.

  Since the quaternary ammonium salt of the present invention has the above structure, if an oxidation reaction catalyst containing the quaternary ammonium salt as a phase transfer catalyst is used as a catalyst in an oxidation reaction of an organic compound with hydrogen peroxide, Separation of the oxidation reaction catalyst from the product (oxidation compound) in the reaction solution can be carried out simply and easily. Therefore, the use of the quaternary ammonium salt of the present invention is advantageous in terms of cost because the oxidation reaction catalyst can be easily recovered and reused, and the oxidation reaction catalyst can be separated from the product with high efficiency. Therefore, a highly pure product (oxidized compound) can be obtained with high productivity.

FIG. 1 is a diagram showing the results of evaluating the temperature responsiveness (temperature dependence) of the distribution behavior of an oxidation reaction catalyst to an organic phase (horizontal axis: temperature, vertical axis: abundance ratio of tungsten to the organic phase). is there.

[Quaternary ammonium salt]
The quaternary ammonium salt of the present invention is a compound (quaternary ammonium salt) represented by the following formula (1).

R ^1, R ^2, R ³ in the formula ^{(1) (R 1 ~R 3} ) each independently represent a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which two or more of these are bonded.

Examples of the aliphatic hydrocarbon group include saturated aliphatic hydrocarbon groups, preferably alkyl groups. Examples of the alkyl group include C _1-20 such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, hexyl group, octyl group, isooctyl group, decyl group, dodecyl group, and octadecyl group (stearyl group). An alkyl group etc. are mentioned.

Examples of the alicyclic hydrocarbon group include C _3-12 cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclododecyl group.

Examples of the aromatic hydrocarbon group include C _6-14 aryl groups (particularly, C _6-10 aryl groups) such as phenyl group and naphthyl group.

Examples of the group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded include a cyclohexylmethyl group and a methylcyclohexyl group. Examples of the group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded include a C _7-18 aralkyl group (particularly a C _7-10 aralkyl group) such as a benzyl group and a phenethyl group, and a C _1-4 such as a tolyl group. Examples include alkyl-substituted aryl groups.

Examples of the substituent that the hydrocarbon group in R ^{1 to} R ³ may have include a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom; a hydroxyl group; a methoxy group, an ethoxy group, a propoxy group, and isopropyl group, a butoxy group, an alkoxy group such as a C _1-6 alkoxy group such as isobutyl group (preferably a C _1-4 alkoxy group); a phenoxy group, tolyloxy group, such as a naphthyloxy groups, C aromatic ring _{1- 4} An aryloxy group such as a C _6-14 aryloxy group which may have a substituent such as an alkyl group, a halogen atom, a C _1-4 alkoxy group; a C _7-18 such as a benzyloxy group or a phenethyloxy group aralkyloxy groups such as aralkyloxy group; an acetyl group, a propionyloxy group, acyloxy such as C _1-12 acyloxy group such as a benzoyloxy group Group; a carboxyl group; - a methoxycarbonyl group, an ethoxycarbonyl group, propoxycarbonyl group, C _1-6 alkoxy such as butoxycarbonyl group alkoxycarbonyl group such as a carbonyl group; phenoxycarbonyl group, tolyloxycarbonyl group, naphthyloxycarbonyl group, etc. _{Aryloxycarbonyl} groups such as C _6-14 aryloxy-carbonyl groups; aralkyloxycarbonyl groups such as C _7-18 aralkyloxy-carbonyl groups such as benzyloxycarbonyl groups; amino groups; methylamino groups, ethylamino groups, Mono- or dialkylamino groups such as mono- or di-C _1-6 alkylamino groups such as dimethylamino group and diethylamino group; acylamino groups such as C _1-11 acylamino groups such as acetylamino group, propionylamino group and benzoylamino group Group containing an epoxy group such as a glycidyloxy group; an oxetanyl group containing group such as an ethyl oxetanyloxy group; an acyl group such as an acetyl group, a propionyl group or a benzoyl group; an oxo group; _And a group bonded through a _1-6 alkylene group.

Especially, as said R < ¹ > -R < ³ >, a C1-C20 ( _C1-20 ) saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a saturated aliphatic hydrocarbon group, and an aromatic hydrocarbon, respectively. A group bonded to a group (particularly an aralkyl group) is preferred.

R ⁴ in the above formula (1) represents a hydrogen atom or a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include the same groups as those described above for R ¹ , R ² and R ³ . Among them, as R ⁴ , a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms (C _1-6 ), an aromatic hydrocarbon group, a group in which a saturated aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded. (In particular, an aralkyl group) is preferable.

X ⁻ in the above formula (1) is a counter anion (counter ion; monovalent anion) of an ammonium cation (quaternary ammonium ion) in the quaternary ammonium salt represented by the formula (1). Examples of the counter anion include a Bronsted acid conjugate base, and are not particularly limited. For example, halide ions (fluoride ions, chloride ions, iodide ions, etc.), hydrogen sulfate ions, nitrate ions, hydrogen carbonates. Ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphite ion, methanesulfonate ion, trifluoromethanesulfonate ion, toluenesulfonate ion, formate ion, acetate ion, trifluoroacetate ion, propionate ion, benzoic acid Acid ions, hydroxide ions, alkoxide ions (methoxide ions, ethoxide ions, etc.) and the like can be mentioned. Among these, as the counter anion, a halide ion, a methanesulfonate ion, and a hydrogen sulfate ion are preferable.

  N in the said Formula (1) shows the integer of 1-20. In particular, n is preferably an integer of 2 to 12, more preferably an integer of 3 to 8, from the viewpoint of separation efficiency of the oxidation reaction catalyst from the product.

Specifically as a quaternary ammonium salt of this invention, the compound (quaternary ammonium salt) represented by a following formula is mentioned, for example.

（式（１ａ）中、Ｒ⁴、ｎは、前記に同じ。）

（式（１ｂ）中、Ｒ⁴、ｎは、前記に同じ。Ｌは、脱離基を示す。）

（式（１ｃ）中、Ｒ¹、Ｒ²、Ｒ³は、前記に同じ。） The quaternary ammonium salt of the present invention can be produced by a known or commonly used method for producing a quaternary ammonium salt, and the production method is not particularly limited. For example, the quaternary ammonium salt is represented by the following formula (1a). A compound represented by the following formula (1b) by using a compound as a raw material and converting a hydroxyl group (the hydroxyl group represented in the formula (1a)) in the compound to a commonly used leaving group in the field of organic synthesis Can be further produced by a method of reacting with a compound (tertiary amine) represented by the following formula (1c).

(In formula (1a), R ⁴ and n are the same as above.)

(In the formula (1b), R ⁴ and n are the same as above. L represents a leaving group.)

(In formula (1c), R ¹ , R ² and R ³ are the same as above.)

  The compound represented by the formula (1a) is polyethylene glycol having a structure in which ethylene glycol is polymerized, or a monoether thereof. As the compound represented by the above formula (1a), a commercially available product can be used. For example, in the case of polyethylene glycol, ethylene glycol can be polycondensed or ethylene oxide can be obtained using a known or conventional method. Can be produced by ring-opening polymerization. Moreover, in the case of the monoether body of polyethylene glycol, it can manufacture by etherifying (for example, alkyl etherification) 1 hydroxyl group of polyethyleneglycol using a well-known thru | or a usual method.

  L (leaving group) in the above formula (1b) includes a leaving group well known in the field of organic synthesis, and is not particularly limited. For example, halogen group (halogen atom), benzenesulfonyloxy group, toluenesulfonyl Examples thereof include an oxy group, a methanesulfonyloxy group, and a trifluoromethanesulfonyloxy group.

  As a compound for converting a hydroxyl group in the compound represented by the above formula (1a) into a leaving group (sometimes referred to as “leaving group introduction compound”), a known or conventional one may be used. Although not particularly limited, for example, a lower alkyl sulfonic acid chloride which may have a substituent such as methanesulfonic acid chloride, trifluoromethanesulfonic acid chloride; a substituent such as benzenesulfonic acid chloride, toluenesulfonic acid chloride, etc. Aromatic sulfonic acid chloride which may have; lower alkyl sulfonic acid anhydride which may have a substituent such as methanesulfonic acid anhydride and trifluoromethanesulfonic acid anhydride; benzenesulfonic acid anhydride, toluenesulfone Aromatic sulfonic acid anhydrides optionally having substituents such as acid anhydrides; Phosphonyl Rukuro lower alkyl phosphoric acid chlorides which may have a substituent such as chloride; diphenyl phosphonyl Rukuro aromatic phosphoric acid chlorides which may have a substituent such as chloride and the like. Examples of the substituent in the leaving group introduction compound include a halogen atom.

  Moreover, as a method of converting the hydroxyl group in the compound represented by the above formula (1a) into a leaving group to produce the compound represented by the formula (1b), a method of reacting the above-mentioned leaving group introducing compound is reacted. In addition, for example, a method of reacting a compound represented by the formula (1a) with thionyl chloride to produce a compound represented by the formula (1b) wherein L is a chlorine atom, or the above L is a chlorine atom And a method for producing a compound represented by the formula (1b) in which L is an iodine atom by further reacting the compound represented by the formula (1b) with sodium iodide, potassium iodide or the like. It is done.

  Reaction conditions and the like for converting the hydroxyl group in the compound represented by the formula (1a) to a leaving group to produce the compound represented by the formula (1b) are not particularly limited, and are commonly used in the field of organic synthesis. It is possible to select appropriately from the above conditions.

  The compound represented by the above formula (1b) may be used in the next reaction after being purified by a conventional method, for example, separation means such as concentration, extraction, column chromatography, or a separation means combining these. Good.

  Next, the quaternary ammonium salt of the present invention can be produced by reacting the compound represented by the above formula (1b) with the tertiary amine represented by the formula (1c). Specific examples of the tertiary amine represented by the formula (1c) include N, N-dimethyl-N-octadecylamine, N, N, N-trioctylamine, and N-benzyl-N-methyl. -N-octadecylamine, N, N-dioctyl-N-methylamine and the like.

The reaction between the compound represented by the formula (1b) and the tertiary amine represented by the formula (1c) can be carried out in the presence of an organic solvent. The organic solvent is not particularly limited as long as it can dissolve both the compound represented by the formula (1b) and the tertiary amine represented by the formula (1c) and does not inhibit the reaction. For example, cyclo C _3-10 alkanols such as cyclopropanol and cyclohexanol; chain ethers such as dimethyl ether and diethyl ether; methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone and the like Ketones; esters (chain esters) such as ethyl acetate, butyl acetate, methyl lactate and ethyl lactate; halogenated hydrocarbons such as chloroform, methylene chloride and chlorobenzene; phenols and the like. The said organic solvent can be used individually by 1 type or in combination of 2 or more types.

  The reaction between the compound represented by the formula (1b) and the tertiary amine represented by the formula (1c) can be caused to proceed by, for example, causing these compounds to coexist and heating. Although the usage-amount of the tertiary amine represented by Formula (1c) is not specifically limited, 1.0-5.0 mol is preferable with respect to 1 mol of compounds represented by Formula (1b), More preferably Is 1.2-1.5 mol.

  The amount of the organic solvent used in the reaction between the compound represented by formula (1b) and the tertiary amine represented by formula (1c) is not particularly limited, but is 100 parts by weight of the compound represented by formula (1b). The amount is preferably 20 to 1000 parts by weight, more preferably 50 to 500 parts by weight.

  Although it does not specifically limit as temperature (reaction temperature) of reaction with the compound represented by Formula (1b), and the tertiary amine represented by Formula (1c), 40-150 degreeC is preferable, More preferably ~ 150 ° C. In addition, the reaction time (reaction time) is not particularly limited, but is preferably 2 to 10 hours, and more preferably 3 to 5 hours.

  The quaternary ammonium salt of the present invention can be purified by a conventional method, for example, separation means such as concentration and column chromatography, or a separation means combining these.

[Catalyst for oxidation reaction]
The quaternary ammonium salt of the present invention can be preferably used as a phase transfer catalyst in an organic compound oxidation reaction catalyst. More specifically, the quaternary ammonium salt of the present invention can be preferably used as a phase transfer catalyst of an oxidation reaction catalyst used in an oxidation reaction in which an organic compound is oxidized with hydrogen peroxide. Hereinafter, the oxidation reaction catalyst containing the quaternary ammonium salt of the present invention as a phase transfer catalyst may be referred to as “the oxidation reaction catalyst of the present invention”.

  The oxidation reaction catalyst of the present invention contains at least the quaternary ammonium salt of the present invention as a phase transfer catalyst. In addition to the quaternary ammonium salt of the present invention as a phase transfer catalyst, the oxidation reaction catalyst of the present invention includes a component that catalyzes the oxidation reaction itself with hydrogen peroxide (referred to as “oxidation reaction catalyst”). . The oxidation reaction catalyst may be a known or conventional oxidation reaction catalyst, and is not particularly limited. Generally, in an oxidation reaction using hydrogen peroxide as an oxidizing agent, a compound containing a metal atom is oxidized. Used as a catalyst. Examples of the compound containing a metal atom include compounds containing a metal atom such as tungsten, manganese, vanadium, molybdenum, titanium, aluminum, and niobium.

  The oxidation reaction catalyst of the present invention preferably contains a heteropolyacid or a salt thereof or a precursor compound thereof as the oxidation reaction catalyst. As the heteropolyacid or salt thereof, various known heteropolyacids or salts thereof can be used, and are not particularly limited. For example, phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, Examples thereof include ribdophosphoric acid, tungstomolybdosilicic acid, and phosphovanadmolybdic acid. Among them, as the heteropolyacid, phosphorus (phosphorus atom) and a heteropolyacid containing at least one (one or more) metal (metal atom) selected from the group consisting of tungsten, manganese, molybdenum, and vanadium Is preferred. Examples of such heteropolyacids include phosphotungstic acid, phosphomanganic acid, phosphomolybdic acid, and phosphovanadic acid. Among these, phosphotungstic acid is particularly preferable from the viewpoint of cost. Examples of the salt of the heteropolyacid include onium salts, alkali metal salts, alkaline earth metal salts, transition metal salts of the above exemplified heteropolyacids.

  The precursor compound of the heteropolyacid or a salt thereof means one or more compounds that can form (prepare) a heteropolyacid or a salt thereof. The precursor compound may not necessarily form a heteropolyacid or a salt thereof in the reaction system. Examples of the precursor compound include metal atoms such as tungsten, manganese, vanadium, molybdenum, titanium, aluminum, and niobium (preferably at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium). ) At least one compound selected from the group consisting of phosphorus, silicon and arsenic (preferably phosphorus (phosphorus atom)) Can be used in combination. That is, the heteropolyacid or salt thereof is a heteropolyacid or salt thereof prepared from a compound containing at least one metal atom selected from the group consisting of tungsten, manganese, and vanadium and a compound containing at least phosphorus. Preferably there is.

  Examples of the compound containing a hetero atom include phosphoric acid, polyphosphoric acid (including pyrophosphoric acid and metaphosphoric acid), (poly) phosphate {metal salt of (poly) phosphoric acid [for example, a compound containing a phosphorus atom] (Poly) alkali metal phosphates such as potassium phosphate, sodium phosphate; (Poly) alkaline earth metal salts such as calcium phosphate; (Poly) hydrogen phosphate such as potassium hydrogen phosphate, sodium hydrogen phosphate Alkali metal salts; (Poly) hydrogen phosphate alkaline earth metal salts such as calcium hydrogen phosphate; (Poly) metal phosphates such as (poly) aluminum phosphate (including aluminum pyrophosphate double salt)] }. In addition, the compound (or raw material) which synthesize | combines the compound containing the said phosphorus atoms, such as a phosphorus pentoxide, is also contained in the compound containing the said phosphorus atom. The said compound containing a phosphorus atom can be used individually by 1 type or in combination of 2 or more types. Among these, phosphorus atom-containing oxo acids such as phosphoric acid or phosphates (particularly phosphoric acid) or salts thereof are preferable from the viewpoints of handleability and cost. Examples of the compound containing a hetero atom include silicic acid (orthosilicate, metasilicic acid, etc.) as a compound containing a silicon atom, and arsenic acid, arsenous acid, etc. as a compound containing an arsenic atom.

  Examples of the metal compound include halides of metals such as tungsten, manganese, vanadium, molybdenum, titanium, aluminum, and niobium, inorganic acid salts, organic acid salts, complexes, and polyacids or salts thereof composed of the above metal atoms. Etc. These metal compounds can be used individually by 1 type or in combination of 2 or more types.

  Among the above metal compounds, examples of the compound containing tungsten (tungsten compound) include tungsten halides (tungsten chloride, etc.); tungsten inorganic acid salts (sulfates, nitrates, etc.); tungsten organic acid salts (acetates) Complex with tungsten as the central metal; isopolyacid or its salt of tungsten (tungstic acid; alkali metal salt of tungstic acid such as sodium tungstate, potassium tungstate, etc.), heteropolyacid or its salt (tungstophosphoric acid ( Or tungstophosphate) (for example, 12-tungstophosphoric acid, 11-tungstophosphoric acid, etc.), vanadium tungstic acid, molybdenum tungstic acid, manganese tungstic acid, cobalt tungstic acid, silicotungstic acid, phosphovanadotan Sten acid, manganese molybdate tungstate or salts thereof (e.g., alkali metal salts), etc.).

  In particular, the metal compound is preferably an inorganic acid (polyacid, isopolyacid) or a salt thereof containing at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium.

  That is, as a precursor compound of the heteropolyacid or a salt thereof, an inorganic acid or a salt thereof containing at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium, and a phosphorus atom-containing oxoacid Or the combination of the salt is preferable.

  When the oxidation reaction catalyst of the present invention contains a heteropolyacid or a salt thereof or a precursor compound thereof, the content (content ratio) of the quaternary ammonium salt of the present invention is not particularly limited, but the heteropolyacid or a salt thereof or 0.01-5 mol is preferable with respect to 1 mol of these precursor compounds (in the case of a precursor compound, an amount corresponding to 1 mol of heteropolyacid or a salt thereof), more preferably 0.03-3 mol, still more preferably. 0.05 to 1 mol.

  The catalyst for oxidation reaction of the present invention may contain other components in addition to the quaternary ammonium salt and heteropolyacid (or its precursor compound) of the present invention. Examples of other components include hydroquinones, trialkylamines, and polyethylene glycol.

  The method for preparing the oxidation reaction catalyst of the present invention is not particularly limited. The quaternary ammonium salt of the present invention may be added to the reaction solution in the form of a composition by mixing other components such as a heteropolyacid or a salt thereof or a precursor compound thereof in advance. The quaternary ammonium salt and other components may be added separately to the reaction solution.

[Method for producing oxidized compound]
The catalyst for oxidation reaction of the present invention is used as a catalyst for oxidation reaction of organic compounds. More specifically, the oxidation reaction catalyst of the present invention can be preferably used in a method for producing an oxidized compound including at least a step of oxidizing an organic compound with hydrogen peroxide to produce a corresponding oxidized compound (product). Hereinafter, a method for producing the above-described oxidized compound using the oxidation reaction catalyst of the present invention (oxidation including at least a step of oxidizing an organic compound with hydrogen peroxide to form an oxidized compound in the presence of the oxidation reaction catalyst of the present invention. The method for producing a compound) may be referred to as “the method for producing an oxidized compound of the present invention”.

(Organic compounds)
The organic compound as a raw material (substrate to be oxidized) used in the method for producing an oxidized compound of the present invention is not particularly limited as long as it is a compound that can be oxidized with hydrogen peroxide. Examples thereof include compounds having a heavy bond (hereinafter sometimes referred to as “olefins”), alcohols and ketones. When an olefin is oxidized with hydrogen peroxide, usually a carbon-carbon double bond (ethylenically unsaturated double bond) is epoxidized to produce a corresponding epoxy compound. Depending on conditions, a diol is generated. When primary alcohol is oxidized with hydrogen peroxide, aldehyde, carboxylic acid and the like are produced. When secondary alcohol is oxidized with hydrogen peroxide, ketone, carboxylic acid and the like are produced. Further, when the ketone is oxidized with hydrogen peroxide, the buyer's billiger oxidation proceeds to produce an ester (in the case of oxidation of a chain ketone) and a lactone (in the case of oxidation of a cyclic ketone). Of the oxidation reactions using hydrogen peroxide, the most typical oxidation reaction is olefin oxidation, particularly epoxidation reaction. Hereinafter, olefin epoxidation (epoxidation of olefin carbon-carbon double bond) will be described in detail. However, the oxidation reaction catalyst of the present invention is not limited to this reaction, and is used in any of the above oxidation reactions. be able to.

  The olefin is not particularly limited as long as it has at least one ethylenically unsaturated double bond (non-aromatic carbon-carbon double bond) in the molecule (in one molecule). That is, the olefin may have one or more ethylenically unsaturated double bonds in the molecule. The olefin contains (i) a linear or branched aliphatic hydrocarbon having a carbon-carbon double bond, and (ii) a cycloalkene ring (including a cycloalkapolyene ring such as a cycloalkadiene ring). And the like. These compounds may have a substituent. When the oxidation reaction is carried out in a liquid phase, a liquid or solid (or miscible with the liquid) olefin is usually selected as the olefin usually under the reaction conditions.

(I) Examples of linear or branched aliphatic hydrocarbons having a carbon-carbon double bond include ethylene, propene, 1-butene, 2-butene, 1-pentene, 2-pentene, and 1-hexene. 2-hexene, 2,3-dimethyl-2-butene, 3-hexene, 1-heptene, 2-heptene, 1-octene, 2-octene, 3-octene, 2-methyl-2-butene, 1 A C _2-40 alkene (preferably a C _2-30 alkene, more preferably a C _2-20 alkene) such as nonene, 2-nonene, decene, undecene, dodecene, tetradecene, hexadecene, octadecene; butadiene, isoprene, 1, C _4-40 alkadiene (preferably C ₄ ) such as 5-hexanediene, 1,6-heptanediene, 1,7-octadiene, decadiene, undecadiene, dodecadiene _-30 alkadienes, more preferably C _4-20 alkadienes); C _6-30 alkatrienes (preferably C _6-20 alkatrienes) such as undecatriene and dodecatriene. The linear or branched aliphatic hydrocarbon having a carbon-carbon double bond can be used alone or in combination of two or more.

These linear or branched aliphatic hydrocarbons include, for example, aromatic hydrocarbon groups (for example, C _6-10 aryl groups such as phenyl groups), hydroxyl groups, halogen atoms (for example, fluorine atoms, chlorine atoms) , Bromine atom, etc.), mercapto group, alkoxy group (for example, C _1-10 alkoxy group such as methoxy group, ethoxy group, propoxy group, butoxy group, t-butoxy group, etc. (for example, C _1-6 alkoxy group), etc. ), A haloalkoxy group, an alkylthio group (eg, a C _1-10 alkylthio group such as a methylthio group or an ethylthio group), a carboxyl group, an alkoxycarbonyl group (eg, a C _1-10 alkoxy such as a methoxycarbonyl group or an ethoxycarbonyl group) carbonyl group (e.g., a C _2-10 alkoxycarbonyl group), etc.), an acyl group (e.g., acetyl group, flop Pioniru group, such as C _2-10 acyl group such as trifluoroacetyl group), an acyloxy group (e.g., acetoxy group, propionyloxy group, C _1-10 acyloxy group such as trifluoroacetoxy group), an amino group, substituted amino A substituent such as a group, a nitro group, a cyano group, or a heterocyclic group (such as a nitrogen atom-containing heterocyclic group such as a pyridyl group) may be included. The number of substituents and the substitution position are not particularly limited.

Examples of the linear or branched aliphatic hydrocarbon having a substituent include the linear or branched aliphatic hydrocarbon having an aryl group (for example, a phenyl group) as a substituent (for example, phenylethylene). (Or styrene), 1-phenylpropene, 2-phenyl-1-butene, 1-phenyl-1,3-butadiene, 1-phenyl-1,3-pentadiene, and the like. In addition, the linear or branched aliphatic hydrocarbon having an aryl group (for example, phenyl group) as a substituent is an alkenyl group (for example, vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, etc.) _Or an aromatic compound substituted with a C _2-10 alkenyl group (preferably a C _2-6 alkenyl group), and the aromatic compound has at least one carbon in the side chain. -As long as it has a carbon double bond, the alkenyl group and / or aromatic ring may have a substituent (for example, the above exemplified substituent), and between the alkenyl group and the aromatic ring. May have a linking group (such as a linking group described below).

(Ii) Examples of the compound containing a cycloalkene ring (including a cycloalkapolyene ring such as a cycloalkadiene ring) include, for example, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, and cycloundecene C _3-20 cycloalkene such as cyclododecene (preferably C _4-14 cycloalkene, more preferably C _5-10 cycloalkene); cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1, C _5-20 cycloalkadiene such as 3-cycloheptadiene, 1,4-cycloheptadiene, 1,5-cyclooctadiene, cyclodecadiene (preferably C _5-14 cycloalkadiene, more preferably C _{5 -10} cycloalkadiene); Shikurookutato Such as C _7-20 cycloalkadienyl triene such as ene. The compound which has a cycloalkene ring can be used individually by 1 type or in combination of 2 or more types. Among these, C _3-20 cycloalkene is preferable, and C _5-10 cycloalkene [for example, C _6-8 cycloalkene (for example, C _5-6 cycloalkene such as cyclohexene)] can be preferably used.

These compounds may have a substituent on the cycloalkene ring. The number of substituents and the substitution position are not particularly limited. Examples of the substituent include (i) a substituent exemplified in the section of a linear or branched aliphatic hydrocarbon having a carbon-carbon double bond, and an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group). Group, butyl group, isobutyl group, C _1-10 alkyl group (preferably C _1-6 alkyl group) such as t-butyl group, etc .; haloalkyl group; alkenyl group (for example, alkenyl group exemplified above); aryl Group (for example, C _6-10 aryl group such as phenyl group) and the like.

  The olefin may be a compound containing a plurality of alkene units and / or cycloalkene units. The plurality of alkene units and / or cycloalkene units in the compound containing the plurality of alkene units and / or cycloalkene units may be the same or different. The plurality of alkene units and / or cycloalkene units may be bonded by a single bond (direct bond) or may be bonded through a linking group. 1 type may be sufficient as the said coupling group, and multiple types may be sufficient as it. The “alkene unit” may be a monovalent or polyvalent group corresponding to the above (i) a linear or branched aliphatic hydrocarbon having a carbon-carbon double bond, such as an alkadiene unit. It is used in the meaning including the alkapolyene unit. The “cycloalkene unit” may be a monovalent or polyvalent group corresponding to the compound (ii) containing a cycloalkene ring, and includes a cycloalkapolyene unit such as a cycloalkadiene unit. Used in.

The linking group is usually a polyvalent group (for example, a divalent group). The linking group includes, for example, an alkylene group (for example, a C _1-20 alkylene group such as an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and 2-methylbutane-1,3-diyl group), a cycloalkylene group (for example, _C4-10 cycloalkylene group such as 1,4-cyclohexylene group), arylene group (eg C _6-10 arylene group such as phenylene group, naphthalenediyl group, etc.), carbonyl bond, ester bond, amide bond And at least one selected from an ether bond and a urethane bond.

  Carbon contained in the carbon number of the olefin (when a substituent and / or a linking group is included, a substituent and / or a linking group (a substituent and a linking group when both a substituent and a linking group are included)) The total number) is not particularly limited, but is preferably 2 to 40, more preferably 6 or more (for example, 6 to 30), further preferably 6 to 25, and particularly preferably 6 to 20 (For example, 7 to 20).

Such olefin can be used individually by 1 type or in combination of 2 or more types. The olefin is preferably a compound containing (ii) a cycloalkene ring (for example, a C _3-20 cycloalkene ring, preferably a C _6-20 cycloalkene ring, particularly a cyclohexene ring). The olefin may have one or more cycloalkene rings (particularly cyclohexene rings).

（式（ａ）中、Ｒ⁵は、水素原子又はアルキル基を示し、Ｒ⁶は、水素原子、アルキル基、アルケニル基、ヒドロキシル基、アルコキシ基、カルボキシル基、又はアルコキシカルボニル基を示す。）
で表される化合物や、下記式（ｂ）

（式（ｂ）中、Ｒ⁷は単結合、又は、直鎖若しくは分岐鎖状アルキレン基を示す。Ｒ⁵は前記に同じ。ｐ及びｑは、同一又は異なって、０又は１以上の整数である）
で表される化合物などが含まれる。なお、ｐ及びｑが０であり、Ｒ⁷が単結合である場合には、上記式（ｂ）で表される化合物は、２つのシクロヘキセン環が直接結合した構造を有する。 Representative olefins include, for example, the following formula (a)

(In formula (a), R ⁵ represents a hydrogen atom or an alkyl group, and R ⁶ represents a hydrogen atom, an alkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, a carboxyl group, or an alkoxycarbonyl group.)
Or a compound represented by the following formula (b)

(In the formula (b), R ⁷ represents a single bond or a linear or branched alkylene group. R ⁵ is the same as defined above. P and q are the same or different and are each 0 or an integer of 1 or more. is there)
And the like. When p and q are 0 and R ⁷ is a single bond, the compound represented by the above formula (b) has a structure in which two cyclohexene rings are directly bonded.

As the linear or branched alkylene group (including alkylidene group) represented by R ⁷ , for example, an alkane optionally having a substituent (for example, ethane, propane, isopentane, 2,2-dimethylpropane, etc.) A divalent group corresponding to a C _1-20 alkane, etc. [specifically, a linear or branched chain such as a methylene group, an ethylene group, a propylene group, a 2,2-dimethylpropane-1,3-diyl group, etc. And a C _2-20 alkylene group (or alkylidene group)]. In the above formula (b), p and q are preferably 1.

Specifically, the olefin includes, for example, cyclohexene in the above formula (a), in which R ⁵ and R ⁶ are hydrogen atoms, R ⁵ is a hydrogen atom, and R ⁶ is a methoxycarbonyl group. -Methyl enecarboxylate (following formula (a-1)), R ⁵ is a hydrogen atom, R ⁶ is an allyl group 4-allylcyclohexene (following formula (a-2)), R ⁵ is a methyl group 2-Methyl-4-vinylcyclohexene (formula (a-3) below) in which R ⁶ is a vinyl group, R ⁵ is a methyl group, and R ⁶ is an isopropenyl group. 2-propenyl) cyclohexene (following formula (a-4)); in the above formula (b), R ⁵ is a hydrogen atom, R ⁷ is a methylene group, p is 1 and q is 0. -Cyclohexenylmethyl enecarboxylate (under Formula (b-1)), R 5 is a hydrogen atom, R ⁷ is 2,2-dimethyl-1,3-diyl, p and q are 1-bis [1,3- (cyclohex - 3-enecarboxylic acid)]-2,2-dimethylpropyl ester (the following formula (b-2)), R ⁵ is a methyl group, and R ⁷ is 2,2-dimethylpropane-1,3-diyl. , P and q are 1, bis [1,3- (4-methylcyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester [4-methylcyclohex-3-enecarboxylic acid = 2 , 2-dimethyl-3- (4-methylcyclohex-3-enecarbonyloxy) propyl] (following formula (b-3)) and bis [1,3- (3-methylcyclohex-3-ene] Carboxylic acid)]-2,2-dimethylpropyl ester [3 -Methylcyclohex-3-enecarboxylic acid = 2,2-dimethyl-3- (3-methylcyclohex-3-enecarbonyloxy) propyl] (following formula (b-4)) and the like are included.

  For example, when cyclohexenyl methyl cyclohex-3-enecarboxylate represented by the above formula (b-1) is used as the olefin, a corresponding epoxy compound (3,4-epoxycyclohexane represented by the following formula (c) is used. Hexenylmethyl (3,4-epoxy) cyclohexanecarboxylate) is obtained. Further, when 2-methyl-4-vinylcyclohexene represented by the above formula (a-3) is used as the olefin, the corresponding epoxy compound (monoepoxy compound represented by the following formula (d-1) and the following formula: A diepoxy compound represented by (d-2) is obtained. Further, as the olefin, bis [1,3- (4-methylcyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester represented by the above formula (b-3) [4-methylcyclohexa When -3-enecarboxylic acid = 2,2-dimethyl-3- (4-methylcyclohex-3-enecarbonyloxy) propyl] is used, a corresponding epoxy compound represented by the following formula (e) is obtained. . In addition, as the olefin, bis [1,3- (3-methylcyclohex-3-enecarboxylic acid)]-2,2-dimethylpropyl ester represented by the above formula (b-4) [3-methylcyclohexa When -3-enecarboxylic acid = 2,2-dimethyl-3- (3-methylcyclohex-3-enecarbonyloxy) propyl] is used, a corresponding epoxy compound represented by the following formula (f) is obtained. .

(hydrogen peroxide)
Hydrogen peroxide (or hydrogen peroxide aqueous solution) used as an oxidizing agent may be synthesized by a conventional method, or a commercially available product may be used. The concentration of hydrogen peroxide in the case of using an aqueous hydrogen peroxide solution is not particularly limited, but is preferably 20 to 70 w / v%, more preferably 22 to 67 w / v%, and still more preferably from the viewpoint of handleability and the like. 25 to 65 w / v%.

  The amount of the hydrogen peroxide (substantially added hydrogen peroxide) is not particularly limited, but is preferably 0.1 to 10 mol, more preferably 0 with respect to 1 mol of the organic compound (olefin, etc.). .2 to 8 mol, more preferably 0.3 to 5 mol.

(Amount of catalyst used for oxidation reaction of the present invention)
In the method for producing an oxidized compound of the present invention, the catalyst for oxidation reaction of the present invention is used as a catalyst in the oxidation reaction of an organic compound. The amount of the quaternary ammonium salt of the present invention used in the oxidation reaction catalyst of the present invention is not particularly limited, but is an oxidizable group (for example, carbon-carbon olefin of an olefin) of an organic compound (such as an olefin) that is an oxide. (E.g., a heavy bond) The amount is preferably 0.01 to 5 mol%, more preferably 0.03 to 3 mol%, still more preferably 0.05 to 2 mol% with respect to 1 mol. When the amount of the quaternary ammonium salt used in the present invention is less than 0.01 mol%, the progress of the oxidation reaction is slow, or the efficiency of separation of the product and the oxidation reaction catalyst in the reaction solution after the reaction is lowered. There is a case.

  Further, when the oxidation reaction catalyst of the present invention contains a heteropolyacid or a salt thereof or a precursor compound thereof, the amount used (in the case of a precursor compound, an amount corresponding to 1 mol of the heteropolyacid or a salt thereof) is particularly limited. Although it is not, 0.01 to 5 mol% is preferable with respect to 1 mol of an oxidizable group (for example, carbon-carbon double bond of an olefin) of an organic compound (olefin or the like) that is an oxide, and more preferably 0. 0.03 to 3 mol%, more preferably 0.05 to 2 mol%. If the amount of the quaternary ammonium salt of the present invention is less than 0.01 mol%, the progress of the oxidation reaction may be slow.

  In addition, when the oxidation reaction catalyst of the present invention contains the precursor compound, and the combination of the metal compound and the compound containing a hetero atom is used as the precursor compound, the amount of the compound containing a hetero atom is not particularly limited. However, 0.05-10 mol% is preferable with respect to 1 mol of oxidizable groups (for example, carbon-carbon double bond of an olefin, etc.) of an organic compound (olefin, etc.) which is an oxide, and more preferably 0.8. It is 1-7 mol%, More preferably, it is 0.2-4 mol%.

  The oxidation reaction (epoxidation reaction, etc.) in the method for producing an oxidized compound of the present invention comprises an organic phase containing an organic compound (olefin, etc.) that is an oxide and an aqueous phase (the oxidation reaction catalyst of the present invention is a heteropolyacid or It is preferable that hydrogen peroxide or an aqueous solution thereof be added to the two-phase solution composed of the salt or a precursor compound thereof, which is included). In addition, the abundance ratio of the quaternary ammonium salt of the present invention in each of the aqueous phase and the organic phase in the oxidation reaction catalyst of the present invention depends on the structure, temperature, and the like.

  In the oxidation reaction, for the purpose of suppressing the rate of oxygen generation during the reaction, the oxidation reaction catalyst of the present invention and an organic compound (olefin or the like) as an oxide (these may be collectively referred to as “raw material”), In addition, after mixing other components (for example, hydroquinones), an oxidation reaction (epoxidation reaction or the like) should be started by adding hydrogen peroxide to the resulting mixed solution. In addition, when adding and mixing each raw material, in each raw material, the whole quantity may be added collectively (or once), and may be added in batch (or divided into multiple times). In addition, when hydrogen peroxide is added all at once (or at one time), in order to suppress the rapid temperature rise of the reaction solution due to reaction heat and the accompanying decomposition of hydrogen peroxide, It is desirable to add (or divide into multiple times). The method of adding hydrogen peroxide in batches (or divided into multiple times) is not particularly limited. For example, if a method of dropping hydrogen peroxide into the reaction solution is used, the reaction rate can be easily adjusted and the reaction can be performed. The rapid temperature rise of the solution can be effectively prevented.

  The oxidation reaction (epoxidation reaction or the like) may be performed in the absence of a solvent, but is usually performed in the presence of a solvent in many cases. In the above oxidation reaction, since hydrogen peroxide is used for oxidation, the solvent usually includes an aqueous solvent. As the aqueous solvent, water is usually used.

In the oxidation reaction, the solvent is preferably a mixed solvent of the aqueous solvent and the organic solvent. The organic solvent is not particularly limited as long as it can be separated from an aqueous solvent, and can be appropriately selected according to the type of the organic compound (olefin, etc.) that is an oxide. For example, cyclopropanol, cyclohexanol, and the like can be selected. C _3-10 alkanols; chain ethers such as dimethyl ether and diethyl ether; ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclopentanone and cyclohexanone; ethyl acetate, butyl acetate, methyl lactate and lactic acid Esters (chain esters) such as ethyl; hydrocarbons (eg, aliphatic hydrocarbons such as pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; toluene, xylene, ethylbenzene, etc. Aromatic hydrocarbons); chloroform And the like phenols; methylene chloride, halogenated hydrocarbons such as chlorobenzene. The said organic solvent can be used individually by 1 type or in combination of 2 or more types. Of these organic solvents, aromatic hydrocarbons (for example, toluene, xylene, ethylbenzene and the like) and halogenated hydrocarbons (for example, chloroform, methylene chloride, chlorobenzene and the like) are preferable from the viewpoint of reaction efficiency, Chlorobenzene and toluene are preferred.

  The ratio of the aqueous solvent to the organic solvent is not particularly limited, but is preferably selected from the range of the former / the latter (weight ratio) 90/10 to 5/95, more preferably 85/15 to 10/90, The ratio is preferably 80/20 to 15/85, particularly preferably 75/25 to 20/80. Moreover, the usage-amount of an organic solvent is although it does not specifically limit, 0.01-20 weight part is preferable with respect to 1 weight part of organic compounds (olefin etc.) which are oxides, More preferably, it is 0.05-15. Parts by weight, more preferably 0.1 to 10 parts by weight (for example, 0.2 to 5 parts by weight).

  The reaction temperature (or the temperature of the reaction system) is not particularly limited, but is preferably 50 to 70 ° C., more preferably 55 to 65 ° C. in consideration of oxygen generation due to decomposition of hydrogen peroxide. When the reaction temperature exceeds 70 ° C., the generation of oxygen becomes remarkable, making it difficult to produce safely. Moreover, the said reaction may be performed under a normal pressure and can also be performed under reduced pressure or pressurization.

  The pH of the reaction system (aqueous phase) is not particularly limited, but is preferably 2 to 7, more preferably 3 to 7, and still more preferably 3.5 to 6.5.

  Although reaction time is not specifically limited, In order to avoid generation | occurrence | production of excess oxygen, it is preferable to complete | finish reaction rapidly after the target oxide produces | generates.

  The obtained oxidized compound (epoxy compound, etc.) is separated and purified from the raw materials and the like according to the purpose by a conventional method, for example, separation means such as filtration, concentration, column chromatography, etc., or a separation means combining these. be able to.

[Method for separating catalyst for oxidation reaction]
Separation of the oxidation reaction catalyst from the oxidation compound in the reaction solution after oxidizing the organic compound with hydrogen peroxide to form an oxidation compound in the presence of the oxidation reaction catalyst of the present invention is performed by the reaction solution. And a method of selectively distributing the oxidation reaction catalyst to the aqueous phase by controlling the temperature of the aqueous solution, and then separating the organic phase and the aqueous phase of the reaction solution by a liquid separation operation (“invention of the present invention”). It may be referred to as “a method for separating the oxidation reaction catalyst”. This is because the distribution ratio of the oxidation reaction catalyst of the present invention to the organic and aqueous phases in the reaction solution (usually a two-phase solution of an organic phase and an aqueous phase) varies greatly depending on the temperature of the reaction solution. This is because there exists a temperature at which the oxidation reaction catalyst of the present invention is not substantially distributed to the organic phase. Such a characteristic is that the distribution ratio of the quaternary ammonium salt of the present invention to the organic phase and the aqueous phase greatly depends on the temperature, and the temperature at which the quaternary ammonium salt of the present invention is not substantially distributed to the organic phase. At this temperature, together with the quaternary ammonium salt of the present invention, an oxidation reaction catalyst (for example, a heteropolyacid or a salt thereof or a precursor compound thereof) in the oxidation reaction catalyst of the present invention is selectively transferred to the aqueous phase. Presumed to be due to distribution. That is, it is presumed that the quaternary ammonium salt of the present invention exhibits a function of separating the oxidation reaction catalyst from the oxidized compound.

  Therefore, in the method for producing an oxidized compound using the oxidation reaction catalyst of the present invention, the product and the oxidation reaction catalyst of the present invention can be separated mainly by temperature control and liquid separation operation. Without being able to recover and reuse the oxidation reaction catalyst of the present invention (in other words, purification of the oxidized compound as a product), it is very advantageous economically. In particular, separation of a compound containing a metal atom as an oxidation reaction catalyst (for example, a heteropolyacid or a salt thereof or a precursor compound thereof) and a product is generally very difficult, but for the oxidation reaction of the present invention. When a catalyst is used, separation of the oxidation reaction catalyst (for example, a heteropolyacid or a salt thereof or a precursor compound thereof) and a product is easily performed by the separation method described above (the separation method of the oxidation reaction catalyst of the present invention). It can be very beneficial.

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

¹ＨＮＭＲ（５００ＭＨｚ、ＣＤＣｌ₃）：δ３．３８（ｓ，３Ｈ，ＣＨ₃）、３．５５（ｄｄ，２Ｈ，Ｊ＝３．０，６．４Ｈｚ，ＣＨ₂）、３．６２−３．６９（ｍ，２６Ｈ，ＣＨ₂）、３．７６（ｔ，２Ｈ，Ｊ＝６．４Ｈｚ，ＣＨ₂）． Production Example 1
[Production of a compound represented by the following formula (1b-1)]
Methanesulfonyl chloride (7.22 g, 62.9 mmol) was added to a solution of polyethylene glycol monomethyl ether (20.0 g, 57.1 mmol) and triethylamine (17.5 g, 171 mmol) in 20 mL of dichloromethane at 40 ° C. The temperature was gradually raised to 60 ° C. and stirred. After 1 hour, the reaction mixture was concentrated under reduced pressure. A solid was precipitated by adding 20 mL of dichloromethane to the resulting yellow slurry, which was removed by filtration. The filtrate was concentrated under reduced pressure and then vacuum-dried for 1 hour to obtain the target product (yield: 22.8 g, yield: 93%) represented by the following formula (1b-1) as a yellow liquid. .

¹ HNMR (500 MHz, CDCl ₃ ): δ 3.38 (s, 3H, CH ₃ ), 3.55 (dd, 2H, J = 3.0, 6.4 Hz, CH ₂ ), 3.62-3.69 _{(m, 26H, CH 2)} , 3.76 (t, 2H, J = 6.4Hz, CH 2).

¹ＨＮＭＲ（５００ＭＨｚ、ＣＤＣｌ₃）：δ３．０８（ｓ，３Ｈ，ＣＨ₃）、３．３８（ｓ，３Ｈ，ＣＨ₃）、３．５３−３．５５（ｍ，２Ｈ，ＣＨ₂）、３．６３−３．６９（ｍ，６Ｈ，ＣＨ₂）、３．７６−３．７８（ｍ，２Ｈ，ＣＨ₂）、４．３８−４．３９（ｍ，２Ｈ，ＣＨ₂）． Production Example 2
[Production of Compound Represented by Formula (1b-2) below]
To a solution of triethylene glycol monomethyl ether (5.00 g, 30.5 mmol) and triethylamine (5.03 g, 45.8 mmol) dissolved in 30 mL of dichloromethane at 40 ° C., methanesulfonyl chloride (3.85 g, 33.5 mmol). ) Was added and stirred. After 15 minutes, the reaction mixture was concentrated under reduced pressure. The obtained yellow solid was dissolved in ethyl acetate and purified by passing through a silica gel column (100 g, ethyl acetate) to obtain the desired product represented by the following formula (1b-2) (yield: 7.29 g, Yield: 93%) was obtained as a yellow liquid.

¹ HNMR (500 MHz, CDCl ₃ ): δ 3.08 (s, 3H, CH ₃ ), 3.38 (s, 3H, CH ₃ ), 3.53-3.55 (m, 2H, CH ₂ ), 3 _{.63-3.69 (m, 6H, CH 2} ), 3.76-3.78 (m, 2H, CH 2), 4.38-4.39 (m, 2H, CH 2).

¹ＨＮＭＲ（５００ＭＨｚ、ＣＤＣｌ₃）：δ３．３５（ｍ，１Ｈ，ＣＨ₂）、３．４２−３．５０（ｍ，４Ｈ，ＣＨ₃ ａｎｄ ＣＨ₂）、３．５９−３．９４（ｍ，２８Ｈ，ＣＨ₂）． Production Example 3
[Production of a compound represented by the following formula (1b-3)]
To a solution of polyethylene glycol monomethyl ether (10.0 g, 28.6 mmol) and pyridine (2.55 g, 32.2 mmol) dissolved in 20 mL of chloroform was added thionyl chloride (4.08 g, 34.3 mmol) at room temperature. The solution dissolved in 9.0 mL was added and stirred at 60 ° C. After 1 hour, the reaction mixture was concentrated under reduced pressure and extracted with chloroform (100 mL × 2). The organic phase was washed with water (300 mL × 1) and dried using magnesium sulfate (50.0 g). After filtering the solid, the filtrate was concentrated under reduced pressure to obtain a yellow liquid (11.0 g).
The yellow solution obtained above was dissolved in acetone (29 mL), sodium iodide (4.29 g, 28.6 mmol) was added at room temperature, and the mixture was stirred at 60 ° C. After 2 hours, the reaction mixture was concentrated under reduced pressure. The obtained solid was dissolved in ethyl acetate and then purified by passing through a silica gel column (20.0 g, ethyl acetate), and the target product represented by the following formula (1b-3) (yield: 12.9 g, Yield over two steps: 98%) was obtained as a yellow liquid.

¹ HNMR (500 MHz, CDCl ₃ ): δ 3.35 (m, 1H, CH ₂ ), 3.42-3.50 (m, 4H, CH ₃ and _{CH 2), 3.59-3.94 (m,} 28H, CH 2).

¹ＨＮＭＲ（５００ＭＨｚ、ＣＤＣｌ₃）：δ０．８８（ｔ，３Ｈ，Ｊ＝７．０Ｈｚ，ＣＨ₃）、１．２４−１．３７（ｍ，３０Ｈ，ＣＨ₂）、１．７２−１．７９（ｍ，２Ｈ，ＣＨ₂）、３．３７５（ｓ，３Ｈ，ＣＨ₃）、３．３７９（ｓ、６Ｈ、ＣＨ₃）、３．５４−３．６９（ｍ，２６Ｈ，ＣＨ₂）、３．８９−３．９１（ｍ，２Ｈ，ＣＨ₂）、３．９９−４．０１（ｍ，２Ｈ，ＣＨ₂）． Example 1
[Production of Compound Represented by Formula (1-1) below (referred to as “PTC-1”)]
In a solution of N, N-dimethyl-N-octadecylamine (6.19 g, 20.2 mmol) dissolved in isobutyl ketone (10 mL), the compound represented by the above formula (1b-3) at 6.degree. C. (6. 48 g, 14.1 mmol) was added and refluxed. After 2 hours, the reaction mixture was concentrated under reduced pressure. The obtained mixture was purified by passing through a silica gel column (150 g, dichloromethane / methanol / NH ₃ aq. = 19/1/1), and the target product represented by the following formula (1-1) (yield: 2. 64 g, yield: 24.7%) was obtained as a yellow liquid.

¹ HNMR (500 MHz, CDCl ₃ ): δ 0.88 (t, 3H, J = 7.0 Hz, CH ₃ ), 1.24-1.37 (m, 30H, CH ₂ ), 1.72-1.79 _{(m, 2H, CH 2)} , 3.375 (s, 3H, CH 3), 3.379 (s, 6H, CH 3), 3.54-3.69 (m, 26H, CH 2), 3 _{.89-3.91 (m, 2H, CH 2} ), 3.99-4.01 (m, 2H, CH 2).

¹ＨＮＭＲ（５００ＭＨｚ、ＣＤＣｌ₃）：δ０．８８（ｔ，３Ｈ，Ｊ＝６．５Ｈｚ，ＣＨ₃）、１．２３−１．３７（ｍ，３０Ｈ，ＣＨ₂）、１．７２−１．８３（ｍ，２Ｈ，ＣＨ₂）、３．３６９（ｓ，３Ｈ，ＣＨ₃）、３．３７３（ｓ、３Ｈ、ＣＨ₃）、３．３８（ｓ，３Ｈ，ＣＨ₃）、３．５３−３．５６（ｍ，４Ｈ，ＣＨ₂）、３．６０−３．６７（ｍ，２６Ｈ，ＣＨ₂）、３．７２（ｍ，１Ｈ，ＣＨ₂）、３．９５−３．９９（ｍ，４Ｈ，ＣＨ₂）． Example 2
[Production of Compound Represented by Formula (1-2) (referred to as “PTC-2”)]
N, N-dimethyl-N-octadecylamine (5) was added to a solution of the compound represented by the above formula (1b-1) (12.3 g, 28.6 mmol) in methyl isobutyl ketone (5 g) at 100 ° C. .67 g, 19.0 mmol) was added and refluxed. After 2 hours, the reaction mixture was concentrated under reduced pressure. The obtained mixture was purified by passing through a silica gel column (100 g, chloroform / methanol = 10/1 to dichloromethane / methanol / triethylamine = 10/1/1), and the desired product represented by the following formula (1-2) (Yield: 13.4 g) was obtained as a yellow liquid.

¹ HNMR (500 MHz, CDCl ₃ ): δ 0.88 (t, 3H, J = 6.5 Hz, CH ₃ ), 1.23-1.37 (m, 30H, CH ₂ ), 1.72-1.83 _{(m, 2H, CH 2)} , 3.369 (s, 3H, CH 3), 3.373 (s, 3H, CH 3), 3.38 (s, 3H, CH 3), 3.53-3 .56 (m, 4H, CH ₂ ), 3.60-3.67 (m, 26H, CH ₂ ), 3.72 (m, 1H, CH ₂ ), 3.95-3.99 (m, 4H) , CH ₂ ).

¹ＨＮＭＲ（５００ＭＨｚ、ＣＤＣｌ₃）：δ０．８９（ｔ，９Ｈ，Ｊ＝７．０Ｈｚ，ＣＨ₃）、１．２３−１．３８（ｍ，３０Ｈ，ＣＨ₂）、１．５８−１．９４（ｍ，６Ｈ，ＣＨ₂）、２．７５（ｓ，３Ｈ，ＣＨ₃）、３．２８−３．３１（ｍ、６Ｈ、ＣＨ₂）、３．３８（ｓ，３Ｈ，ＣＨ₃）、３．５４−３．６９（ｍ，２６Ｈ，ＣＨ₂）、３．８０−３．８２（ｍ，２Ｈ，ＣＨ₂）、３．９１−３．９３（ｍ，２Ｈ，ＣＨ₂）． Example 3
[Production of a compound represented by the following formula (1-3) (referred to as “PTC-3”)]
To a solution of the compound represented by the above formula (1b-1) (2.06 g, 4.67 mmol) in methyl isobutyl ketone (1.2 g), N, N, N-trioctylamine ( 2.52 g) was added and refluxed. After 16 hours, the reaction mixture was concentrated under reduced pressure. The obtained mixture was purified by passing through a silica gel column (100 g, dichloromethane / methanol / triethylamine = 14/1/1), and the desired product represented by the following formula (1-3) (yield: 1.48 g, 1 .89 mmol) as a yellow liquid.

¹ HNMR (500 MHz, CDCl ₃ ): δ 0.89 (t, 9H, J = 7.0 Hz, CH ₃ ), 1.23-1.38 (m, 30H, CH ₂ ), 1.58-1.94 (M, 6H, CH ₂ ), 2.75 (s, 3H, CH ₃ ), 3.28-3.31 (m, 6H, CH ₂ ), 3.38 (s, 3H, CH ₃ ), 3 _{.54-3.69 (m, 26H, CH 2} ), 3.80-3.82 (m, 2H, CH 2), 3.91-3.93 (m, 2H, CH 2).

¹ＨＮＭＲ（５００ＭＨｚ、ＣＤＣｌ₃）：δ０．８８（ｔ，３Ｈ，Ｊ＝７．０Ｈｚ，ＣＨ₃）、１．２５−１．３６（ｍ，３０Ｈ，ＣＨ₂）、１．７２−１．８０（ｍ，２Ｈ，ＣＨ₂）、３．３０（ｓ，３Ｈ，ＣＨ₃）、３．３８（ｓ、６Ｈ、ＣＨ₃）、３．４７−３．５１（ｍ，２Ｈ，ＣＨ₂）、３．５４−３．５６（ｍ、２Ｈ、ＣＨ₂）、３．６１−３．６６（ｍ，２４Ｈ，ＣＨ₂）、３．８４−３．８６（ｍ，２Ｈ，ＣＨ₂）、３．９８−４．００（ｍ，２Ｈ，ＣＨ₂）． Example 4
[Production of a compound represented by the following formula (1-4) (referred to as “PTC-4”)]
An aqueous solution (20 mL) of PTC-2 (3.34 g, 4.60 mmol), sodium chloride (0.791 g, 12.34 mmol), and potassium chloride (0.920 g, 12.34 mmol) was stirred at 50 ° C. for 2 hours. . Thereafter, methanol was added to the reaction mixture, and the mixture was concentrated under reduced pressure. Ethyl acetate was added to the resulting slurry, and the solid was removed by passing through celite. The filtrate was concentrated under reduced pressure, purified by passing through a silica gel column (66.8 g, dichloromethane / methanol / triethylamine = 20/1/1), and the desired product (yield represented by the following formula (1-4)) : 1.18 g, yield: 24.2%) as a yellow liquid.

¹ HNMR (500 MHz, CDCl ₃ ): δ 0.88 (t, 3H, J = 7.0 Hz, CH ₃ ), 1.25-1.36 (m, 30H, CH ₂ ), 1.72-1.80 _{(m, 2H, CH 2)} , 3.30 (s, 3H, CH 3), 3.38 (s, 6H, CH 3), 3.47-3.51 (m, 2H, CH 2), 3 _{.54-3.56 (m, 2H, CH 2} ), 3.61-3.66 (m, 24H, CH 2), 3.84-3.86 (m, 2H, CH 2), 3.98 _{-4.00 (m, 2H, CH 2} ).

¹ＨＮＭＲ（５００ＭＨｚ、ＣＤＣｌ₃）：δ０．８９（ｔ，９Ｈ，Ｊ＝７．０Ｈｚ，ＣＨ₃）、１．２４−１．３６（ｍ，３０Ｈ，ＣＨ₂）、１．６７−１．７１（ｍ，６Ｈ，ＣＨ₂）、３．３３−３．３６（ｍ，４Ｈ，ＣＨ₂）、３．３８（ｓ、３Ｈ、ＣＨ₃）、３．５４−３．５６（ｍ，２Ｈ，ＣＨ₂）、３．６０−３．６７（ｍ，２６Ｈ，ＣＨ₂）、３．９１−３．９３（ｍ，２Ｈ，ＣＨ₂）、３．９６−３．９８（ｍ，２Ｈ，ＣＨ₂）． Example 5
[Production of Compound Represented by Formula (1-5) below (referred to as “PTC-5”)]
An aqueous solution (2 mL) of PTC-3 (1.48 g, 1.89 mmol), sodium chloride (0.221 g, 3.78 mmol), and potassium chloride (0.282 g, 3.78 mmol) was stirred at 50 ° C. for 2 hours. . Thereafter, methanol was added to the reaction mixture, and the mixture was concentrated under reduced pressure. Ethyl acetate was added to the resulting slurry, and the solid was removed by passing through celite. The filtrate was concentrated under reduced pressure, purified by passing through a silica gel column (20 g, dichloromethane / methanol / triethylamine = 20/1/1), and the target product represented by the following formula (1-5) (yield: 1 0.08 g, yield: 79%) was obtained as a yellow liquid.

¹ HNMR (500 MHz, CDCl ₃ ): δ 0.89 (t, 9H, J = 7.0 Hz, CH ₃ ), 1.24 to 1.36 (m, 30 H, CH ₂ ), 1.67-1.71 _{(m, 6H, CH 2)} , 3.33-3.36 (m, 4H, CH 2), 3.38 (s, 3H, CH 3), 3.54-3.56 (m, 2H, CH _{2), 3.60-3.67 (m, 26H} , CH 2), 3.91-3.93 (m, 2H, CH 2), 3.96-3.98 (m, 2H, CH 2) .

¹ＨＮＭＲ（５００ＭＨｚ、ＣＤＣｌ₃）：δ０．８７（ｔ，３Ｈ，Ｊ＝７．０Ｈｚ，ＣＨ₃）、１．２６−１．３４（ｍ，３０Ｈ，ＣＨ₂）、１．７３−１．７５（ｍ，２Ｈ，ＣＨ₂）、２．７４（ｓ，３Ｈ，ＣＨ₃）、３．３６（ｓ，３Ｈ，ＣＨ₃）、３．４０（ｓ、６Ｈ、ＣＨ₃）、３．５１−３．５７（ｍ，４Ｈ，ＣＨ₂）、３．６０−３．６４（ｍ，４Ｈ，ＣＨ₂）、３．６６−３．６９（ｍ，２Ｈ，ＣＨ₂）、３．９３−３．９５（ｍ，２Ｈ，ＣＨ₂）、３．９８−３．９９（ｍ，２Ｈ，ＣＨ₂）． Example 6
[Production of Compound Represented by Formula (1-6) below (referred to as “PTC-6”)]
N, N-dimethyl-N-octadecylamine (5) was added to a solution of the compound represented by the above formula (1b-2) (12.3 g, 28.6 mmol) in methyl isobutyl ketone (5 g) at 100 ° C. .67 g, 19.0 mmol) was added and refluxed. After 2 hours, the reaction mixture was concentrated under reduced pressure. The obtained mixture was purified by passing through a silica gel column (100 g, chloroform / methanol = 10/1 to dichloromethane / methanol / triethylamine = 10/1/1), and the compound represented by the following formula (1-6) ( Yield: 13.7 g, yield: 86%) was obtained as a yellow liquid.

¹ HNMR (500 MHz, CDCl ₃ ): δ 0.87 (t, 3H, J = 7.0 Hz, CH ₃ ), 1.26 to 1.34 (m, 30H, CH ₂ ), 1.73-1.75 _{(m, 2H, CH 2)} , 2.74 (s, 3H, CH 3), 3.36 (s, 3H, CH 3), 3.40 (s, 6H, CH 3), 3.51-3 .57 (m, 4H, CH ₂ ), 3.60-3.64 (m, 4H, CH ₂ ), 3.66-3.69 (m, 2H, CH ₂ ), 3.93-3.95 _{(m, 2H, CH 2)} , 3.98-3.99 (m, 2H, CH 2).

¹ＨＮＭＲ（５００ＭＨｚ、ＣＤＣｌ₃）：δ０．８９（ｔ，３Ｈ，Ｊ＝７．０Ｈｚ，ＣＨ₃）、１．２５−１．３９（ｍ，３０Ｈ，ＣＨ₂）、１．６８−１．７２（ｍ，２Ｈ，ＣＨ₂）、３．３６−３．３９（ｍ，２Ｈ，ＣＨ₂）、３．３７（ｓ、６Ｈ、ＣＨ₃）、３．５２−３．５４（ｍ，２Ｈ，ＣＨ₂）、３．６０−３．６２（ｍ，４Ｈ，ＣＨ₂）、３．６５−３．６８（ｍ，２Ｈ，ＣＨ₂）． Example 7
[Production of Compound Represented by Formula (1-7) below (referred to as “PTC-7”)]
An aqueous solution (20 mL) of PTC-6 (3.34 g, 6.17 mmol), sodium chloride (0.721 g, 12.3 mmol), and potassium chloride (0.920 g, 12.3 mmol) was stirred at 50 ° C. for 2 hours. . Thereafter, methanol was added to the reaction mixture, and the mixture was concentrated under reduced pressure. Ethyl acetate was added to the resulting slurry, and the solid was removed by passing through celite. The filtrate was concentrated under reduced pressure, purified by passing through a silica gel column (69 g, dichloromethane / methanol / triethylamine = 20/1/1), and the target product represented by the following formula (1-7) (yield: 1 .18 g, yield: 34%) was obtained as a yellow liquid.

¹ HNMR (500 MHz, CDCl ₃ ): δ 0.89 (t, 3H, J = 7.0 Hz, CH ₃ ), 1.25-1.39 (m, 30H, CH ₂ ), 1.68-1.72. _{(m, 2H, CH 2)} , 3.36-3.39 (m, 2H, CH 2), 3.37 (s, 6H, CH 3), 3.52-3.54 (m, 2H, CH _{2), 3.60-3.62 (m, 4H} , CH 2), 3.65-3.68 (m, 2H, CH 2).

Example 8
[Epoxidation of 3-vinylcyclohexene using PTC-1 as a phase transfer catalyst]
To an aqueous solution (6.66 g) of sodium dihydrogen phosphate dihydrate (1.21 g, 7.77 mmol) and disodium hydrogen phosphate dodecahydrate (0.330 g, 0.924 mmol), 85% phosphoric acid (0.190 g, 1.94 mmol) and sodium tungstate dihydrate (0.642 g, 1.94 mmol) were added and stirred. This was dissolved in a toluene solution (46.9 g) of 3-vinylcyclohexene (VCH; 10.0 g, 92.4 mmol), PTC-1 (0.385 g, 0.508 mmol), and methoquinone (4.00 mg) at room temperature. And stirred. After 10 minutes, the temperature was raised to 60 ° C., 35% hydrogen peroxide (6.92 g, 71.2 mmol) was added and stirred. After 5 hours, the reaction mixture was separated and the organic phase was concentrated under reduced pressure. When the composition of the obtained liquid was analyzed by ¹ HNMR (500 MHz, CDCl ₃ ), it was found to be a binary mixture of VCH and 1,2-epoxy-4-vinylcyclohexane. The conversion rate of VCH was 38%.

[Evaluation of temperature response]
The temperature responsiveness (temperature dependence) of the partitioning behavior of the oxidation catalyst to the organic phase was evaluated by the following procedure.
To an aqueous solution (6.40 g) of sodium tungstate dihydrate (1.94 mmol), 85% phosphoric acid (2.31 mmol), and disodium hydrogenphosphate dodecahydrate (0.462 mmol), A solution in which a quaternary ammonium salt (0.508 mmol) shown in the following levels 1 to 4 was dissolved in an organic solvent (10.0 g) shown in the following levels 1 to 4 was added, followed by stirring at 30 ° C. After 10 minutes, stirring was stopped and the mixture was allowed to stand for about 30 minutes to 1 hour. After confirming that the upper layer and the lower layer were completely separated, about 0.010 g of the upper layer (organic phase) was collected and dissolved in about 40 g of N, N-dimethylformamide (DMF). Subsequently, the same operations (stirring, standing, separating the upper layer, dissolving in DMF) were performed under heating at 40 ° C., 60 ° C., and 80 ° C. (in order of 40 ° C., 60 ° C., and 80 ° C.). After completion of sampling at 80 ° C. (preparation and dissolution in DMF), the solution was cooled to 30 ° C. and the upper layer was sampled. By this operation, five samples (temperature 30 ° C., 40 ° C., 60 ° C., 80 ° C., 30 ° C .: 20 in total) are prepared for each of the following levels 1 to 4, and the amount of tungsten contained in each sample ( The amount of tungsten contained was analyzed by ICP (ICP emission analysis). The analysis results are shown in FIG. In the table of FIG. 1, the horizontal axis represents temperature, and the vertical axis represents the abundance ratio (%) of tungsten in the organic phase (= 100 × [amount of tungsten present in the organic phase] / ([the amount of tungsten present in the organic phase). Amount] + [amount of tungsten present in the aqueous phase])).
・ Level 1
Quaternary ammonium salt: PTC-1
Organic solvent: Toluene, Level 2
Quaternary ammonium salt: PTC-2
Organic solvent: Toluene, Level 3
Quaternary ammonium salt: PTC-2
Organic solvent: Chlorobenzene, level 4
Quaternary ammonium salt: N-benzyl-N, N-dimethyl-N-octadecylammonium chloride (BDMSAC)
Organic solvent: Toluene

As shown in FIG. 1, in the oxidation reaction catalyst containing the quaternary ammonium salt (PTC-1, PTC-2) of the present invention as a phase transfer catalyst, the partitioning behavior of tungsten into the organic phase varies significantly with temperature. In addition, it was found that there is a temperature at which the partition of tungsten into the organic phase hardly occurs. Therefore, when the oxidation reaction catalyst containing the quaternary ammonium salt of the present invention as a phase transfer catalyst is used, separation of the product present in the organic phase and tungsten (oxidation reaction catalyst) is performed by separating the organic phase from the aqueous phase. Can be performed.
On the other hand, in the oxidation reaction catalyst containing BDMSAC as a phase transfer catalyst, temperature dependence of the distribution behavior of tungsten to the organic phase is hardly observed, and tungsten is distributed to the organic phase by about 40% at any temperature. It was. Therefore, it is difficult to separate the product and tungsten by separating the organic phase and the aqueous phase.

Claims (8)

Following formula (1)

[In formula (1), R ¹ , R ² and R ³ each independently represents a hydrocarbon group which may have a substituent. R ⁴ represents a hydrogen atom or a hydrocarbon group which may have a substituent. X ⁻ represents a counter anion. n is an integer of 1-20. ]
A quaternary ammonium salt represented by   An organic compound oxidation reaction catalyst comprising the quaternary ammonium salt according to claim 1 as a phase transfer catalyst.   The catalyst for oxidation reaction according to claim 2, comprising a heteropolyacid or a salt thereof or a precursor compound thereof.   The oxidation according to claim 3, wherein the heteropolyacid or a salt thereof is a heteropolyacid or a salt thereof containing a phosphorus atom and at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium. Catalyst for reaction.   The precursor compound includes an inorganic acid or a salt thereof containing at least one metal atom selected from the group consisting of tungsten, manganese, molybdenum, and vanadium, and a phosphorus atom-containing oxo acid or a salt thereof. The catalyst for oxidation reaction as described.   The oxidation reaction catalyst according to any one of claims 2 to 5, wherein the oxidation reaction of the organic compound is an olefin epoxidation reaction with hydrogen peroxide.   A method for producing an epoxy compound, comprising the step of epoxidizing a carbon-carbon double bond of an olefin with hydrogen peroxide in the presence of the oxidation reaction catalyst according to claim 6 to produce an epoxy compound.   In the presence of the oxidation reaction catalyst according to any one of claims 2 to 6, the organic compound is oxidized with hydrogen peroxide to form an oxidized compound, and the oxidized compound in the reaction solution is used to generate the oxidized compound. A method for separating a reaction catalyst, the step of selectively distributing the oxidation reaction catalyst to an aqueous phase by controlling the temperature of the reaction solution, and then separating the organic phase and the aqueous phase by a liquid separation operation. And a method for separating the catalyst for oxidation reaction.

Images