JP2008120692A - Manufacturing method of epoxy compound bearing halosulfonyl group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for safely and industrially efficiently manufacturing in a high yield an epoxy compound bearing a halosulfonyl group from an unsaturated compound bearing a halosulfonyl group (sulfohalide group). <P>SOLUTION: The manufacturing method of the epoxy compound bearing a halosulfonyl group comprises oxidizing an unsaturated compound bearing a halosulfonyl group represented by formula (1) with an oxidizing agent to give the epoxy compound bearing a halosulfonyl group represented by formula (2), where the method comprises a step for subjecting the oxidizing agent remaining after oxidation of the unsaturated compound bearing a halosulfonyl compound with the oxidizing agent to a reduction treatment under a condition of pH of 9 or lower. In formula (1), A is an optionally substituted alkylene group or a bivalent group consisting of a plurality of optionally substituted alkylene groups each bonded via a linking group; R<SP>1</SP>-R<SP>3</SP>are each a hydrogen atom or an optionally substituted alkyl group; and X is a halogen atom. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing an epoxy compound having a halosulfonyl group, and more particularly to a method for producing an epoxy compound having a halosulfonyl group by oxidizing an unsaturated compound having a halosulfonyl group with an oxidizing agent. Epoxy compounds having a halosulfonyl group are useful as intermediate raw materials for fine chemicals such as pharmaceuticals and agricultural chemicals, intermediate raw materials for obtaining functional polymer monomers, and the like.

  As a method for producing an epoxy compound having a halosulfonyl group, a method of oxidizing an unsaturated compound having a halosulfonyl group with an oxidizing agent is known. For example, Japanese Patent Application Laid-Open No. 2005-314388 discloses a method of obtaining an epoxy compound having a corresponding fluorosulfonyl group by reacting an alkenesulfonic acid fluoride with an excessive amount of metachloroperbenzoic acid (Example). Japanese Patent Laid-Open No. 2006-104110 discloses a method for producing an epoxy compound having a corresponding fluorosulfonyl group by reacting 2-allyloxyethanesulfonic acid fluoride with an excessive amount of hydrogen peroxide ( Example).

JP 2005-314388 A JP 2006-104110 A

  In the above method, an excessive amount of oxidant is used for the epoxidation of the carbon-carbon double bond, but there is no description of a method for treating the excess oxidant remaining after the reaction. When producing an epoxy compound having a halosulfonyl group on an industrial scale, the presence of unreacted oxidant is not only dangerous, but also complicates the subsequent purification process, Since an undesirable side reaction may occur at the time of use, it is necessary to inactivate by performing a reduction treatment after the completion of the reaction. However, according to the study by the present inventors, when this unreacted oxidant is reduced using, for example, sodium sulfite, an epoxy compound having a halosulfonyl group as a target product is decomposed, and the target compound is obtained in a high yield. I can't get it.

  Accordingly, an object of the present invention is to provide a method for industrially and efficiently producing an epoxy compound having a halosulfonyl group in a safe and high yield from an unsaturated compound having a halosulfonyl group (sulfohalide group). It is in.

  As a result of intensive studies to achieve the above object, the present inventors have oxidized an unsaturated compound having a halosulfonyl group with an oxidant, and then reduced the remaining oxidant under a condition of pH 9 or less to produce a generated halo. The present inventors have found that an excess of an oxidizing agent can be quickly deactivated without decomposing an epoxy compound having a sulfonyl group.

（式中、Ａは、置換基を有していてもよいアルキレン基、又は置換基を有していてもよいアルキレン基の複数個がそれぞれ連結基を介して結合した２価の基を示す。Ｒ¹、Ｒ²、Ｒ³は、同一又は異なって、水素原子、又は置換基を有していてもよいアルキル基を示す。Ａ、Ｒ¹、Ｒ²及びＲ³のうち少なくとも２つの基は互いに結合して隣接する１又は２個の炭素原子とともに環を形成していてもよい。Ｘはハロゲン原子を示す）
で表されるハロスルホニル基を有する不飽和化合物を酸化剤により酸化して、下記式（２）

（式中、Ａ、Ｒ¹、Ｒ²、Ｒ³、Ｘは前記に同じ）
で表されるハロスルホニル基を有するエポキシ化合物を製造する方法であって、前記ハロスルホニル基を有する不飽和化合物を酸化剤により酸化した後、残存する酸化剤をｐＨ９以下の条件で還元処理する工程を含むハロスルホニル基を有するエポキシ化合物の製造法を提供する。 That is, the present invention provides the following formula (1):

(In the formula, A represents a divalent group in which an alkylene group which may have a substituent or a plurality of alkylene groups which may have a substituent are bonded via a linking group, respectively. R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or an optionally substituted alkyl group, and at least two groups of A, R ¹ , R ² and R ³ are And may be bonded to each other to form a ring with adjacent 1 or 2 carbon atoms, X represents a halogen atom)
An unsaturated compound having a halosulfonyl group represented by formula (2) is oxidized with an oxidizing agent, and the following formula (2):

(In the formula, A, R ¹ , R ² , R ³ and X are the same as above)
A process for producing an epoxy compound having a halosulfonyl group represented by the formula: wherein the unsaturated compound having a halosulfonyl group is oxidized with an oxidizing agent, and then the remaining oxidizing agent is reduced under a condition of pH 9 or less. A process for producing an epoxy compound having a halosulfonyl group containing

  As the reducing agent used for the reduction treatment, a reducing agent that is water-soluble and in which a 5% by weight aqueous solution exhibits acidity is preferable. The present invention is particularly useful when X in formula (1) is a fluorine atom.

  According to the present invention, an epoxy compound having a corresponding halosulfonyl group can be obtained from an unsaturated compound having a halosulfonyl group because an excess oxidizing agent can be quickly deactivated without decomposing the generated epoxy compound having a halosulfonyl group. The compound can be produced safely and efficiently in a high yield industrially.

In the present invention, an unsaturated compound having a halosulfonyl group represented by the formula (1) is oxidized with an oxidizing agent to produce an epoxy compound having a halosulfonyl group represented by the following formula (2). In formula (1), A represents an alkylene group which may have a substituent, or a divalent group in which a plurality of alkylene groups which may have a substituent are bonded via a linking group. Show. R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl group which may have a substituent. At least two groups out of A, R ¹ , R ² and R ³ may be bonded to each other to form a ring with adjacent 1 or 2 carbon atoms. X represents a halogen atom.

  Examples of the alkylene group in A include, for example, methylene, ethylidene, isopropylidene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene groups, etc. And a linear or branched alkylene group having about 1 to 11 carbon atoms. Examples of the substituent that these alkylene groups may have include, for example, a halogen atom (fluorine atom, chlorine atom, etc.), a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms (methoxy, ethoxy group, etc.), and a carbon number. 1-8 haloalkoxy groups (such as trifluoromethyloxy group), carboxyl groups, alkoxycarbonyl groups having 1-8 carbon atoms, alkoxy groups having 1-8 carbon atoms, acyloxy groups having 1-8 carbon atoms , A nitro group, a cyano group, and the like. Among these, halogen atoms such as fluorine atoms are preferable.

  Examples of the linking group include an oxygen atom (ether bond), a sulfur atom (thioether bond), a carbonyl group, a thiocarbonyl group, a —N (Z) — group, and a group in which a plurality of these are bonded. Z represents a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group (an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and an isopropyl group) and an alkenyl group (an alkenyl group having 2 to 6 carbon atoms such as an allyl group). An alkynyl group (such as an alkynyl group having 2 to 6 carbon atoms such as a propynyl group), a cycloalkyl group (such as a 3-8 membered cycloalkyl group such as a cyclohexyl group), an aryl group (such as a phenyl group), an aralkyl group (benzyl) Group, etc.).

Examples of the alkyl group in R ¹ , R ² , and R ³ include straight chain or branched chain having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl group, etc. -Like alkyl groups. Examples of the substituent that these alkyl groups may have include those exemplified as the substituent that the alkylene group in A may have.

Examples of the ring formed by combining at least two groups of A, R ¹ , R ² and R ³ together with adjacent one or two carbon atoms include a cyclopentane ring, a cyclohexane ring and a norbornane ring. About 16-membered alicyclic carbocyclic ring (cycloalkane ring, bridged carbocyclic ring, etc.); Non-aromatic heterocyclic ring having about 3 to 16 members including heteroatoms such as oxygen atom, sulfur atom and nitrogen atom It is done.

  As A, in particular, a linear or branched alkylene group having 1 to 12 carbon atoms (particularly 1 to 6) which may be substituted with a substituent such as a halogen atom such as a fluorine atom, or the fluorine atom 2 to 4 of a linear or branched alkylene group having 1 to 12 carbon atoms (especially 1 to 6 carbon atoms) which may be substituted with a substituent such as a halogen atom such as an oxygen atom or a sulfur atom A divalent group bonded through a linking group is preferred. In the present invention, A is a linear or branched alkylene group having 1 to 12 (particularly 1 to 6) carbon atoms, or a linear or branched chain having 1 to 12 (particularly 1 to 6) carbon atoms. Particularly advantageous effects are obtained when 2 to 4 of the alkylene groups are divalent groups bonded via a linking group such as an oxygen atom or a sulfur atom.

R ¹ , R ² , and R ³ are each a hydrogen atom; or a carbon number of 1 to 4 that may be substituted with a halogen atom such as a fluorine atom such as a methyl group, an ethyl group, a propyl group, or a trifluoromethyl group. The alkyl group is preferably a hydrogen atom.

  The halogen atom in X includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. In the present invention, a particularly advantageous effect is obtained when X is a fluorine atom.

  Typical examples of the unsaturated compound having a halosulfonyl group represented by the formula (1) include 1-fluorosulfonyl-2-propene, 1-fluorosulfonyl-3-butene, and 1-fluorosulfonyl-4. -Pentene, 1-fluorosulfonyl-5-hexene, 1-fluorosulfonyl-4-hexene, 1-fluorosulfonyl-3-hexene, 1-fluorosulfonyl-6-heptene, 1-fluorosulfonyl-7-octene, 1- Unsaturated compounds having a fluorosulfonyl group such as fluorosulfonyl-9-decene and 1- (2-fluorosulfonylethyloxy) -2-propene; unsaturated compounds having other halosulfonyl groups corresponding thereto .

  The oxidizing agent is not particularly limited as long as it is an oxidizing agent capable of epoxidizing a carbon-carbon double bond. For example, a peroxide, a peracid, or the like can be used. Examples of the peroxide include organic hydroperoxides such as alkyl or aralkyl hydroperoxide, and hydrogen peroxide. Examples of the peracid include organic peracids such as performic acid, peracetic acid, and m-chloroperbenzoic acid, and inorganic peracids. Among these, hydrogen peroxide is particularly preferable. The concentration of hydrogen peroxide is not particularly limited, but an aqueous solution of 3 to 70% by weight can be used. A peroxide and oxygen can be used in combination.

  The amount of the oxidizing agent (for example, hydrogen peroxide) may be 1 equivalent or more with respect to the unsaturated compound (substrate) having a halosulfonyl group represented by the formula (1). Or the product may be decomposed, and the yield of the target compound may be reduced. This is a phenomenon characteristic of the substrate. When the amount of the oxidizing agent used is less than 1 equivalent to the substrate, the conversion rate of the substrate is lowered and a satisfactory reaction yield cannot be obtained. Moreover, when the usage-amount of an oxidizing agent exceeds 2 equivalent with respect to a substrate, a decomposition by-product will produce | generate as mentioned above, and the yield of a target compound will fall remarkably easily. Therefore, the amount of the oxidizing agent used is preferably in the range of 1 to 2 equivalents, more preferably 1.2 to 1.5 equivalents, relative to the substrate. In the unsaturated compound represented by the formula (1), when an electron-withdrawing group such as a fluorine atom is present at the position adjacent to the halosulfonyl group (sulfohalide group), the substrate can be used even if an excessive amount of oxidizing agent is used. And decomposition of the product is suppressed, and a decrease in the yield of the target compound is suppressed.

When a peroxide such as hydrogen peroxide or organic hydroperoxide is used as the oxidizing agent, a heteropolyacid or a salt thereof is preferably used as the catalyst. The heteropolyacid or salt thereof used in the present invention is not particularly limited as long as it is a heteropolyacid or salt thereof used as an oxidation catalyst, and is selected from P or Si elements and V, Mo and W as constituent elements. In addition, a heteropolyacid containing at least one element or a salt thereof is preferably used. A preferred composition of the heteropolyacid anion can be represented by X ¹ M ₁₂ O ₄₀ . In this composition formula, X ¹ is an element such as Si or P, and M is an element such as Mo, W, or V. Examples of the heteropolyacid anion having such a composition include anions of phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, and phosphovanadomolybdic acid. Particularly preferred heteropolyacid anions are phosphomolybdic acid and phosphotungstic acid anions. Further, the counter cation in the salt of the heteropolyacid is not particularly limited, and examples thereof include monovalent or divalent metal ions and / or quaternary ammonium ions. Specifically, ions of alkali metals such as Li, Na, K, Rb, Cs and Fr; ions of alkaline earth metals such as Be, Mg, Ca, Sr, Ba and Ra; tetramethylammonium, tetraethylammonium, Tetra n-propylammonium, tetraisopropylammonium, tetran-butylammonium, tetran-hexylammonium, tetracyclohexylammonium, trioctylmethylammonium, tetradecylammonium, cetylpyridinium, ethylpicorium, alkylquinolium, benzylmethylstearylammonium And quaternary ammonium ions. In particular, when a quaternary ammonium ion of a heteropoly acid is used, it functions as a correlation transfer, and thus is suitable when the reaction system is a two-layer system of a water-organic solvent. In addition, when preparing the salt of heteropolyacid in a reaction system, what is necessary is just to add the base or salt which has the said metal ion and ammonium ion in a system.

  When preparing a heteropolyacid or a salt thereof in the reaction system, two or more different oxygen acids or salts thereof may be added to the reaction system. For example, oxygenate ions of elements such as P and Si ( For example, two or more oxygen acids selected from a combination of phosphoric acid, silicic acid, etc.) and oxygen acid ions of elements such as V, Mo, W (eg, vanadic acid, molybdic acid, tungstic acid, etc.) What is necessary is just to add the salt. Bull. Chem. Soc. Jpn. , 70, No. 4, (1997), 905-915, the yield may be improved when aminoalkyl phosphoric acid such as aminomethyl phosphoric acid is used as phosphoric acid.

  Although the usage-amount of heteropoly acid or its salt is not specifically limited, For example, 0.00001-0.5 mol with respect to 1 mol of unsaturated compounds which have a halosulfonyl group represented by Formula (1) used as a raw material, Preferably, it is 0.0001-0.1 mol, More preferably, it is 0.001-0.05 mol.

（式中、ＭはＶ、Ｍｏ、Ｗなどの金属原子を示す）
で表される構造を有する高活性なヘテロポリ酸又はその塩の意味にも使用され、前記高活性なヘテロポリ酸は、例えば、Ｊ． Ｏｒｇ． Ｃｈｅｍ． ５３， ３５８７−３５９３（１９８８）、Ｊ． Ｍｏｌ． Ｃａｔａｌ． ３２， １０７−１１０（１９８５）、Ｊ． Ｏｒｇ． Ｃｈｅｍ． ５１， １５９９−１６０２（１９８６）に記載されている方法により調製できる。Ｊ． Ｏｒｇ． Ｃｈｅｍ． ５３， ３５８７−３５９３（１９８８）に記載の方法によれば、リンタングステン酸の３１重量％過酸化水素水溶液に、セチルピリジニウムアンモニウムクロリドの水溶液を添加し、析出した触媒を濾取することで調製できる。これらの高活性なヘテロポリ酸は、予め調製して使用してもよく、反応系中で調製して使用してもよい。 In the present specification, the heteropolyacid or a salt thereof is represented by the following formula (3) in which the polyhedral structure of the polyacid is broken.

(In the formula, M represents a metal atom such as V, Mo, or W)
Is also used to mean a highly active heteropolyacid having a structure represented by the formula (I) or a salt thereof. Org. Chem. 53, 3587-3593 (1988), J. Am. Mol. Catal. 32, 107-110 (1985), J. MoI. Org. Chem. 51, 1599-1602 (1986). J. et al. Org. Chem. 53, 3587-3593 (1988), it can be prepared by adding an aqueous solution of cetylpyridinium ammonium chloride to a 31 wt% aqueous hydrogen peroxide solution of phosphotungstic acid, and collecting the precipitated catalyst by filtration. . These highly active heteropolyacids may be prepared and used in advance, or may be prepared and used in a reaction system.

  The oxidation reaction of the unsaturated compound having a halosulfonyl group represented by formula (1) with an oxidizing agent is performed in the presence or absence of a solvent. Examples of the solvent include organic acids such as acetic acid, propionic acid, and trifluoroacetic acid; alcohols such as methanol, ethanol, propanol, isopropyl alcohol, t-butyl alcohol, amyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. (Monohydric or polyhydric alcohol); ketones such as acetone and methyl ethyl ketone; chain or cyclic ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran; aliphatic hydrocarbons such as hexane and octane; cyclopentane and cyclohexane , Alicyclic hydrocarbons such as methylcyclohexane; nitro compounds such as nitromethane and nitroethane; phosphorus compounds such as phosphate esters; chloroform, dichloromethane, ethylene dichloride, etc. Halogenated hydrocarbons; water; benzene, toluene, xylene and like aromatic hydrocarbons, and the like, and mixed solvents thereof. Although the usage-amount of a solvent is not specifically limited, For example, 0.1-100 weight times with respect to the unsaturated compound represented by Formula (1), Preferably it is 1-50 weight times, More preferably, it is 2-20 weight Is double.

  The reaction temperature can be appropriately selected according to the type of unsaturated compound represented by formula (1) used as a raw material, the type of oxidizing agent, the type of catalyst, and the like, and is, for example, 0 to 200 ° C, preferably 20 to 150 ° C. More preferably, it is about 40-100 degreeC. The reaction may be carried out at normal pressure, or under reduced pressure or under pressure. The reaction atmosphere is not particularly limited as long as the reaction is not inhibited, and may be any of an oxygen atmosphere, an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. Further, the reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  In the reaction mixture thus obtained, a part of the excessively used oxidizing agent remains. An important feature of the present invention is that the oxidizing agent remaining in the reaction mixture is inactivated by reduction treatment under conditions of pH 9 or lower (for example, pH 3 to 9). When the reduction treatment is performed under liquid conditions exceeding pH 9, the produced epoxy compound having a halosulfonyl group represented by the formula (2) is rapidly decomposed, and the target compound cannot be obtained with a high yield. The pH during the reduction treatment is preferably 8 or less (for example, pH 3 to 8), more preferably 7.5 or less (for example, pH 4 to 7.5).

The reduction treatment may be performed in a single layer system or in a two-layer system of an organic layer and an aqueous layer. The reducing agent used for the reduction treatment is preferably a water-soluble compound, and a 5% by weight aqueous solution is acidic (for example, pH 3 or more and lower than 7), particularly weakly acidic (for example, pH 4 to 6.5). Is preferred. Examples of such a reducing agent include, but are not limited to, sodium bisulfite (NaHSO ₃ ) and sodium thiosulfate (Na ₂ S ₂ O ₃ ).

  The amount of the reducing agent used for the reduction treatment is not particularly limited as long as the remaining oxidizing agent can be sufficiently reduced, but is usually about 1 to 10 equivalents relative to the remaining oxidizing agent. The temperature during the reduction treatment is, for example, 0 to 100 ° C., preferably about 0 to 50 ° C.

  After the reduction treatment, the target compound can be separated and purified by separation / purification means such as liquid separation, filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, or a combination thereof. For example, when the reduction treatment is performed in a two-layer system, the epoxy compound having the target halosulfonyl group can be obtained by separating the solution, concentrating the organic layer, and further purifying as necessary. In addition, when the reduction treatment is performed in a single layer system, after performing an extraction operation using water and an organic solvent, the organic layer is concentrated and further purified as necessary to have a target halosulfonyl group. An epoxy compound can be obtained.

  When a quaternary ammonium salt of a heteropolyacid is used as a catalyst during the oxidation reaction, this shifts to the organic layer side, so that the quaternary ammonium salt of the heteropolyacid and the target compound are simply separated or extracted. And difficult to separate. If the quaternary ammonium salt of the heteropoly acid is mixed in the target compound, not only will the purity and quality of the target compound be reduced, but also bumping or foaming will occur during concentration in the subsequent process, The purification operation becomes complicated. As an effective removal method of the quaternary ammonium salt of the heteropolyacid, a removal method by a poor solvent crystallization with an alcohol solvent and / or a treatment with an adsorbent such as silica gel can be mentioned. More specifically, for example, a mixture of a quaternary ammonium salt of a heteropoly acid and an epoxy compound having a target halosulfonyl group (for example, a concentrate of the organic layer after the reduction treatment) is mixed with an alcohol solvent such as methanol. After subjecting to the crystallization treatment used and filtering off the precipitated quaternary ammonium salt of the heteropolyacid, the filtrate was subjected to solvent exchange with a hydrocarbon solvent such as toluene, if necessary, and then adsorbed onto silica gel or the like. By treating with an agent, a quaternary ammonium salt of a heteropolyacid can be removed.

  The epoxy compound having a halosulfonyl group thus obtained can be used as an intermediate raw material for fine chemical products such as pharmaceuticals and agricultural chemicals, an intermediate raw material for obtaining functional polymer monomers, and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. The phosphotungstic acid cetylpyridinium salt used in Examples and Comparative Examples is Y.C. Ishii et al. Org. Chem. 53, 3587-3593 (1988), and separately synthesized from cetylpyridinium chloride (manufactured by Wako Pure Chemical Industries) and 12-tungstophosphoric acid (phosphotungstic acid; manufactured by Kanto Chemical Co., Inc.). The amount of hydrogen peroxide in the aqueous hydrogen peroxide solution was quantified by iodine coulometric titration. The pH value was measured using a standard pH test paper (measurement range: pH = 1 to 14) manufactured by TOYO ROSHI.

Production Example 1
An epoxy compound having a fluorosulfonyl group was synthesized according to the following reaction process formula.

3.4 g (1.6 mmol) of cetylpyridinium salt of phosphotungstic acid and 16.9 g (162 mmol) of 1-fluorosulfonyl-5-hexene (= 5-hexene-1-sulfonyl fluoride) represented by formula (4) Was dissolved in 227 g of chloroform, and 21.3 g (194 mmol of hydrogen peroxide) of a 31 wt% aqueous hydrogen peroxide solution was added thereto and reacted for 4 hours under reflux. After completion of the reaction, quantification was carried out by gas chromatography (internal standard method). As a result, the conversion rate of the unsaturated compound represented by the formula (4) was 99% or more, which is represented by the corresponding formula (5) 1, The yield of 2-epoxy-6-fluorosulfonylhexane was 93.4%. The reaction was allowed to stand at room temperature for 24 hours, but no product decomposition was observed.
In the following Examples 1-2 and Comparative Example 1, the chloroform solution of the epoxy compound represented by the formula (5) obtained under the above reaction conditions was adjusted so that the concentration of the epoxy compound was 10% by weight. Used.

Example 1
While maintaining a two-layer mixed solution of 200 ml of a chloroform solution containing 10 wt% of the epoxy compound represented by the formula (5) and 10 ml of an aqueous hydrogen peroxide solution (hydrogen peroxide concentration: 3 wt%) at 5 ° C. or less, 5 wt% 100 ml of an aqueous sodium hydrogen sulfite solution (pH = 6) was added with thorough stirring. After completion of the addition, the mixture was stirred at room temperature for 1 hour. During this time, the pH of the system was 6. When the chloroform layer was analyzed by gas chromatography, the epoxy compound represented by the formula (5) was quantitatively analyzed, and it was confirmed that no decomposition occurred. Even when stirring was continued for 1 hour, the epoxy compound was not decomposed.

Example 2
While maintaining a two-layer mixed solution of 200 ml of a chloroform solution containing 10 wt% of the epoxy compound represented by the formula (5) and 10 ml of an aqueous hydrogen peroxide solution (hydrogen peroxide concentration: 3 wt%) at 5 ° C. or less, 5 wt% 100 ml of an aqueous sodium thiosulfate solution (pH = 6) was added with thorough stirring. After completion of the addition, the mixture was stirred at room temperature for 1 hour. During this time, the pH of the system was 6. When the chloroform layer was analyzed by gas chromatography, the epoxy compound represented by the formula (5) was quantitatively analyzed, and it was confirmed that no decomposition occurred. Even when stirring was continued for 1 hour, the epoxy compound was not decomposed.

Comparative Example 1
While maintaining a two-layer mixed solution of 200 ml of a chloroform solution containing 10 wt% of the epoxy compound represented by the formula (5) and 10 ml of an aqueous hydrogen peroxide solution (hydrogen peroxide concentration: 3 wt%) at 5 ° C. or less, 5 wt% 100 ml of an aqueous sodium sulfite solution (pH = 10) was added with thorough stirring. After completion of the addition, the mixture was stirred at room temperature for 1 hour. During this time, the pH of the system was 10. When the chloroform layer was analyzed by gas chromatography, it was confirmed that 23% of the epoxy compound represented by the formula (5) was decomposed. When stirring was further continued for 1 hour, it was confirmed that 50% of the epoxy compound represented by the formula (5) was decomposed. FT-IR and FAB-MS measurements confirmed that the decomposition of the epoxy compound represented by formula (5) was SO ₃ Na salt in the aqueous layer.

Production Example 2
An epoxy compound having a fluorosulfonyl group was synthesized according to the following reaction process formula.

6.8 g (3.2 mmol) of cetylpyridinium salt of phosphotungstic acid and 22.4 g (162 mmol) of 1-fluorosulfonyl-3-butene (= 3-butene-1-sulfonyl fluoride) represented by formula (6) Was dissolved in 227 g of chloroform, and 21.3 g (194 mmol of hydrogen peroxide) of 31 wt% hydrogen peroxide aqueous solution was added thereto and reacted at 40 ° C. for 6 hours. After completion of the reaction, quantification was performed by gas chromatography (internal standard method). As a result, the conversion of the unsaturated compound represented by the formula (6) was 97%, and 1,2 represented by the corresponding formula (7). The yield of -epoxy-4-fluorosulfonylbutane was 93.4%. The reaction was allowed to stand at room temperature for 24 hours, but no product decomposition was observed.
In the following Examples 3 to 4 and Comparative Example 2, the chloroform solution of the epoxy compound represented by the formula (7) obtained under the above reaction conditions was adjusted so that the concentration of the epoxy compound was 10% by weight. Used.

Example 3
While maintaining a two-layer mixture of 200 ml of a chloroform solution of 10 wt% of the epoxy compound represented by the formula (7) and 10 ml of an aqueous hydrogen peroxide solution (hydrogen peroxide concentration: 3 wt%) at 5 ° C. or less, 5 wt% 100 ml of an aqueous sodium hydrogen sulfite solution (pH = 6) was added with thorough stirring. After completion of the addition, the mixture was stirred at room temperature for 1 hour. During this time, the pH of the system was 6. When the chloroform layer was analyzed by gas chromatography, the epoxy compound represented by the formula (7) was quantitatively analyzed, and it was confirmed that no decomposition occurred. Even when stirring was continued for 1 hour, the epoxy compound was not decomposed.
Chloroform was distilled off from the chloroform layer after the reduction treatment under reduced pressure to obtain a crude product of the epoxy compound represented by the formula (7). ICP elemental analysis of tungsten confirmed that 17.2% by weight of cetylpyridinium phosphotungstate salt remained in the crude product. When 125 g of methanol was added to 28 g of the above crude product (containing 4.8 g of cetylpyridinium phosphotungstic acid salt) at 5 ° C. or lower while stirring, a white solid was precipitated. The mixture was stirred at 5 ° C. or lower for 1 hour and then filtered. ICP elemental analysis of the filtrate confirmed that 0.03 g of cetylpyridinium phosphotungstic acid salt remained in the filtrate. Thereafter, methanol was distilled off under reduced pressure, 50 g of toluene and 7 g of silica gel (Wakogel C-100, manufactured by Wako Pure Chemical Industries, Ltd.) were added to the residue after the distillation, and the mixture was stirred for 1 hour, and the silica gel was filtered. When the filtrate was analyzed, the cetylpyridinium phosphotungstate content in the filtrate was 0.01 g or less.

Example 4
While maintaining a two-layer mixture of 200 ml of a chloroform solution of 10 wt% of the epoxy compound represented by the formula (7) and 10 ml of an aqueous hydrogen peroxide solution (hydrogen peroxide concentration: 3 wt%) at 5 ° C. or less, 5 wt% 100 ml of an aqueous sodium thiosulfate solution (pH = 6) was added with thorough stirring. After completion of the addition, the mixture was stirred at room temperature for 1 hour. During this time, the pH of the system was 6. When the chloroform layer was analyzed by gas chromatography, the epoxy compound represented by the formula (7) was quantitatively analyzed, and it was confirmed that no decomposition occurred. Even when stirring was continued for 1 hour, the epoxy compound was not decomposed.

Comparative Example 2
While maintaining a two-layer mixture of 200 ml of a chloroform solution of 10 wt% of the epoxy compound represented by the formula (7) and 10 ml of an aqueous hydrogen peroxide solution (hydrogen peroxide concentration: 3 wt%) at 5 ° C. or less, 5 wt% 100 ml of an aqueous sodium sulfite solution (pH = 10) was added with thorough stirring. After completion of the addition, the mixture was stirred at room temperature for 1 hour. During this time, the pH of the system was 10. When the chloroform layer was analyzed by gas chromatography, it was confirmed that 48% of the epoxy compound represented by the formula (7) was decomposed. When stirring was further continued for 1 hour, it was confirmed that 86% of the epoxy compound represented by the formula (7) was decomposed. FT-IR and FAB-MS measurements confirmed that the decomposition of the epoxy compound represented by formula (7) was SO ₃ Na salt in the aqueous layer.

Claims (3)

Following formula (1)

(In the formula, A represents a divalent group in which an alkylene group which may have a substituent or a plurality of alkylene groups which may have a substituent are bonded via a linking group, respectively. R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or an optionally substituted alkyl group, and at least two groups of A, R ¹ , R ² and R ³ are And may be bonded to each other to form a ring with adjacent 1 or 2 carbon atoms, X represents a halogen atom)
An unsaturated compound having a halosulfonyl group represented by formula (2) is oxidized with an oxidizing agent, and the following formula (2):

(In the formula, A, R ¹ , R ² , R ³ and X are the same as above)
A process for producing an epoxy compound having a halosulfonyl group represented by the formula: wherein the unsaturated compound having a halosulfonyl group is oxidized with an oxidizing agent, and then the remaining oxidizing agent is reduced under a condition of pH 9 or less. A process for producing an epoxy compound having a halosulfonyl group containing   The method for producing an epoxy compound having a halosulfonyl group according to claim 1, wherein the reducing agent used for the reduction treatment is a reducing agent that is water-soluble and has a 5% by weight aqueous solution exhibiting acidity.   The method for producing an epoxy compound having a halosulfonyl group according to claim 1, wherein X in the formula (1) is a fluorine atom.