JPH0328429B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for epoxidizing fluoroolefins. More specifically, using hypochlorite as an oxidizing agent, the general formula []
The present invention relates to a method for epoxidizing a fluoroolefin represented by [In general formula [], X ₁ , X ₂ , X ₃ and X ₄
is (a) a fluorine atom, (b) a perfluoroalkyl group having 20 or less carbon atoms, and (c) -CF ₂ Y (Y contains or contains at least one of a halogen atom and an ether bond). A hydrocarbon group having 20 or less carbon atoms (with the exception that Y is not a perfluoroalkyl group). However, at least one of the substituents of X ₁ , X ₂ , X ₃ and X ₄ has a -CF ₂ - group directly bonded to the carbon-carbon double bond shown in the general formula [], The number of carbon atoms contained in the fluoroolefin represented by the general formula [] is between 4 and 25.
Moreover, X ₁ , X ₂ , X ₃ and X ₄ may be linked to each other to form a cyclic compound. ] The fluoroolefin epoxide is highly reactive and is important as an intermediate for the synthesis of various fluorine-containing compounds, and is itself an important substance that can be used as a raw material for polymeric compounds. In general, fluoroolefin epoxides can be produced by the epoxidation reaction of fluoroolefins, but fluoroolefins have very different chemical properties from hydrocarbon olefins such as propylene and chlorinated hydrocarbon olefins such as allyl chloride. Therefore, it is difficult to epoxidize fluoroolefin in the same manner as propylene or allyl chloride. For example, both propylene and allyl chloride are epoxidized by the chlorohydrin method, in which the ring is closed with an alkali via chlorohydrin. On the other hand, when attempting to epoxidize fluoroolefin by the chlorohydrin method, chlorohydrin is unstable and decomposes into carbonyl compounds, so it cannot be converted into fluoroolefin epoxide. Therefore, various methods have been proposed for epoxidizing fluoroolefins that are different from those for hydrocarbon olefins and chlorinated hydrocarbon olefins, but none of them are industrially advantageous. This cannot be said to be a method for producing fluoroolefin epoxide. Conventionally, a method of oxidizing fluoroolefin to fluoroolefin epoxide in an alkaline hydrogen peroxide medium as described in U.S. Pat. A method of oxidizing fluoroolefin to fluoroolefin epoxide with oxygen in the presence of is known as a typical method for producing fluoroolefin epoxide. However, in any of these methods, it is difficult to control the reaction, it is difficult to suppress the decomposition of the produced fluoroolefin epoxide, or a large amount of by-products are produced, making it difficult to obtain the fluoroolefin epoxide in high yield. I can't do anything. Furthermore, in these methods, when the fluoroolefin conversion rate is increased, the fluoroolefin epoxide selectivity decreases, so in order to use the fluoroolefin effectively, the reaction must be stopped at a low fluoroolefin conversion rate, and the unreacted fluoroolefin must be removed. It is necessary to separate and recover the fluoroolefin epoxide and reuse it. However,
In general, the boiling points of fluoroolefin and fluoroolefin epoxide are very close to each other.
Since it is difficult to separate the two by distillation, a special separation operation is required for the separation. Examples include a method in which fluoroolefin and bromine are reacted to form a dibromine with a high boiling point and separated from fluoroolefin epoxide, or the extraction method described in US Pat. No. 3,326,780, US Pat. No. 4,134,796, etc. Distillation separation methods and the like have been proposed, but all of them are complicated separation methods and significantly increase the production cost of fluoroolefin epoxide. On the other hand, as an oxidation method using hypochlorite,
It is known that fluoroolefin epoxide is produced from fluoroolefin in a system in which a polar solvent such as acetonitrile or diglyme is added to an aqueous hypochlorite solution [IZV.AKAD.NAUK.SSSR,
SER.KHIM., 79 , (11) 2509], but when the present inventors investigated this method, the selectivity of fluoroolefin epoxide was low and it was not possible to obtain a high yield. This is because the reaction system is a homogeneous mixture of a polar solvent and an alkaline hypochlorite aqueous solution, so the produced fluoroolefin epoxide easily reacts with water and decomposes under alkaline conditions. Seem. Furthermore, this method requires a troublesome step of recovering the polar solvent from the reaction system after the reaction. From the above points, this reaction method also cannot be a practical technology for producing fluoroolefin epoxide. The inventors of the present invention have conducted intensive studies to overcome the drawbacks of conventional methods and to find a method for producing fluoroolefin epoxide more easily than fluoroolefin and with a higher yield. in the presence of at least one catalyst selected from quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, and lipophilic complexing agents for cations in hypochlorite, The present inventors have discovered that fluoroolefin epoxide can be obtained in higher yield than fluoroolefin when the reaction is carried out in a two-phase system consisting of an aqueous phase and an organic phase, and the present invention has been completed. That is, the present invention uses hypochlorite dissolved or suspended in an aqueous phase as an oxidizing agent, and in the presence or absence of an inorganic base, the general formula [] [In general formula [], X ₁ , X ₂ , X ₃ and X ₄
is (a) a fluorine atom, (b) a perfluoroalkyl group having 20 or less carbon atoms, and (c) -CF ₂ Y (Y contains or contains at least one of a halogen atom and an ether bond). A hydrocarbon group having 20 or less carbon atoms (with the exception that Y is not a perfluoroalkyl group). However, at least one of the substituents of X ₁ , X ₂ , X ₃ and X ₄ has a -CF ₂ - group directly bonded to the carbon-carbon double bond shown in the general formula [], The number of carbon atoms contained in the fluoroolefin represented by the general formula [] is between 4 and 25.
Moreover, X ₁ , X ₂ , X ₃ and X ₄ may be linked to each other to form a cyclic compound. ] In epoxidizing the fluoroolefin represented by (a') a quaternary ammonium salt, (b')
in the presence of at least one catalyst selected from a quaternary phosphonium salt, (c') a quaternary arsonium salt, or (d') a lipophilic complexing agent for the cation in the hypochlorite. The present invention provides a novel method for epoxidizing fluoroolefins, which is characterized in that the reaction is carried out in a two-phase system of organic phases. (Hereafter,
The fluoroolefin represented by the general formula [] is simply referred to as fluoroolefin, and the fluoroolefin epoxide derived from the fluoroolefin represented by the general formula [] is simply referred to as fluoroolefin epoxide. ) In the two-phase system reaction of the present invention, substantially all of the fluoroolefin and produced fluoroolefin epoxide are contained in the organic phase. According to the method of the present invention, fluoroolefin epoxide can be obtained with high selectivity even if the conversion rate of fluoroolefin is increased. This is thought to be because the presence of fluoroolefin epoxide makes it difficult for fluoroolefin epoxide to decompose when it comes into contact with an alkaline aqueous solution. Therefore, according to the method of the present invention, by increasing the fluoroolefin conversion rate, it is also possible to omit the complicated process of separating fluoroolefin and fluoroolefin epoxide and the process of recycling fluoroolefin. After the reaction, the organic phase and the aqueous phase are separated, and the fluoroolefin epoxide is easily isolated from the organic phase by a separation operation such as distillation. In addition, in the remaining organic phase from which the fluoroolefin epoxide has been removed,
It contains a catalyst, and the remaining organic phase can be recycled and reused in the reaction as it is, making it very easy to recover the solvent and catalyst. As described above, in the method of the present invention, fluoroolefin epoxide can be obtained in high yield, and the manufacturing process is extremely simple. Therefore, when carrying out the method of the present invention, the construction and operation costs of the reactor are reduced, and a very economical process for producing fluoroolefin epoxide is made possible. The present invention will be explained in more detail below. In the method of the present invention, the general formula [] [In general formula [], X ₁ , X ₂ , X ₃ and X ₄
is (a) a fluorine atom, (b) a perfluoroalkyl group having 20 or less carbon atoms, and (c) -CF ₂ Y (Y contains or contains at least one of a halogen atom and an ether bond). A hydrocarbon group having 20 or less carbon atoms (with the exception that Y is not a perfluoroalkyl group). However, at least one of the substituents of X ₁ , X ₂ , X ₃ and X ₄ has a -CF ₂ - group directly bonded to the carbon-carbon double bond shown in the general formula [], The number of carbon atoms contained in the fluoroolefin represented by the general formula [] is between 4 and 25.
Moreover, X ₁ , X ₂ , X ₃ and X ₄ may be linked to each other to form a cyclic compound. ] A fluoroolefin represented by the following is used. The substituted or unsubstituted hydrocarbon group Y contained in the general formula [] is one that can stably exist under alkaline conditions and in the presence of hypochlorite in the method of the present invention, or under the reaction conditions of the present invention. If it does not interfere with the reaction of the present invention even if modified with
There are no further restrictions and various substituted or unsubstituted hydrocarbon groups may be used, but those of practical value include carbon atoms containing or not containing at least one of a halogen atom and an ether bond. Examples include hydrocarbon groups having a number of 20 or less. However, Y does not include a perfluoroalkyl group. Further, there is no particular restriction on the length of the perfluoroalkyl group contained in the fluoroolefin of the general formula [], but those having 20 or less carbon atoms are exemplified as substantially useful ones. Examples of fluoroolefins used in the method of the present invention include, for example, perfluoro-2-butene, perfluoro-1-butene, perfluoro-
2-pentene, perfluoro-1-hexene, perfluoro-2-hexene, perfluoroheptene-1, perfluorononene-1, perfluorododecene-1, perfluorooctadecene-1,
Perfluoro-4-methylpentene-2, perfluoro-4-methyl-pentene-3, perfluoro-4,6-dimethylheptene-4, perfluoro-2-methyl-3-isopropylpentene-
3. Perfluoroolefins such as perfluorocyclopentene and perfluorocyclohexene;
4,5-dichloroperfluoro-1-pentene,
5,6-dichloroperfluoro-1-hexene,
6,7-dichloroperfluoro-1-heptene,
9,10-dichloroperfluoro-1-decene,
Chlorofluoroolefins such as 4,6,7-trichloroperfluoro-1-heptene, bromofluoroolefins such as 4-bromoperfluorobutene-1, 5,6-dibromoperfluoro-1-hexene, 4-iodoperfluoro iodofluoroolefins such as butene-1, perfluoro-1,
Perfluorodienes such as 5-hexadiene and perfluoro-1,7-octadiene, ω-hydroperfluoroolefins such as ω-hydroperfluorohexene-1 and ω-hydroperfluorooctene-1, 1,1,2, 3,3-pentafluoro-
Polyfluoroolefins such as 1-butene, polyfluorodienes having both perfluoroallyl groups and vinyl groups, perfluoro-n-propoxy groups, perfluoro-i-propoxy groups, or perfluoropropylene oxide oligomers. Examples include fluoroolefins containing perfluoroalkoxy groups such as fluoroalkoxy groups, and fluoroolefins containing perfluorovinyloxy groups such as 4-perfluorovinyloxyperfluoro-1-butene. Examples of the hypochlorite used in the present invention include alkali metals such as lithium hypochlorite, sodium hypochlorite, potassium hypochlorite, rubidium hypochlorite, and cesium hypochlorite. salts, or alkaline earth metal salts such as magnesium hypochlorite, calcium hypochlorite, strontium hypochlorite, and barium hypochlorite. Among them, especially sodium hypochlorite and calcium hypochlorite, which are industrially mass-produced for use as bleaches, disinfectants, etc., and can be obtained at low cost. Suitable as chlorate. As the hypochlorite, a commercially available product may be used as is, one prepared from an inorganic base and chlorine gas, or one prepared by non-diaphragm electrolysis of an inorganic chloride may be used. In the present invention, the metal hypochlorite salt is mainly used dissolved in the aqueous phase, but there is no particular restriction on its concentration. Usually, the effective chlorine concentration is preferably in the range of 0.5% to 25%, particularly preferably in the range of 1% to 20%. If the available chlorine concentration is too low, it is necessary to handle a large amount of aqueous phase, which is economically disadvantageous. Furthermore, if the available chlorine concentration is too high, hypochlorite becomes unstable and difficult to handle. The ratio of the hypochlorite metal salt and fluoroolefin can be selected arbitrarily, but in order to obtain substantial reaction results, the ratio is usually from 0.5 gram equivalent of hypochlorite ion to 1 mole of fluoroolefin. selected from a range of 30 gram equivalents, preferably
It is selected from the range of 0.8 gram equivalent to 10 gram equivalent, particularly preferably selected from the range of 1 gram equivalent to 5 gram equivalent. Although the method of the present invention can be carried out either in the presence or absence of an inorganic base, better reaction results are often obtained in the presence of an inorganic base. The first effect of the inorganic base is that a high fluoroolefin epoxide selectivity can be obtained even when the fluoroolefin conversion rate is increased.
Therefore, it is possible to increase the fluoroolefin conversion rate and reduce the amount of residual fluoroolefin without significantly impairing the fluoroolefin epoxide selectivity, so high purity can be obtained without the complicated separation process of fluoroolefin and fluoroolefin epoxide. of fluoroolefin epoxide can be obtained in high yield. The second effect of the inorganic base is that it allows good results to be obtained even at a low ratio of hypochlorite to fluoroolefin. In the absence of an inorganic base or in the presence of a very small amount of inorganic base, lowering the ratio of hypochlorite to fluoroolefin will reduce the fluoroolefin epoxide selectivity, and the remaining available chlorine concentration will decrease during the reaction. Since the fluoroolefin conversion rate may reach a plateau due to a decrease in the fluoroolefin conversion rate, it has been necessary to carry out the reaction in the presence of a large excess of hypochlorite in order to obtain good results. However, when carrying out the method of the present invention in the presence of a specific amount or more of an inorganic base, the amount of hypochlorite used may be small, reducing the cost of hypochlorite and making the reactor more compact. This makes it possible to reduce wastewater treatment costs. Examples of inorganic bases used in the method of the present invention include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide;
Examples include alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide, and barium hydroxide. These inorganic bases may be completely dissolved in the aqueous phase, or a portion may not be dissolved in the aqueous phase and may exist in the solid phase. Among various inorganic bases, sodium hydroxide is particularly suitable for the method of the present invention in terms of price, solubility in water, ease of handling, etc. Although the amount of inorganic base used in the method of the present invention can be set arbitrarily, in order to obtain a substantial effect,
0.1 gram equivalent or more is used per mole of fluoroolefin used in the reaction. The entire amount of the inorganic base may be present in the reaction system from the beginning of the reaction, or in some cases, it may be added as appropriate during the reaction. The catalyst used in the method of the present invention is
grade ammonium salt, quaternary phosphonium salt, quaternary
class arsonium salts, and lipophilic complexing agents for the cations in hypochlorous acid. It is desirable that these catalysts have an affinity for the organic phase. Examples of the quaternary ammonium salt used in the method of the present invention include various quaternary ammonium salts represented by the general formula []. However, in [Formula], R ₁ , R ₂ , R ₃ and R ₄ are the same or different and are each substituted with a functional group that is inert under the reaction conditions, or are unsubstituted hydrocarbons. represents a group. The type and length of this hydrocarbon group are appropriately selected depending on the solvent used, the required reaction rate, etc. Types of hydrocarbon groups include, for example, alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups,
Aryl groups, aralkyl groups, alkenylaryl groups, etc. are used, particularly preferably alkyl groups,
Aryl groups, aralkyl groups, etc. are used.
In addition, the length of the hydrocarbon group is usually selected from the range of 4 to 100 carbons per quaternary ammonium ion, as the total number of carbons contained in R ₁ , R ₂ , R ₃ and R ₄ . , preferably selected from the range of 8 to 70 pieces, particularly preferably selected from the range of 10 to 50 pieces. The inert functional group that can be used to replace the above hydrocarbon group is limited depending on the reaction conditions, but halogen, acyl group, carboxyl group, ester group, nitrile group, alkoxyl group, etc. are usually used. In addition, in the formula [], R ₁ , R ₂ or R ₁ , R ₂ , R ₃ may be linked to each other to form a nitrogen-containing heterocycle, or R ₁ , R ₂ , R ₃ or R ₄
may be part of the polymer compound. Examples of quaternary ammonium ions include, for example, tetraethylammonium ion, tetra-
n-propylammonium ion, tetra-n-
Butylammonium ion, tri-n-octylmethylammonium ion, cetyltrimethylammonium ion, benzyltrimethylammonium ion, benzyltriethylammonium ion, cetylbenzylmethylammonium ion, cetylpyridinium ion, n-dodecylpyridinium ion, phenyltrimethylammonium ion, Examples include phenyltriethylammonium ion, N-benzylpicolinium ion, pentamethonium ion, hexamethonium ion, and the like. [] The anion X in the formula is not particularly limited and various anions can be used, but usually halogen ions, various mineral acid ions other than halogen ions, organic acid ions, hydroxide ions, etc. are used. . Examples of the anion X include chloride ion, bromide ion, iodide ion, fluoride ion, hydrogen sulfate ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, hydroxide ion, acetate ion, and benzoic acid. ion, benzenesulfonate ion, p-toluenesulfonate ion, etc., but particularly preferred are chloride ion, hydrogen sulfate ion, and hydroxide ion. Examples of the quaternary phosphonium salt used in the method of the present invention include various quaternary phosphonium salts represented by the general formula []. However, in the [formula], R ₅ , R ₆ , R ₇ and R ₈ are the same or different and are each substituted with a functional group that is inert under the reaction conditions, or are unsubstituted hydrocarbons. represents a group. The type and length of this hydrocarbon group are appropriately selected depending on the solvent used, the required reaction rate, etc. Types of hydrocarbon groups include, for example, alkyl groups, alkenyl groups, cycloalkyl groups, cycloalkenyl groups,
Aryl groups, aralkyl groups, alkenylaryl groups, etc. are used, particularly preferably alkyl groups,
Aryl groups, aralkyl groups, etc. are used.
In addition, the length of the hydrocarbon group is usually selected from the range of 4 to 100 per quaternary phosphonium ion as the total number of carbons contained in R ₅ , R ₆ , R ₇ and R ₈ , The number is preferably selected from the range of 8 to 70, particularly preferably selected from the range of 10 to 50. The inert functional groups that can be used to replace the above hydrocarbon groups are limited depending on the reaction conditions, but
Usually, halogen, acyl group, carboxyl group, ester group, nitrile group, alkoxyl group, etc. are used. In addition, in the formula [], R ₅ , R ₆ or R ₅ ,
R ₆ and R ₇ may be linked to each other to form a heterocycle, and R ₅ , R ₆ , R ₇ or R ₈ may be part of a polymer compound. Examples of quaternary phosphonium ions include, for example, tetraethylphosphonium ion, tetra-
n-Butylphosphonium ion, tri-n-octylethylphosphonium ion, cetyltriethylphosphonium ion, cetyltri-n-butylphosphonium ion, n-butyltriphenylphosphonium ion, n-amyltriphenylphosphonium ion, n-hexyltriphenylphosphonium ion, n-heptyltriphenylphosphonium ion, methyltriphenylphosphonium ion, benzyltriphenylphosphonium ion, tetraphenylphosphonium ion, and the like. The anion Y in the formula [] is not particularly limited and various anions can be used, but usually halogen ions, various mineral acid ions other than halogen ions, organic acid ions, etc. are used. Examples of the anion Y include chloride ion, bromide ion, iodide ion, fluoride ion, hydrogen sulfate ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, p-toluenesulfonate ion, etc. However, particularly preferred are chlorine ion and bromide ion. The quaternary arsonium salt used in the method of the present invention may be any salt that has affinity for the organic layer and allows quaternary arsonium ions to exist stably under the reaction conditions of the present invention. . As an example. Examples include tetraphenylarsonium chloride, triphenylmethylarsonium chloride, tetraphenylarsonium bromide, and polymer derivatives thereof. The lipophilic complexing agent for the cation in the hypochlorite used in the method of the present invention may be any agent as long as it has both the ability to complex the cation and an affinity for the organic phase. , the structure must be stable under the reaction conditions of the present invention. The lipophilic complexing agent used in the method of the invention may include a very wide variety of compounds as long as they meet the above requirements. Examples of lipophilic complexing agents used in the method of the present invention are shown below, but are not limited thereto. (i) Macrocyclic polyethers; macrocyclic polyethers are commonly known as “crown ethers” (e.g.
Pedersen, J.Amer.Chem.Soc., 89 , 2495,
7017 (1967)) and is known to exhibit strong coordination ability for alkali metal ions and alkaline earth metal ions. Most of the "crown ethers" are represented by the general formula [ ] or its substituted products, examples of which are: (n = 4 to 20, m = 1 to n, lm = 2 to 4 (lm represents n numbers from l ₁ to l _o ,
Each is 2, 3 or 4. ) For example, according to Pedersen's nomenclature, 18−
Crown-6, dicyclohexyl-18-crown-6, dibenzo-18-crown-6, benzo-15-crown-5, dibenzo-15-crown-5, dibenzo-21-crown-7, dipenzo-24-crown- 8, dibenzo-30-crown-10, dicyclohexyl-24-crown-8, and the like. (ii) Macrocyclic amino ethers; Examples of macrocyclic amino ethers include bicyclic amino ethers and monocyclic amino ethers. Bicyclic aminoethers are commonly known as "cryptands" (e.g., Lehn, Tetrahedron Lett.,
2885, 2889 (1969)), and is known to exhibit extremely strong coordination ability for alkali metal ions and alkaline earth metal ions.
Most of the "cryptands" are represented by the general formula [ ] or its substitution products, Examples include the following:

【formula】

Examples of monocyclic aminoethers include those represented by the general formula [] or its substituted products. (r=0,1,2; s=0,1,2; R ₉ , R ₁₀
=H or a substituted or unsubstituted hydrocarbon group having 1 to 80 carbon atoms). A specific example is shown below. (iii) Polyethylene glycol or polyethylene glycol derivative; various types of polyethylene glycol can be used, but those with a degree of polymerization of 10 or higher are preferable. Examples of polyethylene glycol derivatives include compounds represented by the general formula [] or [] and substituted products thereof, copolymers of ethylene oxide and other monomers, surfactants containing a polyethylene glycol structure, and the like. R ₁₁ O(-CH ₂ -CH ₂ -O-) _t H [] (t≧5; R ₁₁ = substituted or unsubstituted hydrocarbon group having 1 to 80 carbon atoms) R ₁₂ O(-CH ₂ - CH ₂ −O−) _u R ₁₃ [] (u≧3; R ₁₂ , R ₁₃ = number of carbon atoms 1 to 80
(substituted or unsubstituted hydrocarbon groups up to) As polyethylene glycol derivatives represented by general formula [] or general formula [],
Examples include the following: Examples of copolymers of ethylene oxide and other monomers include ethylene oxide-propylene oxide block copolymers. Examples of surfactants containing a polyethylene glycol structure include polyoxyethylene alkyl thioether, polyoxyethylene alkylamine, polyoxyethylene alkyl ether sulfate salt, polyoxyethylene alkyl phenyl ether sulfate salt,
Examples include polyoxyethylene carboxylic acid ester, polyoxyethylene type alkylolamide, polyoxyethylene alkyl ether, and the like. (iv) Polyvinylpyrrolidone or polyvinylpyrrolidone derivative; Examples of polyvinylpyrrolidone derivatives include copolymers of vinylpyrrolidone and other monomers. (v) Amine oxide or its substituted product represented by the general formula []; R ₁₄ R ₁₅ R ₁₆ N→O [] (R ₁₄ , R ₁₅ , R ₁₆ are hydrocarbon groups, R ₁₄ ,
The total number of carbon atoms contained in R ₁₅ and R ₁₆ is 12
that's all. R ₁₄ and R ₁₅ or R ₁₄ , R ₁₅ and R ₁₆ may be linked to each other to form a nitrogen-containing heterocycle. ) Examples thereof include tri-n-octylamine oxide, 4-(5-nonyl)pyridine-N-oxide, and the like. (vi) Macrocyclic polyethers, macrocyclic aminoethers, polyethylene glycol, polyethylene glycol derivatives, and substituents thereof, in which some of the oxygen atoms are nitrogen atom-containing groups, sulfur atom-containing groups,
Or a compound substituted with a phosphorus atom-containing group, etc. Examples include the following compounds. Examples of various lipophilic complexing agents that can be used in the method of the present invention have been shown above, but other examples include carbonyl groups, sulfinyl groups, sulfonyl groups, phosphoryl groups, and ether groups that have coordination ability for metal cations. , an amino group, a pyridine ring, an imidazole ring, a furan ring, and other functional groups can be used, and the complexing agent is not limited to the examples presented. Further, these lipophilic complexing agents may be supported on a polymer compound or various insoluble carriers by various supporting methods including covalent bonding. The amount of the catalyst used in the method of the present invention is appropriately selected depending on the structure of the catalyst, the type of solvent, the reaction temperature, the required reaction rate, etc., but usually 1 gram of hypochlorite ion is used. 0.0001 for equivalent weight
The amount is selected from the range of mol to 10 mol, particularly preferably from the range of 0.001 mol to 1 mol.
If the amount of catalyst is too small, a substantial reaction rate cannot be obtained, and if it is too large, the reaction rate is too fast, making it difficult to control the reaction or increasing the cost of the catalyst. Economically disadvantageous. The reaction of the present invention is carried out in a two-phase system consisting of an aqueous phase and an organic phase. In this case, the organic layer only needs to contain fluoroolefin and form a phase different from the aqueous phase, and there are no particular restrictions beyond that. Alternatively, it may be a phase consisting of a catalyst that is poorly soluble in water and a fluoroolefin, or furthermore, it may be a phase consisting of a fluoroolefin and an inert solvent that is substantially immiscible or poorly miscible with the aqueous phase. I can do it. Furthermore, when carrying out the method of the present invention, it is sufficient to have an organic phase containing substantially most of the fluoroolefin and an aqueous phase containing the metal hypochlorite; It does not matter if there are other phases. For example, the method of the present invention can be applied even when the organic phase is composed of two types of media with low compatibility to form a two-phase structure, or when the catalyst is supported on an insoluble carrier to form a third phase. It is possible to do this. As the organic solvent for the organic phase used in the method of the present invention, an inert solvent that is substantially immiscible or poorly miscible with the aqueous phase is used. Examples include aliphatic hydrocarbons such as n-hexane, n-octane, and n-decane; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decalin; and aromatic hydrocarbons such as benzene, toluene, and xylene. Hydrocarbons; Ethers such as diisopropyl ether and di-n-butyl ether; methylene chloride, chloroform, carbon tetrachloride, 1,2
-Chlorinated hydrocarbons such as dichloroethane and chlorobenzene; 1,2-dichloro-1,1,2,2-
Chlorofluorocarbons such as tetrafluoroethane, fluorotrichloromethane, 1,1,2-trichloro-1,2,2-trifluoroethane, 1,1,2,2-tetrachloro-1,2-difluoroethane; perfluoro Examples include, but are not limited to, perfluorocarbons such as cyclobutane, perfluorodimethylclobutane, perfluorohexane, perfluorooctane, perfluorodecane, and hexafluorobenzene; or mixed solvents thereof. When selecting an organic solvent, consider the solubility for fluoroolefin and fluoroolefin epoxide, solubility for the catalyst used in the reaction, phase separation from the aqueous phase, and reaction conditions such as reaction pressure and reaction temperature. A suitable organic solvent is selected. Among the various solvents mentioned above, fluorine-containing compounds such as chlorofluorocarbons and perfluorocarbons have high solubility in fluoroolefin and fluoroolefin epoxide, and low compatibility with water.
Chlorinated hydrocarbons are also suitable for the process of the invention because they generally have a high solubility in the catalyst. The volume ratio of the organic phase to the aqueous phase can be arbitrarily selected depending on the reaction method, reaction conditions, etc., but the organic phase is usually preferably 0.05 to 20 times the aqueous phase, and particularly preferably.
It ranges from 0.2 times to 5 times. The reaction temperature when carrying out the present invention is determined depending on the amount of catalyst, reaction liquid composition, required reaction rate, etc., but is usually in the range of -25°C to 80°C, preferably -20°C. to 60°C, particularly preferably from -18°C to 40°C. If the reaction temperature is too low, a substantial reaction rate may not be obtained or, in some cases, the aqueous phase may freeze, making it impossible to carry out the reaction. On the other hand, if the reaction temperature is too high, the decomposition of the fluoroolefin epoxide becomes significant, and the selectivity of the fluoroolefin epoxide decreases. The reaction pressure when carrying out the present invention is not particularly limited as long as it is a pressure sufficient to keep the organic phase containing the fluoroolefin and the fluoroolefin epoxide in a liquid phase. Therefore, the reaction pressure is selected depending on the type and composition of the organic phase, but is usually preferably in the range of 1 atm to 20 atm. As a method for carrying out the two-phase reaction of the present invention,
Any of the batch method, semi-flow method, and flow method can be used. EXAMPLES The present invention will be explained in more detail below using Examples and Comparative Examples, but these explanations are not intended to limit the present invention in any way. Example 1 1,1,2-trichloro-1,2,2-trifluoroethane (hereinafter referred to as F
-113) 18 ml, 20 ml of an aqueous solution of sodium hypochlorite with an effective chlorine concentration of 12% containing 0.6 g of sodium hydroxide, 3.5 perfluoro-1-beptene
g (10 mmol) and tri-n-octylmethylammonium chloride (hereinafter
(abbreviated as TOMAC) 0.12 g (0.3 mmol). Next, this reaction solution is cooled to 0° C., and then a magnetic stirrer is used to rotate a stirrer in the reaction container to mix the reaction solution and start the reaction. The reaction temperature is maintained at 0°C during the reaction. After 1 hour, the rotation of the stirrer was stopped, the reaction solution was kept stationary, and the aqueous phase and F-
When the 113 phase was separated and the perfluoro-1-heptene and 1,2-epoxy perfluoroheptane contained in the F-113 phase were quantified by gas chromatography, the conversion rate of perfluoro-1-heptene was 81%; The selectivity for 1,2-epoxy perfluoroheptane was 72%. Comparative Example 1 A reaction similar to Example 1 was carried out without using TOMAC as a catalyst. As a result, only a trace amount of 1,2-epoxy perfluoroheptane was produced. Example 2 The same operation as in Example 1 is carried out, but instead of the sodium hypochlorite aqueous solution, an effective chlorine content of 65
Using 20 ml of an aqueous solution containing 4.6 g of high-grade salashi powder (the main component is calcium hypochlorite), the reaction temperature was
When the reaction was carried out at 20°C for 30 minutes, the conversion rate of perfluoro-1-heptene was 71%, 1,2
- The selectivity of epoxy perfluoroheptane was 62%. Examples 3 to 9 Reactions similar to those in Example 1 were carried out using 0.12 g of various onium salts in place of TOMAC. The results are shown in Table 1.

[Table] Examples 10 to 14 Reactions similar to those in Example 1 were carried out using chloroform instead of F-113 and various polyethers as catalysts. Table 2 shows the results.
Shown below. Example 15 A reaction similar to Example 1 was carried out using 0.12 g of a nonionic surfactant polyoxyethylene oleyl ether (manufactured by NOF Corporation, HLB16.6) as a catalyst. The reaction results after 3 hours were 62% conversion of perfluoro-1-heptene and 1,2-heptene.
The selectivity for epoxy perfluoroheptane was 63%. Example 16 A reaction similar to Example 10 was carried out using 0.36 g of polyvinylpyrrolidone (average molecular weight 40,000) as a catalyst. The reaction results after 3 hours were that the conversion of perfluoro-1-heptene was 58% and the selectivity of 1,2-epoxy perfluoroheptane was 65%.

【table】

[Table] Example 17 The same reaction as in Example 1 was carried out using 2.0% perfluoro-2-butene instead of perfluoro-1-heptene.
g (10 mmol). As a result, the conversion rate of perfluoro-2-butene was 78%,
Selectivity of 2,3-epoxy perfluorobutane 84
It was %. Example 18 The same reaction as in Example 1 was carried out using perfluorocyclopentene instead of perfluoro-1-heptene.
2.12 g (10 mmol) was used. As a result, the conversion rate of perfluorocyclopentene was 83
%, and the selectivity for perfluoro-1,2-epoxycyclopentane was 81%. Example 19 A reaction similar to Example 1 was carried out using 3.33 g (10 mmol) of 5,6-dichloroperfluoro-1-hexene in place of perfluoro-1-heptene. As a result, the conversion rate of 5,6-dichloroperfluoro-1-hexene was 76%, and the selectivity of 1,2-epoxy-5,6-dichloroperfluorohexane was 63%. Example 20 The same reaction as in Example 1 was carried out using ω-hydroperfluoro-1-instead of perfluoro-1-heptene.
It was carried out using 3.44 g (10 mmol) of octene. As a result, the conversion rate of ω-hydroperfluoro-1-octene was 71%, and the selectivity of 1,2-epoxy-ω-hydroperfluorooctane was 61%. Example 21 A reaction similar to Example 1 was carried out using 2.62 g (10 mmol) of perfluoro-1,5-hexadiene in place of perfluoro-1-heptene. As a result, the conversion rate of perfluoro-1,5-hexadiene was 73%, and the selectivity of 1,2-epoxyperfluoro-5-hexene was 12%. Example 22 A reaction similar to Example 1 was carried out using 5.22 g (10 mmol) of 7,8-dibromoperfluoro-1-octene in place of perfluoro-1-heptene. As a result, the conversion of 7,8-dibromoperfluoro-1-octene was 71%, and the selectivity of 1,2-epoxy-7,8-dibromoperfluorooctane was 63%. Example 23 The same reaction as Example 1 was carried out using 5,6-dibromoperfluoro-1-heptene instead of perfluoro-1-heptene.
It was carried out using 4.22 g (10 mmol) of 1-hexene. As a result, the conversion rate of 5,6-dibromoperfluoro-1-hexene was 81%, and the selectivity of 1,2-epoxy-5,6 dibromoperfluorohexane was 57%. Example 24 A reaction similar to Example 1 was carried out using 3.00 g (10 mmol) of perfluoro-4-methylpentene-2 instead of perfluoro-1-heptene. As a result, the conversion rate of perfluoro-4-methylpentene-2 was 68%, and perfluoro-2,3-
The selectivity for epoxy-4-methylpentane was 56%. Example 25 The same reaction as in Example 1 was carried out using 0.50 g of 1,1,2,3,3,4-hexafluoro-4-chloro-1-butene instead of perfluoro-1-heptene.
(2.5 mmol). the result,
The production of 1,2-epoxy-1,1,2,3,3,4-hexafluoro-4-chlorobutane is GC-
Confirmed by MS analysis (gas chromatography/mass spectrometry). Example 26 The same reaction as in Example 1 was carried out using 0.37 g (25. mmol) of 1,1,2,3,3-pentafluoro-1-butene instead of perfluoro-1-heptene. Ta. As a result, the production of 1,2-epoxy-1,1,2,3,3-pentafluorobutane was confirmed by GC-MS analysis (gas chromatography/mass spectrometry). Example 27 The same reaction as in Example 1 was carried out using 0.56 g (2 mmol) of 4-perfluorovinyloxyperfluoro-1-butene instead of perfluoro-1-heptene.
This was done using . As a result, 12-epoxy-
The production of 4-perfluorovinyloxyperfluorobutane was confirmed by GC-MS analysis (gas chromatography/mass spectrometry).

Claims (1)

[Claims] 1. Using hypochlorite dissolved or suspended in an aqueous phase as an oxidizing agent, in the presence or absence of an inorganic base, the general formula [] [In general formula [], X ₁ , X ₂ , X ₃ and X ₄
is (a) a fluorine atom, (b) a perfluoroalkyl group having 20 or less carbon atoms, and (c) -CF ₂ Y (Y contains or contains at least one of a halogen atom and an ether bond). A hydrocarbon group having 20 or less carbon atoms (with the exception that Y is not a perfluoroalkyl group). However, at least one of the substituents of X ₁ , X ₂ , X ₃ and X ₄ has a -CF ₂ - group directly bonded to the carbon-carbon double bond shown in the general formula [], The number of carbon atoms contained in the fluoroolefin represented by the general formula [] is between 4 and 25.
Moreover, X ₁ , X ₂ , X ₃ and X ₄ may be linked to each other to form a cyclic compound. ] In epoxidizing the fluoroolefin represented by (a') a quaternary ammonium salt, (b')
In the presence of at least one catalyst selected from a quaternary phosphonium salt, (c') a quaternary arsonium salt, or (d') a lipophilic complexing agent for the cation in the hypochlorite, the aqueous phase A method for epoxidizing fluoroolefins, which is characterized by carrying out the reaction in a two-phase system consisting of an organic phase and an organic phase. 2. The method for epoxidizing a fluoroolefin according to claim 1, wherein the reaction is carried out in the presence of an inorganic base of 0.1 gram equivalent or more per mole of the fluoroolefin represented by the general formula []. 3. The method for epoxidizing a fluoroolefin according to claim 2, wherein the inorganic base is sodium hydroxide. 4. The method for epoxidizing fluoroolefins according to claim 1, characterized in that sodium hypochlorite and/or calcium hypochlorite is used as the hypochlorite. 5 The number of carbon atoms contained in the quaternary ammonium ion is 6 per quaternary ammonium ion.
2. The method for epoxidizing a fluoroolefin as claimed in claim 1, characterized in that a quaternary ammonium salt having a concentration of 1 to 100 is used. 6 The number of carbon atoms contained in the quaternary phosphonium ion is 6 per quaternary phosphonium ion.
2. The method for epoxidizing a fluoroolefin according to claim 1, characterized in that the quaternary phosphonium salt is used in a range of from 1 to 100. 7. The method for epoxidizing a fluoroolefin according to claim 1, characterized in that a tetraaryl arsonium salt or a triarylalkyl arsonium salt is used as the quaternary arsonium salt. 8 Using an alkali metal salt of hypochlorous acid or/and an alkaline earth metal salt other than beryllium of hypochlorous acid as an oxidizing agent, and using an alkali metal ion or/and an alkaline earth metal ion other than beryllium as a catalyst. A method for epoxidizing a fluoroolefin according to claim 1, characterized in that an oil-based complexing agent is used. 9. The method for epoxidizing a fluoroolefin according to claim 8, wherein the lipophilic complexing agent is a macrocyclic polyether. 10. The method for epoxidizing fluoroolefins according to claim 8, wherein the lipophilic complexing agent is a macrocyclic aminoether. 11. The method for epoxidizing fluoroolefins according to claim 8, wherein the lipophilic complexing agent is polyethylene glycol or a polyethylene glycol derivative. 12. The method for epoxidizing fluoroolefins according to claim 8, wherein the lipophilic complexing agent is polyvinylpyrrolidone or a polyvinylpyrrolidone derivative.