JP2001240576A - Preparation method of fluoride compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an economically useful method of preparing CF2 ClCFClCFRAFCF2OCF(CF3)COF(RAF is fluorine atom or the like). SOLUTION: CH2=CHCHRACH2OCH(CH3)CH2OH[compound (1)] is reacted with compound (2) such as FCOCF(CF3)OCF2CF2CF3 to form compound (3) such as CH2=CHCHRACH2OCH(CH3)CH2OCOCF(CF3)OCF2CF2CF3, successively reacted with a chlorinating agent to form compounds (4) such as CH2 ClCHClCHRACH2OCH(CH3)CH2OCOCF(CF3)OCF2CF2CF3 and then reacted with fluorine in a liquid phase wherein RA is a hydrogen atom or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a fluoride compound having a vic-dichloro structure, which is useful as an intermediate for producing a monomer for a fluororesin.

[0002]

2. Description of the Related Art A vic-dichloro structure (a structure in which one chlorine atom is bonded to a carbon atom and a carbon atom adjacent to the carbon atom) at the terminal of an alkyl chain, and a fluorocarbonyl group (-COF) Is a compound useful as an intermediate for producing a fluororesin raw material monomer. That is, the compound is reacted with zinc and then dechlorinated to form a perfluorovinyl group (C
F ₂ = CF-) can fluoride compound produced with. The perfluorovinyl group of the compound is a polymerizable group, and various fluorine resins can be produced by polymerizing this. Fluororesin is a useful resin having excellent heat resistance and chemical resistance.

Among these fluororesins, perfluoro (3-butenyl vinyl ether) [CF ₂ ＣＦCFC
The homopolymer of F ₂ CF ₂ OCF = CF ₂ ] is used for various applications as a transparent fluororesin. Conventionally,
Perfluoro (3-butenyl vinyl ether) has been synthesized by the following production route (JP-A-1-1438).
43).

[0004]

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That is, a compound (A) is obtained by reacting CF ₂ ＣＦCFCl with iodine chloride.
And CF ₂ = CF ₂ are reacted to obtain a compound (B), and the compound (B) is reacted with fuming sulfuric acid to obtain a compound (C). Compound (C) is further treated with hexafluoropropylene oxide (HFPO) in the presence of an alkali fluoride such as KF.
With compound (5A-1), and then heating compound (5A-1) to 250 ° C. or higher in the presence of soda ash or glass beads, or compound (5A-1)
COF ₂ is eliminated by thermal decomposition of an alkali carboxylate obtained by reacting the compound with an alkali hydroxide to obtain a compound (D). Further, the compound (D) is reacted with zinc and dechlorinated to obtain perfluoro (3-butenyl vinyl ether).

[0006] As a method of fluorinating all of the C—H portion in the hydrocarbon compound to C—F, a method of fluorination using fluorine, or a method in which hydrogen fluoride is electrolyzed in an electrolytic cell. A method of performing a fluorination reaction using the resulting product as a fluorine source (a method generally called an electrolytic fluorination reaction) is known. The reaction using fluorine includes a reaction of fluorination in a gas phase (hereinafter, referred to as a gas phase reaction),
A reaction that causes fluorine in a liquid phase (hereinafter, referred to as a liquid phase reaction) is known.

There is also known a method of obtaining a fluoride compound by thermally decomposing a perfluorinated ester compound having a perfluoroalkyl group. It is described that this fluoride compound can be obtained by using a hydrocarbon-based ester compound having a corresponding carbon skeleton as a raw material and directly fluorinating this in a liquid phase using fluorine (J. Am. Chem. Soc., 120, 7117.
(1998)).

[0008]

However, in the conventional method for producing perfluoro (3-butenyl vinyl ether), in the step of producing compound (A), compound (A) and its isomer CF ₂ ICFCl are added together with compound (A). ₂ had a problem of by-product. And it was difficult to control the amount of the isomer. In addition, the production method has many reaction steps, the price of raw materials is high, and it is economically disadvantageous. Also,
Since iodine chloride and fuming sulfuric acid are used, there are problems that the apparatus is corroded and that handling of the reaction reagent is difficult.

The electrolytic fluorination reaction includes an isomerization reaction and C-
There is a disadvantage that the C-bond breakage and the recombination reaction are likely to occur, and the target compound cannot be obtained with high purity. Further, when the direct fluorination method is performed by a gas phase reaction, there is a problem that a C—C single bond is broken during the fluorination reaction, and various types of by-products are generated.

It has been reported that the liquid phase reaction is a method for solving the problem of the gas phase reaction (US Pat. No. 5,093,343).
2). In the liquid phase reaction, it is necessary to use a solvent capable of dissolving fluorine as a solvent, and a perfluorinated solvent is generally used as the solvent. Since the solubility of the hydrocarbon compound in the perfluorinated solvent is low, there have been problems that the fluorination reaction does not proceed well and that the production efficiency of the fluorination reaction is low. On the other hand, when fluorinating a hydrocarbon-based compound in a perfluorinated solvent at a high concentration, there is a problem in that the reaction takes place in a suspension system which is disadvantageous to the reaction. Further, when fluorination is carried out by a liquid phase reaction with a low molecular weight hydrocarbon compound, there is a problem that the reaction yield becomes extremely low.

[0011]

SUMMARY OF THE INVENTION The present invention has been made with the object of solving the problems of the conventional method, and provides a method capable of producing a fluoride compound having a vic-dichloro structure in a short step from an inexpensive and easily available starting compound. provide.

That is, the present invention relates to a compound (1) and a compound
(2) to give a compound (3),
Compound (4) is obtained by reacting (3) with a chlorinating agent.
And reacting the compound (4) with fluorine in a liquid phase to form
Compound (5)
A manufacturing method is provided. CH_Two= CHCHR^ACH_TwoOCH (CH_Three) CH_TwoOH ・ ・ ・ (1) FCOR^B ... (2) CH_Two= CHCHR^ACH_TwoOCH (CH_Three) CH_TwoOCOR^B ... (3) CH_TwoClCHClCHR^ACH_TwoOCH (CH_Three) CH_TwoOCOR^B ・ ・ ・ (4) CF_TwoClCFClCFR^AFCF_TwoOCF (CF_Three) COF (5) where R^AIs hydrogen atom, alkyl group or alkoxy
And R is^AR is a hydrogen atom^AFIs fluorine
Child and R^AIs an alkyl group or an alkoxy group
R in case^AFMeans that at least one of the hydrogen atoms in the group is fluorinated
R ^BIs a monovalent organic group.

Further, the present invention provides that the compound (1) is the compound (1A), the compound (2) is the compound (2A), the compound (3) is the compound (3A), and the compound (4) is the compound (4A). (4A), wherein the compound (5) is the compound (5A).

[0014]

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[0015] However, R ^A1 is a hydrogen atom or an alkoxy group, R ^AF1 when R ^A1 is a hydrogen atom is a fluorine atom, R ^AF1 when R ^A1 is an alkoxy group is a perfluoroalkoxy group .

Further, the present invention provides a process for producing a fluoride compound, which comprises reacting compound (4) with fluorine in a liquid phase to obtain compound (5). CH ₂ ClCHClCHR ^A CH ₂ OCH (CH ₃ ) CH ₂ OCOR ^B・ ・ ・ (4) CF ₂ ClCFClCFR ^AF CF ₂ OCF (CF ₃ ) COF ・ ・ ・ (5) However, R ^A , R ^AF and R ^B are It has the same meaning as above.

Further, the present invention provides a compound (7) characterized in that the compound (5) obtained by the above production method is thermally decomposed into a compound (6), and the compound (6) is further dechlorinated.
And a method for producing the same. CF ₂ ClCFClCFR ^AF CF ₂ OCF = CF ₂ (6) CF ₂ = CFCFR ^AF CF ₂ OCF = CF ₂ (7) However, R ^AF has the same meaning as described above.

Further, the present invention provides a method of polymerizing at least one compound (7) obtained by the above-mentioned production method, or a method of polymerizing at least one compound (7) obtained by the above-mentioned production method with the compound (7). Provided is a method for producing a fluororesin, which comprises polymerizing one or more polymerizable monomers.

Further, the present invention provides compound (3A), compound (4A) or compound (5B).

[0020]

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However, R ^A1 has the same meaning as described above, and n
Is an integer of 0 to 9.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, a compound represented by the formula (1) is referred to as a compound (1). The same applies to compounds represented by other formulas. Further, the organic group in the present specification refers to a group having a carbon atom as an essential, and includes those having any of a saturated and unsaturated structure. As the halogen atom, a fluorine atom, a chlorine atom and a bromine atom are preferred.

[Compound (1)] Compound (1)
Is a known compound or a compound which can be easily synthesized from a known compound. As compound (1), compound (1)
A) is preferred. For example, compound (1A) is a known compound, and compound (10) is reacted with compound (11) to give compound (12), and compound (12) is compounded with compound (13) (where X is a monovalent compound). (Showing an ion) to give a compound (14), which can be synthesized by a hydride reduction reaction of the compound (14). However, R ^A1 in the following formula is
A hydrogen atom or an alkoxy group is preferable, and a hydrogen atom or a methoxy group is preferable.

[0024]

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In the above reaction, the reaction of the compound (10) with the compound (11) to give the compound (12) can be carried out by the usual method and conditions for esterification of carboxylic acid. For example, there is a method in which the compound (10) and the compound (11) are heated and reacted in the presence of an acid catalyst such as sulfuric acid.

Next, the compound (13) is reacted with the compound (12) to obtain a compound (14). X ⁺ in the compound (13) is preferably an alkali metal cation,
a ⁺ and K ⁺ are particularly preferred. When X ⁺ is Na ⁺ , compound (13) is obtained by reacting compound (11) with a base such as sodium hydride, or adding methanol solution of sodium methoxide to compound (11) and then distilling methanol. Leave, obtained in a way. The reaction between compound (12) and compound (13) is preferably performed in the presence of a reaction solvent. Examples of the reaction solvent include compound (11), tetrahydrofuran, N, N-dimethylformamide, and the like. The reaction temperature of the reaction is preferably from 25C to the reflux temperature of the reaction solvent, and more preferably from 50C to 100C.

Next, the compound (14) is reduced with a hydride to obtain a compound (1A). As a reducing agent in the hydride reduction reaction, lithium aluminum hydride or bis (2-
Preferred are hydrides such as (methoxyethoxy) aluminum hydride. In the reduction reaction, the compound (1A) is theoretically produced together with the compound (1A) in an equimolar amount to the compound (1A). It is preferable that the compound (1A) is continuously produced by recovering a part or all of the compound (11) and using it again for the reaction with the compound (10). The reduction reaction is preferably performed in the presence of a reaction solvent. As the reaction solvent, tetrahydrofuran, toluene and the like are preferable. The reaction temperature of the reduction reaction is -78 ° C.
To the reflux temperature of the solvent is preferred.

[Compound (2)] Compound (2)
Is a known compound or a compound which can be easily synthesized from a known compound. As R ^B (monovalent organic group) in the compound (2), a monovalent hydrocarbon group, a hetero atom-containing monovalent hydrocarbon group, a halogenated monovalent hydrocarbon group, or a halogenated (hetero atom (Containing monovalent hydrocarbon) groups are preferred. R ^B preferably has 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, from the viewpoint of solubility in the liquid phase used during the fluorination reaction. Further, as the halogen atom in the halogenated group, one or more halogen atoms selected from a fluorine atom, a chlorine atom, and a bromine atom are preferable, and in particular, having only a fluorine atom as a halogen atom from the viewpoint of the usefulness of the compound. Alternatively, it is preferable to have a fluorine atom and a chlorine atom as halogen atoms.

Here, the monovalent hydrocarbon group is preferably an alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples of the monovalent hydrocarbon group include a cycloalkyl group, a bicycloalkyl group, and a spiroalkyl group.

As the hetero atom-containing monovalent hydrocarbon group,
An alkyl group containing an etheric oxygen atom (O of C—C—C) is preferable, and an alkoxyalkyl group is particularly preferable in terms of availability, ease of production, and usefulness of the product. As the alkoxyalkyl group, a group in which one of the hydrogen atoms in the above alkyl group is substituted with an alkoxy group is preferable. The alkoxy group preferably has 1 to 10 carbon atoms.

Furthermore, as the compound (2), since preferably a fluorine-containing compound, R ^B is a fluoroalkyl group, a fluoro (partially chlorinated alkyl) group, a fluoro (hetero atom-containing alkyl) group or a fluoro, ( Partial chloro (heteroatom containing alkyl)) groups are particularly preferred, especially those perfluorinated.

Specific examples of the compound (2) include the following compounds. Among them, compound (2A) is preferable in terms of availability. CF ₃ CF ₂ COF, CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) COF ・ ・ ・ (2A), CF ₃ CF ₂ CF ₂ OCF (CF ₃ ) CF ₂ OCF (CF ₃ ) COF, CF ₂ ClCFClCF ₂ CF ₂ OCF (CF ₃ ) COF.

[Reaction between compound (1) and compound (2)]
A known reaction technique can be applied to the reaction between the compound (1) and the compound (2). For example, when reacting compound (1A) with compound (2A) to give compound (3A), the reaction may be carried out in the presence of a solvent (hereinafter referred to as solvent 1). It is preferable from the viewpoint of volumetric efficiency that the reaction is carried out in the absence of the compound. As the solvent 1, a halogenated hydrocarbon solvent is preferable, and examples thereof include dichloromethane and chloroform. The amount of the solvent 1 used is 0.5 to 5 with respect to the total mass of the compound (1A) and the compound (2A).
Preferably, it is doubled.

In the reaction between the compound (1) and the compound (2), HF is generated. Therefore, a base such as an alkali metal fluoride (for example, sodium fluoride) or a trialkylamine or pyridine is used as a HF scavenger. It may be present inside. When an alkali metal fluoride is used as the HF scavenger, the amount is preferably 1 to 10 moles compared to the compound (2). When an HF scavenger is not used, it is preferable to discharge HF out of the reaction system while entraining HF in a nitrogen stream.

The reaction temperature between compound (1) and compound (2) is usually from -50 ° C to (+ 100 ° C or solvent 1).
Is the boiling point temperature). The reaction time between the compound (1) and the compound (2) is appropriately changed depending on the feed rate of the raw materials and the amount of the compound used for the reaction, and the reaction pressure (gauge pressure,
Hereinafter the same) is preferably 0 to 2 MPa.

[Compound (3)] In the reaction of compound (1) with compound (2), compound (3) is formed. R ^B in the compound (3) corresponds to the R ^B in the compound (2). Compound (3A) is preferable as compound (3).
Some of the compounds (3) are novel compounds, and compound (3A) is a novel compound.

The compound (3A) is obtained by the reaction described below.
Perfluoro (3-butenyl vinyl ether), perfluoro (2-alkoxy-3-butenyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (2-
(Alkoxypropyl vinyl ether). When R ^A1 in compound (3A) is an alkoxy group, it preferably has 1 to 10 carbon atoms, and particularly preferably 1 to 6 carbon atoms. R ^A1 is particularly preferably a hydrogen atom or a methoxy group from the viewpoint of the usefulness of the compound. Specific examples of the compound (3A) include the following compounds.

[0038]

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The crude reaction product containing the compound (3) may be purified to a high purity according to the purpose, or may be used as it is in the next reaction or the like. Purification methods include a method in which the crude product is distilled as it is, a method in which the crude product is treated with dilute alkaline water and the like to separate it, a method in which the crude product is extracted with an appropriate organic solvent and then distilled, and a silica gel column chromatography. And purification method.

[Reaction between compound (3) and chlorinating agent] The reaction of reacting compound (3) with a chlorinating agent to obtain compound (4) can be carried out under the usual chlorination operation and reaction conditions. . As the chlorinating agent, chlorine (Cl ₂ ) is preferable.
The amount of chlorine when used is 1 to compound (3).
A 10-fold mole is preferred, and a 1- to 5-fold mole is particularly preferred.
The reaction between the compound (3) and the chlorinating agent may be carried out in the presence of a solvent (hereinafter referred to as solvent 2), but is preferably carried out in the absence of solvent 2 from the viewpoint of volumetric efficiency. . When the solvent 2 is used, it is preferable to use a halogenated hydrocarbon solvent. As the halogenated hydrocarbon solvent,
Examples include dichloromethane and chloroform. Solvent 2
Is preferably 0.5 to 5 times the mass of the compound (3). The reaction temperature is from -78 ° C to +
200 ° C. is preferred.

[Regarding Compound (4)] The reaction crude product containing the compound (4) produced by the chlorination reaction may be purified to a high purity according to the purpose, and may be used as it is in the next reaction. Is also good. As a method for purifying the crude product containing the compound (4), a method for distilling the crude product as it is, a method for treating the crude product with diluted alkaline water or the like, and a method for separating the crude product from an appropriate organic solvent And then distilling after extraction.

The compound (4) is preferably the compound (4A). Some of the compounds (4) are novel compounds. For example, compound (4A) obtained by chlorination of compound (3A) is a novel compound. Embodiment of the compound (4A) of utilities and preferred R ^A1 is the same as compound (3A). Specific examples of the compound (4A) include the following compounds.

[0043]

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[Fluorination of Compound (4)] Compound (4)
Fluorine (F ₂₎ used in the reaction with fluorine in a liquid phase is preferably introduced into the reaction system as a fluorine gas diluted with an inert gas. As the inert gas, nitrogen gas and helium gas are preferable, and nitrogen gas is particularly preferable for economic reasons. As the fluorine gas diluted with the inert gas, the amount of the fluorine gas in the mixed gas composed of the inert gas and the fluorine gas is preferably from 5 to 95% by volume, particularly preferably from 10 to 60% by volume. .
Note that the fluorine gas in the following reaction may be a diluted fluorine gas or an undiluted fluorine gas, and a diluted fluorine gas is preferable.

The fluorination reaction of the present invention is preferably carried out in the presence of an alkali metal fluoride or an alkaline earth metal fluoride.
It is particularly preferred to carry out in the presence of cesium fluoride,
It is particularly preferable to carry out the reaction in the presence of sodium fluoride from the viewpoint of economy. By the presence of an alkali metal fluoride or an alkaline earth metal fluoride, the fluorination reaction and the concomitant ester decomposition reaction can proceed very efficiently.

The amount of the alkali metal fluoride or alkaline earth metal fluoride may be a catalytic amount or may be used in excess. Usually, 1 to 500 to compound (4)
Mol% is preferable, 10 to 100 mol% is more preferable, and 5 to 50 mol% is particularly preferable.

In the fluorination reaction, HF is produced as a by-product. To remove the HF, an HF scavenger is allowed to coexist in the reaction system, or the HF scavenger is brought into contact with the outlet gas at the reactor gas outlet. Is preferred. Further, the HF scavenger also has an action of accelerating the reaction of the present invention. As the HF scavenger, the same one as described above is used, and sodium fluoride is preferable.

When the HF scavenger is present in the reaction system, the amount thereof is preferably 1 to 20 times, and more preferably 1 to 5 times the molar number of all hydrogen atoms of the compound (4). When the HF scavenger is placed at the reactor gas outlet, (a) a cooler (10
It is preferred that the temperature be maintained at from 0 ° C. to room temperature, especially at about 20 ° C. ), (B) a layer filled with pellets of an HF scavenger such as sodium fluoride, and (c) a cooler (preferably kept at -78 ° C to + 10 ° C,
(Preferably maintained at 30 ° C. to 0 ° C.)
It is preferable to install them in series in the order of (b)-(c). A liquid return line for returning the aggregated liquid from the cooler (c) to the reactor may be provided.

The liquid phase preferably comprises a solvent capable of dissolving fluorine. Since the compound (4) has high solubility in the liquid phase, a compound having a fluorine content of 30% (by mass, hereinafter the same unless otherwise specified) is preferable, and a compound having a fluorine content of 30 to 84% is particularly preferable. In particular, compounds having 50 to 84% are preferred. Further, the molecular weight of the compound (4) is preferably 200 or more, particularly 200 to 1000, because the reaction in the gas phase can be suppressed.
It is preferred that In particular compounds R ^B is perfluorinated monovalent organic group (4) is dissolved in a solvent capable of dissolving the fluorine compound which is likely. As a solvent capable of dissolving fluorine, it is preferable to use an organic solvent which does not contain a CH bond and essentially has a CF bond (hereinafter, referred to as a solvent 3) as an essential component, and contains a CH bond described later. It is preferable that the solvent other than the compound is composed of only the solvent 3.

The solvent 3 is an organic solvent comprising a compound obtained by perfluorinating a hydrogen atom in an organic solvent having at least one atom selected from the group consisting of a chlorine atom, a nitrogen atom and an oxygen atom in its structure. Is preferable, and a solvent capable of dissolving 1% or more of the compound (4) is particularly preferable.

Examples of the solvent 3 include FCOR ¹ (R ¹ is a perhalogenoalkyl group or a perhalogeno (alkoxyalkyl) group), R ² CF ₂ OCOR ³ (R ² is a perfluoromonovalent organic group, and R ³ is a Halogenoalkyl group.),
Perfluoroethers (trade names: Krytox, Fomblin, Galden, Demnum, etc.), chlorofluorocarbons (1,1,2-trichloro-1,2,2-trifluoroethane, low polymers of chlorotrifluoroethylene ( Trade names: Freonlube, etc.), perfluoroalkylamines (eg, perfluorotrialkylamine, etc.), inert fluids (tradename: Fluorinert), etc. Further, as the solvent 3, 1,1,2-trichloro-1, Preferred are 2,2-trifluoroethane, perfluorotrialkylamine, compound (5A) described below, or compound (2A), and the amount of solvent 3 is preferably at least 5 times the mass of compound (4). , 10 to 100 times the amount is particularly preferred.

The reaction with fluorine may be carried out after charging fluorine, or may be carried out while supplying fluorine. The amount of fluorine charged when performing the former reaction, and
The amount of fluorine supplied in the case of performing the latter reaction is preferably an excess equivalent to the hydrogen atom in the compound (4A) from the viewpoint of selectivity, and particularly preferably 1.5 times equivalent or more. It is particularly preferable to use 1.5 to 5 equivalents.

The reaction with fluorine is preferably carried out in a continuous system (part 1) or a continuous system (part 2) described below in view of the reaction yield and selectivity, and particularly preferably in a continuous system (part 2). Is preferred.

Continuous method (1): A method in which the compound (4) and the solvent 3 are charged into a reactor and stirred, and only the fluorine gas or the fluorine gas and the solvent 3 are reacted while being continuously supplied. The reaction temperature in this method is preferably from -60 ° C to the boiling point of the compound (4), and from -50 ° C to +1 in view of the reaction yield, selectivity, and various conditions of industrial implementation.
00 ° C is more preferable, and -20 ° C to + 50 ° C is particularly preferable. The reaction pressure is 0 to 2 MPa, the reaction yield, selectivity,
It is preferable from the viewpoint of easiness of industrial production.

Continuous method (No. 2): A method in which the solvent 3 is charged into the reactor, stirred, and the compound (4), the solvent 3 and the fluorine gas are continuously and simultaneously supplied at a predetermined molar ratio. The reaction temperature of the reaction is preferably from -50 ° C to + 100 ° C,
C. to +50 C. is particularly preferred. The reaction pressure is not particularly limited, and is preferably 0 to 2 MPa from the viewpoints of reaction yield, selectivity, ease of industrial production, and the like. Compound (4)
Is diluted with solvent 3 and supplied, the selectivity increases,
This is preferable because the amount of by-products is reduced. When compound (4) is diluted with solvent 3, the amount of solvent 3 with respect to the mass of compound (4) is preferably at least 5 times, particularly preferably 5 to 20 times.

Further, in the reaction with fluorine, C-
It is preferable to add an H bond-containing compound to the reaction system or to perform ultraviolet irradiation. For example, when the reaction is performed after initially charging fluorine gas, it is preferable to add a C—H bond-containing compound to the reaction system or to perform ultraviolet irradiation at a later stage of the fluorination reaction. When performing the reaction while supplying fluorine gas, the compound (4)
It is preferable to supply the C—H bond-containing compound or to perform ultraviolet irradiation at the point of time when the supply of is completed. Thereby, the compound (4) existing in the reaction system can be efficiently fluorinated, and the reaction rate can be dramatically improved. The ultraviolet irradiation time is preferably set to 0.1 to 3 hours.

The C—H bond-containing compound may be any organic compound other than the compound (4), preferably an aromatic hydrocarbon, particularly preferably benzene, toluene and the like. The amount of the CH bond-containing compound to be added is preferably 0.1 to 5 mol% based on compound (4).

The C—H bond-containing compound is preferably added in a state where fluorine is present in the reaction system. Further, C
When a compound containing an -H bond is added, it is preferable to pressurize the reaction system. The pressure during pressurization is 0.01-5M
Pa is preferred.

[Regarding Compound (5)] In the present invention, when the compound (4) is reacted with fluorine in the liquid phase, not only the compound (4) is fluorinated, but also a decomposition reaction of the ester moiety occurs. And the compound (5) is obtained. The reaction is a reaction that is accelerated particularly when carried out in the presence of an alkali metal fluoride or an alkaline earth metal fluoride. In fluorination, fluorine replaces the hydrogen atom bonded to the carbon atom with a fluorine atom and adds to the carbon-carbon unsaturated bond. Fluorine may act on all or some of the hydrogen atoms and carbon-carbon unsaturated bonds bonded to carbon atoms, and preferably acts on all (ie, completely fluorinated).

The compound (5) is preferably the compound (5A). Some of the compounds (5) are novel compounds. For example, compound (5B) obtained by fluorination of compound (4A) in which R ^A1 is an alkoxy group is a novel compound. Embodiment of the compound (5A) of the utilities and preferred R ^A1 is the same as compound (3A). N of the compound (5B) is preferably from 0 to 5. Compound (5
Specific examples of B) include compound (5B-1). CF ₂ ClCFClCF (OCF ₃ ) CF ₂ OCF (CF ₃ ) COF · (5B-1) Further, in the fluorination of compound (4), compound (2F) is usually added together with compound (5). Generate. In the fluorination of the compound (4A), the compound (5A)
Compound (2A) is formed together with A). FCOR ^BF (2F) where R ^BF when R ^B is a group that does not react with fluorine
Is a monovalent organic group identical to R ^B, R ^BF when R ^B is a group which reacts with fluorine is a monovalent organic group in which R ^B fluorinated.

Compound (5) and compound (2F) can be separated by a usual separation method. For example, each can be isolated by distillation. Further, when the compound (5) with the compound (2F) has selected the structure of R ^B of the compound (2) to be the same structure, because it can omit the separation process is very advantageous.

Compound (5) can be continuously produced by reusing a part or all of compound (2F) obtained by the above method again for reaction with compound (1). For example, the compound (1A) is reacted with the compound (2A) to give a compound (3A), and the compound (3A) is reacted with a chlorinating agent to give a compound (4A). By reacting with fluorine, a crude reaction product containing the compound (5A) and the compound (2A) is obtained, and a part or the whole of the compound (2A) separated from the crude reaction product is again converted to the compound (1A) Compound (5)
The continuous production method of A) can be provided.

[Usefulness of Compound (5)] Compound (5)
Is a compound useful as a raw material for various fluorine-containing functional compounds. For example, the compound (5) obtained by the production method of the present invention can be obtained by removing COF ₂ by heating to 250 ° C. or higher in the presence of soda ash or glass beads, or by compound (5) and an alkali hydroxide. And a carboxylic acid alkali salt obtained by reacting
The compound (6), which is useful as a monomer for fluororesin production, can be obtained by decomposing the compound (6) with zinc or the like by pyrolysis at a temperature of ° C., and further reacting the compound (6) with zinc or the like. .

For example, compound (5) is perfluoro (2-alkoxy-3-butenyl vinyl ether)
Can be led to A fluororesin obtained by polymerizing these monomers is useful as a transparent and useful fluororesin having excellent heat resistance and chemical resistance and being transparent.

For example, the compound (2A) is heated to 250 ° C. or more (preferably 250 to 350 ° C.) in the presence of soda ash or glass beads to desorb COF ₂ , or potassium hydroxide. Can be led to perfluoro (propyl vinyl ether) by thermally decomposing the potassium carboxylate obtained by the reaction with the above at 150 to 300 ° C. Perfluoro (propyl vinyl ether) [CF ₃ CF ₂ CF ₂ OCF = CF ₂ ] is also a useful compound as a raw material monomer for a fluororesin.

[0066]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In addition,
In the following, GC is used for gas chromatography, TMS for tetramethylsilane, D for N, N-dimethylformamide.
MF, dichloropentafluoropropane with AK-22
5,1,1,2-Trichloro-1,2,2-trifluoroethane is denoted by R113, and liter is denoted by L. Also, GC
Purity refers to the purity determined from the peak area ratio by gas chromatography.

[Example 1] CH_Two= CHCH_TwoCH_TwoOCH
(CH_Three) COOCH_TwoCH_TwoCH = CH _Two(R^A1Is a hydrogen source
Production Example of Compound (14)) CH_ThreeCHClCOOH (50 g) and CH_Two= CHCH_Two
CH_TwoOH (75 mL) was placed in the flask, and concentrated sulfuric acid (1
0 mL) was added dropwise and stirred at room temperature for 10 minutes. Saturate reaction
Poured into aqueous sodium carbonate (250 mL). Water (150
mL) and tert-butyl methyl ether (150 m
L) and the mixture was separated, and tert-butyl methyl ether was added.
Phase was obtained as the organic phase. The organic phase with water (150 mL)
After washing and drying with magnesium sulfate, filtration and
I got Concentrate the crude liquid to CH_ThreeCHClCOOCH_TwoCH
_TwoCH = CH_TwoI got

CH ₂ ＣＨCHCH ₂ CH ₂ OH (16.6
g) and DMF (120 mL) were placed in a flask and cooled so that the internal temperature was maintained at 8 to 9 ° C. Sodium hydride (10 g) was added over 30 minutes, stirred at room temperature for 30 minutes, and cooled again. Next, CH ₃ CHClCOOC
H ₂ CH ₂ CH ＝ CH ₂ (50 g) was dissolved in DMF (30 mL) and added dropwise over 1.5 hours. After completion of the dropwise addition, the mixture was heated for 3 hours while maintaining the internal temperature at 80 to 85 ° C. Room temperature (25
° C) and 200 mL of 2 mol / L hydrochloric acid was added.

Mixture 4 of hexane / ethyl acetate = 2/1
Extraction was performed four times with 00 mL to obtain an organic phase. The organic phase was concentrated, washed twice with 500 mL of water, dried over magnesium sulfate, filtered, and concentrated again to obtain CH ₂ ＣＨCHCH ₂ CH.
₂ OCH (CH ₃ ) COOCH ₂ CH ₂ CH = CH ₂ (36
g) was obtained. GC purity was 83%. The NMR spectrum data was as follows.

¹ H-NMR (399.8 MHz, solvent:
CDCl ₃ , standard: TMS) δ (ppm): 1.39
(D, J = 7.0 Hz, 3H), 2.33 to 2.45
(M, 4H), 3.41 (dt, J = 7.0, 9.1H
z, 1H), 3.63 (dt, J = 7.0, 9.1H
z, 1H), 3.96 (q, J = 7.0 Hz, 1H),
4.15 to 4.27 (m, 2H), 5.02 to 5.14
(M, 4H), 5.73-5.88 (m, 2H).

Example 2 CH ₂ ＣＨCHCH ₂ CH ₂ OCH
(CH ₃ ) CH ₂ OH (A compound in which R ^A1 is a hydrogen atom (1
Production Example of A)) Under an argon atmosphere, lithium aluminum hydride (6.
9 g) and dehydrated diethyl ether (240 mL) were placed in a flask and stirred in an ice bath. Here, the CH ₂ ＣＨCHCH ₂ CH ₂ OCH (CH ₃ ) CO having a GC purity of 83% obtained in Example 1
After OCH ₂ CH ₂ CHＣＨCH ₂ (36 g) was added dropwise over 45 minutes, the mixture was stirred at room temperature (25 ° C.) for 3.5 hours. Ice water (100 mL) was added dropwise under an ice bath, and water (100 m
L) and the mixture was brought to room temperature (25 ° C.) and filtered. After washing with diethyl ether (450 mL), the filtrate was separated. The aqueous phase was further extracted with diethyl ether (200 mL)
Extraction was repeated and the collected diethyl ether phase was obtained as an organic phase. The organic phase was dried over magnesium sulfate, then filtered,
A crude liquid was obtained. After the crude liquid was concentrated to 35 g, a fraction (6.6 g) at 28 to 49 ° C./9.33 kPa was removed by distillation under reduced pressure, and CH ₂ ＣＨCHCH ₂ CH ₂ OCH was removed from the remaining fraction.
(CH ₃ ) CH ₂ OH (19.2 g) was obtained. GC purity was 98%. The NMR spectrum data was as follows.

¹ H-NMR (399.8 MHz, solvent:
CDCl ₃ , standard: TMS) δ (ppm): 1.12
(D, J = 6.2 Hz, 3H), 2.35 (tq, J =
1.3, 6.7 Hz, 2H), 3.42 to 3.48.
(M, 2H), 3.51-3.59 (m, 2H), 3.
64-3.69 (m, 1H), 5.04-5.15
(M, 2H), 5.79-5.89 (m, 1H).

Example 3 CH ₂ ＣＨCHCH ₂ CH ₂ OCH
(CH ₃ ) CH ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃
Production Example of (Compound (3A) wherein R ^A1 is a Hydrogen Atom) CH ₂ ＣＨCHCH ₂ CH ₂ O with GC Purity of 98% Obtained in Example 2
CH (CH ₃ ) CH ₂ OH (19.2 g) was charged into the flask and stirred while bubbling nitrogen gas through. FCO
CF a _{(CF 3) OCF 2 CF 2} CF 3 (50g), was added dropwise over 1 hour while maintaining the internal temperature at 25 to 30 ° C.. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, and a saturated aqueous sodium hydrogen carbonate solution (80 mL) was added at an internal temperature of 15 ° C or lower.

Water (50 mL) and chloroform (100 m
L) was added, and the mixture was separated to give a chloroform phase as an organic phase. The organic phase was further washed twice with water (100 mL),
After drying over magnesium sulfate, the mixture was filtered to obtain a crude liquid.
After concentrating the crude liquid, it is purified by silica gel column chromatography (developing solvent: hexane / ethyl acetate = 4/1), and then purified again by silica gel column chromatography (developing solvent: AK-225) to obtain CH ₂ ＣＨCHCH ₂ CH _2.
OCH (CH ₃ ) CH ₂ OCOCF (CF ₃ ) OCF ₂ CF
₂ CF ₃ (37 g) was obtained. GC purity was 99%.
The NMR spectrum data was as follows.

¹ H-NMR (399.8 MHz, solvent:
CDCl ₃ , standard: TMS) δ (ppm): 1.2 (d
d, J = 1.2, 6.4 Hz, 3H), 2.29 (q,
J = 6.7 Hz, 2H), 3.45 to 3.51 (m, 1
H), 3.53-3.59 (m, 1H), 3.67-
3.73 (m, 1H), 4.25 to 4.29 (m, 1
H), 4.35 to 4.41 (m, 1H), 5.01 to
5.10 (m, 2H), 5.75 to 5.85 (m, 1
H).

¹⁹ F-NMR (376.2 MHz, solvent C
DCl _{3, reference: CFCl 3) δ (ppm)} : - 80.5
(D, J = 150 Hz, 1F), -81.9 (s, 3
F), -82.7 (s, 3F), -86.9 (dd, J
= 31, 150 Hz, 1F), -130.3 (s, 2
F), -132.2 (d, J = 18 Hz, 1F).

[Example 4] CH_TwoClCHClCH_TwoCH_TwoO
CH (CH_Three) CH_TwoOCOCF (CF_Three) OCF_TwoCF_Two
CF_Three(R^A1Of compound (4A) wherein is a hydrogen atom
Example CH with 99% GC purity obtained in Example 3_Two= CHCH_TwoCH_TwoO
CH (CH_Three) CH_TwoOCOCF (CF_Three) OCF_TwoCF_Two
CF_Three(36 g) in a flask and stirred in an ice bath.
Was. Keep the internal temperature of chlorine gas (9.5g) at 0-5 ° C
Blew it over three hours. Bring to room temperature and bubbling nitrogen gas
Stir for 1 hour while ringing. Silica gel reaction
By column chromatography (developing solvent: AK-225)
Purified, CH _TwoClCHClCH_TwoCH_TwoOCH (CH_Three)
CH_TwoOCOCF (CF_Three) OCF_TwoCF_TwoCF_Three(22
g) was obtained. GC purity was 88%.

¹ H-NMR (399.8 MHz, solvent:
CDCl ₃ , standard: TMS) δ (ppm): 1.21
(Dd, J = 1.3, 6.3 Hz, 3H), 1.81-
1.93 (m, 1H), 2.19 to 2.26 (m, 1
H), 3.59-3.65 (m, 1H), 3.68-
3.80 (m, 4H), 4.20 to 4.46 (m, 3
H).

¹⁹ F-NMR (376.2 MHz, solvent C
DCl _{3, reference: CFCl 3) δ (ppm)} : - 80.3
(D, J = 150 Hz, 1F), -81.6 (d, J =
5 Hz, 3F), -82.4 (d, J = 7 Hz, 3
F), -86.7 (d, J = 150 Hz, 1F), -1
30.0 (s, 2F), -132.0 (s, 1F).

[Example 5] CF_TwoClCFClCF_TwoCF_TwoO
CF (CF_Three) COF (R^AF1Is a compound in which is a fluorine atom
Production example of (5A)) In a 500 mL nickel autoclave, R113 was added.
(312 g) and sodium fluoride powder (19 g)
And cooled to -10 ° C. Blow nitrogen gas for 1 hour
Fluorine gas diluted to 20% by volume with nitrogen gas
(Hereinafter, this fluorine gas is simply called diluted fluorine gas.
U. ) At a flow rate of 5.77 L / h for 1 hour,
The vessel pressure was adjusted to 0.15 MPa. Diluted fluorine gas
Blow at the same flow rate and keep the reactor pressure at 0.15 MPa.
However, the 88% pure CH obtained in Example 4_TwoClCH
ClCH_TwoCH_TwoOCH (CH_Three) CH_TwoOCOCF (CF
_Three) OCF _TwoCF_TwoCF_Three(4.99 g) was added to R113 (10
The solution dissolved in 2g) was injected over 7 hours.

Next, while diluting fluorine gas is blown in at the same flow rate and keeping the reactor at the same pressure, 90 mL of a mixed solution of benzene having a benzene concentration of 0.01 g / mL and R113 at −10 ° C. is added. -10 ° C to 40 ° C
4 mL was injected while the temperature was raised to. Further, benzene (4 mL) was injected at 40 ° C., the benzene inlet valve of the autoclave was closed, diluted fluorine gas was blown in at the same flow rate, and stirring was continued for 20 minutes while maintaining the same pressure and temperature in the reactor. Further, the injection operation of benzene was similarly repeated four times. The total amount of benzene injected was 1.272 g, R11
The total injection volume of 3 was 125 mL. Further, the diluted fluorine gas is blown in at the same flow rate, stirring is continued for 2 hours while maintaining the same pressure and temperature in the reactor, and nitrogen gas is blown in for 2 hours, and CF ₂ ClCFClCF ₂ CF ₂ OCF (C
F ₃ ) COF was obtained. Quantification by ¹⁹ F-NMR (internal standard:
The yield of C ₆ F ₆ ) was 58%.

¹⁹ F-NMR (376.2 MHz, solvent C
DCl ₃ , standard: CFCl ₃ ) δ (ppm): 26.0
(1F), -64.7 (2F), -77.1 to -77.
7 (1F), -82.5 (3F), -83.9 to -8
4.7 (1F), -117.9 to -119.7 (2
F), -131.3 (1F), -132.3 (1F).

Example 6 CH ₂ ＣＨCHCH ₂ CH ₂ OCH
(CH ₃ ) CH ₂ OH (A compound in which R ^A1 is a hydrogen atom (1
A)) Continuous Production Example The fraction obtained at 28 to 49 ° C./9.33 kPa obtained in Example 2 was analyzed by NMR spectrum to find that CH ₂ ＣＨCHCH ₂ CH
It was confirmed to be ₂ OH. The same reaction as in Examples 1 and 2 was carried out using the fraction (75 mL), and CH ₂ CH
CH ₂ CH ₂ OCH (CH ₃ ) CH ₂ OH was obtained.

[Example 7] CF_TwoClCFClCF_TwoCF_TwoO
CF (CF_Three) COF (R^AF1Is a fluorine atom
Example of continuous production of compound (5A)) CF obtained in Example 5_TwoClCFClCF_TwoCF_TwoOCF (C
F_Three) COF is distilled and purified at normal pressure, and a fraction at 55 ° C is collected.
By doing so, FCOCF (CF_Three) OCF_TwoCF _TwoC
F_Three(40 g) was obtained. The remaining high boilers were saved. Get
FCOCF (CF _Three) OCF_TwoCF_TwoCF_ThreeUsing,
After the reactions of Examples 3 to 5 were performed in the same manner, distillation and purification were performed under normal pressure.
Then, a fraction at 55 ° C. is fractionated and FCOCF (CF_Three) OC
F_TwoCF_TwoCF_Three(32 g) was obtained. The remaining high boiling point
And purified by distillation at normal pressure
By fractionating the fraction at 38 to 139 ° C, CF_TwoC
lCFClCF_TwoCF_TwoOCF (CF_Three) COF was obtained.

Example 8 CH ₃ CHClCOOCH ₂ CH
Production Example of (OCH ₃ ) CH ＝ CH ₂ (Compound (12) wherein R ^A1 is a methoxy group) In a 500 mL three-necked flask, CH ₂ ＣＨCHCH (O
CH ₃ ) CH ₂ OH (70 g) and triethylamine (139 g) were charged and stirred. While keeping the internal temperature at 20 ° C. or less in an ice bath, CH ₃ CHClCOCl (132 g) was used.
Was added dropwise over 2 hours.

After the reaction mixture was added to water (700 mL), methylene chloride (150 mL) was added and two phases were separated.
The aqueous phase was extracted with methylene chloride (150 mL), and the combined organic phases were dried over magnesium sulfate. After filtration, methylene chloride was distilled off to obtain a crude product (142.2 g).
This was distilled under reduced pressure to obtain CH ₃ CHClCOOCH ₂ CH (OCH ₃ ) CH = CH ₂ as a fraction having a GC purity of 94% or more.
(98.7 g).

Boiling point: 102 to 104 ° C./2.7 kPa. ¹ H-NMR (300.40 MHz, solvent: CDCl ₃ ,
Standard: TMS) δ (ppm): 1.70 (dd, J =
1.1, 5.8 Hz, 3H), 3.37 (d, J = 0.
64 Hz, 3H), 3.83 to 3.90 (m, 1H),
4.18 to 4.21 (m, 2H), 4.43 (dq, J
= 1.3, 6.9, 7.1 Hz, 1H), 5.31-
5.40 (m, 2H), 5.63 to 5.76 (m, 1
H).

Example 9 CH ₂ 2CHCH (OCH ₃ ) CH
_{2 OCH (CH 3) COOCH 2} CH (OCH 3) CH = C
Production Example of H ₂ (Compound (1 wherein R ^A1 is a methoxy group)
4)) Production Example DMF (200 mL) was placed in a 500 mL four-necked flask,
Sodium hydride (60% mineral oil dispersion, 22.4 g) was charged and stirred, and under ice-cooling, CH ₂ ＣＨCHCH (OCH ₃ ) C
H ₂ was dropped OH (57.2g). After the addition, the mixture was stirred at room temperature for 1 hour. Next, the CH ₃ CHClC obtained in Example 8 was used.
OOCH ₂ CH (OCH ₃ ) CH = CH ₂ (98 g)
While cooling appropriately so that the internal temperature is maintained at 40 ° C or less,
It was added dropwise over 30 minutes. After the addition, the mixture was stirred at room temperature overnight.

After adding the reaction mixture to water (1 L), 2 m
ol / L hydrochloric acid was added to adjust the pH to 3. The obtained solution is mixed with 200 mL of a mixed solution of hexane / ethyl acetate = 2/1.
And the organic phase was washed twice with water (100 mL). The organic phase was dried over magnesium sulfate, and the solvent was distilled off to obtain a residue (115 g). This is distilled under reduced pressure, and GC
98.6% pure CH ₂ ＣＨCHCH (OCH ₃ ) CH ₂ O
_{CH (CH 3) COOCH 2 CH} (OCH 3) CH = CH 2
(80.2 g).

CH_Two= CHCH (OCH_Three) CH_TwoOH
(40 g) and the same reaction was carried out._Two= CHC
H (OCH_Three) CH_TwoOCH (CH_Three) COOCH_TwoCH
(OCH _Three) CH = CH_Two(46 g) was obtained.

Boiling point: 130 to 131 ° C./1.2 to 1.3
kPa. ¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.40 to 1.45 (m,
3H), 3.31 to 3.43 (m, 6H), 3.36 to
3.48 (m, 1H), 3.61 to 3.69 (m, 1
H), 3.76-3.85 (m, 2H), 4.05-
4.15 (m, 2H), 4.18 to 4.25 (m, 1
H), 5.25-5.38 (m, 4H), 5.63-
5.79 (m, 2H).

Example 10 CH ₂ ＣＨCHCH (OCH ₃ ) C
_{H 2 OCH (CH 3) CH} 2 OH ( Compound R ^{A 1} is a methoxy group (1A)) Preparation nitrogen stream, toluene four-necked flask 2L (750
mL), sodium bis (2-methoxyethoxy) aluminum hydride (65% solution in toluene, 384 mL)
, And stirred at an internal temperature of 20 ° C. or lower to obtain CH obtained in Example 9.
₂ = CHCH (OCH ₃ ) CH ₂ OCH (CH ₃ ) COOC
H ₂ CH (OCH ₃ ) CHＣＨCH ₂ (110 g) was added dropwise over 50 minutes. After stirring at an internal temperature of 50 ° C. for 4.5 hours,
While maintaining the internal temperature at 20 ° C. or lower in an ice bath, 100 mL of 2 mol / L hydrochloric acid was added dropwise.

The reaction mixture was treated with 3.2 m of 2 mol / L hydrochloric acid.
In addition to L, the precipitate was removed by filtration. The obtained filtrate was extracted with methylene chloride (900 mL). The separated aqueous phase was further extracted with methylene chloride (900 mL), and the combined organic phases were washed with water (150 mL). After drying over magnesium sulfate and filtration, the solvent was distilled off to obtain a crude product (92.
9 g) were obtained. This was distilled under reduced pressure to obtain 96% GC purity of CH ₂ ＣＨCHCH (OCH ₃ ) CH ₂ OCH (CH ₃ ) CH.
₂ OH (47 g) was obtained.

Boiling point: 100 to 103 ° C./2.1 kPa. ¹ H-NMR (300.4 MHz, solvent: CDCl ₃ , standard: TMS) δ (ppm): 1.12, 1.12 (d,
J = 6.0 Hz, d, J = 6.2 Hz, 3H), 3.3
3, 3.35 (s, 3H), 3.42 to 3.71 (m,
5H), 3.76 to 3.84 (m, 1H), 5.26 to
5.36 (m, 2H), 5.62 to 5.80 (m, 1
H).

Example 11 CH ₂ 2CHCH (OCH ₃ ) C
H ₂ OCH (CH ₃ ) CH ₂ OCOCF (CF ₃ ) OCF ₂
CF ₂ CF ₃ (Compound (3A) wherein R ^A1 is a methoxy group)
Production example of CH ₂ ＣＨCHCH (OC with a GC purity of 96% obtained in Example 10
H ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ OH (47 g) was placed in a flask and stirred while bubbling nitrogen gas through. FCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (109
g) was added dropwise over 1 hour while maintaining the internal temperature at 25 to 30 ° C. After completion of the dropwise addition, the mixture was stirred at 30 ° C for 2 hours, and triethylamine (8.7 g) was added at an internal temperature of 15 ° C or less.

The obtained crude liquid was purified by silica gel column chromatography (developing solvent: AK-225),
99% pure CH ₂ ＣＨCHCH (OCH ₃ ) CH ₂ OCH
(CH ₃ ) CH ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃
(124 g) was obtained.

¹ H-NMR (300.4 MHz, solvent:
CDCl ₃ , standard: TMS) δ (ppm): 1.21,
1.22 (d, J = 6.3, 6.6 Hz, 3H);
31, 3.32 (s, 3H), 3.42 to 3.59
(M, 2H), 3.67-3.81 (m, 2H), 4.
24-4.43 (m, 2H), 5.24-5.31
(M, 2H), 5.62-5.77 (m, 1H).

¹⁹ F-NMR (282.7 MHz, solvent:
CDCl _{3, reference: CFCl 3) δ (ppm)} : - 80.
0 (1F), -81.3 (3F), -82.1 (3
F), -86.4 (1F), -129.5 (2F),-
131.5 (1F).

Example 12 CH ₂ ClCHCHCH (OC
H ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ OCOCF (CF ₃ )
Production Example of OCF ₂ CF ₂ CF ₃ (Compound (4A) wherein R ^A1 is a methoxy group) CH ₂ ＣＨCHCH (OC with a GC purity of 99% obtained in Example 11
H ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ OCOCF (CF ₃ )
Put OCF ₂ CF ₂ CF ₃ (123 g) into the flask,
The mixture was stirred at a bath temperature of 20 ° C. Chlorine gas (21.8g)
Was blown in over 1.5 hours while maintaining the internal temperature at 0 ° C. or lower. While maintaining the temperature at room temperature and bubbling nitrogen gas,
After stirring for an hour, the resulting crude liquid was purified by silica gel column chromatography (developing solvent: AK-225) to give CH ₂
ClCHClCH (OCH ₃ ) CH ₂ OCH (CH ₃ ) C
H ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (88 g)
I got

¹ H-NMR (300.4 MHz, solvent:
CDCl ₃ , standard: TMS) δ (ppm): 1.22-
1.30 (m, 3H), 3.46, 3.47, 3.5
0, 3.51, 3.53 (each s, total
3H), 3.50-4.02 (m, 6H), 4.19-
4.50 (m, 3H).

¹⁹ F-NMR (282.7 MHz, solvent:
CDCl _{3, reference: CFCl 3) δ (ppm)} : - 80.
0 (1F), -81.3 (3F), -82.1 (3
F), -86.3 (1F), -129.5 (2F),-
131.5 (1F).

Example 13 CF ₂ ClCFClCF (OC
Production example of F ₃ ) CF ₂ OCF (CF ₃ ) COF (compound (5A) in which R ^AF1 is a trifluoromethoxy group) In a 500 mL nickel autoclave, R113 was added.
(312 g) and sodium fluoride powder (8.0 g) were added and stirred, and kept at -5 ° C. At the outlet of the autoclave gas, a cooler maintained at -10 ° C was installed. After blowing nitrogen gas for 1.0 hour, the diluted fluorine gas was supplied at a flow rate of 8.2.
Blowing was performed at 0 L / h for 1 hour. Next, while blowing the diluted fluorine gas at the same flow rate, the CH ₂ Cl obtained in Example 12 was used.
CHClCH (OCH ₃ ) CH ₂ OCH (CH ₃ ) CH ₂ O
A solution of COCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (3.81 g) dissolved in R113 (76.2 g) was injected over 3.8 hours.

Next, while maintaining the reactor pressure at 0.15 MPa, diluted fluorine gas was blown in at the same flow rate, and benzene having a benzene concentration of 0.01 g / mL and R1 were added.
9 mL of the mixed solution with 13 was injected while the temperature was raised from 25 ° C. to 40 ° C., the benzene injection valve of the autoclave was closed, and stirring was continued for 0.3 hour. Next, while maintaining the reactor pressure at 0.15 MPa and the temperature inside the reactor at 40 ° C., 6 mL of the above-mentioned benzene solution was injected, and stirring was continued for 0.3 hour. Further, the same operation was repeated three times. The total amount of benzene injected was 0.34 g, and the total amount of R113 injected was 33 mL. Further, a diluted fluorine gas was blown for 0.7 hours, and then a nitrogen gas was blown for 1.0 hour. As a result of analysis by GC-mass spectrometry, CF ₂ ClCFClCF
(OCF ₃ ) CF ₂ OCF (CF ₃ ) COF (yield 39
%), CF ₃ CF (OCF ₂ CF ₂ CF ₃ ) COF (yield 4
1%). The reaction product contains CF ₃ C
F [OCF ₂ CF (OCF ₃ ) CFClCF ₂ Cl)] C
F ₂ OCOCF (CF ₃ ) OCF ₂ CF ₂ CF ₃ (yield 24
%) Was also included.

Example 14 CF ₂ = CFCF ₂ CF ₂ OCF
= CF ₂ (compound R ^AF is a fluorine atom _{(7)) CF 2 ClCFClCF 2} CF 2 OCF obtained in Production Example Example 7 (C
F ₃₎ known method using a COF (JP 2-4203
The title compound was synthesized according to 8). That is, C
F ₂ ClCFClCF ₂ CF ₂ OCF (CF ₃ ) COF (1
33 g) was slowly added dropwise into ice-cooled methanol (300 mL). Further, a methanol solution of potassium hydroxide was added until the reaction solution became alkaline. After that, methanol was distilled off and dried sufficiently.
Pyrolyzed at 0 ° C. to CF ₂ ClCFClCF ₂ CF ₂ OCF
= CF ₂ (80 g) was obtained.

In a 500 mL four-necked flask, zinc (60
g) and 1,4-dioxane (200 mL), and then the above obtained CF ₂ ClCFClCF ₂ CF ₂ OCF =
CF ₂ (80 g) was slowly added dropwise. One hour after the completion of the dropwise addition, the zinc was filtered off and distilled to obtain CF ₂ = CFCF ₂ CF _2.
OCF = CF ₂ (31.9 g, 50% yield) was obtained.

Example 15 Polymer Production Example Using the CF ₂ ＣＦCFCF ₂ CF ₂ OCF ＝ CF ₂ obtained in Example 14, polymerization was carried out in the same manner as a known method. That is, CF ₂ = CFCF ₂ CF ₂ OCF = CF ₂ (35 g),
Ion-exchanged water (150 g) and a polymerization initiator [((C
H ₃ ) ₂ CHOCOO) ₂ , 90 mg] was placed in a 200 mL pressure-resistant glass autoclave. After this was replaced with nitrogen three times, suspension polymerization was carried out at 40 ° C. for 22 hours. As a result, a polymer was obtained.

Intrinsic viscosity [η] of polymer (measured in perfluoro (2-butyltetrahydrofuran) at 30 ° C.)
Was 0.5 dL / g. The glass transition point of the polymer was 108 ° C., and it was a tough and transparent glassy polymer at room temperature. The 10% thermal decomposition temperature was 460 ° C., the refractive index was 1.34, and the light transmittance was 95% or more, and a polymer equivalent to a polymer obtained by a conventional method was produced.

[0108]

According to the production method of the present invention, vic- can be obtained in a short step and in a high yield from the compound (1) which is inexpensive and easily available.
A fluoride compound (5) having a dichloro structure can be produced. The fluoride compound (5) is a compound useful as a raw material of a monomer for producing a fluororesin. Further, according to the present invention, a novel compound useful as a raw material for the monomer is provided. Further, a method for continuously producing compound (1) by using compound (2) obtained together with compound (5) again for reaction with compound (1) can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 69/708 C07C 69/708 A C08F 14/18 C08F 14/18 // C07B 61/00 300 C07B 61 / 00 300 (72) Inventor Yoko Takebe 1150 Hazawa-cho, Kanagawa-ku, Yokohama-shi, Kanagawa Prefecture F-term in Asahi Glass Co., Ltd. (reference) 4H006 AA01 AA02 AB46 AB84 AC13 AC30 AC47 AC48 BA02 BA06 BA37 BB12 BC14 BC31 BD34 BD52 BE53 BM10 BM71 BM72 BP10 BS10 BS90 KA14 4H039 CA65 CD90 4J100 AC59P AE84P BA04P BB07P CA01 CA04

Claims (17)

[Claims] A compound (1) is reacted with a compound (2).
And reacting the compound (3) with a chlorinating agent
The compound (4) is obtained by
Reacting with fluorine in the liquid phase to obtain compound (5)
A method for producing a fluoride compound, which is a feature of the present invention. CH_Two= CHCHR^ACH_TwoOCH (CH_Three) CH_TwoOH ・ ・ ・ (1) FCOR^B ... (2) CH_Two= CHCHR^ACH_TwoOCH (CH_Three) CH_TwoOCOR^B ... (3) CH_TwoClCHClCHR^ACH_TwoOCH (CH_Three) CH_TwoOCOR^B ・ ・ ・ (4) CF_TwoClCFClCFR^AFCF_TwoOCF (CF_Three) COF (5) where R^AIs hydrogen atom, alkyl group or alkoxy
And R is^AR is a hydrogen atom^AFIs fluorine
Child and R^AIs an alkyl group or an alkoxy group
R in case^AFMeans that at least one of the hydrogen atoms in the group is fluorinated
R ^BIs a monovalent organic group. 2. The process according to claim 1, wherein the compound (2F) is obtained together with the compound (5). FCOR ^BF (2F) where R ^BF when R ^B is a group that does not react with fluorine
Is a monovalent organic group identical to R ^B, R ^BF when R ^B is a group which reacts with fluorine is a monovalent organic group in which R ^B fluorinated. 3. The production method according to claim 1, wherein the compound (2F) obtained by the production method according to claim 2 is used as the compound (2) to be reacted with the compound (1). 4. The method according to claim 1, wherein R ^B is a perfluoroalkyl group, a perfluoro (partial chloroalkyl) group, a perfluoro (heteroatom-containing alkyl) group, or a perfluoro (partial chloro (heteroatom-containing alkyl)) group.
4. The production method according to 2 or 3. 5. Compound (1) is compound (1A), compound (2) is compound (2A), compound (3) is compound (3A), and compound (4) is compound (4A) The method according to claim 1, wherein the compound (5) is the compound (5A). Embedded image Provided that R ^A1 is a hydrogen atom or an alkoxy group;
R ^AF1 when ^A1 is a hydrogen atom is a fluorine atom,
When R ^A1 is an alkoxy group, R ^AF1 is a perfluoroalkoxy group. (6) R ^A1 is a hydrogen atom or a methoxy group,
R ^AF1 when R ^A1 is a hydrogen atom is a fluorine atom, a manufacturing method of claim 5 R ^AF1 when R ^A1 is a methoxy group is trifluoromethoxy group. 7. A compound (2A) is obtained together with a compound (5A), and a part or all of the compound (2A) is converted to a compound (1).
6. The compound (2A) to be reacted with A).
Or the production method according to 6. 8. The compound (4) is reacted with fluorine in a liquid phase.
To obtain a compound (5)
Method of manufacturing a product. CH_TwoClCHClCHR^ACH_TwoOCH (CH_Three) CH_TwoOCOR^B ・ ・ ・ (4) CF_TwoClCFClCFR^AFCF_TwoOCF (CF_Three) COF (5) where R^AIs hydrogen atom, alkyl group or alkoxy
And R is^AR is a hydrogen atom^AFIs fluorine
Child and R^AIs an alkyl group or an alkoxy group
R in case^AFMeans that at least one of the hydrogen atoms in the group is fluorinated
R ^BIs a monovalent organic group. 9. The method according to claim 8, wherein R ^B is a perfluoroalkyl group, a perfluoro (partial chloroalkyl) group, a perfluoro (hetero atom-containing alkyl) group, or a perfluoro (partial chloro (hetero atom-containing alkyl)) group. Manufacturing method. 10. The compound (4) is the compound (4A),
The compound (5) is the compound (5A).
The production method described in 1. Embedded image Provided that R ^A1 is a hydrogen atom or an alkoxy group;
R ^AF1 when ^A1 is a hydrogen atom is a fluorine atom,
When R ^A1 is a hydrogen atom, R ^AF1 is a perfluoroalkoxy group. 11. A liquid phase comprising an organic solvent which does not contain a CH bond and has an essential CF bond as an essential component.
The method according to any one of the above. 12. The process according to claim 1, wherein the reaction is carried out while supplying an excessive amount of fluorine to the liquid phase with respect to the hydrogen atoms in the compound (4). 13. A compound (5) obtained by the production method according to claim 1, which is thermally decomposed into a compound (6), and the compound (6) is further dechlorinated. Production method of compound (7). CF ₂ ClCFClCFR ^AF CF ₂ OCF = CF ₂ (6) CF ₂ = CFCFR ^AF CF ₂ OCF = CF ₂ (7) where R ^AF is one of a fluorine atom and a hydrogen atom of an alkyl group
At least one is a fluorinated group, or at least one of the hydrogen atoms of the alkoxy group is a fluorinated group. 14. The method according to claim 13, wherein at least one kind of the compound (7) obtained by the production method is polymerized, or
A method for producing a fluororesin, comprising polymerizing at least one compound (7) obtained by the production method described in (1) and at least one polymerizable monomer copolymerizable with the compound (7). . 15. The reaction with fluorine in the presence of an alkali metal fluoride or an alkaline earth metal fluoride.
14. The production method according to any one of items 13 to 13. (16) a compound (3A), a compound (4A) or a compound (5B); Embedded image However, R ^A1 is a hydrogen atom or an alkoxy group, and n
Is an integer of 0 to 9. 17. Compound (3A-1), compound (3A-
2), compound (4A-1), compound (4A-2) or compound (5B-1). Embedded image