Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
  • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
  • C07C69/708—Ethers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
  • C07C43/14—Unsaturated ethers
  • C07C43/178—Unsaturated ethers containing hydroxy or O-metal groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
  • C07C51/58—Preparation of carboxylic acid halides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
  • C07C59/125—Saturated compounds having only one carboxyl group and containing ether groups, groups, groups, or groups
  • C07C59/135—Saturated compounds having only one carboxyl group and containing ether groups, groups, groups, or groups containing halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/62—Halogen-containing esters
  • C07C69/63—Halogen-containing esters of saturated acids
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

• the present invention relates to new process for producing an acid fluoride compound having a vic-dichloro structure, which is useful for an intermediate compound for producing a starting monomer of a fluorinated resin.
• a compound having a perfluoroalkyl chain having a vic-dichloro structure (a structure wherein one chlorine atom is bonded to each of two adjacent carbons) at its terminal and a fluorocarbonyl group (-COF) is useful as an intermediate compound for producing a material monomer of a fluorinated resin, or a fluororesin.
• a perfluorovinyl group of such a compound is a polymerizable group and thus various fluorinated resins can be produced by polymerization of such a compound.
• the resulting fluorinated resins are useful resins excellent in heat resistance and chemical resistance.
• a monomer of such a fluorinated resin, perfluoro (3-butenyl vinyl ether) is conventionally prepared by the f ollowing manufacturing route .
• CF 2 CFCl + ICl ⁇ CF 2 C1CFC1 I (A ) ⁇ CF 2 C1CFC1CF 2 CF 2 I ( B )
• the object of the present invention is to provide a process for producing an acid fluoride (III) having a vic-dichloro structure such as perfluoro (3 , 4- dichlorobutyl vinyl ether, which is a precursor to perfluoro (3-butenyl vinyl ether), in a short process from raw material available at a low cost.
• an acid fluoride (III) having a vic-dichloro structure such as perfluoro (3 , 4- dichlorobutyl vinyl ether, which is a precursor to perfluoro (3-butenyl vinyl ether)
• E H1 a bivalent connecting group or a single bond
• E F1 a group corresponding to E H1
• E F1 is a single bond
• E F1 is a single bond
• E H1 is a bivalent connecting group having one or more hydrogen atoms
• E F1 is a group corresponding to E H1 wherein at least one hydrogen atom is fluorinated
• E H1 is a bivalent connecting group having no hydrogen atom
• E F1 is the same group as E H1 ,
• the process of the present invention does not include difficult problems such as corrosion of the apparatus and handling of the reagents since iodine chloride and fuming sulfuric acid etc. are not employed.
• a monovalent saturated hydrocarbon group may be a straight chain structure, a branched structure, a cyclic structure (that is, a cycloalkyl group) means organic or a structure having a partially cyclic structure.
• the carbon number of the monovalent saturated hydrocarbon group is preferably from 1 to 20, particularly preferably from 1 to 10.
• a halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a fluorine atom, a chlorine atom or a bromine atom is preferred.
• partially halogeno means that a hydrogen atom which is not substituted by a halogen atom is present in the group of a halogeno group, “partially fluoro” and “perfluoro”, etc. mean in the same manner.
• the halogeno monovalent hydrocarbon group may be a group having at least one hydrogen atom in the above-mentioned monovalent saturated hydrocarbon group substituted by a halogen atom.
• the halogen atom in the halogeno monovalent hydrocarbon group is preferably a fluorine atom, a chlorine atom or a bromine atom.
• a fluorine atom alone or a fluorine and a halogen atom other than a fluorine atom is particularly preferred.
• the groups disclosed in the examples of the following compounds may be mentioned.
• hetero atom-containing monovalent saturated hydrocarbon group in the present specification, a hetero atom or a group having a hetero atom which undergo no change by the fluorination reaction in the above- mentioned monovalent saturated hydrocarbon group may be mentioned. Particularly preferred is a group having a bivalent hetero atom or a bivalent hetero atom group which undergo no change by the fluorination reaction in the above-mentioned monovalent saturated hydrocarbon group .
• E H1 is a single bond wherein R Hl and a carbon atom bonding R H2 and R H3 are directly bonded.
• E H1 is a bivalent bonding group
• a bivalent saturated hydrocarbon group a halogeno bivalent saturated hydrocarbon group
• a bivalent (hetero atom-containing saturated hydrocarbon group or a halogeno bivalent (hetero atom-containing saturated hydrocarbon group is preferred.
• the bivalent bonding group may be of a straight chain structure, a branched chain structure or a structure containing a cyclic structure.
• R H2 and R H3 may be properly modified depending on the structure of the objective compound and is preferably a hydrogen atom, an alkyl group, a halogeno alkyl group, a hetero atom-containing alkyl group or a hetero atom-containing halogeno alkyl group because of their availability. Since a fluorine atom can be introduced into R H2 and R H3 by the fluorination reaction described later, a group containing a halogen atom other than a fluorine atom is preferred from the economical reason, when R H2 and R H3 are halogeno groups.
• R HB is preferably adjusted so that the compound (I) will be readily soluble in a liquid phase to be used at the time of fluorination.
• R HB is preferably a halogeno alkyl group or a halogeno (hetero atom-containing alkyl) group, and is more preferably a group containing a fluorine atom as an essential atom, among which a perfluoro alkyl group, a perfluoro (partially chlorinated alkyl) group, a perfluoro (hetero atom-containing alkyl) group or a perfluoro (partially chlorinated (hetero atom-containing alkyl) group is particularly preferred.
• R HB is particularly preferably a group containing a fluorine atom as an essential atom, since the compound (I) is satisfactorily soluble in a liquid phase, and the fluorination of the compound (I) can be carried out in a homogeneous phase at the time of the fluorination of the compound (I) in a liquid phase.
• the fluorine content in the compound (I) (the proportion of the fluorine atoms in the molecule) is preferably modified depending on the kind of the liquid phase to be used in the fluorination.
• the lower limit of the fluorine content (the ratio of the fluorine atoms to the molecular weight of the compound) is preferably 10% by mass, particularly preferably 30% by mass and the upper limit is preferably 86% by mass, particularly preferably 80% by mass.
• the molecular weight of the compound (I) is preferably from 300 to 1000, whereby the reaction in a gas phase can be suppressed and the reaction in a liquid phase can be smoothly carried out at the time of fluorination reaction.
• the compound (I) tends to be readily volatile, and it is likely that a decomposition reaction may take place in a gas phase during the fluorination reaction in a liquid phase. On the other hand, if the molecular weight is too large, purification of the compound (I) tends to be difficult.
• the compound (I) various known compounds and new compounds in the following may be mentioned.
• the compound (I) is fluorinated in a liquid phase.
• a method of fluorinating the compound (I) with elemental fluorine in a solvent fluorination method-1) or an electrochemical fluorination (fluorination method-2) may be mentioned, and fluorination method-1 is preferred among them.
• the compound (I) is dissolved in anhydrous hydrofluoric acid to obtain a solution, and the solution is electrolyzed in an electrolytic cell to fluorinate the compound (I) to form the compound (II).
• the compound (I) and fluorine gas are reacted in a solvent (hereinafter referred to solvent-1) to form the compound ( II ) .
• a solvent hereinafter referred to solvent-1
• fluorine gas fluorine gas of 100% or fluorine gas diluted with an inert gas may be used.
• the inert gas nitrogen gas and helium gas are preferred, and nitrogen gas is particularly preferred from an economical reason.
• the amount of fluorine gas in the mixed gas of the inert gas and fluorine gas is preferably at least 5 vol.% from the view point of the efficiency and from 5 to 30 vol.% is particularly preferred since an abstraction of the chlorine atom and a migration of the chlorine atom can be prevented.
• Solvent-1 to be used for fluorination method-1 is preferably a solvent which contains no C-H bond and which necessarily contains a C-F bond. Further, it is preferred to use a perfluoroalkane or an organic solvent obtained by perfluorinating a known organic solvent having at least one atom selected from a chlorine atom, a nitrogen atom and an oxygen atom in its structure. Further, as solvent-1, it is preferred to employ a solvent which provides a high solubility to the compound (I), and it is particularly preferred to employ a solvent which is capable of dissolving at least 1% by mass of the compound ( I ) , particularly a solvent which is capable of dissolving at least 5% by mass.
• solvent-1 may be the compound (II), the compound (III), the compound (IV), perfluoroalkanes (such as FC-72), perfluoroethers (such as FC-75, FC-77), perfluoropolyethers (such as trade names: KRYTOX, FOMBLIN, GALDENE and DEMNUM) , chlorofluorocarbons (trade name: FLONLUBE) , chlorofluropolyethers, perfluoroalkylamines (such as perfluorotrialkylamine) , and an inert fluid (trade name: FLUORINERT) .
• a perflurotrialkylamine or the compound (II) is preferred as solvent-1.
• the compound (I) may be or not diluted with solvent-1, when the compound(I) is supplied. Further, in the continuous system (2), when the compound (I) is diluted with a solvent, it is preferred to adjust the amount of solvent-1 to at least 5 times by mass, particularly preferably at least 10 times by mass, relative to the compound (I) .
• fluorine gas When the reaction is carried out by a batch system, it is preferred to charge fluorine gas so that the amount of fluorine atoms is always excess equivalent, relative to hydrogen atoms in the compound (I) , and it is particularly preferred that fluorine gas is used so that it becomes at least 1.5 times by equivalent (at least 1.5 times by mol) , relative to hydrogen atoms in the compound (I) , from the view point of selectivity.
• reaction when the reaction is carried out by a continuous system, it is preferred to continuously supply fluorine gas so that the amount of fluorine atoms will be excess equivalent, relative to hydrogen atoms in the compound (I), and it is particularly preferred to continuously supply fluorine gas so that it becomes at least 1.5 times by equivalent (at least 1.5 times by mol), relative to hydrogen atoms in the compound (I), from the view point of the selectivity.
• the reaction temperature for the fluorination reaction by fluorination method-1 may be varied depending on the structure of E H1 , and it is preferably at least
• the selectivity and efficiency for industrial operation it is particularly preferably from -50 to +100°C, and it is especially preferably from -20 to +50 o C to prevent abstraction and migration of a chlorine atom.
• the reaction pressure of the fluorination reaction is not particularly limited, and it is particularly preferably from atmospheric pressure to 2 MPa ( gage pressure, the same applies to hereinafter) from the viewpoint of the yield, selectivity and efficiency for industrial operation.
• a C-H bond- containing compound to the reaction system or to carry out under irradiation of ultraviolet ray.
• a C-H bond-containing compound to the reaction system or to irradiating ultraviolet ray at a later stage of the fluorination reaction.
• the time for ultraviolet irradiation is preferably from 0.1 to 3 hours.
• the C-H bond-containing compound is an organic compound other than the compound (I), and an aromatic hydrocarbon is particularly preferred. Especially, for example, benzene or toluene is preferred.
• the amount of such a C-H bond-containing compound is preferably from 0.1 to 10 mol%, particularly from 0.1 to 5 mol%, relative to hydrogen atoms in the compound (I) .
• E H1 is a single bond
• E F1 will be a single bond
• E H1 is a bivalent connecting group having no hydrogen atom
• E F1 will be the same group as the bivalent group
• E H1 is a bivalent connecting group having one or more hydrogen atoms
• E F1 will be the group wherein at least one hydrogen atoms is fluorinated.
• E H1 is a perhalogeno group
• E H1 and E F1 are the same.
• E H1 is an alkylene group or a group wherein an etheric oxygen atom is inserted between the carbon-carbon bond of an alkylene group
• E F1 will be the group wherein at least one hydrogen atom in these groups is substituted by fluorine atom.
• E F1 is preferably a perfluoroalkylene group or a perfluoro (hetero atom-containing ) alkylene group .
• R H2 and R H3 contain a hydrogen atom(for example, each of R H2 and R H3 is a partially fluoro monovalent saturated hydrocarbon) group)
• each of R F2 and R F3 is the group, respectively, wherein at least one hydrogen atom in the group is fluorinated, and is preferably a perfluoro monovalent saturated hydrocarbon group.
• each of H2 and R H3 is a partially chloro monovalent saturated hydrocarbon group
• each of R F2 and R F3 is a fluoro (partially chloro monovalent saturated hydrocarbon group) , respectively, wherein at least one hydrogen atom in the group is fluorinated, and are particularly preferably a perfluoro (partially chloroalkyl) group.
• R F2 and R F3 are preferably fluorine atom, a perfluoro monovalent saturated hydrocarbon group or a perfluoroalkoxyl group.
• R FB is a group corresponding to R HB , and R FB will be the same as R HB , when R HB is a halogeno group.
• R FB When R HB is a hydrogen-containing group, R FB will be a group wherein the hydrogen in the group is fluorinated.
• R FB is preferably a perfluoroalkyl group or a perfluoro (alkoxy alkyl) group.
• HF will be formed as a by-product.
• an HF scavenger in the reaction system or to contact the outlet gas with an HF scavenger at the gas outlet of the reactor.
• a base such as an alkali metal fluoride (for example, sodium fluoride, etc.) is preferred, and may be incorporated in the reaction system.
• the HF scavenger is preferably an alkali metal fluoride, particularly preferably NaF .
• the amount is preferably from 1 to 20 mol times, more preferably from 1 to 5 mol times, relative to the total amount of hydrogen atoms contained in the compound (I) .
• a condenser preferably maintained at a temperature of from 10°C to room temperature, particularly preferably at about 20°C
• a condenser preferably maintained at a temperature of from -78°C to +10°C, more preferably from -30°C to 0°C
• a liquid- returning line may be installed to return the condensed liquid from the condenser of (3) to the reactor.
• the crude product containing the compound (II) obtained by the fluorination reaction may be employed in the next step as it is, or may be purified to a high purity.
• the purification method may, for example, be a method of distilling the crude product under atmospheric pressure or reduced pressure.
• the compound (III) and/or the compound (IV) are obtained by dissociation of an ester bond of the compound (II) .
• the objective compound by the production method of the present invention is the compound (III), the compound (IV) or both of the compound (III) and the compound (IV) .
• the reaction to dissociate the ester bond of the compound (II) is a reaction to form two -COF groups by breaking -CF 2 OCO- .
• Such a reaction is preferably carried out by a thermal decomposition reaction or a decomposition reaction which is carried out in the presence of a nucleophile or an electrophile.
• the thermal decomposition reaction can be conducted by heating the compound (II) .
• the reaction type of the thermal decomposition reaction is preferably selected by the boiling point and the stability of the compound (II) .
• a gas phase thermal decomposition method may be employed in which it is continuously decomposed in a gas phase, and the outlet gas containing the obtained compound (III) is condensed and recovered.
• the reaction temperature of the gas phase thermal decomposition method is preferably from 50 to 350°C ⁇ particularly preferably from 50 to 300°C, especially preferably from 150 to 250°C.
• an inert gas which is not concerned directly with the reaction, may be present in the reaction system.
• nitrogen or carbon dioxide may, for example, be mentioned. It is preferred to add an inert gas in an amount of from 0.01 to 50 vol% relative to the compound (II). If the amount of the inert gas is large, the recovery of the product may sometimes decrease.
• the compound (II) is a compound which is hardly vaporized
• the reaction pressure in this case is not limited.
• the product obtained from the ester decomposition is of a lower boiling point, and it is preferred to carry out the reaction by using a reactor equipped with a distillation column whereby the product having a low boiling is continuously withdrawn.
• reaction temperature for the liquid phase thermal decomposition method is preferably from 50 to 300°C, particularly preferably from 100 to 250°C.
• the decomposition may be conducted in the absence of a solvent or in the present of a solvent (hereinafter referred to as solvent-2).
• Solvent-2 is not particularly limited so long as it is not reactive with the compound (II) , and it is miscible with the compound (II) and is not reactive with the product. Further, as solvent-2, it is preferred to select one which is readily separable at the time of purification of the product.
• solvent-2 is preferably an inert solvent such as perfluorotrialkylamine or perfluorodecalim, or a chlorotrifluorocarbon, particularly preferably chlorotrifluoroethylene oligomer having a high boiling point (for example, trade name: FLONLUBE) .
• the amount of solvent-2 is preferably from 10 to 1000% by mass, relative to the compound (II) .
• F " is nucleophilically added to a carbonyl group present in the ester bond of the compound (II), whereby CF 2 C1CFC1E F1 CR F2 R F3 CF 2 0 ⁇ will be detached, and an acid fluoride [the compound (IV) ] will be formed. From CF 2 C1CFC1E F1 CR F2 R F3 CF 2 0 " , F " will further be detached to form an acid fluoride [the compound (III)]. The detached F " will react with another molecule of the compound (II) in the same manner.
• the nucleophile to be used at the initial stage of the reaction may be in a catalytic amount or may be used excessively.
• the amount of the nucleophile such as F " is preferably from 1 to 500 mol%, particularly preferably from 1 to 100 mol%, especially preferably from 5 to 50 mol%, relative to the compound (II) .
• the lower limit of the reaction temperature is preferably -30°C, and the upper limit is preferably the boiling point of solvent-3 or the compound (II) .
• the reaction temperature is usually particularly preferably from -20°C to 250°C. This method is also preferably carried out by using a reactor equipped with a distillation column.
• the following new compounds may be mentioned.
• the following compounds can be led to the corresponding vic-dichloro acid fluoride compounds by the reaction which will be described in the examples.
• the thermal decomposition reaction can be conducted at low temperature by carrying out the decomposition in the presence of NaF, whereby the decomposition of the compound can be prevented.
• the material production route-1 is a method of producing the compound (I) by reacting the following compound (Al) with the following compound (A2).
• X is a halogen atom
• R H! ,E H1 R H2 and R H3 are the same as defined above.
• the material production route-2 is a method of producing the compound (IB) wherein R H1 - is CX 1 X 2 C1CX 3 C1-, by reacting the following compound (Bl) with the following compound (B2) to form the following compound (B3), followed by reacting the following compound (B3) with a chlorinating agent.
• the symbols in the following formulae mean the same as defined above, and X 10 is a halogen atom, or a hydroxyl group.
• CX 1 X 2 CX 3 -E H] -) CR H2 R H3 CH 2 -OH ( Bl) X 10 COR HB (B 2)
• a reaction of the compound (Al) with the compound (A2) and a reaction of the compound (Bl) with the compound (B2) can be carried out under an usual esterification reaction condition. While these reaction may be conducted in the presence of a solvent (hereinafter referred to as solvent 4) , it is preferred to carried out in the absence of the solvent 4 from the view point of the volume efficiency.
• solvent 4 it is preferably a halogenated hydrocarbon solvent such as dichloromethane and chloroform.
• the amount of the solvent 4 is preferably from 0.5 to 5 times, relative to the total mass of the compound (Al) and the compound (A2) (or the compound (Bl) and the compound (B2)).
• HX is formed as a by-product.
• HF will be formed.
• an alkali metal fluoride such as sodium fluoride
• a base such as trialkylamine and pyridine
• the amount of the scavenger for HF is preferably from 1 to 10 mol times, relative the compound (A2) or the compound (B2) .
• a scavenger for HF it is preferred to remove HF from the reaction system by carrying with nitrogen gas.
• the lower limit of the temperature of the esterification reaction is preferably -50°C and the upper limit is preferably +100°C or the boiling point of the solvent 4, whichever is lower.
• the reaction time is adjusted depending upon the feeding speed of the material and amount of the compound to be used in the reaction, and the reaction pressure is preferably from 0 to 2 MPa.
• the compound (B3) formed by the reaction of the compound (Bl) with the compound (B2) is reacted with a chlorinating agent to form the compound (IB) .
• the reaction can be carried out under methods and conditions in a usual chlorination reaction.
• the chlorinating agent is preferably chlorine (Cl 2 ) .
• chlorine chlorine
• the amount is preferably from 1 to 10 mol times, especially preferably from 1 to 5 mol times, relative the compound (B3) .
• the reaction of the compound (B3) with a chlorinating agent may be conducted in the presence of a solvent (hereinafter referred to as solvent 5), it is preferred to conduct in the absence of the solvent 5 from the viewpoint of the volume efficiency.
• solvent 5 is preferably a halogenated hydrocarbon solvent such as dichloromethane and chloroform.
• the amount of the solvent 5 is preferably from 0.5 to 5 times, relative to the mass of the compound (B3).
• the reaction temperature is preferably from -78°C to+200°C.
• the crude product containing the compound (I) produced by the method described above may be employed in the next reaction as a purified substance after the purification, or as it is.
• the method of purifying the crude product containing the compound (I) may be the one such as a method of distilling the crude product as it is, a method of separating the crude product phase after treated with a diluted aqueous alkali solution and a method of distilling the crude product after extracted by an appropriate organic solvent.
• the process of the present invention can be made to be the following efficient processes 1 to 3 by selecting the kinds of the groups in the compound (I)- (IV) in order to omit a separation step of the compound or modifying the process to a continuous process.
• the groups not defined there have the same meaning as described above.
• R HB is selected so that the compound (IV) will be of the same structure as the compound (A2 ) or the compound (B2) .
• the resulting compound (IV) can be used again for the reaction with the compound (Al) or the compound (Bl), whereby the process of the present invention can be made to be a continuous production process.
• a specific example of the process may be the one wherein a perhalogeno group is used as R HB in the compound (A2) or the compound (B2).
• the process can be made to be the following production process .
• CH 2 -CH(CH 2 )2 ⁇ H (16.6g) and DMF (120 ml) were put into another flask and cooled to maintain the internal temperature at from 8 to 9°C.
• a sodium hydrogen carbonate (10 g) was added thereto over a period of 30 minutes, and cooled again after stirred for 30 minutes at room temperature.
• CH 3 CHC1C00 (CH 2 ) 2 CH CH 2 (50g) , which had been obtained earlier, dissolved in 30 ml of DMF was added dropwise thereto over 1.5 hours. After completion of the dropwise addition, heating was continued for 3 hours while maintaining the internal temperature at from 80 to 85°C.
• FCOCF(CF 3 )OCF 2 CF 2 CF 3 50g was added dropwise thereto over 1 hour while maintaining the internal temperature at from 25 to 30°C. After completion of the dropwise addition, stirring was continued at room temperature for 3 hours and 80 ml of a saturated sodium hydrogen carbonate aqueous solution was added thereto at the internal temperature of not higher than 15°C.
• the resulting reaction product was purified by a silica gel column chromatography (eluent: AK-225), to obtain 22g of CH 3 CH(0(CH 2 ) 2 CHClCH 2 Cl)CH 2 OCOCF(CF 3 )OCF 2 CF 2 CF 3 . Its GC purity was 88%. NMR spectra were as follows.
• CHC1 CC10(CH) 5 0H (13 g) obtained in EXAMPLE 2-1 and triethylamine (25 g) were put into a flask and stirred in an ice bath.
• the resulting crude liquid was subjected to liquid separation, and the lower layer obtained was washed twice with 50 ml of water, dried over magnesium sulfate, followed by filtration to obtain a crude liquid.
• CC1F 2 CC1F0 (CF 2 ) 5 OCOCF (CF 3 OCF 2 CF 2 CF 3 Into a 500 ml autoclave made of nickel, R-113 (312 g) was added, stirred and maintained at 25°C. At the gas outlet of the autoclave, a condenser maintained at 20°C, a NaF packed layer and a condenser maintained at -10°C were installed in series. Further, a liquid returning line was installed to return the condensed liquid from the condenser maintained at -10°C to the autoclave. Nitrogen gas blown thereinto for 1.0 hours, and then 20% fluorine gas diluted with nitrogen gas was blown thereinto for about 1 hour at flow rate of 7.40 L/h.
• the total amount of benzene injected was 0.192 g, and the total amount of R-113 injected was 18 ml. Further, nitrogen gas was blown thereinto for 1.5 hours. The objective product was quantitatively analyzed by 19 F-NMR, whereby the yield of the identified product was 73%.
• a saturated aqueous sodium carbonate solution (250 ml) and water (200 ml) were added to wash the lower layer, followed by liquid separation and washing with water (200 ml) twice, and dried over magnesium sulfate. After filtration followed by distillation to remove the solvent, 98.1 g of was obtained.
• FCOCF(CF 3 )OCF 2 CF 2 CF 3 (30 g) was added dropwise thereto over 1 hour while maintaining the internal temperature not higher than 10°C. After completion of dropwise adding, stirring was continued at room temperature for 2 hours, and 50 ml of water was added thereto at the internal temperature not higher than 15°C.
• the residual high boiling point fraction was mixed with the preserved above-mentioned fraction having high boiling points, and then was purified by a distillation under atmospheric pressure to obtain CF2CICFCICF 2 CF2O (CF 2 ) 2 COF (2.0 g) as a fraction of from 138 to 139°C.

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