BACKGROUND ART A compound having a perfluoroalkyl chain having a vic-dichloro structure (a structure wherein one chlorine atom is bonded to each of two adjacent carbon atoms) at its terminal and a fluorocarbonyl group (-COF) is useful as an intermediate compound for producing a starting monomer of a fluorinated resin, or a fluororesin. For example, such a compound can be reacted with zinc and then dechlorinated to form a fluoride compound having a perfluorovinyl group (CF2=CF-). A perfluorovinyl group of such a compound is a polymerizable group and thus various fluorinated resins can be produced by polymerizing the compound. The resulting fluorinated resins are useful resins excellent in heat resistance and chemical resistance.

Among the above-mentioned fluorinated resins, a homopolymer of perfluoro (3-butenyl vinyl ether) [CF2=CFCF2CF20CF=CF2] is used in various fields as a transparent fluorinated resin. Conventionally, perfluoro (3-butenyl vinyl ether) has been prepared by the

following production route.

CF2=CFC1 + IC1-+ CF2ClCFClI (A) The compound (A) + CF2=CF2-CF2ClCFClCF2CF2I (B) The compound (B) +fumic sulfuric acid-CF2ClCFClCF2COF (C) The compound (C) +HFPO-CF2ClCFClCF2CF20CF (CF3) COF (5A-1) The compound (5A-1) CF2ClCFClCF2CF20CF=CF2 (D) The compound (D) + zinc < CF2=CFCF2CF2OCF=CF2 That is to say, CF2=CFC1 is reacted with iodine chloride to form the compound (A), which is reacted with tetrafluoroethylene to form the compound (B), which is then reacted with fuming sulfuric acid to form the compound (C). Further, the compound (C) is reacted with hexafluoropropylene oxide (HFPO) in the presence of an alkali metal fluoride such as KF etc. to form the compound (5A-1). The compound (5A-1) is heated at least 250°C in the presence of soda ash or a glass bead to form the compound (D). Such a compound (D) can be also produced through the elimination of COF2 by a thermal decomposition of an alkali salt of carboxylic acid to be obtained from the reaction of the compound (5A-1) with an alkali metal hydroxide. The compound (D) is then reacted with zinc to prepare perfluoro (3-butenyl vinyl ether) through dechlorination.

On the other hand, as a method of fluorinating all of C-H bonds to C-F bonds in a hydrocarbon compound, are known a fluorinating method using fluorine gas or a fluorinating method using a product prepared by

electrolyzing hydrogen fluoride in an electrolysis cell (so called as an electrochemical fluorination method).

Among the fluorination using fluorine gas, are known a fluorination in a gas phase (hereinafter, referred to as a gas phase fluorination) and a fluorination in a liquid phase (hereinafter, referred to as a liquid phase fluorination).

Further, it is also known that a fluoride compound is obtained by means of a thermal decomposition of a perfluorinated ester compound having at least 16 carbon atoms. It is described that such a fluoride compound can be produced by using a hydrocarbon ester compound having a carbon skeleton corresponding to its starting material and by directly fluorinating it using fluorine gas in a liquid phase (J. Am. Chem. Soc., 120, 7117 (1998)).

However, such conventional processes for producing perfluoro (3-butenyl vinyl ether) has drawbacks that an isomer, CF2ICFC12, is produced as well as the compound (A) in a step of producing the compound (A). The amount of the isomer is difficult to control. Further, the conventional production processes are economically disadvantageous since it includes a lot of reaction steps and its starting material is expensive. In addition, there are difficult problems such as corrosion of the apparatus and the handling of the reagents resulted from using iodine chloride and fuming sulfuric acid etc.

The electrochemical fluorination method had a

drawback that an objective compound with high purity can not be obtained because an isomerization reaction, dissociation of C-C bonds and a recombination reaction etc. occur easily. Further, when a direct fluorination is carried out in a gas phase, dissociation of C-C single bonds during the reaction occurs, whereby various side products tends to be formed.

It is reported that a liquid phase fluorination can resolve the above mentioned problems in a gas phase fluorination. (U. S. patent 5, 093, 432). In a liquid phase fluorination reaction, a perfluoro solvent capable of dissolving fluorine gas has been usually employed. To such a perfluoro solvent, a hydrocarbon type compound is generally poorly solved. Accordingly, there have been problem that a fluorination reaction can not sufficiently proceed and the production efficiency in the fluorination reaction is poor. On the other hand, when a fluorination reaction of a hydrocarbon type compound is carried out in a perfluoro solvent with a high concentration, a suspension type reaction which is usually unfavorable as a reaction is required.

Moreover, when a low molecular hydrocarbon type compound is fluorinated in a liquid phase, the reaction yield is extremely low, since a gas-phase reaction partly occurs due to high volatility of the substance.

THE DISCLOSURE OF THE INVENTION The present invention was made for resolving the

problems contained in the conventional methods, and is to provide a process for producing a fluoride having a vic- dichloro structure in a short process from raw material available at a low cost.

The present invention provides a process for producing a fluoride compound comprising reacting a compound (1) with a compound (2) to form a compound (3), chlorinating the compound (3) with a chlorinating agent to form a compound (4) and reacting the resulting compound (4) by liquid-phase fluorination to form a compound (5) : CH2=CHCHRACH20CH (CH3) CH20H (1) FCORB (2) CH2=CHCHRACH20CH (CH3) CH2OCORB (3) CH2C1CHC1CHRACH20CH (CH3) CH2OCORB (4) CF2C1CFC1CFRAFCF20CF (CF3) COF (5) wherein RA is a hydrogen atom, an alkyl group or an alkoxy group ; when RA is a hydrogen atom, RAF is a fluorine atom and when RA is an alkyl group or an alkoxy group, RAF is a group corresponding to RA wherein at least one hydrogen atom is fluorinated ; and RB is a monovalent organic group.

Further the present invention provides the process mentioned above wherein the compound (1) is a compound (1A), the compound (2) is a compound (2A), the compound (3) is a compound (3A), the compound (4) is a compound (4A), and the compound (5) is a compound (5A) :

CH2=CHCHRA1CH20CH (CH3) CH20H (1A) FCOCF (CF3) OCF2CF2CF3 (2A) CH2=CHCHRA1CH20CH (CH3) CH2OCOCF (CF3) OCF2CF2CF3 (3A) CH2C1CHC1CHRA1CH20CH (CH3) CH2OCOCF (CF3) OCF2CF2CF3 (4A) CF2ClCFClCFRAFlCF2OCF (CF3) COF (5A) wherein RA1 is a hydrogen atom or an alkoxy group, and R is a fluorine atom when RA1 is a hydrogen atom, or RAF1 is a perfluoro alkoxy group when RA1 is an alkoxy group.

Furthermore, the present invention provides a process for producing a fluoride compound which comprises reacting a compound (4) by liquid-phase fluorination to obtain a compound (5), wherein RA, RAF and RB mean the same as defined above.

Moreover, the present invention provides a process for producing a compound (7) which comprises thermally decomposing the compound obtained by the process mentioned above to form a compound (6), and dechlorinating the resulting compound (6) to obtain the compound (7) : CF2ClCFClCFRAFCF2OCF=CF2 (6) CF2=CFCFRAFCF20CF=CF2 (7) wherein RA and RAF mean the same as defined above.

In addition, the present invention provides a process for producing a fluorinated resin which polymerizing at least one of the compound (7) to be obtained in the process mentioned above, or copolymerizing at least one of the compound (7) to be

obtained in the process mentioned above and at least one monomer polymerizable with the compound (7).

Further more, the present invention provides the following compound (3A), the compound (4A) and the compound (5B).

CH2=CHCHRAlCH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (3A) CH2ClCHClCHRAlCH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (4A) CF2ClCFClCF (O (CF2) nCF3) CF20CF (CF3) COF (5B) wherein RA1 means the same as defined above, and n is an integer of from 0 to 9.

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, a compound represented by the formula (1) is recited as the compound (1). This is the same in the other compounds represented by the formulae. An organic group in the present invention means a group having essentially a carbon atom, and contains either of saturated or unsaturated structure. A halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom.

[Explanation of the compound (1)] The compound (1) is a known compound or a compound which can be easily prepared from a known compound. The compound (1) is preferably the compound (1A). For example a known compound, the compound (1A) can be prepared by reacting the compound (10) with the compound (11) to form the compound (12), and then reacting the resulting the compound (12) with the compound (13)

wherein X is a monovalent counter ion to form the compound (14), followed by reduction of the resulting the compound (14) with a hydride. In the following formulae, RA1 is a hydrogen atom or an alkoxy group, and is preferably a hydrogen atom or a methoxy group.

CH3CHClCOOH (10) CH2= CHCHRA1CH20H (11) CH3CHC 1 COOCH2CHRAlCH=CH2 (12) CH2 = CHCHRAlCH20-X+ (13) CH2 = CHCHRA1CH20CH (CH3) COOCH2CHRAlCH=CH2 (14) In the reaction whereby the compound (10) is reacted with the compound (11) to form the compound (12), it is possible to employ a procedure and a condition in a usual esterification of a carboxylic acid. For example, it can be mentioned that the compound (10) is heated to react with the compound (11) in the presence of an acid catalyst such as sulfuric acid.

Then, the compound (12) is reacted with the compound (13) to form the compound (14). X+ in the compound (13) is preferably an alkali metal cation, and is particularly preferably Na+, K+ etc. The compound (13) wherein X+ is Na+ can be obtained by a method wherein the compound (11) is reacted with a base such as sodium hydride, or by a method wherein a methanol solution of sodium methoxide is added to the compound (11), followed by distilling off methanol. The reaction of the compound (12) with the compound (13) is preferably carried out in the presence

of a reaction solvent. As such a reaction solvent, may be mentioned the compound (11), tetrahydrofuran, N, N- dimethylformamide etc. The reaction temperature is preferably from 25°C to a reflux temperature of the reaction solvent employed and more preferably from 50 to 100°C.

Then, the compound (14) is subjected to reduction with a hydride to form the compound (1A). A reducing agent to be used in such a reduction is preferably a hydride type compound such as lithium aluminum hydride and sodium bis (2-methoxyethoxy) aluminum hydride. In the reduction reaction, the compound (11) is formed in an theoretically equal mole amount to the compound (1A) which is formed simultaneously. It is preferred that apart or all of the compound (11) is recovered, and is used in a reaction with the compound (10), whereby the compound (1A) is continuously produced. The above reduction reaction is preferably carried out in the presence of a reaction solvent. Such a reaction solvent is preferably tetrahydrofuran, toluene, etc. The reaction temperature is preferably from 25°C to a reflux temperature of the reaction solvent to be employed.

[Explanation of the compound (2)] The compound (2) is a known compound or a compound which can be easily prepared from a known compound. RB (a monovalent organic group) in the compound (2) is preferably a monovalent hydrocarbon group, a heteroatom-

containing monovalent hydrocarbon group, a halogenated monovalent hydrocarbon group, or a halogenated (heteroatom-containing monovalent hydrocarbon) group.

From the viewpoint of the solubility in a liquid phase during a fluorination reaction, it is preferred that RB contains a carbon number of from 1 to 20, particularly from 1 to 10. Further, a halogen atom in the halogenated groups is preferably at least one halogen atom selected from the group consisting of a fluorine atom, a chlorine atom and a bromine atom, and particularly preferably a fluorine atom only or a fluorine atom and a chlorine atom.

The above monovalent hydrocarbon group is preferably an alkyl group. As such an alkyl group, may be mentioned a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, tert-butyl group, etc. As a monovalent hydrocarbon group, a cycloalkyl group, a group having more than two cycloalkane structures, etc. may be mentioned.

The above heteroatom containing monovalent hydrocarbon group is preferably an alkyl group containing an etheric oxygen atom (O in C-O-C), and is particularly preferably an alkoxyalkyl group in view of availability, easy productibility and usefulness of a product to be formed therefrom. Such an alkoxyalkyl group is preferably a group wherein one of hydrogen atom in the alkyl group is substituted with an alkoxy group. The

alkoxy group preferably contains a carbon number of from 1 to 10.

Further, the compound (2) is preferably a fluorine- containing compound. Thus, RB is preferably a fluoroalkyl group, a fluoro (partially chloroalkyl) group, a fluoro (heteroatom-containing alkyl) group or a fluoro (partially chloro (heteroatom-containing alkyl)) group, and is particularly preferably a perfluorinated group of each group mentioned above.

As a specific example of the compound (2), may be mentioned the following compounds, and a compound (2A) is preferred in view of its availability.

CF3CF2COF, CF3CF2CF20CF (CF3) COF (2A) CF3CF2CF20CF (CF3) CF20CF (CF3) COF CF2ClCFClCF2CF20CF (CF3) COF [Reaction of the compound (1) with the compound (2)] A known reaction procedure can be applied to the reaction of the compound (1) with the compound (2). For example, the reaction wherein compound (1A) is reacted with the compound (2A) to form the compound (3A) may be carried out in the presence of a solvent (hereinafter, referred to as solvent 1). However, it is preferred to carried out in the absence of solvent from the viewpoint of the volume efficiency. Solvent 1 is preferably a halogenated hydrocarbon type solvent, an example of which is dichloromethane, chloroform, etc. The amount of

solvent 1 is preferably from 0. 5 to 5 mass times based on the total mass of the compound (1A) and the compound (2A).

Since HF will be formed in the reaction of the compound (1) with the compound (2), it is possible to incorporate in the reaction system a base such as an alkali metal fluoride (for example, sodium fluoride), a trialkyl amine and pyridine as the HF scavenger. When an alkali metal fluoride is used as an HF scavenger, the amount is preferably from 1 to 10 mol times, relative to the amount of the compound (2). If an HF scavenger is not used, it is preferred to remove HF from the reaction system by carrying with nitrogen gas.

The temperature in the reaction of the compound (1) with the compound (2) is usually preferably from-50 to 100°C or a boiling point of solvent 1. The reaction time in the reaction of the compound (1) with the compound (2) may be adjusted depending on the feeding rate of the raw material and the amount of the compounds to be used in the reaction, and the reaction pressure is preferably from 0 to 2 MPa (gauge pressure, the same applies to hereinafter).

[Explanation of the compound (3)] The compound (3) will be formed by the reaction of the compound (1) with the compound (2). RB in the compound (3) corresponds to RB in the compound (2). The compound (3) is preferably the compound (3A). Some of the compounds (3) are new compounds, and the compound

(3A) is a new compound.

By the reactions which will be described later, the above compound (3A) can be led to useful compounds as a starting material for a fluorinated resin, such as perfluoro (3-butenyl vinyl ether), a perfluoro (2-alkoxy-3- butenyl vinyl ether), perfluoro (propyl vinyl ether) and a perfluoro (2-alkoxypropyl vinyl ether). When RA1 in the compound (3A) is an alkoxy group, the carbon number is preferably from 1 to 10 and more preferably from 1 to 6.

From the viewpoint of usefulness of such a compound, RA1 is particularly preferably a hydrogen atom or a methoxy group As a specific example, may be mentioned the following compounds.

CH2=CHCH2CH2OCH (CH3) CH20COCF (CF3) OCF2CF2CF3 (3A-1) CH2=CHCH (OCH3) CH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (3A-2) The crude product containing the compound (3) may be purified to a high purity or may be employed as it is in the next step etc., as the case may be. For example, the purification method may be a method such as a method of distilling the crude product as it is, a method of treating the crude product with diluted alkaline water, followed by a liquid-liquid separation, a method of extracting the crude product with an appropriate organic solvent, followed by distillation, and a method of purification using silica gel chromatography.

[Reaction of the compound (3) with a chlorinating agent]

The chlorinating reaction of the compound (3) with a chlorinating agent to form the compound (4) may be carried out by a usual chlorinating method and under a usual reaction condition. The chlorinating agent is preferably chlorine (Cl2). The amount of such chlorine is preferably from 1 to 10 mol times, relative to the amount of the compound (3), and more preferably from 1 to 5 mol times. While the reaction of the compound (3) with the chlorinating agent may be carried out in the presence of a solvent (hereafter, referred to as solvent 2), it is preferred to carry out in the absence of such a solvent 2 in view of the volume efficiency. When solvent 2 is used, it is preferably a halogenated hydrocarbon type solvent.

As such a halogenated hydrocarbon type solvent, may be mentioned dichloromethane, chloroform, etc. The amount of solvent is preferably from 0. 5 to 5 mol times relative to the mass of the compound (3). The reaction temperature is preferably from-78 to +200°C.

[Explanation of the compound (4)] The crude reaction product containing the compound (4) obtained from the chlorinating reaction may be purified to a high purity or may be employed as it is in next step, as the case may be. The purification method of the crude reaction product containing the compound (4) may, for example, be the one such as a method of distilling the crude product as it is, a method of treating the crude product with diluted alkaline water,

followed by a liquid-liquid separation, and a method of extracting the crude product with an appropriate organic solvent, followed by distillation.

The compound (4) is preferably the compound (4A).

Some of the compounds (4) are new compounds. For example, the compound (4A) which can be obtained by chlorinating the compound (3A) is a new compound. The usefulness of the compound (4A), and a preferred embodiment of RA1 are the same as in the compound (3A). As a specific example of the compound (4A), may be mentioned the following compounds.

CH2ClCHClCH2CH2OCH (CH3) CH20COCF (CF3) OCF2CF2CF3 (4A-1) CH2C1CHC1CH (OCH3) CH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (4A-2) [Fluorination of the compound (4)] When the compound (4) is fluorinated by liquid-phase fluorination, elemental fluorine is preferably employed.

In carrying out such a fluorination, it is preferred to introduce fluorine (F2) into the reaction system in the form of fluorine gas diluted with inert gas. Such an inert gas is preferably a nitrogen gas or a helium gas and is particularly preferably a nitrogen gas in view of an economical point. The fluorine gas diluted with an inert gas is preferably a mixed gas of an inert gas and a fluorine gas containing a fluorine gas content of from 5 to 95 vol%, more preferably from 10 to 60 vol%. While the fluorine gas used in the fluorination reaction may be diluted fluorine gas or undiluted fluorine gas, it is

preferred to use diluted fluorine gas.

The fluorination reaction of the present invention is preferably carried out in the presence of an alkali metal fluoride or an alkali earth metal fluoride such as NaF, KF, CsF, preferably NaF from the viewpoint of economical reason. Such presence of an alkali metal fluoride or an alkali earth metal fluoride can facilitate efficiently the fluorination reaction and the ester dissociation reaction which proceed simultaneously. The amount of an alkali metal fluoride or an alkali earth metal fluoride to be used can be a catalytic amount or an excess amount. Such amount is preferably from 1 to 500 mol%, more preferably from 5 to 100 mole%, particularly preferably from 10 to 50 mole%, relative to the amount of the compound (4).

In the liquid-phase fluorination reaction of the compound (1), HF will be formed as a by-product. To remove HF formed as the by-product, it is preferred to incorporate an HF scavenger in the reaction system or to contact the outlet gas with an HF scavenger at the gas outlet of the reactor. Such an HF scavenger, the same substance as previously described may be used, and is preferably NaF.

When the HF scavenger is incorporated in the reaction system, 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 (4). In a case where the HF scavenger is disposed at the outlet of the reactor, it is preferred to arrange (a) a condenser (preferably maintained at a temperature of from 10°C to room temperature, particularly preferably at about 20°C), (b) a packed layer of an HF scavenger such as NaF pellets and (c) a condenser (preferably maintained at a temperature of from -78°C to +10°C, more preferably from-30 to 0°C) in a series in the order of (a)- (b)- (c). Further, a liquid- returning line may be installed to return the condensed liquid from the condenser of (3) to the reactor.

The liquid phase is preferably a solvent into which fluorine gas can be dissolved. To be highly soluble in the liquid phase, the compound (4) is preferably a compound having the fluorine content of at least 30 mass%. more preferably from 30 to 84 mass%, particularly preferably from 50 to 84 mass%. The molecular weight of the compound (4) is preferably at least 200, more preferably from 200 to 1000, since the reaction in a gas phase can be lowered. The compound (4) wherein RB is a perfluoro monovalent organic group is a compound which is readily soluble in a solvent into which fluorine gas can be dissolved. Such a solvent into which fluorine gas can be dissolved is preferably the one containing, as an essential ingredient, an organic solvent (hereinafter, referred to as solvent 3 which has no C-H bond and which necessarily has a C-F bond), and is preferably only

solvent 3 except in a case where a compound having a C-H bond is added to the reaction system which will be mentioned later.

Such solvent 3 is preferably an organic solvent comprising a compound having at least one atom selected from the group consisting of a chlorine atom, a nitrogen atom and an oxygen atom in its structure wherein a hydrogen atom is perfluorinated, and is more preferably a solvent which is capable of dissolving the compound (4) by at least 1 mass%.

Examples of solvent 3 may be FCOR1 (Rl is a perhalogenated alkyl group or a perhalogenated (alkoxyalkyl) group), R2CF2OCOR3 (R2 is a perfluoro monovalent organic group and R3 is a perhalogenated alkyl group.), perfluoroethers (trade names : such as KRYTOX, FOMBLIN, GALDENE and DEMNUM), chlorofluorocarbons (such as 1, 1, 2-trichloro-1, 2, 2-trifluoroethane, a low molecular polymer of chlorotrifluoroethylene (trade name : such as FLON LUBE), a perfluoroalkyl amine (such as a perfluorotrialkyl amine), an inert fluid (trade name : FLUORINERT), etc. Among others, 1, 1, 2-trichloro-1, 2, 2- trifluoroethane, a perfluoroalkyl amine, the compound (5A) described later or the compound (2A) described later is preferred as solvent 3. The amount of solvent 3 is preferably at least 5 times by mass, more preferably from 10 to 100 times by mass, relative to the compound (4).

The liquid phase fluorination may be carried out

after fluorine gas has been charged or may be carried out while supplying fluorine gas. The fluorine to be charged in the former case, and the fluorine to be supplied in the latter case are, in either cases, preferably excess equivalent amount relative to hydrogen atoms in the compound (4A), and are more preferably at least 1. 5 equivalent times, particularly preferably from 1. 5 to 5 equivalent times, from the viewpoint of the selectivity.

The reaction with fluorine is preferably carried out by means of a continuous system-1 or a continuous system- 2, both of which will be described in the following, and is more preferably by a continuous system-2 from the viewpoint of the reaction yield and the selectivity.

Continuous system-1 : a method wherein, the compound (4) and solvent 3 are charged into a reactor and stirring is initiated, and then the reaction is carried out by continuously supplying only fluorine gas or fluorine gas and solvent 3 simultaneously. The temperature in the reaction is preferably from-60°C to a boiling point of the compound (4), and is more preferably from-50 to +100°C, particularly preferably from-20 to +100°C from the various points such as the reaction yield, the selectivity and efficiency of industrial operation. The reaction pressure is particularly preferably from 0 to 2 MPa in view of the reaction yield, the selectivity, the easiness of industrial production, etc.

Continuous system-2 : a method wherein solvent 3 is

charged into a reactor and stirring is initiated, and then the reaction is carried out by supplying the compound (4), solvent 3 and fluorine gas in a predetermined molar ratio continuously and simultaneously.

The reaction temperature is preferably from-50 to +100°C, particularly preferably from-20 to +50°C. While the reaction pressure is not limited, it is preferably from 0 to 2 MPa from the viewpoint of the reaction yield, the selectivity, the easiness of commercial production, etc.

It is preferred to supply the compound (4) in a diluted form with solvent 3, whereby the selectivity will be increased and the amount of by-product will be decreased. When the compound (4) is diluted with solvent 3, the amount of solvent 3 is preferably at least 5 times by mass, especially preferably from 5 to 20 times by mass, relative to the compound (4).

Further, in the liquid phase fluorination, it is preferred to add a C-H bond-containing compound to the reaction system, or to carry out under irradiation of ultraviolet ray. For example, when the reaction is carried out by charging fluorine gas first, it is preferred to add a C-H bond-containing compound to the reaction system, or to irradiate ultraviolet ray at the later stage of the fluorination reaction. When the reaction is carried out while supplying fluorine gas, it is preferred to add a C-H bond-containing compound or to

irradiate ultraviolet ray at the time after the supply of the compound (4) is over. In the above way, the compound (4) in the reaction system can be efficiently fluorinated, and reaction rate can be remarkably improved. 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 (4), 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 5 mol%, relative to hydrogen atoms in the compound (4).

It is preferred to add the C-H bond-containing compound to the reaction system in such a state where elemental fluorine is present. Further, when the C-H bond-containing compound is added, it is preferred to pressurize the reaction system. The pressure during the pressurizing is preferably 0. 01 to 5 MPa.

[Explanation of the Compound (5)] It is one of the characteristics of the present invention that the reaction of the compound (4) with fluorine in a liquid phase brings about not only fluorination of the compound (4), but also dissociation of ester moiety to obtain the compound (5). Particularly, such a reaction can be facilitated in the presence of an alkali metal fluoride or an alkali earth metal fluoride.

In the fluorination reaction, a hydrogen atom connected to a carbon atom is substituted with a fluorine atom and an addition to a carbon-carbon unsaturated bond is conducted. The fluorine may act on a part or all of hydrogen atom connected to a carbon atom and the carbon- carbon unsaturated bonds and preferably act on all of the hydrogen atoms and the carbon-carbon unsaturated bonds (namely, complete fluorination).

The compound (5) is preferably the compound (5A).

Some of the compounds (5) are new compounds. For example, the compound (5B) to be obtained from fluorination of the compound (4A) wherein RA1 is a alkoxy group is a new compound. The usefulness of the compound (5A) and preferable RA1 are the same as in the compound (3A).

Further, n in the compound (5B) is preferably from 0 to 5.

A specific example of the compound (5B) is the compound (5B-1).

CF2ClCFClCF (OCF3) CF20CF (CF3) COF (5B-1) Further, in the fluorination of the compound (4), the compound (2F) is formed as well as the compound (5).

In the fluorination of the compound (4A), the compound (2A) is formed as well as the compound (5A).

FCORBF (2F) When RB is a group which does not reacted with fluorine, RBF in the formula (2F) is the same monovalent organic group as RB, and when RB is a group which react with fluorine, RBF is a monovalent organic group which is

obtained from the fluorination of RB. The compound (5) and the compound (2F) can be separated from each other by a usual separation method. For example, each compound can be isolated by a distillation. Further, it is extremely advantageous to select the structure of RB in the compound (2) so that the compound (5) and the compound (2F) become the same structure, since the above separation step can be omitted.

By using a part or all of the compounds (2F) to be obtained by the above process again in the reaction with the compound (1), the compound (5) can be produced continuously. For example, a continuous production process of the compound (5A) can be provided in the following route : the compound (1A) is reacted with the compound (2A) to form the compound (3A), which is then reacted with a chlorinating agent to form the resulting compound (4A). The compound (4A) is reacted with fluorine in a liquid phase to obtain a crude reaction product containing the compound (5A) and the compound (2A). A part or all of the compound (2A) to be separated from the crude reaction product is used again in the reaction with the compound (1A).

[Usefulness of the compound (5)] The compound (5) is a valuable compound as raw material for various fluorine-containing functional compounds. For example, the compound (5) to be obtained by the process of the present invention is heated at

least 250°C in the presence of soda ash or a glass bead to form the compound (7) through elimination.

Alternatively, the compound (7) can be obtained from the compound (5) in the following. The compound (5) is reacted with alkali metal hydroxide to form alkali metal carboxylate, which is then thermal-decomposed at from 150 to 300°C to form the compound (6), and the resulting compound (6) is reacted with zinc, etc. to form the compound (7) through dechlorination. The resulting compound (7) is useful as a monomer for a fluorinated resin.

For example, the compound (5) which is a new compound can be led to a perfluoro (2-alkoxy-3-butenyl vinyl ether). This monomer can be polymerized to produce a fluorinated resin, which is a useful transparent fluorinated resin excellent in thermal resistance and chemical resistance.

Moreover, for example, the compound (2A) can be led to a perfluoro (propyl vinyl ether) by either of the following production routes : the compound (2A) is heated at least 250°C, preferably from 250 to 350°C, in the presence of soda ash or a glass bead through elimination, and the compound (2A) is reacted with potassium hydroxide to form potassium carboxylate, which is then thermally- decomposed at from 150 to 300°C. The resulting a perfluoro (propyl vinyl ether) [CF3CF2CF2OCF=CF2] is also useful compound as a starting monomer for a fluorinated

resin.

EXAMPLES In the following, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto. Further, in the following, several terms are referred to as their respective abbreviations. gas chromatography : GC, tetramethylsilane : TMS, N, N-dimethylformamide : DMF, dichloropentafluoropropane : AK-225, 1, 1, 2-trichloro- 1, 2, 2-trifluoroethane : R-113, liter : L. GC purity : the purity determined from the peak area ratio of gas chromatography [EXAMPLE 1] Production of CH2=CHCH2CH20CH (CH3) COOCH2CH2CH=CH2 (a compound (14) wherein RA1 is a hydrogen atom.) CH3CHClCOOH (50g) and CH2=CH (CH2) 20H (75 ml) were put into a flask and stirred and 10 ml of concentrated sulfuric acid was added dropwise thereto over period of 10 minutes at room temperature. The resulting reaction solution was added to 250 ml of a saturated sodium carbonate aqueous solution. Water (150 ml) and tert-butyl methyl ether (150 ml) were added thereto, followed by liquid separation to obtain a tert-butyl methyl ether layer as an organic layer. Further, the organic layer was washed with 150 ml of water, dried over magnesium sulfate and then subjected to filtration to obtain a crude liquid. The crude liquid was concentrated to

obtain CH3CHC1C00 (CH2) 2CH=CH2.

CH2=CH (CH2) 20H (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 hydride (10 g) was added thereto over a period of 30 minutes, and cooled again after stirred for 30 minutes at room temperature.

Then, CH3CHClCOO (CH2) 2CH=CH2 (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. After cooled to the room temperature (25°C), 200 ml of 2 mol/l hydrochloric acid was added thereto. An organic layer was obtained by extracting with 400 ml of the hexane/ethyl acetate=2/1 solution by 4 times. The organic layer was concentrated, washed twice by 500 ml of water, dried over magnesium sulfate, filtered and then concentrated again to obtain 36 g of CH3CH (O (CH2) 2CH=CH2) COO (CH2) 2CH=CH2. Its GC purity was 83%.

NMR spectrum was as follows.

'H-NMR (3 99. 8MH z, solvent : C D C l 3, standard : TMS) 3 (p pm) : 1. 3 9 (d, J=7. OHz, 3H), 2. 3 3~2. 4 5 (m, 4H), 3. 4 1 (d t, J=7. 0, 9. 1H z, 1H), 3. 6 3 (d t, J = 7. 0, 9. 1 H z, 1 H), 3. 9 6 (q, J=7. OHz, 1H), 4. 1 5-4. 2 7 (m, 2H), 5. O 2 # 5. 1 4 (m, 4 H), 5. 7 3-5. 8 8 (m, 2 H).

[EXAMPLE 2] Production of CH3CH (O (CH2) 2CH=CH2) CH20H (

a compound (1A) wherein RA1 is a hydrogen atom.) In an argon atmosphere, 6. 9g of lithium aluminum hydride and 240 ml of dehydrated diethyl ether were put into a flask and stirred in an ice bath.

CH3CH (0 (CH2) 2CH=CH2) COO (CH2) 2CH=CH2 (36g) with GC purity of 83% obtained by EXAMPLE 1 was added dropwise thereto over a period of 45 minutes and stirred for 3. 5 hours.

Further, 100 ml of iced water was added thereto dropwise in a ice bath, and then 100 ml of water was added thereto and raised to room temperature (25°C), followed by filtration. The resulting cake was washed with 450 ml of diethyl ether and the filtrate was separated. The water layer was extracted twice with 200 ml of diethyl ether to obtain a collected diethylether layer as an organic layer.

The organic layer was dried over magnesium sulfate and subjected to filtration to obtain a crude liquid. The crude liquid was concentrated to 35 g and then was distilled under the reduced pressure to remove 6. 6 g of the fraction with from 28 to 49°C/9. 33 kPa, whereby 19. 2g of CH3CH (O (CH2) 2CH=CH2) CH20H was obtained from the resulting fraction. Its GC purity was 98%. NMR spectrum was as follows.

1 H-NMR (3 9 9. 8 M H z, solvent : CDC 1 3, standard : TMS) 3 (pom) : 1. 1 2 (d, J = 6. 2 H z, 3 H), 2. 35 (tq, J=1. 3, 6. 7Hz, 2H), 3. 4 2-3. 4 8 (m, 2 H), 3. 5 1-3. 5 9 (m, 2H), 3. 6 4-3. 6 9 (m, 1 H), 5. 0 4-5. 1 5 (m, 2 H), 5. 7 9-5. 8 9 (m, 1 H).

[EXAMPLE 3] Production of CH2=CHCH2CH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (a compound (3A) wherein RA1 is a hydrogen atom.) CH2=CHCH2CH20CH (CH3) CH20H (19. 2g) having a GC purity of 98% obtained in EXAMPLE 2 was put into a flask and stirred while bubbling nitrogen gas thereinto.

FCOCF (CF3) OCF2CF2CF3 (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 a saturated sodium hydrogen carbonate aqueous solution (80 mL) was added thereto at the internal temperature of not higher than 15°C.

Water (50 mL) and chloroform (100 mL) were added thereto, followed by liquid separation to obtain a chloroform layer as an organic layer. The organic layer was washed twice with water (100 mL), dried over magnesium sulfate and subjected to filtration to obtain a crude liquid. The crude liquid was concentrated and purified by a silica gel column chromatography (eluent : hexane/ethyl acetate=4/1), then followed by purification by a silica gel column chromatography (eluent : AK-225), to obtain CH2=CHCH2CH2OCH (CH3) CH20COCF (CF3) OCF2CF2CF3 (37g) Its GC purity was 99%. NMR spectra were as follows.

1 H-NMR (3 9 9. SMH z, solvent : C D C l 3, standard : TMS) o (p pm) : 1. 2 (d d, J = 1. 2, 6.

4 H z, 3 H), 2. 29 (q, J=6. 7Hz, 2H), 3. 45-

3. 5 1 (m, 1 H), 3. 5 3 # 3. 5 9 (m, 1 H), 3. 6 7 ~ 3. 7 3 (m, 1 H), 4. 2 5 # 4. 2 9 (m, 1 H), 4. 3 5~ 4. 4 1 (m, 1 H) , 5. 0 1 # 5. 1 0 (m, 2 H) , 5. 7 5~ 5. 8 5 (m, 1 H), "F-NMR (3 7 6. 2 M H z, solvent C D C l 3, standard : C F C l 3) 8 (p pu) :-8 0. 5 (1 F),-8 1. 9 (3 F),-8 2. 7 (3 F),-8 6. 9 (1 F), - 130. 3 (2F), -1 3 2. 2 (1 F) [EXAMPLE 4] Production of CH2ClCHClCH2CH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (a compound (4A) wherein RA1 is a hydrogen atom.) CH2=CHCH2CH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (3 6g) having a GC purity of 99% obtained in EXAMPLE 3 was put into a flask and stirred in an ice bath Chlorine gas (9. 5 g) was blown thereinto over 3 hours while maintaining the internal temperature at from 0 to 5°C.

Stirring was continued for 1 hour at room temperature while blowing nitrogen gas thereinto. The resulting reaction liquid was purified by a silica gel column chromatography (eluent : AK-225), to obtain CH2ClCHClCH2CH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (22g). Its GC purity was 88%.

'H-NMR (3 9 9. 8 M H z, solvent : C DC 1 3, standard : T M S) # (p p m) : 1. 2 1 (d d, J = 1. 3, 6.

3 H z, 3 H), 1. 8 1-1. 9 3 1 H) 2. 1 9 # 2. 2 6 (m, 1 H) , 3. 5 9-3. 6 5 (m, 1H), 3. 6 8-3. 8 0 (m, 4 H), 4. 2 0-4. 4 6 (m, 3 H).

19F-NMR (3 7 6. 2MH z, solvent CDC I 3 standard : CFC I 3) 8 (p pm) :-8 0. 3 (1 F),-8 1. 6 (3 F),-8 2. 4 (3 F),-8 6. 7 (1 F),-1 3 0. 0 (2 F), -132. 0 (1F).

[EXAMPLE 5] Production of CF2C1CFC1CF2CF20CF (CF3) COF (a compound (5A) wherein RAF1 is a fluorine atom.) Into a 500 mL autoclave made of nickel, R-113 (312 g) and NaF powder (19g) were added, stirred and cooled at -10°C. Nitrogen gas blown thereinto for 1 hour, and then 20 volume% fluorine gas diluted with nitrogen gas (hereinafter, this diluted fluorine gas is referred to as the diluted fluorine gas) was blown thereinto for about 1 hour at a flow rate of 5. 77 L/h, followed by adjusting the internal pressure of the reactor at 0. 15 MPa. Then, while blowing the diluted fluorine gas at the same rate to maintain the internal pressure of the reactor at 0. 15 MPa, a solution of CH2C1CHC1CH2CH2OCH (CH3) CH20COCF (CF3) OCF2CF2CF3 (4. 99 g) with GC purity of 88% obtained in EXAMPLE 4 dissolved in R-113 (102 g) was injected thereinto over a period of 7. 0 hours.

Then, while blowing the diluted fluorine gas at the same rate, 90 mL of a mixed solution of benzene and R- 113 solution (benzene concentration : 0. 01 g/mL) was injected thereinto at-10°C and further 4 mL of the mixed solution while raising the temperature from-10°C to 40°C.

Further, benzene (4 mL) was injected thereinto at 40°C, whereupon the benzene injection inlet of the

autoclave was closed. While the diluted fluorine gas was blown thereinto at the same flow rate to maintain the internal pressure and temperature of the reactor at the same level, stirring was continued for 20 minutes.

Further, the same injection operation of benzene was repeated 4 times. The total amount of benzene injected was 1. 272 g, and the total amount of R-113 injected was 125 mL. Further, the diluted fluorine gas was blown thereinto at the same flow rate, and stirring was continued for 2 hours while maintaining the internal pressure and temperature of the reactor at the same level, followed by blowing nitrogen gas thereinto for 2 hours, whereby CF2C1CFC1CF2CF2OCF (CF3) COF was obtained. The yield obtained by quantitative analysis with 19F-NMR (internal standard : C6F6) was 58%.

"F-NMR (3 7 6. 2Hz, solvent : CDC 1 3, standard : C F C l 3) # (p p m) : 2 6. 0 (1 F),-6 4. 7 (2 F).-7 7. 1--7 7. 7 (1 F),-8 2. 5 (3 F),-83. 9- -84. 7 (1 F), -1 1 7. 9--1 1 9. 7 (2F),-1 31. 3 (1 F),-1 3 2. 3 (1 F).

[EXAMPLE 6] Continuous production of CH2=CHCH2CH20CH (CH3) CH20H (a compound (1A) wherein RAl is a hydrogen atom) By NMR spectrum, it was confirmed that the fraction with from 28 to 49°C/9. 33 kPa obtained in EXAMPLE 2 was CH2=CHCH2CH2OH. By using the above-mentioned fraction (75 mL), the reaction was carried out in the same manner as

in EXAMPLE 1 and 2 to obtain CH2=CHCH2CH20CH (CH3) CH20H.

[EXAMPLE 7] Continuous production of CF2ClCFClCF2CF20CF (CF3) COF (a compound (5A, wherein RAF1 is a fluorine atom.) CF2ClCFClCF2CF20CF (CF3) COF obtained in EXAMPLE 5 was purified by a distillation at atmospheric pressure, and a fraction of 55°C was obtained to be FCOCF (CF3) OCF2CF2CF3 (40g). The resulting fraction having higher boiling points was preserved.

By using FCOCF (CF3) OCF2CF2CF3 obtained above, the reactions were carried out in the same manners as in from EXAMPLE 3 to EXAMPLE 5, and then purified by a distillation at atmospheric pressure to obtain FCOCF (CF3) OCF2CF2CF3 (32g) as a fraction of 55°C. The resulting fraction having higher boiling points was combined with the fraction preserved earlier, and then was distilled at atmospheric pressure to obtain CF2ClCFClCF2CF20CF (CF3) COF as a fraction with from 138 to 139°C.

[EXAMPLE 8] Production of CHCHClCOOCH2CH (OCH3) CH=CH2 (a compound (12) wherein RA1 is a methoxy group.) Into a 500 mL three necked flask, CH2=CHCH (OCH3) CH20H (70g) and triethylamine (139g) were charged and stirred.

While the internal temperature was maintained at most 20°C in an iced bath, CH3CHClCOC1 (132g) was added dropwise over 2 hours.

The resulting reaction mixture was poured into water

(700 m) and then methylene chloride (150 mL) was added thereto, followed by liquid separation into two phases.

The water phase was extracted with methylene chloride (150 mL), and the methylene chloride layer mixed with the organic layer was dried over magnesium sulfate. After filtration, methylene chloride was distilled out to obtain a crude product (142. 2g). By distilling under reduced pressure, CH3CHClCOOCH2CH (OCH3) CH=CH2 (98. 7g) was obtained as a fraction having a GC purity of not less than 94%. Its boiling point was 102-104°C/2. 7 kPa.

'H-NMR (3 0 0. 4 OMH z, solvent : C D C l 3, standard : TMS) 3 (p pm) : 1. 70 (d d, J = 1. 1, 5.

8Hz, 3H), 3. 37 (d, J = 0. 6, 4 H z, 3 H), 3. 8 3- 3. 9 0 (m, 1 H), 4. 1 8 # 4. 2 1 (m, 2 H), 4. 4 3 (d q, J = 1. 3, 6. 9, 7. 1 H z, 1 H), 5. 3 1 # 5. 4 0 (m, 2 H), 5. 6 3-5. 7 6 (m, 1 H) [EXAMPLE 9] Production of CH2=CHCH (OCH3) CH20CH (CH3) COOCH2CH (OCH3) CH=CH2 (a compound (14) wherein RA1 is a methoxy group.) Into a 500 mL four necked flask, DMF (200 mL) and sodium hydride (60% cotent, 22. 4 g) were charged and stirred, and CH2=CHCH (OCH3) CH20H (57. 2g) was added dropwise thereto under cooing on an ice bath. After completion of dropwise adding, stirring was continued at room temperature for 1 hour. Then, CH3CHC1COOCH2CH (OCH3) CH=CH2 (98g) obtained in EXAMPLE 8 was added dropwise thereto over 30 minutes under cooling

to maintain the internal temperature at most 40°C. After completion of dropwise adding, stirring was continued at room temperature for one night.

The resulting reaction mixture was poured into water (1L) and then 2 mol/L of hydrochloric acid was added thereto to adjust the pH 3 The resulting solution was extracted three times with a 2 : 1 mixture of hexane and ethyl acetate (200 mL), and the organic layer was washed twice with water (100 mL). The organic layer was dried over magnesium sulfate, followed by distilling out the solvent to obtain the residue. By distilling the residue at reduced pressure, was obtained CH2=CHCH (OCH3) CH20CH (CH3) COOCH2CH (OCH3) CH=CH2 (80. 2g) having a GC purity of 98. 6%. Its boiling point was 130- 131°C/1. 2-1. 9 kPa.

'H-NMR (3 0 0. 4 0 M H z, solvent : C D C l 3, standard : TMS) 3 (p pm) : 1. 4 0 # 1. 4 5 (m, 3 H), 3. 31-3. 43 (m, 6H), 3. 36-3. 48 (m, 1 H), 3. 6 1 # 3. 6 9 (m, 1 H), 3. 7 6-3. 8 5 (m, 2 H), 4. 0 5-4. 1 5 2 H) 4. 18-4. 25 (m, 1H), 5. 2 5-5. 3 8 (m, 4 H), 5. 6 3-5. 7 9 (m, 2 H).

[EXAMPLE 10] Production of CH2=CHCH (OCH3) CH20CH (CH3) CH20H (a compound (1A) wherein RA1 is a methoxy group.) In a nitrogen atmosphere, to, toluene (750 mL) and sodium bis (2-methoxyethoxy) aluminum hydride (65% toluene solution, 384 mL) were charged into a 2L four necked flask and stirred, and

CH2=CHCH(OCH3)CH2OCH (CH3) COOCH2CH (OCH3) CH=CH2 (110g) obtained in EXAMPLE 9 was added dropwise thereto at the internal temperature of at most 20°C over 50 minutes.

After stirring at the internal temperature of 50°C over 4. 5 hours, 2 mol/L of hydrochloric acid (100 ml) was added dropwise thereto under cooling in an iced bath at the internal temperature of at most 20°C.

The resulting reaction mixture was poured into 2 mol/L of hydrochloric acid (3. 2 mL), followed by filtration to remove the precipitate. The resulting filtrate was extracted with methylene chloride (900 mL).

The water phase obtained by liquid separation was extracted with methylene chloride (900 mL), and the methylene chloride layer mixed with the organic layer was washed with water (150 mL). The resulting liquid was dried over magnesium sulfate and subjected to a filtration, followed by distilling out the solvent to obtain a crude product (92. 9g). By distilling under reduced pressure, CH2=CHCH (OCH3) CH20CH (CH3) CH20H (47 g) was obtained having a GC purity of more than 96%. Its boiling point was 100-103°C/2. 1 kPa.

'H-NMR (3 0 0. 4 M H z, solvent : C D C l3, standard : TMS) 8 (p pm) : 1. 1 2, 1. 1 2 (d, J = 6. 0 Hz, d, J=6. 2Hz, 3H), 3. 3 3, 3. 3 5 (s, 3 H), 3.

4 2-3. 7 1 (m, 5 H), 3. 7 6-3. 8 4 (m, 1 H), 5 . 2 6 ~ 5. 3 6 (m, 2 H), 5. 6 2-5. 8 0 (m, 1 H).

[EXAMPLE 11] Production of

CH2=CHCH (OCH3) CH20CH (CH3) CH2OCOCF (CF3) OCF3CF2CF3 (a compound (3A) wherein RA1 is a methoxy group.) CH2=CHCH (OCH3) CH20CH (CH3) CH20H (47g) having GC purity of 96% obtained in EXAMPLE 10 was placed in a flask and stirred while blowing of nitrogen gas thereinto. Then, FCOCF (CF3) OCF2CF2CF3 (109 g) was added dropwise thereto at the internal temperature of from 25 to 30°C over 1 hours.

After completion of dropwise adding, stirring was continued at 30°C for 2 hours, and triethylamine (8. 7g) was added thereto at the internal temperature of at most 15°C.

The resulting crude liquid was purified by a silica gel column chromatography (eluent : AK-225), to obtain CH2=CHCH (OCH3) CH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (124g).

1 H - N M R (3 0 0 . 4 M H z, solvent : CDC 13 standard ; T M S) # (p p m) : 1. 2 1 , 2. 2 2 (d, J = 6. 3, 6.

6 H z, 3 H) , 3. 3 1 - 3, 3 2 (s, 3 H) , 3. 4 2 - 3, 5 9 (m, 2H), 3. 67-3. 81 (m, 2 H), 4. 2 4 - 4. 4 3 (m, 2 H) 5. 2 4-5. 3 1 (m, 2 H) 5. 6 2 - 5. 7 7 (m, 1 H), "F-NMR (282. 7 MHz, solvent CD Gig, standard ; C FC Is) (ppm) :-8 0. 0 (1 F),-8 1. 3 (3 F),-8 2.

1 (3 F), - 8 6. 4 (1 F),-1 2 9. 5 (2 F), - 1 3 1. 5 (1 F).

[EXAMPLE 12] Production of CH2C1CHC1CH (OCH3) CH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (a compound (4A) wherein RA1 is a methoxy group.)

CH2=CHCH (OCH3) CH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (123g) having GC purity of 99% obtained in EXAMPLE 11 was put into a flask and stirred at-20°C. Chlorine gas (21. 8g) was blown thereinto over 1. 5 hours while maintaining the internal temperature at most 0°C. After raised to room temperature, stirring was continued for 1 hour at room temperature while blowing nitrogen gas thereinto. The resulting reaction liquid was purified by a silica gel column chromatography (eluent : AK-225), to obtain CH2ClCHClCH (OCH3) CH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (88g).

H-NMR (3 0 0. 4 MH z, solvent : C D C l3 , standard : T M S) # (p p m) : 1. 2 2-1. 3 0 (m, 3 H), 3. 4 6 , 3. 4 7, 3. 5 0, 3. 5 1, 3. 5 3 (each s, total 3 H), 3 . 5 0 - 4 . 0 2 (m, 6H), 4. 1 9-4. 5 0 (m, 3 H).

19F-NMR (2 8 2. 7MH z solvent CD Gig, standard : C F C 1 3) o (p pm) :-8 0. 0 (1 F),-8 1. 3 (3 F),-8 2.

1 (3 F), - 8 6. 3 (1 F). - 1 2 9. 5 (2 F), - 1 3 1. 5 (1 F).

[EXAMPLE 13] Production of CF2C1CFC1CF (OCF3) CF20CF (CF3) COF (a compound (5A) wherein RAF1 is a trifluoromethoxy group.) Into a 500 mL autoclave made of nickel, R-113 (312 g) and NaF powder (8. 0g) were added, stirred and maintained at-5°C. At the gas outlet of the autoclave, a condenser maintained at-10°C was installed. Nitrogen gas blown thereinto for 1. 0 hour, and then, the diluted fluorine gas was blown thereinto for about 1 hour at flow

rate of 8. 20 L/h. Then, while blowing the diluted fluorine gas at the same rate, a solution of CH2ClCHClCH (OCH3) CH20CH (CH3) CH20COCF (CF3) OCF2CF2CF3 (3. 81 g) obtained in EXAMPLE 12 dissolved in R-113 (76. 2g) was injected thereinto over a period of 3. 8 hours.

Then, while blowing the diluted fluorine gas at the same rate to maintain the internal pressure of the reactor at 0. 15 MPa, a R-113 solution having a benzene concentration of 0. 01 g/mL was injected thereinto in an amount of 9 mL while raising the temperature from 25°C to 40°C, whereupon the benzene injection inlet of the autoclave was closed and stirring was continued for 0. 3 hours. Then, while maintaining the internal pressure of the autoclave at 0. 15 MPa and the internal temperature of the reactor at 40°C, 6 mL of the above-mentioned benzene solution was injected thereinto, and stirring was continued for 0. 3 hours. Further, the same operation was repeated three times. The total amount of benzene injected was 0. 34 g, and the total amount of R-113 injected was 33 mL. Further, the diluted fluorine gas was blown thereinto for 0. 7 hour and then nitrogen gas was blown thereinto for 1. 0 hour. It was confirmed by analysis with GC-MS that CF2ClCFClCF (OCF3) CF20CF (CF3) COF (yield : 39%) and CF3CF (OCF2CF2CF3) COF (yield : 41%) were prepared.

CF3CF [OCF2CF (OCF3) CFC1CF2C1] CF20COCF (CF3) OCF2CF2CF) (yield : 24%) was also contained in the reaction product.

[EXAMPLE 14] Production of CF2=CFCF2CF20CF=CF2 (a compound (7) wherein RAF is a fluorine atom.) The compound mentioned above was prepared from CF2ClCFClCF2CF2OCF (CF3) COF obtained in EXAMPLE 7 by a known method (JP-A 2-42038). That is, CF2C1CFC1CF2CF2OCF (CF3) COF (133g) was slowly added dropwise thereto into methanol (300 mL) cooled with ice.

Further, a methanol solution of potassium hydroxide was added thereto until the reaction liquid became alkaline.

Then, after methanol was distilled out, the reaction liquid was sufficiently dried, followed by thermal decomposition at 190°C to obtain CF2C1CFC1CF2CF20CF=CF2 (80g).

Into a 500 mL four-necked flask were put zinc (60g) and 1, 4-dioxane (200 mL) and CF2ClCFClCF2CF20CF=CF2 (80g) were slowly added dropwise thereto. At one hour after completion of dropwise adding, the resulting liquid was subjected to filtration to remove zinc, and distilled to obtain CF2=CFCF2CF2OCF=CF2 (31. 9g) with a yield of 50%.

[EXAMPLE 15] Production of polymer By using CF2=CFCF2CF20CF=CF2 obtained in EXAMPLE 14, the polymerization was carried out in the same manner as in a known method. That is, CF2=CFCF2CF2OCF=CF2 (35g), de-ionized water (150 g) and a polymerization initiator [ ( (CH3) 2CHOCOO) 2, 90 mg] were put into a 200 mL autoclave made of pressure-resistant glass. After substituted with nitrogen gas three times, the polymerization was carried

out at 40 for 22 hours to obtain the polymer.

The intrinsic viscosity [C] of the polymer determined in perfluoro (2-butyltetrahydrofuran at 30°C was 0. 5 dL/g. The polymer had a glass transition temperature of 108°C, and was a tough and transparent glass-like polymer at room temperature. Further, the polymer had a 10% thermal decomposition temperature of 460°C, and a refractive index of 1. 34 and a light transmission rate of at least 95%, which was substantially an equal polymer to the one produced by a conventional method.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to produce a fluoride compound (5) having a vic-dichloro structure in a short process and in good yield from the compound (1) which is inexpensive and readily available.

The fluoride compound (5) is a useful compound as raw material for a monomer of a fluorinated resin.

Further, according to the present invention, is provided new compounds useful for raw material for the monomer mentioned above. In addition, there is also provided a continuous preparing method for the compound (1) which is used in a reaction with the compound (2) obtained together with the compound (5).