Method for production of vic-dichlorofluoroanhydride

FIELD: organic chemistry, in particular polymers.

SUBSTANCE: invention relates to new method for production of vic-dichlorofluoroanhydride useful as intermediate of starting monomer for fluorinated polymers with good yield from available raw material. Claimed method includes fluorination of starting material (I): (RH1-EH1-)CRH2RH3CH2-0CORHB in liquid phase to form compound of formula (II): (CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB; ester bond splitting of formula (II) in gaseous phase under solvent absence to form compound of formula (III): (CF2ClCFCl-EF1-)CRF2RF3COF or compound of formula (III) and compound of formula (IV): FCORFB, wherein RH1 is CX1X2ClCX3Cl- or CClX4=CCl, wherein each X1-X4 independently is hydrogen; RH2 and RH3 independently are hydrogen or linear or branched alkyl, optionally substituted with one or more oxygen; EH1 is alkylene, optionally substituted with one or more oxygen; EF1 = EH1 wherein perfluoroalkylene group is optionally substituted with one or more oxygen; RHB = RFB and are linear or branched perfluoroalkyl group, optionally substituted with chlorine one or more oxygen; RF2 is fluorinated RH2; RF3 is fluorinated RH3; with the proviso, that RF2 is fluorinated RH2; RF3 is fluorinated RH3, i.e. RF2 and RF3 represent RH2 or RH3 with at least one fluorinated hydrogen. Also disclosed are new compounds, represented in claims of invention.

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

 

The technical field

The present invention relates to a new method of deriving foramerica acid having a vic-dichlorostyrene, which is useful as intermediate compounds for the receipt of the initial monomer for the fluorinated polymers.

The level of technology

The compound containing performanceline circuit having a vic-dichlorostyrene (a structure in which one chlorine atom is associated with each of two adjacent carbon atoms) at the end of the molecule, and containing percarbonate group (COF), is useful as intermediate compounds for obtaining the substance monomer, fluorinated polymer, or fluorocarbon polymers. For example, the compound containing the group-CF2ClCFCl, may be subjected to interaction with zinc and then subjected to dechlorination with obtaining derived foramerica containing performancenow group (CF2=CF-). Performanceline group of such compounds is a group which is capable of polymerization and, thus, by the polymerization of such compounds can be obtained in different fluorinated polymers. The resultant fluorinated polymers are valuable polymers having high heat resistance and chemical resistance.

Among the above-mentioned fluorinated polymers, for example, gomobo the emer PERFLUORO(3-butylvinyl simple ether) [CF 2=CFCF2CF2OCF=CF2] is used in various fields as a transparent fluorinated polymer. Monomer such fluorinated polymer, PERFLUORO(3-butylvinyl simple ether), usually obtained using the following synthesis scheme:

Namely, CF2=CFCl is subjected to interaction with chloride of iodine with the formation of compound (A), which is subjected to interaction with tetrafluoroethylene, thus obtaining the compound (b)which is subjected to interaction with fuming sulfuric acid, thus obtaining the compound (C). Further, the compound (C) is subjected to interaction with geksaftorpropilenom (HFPO) in the presence of a fluoride of an alkali metal, such as KF and the like, to obtain the compounds (D)which is heated at least up to 250°in the presence of soda ash or glass beads in order to obtain the compound (E), which is subjected to interaction with zinc, while receiving after dechlorination PERFLUORO(3-butylvinyl simple ether).

Such a conventional method for producing a PERFLUORO(3-butylvinyl ether), etc. inherent disadvantage in that the stage of obtaining the compound (A) together with the compound (a) is formed isomer, CF2ICFCl2. The number of isomers are difficult to control. In addition, the conventional STRs is about getting unprofitable, because it includes a lot of reaction stages, and used for its implementation of the source materials are expensive. In addition, there are complex problems, such as corrosion of the equipment and the complexity of treatment with reagents arising from the use of chloride of iodine and fuming sulfuric acid, etc.

On the other hand, as a method of fluorination all C-H linkages with the formation of C-F bonds in the hydrocarbon compound known methods of direct fluorination using elemental fluorine (hereinafter referred to as direct fluorination) and method of fluorination using a product produced by the electrolysis of hydrogen fluoride in an electrolytic cell (also referred to as electrochemical fluorination). As a direct fluorination known method of fluorination in the gas phase (hereinafter referred to as gas-phase reaction) and a method of fluorination in the liquid phase (hereinafter referred to as liquid-phase reaction).

Also known is a method of obtaining derived foramerica by thermal decomposition of perfluorinated derivative of ester containing at least 16 carbon atoms. It was reported that such derived foramerica can be obtained by using as its source material derived complex carbohydrate is a native of ether, with the appropriate carbon skeleton, and by direct fluorination of such compounds using elemental fluorine in a liquid phase (J. Am. Chem. Soc., 120, 7117 (1998)).

Was also offered a way to communicate complex perforaciones ester not containing chlorine atom, in the presence of a nucleophile and solvent with the formation of a perfluorinated floramerica (U.S. patent 5466877).

However, it is usually not mentioned and was not intended that floramite with vic-dichlorostyrene, such as PERFLUORO(3,4-dichlorocarbanilide simple ether), which is a precursor of PERFLUORO(3-butylvinyl simple ether), could be obtained by direct fluorination or by electrochemical fluorination reaction reported above.

The aim of the present invention is to provide a method of producing floramerica (III)having a vic-dichlorostyrene, such as PERFLUORO(3,4-dichlorocarbanilide simple ether), which is a precursor of PERFLUORO(3-butylvinyl simple ether), and the method should be brief and to allow the use of cheap and available raw materials. Usually this method was uneconomical, since it required a large number of reaction stages and expensive starting compounds, the process was associated with significant problems, that is them as corrosion of the equipment and the complexity of treatment with reagents, arising out of the use of chloride of iodine and fuming sulfuric acid, etc.

The invention

The present invention provides a method of obtaining derivatives vic-dichlorphenamide, including fluoridation of the following compound (I) in the liquid phase to obtain the following compound (II) and the cleavage of ester bonds of the compound (II) to obtain the following compound (III) or the following compound (III) and the following compound (IV):

(RH1-EH1-)CRH2RH3CH2-OCORHB(I)

(CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB(II)

(CF2ClCFCl-EF1-)CRF2RFCOF (III)

FCORFB(IV)

where RH1: CX1X2ClCX3Cl - or l4=CCl-, where each of the groups X1-X4represents independently a hydrogen atom or a fluorine atom,

RH2, RH3: each independently represents a hydrogen atom, a fluorine atom, a monovalent saturated hydrocarbon group, a monovalent saturated kalogeropoulou a group containing a heteroatom monovalent saturated hydrocarbon group, or containing a heteroatom monovalent saturated kalogeropoulou group,

EH1: divalent linking group or a simple bond,

EF1: group matching the E H1and, when EH1represents a simple bond, E.F1is a simple relationship, and when EH1represents a divalent linking group containing one or more hydrogen atoms, EF1is a group corresponding to EH1where at least one hydrogen atom is fluorinated, and when EH1represents a divalent linking group containing no hydrogen atom, EF1is the same group as EH1,

RHB: monovalent saturated hydrocarbon group, a monovalent saturated galactoglucomannan group containing a heteroatom monovalent saturated hydrocarbon group, or containing a heteroatom monovalent saturated galactoglucomannan group,

RF2, RF3, RFB: RF2represents a fluorinated group, RH2, RF3represents a fluorinated group, RH3, RFBrepresents a fluorinated group, RHBprovided that when in groups, RH2, RH3or RHBthere is one or more hydrogen atoms, RF2, RF3or RFBrepresents a group corresponding to RH2, RH3or RHBaccordingly, where at least one hydrogen atom is fluorinated, and when in groups of RH2, RH3or RHBnot prisutstvuet is a hydrogen atom, RF2, RF3or RFBis a group corresponding to RH2, RH3or RHBrespectively.

According to the present invention floramite (III)having a vic-dichlorostyrene can be obtained a short way and with a good yield of the compound (I), which is available at a reasonable price, which is described in detail below.

The method according to the present invention is not associated with such complex problems as corrosion of the equipment and the complexity of treatment with reagents, because it does not use chloride of iodine and fuming sulfuric acid, etc.

In addition, it also has a continuous method of producing floramerica (III)having a vic-dichlorostyrene, in which the compound (IV)obtained with floramerica (III)recycle to the stage of processing of the initial substances.

In addition, there are new intermediate compounds formed at various stages of the method according to the present invention.

The best way of carrying out the invention

[Explanation of the terms used in the invention]

In the present description monovalent saturated hydrocarbon group may be a structure with a non-branched chain, a branched structure, a cyclic structure (i.e cycloalkyl group) means an organic group or a structure containing a partially circular with whom ructure. The number of carbon atoms in the monovalent saturated hydrocarbon group is preferably from 1 to 20, particularly preferably from 1 to 10.

In the present description, the halogen atom may be a fluorine atom, chlorine atom, bromine atom or iodine atom, and a fluorine atom, a chlorine atom or a bromine atom is preferred.

In addition, in the present description “halogen” means that at least one hydrogen atom in the group is substituted by at least one halogen atom selected from fluorine atom, chlorine atom, bromine atom and iodine atom. In galactography may or may not be present a hydrogen atom. The term “fluorescent”, etc. is explained in the same way.

The term “partially halogeno” means that the group galactography is a hydrogen atom which is not substituted by a halogen atom. The terms “partially fluorescent” and “perftoran”, etc. are explained similarly.

In the present description monovalent galactoglucomannan group may be a group containing at least one hydrogen atom in the above-mentioned monovalent saturated hydrocarbon group substituted by a halogen atom. The halogen atom in the monovalent halogenopyrimidines group preferably represents a fluorine atom, a chlorine atom or a bromine atom. As such the halogen atom in a single-shaft is Noah halogenopyrimidines group is particularly preferred single fluorine atom or a fluorine atom and halogen atom, other than fluorine atom. As specific examples of such groups may be mentioned groups disclosed in the following examples compounds.

In the present description as containing heteroatom monovalent saturated hydrocarbon group may be mentioned monovalent saturated hydrocarbon group in which the heteroatom or a group containing a heteroatom, do not change when carrying out the fluorination reaction. Especially preferred is the group that contains the bivalent heteroatom or divalent heteroatomic group that does not undergo changes when carrying out the fluorination reaction of the above monovalent saturated hydrocarbon group.

As a divalent heteroatom, which does not change when carrying out the fluorination reaction, it is preferable etheric oxygen atom and a divalent heteroatomic group, which does not change when carrying out the fluorination reaction can be a-C-C(=O) -,- C,-SO2-C - etc.

Monovalent saturated hydrocarbon group that contains a heteroatom, preferably represents an alkyl group containing an etheric oxygen atom, group containing an etheric oxygen atom between carbon atoms-carbon cycloalkyl groups who, or a monovalent saturated hydrocarbon group, which contains etheric oxygen atom between carbon atoms-carbon cycloalkyl group.

In addition, monovalent saturated galactoglucomannan group that contains a heteroatom, may be a group containing at least one hydrogen atom in the above-mentioned monovalent saturated hydrocarbon group that contains a heteroatom, substituted with halogen atom, this may be referred to halogeno(alkoxyalkyl) group or halogenoacetyl group.

[Explanation of compound (I)]

In compound (I) RH1is a CX1X2ClCX3Cl - or CClX4=CCl- (provided that X1-X4independently represents a hydrogen atom or a fluorine atom), and all of X1-X4preferably represent a hydrogen atom, taking into account the availability of the source substances and efficiency of the method according to the present invention.

EH1represents a simple bond, where RH1and the carbon atom linking RH2and RH3directly connected. When EH1represents a divalent linking group, the divalent saturated hydrocarbon group, a divalent saturated galactoglucomannan group containing divalent heteroatom is asimina hydrocarbon group or divalent containing heteroatom rich galactoglucomannan group is preferred. The divalent linking group may be a structure with a straight chain structure, branched chain or a structure containing a cyclic structure.

Structure RH2and RH3can be appropriately modified depending on the structure of the target compound, and preferably RH2and RH3represent a hydrogen atom, alkyl group, halogenoalkane group containing a heteroatom alkyl group or containing a heteroatom halogenoalkane group, depending on their availability. Since the fluorine atom can be introduced in RH2and RH3by the fluorination reaction described below, a group containing a halogen atom other than fluorine atom is preferred for economic reasons, when RH2and RH3are galactography.

EH1, RH2and RH3appropriately selected from structures corresponding to the target compound (III), respectively, and preferably represents a group containing no fluorine atom, from the viewpoint of availability and economic feasibility, etc. of the method of obtaining. In addition, EH1preferably represents alkylenes group or containing a heteroatom alkylenes group, and RH2and RH3preferably represent seboyeta hydrogen or containing a heteroatom alkyl group.

The structure of RHBpreferably selected so that the compound (I) was readily soluble in the liquid phase, which must be used during the fluorination. RHBpreferably represents halogenoalkane group, halogeno(containing heteroatom alkyl) group, more preferably represents a group containing a fluorine atom as a basic atom, among which particularly preferred performanceline group, a PERFLUORO(partially chlorinated alkyl) group, a PERFLUORO(containing heteroatom alkyl) group or a PERFLUORO(partially chlorinated (containing heteroatom alkyl)) group. RHBespecially preferably represents a group containing a fluorine atom as a basic atom, since the compound (I) is sufficiently soluble in the liquid phase and the fluorination of the compound (I) can be carried out in a homogeneous phase during the fluorination of the compound (I) in the liquid phase.

In addition, the fluorine content in the compound (I) (the proportion of fluorine atoms in the molecule) preferably is modified depending on the type of the liquid phase, which should be used when fluoridation. Usually the lower limit of the fluorine content (the ratio of fluorine atoms and the molecular weight compounds) is preferably 10% by mass, particularly preferably 30 mass%, and the top of the third limit is preferably 86% by weight, especially preferably 80% by mass. Molecular weight of the compound (I) is preferably from 300 to 1000, in accordance with what the reaction in the gas phase can be suppressed and the reaction in the liquid phase can be carried out gently during the fluorination reaction. If the molecular weight is too small, the compound (I) tends to be volatile, and it is probable that during the reaction of fluorination in the liquid phase can be reaction of decomposition in the gas phase. On the other hand, if the molecular weight is too large, the purification of compound (I) can be difficult.

As the compound (I) can be mentioned the following various known and new connections:

l=lO(CH2)5OF(CF3)F2CF2CF3

CH2=CH(CH2)2O(CH2)3F(CF3)F2CF2CF3

CH2ClCHCl(CH2)2O(CH2)3F(CF3)F2CF2CF3

[The transformation of the compound (I) in the compound (II)]

According to the present invention the compound (I) is subjected to fluorination in the liquid phase. As a method of fluorination in the liquid phase method can be specified fluorination of the compound (I) using elemental fluorine in the solvent (method fluoridation-1) or electrochemical fluorination (method ftory the cation-2), among which preferred is a method of fluorination-1.

When the fluorination is carried out with the use of the method of fluoridation-2, it is preferable that the compound (I) was dissolved in anhydrous hydrofluoric acid to obtain a solution and the solution was subjected to electrolysis in an electrolytic cell for the fluorination of the compound (I) with the formation of compound (II).

When the fluorination is carried out with the use of the method of fluoridation-1, the compound (I) and gaseous fluorine interact in a solvent (hereinafter referred to as solvent 1) with the formation of compound (II). As of fluorine gas can be used 100%gaseous fluorine or gaseous fluorine diluted with an inert gas. As a preferred inert gas is nitrogen gas and helium gas, nitrogen gas is particularly preferred for economic reasons. The number of fluorine gas in a gas mixture of inert gas and gaseous fluorine is preferably at least 5 vol.% from the point of view of efficiency and particularly preferably from 5 to 30 vol.%, as can be prevented separation of the chlorine atom and the migration of the chlorine atom.

The solvent is 1 that you want to use for implementing the method of fluoridation-1, preferably is with the second solvent, which contains no C-H bond and which necessarily contains the C-F bond. In addition, it is preferable to use perftoran or an organic solvent, obtained by artificially enhancing the uptake of a known organic solvent containing in its structure at least one atom selected from a chlorine atom, nitrogen atom and oxygen atom. In addition, as a solvent 1, it is preferable to use a solvent, which provides high solubility of compound (I), and particularly preferable to use a solvent capable of dissolving at least 1 mass% of compound (I), in particular a solvent, which is capable of dissolving at least 5% by weight of compound (I).

Examples of the solvent 1 may be a compound (II), the compound (III), the compound (IV), perftoran (such as FC-72), simple perforator (such as FC-75, FC-77), simple parfocality (such as having the trade name KRYTOX, FOMBLIN, GALDENE and DEMNUM), chlorofluorocarbons (trade name FLONLUBE), simple hortobagyi, performanceline (such as perftorsilanami) and the inert liquid (trade name FLUORINERT). Additional area as solvent 1 are preferred perftorsilanami or the compound (II). In particular, when used as a compound (II), to the availability of benefits may be marked that treatment after the reaction is facilitated. The amount of solvent 1 is preferably at least 5-fold by weight, preferably from 10 to 100 times by mass relative to the compound (I).

The type of reaction in the case of the fluorination reaction used in the method of fluoridation-1, preferably is a system of periodic action or continuous action. The system of continuous action, which will be described later, is preferred particularly from the viewpoint of the yield of the reaction and selectivity, among them the continuous system (2) is particularly preferred. In addition, in cases where the reaction is carried out using a system of periodic action or continuous action, gaseous fluorine may be diluted with an inert gas such as nitrogen gas.

[System of continuous action (1)]

Charged to the reactor, the compound (I) and the solvent 1 and begin mixing. This is the way of interaction with a predetermined reaction temperature and pressure of reaction, when the continuous supply of fluorine gas.

[System of continuous action (2)]

Charged to the reactor solvent 1 and begin mixing. This is the method of application of compound (I), solvent 1 and gaseous torus when preset the reaction temperature and pressure of reaction, when the pre-molar ratio continuously and simultaneously.

In the system of continuous action (2) compound (I), when submitting, can be diluted or not diluted with solvent 1. In addition, in the system of continuous action (2), when compound (I) diluted with a solvent, it is preferable to increase the number of solvent 1 to at least 5-fold amount by weight relative to the compound (I), particularly preferably to at least 10-fold amount by weight relative to the compound (I).

When the reaction is carried out using a system of periodic action, it is preferable to apply a gaseous fluorine so that the number of fluorine atoms always exceeded the number of equivalent relative to the hydrogen atoms in the compound (I), and particularly preferably gaseous fluorine was used in such quantity that it exceeded the equivalent of at least 1.5 times (at least a 1.5-fold the amount in moles) in relation to the hydrogen atoms in the compound (I), from the viewpoint of selectivity. In addition, when the reaction is carried out using a system of continuous action, preferably continuously feeding a gaseous fluorine, so that the number of fluorine atoms exceeded the equivalent amount from siteline of hydrogen atoms in the compound (I), and particularly preferably continuously feeding a gaseous fluorine so that the amount exceeded the equivalent of at least 1.5 times (at least a 1.5-fold the amount in moles) in relation to the hydrogen atoms in the compound (I), from the viewpoint of selectivity.

The reaction temperature when the reaction of fluorination method-1 fluorination may vary depending on the structure of EH1and is preferably at least -60°and not more than the boiling point of the compound (I). From the point of view of the yield of the reaction, the selectivity and efficiency of industrial synthesis reaction temperature is particularly preferably ranges from -50 to +100°S, most preferably from -20 to +50°C, to prevent separation and migration of the chlorine atom. The reaction pressure when carrying out the fluorination reaction is not particularly limited, in particular, preferably the pressure is from atmospheric up to 2 MPa (gauge pressure, the same pressure is applied hereinafter), from the point of view of yield, selectivity and efficiency of the industrial process.

In addition, in order to carry out the method-1 fluoridation effectively, it is preferable to add to the reaction system compound containing C-H bond, or to carry out the process under ultraviolet irradiation. For example, it is preferable to relax the TB connection, containing C-H bond in the reaction system or when using ultraviolet radiation at the last stage of the fluorination reaction. When using this method the hydrogen atoms, which are usually difficult to fluoridate can be efficiently fluorinated, and the reaction rate can be significantly increased. Time of ultraviolet radiation is preferably from 0.1 to 3 hours.

Compounds containing C-H bond, is an organic compound other than the compound (I), and particularly preferred is an aromatic hydrocarbon. Particularly preferred are, for example, benzene or toluene. The number of such compounds containing C-H bond, is preferably from 0.1 to 10 mol.%, in particular from 0.1 to 5 mol.%, in relation to the number of hydrogen atoms in the compound (I).

It is preferable to add a compound containing C-H bond in the reaction system in such a state, when there is elemental fluorine. In addition, when you add a compound containing C-H bond, it is preferable to create an increased pressure in the reaction system. In this case, the pressure is preferably from 0.01 to 5 MPa.

[Explanation of compound (II)]

In the fluorination reaction of the compound (I) is formed of the compound (II). The hydrogen atoms of the group RH1in soy is ininii (II) when carrying out the fluorination reaction will be substituted by fluorine atoms, and when RH1represents CClX4=CCl-, this group will turn into CF2ClCFCl-because the fluorine atoms will be joined by double bonds.

When EH1represents a simple bond, E.F1will be a simple relationship, and if EH1represents a divalent linking group that does not contain a hydrogen atom, EF1will be the same group as the divalent group, and if EH1represents a divalent linking group containing one or more hydrogen atoms, EF1will be a group in which at least one hydrogen atom is fluorinated. For example, if EH1is perhalogenated, E.H1and EF1will be the same. If EH1represents alkylene group or the group in which the ether oxygen atom is located between the carbon-carbon bond alkalinous group, then EF1will be a group in which at least one hydrogen atom in these groups is substituted by a fluorine atom. EF1preferably represents performancelevel group or PERFLUORO(containing a heteroatom)alkylenes group.

Each of RF2and RF3preferably independently represents a fluorine atom, a partially halogen or paralogue(monovalent saturated hydrocarbon) group, part of halogenide paralogue(containing heteroatom monovalent saturated hydrocarbon) group. If RH2and RH3there is no hydrogen atom, RF2and RF3are the same as RH2and RH3accordingly, since RH2and RH3in this case, are not subject to fluoridation. If RH2and RH3contain a hydrogen atom (for example, each of RH2and RH3is partially fluorinated monovalent saturated hydrocarbon group, each of RF2and RF3is a group, respectively, in which at least one hydrogen atom in the fluorinated group, and preferably represents a perforated monovalent saturated hydrocarbon group. In addition, if each of RH2and RH3is partially chlorinated monovalent saturated hydrocarbon group, each of RF2and RF3represents a fluorinated (partially chlorinated monovalent saturated hydrocarbon) group, respectively, in which at least one hydrogen atom in the fluorinated group, and particularly preferred is a PERFLUORO(partially chloraniline) group.

RF2and RF3preferred are a fluorine atom, a monovalent saturated perftoruglerodnye group or performanceline group.

RFBrepresents a group corresponding to RHBand RFBwill tako the same as RHBwhen RHBis galactography. When RHBrepresents a hydrogen containing group, RFBis the group in which the hydrogen fluoride. RFBpreferably represents performanceline group or PERFLUORO(alkoxyalkyl) group.

In the case of liquid-phase fluorination reaction of the compound (I) as a by-product can be formed HF. To remove HF produced as a by-product, it is preferable to introduce into the reaction system, the HF absorber or to carry out the contacting of the HF absorber with withdrawing gas at the gas outlet of the reactor. As HF absorber is preferred basis, for example, such as a fluoride of an alkali metal (e.g. sodium fluoride and so on), and it can be introduced into the reaction system. The HF absorber preferably is a fluoride of an alkali metal, particularly preferred is NaF.

When the HF absorber is introduced into the reaction system, its amount is preferably 1 to 20-fold in molar ratio, more preferably 1 - to 5-fold in molar ratio relative to the total number of hydrogen atoms contained in the compound (I). In the case where the HF absorber is located at the outlet of the reactor, it is preferable to install: (1 capacitor (preferably, operated at a temperature of from 10°C to room temperature, particularly preferably at a temperature of about 20°C), (2) a compacted layer of absorber HF, such as NaF pellets, and (3) condenser (preferably operated at a temperature of from -78 to +10°S, more preferably from -30 to 0° (C)that are located sequentially in the order(1) - (2) - (3). In addition, it may be installed in the return line fluid to return the condensed liquid from the condenser (3) in the reactor.

The crude product containing the compound (II)obtained by the fluorination reaction, can be used in the next stage as such or may be purified to a high degree of purity. Treatment method may, for example, be a method of distillation of the crude product under atmospheric pressure or reduced pressure.

[The transformation of compound (II) into the compound(III)/the compound (IV)]

Further according to the present invention the compound (III) and/or the compound (IV) obtained by cleavage of the ester bonds of the compound (II). When performing the method of receiving according to the present invention, the target compounds are the compound (III), the compound (IV) or the compound (III)and compound (IV).

The reaction of cleavage of the ester bonds of the compound (II) is a reaction formation TLD the-COF group at destruction-CF 2OCO-. This reaction is preferably carried out by reaction of thermal decomposition or by decomposition reaction, which is carried out in the presence of a nucleophile or electrophile.

The reaction of thermal decomposition can be carried out by heating the compound (II). The type of reaction of thermal decomposition is preferably selected based on the boiling point and stability of compound (II). For example, if the compound (II) is that easily evaporates, it is subjected to thermal decomposition. Can be used a method of gas-phase thermal decomposition, in which the connection is continuously decomposed in the gas phase, and the exit gas containing the resulting compound (III)is subjected to condensation and selection.

The reaction temperature in the process of gas-phase thermal decomposition is preferably from 50 to 350°S, more preferably from 50 to 300°S, particularly preferably from 150 to 250°C. Further, the inert gas, which is not directly associated with the reaction, may be present in the reaction system. As such an inert gas may be indicated, for example, nitrogen or carbon dioxide. It is preferable to add an inert gas in an amount of from 0.01 to 50 vol.% with respect to the compound (II). If the amount of inert gas is high, the output product can sometimes CH is to go on.

On the other hand, when the compound (II) is a compound which is difficult to evaporate, it is preferable to use a method of liquid-phase thermal decomposition, whereby the compound is heated in a liquid state in the reactor. The pressure of the reaction in this case is not limited. In the usual case, the product obtained by the decomposition of ester has a lower boiling point, and it is preferable to carry out the interaction, using a reactor equipped with a distillation column, whereby a product having a lower boiling temperature, is continuously displayed. Otherwise it may be a method in which after completion of the heating of the reactor is shown together the entire product. The reaction temperature for the method of liquid-phase thermal decomposition is preferably from 50 to 300°S, especially preferably from 100 to 250°C.

When thermal decomposition is carried out by the method of liquid-phase thermal decomposition, the decomposition can be carried out in the absence of solvent or in the presence of a solvent (hereinafter referred to as solvent-2). The choice of solvent 2 is not particularly limited, while it does not react with the compound (II), and mixed with compound (II) and does not interact with the product. The dal is, the solvent is preferably 2 to choose a solvent which is easily removed during the cleaning product. A specific example of the solvent-2, preferably in an inert solvent, such as perftorsilanami or perpendicular, or trichloropyridinol, particularly preferably an oligomer of trichloroethylene having a high boiling point (for example, trade name FLONLUBE). The amount of solvent-2 is preferably from 10 to 1000% by weight relative to the compound (II).

Further, when the compound (II) is subjected to degradation by interacting with the electrophile or nucleophile in the liquid phase, this interaction can be carried out in the absence of solvent or in the presence of a solvent (hereinafter referred to as solvent-3). The solvent is preferably 3 is the same as the solvent-2. The nucleophile is preferably a fluoride anion (F-), in particular fluoride anion derived from a fluoride of an alkali metal. The fluoride of the alkali metal preferably is a NaF, NaHF2, KF or CsF. Among them, most preferred is NaF from the point of view of economic efficiency.

When used as a nucleophile, such as F-, F-nucleophile attached to a carbonyl group, present the ester bonds in the compound (II), whereby to separate CF2ClCFClEF1CRF2RF3CF2O-and will generate floramite [compound (IV)]. Of CF2ClCFClEF1CRF2RFCF2O-will additionally be separated F-with the formation of foramerica [compound (III)]. Separated F-in the same way will interact with another molecule of the compound (II). Accordingly, the nucleophile, which must be used at the initial stages of the reaction, may be present in catalytic amounts, or may be used in excess. Namely, the number of nucleophile, such as F-is preferably from 1 to 500 mol.%, particularly preferably from 1 to 100 mol.%, most preferably from 5 to 50 mol.%, with respect to the compound (II). The lower limit of the reaction temperature is preferably -30°and the upper limit is preferably the boiling temperature of the solvent-3 or the compound (II). Usually the reaction temperature is preferably from -20 to +250°C. This method is also preferably carried out using a reactor equipped with a distillation column.

As the compound (II) can be specified below new connections. The following compounds can lead to the appropriate derived vic-dichlorphenamide by which sushestvennee reactions which will be described in the examples.

CClF2CClFO(CF2)5OCOCF(CF3)OCF2CF2CF3

CF2ClCFCl(CF2)2O(CF2)3F(CF3)F2CF2CF3

It is preferable to conduct the reaction of decomposition of the ester bonds in the presence of NaF. The reaction of thermal decomposition can be carried out at low temperature by carrying out the decomposition in the presence of NaF, whereby decomposition of the connection can be prevented.

As compound (III) may include the compounds described below in the examples, and the following new connection

CClF2CClFO(CF2)4COF

CF2ClCFCl(CF2)2O(CF2)2F

[Method of obtaining the source compounds (I)]

The method of obtaining the compound (I) is not limited and can be used a known compound (I) or the compound can be obtained from known compounds. As the compound (I) is easily accessible compounds having different structures that match the structure of the target compounds. They are also available through the following scheme-1 of obtaining the substance. The compound (V)in which RH1is a CX1X2=CX3-related to the number of compounds (I)can also be obtained according to scheme 2 obtaining the substance.

Schemes is -1 of obtaining the substance is a method of obtaining the compound (I) by reacting the following compounds (A1) with the following compound (A2). In the formula X represents a halogen atom, and RH1EH1, RH2and RH3have the same values as above.

(RH1-EH1-)CRH1RH3CH2-OH (A1)

XCORHB(A2)

On the other hand, scheme-2 obtaining the substance is a method of producing compound (IB)in which RH1is a CX1X2ClCX3Cl-, by reacting the following compounds (B1) to the following compound (B2) to obtain the following compounds (EOI), followed by interaction of the following compounds (EOI) with gloriouse agent. Symbols in the formula are the same as defined above, and X10represents a halogen atom or a hydroxyl group.

(CX1X2=CX3-EH1-)CRH2RH3CH2-OH (B1)

X10CORHB(B2)

(CX1X2=CX3-EH1-)CRH2RH3CH2-OCORHB(B3)

(CX1X2ClCX3Cl-EH1-)CRH2RH3CH2-OCORHB(IB)

In the above scheme-1 and scheme-2 receiving substance interaction of the compound (A1) with compound (A2) and the interaction of the compound (B1) with compound (B2) can be conducted under normal esterification reaction. Although this reaction can be carried out in the presence of a solvent (hereinafter referred to as RA the maker of 4), from the point of view of the volumetric productivity, it is preferable to conduct this reaction in the absence of solvent 4. In those cases, when using a solvent 4, it is preferable to use a halogenated hydrocarbon solvent, such as dichloromethane and chloroform. The amount of solvent 4 is preferably 0.5 to 5-fold relative to the total mass of the compounds (A1) and the compound (A2) (or compound (B1) and the compound (B2)).

Specific examples of the implementation of schemes of obtaining the substance will be shown in the examples described below. Among the compounds described in the examples, the following compounds represent new connections:

l=lO(CH2)5HE

CH2=CH(CH2)2Och2CH2CH2HE

CH2=CH(CH2)2OCOCF2CFClCF2Cl

CH2=CH(CH2)2Och(CH3)CH2OCOCF(CF3)

F2CF2CF3

In the above described esterification reaction HX is formed as a by-product. In those cases, when using the compound (A2) or the compound (B2), in which X represents a fluorine atom, to form HF. As absorber such HF in the reaction system may be a fluoride of an alkali metal (such as sodium fluoride) or a base, such as trialkylamine and the feast of the Dean. The number of HF absorber is preferably 1 - to 10-fold in molar ratio relative to the compound (A2) or compound (B2). In cases where the HF absorber is not used, it is preferable to remove HF from the reaction system by passing nitrogen gas.

In the normal case, the lower limit temperature of the esterification reaction is preferably -50°and the upper limit is preferably +100°With or equal to the boiling temperature of the solvent 4 below. The reaction time is set depending on the feed rate of a substance and the number of connections that you want to use in the reaction, and the pressure of the reaction is preferably from 0 to 2 MPa.

The compound (B3), formed by the interaction of the compound (B1) with compound (B2), interacts with gloriouse agent with the formation of compound (IB). The interaction may be carried out using techniques and conditions customary for reactions of chlorination. Gloriouse agent usually represents chlorine (Cl2). In those cases, when using chlorine, its amount is preferably 1 - to 10-fold in molar ratio relative to the compound (B3), particularly preferably 1 - to 5-fold. Although the reaction of the compound (B3) with gloriouse agent can be carried out in the presence of a solvent (hereinafter the seat is raised as a solvent 5), it is preferable to conduct the reaction in the absence of solvent 5, from the viewpoint of volumetric productivity. In those cases, when using a solvent 5, it is preferably a halogenated hydrocarbon solvent, such as dichloromethane and chloroform. The amount of solvent 5 is preferably from 0.5 to 5-fold amount relative to the mass of compound (B3). The reaction temperature is preferably from -78 to +200°C.

The crude product containing the compound (I)obtained by the method described above can be used in the subsequent reaction or after treatment in the form of purified substances or as such. The method of purification of the crude product containing the compound (I)may be a method such as a method of distillation of the crude product as such, a method of separating the phases of the crude product after processing dilute aqueous alkali solution and the method of distillation of the crude product after extraction with a suitable organic solvent.

Further, the method according to the present invention can be implemented using the following appropriate ways 1-3 by selecting the types of groups in the compounds (I)to(IV) to exclude the extraction of the compounds or by modification of the method in a continuous way. Further, the group is s, which is not defined have the same meanings as described above.

[Method 1]

The method, according to which group is chosen so that the compound (III) and compound (IV) represented one and the same connection. In this method, phase separation of the product can be excluded. This method is partially similar to method 3, and will be explained further in the description of method 3.

[Method 2]

The method, according to which RHBchosen so that the compound (IV) had the same structure as the compound (A2) or the compound (B2). According to this method, the obtained compound (IV) can be used again to interact with the compound (A1) or the compound (B1), whereby the method according to the present invention can be carried out in a continuous way to obtain.

A concrete example of the method can be an example that in the compound (A2) or the compound (B2) as RHBuse perhalogenated. For example, when the compound (A) is compound (A2-1), the method can be performed in the following way to obtain.

For example, according to the following scheme for using the compound (A1-1) and the compound (A2-1), the method is a continuous method of obtaining through the use of the resulting joint is (A2-1) again to interact with the compound (A1-1).

CH3(CH2ll(CH2)2O)CHCH2OH (A1-1)

+FCOCF(CF3)OCF2CF2CF3(A2-1)

→ CH3(CH2ll(CH2)2O)SSN2OF(CF3)F2CF2CF3(I-1)

→ CF3(CF2ClCFClCF2CF2O)CFCF2OCOCF(CF3)OCF2CF2CF3(II-1)

→ CF3(CF2ClCFClCF2CF2O)CFCOF (III-1)+ compound (A2-1)

CF3(CF2ClCFClCF2CF2O)CFCOF can lead to substance (CF2=CFCF2CF2OCF=CF2to obtain a fluorinated polymers known method.

Similarly, in the following diagram receipt when using the compounds (A1-2) and compound (A2-2), the scheme is a continuous way to obtain through the use of the resulting compound (A2-2) repeatedly to interact with the compound (A1-2).

CH2ClCHCl(CH2)2OH (A1-2) + FCOCF2CF3(A2-2)

→ CH2ll(CH2)2OF2CF3(I-2)

→ CF2ClCFClCF2CF2OCOCF2CF3(II-2)

→ CF2ClCFClCF2COF (III-2) +compound (A2-2)

[Method 3]

The method, according to which group is chosen so that the resulting compound (III) had the same structure as the compound (IV) and, in addition, they had the same structure as the compound (A2) or the the group (B2). This method is especially preferred because it is not necessary to separate the product, part or all of the resulting product can be used again to interact with the compound (A2) or a compound (B2), the method can be carried out as a continuous process.

For example, can be specified continuous way to obtain used to obtain the compounds (A2-3) according to the following scheme for using the compounds (A1-2) and compound (A2-3).

CH2ll(CH2)2HE (A1-2) + FCOCF2CFClCF2Cl (A2-3)

→ CH2ll(CH2)2OCOCF2CFClCF2Cl (I-3)

→ CF2ClCFClCF2CF2OCOCF2CFClCF2Cl (II-3)

→ the Compound (A2-3)

EXAMPLES

Hereinafter the present invention will be described in detail by bringing examples, but the present invention is not limited to these examples. In the next section describe some of the terms are given in the form of their respective abbreviations, namely gas chromatography GC, gas chromatography combined with mass spectroscopy, GC-MS, TMS, tetramethylsilane was, N,N-dimethylformamide DMF, dichloropentafluoropropane AK-225, 1,1,2-trichloro-1,2,2-trifluoroethane R-113, l: l HS degree of purity it means cleanliness, defined by the ratio of the peak area according to GC. In the NMR spectra: MHz MHz; d - holes is t, m - multiplet, t - triplet, q - Quartet, s-singlet, dd - dvdwhat.

[Example 1]

Getting CF2lFlF2CF2OF(CF3)F and FF(CF3)OCF2CF2CF3

<Example 1-1>

Obtaining CH3CH ((CH2)2CH=CH2)COO(CH2)2CH=CH2

CH3l (50 g) and CH2=CH(CH2)2OH (75 ml) is placed in a flask and stirred, then at room temperature is added dropwise 10 ml of concentrated sulfuric acid for 10 minutes. The resulting reaction solution was added to 250 ml of a saturated aqueous solution of sodium carbonate. There also add water (150 ml) and tert-butylmethylamine simple ether (150 ml), and then divide the liquid, while receiving layer tert-butylmethylether simple ether as the organic layer. Next, the organic layer was washed with 150 ml of water, dried over magnesium sulfate and then filtered, thus obtaining the crude liquid. The crude liquid concentrate and get CH3l(CH2)2CH=CH2.

CH2=CH(CH2)2HE (16.6 g) and DMF (120 ml) was placed in another flask and cooled to maintain the temperature inside the flask at 8-9°C. Add the sodium bicarbonate (10 g) for 30 minutes and then cooled after stirring for 30 minutes at room tempera is ur. Then added dropwise within 1.5 hours of CH3l(CH2)2CH=CH2(50 g), which was obtained previously dissolved in 30 ml of DMF. After completion of adding dropwise continue heating for 3 hours while maintaining the temperature inside the flask at 80 - 85°C. After cooling to room temperature (25° (C) add 200 ml of hydrochloric acid with a concentration of 2 mol/L. Organic layer obtained by extraction, using 400 ml of hexane/ethyl acetate=2/1 4 times. The organic layer is concentrated and washed with twice 500 ml of water, dried over magnesium sulfate, filtered and then concentrated again, while receiving 86 g of CH3CH(O(CH2)2CH=CH2)COO(CH2)2CH=CH2. The purity of this product according to GC is 83%. These NMR spectrum is shown below.

1H-NMR (399,8 MHz, solvent: Dl3standard: TMS), δ (ppm): 1,39 (d, J=7,0 Hz, 3H), 2,33 at 2.45 (m, 4H), to 3.41 (dt, J=7,0, and 9.1 Hz, 1H), 3,63 (dt, J=7,0, and 9.1 Hz, 1H), 3.96 points (q, J=7,0 Hz, 1H), 4,15-4,27 (m, 2H), 5,02-5,14 (m, 4H), 5,73-5,88 (m, 2H).

<Example 1-2>

Obtaining CH3CH ((CH2)2CH=CH2)CH2OH

The flask in an argon atmosphere, of 6.9 g of lithium aluminum hydride and 240 ml of dehydrated diethyl ether and stirred in an ice bath. Added dropwise into the flask over a 45 minute connection of CH3CH(O(CH )2CH=CH2)COO(CH2)2CH=CH2(36 g) with a purity according to GC, equal to 83%, obtained according to example 1-1, and stirred for 3.5 hours. Then in an ice bath is added dropwise 100 ml of ice water and then add 100 ml of water, raise the temperature to room temperature (25°C), then filtered. The precipitate was washed with 450 ml of diethyl ether and the filtrate separated. The aqueous layer was extracted with twice 200 ml of diethyl ether, thus obtaining as the organic layer collected a layer of diethyl ether. This organic layer is dried over magnesium sulfate and filtered, thus obtaining the crude liquid. The crude liquid concentrate to 35 g, and then distilled under reduced pressure to remove 6.6 g fraction from 28 to 49°/was 9.33 kPa, whereby gain of 19.2 g of CH3CH(O(CH2)2CH=CH2)CH2OH from the fractions obtained. The degree of purity according to GC is 98%. These NMR spectrum is shown below.

1H-NMR (399,8 MHz, solvent: CDCl3standard: TMS), δ (ppm): 1,12 (d, J=6,2 Hz, 3H), 2,35 (tq, J=1,3, 6,7 Hz, 2H), 3,42-of 3.48 (m, 2H), 3,51-3,59 (m, 2H), 3,64 at 3.69 (m, 1H), 5,04-of 5.15 (m, 2H), 5,79-of 5.89 (m, 1H).

<Example 1-3>

Obtaining CH3CH ((CH2)2CH=CH2)CH2OCOCF(CF3)OCF2CF2CF3

The flask connection of CH3 CH(O(CH2)2CH=CH2)CH2HE (19,2 g) purity GC 98%, obtained according to example 1-2, and stirred while bubbling nitrogen gas. Is added dropwise within 1 hour FCOCF(CF3)OCF2CF2CF3(50 g), keeping the temperature inside the flask at 25 to 30°C. After completion of adding dropwise continue stirring at room temperature for 3 hours, then add 80 ml of a saturated aqueous solution of sodium bicarbonate at a temperature within the bulb is not more than 15°C.

Then add water (50 ml) and chloroform (100 ml), after which the liquid share, while receiving the organic layer. The organic layer is washed with twice 100 ml of water, dried over magnesium sulfate, filtered, thus obtaining the crude liquid. The crude liquid concentrate and purified column chromatography on silica gel (eluent:hexane/ethyl acetate=4:1), followed by purification column chromatography on silica gel (eluent: AK-225), while receiving 37 g of CH3CH(O(CH2)2CH=CH2)CH2OF(CF3)OF2CF2CF3. The degree of purity of this product according to GC is 99%. NMR spectra are as follows.

1H-NMR (399,8 MHz, solvent: Dl3standard: TMS), δ (ppm): 1,2 (dd, J=1,2, 6,4 Hz, 3H), to 2.29 (q, J=6,7 Hz, 2H), 3,45-3,51 (m, 1H), 3,53-3,59 (m,1H), 3,67-to 3.73 (m, 1H), 4.25 in-the 4.29 (m, 1H), 4,35-to 4.41 (m, 1H), 5,01-5,10 (m, 2H), 5,75-to 5.85 (m, 1H).

19F-NMR (376,2 MHz, solvent: Dl3standard: Fl3), δ (ppm): -80,5 (1F), -81,9 (3F), -82,7 (3F), -86,9 (1F), -130,3 (2F), -132,2 (1F).

<Example 1-4>

Obtaining CH3CH ((CH2)2CHClCH2Cl)CH2OCOCF(CF3)F2CF2CF3

The flask connection of CH3CH(O(CH2)2CH=CH2)CH2F(CF3)F2CF2CF3(36 g), having a degree of purity according to GC equal to 99%, obtained according to example 1-3, and stirred in a bath with ice. Purge gaseous chlorine (9.5 g) for 3 hours, maintaining the internal temperature at 0 - 5°C. Stirring is continued for 1 hour at room temperature while blowing nitrogen gas. The resulting reaction product is purified column chromatography on silica gel (eluent: AK-225), thus obtaining 22 g of CH3CH(O(CH2)2l2CL)CH2OF(CF3)F2CF2CF3. The degree of purity of this product according to GC is 88%. NMR spectra are as follows.

1H-NMR (399,8 MHz, solvent: Dl3standard: TMS), δ (ppm): 1,21 (dd, J=1,3, and 6.3 Hz, 3H), 1,81-of 1.93 (m, 1H), 2,19-of 2.26 (m, 1H), 3,59-the 3.65 (m, 1H), 3,68-of 3.80 (m, 4H), 4,20-to 4.46 (m, 3H).

19F-NMR (376,2 MHz, solvent: Dl3standard: Fl3), δ (ppm): -80,3 (1F), -81,6 (3F),-82,4 (3F), -86,7 (1F), -130,0 (2F), -132,0 (1F).

<Example 1-5>

Getting CF2lFlF2CF2OF(CF3)CF2OF(CF3)F2CF2CF3

In the autoclave with a capacity of 500 ml, made of Nickel, add R-313 (313 g), stirred and incubated at 25°C. At the exit gases from the autoclave set consistently capacitor supported 20°With a compacted layer of NaF, and a condenser supported -10°C. in Addition, install the return line to the fluid to return the condensed liquid from the condenser supported -10°C in the autoclave. Blow for 1.3 hours gaseous nitrogen, and then approximately 1 hour 20% gaseous fluorine diluted with nitrogen gas, a flow rate of 5,77 l/h.

Then equalising 20% gaseous fluorine with the same speed, Inuktitut for 7.3 hours a solution of compound CH3CH(O(CH2)2l2CL)CH2OF(CF3)F2CF2CF3(4,63 g)obtained according to example 1-4, dissolved in R-113 (100 g).

Then equalising 20% gaseous fluorine diluted with nitrogen gas, with the same speed, Inuktitut a solution of R-113, having a concentration of benzene 0.01 g/ml, 6 ml, increasing at this time the temperature from 25 to 40°C, after which the inlet of the autoclave to enter is Anzola close and in addition, close the bleed valve, then close the inlet valve for gaseous fluorine, when the internal pressure in the autoclave reaches of 0.20 MPa. Stirring is continued for 1 hour. Then, setting the internal pressure in the autoclave is equal to atmospheric pressure, and the internal temperature of the reactor is 40°With injected 3 ml of the above solution of benzene, after which the inlet of the autoclave to enter benzene is closed and, in addition, close the bleed valve and then close the inlet valve for gaseous fluorine, when the internal pressure in the autoclave reaches of 0.20 MPa. Stirring is continued for 1 hour.

Further, the same operation is repeated seven times. The total number of benzene is 0,228 g, and the total number of entered R-113 is 29 ml. After that carry out purging with gaseous nitrogen for 1.5 hours. The target product was quantitatively analyzed by the method of19F-NMR and the yield of the identified product is 63%.

19F-NMR (376,0 MHz, solvent: Dl3standard: Fl3), δ (ppm): -64,7 (2F), -76,5-~80,0 (1F), -80,0-~81,0 (4F), -82,2 (3F), -82,5 (3F), -82,0-~82,9 (1F), -86,4-~88,1 (3F), 117,0-~119,7 (2F), -130,4 (2F), -131,9 (1F), -132,3 (1F), -145,9 (1F).

<Example 1-6>

Getting CF2ClCFClCF2CF2OCF(CF3)COF

CF2ClCFClCF2CF2OCF(C 3CF2OCOCF(CF3)OCF2CF2CF3(1.2 g)obtained according to example 1-5, placed in a flask together with NaF powder (0.01 g) and heated at 120°C for 5 hours with vigorous stirring on an oil bath. In the upper part of the flask establish a reflux condenser, adjusted at a temperature of 20°C. After cooling allocate the sample liquid (1.2 g). By GC-MS confirmed that the above product is the main product. The output of the above product according to NMR is 72,3%.

[Example 2]

Getting CClF2CClFO(CF2)4COF and FCOCF(CF3)OCF2CF2CF2

<Example 2-1>

Getting l=lO(CH2)5OH

In chetyrehosnuju flask 500 ml download tetrahydrofuran (THF, 160 ml) and sodium hydride (60%, 24 g) and stirred, and then added dropwise HO(CH2)5OH (260 g) under cooling in a bath with ice. After adding dropwise to the stirring is continued at room temperature for 1 hour. Then there is added dropwise CHCl=CCl2(66 g) for 5 minutes. After adding dropwise to the stirring is continued at a bath temperature of 70°C for 2.5 hours. After cooling to room temperature there when cooled in a bath with ice add water (400 ml) and methylene chloride (400 ml) to follow them the separation of the liquid and receiving as an organic layer methylenchloride layer. Then after washing the organic layer with water (400 ml) and drying over magnesium sulfate obtain the crude product in the form as it is used at the stage of example 2-2.

1H-NMR (300,4 MHz, solvent: Dl3standard: TMS), δ (ppm): 1,37~to 1.79 (m, 6N), to 3.64 (t, J=6,3 Hz, 2H), 4.00 points (t, J=6,5 Hz, 2H), vs. 5.47 (s, 1H).

<Example 2-2>

Getting CHCl=CClO(CH2)5OCOCF(CF3)OCF2CF2CF3

CHCl=CClO(CH2)5OH (13 g)obtained according to example 2-1, and triethylamine (25 g) was placed in a flask and stirred in a bath with ice. Is added dropwise within 1 hour FCOCF(CF3)OCF2CF2CF3(41 g), maintaining the internal temperature not higher than 10°C. After adding dropwise to the stirring is continued at room temperature for 2 hours, then add 30 ml of water at a temperature within less than 15°C.

The crude liquid is subjected to separation of the liquids and the resulting lower layer washed twice with 50 ml water, dried over magnesium sulfate, and then filtered, thus obtaining the crude liquid. After distillation under reduced pressure get l=lO(CH2)5OF(CF3)F2CF2CF3(19 g) in the form of fractions from 118 to 120°/0,5 kPa. The degree of purity of this product according to GC is 77%.

1H-NMR (300,4 MHz, dissolve the l: Dl 3standard: TMS), δ (ppm): 1,41~to 1.83 (m, 6N), of 4.00 (t, J=6,0 Hz, 2H), 4,29~of 4.45 (m, 2H), 5,48 (s, 1H).

19F-NMR (282,7 MHz, solvent: Dl3standard: Fl3), δ (ppm): -79,9 (1F), -81,4 (3F), -82,2 (3F), -86,5 (1F), -129,5 (2F), -131,5 (1F).

<Example 2-3>

Getting CClF2CClFO(CF2)5OCOCF(CF3)F2CF2CF3

In the autoclave with a capacity of 500 ml, made of Nickel, add R-313 (312 g), stirred and incubated at 25°C. At the exit gases from the autoclave set consistently capacitor supported 20°With a compacted layer of NaF and a condenser supported -10°C. in Addition, install the return line to the fluid to return the condensed liquid from the condenser supported -10°C in the autoclave. Purge for 1.0 hour of gaseous nitrogen, and then approximately 1 hour 20% gaseous fluorine diluted with nitrogen gas, a flow rate of 7,40 l/h.

Then equalising 20% gaseous fluorine with the same speed, entering a period of 5.3 hours a solution of compound l=lO(CH2)5OF(CF3)F2CF2CF3(3,37 g)obtained according to example 2-2, dissolved in R-113 (100 g).

Then equalising with the same rate of 20% gaseous fluorine diluted with nitrogen gas injected a solution of R-113, having a concentration of benzene 0.01 g/ml, to the number 6 ml, increasing a temperature of from 25 to 40°C, after which the inlet of the autoclave to enter benzene is closed and, in addition, close the bleed valve and then close the inlet valve for gaseous fluorine, when the internal pressure in the autoclave reaches of 0.20 MPa. Stirring is continued for 0.9 hours. Then, while maintaining the internal pressure in the autoclave is equal to atmospheric pressure, and the internal temperature of the reactor is 40°With injected 3 ml of the above solution of benzene, after which the inlet of the autoclave to enter benzene is closed and, in addition, close the bleed valve and then close the inlet valve for gaseous fluorine, when the internal pressure in the autoclave reaches of 0.20 MPa. Stirring is continued for 0.9 hours.

Next, the same operation is repeated once. The total number of benzene is 0,192 g, and the total number of entered R-113 is 18 ml. After that carry out purging with gaseous nitrogen for 1.5 hours. The target product was quantitatively analyzed by the method of19F-NMR and the yield of the identified product is 73%.

19F-NMR (376,0 MHz, solvent: Dl3standard: Fl3), δ (ppm): -71,5 (2F), -77,3 (1F), -80,1 (1F), -82,1 (3F), -82,3 (3F), -83,4 (1F), -85,1 (1F), -87,2 (2F), -87,3 (1F), -123,2 (2F), -126,2 (2F), -126,3 (2F), -130,4 (2F), -132,4 (1).

<Example 2-4>

Getting CClF2CClFO(CF2)4COF

CClF2CClFO(CF2)5OCOCF(CF3)OCF2CF2CF3(0.8 g)obtained according to example 2-3, placed in a flask together with NaF powder (0.01 g) and heated at 120°C for 4 hours and at 140°With over 12.3 hours with vigorous stirring on an oil bath. In the upper part of the flask establish a reflux condenser, adjusted at a temperature of 20°C. After cooling allocate the sample liquid (0.7 g). By GC-MS confirmed that CF3CF(F2CF2CF3)COF and the above connection are the main products. The output of the above product according to NMR is 54,9%.

19F-NMR (376,0 MHz, solvent: Dl3standard: Fl3), δ (ppm): 24,9 (1F), -71,3 (2F), -77,1 (1F), -83,1 (1F), -84,9 (1F), -118,8 (2F), -123,1 (2F), -125,6 (2F).

[Example 3]

Getting CF2ClCFCl(CF2)2O(CF2)2COF and FCOCF(CF3)OCF2CF2CF3

<Example 3-1>

Obtaining CH2=CH(CH2)2OTs (Ts means p-toluensulfonyl group)

The reactor was placed 3-butene-1-ol (33,2 g) and pyridine (230 ml) and add there the same p-toluensulfonate (96,7 g) for 3.5 hours, while maintaining the inside temperature of not higher than 5°when cooled in a bath with ice. After stirring for 30 minutes reacts the mixture was added to water (250 ml). Add there dichloromethane (250 ml) and carry out the separation of liquids. Add saturated aqueous solution of sodium carbonate (250 ml) and water (200 ml)to rinse the bottom layer, with subsequent separation of liquids and washing with water (200 ml) twice and dried over magnesium sulfate. After filtration, followed by distillation to remove solvent receive 98,1 g CH2=CH(CH2)2OTs.

1H-NMR (300,4 MHz, solvent: Dl3standard: TMS), δ (ppm): 2,36~2,43 (m, 2H), 2,43 (s, 3H), 4,06 (t, J=6,6 Hz, 2H), 5,04~5,11 (m, 2H), ceiling of 5.60~to 5.66 (m, 1 H), 7,34 (d, J=8,4 Hz, 2H), to 7.77 (d, J=8,1 Hz, 2H).

<Example 3-2>

Obtaining CH2=CH(CH2)2O(CH2)3HE

The reactor was placed 1,3-propandiol (46,7 g) and potassium hydroxide (34,5 g) and stirred, is heated at a temperature within 75°C for 30 minutes. When the temperature inside the 80°add CH2=CH(CH2)2OTs (69,5 g)obtained according to example 3-1, in 3 hours and maintained as it is after stirring for 1 hour. The reaction mixture was poured into water (250 ml) and neutralized by adding hydrochloric acid. After filtration the filtrate is extracted with tert-butylmethylamine ether (300 ml) four times. The combined organic layers dried over magnesium sulfate and filtered, then the solvent is distilled off, while receiving 5.5 g CH2=CH(CH2 )2O(CH2)3HE.

1H-NMR (300,4 MHz, solvent: Dl3standard: TMS), δ (ppm): 1,83 (dt, J=5,4 Hz, 11 Hz, 2H), 2,34 (m, 2H), and 2.6 (bs, 1H), 3,50 (t, J=6,6 Hz, 2H), 3,63 (t, J=6,0 Hz, 2H), of 3.77 (t, J=5,4 Hz, 2H), 5,03-5,13 (m, 2H), of 5.81 (ddt, J=6,6, 11, 17 Hz, 1H).

<Example 3-3>

Obtaining CH2=CHCH2CH2OCH2CH2CH2OCF(CF3)F2CF2CF3

CH2=CH(CH2)2O(CH2)3HE (8,3 g)having a purity according to GC, equal to 98%, obtained according to example 3-2, and triethylamine (13,6 g) is placed in a flask and stirred in a bath with ice. Is added dropwise within 1 hour FF(CF3)OF2CF2CF3(30 g), maintaining the internal temperature not higher than 10°C. After adding dropwise to the stirring is continued at room temperature for 2 hours, then add 50 ml of water at a temperature within less than 15°C.

The crude liquid is subjected to separation of the liquids and the resulting lower layer washed twice with 50 ml water, dried over magnesium sulfate, and then filtered, thus obtaining the crude liquid. The crude liquid purified column chromatography on silica gel (eluent: AK-225), while receiving CH2=SNSN2CH2Och2CH2CH2OF(CF3)F2CF2CF3(18.5 g). The degree of purity of the product according to GC is 97%.

1H-NMR (300,4 MHz, solvent: Dl3standard: TMS), δ (ppm): 1.93 and~a 2.01 (m, 2H), 2.26 and~of 2.34 (m, 2H), 3,42~to 3.49 (m, 4H), to 4.41~of 4.54 (m, 2H), 5,02 (d, J=10, 3 Hz, 1H), 5,07 (d, J=17 Hz, 1H), 5,72~of 5.85 (m, 1H).

19F-NMR (282,7 MHz, solvent: CDCl3standard: Fl3), δ (ppm): -79,9 (1F), -81,4 (3F), -82,2 (3F), -86,6 (1F), -129,6 (2F), -131,5 (1F).

<Example 3-4>

Obtaining CH2ClCHClCH2CH2OCH2CH2CH2OCOCF(CF3)OCF2CF2CF3

CH2=SNSN2CH2Och2CH2CH2OCOF(CF3)F2CF2CF3(18,4 g)having a purity according to GC, equal to 97%, obtained according to example 3-3, placed in a flask and stirred in a bath of ice at -10°C. Then purge the flask within 1 hour of gaseous chlorine (4.4 g), maintaining the internal temperature not higher than 0°C. Stirring is continued at room temperature for 1 hour while bubbling nitrogen gas and get CH2ll2CH2Och2CH2CH2OCOF(CF3)F2CF2CF3(19,8 g). The obtained crude product as is used at the stage of example 3-5.

1H-NMR (300,4 MHz, solvent: Dl3standard: TMS), δ (ppm): 1.93 and~a 2.01 (m, 2H), 2.26 and~of 2.34 (m, 2H), 3,44 (t, J=6,6 Hz, 2H), 3,47 (t, J=6,0 Hz, 2H), to 4.41~of 4.54 (m, 2H), 4,99~5,10 (m, 2H), 5,71~of 5.85 (m, 1H).

19F-NMR (282,7 MHz, solvent: CDCl3that standard is RT: Fl 3), δ (ppm): -79,9 (1F), -81,3 (3F), -82,2 (3F), -86,6 (1F), -129,5 (2F), -131,5 (1F).

<Example 3-5>

Getting CF2ClCFCl(CF2)2O(CF2)3F(CF3)F2CF2CF3

In the autoclave with a capacity of 500 ml, made of Nickel, add R-113 (312 g), stirred and support at a temperature of 25°C. At the exit gases from the autoclave set consistently capacitor supported 20°With a compacted layer of NaF and a condenser supported -10°C. Then install the return line to the fluid to return the condensed liquid from the condenser supported -10°C in the autoclave. Purge for 1.0 hour of gaseous nitrogen, and then about 1.5 hours 20% gaseous fluorine diluted with nitrogen gas, the speed of 8.04 l/h.

After equalising 20% gaseous fluorine with the same speed, entering a period of 5.3 hours a solution of compound CH2ll2CH2Och2CH2CH2OF(CF3)F2CF2CF3(4.44 g), obtained according to example 3-4 dissolved in R-113 (100 g).

Then equalising with the same rate of 20% gaseous fluorine diluted with nitrogen gas injected a solution of R-113, having a concentration of benzene 0.01 g/ml, 6 ml, increasing at this time the temperature from 25 to 40°C, after which the volt is the opening of the autoclave to enter close and benzene, in addition, close the bleed valve and then close the inlet valve for gaseous fluorine, when the internal pressure in the autoclave reaches of 0.20 MPa. Stirring is continued for 0.4 hours. Then, while maintaining the internal pressure in the autoclave is equal to atmospheric pressure, and the temperature inside the reactor is 40°With injected 3 ml of the above solution of benzene, after which the inlet of the autoclave to enter benzene is closed and, in addition, close the bleed valve and then close the inlet valve for gaseous fluorine, when the internal pressure in the autoclave reaches of 0.20 MPa. Stirring is continued for 0.4 hours.

Next, the same operation is repeated seven times. The total number of benzene is 0,303 g, and the total number of entered R-113 30 ml. After that carry out purging with gaseous nitrogen for 1.5 hours. The target product was quantitatively analyzed by the method of19F-NMR and the yield of the identified product is 45%.

19F-NMR (376,0 MHz, solvent: Dl3standard: Fl3), δ (ppm): -64,4 (2F), -80,0 (1F), -81,3 (2F), -81,9 (3F), -82,1 (3F), -84,0 (2F), -87,1 (1F), -87,3 (2F), -117,2~-119,4 (2F), -129,4 (2F), -130,3 (2F), -131,8 (1F), -132,3 (1F).

<Example 3-6>

Getting CF2ClCFCl(CF2)2O(CF2)2COF

CF2ClCFCl(CF2)2O(CF2 )3OCOCF(CF3)OCF2CF2CF3(3.0 g)obtained according to example 3-5, placed in a flask together with NaF powder (0.06 g) and heated at 120°for 3.7 hours and at 140°C for 12 hours under vigorous stirring on an oil bath. In the upper part of the flask establish a reflux condenser, adjusted to a temperature of 20°C. After cooling secrete a liquid sample (2.9 g). By GC-MS confirmed that FF(CF3)CF2CF2CF3and the above connection are the main products. The output of the above product according to NMR is 73,0%.

19F-NMR (376,0 MHz, solvent: Dl3standard: Fl3), δ (ppm): 24,3 (1F), -64,8 (2F), -81,7 (2F), -86,4 (2F), -118,8~-120,0 (2F), -122,1 (2F), -131,9 (1F).

[Example 4]

Getting FCOCF2CFClCF2Cl and CF3CF2COF

<Example 4-1>

Getting CF3CF2COO(CH2)2CHClCH2Cl

CH2ClCHCl(CH2)2OH (30 g) was placed in a flask and stirred while bubbling nitrogen gas. Then enter within 3 hours CF2CF2COF (310 g), maintaining the internal temperature at 25 - 30°C. After the feed, add 50 ml of a saturated aqueous solution of sodium bicarbonate at a temperature within the bulb is not more than 15°C.

Then add chloroform (50 ml) with subsequent separation of the liquid and receiving the organic layer of the chloroform layer. Next, the organic layer is washed with twice 200 ml of water, dried over magnesium sulfate and filtered, thus obtaining the crude liquid. The crude liquid concentrate in the evaporator, followed by distillation under reduced pressure, thus obtaining a fraction (24 g) from 73 to 75°/a 0.9 kPa. This fraction is purified column chromatography on silica gel (eluent:hexane/ethyl acetate=20/1), while receiving the purified product (18,8 g). Purity according to GC is 98%. Data NMR spectrum confirmed that the above connection is the main product.

1H-NMR (399,8 MHz, solvent: CDCl3standard: TMS), δ (ppm): 2,11 (m, 1H), 2,52 (m, 1H), 3,69 (dd, J=7,9, or 11.4 Hz, 1H), 3,84 (dd, J=4,7, 11, 4 Hz, 1H), 4,15 (m, 1H), 4,60 (m, 2H).

19F-NMR (376,2 MHz, solvent: CDCl3standard: CFCl3), δ (ppm): -83,8 (3F), -122,5 (2F).

<Example 4-2>

Getting CF3CF2F2CF2FlCF2CL

In the autoclave with a capacity of 500 ml, made of Nickel, add R-113 (201 g) and is stirred and cooled at -10°C. Rinsed for 1 hour with gaseous nitrogen, and then approximately 1 hour 20% gaseous fluorine diluted with nitrogen gas, with the speed to 5.66 l/h. After equalising 20% gaseous fluorine with the same speed, entering a period of 6.9 hours a solution of compound CF3CF2COO(CH2 )2l2CL (6,58 g)obtained according to example 4-1, dissolved in R-113 (134 g).

Then equalising with the same rate of 20% gaseous fluorine diluted with nitrogen gas, there is injected a solution of benzene in R-113 (0.01 g/ml), after which the exhaust valve is closed when the internal pressure in the autoclave reaches 0.12 MPa and inlet valve is closed, the stirring is continued for 1 hour. Such an operation input benzene repeat once with increasing temperature from -10 to 40°and then eight times at 40°C. the Total number of benzene is 0,330 g, and the total number of entered R-113 is 33 ml. then carry out the blowing of nitrogen gas for 2 hours. The target product was quantitatively analyzed by the method of19F-NMR and the yield of the identified product is 51%.

19F-NMR (376,2 MHz, solvent: CDCl3standard: Fl3), δ (ppm): -65,4 (2F), -84,2 (3F), -85,4 (2F), -119,1 (2F), -123,1 (2F), -132,5 (1F).

<Example 4-3>

Getting FCOCF2CFClCF2Cl

CF3CF2COOCF2CF2CFClCF2Cl (1.5 g)obtained according to example 4-2, placed in a flask together with NaF powder (0.03 g) and heated at 120°C for 5 hours with vigorous stirring on an oil bath. In the upper part of the flask establish a reflux condenser, adjusted to the pace of atory 20° C. After cooling secrete a liquid sample (0.8 g) and the gas sample (0.6 g). By GC-MS confirmed that CF3CF2F and above the connection are the main products. The output of the above compounds according to NMR is 75,1%.

[Example 5]

The mixture CF2ClCFClCF2COF and CF2ClCF2CFClCOF

<Example 5-1>

Getting CF2ClCFClCF2COO(CH2)2CHClCH2Cl and CF2ClCF2CFCl(CH2)2l2CL

CH2ll(CH2)2OH (49.5 g) was placed in a flask and stirred, barbotine gaseous nitrogen. Added dropwise a mixture of 86.1 g) CF2ClCClF2COF and CF2ClCF2CFClCOF in the ratio of 89:11 (molar ratio) for 1 hour and 40 minutes, keeping the temperature inside the flask at 25-30°C. After addition there is added a saturated aqueous solution of sodium bicarbonate (100 ml) at a temperature within the flask is not higher than 15°C. Add chloroform (150 ml) followed by separation of the liquid from the receipt of the chloroform layer. Next, the chloroform layer is washed twice with 200 ml of water, dried over magnesium sulfate and filtered, thus obtaining the crude liquid. The crude liquid concentrated with an evaporator, followed by distillation under reduced pressure, thus obtaining a fraction (1) (5,4 g) from 99 to 106° From/to 0.48 kPa and fraction (2) (7.9 g) from 100 to 109°/0,47 kPa. As for purity according to GC, the purity of the fraction (1) is 85%, and fraction (2) 84%.

Fraction (1) (9.4 g) purified column chromatography on silica gel (eluent: hexane/ethyl acetate=20/1), while receiving the purified product (7.5 g). Purity according to GC is 98%. Data of NMR spectroscopy confirmed that the mixture of CF2ClCFClCF2COO(CH2)2CHClCH2Cl and CF2ClCF2CFClCOO(CH2)2l2CL represents the main product and the ratio of these components is 87:13 (molar ratio).

CF2ClCFClCF2COO(CH2)2CHClCH2Cl

1H-NMR (399,8 MHz, solvent: Dl3standard: TMS), δ (ppm): 2,09 (m, 1H), 2,52 (m, 1H), 3,69 (dd, J=7,6, 11, 4 Hz, 1H), 3,84 (dd, J=4,7, 11, 4 Hz, 1H), 4,17 (m, 1H), 4,58 (m, 2H).

19F-NMR (376,2 MHz, solvent: Dl3standard: Fl3), δ (ppm): -63,6 (1F), -64,8 (1F), -110,9 (1F), -114,0 (1F), -131 (1F).

CF2ClCF2CFClCOO(CH2)2CHClCH2Cl

1H-NMR (399,8 MHz, solvent: Dl3standard: TMS), δ (ppm): 2,09 (m, 1H), 2,52 (m, 1H), 3,69 (dd, J=7,6, 11, 4 Hz, 1H), 3,84 (dd, J=4,7, 11, 4 Hz, 1H), 4,17 (m, 1H), 4,58 (m, 2H).

19F-NMR (376,2 MHz, solvent: Dl3standard: Fl3), δ (ppm): -66,9 (1F), -67,0 (1F), -113,4 (1F), -117,6 (1F), -129,0 (1F).

<Example 5-2>

The mixture CF2ClCFClCF2COOCF2CF2CFClCFsub> 2Cl and CF2ClCF2CFClCOOCF2CF2CFClCF2Cl

In the autoclave with a capacity of 500 ml, made of Nickel, add R-113 (200 g) and stirred, rinsed for 1 hour with gaseous nitrogen, and then approximately 1 hour 20% gaseous fluorine diluted with nitrogen gas, with the speed to 5.66 l/h.

After equalising 20% gaseous fluorine with the same speed, entering a period of 11.5 hours, the solution mixture of CF2ClCFClCF2COO(CH2)2CHClCH2Cl and CF2ClCF2CFClCOO(CH2)2l2CL in a ratio of 87:13 (molar ratio), obtained according to example 5-1, dissolved in R-113 (243 g).

Then equalising with the same rate of 20% gaseous fluorine diluted with nitrogen gas, there is injected a solution of benzene in R-113 (0.01 g/ml), after which the exhaust valve is closed when the internal pressure in the autoclave reaches 0.12 MPa, inlet valve of the autoclave was closed and continue stirring for 1 hour. Further, such an operation input benzene repeat once when the temperature increases from room temperature up to 40°and then eight times at 40°C. the Total number of benzene is 0,342 g, and the total number of entered R-113 is 33 ml. then carry out the blowing of nitrogen gas for 2 hours. According to the analysis of the product m is Todd 19F-NMR output the identified product is 80%.

CF2ClCFClCF2COOCF2CF2CFClCF2Cl

19F-NMR (564,6 MHz, solvent: Dl3standard: Fl3), δ (ppm): -64,4~-65,9 (2F), -65,4 (2F), -85,5~-86,3 (2F), -111,1~-115,1 (2F), -118,7~-120,1 (2F), -132,0 (1F), -132,5 (1F).

13C-NMR (150,8 MHz, solvent: Dl3standard: Dl3), δ (ppm): 104,4, 104,5, 109,4, 110,8, 116,6, 124,3, 124,6, 152,0.

CF2ClCF2CFClCOOCF2CF2CFClCF2Cl

19F-NMR (564,6 MHz, solvent: Dl3standard: Fl3), δ (ppm): -64,4~-66,0 (2F), -68,0 (2F), -85,5~-86,3 (2F), -113,7~-115, 3 (2F), -118,7~-120,1 (2F), -130,0 (1F), -132,5 (1F).

13C-NMR (150,8 MHz, solvent: Dl3standard: Dl3), δ (ppm): 99,0, 104,4, 110,2, 110,8, 116,6, 122,8, 124,6, 153,2.

<Example 5-3>

The mixture CF2ClCFClCF2COF and CF2ClCF2CFClCOF

A mixture of (5.6 g) CF2ClCFClCF2COOCF2CF2CFClCF2Cl and CF2ClCF2CFClCOOCF2CF2CFClCF2Cl, obtained according to example 5-2, placed in a flask together with NaF powder (0.12 g) and heated at 140°C for 5 hours with vigorous stirring on an oil bath. In the upper part of the flask establish a reflux condenser, adjusted to a temperature of 20°C. After cooling allocate the sample liquid (5.2 g). By GC-MS confirmed that the above product is particularly the main product. The output of the above product according to NMR is of 83.4%.

[Example 6]

Getting CF2ClCFClCF2COF

<Example 6-1>

Obtaining CH2=CHCH2CH2OCOCF2CFClCF2Cl

CH2=SNSN2CH2HE (and 70.8 g) is placed in a flask and stirred, barbotine gaseous nitrogen. Added dropwise a mixture of (264,5 g) CF2ClCFClCF2COF and CF2ClCF2CFClCOF in the ratio of 89:11 (molar ratio) for 1 hour, keeping the temperature inside the flask is 25 - 30°C. After the addition stirring is continued at room temperature for 4 hours, then add 500 ml of saturated aqueous sodium hydrogen carbonate solution, keeping the temperature inside the flask is not higher than 15°C. the crude liquid is subjected to separation of liquid phases, while receiving ftoruglevodorodnye layer. Then ftoruglevodorodnye layer washed twice with 200 ml of water, dried over magnesium sulfate and filtered, thus obtaining the crude liquid. After distillation under reduced pressure get 81,2 g fraction from 69 to 72°/1,0 kPa. Purity according to GC is 96%. Data of NMR spectroscopy as follows.

1H-NMR (300,4 MHz, solvent: Dl3standard: TMS), δ (ppm): 2,46~-2,50 (m, 2H), to 4.41 (t, J=6,6 Hz, 1H), 5,11~-5,21 (m, 2H), 5,70~-5,84 (m, 1H).

19F-NMR (282,7 MHz, dissolve the ü: Dl 3standard: Fl3), δ (ppm): -62,9 (1F), -64,1 (1F), -110,1 (1F), -113,1 (1F), -130,4 (1F).

<Example 6-2>

Obtaining CH2ClCHClCH2CH2OCOCF2CFClCF2Cl

CH2=CHCH2CH2OCOCF2CFClCF2Cl a (80.0 g) with a purity according to GC, equal to 96%, obtained according to example 6-1, placed in a flask and stirred in a bath with ice at a temperature of -10°C. Then passed into the flask over 1.5 hours gaseous chlorine (24.5 g), keeping the temperature inside the flask is not higher than 0°C. Stirring is continued at room temperature for 1 hour while bubbling nitrogen gas and get the crude liquid. The crude liquid purified column chromatography on silica gel (eluent: AK-225), while receiving CH2ClCHClCH2CH2OCOCF2CFClCF2Cl (93.0 g), characterized by purity according to GC, equal to 85%.

<Example 6-3>

Getting CF2ClCFClCF2CF2OCOCF2CFClCF2Cl

Using CH2ClCHClCH2CH2OCOCF2CFClCF2Cl (93.0 g) with a purity of 85%, obtained according to example 6-2, instead of 12.0 g of the mixture according to example 5-2 and other raw materials 7.7-fold, interact in the same way as in example 5-2, while receiving the specified connection with the release of 80%.

<Example 6-4>

Getting CF2ClCFClCF2COF

Use the Zuya CF 2ClCFClCF2CF2OCOCF2CFClCF2Cl (43,4 g)obtained according to example 6-3, instead of 5.6 g of the mixture according to example 5-3 and other raw materials 7.7-fold, interact in the same way as in example 5-3, while receiving the specified connection with the release of 84%.

<Example 6-5>

Continuous receipt of CF2ClCFClCF2COF

Using CF2ClCFClCF2COF obtained according to example 6-4, instead of the mixture according to example 6-1, interact in the same way as in examples 6-1 to 6-4 in the specified order, while receiving CF2ClCFClCF2COF.

[Example 7]

<Example 7-1>

Continuous receipt of CH3CH(O(CH2)2CH=CH2)CH2OH

Data of NMR spectroscopy confirmed that the faction from 28 to 49°/was 9.33 kPa, obtained according to example 1-2, represents CH2=CH(CH2)2OH. Using the above fraction (75 ml), interact in the same way as in examples 1-1 to 1-4, while receiving CH3-CH ((CH2)2CH=CH2)CH2OH.

<Example 7-2>

Continuous receipt of CF2ClCFClCF2CF2O(CF2)2COF

The reaction product obtained according to example 3-6, purified by distillation at atmospheric pressure, the fraction obtained at 55°represents FF(CF )F2CF2CF3(0.8 g). The fraction having the highest boiling point, save. Using the obtained FCOCF(CF3)OCF2CF2CF3, interact in the same way as in examples 3-3 to 3-6, followed by purification by distillation at atmospheric pressure, while receiving FF(CF3)F2CF2CF3(0.7 g) as a fraction at 55°C. the Remaining fraction with a high boiling point is mixed with stored above the fraction having the highest boiling point, and then purified by distillation at atmospheric pressure, while receiving CF2ClCFClCF2CF2O(CF2)2COF (2.0 g) in the form of fractions from 138 to 139°C.

Industrial applicability

According to the present invention may be obtained quickly and with a good yield derived vic-dichlorphenamide of the compound (I), which is inexpensive and easily available. In particular, according to the present invention it is possible to derive vic-dichlorphenamide with low molecular weight and derived vic-dichlorphenamide complex structures, which are usually difficult to obtain by standard methods.

Furthermore, the method of receiving according to the present invention represents broadly applicable method, which is not limited to the compounds described Viseu specific examples but can be used to obtain various compounds, whereby can be derived vic-dichlorphenamide, with the most preferred structure. Further, by choosing an appropriate group structure-Deputy method of receiving according to the present invention can be a continuous process.

In addition, the compound (III), which can be obtained by the method according to the present invention contains terminal fragments of CF2ClCFCl-. Such a fragment can produce a curable carbon-carbon double bond using known methods. For example, the derived vic-dichlorphenamide (CF2ClCFClCF2COF), which can be obtained by the method according to the present invention can produce PERFLUORO(3-butylvinyl simple ether), which is a fluorinated monomer of the polymer. PERFLUORO(3-butylvinyl simple ether) may be subjected to polymerization to obtain useful fluorinated polymers which have excellent heat resistance, chemical resistance and transparency.

Also among the compounds (III) and/or compound (IV)obtained by the method according to the present invention, is a compound that fragment [C1F-C2-COF] in the end portion of the molecule, which can be converted, with what ispolzovaniem known methods, in the fragment of [1=With2]located in the end portion of the molecule (Methods of Organic Chemistry, 4, Vol.10b, part 1, R, etc). This connection is also a valuable raw material for the production of fluorinated polymers. Namely, the compound (III) and/or the compound (IV)obtained by the method according to the present invention, are useful compounds as precursors of fluorinated polymers. Next, a new connection offered by the present invention is a useful compound as an intermediate connection to its predecessor.

1. The method of deriving vic-dichlorphenamide, including fluoridation of the following compound (I) in the liquid phase to obtain the following compound (II), the cleavage of ester bonds of the compound (II) is carried out in the gas phase in the absence of a solvent to obtain the following compound (III) or the following compound (III) and the following compound (IV):

(RH1-EH1-)CRH2RH3CH2-OCORHB(I)

(CF2ClCFCl-EF1-)CRF2RF3CF2-OCORFB(II)

(CF2ClCFCl-EF1-)CRF2RF3COF (III)

FCORFB(IV)

where

RH1: CX1X2ClCX3Cl - or l4=CCl-, where each of the groups X1-X4represents a hydrogen atom,

RH2, RH3: each independently represents a hydrogen atom or alkyl group, branched or unbranched, optionally containing one or more oxygen atoms,

EH1: Allenova group, optionally containing one or more oxygen atoms,

EF1: EF1represents a group corresponding to EH1where performanceheavy group optionally contains one or more oxygen atoms,

RHB, RFB: the same group and are performanceline group, branched or unbranched, optionally containing chlorine atom and optionally containing one or more oxygen atoms,

RF2represents a fluorinated group, RH2, RF3represents a fluorinated group, RH3provided that RF2represents a fluorinated group, RH2, RF3represents a fluorinated group, RH3i.e. RF2or RF3represent a group corresponding to RH2orRH3, respectively, in which at least one hydrogen atom is fluorinated.

2. The method according to claim 1, in which the molecular weight of the compound (I) is 200 to 1,000 and fluorine content is 30-86 wt. %.

3. The method according to claim 1 or 2, wherein the fluorination reaction is carried out by p is giving excessive amounts of fluoride when compared to an equivalent amount relative to the hydrogen atoms in the compound (I) in the liquid phase with the formation of compound (II).

4. The method according to claim 1 or 2, wherein in the reaction system fluorination in the liquid phase is present compound containing C-H-valence, or the fluorination reaction is conducted under ultraviolet irradiation.

5. The method according to claim 1 or 2, in which the compound (I) are obtained by reaction of the following compounds (A1) with the following compound (A2), provided that X represents a halogen atom, a RH1EH1, RH2and RH3have the same meanings as defined in claim 1.

(RH1-EH1-)CRH2RH3CH2-OH (A1)

XCORHB(A2)

6. The method according to claim 1 or 2, in which the compound (1A), which is compound (I), where RH1means CX1X2ClCX3Cl-, get through interaction of the following compounds (B1) with the following compound (B2) with the formation of the following compound (B3), and the subsequent interaction of the compound (EOI) with gloriouse agent, provided that X1X2X3, RH2, RH3and RHBhave the same meanings as defined in claim 1.

(CX1X2=CX3-EH1-)CRH2RH3CH2-OH (B1)

XCORHB(B2)

(CX1X2=CX3-EH1-)CRH2RH3CH2-RHB(B3)

(CX1X2ClCX3Cl-EH1)CR H2RH3CH2-OCORHB(Ia)

7. The method according to claim 6, in which gloriouse agent is a chlorine.

8. The method according to claim 6, in which the compound (IV) and the compound (B2) are one and the same connection.

9. The method according to claim 5, in which the compound (IV) and the compound (B2) are one and the same connection, and part or all of the resulting compound (IV) is again used to interact with the compound (A1) or the compound (B1).

10. The method according to claim 1 or 2, in which the compound (III) and compound (IV) constitute one and the same connection.

11. The compound represented by the following formula:

l=lO(CH2)5HE

CH2=CH(CH2)2Och2CH2CH2HE

CH2=CH(CH2)2OCOCF2CFClCF2Cl

CH2=CH(CH2)2Och(CH3)CH2OCOCF(CF3)F2CF2CF3

l=lO(CH2)5OCOCF(CF3)F2CF2CF3

CClF2CClFO(CF2)5OCOCF(CF3)OCF2CF2CF3

CH2=CH(CH2)2O(CH2)3F(CF3)F2CF2CF3

CH2ll(CH2)2O(CH2)3F(CF3)F2CF2CF3

CF2ClCFCl(CF2)2O(CF2)3F(CF3 2CF2CF3

CF2ClCFCl(CF2)2O(CF2)2COF

The priority of 12.07.2000 according to claims 1-7 formula, except for the processes a and B shown below; PP-10, except for the process B; item 11.

Priority from 31.08.1999 according to claims 1-7 (process a and B); PP-10 (process).

Process A

CH2ClCHClCH2CH2OH + CF3CF2COF → CH2ClCHClCH2CH2OCOCF2CF3CF2ClCFClCF2CF2OCOCF2CF3CF2ClCFClCF2COF;

B

CH2ClCHClCH2CH2OH + CF2ClCFClCF2COF → CH2ClCHClCH2CH2OCOCF2CFClCF2Cl → CF2ClCFClCF2CF2OCOCF2CFClCF2Cl → CF2ClCFClCF2COF



 

Same patents:

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides improved process for production of a fluorine-containing compound useful as starting material for manufacture of a variety of fluoropolymers with high output when performing short process and using inexpensive and easily accessible chemicals. Process comprises: (i) interaction of indicated below compound 1 with indicated below compound 2 to form indicated below desired compound 3, which is a compound, wherein content of fluorine is at least 30 wt % and which has hydrogen atom or multiple bond capable of being fluorinated; and (ii) liquid-phase fluorination of compound 3 to give indicated below compound 4 followed by (iii) cleaving group EF in compound 4 to produce compound 5 and compound 6: E1-RA-E1 (1), E2-RB (2), RB-E-RA-E-RB (3),

RBF-EF-RAF-EF-RBF (4), EF1-RAF-EF1 (5),

and RBF-EF2 (6), where RAF represents fluorine-containing bivalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether oxygen atoms; RA represents group, which is the same as group RAF or bivalent organic group capable of being converted into group RAF using fluorination reaction; RBF represents fluorine-containing polyvalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether or carbonyl oxygen atoms; RB represents group, which is the same as group RBF or polyvalent organic group capable of being converted into group RBF using fluorination reaction; E1 and E2 are such that, when group E1 is -CH2OH or Q1-CH2OH group, then group E2 is -COX or -SO2X group and, when group E2 is -CH2OH or -Q2-CH2OH group, then group E1 is -COX or -SO2X group, where X is halogen atom and Q1 and Q2 may be identical or different and represent -CH(CH3)- or -CH2CH2- group; E represents group -CH2OCO-, -CH2OSO2-, -Q1-CH2OCO-, -Q2-CH2OCO-, -Q1-CH2OSO2-, or -Q2-CH2OSO2-; EF represents group, which is the same as group E or group obtained by fluorination if group E on conditions that at least one group RAF, RBF, or EF is a group formed by fluorination reaction and groups EF1 and EF2 are groups formed by cleaving group EF. Invention also relates to novel fluorine-containing compounds of formulas 3-12, 3-13, 3-14, 3-15, 3-16, 4-12, 4-13, 4-14, 4-15, 4-16, 5-16, which are indicated in description.

EFFECT: increased resource of raw materials for production of fluoropolymers.

8 cl, 23 ex

The invention relates to the production of fluorine-containing compounds, such as industrial useful derived foramerica acid

The invention relates to new liquid under normal conditions of omega-hygrophoraceae esters, which have the properties of surfactants and can be used to displace water from the surface, in compositions for the removal of pollutant products, compositions for fire extinguishing, foam fabrication, when soldering in the vapor phase

The invention relates to ester compounds, method of their production and their use as a means for spooling the fiber

The invention relates to the field of organic chemistry, namely to new chemical compound gross formula

< / BR>
where x= CF2or bond, the sum n + m + C 3 10

FIELD: industrial organic synthesis.

SUBSTANCE: invention provides improved process for production of a fluorine-containing compound useful as starting material for manufacture of a variety of fluoropolymers with high output when performing short process and using inexpensive and easily accessible chemicals. Process comprises: (i) interaction of indicated below compound 1 with indicated below compound 2 to form indicated below desired compound 3, which is a compound, wherein content of fluorine is at least 30 wt % and which has hydrogen atom or multiple bond capable of being fluorinated; and (ii) liquid-phase fluorination of compound 3 to give indicated below compound 4 followed by (iii) cleaving group EF in compound 4 to produce compound 5 and compound 6: E1-RA-E1 (1), E2-RB (2), RB-E-RA-E-RB (3),

RBF-EF-RAF-EF-RBF (4), EF1-RAF-EF1 (5),

and RBF-EF2 (6), where RAF represents fluorine-containing bivalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether oxygen atoms; RA represents group, which is the same as group RAF or bivalent organic group capable of being converted into group RAF using fluorination reaction; RBF represents fluorine-containing polyvalent saturated, linear or branched hydrocarbon group optionally containing halogen atom other than fluorine and optionally containing one or several ether or carbonyl oxygen atoms; RB represents group, which is the same as group RBF or polyvalent organic group capable of being converted into group RBF using fluorination reaction; E1 and E2 are such that, when group E1 is -CH2OH or Q1-CH2OH group, then group E2 is -COX or -SO2X group and, when group E2 is -CH2OH or -Q2-CH2OH group, then group E1 is -COX or -SO2X group, where X is halogen atom and Q1 and Q2 may be identical or different and represent -CH(CH3)- or -CH2CH2- group; E represents group -CH2OCO-, -CH2OSO2-, -Q1-CH2OCO-, -Q2-CH2OCO-, -Q1-CH2OSO2-, or -Q2-CH2OSO2-; EF represents group, which is the same as group E or group obtained by fluorination if group E on conditions that at least one group RAF, RBF, or EF is a group formed by fluorination reaction and groups EF1 and EF2 are groups formed by cleaving group EF. Invention also relates to novel fluorine-containing compounds of formulas 3-12, 3-13, 3-14, 3-15, 3-16, 4-12, 4-13, 4-14, 4-15, 4-16, 5-16, which are indicated in description.

EFFECT: increased resource of raw materials for production of fluoropolymers.

8 cl, 23 ex

The invention relates to the production of fluorine-containing compounds, such as industrial useful derived foramerica acid
The invention relates to a method for allocation of fluorinated carboxylic acids, allowing you to get them with a high degree of purity

The invention relates to the primary organic synthesis, in particular, to the production of esters halogen-substituted acyclic carboxylic acids

- bromsulfaleinovy acid" target="_blank">

The invention relates to the field of organic and petrochemical synthesis, namely, to obtain ethyl ester-bromsulfaleinovy acid (EEBIC), used in the manufacture of drugs, such as Corvalol, valocordin

The invention relates to derivatives of 2,4-dichlorophenoxyacetic (2,4-D) and 4-chlorophenoxyacetic (4-chlorthal) acids, in particular fatty esters and alkoxy-substituted alcohols, as herbicides and plant growth regulators

The invention relates to an improved process for the preparation of diethyldichlorosilane starting compounds to obtain the quinoline-2,3-dicarboxylic acid

The invention relates to a method for producing (nitroxymethyl)phenyl esters of derivatives of salicylic acid of the formula (I)

where R1means OCOR3group, where R3means methyl, ethyl or a linear or branched C3-C5alkyl;R2means hydrogen

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