Fluorine-containing compound production process

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 technical field

The present invention relates to a method for obtaining a suitable for industrial use fluorine-containing compounds, in particular to a method of producing desilvered containing the-COF group at both ends of the molecule, and compounds containing fluorinated vinyl groups at both ends of the molecule. In addition, the present invention provides a new intermediate compound, suitable for receiving desilvered, which is useful as a precursor for feedstock fluoropolymers.

Prior art

Fluorine-containing monomer such as PERFLUORO(alkylvinyl simple ether), is useful as a raw material monomer to obtain a heat resistant and chemically resistant fluoropolymers. For example, PERFLUORO(alkylvinyl simple ether), the molecule of which contains carboxyl groups, can be used as a raw material monomer for obtaining the ion-exchange membranes and can be synthesized through desilvered (J.Fluorine Chem., 94, 65-68 (1999)).

In addition, as a method of fluorination all C-H fragments of hydrocarbon compounds to C-F the known method according to which the fluorination is carried out by using a fluorine (elemental fluorine), or method, according to which the fluorination is performed with the use of as history is nick fluorine atom product, formed during the electrolysis of hydrogen fluoride in the electrolysis (i.e. the way through the so-called reaction electrochemical fluorination). In addition, for the implementation of the reaction using fluorine-known gas-phase method and liquid phase method.

Also known a method, according to which the derived perfluorinated ether complex containing at least 16 carbon atoms, is subjected to pyrolysis to obtain ftorangidridov connection. It is reported that ftorangidridy connection can be obtained by a method in which a derived complex ester hydrocarbon type, with corresponding carbon skeleton foryouth using a liquid phase method using a gaseous fluorine (J. Am. Chem. Soc., 120, 7117 (1988)).

In addition, as a General method of obtaining desilvered known method using iodine and fuming sulfuric acid.

Moreover, it is informed about the method, according to which as the initial substance use dialdictate that do not contain fluoride, this substance directly foryouth in 1,1,2-trichloro-1,2,2-triptoreline (hereinafter referred to as R-113) and obtaining peritonealdialysis, and then it is subjected to the reaction of dissociati the ester bonds in pyridine to obtain peritonialnogo connection and CF 3COF (U.S. patent 5466877).

In addition, it is proposed a method in which a group of CF2=CF - compounds containing a group of CF2=CF - on one end and a group-CF on the other end of the molecule, halogenous using, for example, chlorine gas, and then the other end group is subjected to pyrolysis to CF2=CF - and then, through dehalogenase, regenerate a group of CF2=CF, in order to obtain the compound containing fluorinated vinyl groups at both ends of the molecule (JP-A-1-143843).

Also reported method of obtaining CF2=FOCF2CF2CF=CF2through pyrolysis of the potassium salt of dicarboxylic acid, such as COSO(CF2)4OCF(CF3)CO2K (J. Org. Chem., 34, 1841 (1969)).

The electrochemical fluorination reaction has such disadvantages as isomerization, decomposition and re-linking-With links and so on, which are quite likely to occur, resulting in the desired connection cannot be obtained with high purity. Along with this there is a problem with the fact that when interacting with the fluorine in the gas phase simple C-C bond undergoing cleavage, resulting in a tendency to the formation of different types of products.

It was reported that the method of carrying out fluorination in the liquid phase is with the persons, allowing to solve the problems inherent in the gas-phase method (U.S. patent 5093432). As the solvent to be used for the reaction in accordance with this liquid-phase method, typically using a solvent capable of dissolving the fluorine. However, non-fluorinated compounds of the hydrocarbon type or hydrocarbon compounds with a low fluorine content of trudnorastvorimy in the solvent, while a problem is found, namely, that the interaction does not proceed uniformly. In addition, in accordance with well-known liquid-phase method, the interaction is carried out at very low concentrations, there is the problem of low output, the interaction will take place in the suspension system, which is unfavorable for interaction. Additionally, there is a problem with the fact that when the liquid-phase method is applied to hydrocarbon compounds with a low molecular weight, the yield of the reaction tends to be very low.

In addition, the conventional method of obtaining desilvered inherent problem, namely, that the cost of raw materials is high, and the method is economically disadvantageous. Moreover, since the use of iodine fuming sulfuric acid, etc., there is a problem of corrosion of equipment or manipulation reagenti for the implementation of the reaction will be hindered.

In addition, if the fluorination in the liquid phase is subjected to dialdictate, not containing fluorine, there is a problem with that observed the reaction of the decomposition of a substance used as a raw material substrate. Also the method of using R-113 inherent problem lies in the fact that this method can not be used in the future.

In addition, the conventional method of obtaining compounds containing fluorinated vinyl groups at both ends of the molecule, has the disadvantage that for two fluorinated vinyl groups requires interaction in two stages, and the substrate for pyrolysis remote and roads.

The invention

The aim of the present invention is to solve the problems inherent in the conventional methods, and to suggest a way in which the fluoride compound can be obtained from inexpensive readily available materials using short process.

Namely, the present invention provides a method of obtaining a fluorine-containing compounds, which includes the interaction of the following compounds (1) with the following compound (2) to obtain the following compound (3) (provided that the compound (3) is a compound in which the fluorine content is at least 30 mA is from.%, and which are a hydrogen atom or an unsaturated bond, which may be fluorinated), the fluorination of the compound (3) in the liquid phase to obtain the following compound (4)with subsequent cleavage reaction EFcompounds (4) to obtain this compound (5) and/or compound (6):

where RA, RB: RAndrepresents a bivalent fluorine-containing organic group, which is the same as RAFor a bivalent organic group, which will be converted to RAFby the fluorination reaction, and RBrepresents a monovalent organic group, which is the same as RFor a monovalent organic group, which will be converted to RFby the fluorination reaction,

RAF, RBF: RAFrepresent a bivalent fluorine-containing organic group, which is the same as or different from RAand when is different, it is a group having a fluorinated RAgroup, and RBFrepresents a fluorine-containing monovalent organic group, of which the traveler is the same as or different from R Inand when is different, it is a group having a fluorinated RIngroup.

E1E2: reactive group that will interact with each other to form a bivalent connecting group (E),

E: a bivalent connecting group formed by the interaction of the E1and E2,

EFgroup, which is the same as group E, or a group having a fluorinated group E, provided that at least one group selected from RAF, RBFand EFrepresents a group formed by the reaction of fluorination and,

EF1EF2each independently represents a group formed from the decomposition of EF.

In addition, the present invention proposes a method in which the compound (5) is the following compound (5-2), and this connection is subjected to pyrolysis to obtain the following compound (7-2):

FCO-QF1-RAF-QF2-COF(5-2)
CF2=CF-RAF-CF=CF2(7-2)

where RAF: as defined above, and

QF1, QF2each represents-CF(CF3)- or-CF2-CF2-.

In addition, the present invention apply the connection, selected from compounds represented by the following formula:

CF3CF2COO(CH2)4OCOCF2CF3

CF3CF2COOCH2CH(CH3)O(CH2)4OCOCF2CF3

CF3CF2COO(CH2)2O(CH2)2OCOCF2CF3

CF3CF2CF2OCF(CF3)COOCH2CH(CH3)O(CH2)5OCOCF(CF3)-OCF2CF2CF3

CF3CF2COO(CH2)2O(CH2)2OCH(CH3)CH2OCOCF2CF3

CF3CF2COOCF2CF2CF2CF2OCOCF2CF3

CF3CF2COOCF2CF(CF3)OCF2CF2CF2CF2OCOCF2CF3

CF3CF2COOCF2CF2OCF2CF2OCOCF2CF3

CF3CF2CF2OCF(CF3)COOCF2CF(CF3)OCF2(CF2)3-

CF2OCOCF(CF3)OCF2CF2CF3

CF3CF2COO(CF2)2O(CF2)2OCF(CF3CF2OCOCF2CF3

FCOCF2O(CF2)2OCF(CF3)COF
(3-12),

(3-13),

(3-14),

(3-15),

(3-16),

(4-12),

(4-13),

(4-14),

(4-15),

(4-16),

(5-16).

The best way of carrying out the invention

This op is sanija organic group is a hydrocarbon group, which may be a saturated group or an unsaturated group. As an organic group which can be fluorinated, can be, for example, the atom which may be substituted by fluorine atom (such as a hydrogen atom attached to a carbon atom) or a group of atoms which can be substituted by fluorine atoms (e.g.,- CF=CF-containing carbon-carbon unsaturated double bond can be converted into CF2CF2by the fluorination reaction, and With≡S-containing carbon-carbon unsaturated triple bond will be converted into CF2CF2- or-CF=CF - through reaction of fluorination). In accordance with the present invention the organic group preferably represents a group containing from 1 to 20 carbon atoms, particularly preferably a group containing 1 to 10 carbon atoms, from the viewpoint of solubility in the liquid phase, which is used for the reaction of fluorination.

As the monovalent organic group is preferable monovalent hydrocarbon group containing a heteroatom monovalent hydrocarbon group, halogenated monovalent hydrocarbon group or halogenated (containing heteroatom monovalent hydrocarbon) group. As a bivalent organic group is predpochtitelnei is a bivalent hydrocarbon group, containing heteroatom bivalent hydrocarbon group, halogenated bivalent hydrocarbon group or halogenated (containing heteroatom bivalent hydrocarbon group.

The hydrocarbon group is a group comprising carbon atoms and hydrogen atoms, and preferably the hydrocarbon group is a group containing from 1 to 20 carbon atoms, particularly preferably from 1 to 10 carbon atoms, from the viewpoint of, for example, solubility in the liquid phase in the implementation of the fluorination reaction. The hydrocarbon group as carbon-carbon connection can be a simple bond or an unsaturated bond. The hydrocarbon group may be an aliphatic hydrocarbon group or aromatic hydrocarbon group. Aliphatic hydrocarbon group is preferred. The structure of the aliphatic hydrocarbon group may be a linear structure, a branched structure, a cyclic structure or a structure that includes a ring structure. As the organic group is preferable rich group in which the carbon-carbon bond presents only simple connections.

In the case where the hydrocarbon group is a monovalent saturated hydrocarbon group is, it can be, for example, alkyl group, cycloalkyl group or a monovalent saturated hydrocarbon group, including cyclic fragment (such as cycloalkyl group, cycloalkenyl group or bicycloalkyl group, a group having a Spiro alicyclic structure, or a group containing such a group as part of the structure), preferred is an alkyl group. In the case when the aliphatic hydrocarbon group is an unsaturated group, it is preferable monovalent aromatic hydrocarbon group, and particularly preferred phenyl group, aryl group or such a group having the Deputy.

In the case when the aliphatic hydrocarbon group is a bivalent saturated hydrocarbon group, it may be a group containing one of the hydrogen atoms of the above-mentioned monovalent saturated hydrocarbon group, turned into a connecting link, and it may be, for example, alkilinity group, cycloalkanones group or a bivalent saturated hydrocarbon group having a cyclic fragment (such as bivalent saturated hydrocarbon group containing as part of the structure group selected from cycloalkyl group, bicycloalkyl group and a monovalent group, having the th Spiro alicyclic structure, cycloalkanones group, bicycloalkyl group, or a bivalent saturated hydrocarbon group containing as part of the structure cycloalkenyl group or bicycloalkyl group, and preferred is Allenova group. As the bivalent aromatic hydrocarbon group is preferable fenelonov group, Allenova group or such a group having the Deputy.

In the present description, the halogen atom is a fluorine atom, chlorine atom, bromine atom or iodine atom, and preferred is a fluorine atom, a chlorine atom or a bromine atom. In addition, halogenated group is a group in which at least one of the hydrogen atoms present in the group, galogenidov at least one type of halogen atoms selected from fluorine atom, chlorine atom, bromine atom and iodine atom, and it may be a group in which there are or are not hydrogen atoms. Partially halogenated group is a group in which a part of hydrogen atoms present in the group, galogenirovannami, and it is this group that has hydrogen atoms not substituted by halogen atoms. Perhalogenated group is a group in which essentially all of the hydrogen atoms present in the group, galogenirovannyie, and she not only is em a group, in which essentially no hydrogen atom. In addition, a PERFLUORO (partially fluorinated monovalent hydrocarbon) group is a group which is the same as performancesanta saturated hydrocarbon group. This value terms halogenated, partially halogenated and perhalogenated similar to the meaning of the terms used fluorinated, partially fluorinated and perfluorinated.

In the present description halogenated hydrocarbon group is a group in which at least one of the hydrogen atoms in the hydrocarbon group substituted by a halogen atom, and it is preferably a halogenated alkyl group. The halogen atom in the halogenated alkyl group preferably represents a fluorine atom, a chlorine atom or a bromine atom. In addition, as a partially halogenated monovalent saturated hydrocarbon group is preferred partially halogenated alkyl group. As perhalogenated monovalent hydrocarbon group is preferable perhalogenated alkyl group. The atoms of halogen in perhalogenated alkyl group preferably represent solely the fluorine atoms or fluorine atoms and the atoms of halogen other, che is the fluorine atoms (preferably chlorine atoms).

Halogenated bivalent saturated hydrocarbon group is a group in which at least one of the hydrogen atoms in the bivalent saturated hydrocarbon group substituted by a halogen atom, and preferably it represents a halogenated alkylenes group. As the halogen atom in the halogenated alkalinous group, preferred is a fluorine atom, a chlorine atom or a bromine atom. As partially halogenated bivalent saturated hydrocarbon group is preferred partially halogenated Allenova group. As perhalogenated bivalent saturated hydrocarbon group is preferable perhalogenated Allenova group. The atoms of halogen in perhalogenated alkalinous group can represent fluorine atoms or may include fluorine atoms and the atoms of halogen other than fluorine atoms (preferably chlorine atoms).

In the present description, containing heteroatom saturated hydrocarbon group is a saturated hydrocarbon group that contains a heteroatom, not changed as a result of the reaction of fluorination, or heteroatomic group, not modified by the reaction of fluorination. As bivalent heteroatom, not changed in the reaction FPO the financing, preferred is an oxygen atom, a simple ester, and as a bivalent hetero-atomic group, not modified by the reaction of fluorination can be mentioned, for example-With-C(O)-or-SO2-C.

As containing heteroatom monovalent saturated hydrocarbon group can be mentioned, for example, an alkyl group containing an oxygen atom of a simple ester, included between the carbon-carbon bond, or cycloalkyl group containing an oxygen atom of a simple ester, included between the carbon-carbon bond (provided that in the group may be one or more atom of oxygen simple ether), and particularly preferred is alkoxyalkyl group.

As containing heteroatom bivalent saturated hydrocarbon group can be mentioned, for example, Allenova group containing an oxygen atom of a simple ester, included between the carbon-carbon bond or located on the connecting end of the group, or cycloalkenes group containing an oxygen atom of a simple ester, included between the carbon-carbon bond, and particularly preferred are oxyalkylene group or polyoxyalkylene group.

As halogenated (containing heteroatom monovalent saturated hydrocarbon) group may be womanthrope, in which at least one of the hydrogen atoms in the above containing monovalent heteroatom

saturated hydrocarbon group substituted by a halogen atom, and preferred is a halogenated (alkoxyalkyl) group.

As halogenated (containing heteroatom bivalent saturated hydrocarbon) group, may be mentioned a group in which at least one of the hydrogen atoms in the above containing heteroatom bivalent saturated hydrocarbon group substituted by a halogen atom, and preferred are halogenated (oxyalkylene) group or halogenated (polyoxyalkylene) group.

As specific examples of such groups can be specified groups are the following specific compounds.

RAin the compound (1) is a bivalent fluorine-containing organic group, which is the same as RAFor a bivalent organic group, which will be converted to RAFby the fluorination reaction. The number of carbon atoms in RAis preferably from 1 to 20, particularly preferably from 1 to 10. RAmay have a linear structure, a branched structure, a cyclic structure or a structure that includes a ring system.

RApreferably, not only the et a bivalent saturated hydrocarbon group, halogenated bivalent saturated hydrocarbon group containing a heteroatom bivalent saturated hydrocarbon group or halogenated (containing heteroatom bivalent saturated hydrocarbon) group, or preferably a group containing hydrogen atoms. In addition, RApreferably represents a group that differs from the given below RAFi.e. the group which will be converted to RAFby the fluorination reaction.

In the case when RAndrepresents a group containing hydrogen atoms, it preferably represents a bivalent saturated hydrocarbon group, a partially halogenated bivalent saturated hydrocarbon group containing a heteroatom bivalent saturated hydrocarbon group or a partially halogenated (containing heteroatom bivalent saturated hydrocarbon) group, and is preferably such a group is alkylenes group, partially fluorinated alkylenes group, partially fluorinated (partially chlorinated alkylenes) group, alkylenes group containing an oxygen atom simple ether (for example, oxyalkylene group), partially fluorinated alkylenes group containing an oxygen atom simple ether (for example, partially fluorinated hydroxy is lkilebu group), partially fluorinated (partially chlorinated alkylenes) a group containing an oxygen atom simple ether (for example, partially fluorinated (partially chlorinated oxyalkylene) group). The oxygen atom of a simple ester is preferably included in one or more positions selected from position between the carbon-carbon bond, the provisions on the end that communicates with the E1and provisions at the end that communicates with the E2.

In addition, in the case when RAndrepresents a group other than mentioned above, this group preferably represents a group containing a fluorine atom in the desired group RAFsubstituted monovalent heteroatomic group (e.g. a carboxyl group or the like), which can be converted into a fluorine atom by the reaction of fluorination (for example, a group containing a fragment-C(O)-, included between the carbon-carbon bond alkalinous group, or the like) or a group containing at least one carbon-carbon simple relations in the desired group RAFsubstituted carbon-carbon double bond or carbon-carbon triple bond.

Preferably, the carbon atoms forming the carbon-carbon double bond, were attached hydrogen atoms or fluorine atoms, and especially predpochtite is) to be attached hydrogen atoms. To carbon atoms forming an unsaturated bond, the fluorine atoms can be added by reaction of fluorination in the liquid phase, and the hydrogen atoms are replaced by fluorine atoms. For example, fenelonov group can be converted into perforcerepository group through the reaction of fluorination. As specific examples of such groups may be mentioned, for example, cyclohexadienone group, fenelonov group, alkenylamine group or akinlana group.

E1in the compound (1) represents a reactive group that will interact with a group of E2with the formation of the bivalent connecting group (E).

Such bivalent connecting group (E) may represent a group that can be changed or cannot be changed by the fluorination reaction.

As the bivalent connecting group (E) are preferred, for example, -CH2OCO -, or-CH2S2- (assuming that the direction this group is not limited), and particularly preferred from the viewpoint of usefulness of the requested connection is a group-CH2OCO-. In the case when E is a preferred group, E1and E2can be such that one of them represents-With the 2HE and the other represents-MOR (X represents a halogen atom) or-SO2X.

Next will be described in detail with reference to the case when the bivalent connecting group (E) represents-CH2Special.

In accordance with the present invention, the compound (5), which is usually difficult to obtain, can be obtained by performing the reaction according to the present invention using the compound (1)containing the group (RA), having a carbon skeleton corresponding to RAFthe desired compound (5). The structure of compound (1), which can be used in accordance with the present invention is practically unlimited.

An example of compound (5), which is usually difficult to obtain, there may be a connection (5), in which the structure of RAFis a complex, or a low molecular weight fluorinated product (5), in accordance with than when carrying out the fluorination reaction produces many by-products. As a low-molecular compound (5) may be the product of the fluorination of the compound (1)having a molecular weight of not more than 200 (preferably a molecular weight of from 50 to 200). Namely, the method according to the present invention, which is carried out using the compound (1)having a molecular weight of not more than 200, the t is made by one of the preferred embodiments of the present invention.

As compounds (1) are preferred is the following compound (1-1)in which E1represents-CH2HE, more preferred is the following compound (1-10)in which RAis an RAH1and the most preferred is the compound (1-11), in which RAis an RAH2.

HO-CH2-RA-CH2OH

HO-CH2-RAH1-CH2OH

HO-CH2-RAH2-CH2OH
(1-1),

(1-10),

(1-11).

where RAhas the same values as the values in the connection (1), and RAH1represents a bivalent saturated hydrocarbon group, halogenated bivalent saturated hydrocarbon group containing a heteroatom bivalent saturated hydrocarbon group or halogenated (containing heteroatom bivalent saturated hydrocarbon) group. RAH1preferably represents alkylenes group, oxyalkylene group, polyoxyalkylene group, halogenated alkylenes group, halogenated (oxyalkylene) group or a halogenated (polyoxyalkylene) group. In the case when such a group contains a halogen atom, it is preferable that it represented, Melsheimer, one member, selected from halogen atoms other than fluorine atom, and the halogen atom are preferred, a chlorine atom, a bromine atom or a chlorine atom and a bromine atom.

RAH2represents alkylenes group or a group containing an oxygen atom of a simple ester, included at least in one or more positions between the carbon-carbon bond in alkalinous group. Particularly preferably, RAH2represents alkylenes group, oxyalkylene group or polyoxyalkylene group.

In accordance with the present invention, it is preferable that one of the compounds (1) and compound (2) represented a compound containing a fluorine atom, and the other was a compound not containing a fluorine atom. Especially from the point of view of usefulness of the compounds preferably, the compound (1) represented a compound not containing a fluorine atom (i.e. a connection in which the fluorine content was 0 wt.%), while the compound (2) represented a compound containing a fluorine atom.

The following compounds may be mentioned as specific examples of the compound (1). The following compounds are known compounds or compounds which can easily be obtained by known methods from known compounds. For these soy is ineni n is an integer, equal to at least 3, preferably from 4 to 10, m is an integer equal to at least 1, preferably from 1 to 10, p is an integer equal to at least 3, preferably an integer from 3 to 5, k is an integer equal to at least 1, preferably from 1 to 10, and r is an integer equal to at least 3, preferably an integer from 3 to 5.

HO(CH2)nOH,

HO[CH2CH(CH3)O]m(CH2)pOH,

HO(CH2CH2O)k(CH2)rOH.

In accordance with the present invention, the compound (1) and the compound (2) interact. RBin the compound (2) is a monovalent organic group, which is the same as RFor a monovalent organic group, which will be converted to RFby the fluorination reaction. It is preferable to choose the structure of RBin accordance with the structure of RAndso that the fluorine content in the resulting compound (3) was at least 30 wt.%.

The number of carbon atoms in RInis preferably from 2 to 20, particularly preferably from 2 to 10. If the number of carbon atoms in RIn1, there is a problem, which consists in the fact that the separation of the compounds (6), in particular compounds (6-1, can be difficult. Consequently, the number of carbon atoms in RInis preferably at least 2. RInmay have a linear structure, a branched structure, a cyclic structure or a structure that includes a ring system.

RIncan be a monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group containing a heteroatom monovalent saturated hydrocarbon group or halogenated (containing heteroatom monovalent saturated hydrocarbon) group, such group may be an alkyl group, an alkyl fluoride group, fluorine (partially chlorinated alkyl) group, a group containing an oxygen atom of a simple ester, included in one or more positions between the atoms of carbon-carbon alkyl group, a group containing an oxygen atom of a simple ester, included in one or more positions between the atoms of carbon-carbon bonds in the alkyl fluoride group, or the group, containing an oxygen atom of a simple ester, included in one or more positions between the atoms of carbon-carbon fluoride (partially chlorinated alkyl) group.

In the case when RInrepresents a group other than mentioned above, this group may be a group containing as the ohms of fluorine in the desired group R BFsubstituted monovalent hetero-atomic group which can be converted into a fluorine atom by a fluorination reaction, or a group containing at least one carbon-carbon simple link in the desired group RBFsubstituted carbon-carbon double bond or carbon-carbon triple bond. Preferably, the hydrogen atoms or fluorine atoms were attached to the carbon atoms forming the carbon-carbon double bond, and particularly preferably to them were attached hydrogen atoms. As specific examples of the group RBcan be given cyclohexenyl group, phenyl group, Alchemilla group or Alchemilla group. In addition, as a monovalent heteroatomic groups can be specified carbonyl group, and as a group containing a monovalent heteroatomic group, may be mentioned a group in which the group-C(O)- is placed between the carbon-carbon bond in the alkyl group (-S-C(O)-S-).

As for RBin accordance with the present invention, in order to facilitate the implementation of the above continuous way, RAndpreferably represents a group containing no fluorine atom, and RBpreferably represents a group containing a fluorine atom.

Chrome is also particularly preferably the above continuous way, so that RBrepresented the same group, and RFand especially preferably, RBrepresented performancecontrol organic group. If performancecontrol organic group such group preferably represents performancecontrol saturated hydrocarbon group, a PERFLUORO (partially halogenated monovalent saturated hydrocarbon) group, a PERFLUORO (containing heteroatom monovalent saturated hydrocarbon) group or a PERFLUORO (partially halogenated (containing heteroatom monovalent saturated hydrocarbon)) group. Especially preferred is such a group containing at least two carbon atoms.

As compounds (2) may be used commercially available product or compound (6)obtained by the above method according to the present invention.

In addition, in accordance with the present invention, the fluorine content in the compound (3) (fluorine content is expressed through the ratio of fluorine atoms to the molecular mass of compound) be selected so that it was at least 30 wt.%. When adjusting the fluoride content so that it was at least 30 wt.%,the reaction of fluorination in the liquid phase can be easily carried out in a homogeneous system, while there is a positive quality, namely, that the yield of the reaction will also increase.

E2in the compound (2) is a reactive group that will interact with the E1with the formation of the bivalent connecting group (E), and this group is especially preferably represents-MOR-or-SO2X (X represents a halogen atom, preferably a chlorine atom or a fluorine atom, and if you carry out the above continuous, X is a fluorine atom). In addition, the compound (2) is preferably a compound (2-1)in which E2is a-MOR, more preferably the compound (2-10)in which RBrepresents the following RBF1particularly preferably the compound (2-11)in which RBis an R2.

XCORB

FCORBF1

FCOR2
(2-1),

(2-10),

(2-11).

In these formulas, RBaccepts the same values as for compounds (2), RBF1represents performancecontrol saturated hydrocarbon group or a PERFLUORO (containing heteroatom monovalent saturated hydrocarbon) group, and R2represents performanceline group, PERFLUORO (h is ichno chlorinated alkyl) group, PERFLUORO (alkoxyalkyl) group or a PERFLUORO (partially chlorinated alkoxyalkyl) group. The number of carbon atoms in RBF1and R2is preferably from 2 to 20, particularly preferably from 2 to 10.

Performancesanta saturated hydrocarbon group may represent, for example, -CF2CF3, -CF2CF2CF3, -CF2CF2CF2CF3, -CF2CClF2, -CF2CBrF2, -CF2CFClCF2Cl, -CF(CF3)2, -CF2CF(CF3)2, -CF(CF3CF2CF3or-C(CF3)3.

PERFLUORO (containing heteroatom monovalent saturated), the group may represent, for example, -CF(CF3)CF2CF2CF3, -CF(CF3)CF2CF2CFClCF2Cl or-CF(CF3)CF2CF2Br.

As specific examples of the compound (2) can be mentioned the following compounds:

CF3CF2COF,

CF2ClCFClCF2COF,

CF2ClCF2CFClCOF,

CF3CF2CF2OCF(CF3)COF,

CF2ClCFClCF2CF2OCF(CF3)COF,

CClF2CF2COF,

CBrF2CF2COF,

CF2BrCF2OCF(CF3)COF,

CF2ClCFClCF2CF(CF3)OCF(CF3)COF,

CF3CF2CF2OCF(CF3CF2OCF(CF3)COF,

CH3CH2CH2OCF(CF3)COF,

CH2 ClCHClCH2COCl,

CF3CF2CF2OCF2CF2COF.

The compound (2) may be a known compound or can be obtained in a known manner from known compounds. For example, the connection CF3CF2CF2CF(CF3)F easily accessible as an intermediate compound to obtain PERFLUORO-(alkylvinyl simple ether).

The interaction of the compound (1) with compound (2) can be carried out using well-known techniques for interaction and conditions, dependent on the structure of E1and E2, and combinations thereof. For example, the interaction of the compound (1-1)in which E1represents-CH2HE, with the compound (2-1)in which E2is a-MOR, can be carried out under the conditions known for the esterification reaction. The esterification reaction may be conducted in the presence of a solvent (hereinafter referred to as the solvent for the esterification reaction), but preferably is carried out in the absence of any solvent in the esterification reaction, from the viewpoint of volumetric productivity.

When using solvent for the esterification reaction, it preferably represents dichloromethane, chloroform, triethylamine or a mixed solvent consisting of triethylamine and tetrahydrofuran. The amount of solvent in the reaction e is verificatie, which must be used is preferably from 50 to 500 wt.%, in the calculation of the total amount of the compounds (1-1) and the compound (2-1).

When interacting compounds (1-1) to compound (2-1) will produce acid represented by the formula HX. When the compounds (2-1) used a compound in which X represents a fluorine atom, can be formed HF, respectively, in the reaction system as acceptor HF may be present, for example, a fluoride of an alkali metal (NaF or KF are preferred) or trialkylamine. It is desirable to use the acceptor HF in the case where the compound (1-1) or the compound (2-1) is a compound which is unstable to acid. In addition, when the acceptor HF is not used, it is preferable to conduct the reaction at the reaction temperature, at which HF can evaporate, and HF are removed from the reaction system with a stream of nitrogen. Acceptor HF is preferable to use 1 to 10-fold amount relative to the amount of the compound (2-1) in moles.

When carrying out the esterification reaction, the amount of the compounds (2-1) to the compound (1-1) in moles is preferably 1.5 to 10-fold, particularly preferably 2-5-fold. The lower temperature limit for the interaction of the compound (1-1) with a compound (2-1) is preferably -50°and in which rhni limit, preferably, corresponds to the temperature which is between +100°and the boiling point of the solvent. In addition, the reaction time can be appropriately changed depending on the feeding speed of the original substance and the number of connections that are used for interaction. The reaction pressure is preferably from 0 to 2 MPa (gauge pressure).

When interacting compounds (1) with compound (2) produces compound (3). In the compound (3) RArepresents the same group as RAin the compound (1), and RInrepresents the same group as RInin the compound (2). E is a bivalent connecting group formed by the interaction of E1and E2and may constitute, for example, -CH2OCO -, or-CH2SO2-.

In addition, since the fluorine content in the compound (3) is at least 30 wt.%, at least one of RAnd, RInand E is a group containing fluorine atoms. In addition, the compound (3) preferably has a molecular weight of more than 200 and not more than 1000 for the fluorination reaction in a liquid phase at the next stage can proceed uniformly. If the molecular weight is too small, the compound (3) has a tendency to easily evaporate, and ve is Aetna, what will be the reaction of the decomposition in the gas phase in the reaction of fluorination. On the other hand, if the molecular weight is too large, there is a tendency that with this connection (3) it will be difficult to work with or difficult to clean such a connection.

Preferably appropriately modify the content of fluoride depending on the type of the liquid phase used for the fluorination reaction. Typically, the fluorine content is adjusted, preferably, from 30 to 86 wt.%, particularly preferably, from 30 to 76 wt.%. Connection (3), in which the fluorine content is at least the specified number is a compound which has a particularly good solubility in the liquid phase for the reaction of fluorination and which is particularly suitable from the viewpoint of efficiency in the reaction of fluorination and allows you to complete the reaction with high yield.

The compound (3) is preferably a compound (3-1), which will be formed in the interaction of the compound (1-1) with a compound (2-1), more preferably, compound (3-10), which will be formed in the interaction of the compound (1-10) with compound (2-10), particularly preferably the compound (3-11), which will be formed in the interaction of the compound (1-11) with compound (2-11):

RBCOOCH2-RA-CH2OCORB

RBF1COOCH2-RAH1-CH2OCORBF1

R2COOCH2-RAH2-CH2OCOR2
(3-1),

(3-10),

(3-11).

In these formulas, RA, RB, RAH1, RBF1, R2and RAH2are as defined above, and their preferred values are also the same.

The following compounds may be mentioned as specific examples of the compound (3). In these formulas, the legend are as defined above.

CF3CF2COO(CH2)nOCOCF2CF3,

CF3CF2COO (CH2CH(CH3)O]m(CH2)pOCOCF2CF3,

CF3CF2COO(CH2CH2O)k(CH2)rOCOCF2CF3,

CF3CF2COO(CH2)2O(CH2)2OCOCF2CF3,

CF3CF2CF2OCF(CF3)COOCH2CH(CH3)O(CH2)5OCOCF(CF3)OCF2CF2CF3,

CF3CF2COO(CH2)2O(CH2)2OCH(CH3)CH2OCOCF2CF3.

The crude product containing the compound (3)formed by the interaction of the compound (1) with compound (2)may be purified or may be used directly, for example, in a subsequent reaction,depending on the objectives. It is preferable to clean from the point of view of the uniform reaction of fluorination at a later stage.

The cleaning method can represent, for example, the method of direct distillation of the crude product, method of treatment of the crude product dilute aqueous alkaline solution, followed by separation of liquids, the method of extracting the crude product with a suitable organic solvent, followed by distillation or column chromatography on silica gel.

In accordance with the present invention, the compound (3) is then subjected to fluorination. The fluorination reaction can be carried out by electrochemical fluorination or by gas-phase fluorination, but is preferred fluorination in the liquid phase. The fluorination in the liquid phase is an excellent method by which the compound (4) can be obtained with high yield while preventing the decomposition reaction of the compound (3). Below we will provide the following description with reference to the case when the fluorination is carried out with the use of the method of fluorination in the liquid phase, in which the interaction with the fluorine is carried out in the liquid phase.

Method of fluorination in the liquid phase method is a method that involves reacting compounds () with fluorine in a liquid phase. The liquid phase can be formed by a substrate or product of interaction, and it is generally preferable to present the solvent (hereinafter referred to as the solvent for the reaction of fluorination). As fluorine, preferably using gaseous fluorine or gaseous fluorine diluted with an inert gas. As the inert gas preferably using gaseous nitrogen or gaseous helium, and nitrogen gas is particularly preferred from the viewpoint of economic advantages. The number of fluorine gas in a gaseous nitrogen is practically not limited, but is preferably at least 10 vol.% from the point of view of efficiency, particularly preferably at least 20 vol.%.

As solvent for the fluorination reaction, it is preferable solvent which essentially contains a C-F bond and contains no C-H bond. Especially preferred is perftoran or an organic solvent, which is a known perfluorinated organic solvent, the structure of which includes at least one atom selected from a chlorine atom, nitrogen atom and oxygen atom. In addition, as a solvent for the fluorination reaction, it is preferable to use a solvent, which provides high solubility is soedineniya (3). Particularly preferred is a solvent capable of dissolving at least 1 mass% of compound (3), and most preferred is a solvent capable of dissolving at least 5 wt% of compound (3).

Examples of fluorinated reaction solvent include the above-mentioned compound (5), the compound (6), perftoran (trade name: FC-72 and the like), simple perforator (trade name: FC-75, FC-77, etc), simple parfocality (trade name: KRYTOX, FOMBLIN, GALDEN, DEMNUM, etc.), chlorofluorocarbons (trade name: FLON LUBE), simple hortobagyi, performanceline (for example, perftorsilanami etc) and inert liquid (trade name: FLUORINERT). It is preferable to perftorsilanami, the compound (5) or the compound (6). Especially preferable to use the compound (5) or the compound (6), and the processing after the interaction is going to be easy.

The amount of fluorinated reaction solvent is preferably at least 5-fold by weight, particularly preferably from 10 to 100-fold weight, relative to the mass of compound (3).

The reaction system for the fluorination reaction is preferably a system of periodic action or continuous action.

Furthermore,the fluorination reaction is preferably carried out using method 2, which will be described later, from the viewpoint of the yield of the reaction and selectivity. In addition, gaseous fluorine is preferably used diluted with an inert gas such as nitrogen gas, as when using a system of periodic action, and continuous action.

Method 1: Method, according to which the compound (3) and fluorinated reaction solvent is loaded into the reactor, start mixing and conduct the reaction in a continuous flow of gaseous fluorine in the fluorinated reaction solvent in the recommended reaction temperature and reaction pressure.

Method 2: the Method, according to which the fluorination solvent loaded into the reactor and stirred, and then continuously served gaseous fluorine, the compound (3) and the solvent of the reaction of fluorination at the recommended molar ratio recommended by the reaction temperature and reaction pressure.

When the compound (3) is served according to the method 2, it is preferable to apply the compound (3) diluted with a solvent for the fluorination reaction, from the viewpoint of improving the selectivity and reducing the amount of by-products. In addition, when the compound (3) is diluted with solvent in accordance with method 2, it is preferable to adjust the amount of the solvent of the reaction of fluorination in relation to soybeans is inniu (3) to a level at least 5 times by mass, particularly preferably at least 10 times by mass.

When used for the reaction of fluorination either periodic or continuous operation, the amount of fluorine (F2) is preferably adjusted so that he was always in excess with respect to the number of hydrogen atoms in the compound (3). Namely, the amount of fluorine is preferably at least 1.1 times higher than the equivalent (i.e. 1,1-fold moles, especially preferably 1.5 times higher than the equivalent (i.e. a 1.5-fold in moles), from the viewpoint of selectivity. The amount of fluoride preferably is redundant from the beginning to the end of the reaction. Accordingly, when the fluorination solvent loaded into the reactor at the beginning of the reaction, it is preferable that in the pre-fluorination solvent was dissolved in sufficient amount of fluoride.

The fluorination reaction is carried out in such conditions that bivalent connecting group (E) was not split. When a bivalent connecting group (E) represents-CF2OCO-, the lower limit of the reaction temperature is preferably -60°and the upper limit preferably represents the boiling point of the compound (3). In addition, from the viewpoint of the yield of the reaction, the selectivity and the industry is slowly applicability the reaction temperature is particularly preferably ranges from -50° C to +100°S, especially preferably from -20°to +50°C. the Reaction pressure for the fluorination reaction is not particularly limited, and it is preferably from atmospheric pressure to 2 MPa (gauge pressure) from the point of view of the yield of the reaction, selectivity and industrial applicability.

In addition, in order for the fluorination reaction takes place effectively, it is preferable in the reaction system to add a compound containing C-H bond, or expose the system to the action of ultraviolet radiation. These operations are preferably performed at the last stage of the fluorination reaction, in accordance with which the compound (3)present in the reaction system can be effectively fluorinated, and the conversion can raise considerably.

Compounds containing C-H bond, is preferably an organic compound other than the compound (3), particularly preferably, organic hydrocarbons, particularly preferably benzene, toluene or the like. The number of compounds containing C-H bond, is preferably from 0.1 to 10 mol.%, particularly preferably, from 0.1 to 5 mol.%, with respect to the hydrogen atoms in the compound (3).

In addition, the compound containing the C-H bond, is preferably added to the reaction system, which contains fluoride. The AOC is e, when you add a compound containing C-H bond, it is preferable to subject the reaction system pressure. Accompanying the pressure is preferably from 0.01 to 5 MPa (gauge pressure). The time of ultraviolet irradiation is preferably from 0.1 to 3 hours.

The reaction of fluorination of the compound (3) to form compound (4). RAFin the compound (4) is a bivalent fluorine-containing organic group, which is the same or different from RAndand when is different, it is a group containing a fluorinated group, RA. RBFrepresents a fluorine-containing monovalent organic group, which is the same or different from RInand when is different, it is a group containing a fluorinated group, RIn.

For example, when RAand RBin the compound (3) represent a group containing hydrogen atoms, respectively, RAFand RBFin which the hydrogen atoms replaced by fluorine atoms, by reaction of fluorination represent groups different from RAand RBrespectively. On the other hand, in the case when RAand RBare groups that do not contain hydrogen atoms (for example, in the case perhalogenated what's groups), RAFand RBFrepresent the same groups as RAand RBrespectively.

RAFand RBFpreferably represents a group formed by the fluorination reaction, and in such groups may be present or absent unsubstituted hydrogen atoms, and preferably essentially not present unsubstituted hydrogen atoms. The number of hydrogen atoms in RAFand RBFpreferably changed depending on a particular purpose.

If the reaction of fluorination in the liquid phase it is difficult to adjust the position, in which are entered the fluorine atoms. Accordingly, when used as a compound (3)in which RAand RBrespectively represent a group containing hydrogen atoms, is preferred to RAFand RBFin the compound (4) represented groups, which are essentially perfluorinated.

RAFin the compound (4) preferably represents a bivalent saturated hydrocarbon group, a partially halogenated bivalent saturated hydrocarbon group containing a heteroatom bivalent saturated hydrocarbon group or a group containing at least one hydrogen atom in RAin a partially halogenated (containing heteroatom bivalent saturated at glevodorodnogo) group, substituted by a fluorine atom by the reaction of fluorination, and especially preferably represents a group in which all hydrogen atoms substituted by fluorine atoms. Particularly preferably, RAFrepresents performancelevel group or the group in which between the atoms of carbon-carbon performancelevel group is an oxygen atom simple ether.

RFpreferably represents a monovalent saturated hydrocarbon group, halogenated monovalent saturated hydrocarbon group containing a heteroatom monovalent saturated hydrocarbon group, or a group in which at least one hydrogen atom in the halogenated (containing heteroatom monovalent saturated hydrocarbon) group substituted with fluorine atom, and particularly preferably represents a group in which all hydrogen atoms substituted by fluorine atoms, and especially preferably is the same group, as in the case when RInrepresents a perfluorinated monovalent organic group.

EFis a group, which is the same as E, or a group having a fluorinated E. as an example, the case when E is a fluorinated group, may be mentioned a group in which at least one atom in Dorada, present in E, replaced by fluorine. As EFin the case when E is a group containing a-CH=CH - fragment can be specified, for example, a group in which one fragment is transformed into-CF2CF2-. In addition, since the compound (4) has the same structure as the compound (3)at least one group selected from RAF, RBFand EFrepresents a group formed by the fluorination reaction, or group in which RA, RBor E changed.

The compound (4) is preferably a compound (4-1), which will be formed by fluorination of the compound (3-1), more preferably, compound (4-10)containing fluorinated compound (3-10), particularly preferably the compound (4-11), having a fully fluorinated compound (3-11).

RBFCOOCF2-RAF-CF2OCORBF

RBF1COOCF2-RAF1-CF2OCORBF1

R2COOCF2-RAF2-CF2OCOR2
(4-1),

(4-10),

(4-11).

In these formulas, RBF, RAF, RBF1and R2are as defined above. RAF1represents a group corresponding to RAN1and when RAN1are the hydrogen atoms, this group represents a group in which essentially all of the hydrogen atoms replaced by fluorine atoms, and in that case, if RAN1are not hydrogen atoms, this group is the same as RAN1. RAF2represents a group corresponding to RAN2and represents the group in which essentially all of the hydrogen atoms in RAN2substituted by fluorine atoms.

The following compounds may be mentioned as specific examples of the compound (4).

CF3CF2COOCF2CF2CF2CF2OCOCF2CF3,

CF3CF2COOCF2CF(CF3)OCF2CF2CF2CF2OCOCF2CF3,

CF3CF3CF2OCF(CF3)COOCF2CF(CF3)OCF2CF2CF2CF2CF2OCO-

CF(CF3)OCF2CF2CF3,

CF3CF2COOCF2CF(CF3)OCF2CF2CF2CF2CF2OCOCF2CF3,

CF3CF2COOCF2CF2OCF2CF2OCOCF2CF3,

CF3CF2COO(CF2)2O(CF2)2OCF(CF3CF2OCOCF2CF3.

If a hydrogen atom in the compound (3) is substituted by a fluorine atom in the reaction of fluorination of the compound (3) in the liquid phase, as a by-product can be formed HF. In order to remove by-product HF, preferred is entrusted, to the reaction system were the acceptor HF, or to provide opportunities for shielding gas coming from the acceptor HF in the outlet gas from the reactor. As such acceptor HF can be used such as the acceptors, as described above, and preferred is NaF.

In the case when Pets presence of acceptor HF in the reaction system, its amount is preferably from 1 to 20 times moles, especially preferably from 1 to 5-fold moles with respect to the total number of hydrogen atoms present in the compound (3). In the case where the acceptor HF is at the gas outlet of the reactor, it is advisable to use (a) the cooler (preferably to maintain the temperature at from 10°C to room temperature, particularly preferably at approximately 20°C), (b) a nozzle with NaF pellets and (C) the cooler (it is preferable to maintain a temperature of -78°C to +10°S, more preferably from -30°0° (C)consistently placed in order (a)-(b)-(C). In addition, it may be installed in the return line fluid to return the condensed liquid from the cooler (s) in the reactor.

The crude product containing the compound (4)obtained by the reaction of fluorination can be used right near St the state at the next stage, or may be subjected to purification to obtain a product of high purity. The cleaning method can represent, for example, the way in which the crude product is subjected to direct distillation at atmospheric pressure or under reduced pressure.

In accordance with the present invention, by subsequent cleavage reaction EFcompounds (4) can be obtained compound (5) and/or the compound (6). EFsplit in order to receive EF1and EF2. The method and conditions for the cleavage reaction may appropriately be changed depending on the structure of the compound (4). In the case where the compound (4) is a compound (4-1), the cleavage reaction is a reaction of dissociation of the ester bonds, i.e. reaction, in which-CF2OCO-split with the formation of two-COF.

The reaction of dissociation of the ester bonds of the compound (4-1) is preferably carried out by pyrolysis or reaction dissociation is carried out in the presence of a nucleophilic agent or an electrophilic agent. As a result of this reaction will form the compound (5-1) and the compound (6-1), in which EF1and EF2represent-COF.

The pyrolysis can be conducted by heating the compound (4-1). It is advisable to choose the type of reaction pyrolysis according to temperature boil and stability of the compound (4-1).

For example, in the case when subjected to pyrolysis of the volatile compound (4-1)may be used in gas-phase pyrolysis, according to which the connection is subjected to continuous pyrolysis in the gas phase, and the exit gas containing the compound (5-1) and (6-1), condensed and recovered.

The reaction temperature gas-phase pyrolysis is preferably from 50 to 350°more preferably, from 50 to 300°S, particularly preferably from 150 to 250°C. furthermore, the reaction system may contain an inert gas that does not directly participate in the reaction. As such an inert gas may be mentioned, for example, gaseous nitrogen or gaseous carbon dioxide. Preferably, the inert gas was added in an amount of from about 0.01 to 50 vol.%, in the calculation of the compound (4-1). If the amount of inert gas is large, the amount of product can be reduced. The method and conditions of gas-phase pyrolysis applicable to compounds within the scope of compound (4-1).

On the other hand, in the case where the compound (4-1) is volatile ingredients, it is advisable to use liquid-phase pyrolysis, whereby the connection of the heated liquid in the reactor. In this case, the reaction pressure is not particularly limited. In the usual case of a product containing soy is inania (5-1), has a low boiling point, and accordingly it is preferably obtained by a method using reactive distillation, where the product is evaporated and continuously divert. In another case, it may be used a method in which after heating the entire product is removed from the reactor. The reaction temperature for such liquid-phase pyrolysis is preferably from 50 to 300°S, especially preferably from 100 to 250°C.

In the case when the pyrolysis is carried out by liquid phase pyrolysis, it can be done in the presence or in the absence of a solvent (hereinafter referred to as the reaction solvent dissociation). It is preferable to carry out the pyrolysis in the absence of any solvent. The solvent dissociation reaction is not particularly limited, while it is a solvent which does not react with the compound (4-1) and is compatible with the compound (4-1), and does not interact with the formed compound (5-1) and the compound (6-1). In addition, as the solvent of the reaction of dissociation is preferable to choose a solvent which can be easily separated during the cleaning. As specific examples of the reaction solvent dissociation is preferred inert solvent, such as perftorsilanami or perforation, or glorf argumentorum, especially oligomer of chlorotrifluoroethylene having a high boiling point (for example, trade name FLON LUBE). The amount of solvent dissociation reaction is preferably from 0.10 to 10-fold by weight with respect to the compound (4).

In addition, in the case where the dissociation reaction of the ester link is implemented by interaction of the compound (4-1) with a nucleophilic agent or an electrophilic agent in the liquid phase, this reaction can be carried out in the presence or in the absence of solvent dissociation reaction, and preferably in the absence of any solvent. As a nucleophilic agent is preferred F-and particularly preferred F-derived fluoride of an alkali metal. As the fluoride of the alkali metal can be used NaF, NaHF2, KF or CsF, and among them, particularly preferred is NaF, from the point of view of economic efficiency. Particularly preferable to conduct the reaction of dissociation of the ester bonds in the absence of any solvent, since the compound (4-1) itself serves as a solvent, and there is no need to separate the solvent from the reaction product.

In addition, in the case where the dissociation reaction of the ester communication is performed with the use of F-as nuclei the high agent, F-nucleophile attached to a carbonyl group, ester bonds present in the compounds (4-1), whereby will be chipped off RBFCF2O-and will produce the compound (5-1). Then F-will be chipped off from the RBFCF2O-with the formation of a compound (6-1). Internationally unrecognized breakaway F-will interact with another molecule of the compound (4) in a similar way. Accordingly nucleophilic agent, originally used for the reaction, may be present in a catalytic amount or in excess. The amount of the nucleophilic agent, such as F-, is preferably from 1 to 500 mol.%, more preferably from 1 to 100 mol.%, particularly preferably from 5 to 50 mol.%, in the calculation of the compound (4-1). The reaction temperature is preferably from -30°C to the boiling point of the solvent or the compound (4-1), more preferably from -20°, 250°C. This method is also preferably implemented in conjunction with distillation using a reaction apparatus comprising a distillation column.

From the reaction product of the reaction of dissociation of the ester bonds of the compound (4-1) can be obtained compound (5-1) and/or (6-1); from the reaction of the reaction product of dissociation of the ester bonds of the compound (4-10) mo the ut can be obtained compound (5-10) and/or (6-10); from the reaction product of the reaction of dissociation of the ester bonds of the compound (4-11) can be obtained compound (5-11) and/or (6-11).

FCO-RAF-COF

RBF-COF

FCO-RAF1-COF

RBF1COF

FCO-RAF2-COF

R2COF
(5-1),

(6-1),

(5-10),

(6-10),

(5-11),

(6-11).

As specific examples of the compound (5-1) can be mentioned the following compounds.

FCOCF2CF2COF,

FCOCF(CF3)OCF2CF2CF2COF,

FCOCF(CF3)OCF2CF2CF2CF2COF,

FCOCF2OCF2COF,

FCOCF2O(CF2)2OCF(CF3)COF.

As specific examples of the compound (6-1) can be mentioned the following compounds.

CF3CF2COF,

CF2ClCFClCF2COF,

CF2ClCF2CFClCOF,

CF3CF2CF2OCF(CF3)COF,

CF2ClCFClCF2CF2OCF(CF3)COF,

CClF2CF2COF,

CBrF2CF2COF,

CF2BrCF2OCF(CF3)COF,

CF2ClCFClCF2CF(CF3)OCF(CF3)COF,

CF3CF2CF2OCF(CF3CF2OCF(CF3)COF,

CF3CF2CF2OCF2CF2COF.

Among the compounds (5) and/or compound (6)obtained by the method according to the present invention, the compound (5-1) and/or the compound (6-1), sod is readie structural fragment C 1F-C2-COF end of the molecule, can be turned into a source of raw materials for the fluoropolymer by turning the end of the fragment molecule in the C1=C2” (where 1 and 2 in C1and C

2
represent numbers which determine the carbon atoms) by known reactions (Methods of Organic Chemistry, 4, Vol.10b, Part 1, p.703, etc.). This connection can be used as a precursor feedstock to obtain a fluoropolymer.

For example, in the case where the method according to the present invention applies the following compounds can be obtained substance useful as a raw material for obtaining the fluoropolymer.

For example, the compound (1-12) and the compound (2-12) interact with the formation of compound (3-12). Connection (3-12) is subjected to fluorination in liquid phase to obtain compound (4-12). Then the ester bond of the compound (4-12) is subjected to reaction dissociation, thus obtaining the compound (5-12) and/or compound (2-12).

HO(CH2)4OH

FCOCF2CF3

CF3CF2COO(CH2)4OCOCF2CF3

CF3CF2COO(CF2)4OCOCF2CF3

FCO(CF2)2COF
(1-2),

(2-12),

(3-12),

(4-12),

(5-12).

Connection (5-12) can lead to useful starting materials for the polymer (CF2=CFO(CF2)3COOCH3) by using the following scheme. This diagram HFPO is geksaftorpropilenom.

FCO(CF2)2COF(5-12)

+HFPO+CsF→FCOCF(CF3)O(CF2)3COF

FCOCF(CF3)O(CF2)3COF→pyrolysis

→CF2=CFO(CF2)3COF

CF2=CFO(CF2)3COF+CH3OH

→CF2=CFO(CF2)3COOCH3

Further, the compound (1-13) and the compound (2-13) interact with the formation of compound (3-13). Connection (3-13) is subjected to fluorination in liquid phase to obtain this connection (4-13). Then the ester bond of the compound (4-13) is subjected to reaction dissociation, thus obtaining the compound (5-13) and/or compound (2-13). Connection (5-13) can also lead to useful starting materials for obtaining the fluoropolymer using the same scheme as above.

HOCH2CH(CH3)O(CH2)4OH

FCOCF2CF3

CF3CF2COOCH2CH(CH3)O(CH2)4OCOCF2CF3

CF3CF2COOCF2CF(CF3)O(CF2)4OCOCF2CF3

FCOCF(CF3)O(CF2)3COF
(1-13),

(2-13),

(3-13),

(4-13),

(5-13).

In addition, the compound (1-14) and the compound (2-14) interact with the formation of compound (3-14). Connection (3-14) is subjected to fluorination in liquid phase to obtain this compound (4-14). Then the ester bond of the compound (4-14) is subjected to reaction dissociation, thus obtaining the compound (5-14) and/or compound (2-14). Connection (5-14) is a compound being in the form of tautomers of the lactone.

HO(CH2)2O(CH2)2OH

FCOCF2CF3

CF3CF2COO(CH2)2O(CH2)2OCOCF2CF3

CF3CF2COO(CF2)2O(CF2)2OCOCF2CF3

FCOCF2OCF2COF
(1-14),

(2-14),

(3-14),

(4-14),

(5-14).

The following intermediate compounds listed in the above schemes of synthesis, are novel compounds useful as starting material for production of fluoropolymers.

CF3CF2COO(CH2)4OCOCF2CF3

CF3CF2COOCH2CH(CH3)O(CH2)4OCOCF2CF3

CF3CF2COO(CH2)2O(CH2)2OCOCF2CF3

CF CF2CF2OCF(CF3)COOCH2CH(CH3)O(CH2)5-

OCOCF(CF3)OCF2CF2CF3

CF3CF2COO(CH2)2O(CH2)2OCH(CH3)CH2OCOCF2CF3

CF3CF2COOCF2CF2CF2CF2OCOCF2CF3

CF3CF2COOCF2CF(CF3)OCF2CF2CF2CF2OCOCF2CF3

CF3CF2COOCF2CF2OCF2CF2OCOCF2CF3
(3-12),

(3-13),

(3-14),

(3-15),

(3-16),

(4-12),

(4-13),

(4-14),
CF3CF2CF2OCF(CF3)COOCF2CF(CF3)OCF2(CF2)3-CF2OCOCF(CF3)OCF2CF2CF3

CF3CF2COO(CF2)2O(CF2)2OCF(CF3CF2OCOCF2CF3
(4-15),

(4-16).

In addition, among the compounds (5) the following compound (5-2) represents a particularly useful compound in which both ends of the molecule can be converted to a fluorinated vinyl group.

FCO-QF1-RAF-QF2-COF(5-2)

where RAF: shall have the meaning given above, and preferred embodiments are also the same as defined above.

QF , QF2: each represents-CF(CF3)- or-CF2CF2-.

The compound (5-2) get together with the compound (6-1) from the reaction product obtained by reacting the compound (1-2) and the compound (2-1) formation of compound (3-2), fluorination of the compound (3-2) in the liquid phase to obtain the compound (4-2) and the reaction of dissociation of the ester bonds of the compound (4-2).

HOCH2-Q1-RA-Q2-CH2OH

XCORB

RBCOOCH2-Q1-RA-Q2-CH2OCORB

RBFCOOCF2-QF1-RAF-QF2-CF2OCORBF

FCO-QF1-RAF-QF2-COF

RBF-COF
(1-2),

(2-1),

(3-2),

(4-2),

(5-2),

(6-1).

where RA, RB, RAF, RBF, X, QF1, QF2: as defined above.

Q1, Q2: may be the same or different, and each represents-CH(CH3)- or-CH2CH2-.

In addition, the above Q1and Q2preferably represents-CH(CH3)-, and QF1and QF2preferably represents-CF(CF3)-.

In accordance with the method of the present invention, from the reaction product after the reaction of dissociation of the ester bonds can be perceived by the s-only connection (5), only the connection (6), or as a compound (5)and the compound (6). For example, in the case where the reaction according to the present invention carried out using the compound (1-1)in which RArepresents a bivalent organic group containing hydrogen atoms, and the compound (2-1)in which RInrepresents perhalogenated monovalent organic group, can be obtained compound (5-1)in which RAis fluorinated. In addition, in the case where the reaction according to the present invention carried out using the compound (1-1)in which RArepresents perhalogenated bivalent organic group, and the compound (2-1)in which RInrepresents a monovalent organic group containing hydrogen atoms, can be obtained compound (6-1), containing two stoichiometric fluorinated molecules.

In addition, in accordance with the method of the present invention, when the resulting compound (6) has the same structure as the compound (2), the compound (6) is used as the compound (2), it may continuously be formed compound (5). For example, you may be specified the way in which some or all of the resulting compound (6-1) is used as the compounds (2-1) and subjected to interaction with connected the eat (1-1). In the case when implementing this method, it is preferable that the number of carbon atoms in RBFpicked up so that it was at least 2, more preferably from 2 to 20, particularly preferably from 4 to 10.

The compound (5-2)obtained in the above manner, can be converted into the compound (7-2) via pyrolysis.

CF2=CF-RAF-CF=CF2(7-2).

In this formula, RAFhas the same meaning as defined above, and preferred embodiments are also the same as defined above. The pyrolysis reaction can be conducted by a known method disclosed, for example, in J. Org. Chem., 34, 1841 (1969).

As specific examples of the compound (7-2) can be mentioned the following compounds.

CF2=CFO(CF2)2CF=CF2,

CF2=CFOCF2CF=CF2.

In accordance with the method of the present invention, when using the compounds (1) and compounds (2), which are available low-cost substances, can be obtained from various fluorine-containing compounds. In particular, when using the compounds (1-1) and the compound (2-1) can be obtained in different diaziridine derivatives and compounds containing fluorinated vinyl groups at both ends of the molecular is s.

As compounds (1) and compounds (2), which is used as the initial substance in the method of the present invention can be applied to a variety of compounds, differing in the structure of RAand RInthese compounds are commercially available and inexpensive. And in accordance with the method of the present invention from those of the original substances short way and with a high output can be obtained fluorine-containing compounds, such as diaziridine derivatives and compounds containing fluorinated vinyl groups at both ends of the molecule. In addition, when using the method of the present invention can be easily obtained low molecular weight fluorine-containing compounds, which are usually difficult to get well-known methods, or fluorine-containing compounds of complex structure. Furthermore, the method according to the present invention is not limited to the compounds disclosed in the above specific examples, and is a way, remarkable for its wide applicability and suitability for different compounds and can be easily obtained fluorine-containing compounds with the desired structure. In addition, by selecting the structure of RAand RInit is possible to carry out an effective way, in accordance with which the product is re-used.

In addition, according to the but the present invention a new intermediate compound that can be used as a starting raw material for production of fluoropolymers.

EXAMPLES

Hereinafter the present invention will be described in more detail with reference to examples. However, the present invention is in no way limited to these examples. Hereinafter gas chromatography indicated as GC, mass spectrometry coupled with gas chromatography as GC-MS. In addition, the purity, dened as the ratio of the peak areas on the chromatogram, denoted as GC purity, and purity is defined as the ratio of the peak areas NMR spectra indicated by NMR purity. For the quantitative analysis method19F-NMR as internal standard used performanta. In addition, tetramethylsilane was designated as TMS (TMS), and dichloropentafluoropropane as R-225, and as R-225 used AC, trade name of the company Asahi Glass Company, Limited. In addition, the NMR spectra are given for the visible interval of the chemical shifts. The default value for the standard substance CDCl3for13C-NMR set as 76,9 ppm

Example 1

Example 1-1. Example of getting CF3CF2COO(CH2)4OCOCF2CF3

BUT(CH2)4OH (200 g) was placed in a flask and stirred while passing nitrogen gas. Support is Eva internal temperature of 25 to 30° To add FCOCF2CF3(800 g) for 2.5 hours. After completion of adding dropwise continue stirring at room temperature for 15 hours, resulting in a separating funnel allocate the crude liquid. To this liquid add saturated aqueous solution of NaHCO3(500 ml) at an internal temperature of not more than 20°and double-neutralize. Then the organic phase is washed three times with water (1 l), and secrete the organic phase. After drying over magnesium sulfate are filtering and receiving untreated liquid.

The crude liquid purified column chromatography on silica gel (developer: R-225), after which the crude liquid concentrated with an evaporator, followed by distillation under reduced pressure, thus receive 254,79 g fraction 91-93°/1,0-1,3 kPa (absolute pressure). GC purity is 99%. In addition, the NMR spectrum of fraction confirms that the main component is the above-mentioned connection.

The NMR spectrum of fraction:

1H-NMR (300,4 MHz, solvent: CDCl3standard: S) δ (ppm): 1,85-1,89 (m, 4H), to 4.41 is 4.45 (m, 4H).

19F-NMR (282,65 MHz, solvent: CDCl3standard: CFCl3) δ (ppm): -83,0(6F), -121,4(4F).

Example 1-2: Example of getting CF3CF2Soo(CF2)4OCOCF2CF3

In the autoclave with a capacity of 300 ml, made of Nickel, is placed in R-113 (3232 g), stirred, maintaining the temperature of 25°C. At the gas outlet of the autoclave install the cooler, supported at the temperature of -10°C. After the filing of gaseous nitrogen for 1.5 hours serves gaseous fluorine, diluted to 20 vol.% nitrogen gas (hereinafter referred to as 20% gaseous fluorine), with a speed 8,49 l/h for 2.3 hours.

Then when applying 20% of fluorine gas at the same speed during 45.7 hours introduce a solution of the compound CF3CF2COO(CH2)4OCOCF2CF3(80 g), obtained in accordance with example 1-1, dissolved in R-113 (800 g). Then served 20% gaseous fluorine at the same speed for 0.5 hours, and then served gaseous nitrogen for 3.0 hours. The resulting product contains the above compound as the main product, the output data19F-NMR is 92%.

19F-NMR (376,0 MHz, solvent: CDCl3standard: CFCl3) δ (ppm): -83,8(6F), -87,3(4F), -122,6(4F), -126,4(4F).

Example 1-3: Example of getting FCOCF2CF2COF through the reaction of dissociation of the ester bonds in the liquid phase

Connection CF3CF2Soo(CF2)4OCOCF2CF3(5.0 g)obtained in example 1-2, put together with 0.4 g of NaF powder in a flask and heated at 100°C for 0.25 hour oil is th bath with vigorous stirring. In the upper part of the flask is placed a reservoir for gas collection. After cooling, the highlight of 3.46 g of a gaseous product. With the help of NMR spectra confirm that the main components are CF3CF2COF and the above connection. The output of the above compounds 52.4%.

19F-NMR (282,65 MHz, solvent: CDCl3standard: CFCl3) δ (ppm): 25,3(2F), -118,2(4F).

Example 2

Example 2-1. Example of getting TsOCH(CH3)CH2OCH2Ph

(where Ts represents a p-toluensulfonyl group, and Ph represents a phenyl group, and then used the same notation)

In chetyrehosnuju flask of NON(CH3)CH2OCH2Ph (50.0 g) and add pyridine (150 ml), followed by stirring. When cooled in a bath with ice while maintaining the internal temperature at 5°gradually over 1 hour add the acid chloride p-toluensulfonate acid (63,1 g). The mixture was added to water (165 ml) and to conduct extraction add dichloromethane (165 ml), then the liquid is divided into two layers separated. The organic layer was washed with NaHCO3(165 ml)and then washed three times with water (130 ml). Dried over magnesium sulfate, filtered and then concentrated using an evaporator. Precipitated precipitated white crystals are collected by filtration and washed with hexane, thus obtaining in sukasana connection (83,2 g).

1H-NMR (300,4 MHz, solvent: CDCl3standard: S) δ (ppm): 1,31 (d, J=6,3 Hz, 3H), 2.40 a (s, 3H), 3.46 in (m, 2H), to 4.41 (d, J=1,8gts, 2H), 4,73 (m, 1H), 7,19-7,34 (m, 7H), 7,75-7,89 (m, 2H).

Example 2-2: Example of a receipt(CH2)4OCH(CH3)CH2OCH2Ph

BUT(CH2)4OH (37 g), potassium hydroxide (23 g) and dioxane (200 ml) is placed in chetyrehosnuju flask and heated to the temperature inside the flask 102°in order to dissolve the potassium hydroxide. The solution TsOCH(CH3)CH2OCH2Ph (63.7 g)obtained in example 2-1, in dioxane (65 ml) is added dropwise over 1 hour and stirred for 4 hours. The mixture is allowed to cool, then poured into water (350 ml) and extracted three times with dichloromethane (100 ml). The organic layer was washed with water (20 ml). Dried over magnesium sulfate, filtered, and then concentrated by evaporation to obtain crude product (52 g). This product is purified column chromatography on silica gel, thus obtaining the above-mentioned compound (27,6 g).

1H-NMR (300,4 MHz, solvent: CDCl3standard: S) δ (ppm): 1,15 (d, J=6.2 Hz, 3H), of 1.64 (m, 4H), 2,98 (Sh.S., 1H), 3,62-3,68 (m, 7H), 4,53 (d, J=2,35Hz, 2H), 7.23 percent-7,29 (m, 5H).

Example 2-3: example of a receipt(CH2)4OCH(CH3)CH2OH

A round bottom flask rinsed with argon and download it powder 5% palladium-carbon (1.5 g). Add Aut ethanol (100 ml) and(CH 2)4OCH(CH3)CH2OCH2Ph (15.2 g), obtained according to example 2-2, then dearyou and rinsed with nitrogen. The mixture is stirred at room temperature for 17 hours and then filtered through zerit. The filtrate is concentrated by evaporation, thus obtaining the above-mentioned compound (8.65 g).

1H-NMR (300,4 MHz, solvent: CDCl3standard: S) δ (ppm): 1,11 (sq, J=6,2 Hz, 3H), by 1.68 (m, 4H), 2,48 (Sh.S., 2H), 3,41-3,68 (m, 7H).

Example 2-4: Sample receipt

CF3CF2COO(CH2)4OCH(CH3)CH2OCOCF2CF3

BUT(CH2)4OCH(CH3)CH2OH (18,8 g)obtained in example 2-3, placed in a round bottom flask and stirred, maintaining the temperature inside the flask at 30°C. Together with the nitrogen serves for 6 hours CF3CF2COF (276 g), keeping the temperature inside the flask at 30°C. After completion of the reaction, the stirring is continued for 2 hours at a temperature within the bulb 30°S, while the flow of nitrogen gas, and then add 5% aqueous solution of NaHCO3(300 ml) at an internal temperature of not more than 15°C.

The crude liquid is subjected to liquid separation. The bottom layer is washed twice with water (100 ml), dried over anhydrous magnesium sulfate, and then filtered, the floor is th untreated liquid. The crude liquid was subjected to purification column chromatography on silica gel (developer: R-225), while receiving the above-mentioned compound (25,9 g). GC purity is 99%.

1H-NMR (300,4 MHz, solvent: CDCl3standard: S) δ (ppm): 1,20 (d, J=6.3 Hz, 3H), 1.56 to~by 1.68 (m, 2H), 1,78~of 1.87 (m, 2H), 3,42~of 3.60 (m, 2H), 3,66~3,76 (m, 1H), 4.26 deaths~was 4.42 (m, 4H).

19F-NMR (282,7 MHz, solvent: CDCl3standard: CFCl3) δ (ppm): -83,0(3F), -83,0(3F), -121,4(2F), -121,5(2F).

Example 2-5: Sample receipt

CF3CF2COO(CF2)4OCF(CF3CF2OCOCF2CF3

In the autoclave with a capacity of 500 ml, made of Nickel, is placed in R-113 (313 g), stirred, maintaining the temperature at 25°C. At the gas outlet of the autoclave set consistently cooler, supported at the temperature of 20°s With the nozzle with the NaF pellets and cooler, supported at the temperature of -10°C. Then install the return line fluid for returning the liquid condensed from the cooler, supported at the temperature of -10°C in the autoclave. After supplying gaseous nitrogen for 1.0 hour serves 20% of the gaseous fluorine with the speed 10,10 l/h for 1.1 hours. Then when applying 20% of fluorine gas at the same rate for 5.5 hours enter solution connection

CF3CF2COO(CH2)4OCH(CH3)CH2OCOCF2 3(4,95 g)obtained according to example 2-4, dissolved in R-113 (100 g).

After that, feeding 20% gaseous fluorine with the same speed, the temperature in the reactor increases from 25°C to 40°C, and at the same time, introduce a solution of R-113 (9 ml)containing 0.01 g/ml of benzene. The insertion opening for benzene and the outlet valve of the autoclave is closed, and when the pressure reaches of 0.20 MPa (gauge pressure), the inlet valve for gaseous fluorine close. Thereafter, stirring is continued for 0.4 hours. Then the pressure in the reactor was returned to normal pressure, and maintaining the temperature at 40°C, enter the above benzene solution (6 ml). The operation of closing the entry opening of benzene and the outlet valve of the autoclave and closing of the inlet valve for gaseous fluorine, when the pressure reaches of 0.20 MPa (gauge pressure), followed by stirring for 0.4 hours, repeat four times.

The total number of benzene is 0,336 g, and the total number of entered R-113 is 33 ml. in Addition, nitrogen gas serves over 1.5 hours. The output of the above compounds contained in the product, according to the19F-NMR is 94%.

19F-NMR (376,0 MHz, solvent: CDCl3standard: CFCl3) δ (ppm): -80,4(3F), -81,0(2F), -83,3(3F), -83,4(3F), -86,8(2F), -86,9(2F), -122,1(4F), -125,92F), -126,2(2F), -145,6(1F).

Example 2-6: Example of getting FCOCF(CF3)O(CF2)3COF through the reaction of dissociation of the ester bonds in the liquid phase

Connection CF3CF2COO(CF2)4OCF(CF3CF2OCOCF2CF3(0.6 g)obtained in example 2-5, put together with NaF powder (0.008 g) in a flask and heated at 100°for 5,66 hours on an oil bath with vigorous stirring. In the upper part of the flask is collected liquid compound (0.65 g) through the reflux condenser adjusted to a temperature of 90°C.

With the help of NMR spectra confirmed that the main component is the above-mentioned connection. The output is 77,1%.

19F-NMR (376 MHz, solvent: CDCl3standard: CFCl3) δ (ppm): 26,5(1F), 25,0(1F), -78,3~-78,8(1F), -82,1(3F), -86,0~-86,4(1F), -118,5(2F), -126,6(2F), -131,0(1F).

Example 3

Example 3-1. An example of obtaining NON2CH(CH3)O(CH2)5HE

The flask CH3CH(OH)CH2Och2Ph (50,0 ml) and pyridine (150 ml) and cooled with ice add the acid chloride p-toluensulfonate acid (63,2 g) for 30 minutes. The mixture is stirred at room temperature for 4 days, after which add water (150 ml), followed by extraction twice with dichloromethane (100 ml). Extracted liquid phase is washed twice with a saturated aqueous solution of knso3(100 ml), and d is every water (100 ml), dried over magnesium sulfate, filtered and then concentrated, while receiving PhC2Och2CH(CH3)OTs (71,2 g).

In another flask CON (25,8 g), BUT(CH2)5HE (47.9 g) and dioxane (200 ml) and stirred at 90°until then, until you dissolve the KOH. Then, using a dropping funnel add PhC2Och2CH(CH3)OTs (71,2 g) and dioxane (75 ml) at 90°C for 20 minutes. After additional stirring at 80°C for 20 minutes add water (350 ml). Extraction with dichloromethane (100 ml) was performed three times, and the extracted organic phase is washed with water (150 ml), then dried over anhydrous magnesium sulfate, filtered and then concentrated. Concentrated liquid purified using column on silica gel (eluent: hexane/ethyl acetate), while receiving PhC2Och2CH(CH3)O(CH2)5HE (20,8 g).

The flask powder 5% palladium-carbon (4 g) and ethanol (200 ml) and serve within 1 hour of nitrogen. The contents of the vacuum and rinsed with hydrogen, and then added with a syringe PhC2Och2CH(CH3)O(CH2)5HE (18 ml) and stirred for 24 hours. The crude liquid was filtered and concentrated, thus obtaining the above-mentioned compound (11.9 g).

Example 3-2: sample receipt

CF3CF2CF2OCF(CF3)COCH 2CH(CH3)O(CH2)5OCOCF(CF3)OCF2CF2CF3

NON2CH(CH3)O(CH2)5HE (11.8 g), obtained in accordance with example 3-1, placed in a flask, add as acceptor HF ethylamine (30,3 g) and stirred. Maintaining the temperature inside the flask is not more than 15°C for 1 hour, added dropwise CF3CF2CF2OCF(CF3)COF (49,8 g). After completion of adding dropwise, the mixture is stirred at room temperature for 2 hours and distilled off the excess CF3CF2CF2OCF(CF3)COF under reduced pressure. The product is washed with water (50 ml) and then washed three times with 0.1 N. aqueous solution of hydrochloric acid (30 ml) to remove the remaining triethylamine. Then the organic layer washed three times with saturated aqueous solution of knso3(30 ml), dried over magnesium sulfate and then filtered, thus obtaining a liquid (53,0 g)having a GC purity of 97%.

The NMR spectrum confirms that the main components are the above product and the mixture of diastereomers.

1H-NMR (300,4 MHz, solvent: CDCl3standard: S) δ (ppm): 1,19 (d, J=6.3 Hz, 3H), 1,39-1,49 (m, 2H), 1,54-to 1.63 (m, 2H), 1,71 and 1.80 (m, 2H), 3,39-of 3.53 (m, 2H), 3,66-and 3.72 (m, 1H), 4,21-to 4.46 (m, 4H).

19F-NMR (282,7 MHz, solvent: CDCl3standard: CFCl3) δ (ppm): -80,9(2F), -82,3(6), -83,1(6F), -87,4(2F), -130,7(4F), -132,7(2F).

Example 3-3: example of getting

CF3(CF2)2OCF(CF3)COOCF2CF(CF3)O(CF2)5OCOCF(CF3)OCF2CF2CF3

In the autoclave with a capacity of 500 ml, made of Nickel, is placed in R-113 (312,2 g) and stirred, regulate the internal temperature of up to 25°C. At the gas outlet of the autoclave set consistently cooler, supported at a temperature of 25°s With the nozzle with the NaF pellets and cooler, supported at a temperature of -8°C. Then install the return line to the fluid in order to return the liquid condensed from the cooler, supported at a temperature of -8°C in the autoclave. After feeding nitrogen gas for 1 hour serves 20% of the gaseous fluorine with the speed of 11.0 l/h for 1 hour. Then, when applying the same speed, within 6 hours of the injected liquid product (10 g), obtained in accordance with example 3-2 dissolved in R-113 (200 g).

Thereafter, the internal temperature was raised to 40°and when applying 20% of fluorine gas with the above speed enter solution of benzene in R-113 (0.01 g/ml). The outlet valve of the autoclave is closed, and when the pressure reaches of 0.20 MPa (gauge pressure), the intake valve closes and continue stirring for 20 minutes. Then the same operation is repeated five RA is. During this period enter the benzene in the total quantity amounting to 0.27 g, and R-113 in the total number 42,1, then nitrogen gas serves over 1 hour and the reaction mixture is separated by decantation. The crude liquid concentrate through the evaporator and subjected to quantitative analysis, the yield according to the19F-NMR is 70%. The crude liquid is distilled under reduced pressure, thus obtaining the above-mentioned connection. The product is a mixture of diastereomers.

19F-NMR (282,7 MHz, solvent: CDCl3/C6F6standard: CFCl3) δ (ppm): -79,2~-80,7(7F), -81,5~-82,0(12F), -85,9~-87(6F), -122,4(2F), -125,3(4F), -129,6(4F), -131,4(2F), -144,9(1F).

Example 3-3: example of getting FCOCF (CF3)O(CF2)4COF

The product (5 g), obtained according to example 3-2, placed in a flask with a capacity of 30 ml, equipped with a reflux condenser at 80°and add potassium fluoride (0.06 g), followed by heating at 150°and mixing the cooled produced gas to -78°and collected in a glass trap. After the interaction and all the liquid from the bulb will disappear, the reaction ceased. In a glass trap obtain 4.8 g of the product.

According to GC analysis confirmed that formed CF3CF2CF2OCF(CF3)COF and FCOCF(CF3)O(CF2)4COF the ratio of 2:1 (molar ratio).

Example 3-4: example of getting CF2=FCF2CF2CF=CF2through pyrolysis

In the same way as in the method described in J. Org. Chem., 34, 1841 (1969), carry out pyrolysis, using FCOCF(CF3)O(CF2)4COF obtained by the reaction described in example 3-3, the formation of the above compounds is confirmed by the GC method.

Example 4

Example 4-1: Example of getting CF3CF2COO(CH2)2O(CH2)2OCOCF2CF3the reaction of esterification

BUT(CH2)2O(CH2)2HE (40 g) was placed in a flask and stirred, maintaining the temperature in the flask at 30°C. Maintaining the temperature in the flask at 30°serves nitrogen and CF3CF2COF (388 g) for 1.5 hours. After completion of the reaction, by gaseous nitrogen, continue mixing at a temperature within the bulb 30°C for 2 hours, after which the temperature inside the flask was adjusted to not more than 15°With, then add 5% NaHCO3(300 ml).

The crude liquid is subjected to liquid separation, and the lower layer is washed twice using 100 ml of water, dried over magnesium sulfate, then filtered, thus obtaining the crude liquid. By distillation under reduced pressure to obtain the above compound (91,8 g) in the form of fractions 81-84°C/1,3 kPa (absolute is the amount of pressure). GC purity is 99%.

1H-NMR (300,4 MHz, solvent: CDCl3standard: S) δ (ppm): of 3.77~of 3.80 (m, 4H), 4,50~a 4.53 (m, 4H).

19F-NMR (282,7 MHz, solvent: CDCl3standard: CFCl3) δ (ppm):-83,0(6F), -121,6(4F).

Example 4-2: Example of getting CF3CF2COO(CF2)2O(CF2)2OCOCF2CF3the fluorination reaction

In the same autoclave as in example 2-5, add R-113 (312 g), and the synthesis is carried out in the same conditions, except that 20% of gaseous fluorine served with speed for 9.47 l/h for 1 hour. Then when applying 20% of fluorine gas at the same speed, for 4.9 hours introducing the solution containing the compound CF3CF2COO(CH2)2O(CH2)2OCOCF2CF3(7.0 g)obtained in example 4-1, dissolved in R-113 (140 g).

After that, feeding 20% gaseous fluorine with the same speed and maintaining the pressure in the reactor at the level of 0.15 MPa (gauge pressure)in the reactor enter a solution of R-113 (9 ml)containing 0.01 g/ml benzene, increasing the temperature from 25°C to 40°and a valve for entry of benzene cover, and continue stirring for 0.3 hour. Then, while maintaining the reactor pressure 0.15 MPa (gauge pressure) and the temperature at 40°enter the above benzene solution (6 ml) and stirred for 0.3 hours Later, maintaining the temperature in the reactor 40°enter the above benzene solution (6 ml) and stirred for 1.1 hours, and serves gaseous nitrogen for 1.0 hour. The output of the above compounds contained in the product, according to the19F-NMR is 94%.

19F-NMR (376,0 MHz, solvent: CDCl3standard: CFCl3) δ (ppm):-83,4(6F), -88,8(4F), -92,2(4F), -122,2(4F).

Example 4-3: example of getting FCOF2OCF2COF through the reaction of dissociation of the ester bonds in the liquid phase

Connection CF3CF2COO(CF2)2O(CF2)2OCOCF2CF3(6.0 g)obtained in example 4-2, put together with NaF powder (0.09 g) in a flask and heated at 100°C for 5 hours on an oil bath with vigorous stirring. In the upper part of the flask consistently set the reflux condenser adjusted to a temperature of 20°and fluoropolymer container to collect the gas. After cooling allocate 0.5 g of a liquid substance and 5.4 g of gaseous product. Data analysis GC-MS confirmed that the gaseous product contains CF3CF2CF and the above compound as main components. Determine the output of the above compounds, which, as found, is 85.6%.

Example 5

Example 5-1.: Example retrieve

BUT(CH2)2O(CH )2Och(CH3)CH2Och2Ph

BUT(CH2)2O(CH2)2HE (21.2 g), potassium hydroxide (11.2 g) and dioxane (100 ml) is placed in chetyrehosnuju flask and heated to the temperature inside the flask, 63°to dissolve the potassium hydroxide. A solution obtained by dissolving 32,0 g TsOCH(CH3)CH2OCH2The Ph obtained in accordance with example 2-1, in dioxane (50 ml)is added dropwise within 30 minutes while maintaining the internal temperature from 60 to 100°C, the stirring is continued for 13.5 hours. The mixture is allowed to cool, then poured into water (200 ml) and extracted three times with dichloromethane (50 ml). The organic layer was washed with water (20 ml). Dried over magnesium sulfate, filtered and then concentrated using an evaporator, thus obtaining the crude product (52 g). This product is purified column chromatography on silica gel, thus obtaining to 9.32 g of the above compound.

1H-NMR (300,4 MHz, solvent: CDCl3standard: S) δ (ppm): 1,17 (d, J=6.3 Hz, 3H), 2,8 (Sh.S., 1H), 3,40-to 3.52 (m, 2H), to 3.58-to 3.73 (m, 7H) of 4.54 (m, 2H), 7,26-7,34 (m, 5H).

Example 5-2: Example of a receipt(CH2)2O(CH2)2Och(CH3)CH2HE

A round bottom flask rinsed inside with argon and download it powder 5% palladium-carbon (0.9 g). Add ethanol (50 ml) and the compound(CH2 )2O(CH2)2Och(CH3)CH2Och2Ph (of 9.21 g)obtained according to example 5-1, then dearyou and rinsed with hydrogen. The mixture is stirred at room temperature for 17 hours and then filtered through zerit. The filtrate is concentrated using an evaporator, while receiving the 5.45 g of the above compound.

1H-NMR (300,4 MHz, solvent: CDCl3standard: S) δ (ppm): 1,13 (d, J=6.2 Hz, 3H), 3,20~3,82 (m, 11N).

Example 5-3: Example of a

CF3CF2COO(CH2)2O(CH2)2Och(CH3)CH2OCOCF2CF3

Connection BUT(CH2)2O(CH2)2Och(CH3)CH2HE (5,1 g)obtained in example 5-2, and chloroform (10 g) are loaded into a flask and stirred, maintaining the temperature inside the flask at 30°C. Together with the nitrogen serves CF3CF2COF (191 g), keeping the temperature inside the flask at 30°C. After completion of the interaction, when the gaseous nitrogen stirring is continued at an internal temperature of 30°C for 2 hours, then add 5% aqueous solution of NaHCO3(30 ml) at a temperature within the bulb is not more than 15°C.

The crude liquid is subjected to liquid separation and purified column chromatography on silica gel (developer: R-225), while receiving in sukasana compound (5.0 g). GC purity is 99%.

1H-NMR (300,4 MHz, solvent: CDCl3standard: S) δ (ppm): to 1.21 (d, J=6.6 Hz, 3H), to 3.58~3,81 (m, 7H), to 4.33 (d, J=5.4 Hz, 2H), 4,50~a 4.53 (m, 2H).

19F-NMR (282,7 MHz, solvent: CDCl3standard: CFCl3) δ (ppm): -82,96(3F), -82,99(3F), -121,46(2F), -121,53(2F).

Example 5-4: Sample receipt

CF3CF2COO(CF2)2O(CF2)2F(CF3CF2OCOCF2CF3

In the same autoclave as in example 2-5, add R-113 (312 g) and the synthesis is carried out in the same conditions, except that 20% of gaseous fluorine served with speed 12,72 l/h for 1 hour.

Then when applying 20% of fluorine gas at the same speed, for 3.9 hours introducing the solution containing the compound CF3CF2COO(CH2)2O(CH2)2Och(CH3)CH2OCOCF2CF3(5.0 g)obtained in example 5-3, dissolved in R-113 (100 g).

After that, feeding 20% gaseous fluorine with the same speed and maintaining the pressure in the reactor at the level of 0.15 MPa (gauge pressure), the temperature was raised from 25°C to 40°and at the same time, introduce a solution of R-113 (9 ml)containing 0.01 g/ml of benzene. The inlet valve of the autoclave to enter benzene cover and continue stirring for 0.3 hour. Then, while maintaining the pressure in the reactor at the level of 0.15 MPa (gauge giving the group) and the temperature at 40° To enter the above-mentioned benzene solution (6 ml) and stirring is continued for 0.3 hour. Next, the operation of introducing the benzene solution (6 ml) and stirring for 0.3 hour is repeated four times in the same conditions, after which stirring is continued for 0.7 hour. Then, nitrogen gas serves for 1 hour. The output of the above compounds contained in the product, according to the19F-NMR is 89%.

19F-NMR (376,0 MHz, solvent: CDCl3standard: CFCl3) δ (ppm): -80,5(3F), -83,4(6F), -85,9~-87,5(4F), -89,0(4F), -92,3(2F), -122,3(4F), -145,6(1F).

Example 5-5: example of getting FCOF2O(CF2)2OF(CF3)COF

Connection CF3CF2COO(CF2)2O(CF2)2F(CF3CF2OCOCF2CF3(5,1 g)obtained in example 5-4, put together with 0.09 g of KF powder in a flask and heated at 40°C for 2 hours on an oil bath with vigorous stirring. In the upper part of the flask consistently set the reflux condenser adjusted to a temperature of 20°and fluoropolymer container to collect the gas. After cooling secrete a liquid substance (3.2 g) and gaseous (1.6 g). Data analysis GC-MS confirmed that the gaseous substance as the main product contains CF3CF2CF, and the liquid substance contains vishey the above compound as the main product. The output of the above compounds contained in the product, according to the19F-NMR is 92%.

19F-NMR (376,0 MHz, solvent: CDCl3standard: CFCl3) δ (ppm): 26,7(1F), 14,6(1F), -77,2(2F), -82,0(3F), -84,2(1F), -88,2(2F), -91,3(1F), -131,0(1F).

Example 6: an example obtaining the FCO(CF2)2CF

In the autoclave with a capacity of 3000 ml, made of Nickel, is placed in R-113 (2767 g), stirred and support at a temperature of 25°C. At the gas outlet of the autoclave set consistently cooler, supported at the temperature of 20°s With the nozzle with the NaF pellets and cooler, supported at the temperature of -10°C. Then install the return line to the fluid in order to return the liquid condensed from the cooler, supported at the temperature of -10°C in the autoclave. After the gaseous nitrogen supply for 2.3 hours serves gaseous fluorine diluted with nitrogen gas up to 50% (hereinafter referred to as 50% gaseous fluorine) with a speed 7,79 l/h for 3 hours. Then when 50% of fluorine gas at the same speed for 6.0 hours injected as the first fluorination solution of the compound CF3CF2COO(CH2)4OCOCF2CF3(25,0 g)obtained in accordance with example 1-1, R-113 (250,2 g), and discharge of the product of the reaction, the crude liquid (241,1 g, the output data19 F-NMR: 51%). The second fluorination is conducted in the same manner as the first fluoridation, and discharge of the product of the reaction, the crude liquid (241,0 g, the output data19F-NMR: 83%). Then spend the third fluoridation in the same way as the first fluoridation, and output a product of the reaction, the crude liquid (240,9 g, the output data19F-NMR: 89%). After that submit gaseous nitrogen for 1.8 hours, and output a product of the reaction, the crude liquid (2804,4 g, the output of the above compounds according to the19F-NMR: 86%).

Based on the above connection, carry out the reaction in the same manner as in example 1-3, and get FCO(CF2)2COF.

Industrial applicability

In accordance with the method of the present invention can be obtained a compound useful as a raw material for production of various fluoropolymers with high yield when making short-term process through the use of inexpensive and readily available starting materials. In addition, according to the present invention, a new compound useful as a raw material for production of fluoropolymers. The method of the present invention is a method that is extremely easy to use and can be used to obtain various compounds using readily available source of washes the century Also, when using the method of the present invention can be obtained well-known connection cost-effective way and it is possible to make a variety of new fluorinated compounds.

1. A method of obtaining a fluorine-containing compounds, including interaction of the following compounds (1) with the following compound (2) obtaining thus the following compounds (3) (provided that the compound (3) is a compound in which the fluorine content is at least 30 wt.%, and is a hydrogen atom or an unsaturated bond, which may be fluorinated), the fluorination of the compound (3) in the liquid phase with obtaining thus the following compounds (4), with subsequent cleavage reaction of group EFcompounds (4) and obtaining this 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)

RBF-EF2(6), where

RAFrepresents a fluorine-containing bivalent saturated hydrocarbon group, linear or branched, optionally containing halogen other than fluorine, and optionally containing one or more atoms sour is kind of simple ether

RAis a group, which is the same as RAFor represents a bivalent organic group which can be converted into the group RAFthe fluorination reaction,

RBFrepresents a fluorine-containing monovalent saturated hydrocarbon group, linear or branched, optionally containing halogen other than fluorine, and optionally containing one or more oxygen atoms of simple ether or carbonyl,

RBis a group, which is the same as RFor represents a monovalent organic group which can be converted into the group RFthe fluorination reaction,

E1and E2are such that if E1represents-CH2HE or Q1-CH2HE then E2is a-YEAR-or-SO2X if E2represents-CH2HE or Q2-CH2HE then E1is a-YEAR-or-SO2X, where X represents a halogen atom, and Q1and Q2may be the same or different and represent-CH(CH3)- or-CH2CH2-and

E represents a group-CH2OCO- , -CH2SO2-, -Q1-CH2OCO-, -Q2CH 2OCO-, -Q1-CH2S2-, -Q2-CH2S2-,

EFis a group, which is the same as E, or represents a group obtained by fluorination of group E, provided that at least one group selected from RAF,RBFand EF, is a group formed in the fluorination,

EF1EF2represent groups resulting from cleavage of the group EF.

2. The method according to claim 1 in which the compound (1) is the following compound (1-1), compound (2) is the following compound (2-1), the compound (3) is the following compound (3-1), the compound (4) is the following compound (4-1), the cleavage reaction EFrepresents the reaction of cleavage of the ester bonds of the compound (4-1), the compound (5) is the following compound (5-1), the compound (6) is the following compound (6-1):

where

RA, RB, RAFand RBFsuch as defined above,

X is a halogen atom.

3. The method according to claim 2, in which the compound (2-1) is used to partially or fully the compound (6-1).

4. The method according to claim 1 in which the compound (1) is predstavljaet a following compound (1-2), the compound (2) is the following compound (2-1), the compound (3) is the following compound (3-2), the compound (4) is the following compound (4-2), the cleavage reaction EFrepresents the reaction of cleavage of the ester bonds of the compound (4-2), the compound (5) is the following compound (5-2), the compound (6) is the following compound (6-1):

where

RA, RB, RAFand RBFsuch as defined in claim 1,

X is a halogen atom,

Q1and Q2are the same and represent-CH(CH3)- or

-CH2CH2-and

QF1represents a group corresponding to Q1; QF2represents a group corresponding to Q2and each represents-CF(CF3)- or-CF2CF2-.

5. The method according to any one of claims 1 to 4, in which the number of carbon atoms in RBFis 2-20.

6. The method according to claim 1, wherein the fluorine content in the compound (1) is 0 wt.%, molecular weight is not more than 200, the connection (3) the content of fluorine is 30-76 wt.% and molecular weight is more than 200 and not more than 1000.

7. The method according to claim 1, wherein the fluorination in the liquid phase is conducted through the your fluoridation fluoride in a solvent.

8. A compound selected from compounds of the following formulas:

Priority points and features:

11.07.2000 - according to claims 1-3, 5, 6, 7 and 8 for connection (3-12), (3-13), (4-12) and (4-13);

27.09.2000 - on item 4 and item 8 for connection (4-15);

05.04.2001 - item 8 for connections (3-14), (4-14);

11.07.2001 - item 8 for connections (3-15), (3-16), (4-16)and (5-16).



 

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