Fluorinated ester compound preparation method

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to industrially useful fluorine-containing compounds such as fluorinated ester compounds and acyl fluoride compounds. Invention, in particular, provides ester compound wherein all C-H groups are fluorinated and which is depicted by general formula RAFCFR1FOCORBF (4), where RAF, CFR1, and RBF are specified elsewhere. Preparation of the ester compound comprises fluorination of ester (4), which has hydroxyl group(s), acyl fluoride group(s) and which has a structure allowing compound to be fluorinated in liquid phase, fluorination being effected in mixture of ester compound and compound having acyl fluoride group(s). Method does not involve environmentally unfriendly solvent such as, for instance, R-113.

EFFECT: enabled fluorination requiring no specific solvent for each reaction and which can be carried out without separation of solvent before next stage.

9 cl, 8 ex

 

Description

The technical field

The present invention relates to a method for industrially useful fluorine-containing compounds, such as fluorinated ester compound and ftorangidridy connection.

Prior

Fluorinated ester compound and a hydrocarbon compound, in which all group C-H f to C To F, can be used, for example, as the predecessor of the fluoropolymer material. As a method of fluorination of hydrocarbon compounds containing C-H, there is a method using cobalt TRIFLUORIDE, the method of direct fluorination using fluorine (F2and the way, in the exercise of which the fluorination reaction is conducted by the electrolysis of hydrogen fluoride in the cell (hereinafter in the description called as a way ECF).

In the case of the reaction of fluorination using fluorine in a liquid phase, usually as a reaction solvent for the formation of a liquid phase is used a solvent which does not react with fluorine, but dissolves the fluorine (such as a solvent consisting of performanceline). As the reaction solvent used in the traditional way, can be called harperperennial solvent, such as CCl2FCClF2(later in description is identified as R-113), or typical fluorinated solvent, such as a fluorocarbon or a simple harpertrophy (JP-A-4-500520). Among these solvents, the chlorofluorocarbon has the potential to Deplete the ozone layer, therefore, its production is limited and in the future it will no longer fit. In addition, the hydrocarbon compound used as a substrate in the reaction of fluorination, in many cases, has a low solubility in the solvent, resulting in the fluorination reaction is carried out at an excessively low concentration, which leads to the problem associated with low productivity, or to the problem arising from the fact that the reaction is carried out in a suspension system, which is unfavorable for the reaction.

Description of the invention

The applicant of the present invention found that in the case of obtaining complex perforator capable of developing, for example, in the original monomer fluorocarbon resin, such as a simple PERFLUORO(alkylvinyl ether), due to the reaction of fluorination in the liquid phase, the reaction process will be very effectively carried out without difficulty, such as a reduction of the yield of the reaction of fluorination, when using the ester compound and allford corresponding to the structure of the ester compounds. In private the tee, the applicant has found that when the substrate in the reaction of fluorination is used partially fluorinated ester having a specific structure, the solubility of the substrate in the liquid phase tends to increase volumetric productivity tends to increase and the reaction process is simplified, and when the fluorination reaction is carried out in the form of a liquid mixture perforaciones corresponding to the structure of the partially fluorinated ether complex, you can make more efficient the reaction process. The present invention provides the following methods:

1. A method of obtaining a fluorinated ester compounds, including fluoridation ester compound that is an ester compounds having hydroxyl(s) group(s), connection with allforyou(s) group(s), and which has a structure which can be fluorinated in a liquid phase, to obtain the fluorinated ester compound, where the fluorination is carried out in the form of a liquid mixture of ester compounds and compounds having allforyou(s) group(s).

2. The above method, in which the ester compound is a compound obtained by esterification of the compounds having hydroxyl(s) group(s), and connections, imeushih allforyou(s) group(s).

3. The above method in which the liquid mixture of the ester compounds and compounds having allforyou(s) group(s), obtained by esterification using compounds having allforyou(s) group(s), where the number of connections that have allforyou(s) group(s), more than the stoichiometric quantity required for the esterification of all hydroxyl groups in the compound having the hydroxyl(s) group(s), and the number is so, in which unreacted compound with allforyou(s) group(s)remains in the reaction product.

4. The above method, in which the ester compound is a compound (3)below, a compound that allforyou(s) group(s), represents the connection (2)below, and fluorinated ester compound is a compound (4)below:

FCORBF(2)

RACHR1OCORBF(3)

RAFCFR1FOCORBF(4)

where each of RAand RAFthat may be the same or different, represents a monovalent organic group, and when RAand RAFdiffer from each other, RAFis a monovalent organic group obtained by fluorination of RA. RBFrepresents a monovalent saturated organic PERFLUORO is the RUPE. R1represents a hydrogen atom or monovalent organic group. R1Frepresents a fluorine atom when R1represents a hydrogen atom when R1represents a monovalent organic group, each of R1and R1Fthat may be the same or different, is a monovalent organic group, and when R1and R1Fdiffer from each other, R1Frepresents a monovalent organic group obtained by fluorination of R1.

5. The above method in which the liquid mixture of the compound (3) and compound (2) is a reaction product obtained by the interaction of the compound (1)below with a compound (2)taken in excess relative to the compound (1):

RACHR1OH (1)

where RAand R1are as defined above.

6. The method of obtaining the compound (5), below, and/or the following compounds (2)below, including the reaction of dissociation of the ester bonds in the compound (4)obtained above:

RAFCOR1F(5)

RBFCOF (2),

where RAFand R1Fare as defined above.

7. The above method in which the reaction of dissociation of the ester bonds of the compound (4) is carried out in the form of a liquid mixture of compound (2) and compound (4)obtained the second fluorination reaction liquid mixture of compound (3) and compounds (2).

8. The above method in which the reaction of dissociation of the ester bonds carried out without added solvent other than the compounds (2)to a liquid mixture of compound (4) and compounds (2).

9. As mentioned above, the way in which some or all of the compound (2)obtained above, or, when R1Fis a fluorine atom, a part or all of the connection (5) and/or compound (2) used as compounds (2) to interact with compound (1).

10. The above method, in which RAFand RBFrepresent groups having the same structure.

11. As mentioned above, the way in which the fluorination in the liquid phase carried out by reaction with fluorine in a liquid phase.

12. As mentioned above, the way in which the fluorination in the liquid phase is carried out in the absence of a solvent other than the compound (2).

The best option of carrying out the invention

In the present description organic group is a group in which significant are carbon atoms, and it may be a saturated group or an unsaturated group. Atom which may be substituted by fluorine, may be a hydrogen atom connected to the carbon.

Atomic group which may be substituted by fluorine, may be, for example, carbon-carbon unsaturated double bond or carbon-carbon unsaturated tro is Noah communication. For example, in the case where the organic group is a carbon-carbon double bond, a fluorine attached to carbon-carbon double bond by fluorination in the liquid phase with the formation of carbon-carbon simple communication. In addition, in the case when the organic group is a carbon-carbon triple bond, a fluorine attached to carbon-carbon triple bond by fluorination in the liquid phase with the formation of carbon-carbon simple communication and carbon-carbon double bond. Saturated organic group, also represents a group having as a carbon-carbon bonds in the group only a simple connection.

As the monovalent organic group preferred group selected from monovalent hydrocarbon groups, monovalent hydrocarbon groups containing a heteroatom, halogenated monovalent hydrocarbon groups and halogenated (monovalent hydrocarbon containing a heteroatom) group, and when the monovalent organic group is a saturated group, from among the above preferred groups is a saturated group. From the standpoint of solubility in the liquid phase used during the fluorination reaction, the organic group has the number of carbon atoms equal predpochtitel is about from 1 to 20, particularly preferably from 1 to 10.

The hydrocarbon group may be an aliphatic hydrocarbon group or aromatic hydrocarbon group, preferred is an aliphatic hydrocarbon group. In addition, in the aliphatic hydrocarbon group as a carbon-carbon bond may be a simple bond, a double bond or a triple bond. Aliphatic hydrocarbon group may be any of a linear structure, a branched structure, a cyclic structure and a structure with a partially cyclic structure.

Monovalent saturated organic group preferably represents a monovalent saturated hydrocarbon group. Monovalent saturated hydrocarbon group may be an alkyl group, and its structure can be any linear structure, a branched structure, a cyclic structure and a structure, which is partially circular.

The number of carbon atoms in the alkyl group is preferably from 1 to 20, particularly preferably from 1 to 10. An alkyl group having a linear structure may be, for example, methyl group, ethyl group, through group or butilkoi group. An alkyl group having a branched structure may be, for example, ISO-propyl group, isobutylene group, the EOS-butilkoi group or tert-butilkoi group. An alkyl group having a cyclic structure may be, for example, cycloalkyl group, bicycloalkyl group or a group having the alicyclic spirotrichous, it preferably represents a 3-6-membered cycloalkyl group and may be, for example, cyclopentyloxy or tsiklogeksilnogo group.

An alkyl group containing a cyclic portion may be an alkyl group (a linear structure or a branched structure), substituted by the above alkyl group having the above-mentioned cyclic structure, or a group having a cyclic portion in the alkyl group, optionally substituted alkyl group (a linear structure or a branched structure). Preferred is a group having at least one hydrogen atom in the alkyl group, substituted 3-6-membered cycloalkyl group, and particularly preferred, for example, cyclopentylmethyl group, cyclohexylethyl group and ethylcyclohexylamine group. As the other group can be called an alkyl group having an aromatic ring (for example, kalkilya group, such as benzyl or penicilina group), or an alkyl group having a heterocyclic ring (for example, pyridylmethylene or purpurella group).

The halogen atom in the halogenated group performance is to place a fluorine atom, the chlorine atom, bromine atom or iodine atom, and preferred is a fluorine atom, a chlorine atom or a bromine atom, and, from the point of view of usefulness of the compounds, particularly preferred fluorine atom or a fluorine atom and a chlorine atom.

In the present description halogenoalkane means replacing at least one hydrogen atom by a halogen atom. Incomplete halogenoalkane means replacing part of the hydrogen atoms by halogen atoms. Thus, in a partially halogenated group is a hydrogen atom. Perhalogenated means that galogenirovannyie all hydrogen atoms. Therefore, in perhalogenated group, a hydrogen atom is absent. The specified values of the terms "halogenoalkane", "incomplete halogenoalkane and perhalogenated" such values in the case where the halogen atom precisely defined.

Halogenated saturated hydrocarbon group is a group having at least one hydrogen atom present in the above-mentioned saturated hydrocarbon group substituted by a halogen atom. In halogenated saturated hydrocarbon group may be present or may not be a hydrogen atom. As the halogen atom in the halogenated saturated hydrocarbon group is preferable fluorine atom, a chlorine atom or a fluorine atom and a chlorine atom.

Partly halo is emirovna saturated hydrocarbon group is a group, with part of the hydrogen atoms present in the above-mentioned saturated hydrocarbon group, substituted by halogen atoms. In a partially halogenated saturated hydrocarbon group is a hydrogen atom.

Perhalogenated saturated hydrocarbon group is a group where all saturated hydrocarbon group, the hydrogen atoms replaced by halogen atoms. In perhalogenated saturated hydrocarbon group, the hydrogen atoms are missing. Present in the halogenated group or perhalogenated group, the halogen atoms may be the same or at least two kinds.

Halogenated saturated hydrocarbon group may be linear or branched structure, a cyclic structure or a structure having a circular part. The number of carbon atoms in halogenated monovalent saturated hydrocarbon group is preferably from 1 to 20. Halogenated monovalent saturated hydrocarbon group may be, for example, alkyl fluoride group or a fluoro(partially chlorinated)alkyl group.

Perhalogenated monovalent saturated hydrocarbon group preferably represents performanceline group or a (partially chlorinated alkyl) performgroup (i.e. group all of the hydrogen atoms is toroi in a partially chlorinated alkyl group, fluorinated). In addition, (partially fluoro-substituted alkyl) performgroup is the same as performanceline group, and (partially fluorinated Allenova) performgroup is the same as performanceheavy group.

Containing heteroatom saturated hydrocarbon group is a group that includes a heteroatom such as oxygen atom, nitrogen or sulfur, carbon atoms and hydrogen atoms. The heteroatom may be a heteroatom as such or it can represent heteroatomic group having heteroatoms or heteroatom and another atom associated with each other. Each of the heteroatoms and heteroatomic groups is preferably not subjected to transformations in reactions of pyrolysis. The heteroatom can be, for example, the oxygen atom in a simple ether (C-O-C) or =O and particularly preferred oxygen atom in a simple ether. The number of carbon atoms in the containing heteroatom saturated hydrocarbon group is preferably from 1 to 20. As containing heteroatom saturated hydrocarbon group, a group having a divalent heteroatom, or a divalent heteroatomic groups inserted between carbon-carbon bond of the above saturated hydrocarbon group, preferred is a group having a heteroatom associated with carbon atom in the above saturated uglev the portly group, or a group having a divalent heteroatom or divalent heteroatomic group associated with the carbon atom in the terminal link above saturated hydrocarbon group.

From the point of view of usefulness, as containing a heteroatom group, particularly preferred is a group containing an oxygen atom in a simple ether. From the viewpoint of availability, ease of obtaining and usefulness of the product, particularly preferred as the monovalent group is an alkyl group containing an oxygen atom (such as alkoxyalkyl group). In addition, as the monovalent aliphatic hydrocarbon group containing a cyclic portion, having an oxygen atom in a simple ether inserted between carbon-carbon atoms, can be named, for example, an alkyl group having a skeleton of dioxolane.

As alkoxyalkyl group, preferred is a group having one hydrogen atom present in the alkyl group, which was specified for the above monovalent aliphatic hydrocarbon groups, substituted CNS group. The number of carbon atoms in the CNS group is preferably from 1 to 10. Alkoxyalkyl group can be, for example, ethoxymethyl group, 1-propoxyethyl group or 2-propoxyethyl group.

As halogenated (containing heteroatom saturated hydrocarbon) group is preferred (containing heteroatom saturated hydrocarbon) vorgruppe or (partially chlorinated (containing heteroatom saturated hydrocarbon)) vorgruppe. The number of carbon atoms in halogenated (containing heteroatom saturated hydrocarbon) group is preferably from 1 to 20.

Perhalogenated (containing heteroatom monovalent saturated hydrocarbon) group may have a linear structure or a branched structure. It preferably represents (containing heteroatom monovalent saturated hydrocarbon) performgroup or (partially chlorinated (containing heteroatom monovalent saturated hydrocarbon)) performgroup, particularly preferably containing a heteroatom alkyl) performgroup or (partially chlorinated (containing heteroatom alkyl)) performgroup, particularly preferably (CNS) performgroup or (partially chlorinated (CNS)) performgroup. Specific examples of these groups are shown installed in the compounds represented in the further description.

Ester compound in the present invention is a compound which is a complex ester compounds having a guide is auxillou(s) group(s), and compounds having allforyou(s) group(s) (FC(O)-group), and which has a structure which can be fluorinated. Method thereof, in particular not limited to, until the ester compound is a compound having a structure formed by in particular, when the compound having hydroxyl(s) group(s), and connection with allforyou(s) group(s), are subjected to esterification. So, for example, ester compounds may be termed a compound obtained by esterification of the compounds having hydroxyl(s) group(s)at least one compound selected from ClC(O)-group, BrC(O)-group and carboxyl group. In addition, the ester compound in the present invention may be a compound obtained by the use of other chemical transformations in a part other than ester bonds, after esterification. Chemical transformation may be a reaction of the attachment of chlorine to carbon-carbon double bond (C=C) with the formation of vicinal dichlorostyrene (CCl-CCl). In addition, the number of ester groups in the ester compound is particularly not limited.

Ester compound preferably is a compound obtained by esterification of the compounds having hydroxyl(s) group(s), link is m, having allforyou(s) group(s). In this case, as the compounds having hydroxyl(s) group(s)may be used in connection with at least one hydroxyl group, and compounds having allforyou(s) group(s)may be used in connection with at least one allforyou group.

Ester compound preferably is a compound obtained by esterification of compounds having one hydroxyl group, the compound having one allforyou group, and particularly preferably the compound (3)below. The compound (3) may be a compound (3A)below, where R1is a hydrogen atom, or a compound (3B)below, where R1is a monovalent organic group (R10):

RACHR1OCORBF(3)

RACH2OCORBF(3A)

RACHR10OCORBF(3B)

RArepresents a monovalent organic group, preferably a group having a hydrogen atom, from the viewpoint of availability of raw materials, more preferably a saturated group having the hydrogen atom, from the viewpoint of the effectiveness of existing in the mind of the reaction and utility connections, which are going to get.

In addition, as RAthe preferred one is camping monovalent saturated hydrocarbon group, partially halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, or a partially halogenated (containing ethereal oxygen atom, a monovalent saturated hydrocarbon) group. Particularly preferably, RArepresents an alkyl group, a partially chlorinated alkyl group, alkoxyalkyl group or a partially chlorinated (alkoxyalkyl) group.

RAnot necessarily varies depending on the structure of RAFin the connection, which are going to get. One advantage of the method of the present invention is that can be used in a variety of patterns with different structures RA.

RBFrepresents a monovalent organic performgroup, preferably a group having all hydrogen atoms present in the group selected from monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group containing an etheric oxygen atom, a monovalent saturated hydrocarbon group, and a partially halogenated (containing ethereal oxygen atom, a monovalent saturated hydrocarbon) group, substituted by fluorine atoms (i.e. perfluorinated group), particularly preferably the group, it is the expansion of all hydrogen atoms, present in the group selected from alkyl group, a partially halogenated alkyl group, alkoxyalkyl group and partially halogenated (alkoxyalkyl) groups, substituted by fluorine atoms.

R1represents a hydrogen atom or monovalent organic group. When R1represents a monovalent organic group, preferred is an alkyl group, particularly preferred is a methyl group.

From the point of view of the simplicity of the fluorination reaction, described below, in particular reaction, which uses fluorine, the compound (3) in the present invention preferably has a fluorine content of at least 30 wt.%, particularly preferably from 30 to 86 wt.%, most preferably from 30 to 76 wt.%. If the fluorine content is too low, solubility in the liquid phase is extremely low, the reaction system fluorination reaction tends to be heterogeneous, and the compound (3)obtained in the continuous reaction, cannot be simultaneously returned to the reaction system. The upper limit of the content of fluorine is not limited, however, if its content is too high, this leads to the difficulty of obtaining compound (3) and increase costs, which is uneconomical.

To prevent adverse reactions fluoridation in the gas phase and the smooth carrying out the fluorination reaction in a liquid phase molecular mass of the compound (3) is preferably from 200 to 1000. If the molecular weight is too small, the compound (3) has a tendency to free evaporation, resulting in a reaction time of fluorination in the liquid phase, reaction may occur dissociation in the gas phase. On the other hand, if the molecular weight is too large, the purification of the compound (3) becomes difficult.

As specific examples of the compound (3A) can be

presents the following connections:

CH3(CH2)2OCOCF2CF3,

CH3(CH2)2OCH(CH3)CH2OCOCF(CF3)OCF2CF2CF3,

CH3(CH2)2OCH(CH3)CH2OCH(CH3)CH2OCOCF(CF3)OCF2CF(CF3)O(CF2)2CF3,

CH2=CHCH(OCH3)CH2OCOCF(CF3)OCF2CF2CF3,

CH2=CHCH2O(CH2)3OCOCF(CF3)OCF2CF(CF3)O(CF2)2CF3,

CHCl=CClO(CH2)5OCOCF(CF3)OCF2CF(CF3)O(CF2)2CF3,

CH2ClCHClCH2CH2OCOCF2CFClCF2The CCl.

As specific examples of the compound (3B) can be represented by the following connections:

(CH3)2CHOCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3,

CH2=CHCH2CH(CH3)OCOCF(CF3)O(CF2)2CF3.

The compound (3) is preferably p is ecstasy a connection, obtained by the esterification of the compound (1) compound (2). As compounds (1) can be specified compound (1A)below, in which R1is a hydrogen atom, the compound (1B)below, in which R1is a monovalent organic group (R10). In this case, RA, R1, R10and RBFare as defined above.

RACHR1OH (1)

FCORBF(2)

RACH2OH (1A)

RACHR10OCORBF(1B)

As specific examples of the compound (1A) can be represented by the following connections:

CH3CH2HE

CH3CH2CH2HE

CH2=SNSN2HE

CH3CH2CH2CH2HE

CH2ClCHClCH2CH2OH,

CH3CH2CH2OCH(CH3)CH2OH,

CH2=CHCH(OCH3)CH2OH,

CH2=CHCH2OCH2CH2CH2OH,

CHCl=CClO(CH2)5OH,

CF2ClCFClCH2CH2OH.

The compound (1A) is readily available or can be easily obtained in a known manner. So, for example, 3,4-dichloro-1-butanol can be easily obtained by a known method described, for example, in U.S. patent 4261901. In addition, can be easily obtained 2-alkoxycarbonyl alcohol by a method disclosed, for example, in J. Am. Chem. Soc., 49, 1080 (1927), Bull. Soc. Chim. Fr.,1813 (1960), Can. J. Chem., 43, 1030 (1965), Synthesis, 280 (1981).

As specific examples of the compound (1B) can be represented by the following connections:

CH2=SSNS(CH3HE,

(CH3)2SNON.

From the point of view of availability of the compound (1) preferably is a compound in which RAis a group containing no fluorine atom. In addition, the compound (1)in which RAis a group containing fluorine atom, preferably is a compound having a fluorine content of less than 20%, particularly preferably less than 10%.

RBFin the compound (2) is a monovalent saturated

organic performgroup. As specific examples of the compound (2) can be represented by the following connections:

CF3CF2COF,

CF3(CF2)2COF,

CF3ClCFClCF2COF,

CF3(CF2)2OCF(CF3)COF,

CF3(CF2)2OCF(CF3CF2OCF(CF3)COF.

In itself, the compound (2) is not ftorida and so it can conveniently be used as a liquid solvent for the liquid phase, intended for the fluorination reaction.

As for the method of obtaining the compound (3) esterification of the compound (1) compound (2), since they have different patterns, the compound (1) may be available in videoengine, with RAcorresponding to RAFthe target compound (3), the compound (3) can be obtained with different structures. In addition, when carrying out the fluorination reaction using the compound (3) can be obtained compound (4), which is difficult to obtain in the traditional way. The compound (4), which is difficult to obtain in the traditional way, can be one in which the structure of RAFpart is coplexes, or can be obtained fluorinated ester compound with low molecular weight, resulting in the fluorination reaction in the gas phase produces many by-products.

In the present invention, the fluorination is carried out in the form of a liquid mixture of ester compounds and the above compounds having allforyou(s) group(s). The liquid mixture can be obtained by inclusion of the ester compound obtained in various ways, in connection with allforyou(s) group(s). However, the liquid mixture in the present invention is preferably obtained by esterification of the compounds having hydroxyl(s) group(s), connection with allforyou(s) group(s).

For example, it is preferable that the liquid mixture of the ester compounds and compounds having allforyou(s) group(s), was obtained by etherification with and is using the connection, having allforyou(s) group(s), and the number of connections that have allforyou(s) group(s), must be greater than the stoichiometric amount required for the esterification of all hydroxyl groups in the compound having the hydroxyl(s) group(s), and the number should be such that unreacted compound with allforyou(s) group(s), remained in the reaction product.

So, for example, to obtain a liquid mixture of compound (3) and compounds (2), when the compound (1) and the compound (2) are subjected to the esterification when carrying out the reaction in the presence of compound (2) in an amount of more than stoichiometric amount relative to the compound (1) (hereinafter in the description referred to as the "excess amount"), the reaction product may be a liquid mixture of compounds (3) and compounds (2). Since esterification is a reaction that can occur with a high degree of transformation, when it is performed with the use of the compounds (2), taken in an excessive amount, then essentially all of the compound (1) is consumed in the reaction, and the reaction product may be a liquid mixture of the compound (3), formed by esterification, and unreacted compounds (2). In this case, the compound (2) is preferably used in a quantity taken in moles of at least 1.1 times greater, particularly Ave is doctitle from 1.1 to 10 times the number of connections (1), taken in moles.

In the process of esterification of compounds having allforyou(s) group(s) (such as the compound (2)), taken in an excessive amount relative to the compound having the hydroxyl(s) group(s) (such as the compound (1)), essentially all of the compound having hydroxyl(s) group(s), consumed in the reaction. As a result, the advantage is that you can not conduct a stage of extraction of the compounds having hydroxyl(s) group(s), from the reaction product before the subsequent fluorination reaction. In addition, the advantage is that you can avoid the conversion of hydroxyl groups in the group-OF in the subsequent fluorination reaction, which requires careful carrying out the reaction. That is the way in which the product of esterification of the compound (1) with compound (2), taken in excessive quantities, is a liquid mixture is the best way, because the subsequent fluorination reaction can be carried out without the stage of selection of the compound (1) after esterification.

The esterification of the compound (1) with compound (2) can be performed in the presence of a solvent other than the compound (2) (hereinafter in the description referred to as the "solvent 1"), however, from the standpoint of process efficiency, it is preferably carried out in an excessive amount of the compound(2) and in the absence of solvent 1. The esterification may occur properly, even if the solvent 1, in particular, is not used because an excessive amount of compound (2) acts also as a solvent.

In addition, in the reaction of the compound (1) with compound (2), will produce HF and, respectively, in the reaction system as HF absorber may be a fluoride of an alkali metal (such as sodium fluoride). The HF absorber is particularly preferably used in the case where the compound (1) or the compound (2) is unstable to the action of acid. In addition, in the case where the HF absorber is not used, preferably the removal of HF from the reaction system, which is carried out in a stream of nitrogen. When using a fluoride of an alkali metal, quantity, taken in moles, more preferably the amount of compound (2) in 1-10 times.

The reaction temperature in the reaction of the compound (1) with compound (2) is preferably at least -50°and at most +100°or usually does not exceed the boiling point of the solvent. In addition, the reaction time can be appropriately changed depending on the feed rate of the feedstock and quantity of the compounds used in the reaction. The pressure in the reaction (manometrically pressure, which means onwards) predpochtite the flax is the range from normal pressure to 2 MPa.

In the present invention, the fluorination is carried out in the form of a liquid mixture of ester compounds and compounds having allforyou(s) group(s). For example, when the ester compound is a compound (3), the fluorination reaction is carried out in the form of a liquid mixture of compound (3) and compounds (2). The compound (2) can act as a liquid phase for the reaction of fluorination.

Because the connection with allforyou(s) group(s), is a compound having a structure that is similar to or has the General structure of the ester compound is a compound that can dissolve the ester compound. In particular, the compound (2) is a compound in which RBFis fluoride group, and the fluorine can be easily dissolved in a liquid mixture containing the compound 2 as a prerequisite. In addition, part of the structure of the compound (2) is similar to or has the General structure of compound (3), and therefore, the compound (2) is a good solvent for compound (3).

The mass of compound (2) in the liquid mixture is preferably at least 5 times, particularly preferably 10-100 times greater than the mass of the compound (3). In addition, as the compound (2) is used in the fluorination reaction, it is preferable to adjust its amount is the amount in the above range optional addition of compound (2) in the reaction system, the reaction of fluorination.

In addition, preferably the structure of RBFin the compound (2) is brought into line with the structure of RAin the compound (1) to compound (3) was easily dissolved in the liquid phase during the fluorination. So, for example, preferably the structure of RBFpick up so that the fluorine content in the compound 3 was at least 30 wt.%. In addition, in the case when R1is a hydrogen atom, particularly preferably to RBFwas chosen similar to RAFthat could facilitate phase separation of the reaction product.

When the liquid mixture is produced by the esterification reaction, the crude product of esterification can be used directly or it can be subjected to further treatment, if necessary. Additional processing of the crude product can be carried out, for example, by the method of direct distillation of the crude product, method of treatment of the crude product is diluted aqueous alkali solution with subsequent liquid separation, the extraction method of the crude product with a suitable organic solvent, followed by distillation or column chromatography on silica gel. In the case when the crude product contains a compound having a hydroxyl(s) group(s) (such as the compound (1)), preferably the delete connection (1) as soon as possible. Content in the liquid phase compounds having hydroxyl(s) group(s), is preferably not more than 10%, particularly preferably not more than 3%, most preferably not more than 1%.

The fluorination reaction in the present invention is a reaction in which the ester compound is introduced at least one fluorine atom. The fluorination reaction is carried out in the form of liquid-phase reactions. The fluorination reaction can be carried out ECF way, way fluorination using cobalt or the way in which is used the reaction with fluorine (F2). Among these methods, preferred is the method in which is used the reaction with fluorine in a liquid phase (hereinafter way designated as a method of liquid-phase fluorination), which provides high output and mainly promotes fluoridation ester compounds.

As the fluorine in the way of liquid-phase fluorination can be used directly gaseous fluorine or can be used with gaseous fluorine diluted with an inert gas. As a preferred inert gas, nitrogen gas or helium gas, from an economic point of view especially preferred nitrogen gas. The number of fluorine gas in a gaseous nitrogen is not particularly limited, but from the point the rhenium efficiency, it is preferably at least 10 vol.%, particularly preferably, at least 20%vol.

As the liquid phase in the reaction liquid-phase fluorination is necessary connection with allforyou(s) group(s). When the fluorination of the compound (3) compound (2) is necessary as the liquid phase. In addition, as the liquid phase can also be used a compound (3)used as substrate in the reaction of fluorination, or the compound (4)formed in the reaction of fluorination. As the liquid phase in the reaction liquid phase fluorination may contain a solvent other than the compounds (2), compounds (3) and compound (4) (hereinafter indicated as the solvent 2), but to obtain the most complete effect in the present invention, the solvent is preferably 2 is not used.

The reaction system for the reaction of liquid-phase fluorination is preferably a periodic system or a continuous system. In addition, the reaction liquid-phase fluorination of the compound (3) is preferably carried out by way of fluoridation 1 or the method of fluorination 2 below, the method of fluorination 2 is preferred from the viewpoint of the yield of the reaction and selectivity. In addition, as a gaseous fluorine in the case of periodic systemiii in the case of a continuous system can be used fluorine, diluted with an inert gas.

The way fluoridation 1: a Liquid mixture of compounds (3) and compound (2) is loaded into the reactor and start mixing. Then carry out the reaction in continuous flow of gaseous fluoride in the liquid phase in the reactor given the reaction temperature and pressure reactions.

Method of fluorination 2: Compound (2) is loaded into the reactor and start mixing. Then, in the liquid phase in the reactor at a given molar ratio, given the reaction temperature and pressure continuously and simultaneously serves the liquid mixture of the compound (3) and compounds (2) and gaseous fluorine.

As a liquid mixture of compound (3) and compound (2) in the method of fluorination 2 can be used immediately in the reaction product obtained by the interaction of the compound (1) with an excess amount of compound (2), or, if necessary, can be used a reaction product containing added the compound (2). In addition, when the method of fluorination 2 connection (3) dilute the concentration of the compound (3) is preferably not more than 20 wt.%, especially preferably not more than 10 wt.%.

With regard to the amount of fluorine used in the fluorination reaction, it is preferable to carry out the reaction in a state where fluorine is present, so that the amount of fluoride has always been from itechno equivalent with respect to the hydrogen atoms in the ester compound, or from the point of view of selectivity, in the case of reaction of a periodic manner, or in case of carrying out the reaction in a continuous way, a particularly preferable to use fluorine in the amount of at least 1.5 times the equivalent (i.e. at least 1.5 times, taken in moles). In addition, it is preferable to always keep the amount of fluoride in excess of the equivalent amount from the beginning of the reaction before it completes.

The temperature of the fluorination reaction is usually preferably is at least -60°and at most the boiling point of the ester compound, from the viewpoint of the yield of the reaction, selectivity and industrial applicability, particularly preferably it is in the range from -50°C to +100°S, and most preferably from -20°to +50°C. the pressure for the fluorination reaction is not particularly limited, and from the point of view of the yield of the reaction, selectivity and industrial applicability, it is particularly preferably is in the range from 0 to 20 MPa.

In addition, to ensure the efficiency of the reaction of fluorination should preferably be added in the reaction system compound containing a bond With-N, or to carry out ultraviolet irradiation. When carry out the specified operation is present in the reaction system, the complex is essential connection can be effectively fluorinated, and can be markedly increased the degree of conversion.

The compound containing the link With the-N, preferably is an organic compound other than ester compounds, particularly preferably an aromatic hydrocarbon, preferably benzene, toluene or the like. The number of compounds containing a bond of C-H, is preferably from 0.1 to 10 mol.% with respect to the hydrogen atoms in the ester compound, particularly preferably from 0.1 to 5 mol.%. In addition, when a compound containing a bond of C-H, diluted with solvent and then added, preferably, the solvent for dilution, too, represented a connection with allforyou(s) group(s) (such as the compound (2)).

The compound containing a bond of C-H, is preferably added in such a way that in the reaction system was attended by gaseous fluorine. In addition, in the case when type compound containing a bond of C-H, preferably, in the reaction system was created increased pressure. The generated pressure is preferably from 0.01 to 5 MPa.

If a hydrogen atom in the reaction of fluorination is substituted by a fluorine atom, as a by-product can be formed HF. To remove a by-product HF is preferable to provide in the reaction system joint is westowne absorber HF or provide contacting the exhaust gas with the HF absorber outlet gas from the reactor. As HF absorber can be used the same absorber, as indicated above, while preferred is NaF.

When the HF absorber are given the opportunity to coexist in the reaction system, its amount is preferably from 1 to 20 mol, particularly preferably from 1 to 5 mol relative to the total number of hydrogen atoms present in the ester compound. When the HF absorber placed in existing in the reactor outlet gas, it is advisable sequentially (a) a refrigerator (preferably to maintain the temperature in the range from 10°C to room temperature, particularly preferably at about 20°C), (b) the attachment of NaF pellets and (C) a refrigerator (preferably to maintain the temperature from -78°C to +10°C, preferably from -30°0°(C) in order (a)-(b)-(C). In addition, to return the condensed liquid from the cooler (s) in the reactor may be provided in the return line of the fluid.

In the present invention fluoridation will produce fluorinated ester compound. In the fluorination reaction can be formed of fluorinated ester compound having a structure corresponding carbon skeleton ester compounds. In this description and in the case of PR is the lack of an ester in the compound of the carbon-carbon unsaturated due to link state changes, at least one unsaturated linkages can be added to the fluorine atoms. For example, when the fluorination of the compound (3) produces compound (4). The compound (4) is a compound which has at least one fluorine atom introduced into the molecule of the compound (3).

RAFin the compound (4) represents a group corresponding to RA. When RAis a hydrogen atom, which may be fluorinated, or a monovalent organic group having an unsaturated bond, and the specified group fluorinated, RAFin this case, represents a group obtained by fluorination of RA. In addition, in the case when RArepresents a monovalent organic group, which may not be fluorinated, or when it is not ftorida, even if it is a group which can be fluorinated, it is a group similar to RA. In RAFand RAthere is no change in the arrangement of carbon atoms before the reaction of fluorination, and after it. In addition, RBFrepresents a group similar to RBFin the compound (3). When R1is a hydrogen atom, R1Frepresents a fluorine atom. When R1is a monovalent organic group, R1Frepresents a monovalent organic group, the same or different from R and when R1and R1Fdiffer from each other, R1Frepresents a monovalent organic group obtained by fluorination of R1.

Fluorinated ester compound is preferably a compound obtained by perftorirovannye ester compounds. Since RAin the compound (3) is preferably a hydrogen-containing group, from the viewpoint of availability of the compound, RAFin the compound (4) is preferably a fluorinated group, particularly preferably a perfluorinated group.

The compound (4) may be a compound (4A) or a compound (4B)below. In this case, RAFand RBFare as defined above.

RAFCFR1FOCORBF(4)

RAFCF2OCORBF(4A)

RAFCFR10FOCORBF(4B)

RAFpreferably represents a group having all hydrogen atoms present in RAwhich are substituted by fluorine atoms, and RArepresents a monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, or a partially halogenated (monovalent saturated hydrocarbon containing etheric oxygen atom is) group. In particular, preferably RAFrepresents a group having all hydrogen atoms present in RAwhich are substituted by fluorine atoms, while RArepresents an alkyl group, a partially chlorinated alkyl group, alkoxyalkyl group or a partially chlorinated (alkoxyalkyl) group.

R10Fin the compound (4B) represents a monovalent organic group, which may be the same or different from R10and when they differ from each other, it represents a monovalent organic group obtained by fluorination of R10. R10Fpreferably represents a monovalent organic group obtained by perftorirovannye R10particularly preferably performanceline group is most preferable, from the viewpoint of utility connections, triptorelin group.

As specific examples of the compound (4A) can be represented by the following connections:

CF3(CF2)2OCOCF2CF3,

CF3(CF2)2OCF(CF3CF2OCOCF(CF3)OCF2CF2CF3,

CF3(CF2)2OCF(CF3CF2OCF(CF3CF2OCOCF(CF3)OCF2CF(CF3)O(CF2)2CF3,

CF3CF2CF(OCF3CF2OCOCF(CF3)OCF2CF2CF3,

CF3 CF2CF2O(CF2)3OCOCF(CF3)OCF2CF(CF3)O(CF2)2CF3,

CF2ClCFClO(CF2)5OCOCF(CF3)OCF2CF(CF3)O(CF2)2CF3,

CF2ClCFClCF2CF2OCOCF2CFClCF2Cl.

As specific examples of the compound (4B) can be represented by the following connections:

(CF3)2CFOCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3,

CF3CF2CF2CF(CF3)OCOCF(CF3)O(CF2)2CF3.

Fluorinated ester compound as the reaction product of fluorination is suitable as such or in the form of chemically transformed into another connection. When the fluorinated ester compound is a compound that is capable of dissociation of the ester bond, in particular when it is a compound (4), it can be entered in another connection the implementation of the dissociation reaction of the ester link.

The reaction product of the fluorination includes fluorinated ester compound. In addition, when the fluorination reaction is carried out in the presence of compounds having allforyou(s) group(s), the product of the fluorination reaction, when the compound having allforyou(s) group(s), is a connection that is not ftorida, includes the same connection that described above, and when the connection with allforyou(s) group(s), ftorida, the reaction product of the fluorination includes a fluorinated compound having allforyou(s) group(s). In addition, when you use the HF absorber or solvent 2, they may be present in the reaction product.

When the dissociation reaction of the ester communication in the fluorinated ester compound, a fluorinated ester compound can be separated from the reaction product of fluorination and cleansed, or the reaction product may be used directly for subsequent reactions of dissociation of the ester bonds, and particularly preferable to carry out the dissociation reaction of the ester of the way. If cleaning can be applied, for example, a method of direct distillation of the crude product under normal pressure or under reduced pressure.

In the case where the dissociation reaction of the ester communication in connection (4), will form a connection (5)below, and the above compound (2). The compound (5) may be a compound (5A) and the compound (5B). In this case, RAF, R1Fand R10Fare as defined above.

RAFCOR1F(5)

RAFCOF (5A)/p>

RAFCOR10F(5B).

The compound (5B), which is a fluorinated ketone, in itself, is a useful compound, for example, as solvent. In addition, it can be converted into fluorine-containing alcohol reaction recovery. In addition, as the monomer for the polymer or fluorine-containing alcohol is a useful compound is the compound (5A).

As specific examples of the compound (5A) can be represented by the following connections:

CF3CF2COF,

CF3(CF2)2COF,

CF2ClCFClCF2COF,

CF3CF2CF2OCF(CF3)COF,

CF3CF2CF2OCF(CF3CF2OCF(CF3)COF,

CF3(CF2)2OCF(CF3CF2OCF(CF3)COF,

CF2ClCFClO(CF2)4COF.

As specific examples of the compound (5B) can be represented by the following connections:

(CF3)2C(O),

CF3CF2CF2C(O)(CF3).

The dissociation reaction of the ester link is preferably carried out by dissociation of the ester bonds by heating or dissociation of the ester bonds in the presence of a nucleophile or electrophile.

When the ester bond is subjected to dissociation by heating (hereinafter in the description is specified as "pyrolysis"), it is advisable to choose the type of feast is Lisa, depending on the boiling point and stability of the fluorinated ester compound. For example, when subjected to pyrolysis of volatile fluorinated ester compound may be selected such gas-phase pyrolysis, when it is continuously subjected to pyrolysis in the gas phase and the product containing exhaust gas is condensed and removed.

The reaction temperature for the gas-phase pyrolysis is preferably from 50 to 350°S, particularly preferably from 50 to 300°S, more preferably from 150 to 250°C. furthermore, the reaction system may contain an inert gas that does not directly participate in the reaction. Can be used an inert gas such as 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 amount of the fluorinated ester compound. If the amount of inert gas is large, the number of extracted product may decrease.

In addition, when the gas-phase pyrolysis is preferable to use a tubular reactor. In the case of using a tubular reactor the residence time in the reactor is preferably from about 0.1 seconds to about 10 minutes in the calculation of the free volume of the column. The pressure of the reaction are not particularly limited. In addition, in the case where the fluorinated ester compound represents Obedinenie with high boiling point, the reaction should preferably be carried out at reduced pressure. When the fluorinated ester compound is a compound with a low boiling point, the reaction should preferably be carried out at increased pressure to suppress decomposition of the product and increase the rate of reaction.

In the case where gas-phase reaction carried out using a tubular reactor, to accelerate the reaction, the reaction tube should preferably be filled with glass, the salt of an alkali metal or alkali earth metal salt. In the case where the dissociation reaction of the ester link is realized in form of a mixture of fluorinated ester compounds and compounds having allforyou(s) group(s), or fluoride specified connection, this filler is preferably selected from fillers, which do not accelerate the reaction of decomposition of compounds having allforyou(s) group(s).

Salt of alkali metal or alkali earth metal salt is preferably a carbonate or fluoride. As glass can be used conventional sodium glass and, in particular, the preferred glass beads, similar to the beads with high fluidity. Salt of the alkali metal may be sodium carbonate, sodium fluoride, potassium carbonate recarbonation lithium. Salt of the alkali earth metal may be, for example, calcium carbonate, calcium fluoride or magnesium carbonate. In addition, when the reaction tube is filled with glass, the salt of an alkali metal or alkali earth metal salt, particularly preferably you should use glass beads or fly ash sodium carbonate having a particle size of from about 100 to about 250 microns, and can therefore be used in the reaction system type fluidized bed.

On the other hand, in the case where the fluorinated ester compound is a volatile ingredients connection, it is expedient to carry out the liquid-phase pyrolysis, in which it is heated in the reactor in the liquid state. In this case, the pressure of the reaction are not particularly limited. In the normal case, the reaction product of dissociation of the ester bonds has a lower boiling point than the boiling point of the fluorinated ester compound, and accordingly it is preferably produced by the method using a reaction system for distillation, where the product evaporates and continuously removed. Or it can be used a method in which after heating the entire product is immediately removed from the reactor. The reaction temperature in the implementation of liquid-phase pyrolysis is preferably from 50 to 300�B0; S, particularly preferably from 100 to 250°C.

When the reaction of dissociation of the ester bonds carry out a liquid-phase pyrolysis, from the point of view of efficiency of the process, the reaction should preferably be carried out using directly the product of the fluorination reaction. The reaction product may be added to the solvent, but preferably the solvent is not added. For example, in the reaction of fluorination liquid mixture of compound (2) and compound (3) compound (2) and the compound (4) is contained in the product and the reaction of dissociation of the ester bonds is preferably carried out in the form of a mixture of compound (2) and compound (4), and the solvent other than the compound (2) (hereinafter indicated as the solvent 3), is not present. In this case, may not necessarily be added to the compound (2). The compound (2) may also be a reaction of dissociation of the ester bonds as liquid phase.

In addition, when the compound (4) is itself a liquid, the dissociation reaction of the ester bond may be carried out in the absence of solvent. The method, implemented in the absence of a solvent is preferable from the viewpoint of the volume efficiency and suppressing the formation of by-products. On the other hand, when the used solvent 3, preferably in order to take such a solvent, which does not react with the compound (4)is compatible with the compound (4) and which does not interact with the product.

As a specific example of a preferred solvent inert solvent, such as perftorsilanami or chlorofluorocarbon, in particular, the oligomer of chlorotrifluoroethylene having a high boiling point (for example, trade name : FLON LUBE).

In addition, when the dissociation reaction of the ester communication interaction fluorinated ester compound with a nucleophile or electrophile in the liquid phase, this reaction can be performed in the presence or absence of a solvent. When the reaction of the compound (4) is carried out in the presence of a solvent, the reaction is preferably carried out in the presence of compound (2). As the preferred nucleophile F-obtained from the fluoride of the alkali metal. As the fluoride of the alkali metal can be used NaF, NaHF2, KF or CsF and from among these, from the viewpoint of economic efficiency, particularly preferredNaF, and from the viewpoint of the reaction efficiency, particularly preferred KF.

When the dissociation reaction of the ester communication by way of interaction of the compound (4) with a nucleophile (such as F-), F-will nucleophile added to bonillas group, present in the ester bonds in the compound (4), resulting in RAFCFR1FO-will be chipped off to form compound (2). In addition, RAFCFR1FO-will be chipped off F-with the formation of compound (5). Depending on the reaction conditions, dissociation of the compound (4) can further decompose with the formation of other compounds (such as unsaturated compound). Split F-will a similar way to interact with another connection (4). Accordingly, initially used in the reaction, the nucleophile may be present in a catalytic amount or in excess. The number of nucleophile, such as F-, is preferably from 1 to 500 mol.%, particularly preferably from 10 to 100 mol.%, most preferably from 5 to 50 mol.% per connection (4). The reaction temperature is preferably from -30°C to the boiling point of the solvent or the compound (4), particularly preferably from -20°, 250°C. This method is also preferably carried out in the system for the distillation of the reaction mass.

When the fluorinated ester compound under normal conditions is a compound (4A), compound (2) with compound (5) is contained in the reaction product of dissociation of the ester bonds. The AOC is e, when the reaction of dissociation of the ester bonds is carried out in the presence of compounds (2), connection (2) is contained in the reaction product.

In the reaction product of the compound (5A) and the compound (2) can be easily separated by conventional separation processes. However, when compounds of the feedstock is selected so that the compound (5A) has the same structure as the compound (2), i.e. when the structure of the groups is chosen so that RAFand RBFhave the same structure in the compound (4A), compound (5) and the compound (2) as the reaction products are one and the same connection, causing the operation to separate the reaction products may be excluded.

As a preferred variant of the present invention can be specified the way in which the structure of the groups is chosen so that RAFand RBFhave the same structure, the compound (3A) is fluorinated in a liquid phase, which has an excessive amount of compound (2) as an essential component, and a mixture of the compound (4A)formed by fluorination, and the compound (2) is introduced in the following dissociation reaction of the ester linkages. In this method, compound (5A) as the reaction product of dissociation of the ester bonds is a compound similar to the compound (2) and stage separation and purification can be simplified. In addition, when the solvent is used for each reaction, using as a solvent only connection (2), the number of types of the used solvent can be reduced, making it possible not to perform additional operations.

As another preferred option can be specified the way in which, when the compound (1) and the compound (2) is subjected to esterification reaction is carried out in the presence of excess amount of compound (2) to form a liquid mixture of compound (3) and compounds (2), which is used in the fluorination reaction. In this way the operation of extraction of the compound (1) before the fluorination reaction is also possible not to include. In addition, can also be specified the way in which the dissociation reaction of the ester communication in the form of a mixture of compound (4)formed by the fluorination reaction, and the compound (2). This sequence of reactions can be performed in one reactor.

As another preferred option can be specified the way in which the compound (5A) or the compound (2)obtained from the reaction product of dissociation of the ester bonds, return to the cycle in the form of compounds (2)subject to interaction with compound (1). This method is a method that enables nepreryvnog the receipt of the compound (5A). That is, the compound (2) obtained from the reaction product of dissociation of the ester bonds with a liquid mixture of compound (4A) and compounds (2) and part or all of the connection (2) again used for the reaction with compound (1A), resulting in the compound (5A) can be obtained continuously. This method is the method that provides the ability to continually obtain the desired compound (5A) of the feedstock compounds (1A), which is available at low cost.

Examples

Now the present invention will be further explained with reference to examples, but the present invention is in no way restricted by these examples. Next, gas chromatography is denoted by GC, gas chromatography with mass spectrometry indicated by GC-MS and ml are presented as "ml". The data of the NMR spectrum is shown in the range of the observed chemical shift. The default value for the reference substance CDCl3in13C-NMR set to 76,9 ppm For the quantitative analysis19F-NMR spectroscopy as an internal reference sample used With6F6.

Example 1

Example 1-1: Example of a liquid mixture

CF3CF2CF2OCF(CF3)COOCH2CH(CH3)OCH2CH2CH3and

CF3CF2CF2OCF(CF3)COF

CH3CH2 CH2OCH(CH3)CH2OH (620,1 g) was placed in a flask and stirred while bubbling nitrogen gas. While maintaining the internal temperature in the range from 25 to 35°C for 8 hours in a flask was added dropwise CF3CF2CF2OCF(CF3)COF (3604 g). After completion of adding dropwise continued stirring at room temperature for 2 hours while bubbling nitrogen gas in the reaction product containing CF3CF2CF2OCF(CF3)COOCH2CH(CH3)OCH2CH2CH3and CF3CF2CF2OCF(CF3)COF, obtaining specified in the header of the liquid mixture. The liquid mixture is directly used in the reaction of example 1-2.

Example 1-2: Sample receipt

CF3CF2CF2OCF(CF3)COOCF2CF(CF3)OCF2CF2CF3

In a 3 l autoclave made of Nickel was added CF3CF2CF2OCF(CF3)COF (2340 g), was stirred and maintained at 25°C. At the gas outlet of the autoclave was consistently set the refrigerator temperature to be maintained at 20°With the nozzle of NaF pellets and the refrigerator with the temperature to be maintained at -10°C. in Addition, for returning the liquid condensed from the refrigerator with the temperature to be maintained at -10°With, in the autoclave, has established a line for returning fluid is STI. After supplying gaseous nitrogen for 1.5 hours gave gaseous fluorine, diluted to 20 vol.% nitrogen gas (hereinafter referred to as 20% gaseous fluorine), within 3 hours volumetric rate 8,91 l/h.

Then when applying 20% of fluorine gas with the same consumption during 45,6 hours were injected 18 ml of liquid mixture (106 g)obtained in example 1-1.

Then when filing with the specified volumetric rate of 20% of fluorine gas was injected a solution of CF3CF2CF2OCF(CF3)COF, with the concentration of benzene 0.01 g/ml, with increasing temperature from 25°C to 40°With, the inlet of the autoclave for injection of benzene was closed also closed the outlet valve of the autoclave and, when the pressure became equal to 0.20 MPa, closing the inlet valve of the autoclave for gaseous fluorine and continued the stirring for 1 hour. Then again installed the normal pressure and while maintaining the internal temperature of the reactor at 40°injected With 6 ml of the above solution of benzene, closing the inlet opening of the autoclave for injection of benzene, closing the outlet valve of the autoclave and, when the pressure became equal to 0.20 MPa, closing the inlet valve of the autoclave for gaseous fluorine and continued the stirring for 1 hour. This operation was repeated once.

The total number of centuries which sought benzene was 0,309 g and the total number of entered CF 3CF2CF2OCF(CF3)COF was 30 ml. in Addition, during the 2 hours was applied nitrogen gas. After the reaction to obtain a reaction product containing the above compound (85,3 g) and CF3CF2CF2OCF(CF3)COF, carried out the purification by distillation. The results of the analysis of the above compounds in the reaction product is shown below.

Boiling point: 46-51°/a 5.2 kPa.

The mass spectrum of high resolution (CI method) 664,9496 (M+N, theoretical value: C12HF24O4=664,9492).

19F-NMR (564,6 MHz, solvent: CDCl3/C6F6reference: CFCl3) δ (ppm): -80,6(1F), -80,8 and -80,9(3F), -81,6 - -83,1(2F), -82,6(6F), -82,8(3F), -86,7(1F), -87,4(1F), -87,5(1F), -130,6(4F), -132,2(1F), -145,7 and -145,9(1F).

13C-NMR (150,8 MHz, solvent: CDCl3/C6F6reference: CDCl3) δ (ppm): 100,26 and 100,28, 102,8, 106,8, 107,0, 116,0, 116,2, 116,5 and 116,6, 117,4, 117,5, 117,9, 117,9, 152,2 and shall be 152.3.

Example 1-3: Example of getting CF3CF2CF2OCF(CF3)COF

The reaction product containing CF3CF2CF2OCF(CF3)COOCF2CF(CF3)OCF2CF2CF3(83,0 g)obtained in example 1-2, downloaded together with NaF powder (1.1 g) in a flask and heated at 140°C for 15 hours on an oil bath with vigorous stirring. Through the reflux condenser with a temperature of 70°With, in the upper part of the flask were collected fluid sample (81.3 g). Prod is CT, obtained by distillation of the sample liquid to clean it, were analyzed by GC-MS, which confirmed the formation of CF3CF2CF2OCF(CF3)COF.

Example 1-4: Example of continuous receipt of CF3CF2CF2OCF(CF3)COF

Obtained by the method of example 1-3 CF3CF2CF2OCF(CF3)COF (81,2 g) and CH3CH2CH2OCH(CH3)CH2OH (14.0 g) was subjected to interaction, following the method of example 1-1, receiving the liquid mixture (94,0 g)containing CF3CF2CF2OCF(CF3)COOCH2CH(CH3)OCH2CH2CH3and CF3CF2CF2OCF(CF3)COF. Using liquid mixture, carried out similar reactions of examples 1-2 and 1-3 with obtaining specified in the connection header.

Example 2

Example 2-1: example of getting a CH2=CHCH(OCH3)CH2OCOCF(CF3)OCF2CF2CF3

CH2=CHCH(OCH3)CH2OH (270 g) was loaded together with NaF (334 g) in a 2 l reactor, designed to work under pressure, equipped with a reflux condenser, in which at 20°circulated With the refrigerant, and was stirred at -10°C. During the production of by-product HF formed during the reaction, from the upper part of the back of the refrigerator by bubbling nitrogen gas into the reactor was added dropwise for 1.5 hours FCOCF(CF3)OCF2CF2CF3(1055). In this in EMA the temperature was regulated so to the internal temperature of the reactor did not exceed 0°C. After adding dropwise to the stirring was carried out at 30°C for 18 hours and then the reaction was completed.

Contained in the raw liquid after completion of the reaction NaF was filtered to obtain the crude product (981 g) (yield 86.4 per cent). The results of NMR analysis confirmed the receipt of the above mixture in the form of a liquid mixture FCOCF(CF3)OCF2CF2CF3. The results of the analysis specified in the title compound were as follows:

1H-NMR (300,4 MHz, solvent: CDCl3reference: TMC) δ (ppm): 3,29 (c, 3H), 3,85-3,90 (m, 1H), 4,24 is 4.45 (m, 2H), 5,34 (c, 1H), 5,39 (d, J=8,4 Hz, 1H), 5,59-5,71 (m, 1H).

19F-NMR (282,7 MHz, solvent: CDCl3reference: CFCl3) δ (ppm): -81,8(3F), -82,6(3F), -79,9 - -87,5(2F), -130,2(2F), -132,3(1F).

Example 2-2: Example of a liquid mixture

CH2ClCHClCH(OCH3)CH2OCOCF(CF3)OCF2CF2CF3and

FCOCF(CF3)OCF2CF2CF3

The liquid mixture containing the CH2=CHCH(OCH3)CH2OCOCF(CF3)OCF2CF2CF3(981 g)obtained by the method of example 2-1 were loaded into a 2 l three-neck flask equipped with a nozzle of Dimroth, cooled at 0°With, and under stirring at a temperature of from -10°0°introduced chlorine gas with a flow rate of 0.8 g/min for the implementation of the response. The reactions is completed, when it was introduced 170 g of gaseous chlorine, and received 1084 g of the crude liquid.

For purification the crude liquid is kept under reduced pressure for 6 to 7 mm Hg with getting 744 g of the product. The analysis of NMR and gas chromatography, it was confirmed the formation of liquid mixtures containing CH2ClCHClCH(OCH3)CH2OCOCF(CF3)OCF2CF2CF3and FCOCF(CF3)OCF2CF2CF3while GC showed a purity of 98%. The results of the analysis of CH2ClCHClCH(OCH3)CH2OCOCF(CF3)OCF2CF2CF3and FCOCF(CF3)OCF2CF2CF3were as follows:

1H-NMR (300,4 MHz, solvent: CDCl3standard: TMS) δ (ppm): 3,45 (d, J=1.5 Hz) and 3,47 (c) and 3,55 (d, J=0.6 Hz) in General 3H, 3,56-of 3.80 (m, 2H), 3,82-4,12 (m, 2H), 4,43-of 4.57 (m, 1H)and 4.65 (DD, J=6.3 Hz, to 11.4 Hz) and 4,89 (DDD, J=42,4 Hz, 12.0 Hz, 3.0 Hz) and 5.49 (kV, J=5,1 Hz) in the 1H whole.

19F-NMR (376,0 MHz, solvent: CDCl3reference: CFCl3δ (ppm): -79,93 - -80,65(1F), -81,72 - -81,80(3F), -82,47 - -82,56(3F), -86,46 - -87,22(1F), -130,07 - -130,19(2F), -132,26 - -132,47(1F).

Example 2-3: Example of getting CF2ClCFClCF(OCF3CF2OCOCF(CF3)OCF2CF2CF3

In a 3 l autoclave made of Nickel was added CF3CF2CF2OCF(CF3)COF (3523 g), was stirred and kept at 5°C. At the gas outlet of the autoclave was set the fridge temperature, supported the Oh at -10° C. After the filing of gaseous nitrogen for 3.5 hours gave 20% gaseous fluorine with volumetric rate 26,52 l/h for 1 hour.

Then when applying 20% of fluorine gas with the same volumetric rate for the 22.5 hour was injected liquid mixture containing CH2ClCHClCH(OCH3)CH2OCOCF(CF3)OCF2CF2CF3(415 g)obtained by the method of examples 2-1 and 2-3, and then the crude reaction liquid (261 g) was extracted (operation 1). Operation 2-3, listed in the following table were carried out in the same way. Then the temperature in the autoclave was brought to 25°C and maintained for 22 hours, then the flow of fluorine gas was stopped, within 3 hours gave gaseous nitrogen and the crude reaction liquid (3530 g) was extracted.

The crude reaction liquid were combined and analyzed by GC-MS and the result was confirmed by the formation of a mixture containing CF3CF2CF2OCF(CF3)COF and indicated in the title compound as main components, and the output is specified in the header of the compound (1A) was 71%.

Table 1
OperationEnter the amount (g)The time of injection (hours)The crude reaction liquid (g)
1 41522,5261
264222,0533
347122,8270

Example 3

Example 3-1: Example of a liquid mixture

(CH3)2CHOCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3and

FCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3

(CH3)2CHOH (7,0 kg) were placed in a reactor and then stirring was carried out while bubbling nitrogen gas. For 25 hours in the reactor was added FCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3(61,0 kg) while maintaining the internal temperature of the reactor from 25 to 30°C. After complete addition, stirring was carried out for 24 hours while maintaining the internal temperature of the reactor at 30°With receipt of 65.1 kg specified in the header of the liquid mixture in the form of a crude liquid. The degree of purity (CH3)2CHOCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3measured by GC, was 98%.

Example 3-2: Sample receipt (CF3)2CFOCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3

In a 4 l autoclave made of Nickel was added CF3CF2CF2OCF(CF3CF2OCF(CF3)COF (4992 g), was stirred and maintained at 20°C. At the exit of the gas from the autoclave was set the fridge temperature, supported 0°C. After the gaseous nitrogen supply for the 2.0 hours, gave gaseous fluorine, diluted to 50% nitrogen gas (hereinafter referred to as 50% gaseous fluorine), with volumetric flow 50,10 l/hour to 2.0 hours.

Then, the inner temperature of the autoclave was brought to 25°and when 50% of fluorine gas with the same volumetric flow rate of the liquid mixture containing (CH3)2CHOCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3(208 g)obtained in example 3-1 was injected for 3.5 h and then the crude reaction liquid (262 g) was extracted (operation 1). Listed in the following table operations 2-8 carried out in the same way.

4,0
Table 2
OperationEnter the amount (g)The time of injection (hours)The crude reaction liquid (g)Output

(%)
12083,526241
22024,026455
32354,052767
44668,053482
528253285
64508,026688
72194,026587
84568,027190

After completion of step 8 in the reactor remained 4950 g of the crude reaction liquid. The crude reaction liquid, extracted in operations 1-8, were combined and analyzed by GC-MS, and the result was confirmed by the formation of a mixture containing CF3CF2CF2OCF(CF3CF2OCF(CF3)COF and indicated in the title compound as main components. The outputs specified in the header of the compounds contained in the crude reaction liquid, extracted at the corresponding operations defined GC, shown in the table.

Example 4

Example of getting CF3CF2CF2OCF(CF3CF2OCOCF(CF3)OCF2CF2CF3

In a 4 l autoclave made of Nickel was added CF3CF2CF2OCF(CF3)COF (5113 g), was stirred and maintained at 20°C. At the gas outlet of the autoclave was set the refrigerator temperature to be maintained at 0°C. After the filing of gaseous nitrogen for 1.5 h gave 50% gaseous fluorine with surround Rashada the 100,37 l/hour for 1.5 hours.

Then, the inner temperature of the autoclave was brought to 25°and when 50% of fluorine gas with the same consumption within 8 hours was injected liquid mixture containing SN3CH2CH2OCH(CH3)CH2OCOCF(CF3)OCF2CF2CF3(190 g)obtained by a reaction similar to example 1-1, and then the crude reaction liquid (262 g) was extracted (operation 1). Operation 2-7 listed in the following table were carried out in the same way.

After completion of step 7 in the reactor remained 4720 g of the crude reaction liquid. The crude reaction liquid, extracted in operations 1-7, were analyzed by GC-MS and the result was confirmed by the formation of a mixture containing CF3CF2CF2OCF(CF3)COF and indicated in the title compound as main components. The outputs specified in the header of the compounds contained in the crude reaction liquid, extracted at the corresponding operations defined GC, shown in the table.

Example 5

Example 5-1: Example of a liquid mixture

CH2=CHCH2OCH2CH2CH2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3and

CF3CF2CF2OCF(CF3CF2OCF(CF3)COF

To obtain specified in the header of the liquid mixture was carried out by a reaction similar to example 1-1, using CH2CHCH2OCH2CH2CH2OH (11.6 kg) and CF3CF2CF2OCF(CF3CF2OCF(CF3)COF (50,8 kg). The degree of purity of CH2=CHCH2OCH2CH2CH2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3measured by GC, was 98%.

Example 5-2: Example of getting CF3CF2CF2OCF2CF2CF2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3

4 l autocl is in, made of Nickel was added CF3CF2CF2OCF(CF3CF2OCF(CF3)COF (5003 g), was stirred and kept at 25°C. At the gas outlet of the autoclave was set the refrigerator temperature to be maintained at -10°C. After the gaseous nitrogen supply for 2.0 hours gave 50% gaseous fluorine with volumetric rate 65,33 l/h for 1 hour.

Then when 50% of fluorine gas with the same volumetric rate for 8 hours was injected liquid mixture containing CH2=CHCH2OCH2CH2CH2OCOCF(CF3)OCF2CF(CF3)OCF2CF2CF3(214 g)obtained by the method of example 5-1, and then the crude reaction liquid (264 g) was extracted (operation 1). Operation 2-10 specified in the following table were carried out in the same way. Operations 3 and subsequent operations volume flow 50% of fluorine gas was changed to for 98.00 l/h.

Table 3
OperationEnter the amount (g)The time of injection (hours)The crude reaction liquid (g)Output

(%)
11908,026278
24354,026190
33358,026491
480818,026493
52758,026593
63578,026495
73728,029595
Table 4
OperationEnter the amount (g)The time of injection (hours)The crude reaction liquid (g)Output

(%)
12148,026480
2331to 12.02615
32588,026384
41364,026277
51474,026075
63748,026377
71684,026577
81664,026678
91404,027079
1070516,026878

After operation 10 in the reactor remained 4770 g of the crude reaction liquid. The crude reaction liquid, extracted in operations 1-10, combined, were analyzed by GC-MS and the result was confirmed by the formation of a mixture containing CF3CF2CF2OCF(CF3CF2OCF(CF3)COF and indicated in the title compound as main components. The outputs specified in the header of the compounds contained in the crude reaction liquid, extracted at the corresponding operations defined GC, shown in the table.

Example 6

Example 6-1: example of getting a CH2=CHCH2CH(CH3)OOCF(CF 3)OCF2CF2CF3

CH2=CHCH2CH(CH3)OH (13,08 kg) were placed in a reactor and stirred while bubbling nitrogen gas. While maintaining the internal temperature between 25 and 30°downloaded FCOCF(CF3)OCF2CF2CF3(54,29 kg) for 5 hours. After the download is complete when bubbling nitrogen gas mixing was carried out at an internal temperature of 30 to 50°C for 70 hours.

The crude liquid (58,32 kg) was used in the next stage without purification. The purity measured by GC, was 96.6 percent. The data of the NMR spectrum were as follows.

1H NMR (300,4 MHz, solvent: CDCl3standard: TMS): δ to 1.32 (d, J=6.0 Hz, 3H), 2,30-of 2.50 (m, 2H), 5,07-to 5.21 (m, 3H), 5,61-USD 5.76 (m, 1H).

19F-NMR (282,7 MHz, solvent: CDCl3reference: CFCl3) δ (ppm): -79,6(1F), -81,3(3F), -82,0(3F), -86,3(1F), -129,4(2F), -131,5(1F).

Example 6-2: Example of getting CF3CF2CF2OCF(CF3)COOCH(CH3)CH2CHClCH2Cl

A 5 l flask, equipped with reflux condenser, at 20°loaded With the crude liquid containing CF3CF2CF2OCF(CF3)COOCH(CH3)CH2CH=CH2(5000 g)obtained in example 6-1, and the reactor was cooled to -30°C. Then continuously applied Cl2and barbotirovany in the reaction liquid, and the feed speed Cl2regulated so about what atom, to the increase of temperature due to the heat of reaction was not more than 10°C. When the reaction was not observed generation of heat, the reaction was completed. After completion of the reaction, the reactor temperature was brought to room temperature and the reaction liquid within 24 hours blew, barbotine gaseous nitrogen for extraction of excess Cl2when this was received untreated liquid (5900 g)containing FCOCF(CF3)OCF2CF2CF3and specified in the header connection. As shown by GC analysis, CF3CF2CF2OCF(CF3)COOCH(CH3)CH2CHClCH2Cl 95%.

Example 6-3: Example of getting CF2ClCFClCF2CF(CF3)OCOCF(CF3)OCF2CF2CF3

In a 4 l autoclave made of Nickel, as a solvent was added CF3CF2CF2OCF(CF3)COF (4732 g), was stirred and kept at 25°C. At the gas outlet of the autoclave was set the refrigerator temperature to be maintained at -10°C. After the gaseous nitrogen supply for 2.0 hours gave 20% gaseous fluorine with volumetric rate 144,30 l/h. within 1 hour.

Then when applying 20% of fluorine gas with a volumetric rate 144,30 l/h for 22 hours was injected crude liquid containing CF3CF2CF2OCF(CF3)COOCH(CH3)CH2CHClCH 2Cl (740 g)obtained by the method of example 6-2, and then the crude reaction liquid (820 g) was extracted (operation 1). Some GC purity specified in the header of the compounds contained in the crude reaction liquid (excluding the solvent), was 28%. Listed in the following table operation 2-7 carried out in the same way. After completion of step 7 in the reactor remained 3731 g of the crude reaction liquid.

Table 5
Opera tionEnter the amount (g)The time of injection (hours)The crude reaction liquid (g)Output (g)The degree of purity(%)
174022144,3084028
27652180,57110739
378324111749
476024106,4684456
599230113362
632611111,03 28865
7116142114571

Example 7

Example 7-1: Getting CHCl=CClO(CH2)5OH

500 ml chetyrehosnuju flask was loaded tetrahydrofuran (THF), 160 ml) and sodium hydride (60%, 24 g) and stirred under ice cooling to the flask was added dropwise HO(CH2)5OH (260 g). After adding dropwise to the stirring was carried out at room temperature for 1 hour. Then within 5 minutes to the mixture was added dropwise CHCl=CCl2(66 g). After adding dropwise to the stirring was carried out at a bath temperature of 70°C for 2.5 hours. The mixture was left to cool, then under ice cooling, thereto was added water (400 ml) and methylene chloride (400 ml) and was carried out by liquid phase separation with getting methylenchloride layer as the organic layer. Then the organic layer was washed with water (400 ml) and dried to highlight specified in the connection header. The results of the analysis specified in the title compound were as follows.

1H-NMR (300,4 MHz, solvent: CDCl3standard: TMS) δ 1,37-to 1.79 (m, 6H), to 3.64 (t, J=6.3 Hz, 2H), 4.00 points (t, J=6.5 Hz, 2H), 5,47 (c, 1H).

Example 7-2: Example of getting CHCl=CClO(CH2)5OCOCF(CF3)OCF2CF(CF3CF2OCF2CF2CF3

CHCl=CClO(C 2)5OH (1.3 kg)obtained by the method according to example 7-1, and triethylamine (2.5 kg) were placed in a reactor and stirred under cooling with ice. In the reactor for 10 hours was added dropwise CF3CF2CF2OCF(CF3CF2OCF(CF3)COF (3.4 kg) while maintaining the internal temperature is not more than 10°C. After adding dropwise to the stirring was carried out at room temperature for 2 hours at an internal temperature not exceeding 15°C, was added 30 l of water.

The crude liquid was subjected to separation of the phases, the bottom layer was twice washed with 50 l of water, then was carried out by liquid phase separation, dehydration using molecular sieves and filtered, resulting in received above the liquid mixture. Some GC purity specified in the title compound was 92%.

The results of the analysis

CHCl=CClO(CH2)5OCOCF(CF3)OCF2CF(CF3CF2OCF2CF2CF3were as follows:

1H-NMR (300,4 MHz, solvent: CDCl3standard: TMS) δ 1,41 of-1.83 (m, 6H), 4.00 points (t, J=6.0 Hz, 2H), 4,29 is 4.45 (m, 2H), 5,48 (c, 1H).

19F-NMR (282,7 MHz, solvent: CDCl3reference: CFCl3) δ (ppm) -79,9(1F), -81,4(3F), -82,2(3F), -86,5(1F), -129,5(2F), -131,5(1F).

Example 7-3: Example of getting CF2ClCFClO(CF2)5OCOCF(CF3)OCF2CF(CF3CF2CF2 CF3

In a 3 l autoclave made of Nickel was added CF3CF2CF2OCF(CF3CF2OCF(CF3)COF (3807 g), was stirred and kept at 20°C. At the gas outlet of the autoclave was set the refrigerator temperature to be maintained at -10°C. After the filing of gaseous nitrogen for 1.5 h gave 20% gaseous fluorine with volumetric rate 205,23 l/hour for 1.5 hours.

Then, the inner temperature of the autoclave was brought to 25°and when applying 20% of fluorine gas with the same flow rate for 5 hours was injected CHCl=CClO(CH2)5OCOCF(CF3)OCF2CF(CF3CF2CF2CF3(169 g)obtained in example 7-2, and then the crude reaction liquid (262 g) was extracted (operation 1). Listed in the following table operations 2-6 were carried out in the same manner.

Table 6
OperationEnter the amount (g)The time of injection (hours)The crude reaction liquid (g)Output (g)
11695,026241
21374,026543
3432to 12.02674
41804,026954
51824,026854
61854,026762

After completion of operation 6 in the reactor remained 3386 g of the crude reaction liquid. The crude reaction liquid, extracted in operations 1-6 were combined and analyzed by GC-MS, it was confirmed that the mixture containing CF3CF2CF2OCF(CF3CF2OCF(CF3)COF and indicated in the title compound as main components. The outputs specified in the header of the compounds contained in the crude reaction liquid, extracted at the corresponding operations defined GC, shown in the table.

Example 8

Example of getting CF2ClCFClCF2CF2OCOCF2CFClCF2Cl

In a 4 l autoclave made of Nickel, as a solvent was added CF2ClCFClCF2COF (3600 g), was stirred and kept at 25°C. At the gas outlet of the autoclave was set the refrigerator temperature to be maintained at -10°C. After the gaseous nitrogen supply for 2.0 hours gave 50% gaseous fluorine 201,42 l/h for 1 hour. Then when applying 20% of fluorine gas with a volumetric rate 201,42 l/h) the internal temperature of the reactor was changed to 5° With and within 18 h were injected liquid mixture containing CH2ClCHClCH2CH2OCOCF2CFClCF2Cl (590 g) and CF2ClCFClCF2COF, and the crude reaction liquid (534 g) was extracted (operation 1). Some GC purity specified in the header of the compounds contained in the crude reaction liquid (excluding the solvent), was 11%. Listed in the following table operations 2-6 were carried out in the same way.

Table 7
OperationEnter the number-

in (g)
Time Priscila-

of (h)
Volumetric flow rate of gotoblas-

aqueous fluorine (l/h)
The crude reaction liquid (g)The degree of purity (%)
159018201,4253411
266216258,5053818
36631681031
471822201,4281848
56382056455
6 7172456461

Then, while maintaining the internal temperature of the reactor at 25°filed With gaseous fluorine, diluted to 20% nitrogen gas, the volumetric flow rate 240,57 l/h for 24 hours and, in addition, gave gaseous fluorine, diluted to 50% nitrogen gas, the volumetric flow rate 95,84 l/h for 8 hours. Then took 270 g of the crude reaction liquid. The degree of purity specified in the header of the compounds contained in the crude reaction liquid was 70% (excluding the solvent).

Then gave gaseous fluorine, diluted to 50% nitrogen gas, the volumetric flow rate 126,26 l/h and while maintaining the internal temperature of the reactor at 25°C for 10 h was injected liquid mixture containing CH2ClCHClCH2CH2OCOCF2CFClCF2Cl (249 g) and CF2ClCFClCF2COF. Extracted 275 g of the crude reaction liquid. In the reactor remained 2634 g of the crude reaction liquid. The degree of purity specified in the header of the compounds contained in the crude reaction liquid was 86% (excluding the solvent).

Industrial applicability

In accordance with the method of the present invention fluorinated ester compound may be receiving what about the high yield in the implementation of the fluorination reaction of the ester compound in the presence of compounds having allforyou(s) group(s), which has a high ability to dissolve the ester compound and which can also act as a liquid phase for the reaction of fluorination.

The liquid mixture of the ester compounds used for the fluorination reaction, and compounds having allforyou(s) group(s), can be obtained by etherification of compounds having allforyou(s) group(s)taken in excessive quantities, and compounds having hydroxyl(s) group(s). Etherification is also convenient from the point of view that the number of compounds containing a hydroxyl group remaining in the reaction product, can be reduced. In addition, the advantage is that carried out after the esterification stage of purification can be simplified.

In addition, the reaction product of the fluorination may be a mixture of fluorinated ester compounds and compounds having allforyou(s) group(s). When the fluorinated ester compound is, for example, the compound (4)in which the ester bond can be subjected to dissociation, an effective method is a method of implementation of the dissociation reaction with the direct use of the reaction product of fluorination.

In addition, when the method of the present invention group is s chosen what RAFand RBFare the same, fluorinated ester compound (5A)formed by the dissociation reaction of the ester, and the compound (2) are the same compounds, allowing the separation and purification of the product can be simplified.

Furthermore, the method of using compound (2)obtained from the reaction product of dissociation of the ester bonds of the compound (4), in the form of compounds (2)subject to interaction with compound (1), is a convenient way to continuously get the desired compounds (4) and (5) with high efficiency.

The method of the present invention is a method, which can be done without preparation of solvent for each reaction. Moreover, it is a method that can be performed without separating the solvent before implementation of the next stage. In addition, it is a convenient way that can be done without the use of adverse environmental solvent, such as R-113.

1. A method of obtaining a fluorinated ester compound (4), including fluoridation of ester compound (3), which is an ester compound (1)having hydroxyl(s) group(s), compound (2)having allforyou(s) group(s), and which has a structure that mo is et to be fluorinated in a liquid phase to obtain fluorinated ester compound (4), where fluoridation is carried out in a liquid mixture of the ester compound (3) and compound (2)having allforyou(s) group(s), where formula (1) to (4) below:

RACHR1OH (1);

FCORBF(2);

RACHR1OCORBF(3);

RAFCFR1FOCORBF(4),

where RBFrepresents a group having all hydrogen atoms present in the group selected from monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, substituted by fluorine atoms;

RArepresents a monovalent saturated hydrocarbon group, a partially halogenated monovalent saturated hydrocarbon group, a monovalent saturated hydrocarbon group containing an etheric oxygen atom, or a partially halogenated monovalent saturated hydrocarbon group containing an etheric oxygen atom;

R1represents a hydrogen atom or alkyl group;

R1Frepresents a fluorine atom, if R1represents a hydrogen atom; if R1represents an alkyl group, R1Frepresents an alkyl group, which may be the same or different from R1; and, when the R 1and R1Fdiffer from each other, R1Frepresents a fluorinated alkyl group obtained by fluorination of R1; and

RAFrepresents a group having all hydrogen atoms present in the group RAsubstituted by fluorine atoms in this way.

2. The method according to claim 1, where the liquid mixture of the ester compound (3) and compounds having allforyou(s) group(s)obtained by esterification using compound (2)having allforyou(s) group(s), and where the amount of compound (2)having allforyou(s) group(s), more than the stoichiometric quantity which is necessary for the esterification of all hydroxyl groups in the compound (1)having hydroxyl(s) group(s), and the number is such that the unreacted compound (2)having allforyou(s) group(s)remains in the reaction product.

3. The method of obtaining the compound (5), below, and/or compound (2)shown below, comprising the reaction of dissociation of the ester bonds in the compound (4)obtained by the method defined in claim 1:

RAFCOR1F(5);

RBFCOF (2),

where RAFand R1Fdefined in claim 1.

4. The method according to claim 3, where the reaction of dissociation of the ester bonds is carried out in a liquid mixture of compound (2) and compound (4)obtained by the reaction of fluorination W is dcoi mixture of compound (3) and compounds (2).

5. The method according to claim 3, where the dissociation reaction of the ester of communication carried out without added solvent, different from the compounds (2), in a liquid mixture of compounds (4) and compounds (2).

6. The method according to claim 3, where part or all of the compound (2)obtained by the method specified in one of PP-5, or when R1Frepresents a fluorine atom, a part or all of the connection (5) and/or compound (2) is used as the compound (2)subject to interaction with compound (1).

7. The method according to claim 3, where RAFand RBFrepresent groups having the same structure.

8. The method according to claim 3, where the fluorination in the liquid phase carried out by reaction with fluorine in a liquid phase.

9. The method according to claim 3, where the fluorination in the liquid phase is carried out in the absence of a solvent other than the compound (2).



 

Same patents:

FIELD: organic chemistry, in particular polymers.

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

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

FIELD: industrial organic synthesis.

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

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

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

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

8 cl, 23 ex

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

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

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

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

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

FIELD: organic chemistry, in particular polymers.

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

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

FIELD: industrial organic synthesis.

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

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

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

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

8 cl, 23 ex

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

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

- bromsulfaleinovy acid" target="_blank">

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

FIELD: organic chemistry, in particular polymers.

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

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

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

FIELD: organic chemistry, in particular polymers.

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

EFFECT: new intermediates useful in polymer fluorination.

11 cl, 7 ex

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

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

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