Method of production of the diene compound

FIELD: chemical industry; methods of production of the diene compounds.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the method of production of the diene compound of the formula CR1R2=CR3CFR4CR5R6OCR7=CR8R9 (1), which includes the initiation of the reaction of Claisen rearrangement for the compound of the formula CFR1R2CR3=CR4CR5R6OCR7=CR8R9 (2) in the mixture containing the diene compound of the formula (1) and compound of the formula (2), with production the product containing the reaction product of Claisen rearrangement of the formula CR5R6=CR4CR3 (CFR1R2) CR8R9CR7=O (3) and the diene compound of the formula (1), and separation of the diene compound of the formula (1) from the reaction product of Claisen rearrangement. At that R1-R9 in the above-stated formulas may be similar or different, and represent the atom of halogen, the atom of hydrogen, the trifluoromethyl group or the trifluoromethoxy group. The method allows to produce the diene compound of the formula (1) with the high degree of purity.

EFFECT: the invention ensures production of the diene compound of the formula (1) with the high degree of purity.

8 cl, 9 ex

 

The invention relates to a method for producing diene compounds with a high degree of purity. In addition, the present invention relates to a method for producing diene compound using a rearrangement reaction of Clausena.

Upon receipt of olefinic compounds reaction rearrangement of the double bond can be carried out during or after the process of obtaining obtaining structural isomer, which has the same molecular formula, but unsaturated bond in a different position. If structural isomer has a reactivity comparable to the reactivity of the desired olefinic compounds the problem by changing the properties of olefinic compounds. On the other hand, if the reactivity of the structural isomer is low, there is another problem related to the fact that it interferes with the reaction of the desired olefin.

There is another problem caused by the fact that the structural isomer has a boiling point that is too close to the temperature desired olefin, which makes separating it by distillation. In addition, even if an attempt is made to separate the isomers by azeotropic distillation, extractive distillation or chromatography, available for the separation of compounds having close to each other temperatures the boiling point, properties of structural isomers (e.g., polarity, etc. will be so similar to the properties of the desired olefin, which would be difficult to separate them from each other.

We offer the following ways to obtain one of the desired olefin, by so small a number of structural isomer as possible.

(a) the Manner in which the compound represented by the following formula (A1-2), obtained by pyrolysis in the vapor phase compound of the formula (A1-1) and then carry out the reaction of dechlorination in the presence of zinc with 3 bouteilles group, you get a simple 3-butylvinyl ether represented by the following formula (A) (application JP-A-1-143843).

FC(O)CF(CF3)OCF2CF2CFClCF2Cl(A1-1)
CF2=CFOCF2CF2CFClCF2Cl(A1-2)
CF2=CFOCF2CF2CF=CF2(A)

(b) the Manner in which the compound represented by the following formula (A2-2a), obtained by pyrolysis of compounds of formula (A2-1)as the starting material, and then carry out the reaction dechlorination connection, you get a simple 3-butylvinyl ether represented by the following formula (A) (application JP-A-2-311438).

CF2ClCFClOCF2CF2CF2CF2COF(A2-1)CF2ClCFClOCF2CF2CF=CF2(A2-2a)CF2=CFOCF2CF2CF=CF2(A)CF2ClCFClOCF2CF=CFCF3(A2-2b)CF2=CFOCF2CF=CFCF3(A-3)

However, for the synthesis of compounds of formula (A1-1)used in method (a)requires a number of stages. In addition, there is a problem with the fact that the connection requires the use of reagents that are difficult to handle, such as fuming sulfuric acid, monochloride iodine, etc.

Furthermore, the method (b), as shown, is connected with the fact that the reaction is a rearrangement of the double bond takes place in 3-bouteilles group having a fluorine atom in the 1-position in the compound of the formula (A2-2a), thereby forms a thermodynamically more stable compound of the formula (A2-2b). If dechlorination is carried out in the presence of compounds of the formula (A2-2b), there is a problem related to the fact that the compound represented by formula (A-3), is mixed with the final product.

In this case, the compound of the formula (A2-2a) has basically the same properties, including boiling point, since the compound of the formula (A2-2b) and the compound of formula (A) also have, is mainly the same properties, including boiling point, as the compound represented by formula (A-3). Therefore, there is a problem related to the fact that these compounds are difficult to separate, and it is impossible to obtain the compound of formula (A) high purity.

The compound of formula (A)obtained using these methods is suitable as a starting monomer for fluorocarbon polymers. However, if the compound of formula (A) is polymerized in the presence of the compounds of formula (A-3), the polymerization is slowed down so much that it is impossible to obtain fluorocarbon polymer with high molecular weight.

On the other hand, the rearrangement reaction of Clausena, in itself, is a well known reaction. As examples of the rearrangement reaction of Clausena in the fluorine-containing compound have been reported such compounds as CF2=CFOCH2CH=CH2, CF3(CF3)C=CFOCH2CH=CH2, Cl2C=CFOCH2CH=CH2, ClFC=CFOCH2CH=CH2and H(CF3)C=CH(CF3)=CH2CH=CH2(J. Fluorine Chemistry, 1992, 56, 165), the compounds CH2=CH(CF3)OCH2CH=CH2and CH2=CHOCH(CF3)CH=CH2(J. Org. Chem., 1990, 55, 1813), on rearrangement reaction of Clausena of CF2=CFCF2OCF=CF2in CF2=CFCF2CF2CF=O (application JP-A-2-42038) etc.

However, none of these documents describes pereg is upperhouse of Clausena in connection with a 2-butonly fragment with a fluorine atom, linked at the 4-position. The document describing this example, reveals the connection CH2=CHOCH2CH=CHCF2PO(OCH2CH3)2with a group containing phosphorus atom in 4-position, which is converted to CH2=CHCH(CF2PO(OCH2CH3)2)CH2CH=O by heating at 140°C (Chem. Commun., 2000, 1691). However, when conducting the reaction under the same conditions with the compound of the formula (2) according to the invention, which does not contain phosphorus atom, discovered that the klaisen rearrangement does not occur.

The task of the invention to provide a diene compound of formula (1) higher purity by rearrangement reaction of Clausena the compounds of formula (2) to remove it from the mixture of diene compounds of formula (1), having the ability to rearrange the double bond, and the compounds of formula (2), with the structure obtained by rearrangement of the double bonds of diene compounds of formula (1). In addition, the present invention provides a method of obtaining a diene compounds by initiating a rearrangement reaction of Clausena in the new substrate, which has never before been used.

The present invention encompasses each of the following objects of the invention.

1. A method of obtaining a diene compound high h is the frequency, represented by the following formula (1), including the initiation of the rearrangement reaction of Clausena the compounds of formula (2), in a mixture containing the diene compound of formula (1), and the compound of the formula (2), to obtain the product containing the reaction product of the rearrangement of Clausena and diene compound of formula (1), and the separation of diene compounds of formula (1) from the reaction product of the rearrangement of Clausena, or the conversion of the reaction product of the rearrangement of Clausena in its derivative, and then the separation of diene compounds of formula (1) derived from the reaction product of the rearrangement of Clausena,

thus R1-R9in the following formulas may be the same or different and represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, a monovalent hydrocarbon group containing an oxygen atom simple ester group, a halogenated monovalent hydrocarbon group or a monovalent hydrocarbon group containing an oxygen atom, a halogenated simple ester group.

CR1R2=CR3CFR4CR5R6OCR7=CR8R9(1)
CFR1R2CR3=CR4CR5R6OCR7=CR8R9(2)

2. The method in accordance with claim 1 wherein the compound represented by the following formula (3), produced using the rearrangement reaction of Clausena,

the characters in the following formula have the meanings as defined above.

CR5R6=CR4CR3(CFR1R2)CR8R9CR7=O(3)

3. The method in accordance with paragraph 1 or 2, where the compound of the formula (3a) are obtained by rearrangement reaction of Clausena, and the connection formula (2) is a compound of the formula (2a),

the characters in the following formula have the meanings as defined above.

CFR1R2CF=CR4CR5R6OCF=CR8R9(2a)
CR5R6=CR4C(CFR1R2)=CR8R9(3a)

4. Method according to any paragraph 1, 2 and 3, where R1-R9may be the same or different and represent fluorine atom, a hydrogen atom, a chlorine atom, triptorelin group or cryptometer.

5. Method according to any paragraph 1, 2, 3 and 4, where all R1-R9independently of one another represent fluorine atom.

6. The method according to the according to any paragraph 1, 2, 3, 4 and 5, where the reaction rearrangement of Clausena initiated by heating the mixture in the vapor phase.

7. The method in accordance with paragraph 6, where the reaction rearrangement of Clausena initiate in the presence of an inert gas or an inert solvent, which turns into a gas at the reaction temperature.

8. Method according to any paragraph 1 to 7, where the reaction rearrangement of Clausena carried out in the presence of a polymerization inhibitor.

9. Method according to any paragraph 1 to 8, where the reaction rearrangement of Clausena initiated by heating the mixture at a temperature of from 150 to 400°C.

10. The method in accordance with any of paragraphs 1-9, where the compound of the formula (2) is a compound obtained by reaction of a rearrangement of the double bond in the compound of formula (1), or a compound obtained by dechlorination reaction of compounds of formula (1B-3),

the characters in the following formula have the meanings as defined above.

CFR1R2CR3=CR4CR5R6OCClR7-CClR8R9(1B-3)

11. A method of obtaining a fluorine-containing polymer comprising the polymerization of diene compounds of formula (1) high purity, obtained by using one of the methods defined in the above paragraph is x 1-10, or the polymerization of diene compounds and compounds, copolymerizable with diene compound.

12. The method of obtaining the compounds of formula (3), comprising the rearrangement reaction of Clausena in the compound of the formula (2),

thus R1-R9in the following formulas may be the same or different and represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, a monovalent hydrocarbon group containing an oxygen atom simple ester group, a halogenated monovalent hydrocarbon group or a monovalent hydrocarbon group containing an oxygen atom, a halogenated simple ester group.

CFR1R2CR3=CR4CR5R6OCR7=CR8R9(2)
CR5R6=CR4CR3(CFR1R2)CR8R9CR7=O(3)

13. The method of obtaining the compounds of formula (3a), comprising heating the compounds of formula (2a), in the presence of soda ash or glass balls,

thus R1, R2, R4, R5, R6, R8and R9in the following formulas may be the same or different and represent a hydrogen atom, halogen atom, monovalent have glevodorodnogo group, monovalent hydrocarbon group containing an oxygen atom simple ester group, a halogenated monovalent hydrocarbon group or a monovalent hydrocarbon group containing an oxygen atom, a halogenated simple ester group.

CFR1R2CF=CR4CR5R6OCF=CR8R9(2a)
CR5R6=CR4C(CFR1R2)=CR8R9(3a)

In the present description diene compound represented by the formula (1)will be referred to as diene compound (1). Other connections will be specified similar to.

In the diene compound (1) R1-R9may be the same or different, represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, a monovalent hydrocarbon group containing an oxygen atom simple ester group, a halogenated monovalent hydrocarbon group or a monovalent hydrocarbon group containing an oxygen atom, a halogenated simple ester group. The halogen atom is preferably fluorine atom or chlorine, particularly preferably a fluorine atom. Monovalent hydrocarbon group preferably represents an alkyl group. One is valent hydrocarbon group, containing an oxygen atom simple ester group, preferably represents alkoxygroup.

If R1-R9independently represent a halogenated group, a halogenated group is preferably a fluorinated group. Halogenated monovalent hydrocarbon group preferably represents an alkyl fluoride group, particularly preferably performanceline group. Monovalent hydrocarbon group containing an oxygen atom, a halogenated simple ester group, preferably represents forelcosure, particularly preferably, performancehow.

Preferably R1-R9independently represent a hydrogen atom, a fluorine atom, fluorinated monovalent hydrocarbon group or a monovalent hydrocarbon group containing an oxygen atom, a fluorinated simple ester group, particularly preferably a fluorine atom or a fluorinated monovalent saturated organic group, and most preferably a fluorine atom, a hydrogen atom, an alkyl fluoride group, or forelcosure. In addition, preferably, R1-R9independently represent a fluorine atom or a perfluorinated group, one of these groups, particularly preferably a fluorine atom, triptorelin the Yu group, or cryptometer.

Diene compound (1) according to the invention is preferably a compound where R1, R2, R7and R8independently represent fluorine atoms, because the connection with the polymerized unsaturated bond, is especially suitable for use. In addition, other groups (R3-R6and R9) independently represent, preferably, a fluorine atom, performanceline group or performancehow, particularly preferably a fluorine atom.

There are no restrictions on obtaining a diene compound (1). Specific examples of the diene compound (1) include the compounds listed below. The configuration of the two double bonds in the compounds may constitute, for each, either E or Z.

CF2=CF-CF2-CF2-O-CF=CF2,

CF2=CF-CF2-CF(CF3)-O-CF=CF2,

CF2=CF-CF(OCF3)-CF2-O-CF=CF2,

CH2=CH-CF2-CF2-O-CF=CF2,

CH2=CH-CF(CF3)-CF2-O-CF=CF2,

CF2=CH-CF2-CF2-O-CF=CF2,

CF2=CH-CF(CF3)-CF2-O-CF=CF2,

CF2=CF-CF2-CH2-O-CF=CF2,

CF2=CF-CF2-CCl2-O-CF=CF2and

CF2=CF-CF2-CHCl-O-CF=CF2.

The present invention uses a mixture containing dienes is e connection (1) and the compound (2). Group (R1-R9in the compound (2) have the same meanings as defined above, and correspond to the groups in the diene compound (1). These compounds are compounds having a 2-butonly structural fragment in which the fluorine atom is attached at the 4-position. The configuration of the two double bonds in the compound (2) can represent, for each, either E or Z.

CF3-CF=CF-CF2-O-CF=CF2,

CF3-CF=CF-CF(CF3)-O-CF=CF2,

CF3-CF=C(OCF3)-CF2-O-CF=CF2,

CH2F-CH=CF-CF2-O-CF=CF2,

CH2F-CH=C(CF3)-CF2-O-CF=CF2,

CHF2-CH=CF-CF2-O-CF=CF2,

CF3-CH=C(CF3)-CF2-O-CF=CF2,

CF3-CF=CF-CH2-O-CF=CF2,

CF3-CF=CF-CCl2-O-CF=CF2and

CF3-CF=CF-CHCl-O-CF=CF2.

The upper limit of the content of the compound (2) in the mixture is preferably 50 wt.%, particularly preferably, 10 wt.%, in relation to the total number of diene compounds (1) and compounds (2). On the other hand, the lower limit of the content of the compound (2) is not limited in any way and usually is preferably of 0.003 wt.%, particularly preferably, 0.03 wt.%, in relation to the total number of diene compounds (1) and compounds (2). Using the method according to the invention, the compound (2) can be Department is but even if the amount of the compound (2) is approximately 300 ppm mass; therefore, can be obtained diene compound (1) with a high degree of purity.

There are no limitations to obtain the compound (2)compound (2) according to the invention preferably is a compound obtained by rearrangement of the double bonds in the diene compound (1). Because the diene compound (1) is a compound having a specific structure in which a fluorine atom linked to the carbon atom connected with R4it represents the connection is subjected to rearrangement reaction of a double bond. The implementation of the rearrangement will result in compounds (2).

For example, the rearrangement of the following compound (1A-1), where all R1-R9in the diene compound (1) are fluorine atoms, is carried out by the mechanism described below, and the resulting product typically is a mixture of compounds (1a-1) and compounds (2a-l).

The mixture according to the invention preferably is a mixture of diene compounds (1) and compound (2)containing the compound (2)obtained by rearrangement reaction of double bonds in the diene compound (1). Thus, the present invention prefer is Ino used as a method of separating compounds (2) and mixtures obtained by rearrangement reaction of a double bond in part of the desired diene compound (1).

An example of a mixture according to the invention is a reaction product formed when receiving diene compound (1). If reaction conditions upon receipt of diene compounds (1) are sufficient to initiate the rearrangement reaction of diene compounds (1), connection (2) may be present in the reaction product.

An example of the mixture according to the invention is the reaction product of pyrolysis of the following compound (1B-1), the reaction product of dechlorination of the compound (1B-2), etc. In the case that the compound (1B-2) is mixed with compound (1B-3), during the dechlorination reaction of the compound (1B-2), the reaction product of dechlorination may be a mixture of compounds (1) and compounds (2). In this case, the characters in the following formulas have the same meanings as defined above.

FCOCR1R2CR3FCFR4CR5R6OCR7=CR8R9(1B-1),
CR1R2=CR3CFR4CR5R6OCClR7-CClR8R9(1B-2)
CFR1R2CR3=CR4CR5R6OCClR7-CClR8R9(1B-3).

p> Compound (1B-3) is a compound which can easily be obtained by rearrangement of the double bond in the compound (1B-2).

The mixture according to the invention may contain another connection in addition to the diene compound (1) and the compound (2). This is another compound preferably is a compound selected from the compounds which can be separated from diene compounds (1), and the product of the rearrangement reaction of the compound (2), and a compound that does not react with the diene compound (1), connecting (2) and reaction product of the rearrangement of the compound (2), and in respect of the other compounds do not have any restrictions.

In the present invention, the reaction rearrangement of Clausena is initiated in a mixture with compounds (2) to obtain the product containing the reaction product of the rearrangement of Clausena and diene compound (1). The rearrangement reaction of Clausena can be carried out by bringing the mixture to a temperature higher than the temperature at which may be a reaction to regroup Clausen, and, as a rule, the reaction can be carried out due to the heat. The temperature during heating is preferably higher than the boiling point of diene compounds (1) and compounds (2), and, as a rule, preferably, with whom is from 150 to 400° C, particularly preferably from 200°C to 350°C, and most preferably from 270 to 320°C. if the mixture is a product of low-temperature reactions, and the reaction rearrangement of Clausena can occur at room temperature or below, klaisen rearrangement may be carried out by maintaining the reaction product only at room temperature.

The klaisen rearrangement is preferably carried out as a reaction in the vapor phase and preferably carrying out rearrangement reaction by heating the mixture in the vapor phase. In addition, since the rate of rearrangement of the compound (2) depends on temperature, the reaction time can be reduced if it is carried out in the vapor phase, in which the temperature is maintained high. A shorter reaction time is a great advantage, as it can only be desired reaction rearrangement of Clausena, while polymerization of the compounds (1) and compounds (2), which are polymerized compounds is prevented.

During the reaction in the vapor phase, it is preferable to heat the mixture by introducing her to the evaporator, heated to a temperature higher than the boiling point of diene compounds (1) and compounds (2), for vaporization of the mixture, and then the introduction of parool aznoe mixture in a heated reactor. There are no restrictions regarding the form or type of reactor, and, as a rule, it is preferable for the tubular reactor. In addition, it is preferred continuous introduction of the mixture in the reactor and the continuous release of the product. The residence time of the gaseous mixture in the reactor is preferably from about 1 to 30, particularly preferably from 4 to 20, most preferably from 6 to 15 C. By regulating the residence time in the corresponding range of the desired response to regroup Clausena can be carried out without polymerization.

In addition, dilute vapors of the reaction mixture is preferably diluted with an inert gas or an inert solvent, which passes into the gaseous state at the reaction temperature. The inert gas may be a gaseous argon, nitrogen gas, helium gas or the like, the Quantity of inert gas is preferably greater than 3-10 times the amount of the original gaseous mixture. The presence of the inert gas can improve the manufacturability of the reaction. In addition, the presence of an inert solvent can prevent polymerization. The inert solvent is selected from such liquids into gas and are inert at the temperature to which they are heated, and can be selected, for example, perfluorocarbons is in, chlorinated fluorinated hydrocarbons and the like, the Amount of inert solvent is preferably determined such that the total concentration of diene compounds (1) and compounds (2) becomes equal to from about 10 to 30 mol.%

On the other hand, if the klaisen rearrangement is carried out as a liquid-phase reaction is preferred as the reaction by heating under pressure.

In addition, if the diene compound (1), connection (2) and reaction product of the rearrangement are polymerized compounds, the reaction rearrangement of Clausena preferably carried out in the presence of a polymerization inhibitor, regardless of whether the reaction is carried out in the vapor or in the liquid phase. The polymerization inhibitor may be selected from α-pinene, diphenylpicrylhydrazyl, three-p-nitrophenylthio, p-benzoquinone, p-tert-butylcatechol, nitrosobenzene, picric acid, dithiobenzyl disulfide, etc. the Amount of the polymerization inhibitor to be used, is preferably from 0.01 to 10 wt.%, particularly preferably, from 0.01 to 5 wt.%, most preferably, from 0.2 to less than 1 wt.%, in relation to the total number of diene compounds (1) and compounds (2).

In addition, if the rearrangement reaction of Clausena implementation through the Xia as liquid-phase reaction, the reaction system is preferably carefully desarrolla to prevent polymerization. Liquid-phase reaction should be carried out in the presence of a solvent. As the preferred solvent is a polar solvent. In addition, the reaction may be carried out in the presence of a catalyst (acid or the like), if necessary.

According to the invention the reaction rearrangement of Clausena initiated connection (2). As the compound (2) is a compound that accepts the transition state 6-membered rings, as shown in the following formula, klaisen rearrangement is carried out with the formation of the reaction product represented by the following formula (3).

CR5R6=CR4CR3(CFR1R2)CR8R9CR7=O(3)

The product of the rearrangement of Clausena, as a rule, represents a connection (3), but, in the case of compound (2a), where R3and R7in the compound (2) independently represent fluorine atoms, depending on the reaction conditions can be obtained the following compound (3a). In this case, in the following formulas, the symbols have the same meanings as defined above.

CR5R6=CR4C(CFR1R2)=CR8R9(3A)

Conditions, which can be obtained compound (3a), is that the rearrangement reaction of Clausena is carried out by heating in the presence of soda ash or glass beads.

Specific examples of the compounds (3) include the following compounds.

CF2=CF-CF(CF3)-CF2-COF,

CF2CF=CF2-CF(CF3)-CF2-COF,

CF2=C(OCF3)-CF(CF3)-CF2-COF,

CF2=CF-CF(CH2F)-CF2COF,

CF2=C(CF3)-CH(CHF2)-CF2-COF,

CF2=CF-CF(CHF2)-CF2-COF,

CF2=C(CF3)-CH(CF3)-CF2-COF,

CH2=CF-CF(CF3)-CF2COF,

CCl2=CF-CF(CF3)-CF2-COF and

CHCl=CF-CF(CF3)-CF2-COF.

Specific examples of the compound (3a) include the following compounds.

CF2=CF-C(CF3)=CF2,

CF2CF=CF2-C(CF3)=CF2,

CF2=C(OCF3)-CF(CF3)=CF2,

CF2=CF-CF(CH2F)=CF2,

CF2=CF-C(CHF2)=CF2,

CH2=CF-C(CF3)=CF2,

CCl2=CF-C(CF3)=CF2and

CHCl=CF-C(CF3)=CF2.

On the other hand, since the diene compound (1) is a compound which is n who can take the transition state 6-membered ring, it can be retrieved directly from the reaction product after the rearrangement of Clausena.

The present invention includes one of the following stages, method 1; diene compound (1) is separated from the reaction product of the rearrangement of Clausena, or method 2; the reaction product of the rearrangement of Clausena converted into the derivative, and then diene compound (1) is separated from the derivative of the reaction product of the rearrangement of Clausena, you get a diene compound (1) high purity.

In method 1 does not provide for any restrictions for the separation of diene compounds (1) and the product of the rearrangement reaction in the resulting product of one from the other, and usable methods include distillation, chromatography, washing water, etc. for Example, if the boiling point of diene compounds (1) and reaction product of the rearrangement of Clausena differ from each other, they are easily separated by distillation. In addition, if at the end of the slice product rearrangement reaction is a water-soluble group (for example, group-COF group-COCl and the like), they are easy to share with each other by rinsing with water. In addition to this may be used another method of separation (for example, separation by chromatography). If the reaction product paragrapher the Cai of Clausena represents a connection (3), this compound (3) has the same molecular weight as the diene compound (1), but in the compound (3) is a carbonyl group having a different polarity; therefore, it can be easily separated from the diene compound (1) by chromatography, distillation, a method of forming hydrate on a carbonyl group or another similar method.

In method 2, after the conversion of the reaction product of the rearrangement of Clausena in a derived, the diene compound (1) is separated from the derivative of the reaction product of the rearrangement of Clausena. For example, if the product of the rearrangement is a compound (3), it is converted into another derivative due to the reactivity of the carbonyl residue, and then the derivative is separated from the diene compound (1) using a known method. Some of the other ways of converting the compound (3) in the second derivative represents a way of increasing the molecular weight by the reaction of the combination, the method of recovery of the carbonyl group to a hydroxyl group, etc. furthermore, the method of separation after the stage of forming derivative may be selected from methods similar to those used in method 1.

In accordance with the method according to the invention, the compound (1) is separated from the mixture of compound (1) and compounds (2) by reaction of transport is piroski of Clausena, you get a connection (1) of high purity. If the compound (1)obtained using the method according to the invention is a curable compound can be obtained fluorocarbon polymer with a high molecular weight, since the compound (2)which adversely affects the polymerization is separated.

In addition, the present invention also provides a method of obtaining the following compounds (3), comprising the rearrangement reaction of Clausena in connection (2). The present invention also provides a method of obtaining a compound (3a), comprising heating the compound (2a) in the presence of glass beads or soda ash. In this case, the symbols in the formula have the same meanings as defined above. These methods of obtaining can be carried out also during the rearrangement reaction of Clausena in a mixture of compounds (2) and compounds (1).

CFR1R2CR3=CR4CR5R6OCR7=CR8R9(2)
CR5R6=CR4CR3(CFR1R2)CR8R9CR7=O(3)
CR5R6=CR4C(CFR1R2)=CR8R9(3a)

EXAMPLES

Next, the image is giving will be described with additional detail examples of execution. Note, however, that the invention is not limited to these examples.

REFERENCE EXAMPLE 1

1-inch tubular reactor made of INCONEL fill the glass ball, the layer height of 20 cm, and heated to 330°C. the Compound of the formula CF2ClCFClO(CF2)4COF (300 g, 0,725 mol), diluted to 10 vol.% gaseous nitrogen is introduced into the tubular reactor. The reaction is carried out, simultaneously locking the velocity of the gas when the value of 2.0 cm/s and maintaining the residence time of the reaction gas in the layer of glass balls with the value 10 S. the Exiting gas from the tubular reactor is captured by the trap dry ice - ethanol. The captured liquid (250 g) analyzed by gas chromatography (GC) and find that the degree of conversion of the source material is 99.9%, CF2ClCFClOCF2CF2CF=CF2get with selectivity to 90.4%, and CF2ClCFClOCF2CF=CFCF3(mixture of CIS-form and TRANS-form)derived from the rearrangement of the double bond, get with the selectivity of 4.8%. Trying to identify CF2ClCFClOCF2CF=CFCF3by distillation and purification using chromatography on a column of silica gel, but provide a separation is not possible.

REFERENCE EXAMPLE 2

A mixture of 0.7 mole) of the product obtained in reference example 1, is introduced into the addition funnel. On the other hand, digitiform the foreign Ministry of 7.0 mol) and zinc (3,5 mol) are loaded into a 1 l flask. The distillation column is attached to the upper part of the 1 l flask, and carry out the distillation, continuously adding dropwise the mixture from a dropping funnel. Dekhlorirovanie product is continuously distilled in distillation. The distilled liquid (156 g) analyzed by GC and, as shown, receive CF2=CFOCF2CF2CF=CF2with the release of 72%.

The liquid contains CF2=CFOCF2CF=CFCF3that is dekhlorirovanie product CF2ClCFClOCF2CF=CFCF3and his number is 10% (% by area peak in GC) in relation to CF2=CFOCF2CF2CF=CF2. Found that CF2=CFOCF2CF=CFCF3unable to select it using the distillation and purification using chromatography on a column of silica gel.

EXAMPLE 1

The distilled liquid (50 g)containing CF2=CFOCF2CF2CF=CF2and CF2=CFOCF2CF=CFCF3obtained in reference example 2, is introduced into the evaporator heated at 100°C, evaporation and then diluted to 30% vol. gaseous nitrogen. Gas is injected in a 100-cm (1/2-inch reactor made of INCONEL, heated at 310°C. the velocity of the gas control with a value of 8.3 cm/s, and the residence time of the reaction gas is maintained at the value 12 S. the Products in the outgoing gas is collected by passing through stekljannoe the trap, cooled at -78°C using a dry ice - ethanol, and extracted 48 g of liquid. The extracted liquid is analyzed by GC, and the analysis confirms the presence of CF2=CFOCF2CF2CF=CF2and CF2=CFCF(CF3CF2COF and the absence of CF2=CFOCF2CF=CFCF3. The output CF2=CFOCF2CF2CF=CF2is 92%. The extracted liquid distil with getting CF2=CFOCF2CF2CF=CF2purity according to GC to at least 99.9 percent.

EXAMPLE 2

Distilled water (30 g)obtained in reference example 2, is mixed with CF2ClCF2CHClF (R225cb, 70 g) to obtain a solution. This solution is evaporated in the evaporator heated at 100°C, and then diluted to 90 vol.% gaseous nitrogen. Gas is injected in a 100-cm (1/2-inch tubular reactor made of INCONEL, heated at 310°C. the velocity of the gas is controlled at 8.3 cm/s, and the residence time of the reaction gas is maintained at the value 12 S. the reaction Products leaving gas is collected by passing through a glass trap cooled at 0°C, using traps of ice water and extract (98 g). The extracted liquid is analyzed by GC, and the analysis confirms the presence of CF2=CFOCF2CF2CF=CF2and CF2=CFCF(CF3CF2COF and the absence of CF2=CFOCF2CF=CFCF3. The output CF2 2CF2CF=CF2is 93%. The extracted liquid distil with getting CF2=CFOCF2CF2CF=CF2purity according to GC to at least 99.9 percent.

EXAMPLE 3

The distilled liquid (50 g)obtained in reference example 2, the pre-evaporated in the evaporator heated at 100°C and then directly injected into a 100-cm (1/2-inch tubular reactor made of INCONEL, heated at 310°C. the velocity of the gas control with a value of 8.3 cm/s, and the residence time of the reaction gas support when the value 12 S. the reaction Products in the outgoing gas is collected by passing through a glass trap cooled at 0°C, using traps out of the water with ice and extract (48 g). The extracted liquid is analyzed by GC, and the analysis confirms the presence of CF2=CFOCF2CF2CF=CF2and CF2=CFCF(CF3CF2COF and the absence of CF2=CFOCF2CF=CFCF3. There is a poor polymerization CF2=CFOCF2CF2CF=CF2and the output of CF2=CFOCF2CF2CF=CF2is 79%. The extracted liquid distil with getting CF2=CFOCF2CF2CF=CF2purity according to GC to at least 99.9 percent.

EXAMPLE 4

Inhibitor of polymerization (2-pinene, 1 g) is added to the distilled liquid (49 g)obtained in sprawozdanie 2, to obtain the solution. This solution is evaporated in the evaporator heated at 100°C and then injected in a 100-cm (1/2-inch tubular reactor made of INCONEL, heated at 310°C. the velocity of the gas control with a value of 8.3 cm/s, and the residence time of the reaction gas is maintained at the value 12 S. the reaction Products in the outgoing gas is collected by passing through a glass trap cooled at 0°C, using traps of ice water and extracted (48 g). The extracted liquid is analyzed by GC, and the analysis confirms the presence of CF2=CFOCF2CF2CF=CF2and CF2=CFCF(CF3CF2COF and the absence of CF2=CFOCF2CF=CFCF3. The output CF2=CFOCF2CF2CF=CF2is 92%. The extracted liquid distil with getting CF2=CFOCF2CF2CF=CF2purity according to GC to at least 99.9 percent.

EXAMPLE 5

CF2=CFOCF2CF2CF=CF2(150 g), not containing CF2=CFOCF2CF=CFCF3obtained in example 1, methanol (23.7 g), initiator ([(CH3)2CHOCO]23 g), dispersant (6.7 g, trade name: LEVENOL WZ, manufactured by Kao Corporation) and ultrapure water (800 g) are loaded into a 1 l separating flask and stirred generally for 26 h, 20 h at 40°C and 6 h at 50°to perform the polymerization. The resulting suspension is passed che is ez 4-μm filtration film, on the filter, dried at 100°C for 20 h, while getting a cyclic polymer having a repeating link below formula. The output of the cyclic polymer is 93%, and a characteristic viscosity equal to 0.35.

COMPARATIVE EXAMPLE 1

The polymerization reaction carried out analogously to example 5, using CF2=CFOCF2CF2CF=CF2containing 0.08 wt.% CF2=CFOCF2CF=CFCF3. The output of the cyclic polymer is 87%, and the characteristic viscosity equal to 0.31 in.

COMPARATIVE EXAMPLE 2

The polymerization reaction carried out analogously to example 5, using CF2=CFOCF2CF2CF=CF2,containing about 0.15 wt.% CF2=CFOCF2CF=CFCF3. The output of the cyclic polymer is 85%, and a characteristic viscosity of 0.30.

In accordance with the method according to the invention compound (2) is separated from a mixture containing the compound (1) and the compound (2)having the same molecular formula and molecular weight as the compound (1), without using any special reagent or complex technology, it is possible obtain the compound (1) with a high degree of purity. If the compound (1)obtained by the method according to the invention is a curable compound, the method according to image meniu also provides the opportunity to separate the compounds (2) without substantial polymerization of the compound (1). In addition, if the compound (1) is polymerized, since the separated compound (2)which adversely affect the polymerization, by polymerization of the compound (1)can be obtained fluorocarbon polymer having a higher molecular weight.

1. A method of obtaining a diene compound of formula (1), including the initiation of the rearrangement reaction of Clausena the compounds of formula (2) in a mixture containing the diene compound of formula (1) and the compound of the formula (2), to obtain the product containing the reaction product of the rearrangement of Clausena formulas (3) and the diene compound of formula (1), and the separation of diene compounds of formula (1) from the reaction product of the rearrangement of Clausena, R1-R9in the following formulas may be the same or different, represent a halogen atom, a hydrogen atom, triptorelin group or cryptometer,

CR1R2=CR3CFR4CR5R6OCR7=CR8R9(1)

CFR1R2CR3=CR4CR5R6OCR7=CR8R9(2)

CR5R6=CR4CR3(CFR1R2)CR8R9CR7=O (3).

2. The method according to claim 1, characterized in that in the case of use as the source connection of the formula (2A) when heated in the presence of altimirano soda or glass beads, as a product of the rearrangement of Clausena get compound of formula (3A), R1, R2, R4-R6, R8, R9the following formulas have the meanings as defined above,

CFR1R2CF=CR4CR5R6OCF=CR8R9(2a)

CR5R6=CR4C(CFR1R2)=CR8R9(3a).

3. The method according to claim 1 or 2, characterized in that all R1-R9independently of one another represent fluorine atom.

4. The method according to claim 1, characterized in that the reaction rearrangement of Clausena initiated by heating the mixture in the vapor phase.

5. How to claim 4, characterized in that the reaction rearrangement of Clausena initiate in the presence of an inert gas or an inert solvent, which passes into the gaseous state at the reaction temperature.

6. The method according to claim 1 or 2, characterized in that the reaction rearrangement of Clausena carried out in the presence of a polymerization inhibitor.

7. The method according to claim 1 or 2, characterized in that the reaction rearrangement of Clausena initiated by heating the mixture at a temperature of from 150 to 400°C.

8. The method according to claim 1 or 2, characterized in that the compound of the formula (2) is a compound obtained by reaction of a rearrangement of the double bond in the compound of formula (1)or the compound obtained by the reaction of DEH is aerovane compounds of the following formulas (1B-3), thus R1-R9in the following the formula have the meanings as defined above:

CFR1R2CR3=CR4CR5R6OCClR7-CClR8R9(1B-3).



 

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