WO1998043933A1

WO1998043933A1 - Process for producing aliphatic unsaturated fluorinated hydrocarbon compounds

Info

Publication number: WO1998043933A1
Application number: PCT/JP1998/001463
Authority: WO
Inventors: Toshirou Yamada; Mitsuru Sugawara; Hiromi Goto
Original assignee: Nippon Zeon Co., Ltd.
Priority date: 1997-03-31
Filing date: 1998-03-31
Publication date: 1998-10-08

Abstract

A process for producing a high yield of an aliphatic unsaturated fluorinated hydrocarbon with a high purity at a low cost by reacting an aliphatic unsaturated hydrocarbon compound having a carbon-to-carbon double bond and at least one chlorine atom replaceable with a fluorine atom on the carbon atom forming the double bond with at least 0.5 equivalent, per equivalent of the chlorine atom of the aliphatic unsaturated hydrocarbon compound as the base, of a mechanically pulverized alkali metal fluoride having a particle diameter of not larger than 100 νm.

Description

Description Method for producing aliphatic unsaturated hydrofluorinated hydrocarbon compounds

The invention of this application relates to a method for producing an aliphatically unsaturated fluorinated hydrocarbon compound. More specifically, the invention of the present application is useful as an alternative fluorocarbon and an intermediate for the production thereof, and as a synthetic raw material such as pharmaceuticals, agricultural chemicals, liquid crystals, and polymers. The present invention relates to a method for producing a highly unsaturated unsaturated hydrofluorinated hydrocarbon compound. Conventional technology

Conventionally, unsaturated compounds having a fluorine atom on a carbon atom constituting a carbon-carbon double bond have been known as a raw material monomer of a fluorinated polymer. It has also been noted as an alternative fluorocarbon and its intermediates, as a raw material for the synthesis of pharmaceuticals, agricultural chemicals, liquid crystals, and the like.

As for such a fluorinated compound, a method of producing the compound by a reaction in which a chlorine atom bonded to a carbon atom is replaced by a fluorine atom is known. You. For example, a halo of a hydrocarbon having a carbon-carbon double bond and having at least one fluorine-substitutable chlorine atom on the carbon constituting the double bond. For example, a reaction in which a gen atom is reacted with an alkali metal fluoride such as potassium fluoride in a non-protonic polar solvent to obtain a fluorine compound is exemplified. U.S. Patent No. 3,024,290, U.S. Patent There are many known such as No. 356, No. 88, J. Or. Chem., 28, 112 (1963). However, in practice, it is difficult to obtain high-purity fluorinated compounds inexpensively, in high yield, and by these conventional methods. Is the actual situation. For example, since expensive fluoride conventionally manufactured by the spread-line method is used, its manufacture is expensive. In the case of producing a chain or cyclic aliphatic unsaturated fluorinated hydrocarbon compound, there is a problem that decomposition and polymerization of the product are liable to occur. I did. Disclosure of the invention

Therefore, the invention of the present application solves the above-mentioned problems of the prior art, and uses an industrial grade alkali metal fluoride to be less expensive and more expensive. In a high yield and high purity, aliphatic unsaturated fluorine is useful as a substitute for fluorocarbon and its intermediates, pharmaceuticals, agricultural chemicals, liquid crystals, and as a raw material for synthesizing various polymers. It is an object of the present invention to provide a new method for producing a hydrogenated hydrocarbon compound.

This application provides the following inventions in order to solve such a problem.

1. An aliphatic unsaturated hydrocarbon compound having a carbon-carbon double bond and having at least one fluorine-substituted chlorine atom on the carbon constituting the double bond. And mechanically pulverized Alkali metal fluoride having a particle diameter of 100 m or less with respect to chlorine atoms in the aliphatic unsaturated hydrocarbon compound. Luo Lidoca 《React at a rate of 0.5 equivalent or more A process for producing an aliphatically unsaturated fluorinated hydrocarbon compound, wherein a chlorine atom is replaced by a fluorine atom by causing the compound to undergo a substitution.

2. The method according to the above item 1, wherein the aliphatically unsaturated hydrocarbon compound having a fluorine atom which can be substituted with fluorine has a fluorine atom in addition to a chlorine atom.

3. The process according to 1 or 2 above, wherein the aliphatic unsaturated hydrocarbon compound having a fluorine atom which can be substituted by fluorine is an alicyclic compound having 3 to 8 carbon atoms.

4. The process according to the above item 3, wherein the aliphatic unsaturated hydrocarbon compound having a chlorine atom capable of being substituted by fluorine is a compound of a pentopenpentene.

5. The method according to any one of the above items 1 to 4, wherein the alkali metal fluoride having a particle diameter of 10 ° m or less has a particle diameter of 50 m or less.

6. The method of any one of 1 to 5 above, wherein the metal alkali fluoride having a particle size of 100 jum or less is NaF or KF.

7. The method according to any one of 1 to 6, wherein the amount of the alkali metal fluoride having a particle diameter of 100 m or less is 1 to 5 equivalents.

8. The process according to any one of the above-mentioned 1 or 2, wherein the reaction is carried out in the presence of an aprotic polar solvent.

9. The process according to 8 above, wherein the solvent is at least one of a chain amide, a cyclic amide, and a sulfur-containing solvent.

10. Has a carbon-carbon double bond and forms a double bond Alkali metal with a particle size of 100 m or less, obtained by mechanically grinding an aliphatic unsaturated hydrocarbon compound having at least one fluorine-substituted chlorine atom on carbon By sequentially supplying the fluoride to an apolar polar solvent in which the fluoride is dispersed, and sequentially removing the reaction product in which the chlorine atom is replaced by the fluorine atom to the outside of the system. A method for producing an aliphatically unsaturated fluorinated hydrocarbon compound.

11. The method according to 10 above, wherein a reaction product equipped with a rectification column is used, and a reaction product is extracted from the top of the column.

12. The process according to 11 above, wherein the reflux ratio of the rectification column is 0.5 to 70.

13. Before the above-mentioned aliphatically unsaturated hydrocarbon compound having a fluorine atom which can be substituted by fluorine has a fluorine atom other than a chlorine atom

The manufacturing method of any of S10 or S12.

14. Any of the foregoing 10 or 13 wherein the aliphatic unsaturated hydrocarbon compound having a fluorine atom which can be substituted by fluorine is an alicyclic compound having 3 to 8 carbon atoms. Manufacturing method.

15. The production method according to the above item 14, wherein the aliphatic unsaturated hydrocarbon compound having a fluorine atom which can be substituted by fluorine is a compound having a pen mouth.

16. Manufacturing of any of the above 100 to 150 Alkali metal fluoride having a particle size of 100 m or less, which is NaF or KF having a particle size of 50 μm or less. Law.

17. The method of any one of the above-mentioned 100 to 16 wherein the use of an alkali metal fluoride having a particle diameter of 100 m or less is 1 to 5 equivalents. 18. The process according to any one of the above 10 to 17, wherein the solvent is at least one of a chain amide, a cyclic amide and a sulfur-containing solvent.

19. Any of the above 10 or 18 wherein the amount of the solvent used is 1 to 10 times the amount of the above-mentioned aliphatically unsaturated hydrocarbon compound having a fluorine atom which can be substituted with fluorine. Manufacturing method.

20. The process according to any one of the above 10 to 19, wherein the reaction temperature is 50 to 25 ° C. and the reaction time is 0.5 to 25 hours. Best mode for carrying out the invention

As a raw material in the present invention, at least one fluorine-substituted chlorine atom having a carbon-carbon double bond and having carbon on the double bond. The type of the aliphatic unsaturated hydrocarbon compound having the general formula (1) is not particularly limited. In addition, it may have a suitable substituent as long as it does not inhibit a substitution reaction from a chlorine atom to a fluorine atom.

Such a raw material hydrocarbon compound is, for example, a compound represented by the general formula

(In the formula, R, and R ₂ each independently represent an alkyl group, a chlorine atom, a fluorine atom, an alkyl chloride group, an alkyl fluoride group, an alkyl chloride fluoride group. , Or R, and R ₂ (Shown as an alkylene group, an alkylene chloride group, an alkylene fluoride group, or an alkylene chloride group) which are bonded to each other to form a ring. Chlorinated hydrocarbon compounds or fluorinated fluorinated hydrocarbon compounds. When these compounds are used as a raw material, for example, the following products may be used. The general formula

R

(In the formula, R ₃ and R ₄ are each independently an alkyl group, a fluorine atom, an alkyl fluoride group, or R ₃ and R are bonded to each other to form a ring Which represents an alkylene group or a fluorinated alkylene group which forms an alkylene group), thereby obtaining an aliphatically unsaturated fluorinated hydrocarbon compound represented by the formula:

Also, R,, R ₂ is chloride A alkyl group, in the case that having a chlorine atom such as chloride A Ruki les down group, the amount of Al Ca Li metal carrier Luo Li de, control of the other reaction conditions According to the above, as R ₃ and R *, an alkyl chloride group, an alkyl chloride fluoride group, or R and R ₄ are bonded to each other to form a ring. It can be an alkylene chloride group or a fluorinated alkylene group.

Alkyl chloride group, fluorinated alkyl group, fluorinated alkyl group corresponding to R 1, R ₂ , R a, and R in the above formula, or a ring bonded to each other; , Alkylene chloride, fluorinated alkylene, and fluorinated alkylene The carbon number of the len group is not particularly limited, but is usually 11 to 15, preferably 2 to 10, and more preferably 2 to 6.

As a specific example of the chain hydrocarbon compound represented by the above formula as a raw material compound, for a linear hydrocarbon compound, 1,2-dichloro-1- , 3, 3, 3 — Trifluoropropene, 1, 2, 3 — Trichlore 1, 3, 3 — Trifluoropropene, 1, 1,, 2 — Trichloro3,3,3,3—Trifluoropropene, 2,3—Dicyclo mouth 1,1,1,1,4,4,4,4-hexafluoro 2 — Bun, 1, 2, 3, 3 — Trichlore 1, 1, 4, 4, 4 1 Pen Fluoro 2 — Bun, 1, 1, 1, 2, 3 — 亍Trachloro 1,4,4,4 ー Trafluoro2 — bun, 1,1,1,1,2,3—Pentacro mouth_4,4,4— Trifluoro 2 — bun, 1, 1, 1, 2, 3, 4 — hexacyclo 1 , 4 — difluoro 2 — butene, 1, 1, 1, 1, 2, 3, 4, 4 — heptachloro 1-4 1 fluoro 2 — benzene, 1, 1, 1 1, 2, 3, 4,

4,4 octacyclo mouth 1 2—butene and 2—butenes composed of these positional isomers, 1 and 2—dicyclo mouth

— 2, 3, 3, 4, 4, 5, 5, 5 — 5 years old

— Penten, 2, 3 — Dichloro 1, 1, 1, 114, 4, 5, 5, 5, 5 — Octofluoro 2 — Penta, 2, 3, 3, 5 — Trichlore 1,1,1,1,4,4,5,5 —Heptafluoro2—Pentene, 2,3—Tricyclo-1,1,1,1,4,

4, 5, 5, 6, 6, 6 — Decafluoro 2 — Hexene,-

1,1,1,2,3,4,4,5,5,5,6,6,7, f,

7 — ラ Trade Deca Crawl 2 — to open and their locations Pentenes, hexenes or heptanes composed of isomers, and 1,2-diamines for alicyclic hydrocarbon compounds. Chloro-3,3,4,4 亍フフフフォ、 1 1 1 2 1,2,3,3,3,4,4—hexacyclocyclobutene, 1,2 — Dichloro 3, 4, 3, 4, 5, 5 — Hexafluorocyclopentane, 1, 2, 3 — Trichlor 3, 4, 4, 5, 5, 5 — Pentafluorocyclopentene, 1,2,3,3 — Petrochrome mouth 1,4,4,5,5 — Petrafluorocyclopen Pen, 1,2,3,3,4 One pen mouth row 4,5,5 — Trifluorocyclopenpen, 1,2,3,3,4,4 1 Hexachlor-5, 5 — diphenylorosic mouth pen, 1 , 2,3,3,4,4,5 — Heptachloro-5—Fluorocyclopentane, 1,2,3,3,4,4,5,5—octa Chromocyclopendin, 1, 2—Dichloro 3, 3, 4, 4, 4, 5, 5, 6, 6 — 6-year-old Quantafluorocyclohexene, 1, 2, 4, 5 — Tetraclo mouth 1, 3, 3, 4, 5, 6, 6 — Hexafluorocyclohexene, 1, 2, 3, 3, 4, 4, 5 , 5,6,6 — Decachlorocyclohexene, 1,2 — Dichloro3,3,3,4,4,5,5,5,6,6 — Octafluoros Lohepten, 1,2,3,3,4,4,5,5,6,6,6, F, Food Decacrocyclone, 1,2—Dichloro3, 3,4,4,5,5,6,6,7,7—Decafluorocyclone, and these Cycloglobins, cyclohexenes, cycloheptenes, cyclooctenes, etc. composed of regioisomers Are listed. Among them, alicyclic hydrocarbon conversion Compounds are preferred.

The metal fluoride used is not particularly limited, but for example, lithium fluoride, sodium fluoride, fluoride fluoride, and the like. Cesium fluoride, rubidium fluoride, etc. are exposed. Of these, sodium fluoride and potassium fluoride are preferred from the viewpoint of reactivity, and potassium fluoride is particularly preferred. In the reaction, two or more kinds of the above-mentioned alkali metal fluorides may be used as a mixture.

The particle size of the alkali metal fluoride may be 100 m or less, but is preferably 50 m or less, particularly preferably 30; um or less from the viewpoint of reaction efficiency. It is. The particle diameter in this case is the longest diameter (major diameter) of the particles measured on the SEM photograph.

The lower limit of the particle size is not particularly limited.However, from the viewpoint of mechanical pulverization and cost and handling, the lower limit of the particle size is not limited. In general, a standard of about 5 to 10 m can be set.

The mechanical pulverization method provides an alkali metal fluoride at a low cost, and in the reaction of the present invention, the one having the above particle size exhibits excellent reaction activity. Become. When the particle diameter is 100 m or less, the surface activation is remarkable due to the pulverization, and an efficient fluorination reaction is possible even with a small amount of use. In addition, particles having a particle diameter exceeding 100 μm may be mixed with particles having a particle diameter of less than 1 ◦ 0 m.However, considering economics, etc. It is most preferred to use an alkali metal fluoride of 0 jum or less. The method of mechanically pulverizing Alkali metal fluoride is not particularly limited.For example, an atomizer, a disk friction pulverizer, a rotary compression pulverizer, a vibrating ball Dry milling method for mill, tube mill, hammer mill, blender, ball mill, mixer, mill, roll crusher, rod mill, etc. Solvents such as colloid mills, jet mills, dispersers, hammer mills, homogenizers, filter mills, ball mills, and mixers One example is the use of a wet pulverization method in which a slurry is formed. Of these, wet pulverization is preferred in order to prevent moisture absorption before pulverization and before charging into the reactor.o

In the entire alkali metal fluoride, the content of the alkali metal fluoride having a particle diameter of 100 m or less is at least 0.5 equivalent to the chlorine atom of the substrate. J is usually 0.5-5 equivalents, preferably 13 equivalents, more preferably 1-2 equivalents. Alkali metal fluorides may include those having a particle size of more than 100 m, and in that case, the total amount of alkali metal fluorides Is at least 1.0 equivalent, usually 1 to 5 equivalents, preferably 1 to 3 equivalents, more preferably 112 equivalents, based on the chlorine atom of the substrate. .

The solvent for the fluorination reaction of the present invention is not particularly limited as long as it is an aromatic polar solvent, and dimethylformamide, dimethylacetate Chain amides such as amides, N—Methylpyrrolidon, N—Cyclic amides such as methylbiperidone—, N, N—Dimethylimidida Urethanes such as zolidinone, dimethylsulfoxide, dimethylsulfoxide, dimethyls

0 Examples include sulfur-containing solvents such as rufone and sulfolane. Preferably, dimethylformamide, N—methylpyrrolidon, N, N—dimethylimidazolidinone, dimethylsulfoxynide, etc. are used. You. In the reaction, two or more of the above polar solvents may be used in combination.

The amount of the solvent used is 110 to 110 times, preferably 1.2 to 6 times, and more preferably 1.5 to the weight of the alkali metal fluoride used. The range is three times as large. If the amount of the solvent is too small, stirring may be poor, and if the amount is too large, a side reaction product may be generated, and any of these may reduce the yield of the target compound. It's better.

The reaction temperature employed in the method of the present invention is 50-25 ° C, preferably 8 °-180 ° C, more preferably 100-16 It is in the range of 0 ° C. If the reaction temperature is too low, the reaction does not proceed sufficiently.On the other hand, if the reaction temperature is too high, the intermediate product is released out of the reaction system quickly, and side reactions occur. However, neither of these methods is preferable because it decreases the yield of the target substance.

The reaction time is appropriately selected depending on the reaction conditions, but is usually 0.5 to 25 hours, preferably "!" To 9 hours.

The reaction pressure is not particularly limited, and may be pressurized or depressurized depending on the case.

Further, the method of the present invention is performed in an open system. For example, when reacted in a closed system as described in U.S. Pat. No. 3,024,290, relatively large amounts of solvent and alkaline metal fluoride are used. However, it is not possible to obtain an aliphatic unsaturated hydrofluorinated hydrocarbon compound in a high yield. This is the formation in the reaction system. This is thought to be due to the decomposition or polymerization of the aliphatically unsaturated fluorinated hydrocarbon compound. By carrying out the reaction in an open system as in the present invention, the produced aliphatic unsaturated hydrofluorinated hydrocarbon compound is taken out of the system without staying in the reaction system. Thus, the desired product can be obtained in high yield.

As a method of the fluorination reaction, it is preferable to use a reaction vessel equipped with a rectification column and to carry out the reaction in a solvent in which alkali metal fluoride is dispersed. No. At this time, only the target product is concentrated and isolated with good purity from the top of the rectification column, and at the same time, the raw materials and the reaction intermediates are refluxed without escaping out of the system. It is desirable to carry out the reaction while returning it to the reaction vessel.

By utilizing the fact that the boiling point of the aliphatic unsaturated hydrofluorinated hydrocarbon compound, which is a product, is lower than that of the raw material and the intermediate during the reaction, a rectification column should be installed directly in the reaction vessel. By this means, the target product is withdrawn sequentially from the top of the rectification column simultaneously with the sequential dropwise supply of the raw materials, and the raw materials and reaction intermediates are always returned to the reaction vessel. By using, the amount of solvent and the amount of metal fluoride can be significantly reduced while improving the yield while improving the yield. Is possible.

The reaction product can be obtained by controlling the temperature at the top of the rectification column. The temperature at the top of the column can be set near the boiling point of the product (specifically determined by the pressure) by setting a reflux ratio commensurate with the capacity of the rectification column. The collection of the object can be carried out in accordance with ordinary law.

For example, according to the invention described above, the particle size of the alkali metal fluoride is appropriately adjusted, including the ease of access. By the determination, an aliphatically unsaturated fluorinated hydrocarbon compound can be produced in a cost-effectively and selectively in a higher yield than in the conventional method. Example

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples. Example 1

Under a nitrogen stream, a 500-milliliter four-port flask equipped with a dropping funnel, a rectification tower, a thermometer, and a stirrer was used. 30.0 g (purity 9% by weight, average particle diameter 26 m, 0.516 moI) of calcium fluoride ground to 0 m or less, dimethylformamide 50 milliliters were charged, a refrigerant at 120 ° C was passed through a Jimroth cooler provided at the top of the rectification tower, and the fraction trap was collected. It was cooled to 70 ° C. 1, 2-dichloro-1, 3, 3, 4, 4, 5, 5-hexafluorocyclopentane 30.4 milliliter (5 0.20 g O.205 mol) was charged. In 0.5 hours, the temperature was raised until the temperature inside the flask became <135 ° C. The raw materials were sequentially dropped during 0.5 to 3.5 hours after the start of the temperature rise. When 0.7 hours (1.5 hours from the start of the reaction) had passed after the temperature at the top of the column had stabilized at the boiling point of the product (27 ° C), the top of the rectification column and Jim Roth were used. Drainage of the distillate started from the discharge opening located in the middle of the cooling section. Withdrawal starts when the temperature at the top of the tower starts to rise and the boiling point of dimethylformamide is reached. It was about 1,2,3,3,4,4,4,5,5-5 years old. 38.24 g (0.18 mol, yield 87.8%, purity 99.8%) was obtained.

Example 2

In a nitrogen atmosphere, the granular calcium fluoride was ground using an Oster Mini Blender for 15 minutes so that the particle major diameter became 10 ◦m or less. The average particle diameter after pulverization was 30 m.

Fluorinated calcium milled into a 200-milliliter 4-port flask equipped with a dropping funnel, rectification tower, thermometer, and stirring device under a nitrogen stream 30.6 g (purity 97%, 0.516 moI), dimethylformamide 50 milliliters were charged and installed at the top of the rectification column. A refrigerant at 120 ° C. was passed through the Jim-Roat cooler, and the fraction trap was cooled to 170 ° C. One or two drops per dropper mouth 3, 3, 4, 4, 5, 5 or 5 — hexafluorocyclopentane 30.3 milliliters (5 0.000 g, ..204 mol). The temperature was raised until the temperature in the flask became <135 ° C within 0.4 hours. The raw materials were successively dropped from 0.4 to 2.0 hours after the start of the temperature rise. When 0.6 hours (1.9 hours from the start of the reaction) had passed after the temperature at the top of the column had stabilized at the boiling point of the product (2 ° C), the top of the rectification column and the Jim Lot Withdrawal of the distillate started from the discharge port installed in the middle of the cooler. The extraction was started when the temperature at the top of the column started to rise and reached the boiling point of dimethylformamide (7.4 hours after the start of the reaction). , 3,4,4,5,5 — Octafluorocyclopentene 40.93 g (0.193moI, yield 94.7%, purity 99.9). 3%).

Example 3

The reaction was carried out in the same manner as in Example 2 except that N-methylpyrrolidone was used in place of dimethylformamide, and as a result, 1, 2, 3, 3, 4, The yield of 4,5,5—octafluorocyclopentene was 93% (99.2% of purity).

Comparative Example 1

Under a nitrogen stream, particulate fluoride obtained by a precipitation method in a 200-milliliter four-neck flask equipped with a dropping funnel, a rectification tower, a thermometer, and a stirrer Calium 29.65 g (average particle diameter 300 m, purity 97%, 0.495 mol), N-methylpyrrolidone 50 milliliter The fraction trap was cooled to 170 ° C by flowing a refrigerant at 120 ° C through a Jimroth cooler provided at the top of the rectification tower. . 1, 2-dicyclo mouth 1, 3, 3, 4, 4, 5, 5 — Hexafluorocyclopentene 30.3 milliliter (4 9.977 g, 0.204 mol) were charged. The temperature inside the flask was raised to 135 ° C for 0.3 hours. After the start of temperature rise, the raw materials were sequentially dropped within a period of 3 to 3.0 hours. After 1.9 hours (3.6 hours from the start of the reaction) after the temperature at the top of the column has stabilized at the boiling point of the product (27 ° C), the distillate is removed. did. Withdrawal was carried out until the temperature at the top of the column started to rise and reached the boiling point of dimethylformamide (6.7 hours from the start of the reaction). 3,3,4,4,5,5—age Kutafluorocyclopentane was obtained in a yield of 51%.

Example 4

The reaction was carried out for 7.5 hours in the same manner as in Example 1 except that the method of sequentially dropping the raw materials was changed to a method in which all the raw materials were charged from the beginning. , 4,5,5—octafluorocyclopentene was obtained in a yield of 70%.

Industrial applicability

According to the method of the invention of the present application, the selection of the particle size of the aluminum metal fluoride allows the conversion of the aliphatic unsaturated hydrocarbon compound having a chlorine atom to the aliphatic unsaturated hydrocarbon compound. Fluorohydrocarbon compounds can be obtained inexpensively and in good yield.

The reaction is carried out in an open system while feeding the aliphatic unsaturated hydrocarbon compound having a chlorine atom as the raw material and extracting the intended reaction product from the top of the rectification column. As a result, the target substance can be obtained with high efficiency and high purity.

Fluorinated hydrocarbons such as fluoroalkene obtained by the method of the present invention can be more easily hydrolyzed by a conventional method. It is possible to manufacture ruro alkanes.

The fluoroalkene obtained by the process of the present invention and the fluoroalkane obtained by hydrogenating it are used as an alternative fluorone and an intermediate thereof, and It is also useful as a raw material for the synthesis of pharmaceuticals, agricultural chemicals, liquid crystals, polymers and the like.

Claims

The scope of the claims

An aliphatic unsaturated hydrocarbon compound having a 1-carbon-carbon double bond and having at least one fluorine-substitutable chlorine atom on carbon constituting the double bond; Mechanically pulverized alkali metal fluoride having a particle diameter of 100) Um or less is mixed with the alkali metal fluoride described above with respect to the chlorine atom in the aliphatic unsaturated hydrocarbon compound. Doka << Aliphatic unsaturated fluorinated hydrocarbon characterized in that chlorine atoms are replaced by fluorine atoms by reacting at a ratio of 0.5 equivalent or more Compound production method

2. An aliphatic unsaturated hydrocarbon compound having a carbon-carbon double bond and having at least one fluorine-substitutable chlorine atom on the carbon constituting the double bond is obtained. 2. The method according to claim 1, wherein the compound has a fluorine atom in addition to the chlorine atom.

3. An aliphatic unsaturated hydrocarbon compound having a carbon-carbon double bond and having at least one fluorine-substitutable chlorine atom on the carbon constituting the double bond is carbon-containing. The method according to claim 1 or 2, wherein the method is an alicyclic compound represented by the formulas (3) to (8).

4. Cyclic aliphatic unsaturated hydrocarbon compounds having a carbon-carbon double bond and having at least one fluorine-substituted chlorine atom on the carbon constituting the double bond. 4. The production method according to claim 3, which is a compound of mouth penten.

5. The method according to any one of claims 1 to 4, wherein the mechanically pulverized alkali metal fluoride having a particle diameter of 100 m or less has a particle diameter of 50 m or less.

6. Mechanically pulverized alkaloids with a particle diameter of 100 m or less. 6. The method according to any one of claims 1 to 5, wherein the metal fluoride is NaF or KF.

7. The method according to any one of claims 1 to 6, wherein the amount of mechanically pulverized alkali metal fluoride having a particle diameter of 100 m or less is 1 to 5 equivalents.

8. The method of claim 1, wherein the reaction is carried out in the presence of an aromatic polar solvent.

9. The process according to claim 8, wherein the solvent is at least one of a chain amide, a cyclic amide, and a sulfur-containing solvent.

10. An aliphatically unsaturated hydrocarbon compound having a carbon-carbon double bond and having at least one fluorine-substitutable chlorine atom on the carbon constituting the double bond Are sequentially supplied to an apolar polar solvent in which an alkali metal fluoride having a particle diameter of 100 m or less mechanically pulverized is dispersed, and chlorine atoms are fluorinated. A process for producing an aliphatically unsaturated fluorinated hydrocarbon compound, characterized in that a reaction product substituted with an elemental atom is sequentially drawn out of the system.

11. The method according to claim 10, wherein a reaction vessel equipped with a rectification column is used, and a reaction product is discharged from the top of the column.

12. The process according to claim 11, wherein the reflux ratio of the rectification column is 0.5 to 70.

13. An aliphatic unsaturated hydrocarbon compound having a carbon-carbon double bond and having at least one fluorine-substitutable chlorine atom on the carbon constituting the double bond is obtained. The method according to any one of claims 10 to 12, further comprising a fluorine atom in addition to the chlorine atom.

14. An aliphatically unsaturated hydrocarbon compound having a carbon-carbon double bond and having at least one fluorine-substituted chlorine atom on the carbon constituting the double bond is obtained. The method according to any one of claims 10 to 13, which is an alicyclic compound having 3 to 8 carbon atoms.

15. An aliphatically unsaturated hydrocarbon compound having a carbon-carbon double bond and having at least one fluorine-substitutable chlorine atom on the carbon constituting the double bond is obtained by the following method. 15. The method according to claim 14, which is a compound of a pentene.

16. The mechanically pulverized Alkali metal fluoride having a particle size of 10 ° m or less is NaF or KF having a particle size of 50 m or less. Any manufacturing method.

17. The method according to any one of claims 10 to 16, wherein the amount of mechanically pulverized alkali metal fluoride having a particle diameter of 100 m or less is 1 to 5 equivalents. Law.

18. The process according to any one of claims 10 to 11, wherein the solvent is at least one of a chain amide, a cyclic amide, and a sulfur-containing solvent.

19. The amount of the solvent used is 1 to 10 times that of the mechanically pulverized alkali metal fluoride having a particle diameter of 100 m or less. Manufacturing method.

20. The process according to any one of claims 10 to 19, wherein the reaction temperature is 50 to 250 ° C and the reaction time is 0.5 to 25 hours.

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