JP5439739B2 - Fluorine-containing alkene compound and method for producing the same - Google Patents

Description

  A method for producing a perfluoroalkyne compound that is useful as a dry etching gas and a CVD gas used in the semiconductor manufacturing field, and also useful as a raw material for a fluorine-containing polymer, and a novel fluorine-containing alkene that is a precursor of a perfluoroalkyne compound The present invention relates to a compound and a production method thereof.

  A perfluoroalkyne compound is a hydrocarbon compound in which a hydrogen atom is completely substituted with a fluorine atom and has a carbon-carbon triple bond, and is used in a raw material for producing a fluorine-containing polymer, a medical and agrochemical, and a semiconductor production process. It is useful as a plasma reaction gas. In particular, a perfluoroalkyne compound having a relatively low molecular weight such as perfluoro-2-pentyne has an appropriate boiling point and is easy to handle and thus has high utility value, and establishment of an industrial production method thereof is demanded.

  In Patent Document 1, 2,3-dihydrodecafluoropentane is used as a starting material, and the perfluoro-2-pentyne which is the target product is obtained by performing a dehydrofluorination reaction at 200 ° C. in the presence of an alkali. . However, 2,3-dihydrodecafluoropentane used as a starting material has a long life in the atmosphere of 17 years and a high global warming potential GWP of 1300 (100-year accumulation). It is a substance that is becoming worried about whether it can be used in the future. Moreover, since the reaction requires a high temperature, there are many by-products, and as a result, the yield of perfluoro-2-pentyne is about 30%.

Japanese Patent Laid-Open No. 2003-146917

  An object of the present invention is to provide a novel fluorine-containing alkene compound and a novel compound thereof, which are useful precursors for efficiently synthesizing the above perfluoroalkyne compound.

As a result of intensive studies to solve the above problems, the present inventors have found that a novel fluorine-containing alkene compound can be obtained by reacting a certain type of chlorine-containing alkene compound with sodium borohydride. It has also been found that the novel fluorine-containing alkene compound can be obtained by reacting a certain halogen-containing alkene compound or a certain halogen-containing alkane compound with hydrogen fluoride in the presence of a fluorination catalyst.
This novel fluorine-containing alkene compound can be obtained with high productivity and high yield by dehydrochlorination by a method such as reaction with an aqueous alkali solution.

Thus, according to the present invention, first, a fluorine-containing alkene compound represented by the general formula A is provided.
Formula A: CF ₃ CCl═CH (CF ₂ ) _n CF ₃
(In general formula A, n is 0-5.)

Moreover, according to this invention, the following two methods of manufacturing the fluorine-containing alkene compound represented by the said general formula A are provided.
(1) A tetrahydroboric acid metal salt is reacted with a chlorine-containing alkene compound of the following general formula B.
Formula B: CF ₃ CCl═CCl (CF ₂ ) _n CF ₃
(In general formula B, n is 0-5.)
(2) A halogenated alkene compound represented by the following general formula C or a halogenated alkane compound represented by the following general formula D is reacted with hydrogen fluoride in the presence of a fluorination catalyst.
Formula C: CF ₃ CCl═CH (CX ₂ ) _n CX ₃
(In general formula C, each X is independently a chlorine atom, a bromine atom or an iodine atom, and n is 0 to 5.)
Formula D: CF ₃ CCl ₂ CH ₂ (CX ₂ ) _n CX ₃
(In general formula D, each X is independently a chlorine atom, a bromine atom or an iodine atom, and n is 0 to 5.)

  Furthermore, according to the present invention, there is provided a method for producing a perfluoroalkyne compound by dehydrochlorinating the fluorine-containing alkene compound represented by the general formula A.

First, the compound represented by the general formula A of the present invention and the production method thereof will be described.
The compound represented by the general formula A is a fluorine-containing alkene compound. In the general formula A, n is 0 to 5, preferably 0 to 2, and more preferably 1.
Specific examples of the fluorine-containing alkene compound include 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene, 2-chloro-1,1,1,4,4,5. , 5,5-octafluoro-2-pentene, 2-chloro-1,1,1,4,4,5,5,6,6,6-decafluoro-2-hexene, 2-chloro-1,1 , 1,4,4,5,5,6,6,7,7,7-dodecafluoro-2-heptene, 2-chloro-1,1,1,4,4,5,5,6,6 7,7,8,8,8-tetradecafluoro-2-octene, 2-chloro-1,1,1,4,4,5,5,6,6,7,7,8,8,9, 9,9-hexadecafluoro-2-nonene is mentioned, and a particularly preferable compound is 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2. Pentene and the like.

The fluorine-containing alkene compound represented by the general formula A can be obtained, for example, by reacting the compound represented by the general formula B with sodium borohydride.
Specific examples of the chlorine-containing alkene compound represented by the general formula B include 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene, 2,3, and the like. -Dichloro-1,1,1,4,4,5,5,5-octafluoro-2-pentene, 2,3-dichloro-1,1,1,4,4,5,5,6,6 6-decafluoro-2-hexene, 2,3-dichloro-1,1,1,4,4,5,5,6,6,7,7,7-dodecafluoro-2-heptene, 2,3- Dichloro-1,1,1,4,4,5,5,6,6,7,7,8,8,8-tetradecafluoro-2-octene, 2,3-dichloro-1,1,1, 4,4,5,5,6,6,7,7,8,8,9,9,9-hexadecafluoro-2-nonene, preferred chlorine-containing alkene compound The include 2,3-dichloro -1,1,1,4,4,5,5,5- octafluoro-2-pentene.
The method for obtaining the chlorine-containing alkene compound is not particularly limited, and a commercially available one may be used. Am. Chem. Soc. , 76,610-12 (1954), 2,3-dichloro-1,1,1,4,4,5,5,5-octafluoro-2-pentene is perfluoro-2-pentyne. It can also be easily produced by reacting chlorine with chlorine under ultraviolet light irradiation.
If necessary, an inert gas such as helium, nitrogen, or argon may be accompanied.

As the tetrahydroboric acid metal salt, tetrahydroboric acid alkali metal salts such as LiBH ₄ , NaBH ₄ and KBH ₄ are preferably used, and NaBH ₄ is particularly preferable from the viewpoint of operability. The method for obtaining the tetrahydroboric acid metal salt is not particularly limited, and a commercially available one can be used.
The amount of the tetrahydroboric acid metal salt used is usually 0.5 to 1.5 equivalents, preferably 1.0 to 1.2 equivalents, relative to the number of moles of the chlorine-containing alkene compound represented by the general formula B.

  The reaction temperature when sodium borohydride is reacted with the compound represented by the general formula B is usually -30 to 60 ° C, preferably -20 to 40 ° C, more preferably -10 to 0 ° C. . If the reaction temperature is too low, the reaction rate is too slow to be practical. Also, if the reaction temperature is too high, undesirable by-products tend to be formed.

The reaction between the compound represented by the general formula B and sodium borohydride may be performed in a solvent or without a solvent, but may be performed in the presence of a solvent from the viewpoint of improving the reaction yield. preferable.
When using a reaction solvent, it is not particularly limited as long as it does not adversely affect the hydrogenation reaction. Specific examples include aromatic compounds such as benzene and toluene, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, diethyl ether, dibutyl ether, methyl-tert-butyl ether, ethylene glycol dimethyl ether, and diethylene glycol. Examples include aliphatic ether compounds such as dimethyl ether, and cyclic ether compounds such as tetrahydrofuran and dioxane. Of these, polar compounds are preferable from the viewpoint of improving the conversion rate of the reaction, and ether solvents such as diethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran are particularly preferable. Furthermore, diethylene glycol dimethyl ether is particularly preferred because of its ease of distillation.
Moreover, the usage-amount is 0.5-20 times normally with respect to the weight of the chlorine-containing alkene compound represented by the said general formula B, Preferably it is 1-10 times, More preferably, it is 3-6 times.

  After completion of the reaction, the target product can be separated and purified from the reaction solution by a method used in ordinary organic synthesis. For example, in order to remove excess sodium borohydride and by-product salts, water is added to the reaction solution and stirred well, and the separated organic layer is washed with water. Next, after drying with a drying agent such as anhydrous sodium sulfate, the desired product can be obtained by distillation under reduced pressure. Moreover, the target product can also be obtained by direct distillation without performing an extraction operation.

  The fluorine-containing alkene compound represented by the general formula A can be obtained by reacting the compound represented by the general formula C and / or D with hydrogen fluoride in the presence of a fluorination catalyst, in addition to the above-described general formula B. Can also be obtained.

The compound represented by the general formula C is a halogen-containing alkene compound. In the general formula C, each X is independently a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom.
Specific examples of the halogen-containing alkene compound include 2,4,4,4-tetrachloro-1,1,1-trifluoro-2-butene, 2,4,4,5,5,5-hexachloro-1,1. , 1-trifluoro-2-pentene, 2,4,4,5,5,6,6,6-octachloro-1,1,1-trifluoro-2-hexene, 2,4,4,5,5 , 6,6,7,7,7-decachloro-1,1,1-trifluoro-2-heptene, 2,4,4,5,5,6,6,7,7,8,8,8- Dodecachloro-1,1,1-trifluoro-2-octene, 2,4,4,5,5,6,6,7,7,8,8,9,9,9-tetradecachloro-1,1 , Chlorine-containing alkene compounds such as 1-trifluoro-2-nonene;

2,4,4,4-tetrabromo-1,1,1-trifluoro-2-butene, 2,4,4,5,5,5-hexabromo-1,1,1-trifluoro-2-pentene, 2,4,4,5,5,6,6,6-octabromo-1,1,1-trifluoro-2-hexene, 2,4,4,5,5,6,6,7,7,7 Decabromo-1,1,1-trifluoro-2-heptene, 2,4,4,5,5,6,6,7,7,8,8,8-dodecabromo-1,1,1-trifluoro -2-octene, 2,4,4,5,5,6,6,7,7,8,8,9,9,9-tetradecabromo-1,1,1-trifluoro-2-nonene, etc. Brominated alkene compounds of

1,1,1-trifluoro-2,4,4,4-tetraiodo-2-butene, 1,1,1-trifluoro-2,4,4,5,5,5-hexaiodo-2-pentene, 1,1,1-trifluoro-2,4,4,5,5,6,6,6-octaiodo-2-hexene, 1,1,1-trifluoro-2,4,4,5,5 6,6,7,7,7-decayodo-2-heptene, 1,1,1-trifluoro-2,4,4,5,5,6,6,7,7,8,8,8-dodecayodo -2-octene, 1,1,1-trifluoro-2,4,4,5,5,6,6,7,7,8,8,9,9,9-tetradecaiodo-2-nonene These are iodine-containing alkene compounds.

  Among these, 2,4,4,4-tetrachloro-1,1,1-trifluoro-2-butene, 2,4,4,5,5,5-hexachloro-1,1,1-trifluoro -2-pentene, 2,4,4,5,5,6,6,6-octachloro-1,1,1-trifluoro-2-hexene, 2,4,4,5,5,6,6 7,7,7-decachloro-1,1,1-trifluoro-2-heptene, 2,4,4,5,5,6,6,7,7,8,8,8-dodecachloro-1,1 , 1-trifluoro-2-octene, 2,4,4,5,5,6,6,7,7,8,8,9,9,9-tetradecachloro-1,1,1-trifluoro Preferred are those in which X is a chlorine atom, such as 2-nonene, and n is 1, 2,4,4,5,5,5-hexachloro-1,1,1-trifluoro 2-pentene are more preferable.

The compound represented by the general formula D is a halogen-containing alkane compound. In the general formula D, each X is independently a chlorine atom, bromine atom or iodine atom, preferably a chlorine atom.
Specific examples of the halogen-containing alkane compound include 2,2,4,4,4-pentachloro-1,1,1-trifluorobutane, 2,2,4,4,5,5,5-heptachloro-1,1. , 1-trifluoropentane, 2,2,4,4,5,5,6,6,6-nonachloro-1,1,1-trifluorohexane, 2,2,4,4,5,5,6 , 6,7,7,7-undecachloro-1,1,1-trifluoroheptane, 2,2,4,4,5,5,6,6,7,7,8,8,8-tridecachloro-1 , 1,1-trifluorooctane, 2,2,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecachloro-1,1,1-tri Chlorine-containing alkane compounds such as fluorononane;

2,2,4,4,4-pentabromo-1,1,1-trifluorobutane, 2,2,4,4,5,5,5-heptabromo-1,1,1-trifluoropentane, 2, 2,4,4,5,5,6,6,6-nonabromo-1,1,1-trifluorohexane, 2,2,4,4,5,5,6,6,7,7,7- Undecabromo-1,1,1-trifluoroheptane, 2,2,4,4,5,5,6,6,7,7,8,8,8-tridecabromo-1,1,1-trifluorooctane, Brominated alkane compounds such as 2,2,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecabromo-1,1,1-trifluorononane ;

1,1,1-trifluoro 2,2,4,4,4-pentaiodobutane, 1,1,1-trifluoro-2,2,4,4,5,5,5-heptiodopentane, , 1,1-trifluoro-2,2,4,4,5,5,6,6,6-nonaiodohexane, 1,1,1-trifluoro-2,2,4,4,5,5 , 6,6,7,7,7-undecaiodoheptane, 1,1,1-trifluoro-2,2,4,4,5,5,6,6,7,7,8,8,8 -Tridecaiodooctane, 1,1,1-trifluoro-2,2,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecaiodononane These are iodine-containing alkane compounds.

  Among these, 2,2,4,4,4-pentachloro-1,1,1-trifluorobutane, 2,2,4,4,5,5,5-heptachloro-1,1,1- Trifluoropentane, 2,2,4,4,5,5,6,6,6-nonachloro-1,1,1-trifluorohexane, 2,2,4,4,5,5,6,6 7,7,7-undecachloro-1,1,1-trifluoroheptane, 2,2,4,4,5,5,6,6,7,7,8,8,8-tridecachloro-1,1, 1-trifluorooctane, 2,2,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecachloro-1,1,1-trifluorononane, etc. 2,2,4,4,5,5,5-heptachloro-1,1,1-trifluoro, wherein X is a chlorine atom and n is 1 Pentane is more preferable.

The method for obtaining these compounds is not particularly limited, and for example, they can be produced by the following method.
Halogen is reacted with a ketone compound represented by CF ₃ COCH ₂ (CH ₂ ) _n CH ₃ such as 1,1,1-trifluoro-2-pentanone to produce 4,4,5,5,5-pentachloro- A halogen-containing ketone compound represented by CF ₃ COCH ₂ (CX ₂ ) _n CX ₃ such as 1,1,1-trifluoro-2-pentanone is obtained, and this is reacted with phosphorus pentachloride to obtain 2, 4, A halogen-containing alkene compound represented by CF ₃ CCl═CH (CX ₂ ) _n CX ₃ such as 4,5,5,5-hexachloro-1,1,1-trifluoro-2-pentene; A halogen-containing alkane compound represented by CF ₃ CCl ₂ CH ₂ (CX ₂ ) _n CX ₃ such as 4,4,5,5,5-heptachloro-1,1,1-trifluoropentane, Fluorinated touch Presence, and a method of reacting the hydrogen fluoride. Here, in each formula, n is 0-5, and X is independently a chlorine atom, a bromine atom, or an iodine atom.

In the reaction between the ketone compound and the halogen, the amount of halogen used is usually 5 to 40 equivalents, preferably 5 to 20 equivalents, more preferably 5 to 10 equivalents, relative to the number of moles of the ketone compound. Moreover, reaction temperature is 0-150 degreeC normally, Preferably it is 20-120 degreeC. If the reaction temperature is too low, the reaction rate is too slow to be practical. Also, if the reaction temperature is too high, undesirable by-products tend to be formed. Although this reaction may be carried out in the presence of a solvent or without a solvent, it is preferably carried out without a solvent from the viewpoint of improving the reaction yield. When a reaction solvent is used, halogen solvents such as methylene chloride, chloroform, carbon tetrachloride and 1,1,2-trichlorotrifluoroethane, which do not adversely affect the halogenation reaction, are preferred, and carbon tetrachloride is particularly preferred. The use amount of the reaction solvent is usually 0.5 to 20 times, preferably 1 to 10 times, more preferably 1.5 to 5 times the ketone compound from the viewpoint of reaction rate and reaction yield.
Further, in order to promote the halogenation reaction, ultraviolet light may be irradiated using a mercury lamp or the like. The mercury lamp may be a high-pressure mercury lamp or a low-pressure mercury lamp. Furthermore, an additive such as a Lewis acid may be added to promote the halogenation reaction. As the additive, aluminum chloride, iron chloride, antimony chloride, zinc chloride, tin chloride, aluminum bromide, iron bromide, antimony bromide, zinc bromide, tin bromide can be used. The addition amount thereof is usually 0.001 to 0.3 equivalent, preferably 0.01 to 0.2 equivalent, with respect to the ketone compound.

  In the reaction of the halogen-containing ketone compound and phosphorus pentachloride, the amount of phosphorus pentachloride used is usually 1 to 3 equivalents, preferably 1.5 to 2 equivalents, relative to the number of moles of the halogen-containing ketone compound. The reaction temperature is usually 0 to 200 ° C, preferably 50 to 200 ° C, more preferably 120 to 180 ° C. If the reaction temperature is too low, the reaction rate is too slow to be practical. Also, if the reaction temperature is too high, undesirable by-products tend to be formed. This reaction may be performed in the presence of a solvent or without a solvent, but it is preferably performed in the presence of a solvent from the viewpoint of improving the reaction yield. When using a reaction solvent, it is not particularly limited as long as it does not adversely affect the chlorination reaction. Benzene, toluene, chlorobenzene, dichlorobenzene and trichlorobenzene are preferred, and chlorobenzene is particularly preferred. The amount of the reaction solvent used is usually 0.5 to 20 times, preferably 1 to 10 times, more preferably 1.5 to 5 times the halogen-containing ketone compound from the viewpoint of reaction rate and reaction yield. .

  The halogen-containing alkene compound and the halogen-containing alkane compound thus obtained are reacted with hydrogen fluoride in the presence of a fluorination catalyst. The fluorination catalyst is a conventionally known solid catalyst or supported catalyst suitable for fluorination in the gas phase, and is preferably a supported catalyst from the viewpoint of stability during the reaction. Supported carriers include activated carbon, metallic aluminum, zirconia, magnesia, titania, clay desilicaated with hydrogen fluoride, etc., aluminum oxide (alumina), fluoride, chloride, fluorinated chloride, oxyfluoride (partially fluorinated alumina) ), Oxychloride, oxyfluoride chloride, and the like. Among these, activated carbon is preferable.

  Activated carbon is a plant based on wood, sawdust, charcoal, coconut shell charcoal, palm kernel charcoal, raw ash, etc., coal based on peat, lignite, lignite, bituminous, anthracite, etc., petroleum residue In addition, there are petroleum-based or synthetic resin raw materials that use sulfuric acid sludge, oil carbon, and the like as raw materials. Since such activated carbon is commercially available, it can be selected from among them. For example, activated carbon manufactured from bituminous coal (for example, Calgon granular activated carbon CAL (manufactured by Toyo Calgon Co., Ltd.), coconut shell charcoal (eg, manufactured by Takeda Pharmaceutical Co., Ltd.), etc. can be mentioned. These activated carbons are usually used in a granular form, but the shape and size are not particularly limited, and can be determined based on the size of the reactor with ordinary knowledge.

  Activated carbon is an oxide, fluoride, chloride, fluorinated chloride, oxyfluoride, oxychloride of one or more metals selected from aluminum, chromium, manganese, nickel, cobalt, titanium, Activated carbon carrying oxyfluoride chloride or the like may be used.

  The method for preparing these metal-supported activated carbon catalysts is not limited, but the activated carbon itself or chromium, titanium, manganese, nickel, activated carbon previously modified with halogen by hydrogen fluoride, hydrogen chloride, chlorinated fluorinated hydrocarbon, etc. It is prepared by impregnating or spraying a solution in which a soluble compound of one or more metals selected from cobalt is dissolved.

  The metal loading is 0.1 to 80% by weight, preferably 1 to 40% by weight. Examples of the soluble compound of the metal supported on the activated carbon include nitrates, chlorides, oxides, and the like of the corresponding metal that dissolves in a solvent such as water, ethanol, and acetone. Specifically, chromium nitrate, chromium trichloride, chromium trioxide, potassium dichromate, titanium trichloride, manganese nitrate, manganese chloride, manganese dioxide, nickel nitrate, nickel chloride, cobalt nitrate, cobalt chloride, etc. may be used. it can.

  A catalyst carrying a metal by any method is treated in advance with a fluorinating agent such as hydrogen fluoride, fluorinated (and chlorinated) hydrocarbon at a temperature equal to or higher than a predetermined reaction temperature before use, and the catalyst during the reaction. It is effective to prevent changes in the composition. In addition, supplying oxygen, chlorine, fluorinated or chlorinated hydrocarbons into the reactor during the reaction is effective for extending the catalyst life, improving the reaction rate, and the reaction yield.

  The reaction temperature is 200 to 600 ° C., preferably 300 to 500 ° C. If the reaction temperature is lower than 200 ° C., the reaction is slow and not practical. If the reaction temperature exceeds 600 ° C., the catalyst life is shortened, and the reaction proceeds rapidly, but decomposition products and the like are generated, and the selectivity of the fluorine-containing alkene compound is lowered, which is not preferable.

  In the method of the present invention, the total ratio of the halogen-containing alkene compound and the halogen-containing alkane compound to be supplied to the reaction region / the molar ratio of hydrogen fluoride can vary depending on the reaction temperature, but is 1/20 to 1/800, preferably 1 / 20 to 1/400. If the hydrogen fluoride exceeds 800 moles of the halogen-containing alkene compound, the amount of organic matter treated in the same reactor will be reduced and the mixture of unreacted hydrogen fluoride and product discharged from the reaction system will be hindered. If the amount of hydrogen fluoride is less than 20 moles, the reaction rate decreases and the selectivity decreases, which is not preferable.

  In the method of the present invention, it is preferable to use an excessive amount of hydrogen fluoride. In that case, unreacted hydrogen fluoride is separated from unreacted organic substances and products and recycled to the reaction system. Separation of hydrogen fluoride and organic matter can be performed by known means.

Although reaction pressure is not specifically limited, It is preferable to carry out by 1-10 kg / cm < ² > from the surface of an apparatus. It is desirable to select conditions so that the raw organic substances, intermediate substances and hydrogen fluoride present in the system do not liquefy in the reaction system.
The contact time is usually 0.1 to 300 seconds, preferably 5 to 60 seconds.

  The reactor may be made of a material having heat resistance and corrosion resistance to hydrogen fluoride, hydrogen chloride and the like, and stainless steel, hastelloy, monel, platinum and the like are preferable. It can also be made from materials lined with these metals.

  The product containing the fluorine-containing alkene compound which is treated by the method of the present invention and flows out of the reactor can be purified by a known method. Although the purification method is not limited, for example, the product from which hydrogen fluoride to be recovered in advance is separated is first washed with water or / and an alkaline solution to remove acidic substances such as hydrogen chloride and hydrogen fluoride, and then dried. Then, it can be performed by subjecting it to distillation to remove organic impurities.

A perfluoroalkyne compound is obtained by subjecting the fluorine-containing alkene compound represented by the general formula A thus obtained to a dehydrochlorination reaction in the presence of an alkali compound.
The basic compound is not particularly limited, and examples thereof include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide; sodium oxide or potassium oxide. Alkali metal oxides; alkaline earth metal hydroxides such as beryllium hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide or strontium hydroxide; beryllium oxide, magnesium oxide, calcium oxide, strontium oxide or barium oxide Alkaline earth metal oxides; organic alkalis such as methyl lithium, ethyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, phenyl lithium, lithium diisopropylamide or lithium hexamethyldisilazide Genus; organic alkaline earth metal compounds such as dimethylmagnesium, diethylmagnesium, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide or phenylmagnesium bromide; such as sodium methoxide, sodium ethoxide, sodium propoxide or potassium t-butoxide Alkoxy compounds; metal hydrides such as sodium hydride, potassium hydride or calcium hydride; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide or tetrabutylammonium hydroxide; Inorganic basic compounds such as hydroxides, alkali metal oxides, alkaline earth metal hydroxides, alkaline earth metal oxides are preferred. Ku, more preferably an alkali metal hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide or cesium hydroxide are particularly preferred, potassium hydroxide is more preferable. In addition, a commercially available thing can be used for potassium hydroxide.

  The usage-amount of an alkali compound is 1-5 equivalent normally with respect to the number-of-moles of a fluorine-containing alkene compound, Preferably it is 1.2-4 equivalent. This reaction is usually allowed to proceed under warming conditions after the compound is dissolved in water. The reaction temperature is usually 100 to 250 ° C, preferably 100 to 200 ° C, more preferably 120 to 180 ° C. If the reaction temperature is too low, the reaction rate is too slow to be practical. Also, if the reaction temperature is too high, undesirable by-products tend to be formed. The amount of water used is usually 1 to 4 times, preferably 1.2 to 3.5 times, more preferably 1.5 to 3 times the fluorine-containing alkene compound from the viewpoint of reaction rate and reaction yield. preferable.

  The perfluoroalkyne compound obtained by the method of the present invention can be purified by a known method. Although the purification method is not limited, for example, the product from which hydrogen fluoride to be recovered in advance is separated is first washed with water or / and an alkaline solution to remove acidic substances such as hydrogen chloride and hydrogen fluoride, and then dried. Then, it can be performed by subjecting it to distillation to remove organic impurities.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Unless otherwise specified, “parts” in the examples means “parts by weight”.

  The analysis of the reaction product was performed by gas chromatography (GC) method, gas chromatography mass spectrometry (GC-MS) method and nuclear magnetic resonance spectroscopy (NMR) method.

<GC measurement conditions>
Apparatus: Gas chromatograph mass spectrometer “HP6890” manufactured by Hewlett-Packard Company
Column: Inert Cap1 (registered trademark; manufactured by GL Sciences Inc.), length 60 m, inner diameter 250 μm, film thickness 1.50 μm
Injection temperature: 150 ° C
Detector temperature: 250 ° C
Carrier gas: Nitrogen (53.0 mL / min)
Make-up gas: nitrogen (30 mL / min), hydrogen (50 mL / min), air (400 mL / min)
Split ratio: 100/1
Temperature increase program: (1) Hold at 100 ° C. for 10 minutes, (2) Temperature increase at 40 ° C./min, (3) Hold at 250 ° C. for 26.25 minutes.

<GC-MS measurement conditions>
Apparatus: Gas chromatograph mass spectrometer “HP6890” manufactured by Hewlett-Packard Company
Column: Ultra ALLOY (registered trademark) ⁺ -1 (s) manufactured by Frontier Laboratories, length 30 m, inner diameter 250 μm, film thickness 1.50 μm
Injection temperature: 150 ° C
Carrier gas: helium (282 mL / min)
Split ratio: 170/1
Temperature increase program: (1) Hold at 40 ° C for 20 minutes, (2) Increase temperature at 40 ° C / minute, (3) Hold at 1250 minutes at 250 ° C

<NMR measurement conditions>
Equipment: JEOL nuclear magnetic resonance equipment "JNM-ECA400 type"

(Example 1) Production of 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-pentene using sodium borohydride Stirrer, thermometer, dry ice-ethanol 2,3-dichloro-1,1,1,4,4,5,5,5-octafluoro-2-pentene (750 parts) and diethylene glycol in a reactor equipped with a bath-soaked trap (−78 ° C.) Dimethyl ether (600 parts) was added. While maintaining the reaction solution at 0 ° C., sodium borohydride (95 parts) dissolved in diethylene glycol dimethyl ether (1400 parts) was slowly added dropwise. The mixture was stirred for 4 hours while maintaining the same temperature. After completion of the reaction, 403 parts of 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-pentene and other impurities were distilled under reduced pressure (10 mmHg) while maintaining the same temperature. Obtained.

  When the obtained crude product was analyzed by gas chromatography, it was found that 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-pentene (0.64% ), 3-chloro-1,1,1,4,4,5,5,5-octafluoro-2-pentene (4.96%), diethylene glycol dimethyl ether (89.83%) and other impurities. It was.

  The crude product was distilled at atmospheric pressure to give 26.3% 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-pentene, 3-chloro-1,1 , 1, 4, 4, 5, 5, 5-octafluoro-2-pentene, 122 parts of a mixture were obtained.

(Weight of crude product) × (area% measured by gas chromatography) = weight of target product, 2,3-dichloro-1,1,1,4,4,5,5,5-octa The yield of 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-pentene from fluoro-2-pentene was 5%.

Spectral data of 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-pentene: the NMR spectrum of this compound is known from the spectrum of the mixture 3-chloro-1,1 , 1,4,4,5,5,5-octafluoro-2-pentene.
¹ H-NMR (TMS, CDCl ₃ ) δ 6.35 (t, 1H, J = 7.1, CF ₃ CCl═C H CF ₂ )
¹⁹ F-NMR (CDCl ₃ ) —63.75 (s, 3F, C F ₃ CCl═CH), −85.46 (m, 3F, CF ₂ C F ₃ ), −110.00 (m, 2F, C F ₂ CF ₃ )
GC / MS: m / e 248, 250 (C ₅ HClF ₈ ), 229, 231 (C ₅ HClF ₇ ), 179, 181 (C ₄ HClF ₅ ), 129, 131 (C ₃ HClF ₃ )

(Production Example 1) Production of 4,4,5,5,5-pentachloro-1,1,1-trifluoro-2-pentanone Stirrer, thermometer, dewar bottle type trap (dry ice-ethanol: -78 ° C ), 1,1,1-trifluoro-2-pentanone (151.8 parts) in a reactor equipped with three water traps, 10% sodium hydroxide aqueous solution trap, and a nitrogen purge of 0.01 L / min For 30 minutes. While maintaining the reaction solution at 20 to 70 ° C., chlorine was introduced over 30 hours at a flow rate of 0.01 to 0.05 L / min under irradiation of ultraviolet light with a 500 W mercury lamp. After completion of the reaction, nitrogen purge was performed at 0.1 L / min for 1 hour to remove excess chlorine gas, and saturated aqueous sodium hydrogen carbonate solution (1000 parts) was added. After neutralizing the reaction solution, 50 parts of magnesium sulfate was added and the reaction solution was dried.

  The obtained crude product was analyzed by gas chromatography. As a result, 4,4,5,5,5-pentachloro-1,1,1-trifluoro-2-pentanone (29.42%) and It was a mixture of 3,4,4,5,5,5-hexachloro-1,1,1-trifluoro-2-pentanone (25.84%) and other impurities.

  The crude product was distilled under reduced pressure to obtain 57.4 parts of 4,4,5,5,5-pentachloro-1,1,1-trifluoro-2-pentanone in a yield of 18%.

Spectral data of 4,4,5,5,5-pentachloro-1,1,1-trifluoro-2-pentanone
^{1 H-NMR (TMS, CDCl} 3) δ4.07 (s, 2H, COC H 2 CCl 2)
¹⁹ F-NMR (CDCl ₃ ) −78.95 (s, 3H, C F ₃ COCH ₂ )
¹³ C-NMR (CDCl ₃ ) 182.39-183.13, 110.58-119.30, 104.37, 91.44, 46.73
GC / MS: m / e 241, 243, 245, 247, 249, 251 (C ₄ H ₂ Cl ₅ O); 193, 195, 197 (C ₄ H ₂ Cl ₂ F ₃ O); 143, 147, 149 ( C ₃ H ₂ Cl ₃ ); 117, 119, 121, 123 (CCl ₃ ); 97 (C ₂ F ₃ O); 69 (CF ₃ )

(Production Example 2) 2,4,4,5,5,5-hexachloro-1,1,1-trifluoro-2-pentene and 2,2,4,4,5,5,5-heptachloro-1, Production of 1,1-trifluoropentane A reactor equipped with a stirrer, thermometer, Dimroth condenser, 10% aqueous sodium hydroxide trap was added to phosphorus pentachloride (30 parts), chlorobenzene (50 parts) and 1,1, 1-Trifluoro-4,4,5,5,5-pentachloro-2-pentanone (30 parts) was charged. A −10 ° C. refrigerant was circulated through the Dimroth condenser. The reaction solution was heated to 130 ° C. while stirring, and stirring was continued for 8 hours while maintaining the same temperature. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution (100 parts) was added. After neutralizing the reaction solution, 50 parts of magnesium sulfate was added and the reaction solution was dried.

  When the obtained crude product was analyzed by gas chromatography, chlorobenzene (87.06%) and the desired product, 2,4,4,5,5,5-hexachloro-1,1,1-trifluoro- It was a mixture of 2-pentene (6.05%) and 2,2,4,4,5,5,5-heptachloro-1,1,1-trifluoropentane (3.17%) and other impurities. .

  The crude product was distilled under reduced pressure to produce 2,4,4,5,5,5-hexachloro-1,1,1-trifluoro-2-pentene and 2,2,4,4,5,5,5. -Heptachloro-1,1,1-trifluoropentane was obtained.

Spectral data of 2,4,4,5,5,5-hexachloro-1,1,1-trifluoro-2-pentene
¹ H-NMR (TMS, CDCl ₃ ) δ 7.24 (s, 1H, CF ₃ CCl═CH)
¹⁹ F-NMR (CDCl ₃ ) −69.66 (s, 3F, C F ₃ CCl═CH)
_{GC / MS: m / e 293,295,297,299,231} (C 5 HCl 5 F 3); 211,213,215,217 (C 4 HCl 3 F 3); 164,166,168,170 (C ₂ Cl ₄ ); 129, 131 (C ₃ HClF ₃ ); 117, 119, 121, 123 (CCl ₃ ); 69 (CF ₃ )

Spectral data of 2,2,4,4,5,5,5-heptachloro-1,1,1-trifluoropentane
^{1 H-NMR (TMS, CDCl} 3) δ3.59 (s, 2H, CF 3 CCl 2 C H 2)
¹⁹ F-NMR (CDCl ₃ ) −80.11 (s, 3F, C F ₃ CCl ₂ )
GC / MS: m / e 329,331,333,335 (C 5 H 2 Cl 6 F 3); 293,295,297,299 (C 5 HCl 5 F 3); 247,249,251,253,255 (C ₄ H ₂ Cl ₄ F ₃ ); 199, 201, 203, 205 (C ₂ Cl ₅ ); 151, 153, 155 (C ₂ Cl ₂ F ₃ ); 117, 119, 121, 123 (CCl ₃ ) , 69 (CF ₃ )

(Preparation Example 1)
Toyo Calgon Corp. coconut shell crushed charcoal 100g (product name "PCB"; 4 × 10 mesh) was immersed in pure water 150g, was prepared dissolved separately special grade reagent CrCl ₃ · 6H ₂ O of 40g of pure water 100g solution And stirred for a whole day and night. Next, the activated carbon is taken out by filtration, kept at 200 ° C. in an electric furnace, and fired for 2 hours. When the obtained chromium-supported activated carbon was filled into a cylindrical SUS316L reaction tube having a diameter of 5 cm and a length of 30 cm equipped with an electric furnace, the temperature was raised to 200 ° C. while flowing nitrogen gas, and no water outflow was observed. Then, nitrogen gas is accompanied by hydrogen fluoride and the concentration is gradually increased. When a hot spot due to adsorption of hydrogen fluoride on the packed chromium-supported activated carbon reaches the outlet end of the reaction tube, the reactor temperature is raised to 400 ° C., and this state is maintained for 2 hours to prepare a catalyst.

(Example 2)
150 parts of the catalyst prepared in Preparation Example 1 as a gas phase fluorination catalyst is charged into a gas phase reactor (made of SUS316L, diameter 1 inch, length 30 cm) comprising a cylindrical reaction tube equipped with an electric furnace. While flowing nitrogen gas at a flow rate of about 100 parts / 10 minutes, the temperature of the reaction tube is raised to 200 ° C., and hydrogen fluoride is entrained with nitrogen gas at a rate of about 0.10 parts / minute. The temperature of the reaction tube is raised to 500 ° C. and maintained for 1 hour. Next, the temperature of the reaction tube was lowered to 400 ° C., hydrogen fluoride was supplied at a rate of 0.15 part / min, and 2,4,4,5,5,5-hexachloro-1,1,1-trifluoro- 2-Pentene is vaporized in advance and feed to the reactor is started at a rate of 0.06 parts / minute.

  Since the reaction is stable 1 hour after the start of the reaction, the product gas flowing out from the reactor is blown into water for 2 hours to remove the acid gas, and then 2 in a glass trap immersed in a dry ice-acetone bath. Collect a mixture of chloro-1,1,1,4,4,5,5,5-octafluoro-2-pentene and other impurities.

(Example 3) Production of perfluoro-2-pentyne 85% potassium hydroxide (160 parts) and water (160 parts) were charged into a reactor equipped with a stirrer, a thermometer, and a Dimroth condenser. A refrigerant of −20 ° C. was circulated through the condenser. The reaction solution was heated to 150 ° C. with stirring, and after the reaction solution reached 150 ° C., 2-chloro-1,1,1,4,4,5,5,5-octa obtained in Example 1 was used. Maintain the same temperature while slowly dropping a mixture of fluoro-2-pentene and 3-chloro-1,1,1,4,4,5,5,5-octafluoro-2-pentene (100 parts), The reaction was continued for 30 hours. The obtained product was collected in a glass trap cooled to −78 ° C. in a dry ice-acetone bath. As a result of analyzing the product collected in the glass trap by gas chromatography, 67.4 parts of the target perfluoro-2-pentyne was obtained in a yield of 79%. The obtained perfluoro-2-pentyne was subjected to NMR analysis and GC-MS analysis. The data is shown below.

Spectral data of perfluoro-2-pentyne
¹⁹ F-NMR (CDCl ₃ ) -54.1 (s, 3F, C F ₃ C≡C), −86.0 (m, 3F, CF ₂ C F ₃ ), −106.4 (m, 2F, C F ₂ CF ₃ )
¹³ C-NMR (CDCl ₃ ) 72.18, 77.31, 105.4, 113.9, 118.4
GC / MS: m / e 193 (C ₅ F ₇ ), 143 (C ₄ F ₅ ), 124 (C ₄ F ₄ ), 105 (C ₄ F ₃ ), 93 (C ₃ F ₃ ), 74 (C ₃ F ₂ ), 69 (CF ₃ ) 55 (C ₃ F), 31 (CF)

Claims (3)

The manufacturing method of the fluorine-containing alkene compound of the following general formula A which makes the tetrahydroboric acid metal salt react with the chlorine-containing alkene compound of the following general formula B.
Formula B: CF ₃ CCl═CCl (CF ₂ ) nCF ₃
(In general formula B, n is 0-5.)
Formula A: CF ₃ CCl═CH (CF ₂ ) nCF ₃
(In general formula A, n is 0-5.) Method for producing a halogen-containing alkene compound of the following general formulas C and / or halogen-containing alkane compound of the following general formula D, fluorination catalyst presence, fluorinated alkene compound of the following general formula A is reacted with hydrogen fluoride.
Formula C: CF ₃ CCl═CH (CX ₂ ) _n CX ₃
(In general formula C, each X is independently a chlorine atom, a bromine atom or an iodine atom, and n is 0 to 5.)
Formula D: CF ₃ CCl ₂ CH ₂ (CX ₂ ) _n CX ₃
(In general formula D, each X is independently a chlorine atom, a bromine atom or an iodine atom, and n is 0 to 5.)
Formula A: CF ₃ CCl═CH (CF ₂ ) nCF ₃
(In general formula A, n is 0-5.) A method for producing a perfluoroalkyne compound by dehydrochlorinating the fluorine-containing alkene compound of the general formula A obtained by the method according to claim 1 or 2.