JP2012518599A - Method for producing fluorine-containing alkyne compound - Google Patents

Abstract

（式中、Ｒｆは上記に同じ）で表される含フッ素アルキン化合物の製造方法を提供する。本発明の方法によれば、３，３，３−トリフルオロプロピン等の含フッ素アルキン化合物を、比較的簡単な方法によって高い選択率で製造できる。
【選択図】なしThe present invention is at least one selected from the group consisting of halides containing alkali metals or alkaline earth metals, oxides containing alkali metals or alkaline earth metals, and compounds containing alkali metal hydroxides or alkaline earth metals. In the gas phase in the presence of a compound of the formula: RfCX = CHY (wherein it is a fluorine-containing alkyl group, one of X and Y is a halogen atom and the other is a hydrogen atom). A dehydrohalogenation reaction of a fluorine-containing alkene compound is represented by the chemical formula:

(Wherein Rf is the same as above), a method for producing a fluorine-containing alkyne compound is provided. According to the method of the present invention, fluorine-containing alkyne compounds such as 3,3,3-trifluoropropyne can be produced with high selectivity by a relatively simple method.
[Selection figure] None

Description

  The present invention relates to a method for producing a fluorine-containing alkyne compound.

  Fluorine-containing alkyne compounds such as 3,3,3-trifluoropropyne are useful compounds as materials such as refrigerants, etching agents and aerosols, and also as intermediates of various materials and monomer components of polymer compounds It is a highly useful compound that can be used.

  For example, as a method for producing 3,3,3-trifluoropropyne, a method according to the following production process using 2,3-dibromo-1,1,1-trifluoropropene as a raw material is known (the following non- Patent Literatures 1 to 3).

  However, this method is very complicated because it requires a multi-step reaction process, and it is not preferable as an industrial production method because it uses bromine which is highly corrosive.

  As another method for producing 3,3,3-trifluoropropyne, a method for producing 3,3,3-trifluoropropyne from 1,1,2-trichloro-3,3,3-trifluoropropene is known. (See Non-Patent Document 4 below). However, in this method, since a zinc compound is used as a raw material, the treatment of zinc waste liquid becomes a problem.

  In addition, a method of reacting 1-iodo-3,3,3-trifluoropropene with potassium fluoride (KF) is also known (see Non-Patent Document 5 below). This method has the problem that the raw materials are expensive, the yield is very low, and many by-products are produced.

Furthermore, although a method of reacting acetylene carboxylic acid (HC≡CCOOH) with sulfur tetrafluoride (SF ₄ ) has been reported (see Non-patent Document 6 below), the raw material acetylene carboxylic acid is expensive. Since it is difficult to handle sulfur fluoride, it is not an industrially advantageous method.

  A method of reacting a base in a liquid phase using (Z) -1-halogeno-3,3,3-trifluoropropene as a raw material has also been reported (see Patent Document 1 below). However, this method proceeds only when a Z-form is used as a raw material, and a large amount of alkaline waste is generated because a base is used for the reaction.

WO2008 / 132964 A1

Journal of the American Chemical Society, 1951, 73, 1042-3. Journal of the Chemical Society, 1951, 2495-504. Journal of the Chemical Society, 1952,3483-90. Journal of Organic Chemistry, 1963, 28, 1139-40. Journal of Fluorine Chemistry, 1978, 12 (4), 321-4. Journal of the American Chemical Society, 1959, 81, 3165-6.

  The present invention has been made in view of the above-described state of the art, and its main purpose is to produce a fluorine-containing alkyne compound such as 3,3,3-trifluoropropyne by a relatively simple production method. It is to provide a novel method that can be produced with high selectivity.

  The present inventor has intensively studied to achieve the above-described object. As a result, a specific fluorine-containing alkene compound is used as a raw material, and in the gas phase, a halide containing an alkali metal or alkaline earth metal, an oxide containing an alkali metal or alkaline earth metal, and an alkali metal or alkaline earth When the dehydrohalogenation reaction is carried out in the presence of at least one compound selected from the group consisting of metal-containing hydroxides, the desired fluorine-containing alkyne compound can be produced with high selectivity and a continuous reaction Therefore, it has been found that a fluorine-containing alkyne compound can be produced very efficiently. The present invention has been completed based on these findings.

That is, this invention provides the manufacturing method of the following fluorine-containing alkyne compound.
Item 1. Presence of at least one compound selected from the group consisting of halides containing alkali metals or alkaline earth metals, oxides containing alkali metals or alkaline earth metals, and hydroxides containing alkali metals or alkaline earth metals Below, in the gas phase, it is represented by the chemical formula: RfCX = CHY (wherein Rf is a fluorine-containing alkyl group, one of X and Y is a halogen atom, and the other is a hydrogen atom). A chemical formula characterized by carrying out a dehydrohalogenation reaction of a fluorine-containing alkene compound:

(Wherein Rf is the same as above).
Item 2. Item 2. The method for producing a fluorinated alkyne compound according to Item 1, wherein the catalyst is an alkali metal or alkaline earth metal fluoride.
Item 3. The catalyst is a carrier, a halide containing an alkali metal or an alkaline earth metal, an oxide containing an alkali metal or an alkaline earth metal, and a hydroxide containing an alkali metal or an alkaline earth metal supported on the carrier. Item 3. The method for producing a fluorinated alkyne compound according to Item 1 or 2, which comprises at least one compound selected from the group consisting of:
4). Item 4. The method according to any one of Items 1 to 3, wherein Rf is a trifluoromethyl group.

  Hereafter, the manufacturing method of the fluorine-containing alkyne compound of this invention is demonstrated concretely.

Raw Material Compound In the present invention, a fluorine-containing alkene compound represented by the chemical formula: RfCX = CHY is used as the raw material.

  In the above chemical formula, Rf is a fluorine-containing alkyl group, and examples thereof include a perfluoroalkyl group having about 1 to 10 carbon atoms and a fluorinated alkyl group having about 1 to 10 carbon atoms. Specific examples of the fluorine-containing alkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a heptafluoroisopropyl group, a nonafluorobutyl group, and a nonafluoro-t-butyl group.

  One of X and Y is a halogen atom, and the other is a hydrogen atom. Here, examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.

  When Y is a halogen atom, the fluorine-containing alkene compound can exist as a Z (cis) isomer or an E (trans) isomer, but in the present invention, either the Z isomer or the E isomer can be used as a raw material. . This is a major difference between the method of Patent Document 1 and the method of the present invention in which the reaction does not proceed in the E form.

Reaction Method The production method of the present invention comprises a group consisting of a halide containing an alkali metal or alkaline earth metal, an oxide containing an alkali metal or alkaline earth metal, and a hydroxide containing an alkali metal or alkaline earth metal. In the gas phase in the presence of at least one selected compound, the chemical formula: RfCX = CHY (wherein Rf is a fluorine-containing alkyl group, one of X and Y is a halogen atom, and the other is a hydrogen atom) The dehydrohalogenation reaction of the fluorinated alkene compound represented by formula (1) is performed. According to this method, the chemical formula

A fluorine-containing alkyne compound represented by the formula (wherein Rf is a fluorine-containing alkyl group) can be obtained with high selectivity.

  At least one selected from the group consisting of halides containing alkali metals or alkaline earth metals used as catalysts, oxides containing alkali metals or alkaline earth metals, and hydroxides containing alkali metals or alkaline earth metals In the compound, examples of the alkali metal include Na, K, Li, Rb, and Cs, and examples of the alkaline earth metal include Ca, Mg, Sr, and Ba. Examples of the halide include fluoride, chloride, iodide, bromide and the like.

Specific examples of the alkali metal or alkaline earth metal _{halides, NaF, KF, LiF, RbF} , CsF, CaF 2, MgF 2, BaF 2, fluorides such as _{SrF 2, NaCl, KCl, LiCl} , RbCl, _{CsCl, CaCl 2, MgCl 2,} BaCl 2, SrCl 2 , etc. _{chloride, NaI, KI, LiI, RbI} , CsI, CaI 2, MgI 2, BaI 2, iodides such _{SrI 2, NaBr, KBr, LiBr} , Examples thereof include bromides such as RbBr, CsBr, CaBr ₂ , MgBr ₂ , BaBr ₂ , and SrBr ₂ . Specific examples of the alkali metal or alkaline earth metal oxide include Na ₂ O, K ₂ O, Li ₂ O, Rb ₂ O, Cs ₂ O, CaO, MgO, BaO, and SrO. Specific examples of the alkali metal or alkaline earth metal hydroxide include NaOH, KOH, LiOH, RbOH, CsOH, Ca (OH) ₂ , Mg (OH) ₂ , Ba (OH) ₂ , and Sr (OH) _2. Etc. These halides containing alkali metals or alkaline earth metals, oxides containing alkali metals or alkaline earth metals, and hydroxides containing alkali metals or alkaline earth metals can be used alone or in combination of two or more. Can be used. In the present invention, an alkali metal or alkaline earth metal fluoride is particularly preferable.

  Also, from the group consisting of the above catalyst components, that is, halides containing alkali metals or alkaline earth metals, oxides containing alkali metals or alkaline earth metals, and hydroxides containing alkali metals or alkaline earth metals. At least one selected compound may be supported on a carrier. The carrier can be used as long as it is stable to the dehydrohalogenation reaction, and may be appropriately selected from known carriers. For example, activated carbon, metallic aluminum, silica, alumina, zirconia, magnesia, titania, celite, zeolite, silicon carbide, diatomaceous earth and the like can be suitably used as the carrier. Activated carbon is particularly preferable.

As the carrier for carrying the catalyst component, a specific surface area preferably has a large specific surface area of about 50~1500m ² / g, more preferably about 300~1500m ² / g.

  The amount of the catalyst component supported on the carrier is about 1 to 60% by weight, where the total weight of the catalyst component and the carrier is 100% by weight.

  By supporting the catalyst component on the carrier having a large specific surface area as described above, the contact efficiency between the raw material and the catalyst component is improved, and the desired fluorine-containing alkyne compound can be obtained with high selectivity.

  The dehydrohalogenation reaction can proceed by bringing the fluorine-containing alkene compound as a raw material into contact with the above-described catalyst in a gas phase state.

  The dehydrohalogenation reaction can usually be carried out by supplying the fluorine-containing alkene compound as a raw material in a gaseous state to the reactor filled with the catalyst. The fluorine-containing alkene compound may be supplied to the reactor as it is, or may be supplied after being diluted with an inert gas such as nitrogen, helium, or argon.

  The kind of the reactor is not particularly limited, and for example, an adiabatic reactor filled with a catalyst, a multi-tube reactor removed with a heat medium, or the like can be used. As the reactor, it is preferable to use a reactor made of a material resistant to the corrosive action of hydrogen fluoride, such as HASTALLOY, INCONEL, and MONEL.

  The temperature of the dehydrohalogenation reaction is preferably about 200 to 650 ° C, more preferably about 300 to 550 ° C as the temperature in the reactor. If the temperature is higher than this temperature range, the selectivity tends to decrease. Conversely, if the temperature is lower, the raw material conversion rate tends to decrease.

  About the pressure at the time of reaction, it does not specifically limit, Reaction can be performed under a normal pressure or pressurization. That is, the dehydrohalogenation reaction in the present invention can be carried out under atmospheric pressure (0.1 MPa), but may be carried out under pressure up to about 1.0 MPa.

  The reaction time is not particularly limited, but the ratio of the catalyst filling amount W (g) to the total flow rate Fo (flow rate at 0 ° C., 0.1 MPa: cc / sec) of the raw material gas flowing into the reaction system is usually W / The contact time represented by Fo may be in the range of 0.1 to 300 g · sec / cc, preferably about 10 to 180 g · sec / cc. In this case, the catalyst filling amount is the total amount of the catalyst component and the carrier when the catalyst supported on the carrier is used.

  According to the method described above, the fluorine-containing compound represented by the chemical formula: RfCX = CHY (wherein Rf is a fluorine-containing alkyl group, one of X and Y is a halogen atom, and the other is a hydrogen atom). The hydrogen halide represented by XY is eliminated from the alkene compound, and the chemical formula

A fluorine-containing alkyne compound represented by the formula (wherein Rf is a fluorine-containing alkyl group) can be obtained.

  According to the method of the present invention, the target fluorine-containing alkyne compound can be obtained with high selectivity. Moreover, since it is a gas phase reaction, a continuous reaction can be easily performed, and the target fluorine-containing alkyne compound can be produced efficiently. Furthermore, since both Z body and E body can be used as a raw material, the range of selection of a raw material is wide.

  For this reason, the method of the present invention is a very useful method as an industrial production method of a fluorine-containing alkyne compound.

  Hereinafter, the present invention will be described in more detail with reference to preparation examples of the catalyst used in the present invention and examples of the present invention.

Preparation Example 1
Cesium fluoride (CsF, purity 99%) dried at 400 ° C. for 4 hours in a nitrogen stream was allowed to cool to room temperature, and 25.0 g was dissolved in 150 ml of pure water. To this aqueous solution, 30.0 g of activated carbon (Calgon, BPL4 × 10, specific surface area: 1150 m ² / g) previously dried at 250 ° C. for 4 hours in a nitrogen stream was cooled to room temperature, and bubbles were completely removed under reduced pressure. Gently stirred until no more occurred. The mixture was aged at room temperature for 5 hours and dried at 150 ° C. for 12 hours in a nitrogen stream. The obtained solid was calcined in a nitrogen stream at 400 ° C. for 3 hours to obtain 53.9 g of a solid. This solid is referred to as catalyst A.

Preparation Example 2
Potassium fluoride (KF, purity 99%) dried at 400 ° C. for 4 hours in a nitrogen stream was allowed to cool to room temperature, and 5.0 g was dissolved in 200 ml of pure water. To this aqueous solution, 45.2 g of activated carbon (granular white birch, C2X4 / 6-2, specific surface area: 1050 m ² / g) previously dried at 250 ° C. for 4 hours in a nitrogen stream is cooled to room temperature, and bubbles are added under reduced pressure Gently stirred until no more occurred. The mixture was aged for 5 hours at room temperature and dried at 120 ° C. for 15 hours in a nitrogen stream. The obtained solid was calcined in a nitrogen stream at 400 ° C. for 3 hours to obtain 49.8 g of a solid. This solid is referred to as catalyst B.

Example 1
30 g of catalyst A was packed in a tubular Hastelloy reactor having an inner diameter of 15 mm and a length of 1 m.

The reactor was maintained at atmospheric pressure (0.1 MPa) and 300 ° C., and nitrogen (N ₂ ) was supplied to the reactor at 100 cc / min (flow rate at 0 ° C. and 0.1 MPa) for 2 hours. Then, 2-chloro-3,3,3-trifluoropropene (HCFC-1233xf, purity 99.9%) was supplied as a raw material at a rate of 20 cc / min (flow rate at 0 ° C. and 0.1 MPa), and immediately nitrogen ( After stopping the supply of N ₂ ), the reaction temperature was raised to 350 ° C. The contact time (W / F ₀ ) was 90.0 g · sec / cc. A gas chromatograph was used to analyze the outflow gas at the reactor outlet 1.5 hours after the target reaction temperature was reached. The results are shown in Table 1.

  The chemical formula for each product is as follows:

CF ₃ CF = CH ₂ (HFC-1234yf)
CF ₃ CH = CHCl (HCFC-1233zd-E + Z)
CF ₃ CH = CHF (HFC-1234ze-E body + Z body)
CF ₃ CH = CH ₂ (HFC-1243zf)
Example 2
The experiment was conducted under the same reaction conditions as in Example 1 except that the reaction temperature was 400 ° C. The contact time (W / F ₀ ) was 90.0 g · sec / cc. A gas chromatograph was used to analyze the outflow gas at the reactor outlet 1.5 hours after the target reaction temperature was reached. The results are shown in Table 1.

Example 3
The experiment was conducted under the same reaction conditions as in Example 1 except that the reaction temperature was 500 ° C. The contact time (W / F ₀ ) was 90.0 g · sec / cc. A gas chromatograph was used to analyze the outflow gas at the reactor outlet 1.5 hours after the target reaction temperature was reached. The results are shown in Table 1.

Example 4
30 g of catalyst B was charged into a tubular Hastelloy reactor having an inner diameter of 20 mm and a length of 1 m.

The reactor was maintained at atmospheric pressure (0.1 MPa) and 300 ° C., and nitrogen (N ₂ ) was supplied to the reactor at 100 cc / min (flow rate at 0 ° C., 0.1 MPa) for 2 hours. Thereafter, 1-chloro-3,3,3-trifluoropropene-E (HCFC-1233zd-E, purity 99.9%) is supplied as a raw material at a rate of 20 cc / min (flow rate at 0 ° C. and 0.1 MPa). Immediately after the supply of nitrogen (N ₂ ) was stopped, the reaction temperature was brought to 400 ° C. The contact time (W / F ₀ ) was 60.0 g · sec / cc. A gas chromatograph was used to analyze the outflow gas at the outlet of the reactor 2 hours after the target reaction temperature was reached. The results are shown in Table 2. The above reaction also produced a 1-chloro-3,3,3-trifluoropropene-Z isomer, which is an isomer of the 1-chloro-3,3,3-trifluoropropene-E isomer used as a raw material. In Table 2, the 1-chloro-3,3,3-trifluoropropene-Z form is shown as a part of the raw material, excluding the raw material conversion rate.

Example 5
The experiment was performed under the same reaction conditions as in Example 4 except that the reaction temperature was 500 ° C. The contact time (W / F ₀ ) was 60.0 g · sec / cc. A gas chromatograph was used to analyze the outflow gas at the reactor outlet 1.5 hours after the target reaction temperature was reached. The results are shown in Table 2.

Claims (4)

Presence of at least one compound selected from the group consisting of halides containing alkali metals or alkaline earth metals, oxides containing alkali metals or alkaline earth metals, and hydroxides containing alkali metals or alkaline earth metals Below, in the gas phase, it is represented by the chemical formula: RfCX = CHY (wherein Rf is a fluorine-containing alkyl group, one of X and Y is a halogen atom, and the other is a hydrogen atom). A chemical formula characterized by carrying out a dehydrohalogenation reaction of a fluorine-containing alkene compound:

(Wherein Rf is the same as above). The method for producing a fluorinated alkyne compound according to claim 1, wherein the catalyst is an alkali metal or alkaline earth metal fluoride. The catalyst is a carrier, a halide containing an alkali metal or an alkaline earth metal, an oxide containing an alkali metal or an alkaline earth metal, and a hydroxide containing an alkali metal or an alkaline earth metal supported on the carrier. The method for producing a fluorinated alkyne compound according to claim 1 or 2, comprising at least one compound selected from the group consisting of: The method according to claim 1, wherein Rf is a trifluoromethyl group.