TWI808318B - Production method of perfluoroalkyne compound - Google Patents

Abstract

(1) In an organic solvent, in the presence of iodine-containing inorganic materials, and zinc or zinc alloys, use [The bond shown by the solid line and the broken line is a single bond or a double bond. When the bond shown by the solid line and the dotted line is a single bond, the n series all represent 2, and when the bond shown by the solid line and the dotted line is a double bond, the n series all represent 1. R ¹ and R ² represent either a fluorine atom or a perfluoroalkyl group identically or differently. X ¹ and X ² represent halogen atoms identically or differently. ] Reaction of the halogenated hydrocarbon compound represented, or (2) by making X ¹ R ¹ C=CR ² X ² in a specific nitrogen-containing polar organic solvent in the presence of zinc or zinc alloy [wherein, R ¹ , R ² , X ¹ and X ² are the same as above. ] The reaction of the halogenated olefin compound represented by ] can obtain the perfluorocarbon compound with double bond or triple bond in high yield.

Description

Production method of perfluoroalkyne compound

The present invention relates to a method for producing perfluoroalkyne compounds.

Perfluoroalkyne compounds are not only dry etching gases for semiconductors, but also useful as cleaning gases, building blocks for organic synthesis, etc., and have a triple bond between carbon and carbon. In particular, 1,1,1,4,4,4-hexafluoro-2-butyne having 4 carbon atoms is used in various applications.

As a method for producing this perfluoroalkyne compound, it is known to use N,N-dimethylformamide, N,N-diethylformamide, 1,3-dimethyl-2-imidazolidinone, etc. as a solvent, and to obtain 1,1,1,4,4,4-hexafluoro - A method of 2-butyne (for example, refer to Patent Document 1). [Prior Art Literature] [Patent Document]

[Patent Document 1] Specification of Chinese Patent Application Publication No. 106008147

[Problem to be Solved by the Invention]

The object of the present invention is to provide a method for obtaining perfluorocarbons having double or triple bonds in high yield. [Means used to solve problems]

The present invention includes the following constitutions.

Item 1. A manufacturing method, which is general formula (1):

[In the formula, the bond shown by the double line and the dotted line is a double bond or a triple bond. When the bond shown by the double line and the dotted line is a double bond, the n series all represent 2, and when the bond shown by the double line and the dotted line is a triple bond, the n series all represent 1. R ¹ and R ² represent either a fluorine atom or a perfluoroalkyl group identically or differently. ] represents a method for producing perfluorocarbons, wherein, in an organic solvent, in the presence of an iodine-containing inorganic material, and zinc or zinc alloy, the general formula (2):

[In the formula, the bond shown by the solid line and the dashed line is a single bond or a double bond. When the bond shown by the solid line and the dotted line is a single bond, the n series all represent 2, and when the bond shown by the solid line and the dotted line is a double bond, the n series all represent 1. R ¹ and R ² are the same as above. X ¹ and X ² represent halogen atoms identically or differently. ] reacting the halogenated hydrocarbon compound represented by the above-mentioned general formula (1) to obtain the step of perfluorocarbon compound represented.

Item 2. The production method according to Item 1, wherein the amount of the iodine-containing inorganic material used is 0.0005 mol or more relative to 1 mol of the zinc or zinc alloy.

Item 3. The production method according to Item 1 or 2, wherein the iodine-containing inorganic material is at least one selected from the group consisting of iodine, metal iodides, and interhalogen compounds containing iodine.

Item 4. A manufacturing method, which is the general formula (1A): [wherein, R ¹ and R ² are the same or different representations of a fluorine atom or a perfluoroalkyl group. ] A method for producing a perfluoroalkyne compound, wherein zinc or zinc alloy In the presence of , make the general formula (2A): [wherein, R ¹ and R ² are the same as above. X ¹ and X ² represent halogen atoms identically or differently. ] The step of reacting the halogenated olefin compound represented by the above-mentioned general formula (1A) to obtain the perfluoroalkyne compound represented by the aforementioned general formula (1A).

Item 5. The production method according to any one of Items 1 to 4, wherein the reaction temperature is 0 to 250°C.

Item 6. A composition comprising the general formula (1A): [wherein, R ¹ and R ² are the same or different representations of a fluorine atom or a perfluoroalkyl group. ] represented by the perfluoroalkyne compound, and the general formula (3): [wherein, R ¹ and R ² are the same as above. ] represents the compound.

Item 7. The composition as described in Item 6, wherein the total amount of the aforementioned composition is 100 mol %, and the content of the perfluoroalkyne compound represented by the aforementioned general formula (1A) is 85 to 99.9 mol %.

Item 8. The composition as described in Item 6 or 7, which is used as a cleaning gas, an etching gas, or a building block for organic synthesis. [Effect of Invention]

According to the present invention, perfluorocarbon compounds having double bonds or triple bonds can be obtained in high yield.

In this specification, "contains" includes any concept of "comprise", "consist essentially of" and "consist of". In addition, in this specification, when a numerical range is represented by "A-B", it means that it is A or more and B or less.

In the present invention, the so-called "selectivity" means the ratio (mole %) of the total molar amount of the target compound contained in the effluent gas to the total molar amount of compounds other than the raw material compound in the effluent gas flowing out from the reactor outlet.

In the present invention, the so-called "conversion rate" means the ratio (mole %) of the total molar amount of compounds other than the raw material compound contained in the effluent gas flowing out from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

In the past, according to the method of Patent Document 1, N,N-dimethylformamide, N,N-diethylformamide, 1,3-dimethyl-2-imidazolidinone, etc. were used as solvents, and in the presence of zinc, by dechlorination reaction from 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (1316mxx) to obtain 1,1,1,4,4,4-hexafluoro-2- Butyne, however, its highest yield is only 62%.

From the above, the yield according to the conventional method is not sufficient. According to the production method of the present invention, perfluoroalkyne compounds can be synthesized in a higher yield than conventional ones. In addition, perfluoroalkene compounds can also be synthesized in a high-yield manner by the same method.

1. Manufacturing method of perfluorocarbons The production method of the perfluoroalkyne compound of the first aspect of the present invention is the general formula (1):

[In the formula, the bond shown by the double line and the dotted line is a double bond or a triple bond. When the bond shown by the double line and the dotted line is a double bond, the n series all represent 2, and when the bond shown by the double line and the dotted line is a triple bond, the n series all represent 1. R ¹ and R ² represent either a fluorine atom or a perfluoroalkyl group identically or differently. ] represents a method for producing perfluorocarbons, wherein, in an organic solvent, in the presence of an iodine-containing inorganic material, and zinc or zinc alloy, the general formula (2):

[In the formula, the bond shown by the solid line and the dotted line is a single bond or a double bond. When the bond shown by the solid line and the dotted line is a single bond, the n series all represent 2, and when the bond shown by the solid line and the dotted line is a double bond, the n series all represent 1. R ¹ and R ² are the same as above. X ¹ and X ² represent halogen atoms identically or differently. ] the step of reacting the halogenated hydrocarbon compound represented by the aforementioned general formula (1) to obtain the perfluorocarbon compound represented by the aforementioned general formula (1).

That is, the manufacturing method of the present invention comprises general formula (2A): [In the formula, R ¹ , R ² , X ¹ and X ² are the same as above. ] represented by the perfluoroalkene compound as a substrate, the general formula (1A) is obtained: [wherein, R ¹ and R ² are the same as above. ] represents the method of perfluoroalkyne compound, and the general formula (2B): [In the formula, R ¹ , R ² , X ¹ and X ² are the same as above. ] represented by the perfluoroalkane compound as a substrate, the general formula (1B) is obtained: [wherein, R ¹ and R ² are the same as above. ] Both of the methods of the perfluoroalkene compound represented.

According to the present invention, by carrying out the dehalogenation reaction of the halogenated hydrocarbon compound represented by the above-mentioned general formula (2) in the presence of an iodine-containing inorganic material and zinc or zinc alloy in an organic solvent, ^X1 and ^X2 are separated from the halogenated hydrocarbon compound represented by the general formula (2), and the perfluorocarbon compound represented by the above-mentioned general formula (1) can be obtained.

As the halogenated hydrocarbon compound that can be used as the substrate in the production method of the present invention, it is the halogenated hydrocarbon compound represented by the general formula (2):

[In the formula, the bond shown by the solid line and the dotted line is a single bond or a double bond. When the bond shown by the solid line and the dotted line is a single bond, the n series all represent 2, and when the bond shown by the solid line and the dotted line is a double bond, the n series all represent 1. R ¹ and R ² represent either a fluorine atom or a perfluoroalkyl group identically or differently. X ¹ and X ² represent halogen atoms identically or differently. ].

In the general formula (2), the perfluoroalkyl group represented by R ¹ and R ² means an alkyl group in which all hydrogen atoms are substituted with fluorine atoms. Such a perfluoroalkyl group is preferably, for example, a perfluoroalkyl group having 1 to 20 carbons, preferably 1 to 12 carbons, more preferably 1 to 6 carbons, still more preferably 1 to 4 carbons, particularly preferably 1 to 3 carbons. The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group. As such a perfluoroalkyl group, for example, trifluoromethyl (CF ₃ -), pentafluoroethyl (C ₂ F ₅ -) and the like are preferable.

In the general formula (2), examples of the halogen atoms represented by ^X1 and ^X2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. However, it is preferable to use a substrate that does not contain iodine from the viewpoint of easily obtaining the perfluorocarbon compound represented by the above-mentioned general formula (1) by the production method of the present invention. From such a viewpoint, the halogen atoms represented by ^X1 and ^X2 are preferably fluorine atoms, chlorine atoms, and bromine atoms. However, from the viewpoint of easily obtaining the perfluorocarbon compound represented by the above-mentioned general formula (1) by the production method of the present invention, both of ^X1 and ^X2 of the particularly preferred series are not fluorine atoms. That is, it is preferable that at least one of ^X1 and ^X2 is a chlorine atom or a bromine atom.

As the halogenated hydrocarbon compound of the substrate, especially in the viewpoint that perfluorocarbons can be produced with high conversion rate, yield and selectivity, the particularly preferred series ^R1 and ^R2 are both trifluoromethyl groups, and the particularly preferred series ^X1 and ^X2 are both chlorine atoms.

The above-mentioned R ¹ and R ² systems may be the same or different. In addition, R ¹ may be the same or different from each other. In addition, R ² may be the same or different from each other. In addition, the above X ¹ and X ² systems may be the same or different.

作為滿足上述條件之基質之鹵化烴化合物，具體而言，作為鹵化烯烴化合物，可舉出CFCl=CFCl、CFBr=CFBr、CFCl=CFBr、CF ₃ CCl=CClCF ₃ 、CF ₃ CCl=CBrCF ₃ 、CF ₃ CBr=CBrCF ₃ 、C ₂ F ₅ CCl=CClC ₂ F ₅ 、C ₂ F ₅ CCl=CBrC ₂ F ₅ 、C ₂ F ₅ CBr=CBrC ₂ F ₅等，作為鹵化鏈烷化合物，可舉出CF ₂ ClCF ₂ Cl、ClCF ₂ CF ₂ Br、CF ₂ BrCF ₂ Br、CF ₃ CClFCClFCF ₃ 、CF ₃ CBrFCBrFCF ₃ 、(CF ₃ ) ₂ CClCCl(CF ₃ ) ₂ 、(CF ₃ ) ₂ CClCBr(CF ₃ ) ₂ 、(CF ₃ ) ₂ CBrCBr(CF ₃ ) ₂ 、(C ₂ F ₅ ) ₂ CClCCl(C ₂ F ₅ ) ₂ 、(C ₂ F ₅ ) ₂ CClCBr(C ₂ F ₅ ) ₂ 、(C ₂ F ₅ ) ₂ CBrCBr(C ₂ F ₅ ) ₂等。 These halogenated hydrocarbon compounds may be used alone or in combination of two or more. As such halogenated hydrocarbon compounds, known or commercially available ones can be used.

In the step of obtaining the perfluorocarbon compound from the halogenated hydrocarbon compound in the present invention, for example, as a substrate, R ^{and R} in the halogenated hydrocarbon compound represented by the general formula (2) are particularly preferred as fluorine atoms or trifluoromethyl groups, and particularly preferred as X ^{and X} are both chlorine atoms.

Specifically, the dehalogenation reaction (especially the dechlorination reaction) according to the following reaction formula is preferred: .

In the production method of the first aspect of the present invention, it is provided with the step of reacting the halogenated hydrocarbon compound represented by the above general formula (2) in the presence of an iodine-containing inorganic material and zinc or zinc alloy in an organic solvent to obtain the perfluorocarbon compound represented by the above general formula (1).

At this time, the amount of the halogenated hydrocarbon compound represented by the general formula (2) is preferably 0.05-30 moles, more preferably 0.1-10 moles, and even more preferably 0.2-5 moles relative to 1 mole of zinc or zinc alloy described later from the viewpoint of the yield and selectivity of perfluorocarbons.

In the present invention, since the iodine-containing inorganic material is used, the surface of zinc or zinc alloy is activated, and the reaction of the halogenated hydrocarbon compound represented by the general formula (2) is promoted, thereby obtaining the halogenated hydrocarbon compound represented by the general formula (2) in high yield. The iodine-containing inorganic material used is not particularly limited if it is an inorganic material containing an iodine atom. For example, iodine; typical metal iodides (sodium iodide, potassium iodide, magnesium iodide, calcium iodide, etc.), transition metal iodides (zinc iodide, etc.) In addition, according to the production method of the present invention, zinc halide (a mixture of zinc fluoride, zinc chloride, and zinc iodide) can be produced as an impurity in the product. The impurity zinc halide contained in this product is used as an iodine-containing inorganic material and can be reused in the production method of the present invention. These iodine-containing inorganic materials may be used alone or in combination of two or more. Among them, from the viewpoint of the yield and selectivity of the perfluorocarbon compound represented by the general formula (1), iodine, a typical metal iodide, a transition metal iodide, an interhalogen compound containing iodine, etc. are preferable, iodine, a typical metal iodide, an interhalogen compound containing iodine, etc. are more preferable, and iodine is even more preferable. In addition, in the case of using an iodine-free material such as zinc fluoride or zinc chloride instead of an iodine-containing inorganic material as the halogen-containing material, the effect of improving the yield and selectivity of the perfluorocarbon represented by the general formula (1) cannot be obtained.

The amount of this iodine-containing inorganic material used is preferably 0.0005 mole or more, more preferably 0.001 mole or more, relative to 1 mole of zinc or zinc alloy described later, from the viewpoint of the yield and selectivity of the perfluorocarbon compound represented by the general formula (1). In addition, the upper limit of the usage amount of the iodine-containing inorganic material is not particularly limited, but from the perspectives of the yield, selectivity, and cost of perfluorocarbons represented by the general formula (1), it is usually preferably 2 moles or less, more preferably 0.1 moles or less, relative to 1 mole of zinc or zinc alloy described later.

In addition, the amount of the iodine-containing inorganic material used is preferably 0.00002 mole or more, more preferably 0.00005 mole or more, relative to 1 mole of the organic solvent described later, from the viewpoints of the yield, selectivity, and cost of the perfluorocarbon compound represented by the general formula (1). In addition, the upper limit of the usage amount of the iodine-containing inorganic material is not particularly limited, but from the perspectives of the yield, selectivity, and cost of the perfluorocarbon compound represented by the general formula (1), it is usually preferably below the solubility of the organic solvent described below, and more preferably below 0.08 mole relative to 1 mole of the organic solvent described below.

Among zinc or zinc alloys, elements that may be contained when zinc alloys are used include, for example, lead, cadmium, iron, and the like. In addition, commercially available zinc may contain impurities such as lead, cadmium, and iron. Those containing such impurities are also included in the present invention.

The organic solvent is preferably a polar organic solvent from the viewpoint of dissolving the halogenated hydrocarbon compound represented by the general formula (2). In addition, from the viewpoint of the yield and selectivity of the perfluorocarbon compound represented by the general formula (1), a nitrogen-containing polar solvent is more preferable. Examples of such organic solvents include amide compounds (N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric acid triamide amines, etc.), amine compounds (triethylamine, 1-methylpyrrolidine, etc.), pyridine compounds (pyridine, picoline, etc.), quinoline compounds (quinoline, methylquinoline, etc.), and the like. These organic solvents may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining perfluoroalkyne compounds in a higher yield, amide compounds are preferred, and N,N-dimethylformamide, N,N-diethylformamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidinone, and hexamethylphosphoric trisamide are more preferred. N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric acid triamide, etc. are more preferred, and N-methyl-2-pyrrolidone is particularly preferred.

The usage amount of the organic solvent is not particularly limited as long as it is the amount of the solvent. From the viewpoint of the yield and selectivity of the perfluorocarbon compound represented by the general formula (1), it is preferably 0.01-20 moles, more preferably 0.1-10 moles relative to 1 mole of zinc or zinc alloy.

In addition, in the present invention, from the viewpoint of the yield and selectivity of the perfluorocarbon compound represented by the general formula (1), it is particularly preferable to use N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric triamide, etc. (especially N-methyl-2-pyrrolidone) as organic solvents, and to use iodine-containing inorganic materials.

In the production method of the present invention, the halogenated hydrocarbon compound represented by the general formula (2) is reacted in an organic solvent in the presence of an iodine-containing inorganic material and zinc or zinc alloy. The order of adding them is not particularly limited, and they can be added simultaneously or sequentially.

The reaction environment is not particularly limited, but in view of the yield and selectivity of the perfluorocarbon compound represented by the general formula (1), an inert gas environment (nitrogen environment, argon environment, etc.) is preferred. The reaction temperature is not particularly limited, but it is preferably 0-250°C, more preferably 20-200°C from the viewpoint of the yield and selectivity of the perfluorocarbon compound represented by the general formula (1). The reaction time (maintaining time of the highest temperature) can be set to the extent that the reaction can be fully carried out. From the viewpoint of the yield and selectivity of the perfluorocarbon compound represented by the general formula (1), it is preferably 0.5 to 20 hours, more preferably 1 to 10 hours. After the reaction is completed, it can be purified according to the needs and according to common methods to obtain the perfluorocarbon compound represented by the general formula (1).

The object compound of the present invention thus obtained is a perfluorocarbon compound represented by the general formula (1):

[In the formula, the bond shown by the double line and the dotted line is a double bond or a triple bond. When the bond shown by the double line and the dotted line is a double bond, the n series all represent 2, and when the bond shown by the double line and the dotted line is a triple bond, the n series all represent 1. R ¹ and R ² represent either a fluorine atom or a perfluoroalkyl group identically or differently. ].

R ¹ and R ² in the general formula (1) correspond to R ¹ and R ² in the above general formula (2). Therefore _{, the} perfluorocarbon compound represented by _the general _formula (1 _{) to} be _{produced is} , for example, CF≡CF _{, CF3C≡CCF3 , C2F5C≡CC2F5 , etc. 2} F ₅ ) _{2 etc.}

According to the production method of the present invention, the yield and selectivity of perfluorocarbons represented by the general formula (1) can be improved.

The perfluorocarbon compound represented by the general formula (1) thus obtained can be effectively used in various applications such as etching gas for forming the latest microstructure of semiconductors, liquid crystals, etc., cleaning gas, and building blocks for organic synthesis. The building blocks for organic synthesis will be described later.

2. The production method of the perfluoroalkyne compound The production method of the perfluoroalkyne compound in the second aspect of the present invention is the general formula (1A): [wherein, R ¹ and R ² are the same or different representations of a fluorine atom or a perfluoroalkyl group. ] the production method of the perfluoroalkyne compound, wherein, in zinc or zinc alloy In the presence of , make the general formula (2A): [wherein, R ¹ and R ² are the same as above. X ¹ and X ² represent halogen atoms identically or differently. ] the step of reacting the halogenated olefin compound represented by the aforementioned general formula (1A) to obtain the perfluoroalkyne compound represented by the aforementioned general formula (1A).

According to the present invention, the general formula (2A ) in the dehalogenation reaction of the halogenated alkene compound represented by the general formula (2A), ^X1 and ^X2 are dehalogenated from the halogenated alkene compound represented by the general formula (2A), and the perfluoroalkyne compound represented by the above general formula (1A) can be obtained.

As the halogenated olefin compound that can be used as a substrate in the production method of the present invention, those described for the halogenated olefin compound in the above "1. Production method of perfluorocarbon compounds" can be used. Preferred specific examples are also the same.

The production method in the second aspect of the present invention comprises at least one nitrogen-containing polar organic solvent selected from the group consisting of N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric acid triamide, amine compounds, pyridine compounds, and quinoline compounds, in the presence of zinc or a zinc alloy. The step of obtaining the perfluoroalkyne compound represented by the above general formula (1A) by reacting the halogenated olefin compound represented by the above general formula (2A).

At this time, the usage amount of the halogenated olefin compound represented by the general formula (2A) belonging to the substrate can be the same as that described for the usage amount of the halogenated hydrocarbon compound represented by the general formula (2) in the above "1. Production method of perfluorocarbon compounds". The preferred range is also the same.

In addition, zinc or a zinc alloy system can be used as described in the above "1. Production method of perfluorocarbon compounds". Preferred specific examples are also the same.

In addition, the reaction of the halogenated olefin compound represented by the general formula (2A) can also be carried out in the presence of an iodine-containing inorganic material. Thereby, the yield and selectivity of the perfluoroalkyne compound represented by general formula (1A) can be further improved. The iodine-containing materials that can be used are those described in the above "1. Production method of perfluorocarbon compounds". Preferred specific examples and contents are also the same.

At least one nitrogen-containing polar organic solvent selected from the group consisting of N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric triamide, amine compound, pyridine compound, and quinoline compound may be used alone or in combination of two or more. Among them, from the viewpoint of the yield and selectivity of perfluoroalkyne compounds, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric triamide, etc. are preferable, and N-methyl-2-pyrrolidone is more preferable.

The amount of at least one nitrogen-containing polar organic solvent selected from the group consisting of N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric acid triamide, amine compound, pyridine compound and quinoline compound is not particularly limited, so that perfluoroalkyne can be obtained in a higher yield From the viewpoint of the hydrocarbon compound, it is preferably 0.01 to 20 mol, more preferably 0.1 to 10 mol, relative to 1 mol of zinc or zinc alloy.

In addition, in the present invention, from the viewpoint of the yield and selectivity of perfluoroalkyne compounds, it is particularly preferable to use N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethylphosphoric triamide, etc. (especially N-methyl-2-pyrrolidone) as organic solvents, and to use iodine-containing inorganic materials.

In the production method of the present invention, the halogenated olefin compound represented by the general formula (2A) is reacted in an organic solvent, in the presence of zinc or zinc alloy, and if necessary, an iodine-containing inorganic material. The order of adding them is not particularly limited, and they can be added simultaneously or sequentially.

The reaction environment is not particularly limited, but an inert gas environment (nitrogen environment, argon environment, etc.) is preferred from the viewpoint of obtaining perfluoroalkyne compounds in a higher yield. The reaction temperature is not particularly limited, but it is preferably 0-250°C, more preferably 20-200°C from the viewpoint of the yield and selectivity of the perfluoroalkyne compound. The reaction time (holding time at the highest attained temperature) can be set to such an extent that the reaction can proceed sufficiently, and is preferably 0.5 to 20 hours, more preferably 1 to 10 hours from the viewpoint of the yield and selectivity of the perfluoroalkyne compound. After the reaction is finished, the perfluoroalkyne compound represented by the general formula (1A) can be obtained by refining according to the need and according to common methods.

The target compound of the present invention obtained in this way is the one described as the perfluoroalkyne compound in the above "1. Production method of perfluorocarbon compound (Part 1)".

According to the production method of the present invention, the yield and selectivity of the perfluoroalkyne compound represented by the general formula (1A) can be improved.

The obtained perfluoroalkyne compound represented by the general formula (1A) can be effectively used in various applications such as etching gas for forming the latest microstructure of semiconductors, liquid crystals, etc., cleaning gas, and building blocks for organic synthesis. The building blocks for organic synthesis will be described later.

3. Perfluoroalkyne composition According to the first aspect or the second aspect above, the perfluoroalkyne compound can be obtained, but it may also be obtained as a composition containing the perfluoroalkyne compound represented by the general formula (1A). For example, there are also perfluoroalkyne compounds represented by general formula (1A), and general formula (3): [wherein, R ¹ and R ² are the same as above. ] In the case of the composition (perfluoroalkyne composition) of the indicated compound.

This composition also contains the general formula (4): [In the formula, ^R3 and ^R4 represent a fluoroalkyl group with one hydrogen atom. ] The compound represented by the general formula (5): [In the formula, R ¹ , R ² and X ¹ are the same as above. ] is the case of the indicated compound.

In the general formulas (1A), (3) and (5), the perfluoroalkyl group represented by R ¹ and R ² means an alkyl group in which all hydrogen atoms are substituted with fluorine atoms. Such a perfluoroalkyl group is preferably, for example, a perfluoroalkyl group having 1 to 20 carbons, preferably 1 to 12 carbons, more preferably 1 to 6 carbons, still more preferably 1 to 4 carbons, particularly preferably 1 to 3 carbons. The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group. As such a perfluoroalkyl group, for example, trifluoromethyl (CF ₃ -), pentafluoroethyl (C ₂ F ₅ -) and the like are preferable.

In the general formula (4), the fluoroalkyl group having one hydrogen atom represented by ^R3 and ^R4 refers to a fluoroalkyl group in which one fluorine atom is replaced by a hydrogen atom among the above-mentioned perfluoroalkyl groups in which all hydrogen atoms are substituted by fluorine atoms. Such a fluoroalkyl group is preferably, for example, a fluoroalkyl group having 1 to 20 carbons, preferably 1 to 12 carbons, more preferably 1 to 6 carbons, still more preferably 1 to 4 carbons, particularly preferably 1 to 3 carbons and one hydrogen atom. These fluoroalkyl groups are preferably straight-chain or branched-chain fluoroalkyl groups. As such a fluoroalkyl group, for example, difluoromethyl (CF ₂ H-), tetrafluoroethyl (CF ₃ CFH-, CF ₂ HCF ₂ -) and the like are preferable.

In the general formula (5), examples of the halogen atom represented by ^X1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. However, it is preferable to use a substrate that does not contain iodine from the viewpoint of easily obtaining the perfluoroalkyne compound represented by the above-mentioned general formula (1A) by the production method of the present invention. From such a viewpoint, the halogen atom represented by ^X1 is preferably a fluorine atom, a chlorine atom, or a bromine atom.

In the perfluoroalkyne composition of the present invention, the total amount of the perfluoroalkyne composition of the present invention is determined as 100 mol%, the content of the perfluoroalkyne compound represented by the general formula (1A) is preferably 85-99.9 mol% (especially 90-99.8 mol%), the content of the compound represented by the general formula (3) is preferably 0.3-15 mol% (especially 0.5-8 mol%), and the compound represented by the general formula (4) The content is preferably 0.20-2.00 mol% (especially 1.10-1.80 mol%), and the content of the compound represented by general formula (5) is preferably 0.2-3.0 mol% (especially 0.25-2.5 mol%).

In addition, according to the production method of the present invention, even in the case of obtaining a perfluoroalkyne composition, the perfluoroalkyne compound represented by the general formula (1A) can be obtained with high yield as described above, so since components other than the perfluoroalkyne compound represented by the general formula (1A) in the perfluoroalkyne composition can be reduced, the labor for purification for obtaining the perfluoroalkyne compound represented by the general formula (1A) can be reduced.

As such, the perfluoroalkyne composition of the present invention can be effectively used in various applications such as building blocks for organic synthesis, cleaning gases, etc., in addition to etching gases used to form the latest microstructures of semiconductors and liquid crystals. In addition, the term "building block for organic synthesis" means a substance that can be a precursor of a compound having a highly reactive skeleton. For example, if the perfluoroalkyne composition of the present invention is reacted with a fluorine-containing organosilicon compound such as CF ₃ Si(CH ₃ ) ₃ , it can be converted into a substance that introduces a fluoroalkyl group such as a CF ₃ group and can be used as a cleaning agent or a fluorine-containing pharmaceutical intermediate.

As mentioned above, although embodiment of this invention was described, various changes in form and detail can be made without deviating from the gist and range of a claim. [Example]

Examples are shown below to clarify the characteristics of the present invention. The present invention is not limited by these examples.

In the production methods of the halogenated alkyne compounds of Examples 1-6 and Comparative Examples 1-3, the raw material compound is the halogenated olefin compound represented by the general formula (2A), ^R1 and ^R2 are trifluoromethyl, ^X1 and ^X2 are chlorine atoms, and according to the following reaction formula: , by dechlorination reaction to obtain perfluoroalkyne compounds.

In the production method of the halogenated olefin compound of Example 7 and Comparative Example 4, the raw material compound is a halogenated alkane compound represented by the general formula (2B), ^R1 and ^R2 are trifluoromethyl, ^X1 and ^X2 are chlorine atoms, and according to the following reaction formula: , by dechlorination reaction to obtain perfluoroalkene compounds.

Example 1 (alkyne synthesis): DMF; I ₂ 1 mole % In an eggplant-shaped flask with a capacitor connected to a water filter valve cooled to -78°C, add 10 g (0.04 mol) of CF ₃ CCl=CClCF ₃ (substrate), 45 g (0.62 mol) of N,N-dimethylformamide (solvent), 3.65 g (0.056 mol) of zinc, 0.1 4g (0.0006 mol; 1 mol% relative to zinc) of I ₂ was heated to 50°C under stirring. After becoming a fixed internal temperature, it was made to react for 5 hours, stirring. After the reaction, analyze the gas phase, liquid phase and reaction liquid of the captured steel cylinder by gas chromatography, and calculate the conversion and selectivity respectively. The conversion rate is 88.73 mol%, and the selectivity of each component is 89.70 mol% for CF ₃ C≡CCF ₃ (yield 79.6 mol _% ), 9.27 mol % for 1336mzz (CF ₃ CH=CHCF ₃ ), 9.27 mol % for CF HC≡CCF ₂ H is 0.26 mol%, CF ₃ CF=CHCF ₃ is 0.00 mol%, CF ₃ CCl=CHCF ₃ is 0.57 mol%, and other by-products are 0.19 mol% in total.

Example 2 (alkyne synthesis): NMP; I ₂ 1 mol % The reaction was carried out in the same manner as in Example 1, except that N-methyl-2-pyrrolidone was used as a solvent instead of N,N-dimethylformamide. After the reaction, the gas phase _, liquid _{phase and reaction liquid of the captured steel cylinder were analyzed by gas chromatography, and the conversion rate and selectivity were calculated respectively. The conversion rate was 99.1 mol%. H is 1.58 mol%, CF 3 CF =} CHCF _{3 is 0.00 mol%, CF 3 CCl} =CHCF ₃ is 0.31 mol%, and other _by -products are 2.18 mol% _in total.

Example 3 (Alkyne Synthesis): NMP; ZnI ₁ mol% Except that N,N-dimethylformamide is used instead of N-methyl-2-pyrrolidone as a solvent, and ZnI is used as an iodine-containing inorganic material instead of I ₂ , _the reaction is carried out in the same manner as in Example 1. After the reaction, the gas phase, liquid phase and reaction liquid of the trap cylinder were analyzed by gas chromatography, and the conversion rate and selectivity were calculated respectively. The conversion rate was 99.2 mol%, and the selectivity of each component was 91.10 mol% for CF ₃ C≡CCF ₃ (yield _{90.4 mol %), 0.92 mol% for 1336mzz (CF 3 CH=CHCF 3 ), and 0.92 mol % for CF 2 HC≡CCF 2 H is 1.33 mol%, CF 3 CF=CHCF 3 is 1.10 mol%, CF 3 CCl = CHCF 3 is 1.31 mol} %, and other by-products are 4.24 mol% in total.

Example 4 (Alkyne Synthesis): NMP; NaI 1 mol% Except that N,N-dimethylformamide is used instead of N-methyl-2-pyrrolidone as a solvent, and NaI is used as an iodine-containing inorganic material instead of _I2 , the reaction is carried out in the same manner as in Example 1. After the reaction, the gas phase _, liquid phase and reaction liquid of the _captured cylinder were analyzed by gas chromatography, and the conversion rate and selectivity were calculated respectively. The conversion rate was 98.4 mol%. H is 1.19 mol%, CF ₃ CF=CHCF _{3 is 0.41 mol%, CF 3 CCl} =CHCF ₃ is 0.31 mol% _, and other _by -products are 4.46 mol _% in total.

Example 5 (alkyne synthesis): NMP; no iodine-containing inorganic material except that N,N-dimethylformamide is used instead of N-methyl-2-pyrrolidone as a solvent, and _I2 is not used, and the reaction is carried out in the same manner as in Example 1. After the reaction was finished, the gas phase _, liquid phase and reaction _liquid of the trapping steel cylinder were analyzed by gas chromatography, and the conversion rate _and selectivity were calculated respectively. The conversion rate was 99.6 mol%. 2.2 mol%, CF ₃ CF=CHCF ₃ is 1.1 mol%, CF _{3 CCl} =CHCF _{3 is} 2.1 mol% _, and other by-products are 43.4 mol%.

Example 6 (Alkyne Synthesis): NMP; ICL 1 mol %, except that N,N-dimethylformamide was used instead of N-methyl-2-pyrrolidone as a solvent, and _I2 was used instead of I2. Iodine monochloride (ICL) was used as an iodine-containing inorganic material, and the reaction was carried out in the same manner as in Example 1. After the reaction, the gas phase, liquid phase and reaction liquid of the captured steel cylinder were analyzed by gas chromatography, and the conversion rate _and selectivity were calculated respectively. The conversion rate was 99.5 mol%, and the selectivity of each component was 93.11 mol% for CF ₃ C≡CCF ₃ (yield 92.6 mol %), 3.20 mol% for 1336mzz (CF ₃ CH=CHCF ₃ ), 3.20 mol % for CF ₂ HC≡CCF ₂ H is 0.22 mol%, CF 3 CF=CHCF ₃ is 0.22 mol%, CF ₃ CCl=CHCF ₃ is 0.11 mol%, and other by-products are 2.51 mol% in total.

Comparative Example 1 (alkyne synthesis): DMF; no iodine-containing inorganic material was reacted in the same manner as in Example 1 except that _I2 was not used. After the reaction, the gas phase _, liquid _phase and reaction liquid of the trap cylinder were analyzed by gas _{chromatography} , _{and the conversion rate and selectivity were calculated respectively. The conversion rate was 98.06 mol%. 2 H is 1.03 mol%, CF 3 CF=CHCF 3 is 0.35 mol%, CF 3 CCl = CHCF 3 is} 0.47 mol%, and other by-products are 41.70 mol% in total.

Comparative Example 2 (Alkyne Synthesis): Xylene; I ₂ 1 mol % The same treatment as in Example 1 was performed except that xylene was used as a solvent instead of N,N-dimethylformamide. However, the reaction did not proceed at all, and CF ₃ C≡CCF ₃ could not be obtained.

Comparative example 3 (synthesis of alkynes): dibutyl ether; I ₂ 1 mol % The same treatment as in Example 1 was performed except that dibutyl ether was used as a solvent instead of N,N-dimethylformamide. However, the reaction did not proceed at all, and CF ₃ C≡CCF ₃ could not be obtained.

Example 7 (Olefin Synthesis): NMP; I ₂ 1 mole % In an eggplant-shaped flask with a capacitor connected to a water filter valve cooled to -78°C, add 10 g (0.037 mol) of CF ₃ CCLF-CCLFCF ₃ (substrate), 45 g (0.45 mol) of N-methyl-2-pyrrolidone (solvent), 2.90 g (0.044 mol) of zinc, 0 .11g (0.0004 mol; 1 mol% relative to zinc) of I ₂ , under stirring, heat the inner temperature to 60°C. After becoming a fixed internal temperature, it was made to react for 5 hours, stirring. After the reaction, analyze the gas phase, liquid phase and reaction solution of the captured steel cylinder with gas chromatography, consider and calculate _the conversion rate and selectivity respectively, the conversion rate is 98.3 mol%, the selectivity of each component is CF ₃ CF= _CFCF 94.3 mol % (yield 92.7 mol %), CF ₃ CFHCClFCF 1.9 mol %, CF ₃ CFHCFHCF 0.65 mol %, CF ₃ CH=CFCF _{3 is} 0.01 mol%, and the total of other by-products is 3.14 mol%.

Comparative Example 4 (Olefin Synthesis): NMP; no iodine-containing inorganic material was reacted in the same manner as in Example 6 except that _I2 was not used. After the reaction finishes, analyze the gas phase, liquid phase and reaction solution of the trapped steel cylinder with gas chromatography, consider and calculate the conversion rate and selectivity respectively, the conversion rate is 87.3 mol%, the selectivity of each component is CF ₃ CF=CFCF _52.4 mol % (yield 45.7 mol %), CF ₃ CFHCClFCF 5.3 mol %, CF ₃ CFHCFHCF ₃ is 3.1 mol %, CF ₃ CH=CFCF _{3 is} 0.1 mol%, and other by-products are 39.1 mol%.

Table 1 shows the results of Examples 1-6 and Comparative Examples 1-3, and Table 2 shows the results of Example 7 and Comparative Example 4.

Claims (8)

A kind of manufacture method of perfluorocarbon compound, it is general formula (1):

[wherein, the bond shown by double line and dotted line is a double bond or triple bond; when the bond shown by double line and dotted line is a double bond, n system all represents 2, and when the bond shown by double line and dotted line is a triple bond, n system all represents 1; R ¹ and R ² represent a fluorine atom or a perfluoroalkyl group identically or differently] The manufacturing method of the represented perfluorocarbon compound, wherein, possesses in organic solvent, in the presence of metal iodide, and zinc or zinc alloy, make general formula ( 2):

[wherein, the bonding shown in solid line and dotted line is a single bond or double bond; when the bonding shown in solid line and dotted line is a single bond, n means 2, and in the case of double bond shown in solid line and dotted line, n means 1; ^R1 and ^R2 are the same as above; ^X1 and ^X2 represent a halogen atom identically or differently] the reaction of the halogenated hydrocarbon compound represented, obtains the step of the perfluorocarbon compound represented by the aforementioned general formula (1). The production method described in claim 1, wherein the amount of the metal iodide used is 0.0005 mole or more relative to 1 mole of the zinc or zinc alloy. A method for producing a perfluoroalkyne compound, which is the general formula (1A): R¹C≡CR² (1A) [wherein, R¹and R²A method for producing a perfluoroalkyne compound represented by the same or different representations of a fluorine atom or a perfluoroalkyl], wherein, in the presence of zinc or a zinc alloy, in the presence of zinc or a zinc alloy in at least one nitrogen-containing polar organic solvent Formula (2A): X¹R¹C=CR²x² (2A) [where, R¹and R²The system is the same as above; X¹and X²Represent the same or different halogen atom]; the step of reacting the represented halogenated olefin compound to obtain the perfluoroalkyne compound represented by the aforementioned general formula (1A). The production method described in any one of Claims 1 to 3, wherein the reaction temperature is 0 to 250°C. A perfluoroalkyne compound containing a general formula (1A): R ¹ C≡CR ² (1A) [wherein, R ^{1 and R 2 represent fluorine atoms or perfluoroalkyl groups identically or differently], and a compound of the general formula (3): R 1 CH=CHR 2 (3) [wherein, R 1 and R 2 are the same as} the above] Composition, wherein, the total amount of the aforementioned composition is determined as 100 mol%, and the aforementioned general formula (1 The content of the perfluoroalkyne compound represented by A) is 85-99.9 mol%, and the content of the compound represented by the aforementioned general formula (3) is 3.82 mol% or less. The composition described in Claim 5 further contains a compound represented by the general formula (4): R ³ C≡CR ⁴ (4) [wherein, R ³ and R ⁴ represent a fluoroalkyl group having one hydrogen atom]. The composition as described in Claim 5 or 6 further contains a compound represented by general formula (5): X ¹ R ¹ C=CHR ² (5) [wherein, R ¹ and R ² are the same as above; X ¹ represents a halogen atom]. The composition as described in claim 5 or 6 is used as a cleaning gas, an etching gas, or a building block for organic synthesis.