阅读说明：本技术 全氟炔烃化合物的制造方法 (Process for producing perfluoroalkine compound ) 是由 江藤友亮 中村新吾 于 2020-04-02 设计创作，主要内容包括：通过(1)在有机溶剂中,在含碘无机材料、以及锌或锌合金的存在下,使下述通式(2)[实线和虚线所示的键为单键或双键。在实线和虚线所示的键为单键的情况下,n均表示2,在实线和虚线所示的键为双键的情况下,n均表示1。R～(1)和R～(2)相同或不同,表示氟原子或全氟烷基。X～(1)和X～(2)相同或不同,表示卤原子。]所示的卤代烃化合物反应,或(2)在特定的含氮极性有机溶剂中,在锌或锌合金的存在下,使X～(1)R～(1)C＝CR～(2)X～(2)[式中,R～(1)、R～(2)、X～(1)和X～(22)的含义与上述相同。]所示的卤代烯烃化合物反应,能够高产率地获得具有双键或三键的全氟碳化合物。(The method comprises (1) making a bond represented by the following general formula (2) [ solid line and dotted line ] a single bond or a double bond in an organic solvent in the presence of an iodine-containing inorganic material and zinc or a zinc alloy. When the bonds shown by the solid lines and the broken lines are single bonds, n represents 2, and when the bonds shown by the solid lines and the broken lines are double bonds, n represents 1. R 1 And R 2 The same or different, represent a fluorine atom or a perfluoroalkyl group. X 1 And X 2 The same or different, represent a halogen atom.]Reacting a halogenated hydrocarbon compound shown in the formula, or (2) reacting X in a specific nitrogen-containing polar organic solvent in the presence of zinc or a zinc alloy 1 R 1 C＝CR 2 X 2 [ in the formula, R 1 、R 2 、X 1 And X 22 The meaning of (a) is the same as above.]The halogenated olefin compound shown is reacted to obtain a perfluorocarbon compound having a double bond or a triple bond in high yield.)

1. A process for producing a perfluorocarbon compound represented by the following general formula (1),

wherein the bonds shown by the double and dotted lines are double or triple bonds, n represents 2 in the case where the bonds shown by the double and dotted lines are double bonds, n represents 1 in the case where the bonds shown by the double and dotted lines are triple bonds, and R¹And R²Identical or different, represent a fluorine atom or a perfluoroalkyl group,

the manufacturing method comprises the following steps:

reacting a halogenated hydrocarbon compound represented by general formula (2) in an organic solvent in the presence of an iodine-containing inorganic material and zinc or a zinc alloy to obtain a perfluorocarbon compound represented by general formula (1),

wherein the bonds shown by the solid and dotted lines are single bonds or double bonds, n represents 2 in the case where the bonds shown by the solid and dotted lines are single bonds, n represents 1 in the case where the bonds shown by the solid and dotted lines are double bonds, and R is¹And R²Has the same meaning as described above, X¹And X²The same or different, represent a halogen atom.

2. The manufacturing method according to claim 1, characterized in that:

the amount of the iodine-containing inorganic material used is 0.0005 mol or more based on 1mol of the zinc or zinc alloy.

3. The manufacturing method according to claim 1 or 2, characterized in that:

the iodine-containing inorganic material is at least one selected from iodine, a metal iodide and an iodine-containing interhalogen compound.

4. A process for producing a perfluoroalkyne compound represented by the following general formula (1A),

R¹C≡CR² (1A)

in the formula, R¹And R²Identical or different, represent a fluorine atom or a perfluoroalkyl group,

the manufacturing method comprises the following steps:

reacting a halogenated olefin compound represented by the general formula (2A) in the presence of zinc or a zinc alloy in at least one nitrogen-containing polar organic solvent selected from the group consisting of N, N-dimethylacetamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, an amine compound, a pyridine compound and a quinoline compound to obtain a perfluoroalkyne compound represented by the general formula (1A),

X¹R¹C＝CR²X² (2A)

in the formula, R¹And R²Has the same meaning as described above, X¹And X²The same or different, represent a halogen atom.

5. The manufacturing method according to any one of claims 1 to 4, characterized in that:

the reaction temperature is 0-250 ℃.

6. A composition comprising a perfluoroalkyne compound represented by the general formula (1A) and a compound represented by the general formula (3),

R¹C≡CR² (1A)

in the formula, R¹And R²Identical or different, represent a fluorine atom or a perfluoroalkyl group,

R¹CH＝CHR² (3)

in the formula, R¹And R²The meaning of (a) is the same as above.

7. The composition of claim 6, wherein:

the total amount of the composition is 100 mol%, and the content of the perfluoroalkyne compound represented by the general formula (1A) is 85 to 99.9 mol%.

8. The composition according to claim 6 or 7, characterized in that:

is used as a cleaning gas, an etching gas or a block for organic synthesis.

Technical Field

The present invention relates to a method for producing a perfluoroalkine compound.

Background

The perfluoroalkyne compound is a compound which is useful as a cleaning gas, a block for organic synthesis, or the like, in addition to a dry etching gas for semiconductors, and has 1 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 the perfluoroalkyne compound, a method is known in which 1,1,1,4,4, 4-hexafluoro-2-butyne is obtained by performing a dechlorination reaction from 2, 3-dichloro-1, 1,1,4,4, 4-hexafluoro-2-butene (1316mxx) in the presence of zinc using N, N-dimethylformamide, N-diethylformamide, 1, 3-dimethyl-2-imidazolidinone, or the like as a solvent (for example, see patent document 1).

Documents of the prior art

Patent document

Patent document 1: chinese patent application publication No. 106008147 specification

Disclosure of Invention

Technical problem to be solved by the invention

The object of the present invention is to provide a process for obtaining perfluorocarbon compounds having double bonds or triple bonds in high yield.

Technical solution for solving technical problem

The present invention includes the following configurations.

Item 1. A process for producing a perfluorocarbon compound represented by the following general formula (1),

[ in the formula, the bonds shown by the double and dotted lines are double or triple bonds. In the case where the bonds shown by the double lines and the dotted lines are double bonds, n represents 2, and in the case where the bonds shown by the double lines and the dotted lines are triple bonds, n represents 1. R¹And R²The same or different, represent a fluorine atom or a perfluoroalkyl group.]，

The manufacturing method comprises the following steps:

reacting a compound represented by the general formula (2):

[ in the formula, the bonds shown by the solid lines and the broken lines are single bonds or double bonds. When the bonds shown by the solid lines and the broken lines are single bonds, n represents 2, and when the bonds shown by the solid lines and the broken lines are double bonds, n represents 1. R¹And R²The meaning of (a) is the same as above. X¹And X²The same or different, represent a halogen atom.]The halogenated hydrocarbon compound is reacted to obtain a perfluorocarbon compound represented by the general formula (1).

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

The method according to item 1 or 2, wherein the iodine-containing inorganic material is at least 1 selected from iodine, a metal iodide and an iodine-containing interhalogen compound.

Item 4. A process for producing a perfluoroalkyne compound represented by the following general formula (1A),

R¹C≡CR² (1A)

[ in the formula, R¹And R²The same or different, represent a fluorine atom or a perfluoroalkyl group.]，

The manufacturing method comprises the following steps:

reacting at least 1 nitrogen-containing polar organic solvent selected from the group consisting of N, N-dimethylacetamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, an amine compound, a pyridine compound and a quinoline compound in the presence of zinc or a zinc alloy, a compound represented by the general formula (2A):

X¹R¹C＝CR²X² (2A)

[ in the formula, R¹And R²The meaning of (a) is the same as above. X¹And X²The same or different, represent a halogen atom.]The halogenated olefin compound shown above is reacted to obtain a perfluoroalkyne compound represented by the above general formula (1A).

The process according to any one of the above 1 to 4, wherein the reaction temperature is 0 to 250 ℃.

A composition comprising:

general formula (1A):

R¹C≡CR² (1A)

[ in the formula, R¹And R²The same or different, represent a fluorine atom or a perfluoroalkyl group.]A perfluoroalkyne compound shown, and

general formula (3):

R¹CH＝CHR² (3)

[ in the formula, R¹And R²The meaning of (a) is the same as above.]The compounds shown.

The composition according to item 6, wherein the content of the perfluoroalkyne compound represented by the general formula (1A) is 85 to 99.9 mol% based on 100 mol% of the total amount of the composition.

The composition according to item 6 or 7, wherein the composition is used as a cleaning gas, an etching gas or a block for organic synthesis.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a perfluorocarbon compound having a double bond or a triple bond can be obtained in high yield.

Detailed Description

In the present specification, "including" is a concept including any one of "including (contains)", "consisting essentially of only … … (consistency addressing of)", and "consisting of only … … (consistency of)". In the present specification, the numerical range represented by "a to B" means a range from a to B.

In the present invention, the "selectivity" refers to the ratio (mol%) of the total molar amount of the target compound contained in the effluent gas from the reactor outlet to the total molar amount of the compounds other than the raw material compound in the effluent gas.

In the present invention, the "conversion" refers to the ratio (mol%) of the total molar amount of compounds other than the raw material compound contained in the effluent gas from the reactor outlet to the molar amount of the raw material compound supplied to the reactor.

Conventionally, according to the method of patent document 1,1,1,4,4, 4-hexafluoro-2-butyne was obtained by dechlorinating from 2, 3-dichloro-1, 1,1,4,4, 4-hexafluoro-2-butene (1316mxx) in the presence of zinc using N, N-dimethylformamide, N-diethylformamide, 1, 3-dimethyl-2-imidazolidinone, or the like as a solvent, but the yield thereof was only 62% at the maximum.

As described above, according to the conventional method, the yield is not sufficient. According to the production method of the present invention, a perfluoroalkyne compound can be synthesized with a higher yield than in the conventional method. Further, the perfluoroolefin compound can be synthesized in a high yield by the same method.

1. Process for producing perfluorocarbon compound

A process for producing a perfluoroalkyne compound according to a first aspect of the present invention is a process for producing a perfluorocarbon compound represented by the following general formula (1),

[ in the formula,the bonds shown by the double and dashed lines are double or triple bonds. In the case where the bonds shown by the double lines and the dotted lines are double bonds, n represents 2, and in the case where the bonds shown by the double lines and the dotted lines are triple bonds, n represents 1. R¹And R²The same or different, represent a fluorine atom or a perfluoroalkyl group.]

The method comprises the following steps:

reacting a halogenated hydrocarbon compound represented by the general formula (2) in an organic solvent in the presence of an iodine-containing inorganic material and zinc or a zinc alloy to obtain a perfluorocarbon compound represented by the general formula (1),

[ in the formula, the bonds shown by the solid lines and the broken lines are single bonds or double bonds. When the bonds shown by the solid lines and the broken lines are single bonds, n represents 2, and when the bonds shown by the solid lines and the broken lines are double bonds, n represents 1. R¹And R²The meaning of (a) is the same as above. X¹And X²The same or different, represent a halogen atom.]。

That is, the manufacturing method of the present invention includes the following two methods:

a process for producing a perfluoroalkyne compound represented by the general formula (1A) using a perfluoroolefin compound represented by the general formula (2A) as a substrate,

X¹R¹C＝CR²X² (2A)

[ in the formula, R¹、R²、X¹And X²The meaning of (a) is the same as above.]

R¹C≡CR² (1A)

[ in the formula, R¹And R²The meaning of (a) is the same as above.]；

A method for obtaining a perfluoroalkene compound represented by the general formula (1B) using a perfluoroalkane compound represented by the general formula (2B) as a substrate,

(R¹)₂X¹C-C(R²)₂X² (2B)

[ in the formula, R¹、R²、X¹And X²The meaning of (a) is the same as above.]

(R¹)₂C＝C(R²)₂ (1B)

[ in the formula, R¹And R²The meaning of (a) is the same as above.]。

According to the present invention, X is obtained by carrying out a dehalogenation reaction of a halogenated hydrocarbon compound represented by the above general formula (2) in an organic solvent in the presence of an inorganic material containing iodine and zinc or a zinc alloy¹And X²The perfluorocarbon compound represented by the above general formula (1) can be obtained by separating the perfluorocarbon compound represented by the general formula (2) from the halogenated hydrocarbon compound.

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

[ in the formula, the bonds shown by the solid lines and the broken lines are single bonds or double bonds. When the bonds shown by the solid lines and the broken lines are single bonds, n represents 2, and when the bonds shown by the solid lines and the broken lines are double bonds, n represents 1. R¹And R²The same or different, represent a fluorine atom or a perfluoroalkyl group. X¹And X²The same or different, represent a halogen atom.]。

In the general formula (2), R¹And R²The perfluoroalkyl group shown means an alkyl group in which all hydrogen atoms are substituted with fluorine atoms. Such perfluoroalkyl groups are preferably perfluoroalkyl groups of, for example, 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group. Such a perfluoroalkyl group is preferably a trifluoromethyl group (CF), for example₃-) pentafluoroethyl (C)₂F₅-) and the like.

In the general formula (2), as X¹And X²Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, from the viewpoint of easily obtaining the perfluorocarbon compound represented by the above general formula (1) by the production method of the present invention, it is preferable to use a substrate containing no iodine. From such a viewpoint, X is¹And X²The halogen atom shown is preferably a fluorine atom, a chlorine atom or a bromine atom. Among these, X is particularly preferable from the viewpoint of facilitating the production of the perfluorocarbon compound represented by the above general formula (1) by the production method of the present invention¹And X²Both of which are not fluorine atoms. That is, X is preferable¹And X²At least one of them is a chlorine atom or a bromine atom.

The halogenated hydrocarbon compound as the substrate is particularly preferably R from the viewpoint of being capable of producing a perfluorocarbon compound with high conversion, yield and selectivity¹And R²Are each trifluoromethyl, particularly preferably X¹And X²Are all chlorine atoms.

R is as defined above¹And R²May be the same or different. Furthermore, R¹May be the same as or different from each other. Furthermore, R²May be the same as or different from each other. Further, the above-mentioned X¹And X²May be the same or different.

Specific examples of the halogenated hydrocarbon compound serving as a substrate satisfying the above conditions include halogenated olefin compounds, such as CFCl ═ CFCl, CFBr ═ CFBr, CFCl ═ CFBr, and CF₃CCl＝CClCF₃、CF₃CCl＝CBrCF₃、CF₃CBr＝CBrCF₃、C₂F₅CCl＝CClC₂F₅、C₂F₅CCl＝CBrC₂F₅、C₂F₅CBr＝CBrC₂F₅Examples of the haloalkane compound include CF₂ClCF₂Cl、ClCF₂CF₂Br、CF₂BrCF₂Br、CF₃CClFCClFCF₃、CF₃CBrFCBrFCF₃、(CF₃)₂CClCCl(CF₃)₂、(CF₃)₂CClCBr(CF₃)₂、(CF₃)₂CBrCBr(CF₃)₂、(C₂F₅)₂CClCCl(C₂F₅)₂、(C₂F₅)₂CClCBr(C₂F₅)₂、(C₂F₅)₂CBrCBr(C₂F₅)₂And the like. These halogenated hydrocarbon compounds can be used alone, or 2 or more kinds can be used in combination. The halogenated hydrocarbon compound can be a known or commercially available product.

In the step of obtaining a perfluorocarbon compound from the halogenated hydrocarbon compound in the present invention, for example, R in the halogenated hydrocarbon compound represented by the general formula (2) is particularly preferable as a substrate¹And R²Are each fluorine atom or trifluoromethyl, particularly preferably X¹And X²Are all chlorine atoms.

Specifically, a dehalogenation reaction (in particular, a dechlorination reaction) according to the following reaction formula is preferable:

CF₃CCl＝CClCF₃→CF₃C≡CCF₃+Cl₂

CF₃CClFCClFCF₃→CF₃CF＝CFCF₃+Cl₂

the manufacturing method according to the first aspect of the present invention includes the steps of: a perfluorocarbon compound represented by the general formula (1) is obtained by reacting a halogenated hydrocarbon compound represented by the general formula (2) in an organic solvent in the presence of an iodine-containing inorganic material and zinc or a zinc alloy.

In this case, the amount of the halogenated hydrocarbon compound represented by the general formula (2) is preferably 0.05 to 30 mol, more preferably 0.1 to 10 mol, and still more preferably 0.2 to 5mol, based on 1mol of zinc or zinc alloy described later, from the viewpoint of the yield and selectivity of the perfluorocarbon compound.

In the present invention, the use of the iodine-containing inorganic material activates the surface of zinc or zinc alloy and promotes the reaction of the halogenated hydrocarbon compound represented by the general formula (2), thereby enabling the halogenated hydrocarbon compound represented by the general formula (2) to be obtained in high yield. The iodine-containing inorganic material to be used is not particularly limited as long as it is an inorganic material containing an iodine atom, and examples thereof include iodine; metal iodides such as typical metal iodides (sodium iodide, potassium iodide, magnesium iodide, calcium iodide, etc.), transition metal iodides (zinc iodide, etc.); and interhalogen compounds containing iodine (iodine fluoride, iodine chloride, iodine bromide, etc.), and the like. Further, according to the production method of the present invention, zinc halide (a mixture of zinc fluoride, zinc chloride, and zinc iodide) can be generated as an impurity in the product. The zinc halide contained in the product as an impurity can be used as an iodine-containing inorganic material and reused in the production method of the present invention. These iodine-containing inorganic materials can be used alone, or 2 or more kinds can be used in combination. 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 iodine-containing interhalogen compound and the like are preferable, iodine, a typical metal iodide, an iodine-containing interhalogen compound and the like are more preferable, and iodine is further preferable. Further, in the case of using a material containing no iodine, such as zinc fluoride or zinc chloride, instead of an inorganic material containing iodine as the halogen-containing material, the effect of improving the yield and selectivity of the perfluorocarbon compound represented by the general formula (1) cannot be obtained.

The amount of the iodine-containing inorganic material used is preferably 0.0005 mol or more, more preferably 0.001 mol or more, based on 1mol of zinc or a zinc alloy described later, from the viewpoint of the yield and selectivity of the perfluorocarbon compound represented by the general formula (1). The upper limit of the amount of the iodine-containing inorganic material is not particularly limited, but is usually preferably 2 moles or less, more preferably 0.1 mole or less, per 1 mole of zinc or zinc alloy described later, from the viewpoints of the yield, selectivity, cost, and the like of the perfluorocarbon compound represented by the general formula (1).

The amount of the iodine-containing inorganic material used is preferably 0.00002 mol or more, and more preferably 0.00005 mol or more, based on 1mol of the organic solvent described later, from the viewpoints of the yield, selectivity, cost, and the like of the perfluorocarbon compound represented by the general formula (1). The upper limit of the amount of the iodine-containing inorganic material is not particularly limited, but from the viewpoints of the yield, selectivity, cost, and the like of the perfluorocarbon compound represented by the general formula (1), the solubility of the organic solvent to be described later is generally preferably not more than 0.08 mol per 1mol of the organic solvent to be described later.

In zinc or a zinc alloy, examples of the element that can be contained when a zinc alloy is used include lead, cadmium, iron, and the like. Commercially available zinc may contain impurities such as lead, cadmium, and iron. Substances containing these impurities are also included in the present invention.

The organic solvent is preferably a polar organic solvent, particularly from the viewpoint of dissolving the halogenated hydrocarbon compound represented by the general formula (2) or the like. Further, 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 an organic solvent include amide compounds (e.g., N-dimethylformamide, N-diethylformamide, N-dimethylacetamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide), amine compounds (e.g., triethylamine and 1-methylpyrrolidine), pyridine compounds (e.g., pyridine and picoline), and quinoline compounds (e.g., quinoline and methylquinoline). These organic solvents can be used alone, or 2 or more kinds can be used in combination. Among them, from the viewpoint of obtaining the perfluoroalkyne compound in a higher yield, an amide compound is preferable, and N, N-dimethylformamide, N-diethylformamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone are more preferable, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide and the like, more preferably N, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide and the like, and particularly preferably N-methyl-2-pyrrolidone.

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

Further, 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 or the like (particularly N-methyl-2-pyrrolidone) as the organic solvent, and use an iodine-containing inorganic material.

In the production method of the present invention, a 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 a zinc alloy. The addition sequence is not particularly limited, and the addition can be carried out simultaneously or sequentially.

The reaction atmosphere is not particularly limited, and an inert gas atmosphere (nitrogen atmosphere, argon atmosphere, etc.) is preferable from the viewpoint of the yield and selectivity of the perfluorocarbon compound represented by the general formula (1). The reaction temperature is not particularly limited, but is preferably 0 to 250 ℃ and more preferably 20 to 200 ℃ from the viewpoint of the yield and selectivity of the perfluorocarbon compound represented by the general formula (1). The reaction time (the time for maintaining the maximum temperature) can be set to a level sufficient for the reaction to proceed, and is preferably 0.5 to 20 hours, more preferably 1 to 10 hours, from the viewpoint of the yield and selectivity of the perfluorocarbon compound represented by the general formula (1). After the completion of the reaction, the perfluorocarbon compound represented by the general formula (1) can be obtained by purification treatment according to a conventional method if necessary.

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

[ in the formula, the bonds shown by the double and dotted lines are double or triple bonds. In the case where the bonds shown by the double lines and the dotted lines are double bonds, n represents 2, and in the case where the bonds shown by the double lines and the dotted lines are triple bonds, n represents 1. R¹And R²The same or different, represent a fluorine atom or a perfluoroalkyl group.]。

R in the general formula (1)¹And R²And R in the above general formula (2)¹And R²And (7) corresponding. Thus, as the perfluorocarbon compound represented by the general formula (1) to be produced, for example, specific examples of the perfluoroalkyne compound include CF ≡ CF and CF₃C≡CCF₃、C₂F₅C≡CC₂F₅Examples of the perfluoroolefin compound include CF₂＝CF₂、C(CF₃)₂＝C(CF₃)₂、C(C₂F₅)₂＝C(C₂F₅)₂And the like.

According to the production method of the present invention, the yield and selectivity of the perfluorocarbon compound 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 gases, cleaning gases, and organic synthesis blocks for forming the most advanced fine structures of semiconductors, liquid crystals, and the like. The organic synthesis block will be described later.

2. Process for producing perfluoroalkine compound

The process for producing a perfluoroalkyne compound according to the second aspect of the present invention is a process for producing a perfluoroalkyne compound represented by the general formula (1A),

R¹C≡CR² (1A)

[ in the formula, R¹And R²The same or different, represent a fluorine atom or a perfluoroalkyl group.]，

The manufacturing method comprises the following steps:

a perfluoroalkyne compound represented by the general formula (1A) is obtained by reacting a halogenated olefin compound represented by the general formula (2A) in the presence of zinc or a zinc alloy in at least 1 nitrogen-containing polar organic solvent selected from the group consisting of N, N-dimethylacetamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, an amine compound, a pyridine compound and a quinoline compound,

X¹R¹C＝CR²X² (2A)

[ in the formula, R¹And R²The meaning of (a) is the same as above. X¹And X²The same or different, represent a halogen atom.]。

According to the present invention, a dehalogenation reaction of a halogenated olefin compound represented by the above general formula (2A) is carried out in the presence of zinc or a zinc alloy in at least 1 nitrogen-containing polar organic solvent selected from the group consisting of N, N-dimethylacetamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, an amine compound, a pyridine compound and a quinoline compound, X¹And X²The perfluoroalkyne compound represented by the above general formula (1A) can be obtained by separating the halogenated olefin compound represented by the general formula (2A).

As the halogenated olefin compound which can be used as a substrate in the production method of the present invention, the compounds described as the halogenated olefin compounds in the above "1. method for producing a perfluorocarbon compound" can be used. The same applies to preferred embodiments.

The manufacturing method according to the second aspect of the present invention includes the steps of: the perfluoroalkyne compound represented by the general formula (1A) is obtained by reacting a halogenated olefin compound represented by the general formula (2A) with at least 1 nitrogen-containing polar organic solvent selected from the group consisting of N, N-dimethylacetamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, amine compounds, pyridine compounds and quinoline compounds in the presence of zinc or a zinc alloy.

In this case, the amount of the halogenated olefin compound represented by the general formula (2A) used as the substrate can be the amount explained as the amount of the halogenated hydrocarbon compound represented by the general formula (2) used in the above-mentioned "1. method for producing a perfluorocarbon compound". The preferred ranges are also the same.

The zinc or zinc alloy used in the above "method for producing 1. perfluorocarbon compound" can be the same as that used in the above description. The same applies to preferred embodiments.

Further, 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. This can further improve the yield and selectivity of the perfluoroalkyne compound represented by the general formula (1A). The iodine-containing material that can be used can be the material described in the above "1. method for producing perfluorocarbon compound". Preferred specific examples and contents are also the same.

At least 1 nitrogen-containing polar organic solvent selected from the group consisting of N, N-dimethylacetamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, amine compounds, pyridine compounds and quinoline compounds can be used alone or in combination of 2 or more. Among them, from the viewpoint of the yield and selectivity of the perfluoroalkyne compound, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, and the like are preferable, and N-methyl-2-pyrrolidone is more preferable.

The amount of the at least 1 nitrogen-containing polar organic solvent selected from the group consisting of N, N-dimethylacetamide, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, amine compounds, pyridine compounds, and quinoline compounds is not particularly limited as long as it is a solvent amount, and is preferably 0.01 to 20 moles, more preferably 0.1 to 10 moles, based on 1 mole of zinc or zinc alloy from the viewpoint of obtaining a perfluoroalkyne compound in higher yield.

Further, in the present invention, from the viewpoint of the yield and selectivity of the perfluoroalkyne compound, it is particularly preferable to use N, N-diisopropylformamide, N-methyl-2-pyrrolidone, 1, 3-dimethyl-3, 4,5, 6-tetrahydropyrimidinone, hexamethylphosphoric triamide, or the like (particularly N-methyl-2-pyrrolidone), as the organic solvent, and use an iodine-containing inorganic material.

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

The reaction atmosphere is not particularly limited, and an inert gas atmosphere (nitrogen atmosphere, argon atmosphere, or the like) is preferable from the viewpoint of obtaining the perfluoroalkyne compound in a higher yield. The reaction temperature is not particularly limited, and is preferably 0 to 250 ℃ and more preferably 20 to 200 ℃ from the viewpoint of the yield and selectivity of the perfluoroalkyne compound. The reaction time (the time for maintaining the maximum temperature) can be set to a level sufficient for the reaction to proceed, 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, the perfluoroalkyne compound represented by the general formula (1A) can be obtained by purification treatment according to a conventional method as needed.

The target compound of the present invention thus obtained is a compound described as a perfluoroalkyne compound in the above "method for producing 1. perfluorocarbon compound (1 thereof)".

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 perfluoroalkyne compound represented by the general formula (1A) thus obtained can be effectively used in various applications such as etching gases, cleaning gases, and organic synthesis blocks for forming the most advanced fine structures of semiconductors, liquid crystals, and the like. The organic synthesis block will be described later.

3. Perfluoroalkyne composition

According to the first or second aspect described above, the perfluoroalkyne compound can be obtained, but is sometimes obtained in the form of a composition containing the perfluoroalkyne compound represented by the general formula (1A). For example, a composition (perfluoroalkyne composition) containing a perfluoroalkyne compound represented by the general formula (1A) and a compound represented by the general formula (3) may be obtained,

R¹CH＝CHR² (3)

[ in the formula, R¹And R²The meaning of (a) is the same as above.]

The composition may contain a compound represented by the general formula (4) and a compound represented by the general formula (5),

R³C≡CR⁴ (4)

[ in the formula, R³And R⁴Represents a fluoroalkyl group having 1 hydrogen atom.]

X¹R¹C＝CHR² (5)

[ in the formula, R¹、R²And X¹The meaning of (a) is the same as above.]

In the general formulae (1A), (3) and (5), R¹And R²The perfluoroalkyl group shown means an alkyl group in which all hydrogen atoms are substituted with fluorine atoms. Such perfluoroalkyl groups are preferably perfluoroalkyl groups of, for example, 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group. Such a perfluoroalkyl group is preferably a trifluoromethyl group (CF), for example₃-) pentafluoroethyl (C)₂F₅-) and the like.

In the general formula (4), R³And R⁴The fluoroalkyl group having 1 hydrogen atom shown is a fluoroalkyl group in which 1 fluorine atom is substituted with a hydrogen atom in the above perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms. Such fluoroalkyl groups are preferably fluoroalkyl groups having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms and having 1 hydrogen atom. These fluoroalkyl groups are preferably linear or branched fluoroalkyl groups. Such fluoroalkyl group is preferably difluoromethyl (CF), for example₂H-), tetrafluoroethyl (CF)₃CFH-、CF₂HCF₂-) and the like.

In the general formula (5), as X¹Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, from the viewpoint of easily obtaining the perfluoroalkyne compound represented by the above general formula (1A) by the production method of the present invention, it is preferable to use a substrate containing no iodine. From such a viewpoint, X is¹The halogen atom 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 100 mol%, the content of the perfluoroalkyne compound represented by the general formula (1A) is preferably 85 to 99.9 mol% (particularly 90 to 99.8 mol%), the content of the compound represented by the general formula (3) is preferably 0.3 to 15 mol% (particularly 0.5 to 8 mol%), the content of the compound represented by the general formula (4) is preferably 0.20 to 2.00 mol% (particularly 1.10 to 1.80 mol%), and the content of the compound represented by the general formula (5) is preferably 0.2 to 3.0 mol% (particularly 0.25 to 2.5 mol%).

Further, according to the production method of the present invention, even when the compound is obtained as a perfluoroalkine composition, the perfluoroalkine compound represented by the general formula (1A) can be obtained with high yield as described above, and therefore, components other than the perfluoroalkine compound represented by the general formula (1A) in the perfluoroalkine composition can be reduced, and therefore, the labor for refining the compound represented by the general formula (1A) can be reduced.

The perfluoroalkyne composition of the present invention can be effectively used for various applications such as a block for organic synthesis and a cleaning gas, in addition to an etching gas for forming the most advanced fine structure of a semiconductor, a liquid crystal, or the like. The organic synthesis block is a substance that can be a precursor of a compound having a highly reactive skeleton. For example, if the perfluoroalkyne compositions of the present invention are reacted with CF₃Si(CH₃)₃When a fluorine-containing organosilicon compound is reacted, CF can be introduced₃Fluoroalkyl groups such as a fluoroalkyl group, and can be converted into a substance that can be used as a detergent or a fluorine-containing pharmaceutical intermediate.

While the embodiments of the present invention have been described above, various changes in form and details may be made therein without departing from the spirit and scope of the invention as claimed.

Examples

The following examples are presented to illustrate the features of the present invention. The present invention is not limited to these examples.

Preparation of halogenated alkyne Compounds in examples 1 to 6 and comparative examples 1 to 3In the production process, R is added to a halogenated olefin compound represented by the general formula (2A) as a starting compound¹And R²To trifluoromethyl, the reaction is carried out by reacting X with¹And X²Is a chlorine atom and is according to the following reaction formula:

CF₃CCl＝CClCF₃→CF₃C≡CCF₃+Cl₂

and (3) obtaining the perfluoroalkine compound through dechlorination.

In the processes for producing halogenated olefin compounds in example 7 and comparative example 4, R is added to a halogenated alkane compound represented by the general formula (2B) as a starting compound¹And R²To trifluoromethyl, the reaction is carried out by reacting X with¹And X²Is a chlorine atom and is according to the following reaction formula:

CF₃CClFCClFCF₃→CF₃CF＝CFCF₃+Cl₂

through dechlorination reaction, the perfluoroolefin compound is obtained.

₂Example 1 (alkyne synthesis): DMF; i1 mol%

10g (0.04mol) of CF was added to a flask of eggplant type with a condenser having a steam trap connected thereto and cooled to-78 DEG C₃CCl＝CClCF₃(substrate), 45g (0.62mol) of N, N-dimethylformamide (solvent), 3.65g (0.056mol) of zinc, 0.14g (0.0006 mol; 1 mol% relative to zinc) of I₂The internal temperature was heated to 50 ℃ with stirring. After the internal temperature was fixed, the reaction was carried out for 5 hours while stirring. After the reaction was completed, the gas phase, the liquid phase and the reaction solution in the trap cylinder were analyzed by gas chromatography, and the conversion rate and the selectivity were calculated in consideration of each of them, the conversion rate was 88.73 mol%, and the selectivity of each component was: CF (compact flash)₃C≡CCF₃89.70 mol% (yield 79.6 mol%), 1336mzz (CF)₃CH＝CHCF₃) 9.27 mol% and CF₂HC≡CCF₂H0.26 mol%, CF₃CF＝CHCF₃0.00 mol% and CF₃CCl＝CHCF₃0.57 mol%, and the other by-products amounted to 0.19 mol%.

₂Example 2 (alkyne synthesis): NMP; i1 mol%

The reaction was carried out in the same manner as in example 1 except that N, N-dimethylformamide was not used and N-methyl-2-pyrrolidone was used as a solvent. After the reaction was completed, the gas phase, the liquid phase and the reaction solution of the trap cylinder were analyzed by gas chromatography, and the conversion rate and the selectivity were calculated in consideration of each of the gas phase, the liquid phase and the reaction solution, respectively, with the conversion rate of 99.1 mol%, and the selectivity of each component: CF (compact flash)₃C≡CCF₃92.11 mol% (yield 91.3 mol%), 1336mzz (CF)₃CH＝CHCF₃) 3.82 mol% and CF₂HC≡CCF₂H was 1.58 mol%, CF₃CF＝CHCF₃0.00 mol% and CF₃CCl＝CHCF₃0.31 mol%, and the other by-products amounted to 2.18 mol%.

₂Example 3 (alkyne synthesis): NMP; ZnI 1 mol%

Except that instead of N, N-dimethylformamide, N-methyl-2-pyrrolidone was used as solvent and I was not used₂While using ZnI₂The reaction was carried out in the same manner as in example 1 except that the iodine-containing inorganic material was used. After the reaction was completed, the gas phase, the liquid phase and the reaction solution of the trap cylinder were analyzed by gas chromatography, and the conversion rate and the selectivity were calculated in consideration of each of the gas phase, the liquid phase and the reaction solution, respectively, with the conversion rate of 99.2 mol%, and the selectivity of each component: CF (compact flash)₃C≡CCF₃91.10 mol% (yield 90.4 mol%), 1336mzz (CF)₃CH＝CHCF₃) 0.92 mol% and CF₂HC≡CCF₂H was 1.33 mol%, CF₃CF＝CHCF₃1.10 mol% and CF₃CCl＝CHCF₃1.31 mol%, and the other by-products amounted to 4.24 mol%.

Example 4 (alkyne synthesis): NMP; NaI 1 mol%

Except that instead of N, N-dimethylformamide, N-methyl-2-pyrrolidone was used as solvent and I was not used₂The reaction was carried out in the same manner as in example 1 except that NaI was used as the iodine-containing inorganic material. After the reaction, the reaction mixture was analyzed by gas chromatographyGas phase, liquid phase and reaction liquid of the gas cylinder are collected, conversion rate and selectivity are respectively considered and calculated, the conversion rate is 98.4 mol%, and the selectivity of each component is as follows: CF (compact flash)₃C≡CCF₃92.51 mol% (yield 91.0 mol%), 1336mzz (CF)₃CH＝CHCF₃) 1.12 mol% and CF₂HC≡CCF₂H was 1.19 mol%, CF₃CF＝CHCF₃0.41 mol% and CF₃CCl＝CHCF₃0.31 mol%, and the other by-products amounted to 4.46 mol%.

Example 5 (alkyne synthesis): NMP; inorganic material containing no iodine

Except that N, N-dimethylformamide is not used and N-methyl-2-pyrrolidone is used as a solvent, and I is not used₂Except for this, the reaction was carried out in the same manner as in example 1. After the reaction was completed, the gas phase, the liquid phase and the reaction solution of the trap cylinder were analyzed by gas chromatography, and the conversion rate and the selectivity were calculated in consideration of each of the gas phase, the liquid phase and the reaction solution, respectively, with the conversion rate of 99.6 mol%, and the selectivity of each component: CF (compact flash)₃C≡CCF₃48.9 mol% (yield 48.7 mol%), 1336mzz (CF)₃CH＝CHCF₃) 2.2 mol%, CF₂HC≡CCF₂H2.2 mol%, CF₃CF＝CHCF₃1.1 mol%, CF₃CCl＝CHCF₃2.1 mol%, and the other by-products amounted to 43.4 mol%.

Example 6 (alkyne synthesis): NMP; ICL 1 mol%

Except that instead of N, N-dimethylformamide, N-methyl-2-pyrrolidone was used as solvent and I was not used₂The reaction was carried out in the same manner as in example 1 except that iodine monochloride (ICL) was used as the iodine-containing inorganic material. After the reaction was completed, the gas phase, the liquid phase and the reaction solution of the trap cylinder were analyzed by gas chromatography, and the conversion rate and the selectivity were calculated in consideration of each of the gas phase, the liquid phase and the reaction solution, respectively, with the conversion rate of 99.5 mol%, and the selectivity of each component: CF (compact flash)₃C≡CCF₃93.11 mol% (yield 92.6 mol%), 1336mzz (CF)₃CH＝CHCF₃) 3.20 mol% and CF₂HC≡CCF₂H is 022 mol%, CF₃CF＝CHCF₃0.22 mol% and CF₃CCl＝CHCF₃0.11 mol%, and the other by-products amounted to 2.51 mol%.

Comparative example 1 (alkyne synthesis): DMF; inorganic material containing no iodine

Except that I is not used₂Except for this, the reaction was carried out in the same manner as in example 1. After the reaction was completed, the gas phase, the liquid phase and the reaction solution of the trap cylinder were analyzed by gas chromatography, and the conversion rate and the selectivity were calculated in consideration of each other, the conversion rate was 98.06 mol%, and the selectivity of each component was: CF (compact flash)₃C≡CCF₃56.20 mol% (yield 55.1 mol%), 1336mzz (CF)₃CH＝CHCF₃) 0.24 mol% and CF₂HC≡CCF₂H1.03 mol%, CF₃CF＝CHCF₃0.35 mol% and CF₃CCl＝CHCF₃0.47 mol%, and the other by-products amounted to 41.70 mol%.

₂Comparative example 2 (alkyne synthesis): xylene; i1 mol%

The same treatment as in example 1 was carried out, except that N, N-dimethylformamide was not used and xylene was used as a solvent. However, the reaction did not proceed at all, and CF could not be obtained₃C≡CCF₃。

₂Comparative example 3 (alkyne synthesis): dibutyl ether; i1 mol%

The same procedure as in example 1 was repeated except that N, N-dimethylformamide was not used and dibutyl ether was used as a solvent. However, the reaction did not proceed at all, and CF could not be obtained₃C≡CCF₃。

₂Example 7 (olefin synthesis): NMP; i1 mol%

10g (0.037mol) of CF was added to a flask of eggplant type with condenser having a steam trap connected thereto and cooled to-78 deg.C₃CCLF-CCLFCF₃(substrate), 45g (0.45mol) of N-methyl-2-pyrrolidone (solvent), 2.90g (0.044mol) of zinc, 0.11g (0.0004 mol; based on zinc)1 mol%) of I₂The internal temperature was heated to 60 ℃ with stirring. After the internal temperature became constant, the reaction was carried out for 5 hours while stirring. After the reaction was completed, the gas phase, the liquid phase and the reaction solution of the trap cylinder were analyzed by gas chromatography, and the conversion rate and the selectivity were calculated in consideration of each of the gas phase, the liquid phase and the reaction solution, respectively, with the conversion rate of 98.3 mol% and the selectivity of each component: CF (compact flash)₃CF＝CFCF₃94.3 mol% (yield 92.7 mol%), CF₃CFHCClFCF₃1.9 mol% CF₃CFHCFHCF₃0.65 mol% and CF₃CH＝CFCF₃0.01 mol%, and the other by-products amounted to 3.14 mol%.

Comparative example 4 (olefin synthesis): NMP; inorganic material containing no iodine

Except that I is not used₂Except for this, the reaction was carried out in the same manner as in example 6. After the reaction was completed, the gas phase, the liquid phase and the reaction solution of the trap cylinder were analyzed by gas chromatography, and the conversion rate and the selectivity were calculated in consideration of each of them, the conversion rate was 87.3 mol%, and the selectivity of each component was: CF (compact flash)₃CF＝CFCF₃52.4 mol% (yield 45.7 mol%), CF₃CFHCClFCF₃5.3 mol% and CF₃CFHCFHCF₃3.1 mol%, CF₃CH＝CFCF₃0.1 mol%, and the other by-products amounted to 39.1 mol%.

The results of examples 1 to 6 and comparative examples 1 to 3 are shown in Table 1, and the results of example 7 and comparative example 4 are shown in Table 2.

TABLE 1

TABLE 2