TW202104142A - Method for producing perfluoroalkyne compound - Google Patents

Method for producing perfluoroalkyne compound Download PDF

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TW202104142A
TW202104142A TW109111459A TW109111459A TW202104142A TW 202104142 A TW202104142 A TW 202104142A TW 109111459 A TW109111459 A TW 109111459A TW 109111459 A TW109111459 A TW 109111459A TW 202104142 A TW202104142 A TW 202104142A
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江藤友亮
中村新吾
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日商大金工業股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/22—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon triple bonds
    • H—ELECTRICITY
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
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    • H01L21/3065—Plasma etching; Reactive-ion etching

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Abstract

According to the present invention, a perfluorocarbon compound having a double bond or a triple bond is able to be obtained with high yield by: (1) reacting a halogenated hydrocarbon compound represented by formula (2) (wherein the bond expressed by a solid line and a dotted line represents a single bond or a double bond; in cases where the bond expressed by a solid line and a dotted line is a single bond, each n represents 2, while in cases where the bond expressed by a solid line and a dotted line is a double bond, each n represents 1; R1 and R2 may be the same or different and each represents a fluorine atom or a perfluoroalkyl group; and X1 and X2 may be the same or different and each represents a halogen atom) in an organic solvent in the presence of an iodine-containing inorganic material and zinc or a zinc alloy; or (2) reacting a halogenated alkene compound represented by X1R1C=CR2X2 (wherein R1, R2, X1 and X2 are as defined above) in a specific nitrogen-containing polar organic solvent in the presence of zinc or a zinc alloy.

Description

全氟炔烴化合物之製造方法Manufacturing method of perfluoroalkynes

本發明係關於全氟炔烴化合物之製造方法。The present invention relates to a manufacturing method of perfluoroalkynes compounds.

全氟炔烴化合物係除了半導體用乾式蝕刻氣體以外，作為清洗氣體、有機合成用建構組元等亦有用的化合物，且碳－碳間具有1個三鍵。尤其，碳數為4個之1,1,1,4,4,4-六氟-2-丁炔係活用於各式各樣的用途中。Perfluoroalkynes are compounds that are useful as cleaning gases and building elements for organic synthesis in addition to dry etching gases for semiconductors, and have one triple bond between carbon and carbon. In particular, 1,1,1,4,4,4-hexafluoro-2-butyne with 4 carbon atoms can be used in various applications.

作為該全氟炔烴化合物之製造方法，已知有將N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、1,3-二甲基-2-咪唑啉酮等作為溶媒使用，並於鋅之存在下，藉由自2,3-二氯-1,1,1,4,4,4-六氟-2-丁烯(1316mxx)進行脫氯反應，獲得1,1,1,4,4,4-六氟-2-丁炔之方法(例如，參照專利文獻1)。 [先前技術文獻] [專利文獻]As a method for producing the perfluoroalkynes compound, N,N-dimethylformamide, N,N-diethylformamide, 1,3-dimethyl-2-imidazolinone are known Used as a solvent, 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 The method of 1,1,1,4,4,4-hexafluoro-2-butyne (for example, refer to Patent Document 1). [Prior Technical Literature] [Patent Literature]

[專利文獻1]中國專利申請公開第106008147號說明書[Patent Document 1] Specification of Chinese Patent Application Publication No. 106008147

[發明所欲解決之課題][The problem to be solved by the invention]

本發明之目的在於提供一種可高產率地獲得具有雙鍵或三鍵之全氟碳化合物之方法。 [用於解決課題之手段]The object of the present invention is to provide a method for obtaining perfluorocarbon compounds with double bonds or triple bonds in high yield. [Means used to solve the problem]

本發明係包含以下之構成。The present invention includes the following constitutions.

項1.一種製造方法，其係一般式(1)：Item 1. A manufacturing method, which is the general formula (1):

Figure 02_image001
[式中，雙線與虛線所示之鍵結為雙鍵或三鍵。雙線與虛線所示之鍵結為雙鍵之情況，n係皆表示2，雙線與虛線所示之鍵結為三鍵之情況，n係皆表示1。R1 及R2 係相同或相異地表示氟原子或全氟烷基。] 所表示之全氟碳化合物之製造方法，其中，具備 於有機溶媒中，在含碘無機材料，以及鋅或者鋅合金之存在下， 使一般式(2)：
Figure 02_image001
[In the formula, the bond shown by the double line and the dashed line is a double bond or a triple bond. In the case where the bond shown by the double line and the dashed line is a double bond, the n system all represents 2, and the bond shown by the double line and the dashed line is a triple bond, and the n system both represent 1. R 1 and R 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. ] The method for producing perfluorocarbon compounds represented by the formula (2) is provided in an organic solvent, in the presence of iodine-containing inorganic materials, and zinc or zinc alloys:

Figure 02_image003
[式中，實線與虛線所示之鍵結為單鍵或雙鍵。實線與虛線所示之鍵結為單鍵之情況，n係皆表示2，實線與虛線所示之鍵結為雙鍵之情況，n係皆表示1。R1 及R2 係與前述相同。X1 及X2 係相同或相異地表示鹵素原子。] 所表示之鹵化烴化合物反應，獲得前述一般式(1)所表示之全氟碳化合物之步驟。
Figure 02_image003
[In the formula, the bond shown by the solid line and the dashed line is a single bond or a double bond. In the case where the bond shown by the solid line and the broken line is a single bond, the n system both represent 2, and the bond shown by the solid line and the dashed line is a double bond, and the n system both represent 1. R 1 and R 2 are the same as described above. X 1 and X 2 represent the same or different halogen atoms. ] The step of reacting the halogenated hydrocarbon compound represented to obtain the perfluorocarbon compound represented by the aforementioned general formula (1).

項2.如項1所記載之製造方法，其中，前述含碘無機材料之使用量係相對於前述鋅或者鋅合金1莫耳，為0.0005莫耳以上。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 with respect to 1 mol of the zinc or zinc alloy.

項3.如項1或2所記載之製造方法，其中，前述含碘無機材料係由碘、金屬碘化物，及包含碘之鹵素間化合物所成之群所選出之至少1種。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 iodide, and an interhalogen compound containing iodine.

項4.一種製造方法，其係一般式(1A)：

Figure 02_image005
[式中，R1 及R2 係相同或相異地表示氟原子或全氟烷基。] 所表示之全氟炔烴化合物之製造方法，其中，具備 於由N,N-二甲基乙醯胺、N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1.3‐二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺、胺化合物、吡啶化合物及喹啉化合物所構成之群所選出之至少1種含氮之極性有機溶媒中，在鋅或者鋅合金之存在下， 使一般式(2A)：
Figure 02_image007
[式中，R1 及R2 係與前述相同。X1 及X2 係相同或相異地表示鹵素原子。] 所表示之鹵化烯烴化合物反應，獲得前述一般式(1A)所表示之全氟炔烴化合物之步驟。Item 4. A manufacturing method, which is a general formula (1A):
Figure 02_image005
[In the formula, R 1 and R 2 are the same or different from each other and represent a fluorine atom or a perfluoroalkyl group. ] The method for producing perfluoroalkynes compounds represented by N,N-dimethylacetamide, N,N-diisopropylmethamide, N-methyl-2-pyrrolidone, 1.3-Dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethyltriamide phosphate, amine compounds, pyridine compounds, and quinoline compounds are selected from at least one nitrogen-containing polarity In the organic solvent, in the presence of zinc or zinc alloy, the general formula (2A):
Figure 02_image007
[In the formula, R 1 and R 2 are the same as described above. X 1 and X 2 represent the same or different halogen atoms. ] The step of reacting the halogenated olefin compound to obtain the perfluoroalkyne compound represented by the general formula (1A).

項5.如項1～4中之任1項所記載之製造方法，其中，反應溫度為0～250℃。Item 5. The production method according to any one of Items 1 to 4, wherein the reaction temperature is 0 to 250°C.

項6.一種組成物，其係含有一般式(1A)：

Figure 02_image009
[式中，R1 及R2 係相同或相異地表示氟原子或全氟烷基。] 所表示之全氟炔烴化合物，及 一般式(3)：
Figure 02_image011
[式中，R1 及R2 係與前述相同。] 所表示之化合物。Item 6. A composition containing general formula (1A):
Figure 02_image009
[In the formula, R 1 and R 2 are the same or different from each other and represent a fluorine atom or a perfluoroalkyl group. ] Perfluoroalkynes compound represented by the general formula (3):
Figure 02_image011
[In the formula, R 1 and R 2 are the same as described above. ] The compound represented.

項7.如項6所記載之組成物，其中，將前述組成物之總量定為100莫耳%，前述一般式(1A)所表示之全氟炔烴化合物之含量為85～99.9莫耳%。Item 7. The composition as described in Item 6, wherein the total amount of the aforementioned composition is set to 100 mol%, and the content of the perfluoroalkynyl compound represented by the aforementioned general formula (1A) is 85 to 99.9 mol% %.

項8.如項6或7所記載之組成物，其係作為清洗氣體、蝕刻氣體或有機合成用建構組元使用。 [發明之效果]Item 8. The composition described in Item 6 or 7, which is used as a cleaning gas, an etching gas, or a building block for organic synthesis. [Effects of Invention]

依據本發明，可高產率地獲得具有雙鍵或三鍵之全氟碳化合物。According to the present invention, a perfluorocarbon compound having a double bond or a triple bond can be obtained in a high yield.

本說明書中，「含有」係包含「包含(comprise)」、「實質上僅由……所構成(consist essentially of)」及「僅由……所構成(consist of)」中的任一種概念。此外，本說明書中，將數值範圍以「A～B」表示之情況中，係意指A以上B以下。In this specification, "containing" includes any of the concepts of "comprise", "consist essentially of", and "consist of". In addition, in this specification, when the numerical range is represented by "A-B", it means A or more and B or less.

本發明中，所謂「選擇率」，係意指該流出氣體所包含之目的化合物之合計莫耳量相對於自反應器出口流出之流出氣體中之原料化合物以外之化合物之合計莫耳量之比例(莫耳%)。In the present invention, the "selectivity" refers to the ratio of the total molar amount of the target compound contained in the effluent gas to the total molar amount of the compound other than the raw material compound in the effluent gas flowing out from the reactor outlet (Mole%).

本發明中，所謂「轉化率」，係意指自反應器出口流出之流出氣體所包含之原料化合物以外之化合物之合計莫耳量相對於供給至反應器之原料化合物之莫耳量之比例(莫耳%)。In the present invention, the "conversion rate" means the ratio of the total molar amount of compounds other than the raw material compounds contained in the effluent gas flowing from the reactor outlet to the molar amount of the raw material compounds supplied to the reactor ( Mol%).

以往係依據專利文獻1之方法，將N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、1,3-二甲基-2-咪唑啉酮等作為溶媒使用，並於鋅之存在下，藉由自2,3-二氯-1,1,1,4,4,4-六氟-2-丁烯(1316mxx)進行脫氯反應，獲得1,1,1,4,4,4-六氟-2-丁炔，然而其產率最高僅為62%。In the past, according to the method of Patent Document 1, N,N-dimethylformamide, N,N-diethylformamide, 1,3-dimethyl-2-imidazolinone, etc. were used as solvents. And in the presence of zinc, 1,1,1 is obtained by dechlorination reaction from 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene (1316mxx) ,4,4,4-hexafluoro-2-butyne, but its highest yield is only 62%.

綜上所述，根據以往之方法之產率係稱不上充足。依據本發明之製造方法，與以往相比，可以高產率的方式合成全氟炔烴化合物。此外，藉由同樣之方法，亦可以高產率的方式合成全氟烯烴化合物。In summary, the yield rate according to the previous method is not sufficient. According to the manufacturing method of the present invention, perfluoroalkynes compounds can be synthesized in a high-yield manner compared with the past. In addition, by the same method, perfluoroolefin compounds can also be synthesized in a high-yield manner.

1.全氟碳化合物之製造方法 本發明之第1態樣之全氟炔烴化合物之製造方法，係一般式(1)：1. Manufacturing method of perfluorocarbon The manufacturing method of the perfluoroalkynes compound of the first aspect of the present invention is general formula (1):

Figure 02_image013
[式中，雙線與虛線所示之鍵結為雙鍵或三鍵。雙線與虛線所示之鍵結為雙鍵之情況，n係皆表示2，雙線與虛線所示之鍵結為三鍵之情況，n係皆表示1。R1 及R2 係相同或相異地表示氟原子或全氟烷基。] 所表示之全氟碳化合物之製造方法，其中，具備 於有機溶媒中，在含碘無機材料，以及鋅或者鋅合金之存在下， 使一般式(2)：
Figure 02_image013
[In the formula, the bond shown by the double line and the dashed line is a double bond or a triple bond. In the case where the bond shown by the double line and the dashed line is a double bond, the n system all represents 2, and the bond shown by the double line and the dashed line is a triple bond, and the n system both represent 1. R 1 and R 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. ] The method for producing perfluorocarbon compounds represented by the formula (2) is provided in an organic solvent, in the presence of iodine-containing inorganic materials, and zinc or zinc alloys:

Figure 02_image015
[式中，實線與虛線所示之鍵結為單鍵或雙鍵。實線與虛線所示之鍵結為單鍵之情況，n係皆表示2，實線與虛線所示之鍵結為雙鍵之情況，n係皆表示1。R1 及R2 係與前述相同。X1 及X2 係相同或相異地表示鹵素原子。] 所表示之鹵化烴化合物反應，獲得前述一般式(1)所表示之全氟碳化合物之步驟。
Figure 02_image015
[In the formula, the bond shown by the solid line and the dashed line is a single bond or a double bond. In the case where the bond shown by the solid line and the broken line is a single bond, the n system both represent 2, and the bond shown by the solid line and the dashed line is a double bond, and the n system both represent 1. R 1 and R 2 are the same as described above. X 1 and X 2 represent the same or different halogen atoms. ] The step of reacting the halogenated hydrocarbon compound represented to obtain the perfluorocarbon compound represented by the aforementioned general formula (1).

亦即，本發明之製造方法包含 將一般式(2A)：

Figure 02_image017
[式中，R1 、R2 、X1 及X2 係與前述相同。] 所表示之全氟烯烴化合物作為基質，獲得一般式(1A)：
Figure 02_image019
[式中，R1 及R2 係與前述相同。] 所表示之全氟炔烴化合物之方法，及 將一般式(2B)：
Figure 02_image021
[式中，R1 、R2 、X1 及X2 係與前述相同。] 所表示之全氟鏈烷化合物作為基質，獲得一般式(1B)：
Figure 02_image023
[式中，R1 及R2 係與前述相同。] 所表示之全氟烯烴化合物之方法之兩者。That is, the manufacturing method of the present invention includes general formula (2A):
Figure 02_image017
[In the formula, R 1 , R 2 , X 1 and X 2 are the same as described above. ] The represented perfluoroolefin compound is used as the matrix to obtain the general formula (1A):
Figure 02_image019
[In the formula, R 1 and R 2 are the same as described above. ] The method of perfluoroalkynes compounds represented, and the general formula (2B):
Figure 02_image021
[In the formula, R 1 , R 2 , X 1 and X 2 are the same as described above. ] The expressed perfluoroalkane compound is used as the matrix to obtain the general formula (1B):
Figure 02_image023
[In the formula, R 1 and R 2 are the same as described above. ] Two of the methods of perfluoroolefin compounds indicated.

依據本發明，藉由於有機溶媒中，在含碘無機材料，以及鋅或者鋅合金之存在下，進行上述一般式(2)所表示之鹵化烴化合物之脫鹵反應，X1 及X2 係由一般式(2)所表示之鹵化烴化合物脫離，而可獲得上述一般式(1)所表示之全氟碳化合物。According to the present invention, by carrying out the dehalogenation reaction of the halogenated hydrocarbon compound represented by the above general formula (2) in the presence of iodine-containing inorganic materials and zinc or zinc alloy in an organic solvent, X 1 and X 2 are determined by The halogenated hydrocarbon compound represented by the general formula (2) is removed, and the perfluorocarbon compound represented by the above general formula (1) can be obtained.

作為可於本發明之製造方法中使用之基質之鹵化烴化合物，係如同上述，為一般式(2)所表示之鹵化烴化合物：The halogenated hydrocarbon compound as a substrate that can be used in the production method of the present invention is the halogenated hydrocarbon compound represented by the general formula (2) as described above:

Figure 02_image025
[式中，實線與虛線所示之鍵結為單鍵或雙鍵。實線與虛線所示之鍵結為單鍵之情況，n係皆表示2，實線與虛線所示之鍵結為雙鍵之情況，n係皆表示1。R1 及R2 係相同或相異地表示氟原子或全氟烷基。X1 及X2 係相同或相異地表示鹵素原子。]。
Figure 02_image025
[In the formula, the bond shown by the solid line and the dashed line is a single bond or a double bond. In the case where the bond shown by the solid line and the broken line is a single bond, the n system both represent 2, and the bond shown by the solid line and the dotted line is a double bond, and the n system both represent 1. R 1 and R 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. X 1 and X 2 represent the same or different halogen atoms. ].

一般式(2)中，R1 及R2 所示之全氟烷基係意指所有的氫原子皆被取代為氟原子之烷基。這樣的全氟烷基係較佳為例如，碳數1～20，較佳為碳數1～12，更佳為碳數1～6，再更佳為碳數1～4，特佳為碳數1～3之全氟烷基。全氟烷基係較佳為直鏈狀或分枝鏈狀之全氟烷基。作為這樣的全氟烷基，例如，較佳為三氟甲基(CF3 -)、五氟乙基(C2 F5 -)等。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 carbon number of 1 to 20, preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, still more preferably a carbon number of 1 to 4, and particularly preferably a carbon number A perfluoroalkyl group of 1 to 3. 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 -), etc. are preferable.

一般式(2)中，作為X1 及X2 所示之鹵素原子，可舉出氟原子、氯原子、溴原子及碘原子。惟，由容易藉由本發明之製造方法獲得上述一般式(1)所表示之全氟碳化合物之觀點來看，較佳係使用不含碘之基質。由這樣的觀點來看，作為X1 及X2 所示之鹵素原子，較佳為氟原子、氯原子及溴原子。惟，由容易藉由本發明之製造方法獲得上述一般式(1)所表示之全氟碳化合物之觀點來看，特佳係X1 及X2 之雙方皆不為氟原子。亦即，較佳係X1 及X2 中之至少一方為氯原子或溴原子。In general formula (2), examples of the halogen atom represented by X 1 and X 2 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. However, from the viewpoint that the perfluorocarbon represented by the general formula (1) can be easily obtained by the production method of the present invention, it is preferable to use a matrix that does not contain iodine. From such a viewpoint, the halogen atom represented by X 1 and X 2 is preferably a fluorine atom, a chlorine atom, and a bromine atom. However, from the viewpoint of easily obtaining the perfluorocarbon represented by the above general formula (1) by the production method of the present invention, neither of the particularly preferred systems X 1 and X 2 are fluorine atoms. That is, it is preferable that at least one of X 1 and X 2 is a chlorine atom or a bromine atom.

作為基質之鹵化烴化合物，尤其在全氟碳化合物可以以高轉化率、產率及選擇率來製造之觀點中，特佳係R1 及R2 皆為三氟甲基，特佳係X1 及X2 皆為氯原子。As the halogenated hydrocarbon compound as the substrate, especially from the viewpoint that perfluorocarbons can be manufactured with high conversion rate, yield and selectivity, the particularly preferred R 1 and R 2 are trifluoromethyl, and the particularly preferred X 1 And X 2 are both chlorine atoms.

上述R1 及R2 係可各自相同，亦可相異。此外，R1 彼此係可相同亦可相異。此外，R2 彼此係可相同亦可相異。此外，上述X1 及X2 係可各自相同，亦可相異。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 aforementioned 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、CF3 CCl=CClCF3 、CF3 CCl=CBrCF3 、CF3 CBr=CBrCF3 、C2 F5 CCl=CClC2 F5 、C2 F5 CCl=CBrC2 F5 、C2 F5 CBr=CBrC2 F5 等，作為鹵化鏈烷化合物，可舉出CF2 ClCF2 Cl、ClCF2 CF2 Br、CF2 BrCF2 Br、CF3 CClFCClFCF3 、CF3 CBrFCBrFCF3 、(CF3 )2 CClCCl(CF3 )2 、(CF3 )2 CClCBr(CF3 )2 、(CF3 )2 CBrCBr(CF3 )2 、(C2 F5 )2 CClCCl(C2 F5 )2 、(C2 F5 )2 CClCBr(C2 F5 )2 、(C2 F5 )2 CBrCBr(C2 F5 )2 等。此等鹵化烴化合物係可單獨使用，亦可組合2種以上使用。這樣的鹵化烴化合物係可採用習知或市售品。As a halogenated hydrocarbon compound that satisfies the above conditions, specifically, as halogenated olefin compounds, 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, etc. As the halogenated alkane compound, 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 and so on. These halogenated hydrocarbon compounds may be used alone or in combination of two or more kinds. As such halogenated hydrocarbon compounds, conventional or commercially available products can be used.

由本發明中之鹵化烴化合物獲得全氟碳化合物之步驟中，例如，作為基質，特佳係一般式(2)所表示之鹵化烴化合物中R1 及R2 皆為氟原子或三氟甲基，特佳係 X1 及X2 皆為氯原子。In the step of obtaining a perfluorocarbon compound from the halogenated hydrocarbon compound of the present invention, for example, as a substrate, it is particularly preferred that the halogenated hydrocarbon compound represented by the general formula (2) in which R 1 and R 2 are both fluorine atoms or trifluoromethyl , Particularly preferred X 1 and X 2 are chlorine atoms.

具體而言，較佳係依據以下之反應式之脫鹵反應(尤其是脫氯反應)：

Figure 02_image027
。Specifically, the dehalogenation reaction (especially the dechlorination reaction) according to the following reaction formula is preferred:
Figure 02_image027
.

本發明之第1態樣之製造方法中，係具備於有機溶媒中，在含碘無機材料，以及鋅或者鋅合金之存在下，使上述一般式(2)所表示之鹵化烴化合物反應，獲得前述一般式(1)所表示之全氟碳化合物之步驟。The production method of the first aspect of the present invention is provided in an organic solvent, in the presence of an iodine-containing inorganic material, and zinc or zinc alloy, the halogenated hydrocarbon compound represented by the above general formula (2) is reacted to obtain The step of the perfluorocarbon compound represented by the aforementioned general formula (1).

此時，一般式(2)所表示之鹵化烴化合物之使用量，由全氟碳化合物之產率及選擇率之觀點來看，相對於後述之鋅或者鋅合金1莫耳，較佳為0.05～30莫耳，更佳為0.1～10莫耳，再更佳為0.2～5莫耳。At this time, the usage amount of the halogenated hydrocarbon compound represented by the general formula (2), from the viewpoint of the yield and selectivity of the perfluorocarbon compound, is preferably 0.05 relative to 1 mol of zinc or zinc alloy described later ~30 mol, more preferably 0.1-10 mol, still more preferably 0.2-5 mol.

本發明中，由於使用含碘無機材料，使鋅或者鋅合金之表面活性化，並促進一般式(2)所表示之鹵化烴化合物之反應，因而可高產率地獲得一般式(2)所表示之鹵化烴化合物。作為所使用之含碘無機材料，若為含有碘原子之無機材料則無特別限制，例如，可舉出碘；典型金屬碘化物(碘化鈉、碘化鉀、碘化鎂、碘化鈣等)、過渡金屬碘化物(碘化鋅等)等之金屬碘化物等；包含碘之鹵素間化合物(氟化碘、氯化碘、溴化碘等)等。此外，依據本發明之製造方法，可於生成物中生成作為雜質之鹵化鋅(氟化鋅、氯化鋅及碘化鋅之混合物)。將此生成物中所包含之雜質之鹵化鋅作為含碘無機材料使用，可再利用於本發明之製造方法中。此等含碘無機材料係可單獨使用，亦可組合2種以上使用。其中，由一般式(1)所表示之全氟碳化合物之產率及選擇率之觀點來看，較佳為碘、典型金屬碘化物、過渡金屬碘化物、包含碘之鹵素間化合物等，更佳為碘、典型金屬碘化物、包含碘之鹵素間化合物等，再更佳為碘。此外，使用如同氟化鋅或氯化鋅等之不含碘之材料取代含碘無機材料作為含鹵素材料之情況下，係無法獲得提高一般式(1)所表示之全氟碳化合物之產率及選擇率之效果。In the present invention, since the iodine-containing inorganic material is used to activate the surface of zinc or zinc alloy and promote the reaction of the halogenated hydrocarbon compound represented by the general formula (2), the general formula (2) can be obtained in a high yield The halogenated hydrocarbon compounds. The iodine-containing inorganic material used is not particularly limited if it is an inorganic material containing iodine atoms. For example, iodine; typical metal iodides (sodium iodide, potassium iodide, magnesium iodide, calcium iodide, etc.), Transition metal iodides (zinc iodide, etc.) and other metal iodides; iodine-containing inter-halogen compounds (iodine fluoride, iodine chloride, iodine bromide, etc.), etc. In addition, according to the manufacturing 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 manufacturing method of the present invention. These iodine-containing inorganic materials can be used alone or in combination of two or more kinds. Among them, from the viewpoint of the yield and selectivity of the perfluorocarbon represented by the general formula (1), iodine, typical metal iodides, transition metal iodides, interhalogen compounds containing iodine, etc. are preferred, and more Preferred is iodine, typical metal iodides, interhalogen compounds containing iodine, etc., and still more preferred is iodine. In addition, when iodine-free materials such as zinc fluoride or zinc chloride are used instead of iodine-containing inorganic materials as halogen-containing materials, it is impossible to improve the yield of the perfluorocarbon represented by the general formula (1) And the effect of selection rate.

此含碘無機材料之使用量，由一般式(1)所表示之全氟碳化合物之產率及選擇率之觀點來看，較佳係相對於後述之鋅或者鋅合金1莫耳，為0.0005莫耳以上，更佳係0.001莫耳以上。此外，針對含碘無機材料之使用量之上限值係無特別限制，然而由一般式(1)所表示之全氟碳化合物之產率及選擇率、成本等之觀點來看，通常較佳係相對於後述之鋅或者鋅合金1莫耳，為2莫耳以下，更佳為0.1莫耳以下。The use amount of the iodine-containing inorganic material, from the viewpoint of the yield and selectivity of the perfluorocarbon represented by the general formula (1), is preferably 0.0005 relative to 1 mol of zinc or zinc alloy described later More than mol, more preferably 0.001 mol or more. In addition, the upper limit of the use amount of iodine-containing inorganic materials is not particularly limited, but from the viewpoint of the yield, selectivity, and cost of the perfluorocarbon represented by the general formula (1), it is usually better It is 2 mol or less with respect to 1 mol of zinc or zinc alloy described later, more preferably 0.1 mol or less.

此外，含碘無機材料之使用量，由一般式(1)所表示之全氟碳化合物之產率及選擇率、成本等之觀點來看，較佳係相對於後述之有機溶媒1莫耳，為0.00002莫耳以上，更佳為0.00005莫耳以上。此外，針對含碘無機材料之使用量之上限值係無特別限制，然而由一般式(1)所表示之全氟碳化合物之產率及選擇率、成本等之觀點來看，通常較佳為後述之有機溶媒之溶解度以下，更佳係相對於後述之有機溶媒1莫耳，為0.08莫耳以下。In addition, the amount of iodine-containing inorganic material used, from the viewpoint of the yield and selectivity of the perfluorocarbon represented by the general formula (1), the cost, etc., is preferably relative to 1 mol of the organic solvent described later, It is 0.00002 mol or more, more preferably 0.00005 mol or more. In addition, the upper limit of the use amount of iodine-containing inorganic materials is not particularly limited, but from the viewpoint of the yield, selectivity, and cost of the perfluorocarbon represented by the general formula (1), it is usually better It is less than the solubility of the organic solvent mentioned later, and it is more preferable that it is 0.08 mol or less with respect to 1 mol of the organic solvent mentioned later.

作為鋅或者鋅合金中，使用鋅合金之情況中可包含之元素，可舉出例如，鉛、鎘、鐵等。此外，市售之鋅中，亦有包含鉛、鎘、鐵等之雜質之情況。本發明中亦包含含有此等之雜質者。Examples of elements that can be contained in zinc or zinc alloys when zinc alloys are used include lead, cadmium, and iron. In addition, commercially available zinc also contains impurities such as lead, cadmium, and iron. The present invention also includes those containing these impurities.

作為有機溶媒，尤其由使一般式(2)所表示之鹵化烴化合物等溶解之觀點來看，較佳為極性有機溶媒。此外，由一般式(1)所表示之全氟碳化合物之產率及選擇率之觀點來看，更佳為含氮之極性溶媒。作為這樣的有機溶媒，例如，可舉出醯胺化合物(N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二甲基乙醯胺、N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1,3-二甲基-2-咪唑啉酮、1.3‐二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺等)、胺化合物(三乙胺、1-甲基吡咯烷等)、吡啶化合物(吡啶、甲基吡啶等)、喹啉化合物(喹啉、甲基喹啉等)等。此等有機溶媒係可單獨使用，亦可組合2種以上使用。其中，由以更高產率的方式獲得全氟炔烴化合物之觀點來看，較佳為醯胺化合物，更佳為 N,N-二甲基甲醯胺、N,N-二乙基甲醯胺、N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1,3-二甲基-2-咪唑啉酮、1.3‐二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺等，再更佳為N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1.3‐二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺等，特佳為N-甲基-2-吡咯烷酮。As an organic solvent, a polar organic solvent is especially preferable from a viewpoint of dissolving the halogenated hydrocarbon compound etc. represented by general formula (2). In addition, from the viewpoint of the yield and selectivity of the perfluorocarbon represented by the general formula (1), a nitrogen-containing polar solvent is more preferable. As such an organic solvent, for example, amide compounds (N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N, N-diisopropylmethamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidine Ketones, hexamethyltriamide phosphate, etc.), amine compounds (triethylamine, 1-methylpyrrolidine, etc.), pyridine compounds (pyridine, picoline, etc.), quinoline compounds (quinoline, methylquinoline, etc.) and many more. These organic solvent systems may be used alone or in combination of two or more kinds. Among them, from the viewpoint of obtaining perfluoroalkynes compounds in a higher yield, amide compounds are preferred, and N,N-dimethylformamide and N,N-diethylformamide are more preferred. Amine, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1.3-dimethyl-3,4,5,6 -Tetrahydropyrimidinone, hexamethyltriamide phosphate, etc., more preferably N,N-diisopropylmethamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3,4, 5,6-Tetrahydropyrimidinone, hexamethyltriamide phosphate, etc., particularly preferably N-methyl-2-pyrrolidone.

有機溶媒之使用量若為溶媒量則無特別限制，由一般式(1)所表示之全氟碳化合物之產率及選擇率之觀點來看，較佳係相對於鋅或者鋅合金1莫耳，為0.01～20莫耳，更佳為0.1～10莫耳。The amount of organic solvent used is not particularly limited if it is the amount of solvent. From the viewpoint of the yield and selectivity of the perfluorocarbon represented by the general formula (1), it is preferably 1 mol relative to zinc or zinc alloy , Is 0.01-20 mol, more preferably 0.1-10 mol.

此外，本發明中，由一般式(1)所表示之全氟碳化合物之產率及選擇率之觀點來看，特佳係使用N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1.3‐二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺等(尤其是N-甲基-2-吡咯烷酮)作為有機溶媒，且使用含碘無機材料。In addition, in the present invention, from the viewpoint of the yield and selectivity of the perfluorocarbon represented by the general formula (1), it is particularly preferable to use N,N-diisopropylmethamide, N-methyl -2-pyrrolidone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethyltriamide phosphate, etc. (especially N-methyl-2-pyrrolidone) are used as organic solvents Iodine-containing inorganic materials.

本發明之製造方法中，係於有機溶媒中，在含碘無機材料，以及鋅或者鋅合金之存在下，使一般式(2)所表示之鹵化烴化合物反應。其添加順序係無特別限制，可同時投入，亦可依序投入。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 a zinc alloy. The order of addition is not particularly limited, and it can be added at the same time or sequentially.

反應環境係無特別限制，由一般式(1)所表示之全氟碳化合物之產率及選擇率之觀點來看，較佳係惰性氣體環境(氮氣環境、氬氣環境等)。反應溫度係無特別限制，由一般式(1)所表示之全氟碳化合物之產率及選擇率之觀點來看，較佳為0～250℃，更佳為20～200℃。反應時間(最高到達溫度之維持時間)係可設定為可使反應充分地進行之程度，由一般式(1)所表示之全氟碳化合物之產率及選擇率之觀點來看，較佳為0.5～20小時，更佳為1～10小時。反應結束後係可依需要並依據常見方法進行精製處理，獲得一般式(1)所表示之全氟碳化合物。The reaction environment is not particularly limited. From the viewpoint of the yield and selectivity of the perfluorocarbon represented by the general formula (1), an inert gas environment (nitrogen environment, argon environment, etc.) is preferred. The reaction temperature is not particularly limited. From the viewpoint of the yield and selectivity of the perfluorocarbon represented by the general formula (1), it is preferably 0 to 250°C, more preferably 20 to 200°C. The reaction time (maintenance time for the highest temperature) can be set to the extent that the reaction can proceed fully. From the viewpoint of the yield and selectivity of the perfluorocarbon 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, the refining treatment can be carried out according to common methods as needed to obtain the perfluorocarbon compound represented by general formula (1).

藉此所獲得之本發明之目的化合物係由一般式(1)所表示之全氟碳化合物：The target compound of the present invention thus obtained is a perfluorocarbon compound represented by general formula (1):

Figure 02_image029
[式中，雙線與虛線所示之鍵結為雙鍵或三鍵。雙線與虛線所示之鍵結為雙鍵之情況，n係皆表示2，雙線與虛線所示之鍵結為三鍵之情況，n係皆表示1。R1 及R2 係相同或相異地表示氟原子或全氟烷基。]。
Figure 02_image029
[In the formula, the bond shown by the double line and the dashed line is a double bond or a triple bond. In the case where the bond shown by the double line and the dashed line is a double bond, the n system all represents 2, and the bond shown by the double line and the dashed line is a triple bond, and the n system both represent 1. R 1 and R 2 are the same or different and represent a fluorine atom or a perfluoroalkyl group. ].

一般式(1)中之R1 及R2 係對應上述一般式(2)中之R1 及R2 。因此，所欲製造之一般式(1)所表示之全氟碳化合物，例如，具體而言，作為全氟炔烴化合物，可舉出CF≡CF、CF3 C≡CCF3 、C2 F5 C≡CC2 F5 等，作為全氟烯烴化合物，可舉出CF2 =CF2 、C(CF3 )2 =C(CF3 )2 、 C(C2 F5 )2 =C(C2 F5 )2 等。(1) In the general formula R 1 and R 2 lines corresponding to R (2) and R 1 in the above general formula 2. Therefore, the perfluorocarbon compound represented by the general formula (1) to be produced, for example, specifically, the perfluoroalkynes compound includes CF≡CF, CF 3 C≡CCF 3 , and C 2 F 5 C≡CC 2 F 5 and the like. Examples of perfluoroolefin compounds include CF 2 =CF 2 , C(CF 3 ) 2 =C(CF 3 ) 2 , C(C 2 F 5 ) 2 =C(C 2 F 5 ) 2 and so on.

依據本發明之製造方法，可提高一般式(1)所表示之全氟碳化合物之產率及選擇率。According to the manufacturing method of the present invention, the yield and selectivity of the perfluorocarbon compound represented by the general formula (1) can be improved.

藉此所獲得之一般式(1)所表示之全氟碳化合物係可有效地利用於用於形成半導體、液晶等之最新的微細構造之蝕刻氣體、清洗氣體、有機合成用建構組元等之各種用途中。針對有機合成用建構組元係於後續進行描述。The perfluorocarbon system represented by the general formula (1) obtained by this can be effectively used in the etching gas, cleaning gas, building elements for organic synthesis, etc. used to form the latest fine structures of semiconductors, liquid crystals, etc. In various uses. The building blocks for organic synthesis will be described later.

2.全氟炔烴化合物之製造方法 本發明之第2態樣中之全氟炔烴化合物之製造方法，係一般式(1A)：

Figure 02_image031
[式中，R1 及R2 係相同或相異地表示氟原子或全氟烷基。] 所表示之全氟炔烴化合物之製造方法，其中，具備 於由N,N-二甲基乙醯胺、N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1.3‐二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺、胺化合物、吡啶化合物及喹啉化合物所構成之群所選出之至少1種含氮之極性有機溶媒中，在鋅或者鋅合金之存在下， 使一般式(2A)：
Figure 02_image033
[式中，R1 及R2 係與前述相同。X1 及X2 係相同或相異地表示鹵素原子。] 所表示之鹵化烯烴化合物反應，獲得前述一般式(1A)所表示之全氟炔烴化合物之步驟。2. Manufacturing method of perfluoroalkynes compound The method for manufacturing perfluoroalkynes in the second aspect of the present invention is general formula (1A):
Figure 02_image031
[In the formula, R 1 and R 2 are the same or different from each other and represent a fluorine atom or a perfluoroalkyl group. ] The method for producing perfluoroalkynes compounds represented by N,N-dimethylacetamide, N,N-diisopropylmethamide, N-methyl-2-pyrrolidone, 1.3-Dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethyltriamide phosphate, amine compounds, pyridine compounds, and quinoline compounds are selected from at least one nitrogen-containing polarity In the organic solvent, in the presence of zinc or zinc alloy, the general formula (2A):
Figure 02_image033
[In the formula, R 1 and R 2 are the same as described above. X 1 and X 2 represent the same or different halogen atoms. ] The step of reacting the halogenated olefin compound to obtain the perfluoroalkyne compound represented by the general formula (1A).

依據本發明，藉由在由N,N-二甲基乙醯胺、N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1.3‐二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺、胺化合物、吡啶化合物及喹啉化合物所構成之群所選出之至少1種含氮之極性有機溶媒中，在鋅或者鋅合金之存在下，進行上述一般式(2A)所表示之鹵化烯烴化合物之脫鹵反應，X1 及X2 係由一般式(2A)所表示之鹵化烯烴化合物脫離，而可獲得上述一般式(1A)所表示之全氟炔烴化合物。According to the present invention, by combining N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3,4, At least one nitrogen-containing polar organic solvent selected from the group consisting of 5,6-tetrahydropyrimidinone, hexamethyltriamide phosphate, amine compounds, pyridine compounds and quinoline compounds, in zinc or zinc alloy In the presence, the dehalogenation reaction of the halogenated olefin compound represented by the above general formula (2A) is performed, and X 1 and X 2 are separated from the halogenated olefin compound represented by the general formula (2A) to obtain the above general formula (1A) The represented perfluoroalkynes compounds.

作為可於本發明之製造方法中使用之基質之鹵化烯烴化合物係可採用上述「1.全氟碳化合物之製造方法」中針對鹵化烯烴化合物所進行說明者。較佳之具體例亦相同。As the halogenated olefin compound that can be used as the substrate in the production method of the present invention, the halogenated olefin compound described in the above-mentioned "1. Production method of perfluorocarbon" can be used. The preferred specific examples are also the same.

本發明之第2態樣中之製造方法，具備於由N,N-二甲基乙醯胺、N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1.3‐二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺、胺化合物、吡啶化合物及喹啉化合物所構成之群所選出之至少1種含氮之極性有機溶媒中，在鋅或者鋅合金之存在下，使上述一般式(2A)所表示之鹵化烯烴化合物反應，獲得前述一般式(1A)所表示之全氟炔烴化合物之步驟。The production method in the second aspect of the present invention is provided with N,N-dimethylacetamide, N,N-diisopropylmethamide, N-methyl-2-pyrrolidone, 1.3-di At least one nitrogen-containing polar organic solvent selected from the group consisting of methyl-3,4,5,6-tetrahydropyrimidinone, hexamethyltriamide phosphate, amine compounds, pyridine compounds and quinoline compounds , In the presence of zinc or zinc alloy, the step of reacting the halogenated olefin compound represented by the above general formula (2A) to obtain the perfluoroalkyne compound represented by the above general formula (1A).

此時，屬於基質之一般式(2A)所表示之鹵化烯烴化合物之使用量係可採用上述「1.全氟碳化合物之製造方法」中針對一般式(2)所表示之鹵化烴化合物之使用量所進行說明者。較佳之範圍亦相同。At this time, the usage amount of the halogenated olefin compound represented by the general formula (2A) belonging to the substrate can be used for the halogenated hydrocarbon compound represented by the general formula (2) in the above "1. Manufacturing method of perfluorocarbon" The amount explained by the person. The preferred range is also the same.

此外，鋅或者鋅合金係可採用於上述「1.全氟碳化合物之製造方法」中所說明者。較佳之具體例亦相同。In addition, zinc or zinc alloy systems can be adopted as described in the above-mentioned "1. Manufacturing method of perfluorocarbon". The preferred specific examples are also the same.

此外，一般式(2A)所表示之鹵化烯烴化合物之反應亦可於含碘無機材料之存在下進行。藉此，可進一步提升一般式(1A)所表示之全氟炔烴化合物之產率及選擇率。可使用之含碘材料係可採用上述「1.全氟碳化合物之製造方法」中所說明者。較佳之具體例及含量亦相同。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 perfluoroalkynes compound represented by the general formula (1A) can be further improved. The usable iodine-containing materials can be those described in the above-mentioned "1. Manufacturing method of perfluorocarbon". The preferred specific examples and contents are also the same.

作為由N,N-二甲基乙醯胺、N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1.3‐二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺、胺化合物、吡啶化合物及喹啉化合物所構成之群所選出之至少1種含氮之極性有機溶媒，係可單獨使用，亦可組合2種以上使用。其中，由全氟炔烴化合物之產率及選擇率之觀點來看，較佳為N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1.3‐二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺等，更佳為N-甲基-2-吡咯烷酮。It is composed of N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3,4,5,6-tetrahydro At least one nitrogen-containing polar organic solvent selected from the group consisting of pyrimidinone, hexamethyltriamide phosphate, amine compounds, pyridine compounds, and quinoline compounds can be used alone or in combination of two or more. Among them, from the viewpoint of the yield and selectivity of the perfluoroalkynes compound, N,N-diisopropylcarbamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3 , 4,5,6-tetrahydropyrimidinone, hexamethyltriamide phosphate, etc., more preferably N-methyl-2-pyrrolidone.

由N,N-二甲基乙醯胺、N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1.3‐二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺、胺化合物、吡啶化合物及喹啉化合物所構成之群所選出之至少1種含氮之極性有機溶媒之使用量，若為溶媒量則無特別限制，由以更高產率的方式獲得全氟炔烴化合物之觀點來看，較佳係相對於鋅或者鋅合金1莫耳，為0.01～20莫耳，更佳為0.1～10莫耳。From N,N-dimethylacetamide, N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidine The use amount of at least one nitrogen-containing polar organic solvent selected from the group consisting of ketones, hexamethyltriamide phosphate, amine compounds, pyridine compounds, and quinoline compounds. From the viewpoint of obtaining the perfluoroalkyne compound in a higher yield, it is preferably 0.01-20 mol, more preferably 0.1-10 mol, relative to 1 mol of zinc or zinc alloy.

此外，本發明中，由全氟炔烴化合物之產率及選擇率之觀點來看，特佳係使用N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1.3‐二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺等(尤其是N-甲基-2-吡咯烷酮)作為有機溶媒，且使用含碘無機材料。In addition, in the present invention, from the viewpoint of the yield and selectivity of perfluoroalkynes compounds, it is particularly preferable to use N,N-diisopropylmethamide, N-methyl-2-pyrrolidone, 1.3- Dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethyltriamide phosphate, etc. (especially N-methyl-2-pyrrolidone) are used as organic solvents, and iodine-containing inorganic materials are used.

本發明之製造方法中，係於有機溶媒中，鋅或者鋅合金，以及依需要之含碘無機材料之存在下，使一般式(2A)所表示之鹵化烯烴化合物反應。其添加順序係無特別限制，可同時投入，亦可依序投入。In the production method of the present invention, the halogenated olefin compound represented by the general formula (2A) is reacted in the presence of an organic solvent, zinc or a zinc alloy, and optionally an iodine-containing inorganic material. The order of addition is not particularly limited, and can be added at the same time or sequentially.

反應環境係無特別限制，由以更高產率的方式獲得全氟炔烴化合物之觀點來看，較佳為惰性氣體環境(氮氣環境、氬氣環境等)。反應溫度係無特別限制，由全氟炔烴化合物之產率及選擇率之觀點來看，較佳為0～250℃，更佳為20～200℃。反應時間(最高到達溫度中之維持時間)係可設定為可使反應充分地進行之程度，由全氟炔烴化合物之產率及選擇率之觀點來看，較佳為0.5～20小時，更佳為1～10小時。反應結束後係可依需要並依據常見方法進行精製處理，獲得一般式(1A)所表示之全氟炔烴化合物。The reaction environment is not particularly limited. From the viewpoint of obtaining the perfluoroalkyne compound in a higher yield, an inert gas environment (nitrogen environment, argon environment, etc.) is preferred. The reaction temperature is not particularly limited. From the viewpoint of the yield and selectivity of the perfluoroalkyne compound, it is preferably 0 to 250°C, more preferably 20 to 200°C. The reaction time (maintenance time at the highest temperature) can be set to the extent that the reaction can proceed fully. From the viewpoint of the yield and selectivity of the perfluoroalkyne compound, it is preferably 0.5 to 20 hours, and more Preferably, it is 1 to 10 hours. After the reaction is completed, it can be refined according to needs and according to common methods to obtain the perfluoroalkynes compound represented by general formula (1A).

藉此所獲得之本發明之目的化合物為上述「1.全氟碳化合物之製造方法(其1)」中作為全氟炔烴化合物所說明者。The target compound of the present invention thus obtained is the one described as the perfluoroalkyne compound in the above-mentioned "1. Manufacturing method of perfluorocarbon (Part 1)".

依據本發明之製造方法，可提高一般式(1A)所表示之全氟炔烴化合物之產率及選擇率。According to the manufacturing method of the present invention, the yield and selectivity of the perfluoroalkynes compound represented by the general formula (1A) can be improved.

藉此所獲得之一般式(1A)所表示之全氟炔烴化合物係可有效地利用於用於形成半導體、液晶等之最新的微細構造之蝕刻氣體、清洗氣體、有機合成用建構組元等之各種用途中。針對有機合成用建構組元係於後續進行描述。The perfluoroalkynes compound represented by the general formula (1A) obtained by this can be effectively used in etching gas, cleaning gas, building elements for organic synthesis, etc., used to form the latest fine structures of semiconductors, liquid crystals, etc. For various purposes. The building blocks for organic synthesis will be described later.

3.全氟炔烴組成物 根據上述之第1態樣或第2態樣，可獲得全氟炔烴化合物，然而亦有以包含一般式(1A)所表示之全氟炔烴化合物之組成物的形式獲得之情況。例如，亦有獲得包含一般式(1A)所表示之全氟炔烴化合物，及一般式(3)：

Figure 02_image035
[式中，R1 及R2 係與前述相同。] 所表示之化合物之組成物(全氟炔烴組成物)之情況。3. Perfluoroalkynes composition According to the above-mentioned first aspect or second aspect, perfluoroalkynes compounds can be obtained, but there are also compositions containing perfluoroalkynes compounds represented by general formula (1A) The situation is obtained in the form of. For example, there are also perfluoroalkynes compounds represented by general formula (1A), and general formula (3):
Figure 02_image035
[In the formula, R 1 and R 2 are the same as described above. ] In the case of the composition (perfluoroalkynes composition) of the indicated compound.

此組成物亦有包含一般式(4)：

Figure 02_image037
[式中，R3 及R4 係表示具有1個氫原子之氟烷基。] 所表示之化合物、一般式(5)：
Figure 02_image039
[式中，R1 、R2 及X1 係與前述相同。] 所表示之化合物之情況。This composition also contains general formula (4):
Figure 02_image037
[In the formula, R 3 and R 4 represent a fluoroalkyl group having one hydrogen atom. ] The compound represented, general formula (5):
Figure 02_image039
[In the formula, R 1 , R 2 and X 1 are the same as described above. ] The situation of the compound represented.

一般式(1A)、(3)及(5)中，R1 及R2 所示之全氟烷基係意指所有的氫原子皆被取代為氟原子之烷基。這樣的全氟烷基係較佳為例如，碳數1～20，較佳為碳數1～12，更佳為碳數1～6，再更佳為碳數1～4，特佳為碳數1～3之全氟烷基。全氟烷基係較佳為直鏈狀或分枝鏈狀之全氟烷基。作為這樣的全氟烷基，例如，較佳為三氟甲基(CF3 -)、五氟乙基(C2 F5 -)等。In 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 carbon number of 1 to 20, preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, still more preferably a carbon number of 1 to 4, and particularly preferably a carbon number A perfluoroalkyl group of 1 to 3. 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 -), etc. are preferable.

一般式(4)中，R3 及R4 所示之具有1個氫原子之氟烷基係意指在所有的氫原子皆被氟原子取代之上述全氟烷基中，將1個氟原子取代為氫原子之氟烷基。這樣的氟烷基較佳係例如，為碳數1～20，較佳為碳數1～12，更佳為碳數1～6，再更佳為碳數1～4，特佳為碳數1～3之具有1個氫原子之氟烷基。此等氟烷基，較佳為直鏈狀或分枝鏈狀之氟烷基。作為這樣的氟烷基，例如，較佳為二氟甲基(CF2 H-)、四氟乙基(CF3 CFH-、CF2 HCF2 -)等。In general formula (4), the fluoroalkyl group with one hydrogen atom represented by R 3 and R 4 means that in the above-mentioned perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms, one fluorine atom Fluoroalkyl substituted with a hydrogen atom. Such a fluoroalkyl group is preferably, for example, a carbon number of 1 to 20, preferably a carbon number of 1 to 12, more preferably a carbon number of 1 to 6, still more preferably a carbon number of 1 to 4, and particularly preferably a carbon number 1-3 fluoroalkyl groups with 1 hydrogen atom. These fluoroalkyl groups are preferably linear or branched fluoroalkyl groups. As such a fluoroalkyl group, for example, difluoromethyl (CF 2 H-), tetrafluoroethyl (CF 3 CFH-, CF 2 HCF 2 -), etc. are preferred.

一般式(5)中，作為X1 所示之鹵素原子，可舉出氟原子、氯原子、溴原子及碘原子。惟，由容易藉由本發明之製造方法獲得上述一般式(1A)所表示之全氟炔烴化合物之觀點來看，較佳係使用不含碘之基質。由這樣的觀點來看，作為X1 所示之鹵素原子，較佳為氟原子、氯原子及溴原子。In general formula (5), examples of the halogen atom represented by X 1 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. However, from the viewpoint that the perfluoroalkynes compound represented by the above general formula (1A) can be easily obtained by the production method of the present invention, it is preferable to use an iodine-free substrate. From such a viewpoint, the halogen atom represented by X 1 is preferably a fluorine atom, a chlorine atom, and a bromine atom.

此本發明之全氟炔烴組成物中，將本發明之全氟炔烴組成物之總量定為100莫耳%，一般式(1A)所表示之全氟炔烴化合物之含量較佳為85～99.9莫耳%(尤其是90～99.8莫耳%)，一般式(3)所表示之化合物之含量較佳為0.3～15莫耳%(尤其是0.5～8莫耳%)，一般式(4)所表示之化合物之含量較佳為0.20～2.00莫耳%(尤其是1.10～1.80莫耳%)，一般式(5)所表示之化合物之含量較佳為0.2～3.0莫耳%(尤其是0.25～2.5莫耳%)。In the perfluoroalkynes composition of the present invention, the total amount of the perfluoroalkynes composition of the present invention is set to 100 mol%, and the content of the perfluoroalkynes 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 general formula (3) is preferably 0.3-15 mol% (especially 0.5-8 mol%), general formula The content of the compound represented by (4) is preferably 0.20 to 2.00 mol% (especially 1.10 to 1.80 mol%), and the content of the compound represented by general formula (5) is preferably 0.2 to 3.0 mol% ( Especially 0.25 ~ 2.5 mol%).

此外，依據本發明之製造方法，即使在獲得全氟炔烴組成物之情況中，亦可如同上述般高產率地獲得一般式(1A)所表示之全氟炔烴化合物，故由於可減少全氟炔烴組成物中之一般式(1A)所表示之全氟炔烴化合物以外之成分，故可減少用於獲得一般式(1A)所表示之全氟炔烴化合物之精製之勞力。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 in a high yield as described above, so that the total amount can be reduced. The components other than the perfluoroalkynes represented by the general formula (1A) in the fluoroalkynes composition can reduce the labor for refining the perfluoroalkynes represented by the general formula (1A).

如此之本發明之全氟炔烴組成物係除了用於形成半導體、液晶等之最新的微細構造之蝕刻氣體以外，亦可有效地利用於有機合成用建構組元、清洗氣體等之各種用途中。此外，所謂有機合成用建構組元，係意指可成為具有反應性高之骨架之化合物之前驅物之物質。例如，若使本發明之全氟炔烴組成物與CF3 Si(CH3 )3 等之含氟有機矽化合物反應，則可轉換為導入CF3 基等之氟烷基且可成為洗淨劑或含氟醫藥中間體之物質。In this way, the perfluoroalkynes composition of the present invention can be effectively used in various applications such as building elements for organic synthesis, cleaning gases, etc., in addition to the etching gas used to form the latest fine structures of semiconductors and liquid crystals. . In addition, the so-called building element for organic synthesis means a substance that can become a precursor of a compound with a highly reactive skeleton. For example, if the perfluoroalkynes composition of the present invention is reacted with fluorine-containing organosilicon compounds such as CF 3 Si(CH 3 ) 3 , it can be converted into fluoroalkyl groups such as CF 3 groups and can be used as a detergent Or fluorine-containing pharmaceutical intermediates.

以上，說明本發明之實施形態，然而在不脫離申請專利範圍之要旨及範圍之情況下，可以進行形態或細節上之各種變更。 [實施例]As mentioned above, the embodiments of the present invention have been described. However, various changes in form or details can be made without departing from the spirit and scope of the scope of the patent application. [Example]

以下示出實施例，使本發明之特徵更加明確。本發明並非受到此等實施例所限定者。Examples are shown below to clarify the characteristics of the present invention. The present invention is not limited by these embodiments.

實施例1～6及比較例1～3之鹵化炔烴化合物之製造方法中，原料化合物係一般式(2A)所表示之鹵化烯烴化合物中，R1 及R2 為三氟甲基、X1 及X2 為氯原子者，並依據以下之反應式：

Figure 02_image041
，藉由脫氯反應，獲得全氟炔烴化合物。In the production methods of halogenated alkyne compounds of Examples 1 to 6 and Comparative Examples 1 to 3, the raw material compound is a halogenated olefin compound represented by general formula (2A), and R 1 and R 2 are trifluoromethyl, X 1 And X 2 is a chlorine atom, and according to the following reaction formula:
Figure 02_image041
, Through the dechlorination reaction, perfluoroalkynes compounds are obtained.

實施例7及比較例4之鹵化烯烴化合物之製造方法中，原料化合物係一般式(2B)所表示之鹵化鏈烷化合物中，R1 及R2 為三氟甲基、X1 及X2 為氯原子者，並依據以下之反應式：

Figure 02_image043
，藉由脫氯反應，獲得全氟烯烴化合物。In the method for producing halogenated olefin compounds of Example 7 and Comparative Example 4, the raw material compound is a halogenated alkane compound represented by the general formula (2B), R 1 and R 2 are trifluoromethyl, and X 1 and X 2 are For chlorine atoms, according to the following reaction formula:
Figure 02_image043
, Through the dechlorination reaction, perfluoroolefin compounds are obtained.

實施例1(炔烴合成)：DMF；I2 1莫耳% 於冷卻至-78℃之連結有濾水閥之附電容器之茄型燒瓶中，添加10g(0.04 mol)之CF3 CCl=CClCF3 (基質)、45g (0.62 mol)之N,N-二甲基甲醯胺(溶媒)、3.65g(0.056 mol)之鋅、0.14g(0.0006 mol；相對於鋅為1 mol%)之I2 ，於攪拌下，將內溫加熱至50℃為止。成為固定的內溫後，一邊攪拌一邊使其反應5小時。反應結束後，以氣相色譜法分析捕集鋼瓶之氣相、液相及反應液，各自進行考慮並算出轉化率及選擇率，轉化率為88.73莫耳%，各成分之選擇率係CF3 C≡CCF3 為89.70莫耳%(產率79.6莫耳%)、1336mzz (CF3 CH=CHCF3 )為9.27莫耳%、CF2 HC≡CCF2 H為0.26莫耳%、CF3 CF=CHCF3 為0.00莫耳%、CF3 CCl=CHCF3 為0.57莫耳%，其他副產物合計為0.19莫耳%。Example 1 (alkyne synthesis): DMF; I 2 1 mol% In an eggplant-shaped flask with a capacitor attached to a filter valve and cooled to -78°C, add 10 g (0.04 mol) of CF 3 CCl=CClCF 3 (Substrate), 45g (0.62 mol) of N,N-dimethylformamide (solvent), 3.65g (0.056 mol) of zinc, 0.14g (0.0006 mol; 1 mol% relative to zinc) of I 2. Under stirring, heat the inner temperature to 50°C. After reaching a fixed internal temperature, it was allowed to react for 5 hours while stirring. After the reaction, the gas phase, liquid phase, and reaction liquid of the trapped cylinder were analyzed by gas chromatography, and the conversion rate and selectivity were calculated separately. The conversion rate was 88.73 mol%, and the selectivity of each component was CF 3 C≡CCF 3 is 89.70 mol% (yield 79.6 mol%), 1336mzz (CF 3 CH=CHCF 3 ) is 9.27 mol%, CF 2 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 the total of other by-products is 0.19 mol%.

實施例2(炔烴合成)：NMP；I2 1莫耳% 除了不使用N,N-二甲基甲醯胺而使用N-甲基-2-吡咯烷酮作為溶媒以外，使其與實施例1同樣地進行反應。反應結束後，以氣相色譜法分析捕集鋼瓶之氣相、液相及反應液，各自進行考慮並算出轉化率及選擇率，轉化率為99.1莫耳%，各成分之選擇率係CF3 C≡CCF3 為92.11莫耳% (產率91.3莫耳%)、1336mzz(CF3 CH=CHCF3 )為3.82莫耳%、CF2 HC≡CCF2 H為1.58莫耳%、CF3 CF=CHCF3 為0.00莫耳%、CF3 CCl=CHCF3 為0.31莫耳%，其他副產物合計為2.18莫耳%。Example 2 (alkyne synthesis): NMP; I 2 1 mol% Except that N,N-dimethylformamide is not used and N-methyl-2-pyrrolidone is used as a solvent, it is compared with Example 1 The reaction is carried out in the same way. After the reaction, the gas phase, liquid phase, and reaction liquid of the trapped cylinder were analyzed by gas chromatography, and the conversion rate and selectivity were calculated separately. The conversion rate was 99.1 mol%, and the selectivity of each component was CF 3 C≡CCF 3 is 92.11 mol% (yield 91.3 mol%), 1336mzz (CF 3 CH=CHCF 3 ) is 3.82 mol%, CF 2 HC≡CCF 2 H is 1.58 mol%, CF 3 CF= CHCF 3 is 0.00 mol%, CF 3 CCl=CHCF 3 is 0.31 mol%, and the total of other by-products is 2.18 mol%.

實施例3(炔烴合成)：NMP；ZnI2 1莫耳% 除了不使用N,N-二甲基甲醯胺而使用N-甲基-2-吡咯烷酮作為溶媒，不使用I2 而使用ZnI2 作為含碘無機材料以外，使其與實施例1同樣地進行反應。反應結束後，以氣相色譜法分析捕集鋼瓶之氣相、液相及反應液，各自進行考慮並算出轉化率及選擇率，轉化率為99.2莫耳%，各成分之選擇率係CF3 C≡CCF3 為91.10莫耳%(產率90.4莫耳%)、1336mzz(CF3 CH=CHCF3 )為0.92莫耳%、CF2 HC≡CCF2 H為1.33莫耳%、CF3 CF=CHCF3 為1.10莫耳%、CF3 CCl=CHCF3 為1.31莫耳%，其他副產物合計為4.24莫耳%。Example 3 (alkyne synthesis): NMP; ZnI 2 1 mol% Except that N,N-dimethylformamide is not used, N-methyl-2-pyrrolidone is used as a solvent, and I 2 is used instead of ZnI 2 Except for the iodine-containing inorganic material, 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 trapped cylinder were analyzed by gas chromatography, and the conversion rate and selectivity were calculated separately. The conversion rate was 99.2 mol%, and the selectivity of each component was CF 3 C≡CCF 3 is 91.10 mol% (yield 90.4 mol%), 1336mzz (CF 3 CH=CHCF 3 ) is 0.92 mol%, 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 total 4.24 mol%.

實施例4(炔烴合成)：NMP；NaI 1莫耳% 除了不使用N,N-二甲基甲醯胺而使用N-甲基-2-吡咯烷酮作為溶媒，不使用I2 而使用NaI作為含碘無機材料以外，使其與實施例1同樣地進行反應。反應結束後，以氣相色譜法分析捕集鋼瓶之氣相、液相及反應液，各自進行考慮並算出轉化率及選擇率，轉化率為98.4莫耳%，各成分之選擇率係CF3 C≡CCF3 為92.51莫耳%(產率91.0莫耳%)、1336mzz(CF3 CH=CHCF3 )為1.12莫耳%、CF2 HC≡CCF2 H為1.19莫耳%、CF3 CF=CHCF3 為0.41莫耳%、CF3 CCl=CHCF3 為0.31莫耳%，其他副產物合計為4.46莫耳%。Example 4 (alkyne synthesis): NMP; NaI 1 mol% Except that N,N-dimethylformamide is not used but N-methyl-2-pyrrolidone is used as the solvent, and I 2 is not used but NaI is used as the solvent Except for the iodine-containing inorganic material, 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 trapped cylinder were analyzed by gas chromatography, and the conversion rate and selectivity were calculated separately. The conversion rate was 98.4 mol%, and the selectivity of each component was CF 3 C≡CCF 3 is 92.51 mol% (yield 91.0 mol%), 1336mzz (CF 3 CH=CHCF 3 ) is 1.12 mol%, CF 2 HC≡CCF 2 H is 1.19 mol%, CF 3 CF= CHCF 3 is 0.41 mol%, CF 3 CCl=CHCF 3 is 0.31 mol%, and the total amount of other by-products is 4.46 mol%.

實施例5(炔烴合成)：NMP；無含碘無機材料 除了不使用N,N-二甲基甲醯胺而使用N-甲基-2-吡咯烷酮作為溶媒，且不使用I2 以外，使其與實施例1同樣地進行反應。反應結束後，以氣相色譜法分析捕集鋼瓶之氣相、液相及反應液，各自進行考慮並算出轉化率及選擇率，轉化率為99.6莫耳%，各成分之選擇率係CF3 C≡CCF3 為48.9莫耳%(產率48.7莫耳%)、1336mzz(CF3 CH=CHCF3 )為2.2莫耳%、CF2 HC≡CCF2 H為2.2莫耳%、CF3 CF=CHCF3 為1.1莫耳%、CF3 CCl=CHCF3 為2.1莫耳%，其他副產物合計為43.4莫耳%。Example 5 (alkyne synthesis): NMP; no iodine-containing inorganic materials except that N,N-dimethylformamide is not used but N-methyl-2-pyrrolidone is used as a solvent, and I 2 is not used. 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 trapped cylinder were analyzed by gas chromatography, and the conversion rate and selectivity were calculated separately. The conversion rate was 99.6 mol%, and the selectivity of each component was CF 3 C≡CCF 3 is 48.9 mol% (yield 48.7 mol%), 1336mzz (CF 3 CH=CHCF 3 ) is 2.2 mol%, CF 2 HC≡CCF 2 H is 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 total 43.4 mol%.

實施例6(炔烴合成)：NMP；ICL 1莫耳% 除了不使用N,N-二甲基甲醯胺而使用N-甲基-2-吡咯烷酮作為溶媒，不使用I2 而使用一氯化碘(ICL)作為含碘無機材料以外，使其與實施例1同樣地進行反應。反應結束後，以氣相色譜法分析捕集鋼瓶之氣相、液相及反應液，各自進行考慮並算出轉化率及選擇率，轉化率為99.5莫耳%，各成分之選擇率係CF3 C≡CCF3 為93.11莫耳%(產率92.6莫耳%)、1336mzz(CF3 CH=CHCF3 )為3.20莫耳%、CF2 HC≡CCF2 H為0.22莫耳%、CF3 CF=CHCF3 為0.22莫耳%、CF3 CCl=CHCF3 為0.11莫耳%，其他副產物合計為2.51莫耳%。Example 6 (alkyne synthesis): NMP; ICL 1 mol% Except that N,N-dimethylformamide is not used but N-methyl-2-pyrrolidone is used as a solvent, and I 2 is not used but monochloride is used Iodide (ICL) was made to react in the same manner as in Example 1, except that the iodine-containing inorganic material was used. After the reaction, the gas phase, liquid phase, and reaction liquid of the trapped cylinder were analyzed by gas chromatography, and the conversion rate and selectivity were calculated separately. The conversion rate was 99.5 mol%, and the selectivity of each component was CF 3 C≡CCF 3 is 93.11 mol% (yield 92.6 mol%), 1336mzz (CF 3 CH=CHCF 3 ) is 3.20 mol%, 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 the total amount of other by-products is 2.51 mol%.

比較例1(炔烴合成)：DMF；無含碘無機材料 除了不使用I2 以外，使其與實施例1同樣地進行反應。反應結束後，以氣相色譜法分析捕集鋼瓶之氣相、液相及反應液，各自進行考慮並算出轉化率及選擇率，轉化率為98.06莫耳%，各成分之選擇率係CF3 C≡CCF3 為56.20莫耳%(產率55.1莫耳%)、1336mzz(CF3 CH=CHCF3 )為0.24莫耳%、CF2 HC≡CCF2 H為1.03莫耳%、CF3 CF=CHCF3 為0.35莫耳%、CF3 CCl=CHCF3 為0.47莫耳%，其他副產物合計為41.70莫耳%。Comparative example 1 (alkyne synthesis): DMF; non-iodine-containing inorganic material was reacted in the same manner as in Example 1, except that I 2 was not used. After the reaction, the gas phase, liquid phase, and reaction liquid of the trapped cylinder were analyzed by gas chromatography, and the conversion rate and selectivity were calculated separately. The conversion rate was 98.06 mol%, and the selectivity of each component was CF 3 C≡CCF 3 is 56.20 mol% (yield 55.1 mol%), 1336mzz (CF 3 CH=CHCF 3 ) is 0.24 mol%, CF 2 HC≡CCF 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 total 41.70 mol%.

比較例2(炔烴合成)：二甲苯；I2 1莫耳% 除了不使用N,N-二甲基甲醯胺而使用二甲苯作為溶媒以外，與實施例1進行同樣的處理。然而，反應完全未進行，無法獲得CF3 C≡CCF3 。Comparative example 2 (alkyne synthesis): xylene; I 2 1 mol% The same treatment as in Example 1 was performed 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 3 C≡CCF 3 could not be obtained.

比較例3(炔烴合成)：二丁醚；I2 1莫耳% 除了不使用N,N-二甲基甲醯胺而使用二丁醚作為溶媒以外，與實施例1進行同樣的處理。然而，反應完全未進行，無法獲得CF3 C≡CCF3 。Comparative Example 3 (alkyne synthesis): dibutyl ether; I 2 1 mol% The same treatment as in Example 1 was performed 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 3 C≡CCF 3 could not be obtained.

實施例7(烯烴合成)：NMP；I2 1莫耳% 於冷卻至-78℃之連結有濾水閥之附電容器之茄型燒瓶中，添加10g(0.037 mol)之CF3 CCLF-CCLFCF3 (基質)、45g(0.45 mol)之N-甲基-2-吡咯烷酮(溶媒)、2.90g(0.044 mol)之鋅、0.11g(0.0004 mol；相對於鋅為1 mol%)之I2 ，於攪拌下，將內溫加熱至60℃為止。成為固定的內溫後，一邊攪拌一邊使其反應5小時。反應結束後，以氣相色譜法分析捕集鋼瓶之氣相、液相及反應液，各自進行考慮並算出轉化率及選擇率，轉化率為98.3莫耳%，各成分之選擇率係CF3 CF=CFCF3 為94.3莫耳%(產率92.7莫耳%)、CF3 CFHCClFCF3 為1.9莫耳%、CF3 CFHCFHCF3 為0.65莫耳%、CF3 CH=CFCF3 為0.01莫耳%，其他副產物合計為3.14莫耳%。Example 7 (Olefin synthesis): NMP; I 2 1 mol% In an eggplant-shaped flask with a capacitor attached to a filter valve and cooled to -78°C, add 10 g (0.037 mol) of CF 3 CCLF-CCLFCF 3 (Substrate), 45g (0.45 mol) of N-methyl-2-pyrrolidone (solvent), 2.90g (0.044 mol) of zinc, 0.11g (0.0004 mol; 1 mol% relative to zinc) of I 2 , in While stirring, heat the inner temperature to 60°C. After reaching a fixed internal temperature, it was allowed to react for 5 hours while stirring. After the reaction, the gas phase, liquid phase, and reaction liquid of the trapped cylinder were analyzed by gas chromatography, and the conversion rate and selectivity were calculated separately. The conversion rate was 98.3 mol%, and the selectivity of each component was CF 3 CF=CFCF 3 is 94.3 mol% (yield 92.7 mol%), CF 3 CFHCClFCF 3 is 1.9 mol%, CF 3 CFHCFHCF 3 is 0.65 mol%, CF 3 CH=CFCF 3 is 0.01 mol%, The other by-products totaled 3.14 mol%.

比較例4(烯烴合成)：NMP；無含碘無機材料 除了不使用I2 以外，使其與實施例6同樣地進行反應。反應結束後，以氣相色譜法分析捕集鋼瓶之氣相、液相及反應液，各自進行考慮並算出轉化率及選擇率，轉化率為87.3莫耳%，各成分之選擇率係CF3 CF=CFCF3 為52.4莫耳%(產率45.7莫耳%)、CF3 CFHCClFCF3 為5.3莫耳%、CF3 CFHCFHCF3 為3.1莫耳%、CF3 CH=CFCF3 為0.1莫耳%，其他副產物合計為39.1莫耳%。Comparative example 4 (olefin synthesis): NMP; non-iodine-containing inorganic material was reacted in the same manner as in Example 6 except that I 2 was not used. After the reaction, the gas phase, liquid phase, and reaction liquid of the trapped cylinder were analyzed by gas chromatography, and the conversion rate and selectivity were calculated separately. The conversion rate was 87.3 mol%, and the selectivity of each component was CF 3 CF=CFCF 3 is 52.4 mol% (yield 45.7 mol%), CF 3 CFHCClFCF 3 is 5.3 mol%, CF 3 CFHCFHCF 3 is 3.1 mol%, CF 3 CH=CFCF 3 is 0.1 mol%, The other by-products totaled 39.1 mol%.

實施例1～6及比較例1～3之結果示於表1，實施例7及比較例4之結果示於表2。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.

Figure 02_image045
Figure 02_image045

Figure 02_image047
Figure 02_image047

Claims (8)

一種製造方法，其係一般式(1)：
Figure 03_image001
[式中，雙線與虛線所示之鍵結為雙鍵或三鍵；雙線與虛線所示之鍵結為雙鍵之情況，n係皆表示2，雙線與虛線所示之鍵結為三鍵之情況，n係皆表示1；R1 及R2 係相同或相異地表示氟原子或全氟烷基] 所表示之全氟碳化合物之製造方法，其中，具備 於有機溶媒中，在含碘無機材料，以及鋅或者鋅合金之存在下， 使一般式(2)：
Figure 03_image003
[式中，實線與虛線所示之鍵結為單鍵或雙鍵；實線與虛線所示之鍵結為單鍵之情況，n係皆表示2，實線與虛線所示之鍵結為雙鍵之情況，n係皆表示1；R1 及R2 係與前述相同；X1 及X2 係相同或相異地表示鹵素原子] 所表示之鹵化烴化合物反應，獲得前述一般式(1)所表示之全氟碳化合物之步驟。A manufacturing method, which is the general formula (1):
Figure 03_image001
[In the formula, the bond shown by the double line and the dashed line is a double bond or a triple bond; the bond shown by the double line and the dashed line is a double bond, and n is both represented by 2, and the bond shown by the double line and the dashed line In the case of a triple bond, n both represent 1; R 1 and R 2 represent the same or different fluorine atoms or perfluoroalkyl groups] The method for producing perfluorocarbon compounds represented by, in which it is contained in an organic solvent, In the presence of iodine-containing inorganic materials and zinc or zinc alloys, the general formula (2):
Figure 03_image003
[In the formula, the bond shown by the solid line and the dashed line is a single bond or double bond; the bond shown by the solid line and the dashed line is a single bond, and n is both represented by 2, and the bond shown by the solid line and the dashed line In the case of a double bond, n represents 1; R 1 and R 2 are the same as described above; X 1 and X 2 represent the same or different halogen atoms] The halogenated hydrocarbon compound represented by the reaction to obtain the general formula (1 ) Represents the step of perfluorocarbon. 如請求項1所記載之製造方法，其中，前述含碘無機材料之使用量係相對於前述鋅或者鋅合金1莫耳，為0.0005莫耳以上。The manufacturing method according to claim 1, wherein the usage amount of the iodine-containing inorganic material is 0.0005 mol or more with respect to 1 mol of the zinc or zinc alloy. 如請求項1或2所記載之製造方法，其中，前述含碘無機材料係由碘、金屬碘化物，及包含碘之鹵素間化合物所成之群所選出之至少1種。The manufacturing method according to claim 1 or 2, wherein the iodine-containing inorganic material is at least one selected from the group consisting of iodine, metal iodide, and an interhalogen compound containing iodine. 一種製造方法，其係一般式(1A)：
Figure 03_image005
[式中，R1 及R2 係相同或相異地表示氟原子或全氟烷基] 所表示之全氟炔烴化合物之製造方法，其中，具備 於由N,N-二甲基乙醯胺、N,N-二異丙基甲醯胺、N-甲基-2-吡咯烷酮、1.3-二甲基-3,4,5,6-四氫嘧啶酮、六甲基磷酸三醯胺、胺化合物、吡啶化合物及喹啉化合物所構成之群所選出之至少1種含氮之極性有機溶媒中，在鋅或者鋅合金之存在下， 使一般式(2A)：
Figure 03_image007
[式中，R1 及R2 係與前述相同；X1 及X2 係相同或相異地表示鹵素原子]； 所表示之鹵化烯烴化合物反應，獲得前述一般式(1A)所表示之全氟炔烴化合物之步驟。A manufacturing method, which is the general formula (1A):
Figure 03_image005
[In the formula, R 1 and R 2 are the same or differently represent a fluorine atom or a perfluoroalkyl group] The method for producing a perfluoroalkyne compound represented by N,N-dimethylacetamide , N,N-diisopropylformamide, N-methyl-2-pyrrolidone, 1.3-dimethyl-3,4,5,6-tetrahydropyrimidinone, hexamethyltriamide phosphate, amine At least one nitrogen-containing polar organic solvent selected from the group consisting of compound, pyridine compound and quinoline compound, in the presence of zinc or zinc alloy, the general formula (2A):
Figure 03_image007
[In the formula, R 1 and R 2 are the same as above; X 1 and X 2 are the same or different from each other representing a halogen atom]; The halogenated olefin compound represented by reacts to obtain the perfluoroalkynes represented by the aforementioned general formula (1A) Steps for hydrocarbon compounds. 如請求項1～4中之任1項所記載之製造方法，其中，反應溫度為0～250℃。The production method according to any one of claims 1 to 4, wherein the reaction temperature is 0 to 250°C. 一種組成物，其係含有一般式(1A)：
Figure 03_image009
[式中，R1 及R2 係相同或相異地表示氟原子或全氟烷基] 所表示之全氟炔烴化合物，及 一般式(3)：
Figure 03_image011
[式中，R1 及R2 係與前述相同] 所表示之化合物。A composition containing the general formula (1A):
Figure 03_image009
[In the formula, R 1 and R 2 are the same or differently represent a fluorine atom or a perfluoroalkyl] perfluoroalkynes compound represented by the general formula (3):
Figure 03_image011
[In the formula, R 1 and R 2 are the same as described above]. 如請求項6所記載之組成物，其中，將前述組成物之總量定為100莫耳%，前述一般式(1A)所表示之全氟炔烴化合物之含量為85～99.9莫耳%。The composition described in claim 6, wherein the total amount of the aforementioned composition is set to 100 mol%, and the content of the perfluoroalkynyl compound represented by the aforementioned general formula (1A) is 85 to 99.9 mol%. 如請求項6或7所記載之組成物，其係作為清洗氣體、蝕刻氣體或有機合成用建構組元使用。The composition described in claim 6 or 7, which is used as a cleaning gas, an etching gas, or a building block for organic synthesis.
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