CN113661155A - Process for producing perfluoroalkine compound - Google Patents
Process for producing perfluoroalkine compound Download PDFInfo
- Publication number
- CN113661155A CN113661155A CN202080026816.5A CN202080026816A CN113661155A CN 113661155 A CN113661155 A CN 113661155A CN 202080026816 A CN202080026816 A CN 202080026816A CN 113661155 A CN113661155 A CN 113661155A
- Authority
- CN
- China
- Prior art keywords
- general formula
- compound represented
- mol
- bonds
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 25
- 150000001875 compounds Chemical class 0.000 title claims description 78
- -1 olefin compound Chemical class 0.000 claims abstract description 81
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 42
- 239000011630 iodine Substances 0.000 claims abstract description 39
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 32
- 239000011701 zinc Substances 0.000 claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 30
- 239000011147 inorganic material Substances 0.000 claims abstract description 30
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 24
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 24
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 21
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 70
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 53
- 238000004519 manufacturing process Methods 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 21
- 238000003786 synthesis reaction Methods 0.000 claims description 20
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 claims description 13
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910001511 metal iodide Inorganic materials 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 5
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 38
- 125000004432 carbon atom Chemical group C* 0.000 description 16
- 239000007791 liquid phase Substances 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 150000001345 alkine derivatives Chemical class 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 9
- 125000001309 chloro group Chemical group Cl* 0.000 description 9
- 125000003709 fluoroalkyl group Chemical group 0.000 description 9
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 9
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 9
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 5
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000006298 dechlorination reaction Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 150000003222 pyridines Chemical class 0.000 description 4
- 150000003248 quinolines Chemical class 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 4
- QZRGKCOWNLSUDK-UHFFFAOYSA-N Iodochlorine Chemical compound ICl QZRGKCOWNLSUDK-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005695 dehalogenation reaction Methods 0.000 description 3
- WBCLXFIDEDJGCC-UHFFFAOYSA-N hexafluoro-2-butyne Chemical compound FC(F)(F)C#CC(F)(F)F WBCLXFIDEDJGCC-UHFFFAOYSA-N 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- UNBDDZDKBWPHAX-UHFFFAOYSA-N n,n-di(propan-2-yl)formamide Chemical compound CC(C)N(C=O)C(C)C UNBDDZDKBWPHAX-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000009518 sodium iodide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XDIDQEGAKCWQQP-OWOJBTEDSA-N (e)-2,3-dichloro-1,1,1,4,4,4-hexafluorobut-2-ene Chemical compound FC(F)(F)C(\Cl)=C(/Cl)C(F)(F)F XDIDQEGAKCWQQP-OWOJBTEDSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- 244000061458 Solanum melongena Species 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical compound C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910021573 transition metal iodide Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- 101000965172 Glycine max Isocitrate lyase 1 Proteins 0.000 description 1
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- PDJAZCSYYQODQF-UHFFFAOYSA-N iodine monofluoride Chemical compound IF PDJAZCSYYQODQF-UHFFFAOYSA-N 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 125000006337 tetrafluoro ethyl group Chemical group 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical class FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- H01—ELECTRIC ELEMENTS
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/3065—Plasma etching; Reactive-ion etching
Abstract
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. R1And R2The same or different, represent a fluorine atom or a perfluoroalkyl group. X1And X2The 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 alloy1R1C＝CR2X2[ in the formula, R1、R2、X1And X22The 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.
Description
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
Claims (8)
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.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019071725A JP6860032B2 (en) | 2019-04-04 | 2019-04-04 | Method for producing perfluoroalkyne compound |
| JP2019-071725 | 2019-04-04 | ||
| PCT/JP2020/015239 WO2020204146A1 (en) | 2019-04-04 | 2020-04-02 | Method for producing perfluoroalkyne compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113661155A true CN113661155A (en) | 2021-11-16 |
Family
ID=72668561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080026816.5A Pending CN113661155A (en) | 2019-04-04 | 2020-04-02 | Process for producing perfluoroalkine compound |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP6860032B2 (en) |
| KR (1) | KR20210149785A (en) |
| CN (1) | CN113661155A (en) |
| SG (1) | SG11202111060VA (en) |
| TW (1) | TWI808318B (en) |
| WO (1) | WO2020204146A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2024023159A (en) * | 2022-08-08 | 2024-02-21 | ダイキン工業株式会社 | Method for producing halogenated alkene compounds |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4947006A (en) * | 1988-06-30 | 1990-08-07 | Ausimont S.R.L. | Process for preparing fluorinated conjugated olefinic products and new products thus obtained |
| CN102264674A (en) * | 2008-12-22 | 2011-11-30 | 纳幕尔杜邦公司 | Method of hydrodechlorination to produce dihydrofluorinated olefins |
| CN103420783A (en) * | 2012-05-22 | 2013-12-04 | 中化蓝天集团有限公司 | Preparation method of 1,1,1,4,4,4-hexafluoro-2-butyne |
| CN106008147A (en) * | 2016-05-23 | 2016-10-12 | 北京宇极科技发展有限公司 | Preparation method of Z-1,1,1,4,4,4-hexafluoro-2-butene |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4010160B2 (en) * | 2002-03-04 | 2007-11-21 | 旭硝子株式会社 | Resist composition |
| EP2003109B1 (en) * | 2006-03-31 | 2011-03-16 | Zeon Corporation | Process for production of perfluoroalkine compound |
| US8530709B2 (en) * | 2010-05-21 | 2013-09-10 | Honeywell International Inc. | Process for the production of fluorinated alkenes |
| JP2012000842A (en) * | 2010-06-16 | 2012-01-05 | Asahi Glass Co Ltd | Method of manufacturing molded body with fine pattern on surface |
-
2019
- 2019-04-04 JP JP2019071725A patent/JP6860032B2/en active Active
-
2020
- 2020-04-02 KR KR1020217035954A patent/KR20210149785A/en not_active Application Discontinuation
- 2020-04-02 WO PCT/JP2020/015239 patent/WO2020204146A1/en active Application Filing
- 2020-04-02 CN CN202080026816.5A patent/CN113661155A/en active Pending
- 2020-04-02 SG SG11202111060VA patent/SG11202111060VA/en unknown
- 2020-04-06 TW TW109111459A patent/TWI808318B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4947006A (en) * | 1988-06-30 | 1990-08-07 | Ausimont S.R.L. | Process for preparing fluorinated conjugated olefinic products and new products thus obtained |
| CN102264674A (en) * | 2008-12-22 | 2011-11-30 | 纳幕尔杜邦公司 | Method of hydrodechlorination to produce dihydrofluorinated olefins |
| CN103420783A (en) * | 2012-05-22 | 2013-12-04 | 中化蓝天集团有限公司 | Preparation method of 1,1,1,4,4,4-hexafluoro-2-butyne |
| CN106008147A (en) * | 2016-05-23 | 2016-10-12 | 北京宇极科技发展有限公司 | Preparation method of Z-1,1,1,4,4,4-hexafluoro-2-butene |
Non-Patent Citations (1)
| Title |
|---|
| 孙晓刚等: "制备六氟-2-丁炔的工艺研究", 《有机氟工业》, no. 2, pages 14 - 17 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6860032B2 (en) | 2021-04-14 |
| TWI808318B (en) | 2023-07-11 |
| TW202104142A (en) | 2021-02-01 |
| SG11202111060VA (en) | 2021-11-29 |
| JP2020169140A (en) | 2020-10-15 |
| KR20210149785A (en) | 2021-12-09 |
| WO2020204146A1 (en) | 2020-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3572077B2 (en) | Method for producing perfluoroalkyl iodides | |
| KR102556278B1 (en) | Method for producing a perfluoroalkadiene compound | |
| JP7166911B2 (en) | Method for producing cyclobutene | |
| TW202014396A (en) | Method for producing perfluoroalkadiene compound | |
| CN113661155A (en) | Process for producing perfluoroalkine compound | |
| JP2004345967A (en) | Method for producing fluorine-containing ether compound | |
| CN106632014B (en) | Preparation method of 2-amino-5-chloropyridine | |
| JP2022048291A (en) | Methods for producing iodofluoroalkane and fluoroolefin | |
| JP3257029B2 (en) | Phenylboronic acid derivative and production method | |
| JP7184055B2 (en) | Method for producing 1,3-dioxolane compound and perfluoro(2,2-dimethyl-1,3-dioxole) | |
| JP7337759B2 (en) | Method for producing perfluoroalkadiene compound | |
| EP0450584B1 (en) | Bromination method | |
| JP2008127318A (en) | Method for producing fluorine-containing fluorosulfonylalkyl vinyl ether | |
| JP2023021148A (en) | Method for producing perfluoroalkadiene compound | |
| JP2005213256A5 (en) | ||
| JP5088253B2 (en) | Method for producing fluoroalkyl halide | |
| JP2010001272A (en) | Method of preparing ethyl iodides substituted with fluorine-containing alkyl | |
| JP6897469B2 (en) | Method for producing diol | |
| EP3237367B1 (en) | Methods of making halogenated partially fluorinated compounds | |
| WO2001081287A1 (en) | Process for the preparation of perfluoroalkanones | |
| JPH0977700A (en) | Production of fluorine-containing olefin | |
| WO2021054414A1 (en) | Method for producing fluorine-containing compounds | |
| JP6349329B2 (en) | Process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1H-pyrazole-4-carbaldehyde | |
| JPH04283524A (en) | Production of trifluoromethyl-substituted aromatic compound | |
| JP2006342088A (en) | Fluorine-containing ether compound and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |