CN113227025B - Method for producing cyclobutene - Google Patents
Method for producing cyclobutene Download PDFInfo
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- CN113227025B CN113227025B CN201980085661.XA CN201980085661A CN113227025B CN 113227025 B CN113227025 B CN 113227025B CN 201980085661 A CN201980085661 A CN 201980085661A CN 113227025 B CN113227025 B CN 113227025B
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- CN
- China
- Prior art keywords
- reaction
- halogen atom
- general formula
- represented
- cyclobutene
- Prior art date
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- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 124
- 125000005843 halogen group Chemical group 0.000 claims abstract description 77
- 238000003379 elimination reaction Methods 0.000 claims abstract description 42
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 28
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 24
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 description 45
- 125000001153 fluoro group Chemical group F* 0.000 description 22
- 239000000203 mixture Substances 0.000 description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000002585 base Substances 0.000 description 15
- 238000005796 dehydrofluorination reaction Methods 0.000 description 15
- 229910052731 fluorine Inorganic materials 0.000 description 15
- 239000007789 gas Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 12
- 239000007858 starting material Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000012916 structural analysis Methods 0.000 description 9
- 239000003513 alkali Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001931 cyclobutenes Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- -1 hydrocarbon alkoxide Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- FEWLNYSYJNLUOO-UHFFFAOYSA-N 1-Piperidinecarboxaldehyde Chemical compound O=CN1CCCCC1 FEWLNYSYJNLUOO-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- CMNQIVHHHBBVSC-UHFFFAOYSA-N 5-hydroxy-3,4-dihydro-2h-isoquinolin-1-one Chemical compound O=C1NCCC2=C1C=CC=C2O CMNQIVHHHBBVSC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- 229910007161 Si(CH3)3 Inorganic materials 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- UDYGXWPMSJPFDG-UHFFFAOYSA-M benzyl(tributyl)azanium;bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 UDYGXWPMSJPFDG-UHFFFAOYSA-M 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- PRAANDQMEYFSAE-UHFFFAOYSA-M benzyl(tributyl)azanium;fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 PRAANDQMEYFSAE-UHFFFAOYSA-M 0.000 description 1
- QVGHRPSUYBFXLH-UHFFFAOYSA-M benzyl(tributyl)azanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QVGHRPSUYBFXLH-UHFFFAOYSA-M 0.000 description 1
- CHQVQXZFZHACQQ-UHFFFAOYSA-M benzyl(triethyl)azanium;bromide Chemical compound [Br-].CC[N+](CC)(CC)CC1=CC=CC=C1 CHQVQXZFZHACQQ-UHFFFAOYSA-M 0.000 description 1
- DSTSOVPKKRBGSU-UHFFFAOYSA-M benzyl(triethyl)azanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC1=CC=CC=C1 DSTSOVPKKRBGSU-UHFFFAOYSA-M 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- QLPMKRZYJPNIRP-UHFFFAOYSA-M methyl(trioctyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC QLPMKRZYJPNIRP-UHFFFAOYSA-M 0.000 description 1
- NVVLMKLCGJCBMM-UHFFFAOYSA-M methyl(trioctyl)azanium;fluoride Chemical compound [F-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC NVVLMKLCGJCBMM-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- UQFSVBXCNGCBBW-UHFFFAOYSA-M tetraethylammonium iodide Chemical compound [I-].CC[N+](CC)(CC)CC UQFSVBXCNGCBBW-UHFFFAOYSA-M 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 description 1
- POSYVRHKTFDJTR-UHFFFAOYSA-M tetrapropylazanium;fluoride Chemical compound [F-].CCC[N+](CCC)(CCC)CCC POSYVRHKTFDJTR-UHFFFAOYSA-M 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- DHAWHVVWUNNONG-UHFFFAOYSA-M tributyl(methyl)azanium;bromide Chemical compound [Br-].CCCC[N+](C)(CCCC)CCCC DHAWHVVWUNNONG-UHFFFAOYSA-M 0.000 description 1
- IPILPUZVTYHGIL-UHFFFAOYSA-M tributyl(methyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](C)(CCCC)CCCC IPILPUZVTYHGIL-UHFFFAOYSA-M 0.000 description 1
- XJMFORMFPOEHCH-UHFFFAOYSA-M tributyl(methyl)azanium;fluoride Chemical compound [F-].CCCC[N+](C)(CCCC)CCCC XJMFORMFPOEHCH-UHFFFAOYSA-M 0.000 description 1
- DXJLCRNXYNRGRA-UHFFFAOYSA-M tributyl(methyl)azanium;iodide Chemical compound [I-].CCCC[N+](C)(CCCC)CCCC DXJLCRNXYNRGRA-UHFFFAOYSA-M 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C23/00—Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
- C07C23/02—Monocyclic halogenated hydrocarbons
- C07C23/06—Monocyclic halogenated hydrocarbons with a four-membered ring
-
- 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 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
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/3065—Plasma etching; Reactive-ion etching
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Plasma & Fusion (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention aims at: the production of cyclobutene containing halogen atoms is carried out at a high conversion (yield) and a high selectivity. A process for producing cyclobutene represented by the general formula (1) (wherein X 1、X2、X3 and X 4 are the same or different and represent a hydrogen atom, a halogen atom or a perfluoroalkyl group, and Y represents a halogen atom.) which comprises a step of subjecting cyclobutane represented by the general formula (2) (wherein X 1、X2、X3、X4 and Y are the same as or different from the above-mentioned X 5 and X 6 and represent a hydrogen atom, a halogen atom or a perfluoroalkyl group) to an elimination reaction, wherein the elimination reaction is carried out in the presence of a base in a closed reaction system, or wherein the elimination reaction is carried out at a reaction temperature of 20 ℃ or higher and a reaction pressure of 0kPa or higher and in the presence of a base.
Description
Technical Field
The present invention relates to a method for producing cyclobutene.
Background
In addition to dry etching gases for semiconductors, cyclobutenes containing halogen atoms are also useful compounds for various refrigerants, blowing agents, heat transfer media, and the like.
Among the cyclobutenes containing halogen atoms, a method of producing 1H-pentafluorobutylene from 1H, 2H-hexafluorocyclobutane by a dehydrofluorination reaction is known (for example, non-patent documents 1 and 2). This technique synthesizes 1H-pentafluorobutylene in an open reaction system using glassware.
Prior art literature
Non-patent literature
Non-patent document 1: buxton; tatlow; journal of THE CHEMICAL Society; (1954); p.1177-1179
Non-patent document 2: fuller, g.; tatlow, j.c.; journal of THE CHEMICAL Society; (1961); p.3198-3203
Disclosure of Invention
Technical problem to be solved by the invention
The invention aims at: the production of cyclobutene containing halogen atoms is carried out at a high conversion (yield) and a high selectivity.
Technical scheme for solving technical problems
The invention comprises the following technical proposal.
The process for producing cyclobutene represented by the general formula (1) comprises a step of subjecting cyclobutane represented by the general formula (2) to elimination reaction, wherein the elimination reaction is carried out in the presence of a base in a closed reaction system.
( Wherein X 1、X2、X3 and X 4 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group. Y represents a halogen atom. )
( Wherein X 1、X2、X3、X4 and Y are the same as described above. X 5 and X 6 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group. )
The process for producing cyclobutene represented by the general formula (1) comprises a step of subjecting cyclobutane represented by the general formula (2) to an elimination reaction, wherein the elimination reaction is carried out in the presence of a base under conditions in which the reaction temperature is 20 ℃ or higher and the reaction pressure is 0kPa or higher.
( Wherein X 1、X2、X3 and X 4 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group. Y represents a halogen atom. )
( Wherein X 1、X2、X3、X4 and Y are the same as described above. X 5 and X 6 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group. )
The method according to item 3, wherein X 5 is a hydrogen atom, X 6 is a halogen atom, and the elimination reaction is a dehydrohalogenation reaction.
The composition of item 4, which contains cyclobutene represented by the general formula (1), wherein the content of cyclobutene represented by the general formula (1) is 99mol% or more, based on 100mol% of the total composition.
( Wherein X 1、X2、X3 and X 4 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group. Y represents a halogen atom. )
The composition according to item 4 above, wherein the content of 1H-perfluorocyclobutene (1H-cC 4F5 H) is 99mol% or more and the content of 3H-perfluorocyclobutene (3H-cC 4F5 H) is 1mol% or less.
Item 6. The composition of item 4 or 5 above, which is used as a cleaning gas, etching gas, deposition gas or block for organic synthesis.
Effects of the invention
With the present invention, cyclobutene containing halogen atoms can be produced with high conversion (yield) and high selectivity.
Detailed Description
As a result of intensive studies, the inventors of the present invention have found that a process for elimination reaction of a raw material compound in the presence of a base in a closed reaction system can produce a halogen atom-containing cyclobutene represented by the above general formula (1) with a high conversion (yield) and a high selectivity.
The present invention has been completed based on the above findings.
The present invention includes the following embodiments.
The method for producing cyclobutene represented by the general formula (1) of the present invention comprises a step of subjecting cyclobutane represented by the general formula (2) to elimination reaction.
( Wherein X 1、X2、X3 and X 4 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group. Y represents a halogen atom. )
( Wherein X 1、X2、X3、X4 and Y are the same as described above. X 5 and X 6 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group. )
In the present invention, the elimination reaction is performed in the presence of a base in a closed reaction system.
In the present invention, the elimination reaction is performed in the presence of a base under conditions where the reaction temperature is 20℃or higher and the reaction pressure is 0kPa or higher.
In the present invention, the reaction pressure means gauge pressure, unless otherwise specified.
In the present invention, by satisfying the above conditions, it is possible to produce cyclobutene having a halogen atom with a high conversion (yield) and a high selectivity.
In the present invention, the "conversion" means a ratio (mol%) of the total molar amount of compounds (such as cyclobutene having a halogen atom) other than the raw material compound contained in the effluent gas from the outlet of the reactor to the molar amount of the raw material compound (cyclobutane having a halogen atom) supplied to the reactor.
In the present invention, the term "selectivity" means a ratio (mol%) of the total molar amount of the target compound (halogen atom-containing cyclobutene) contained in the effluent gas from the outlet of the reactor to the total molar amount of the compounds (halogen atom-containing cyclobutene, etc.) other than the raw material compound in the effluent gas.
The method for producing cyclobutene of the present invention is different from the reaction using a glass vessel in the prior art, and can increase the yield of the target compound by increasing the boiling point of the raw material and increasing the liquid component by applying pressure using a metal vessel, for example.
(1) Raw material compound
In the present invention, the starting compound is a cyclobutane represented by the general formula (2).
( Wherein X 1、X2、X3、X4、X5 and X 6 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group. Y represents a halogen atom. )
X 1、X2、X3、X4、X5 and X 6 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group.
Y represents a halogen atom.
As the halogen atom of X 1、X2、X3、X4、X5、X6 and Y, fluorine atom, chlorine atom, bromine atom and iodine atom can be cited.
The perfluoroalkyl groups of X 1、X2、X3、X4、X5 and X 6 are alkyl groups in which all hydrogen atoms are replaced with fluorine atoms. The perfluoroalkyl group is, for example, preferably a perfluoroalkyl group 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. The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group. As the above perfluoroalkyl group, trifluoromethyl (CF 3 -) and pentafluoroethyl (C 2F5 -) are preferred.
In view of the ability to produce a halogen atom-containing cyclobutane of the general formula (2) as a starting compound with a high selectivity, X 1、X2、X3 and X 4 are more preferably the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group, X 5 is a hydrogen atom, X 6 is a fluorine atom, and Y is a fluorine atom.
As the starting compound, cyclobutane represented by the general formula (2) may be mentioned, for example
And the like.
The cyclobutane represented by the general formula (2) may be used alone or in combination of 2 or more. Such cyclobutane may be used as known or commercially available products.
In the cyclobutane containing a halogen atom represented by the general formula (2), X 1、X2、X3、X4 and X 6 are more preferably fluorine atoms, X 5 is hydrogen atoms, and Y is fluorine atom, from the viewpoint that the cyclobutane containing a halogen atom can be produced with high selectivity and high conversion (yield).
(2) Elimination reaction
In the method for producing a halogen atom-containing cyclobutene of the present invention, a solution of a raw material compound represented by the general formula (2) is first prepared.
In the elimination reaction step of the present invention, elimination reaction is performed in a closed reaction system in the presence of a base.
In the elimination reaction step of the present invention, it is preferable that X 5 be a hydrogen atom, X 6 be a halogen atom, and the elimination reaction be a dehydrohalogenation reaction. In the elimination reaction step of the present invention, it is preferable that X 5 be a hydrogen atom, X 6 be a fluorine atom, and the elimination reaction be a dehydrofluorination reaction.
For example, in the cyclobutane containing a halogen atom represented by the general formula (2), it is preferable that X 1、X2、X3、X4 and X 6 are fluorine atoms, X 5 is a hydrogen atom, and Y is a fluorine atom as a raw material compound.
The elimination reaction is preferably dehydrofluorination reaction according to the following reaction formula.
Solvent(s)
The solvent is preferably water. In addition, as the nonaqueous solvent, carbonates such as dimethyl carbonate, methylethyl carbonate, diethyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, and the like are preferable; ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, ketones such as acetone, methyl ethyl ketone, and diethyl ketone, lactones such as gamma-butyrolactone, gamma-valerolactone, tetrahydrofuran, and tetrahydropyran, ethers such as diethyl ether, dibutyl ether, diisopropyl ether, 1, 2-dimethoxyethane, 1, 2-diethoxyethane, and tetrahydrofuran, nitriles such as acetonitrile, propionitrile, and benzonitrile, amides such as N, N-dimethylformamide, and sulfones such as dimethyl sulfoxide and sulfolane. The solvent is preferably at least 1 selected from the above-mentioned aqueous and nonaqueous solvents.
Alkali
In this step, as the base (base), an alkaline substance (alkili) is preferably used.
The alkaline substance used in the present step is preferably an alkali metal or alkaline earth metal hydroxide, more preferably sodium hydroxide or potassium hydroxide. In this step, an aqueous solution of an alkali metal or alkaline earth metal hydroxide is preferably formed, and an aqueous solution of sodium hydroxide or potassium hydroxide is more particularly preferred. By using the above basic substance, the target compound can be obtained with higher selectivity and higher conversion.
The content of the alkali metal or alkaline earth metal hydroxide in the aqueous solution in the reaction solution is not particularly limited, but is preferably 20 to 60% by mass, more preferably 40 to 55% by mass, based on the whole reaction solution. By making the content of the basic substance in the reaction solution within the above range, the target compound can be obtained with higher selectivity and higher conversion.
In this step, an alkoxide of an organic material can be preferably used as the base. As the alkoxide of the organic substance, for example, potassium methoxide, potassium ethoxide, potassium tert-butoxide and the like can be preferably used.
Catalyst
In this step, a catalyst may be used as needed. The catalyst used in the present step is preferably a hydrocarbon alkoxide. The alkoxide of the hydrocarbon system is preferably at least one selected from the group consisting of tetramethyl ammonium fluoride, tetramethyl ammonium chloride, tetramethyl ammonium bromide, tetramethyl ammonium iodide, tetraethyl ammonium fluoride, tetraethyl ammonium chloride, tetraethyl ammonium bromide, tetraethyl ammonium iodide, tetrapropyl ammonium fluoride, tetrapropyl ammonium chloride, tetrapropyl ammonium bromide, tetrapropyl ammonium iodide, tetrabutyl ammonium fluoride, tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium iodide, benzyl triethyl ammonium fluoride, benzyl triethyl ammonium chloride, benzyl triethyl ammonium bromide, benzyl triethyl ammonium iodide, benzyl tributyl ammonium fluoride, benzyl tributyl ammonium chloride, benzyl tributyl ammonium bromide, benzyl tributyl ammonium iodide, methyl tributyl ammonium fluoride, methyl tributyl ammonium chloride, methyl tributyl ammonium bromide, methyl tributyl ammonium iodide, methyl trioctyl ammonium fluoride, methyl trioctyl ammonium chloride (trade mark Aliquat 336), methyl trioctyl ammonium bromide, and methyl trioctyl ammonium iodide. By using the above catalyst, the target compound can be obtained with higher selectivity and higher conversion.
Closed reaction system
In the erasing reaction step of the present invention, the method is characterized in that: the reaction is carried out in a closed reaction system in the presence of the above-mentioned base.
The target compound of the present invention has a low boiling point of cyclobutene having a halogen atom, and exists as a gas (gas) at room temperature. Therefore, in the elimination reaction step of the present invention, the reaction system is made a closed reaction system, and the pressure in the closed reaction system naturally increases, whereby the reaction is carried out under a pressurized condition.
In this way, since the boiling point of the target compound is low, the closed reaction system is pressurized, and the concentration of the substrate (raw material compound) in the reaction solution (alkali solution) increases, so that the reactivity can be improved. The closed reaction system is preferably a batch pressure-resistant reaction vessel, and the reaction system is closed to carry out the reaction. In the case of batch reaction, for example, it is preferable to add a raw material compound, an alkali solution (aqueous alkali solution), a catalyst, etc. to a pressure vessel such as an autoclave, raise the temperature to an appropriate reaction temperature by a heater, and react for a certain period of time with stirring. The reaction atmosphere is preferably an inert gas atmosphere such as nitrogen, helium, or carbon dioxide.
In the elimination reaction step of the present invention, the lower limit of the reaction temperature of the closed pressure reaction system is usually 20 ℃, preferably 25 ℃, more preferably 30 ℃, still more preferably 40 ℃ from the viewpoint of more effectively performing the elimination reaction, obtaining the target compound with higher selectivity, and suppressing the decrease in conversion.
In the elimination reaction step of the present invention, the upper limit of the reaction temperature in the closed reaction system is usually 50 ℃, preferably 45 ℃, from the viewpoint of more efficiently carrying out the dehydrofluorination reaction, obtaining the target compound with higher selectivity, and suppressing the decrease in selectivity due to the decomposition or polymerization of the reaction product.
In the elimination reaction step of the present invention, the target compound can be obtained with a higher selectivity and a higher conversion rate by conducting the elimination reaction in a closed reaction system.
Pressurized reaction system
In the erasing reaction step of the present invention, the method is characterized in that: the reaction is carried out in the presence of the base under conditions where the reaction temperature is 20 ℃ or higher and the reaction pressure is 0kPa or higher.
In this way, when the reaction system is pressurized, the concentration of the matrix (raw material compound) in the reaction solution (alkali solution, aqueous alkaline substance solution) increases, and the reactivity can be improved. The pressurized reaction system is preferably carried out by sealing the reaction system using a batch pressure-resistant reaction vessel. In the case of batch reaction, for example, it is preferable to add a raw material compound, an alkali solution (aqueous alkali solution), a catalyst, etc. to a pressure vessel such as an autoclave, raise the temperature to an appropriate reaction temperature by a heater, and react for a certain period of time with stirring.
In the erasing reaction step of the present invention, the reaction pressure is set to 0kPa or more with respect to the pressurizing condition.
The reaction pressure is the pressure inside the reaction vessel used to pressurize the reaction system. In the erasing reaction step of the present invention, the reaction is preferably carried out at a pressure of preferably 0kPa or more, more preferably 10kPa or more, still more preferably 20kPa or more, particularly preferably 30kPa or more, with respect to the reaction pressure.
In the erasing reaction step of the present invention, the reaction is preferably carried out under a pressure of preferably 101.3kPa or more, more preferably 111.3kPa or more, still more preferably 121.3kPa or more, particularly preferably 131.3kPa or more, in terms of the pressurizing condition.
When the pressure is increased, the pressure in the reaction system can be increased by introducing inert gas such as nitrogen, helium, or carbon dioxide into the reaction system.
In the elimination reaction step of the present invention, the lower limit of the reaction temperature of the pressurized reaction system is usually 20 ℃, preferably 25 ℃, more preferably 30 ℃, and even more preferably 40 ℃ from the viewpoint of more effectively performing the elimination reaction, obtaining the target compound with higher selectivity, and suppressing the decrease in conversion.
In the erasing reaction step of the present invention, the lower limit of the reaction temperature of the pressurized reaction system is usually 20℃in order to adjust the reaction pressure to 0kPa or more or to adjust the reaction pressure to 101.3kPa or more in absolute pressure as the pressurizing condition. In this way, in the erasing reaction step of the present invention, it is preferable to heat and pressurize the inside of the reaction vessel to perform the erasing reaction.
In the elimination reaction step of the present invention, the upper limit of the reaction temperature of the pressurized reaction system is usually 50 ℃, preferably 45 ℃, from the standpoint that the dehydrofluorination reaction is more efficiently performed, the target compound can be obtained with higher selectivity, and the decrease in selectivity due to the decomposition or polymerization of the reaction product is suppressed.
In the elimination reaction step of the present invention, the target compound can be obtained with a higher selectivity and a higher conversion rate by conducting the elimination reaction in a pressurized reaction system.
After the elimination reaction is completed, if necessary, the resultant may be purified by a usual method to obtain a halogen atom-containing cyclobutene represented by the general formula (1).
Combination of closed reaction system and pressurized reaction system
In the elimination reaction step of the present invention, the reaction may be performed continuously and under pressure by a method such as connecting a back pressure valve to a continuous phase tank reactor (CSTR) while extracting a liquid or by gasifying and then extracting a product.
(3) Target compound
The target compound of the present invention is a cyclobutene containing a halogen atom represented by the general formula (1).
( Wherein X 1、X2、X3 and X 4 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group. Y represents a halogen atom. )
X 1、X2、X3 and X 4 and Y are the same as described above.
The following can be mentioned as examples of the cyclobutene of the general formula (1) to be produced
And the like.
In the halogen atom-containing cyclobutene represented by the general formula (1), X 1、X2、X3 and X 4 are preferably the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group, and Y is a fluorine atom. In the halogen atom-containing cyclobutene represented by the general formula (1), more preferably, X 1、X2、X3 and X 4 are fluorine atoms, and Y is a fluorine atom.
In the method for producing a halogen atom-containing cyclobutene of the present invention, it is preferable that the starting compound is a halogen atom-containing cyclobutane represented by the general formula (2), and X 1、X2、X3、X4 and X 6 are fluorine atoms, X 5 is a hydrogen atom, and Y is a fluorine atom.
The elimination reaction is preferably dehydrofluorination reaction according to the following reaction formula.
The target compound is a cyclobutene having a halogen atom represented by the general formula (1), preferably X 1、X2、X3 and X 4 are fluorine atoms, and Y is a fluorine atom.
(4) Composition comprising cyclobutene containing halogen atoms
In the above-described manner, the halogen atom-containing cyclobutene represented by the general formula (1) can be obtained, but as described above, the halogen atom-containing cyclobutene represented by the general formula (1) and the halogen atom-containing cyclobutane represented by the general formula (2) can be obtained as a composition.
The halogen atom-containing cyclobutene represented by the general formula (1) contained in the composition is preferably one in which X 1、X2、X3 and X 4 are fluorine atoms and Y is fluorine atom.
In the composition of the present invention containing a halogen atom-containing cyclobutene represented by the general formula (1), the content of the halogen atom-containing cyclobutene represented by the general formula (1) is preferably 99mol% or more, assuming that the total amount of the composition is 100 mol%.
In the composition of the present invention containing a halogen atom-containing cyclobutene represented by the general formula (1), the content of the halogen atom-containing cyclobutene represented by the general formula (1) is preferably 1mol% to 99.9mol%, more preferably 5mol% to 99.9mol%, and even more preferably 10mol% to 99.9mol%, based on 100mol% of the total amount of the composition.
In the method for producing a halogen atom-containing cyclobutene of the present invention, the following compounds may be produced as impurities in the elimination reaction described above.
In the composition of the present invention containing a halogen atom-containing cyclobutene represented by the general formula (1), the content of 1H-perfluorocyclobutene (1H-cC 4F5 H) is preferably 99mol% or more and the content of 3H-perfluorocyclobutene (3H-cC 4F5 H) is preferably 1mol% or less, based on 100mol% of the total amount of the composition.
Even when the production method of the present invention is used for producing a composition containing a halogen atom-containing cyclobutene represented by the general formula (1), a halogen atom-containing cyclobutene represented by the general formula (1) can be produced with a particularly high selectivity, and as a result, components other than the halogen atom-containing cyclobutene represented by the general formula (1) in the composition can be reduced. The production method of the present invention can reduce the labor required for purification of the halogen atom-containing cyclobutene represented by the general formula (1).
The composition containing a halogen atom-containing cyclobutene represented by the general formula (1) of the present invention can be effectively used for various applications such as deposition gas, block for organic synthesis, cleaning gas, etc., in addition to etching gas for forming the forefront microstructure of semiconductor, liquid crystal, etc., as in the case of the halogen atom-containing cyclobutene represented by the general formula (1) alone.
The deposition gas is a gas for depositing an etching-resistant polymer layer.
The block for organic synthesis refers to a substance capable of forming a precursor of a compound having a skeleton with high reactivity. For example, if the cyclobutene having a halogen atom represented by the general formula (1) of the present invention and the composition containing the same are reacted with a fluorine-containing organosilicon compound such as CF 3Si(CH3)3, fluoroalkyl groups such as CF 3 groups can be introduced and converted into a detergent or a substance capable of forming a fluorine-containing pharmaceutical intermediate.
The embodiments of the present invention have been described above, but various modifications may be made to the embodiments and the details without departing from the spirit and scope of the claimed invention.
Examples
The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
< Embodiment >
In the method for producing a halogen atom-containing cyclobutene of the example, in the halogen atom-containing cyclobutane represented by the general formula (2), X 1、X2、X3、X4 and X 6 are fluorine atoms, X 5 is a hydrogen atom, and Y is a fluorine atom.
The elimination reaction is dehydrofluorination reaction according to the following reaction formula.
Regarding the target compound, in the halogen atom-containing cyclobutene represented by the general formula (1), X 1、X2、X3 and X 4 are fluorine atoms, and Y is a fluorine atom.
In the elimination reaction, the following compounds may be produced as impurities.
Examples
As a reaction system, an autoclave (200 cc) was used.
The reaction system is represented by (i) a closed reaction system in the presence of a base (alkaline substance) or (ii) a pressurized reaction system carried out under conditions where the reaction temperature is 20 ℃ or higher and the reaction pressure is 0kPa or higher and in the presence of a base (alkaline substance) by using an autoclave as the reaction system. Thus, the sealing is accompanied when the pressurization is performed.
Example 1
A50 wt% KOH aqueous solution was added as a reaction solution to the autoclave, a starting compound (cC 4F6H2) was added thereto, and after the autoclave was capped to form a closed system, nitrogen gas was introduced thereinto. The pressure at this time was 20kPa. Thereafter, the mixture was stirred at room temperature (25 ℃) to effect a reaction. Sampling is carried out at proper time after the dehydrofluorination reaction is started, and the reaction is ended when the composition in the reaction system is not changed. The pressure at the end of the reaction was 80kPa.
After the stirring was stopped, the mixture was cooled to 0℃and mass analysis was performed by gas chromatography/mass spectrometry (GC/MS) using gas chromatography (trade name "GC-2014" manufactured by Shimadzu corporation) and structural analysis was performed by NMR using NMR (trade name "400YH" manufactured by JEOL corporation).
Based on the results of mass analysis and structural analysis, it was confirmed that cC 4F5 H was produced as the target compound. In example 1, the conversion from cC 4F6H2 (starting compound) was 92.1mol%, and the selectivity (yield) of cC 4F5 H (target compound) was 97.8mol%.
Example 2
Dehydrofluorination was initiated following the procedure described above for example 1 using methyltrioctylammonium chloride (trademark Aliquat 336) as the catalyst. Except for the above conditions, dehydrofluorination reaction, mass analysis and structural analysis were carried out in the same manner as in example 1.
Based on the results of mass analysis and structural analysis, it was confirmed that cC 4F5 H was produced as the target compound. In example 2, the conversion from cC 4F6H2 (starting compound) was 93.2mol%, and the selectivity of cC 4F5 H (target compound) was 98.9mol%.
Example 3
According to the experimental method of example 1 described above, KOH (alkaline material, alkili) was added as a base to dibutyl ether (reaction solvent) as a reaction solution, and dehydrofluorination reaction was started using the resulting 50wt% KOH dibutyl ether solution. Except for the above conditions, dehydrofluorination reaction, mass analysis and structural analysis were carried out in the same manner as in example 1.
Based on the results of mass analysis and structural analysis, it was confirmed that cC 4F5 H was produced as the target compound. In example 3, the conversion from cC 4F6H2 (starting compound) was 93.4mol% and the selectivity of cC 4F5 H (target compound) was 98.5mol%.
Example 4
According to the experimental method of example 1 above, potassium t-butoxide (t-BuOK) (1.2 equivalent) was added as a base to dibutyl ether (reaction solvent) as a reaction solution, and dehydrofluorination reaction was started using the obtained dibutyl ether solution. Except for the above conditions, dehydrofluorination reaction, mass analysis and structural analysis were carried out in the same manner as in example 1.
Based on the results of mass analysis and structural analysis, it was confirmed that cC 4F5 H was produced as the target compound. In example 3, the conversion from cC 4F6H2 (starting compound) was 95.4mol% and the selectivity to cC 4F5 H (target compound) was 98.9mol%.
Comparative example 1
Comparative example 1 is an open system reaction system. To a flask (200 cc) was added 50wt% KOH, and a dry ice condenser and a dropping funnel were mounted. The raw material compound (cC 4F6H2) was added to a dropping funnel, and the addition was performed. After that, stirring was performed at room temperature. Sampling is carried out at proper time after the dehydrofluorination reaction is started, and the reaction is ended when the composition in the reaction system is not changed. This is an open system reaction, the pressure always being 0kPa.
After stirring was stopped, it was cooled to 0 ℃. Based on the results of mass analysis and structural analysis, it was confirmed that cC 4F5 H was produced as the target compound. In example 3, the conversion from cC 4F6H2 (starting compound) was 51.7mol% and the selectivity of cC 4F5 H (target compound) was 97.1mol%.
TABLE 1
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Claims (3)
1. A process for producing cyclobutene represented by the general formula (1) which comprises:
comprising a step of causing a cyclobutane represented by the general formula (2) to undergo an elimination reaction,
The process comprises the step of carrying out the elimination reaction in the presence of a base in a closed reaction system using a batch pressure-resistant reaction vessel or a continuous phase tank reactor to which a back pressure valve is connected,
In the formula (1), X 1、X2、X3 and X 4 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group, Y represents a halogen atom,
In the formula (2), X 1、X2、X3、X4 and Y are the same as described above, and X 5 and X 6 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group.
2. A process for producing cyclobutene represented by the general formula (1) which comprises:
comprising a step of causing a cyclobutane represented by the general formula (2) to undergo an elimination reaction,
The method comprises the step of performing the elimination reaction in the presence of a base under conditions where the reaction temperature is 20 ℃ or higher and the reaction pressure is 10kPa or higher in a gauge pressure using a batch pressure-resistant reaction vessel or a continuous phase tank reactor to which a back pressure valve is connected,
In the formula (1), X 1、X2、X3 and X 4 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group, Y represents a halogen atom,
In the formula (2), X 1、X2、X3、X4 and Y are the same as described above, and X 5 and X 6 are the same or different and each represents a hydrogen atom, a halogen atom or a perfluoroalkyl group.
3. The manufacturing method according to claim 1 or 2, characterized in that:
The elimination reaction is dehydrohalogenation reaction, wherein X 5 is a hydrogen atom, X 6 is a halogen atom.
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