JPS6354331A - Production of 1,1-difluorocyclohexane - Google Patents
Production of 1,1-difluorocyclohexaneInfo
- Publication number
- JPS6354331A JPS6354331A JP19810386A JP19810386A JPS6354331A JP S6354331 A JPS6354331 A JP S6354331A JP 19810386 A JP19810386 A JP 19810386A JP 19810386 A JP19810386 A JP 19810386A JP S6354331 A JPS6354331 A JP S6354331A
- Authority
- JP
- Japan
- Prior art keywords
- trifluoroacetic acid
- cyclohexanone
- difluorocyclohexane
- acid
- hydrogen fluoride
- 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.)
- Granted
Links
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 72
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 48
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims abstract description 42
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 25
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 13
- XIEADFPBUGUUSG-UHFFFAOYSA-N [1-(2,2,2-trifluoroacetyl)oxycyclohexyl] 2,2,2-trifluoroacetate Chemical compound FC(F)(F)C(=O)OC1(OC(=O)C(F)(F)F)CCCCC1 XIEADFPBUGUUSG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000011084 recovery Methods 0.000 claims description 15
- 239000012024 dehydrating agents Substances 0.000 claims description 10
- 230000010933 acylation Effects 0.000 claims description 8
- 238000005917 acylation reaction Methods 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 12
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001412 amines Chemical class 0.000 abstract description 6
- 230000018044 dehydration Effects 0.000 abstract description 5
- 238000006297 dehydration reaction Methods 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- -1 molybdenum gold hexafluoride Chemical compound 0.000 description 15
- 238000003756 stirring Methods 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 8
- QHMQWEPBXSHHLH-UHFFFAOYSA-N sulfur tetrafluoride Chemical compound FS(F)(F)F QHMQWEPBXSHHLH-UHFFFAOYSA-N 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- BUAKPITZELZWNI-UHFFFAOYSA-N 1-chlorocyclohexene Chemical compound ClC1=CCCCC1 BUAKPITZELZWNI-UHFFFAOYSA-N 0.000 description 3
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 3
- WSWMGHRLUYADNA-UHFFFAOYSA-N 7-nitro-1,2,3,4-tetrahydroquinoline Chemical compound C1CCNC2=CC([N+](=O)[O-])=CC=C21 WSWMGHRLUYADNA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HGTYEBNTDPDGIC-UHFFFAOYSA-N [N].[Au] Chemical compound [N].[Au] HGTYEBNTDPDGIC-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- MJNDVDVTLSBDLB-UHFFFAOYSA-N cyclohexyl 2,2,2-trifluoroacetate Chemical compound FC(F)(F)C(=O)OC1CCCCC1 MJNDVDVTLSBDLB-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 229910052500 inorganic mineral Chemical class 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Chemical class 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- LSJNBGSOIVSBBR-UHFFFAOYSA-N thionyl fluoride Chemical compound FS(F)=O LSJNBGSOIVSBBR-UHFFFAOYSA-N 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- JTPNRXUCIXHOKM-UHFFFAOYSA-N 1-chloronaphthalene Chemical compound C1=CC=C2C(Cl)=CC=CC2=C1 JTPNRXUCIXHOKM-UHFFFAOYSA-N 0.000 description 1
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- WKGHUAZJNBXABN-UHFFFAOYSA-N 3-bromo-2-chloro-6-methyl-5-nitropyridine Chemical compound CC1=NC(Cl)=C(Br)C=C1[N+]([O-])=O WKGHUAZJNBXABN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000012973 diazabicyclooctane Substances 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- BTZNPZMHENLISZ-UHFFFAOYSA-N fluoromethanesulfonic acid Chemical class OS(=O)(=O)CF BTZNPZMHENLISZ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- QRNDDJXJUHBGSG-UHFFFAOYSA-N methoxyethyne Chemical group COC#C QRNDDJXJUHBGSG-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- FRQONEWDWWHIPM-UHFFFAOYSA-N n,n-dicyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)C1CCCCC1 FRQONEWDWWHIPM-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical compound [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N quinaldine Chemical class C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229960004319 trichloroacetic acid Drugs 0.000 description 1
- VYGSFTVYZHNGBU-UHFFFAOYSA-N trichloromethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)(Cl)Cl VYGSFTVYZHNGBU-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
発明BAIIi″1.1−ジフルオロシクロヘキサンの
製造方法に関する。さらに詳しくはシクロヘキサノンヲ
原料として1.1−ジフルオロシクロヘキサンを高収率
で製造する方法に関する。Detailed Description of the Invention [Industrial Application Field] The invention BAIIi'' relates to a method for producing 1,1-difluorocyclohexane. More specifically, it relates to a method for producing 1,1-difluorocyclohexane in high yield using cyclohexanone as a raw material. .
従来i、i−ジフルオロシクロヘキサンハシクロヘキサ
ノンと四フッ化イオウとの反応(ジャーナル・オプ・オ
ーガニック・ケミストリー、36巻、818頁(197
1ン)や、シクロヘキサノンと六フッ化モリブデンとの
反応(テトラヘドロン、27巻、6965頁(1971
))、あるいは1−クロロシクロヘキセンとフッ化水素
との反応(ヘルベチカ・ヒミカ・アクタ、46巻、18
18頁(1963))によって合成されている。Conventional reaction of i,i-difluorocyclohexane and sulfur tetrafluoride (Journal of Organic Chemistry, Vol. 36, p. 818 (197
1) and the reaction between cyclohexanone and molybdenum hexafluoride (Tetrahedron, Vol. 27, p. 6965 (1971)
)) or the reaction of 1-chlorocyclohexene with hydrogen fluoride (Helvetica Himica Acta, Vol. 46, 18
18 (1963)).
しかしながら従来の方法にはいくつかの欠点があった。 However, conventional methods had several drawbacks.
例えば、四フッ化イオウや六フッ化モリブデン金用いる
方法では、これらのフッ素化試剤の合成が極めて厳しい
反応条件を必要とし工業的に実施することが困難である
。例えは四7ツ化イオウの製造は通常、ハステロイCの
オートクレープヘイオウとフッ化ナトリウムと塩素を仕
込んだ後に長時間高温(最終的には225〜250°C
)に保った後に反応混合物を低温で蒸留して生成物であ
る四フッ化イオウ(沸点−40°C)を得ている。(ジ
ャーナル・オシ・ジ・アメリカン・ケミカル・ソサエテ
ィー、82巻、539頁(1960))また、これらの
フッ素化試剤では含有されるフッ素原子のうち実際にシ
クロヘキサン環に導入されるものは半分以下にすぎない
。四フッ化イオウとシクロヘキサノンの反応を例にとれ
ば次式に示すように
四7ツ化イオウはシクロヘキサノンのフッ素化によジフ
ツ化チオニルへ転化するが、このものはもはやフッ素化
反応の活性をもっていない。工業的に1.1−ジフルオ
ロシクロヘキサンを製造する場合には、高価なフッ素原
子全回収することが必要であり、従って前出のフッ化チ
オニルから原料である四フッ化イオウを再び合成せねば
なら々い。For example, methods using sulfur tetrafluoride or molybdenum gold hexafluoride require extremely harsh reaction conditions for the synthesis of these fluorinating agents, and are difficult to implement industrially. For example, the production of sulfur tetra7ide is usually done by charging Hastelloy C autoclave sulfur, sodium fluoride, and chlorine, and then heating it for a long time (finally at 225-250°C).
), the reaction mixture was distilled at low temperature to obtain the product sulfur tetrafluoride (boiling point -40°C). (Journal of the American Chemical Society, Vol. 82, p. 539 (1960)) In addition, less than half of the fluorine atoms contained in these fluorinating reagents are actually introduced into the cyclohexane ring. Only. Taking the reaction of sulfur tetrafluoride and cyclohexanone as an example, sulfur tetrafluoride is converted to thionyl difluoride by fluorination of cyclohexanone, as shown in the following formula, but this substance no longer has fluorination reaction activity. . When producing 1,1-difluorocyclohexane industrially, it is necessary to recover all of the expensive fluorine atoms, and therefore the raw material sulfur tetrafluoride must be synthesized again from the above-mentioned thionyl fluoride. Many.
しかしそのためには、7ツ化チオニルをアルカリ加水分
解することによりアルカリ金属フッ化物全製造した後に
前述の四フッ化イオウ製造工程の原料の一部とするとい
う極めて複雑な回収工程を必要とする。六フッ化モリブ
デンとシクロヘキサノンの反応によシ1.1−ジフルオ
ロシクロヘキサンを製造する場合にも同様に複雑な回収
工程を必要とし、回収工程によp生成するアルカリ金属
フッ化物の量は四フッ化イオウの場合よりもさらに多い
。また四フッ化イオウ會用いる反応では耐圧反応容器を
必要とし、六フッ化モリブデンを用いる方法では重金属
であるモリブデンの回収が問題である。However, this requires an extremely complicated recovery process in which the alkali metal fluoride is completely produced by alkali hydrolysis of thionyl heptadide and then used as part of the raw material for the above-mentioned sulfur tetrafluoride production process. Similarly, when producing 1,1-difluorocyclohexane by the reaction of molybdenum hexafluoride and cyclohexanone, a complicated recovery process is required, and the amount of alkali metal fluoride produced in the recovery process is smaller than that of tetrafluoride. Even more than in the case of sulfur. Furthermore, reactions using sulfur tetrafluoride require a pressure-resistant reaction vessel, and methods using molybdenum hexafluoride have the problem of recovering molybdenum, which is a heavy metal.
1.1−ジフルオロシクロヘキサンを製造する従来技術
の他の一つは1−クロロシクロヘキセンとフッ化水素と
の反応により行なうものであり比較的温和な反応条件に
より反応が進行するが、収率は良くない。また原料とし
て用いる1−クロロシクロヘキセンは通常、高価な塩素
化試剤である五塩化リンとシクロヘキサノンから製造さ
れるため、工業的には行ない難い。Another conventional technique for producing 1.1-difluorocyclohexane involves the reaction of 1-chlorocyclohexene with hydrogen fluoride, and although the reaction proceeds under relatively mild reaction conditions, the yield is good. do not have. Moreover, 1-chlorocyclohexene used as a raw material is usually produced from phosphorus pentachloride and cyclohexanone, which are expensive chlorinating reagents, and therefore it is difficult to produce it industrially.
本発明者らはシクロヘキサンヲ原料として1.1−ジフ
ルオロシクロヘキサンを製造する方法に関して鋭意研究
tXねた結果、アシラール化工程、フッ素化工程、及び
トリフルオロ酢酸回収工程を組合わせることにより、目
的とする1、1−ジフルオロシクロヘキサンを高収率・
高選択率で製造できることを見出し、本発明を完成する
に至った。The present inventors have conducted intensive research on a method for producing 1,1-difluorocyclohexane using cyclohexane as a raw material, and as a result, by combining an acylation process, a fluorination process, and a trifluoroacetic acid recovery process, the objective has been achieved. High yield of 1,1-difluorocyclohexane
They discovered that it can be produced with high selectivity and completed the present invention.
すなわち、本発明はシクロヘキサノンから1゜1−ジフ
ルオロシクロヘキサンを製造するに当り、(■)シクロ
ヘキサノンにトリフルオロ酢酸無水物を反応させること
によジ1.1−ビス(トリフルオロアセトキシ)シクロ
ヘキサンを得るアシラール化工程、
(lD 該1.1−ビス(トリフルオロアセトキシ)
シクロヘキサンにフッ化水素を反応させることにより1
.1−ジフルオロシクロヘキサンとトリフルオロ酢酸を
得るフッ素化工程、
及び
(1) 前記(II)において生成したトリフルオロ
酢酸に脱水剤に反応させることによりトリフルオロ酢酸
無水物を得るトリフルオロ酢酸回収工程を包含すること
を特徴とする1、1−ジフルオロシクロヘキサンの製造
方法を提供するものである。That is, in producing 1゜1-difluorocyclohexane from cyclohexanone, the present invention deals with (■) an acylar which obtains di-1,1-bis(trifluoroacetoxy)cyclohexane by reacting cyclohexanone with trifluoroacetic anhydride. (1.1-bis(trifluoroacetoxy))
By reacting hydrogen fluoride with cyclohexane, 1
.. Includes a fluorination step to obtain 1-difluorocyclohexane and trifluoroacetic acid, and (1) a trifluoroacetic acid recovery step to obtain trifluoroacetic anhydride by reacting the trifluoroacetic acid produced in (II) above with a dehydrating agent. The present invention provides a method for producing 1,1-difluorocyclohexane, characterized in that:
本発明におけるアシラール化工程は式(1)で示される
ようにシクロヘキサノンにトリフルオロ酢酸無水物を反
応させることによる1、1−ビス(トリフルオロア七ト
キシ)シクロヘキサンの製造方法からなっている。The acylation step in the present invention consists of a method for producing 1,1-bis(trifluoro7toxy)cyclohexane by reacting cyclohexanone with trifluoroacetic anhydride as shown in formula (1).
本アシラール化工程は無溶媒で行なうこともできるが、
反応に悪影響を及ぼさない溶媒音用いることもできる。This acylation step can be carried out without solvent, but
Solvents that do not adversely affect the reaction can also be used.
例えは、ジエチルエーテル、テトラヒドロフラン、ビフ
ェニルエーテルナトのエーテル類:二硫化炭素:塩化メ
チレン、クロロホルム、四塩化炭素、ジクロロエタン、
トリクロロエタン、テトラクロロエタンなどのハロゲン
化炭化水素類;クロロベンゼン、ジクロロベンゼン、ブ
ロモベンゼン、クロロナフタレンなどのハロダン化芳香
族炭化水素類:ニトロベンゼン、ニトロトルエン、ニト
ロメタンなどのニトロ化合物類;ヘキサン等の脂肪族炭
化水素類;シクロヘキサン等の脂環式炭化水素類などが
使用される。Examples include diethyl ether, tetrahydrofuran, biphenyl ether, carbon disulfide, methylene chloride, chloroform, carbon tetrachloride, dichloroethane,
Halogenated hydrocarbons such as trichloroethane and tetrachloroethane; Halodanated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, bromobenzene, and chloronaphthalene; Nitro compounds such as nitrobenzene, nitrotoluene, and nitromethane; Aliphatic hydrocarbons such as hexane alicyclic hydrocarbons such as cyclohexane are used.
アシラール化工程において原料として用いるシクロヘキ
サノンは、どのような方法によって製造されたものであ
ってもよい。Cyclohexanone used as a raw material in the acylation step may be produced by any method.
アシラール化工程において原料として用いるシクロヘキ
サノンとトリフルオロ酢酸無水物の量比はシクロヘキサ
ノンに対するトリフルオロ酢酸無水物のモル比で表わす
と、通常0.01〜100、好ましくは0.1〜50が
用いられる。The quantitative ratio of cyclohexanone and trifluoroacetic anhydride used as raw materials in the acylation step is usually 0.01 to 100, preferably 0.1 to 50, expressed as a molar ratio of trifluoroacetic anhydride to cyclohexanone.
また、触媒を添加することも良い。触媒としては例えば
、トリフルオロ酢酸、トリクロロ酢酸等のカルボン酸、
三フッ化ホウ素等のルイス酸、パラトルエンスルホン酸
、メタンスルホン酸、)IJフルオロメタンスルホン酸
等の有機スルホン酸、硫酸等の鉱酸など全使用すること
ができる。It is also good to add a catalyst. Examples of catalysts include carboxylic acids such as trifluoroacetic acid and trichloroacetic acid;
Lewis acids such as boron trifluoride, organic sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, )IJ fluoromethanesulfonic acid, and mineral acids such as sulfuric acid can all be used.
アシラール化工程全行なう場合の反応温度及び反応時間
は原料の量比や、溶媒の有無によって異なるが、通常−
40〜250’C,5分〜500時間であジ、好ましく
は0〜150℃、10分〜200時間である。The reaction temperature and reaction time when performing the entire acylation process vary depending on the ratio of raw materials and the presence or absence of a solvent, but usually -
The temperature is 40 to 250°C for 5 minutes to 500 hours, preferably 0 to 150°C for 10 minutes to 200 hours.
本発明におけるフッ素化工程は式(2)で示されるよう
に1,1−ビス(トリフルオロアセトキシ)シクロヘキ
サンにフッ化水素を反応させることによるl、1−ジフ
ルオロシクロヘキサンの製造方法からなっている。The fluorination step in the present invention consists of a method for producing 1,1-difluorocyclohexane by reacting 1,1-bis(trifluoroacetoxy)cyclohexane with hydrogen fluoride, as shown in formula (2).
フッ素化工程は上式に示すように、1.1−ビス(トリ
フルオロアセトキシ)シクロヘキサン1モルが、2モル
のフッ化水素と反応することにより’+、1−ジフルオ
ロシクロヘキサン1モルトトリフルオロ酢酸2モルと全
生成する。反応生成物である1、1−ジフルオロシクロ
ヘキサンとトリフルオロ酢酸は蒸留等の通常の分離操作
により簡単に精製することができる。As shown in the above formula, the fluorination process involves reacting 1 mole of 1,1-bis(trifluoroacetoxy)cyclohexane with 2 moles of hydrogen fluoride to form 1 mole of 1-difluorocyclohexane and 2 moles of trifluoroacetic acid. Moles and total production. The reaction products, 1,1-difluorocyclohexane and trifluoroacetic acid, can be easily purified by conventional separation operations such as distillation.
フッ素化工程において使用されるフッ化水素とは、フッ
化水素全含有するものであればどのような組成のもので
もよい。通常はフッ化水素あるいはフッ化水素とアミン
の混合物が用いられ、好ましくは無水フッ化水素あるい
は無水フッ化水素とアミンの混合物が用いられる。The hydrogen fluoride used in the fluorination step may have any composition as long as it contains all hydrogen fluoride. Usually, hydrogen fluoride or a mixture of hydrogen fluoride and an amine is used, preferably anhydrous hydrogen fluoride or a mixture of anhydrous hydrogen fluoride and an amine.
フッ素化工程において使用されるフッ化水素は通常水含
有量が103IC量チ以下、好ましくは3重量%以下、
さらに好ましくは1mfik%以下のものが使用される
。The hydrogen fluoride used in the fluorination step usually has a water content of 103 IC or less, preferably 3% by weight or less,
More preferably, 1 mfik% or less is used.
フッ素化工程でフッ化水素と混合して用いることのでき
るアミンとしてはメチルアミン、エチルアミン、プロぎ
ルアミン、イソプロピルアミン、ブチルアミ〉・、シク
ロヘキシルアミン等の脂肪族−級アミン類;ジメチルア
ミン、ジエチルアミン、ジプロピルアミン、ジイソプロ
ピルアミン、ジブチルアミン、モルホリン、ピペリジン
、ぜペラジン、ジシクロヘキシルアミン等の脂肪族二級
アミン類;トリメチルアミン、トリエチルアミン、トリ
ゾロぎルアミン、トリブチルアミン、トリシクロヘキシ
ルアミン、1.4−シアずビシクロ〔2゜2.2〕オク
タン(DABCO)等の脂肪族三級アミン;アニリン、
ジフェニルアミン、トリフェニルアミン等の芳香族アミ
ン類;ぎリジン、2−ピコリン、6−ピコリン、4−ピ
コリン、キノリン、メチルキノリン類、メラミン等の含
窒素芳香族化合物などがあげられる。特にブチルアミン
、シクロヘキシルアミン、ジエチルアミン、ジグチルア
ミン、トリエスルアミン、トリブチルアミン、アニリン
、ピリジン、ピコリン類、メラミンが好ましく用いられ
る。Examples of amines that can be mixed with hydrogen fluoride in the fluorination step include aliphatic amines such as methylamine, ethylamine, progylamine, isopropylamine, butylamine, and cyclohexylamine; dimethylamine, diethylamine, Aliphatic secondary amines such as dipropylamine, diisopropylamine, dibutylamine, morpholine, piperidine, zeperazine, dicyclohexylamine; trimethylamine, triethylamine, trizorogylamine, tributylamine, tricyclohexylamine, 1,4-cyazubicyclo [2゜2.2] Aliphatic tertiary amines such as octane (DABCO); aniline,
Examples include aromatic amines such as diphenylamine and triphenylamine; nitrogen-containing aromatic compounds such as gylysine, 2-picoline, 6-picoline, 4-picoline, quinoline, methylquinolines, and melamine. In particular, butylamine, cyclohexylamine, diethylamine, digtylamine, triethylamine, tributylamine, aniline, pyridine, picolines, and melamine are preferably used.
フッ素化工程において使用することのできる7ツ化水素
−アミン混合物とは前述のフッ化水素とアミン金混合し
たもの金指すが、その組成はアミンに対するフッ化水素
分子のモル比で表わして、通常0.1〜100、好まし
くは1〜50のものが用いられる。The hydrogen heptadide-amine mixture that can be used in the fluorination process refers to the above-mentioned mixture of hydrogen fluoride and amine gold, but its composition is usually expressed as a molar ratio of hydrogen fluoride molecules to amine. The number used is 0.1 to 100, preferably 1 to 50.
フッ素化工程においては反応速度金玉げる目的で酸全触
媒として添加することも好ましい方法である。このよう
な酸としては、ギ酸、フルオロ酢酸、ジフルオロ酢酸、
トリフルオロ酢酸、クロロ酢酸、ジクロロ酢酸、トリク
ロロ酢酸等のカルボン徹類;メタンスルホン酸、トリフ
ルオロメタンスルホン酸、トリクロロメタンスルホン酸
、パラトルエンスルホン酸等のスルホン酸類;塩酸、m
酸等の鉱酸類;三フッ化ホウ素、塩化アルミニウム、フ
ッ化アルミニウム、三塩化チタン、四塩化チタン、三塩
化鉄、三フッ化鉄等のルイス酸類などが挙げられる。フ
ッ素化工程では反応が進行するにつれて副生物としてト
リフルオロ酢酸が生成してくるため、トリフルオロ酢酸
を酸触媒として使用することは反応混合物の分IRI容
易にするため特に好ましい。また副生じて(るトリフル
オロ酢酸も触媒として作用するため、添加する酸触媒の
量も少なくてよい。In the fluorination step, it is also preferable to add the acid as a total catalyst for the purpose of speeding up the reaction rate. Such acids include formic acid, fluoroacetic acid, difluoroacetic acid,
Carboxylic acids such as trifluoroacetic acid, chloroacetic acid, dichloroacetic acid, and trichloroacetic acid; Sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, trichloromethanesulfonic acid, and paratoluenesulfonic acid; hydrochloric acid,
Mineral acids such as acids; Lewis acids such as boron trifluoride, aluminum chloride, aluminum fluoride, titanium trichloride, titanium tetrachloride, iron trichloride, iron trifluoride, and the like. In the fluorination step, trifluoroacetic acid is produced as a by-product as the reaction progresses, so it is particularly preferable to use trifluoroacetic acid as an acid catalyst in order to facilitate IRI of the reaction mixture. Furthermore, since trifluoroacetic acid produced as a by-product also acts as a catalyst, the amount of acid catalyst added may be small.
フッ素化工程においてはまたフッ化セシウム、フッ化ル
ビジウム、フッ化カリウム、フッ化ナトリウム等の金属
フッ化物を添加することもできる。In the fluorination step, metal fluorides such as cesium fluoride, rubidium fluoride, potassium fluoride, and sodium fluoride can also be added.
フッ素化工程は無溶媒で行なうこともできる力ζ反応に
悪影響を及ぼさない溶媒を用いることもできる。例えば
、ジエチルエーテル、テトラヒドロ7ラン、ビフェニル
エーテルナトノエーテル類;塩化メチレン、クロロホル
ム、四塩化炭素、ジクロロエタン、トリクロロエタン、
テトラクロロエタン、フロン類などのハロゲン化炭化水
素類;クロロベンゼン、ジクロロベンゼンナトのハロゲ
ン化芳香族炭化水素類;ヘキサン、オクタン、デカン等
の脂肪族炭化水素類:ベンゼン、トルエン、キシレン等
の芳香族炭化水素類;シクロヘキサン等の脂環式炭化水
素類などが使用される。The fluorination step can be carried out without a solvent, and a solvent that does not adversely affect the force ζ reaction can also be used. For example, diethyl ether, tetrahydro7rane, biphenyl ether natonoethers; methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane,
Halogenated hydrocarbons such as tetrachloroethane and fluorocarbons; Halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzenato; Aliphatic hydrocarbons such as hexane, octane, and decane; Aromatic carbons such as benzene, toluene, and xylene Hydrogen; alicyclic hydrocarbons such as cyclohexane are used.
フッ素化工程において使用される1、1−ビス(トリフ
ルオロアセトキシ)シクロヘキサンと、フッ化水素との
量比は、フッ化水素分子の1.1−ビス(トリフルオロ
アセトキシクシクロヘキサンに対するモル比で表わして
、通常0.1〜2000、好ましくは2〜1000が用
いられる。The quantitative ratio of 1,1-bis(trifluoroacetoxy)cyclohexane and hydrogen fluoride used in the fluorination step is expressed as the molar ratio of hydrogen fluoride molecules to 1,1-bis(trifluoroacetoxycyclohexane). The number is usually 0.1 to 2000, preferably 2 to 1000.
フッ素化工程において酸触媒を添加する場合、その量は
使用する酸触媒の酸性度によっても変わるが、使用する
酸触媒の1.1−ビス(トリフルオロアセトキシ)シク
ロヘキサンに対するモル比で表わして、通常0.000
1〜1、好ましくは0.001〜0.1で充分である。When an acid catalyst is added in the fluorination step, the amount varies depending on the acidity of the acid catalyst used, but is usually expressed as a molar ratio of the acid catalyst used to 1,1-bis(trifluoroacetoxy)cyclohexane. 0.000
1 to 1, preferably 0.001 to 0.1 is sufficient.
フッ素化工程を行なう場合の反応温度及び反応時間は用
いる原料と7ツ化水素の量比、触媒の有無及び種類、溶
媒の有無などにより異なるが、通常−76℃〜150℃
、5分〜100時間であり、好ましくは一40°C〜1
00℃、5分〜50時間である。The reaction temperature and reaction time when carrying out the fluorination step vary depending on the quantitative ratio of the raw materials and hydrogen heptadide used, the presence or absence of a catalyst, the type of catalyst, the presence or absence of a solvent, etc., but are usually -76°C to 150°C.
, 5 minutes to 100 hours, preferably -40°C to 1
00°C for 5 minutes to 50 hours.
本発明におけるトリフルオロ酢酸回収工程は、前記フッ
素化工程において生成するトリフルオロ酢酸に脱水剤を
反応させることによってトリフルオロ酢酸無水物を得る
ことからなっている。The trifluoroacetic acid recovery step in the present invention consists of obtaining trifluoroacetic anhydride by reacting the trifluoroacetic acid produced in the fluorination step with a dehydrating agent.
トリフルオロ酢酸回収工程において用いられる脱水剤は
、トリフルオロ酢酸を脱水してトリフルオロ酢酸無水物
を生成し得るものであれば良く、物にその種類を規定す
るものではなく、無水酢酸、ジシクロへキシルカーポジ
イミド、メトキシアセチレン、五酸リンなどを用いるこ
とができる。五酸化リンの場合には、脱水後はリン酸と
して回収することができるため特に好ましい。The dehydrating agent used in the trifluoroacetic acid recovery process may be one that can dehydrate trifluoroacetic acid to produce trifluoroacetic anhydride, and the type is not specified. Xylcarposiimide, methoxyacetylene, phosphorus pentate, etc. can be used. In the case of phosphorus pentoxide, it is particularly preferable because it can be recovered as phosphoric acid after dehydration.
トリフルオロ酢酸回収工程において使用されるトリフル
オロ酢酸と脱水剤の量比は、使用する脱水剤の脱水能や
、脱水条件によっても変り得る。The quantitative ratio of trifluoroacetic acid and dehydrating agent used in the trifluoroacetic acid recovery step may vary depending on the dehydrating ability of the dehydrating agent used and the dehydrating conditions.
ここで脱水能を、トリフルオロ酢酸2分子がら水1分子
を脱水するのに必要な脱水剤のモル数と定義し、これを
脱水当量と呼ぶことにする。本トリフルオロ酢酸回収工
程において使用されるトリフルオロ酢酸と脱水剤の脱水
当量との比は、トリフルフルオロ酢酸に対する脱水剤の
脱水当量の比の値で表わして通常0.1〜100が使用
されるが、トリフルオロ酢酸回収効率を良好とするため
には上記の比を高くすることが好ましく、また経済的な
点から、あまり大きな比は好ましくない、従って好まし
くは上記の比の値が1〜20の範囲が用いられる。Here, the dehydration ability is defined as the number of moles of the dehydrating agent required to dehydrate one molecule of water from two molecules of trifluoroacetic acid, and this will be referred to as the dehydration equivalent. The ratio of trifluoroacetic acid used in this trifluoroacetic acid recovery step to the dehydration equivalent of the dehydrating agent is usually 0.1 to 100, expressed as the ratio of the dehydrating equivalent of the dehydrating agent to trifluoroacetic acid. However, in order to improve the trifluoroacetic acid recovery efficiency, it is preferable to make the above ratio high, and from an economic point of view, a too large ratio is not preferable. Therefore, preferably the value of the above ratio is 1 to 20. range is used.
トリフルオロ酢酸回収工程における反応温度・時間は使
用する脱水剤の種類や量によっても変化するが、通常0
−300℃、5分〜100時間であり、好ましくは10
〜150℃、10分〜50時間である。The reaction temperature and time in the trifluoroacetic acid recovery process vary depending on the type and amount of dehydrating agent used, but are usually 0.
-300℃, 5 minutes to 100 hours, preferably 10
-150°C, 10 minutes - 50 hours.
トリフルオロ酢酸回収工程において生成するトリフルオ
ロ酢酸無水物は蒸留等の操作により容易に反応混合物か
ら留去することができ、前記アシラール化工程の原料と
することができる。すなわちトリフルオロ酢酸無水物は
効率良く循環してくジかえし使用することができるため
、損失は少ない。また循環使用できない副生物は極めて
少量であジ経済的に好ましい。Trifluoroacetic anhydride produced in the trifluoroacetic acid recovery step can be easily distilled off from the reaction mixture by distillation or the like, and can be used as a raw material for the acylation step. That is, since trifluoroacetic anhydride can be efficiently circulated and reused, there is little loss. Furthermore, the amount of by-products that cannot be recycled is extremely small, which is favorable from a geoeconomic perspective.
本発明により、シクロヘキサノンとフッ化水素から、従
来は合成の容易でなかった1、1−ジフルオロシクロヘ
キサンを高収率・高選択率で製造することができる。According to the present invention, 1,1-difluorocyclohexane, which was conventionally difficult to synthesize, can be produced from cyclohexanone and hydrogen fluoride in high yield and high selectivity.
以下に実施例を示し、本発明を具体的に述べる。 EXAMPLES The present invention will be specifically described with reference to Examples below.
実施例1
シクロヘキサノン51.6 、? (0,526モル)
とトリフルオロ酢酸無水物291.1 g(1,39モ
ル)とを、予め系内金窒素置換した反応器に入れ、25
°Cで3時間攪拌した後、25°Cで72時間靜装した
。未反応のトリフルオロ酢酸無水物全留去した後の反応
混合物を蒸留することによりシクロへキサノン2.5.
9 (0,025モル)と1.1−ビス(トリフルオロ
アセトキシ)シクロヘキサン154.9(0,50モル
)を得た。Example 1 Cyclohexanone 51.6,? (0,526 mol)
and 291.1 g (1.39 mol) of trifluoroacetic anhydride were placed in a reactor in which the system was previously purged with gold nitrogen.
After stirring at °C for 3 hours, the mixture was stored at 25 °C for 72 hours. After all unreacted trifluoroacetic anhydride was distilled off, the reaction mixture was distilled to obtain cyclohexanone 2.5.
9 (0,025 mol) and 154.9 (0.50 mol) of 1,1-bis(trifluoroacetoxy)cyclohexane were obtained.
予め系内t−窒素置換した反応器へ無水フッ化水素−ぎ
りジン混合物(フッ化水素含量70重量%)600.9
(フッ化水素を21モル含有)を入れ、−30℃まで冷
却した後、攪拌しながら1.1−ビス(トリフルオロア
セトキシ)シクロヘキサン1549 (0,50モル〕
とトリフルオロ酢酸2.679 (0,02モル)を添
加した。攪拌を行ないつつ反応温度t−30℃に2時間
保った後、除々に加温することにより1時間で20℃ま
で昇温し、さらに20℃に2時間保った。反応混合物を
精留することにより、トリフルオロ酢酸114.0 <
9(1,0モル) (!: 1 、1−ジフルオロシク
ロヘキサン58.8.9 (0,49モル)1得た。Anhydrous hydrogen fluoride-Giridine mixture (hydrogen fluoride content 70% by weight) 600.9
(containing 21 moles of hydrogen fluoride), cooled to -30°C, and then added 1,1-bis(trifluoroacetoxy)cyclohexane 1549 (0.50 moles) with stirring.
and 2.679 (0.02 mol) of trifluoroacetic acid were added. After maintaining the reaction temperature at t-30°C for 2 hours while stirring, the temperature was gradually increased to 20°C in 1 hour, and further maintained at 20°C for 2 hours. By rectifying the reaction mixture, trifluoroacetic acid 114.0 <
9 (1.0 mol) (!: 58.8.9 (0.49 mol) 1 of 1,1-difluorocyclohexane was obtained.
精留塔付きの反応容器へ五酸化リン170.0.9(1
,20モルノと上記のトリフルオロ酢酸114.0、!
17 (1,0モル〕を入れ、攪拌しつつ加熱し、反応
温度を70℃に保ちながら、留出する低沸生成物全ドラ
イアイス−アセトントラップで補集した。Phosphorus pentoxide 170.0.9 (1
, 20 mol and the above trifluoroacetic acid 114.0,!
17 (1.0 mol) was added, heated with stirring, and while maintaining the reaction temperature at 70° C., all of the low-boiling products distilled out were collected in a dry ice-acetone trap.
加熱・攪拌を5時間行なった後に留出した成分全分析し
たところ、トリフルオロ酢酸無水物102.9j;l
(0,490モル)が生成していた。After heating and stirring for 5 hours, all components distilled out were analyzed and found to be 102.9j of trifluoroacetic anhydride;
(0,490 mol) was produced.
本実施例は1.1−ジフルオロシクロヘキサンがシクロ
ヘキサノンを基単として転化率95%、選択率98%で
得られること、及びトリフルオロ酢酸無水物が、反応に
より生成するトリフルオロ酢酸から、収率98%で回収
できることを示す。This example shows that 1,1-difluorocyclohexane is obtained from cyclohexanone at a conversion rate of 95% and a selectivity of 98%, and that trifluoroacetic anhydride is obtained from trifluoroacetic acid produced by the reaction at a yield of 98%. % recovery.
実施例2
シクロヘキサノン392.6 g(,1,00モルント
トリフルオロ酢酸無水物21009 (10,0モル)
とを、予め系内金窒素置換した反応器に入れ、25℃で
3時間攪拌した後、25°Cで72時間靜装した。未反
応のトリフルオロ酢酸無水物全留去した後の反応混合物
([)の組成はシクロヘキサノン15.79 (0,1
6モルノと1.1−ビス(トリフルオロアセトキシ)シ
クロヘキサン1183.!i’(3,84モル)とから
成っていた。Example 2 Cyclohexanone 392.6 g (1,00 mol) Trifluoroacetic anhydride 21009 (10,0 mol)
The mixture was placed in a reactor in which the inside of the system had been purged with gold nitrogen in advance, and the mixture was stirred at 25°C for 3 hours, and then cooled at 25°C for 72 hours. The composition of the reaction mixture ([) after all unreacted trifluoroacetic anhydride was distilled off was cyclohexanone 15.79 (0,1
6 molar and 1,1-bis(trifluoroacetoxy)cyclohexane 1183. ! i' (3.84 mol).
予め系内′に窒素置換した反応器へ無水フッ化水素39
00.!;’(195モル)?入れ、−60°Cまで冷
却した後、攪拌しながら、1.1−ビス(トリフルオロ
アセトキシクシクロヘキサンを含む上記の反応混合物(
I)を6≦加した。攪拌を行ないつつ温度’t−30’
Cに2時間保った後、除々に加温することにより1時間
で20℃まで昇温し、さらに20℃に4時間保った。反
応混合物全精留することにより、無水フッ化水素374
6g、トリフルオコ(fL8876&<7.68モル)
、シクロへキサノン15.0.9 (0,15モル)、
1.1−ジフルオロシクロヘキサン456 g(3,8
0モル)を得り。Anhydrous hydrogen fluoride 39 was added to the reactor whose system was replaced with nitrogen in advance.
00. ! ;'(195 moles)? After cooling to -60°C, the above reaction mixture containing 1,1-bis(trifluoroacetoxycyclohexane) was mixed with stirring.
6≦I) was added. Temperature 't-30' while stirring
After being kept at 20° C. for 2 hours, the temperature was gradually raised to 20° C. in 1 hour, and the temperature was further kept at 20° C. for 4 hours. By rectifying the entire reaction mixture, anhydrous hydrogen fluoride 374
6g, trifluoroco (fL8876&<7.68mol)
, cyclohexanone 15.0.9 (0.15 mol),
456 g of 1,1-difluorocyclohexane (3,8
0 mol) was obtained.
精留塔付きの反応容器へ五酸化リン1300g(9,1
5モル)と上記のトリフルオロ酢酸876.9 (7,
68モル)k入れ、攪拌しつつ加熱し、反応温度を70
°Cに保ちながら、留出する低沸生成物全ドライアイス
−アセトントラップで補集した。1300 g of phosphorus pentoxide (9,1
5 mol) and the above trifluoroacetic acid 876.9 (7,
Add 68 mol) k, heat with stirring, and raise the reaction temperature to 70 mol).
While maintaining the temperature at °C, all of the low-boiling products distilled out were collected in a dry ice-acetone trap.
加熱・攪拌全6時間行なった後に留出した成分を分析し
たところ、トリフルオロ酢酸無水物790g(3,76
モル)が生成していた。After heating and stirring for a total of 6 hours, the distilled components were analyzed and found to be 790 g (3,76 g) of trifluoroacetic anhydride.
mole) was generated.
本実施例は1.1−ジフルオロシクロヘキサンがシクロ
ヘキサノン全基準として転化率95%、選択率99%で
得られること、及びトリフルオロ酢酸無水物が、反応に
よシ生成するトリフルオロ酢酸から、収率98%で回収
できること金示す。This example shows that 1,1-difluorocyclohexane can be obtained with a conversion rate of 95% and a selectivity of 99% based on the total cyclohexanone, and that trifluoroacetic anhydride can be obtained from trifluoroacetic acid produced by the reaction in a high yield. It shows that the recovery rate is 98%.
Claims (2)
ヘキサンを製造するに当り、 ( I )シクロヘキサノンにトリフルオロ酢酸無水物を
反応させることにより1,1−ビス(トリフルオロアセ
トキシ)シクロヘキサンを得るアシラール化工程、 (II)該1,1−ビス(トリフルオロアセトキシ)シク
ロヘキサンにフッ化水素を反応させることにより1,1
−ジフルオロシクロヘキサンとトリフルオロ酢酸を得る
フッ素化工程、 及び (III)前記(II)において生成したトリフルオロ酢酸
に脱水剤を反応させることによりトリフルオロ酢酸無水
物を得るトリフルオロ酢酸回収工程 を包含することを特徴とする1,1−ジフルオロシクロ
ヘキサンの製造方法。(1) In producing 1,1-difluorocyclohexane from cyclohexanone, (I) an acylation step in which 1,1-bis(trifluoroacetoxy)cyclohexane is obtained by reacting cyclohexanone with trifluoroacetic anhydride; II) By reacting the 1,1-bis(trifluoroacetoxy)cyclohexane with hydrogen fluoride, 1,1
- a fluorination step to obtain difluorocyclohexane and trifluoroacetic acid, and (III) a trifluoroacetic acid recovery step to obtain trifluoroacetic anhydride by reacting the trifluoroacetic acid produced in (II) with a dehydrating agent. A method for producing 1,1-difluorocyclohexane, characterized in that:
請求の範囲第1項記載の方法。(2) The method according to claim 1, wherein the fluorination step is carried out in the presence of an acid catalyst.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19810386A JPH0717548B2 (en) | 1986-08-26 | 1986-08-26 | Method for producing 1,1-difluorocyclohexane |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19810386A JPH0717548B2 (en) | 1986-08-26 | 1986-08-26 | Method for producing 1,1-difluorocyclohexane |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6354331A true JPS6354331A (en) | 1988-03-08 |
JPH0717548B2 JPH0717548B2 (en) | 1995-03-01 |
Family
ID=16385539
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP19810386A Expired - Lifetime JPH0717548B2 (en) | 1986-08-26 | 1986-08-26 | Method for producing 1,1-difluorocyclohexane |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0717548B2 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006335720A (en) * | 2005-06-03 | 2006-12-14 | Asahi Kasei Corp | Method for producing polyacene compound and organic semiconductor element |
EP1985603A1 (en) * | 2007-04-27 | 2008-10-29 | SOLVAY (Société Anonyme) | Process for preparing difluorocyclohexanoic acid derivatives |
WO2008132128A2 (en) * | 2007-04-27 | 2008-11-06 | Solvay (Société Anonyme) | Synthesis of a pharmaceutically active compound |
WO2013018465A1 (en) * | 2011-07-29 | 2013-02-07 | セントラル硝子株式会社 | Method for producing geminal difluoro compound |
WO2024029524A1 (en) * | 2022-08-02 | 2024-02-08 | ダイキン工業株式会社 | Method for producing fluorine-containing aromatic compound |
-
1986
- 1986-08-26 JP JP19810386A patent/JPH0717548B2/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2006335720A (en) * | 2005-06-03 | 2006-12-14 | Asahi Kasei Corp | Method for producing polyacene compound and organic semiconductor element |
EP1985603A1 (en) * | 2007-04-27 | 2008-10-29 | SOLVAY (Société Anonyme) | Process for preparing difluorocyclohexanoic acid derivatives |
WO2008132128A2 (en) * | 2007-04-27 | 2008-11-06 | Solvay (Société Anonyme) | Synthesis of a pharmaceutically active compound |
WO2008132128A3 (en) * | 2007-04-27 | 2009-02-05 | Solvay | Synthesis of a pharmaceutically active compound |
WO2013018465A1 (en) * | 2011-07-29 | 2013-02-07 | セントラル硝子株式会社 | Method for producing geminal difluoro compound |
WO2024029524A1 (en) * | 2022-08-02 | 2024-02-08 | ダイキン工業株式会社 | Method for producing fluorine-containing aromatic compound |
Also Published As
Publication number | Publication date |
---|---|
JPH0717548B2 (en) | 1995-03-01 |
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