JP2011073985A - Method for producing difluoroacetate - Google Patents
Method for producing difluoroacetate Download PDFInfo
- Publication number
- JP2011073985A JP2011073985A JP2009224263A JP2009224263A JP2011073985A JP 2011073985 A JP2011073985 A JP 2011073985A JP 2009224263 A JP2009224263 A JP 2009224263A JP 2009224263 A JP2009224263 A JP 2009224263A JP 2011073985 A JP2011073985 A JP 2011073985A
- Authority
- JP
- Japan
- Prior art keywords
- difluoroacetic acid
- group
- reaction
- fluoride
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- PBWZKZYHONABLN-UHFFFAOYSA-M difluoroacetate Chemical compound [O-]C(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-M 0.000 title abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- KURKJXZWCPWPFX-UHFFFAOYSA-N 2,2-difluoroacetyl chloride Chemical compound FC(F)C(Cl)=O KURKJXZWCPWPFX-UHFFFAOYSA-N 0.000 claims abstract description 44
- CRLSHTZUJTXOEL-UHFFFAOYSA-N 2,2-difluoroacetyl fluoride Chemical compound FC(F)C(F)=O CRLSHTZUJTXOEL-UHFFFAOYSA-N 0.000 claims abstract description 35
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims description 89
- -1 difluoroacetic acid ester Chemical class 0.000 claims description 84
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 27
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 8
- 125000000962 organic group Chemical group 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 28
- 229910000040 hydrogen fluoride Inorganic materials 0.000 abstract description 25
- 238000000034 method Methods 0.000 description 47
- 235000019441 ethanol Nutrition 0.000 description 41
- 239000003054 catalyst Substances 0.000 description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 230000007062 hydrolysis Effects 0.000 description 18
- 238000006460 hydrolysis reaction Methods 0.000 description 18
- 238000011282 treatment Methods 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- 238000004821 distillation Methods 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- 239000007789 gas Substances 0.000 description 13
- 235000021317 phosphate Nutrition 0.000 description 13
- 229910052731 fluorine Inorganic materials 0.000 description 12
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 238000009835 boiling Methods 0.000 description 11
- 239000010452 phosphate Substances 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 235000011007 phosphoric acid Nutrition 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 8
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000007701 flash-distillation Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- YQQHEHMVPLLOKE-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-methoxyethane Chemical compound COC(F)(F)C(F)F YQQHEHMVPLLOKE-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical group O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000001349 alkyl fluorides Chemical class 0.000 description 4
- 239000000010 aprotic solvent Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- 238000010908 decantation Methods 0.000 description 4
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- ZRNSSRODJSSVEJ-UHFFFAOYSA-N 2-methylpentacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(C)C ZRNSSRODJSSVEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- GZKHDVAKKLTJPO-UHFFFAOYSA-N ethyl 2,2-difluoroacetate Chemical compound CCOC(=O)C(F)F GZKHDVAKKLTJPO-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 238000004255 ion exchange chromatography Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- PDCBZHHORLHNCZ-UHFFFAOYSA-N 1,4-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(C(F)(F)F)C=C1 PDCBZHHORLHNCZ-UHFFFAOYSA-N 0.000 description 2
- DEYAWNMYIUDQER-UHFFFAOYSA-N 1-(1,1,2,2-tetrafluoroethoxy)propane Chemical compound CCCOC(F)(F)C(F)F DEYAWNMYIUDQER-UHFFFAOYSA-N 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910000792 Monel Inorganic materials 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002802 bituminous coal Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000004775 chlorodifluoromethyl group Chemical group FC(F)(Cl)* 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000003759 ester based solvent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000003077 lignite Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- CSSYKHYGURSRAZ-UHFFFAOYSA-N methyl 2,2-difluoroacetate Chemical compound COC(=O)C(F)F CSSYKHYGURSRAZ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- CWIFAKBLLXGZIC-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-(2,2,2-trifluoroethoxy)ethane Chemical compound FC(F)C(F)(F)OCC(F)(F)F CWIFAKBLLXGZIC-UHFFFAOYSA-N 0.000 description 1
- MEVYDFZGEHEVSM-UHFFFAOYSA-N 1,1,2,2-tetrafluoro-1-(trifluoromethoxy)ethane Chemical compound FC(F)C(F)(F)OC(F)(F)F MEVYDFZGEHEVSM-UHFFFAOYSA-N 0.000 description 1
- WXGNWUVNYMJENI-UHFFFAOYSA-N 1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)F WXGNWUVNYMJENI-UHFFFAOYSA-N 0.000 description 1
- CIVGBESMFDRXNF-UHFFFAOYSA-N 1-(1,1,2,2-tetrafluoroethoxy)butane Chemical compound CCCCOC(F)(F)C(F)F CIVGBESMFDRXNF-UHFFFAOYSA-N 0.000 description 1
- SLSZYCUCKFSOCN-UHFFFAOYSA-N 1-(difluoromethoxy)-1,1,2,2-tetrafluoroethane Chemical compound FC(F)OC(F)(F)C(F)F SLSZYCUCKFSOCN-UHFFFAOYSA-N 0.000 description 1
- HBRLMDFVVMYNFH-UHFFFAOYSA-N 1-ethoxy-1,1,2,2-tetrafluoroethane Chemical compound CCOC(F)(F)C(F)F HBRLMDFVVMYNFH-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
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- 239000000908 ammonium hydroxide Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 1
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- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 0.000 description 1
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical compound FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 1
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- 125000004774 dichlorofluoromethyl group Chemical group FC(Cl)(Cl)* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
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- 239000010903 husk Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N monoethanolamine hydrochloride Natural products NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- YSWLZODWSKQJNC-UHFFFAOYSA-N propan-2-yl 2,2-difluoroacetate Chemical compound CC(C)OC(=O)C(F)F YSWLZODWSKQJNC-UHFFFAOYSA-N 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
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- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical compound FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 description 1
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、医農薬中間体、機能性材料の中間体として有用なジフルオロ酢酸エステルの製造方法に関し、より詳しくは、ジフルオロ酢酸フルオライドとアルコールとのエステル化による製造方法に関する。 The present invention relates to a method for producing difluoroacetate useful as an intermediate for medical and agricultural chemicals and functional materials, and more particularly to a method for producing esterification of difluoroacetic acid fluoride and alcohol.
ジフルオロ酢酸エステルは、（１）ジフルオロ酢酸とアルコールをエステル化する方法、（２）１−アルコキシ−１，１，２，２−テトラフルオロエタンと硫酸とシリカを反応させる方法（非特許文献１）、（３）ジフルオロ酢酸フルオライドを含む反応粗ガスをエタノールとトリエチルアミンの混合物にバブリングさせて続く水洗後塩化メチレンで抽出してジフルオロ酢酸エチルを得る方法（特許文献１）、などが知られている。 Difluoroacetic acid ester is (1) a method of esterifying difluoroacetic acid and alcohol, (2) a method of reacting 1-alkoxy-1,1,2,2-tetrafluoroethane, sulfuric acid and silica (Non-patent Document 1) (3) A method in which a reaction crude gas containing difluoroacetic acid fluoride is bubbled into a mixture of ethanol and triethylamine, followed by washing with water and extraction with methylene chloride to obtain ethyl difluoroacetate (Patent Document 1) is known.
（１）の方法では触媒が必須であるだけでなく、ジフルオロ酢酸の入手が困難であり（２）の方法では反応に伴う廃棄物が多大であるので大規模な生産には適用しがたい。（３）の方法は、得られたジフルオロ酢酸エステルを水で洗浄するところで加水分解を受けて収率を下げるおそれがある。 In the method (1), not only is a catalyst essential, but it is difficult to obtain difluoroacetic acid, and in the method (2), the amount of waste associated with the reaction is great, so that it is difficult to apply to large-scale production. In the method (3), the obtained difluoroacetic acid ester may be subjected to hydrolysis when it is washed with water, thereby reducing the yield.
一方、カルボン酸フルオライドを用いるエステル化においては副生成物としてフッ化水素が発生するため、反応装置の保護あるいは生成物への混入を避けるために種々の方法が採られている。前記特許文献文献のようにジフルオロ酢酸フルオライドとエタノールとの反応系にトリエチルアミンを添加する方法（特許文献１）、（４）アシルフルオライド基を有する化合物と酸素原子を介したケイ素原子と炭素原子の結合を有するシラン化合物を反応させる方法（特許文献２）、（５）パーフルオロカルボン酸フルオライド（例えば、ＦＯＣＣＦ（ＣＦ3）Ｏ（ＣＦ2）5ＣＯＦ）とプロパノールをモノエステル化する際に反応系にフッ化ナトリウムを添加しフッ化水素を吸着させる方法（特許文献３）など、また、反応後の反応液に含まれるフッ化水素を除くために、蒸留分離する処理または水洗する処理や（６）フッ化水素を含むジフルオロ酢酸エチル（ＣＨＦ2ＣＯＯＣ2Ｈ5）を飽和食塩水で洗浄する方法（特許文献４）などが報告されている。 On the other hand, in esterification using carboxylic acid fluoride, hydrogen fluoride is generated as a by-product, and therefore various methods have been adopted to protect the reactor or avoid mixing into the product. A method of adding triethylamine to a reaction system of difluoroacetic acid fluoride and ethanol as in the above-mentioned patent document (Patent Document 1), (4) a compound having an acyl fluoride group, a silicon atom and a carbon atom via an oxygen atom A method of reacting a silane compound having a bond (Patent Document 2), (5) a reaction system when monoesterifying perfluorocarboxylic acid fluoride (for example, FOCCF (CF 3 ) O (CF 2 ) 5 COF) and propanol For example, a method of adding sodium fluoride to adsorb hydrogen fluoride (Patent Document 3), a process of separating by distillation or a process of washing with water in order to remove hydrogen fluoride contained in the reaction liquid after the reaction (6 ) and a method of cleaning ethyl difluoroacetate containing hydrogen fluoride (CHF 2 COOC 2 H 5) with brine (Patent Document 4) It has been reported.
ジフルオロ酢酸フルオライドとアルコールからジフルオロ酢酸エステルを製造する際に副生するフッ化水素が生成物中に含まれない製造方法を提供する。 Provided is a production method in which hydrogen fluoride produced as a by-product in producing a difluoroacetic acid ester from difluoroacetic acid fluoride and alcohol is not contained in the product.
本発明者らは、ジフルオロ酢酸フルオライドからジフルオロ酢酸エステルを製造する際に副生するフッ化水素を慣用的な水洗浄により除去するとジフルオロ酢酸エステルの加水分解が顕著で収率の低下を招くため、その方法に代えるべく反応系中において実質的にフッ化水素を固定する方法について検討したところ、一旦ジフルオロ酢酸フルオライドをジフルオロ酢酸クロライドに転換した後、ジフルオロ酢酸クロライドとアルコールを接触させることでフッ化水素が実質的に含まないジフルオロ酢酸エステルを効率的に得られることを見出し、本発明に至った。また、ジフルオロ酢酸フルオライドを塩化リチウムと接触させた後、その系中へアルコール導入して反応させることでジフルオロ酢酸エステルが得られることを見出した。 When the present inventors remove hydrogen fluoride by-produced when producing difluoroacetic acid ester from difluoroacetic acid fluoride by conventional water washing, hydrolysis of difluoroacetic acid ester is remarkable, resulting in a decrease in yield. In order to replace the method, the method of substantially fixing hydrogen fluoride in the reaction system was examined. After difluoroacetic acid fluoride was once converted to difluoroacetic acid chloride, hydrogen fluoride was brought into contact with difluoroacetic acid chloride and alcohol. The present inventors have found that a difluoroacetic acid ester substantially free from can be obtained efficiently and have reached the present invention. Further, it was found that difluoroacetic acid ester can be obtained by bringing difluoroacetic acid fluoride into contact with lithium chloride and then introducing alcohol into the system for reaction.
本発明に係る反応は次の反応式に従う。 The reaction according to the present invention follows the following reaction formula.
ＣＨＦ2ＣＯＦ ＋ ＬｉＣｌ → ＣＨＦ2ＣＯＣｌ ＋ ＬｉＦ
ＣＨＦ2ＣＯＣｌ ＋ ＲＯＨ → ＣＨＦ2ＣＯＯＲ ＋ ＨＣｌ
− − − − − − − − − − − − − − − − − − − −
ＣＨＦ2ＣＯＦ ＋ ＲＯＨ ＋ ＬｉＣｌ →
→ ＣＨＦ2ＣＯＯＲ ＋ ＨＣｌ ＋ ＬｉＦ
ここで、イオン半径の小さいフッ素アニオンは、イオン半径の大きなカリウムカチオンやナトリウムカチオンよりも、イオン半径の小さいリチウムカチオンと安定な塩を形成する。すなわち、塩化リチウムに代えて、塩化ナトリウムや塩化カリウムを用いた場合、逆反応が起こり、目論み通りにエステルを効率的に合成することは困難である。また、本発明の方法は、ジフルオロ酢酸フルオライドが塩化リチウムによりジフルオロ酢酸クロライドとした後にアルコールを添加することによっても実施することができるが、予めアルコールを仕込んだ反応系における反応機構は審らかでない。
CHF 2 COF + LiCl → CHF 2 COCl + LiF
CHF 2 COCl + ROH → CHF 2 COOR + HCl
--------------------
CHF 2 COF + ROH + LiCl →
→ CHF 2 COOR + HCl + LiF
Here, the fluorine anion having a small ionic radius forms a more stable salt with a lithium cation having a smaller ionic radius than a potassium cation or a sodium cation having a larger ionic radius. That is, when sodium chloride or potassium chloride is used instead of lithium chloride, a reverse reaction occurs and it is difficult to efficiently synthesize an ester as intended. The method of the present invention can also be carried out by adding alcohol after difluoroacetic acid fluoride is converted to difluoroacetic acid chloride with lithium chloride, but the reaction mechanism in the reaction system charged with alcohol in advance is not suspected. .
本発明は次の通りである。
［発明１］一般式（１）
ＲＯＨ （１）
（式中、Ｒはアルキル基である。）で表されるアルコールとジフルオロ酢酸クロライドとを反応させることからなる一般式（２）
ＣＨＦ2ＣＯＯＲ （２）
（式中、Ｒは一般式（１）におけると同じ。）で表されるジフルオロ酢酸エステルの製造方法。
［発明２］一般式（１）で表されるアルコールが、式中のＲが炭素数１〜４のアルキル基である発明１。
［発明３］ジフルオロ酢酸クロライドが、ジフルオロ酢酸フルオライドと塩化リチウムとを接触させて得られたジフルオロ酢酸クロライドである発明１または２。
［発明４］ジフルオロ酢酸クロライドが、ジフルオロ酢酸フルオライドと塩化リチウムとを０〜１００℃において接触させて得られたジフルオロ酢酸クロライドである発明１〜３のいずれか。
［発明５］ジフルオロ酢酸フルオライドが、ＣＨＦ2ＣＦ2ＯＲ’（Ｒ’は、一価の有機基を表す。）で表される１−アルコキシ−１，１，２，２−テトラフルオロエタンを熱分解して得られた熱分解生成物である発明１〜４のいずれか。
［発明６］発明１〜５のいずれかの製造方法を溶媒の存在下で行うことからなるジフルオロ酢酸エステルの製造方法。
［発明７］溶媒が該反応により製造されるべきジフルオロ酢酸エステルである発明６。
［発明８］ジフルオロ酢酸クロライドをジフルオロ酢酸フルオライドと塩化リチウムとを接触させて得る工程と発明１〜７のいずれかの製造方法を同一の反応容器で行うジフルオロ酢酸エステルの製造方法。
［発明９］ジフルオロ酢酸エステルを生成する反応を−５０〜１２０℃で行うことからなる請求項１〜８のいずれか。
The present invention is as follows.
[Invention 1] General formula (1)
ROH (1)
(Wherein R is an alkyl group) and the general formula (2) comprising reacting an alcohol represented by difluoroacetic acid chloride
CHF 2 COOR (2)
(Wherein R is the same as in general formula (1)).
[Invention 2] Invention 1 wherein the alcohol represented by the general formula (1) is an alkyl group having 1 to 4 carbon atoms in the formula.
[Invention 3] Invention 1 or 2, wherein the difluoroacetic acid chloride is difluoroacetic acid chloride obtained by contacting difluoroacetic acid fluoride with lithium chloride.
[Invention 4] Any of Inventions 1 to 3, wherein the difluoroacetic acid chloride is difluoroacetic acid chloride obtained by contacting difluoroacetic acid fluoride and lithium chloride at 0 to 100 ° C.
[Invention 5] Difluoroacetic acid fluoride heats 1-alkoxy-1,1,2,2-tetrafluoroethane represented by CHF 2 CF 2 OR ′ (R ′ represents a monovalent organic group). Any one of inventions 1 to 4 which is a thermal decomposition product obtained by decomposition.
[Invention 6] A process for producing a difluoroacetic acid ester comprising performing the production process of any one of Inventions 1 to 5 in the presence of a solvent.
[Invention 7] Invention 6 wherein the solvent is a difluoroacetic acid ester to be produced by the reaction.
[Invention 8] A process for producing difluoroacetic acid ester, wherein the step of obtaining difluoroacetic acid chloride by contacting difluoroacetic acid fluoride and lithium chloride and the production process of any one of Inventions 1 to 7 in the same reaction vessel.
[Invention 9] The reaction according to any one of claims 1 to 8, wherein the reaction for producing a difluoroacetic acid ester is carried out at -50 to 120 ° C.
本発明の方法は、生成物中にフッ化水素が混入することがなく水洗による精製操作を要しないため、工程が簡略化されるだけでなく、加水分解による損失がなく高い収率を達成できる。 The method of the present invention does not include hydrogen fluoride in the product and does not require a purification operation by washing with water, so that not only the process is simplified but also a high yield can be achieved without loss due to hydrolysis. .
本発明は、一般式（１）
ＲＯＨ （１）
（式中、Ｒはアルキル基である。）で表されるアルコールとジフルオロ酢酸クロライドとを反応させることからなる一般式（２）
ＣＨＦ2ＣＯＯＲ （２）
（式中、Ｒは一般式（１）におけると同じ。）で表されるジフルオロ酢酸エステルの製造方法であり、ジフルオロ酢酸クロライドは任意の方法で得られたものが使用可能であるが、ジフルオロ酢酸フルオライドからハロゲン変換で容易に得ることができる。本明細書において、ジフルオロ酢酸クロライドを製造する工程を第一工程、ジフルオロ酢酸エステルを製造する工程を第二工程と称する。
The present invention relates to a general formula (1)
ROH (1)
(Wherein R is an alkyl group) and the general formula (2) comprising reacting an alcohol represented by difluoroacetic acid chloride
CHF 2 COOR (2)
(Wherein R is the same as in general formula (1)), and difluoroacetic acid chloride can be obtained by any method, but difluoroacetic acid chloride can be used. It can be easily obtained from fluoride by halogen conversion. In this specification, the process for producing difluoroacetic acid chloride is referred to as the first process, and the process for producing difluoroacetic acid ester is referred to as the second process.
第一工程で得られるジフルオロ酢酸クロライドを精製してから第二工程の原料とすることができ、また、第一工程で得られるジフルオロ酢酸クロライドを精製しないで、反応系にアルコールを追加導入して第二工程の反応を行うこともできる。 After purifying the difluoroacetic acid chloride obtained in the first step, it can be used as the raw material for the second step, and without introducing the difluoroacetic acid chloride obtained in the first step, an additional alcohol is introduced into the reaction system. The reaction in the second step can also be performed.
第一工程でジフルオロ酢酸クロライドの製造について詳述する。 The production of difluoroacetic acid chloride in the first step will be described in detail.
一般式（１）で表されるアルコールのＲは、炭素数１〜８のアルキル基（明細書において「アルキル基」は、別途限定がない限り、直鎖状、分岐状、および環状を併せ称する。）または炭素数１〜８の含フッ素アルキル基であり、炭素数１〜４のアルキル基または炭素数１〜４の含フッ素アルキル基であるのが好ましい。具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基を例として挙げることができ、好ましい低級アルキル基としては、具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基が該当し、メチル基、エチル基、イソプロピル基が好ましく、エチル基が特に好ましい。 R of the alcohol represented by the general formula (1) is an alkyl group having 1 to 8 carbon atoms (in the specification, the “alkyl group” collectively refers to linear, branched, and cyclic unless otherwise specified. Or a fluorine-containing alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms or a fluorine-containing alkyl group having 1 to 4 carbon atoms. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, and an isopentyl group can be mentioned as examples. Specific examples of the lower alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, and a t-butyl group. Group is preferred, and ethyl group is particularly preferred.
シクロアルキル基としては、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基などを挙げることができる。 Examples of the cycloalkyl group include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
含フッ素アルキル基としては、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、ジクロロフルオロメチル基、クロロジフルオロメチル基、ブロモジフルオロメチル基、ジブロモフルオロメチル基、２，２，２−トリフルオロエチル基、ペンタフルオロエチル基、２，２，３，３，３−ペンタフルオロプロピル基、ｎ−ヘプタフルオロプロピル基、１，１，１，３，３，３−ヘキサフルオロイソプロピル基などを例として挙げることができる。 The fluorine-containing alkyl group includes a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichlorofluoromethyl group, a chlorodifluoromethyl group, a bromodifluoromethyl group, a dibromofluoromethyl group, and a 2,2,2-trifluoroethyl group. , Pentafluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, n-heptafluoropropyl group, 1,1,1,3,3,3-hexafluoroisopropyl group, etc. Can do.
アルコールとして好ましいものとしては、メチルアルコール、エチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、ｓ−ブチルアルコール、ｔ−ブチルアルコールを挙げることができる。特に好ましいものとしては、メチルアルコール、エチルアルコール、イソプロピルアルコールを挙げることができる。 Preferred examples of the alcohol include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, s-butyl alcohol, and t-butyl alcohol. Particularly preferred are methyl alcohol, ethyl alcohol, and isopropyl alcohol.
ジフルオロ酢酸フルオライドは、どの様な方法で製造されたものであってよい。例えば、（１）ジフルオロ酢酸を五酸化リンや塩化チオニルなどと反応させてからフッ化カリウムなどの金属フッ化物でフッ素化させる方法、（２）ＣＨＦ2ＣＦ2ＯＲで表される１−アルコキシ−１，１，２，２−テトラフルオロエタンを三酸化硫黄とフルオロ硫酸の存在下で分解させる方法（非特許文献１）、（３）１−アルコキシ−１，１，２，２−テトラフルオロエタンをハロゲン化アンチモン、ハロゲン化チタンなどの触媒存在下で反応させる方法（特許文献１）、（４）１−アルコキシ−１，１，２，２−テトラフルオロエタンを、触媒の存在下に熱分解させてジフルオロ酢酸フルオライドを製造する方法（特許文献２）が知られている。 The difluoroacetic acid fluoride may be produced by any method. For example, (1) a method in which difluoroacetic acid is reacted with phosphorus pentoxide, thionyl chloride, etc. and then fluorinated with a metal fluoride such as potassium fluoride, (2) 1-alkoxy- represented by CHF 2 CF 2 OR Method of decomposing 1,1,2,2-tetrafluoroethane in the presence of sulfur trioxide and fluorosulfuric acid (Non-patent Document 1), (3) 1-alkoxy-1,1,2,2-tetrafluoroethane In the presence of a catalyst such as antimony halide or titanium halide (Patent Document 1), (4) 1-alkoxy-1,1,2,2-tetrafluoroethane is thermally decomposed in the presence of a catalyst And a method for producing difluoroacetic acid fluoride (Patent Document 2) is known.
本発明の第一工程の方法では、ジフルオロ酢酸フルオライドは、１−アルコキシ−１，１，２，２−テトラフルオロエタンを、触媒の存在下に熱分解させて得られたものが好ましく用いられる。この反応は、以下の式で表わされる。 In the method of the first step of the present invention, difluoroacetic acid fluoride is preferably obtained by thermally decomposing 1-alkoxy-1,1,2,2-tetrafluoroethane in the presence of a catalyst. This reaction is represented by the following formula.
ＣＨＦ2ＣＦ2ＯＲ’ → ＣＨＦ2ＣＯＦ ＋ Ｒ’Ｆ
この反応の出発原料である一般式ＣＨＦ2ＣＦ2ＯＲ’（Ｒ’は、一価の有機基を表す。）で表される１−アルコキシ−１，１，２，２−テトラフルオロエタンのＲ’は脱離基であるので特に限定されないが、分岐を有することもある炭素数１〜８のアルキル基、アルキル基を置換基として有することもあるシクロアルキル基、含フッ素アルキル基、アリール基、アラルキル基を挙げることができ、これらのうちアルキル基または含フッ素アルキル基が好ましく、アルキル基がより好ましく、低級アルキル基がさらに好ましい。低級アルキル基とは、炭素数１〜４のアルキル基をいう。
CHF 2 CF 2 OR '→ CHF 2 COF + R'F
R of 1-alkoxy-1,1,2,2-tetrafluoroethane represented by the general formula CHF 2 CF 2 OR ′ (R ′ represents a monovalent organic group) which is a starting material for this reaction. 'Is a leaving group and is not particularly limited. However, it may have a branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group that may have an alkyl group as a substituent, a fluorine-containing alkyl group, an aryl group, An aralkyl group can be mentioned, and among these, an alkyl group or a fluorine-containing alkyl group is preferable, an alkyl group is more preferable, and a lower alkyl group is more preferable. The lower alkyl group refers to an alkyl group having 1 to 4 carbon atoms.
分岐を有することもある炭素数１〜８のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基を例として挙げることができ、低級アルキル基としては、具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基が該当する。 Examples of the alkyl group having 1 to 8 carbon atoms that may have a branch include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, and n-pentyl group. An isopentyl group can be given as an example. Specific examples of the lower alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, and a t-butyl group. Is applicable.
アルキル基を置換基として有することもあるシクロアルキル基としては、シクロブチル基、シクロペンチル基、２−メチルシクロペンチル基、３−メチルシクロペンチル基、２−エチルシクロペンチル基、３−エチルシクロペンチル基、シクロヘキシル基、２−メチルシクロヘキシル基、３−メチルシクロヘキシル基、４−メチルシクロヘキシル基、２−エチルシクロヘキシル基、３−エチルシクロヘキシル基、４−エチルシクロヘキシル基、シクロヘプチル基、２−メチルシクロヘプチル基、３−メチルシクロヘプチル基、３−メチルシクロヘプチル基、４−メチルシクロヘプチル基などを挙げることができる。 Examples of the cycloalkyl group that may have an alkyl group as a substituent include a cyclobutyl group, a cyclopentyl group, a 2-methylcyclopentyl group, a 3-methylcyclopentyl group, a 2-ethylcyclopentyl group, a 3-ethylcyclopentyl group, a cyclohexyl group, and 2 -Methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2-ethylcyclohexyl group, 3-ethylcyclohexyl group, 4-ethylcyclohexyl group, cycloheptyl group, 2-methylcyclohexyl group, 3-methylcyclohexane A heptyl group, 3-methylcycloheptyl group, 4-methylcycloheptyl group, etc. can be mentioned.
アリール基としては、フェニル基、２−メチルフェニル基、３−メチルフェニル基、４−メチルフェニル基、２，３−ジメチルフェニル基、２，４−ジメチルフェニル基、２，５−ジメチルフェニル基、２，６−ジメチルフェニル基、３，４−ジメチルフェニル基、３，５−ジメチルフェニル基、３，６−ジメチルフェニル基、２−メトキシフェニル基、３−メトキシフェニル基、４−メトキシフェニル基、１−ナフチル基、２−ナフチル基などを例として挙げることができる。 As the aryl group, phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 3,6-dimethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, Examples include 1-naphthyl group, 2-naphthyl group and the like.
含フッ素アルキル基としては、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基、クロロフルオロメチル基、クロロジフルオロメチル基、ブロモフルオロメチル基、ジブロモフルオロメチル基、２，２，２−トリフルオロエチル基、ペンタフルオロエチル基、２，２，３，３，３−ペンタフルオロプロピル基、ｎ−ヘキサフルオロプロピル基、ヘキサフルオロイソプロピル基などを例として挙げることができる。 The fluorine-containing alkyl group includes a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chlorofluoromethyl group, a chlorodifluoromethyl group, a bromofluoromethyl group, a dibromofluoromethyl group, and a 2,2,2-trifluoroethyl group. And pentafluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, n-hexafluoropropyl group, hexafluoroisopropyl group and the like.
アラルキル基としては、フェネチル基、２−メチルフェニルメチル基、３−メチルフェニルメチル基、４−メチルフェニルメチル基、２，３−ジメチルフェニルメチル基、２，４−ジメチルフェニルメチル基、２，５−ジメチルフェニルメチル基、２，６−ジメチルフェニルメチル基、３，４−ジメチルフェニルメチル基、３，５−ジメチルフェニルメチル基、３，６−ジメチルフェニルメチル基、４−エチルフェニルメチル基、４−（ｎ−プロピル）メチルフェニルメチル基、４−（ｎ−ブチル）メチルフェニルメチル基などを例として挙げることができる。 Examples of the aralkyl group include phenethyl group, 2-methylphenylmethyl group, 3-methylphenylmethyl group, 4-methylphenylmethyl group, 2,3-dimethylphenylmethyl group, 2,4-dimethylphenylmethyl group, 2,5 -Dimethylphenylmethyl group, 2,6-dimethylphenylmethyl group, 3,4-dimethylphenylmethyl group, 3,5-dimethylphenylmethyl group, 3,6-dimethylphenylmethyl group, 4-ethylphenylmethyl group, 4 Examples include-(n-propyl) methylphenylmethyl group and 4- (n-butyl) methylphenylmethyl group.
１−アルコキシ−１，１，２，２−テトラフルオロエタンは、公知の製造方法で得ることができる。例えば、アルコール（Ｒ’ＯＨ）とテトラフルオロエチレンを塩基の存在下に反応させる方法で合成できる。 1-alkoxy-1,1,2,2-tetrafluoroethane can be obtained by a known production method. For example, it can be synthesized by a method in which alcohol (R′OH) and tetrafluoroethylene are reacted in the presence of a base.
具体的には、メタノールとテトラフルオロエチレンとを水酸化カリウムの存在下に反応させる方法により１−メトキシ−１，１，２，２−テトラフルオロエタンが合成できる（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，７３，１３２９（１９５１））。 Specifically, 1-methoxy-1,1,2,2-tetrafluoroethane can be synthesized by a method in which methanol and tetrafluoroethylene are reacted in the presence of potassium hydroxide (J. Am. Chem. Soc. 73, 1329 (1951)).
本発明の第一工程において使用できる含フッ素エーテルの具体例としては、以下のものが挙げられるが、これらに限定されない。
１−メトキシ−１，１，２，２−テトラフルオロエタン（ＣＨＦ2ＣＦ2ＯＭｅ）、１−エトキシ−１，１，２，２−テトラフルオロエタン（ＣＨＦ2ＣＦ2ＯＥｔ）、１−（ｎ−プロポキシ）−１，１，２，２−テトラフルオロエタン、１−イソプロポキシ−１，１，２，２−テトラフルオロエタン、１−（ｎ−ブトキシ）−１，１，２，２−テトラフルオロエタン、１−（ｓ−ブトキシ）−１，１，２，２−テトラフルオロエタン、１−（ｔ−ブトキシ）−１，１，２，２−テトラフルオロエタン、１−トリフルオロメトキシ−１，１，２，２−テトラフルオロエタン、１−ジフルオロメトキシ−１，１，２，２−テトラフルオロエタン、１−（２，２，２−トリフルオロエトキシ）−１，１，２，２−テトラフルオロエタン、１−ペンタフルオロエトキシ−１，１，２，２−テトラフルオロエタン、１−（２，２，２，３，３−ペンタフルオロプロポキシ）−１，１，２，２−テトラフルオロエタン、１−ヘキサフルオロイソプロポキシ−１，１，２，２−テトラフルオロエタンなどを挙げることができる。
Specific examples of the fluorine-containing ether that can be used in the first step of the present invention include, but are not limited to, the following.
1-methoxy-1,1,2,2-tetrafluoroethane (CHF 2 CF 2 OMe), 1-ethoxy-1,1,2,2-tetrafluoroethane (CHF 2 CF 2 OEt), 1- (n -Propoxy) -1,1,2,2-tetrafluoroethane, 1-isopropoxy-1,1,2,2-tetrafluoroethane, 1- (n-butoxy) -1,1,2,2-tetra Fluoroethane, 1- (s-butoxy) -1,1,2,2-tetrafluoroethane, 1- (t-butoxy) -1,1,2,2-tetrafluoroethane, 1-trifluoromethoxy-1 , 1,2,2-tetrafluoroethane, 1-difluoromethoxy-1,1,2,2-tetrafluoroethane, 1- (2,2,2-trifluoroethoxy) -1,1,2,2- Tetrafluoroethane, 1-pen Fluoroethoxy-1,1,2,2-tetrafluoroethane, 1- (2,2,2,3,3-pentafluoropropoxy) -1,1,2,2-tetrafluoroethane, 1-hexafluoroiso Examples thereof include propoxy-1,1,2,2-tetrafluoroethane.
熱分解に使用する触媒は固体触媒であり、特開平８−９２１６２号公報に記載された金属酸化物、金属フッ素化酸化物を触媒として使用できる。触媒としてはさらにリン酸塩も使用できる。リン酸塩は、担体に担持されたものであってもよい。 The catalyst used for thermal decomposition is a solid catalyst, and metal oxides and metal fluorinated oxides described in JP-A-8-92162 can be used as the catalyst. Phosphate can also be used as the catalyst. The phosphate may be supported on a carrier.
リン酸としては、オルトリン酸、ポリリン酸、メタリン酸のいずれであってもよい。ポリリン酸としては、ピロリン酸などが挙げられる。リン酸塩は、これらのリン酸の金属塩である。取り扱いが容易であるのでオルトリン酸であるのが好ましい。リン酸塩とは、これらのリン酸の金属塩をいうが、本明細書では金属が水素原子に置換した酸をも金属塩というものとする。 As phosphoric acid, any of orthophosphoric acid, polyphosphoric acid, and metaphosphoric acid may be used. Examples of polyphosphoric acid include pyrophosphoric acid. Phosphate is the metal salt of these phosphoric acids. Since it is easy to handle, orthophosphoric acid is preferred. Phosphate refers to a metal salt of these phosphoric acids. In this specification, an acid in which a metal is substituted with a hydrogen atom is also referred to as a metal salt.
リン酸塩としては、特に限定されないが、水素、アルミニウム、ホウ素、アルカリ土類金属、チタン、ジルコニウム、ランタン、セリウム、イットリウム、希土類金属、バナジウム、ニオブ、クロム、マンガン、鉄、コバルト、ニッケルからなる群より選ばれた、少なくとも１種の金属のリン酸塩が挙げられる。好ましくは、主成分としてリン酸アルミニウム、リン酸セリウム、リン酸ホウ素、リン酸チタン、リン酸ジルコニウム、リン酸クロムなどである。副成分の金属を含むことも好ましい。具体的な副成分としてはセリウム、ランタン、イットリウム、クロム、鉄、コバルト、ニッケル等が好ましいが、セリウム、鉄、イットリウムがより好ましい。これらのうちで、さらに好ましくは、リン酸アルミニウム、リン酸セリウムおよびこれら二種からなるリン酸塩である。 The phosphate is not particularly limited, but is composed of hydrogen, aluminum, boron, alkaline earth metal, titanium, zirconium, lanthanum, cerium, yttrium, rare earth metal, vanadium, niobium, chromium, manganese, iron, cobalt, nickel. And at least one metal phosphate selected from the group. Preferably, the main component is aluminum phosphate, cerium phosphate, boron phosphate, titanium phosphate, zirconium phosphate, chromium phosphate, or the like. It is also preferable that the metal of a subsidiary component is included. As specific subcomponents, cerium, lanthanum, yttrium, chromium, iron, cobalt, nickel and the like are preferable, but cerium, iron and yttrium are more preferable. Of these, aluminum phosphate, cerium phosphate, and phosphates composed of these two types are more preferable.
触媒の調製方法に特に制限はなく、市販のリン酸塩をそのまま使っても良いし、一般的な沈殿方法でも良い。沈殿方法の具体的な調製方法としては、例えば、金属の硝酸塩（複数の原料塩の場合はそれぞれの原料塩の溶液を調製する）とリン酸の混合水溶液に、希釈アンモニア水を滴下してｐＨを調節して沈殿させ、必要に応じて熟成させるために放置する。その後、水洗し、洗浄水の電導度などで十分に水洗したことを確認する。場合によっては、スラリーの一部を取り含有するアルカリ金属を測定する。次いで濾過し乾燥する。乾燥する温度に特に制限はない。好ましくは８０℃〜１５０℃がよい。さらに好ましくは１００℃〜１３０℃である。得られた乾燥体は粉砕し粒度を揃えるか、さらに粉砕し成型する。その後、２００℃〜１５００℃の条件で空気や窒素雰囲気で焼成する。好ましくは４００〜１３００℃、さらに好ましくは５００℃〜９００℃で焼成を行うことがよい。 The method for preparing the catalyst is not particularly limited, and a commercially available phosphate may be used as it is, or a general precipitation method may be used. As a specific preparation method of the precipitation method, for example, diluted ammonia water is added dropwise to a mixed aqueous solution of metal nitrate (in the case of a plurality of raw salt, each raw salt solution is prepared) and phosphoric acid to adjust the pH. To allow precipitation to occur and leave for aging if necessary. Then, it is washed with water and it is confirmed that it has been sufficiently washed with the conductivity of the washing water. In some cases, alkali metal containing a portion of the slurry is measured. It is then filtered and dried. There is no particular limitation on the drying temperature. Preferably 80 to 150 degreeC is good. More preferably, it is 100 degreeC-130 degreeC. The obtained dried product is pulverized to uniform particle size, or further pulverized and molded. Thereafter, firing is performed in an air or nitrogen atmosphere at 200 ° C. to 1500 ° C. The firing is preferably performed at 400 to 1300 ° C, more preferably 500 to 900 ° C.
焼成時間は温度にもよるが１時間〜５０時間程度で、好ましくは２時間〜２４時間程度である。焼成処理は、リン酸塩の安定化に必要な処理であるので、上記の温度範囲より低温で処理を行ったり、処理時間が短い場合は、反応初期において十分に触媒活性を示さないことがある。また、上記の温度範囲以上でまたは長時間焼成処理を行うことは、過剰な加熱エネルギーを要するだけでなく、触媒の結晶化を引き起こすことがあるので好ましくない。 Although depending on the temperature, the firing time is about 1 to 50 hours, preferably about 2 to 24 hours. Since the calcination treatment is a treatment necessary for stabilizing the phosphate, if the treatment is performed at a temperature lower than the above temperature range or the treatment time is short, the catalyst activity may not be sufficiently exhibited at the initial stage of the reaction. . In addition, it is not preferable to perform the calcination treatment at a temperature higher than the above temperature range or for a long time because not only excessive heating energy is required but also crystallization of the catalyst may occur.
主成分以外の金属成分の添加の操作は、金属塩で行うことが好ましく、前記金属の硝酸塩、塩化物、酸化物、リン酸塩などが好ましい。中でも、硝酸塩が調製しやすく好ましい。添加量に特に制限はないが、一般にはリン１グラム原子に対し１グラム原子以下であり、好ましくは０．５グラム原子以下である。より好ましくは０．３グラム原子以下である。これらの金属成分の添加は、触媒調製時に行っても良く、また、触媒焼成後のリン酸塩に行っても良い。得られた触媒は、金属塩の種類及び調製方法や条件により物性が異なる。触媒は、そのまま使用してよいが、担体に担持した状態で使用することも可能である。担体としては、アルミナ、チタニア、ジルコニア、硫酸ジルコニア（ＺｒＯ（ＳＯ4））
などの金属酸化物などの金属酸化物、炭化珪素、窒化珪素、活性炭等が挙げられるが、比表面積の大きい活性炭は特に好ましい。
The operation of adding a metal component other than the main component is preferably performed with a metal salt, and nitrates, chlorides, oxides, phosphates, and the like of the metal are preferable. Among them, nitrate is preferable because it is easy to prepare. Although there is no restriction | limiting in particular in addition amount, Generally it is 1 gram atom or less with respect to 1 gram atom of phosphorus, Preferably it is 0.5 gram atom or less. More preferably, it is 0.3 gram atom or less. The addition of these metal components may be performed at the time of catalyst preparation, or may be performed on the phosphate after the catalyst is calcined. The obtained catalyst has different physical properties depending on the type of metal salt and the preparation method and conditions. The catalyst may be used as it is, but it can also be used in a state of being supported on a carrier. As support, alumina, titania, zirconia, zirconia sulfate (ZrO (SO4))
Examples thereof include metal oxides such as metal oxides, silicon carbide, silicon nitride, activated carbon, etc., and activated carbon having a large specific surface area is particularly preferable.
リン酸またはリン酸塩を坦持した活性炭は、リン酸に浸漬して含浸させ、またはスプレーにより被覆もしくは吸着させたものを乾燥させて調製できる。化合物を担持させる場合、担持させる化合物の溶液を含浸させ、またはスプレーにより被覆もしくは吸着させたものを乾燥させて調製できる。また、その化合物の溶液を含浸させ、またはスプレーにより被覆もしくは吸着させた活性炭に対し第二の化合物を作用させて活性炭表面で沈殿反応等を生じさせることで最初の化合物と異なる化合物を担持することもできる。また、先に述べた、リン酸塩の調整方法を活性炭などの担体の存在下で行うことでもリン酸塩担持触媒を調製することができる。具体例として実施例にリン酸アルミニウム担持活性炭を示す。 Activated carbon carrying phosphoric acid or phosphate can be prepared by immersing it in phosphoric acid and impregnating it, or drying and coating or adsorbing it by spraying. In the case of loading a compound, it can be prepared by impregnating a solution of the compound to be loaded, or drying a coating or adsorbed by spraying. In addition, a second compound is allowed to act on activated carbon impregnated with a solution of the compound, or coated or adsorbed by spraying, thereby causing a precipitation reaction or the like on the activated carbon surface to carry a compound different from the first compound. You can also. Further, the phosphate-carrying catalyst can also be prepared by carrying out the above-described phosphate preparation method in the presence of a support such as activated carbon. As an example, activated carbon supporting aluminum phosphate is shown in the examples.
活性炭は、木材、木炭、椰子殻炭、パーム核炭、素灰等を原料とする植物系、泥炭、亜炭、褐炭、瀝青炭、無煙炭等を原料とする石炭系、石油残滓、オイルカーボン等を原料とする石油系または炭化ポリ塩化ビニリデン等の合成樹脂系等のいずれのものでもよい。これら市販の活性炭から選択し使用することができ、例えば、瀝青炭から製造された活性炭（東洋カルゴン製ＢＰＬ粒状活性炭）、椰子殻炭（日本エンバイロケミカルズ製粒状白鷺ＧＸ、ＳＸ、ＣＸ、ＸＲＣ、東洋カルゴン製ＰＣＢ）等が挙げられるが、これらに限定されない。形状、大きさも通常粒状で用いられるが、球状、繊維状、粉体状、ハニカム状等反応器に適合すれば通常の知識範囲の中で使用することができる。 Activated carbon is made from plant-based, peat, lignite, lignite, bituminous coal, anthracite, etc. that are made from wood, charcoal, coconut husk, palm kernel charcoal, raw ash, etc. Any of petroleum type or synthetic resin type such as carbonized polyvinylidene chloride may be used. These activated carbons can be selected and used. For example, activated carbon produced from bituminous coal (BPL granular activated carbon manufactured by Toyo Calgon), coconut shell charcoal (granular white birch GX, SX, CX, XRC manufactured by Nippon Enviro Chemicals), Toyo Calgon PCB) and the like, but is not limited thereto. The shape and size are usually used in a granular form, but can be used within a normal knowledge range as long as it is suitable for a reactor such as a sphere, fiber, powder, or honeycomb.
熱分解反応の担体として使用する活性炭は比表面積の大きな活性炭が好ましい。活性炭の比表面積は、市販品の規格の範囲で十分であるが、それぞれ４００ｍ2／ｇ〜３０００ｍ2／ｇであり、８００ｍ2／ｇ〜２０００ｍ2／ｇが好ましい。さらに活性炭を担体に用いる場合、水酸化アンモニウム、水酸化ナトリウム、水酸化カリウム等の塩基性水溶液に常温付近で１０時間程度またはそれ以上の時間浸漬するか、活性炭を触媒担体に使用する際に通常行われる硝酸、塩酸、フッ酸等の酸による前処理を施し、予め担体表面の活性化ならびに灰分の除去を行うことが望ましい。 The activated carbon used as the carrier for the thermal decomposition reaction is preferably activated carbon having a large specific surface area. The specific surface area of the activated carbon is sufficient within the range of the standard of commercial products, but is 400 m 2 / g to 3000 m 2 / g, preferably 800 m 2 / g to 2000 m 2 / g. Furthermore, when using activated carbon as a support, it is usually immersed in a basic aqueous solution such as ammonium hydroxide, sodium hydroxide, potassium hydroxide or the like for about 10 hours or longer at room temperature or when activated carbon is used as a catalyst support. It is desirable to perform pretreatment with acid such as nitric acid, hydrochloric acid, hydrofluoric acid, etc. to activate the carrier surface and remove ash in advance.
また、本発明の酸化物などの担体は、金属成分と酸素以外の他の原子を含んでいてもよく、他の原子としては、フッ素原子、塩素原子等が好ましい。たとえば、部分フッ素化アルミナ、部分塩素化アルミナ、部分フッ素化塩素化アルミナ、部分フッ素化ジルコニア、部分フッ素化チタニア等であってもよい。酸化物触媒中の塩素原子やフッ素原子の割合は、特に限定されない。 Further, the carrier such as an oxide of the present invention may contain a metal component and an atom other than oxygen, and the other atom is preferably a fluorine atom or a chlorine atom. For example, partially fluorinated alumina, partially chlorinated alumina, partially fluorinated chlorinated alumina, partially fluorinated zirconia, partially fluorinated titania and the like may be used. The ratio of chlorine atoms and fluorine atoms in the oxide catalyst is not particularly limited.
本明細書および特許請求の範囲においては、特に限定されない限り、前記のように部分的にフッ素化、塩素化などされたアルミナ、ジルコニアなどの酸化物を「アルミナ」、「ジルコニア」などの酸化物名称で表示する。 In the present specification and claims, unless otherwise specified, partially fluorinated or chlorinated oxides such as alumina and zirconia as described above are oxides such as “alumina” and “zirconia”. Display by name.
これらの担体としては、アルミナ（Ａｌ2Ｏ3）、ジルコニア（ＺｒＯ2）、およびチタニア（ＴｉＯ2）および硫酸ジルコニアならびにこれらの部分フッ素化酸化物からなる群より選ばれる少なくとも１種の金属酸化物触媒が好ましく、アルミナおよび部分フッ素化アルミナが反応性および触媒寿命の点でさらに好ましい。 These supports include at least one metal oxide selected from the group consisting of alumina (Al 2 O 3 ), zirconia (ZrO 2 ), titania (TiO 2 ), zirconia sulfate, and partially fluorinated oxides thereof. Catalysts are preferred, and alumina and partially fluorinated alumina are more preferred in terms of reactivity and catalyst life.
これらの部分フッ素化酸化物はジフルオロ酢酸フルオライド合成触媒の担体として使用できると共に、触媒として使用することもできる。触媒としての調製、前処理、使用等は、本明細書において担体としての調製、前処理、使用等についての説明がそのまま、あるいは技術常識に従って適宜変更して適用することができる。すなわち、アルミナ（Ａｌ2Ｏ3）、ジルコニア（ＺｒＯ2）、チタニア（ＴｉＯ2）などの金属酸化物を触媒として使用等する際には、金属化合物等が担持された担持触媒と同様に取り扱えばよい。 These partially fluorinated oxides can be used as a support for a difluoroacetic acid fluoride synthesis catalyst, and can also be used as a catalyst. Preparation, pretreatment, use, etc. as a catalyst can be applied as described in the present specification for preparation, pretreatment, use, etc. as a support as it is or according to common general technical knowledge. That is, when a metal oxide such as alumina (Al 2 O 3 ), zirconia (ZrO 2 ), titania (TiO 2 ) or the like is used as a catalyst, it can be handled in the same manner as a supported catalyst on which a metal compound or the like is supported. Good.
触媒は、通常は粒子または造粒体の形態で用いられる。粒子または造粒体の直径（いずれも、「粒径」ということがある。）は、特に限定されず、通常は、２０μｍ〜１０ｍｍ程度である。また、触媒が塩素原子やフッ素原子を含む場合、金属酸化物の表面のみに塩素原子やフッ素原子が存在していてもよい。 The catalyst is usually used in the form of particles or granules. The diameter of the particles or the granulated body (all may be referred to as “particle diameter”) is not particularly limited, and is usually about 20 μm to 10 mm. When the catalyst contains a chlorine atom or a fluorine atom, the chlorine atom or the fluorine atom may exist only on the surface of the metal oxide.
触媒は、使用の前に予めフッ化水素、フッ素化炭化水素またはフッ素化塩素化炭化水素などの含フッ素化合物と接触させて部分フッ素化しておき、反応中の触媒の組成変化、短寿命化、異常反応などを防止することが有効である。 Before use, the catalyst is partially fluorinated by contacting with a fluorine-containing compound such as hydrogen fluoride, fluorinated hydrocarbon or fluorinated chlorinated hydrocarbon in advance to change the composition of the catalyst during the reaction, shorten the life, It is effective to prevent abnormal reactions.
特にフッ化水素で処理することで反応の活性を著しく高めることができる。フッ化水素によるフッ素化処理は、少なくとも本発明にかかる反応の反応温度よりも高い温度において、フッ化水素と接触させることで行うのが好ましい。 In particular, treatment with hydrogen fluoride can significantly increase the activity of the reaction. The fluorination treatment with hydrogen fluoride is preferably performed by contacting with hydrogen fluoride at least at a temperature higher than the reaction temperature of the reaction according to the present invention.
具体的には、リン酸塩単体の場合、２００〜７００℃程度であり、２５０〜６００℃程度が好ましく、３００〜５５０℃がより好ましい。一方、酸化物または活性炭等を担体とする担持触媒の場合、２００〜６００℃程度であり、２５０〜５００℃程度が好ましく、３００〜４００℃がより好ましい。いずれも２００℃未満では処理に時間を要し、最高温度範囲を超えて処理を行うことは、過剰な加熱エネルギーを要するので好ましくない。また、処理時間は、処理温度とも関係するので限定できないが、１時間〜１０日程度、好ましくは、３時間〜３日間程度である。 Specifically, in the case of a phosphate simple substance, it is about 200 to 700 ° C, preferably about 250 to 600 ° C, and more preferably 300 to 550 ° C. On the other hand, in the case of a supported catalyst using an oxide or activated carbon as a carrier, the temperature is about 200 to 600 ° C, preferably about 250 to 500 ° C, more preferably 300 to 400 ° C. In any case, if the temperature is lower than 200 ° C., it takes time for the treatment, and it is not preferable to perform the treatment beyond the maximum temperature range because excessive heating energy is required. The treatment time is also related to the treatment temperature and cannot be limited, but it is about 1 hour to 10 days, preferably about 3 hours to 3 days.
リン酸を担持しない活性炭の場合、フッ化水素処理を施しても、殆ど活性を示さないが、リン酸処理をした活性炭にフッ化水素処理を行うと、同じ反応条件で、転化率：９６．１％、選択率：９８．０％という触媒活性を示した。このことからも、フッ化水素処理の効果は容易に見て取ることができる。 In the case of activated carbon not supporting phosphoric acid, even if it is treated with hydrogen fluoride, it shows little activity. However, when activated carbon treated with phosphoric acid is treated with hydrogen fluoride, the conversion rate is 96. under the same reaction conditions. The catalyst activity was 1% and selectivity: 98.0%. Also from this, the effect of the hydrogen fluoride treatment can be easily seen.
さらに、反応に先立って、活性化処理を施すのが好ましい。活性化処理としては、２５０℃〜３００℃程度の窒素気流中で充分に脱水し、ジクロロジフルオロメタン、クロロジフルオロメタンなどの有機フッ素化合物、またはフッ化水素、三フッ化塩素などの気体もしくは触媒処理状態で十分な蒸気圧を示す無機フッ素化合物で活性化させるのが好ましい。これらのうちフッ化水素が特に好ましい。この活性化処理によって、触媒の表面または全体に、フッ素原子を含む活性な触媒が生成すると考えられる。 Furthermore, it is preferable to perform an activation treatment prior to the reaction. As the activation treatment, it is sufficiently dehydrated in a nitrogen stream at about 250 ° C. to 300 ° C., and an organic fluorine compound such as dichlorodifluoromethane or chlorodifluoromethane, or a gas or catalyst treatment such as hydrogen fluoride or chlorine trifluoride. It is preferable to activate with an inorganic fluorine compound showing a sufficient vapor pressure in the state. Of these, hydrogen fluoride is particularly preferred. This activation treatment is considered to generate an active catalyst containing fluorine atoms on the entire surface of the catalyst.
また、熱分解の原料である１−アルコキシ−１，１，２，２−テトラフルオロエタン（ＣＨＦ2ＣＦ2ＯＲ’）のＲ’が炭素数２以上の基である場合、生成したＲ’Ｆが反応領域において分解してフッ化水素を発生することが推測されるが、これが触媒の活性を高める効果を示すことがある。 Further, when R ′ of 1-alkoxy-1,1,2,2-tetrafluoroethane (CHF 2 CF 2 OR ′), which is a raw material for thermal decomposition, is a group having 2 or more carbon atoms, R′F produced Is decomposed in the reaction region to generate hydrogen fluoride, which may have an effect of increasing the activity of the catalyst.
熱分解反応は、気相流通連続方式が最も好ましい形式として推奨されるが、これに限定されない。反応器の形式は固定床タイプまたは流動床タイプが好ましく、反応器の寸法・形状は、反応物の量等に応じて適宜変更できる。 The thermal decomposition reaction is recommended as a most preferable form of the gas phase flow continuous system, but is not limited thereto. The type of the reactor is preferably a fixed bed type or a fluidized bed type, and the dimensions and shape of the reactor can be appropriately changed according to the amount of the reactants and the like.
熱分解においては、当該反応条件で不活性なガスを存在させてもよい。不活性ガスとしては、窒素または希ガス類が挙げられ、扱いやすさおよび入手しやすさ等の点から、窒素またはヘリウムが好ましい。不活性ガスを存在させる場合の量は、特に限定されないが、多すぎる場合には回収率が下がる恐れがあるため、通常の場合、原料の１−アルコキシ−１，１，２，２−テトラフルオロエタンの供給速度よりも少ない量が好ましい。 In pyrolysis, an inert gas may exist in the reaction conditions. Examples of the inert gas include nitrogen or rare gases, and nitrogen or helium is preferable from the viewpoint of ease of handling and availability. The amount in the presence of the inert gas is not particularly limited, but if it is too much, there is a possibility that the recovery rate is lowered. Therefore, in the usual case, the raw material 1-alkoxy-1,1,2,2-tetrafluoro An amount less than the ethane feed rate is preferred.
熱分解の反応温度は、触媒の種類および原料によって異なる。通常１００〜４００℃であり、１５０〜３５０℃程度が好ましく、１８０〜２８０℃がさらに好ましい。反応温度が１００℃未満では転化率が低くなる傾向があり好ましくない。反応温度が４００℃を超えると反応装置に過酷な耐熱性が必要となり、過剰な加熱エネルギーを要するので経済的に好ましくない。 The reaction temperature for thermal decomposition varies depending on the type of catalyst and the raw material. Usually, it is 100-400 degreeC, about 150-350 degreeC is preferable and 180-280 degreeC is more preferable. If the reaction temperature is less than 100 ° C., the conversion tends to be low, which is not preferable. When the reaction temperature exceeds 400 ° C., severe heat resistance is required for the reaction apparatus, and excessive heating energy is required, which is not economically preferable.
反応時間（接触時間）は通常０．１〜３００秒であり、０．５〜２００秒が好ましく、１〜６０秒がより好ましい。反応時間が短すぎる場合にも、転化率が低くなる恐れがあり、一方、長すぎると生産性が低下するのでそれぞれ好ましくない。反応圧力は、特に限定されず、常圧、減圧、または加圧のいずれであってもよい。０．０５〜０．５ＭＰａ（０．５〜５気圧）程度が好ましく、通常は、操業が容易な大気圧近傍の圧力が好ましい。 The reaction time (contact time) is usually 0.1 to 300 seconds, preferably 0.5 to 200 seconds, and more preferably 1 to 60 seconds. If the reaction time is too short, the conversion rate may be lowered. On the other hand, if the reaction time is too long, productivity is lowered, which is not preferable. The reaction pressure is not particularly limited and may be normal pressure, reduced pressure, or increased pressure. A pressure of about 0.05 to 0.5 MPa (0.5 to 5 atmospheres) is preferable, and usually a pressure in the vicinity of atmospheric pressure that facilitates operation is preferable.
触媒は、経時的にコーキングが発生することがあり、触媒の活性が低下することがある。活性の低下した触媒は、２００℃〜１２００℃、好ましくは、４００℃〜８００℃において、酸素と接触させることで容易に活性を再生させることができる。酸素処理は反応管に装填したまま又は外部の装置に装填して行うのが簡便である。そこへ酸素を流通させて行う。酸素の流通方法としては他のガスが共存してもよく、窒素で希釈した空気または空気が経済的に好ましい。また、塩素、フッ素等の酸化力のある気体も使用できる。 In the catalyst, coking may occur over time, and the activity of the catalyst may decrease. The catalyst having reduced activity can be easily regenerated by contacting with oxygen at 200 ° C. to 1200 ° C., preferably 400 ° C. to 800 ° C. It is convenient to perform the oxygen treatment while it is loaded in the reaction tube or in an external device. This is done by circulating oxygen there. As a method of circulating oxygen, other gas may coexist, and air diluted with nitrogen or air is economically preferable. Further, a gas having oxidizing power such as chlorine and fluorine can be used.
熱分解反応においては、目的とするジフルオロ酢酸フルオライドの他に、副生成物としてフッ化アルキル（Ｒ’Ｆ）やフッ化アルキルがさらに分解した化合物が生成する。例えば、フッ化アルキルとしてフッ化エチルが生成する場合、エチレンとフッ化水素となることがある。反応によって得られる副生成物を含む粗生成物は、精製処理をしないでフッ化アルキルを含んだまま第一工程のジフルオロ酢酸フルオライド原料として使用することもでき、主としてフッ化アルキルを除去して得られる粗生成物を使用することもでき、さらに精製して高純度にしたジフルオロ酢酸フルオライドを使用することもでき、あるいはこれらの各種精製程度の異なるガスを冷却または圧縮して耐圧容器に保存することもできる。ジフルオロ酢酸フルオライドの精製は蒸留により行うことができる。ここで、１−メトキシ−１，１，２，２−テトラフルオロエタン（ＣＨＦ2ＣＦ2ＯＭｅ）を出発原料として熱分解を行ったときは、目的化合物であるジフルオロ酢酸フルオライド（沸点：２℃）とフッ化メチル（沸点：−７８℃）が生成する。フッ化メチルは次工程の反応に不活性であるが、低沸点ガスであるので、取り扱いを容易にするために、分離することが好ましい。 In the thermal decomposition reaction, in addition to the target difluoroacetic acid fluoride, a compound in which alkyl fluoride (R′F) or alkyl fluoride is further decomposed is generated as a by-product. For example, when ethyl fluoride is generated as the alkyl fluoride, ethylene and hydrogen fluoride may be formed. The crude product containing a by-product obtained by the reaction can be used as a raw material for difluoroacetic acid fluoride in the first step without containing a purification process without purification, and is mainly obtained by removing the alkyl fluoride. The crude product can be used, and further purified and highly purified difluoroacetic acid fluoride can be used, or these variously purified gases can be cooled or compressed and stored in a pressure vessel. You can also. Difluoroacetic acid fluoride can be purified by distillation. Here, when pyrolysis is performed using 1-methoxy-1,1,2,2-tetrafluoroethane (CHF 2 CF 2 OMe) as a starting material, difluoroacetic acid fluoride as a target compound (boiling point: 2 ° C.) And methyl fluoride (boiling point: −78 ° C.) are produced. Methyl fluoride is inert to the reaction in the next step, but is a low-boiling point gas. Therefore, it is preferably separated for easy handling.
本発明の方法に用いる塩化リチウムは、無水塩化リチウムであるのが好ましく、試薬、工業用を問わず使用でき、使用に先立って乾燥することが望ましい。第一工程の反応においては、ジフルオロ酢酸フルオライドの１モルに対し、１モルが当量であるが、１〜５モルを使用し、１〜２モルが好ましく、１．０５〜１．５モルがより好ましい。１モルよりも少ないと反応が完結せず、５モル以上では反応後生成物との分離回収が煩雑になるので、それぞれ好ましくない。 The lithium chloride used in the method of the present invention is preferably anhydrous lithium chloride, and can be used regardless of whether it is a reagent or industrial use, and is preferably dried prior to use. In the reaction of the first step, 1 mol is equivalent to 1 mol of difluoroacetic acid fluoride, but 1 to 5 mol is used, preferably 1 to 2 mol, more preferably 1.05 to 1.5 mol. preferable. When the amount is less than 1 mol, the reaction is not completed, and when the amount is 5 mol or more, separation and recovery from the product after the reaction become complicated, which is not preferable.
本発明にかかるジフルオロ酢酸フルオライドをジフルオロ酢酸クロライドに変換する第一工程においては、ジフルオロ酢酸フルオライドと塩化リチウムを接触させる方法は限定されない。槽型の容器中で攪拌または容器を振盪する方法、管型の反応器に充填した塩化リチウムにジフルオロ酢酸フルオライドを流通させる方法などを採り得る。反応温度は−８０℃〜２００℃が好ましく、０℃〜１００℃が特に好ましい。−８０℃未満では反応時間が長くなり、１００℃超で操業を実施する場合、不必要なエネルギーを要するので好ましくない。反応圧力は、反応温度に依存するが、通常０〜１ＭＰａである。反応時間は反応温度に依存するが、通常１分〜５０時間で行い、５分〜２０時間が好ましく、１０分〜１０時間がより好ましい。５０時間を越えても低温度で行う場合を除き反応率が向上することはないので、このような時間で行うのは事実上不必要である。 In the first step of converting difluoroacetic acid fluoride to difluoroacetic acid chloride according to the present invention, the method of contacting difluoroacetic acid fluoride and lithium chloride is not limited. A method of stirring or shaking the vessel in a tank-type container, a method of circulating difluoroacetic acid fluoride in lithium chloride charged in a tubular reactor, and the like can be employed. The reaction temperature is preferably -80 ° C to 200 ° C, particularly preferably 0 ° C to 100 ° C. If it is less than −80 ° C., the reaction time becomes long. When the operation is carried out at over 100 ° C., unnecessary energy is required, which is not preferable. The reaction pressure depends on the reaction temperature, but is usually 0 to 1 MPa. The reaction time depends on the reaction temperature, but it is usually 1 minute to 50 hours, preferably 5 minutes to 20 hours, more preferably 10 minutes to 10 hours. Since the reaction rate does not improve except when it is performed at a low temperature even after 50 hours, it is practically unnecessary to carry out in such a time.
本発明の第一工程の方法において、無溶媒でも実施できるが、反応試剤または生成物に不活性な溶媒を所望により用いることもできる。このような溶媒としては、非プロトン性の溶媒が好ましい。非プロトン性の溶媒としては、芳香族系溶媒、鎖状エーテル、環状エーテル、エステル系溶媒、アミド系溶媒、スルホキシド類、パラフィン類等が挙げられ、具体的には、Ｎ，Ｎ−ジメチルホルムアミド（DMF）、Ｎ，Ｎ−ジメチルアセトアミド（DMAc）、1,3-ジメチル-2-イミダゾリジノン（ＤＭＩ）、Ｎ−メチル−２−ピロリドン（ＭＮＰ）、ジグライム、トリグライム、テトラグライム、ポリグライム、トルエン、キシレン、エチルベンゼン、ジメチルスルホキシド（DMSO）、スルフォラン、ｏ−、ｍ−またはｐ−ビストリフルオロメチルベンゼン、炭素数８〜20のデカン等の鎖状炭化水素が例示される。塩化リチウムは反応系で溶解していてもあるいは溶解せずスラリー状態でもよい。溶媒の沸点は反応には関与しないので任意の沸点の溶媒が使用可能であるが、蒸留精製では沸点が目的のジフルオロ酢酸クロライドおよび第二工程の目的生成物のジフルオロ酢酸エステルと近接していないものが蒸留分離に負荷が掛からず好ましい。また、目的のジフルオロ酢酸エステルよりも高沸点の溶媒の方が、蒸留の簡便さの点で推奨される。溶媒の沸点の上限は特にないが、高沸点化合物は、室温で凝固したり、粘性が高くて取り扱いが不便なことが多い。溶媒は、ゼオライト等による吸着や蒸留で水の含有量を可能な限り低減しておくのが好ましい。これらは生成物中へのアルコールなどの混入の原因となって精製が煩雑になり好ましくない。 In the method of the first step of the present invention, it can be carried out without a solvent, but a solvent inert to the reaction reagent or product can be used as desired. As such a solvent, an aprotic solvent is preferable. Examples of the aprotic solvent include aromatic solvents, chain ethers, cyclic ethers, ester solvents, amide solvents, sulfoxides, paraffins, and the like. Specifically, N, N-dimethylformamide ( DMF), N, N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), N-methyl-2-pyrrolidone (MNP), diglyme, triglyme, tetraglyme, polyglyme, toluene, Examples are xylene, ethylbenzene, dimethyl sulfoxide (DMSO), sulfolane, o-, m- or p-bistrifluoromethylbenzene, chain hydrocarbons such as decane having 8 to 20 carbon atoms. Lithium chloride may be dissolved in the reaction system or may be in a slurry state without being dissolved. Since the boiling point of the solvent is not involved in the reaction, a solvent having an arbitrary boiling point can be used, but in the distillation purification, the boiling point is not close to the target difluoroacetic acid chloride and the target product difluoroacetic acid ester in the second step. Is preferable because it does not impose a load on the distillation separation. In addition, a solvent having a higher boiling point than the target difluoroacetic acid ester is recommended in terms of ease of distillation. There is no particular upper limit on the boiling point of the solvent, but high boiling point compounds often solidify at room temperature or have high viscosity and are inconvenient to handle. It is preferable to reduce the water content of the solvent as much as possible by adsorption or distillation with zeolite or the like. These are undesirable because they cause contamination of the product with alcohol and the like, and the purification becomes complicated.
また、第二工程の目的化合物と同一のジフルオロ酢酸エステルを溶媒として使用することも可能である。この目的化合物と溶媒として使用すると溶媒と生成物の分離が不要となるので、プロセスが簡便化され特に好ましい。溶媒の使用量は塩化リチウムの質量の３〜２０倍であり、好ましくは５〜１０倍である。３倍よりも少ないと攪拌が困難であり反応に長時間を要し、２０倍を越えると溶媒の回収等の操作が煩雑になるので、それぞれ好ましくない。 It is also possible to use the same difluoroacetic acid ester as the target compound in the second step as a solvent. When the target compound and the solvent are used, separation of the solvent and the product becomes unnecessary, and therefore the process is simplified and it is particularly preferable. The usage-amount of a solvent is 3-20 times of the mass of lithium chloride, Preferably it is 5-10 times. If it is less than 3 times, stirring is difficult and a long time is required for the reaction, and if it exceeds 20 times, operations such as recovery of the solvent become complicated.
また、不活性な気体を伴わせることもできる、このような気体としては、窒素、アルゴン、ヘリウムなどが挙げられる。本反応に用いる反応器には、ステンレス鋼、ハステロイ（登録商標）、モネル（登録商標）、フッ素樹脂またはこれらをライニングした材料が用いられる。 In addition, examples of such a gas that can be accompanied by an inert gas include nitrogen, argon, and helium. For the reactor used in this reaction, stainless steel, Hastelloy (registered trademark), Monel (registered trademark), fluororesin or a material lined with these is used.
本発明にかかる反応生成物を含む混合物は、ジフルオロ酢酸クロライドと固体のフッ化リチウムと未反応塩化リチウムを含む。固体成分はフラッシュ蒸留またはデカンテーションで分離し、粗ジフルオロ酢酸クロライドを得ることができる。粗ジフルオロ酢酸クロライドは蒸留することで不活性溶媒や不純物を除去し純度を挙げることができる。 The mixture containing the reaction product according to the present invention contains difluoroacetic acid chloride, solid lithium fluoride and unreacted lithium chloride. The solid components can be separated by flash distillation or decantation to obtain crude difluoroacetic acid chloride. The crude difluoroacetic acid chloride can be purified by removing the inert solvent and impurities by distillation.
次に第二工程を詳述する。第二工程は、ジフルオロ酢酸クロライドとアルコールを接触させることからなる。 Next, the second step will be described in detail. The second step consists of contacting difluoroacetic acid chloride with alcohol.
本発明において、ジルフルオロ酢酸クロライドとアルコールの量論モル比は、１価のアルコールの場合は、１：１、ｎ価のアルコールの場合は、ｎ：１となる。ここで、いずれかを過剰に用いることも可能である。過剰量は任意であるが、１−２０％程度の過剰量が推奨される。もし、ジフルオロ酢酸クロライドを過剰に用いるとアルコールが実質的に全て消費され、未反応のジフルオロ酢酸クロライドが溶存する。逆に、アルコールを過剰に用いると、ジフルオロ酢酸クロライドが実質的に全て消費されて、未反応のアルコールが残る。また、何れを選択するかは当業者に任意であるが、ジフルオロ酢酸エステルの単離を所望する場合は、前者が好ましい。ジフルオロ酢酸エステルとジフルオロ酢酸クロライドは容易に蒸留分離可能であるが、ジフルオロ酢酸エステルとアルコールは共沸もしくは擬共沸現象を起こすことが多く、蒸留分離が困難である。慣用的な方法として、水洗浄でもアルコールを除去することが可能であるが、そのときジフルオロ酢酸エステルの加水分解が生じるおそれがある。本発明に使用するアルコールは使用に当たって、ジフルオロ酢酸クロライドの加水分解の原因となる水の含有量を可能な限り低減するのが好ましい。 In the present invention, the stoichiometric molar ratio of difluorofluoroacetic acid chloride and alcohol is 1: 1 for monohydric alcohols and n: 1 for nvalent alcohols. Here, either of them can be used excessively. The excess amount is arbitrary, but an excess amount of about 1-20% is recommended. If difluoroacetic acid chloride is used in excess, substantially all of the alcohol is consumed and unreacted difluoroacetic acid chloride is dissolved. Conversely, when alcohol is used in excess, substantially all of the difluoroacetic acid chloride is consumed, leaving unreacted alcohol. Moreover, although it is arbitrary for those skilled in the art to select which is preferable, when isolation of difluoroacetic acid ester is desired, the former is preferable. Although difluoroacetic acid ester and difluoroacetic acid chloride can be easily separated by distillation, difluoroacetic acid ester and alcohol often cause an azeotropic or pseudo-azeotropic phenomenon and are difficult to separate by distillation. As a conventional method, alcohol can be removed by washing with water, but hydrolysis of the difluoroacetic acid ester may occur at that time. In using the alcohol used in the present invention, it is preferable to reduce the content of water causing hydrolysis of difluoroacetic acid chloride as much as possible.
第一工程で得られたジフルオロ酢酸クロライドを溶媒等から分離した実質的にジフルオロ酢酸クロライドのみからなる原料を使用する場合は、改めて必要に応じて溶媒を使用することができるが、通常使用しない。第一工程の反応生成物をそのまま使用してアルコールを添加して第二工程に供する場合は溶媒が存在することとなる。このような溶媒としては、非プロトン性の溶媒が好ましい。非プロトン性の溶媒としては、芳香族系溶媒、鎖状エーテル、環状エーテル、エステル系溶媒、アミド系溶媒、スルホキシド類、パラフィン類等が挙げられ、具体的には、Ｎ，Ｎ−ジメチルホルムアミド（DMF）、Ｎ，Ｎ−ジメチルアセトアミド（DMAc）、1,3-ジメチル-2-イミダゾリジノン（ＤＭＩ）、Ｎ−メチル−２−ピロリドン（ＭＮＰ）、ジグライム、トリグライム、テトラグライム、ポリグライム、トルエン、キシレン、エチルベンゼン、ジメチルスルホキシド（DMSO）、スルフォラン、ｏ−、ｍ−またはｐ−ビストリフルオロメチルベンゼン、炭素数８〜20のデカン等の鎖状炭化水素が例示される。溶媒は、アルコール１質量部に対し１００質量部以下を使用する。また、不活性な気体を伴わせることもできる、このような気体としては、窒素、アルゴン、ヘリウムなどが挙げられる。本反応に用いる反応器には、ステンレス鋼、ハステロイ（登録商標）、モネル（登録商標）、フッ素樹脂、ガラスまたはこれらをライニングした材料が用いられる。 When using the raw material which consists only of difluoroacetic acid chloride which isolate | separated the difluoroacetic acid chloride obtained at the 1st process from the solvent etc., a solvent can be used anew as needed, but it is not normally used. When the reaction product of the first step is used as it is and an alcohol is added to provide the second step, a solvent is present. As such a solvent, an aprotic solvent is preferable. Examples of the aprotic solvent include aromatic solvents, chain ethers, cyclic ethers, ester solvents, amide solvents, sulfoxides, paraffins, and the like. Specifically, N, N-dimethylformamide ( DMF), N, N-dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), N-methyl-2-pyrrolidone (MNP), diglyme, triglyme, tetraglyme, polyglyme, toluene, Examples are xylene, ethylbenzene, dimethyl sulfoxide (DMSO), sulfolane, o-, m- or p-bistrifluoromethylbenzene, chain hydrocarbons such as decane having 8 to 20 carbon atoms. A solvent uses 100 mass parts or less with respect to 1 mass part of alcohol. In addition, examples of such a gas that can be accompanied by an inert gas include nitrogen, argon, and helium. For the reactor used in this reaction, stainless steel, Hastelloy (registered trademark), Monel (registered trademark), fluororesin, glass or a material lined with these is used.
第二工程は、ジフルオロ酢酸クロライドとアルコールを反応器中で混合することで行われる。反応においてジフルオロ酢酸エステルの副生成物として発生する塩化水素は、反応器から排気しながら反応をすることができ、耐圧容器を用いる場合は排気をしないで反応をすることもできる。 The second step is performed by mixing difluoroacetic acid chloride and alcohol in the reactor. Hydrogen chloride generated as a by-product of difluoroacetate ester in the reaction can be reacted while being exhausted from the reactor, and when a pressure vessel is used, the reaction can be performed without exhausting.
反応生成物を含む混合物は、ジフルオロ酢酸クロライドと固体のフッ化リチウムと未反応塩化リチウムを含む。固体成分はフラッシュ蒸留またはデカンテーションで分離し、粗ジフルオロ酢酸エステルを得ることができる。粗ジフルオロ酢酸エステルは蒸留することで不活性溶媒や不純物を除去し純度を挙げることができる。 The mixture containing the reaction product contains difluoroacetic acid chloride, solid lithium fluoride and unreacted lithium chloride. The solid component can be separated by flash distillation or decantation to obtain the crude difluoroacetate ester. The crude difluoroacetate can be purified by removing the inert solvent and impurities by distillation.
反応は、室温（約２５℃）で進行し、通常、反応温度は−８０℃〜５０℃であり、−５０℃〜２５℃が好ましい。本発明に係る反応は発熱的な反応であるので、反応熱を冷却によって除熱しながら、適切な温度領域に制御することが好ましい。したがって、反応初期は、所定温度よりも１０℃から２０℃程度過冷却することも好ましい。発熱が収束した後は、反応の完結のために、最高１２０℃程度まで加熱してもよい。 The reaction proceeds at room temperature (about 25 ° C.), and the reaction temperature is usually −80 ° C. to 50 ° C., preferably −50 ° C. to 25 ° C. Since the reaction according to the present invention is an exothermic reaction, it is preferable to control the reaction heat to an appropriate temperature range while removing heat by cooling. Therefore, at the initial stage of the reaction, it is also preferable to supercool by about 10 to 20 ° C. from the predetermined temperature. After the exotherm has converged, it may be heated up to about 120 ° C. for the completion of the reaction.
反応時間は反応温度に依存し極短時間で反応完結させることもでき、通常５分〜５０時間で行い、１０分〜１０時間が好ましく、３０分〜５時間がより好ましい。５０時間を越えても非常な低温度で行う場合を除き反応率が向上することはないので、このような長時間で行うのは事実上不必要である。 The reaction time depends on the reaction temperature and can be completed in a very short time. Usually, the reaction time is 5 minutes to 50 hours, preferably 10 minutes to 10 hours, more preferably 30 minutes to 5 hours. Since the reaction rate does not improve except when it is carried out at a very low temperature even if it exceeds 50 hours, it is practically unnecessary to carry out in such a long time.
反応形式としては、バッチ式、連続式、循環式の何れも適用できる。反応には攪拌を行ってもよく、攪拌は攪拌羽根、循環、振盪その他の公知の手段で行えばよい。 As the reaction mode, any of batch type, continuous type and circulation type can be applied. The reaction may be agitated, and the agitation may be carried out by a known means such as a stirring blade, circulation, shaking or the like.
第二工程の反応が完了した後、反応器に残留する反応器内容物には、ジフルオロ酢酸エステル、塩化水素、未反応のジフルオロ酢酸クロライドが含まれ、第一工程に引き続き第二工程を行った場合はさらにフッ化リチウム、塩化リチウム、溶媒が含まれることがある。塩化水素をアミンやアルカリ金属水酸化物、アルカリ金属酸化物などの塩基性物質で捕獲することもできるが、蒸留または加熱還流で排出するのが好ましい。フッ化リチウム、塩化リチウム等の固形分が含まれる場合はフラッシュ蒸留やデカンテーションで分離することができる。これらの処理により得られたジフルオロ酢酸エステルを主とする有機成分はさらに蒸留または精留で溶媒などの不純物を除去することで高純度のジフルオロ酢酸エステルとすることができる。 After the reaction in the second step is completed, the reactor contents remaining in the reactor contain difluoroacetic acid ester, hydrogen chloride, and unreacted difluoroacetic acid chloride, and the second step was performed following the first step. In some cases, lithium fluoride, lithium chloride and a solvent may be further contained. Although hydrogen chloride can be captured by basic substances such as amines, alkali metal hydroxides, and alkali metal oxides, it is preferably discharged by distillation or heating under reflux. When solid content such as lithium fluoride and lithium chloride is contained, it can be separated by flash distillation or decantation. The organic component mainly composed of difluoroacetate obtained by these treatments can be made into high-purity difluoroacetate by further removing impurities such as a solvent by distillation or rectification.
本発明の方法によるジフルオロ酢酸エステルの製造方法をバッチ式について説明する。連続式については、この説明および上記説明に基づいて適宜反応条件、手順を改変することは当業者にとって容易である。 The production method of difluoroacetic acid ester according to the method of the present invention will be described with respect to a batch system. Regarding the continuous type, it is easy for those skilled in the art to modify reaction conditions and procedures as appropriate based on this explanation and the above explanation.
第一工程（ジフルオロ酢酸フルオライドの塩素化工程）の反応内容物からデカンテーションまたはフラッシュ蒸留等の分離操作により粗ジフルオロ酢酸クロライドを回収する。第一工程で生成した粗ジルフロ酢酸クロライドを中間槽に一旦回収することなく、直接、第二工程に供することも可能であるが、安全な操業を行うために、一度捕集することが推奨される。第二工程（エステル化工程）は、望ましくは攪拌機と還流塔を備えた反応容器に所定量のアルコールと任意に溶媒を仕込み、そこへ粗ジフルオロ酢酸クロライドまたはこれを精留して得た精製ジフルオロ酢酸クロライドの所定量を導入し、その後攪拌しながら所定の温度に昇温しその温度で反応を継続する。また、ジフルオロ酢酸クロライドの添加方法としては、アルコールを仕込み所定の温度に保った同様の反応器にジフルオロ酢酸クロライドの所定量を反応の進行に応じて徐々に添加することもできる。還流塔を備える場合は副生する塩化水素を逐次反応系から放出でき、耐圧容器を用い還流塔を備えない場合は閉止系として塩化水素を反応系にとどめることができる。反応完了後、加熱または不活性ガスのバブリング等の手段により反応容器に滞留している塩化水素を追い出して酸性成分を除去する。次いで、フラッシュ蒸留によりジフルオロ酢酸エステルを主成分とする有機物を回収し、所望により精留して高純度のジフルオロ酢酸エステルを得ることができる。
Crude difluoroacetic acid chloride is recovered from the reaction contents of the first step (chlorination step of difluoroacetic acid fluoride) by separation operation such as decantation or flash distillation. The crude zircuroacetic acid chloride produced in the first step can be used directly in the second step without being once recovered in the intermediate tank, but it is recommended to collect it once for safe operation. The In the second step (esterification step), preferably, a predetermined amount of alcohol and an optional solvent are charged into a reaction vessel equipped with a stirrer and a reflux tower, and crude difluoroacetic acid chloride or purified difluoro obtained by rectifying the same. A predetermined amount of acetic acid chloride is introduced, and then the temperature is raised to a predetermined temperature while stirring, and the reaction is continued at that temperature. In addition, as a method for adding difluoroacetic acid chloride, a predetermined amount of difluoroacetic acid chloride can be gradually added to a similar reactor charged with alcohol and maintained at a predetermined temperature as the reaction proceeds. When a reflux tower is provided, by-product hydrogen chloride can be sequentially released from the reaction system. When a pressure vessel is used and a reflux tower is not provided, hydrogen chloride can be kept in the reaction system as a closed system. After the completion of the reaction, the acidic components are removed by expelling the hydrogen chloride remaining in the reaction vessel by means such as heating or bubbling with an inert gas. Subsequently, the organic substance which has difluoroacetate as a main component is collect | recovered by flash distillation, and it can rectify as needed and can obtain high purity difluoroacetate.
以下、実施例により、本発明を説明するが、本発明はこれらの実施態様には限られない。 Hereinafter, although an example explains the present invention, the present invention is not limited to these embodiments.
［調製例１］
アルドリッチ製リン酸アルミニウム（Ａｌｕｍｉｎｕｍ ｐｈｏｓｐｈａｔｅ）を５ｍｍφ×５ｍｍＬのペレットに打錠成形し、窒素気流中７００℃で５時間焼成して、リン酸アルミニウム触媒を調製した。これを気化器付ステンレス製反応管（内径３７．１ｍｍφ×５００ｍｍＬ）に２００ｃｃ充填した。窒素１５ｃｃ／分を流しながら反応管を外部に設けた電気炉で加熱した。触媒の温度が５０℃に達した時に、フッ化水素（ＨＦ）を０．６ｇ／分の速度で気化器を通して導入した。ＨＦを流通させたまま、３００℃までゆっくりと昇温し、３００℃で５時間保持した後、ヒーター設定温度を２００℃に下げ、２００℃になった時点で、ＨＦの流通を止め、窒素流量を２００ｃｃ／分に増やして２時間保持した後、１−メトキシ−１，１，２，２−テトラフルオロエタン（ＨＦＥ−２５４ｐｃ）を０．２ｇ／分の速度で、気化器を通して導入した。３０分後窒素を止めて、ＨＦＥ−２５４ｐｃのみを流通させ、定常状態時にガスサンプリングし、ガスクロマトグラフで分析したところ、ほぼ定量的に、ジフルオロ酢酸フルオライド（ＣＨＦ2ＣＯＦ）とフッ化メチル（ＣＨ3Ｆ）が含まれていた（転化率：９９．７％）。
この粗ジフルオロ酢酸フルオライドを蒸留して純度９９％以上の精製ジフルオロ酢酸フルオライドを得た。
[Preparation Example 1]
Aluminum phosphate manufactured by Aldrich was tableted into 5 mmφ × 5 mmL pellets and calcined in a nitrogen stream at 700 ° C. for 5 hours to prepare an aluminum phosphate catalyst. 200 cc of this was filled into a stainless steel reaction tube with a vaporizer (inner diameter: 37.1 mmφ × 500 mmL). While flowing nitrogen at 15 cc / min, the reaction tube was heated in an electric furnace provided outside. When the catalyst temperature reached 50 ° C., hydrogen fluoride (HF) was introduced through the vaporizer at a rate of 0.6 g / min. Slowly raise the temperature to 300 ° C with HF flowing, hold at 300 ° C for 5 hours, lower the heater set temperature to 200 ° C, stop the flow of HF when the temperature reaches 200 ° C, Was increased to 200 cc / min and held for 2 hours, after which 1-methoxy-1,1,2,2-tetrafluoroethane (HFE-254pc) was introduced through the vaporizer at a rate of 0.2 g / min. It stopped 30 minutes after nitrogen, was circulated only HFE-254pc, and gas sampling during steady state was analyzed by gas chromatography, almost quantitatively, difluoroacetate fluoride (CHF 2 COF) and methyl fluoride (CH 3 F) was included (conversion: 99.7%).
The crude difluoroacetic acid fluoride was distilled to obtain purified difluoroacetic acid fluoride having a purity of 99% or more.
［調製例２］
攪拌器を備えた１０００ｃｃステンレス製オートクレーブに、ＬｉＣｌ（１６８．７ｇ、４．０ｍｏｌ）を仕込み内部を減圧した。ドライアイス−アセトン浴で内温−４０℃に冷却後、シリンダーに小分けされた調製例１で準備した精製ジフルオロ酢酸フルオライド（３００ｇ、３．０６ｍｏｌ）を攪拌しながら圧入した。その後、浴を外し、室温（約２５℃）で１時間攪拌し、次にバンドヒーターを用いて１時間かけて７０℃に昇温し４時間そのまま保持した。その時の圧力は０．５６ＭＰａＧ（ゲージ圧）であった。反応終了後、内容物を回収し、フラッシュ蒸留し、ガスクロマトグラフィで分析したところ９８．６４面積％のジフルオロ酢酸クロライド（ＣＨＦ2ＣＯＣｌ）であった（回収率９６％）。主な不純物は、原料のジフルオロ酢酸フルオライド中不純物由来のＣＨ3Ｆ（０．３６ＧＣ％）、未反応原料（０．１５％）、ＣＨＦ2ＣＯＯＨ（０．３３％）であった。
[Preparation Example 2]
LiCl (168.7 g, 4.0 mol) was charged into a 1000 cc stainless steel autoclave equipped with a stirrer, and the pressure was reduced. After cooling to an internal temperature of −40 ° C. in a dry ice-acetone bath, the purified difluoroacetic acid fluoride (300 g, 3.06 mol) prepared in Preparation Example 1 divided into cylinders was injected with stirring. Thereafter, the bath was removed, and the mixture was stirred at room temperature (about 25 ° C.) for 1 hour, then heated to 70 ° C. over 1 hour using a band heater, and held there for 4 hours. The pressure at that time was 0.56 MPaG (gauge pressure). After completion of the reaction, the content was recovered, flash distilled, and analyzed by gas chromatography to be 98.64 area% difluoroacetic acid chloride (CHF 2 COCl) (recovery rate 96%). The main impurities were CH 3 F (0.36 GC%) derived from impurities in the raw material difluoroacetic acid fluoride, unreacted raw material (0.15%), and CHF 2 COOH (0.33%).
［実施例１］
コンデンサー、吹き込み管、温度計を有する３口ＰＦＡ製フラスコ（５００ｃｃ）に、エタノール（４６ｇ、１ｍｏｌ）を仕込みスターラーで攪拌しながら冷却装置（ＥＹＥＬＡ ＰＳＬ−２０００）で−５０℃に冷却した。そのまま攪拌しながら吹き込み管を通して、シリンダーに小分けされた調製例２で作成したＣＨＦ2ＣＯＣｌ（１２６．０ｇ、１．１ｍｏｌ）をエタノールに吸収させた。ＣＨＦ2ＣＯＣｌ導入速度は内温が−４０℃から−３０℃になるように制御した。全量導入後、１時間攪拌を継続してから冷却装置を外し、室温に戻してさらに２時間攪拌を継続した。その後、反応器内に残留する塩化水素（ＨＣｌ）を除去するためにＮ2ガスをバブリングさせながら、バス温を室温から徐々に１２０℃まで昇温し、２時間加熱還流した。フラッシュ蒸留で固形分を残留させ、反応液を回収し、ガスクロマトグラフで分析したところ、ジフルオロ酢酸エチル（ＣＨＦ2ＣＯＯＣ2Ｈ5）純度は９９．６７面積％であった。これをサンプリングしてイオン交換水でハロゲンイオンを抽出し、ＮａＯＨ水溶液で中和後、Ｆアニオン、Ｃｌアニオンをイオンクロマトグラフで分析したところ、定量下限界以下であった（Ｆアニオンの定量下限界：５ｐｐｍ、Ｃｌアニオンの定量下限界：１０ｐｐｍ）。
[Example 1]
A three-necked PFA flask (500 cc) having a condenser, a blowing tube and a thermometer was charged with ethanol (46 g, 1 mol) and cooled to −50 ° C. with a cooling device (EYELA PSL-2000) while stirring with a stirrer. The CHF 2 COCl (126.0 g, 1.1 mol) prepared in Preparation Example 2, which was subdivided into cylinders, was absorbed in ethanol through the blowing tube while stirring as it was. The CHF 2 COCl introduction rate was controlled so that the internal temperature was −40 ° C. to −30 ° C. After the introduction of the entire amount, stirring was continued for 1 hour, the cooling device was removed, the temperature was returned to room temperature, and stirring was continued for another 2 hours. Thereafter, in order to remove hydrogen chloride (HCl) remaining in the reactor, the bath temperature was gradually raised from room temperature to 120 ° C. while bubbling N 2 gas, and heated to reflux for 2 hours. The solid content remained by flash distillation, and the reaction solution was collected and analyzed by gas chromatography. As a result, the purity of ethyl difluoroacetate (CHF 2 COOC 2 H 5 ) was 99.67 area%. This was sampled, halogen ions were extracted with ion-exchanged water, neutralized with an aqueous NaOH solution, and F anion and Cl anion were analyzed with an ion chromatograph. : 5 ppm, lower limit of determination of Cl anion: 10 ppm).
［参考例１］
各々予め氷浴で冷却したジフルオロ酢酸メチル（ＣＨＦ2ＣＯＯＣＨ3、１０ｇ）とイオン交換水（２０ｇ）を混合し、氷浴で冷却しながら５分間攪拌した。水相をＮａＯＨ水溶液で中和し、ＣＨＦ2ＣＯＯＣＨ3の加水分解によって生成するＣＨＦ2ＣＯＯ-イオンをイオンクロマトグラフィで定量し、加水分解率を求めた。その結果、５．０％の加水分解率であった。加水分解率は、ＣＨＦ2ＣＯＯ-イオン量を、ジフルオロ酢酸メチル重量に換算し、試料のジフルオロ酢酸メチル重量１０ｇで除して加水分解率を求めた。
[Reference Example 1]
Methyl difluoroacetate (CHF 2 COOCH 3 , 10 g), which had been previously cooled in an ice bath, and ion-exchanged water (20 g) were mixed and stirred for 5 minutes while cooling in an ice bath. The aqueous phase was neutralized with an aqueous NaOH solution, and CHF 2 COO − ions produced by hydrolysis of CHF 2 COOCH 3 were quantified by ion chromatography to determine the hydrolysis rate. As a result, the hydrolysis rate was 5.0%. Degree of hydrolysis, CHF 2 COO - ion amount, in terms of methyl difluoroacetate weight was determined hydrolysis rate by dividing the difluoromethyl methyl acetate by weight 10g of the sample.
［参考例２］
各々予め氷浴で冷却したＣＨＦ2ＣＯＯＣＨ3（２０ｇ）と３８％ＨＦ水溶液（２０ｇ）を混合し、氷浴で冷却しながら５分間攪拌した。水相をＮａＯＨ水溶液で中和し、ＣＨＦ2ＣＯＯＣＨ3の加水分解によって生成するＣＨＦ2ＣＯＯ-イオンをイオンクロマトグラフィで定量し、加水分解率を求めた。その結果、４３．０％の加水分解率であった。加水分解率は、参考例１と同様の方法で計算して求めた。
[Reference Example 2]
Each of CHF 2 COOCH 3 (20 g) cooled in an ice bath and 38% HF aqueous solution (20 g) were mixed and stirred for 5 minutes while cooling in an ice bath. The aqueous phase was neutralized with an aqueous NaOH solution, and CHF 2 COO − ions produced by hydrolysis of CHF 2 COOCH 3 were quantified by ion chromatography to determine the hydrolysis rate. As a result, the hydrolysis rate was 43.0%. The hydrolysis rate was calculated by the same method as in Reference Example 1.
［参考例３］
各々予め氷浴で冷却したジフルオロ酢酸イソプロピル（ＣＨＦ2ＣＯＯＣＨ（ＣＨ3）2、５ｇ）と３８％ＨＦ水溶液（１０ｇ）を混合し、氷浴で冷却しながら５分間攪拌した。水相をＮａＯＨ水溶液で中和し、ＣＨＦ2ＣＯＯＣＨ（ＣＨ3）2の加水分解によって生成するＣＨＦ2ＣＯＯ-イオンをイオンクロマトグラフィで定量し、加水分解率を求めた。その結果、６．９％の加水分解率であった。加水分解率は、参考例１と同様の方法で計算して求めた。
[Reference Example 3]
Isopropyl difluoroacetate (CHF 2 COOCH (CH 3 ) 2 , 5 g), each cooled in an ice bath, and 38% HF aqueous solution (10 g) were mixed and stirred for 5 minutes while cooling in an ice bath. The aqueous phase was neutralized with an aqueous NaOH solution, and CHF 2 COO − ions generated by hydrolysis of CHF 2 COOCH (CH 3 ) 2 were quantified by ion chromatography to determine the hydrolysis rate. As a result, the hydrolysis rate was 6.9%. The hydrolysis rate was calculated by the same method as in Reference Example 1.
［参考例４］
温度計、吹き込み管、環流塔を設けた１０００ｍｌのガラス製４口フラスコに窒素置換後、２０％ナトリウムエトキシド（ＥｔＯＮａ）／エタノール（ＥｔＯＨ）液（３４０ｇ）を仕込み、氷浴で冷却し、スターラーで攪拌しながら約０．７ｇ／分の速度でＣＨＦ2ＣＯＦ（１０３．７ｇ，１．０６ｍｏｌ）を吹き込み管よりバブリングさせながら導入し、そのまま２時間攪拌を続けたところ、反応液のｐＨは７以下を示した。１０ｋＰａの減圧下でフラッシュ蒸留して内容物を回収した。得られた有機物をガスクロマトグラフィ（ＦＩＤ）で分析したところ、エタノール：８２．６面積％、ジフルオロ酢酸エチル（ＣＨＦ2ＣＯＯＣ2Ｈ5）：１７．４面積％であった。この有機物（１７０．６ｇ）を理論段数１５段の蒸留塔で常圧蒸留した結果、留出温度：７３．７℃〜７５．８℃の主留分（１５１．２ｇ）を得た。得られた有機物のガスクロマトグラフ組成はエタノール：８１．０面積％、ＣＨＦ2ＣＯＯＣ2Ｈ5：１８．８面積％であり、共沸現象を示した。これは、蒸留でのエタノールとＣＨＦ2ＣＯＯＣ2Ｈ5の分離精製は実質的に困難であることを示唆している。ちなみに、エタノールの沸点は７７℃、ＣＨＦ2ＣＯＯＣ2Ｈ5の沸点は９７℃である。
[Reference Example 4]
A 1000 ml glass four-necked flask equipped with a thermometer, blowing tube, and reflux tower was purged with nitrogen, charged with 20% sodium ethoxide (EtONa) / ethanol (EtOH) solution (340 g), cooled in an ice bath, and stirred. While stirring, the CHF 2 COF (103.7 g, 1.06 mol) was introduced at a rate of about 0.7 g / min while bubbling from the blowing tube and stirring was continued for 2 hours. As a result, the pH of the reaction solution was 7 The following was shown. The contents were recovered by flash distillation under reduced pressure of 10 kPa. When the obtained organic substance was analyzed by gas chromatography (FID), ethanol: 82.6 area% and difluoroethyl acetate (CHF 2 COOC 2 H 5 ): 17.4 area%. As a result of atmospheric distillation of this organic substance (170.6 g) in a distillation column having 15 theoretical plates, a main fraction (151.2 g) having a distillation temperature of 73.7 ° C. to 75.8 ° C. was obtained. The obtained organic substance had a gas chromatographic composition of ethanol: 81.0 area% and CHF 2 COOC 2 H 5 : 18.8 area%, and showed an azeotropic phenomenon. This suggests that separation and purification of ethanol and CHF 2 COOC 2 H 5 by distillation are substantially difficult. Incidentally, the boiling point of ethanol is 77 ° C., and the boiling point of CHF 2 COOC 2 H 5 is 97 ° C.
医農薬中間体、機能性材料の中間体として有用なジフルオロ酢酸エステルの製造方法として有用である。 It is useful as a method for producing difluoroacetic acid esters useful as intermediates for medicines and agricultural chemicals and functional materials.
Claims (9)
ＲＯＨ （１）
（式中、Ｒはアルキル基である。）で表されるアルコールとジフルオロ酢酸クロライドとを反応させることからなる一般式（２）
ＣＨＦ2ＣＯＯＲ （２）
（式中、Ｒは一般式（１）におけると同じ。）で表されるジフルオロ酢酸エステルの製造方法。 General formula (1)
ROH (1)
(Wherein R is an alkyl group) and the general formula (2) comprising reacting an alcohol represented by difluoroacetic acid chloride
CHF 2 COOR (2)
(Wherein R is the same as in general formula (1)).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2012176927A (en) * | 2010-03-29 | 2012-09-13 | Central Glass Co Ltd | Method for producing difluoroacetyl chloride |
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| JP2012176927A (en) * | 2010-03-29 | 2012-09-13 | Central Glass Co Ltd | Method for producing difluoroacetyl chloride |
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