JP5517202B2 - Method for producing fluorine-containing oxetane compound - Google Patents
Method for producing fluorine-containing oxetane compound Download PDFInfo
- Publication number
- JP5517202B2 JP5517202B2 JP2010095117A JP2010095117A JP5517202B2 JP 5517202 B2 JP5517202 B2 JP 5517202B2 JP 2010095117 A JP2010095117 A JP 2010095117A JP 2010095117 A JP2010095117 A JP 2010095117A JP 5517202 B2 JP5517202 B2 JP 5517202B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- fluorine
- atom
- oxetane compound
- methyloxetane
- 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.)
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- -1 oxetane compound Chemical class 0.000 title claims description 111
- 229910052731 fluorine Inorganic materials 0.000 title claims description 34
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 27
- 239000011737 fluorine Substances 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000003444 phase transfer catalyst Substances 0.000 claims description 17
- 150000001298 alcohols Chemical class 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- 150000003983 crown ethers Chemical group 0.000 claims description 3
- 150000004714 phosphonium salts Chemical group 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 238000006266 etherification reaction Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 52
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 44
- 239000012044 organic layer Substances 0.000 description 38
- 238000004817 gas chromatography Methods 0.000 description 26
- 239000000243 solution Substances 0.000 description 26
- 238000004821 distillation Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 22
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 238000000926 separation method Methods 0.000 description 13
- CVMBZULCJCBJFZ-UHFFFAOYSA-N 3-bromo-2-(bromomethyl)-2-methylpropan-1-ol Chemical compound OCC(C)(CBr)CBr CVMBZULCJCBJFZ-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 238000000746 purification Methods 0.000 description 12
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 10
- KNLXBOKBOCQJTG-UHFFFAOYSA-N 3-methyl-3-(2,2,2-trifluoroethoxymethyl)oxetane Chemical compound FC(F)(F)COCC1(C)COC1 KNLXBOKBOCQJTG-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003513 alkali Substances 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WXJFKAZDSQLPBX-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)F WXJFKAZDSQLPBX-UHFFFAOYSA-N 0.000 description 3
- LRPYTEPQYSEINP-UHFFFAOYSA-N 2,2-bis(bromomethyl)butan-1-ol Chemical compound CCC(CO)(CBr)CBr LRPYTEPQYSEINP-UHFFFAOYSA-N 0.000 description 3
- QZYAQRJJGPOBHO-UHFFFAOYSA-N 3-(2,2,3,3,4,4,4-heptafluorobutoxymethyl)-3-methyloxetane Chemical compound FC(F)(F)C(F)(F)C(F)(F)COCC1(C)COC1 QZYAQRJJGPOBHO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KPGKUVSAZAQEDI-UHFFFAOYSA-N CCC1(COC1)COCC(C(C(F)(F)F)(F)F)(F)F Chemical compound CCC1(COC1)COCC(C(C(F)(F)F)(F)F)(F)F KPGKUVSAZAQEDI-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 229940090181 propyl acetate Drugs 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- GJPGDCXOXFQINC-UHFFFAOYSA-N 3-ethyl-3-(2,2,2-trifluoroethoxymethyl)oxetane Chemical compound FC(F)(F)COCC1(CC)COC1 GJPGDCXOXFQINC-UHFFFAOYSA-N 0.000 description 2
- XCBUJZSDVFFWHE-UHFFFAOYSA-N 3-methyl-3-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctoxymethyl)oxetane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)COCC1(C)COC1 XCBUJZSDVFFWHE-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000002921 oxetanes Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical group [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical group [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- FIARMZDBEGVMLV-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanolate Chemical group [O-]C(F)(F)C(F)(F)F FIARMZDBEGVMLV-UHFFFAOYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- ZYCZHMITGWGHQV-UHFFFAOYSA-N 1,4,7,10-tetraoxacyclotridecane Chemical compound C1COCCOCCOCCOC1 ZYCZHMITGWGHQV-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- AMCWGHNIYLEOOO-UHFFFAOYSA-N 1-bromopentan-2-ol Chemical compound CCCC(O)CBr AMCWGHNIYLEOOO-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- PSQZJKGXDGNDFP-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropan-1-ol Chemical compound OCC(F)(F)C(F)(F)F PSQZJKGXDGNDFP-UHFFFAOYSA-N 0.000 description 1
- QZFZPVVDBGXQTB-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QZFZPVVDBGXQTB-UHFFFAOYSA-N 0.000 description 1
- STLNAVFVCIRZLL-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F STLNAVFVCIRZLL-UHFFFAOYSA-N 0.000 description 1
- PJDOLCGOTSNFJM-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F PJDOLCGOTSNFJM-UHFFFAOYSA-N 0.000 description 1
- KVNMZZLHGQPPIG-UHFFFAOYSA-N 2,2-difluoro-2-(1,1,2,2,2-pentafluoroethoxy)ethanol Chemical compound OCC(F)(F)OC(F)(F)C(F)(F)F KVNMZZLHGQPPIG-UHFFFAOYSA-N 0.000 description 1
- SFESMARWLHCUBQ-UHFFFAOYSA-N 2,2-difluoro-2-[1,1,2,2-tetrafluoro-2-[1,1,2,2-tetrafluoro-2-(1,1,2,2,2-pentafluoroethoxy)ethoxy]ethoxy]ethanol Chemical compound OCC(F)(F)OC(F)(F)C(F)(F)OC(F)(F)C(F)(F)OC(F)(F)C(F)(F)F SFESMARWLHCUBQ-UHFFFAOYSA-N 0.000 description 1
- QKQPFGZTCWEPEF-UHFFFAOYSA-N 2,2-difluoro-2-[1,1,2,2-tetrafluoro-2-[1,1,2,2-tetrafluoro-2-[1,1,2,2-tetrafluoro-2-(1,1,2,2,2-pentafluoroethoxy)ethoxy]ethoxy]ethoxy]ethanol Chemical compound OCC(F)(F)OC(F)(F)C(F)(F)OC(F)(F)C(F)(F)OC(F)(F)C(F)(F)OC(F)(F)C(F)(F)F QKQPFGZTCWEPEF-UHFFFAOYSA-N 0.000 description 1
- MSOLHCPBFWYOSH-UHFFFAOYSA-N 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)propan-1-ol Chemical compound OCC(F)(C(F)(F)F)OC(F)(F)C(F)(F)C(F)(F)F MSOLHCPBFWYOSH-UHFFFAOYSA-N 0.000 description 1
- GQNDYKSJNXAEBI-UHFFFAOYSA-N 2-(bromomethyl)-3-chloro-2-methylpropan-1-ol Chemical compound OCC(C)(CCl)CBr GQNDYKSJNXAEBI-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- HDBGBTNNPRCVND-UHFFFAOYSA-N 3,3,3-trifluoropropan-1-ol Chemical compound OCCC(F)(F)F HDBGBTNNPRCVND-UHFFFAOYSA-N 0.000 description 1
- JPMHUDBOKDBBLG-UHFFFAOYSA-N 3,3,4,4,4-pentafluorobutan-1-ol Chemical compound OCCC(F)(F)C(F)(F)F JPMHUDBOKDBBLG-UHFFFAOYSA-N 0.000 description 1
- ROTSWXZIBBJEPH-UHFFFAOYSA-N 3,3,4,4,5,5,5-heptafluoropentan-1-ol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)F ROTSWXZIBBJEPH-UHFFFAOYSA-N 0.000 description 1
- JCMNMOBHVPONLD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohexan-1-ol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F JCMNMOBHVPONLD-UHFFFAOYSA-N 0.000 description 1
- NPOAVCPGPRUNOX-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptan-1-ol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F NPOAVCPGPRUNOX-UHFFFAOYSA-N 0.000 description 1
- GRJRKPMIRMSBNK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctan-1-ol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GRJRKPMIRMSBNK-UHFFFAOYSA-N 0.000 description 1
- JJUBFBTUBACDHW-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JJUBFBTUBACDHW-UHFFFAOYSA-N 0.000 description 1
- WOBDSRMWHWAQFO-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluorononan-1-ol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F WOBDSRMWHWAQFO-UHFFFAOYSA-N 0.000 description 1
- ZWDCXRWHPBYVKX-UHFFFAOYSA-N 3-bromo-2-(bromomethyl)propan-1-ol Chemical compound OCC(CBr)CBr ZWDCXRWHPBYVKX-UHFFFAOYSA-N 0.000 description 1
- DOANJBQUOFJQHC-UHFFFAOYSA-N 3-chloro-2-(chloromethyl)-2-methylpropan-1-ol Chemical compound OCC(C)(CCl)CCl DOANJBQUOFJQHC-UHFFFAOYSA-N 0.000 description 1
- ZUWNSCHEAVERRA-UHFFFAOYSA-N 3-chloro-2-(chloromethyl)propan-1-ol Chemical compound OCC(CCl)CCl ZUWNSCHEAVERRA-UHFFFAOYSA-N 0.000 description 1
- BMFCOKBDBKQIMW-UHFFFAOYSA-N 3-ethyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctoxymethyl)oxetane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOCC1(CC)COC1 BMFCOKBDBKQIMW-UHFFFAOYSA-N 0.000 description 1
- QMWCJNSLCFGXLC-UHFFFAOYSA-N 3-iodo-2-(iodomethyl)propan-1-ol Chemical compound OCC(CI)CI QMWCJNSLCFGXLC-UHFFFAOYSA-N 0.000 description 1
- WTXTVOBDAYMETL-UHFFFAOYSA-N 3-methyl-3-(2,2,3,3,3-pentafluoropropoxymethyl)oxetane Chemical compound FC(F)(F)C(F)(F)COCC1(C)COC1 WTXTVOBDAYMETL-UHFFFAOYSA-N 0.000 description 1
- RLXHIMBSZODLLI-UHFFFAOYSA-N 3-methyl-3-(3,3,4,4,4-pentafluorobutoxymethyl)oxetane Chemical compound CC1(COCCC(F)(F)C(F)(F)F)COC1 RLXHIMBSZODLLI-UHFFFAOYSA-N 0.000 description 1
- DTJCOUKHJQCCKV-UHFFFAOYSA-N 3-methyl-3-(3,3,4,4,5,5,6,6,6-nonafluorohexoxymethyl)oxetane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOCC1(C)COC1 DTJCOUKHJQCCKV-UHFFFAOYSA-N 0.000 description 1
- FUKBVIWXOZPQGY-UHFFFAOYSA-N 3-methyl-3-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctoxymethyl)oxetane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCOCC1(C)COC1 FUKBVIWXOZPQGY-UHFFFAOYSA-N 0.000 description 1
- SPFCTADHPPKFTO-UHFFFAOYSA-N 3-methyl-3-(4,4,5,5,6,6,7,7,7-nonafluoroheptoxymethyl)oxetane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)CCCOCC1(C)COC1 SPFCTADHPPKFTO-UHFFFAOYSA-N 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- QROUUECTKRZFHF-UHFFFAOYSA-N 4,4,5,5,5-pentafluoropentan-1-ol Chemical compound OCCCC(F)(F)C(F)(F)F QROUUECTKRZFHF-UHFFFAOYSA-N 0.000 description 1
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- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003104 hexanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical class [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QLPMKRZYJPNIRP-UHFFFAOYSA-M methyl(trioctyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC QLPMKRZYJPNIRP-UHFFFAOYSA-M 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 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 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- SWYHWLFHDVMLHO-UHFFFAOYSA-N oxetan-3-ylmethanol Chemical compound OCC1COC1 SWYHWLFHDVMLHO-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001325 propanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical group [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 125000004205 trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- GNMJFQWRASXXMS-UHFFFAOYSA-M trimethyl(phenyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1=CC=CC=C1 GNMJFQWRASXXMS-UHFFFAOYSA-M 0.000 description 1
- MQAYPFVXSPHGJM-UHFFFAOYSA-M trimethyl(phenyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C1=CC=CC=C1 MQAYPFVXSPHGJM-UHFFFAOYSA-M 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Epoxy Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、含フッ素オキセタン化合物の製造方法に関する。本発明の製造によって得られる含フッ素オキセタン化合物は、含フッ素モノマー、低屈折率樹脂組成物等の原料あるいはカチオン硬化性成分やラジカル硬化性成分として極めて有用である。 The present invention relates to a method for producing a fluorine-containing oxetane compound. The fluorine-containing oxetane compound obtained by the production of the present invention is extremely useful as a raw material such as a fluorine-containing monomer and a low refractive index resin composition, a cationic curable component, or a radical curable component.
3−アルコキシメチルオキセタン化合物を製造する方法として、3−ハロメチルオキセタン化合物をフェノール類またはアルコール類と反応させる方法が知られている。
例えば、エチレングリコール類を溶媒に使用して、3−アルキル−3−ハロメチルオキセタン化合物と二価フェノール類のアルカリ金属塩とを反応させてビスオキセタンエーテル化合物を合成する方法(例えば特許文献1参照)、アルカリ水溶液または水懸濁液中、相間移動触媒の存在下、3−アルキル−3−ハロメチルオキセタン化合物を3−アルキル−3−ハロメチルオキセタン化合物の加水分解によって生成する3−アルキル−3−ヒドロキシメチルオキセタン化合物と反応させてビスオキセタンエーテル化合物を合成する方法(例えば特許文献2参照)、3−ヒドロキシメチルオキセタン化合物と有機スルホン酸ハライドを、有機塩基の存在下、反応中に生成する有機塩基のハロゲン化水素酸塩が溶解する状態で反応させ、次いで、生成した3−ハロメチルオキセタン化合物とアルコール類を固体又は非水溶液のアルカリの添加下で反応させて3−アルコキシメチルオキセタン化合物を合成する方法(例えば特許文献3参照)、アルカリ存在下、フェノール類またはアルコール類と3−アルキル−3−ハロメチルオキセタン化合物を反応させる方法において、反応系外に水を除去しながら反応させてオキセタンエーテル化合物を合成する方法(例えば特許文献4参照)、アルカリ存在下、レゾルシンと3−アルキル−3−ハロメチルオキセタン化合物を反応させる方法において、アルカリを連続的または非連続的に供給し、かつ反応系内の水を反応系外へ除去しながら反応させてオキセタンエーテル化合物を合成する方法(例えば特許文献5参照)、アルカリおよびポリアルキルエーテル化合物の存在下、3−アルキル−3−ハロメチルオキセタン化合物とアルコール類を反応させてオキセタンエーテル化合物を合成する方法(例えば特許文献6参照)などが知られている。
As a method for producing a 3-alkoxymethyloxetane compound, a method in which a 3-halomethyloxetane compound is reacted with phenols or alcohols is known.
For example, a method of synthesizing a bisoxetane ether compound by reacting a 3-alkyl-3-halomethyloxetane compound with an alkali metal salt of a dihydric phenol using ethylene glycol as a solvent (see, for example, Patent Document 1). 3-alkyl-3 produced by hydrolysis of a 3-alkyl-3-halomethyloxetane compound in an aqueous alkali or water suspension in the presence of a phase transfer catalyst. A method of synthesizing a bisoxetane ether compound by reacting with a -hydroxymethyloxetane compound (see, for example, Patent Document 2), an organic compound produced during the reaction of a 3-hydroxymethyloxetane compound and an organic sulfonic acid halide in the presence of an organic base The base hydrohalide is reacted in the dissolved state, then A method of synthesizing a 3-alkoxymethyloxetane compound by reacting the formed 3-halomethyloxetane compound with an alcohol in the presence of a solid or non-aqueous alkali (see, for example, Patent Document 3), in the presence of an alkali, In the method of reacting an alcohol with a 3-alkyl-3-halomethyloxetane compound, a method of synthesizing an oxetane ether compound by removing water outside the reaction system (see, for example, Patent Document 4), in the presence of an alkali, In a method of reacting resorcin with a 3-alkyl-3-halomethyloxetane compound, an oxetane ether compound is prepared by supplying alkali continuously or discontinuously and removing water from the reaction system outside the reaction system. (See, for example, Patent Document 5), alkali and poly Presence of Kill ether compounds, a method of synthesizing a 3-alkyl-3-halo-methyl oxetane compound and an alcohol are reacted oxetane ether compounds (for example, see Patent Document 6) are known.
また、3−ハロメチルオキセタン化合物を含フッ素アルコール類と反応させて3−含フッ素アルコキシメチルオキセタン化合物を製造する方法としては、例えば、アルカリ存在下、α,ω−(ジメチロール)パーフルオロアルカンと3−アルキル−3−クロロメチルオキセタン化合物または3−クロロメチルオキセタン化合物とを反応させてオキセタン環を有するα,ω−(ジメチロール)パーフルオロアルカン誘導体を製造する方法(例えば特許文献7参照)、塩基および相間移動触媒の存在下、3−アルキル−3−ハロメチルオキセタン化合物を含フッ素アルコール類と反応させる方法(例えば特許文献7、特許文献8、特許文献9参照)などが知られている。
これら3−ハロメチルオキセタン化合物をアルコール類若しくは含フッ素アルコール類とアルカリ条件下で反応させて3−アルコキシメチルオキセタン化合物若しくは3−含フッ素アルコキシメチルオキセタン化合物を製造する方法においては、収率は良好である。
Moreover, as a method for producing a 3-fluorinated alkoxymethyloxetane compound by reacting a 3-halomethyloxetane compound with a fluorinated alcohol, for example, α, ω- (dimethylol) perfluoroalkane and 3 in the presence of an alkali can be used. A method for producing an α, ω- (dimethylol) perfluoroalkane derivative having an oxetane ring by reacting an alkyl-3-chloromethyloxetane compound or a 3-chloromethyloxetane compound (see, for example, Patent Document 7), a base and A method of reacting a 3-alkyl-3-halomethyloxetane compound with a fluorinated alcohol in the presence of a phase transfer catalyst (see, for example, Patent Document 7, Patent Document 8, and Patent Document 9) is known.
In the method of producing a 3-alkoxymethyl oxetane compound or a 3-fluorinated alkoxymethyloxetane compound by reacting these 3-halomethyloxetane compounds with alcohols or fluorine-containing alcohols under alkaline conditions, the yield is good. is there.
しかしながら、原料に使用する3−ハロメチルオキセタン化合物の製造に課題がある。3−ハロメチルオキセタン化合物の製造方法としては、2−置換−3−ハロ−2−ハロメチルプロパノールまたはそのカルボン酸エステルをアルカリ水溶液または水懸濁液中で反応させる方法(例えば特許文献10参照)、アルカリ水溶液と相間移動触媒を用いる方法(例えば特許文献8、特許文献11、特許文献12参照)などが知られている。特許文献8の記載によると、3−ハロメチルオキセタンを製造する方法において、2−アルキル−3−ハロ−2−ハロメチルプロピルアセテートを四塩化炭素あるいは塩化n−ブチル溶媒中、アルカリ水溶液および相間移動触媒の存在下で処理することで、目的とする3−アルキル−3−ハロメチルオキセタンを収率良く合成可能である。しかしながら、四塩化炭素あるいは塩化n−ブチルを使用しない場合、副反応が促進されて収率が著しく低下する。副反応を抑制するためには、四塩化炭素を溶媒に使用し、相間移動触媒の存在下で反応させることが必須であり、この方法は溶媒に四塩化炭素を使用しているため工業的な製法とは言えない。2−置換−3−ハロ−2−ハロメチルプロパノールまたはそのカルボン酸エステルを原料に用いて含フッ素オキセタン化合物を製造する過程において、四塩化炭素を溶媒として使用しなくても高収率で目的化合物を合成可能な環境調和型製法の開発が望まれている。 However, there is a problem in the production of 3-halomethyloxetane compounds used as raw materials. As a method for producing a 3-halomethyloxetane compound, a method in which 2-substituted-3-halo-2-halomethylpropanol or a carboxylic acid ester thereof is reacted in an alkaline aqueous solution or an aqueous suspension (for example, see Patent Document 10). A method using an aqueous alkali solution and a phase transfer catalyst (see, for example, Patent Document 8, Patent Document 11, and Patent Document 12) is known. According to the description of Patent Document 8, in the process for producing 3-halomethyloxetane, 2-alkyl-3-halo-2-halomethylpropyl acetate is mixed with an aqueous alkali solution and a phase transfer in a carbon tetrachloride or n-butyl chloride solvent. By treating in the presence of a catalyst, the target 3-alkyl-3-halomethyloxetane can be synthesized with high yield. However, when carbon tetrachloride or n-butyl chloride is not used, side reactions are promoted and the yield is significantly reduced. In order to suppress side reactions, it is essential to use carbon tetrachloride as a solvent and to react in the presence of a phase transfer catalyst. This method uses carbon tetrachloride as a solvent and is therefore industrial. It's not a manufacturing method. In the process of producing a fluorine-containing oxetane compound using 2-substituted-3-halo-2-halomethylpropanol or a carboxylic acid ester thereof as a raw material, the target compound is obtained in a high yield without using carbon tetrachloride as a solvent. The development of an environmentally harmonious manufacturing method that can synthesize compounds is desired.
また、本発明には直接関係しないが、3−ハロメチルオキセタン化合物のその他の製造方法として、有機塩基の存在下、3−ヒドロキシメチルオキセタン化合物に有機スルホン酸ハライドを接触させ、副生する有機塩基のハロゲン化水素酸塩を3−ハロメチルオキセタン化合物のハロゲン源として、3−ハロメチルオキセタン化合物を合成する方法(例えば、特許文献13参照)、トリメチロールメタン化合物をハロゲン化チオニルと反応させて、環状亜硫酸エステル化合物を生成させ、次いで、この環状亜硫酸エステル化合物を有機オニウム塩の存在下で脱二酸化硫黄反応させて3−ハロメチルオキセタン化合物を合成する方法(例えば特許文献14参照)などが知られているが、これらの方法では、有機溶剤の使用および反応操作が煩雑などの問題が挙げられ、より経済的かつ簡便な製法開発が望まれている。 Although not directly related to the present invention, as another method for producing a 3-halomethyloxetane compound, an organic sulfonic acid halide is brought into contact with a 3-hydroxymethyloxetane compound in the presence of an organic base, thereby forming an organic base as a by-product. A method for synthesizing a 3-halomethyloxetane compound (for example, see Patent Document 13), using a hydrohalide salt of the above as a halogen source of a 3-halomethyloxetane compound, reacting a trimethylolmethane compound with thionyl halide, A method is known in which a cyclic sulfite compound is produced, and then this cyclic sulfite compound is desulfurized in the presence of an organic onium salt to synthesize a 3-halomethyloxetane compound (see, for example, Patent Document 14). However, in these methods, the use of organic solvents and the reaction operation are complicated. Which problems can be mentioned, more economical and convenient process development is desired.
また、本発明には直接関係しないが、含フッ素オキセタン化合物のその他の製造方法としては、3−アルキル−3−ヒドロキシメチルオキセタンのp−トルエンスルホネートと含フッ素アルコール類を塩基性条件下で反応させる方法(例えば特許文献8参照)、また、3−ヒドロキシメチルオキセタンと含フッ素オレフィンを塩基性条件下で反応させる方法(例えば特許文献15、特許文献16参照)なども知られているが、3−アルキル−3−ヒドロキシメチルオキセタンのp−トルエンスルホネートと含フッ素アルコール類を塩基性条件下で反応させる方法では、収率が低く、高収率で含フッ素オキセタン類を合成する実用的製法の開発が望まれている。 Although not directly related to the present invention, as another method for producing a fluorine-containing oxetane compound, p-toluenesulfonate of 3-alkyl-3-hydroxymethyloxetane and a fluorine-containing alcohol are reacted under basic conditions. A method (for example, see Patent Document 8) and a method in which 3-hydroxymethyloxetane and a fluorine-containing olefin are reacted under basic conditions (for example, see Patent Document 15 and Patent Document 16) are also known. In the method of reacting alkyl-3-hydroxymethyloxetane p-toluenesulfonate with fluorinated alcohols under basic conditions, there is a low yield, and there is a development of a practical process for synthesizing fluorinated oxetanes with high yield. It is desired.
本発明は、上記課題に鑑みてなされたものであり、その目的は従来技術では満足できなかった含フッ素オキセタン化合物の製造方法を提供することにある。即ち、効率的に高収率で含フッ素オキセタン化合物を製造することができる環境調和型製法を提供することにある。 The present invention has been made in view of the above problems, and an object of the present invention is to provide a method for producing a fluorine-containing oxetane compound which has not been satisfied by the prior art. That is, it is to provide an environmentally conscious production method that can efficiently produce a fluorine-containing oxetane compound with high yield.
本発明者らは、上記課題を解決するために鋭意検討した結果、2−置換−3−ハロ−2−ハロメチルプロパノール誘導体を塩基の存在下、あるいは、塩基および相間移動触媒の存在下で、含フッ素アルコール類と反応させることにより、従来複数のステップ数で反応する必要があった含フッ素オキセタン化合物の製造を1ステップに短縮可能であり、かつ、環境調和に配慮して四塩化炭素などの有機溶媒を使用せずに高収率で含フッ素オキセタン化合物を製造可能であることを見出し、本発明を完成させるに至った。
すなわち本発明は、下記一般式(1)
As a result of diligent studies to solve the above problems, the present inventors have found that a 2-substituted-3-halo-2-halomethylpropanol derivative is present in the presence of a base or in the presence of a base and a phase transfer catalyst. By reacting with fluorine-containing alcohols, the production of fluorine-containing oxetane compounds, which conventionally had to be reacted in a plurality of steps, can be shortened to one step, and in consideration of environmental harmony, such as carbon tetrachloride. It has been found that a fluorine-containing oxetane compound can be produced in a high yield without using an organic solvent, and the present invention has been completed.
That is, the present invention provides the following general formula (1)
[式中、R1は水素原子、メチル基、エチル基又は、炭素数3〜6の直鎖状若しくは分岐状若しくは環状のアルキル基を表し、R2は水素原子、炭素数2〜7のアシル基を表し、X1およびX2は各々独立してフッ素原子、塩素原子、臭素原子又はヨウ素原子のいずれかを表す。]
で示される2−置換−3−ハロ−2−ハロメチルプロパノール誘導体を、塩基の存在下、あるいは、塩基および相間移動触媒の存在下で、分子内環化反応および下記一般式(2)
[Wherein R 1 represents a hydrogen atom, a methyl group, an ethyl group or a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, and R 2 represents a hydrogen atom or an acyl having 2 to 7 carbon atoms. Represents a group, and X 1 and X 2 each independently represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ]
In the presence of a base or in the presence of a base and a phase transfer catalyst, an intramolecular cyclization reaction and the following general formula (2)
[式中、Yはフッ素原子で置換された炭素数1〜18のアルキル基であり、エーテル結合を有していてもよい。]
で示される含フッ素アルコールとエーテル化反応させて下記一般式(3)
[Wherein, Y is an alkyl group having 1 to 18 carbon atoms substituted with a fluorine atom, and may have an ether bond. ]
And the following general formula (3)
[式中、R1は水素原子、メチル基、エチル基又は、炭素数3〜6の直鎖状若しくは分岐状若しくは環状のアルキル基を表し、Yはフッ素原子で置換された炭素数1〜18のアルキル基であり、エーテル結合を有していてもよい。]
で示される含フッ素オキセタン化合物を得ることを特徴とする含フッ素オキセタン化合物の製造方法に関するものである。
[Wherein, R 1 represents a hydrogen atom, a methyl group, an ethyl group, or a linear, branched or cyclic alkyl group having 3 to 6 carbon atoms, and Y represents a C 1-18 carbon atom substituted with a fluorine atom. And may have an ether bond. ]
It is related with the manufacturing method of the fluorine-containing oxetane compound characterized by obtaining the fluorine-containing oxetane compound shown by these.
本発明の製造方法によれば、四塩化炭素などの有機溶媒および相間移動触媒を使用しなくても、上記一般式(3)で示される含フッ素オキセタン化合物を効率的に高収率で製造することができる。 According to the production method of the present invention, the fluorine-containing oxetane compound represented by the general formula (3) is efficiently produced at a high yield without using an organic solvent such as carbon tetrachloride and a phase transfer catalyst. be able to.
以下、本発明を詳細に説明する。
本発明において、一般式(1)中、R1である「炭素数3〜6の直鎖状若しくは分岐状若しくは環状のアルキル基」としては、n−プロピル基、n−ブチル基、n−ペンチル基、n−ヘキシル基、i−プロピル基、i−ブチル基、s−ブチル基、t−ブチル基、1−メチルブチル基、2−メチルブチル基、3−メチルブチル基、1,1−ジメチルプロピル基、2,2−ジメチルプロピル基、1,2−ジメチルプロピル基、1−メチルペンチル基、2−メチルペンチル基、3−メチルペンチル基、4−メチルペンチル基、1,1−ジメチルブチル基、1,2−ジメチルブチル基、1,3−ジメチルブチル基、2,2−ジメチルブチル基、2,3−ジメチルブチル基、3,3−ジメチルブチル基、1,1,2−トリメチルプロピル基、1,2,2−トリメチルプロピル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基などが挙げられる。
Hereinafter, the present invention will be described in detail.
In the present invention, in the general formula (1), R 1 represents a “C3-C6 linear, branched or cyclic alkyl group” as an n-propyl group, an n-butyl group, an n-pentyl group. Group, n-hexyl group, i-propyl group, i-butyl group, s-butyl group, t-butyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1, 2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1,1,2-trimethylpropyl group, 1, 2, 2 -A trimethylpropyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.
また、一般式(1)中、R2である「炭素数2〜7のアシル基」としては、アセチル基、プロパノイル基、ブタノイル基、2−メチルプロパノイル基、ペンタノイル基、2−メチルブタノイル基、3−メチルブタノイル基、2,2−ジメチルプロパノイル基、ヘキサノイル基、ベンゾイル基などが挙げられ、好ましくはアセチル基である。 In the general formula (1), the “acyl group having 2 to 7 carbon atoms” as R 2 includes an acetyl group, a propanoyl group, a butanoyl group, a 2-methylpropanoyl group, a pentanoyl group, and 2-methylbutanoyl. Group, 3-methylbutanoyl group, 2,2-dimethylpropanoyl group, hexanoyl group, benzoyl group and the like, and acetyl group is preferable.
本発明において上記一般式(1)で示される2−置換−3−ハロ−2−ハロメチルプロパノール誘導体としては、特に限定するものではないが、3−クロロ−2−(クロロメチル)プロパン−1−オール、3−ブロモ−2−(ブロモメチル)プロパン−1−オール、3−ヨード−2−(ヨードメチル)プロパン−1−オール、3−クロロ−2−(クロロメチル)−2−メチルプロパン−1−オール、3−ブロモ−2−(ブロモメチル)−2−メチルプロパン−1−オール、3−ブロモ−2−(クロロメチル)−2−メチルプロパン−1−オール、2,2−ビス(クロロメチル)ブタン−1−オール、2,2−ビス(ブロモメチル)ブタン−1−オール、2,2−ビス(ヨードメチル)ブタン−1−オール、3−クロロ−2−(クロロメチル)プロピルアセテート、3−ブロモ−2−(ブロモメチル)プロピルアセテート、3−ヨード−2−(ヨードメチル)プロピルアセテート、3−クロロ−2−(クロロメチル)−2−メチルプロピルアセテート、3−ブロモ−2−(ブロモメチル)−2−メチルプロピルアセテート、2,2−ビス(クロロメチル)ブチルアセテート、2,2−ビス(ブロモメチル)ブチルアセテートなどが挙げられる。 In the present invention, the 2-substituted-3-halo-2-halomethylpropanol derivative represented by the general formula (1) is not particularly limited, but 3-chloro-2- (chloromethyl) propane-1 -Ol, 3-bromo-2- (bromomethyl) propan-1-ol, 3-iodo-2- (iodomethyl) propan-1-ol, 3-chloro-2- (chloromethyl) -2-methylpropane-1 -Ol, 3-bromo-2- (bromomethyl) -2-methylpropan-1-ol, 3-bromo-2- (chloromethyl) -2-methylpropan-1-ol, 2,2-bis (chloromethyl) ) Butan-1-ol, 2,2-bis (bromomethyl) butan-1-ol, 2,2-bis (iodomethyl) butan-1-ol, 3-chloro-2- (chloromethyl) Lopyl acetate, 3-bromo-2- (bromomethyl) propyl acetate, 3-iodo-2- (iodomethyl) propyl acetate, 3-chloro-2- (chloromethyl) -2-methylpropyl acetate, 3-bromo-2 -(Bromomethyl) -2-methylpropyl acetate, 2,2-bis (chloromethyl) butyl acetate, 2,2-bis (bromomethyl) butyl acetate and the like.
本発明において、一般式(2)中、Yである「フッ素原子で置換された炭素数1〜18のアルキル基であり、エーテル結合を有してもよい」としては、2,2,2−トリフルオロエチル基、2,2,3,3,3−ペンタフルオロプロピル基、2,2,3,3,4,4,4−ヘプタフルオロブチル基、2,2,3,3,4,4,5,5,5−ノナフルオロペンチル基、2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロヘキシル基、2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチル基、2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチル基、2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ヘプタデカフルオロノニル基、3,3,3−トリフルオロプロピル基、3,3,4,4,4−ペンタフルオロブチル基、3,3,4,4,5,5,5−ヘプタフルオロペンチル基、3,3,4,4,5,5,6,6,6−ノナフルオロヘキシル基、3,3,4,4,5,5,6,6,7,7,7−ウンデカフルオロヘプチル基、3,3,4,4,5,5,6,6,7,7,8,8,8−トリデカフルオロオクチル基、3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ペンタデカフルオロノニル基、3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ヘプタデカフルオロデシル基、4,4,4−トリフルオロブチル基、4,4,5,5,5−ペンタフルオロペンチル基、4,4,5,5,6,6,6−ヘプタフルオロヘキシル基、4,4,5,5,6,6,7,7,7−ノナフルオロヘプチル基、4,4,5,5,6,6,7,7,8,8,8−ウンデカフルオロオクチル基、4,4,5,5,6,6,7,7,8,8,9,9,9−トリデカフルオロノニル基、4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ペンタデカフルオロデシル基、4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11−ヘプタデカフルオロウンデシル基、5,5,5−トリフルオロペンチル基、5,5,6,6,6−ペンタフルオロヘキシル基、5,5,6,6,7,7,7−ヘプタフルオロヘプチル基、5,5,6,6,7,7,8,8,8−ノナフルオロオクチル基、5,5,6,6,7,7,8,8,9,9,9−ウンデカフルオロノニル基、5,5,6,6,7,7,8,8,9,9,10,10,10−トリデカフルオロデシル基、5,5,6,6,7,7,8,8,9,9,10,10,11,11,11−ペンタデカフルオロウンデシル基、5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12−ヘプタデカフルオロドデシル基、6,6,6−トリフルオロヘキシル基、6,6,7,7,7−ペンタフルオロヘプチル基、6,6,7,7,8,8,8−ヘプタフルオロオクチル基、6,6,7,7,8,8,9,9,9−ノナフルオロノニル基、6,6,7,7,8,8,9,9,10,10,10−ウンデカフルオロデシル基、6,6,7,7,8,8,9,9,10,10,11,11,11−トリデカフルオロウンデシル基、6,6,7,7,8,8,9,9,10,10,11,11,12,12,12−ペンタデカフルオロドデシル基、6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13−ヘプタデカフルオロトリデシル基、2−(ペンタフルオロエトキシ)−2,2−ジフルオロエチル基、2,2,4,4,5,5,7,7,8,8,8−ウンデカフルオロ−3,6−ジオキサオクチル基、2,2,4,4,5,5,7,7,8,8,10,10,11,11,11−ペンタデカフルオロ−3,6,9−トリオキサウンデシル基、2,2,4,4,5,5,7,7,8,8,10,10,11,11,13,13,14,14,14−ノナデカフルオロ−3,6,9,12−テトラオキサテトラデシル基、2−ヘプタフルオロプロポキシ−2,3,3,3−テトラフルオロプロピル基、2,4,4,5,7,7,8,8,9,9,9−ウンデカフルオロ−2,5−ビス(トリフルオロメチル)−3,6−ジオキサノニル基、2,4,4,5,7,7,8,10,10,11,11,12,12,12−テトラデカフルオロ−2,5,8−トリス(トリフルオロメチル)−3,6,9−トリオキサドデシル基などが挙げられる。 In the present invention, in the general formula (2), Y is “an alkyl group having 1 to 18 carbon atoms substituted with a fluorine atom and may have an ether bond”. Trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,3,3,4,4,4-heptafluorobutyl group, 2,2,3,3,4,4 , 5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl group, 2,2,3,3,4, 4,5,5,6,6,7,7,7-tridecafluoroheptyl group, 2,2,3,3,4,5,5,6,6,7,7,8,8, 8-pentadecafluorooctyl group, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyl group, , 3,3-trifluoropropyl group, 3,3,4,4,4-pentafluorobutyl group, 3,3,4,4,5,5,5-heptafluoropentyl group, 3,3,4, 4,5,5,6,6,6-nonafluorohexyl group, 3,3,4,4,5,5,6,6,7,7,7-undecafluoroheptyl group, 3,3,4 , 4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl group, 3,3,4,4,5,5,6,6,7,7,8,8 , 9,9,9-pentadecafluorononyl group, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro Decyl group, 4,4,4-trifluorobutyl group, 4,4,5,5,5-pentafluoropentyl group, 4,4,5,5,6,6,6-heptafluorohexyl 4,4,5,5,6,6,7,7,7-nonafluoroheptyl group, 4,4,5,5,6,6,7,7,8,8,8-undecafluorooctyl Group 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononyl group, 4,4,5,5,6,6,7,7, 8,8,9,9,10,10,10-pentadecafluorodecyl group, 4,4,5,5,6,6,7,7,8,8,9,9,10,10,11, 11,11-heptadecafluoroundecyl group, 5,5,5-trifluoropentyl group, 5,5,6,6,6-pentafluorohexyl group, 5,5,6,6,7,7,7 -Heptafluoroheptyl group, 5,5,6,6,7,7,8,8,8-nonafluorooctyl group, 5,5,6,6,7,7,8,8,9,9,9 -Unde cuff Luononyl group, 5,5,6,6,7,7,8,8,9,9,10,10,10-tridecafluorodecyl group, 5,5,6,6,7,7,8,8 , 9,9,10,10,11,11,11-pentadecafluoroundecyl group, 5,5,6,6,7,7,8,8,9,9,10,10,11,11, 12,12,12-heptadecafluorododecyl group, 6,6,6-trifluorohexyl group, 6,6,7,7,7-pentafluoroheptyl group, 6,6,7,7,8,8, 8-heptafluorooctyl group, 6,6,7,7,8,8,9,9,9-nonafluorononyl group, 6,6,7,7,8,8,9,9,10,10, 10-undecafluorodecyl group, 6,6,7,7,8,8,9,9,10,10,11,11,11-tridecafluoroun Sil group, 6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-pentadecafluorododecyl group, 6,6,7,7,8,8 , 9, 9, 10, 10, 11, 11, 12, 12, 13, 13, 13-heptadecafluorotridecyl group, 2- (pentafluoroethoxy) -2,2-difluoroethyl group, 2, 2, 4,4,5,5,7,7,8,8,8-undecafluoro-3,6-dioxaoctyl group, 2,2,4,4,5,5,7,7,8,8 , 10,10,11,11,11-pentadecafluoro-3,6,9-trioxaundecyl group, 2,2,4,4,5,5,7,7,8,8,10,10 , 11, 11, 13, 13, 14, 14, 14-nonadecafluoro-3,6,9,12-tetraoxatetradecyl group, -Heptafluoropropoxy-2,3,3,3-tetrafluoropropyl group, 2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis ( (Trifluoromethyl) -3,6-dioxanonyl group, 2,4,4,5,7,7,8,10,10,11,11,12,12,12-tetradecafluoro-2,5,8- And tris (trifluoromethyl) -3,6,9-trioxadodecyl group.
本発明において上記一般式(2)で示される含フッ素アルコールとしては、特に限定するものでないが、例えば2,2,2−トリフルオロエタノール、2,2,3,3,3−ペンタフルオロプロパン−1−オール、2,2,3,3,4,4,4−ヘプタフルオロブタン−1−オール、2,2,3,3,4,4,5,5,5−ノナフルオロペンタン−1−オール、2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロヘキサン−1−オール、2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプタン−1−オール、2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクタン−1−オール、2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ヘプタデカフルオロノナン−1−オール、3,3,3−トリフルオロプロパン−1−オール、3,3,4,4,4−ペンタフルオロブタン−1−オール、3,3,4,4,5,5,5−ヘプタフルオロペンタン−1−オール、3,3,4,4,5,5,6,6,6−ノナフルオロヘキサン−1−オール、3,3,4,4,5,5,6,6,7,7,7−ウンデカフルオロヘプタン−1−オール、3,3,4,4,5,5,6,6,7,7,8,8,8−トリデカフルオロオクタン−1−オール、3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ペンタデカフルオロノナン−1−オール、3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ヘプタデカフルオロデカン−1−オール、4,4,4−トリフルオロブタン−1−オール、4,4,5,5,5−ペンタフルオロペンタン−1−オール、4,4,5,5,6,6,6−ヘプタフルオロヘキサン−1−オール、4,4,5,5,6,6,7,7,7−ノナフルオロヘプタン−1−オール、4,4,5,5,6,6,7,7,8,8,8−ウンデカフルオロオクタン−1−オール、4,4,5,5,6,6,7,7,8,8,9,9,9−トリデカフルオロノナン−1−オール、4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ペンタデカフルオロデカン−1−オール、4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11−ヘプタデカフルオロウンデカン−1−オール、5,5,5−トリフルオロペンタン−1−オール、5,5,6,6,6−ペンタフルオロヘキサン−1−オール、5,5,6,6,7,7,7−ヘプタフルオロヘプタン−1−オール、5,5,6,6,7,7,8,8,8−ノナフルオロオクタン−1−オール、5,5,6,6,7,7,8,8,9,9,9−ウンデカフルオロノナン−1−オール、5,5,6,6,7,7,8,8,9,9,10,10,10−トリデカフルオロデカン−1−オール、5,5,6,6,7,7,8,8,9,9,10,10,11,11,11−ペンタデカフルオロウンデカン−1−オール、5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12−ヘプタデカフルオロドデカン−1−オール、6,6,6−トリフルオロヘキサン−1−オール、6,6,7,7,7−ペンタフルオロヘプタン−1−オール、6,6,7,7,8,8,8−ヘプタフルオロオクタン−1−オール、6,6,7,7,8,8,9,9,9−ノナフルオロノナン−1−オール、6,6,7,7,8,8,9,9,10,10,10−ウンデカフルオロデカン−1−オール、6,6,7,7,8,8,9,9,10,10,11,11,11−トリデカフルオロウンデカン−1−オール、6,6,7,7,8,8,9,9,10,10,11,11,12,12,12−ペンタデカフルオロドデカン−1−オール、6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,13−ヘプタデカフルオロトリデカン−1−オール、2−(ペンタフルオロエトキシ)−2,2−ジフルオロエタノール、2,2,4,4,5,5,7,7,8,8,8−ウンデカフルオロ−3,6−ジオキサオクタン−1−オール、2,2,4,4,5,5,7,7,8,8,10,10,11,11,11−ペンタデカフルオロ−3,6,9−トリオキサウンデカン−1−オール、2,2,4,4,5,5,7,7,8,8,10,10,11,11,13,13,14,14,14−ノナデカフルオロ−3,6,9,12−テトラオキサテトラデカン−1−オール、2−ヘプタフルオロプロポキシ−2,3,3,3−テトラフルオロプロパン−1−オール、2,4,4,5,7,7,8,8,9,9,9−ウンデカフルオロ−2,5−ビス(トリフルオロメチル)−3,6−ジオキサノナン−1−オール、2,4,4,5,7,7,8,10,10,11,11,12,12,12−テトラデカフルオロ−2,5,8−トリス(トリフルオロメチル)−3,6,9−トリオキサドデカン−1−オールなどが挙げられる。 In the present invention, the fluorinated alcohol represented by the general formula (2) is not particularly limited. For example, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropane- 1-ol, 2,2,3,3,4,4,4-heptafluorobutan-1-ol, 2,2,3,3,4,4,5,5,5-nonafluoropentane-1- All, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexane-1-ol, 2,2,3,3,4,4,5,5,6 , 6,7,7,7-tridecafluoroheptan-1-ol, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadeca Fluoroctan-1-ol, 2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,9-hept Tadecafluorononan-1-ol, 3,3,3-trifluoropropan-1-ol, 3,3,4,4,4-pentafluorobutan-1-ol, 3,3,4,4,5 , 5,5-heptafluoropentan-1-ol, 3,3,4,4,5,5,6,6,6-nonafluorohexane-1-ol, 3,3,4,4,5,5 , 6,6,7,7,7-undecafluoroheptan-1-ol, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctane -1-ol, 3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-pentadecafluorononan-1-ol, 3,3,4, 4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecan-1-ol, 4,4,4-tri Luolobutan-1-ol, 4,4,5,5,5-pentafluoropentan-1-ol, 4,4,5,5,6,6,6-heptafluorohexane-1-ol, 4,4 5,5,6,6,7,7,7-nonafluoroheptan-1-ol, 4,4,5,5,6,6,7,7,8,8,8-undecafluorooctane-1 -Ol, 4,4,5,5,6,6,7,7,8,8,9,9,9-tridecafluorononan-1-ol, 4,4,5,5,6,6 7,7,8,8,9,9,10,10,10-pentadecafluorodecan-1-ol, 4,4,5,5,6,6,7,7,8,8,9,9 , 10, 10, 11, 11, 11-heptadecafluoroundecan-1-ol, 5,5,5-trifluoropentan-1-ol, 5,5, , 6,6-pentafluorohexane-1-ol, 5,5,6,6,7,7,7-heptafluoroheptan-1-ol, 5,5,6,6,7,7,8,8 , 8-nonafluorooctane-1-ol, 5,5,6,6,7,7,8,8,9,9,9-undecafluorononan-1-ol, 5,5,6,6 7,7,8,8,9,9,10,10,10-tridecafluorodecan-1-ol, 5,5,6,6,7,7,8,8,9,9,10,10 , 11, 11, 11-pentadecafluoroundecan-1-ol, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 12, 12, 12- Heptadecafluorododecan-1-ol, 6,6,6-trifluorohexane-1-ol, 6,6,7,7,7-pentafluo Loheptan-1-ol, 6,6,7,7,8,8,8-heptafluorooctane-1-ol, 6,6,7,7,8,8,9,9,9-nonafluorononane- 1-ol, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 10-undecafluorodecan-1-ol, 6, 6, 7, 7, 8, 8, 9, 9 , 10, 10, 11, 11, 11-tridecafluoroundecan-1-ol, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 12, 12, 12- Pentadecafluorododecan-1-ol, 6, 6, 7, 7, 8, 8, 9, 9, 10, 10, 11, 11, 12, 12, 13, 13, 13-heptadecafluorotridecan-1 -Ol, 2- (pentafluoroethoxy) -2,2-difluoroethanol, 2,2,4,4,5 5,7,7,8,8,8-undecafluoro-3,6-dioxaoctan-1-ol, 2,2,4,4,5,5,7,7,8,8,10, 10,11,11,11-pentadecafluoro-3,6,9-trioxaundecan-1-ol, 2,2,4,4,5,5,7,7,8,8,10,10, 11, 11, 13, 13, 14, 14, 14-nonadecafluoro-3,6,9,12-tetraoxatetradecan-1-ol, 2-heptafluoropropoxy-2,3,3,3-tetrafluoro Propan-1-ol, 2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2,5-bis (trifluoromethyl) -3,6-dioxanonane-1 -All, 2,4,4,5,7,7,8,10,10,11,11,12,12, 2-tetradecanol fluoro -2,5,8- tris (trifluoromethyl) -3,6,9-like trioxatridecan dodecane-1-ol.
含フッ素アルコールの使用量としては、特に制限するものではないが、通常、2−置換−3−ハロ−2−ハロメチルプロパノール誘導体に対して0.5〜10当量であるが、好ましくは1〜3当量である。ただし、含フッ素アルコールを反応溶媒として使用する場合はこの限りではない。 The amount of the fluorinated alcohol used is not particularly limited, but is usually 0.5 to 10 equivalents relative to the 2-substituted-3-halo-2-halomethylpropanol derivative, preferably 1 to 3 equivalents. However, this is not the case when a fluorinated alcohol is used as a reaction solvent.
本発明において塩基としては、特に限定するものではないが、例えば水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物、水酸化カルシウム、水酸化マグネシウムなどのアルカリ土類金属水酸化物、炭酸ナトリウム、炭酸カリウムなどのアルカリ金属炭酸塩、炭酸カルシウム、炭酸マグネシウムなどのアルカリ土類金属炭酸塩、炭酸水素ナトリウム、炭酸水素カリウムなどのアルカリ金属炭酸水素塩、炭酸水素カルシウム、炭酸水素マグネシウムなどのアルカリ土類金属炭酸水素塩、リン酸ナトリウム、リン酸カリウムなどのアルカリ金属リン酸塩、リン酸カルシウム、リン酸マグネシウムなどのアルカリ土類金属リン酸塩などが挙げられるが、好ましくは水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物、さらに好ましくは水酸化ナトリウム、水酸化カリウムである。
塩基の使用量としては、特に制限するものではないが、通常、2−置換−3−ハロ−2−ハロメチルプロパノール誘導体に対して0.5〜10当量であるが、好ましくは2〜5当量である。
In the present invention, the base is not particularly limited. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, sodium carbonate Alkaline metal carbonates such as potassium carbonate, alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate, alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, alkaline earth such as calcium hydrogen carbonate and magnesium hydrogen carbonate Alkali metal phosphates such as alkali metal hydrogen carbonates, sodium phosphates and potassium phosphates, alkaline earth metal phosphates such as calcium phosphates and magnesium phosphates, and the like, preferably sodium hydroxide and potassium hydroxide Alkali metal hydroxides, etc. Preferably sodium hydroxide and potassium hydroxide.
The amount of the base used is not particularly limited, but is usually 0.5 to 10 equivalents, preferably 2 to 5 equivalents, relative to the 2-substituted-3-halo-2-halomethylpropanol derivative. It is.
本発明においては、相間移動触媒を使用しなくても含フッ素オキセタン化合物を効率的に収率良く製造することができるが、相間移動触媒を添加すると、さらに反応速度が向上し、収率も向上する。
本発明において、使用する相間移動触媒としては、特に限定するものではないが、4級アンモニウム塩、4級ホスホニウム塩、クラウンエーテル等が挙げられるが、反応性と経済的な面から安価な4級アンモニウム塩が好ましく、特に容易かつ安価に入手可能なテトラブチルアンモニウムブロマイドが好ましい。
In the present invention, a fluorine-containing oxetane compound can be produced efficiently and with good yield without using a phase transfer catalyst. However, when a phase transfer catalyst is added, the reaction rate is further improved and the yield is also improved. To do.
In the present invention, the phase transfer catalyst to be used is not particularly limited, and examples thereof include quaternary ammonium salts, quaternary phosphonium salts, crown ethers, etc., but they are inexpensive quaternary from the viewpoint of reactivity and economy. Ammonium salts are preferred, and tetrabutylammonium bromide that is easily and inexpensively available is particularly preferred.
4級アンモニウム塩としては、特に限定するものではないが、テトラブチルアンモニウムフルオライド、テトラブチルアンモニウムクロライド、テトラブチルアンモニウムブロマイド、テトラブチルアンモニウムヨーダイド、ドデシルトリメチルアンモニウムクロライド、ドデシルトリメチルアンモニウムブロマイド、メチルトリオクチルアンモニウムクロライド、メチルトリオクチルアンモニウムブロマイド、フェニルトリメチルアンモニウムクロライド、フェニルトリメチルアンモニウムブロマイド、ベンジルトリメチルアンモニウムクロライド、ベンジルトリメチルアンモニウムブロマイド、ベンジルトリブチルアンモニウムクロライド、ベンジルトリブチルアンモニウムブロマイドなどが代表例として挙げられる。 The quaternary ammonium salt is not particularly limited, but is tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, methyltrioctyl. Representative examples include ammonium chloride, methyltrioctylammonium bromide, phenyltrimethylammonium chloride, phenyltrimethylammonium bromide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltributylammonium chloride, benzyltributylammonium bromide and the like.
4級ホスホニウム塩としては、特に限定するものではないが、テトラブチルホスホニウムクロライド、テトラブチルホスホニウムブロマイド、ベンジルトリフェニルホスホニウムクロライド、ベンジルトリフェニルホスホニウムブロマイド、ブチルトリフェニルホスホニウムクロリド、ブチルトリフェニルホスホニウムブロマイド、テトラフェニルホスホニウムブロマイドなどが代表例として挙げられる。 Although it does not specifically limit as a quaternary phosphonium salt, Tetrabutylphosphonium chloride, Tetrabutylphosphonium bromide, Benzyltriphenylphosphonium chloride, Benzyltriphenylphosphonium bromide, Butyltriphenylphosphonium chloride, Butyltriphenylphosphonium bromide, Tetra A representative example is phenylphosphonium bromide.
クラウンエーテルとしては、特に制限するものではないが、18−クラウン−6、ジベンゾ−18−クラウン−6、ジシクロヘキシル−18−クラウン−6、12−クラウン−4、13−クラウン−4、15−クラウン−5などが代表例として挙げられる。 The crown ether is not particularly limited, but 18-crown-6, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, 12-crown-4, 13-crown-4, 15-crown. -5 and the like are typical examples.
相間移動触媒の使用量は、反応に用いる2−置換−3−ハロ−2−ハロメチルプロパノール誘導体に対して、通常、0.01〜100モル%であるが、経済的な面から好ましくは1〜25モル%である。
本発明において、反応に相間移動触媒を用いる場合には、通常一種のみを使用するが、複数の相間移動触媒を混合して使用しても良い。
The amount of the phase transfer catalyst used is usually 0.01 to 100 mol% with respect to the 2-substituted-3-halo-2-halomethylpropanol derivative used in the reaction, but preferably 1 from the economical aspect. ~ 25 mol%.
In the present invention, when a phase transfer catalyst is used for the reaction, usually only one kind is used, but a plurality of phase transfer catalysts may be mixed and used.
本発明において反応溶媒は水のみで良いが、有機溶媒を混合して使用することもできる。
使用可能な有機溶媒としては、特に限定するものではないが、アセトン、アセトニトリル、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、ジメチルスルホキシド、N−メチル−2−ピロリドンなどの非プロトン性極性溶媒、ペンタン、ヘキサン、ヘプタンなどの直鎖状脂肪族炭化水素、2−メチルブタン、2−メチルペンタンなどの分岐状脂肪族炭化水素、シクロヘキサン、メチルシクロヘキサンなどの環状脂肪族炭化水素、ベンゼン、トルエン、キシレンなどの芳香族炭化水素、ジクロロメタン、クロロホルムなどの脂肪族ハロゲン化合物、クロロベンゼン、ジクロロベンゼンなどの芳香族ハロゲン化合物、含フッ素アルコール類などが代表例として挙げられ、これら有機溶媒を単独あるいは2種以上混合して用いることができる。
これらの反応溶媒の使用量は、通常、反応に用いられる2−置換−3−ハロ−2−ハロメチルプロパノール誘導体に対して重量比で0.1〜20倍量である。
In the present invention, the reaction solvent may be water alone, but an organic solvent may be mixed and used.
Although it does not specifically limit as an organic solvent which can be used, Aprotic polarities, such as acetone, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, etc. Solvent, linear aliphatic hydrocarbon such as pentane, hexane, heptane, etc., branched aliphatic hydrocarbon such as 2-methylbutane, 2-methylpentane, cycloaliphatic hydrocarbon such as cyclohexane, methylcyclohexane, benzene, toluene, Representative examples include aromatic hydrocarbons such as xylene, aliphatic halogen compounds such as dichloromethane and chloroform, aromatic halogen compounds such as chlorobenzene and dichlorobenzene, and fluorinated alcohols. These organic solvents can be used alone or in combination. Mix and use Can.
The amount of these reaction solvents used is usually 0.1 to 20 times by weight with respect to the 2-substituted-3-halo-2-halomethylpropanol derivative used in the reaction.
本発明において反応温度としては、25〜150℃が好ましく、さらに好ましくは60〜100℃である。反応温度が25℃より低い場合には反応時間が長くなる傾向にあり、一方、反応温度が150℃より高い場合には、副反応が発生しやすくなる。反応は常圧または加圧下で実施できる。
本発明において、反応時間としては、基質の種類、相間移動触媒の種類及び反応温度の違いにより異なるため、特に限定するものではないが、通常、1時間〜36時間の範囲内で反応は完結する。
In this invention, as reaction temperature, 25-150 degreeC is preferable, More preferably, it is 60-100 degreeC. When the reaction temperature is lower than 25 ° C, the reaction time tends to be longer. On the other hand, when the reaction temperature is higher than 150 ° C, side reactions tend to occur. The reaction can be carried out at normal pressure or under pressure.
In the present invention, the reaction time varies depending on the type of substrate, the type of phase transfer catalyst, and the reaction temperature, and is not particularly limited, but the reaction is usually completed within a range of 1 hour to 36 hours. .
生成した含フッ素オキセタン化合物は、分液操作で有機層を分離し、得られた有機層を、水もしくは食塩水、または酸水溶液もしくはアルカリ水溶液等で洗浄した後、蒸留またはカラムクロマトグラフィー等の一般的な方法によって単離精製することができる。 The produced fluorine-containing oxetane compound is separated into an organic layer by a liquid separation operation, and the obtained organic layer is washed with water or brine, an acid aqueous solution or an alkaline aqueous solution, etc. Can be isolated and purified by conventional methods.
このようにして得られる一般式(3)で表される含フッ素オキセタン化合物の具体例としては、3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタン、3−(2,2,2−トリフルオロエトキシメチル)−3−エチルオキセタン、3−(2,2,3,3,3−ペンタフルオロプロポキシメチル)−3−メチルオキセタン、3−(2,2,3,3,3−ペンタフルオロプロポキシメチル)−3−エチルオキセタン、3−(2,2,3,3,4,4,4−ヘプタフルオロブトキシメチル)−3−メチルオキセタン、3−(2,2,3,3,4,4,4−ヘプタフルオロブトキシメチル)−3−エチルオキセタン、3−(2,2,3,3,4,4,5,5,5−ノナフルオロペンチルオキシメチル)−3−メチルオキセタン、3−(2,2,3,3,4,4,5,5,5−ノナフルオロペンチルオキシメチル)−3−エチルオキセタン、3−(2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロヘキシルオキシメチル)−3−メチルオキセタン、3−(2,2,3,3,4,4,5,5,6,6,6−ウンデカフルオロヘキシルオキシメチル)−3−エチルオキセタン、3−(2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチルオキシメチル)−3−メチルオキセタン、3−(2,2,3,3,4,4,5,5,6,6,7,7,7−トリデカフルオロヘプチルオキシメチル)−3−エチルオキセタン、3−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチルオキシメチル)−3−メチルオキセタン、3−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチルオキシメチル)−3−エチルオキセタン、3−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ヘプタデカフルオロノニルオキシメチル)−3−メチルオキセタン、3−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ヘプタデカフルオロノニルオキシメチル)−3−エチルオキセタン、3−(3,3,3−トリフルオロプロポキシメチル)−3−メチルオキセタン、3−(3,3,3−トリフルオロプロポキシメチル)−3−エチルオキセタン、3−(3,3,4,4,4−ペンタフルオロブトキシメチル)−3−メチルオキセタン、3−(3,3,4,4,4−ペンタフルオロブトキシメチル)−3−エチルオキセタン、3−(3,3,4,4,5,5,5−ヘプタフルオロペンチルオキシメチル)−3−メチルオキセタン、3−(3,3,4,4,5,5,5−ヘプタフルオロペンチルオキシメチル)−3−エチルオキセタン、3−(3,3,4,4,5,5,6,6,6−ノナフルオロヘキシルオキシメチル)−3−メチルオキセタン、3−(3,3,4,4,5,5,6,6,6−ノナフルオロヘキシルオキシメチル)−3−エチルオキセタン、3−(3,3,4,4,5,5,6,6,7,7,7−ウンデカフルオロヘプチルオキシメチル)−3−メチルオキセタン、3−(3,3,4,4,5,5,6,6,7,7,7−ウンデカフルオロヘプチルオキシメチル)−3−エチルオキセタン、3−(3,3,4,4,5,5,6,6,7,7,8,8,8−トリデカフルオロオクチルオキシメチル)−3−メチルオキセタン、3−(3,3,4,4,5,5,6,6,7,7,8,8,8−トリデカフルオロオクチルオキシメチル)−3−エチルオキセタン、3−(3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ペンタデカフルオロノニルオキシメチル)−3−メチルオキセタン、3−(3,3,4,4,5,5,6,6,7,7,8,8,9,9,9−ペンタデカフルオロノニルオキシメチル)−3−エチルオキセタン、3−(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ヘプタデカフルオロデシルオキシメチル)−3−メチルオキセタン、3−(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ヘプタデカフルオロデシルオキシメチル)−3−エチルオキセタン、3−(4,4,4−トリフルオロブトキシメチル)−3−メチルオキセタン、3−(4,4,4−トリフルオロブトキシメチル)−3−エチルオキセタン、3−(4,4,5,5,5−ペンタフルオロペンチルオキシメチル)−3−メチルオキセタン、3−(4,4,5,5,5−ペンタフルオロペンチルオキシメチル)−3−エチルオキセタン、3−(4,4,5,5,6,6,6−ヘプタフルオロヘキシルオキシメチル)−3−メチルオキセタン、3−(4,4,5,5,6,6,6−ヘプタフルオロヘキシルオキシメチル)−3−エチルオキセタン、3−(4,4,5,5,6,6,7,7,7−ノナフルオロヘプチルオキシメチル)−3−メチルオキセタン、3−(4,4,5,5,6,6,7,7,7−ノナフルオロヘプチルオキシメチル)−3−エチルオキセタン、3−(4,4,5,5,6,6,7,7,8,8,8−ウンデカフルオロオクチルオキシメチル)−3−メチルオキセタン、3−(4,4,5,5,6,6,7,7,8,8,8−ウンデカフルオロオクチルオキシメチル)−3−エチルオキセタン、3−(4,4,5,5,6,6,7,7,8,8,9,9,9−トリデカフルオロノニルオキシメチル)−3−メチルオキセタン、3−(4,4,5,5,6,6,7,7,8,8,9,9,9−トリデカフルオロノニルオキシメチル)−3−エチルオキセタン、3−(4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ペンタデカフルオロデシルオキシメチル)−3−メチルオキセタン、3−(4,4,5,5,6,6,7,7,8,8,9,9,10,10,10−ペンタデカフルオロデシルオキシメチル)−3−エチルオキセタン、3−(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11−ヘプタデカフルオロウンデシルオキシメチル)−3−メチルオキセタン、3−(4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,11−ヘプタデカフルオロウンデシルオキシメチル)−3−エチルオキセタン、3−(2−(ペンタフルオロエトキシ)−2,2−ジフルオロエトキシメチル)−3−メチルオキセタン、3−(2−(ペンタフルオロエトキシ)−2,2−ジフルオロエトキシメチル)−3−エチルオキセタン、3−(2,2,4,4,5,5,7,7,8,8,8−ウンデカフルオロ−3,6−ジオキサオクチルオキシメチル)−3−メチルオキセタン、3−(2,2,4,4,5,5,7,7,8,8,8−ウンデカフルオロ−3,6−ジオキサオクチルオキシメチル)−3−エチルオキセタン、3−(2,2,4,4,5,5,7,7,8,8,10,10,11,11,11−ペンタデカフルオロ−3,6,9−トリオキサウンデシルオキシメチル)−3−メチルオキセタン、3−(2,2,4,4,5,5,7,7,8,8,10,10,11,11,11−ペンタデカフルオロ−3,6,9−トリオキサウンデシルオキシメチル)−3−エチルオキセタン、3−(2,2,4,4,5,5,7,7,8,8,10,10,11,11,13,13,14,14,14−ノナデカフルオロ−3,6,9,12−テトラオキサテトラデシルオキシメチル)−3−メチルオキセタン、3−(2,2,4,4,5,5,7,7,8,8,10,10,11,11,13,13,14,14,14−ノナデカフルオロ−3,6,9,12−テトラオキサテトラデシルオキシメチル)−3−エチルオキセタン、3−(2−ヘプタフルオロプロポキシ−2,3,3,3−テトラフルオロプロポキシメチル)−3−メチルオキセタン、3−(2−ヘプタフルオロプロポキシ−2,3,3,3−テトラフルオロプロポキシメチル)−3−エチルオキセタン、3−(2,4,4,5,7,7,8,8,9,9,9−ウンデカフルオロ−2,5−ビス(トリフルオロメチル)−3,6−ジオキサノニルオキシメチル)−3−メチルオキセタン、3−(2,4,4,5,7,7,8,8,9,9,9−ウンデカフルオロ−2,5−ビス(トリフルオロメチル)−3,6−ジオキサノニルオキシメチル)−3−エチルオキセタン、3−(2,4,4,5,7,7,8,10,10,11,11,12,12,12−テトラデカフルオロ−2,5,8−トリス(トリフルオロメチル)−3,6,9−トリオキサドデシルオキシメチル)−3−メチルオキセタン、3−(2,4,4,5,7,7,8,10,10,11,11,12,12,12−テトラデカフルオロ−2,5,8−トリス(トリフルオロメチル)−3,6,9−トリオキサドデシルオキシメチル)−3−エチルオキセタンなどが挙げられる。 Specific examples of the fluorine-containing oxetane compound represented by the general formula (3) thus obtained include 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane, 3- (2, 2,2-trifluoroethoxymethyl) -3-ethyloxetane, 3- (2,2,3,3,3-pentafluoropropoxymethyl) -3-methyloxetane, 3- (2,2,3,3 3-pentafluoropropoxymethyl) -3-ethyloxetane, 3- (2,2,3,3,4,4,4-heptafluorobutoxymethyl) -3-methyloxetane, 3- (2,2,3, 3,4,4,4-heptafluorobutoxymethyl) -3-ethyloxetane, 3- (2,2,3,3,4,4,5,5,5-nonafluoropentyloxymethyl) -3-methyl Oxetane, -(2,2,3,3,4,4,5,5,5-nonafluoropentyloxymethyl) -3-ethyloxetane, 3- (2,2,3,3,4,4,5,5 , 6,6,6-undecafluorohexyloxymethyl) -3-methyloxetane, 3- (2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyloxy) Methyl) -3-ethyloxetane, 3- (2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyloxymethyl) -3-methyloxetane, 3- (2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyloxymethyl) -3-ethyloxetane, 3- (2,2,3 , 3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxymethyl ) -3-Methyloxetane, 3- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxymethyl) -3- Ethyloxetane, 3- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyloxymethyl) -3- Methyl oxetane, 3- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononyloxymethyl) -3- Ethyl oxetane, 3- (3,3,3-trifluoropropoxymethyl) -3-methyloxetane, 3- (3,3,3-trifluoropropoxymethyl) -3-ethyloxetane, 3- (3,3, 4,4,4-pentafluorobutoxymethyl) -3-methyloxetane, 3- (3,3, 4,4,4-pentafluorobutoxymethyl) -3-ethyloxetane, 3- (3,3,4,4,5,5,5-heptafluoropentyloxymethyl) -3-methyloxetane, 3- (3 , 3,4,4,5,5,5-heptafluoropentyloxymethyl) -3-ethyloxetane, 3- (3,3,4,4,5,5,6,6,6-nonafluorohexyloxy Methyl) -3-methyloxetane, 3- (3,3,4,4,5,5,6,6,6-nonafluorohexyloxymethyl) -3-ethyloxetane, 3- (3,3,4, 4,5,5,6,6,7,7,7-undecafluoroheptyloxymethyl) -3-methyloxetane, 3- (3,3,4,4,5,5,6,6,7, 7,7-undecafluoroheptyloxymethyl) -3-ethyl Xetane, 3- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxymethyl) -3-methyloxetane, 3- (3,3 , 4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyloxymethyl) -3-ethyloxetane, 3- (3,3,4,4,5,5) , 6,6,7,7,8,8,9,9,9-pentadecafluorononyloxymethyl) -3-methyloxetane, 3- (3,3,4,4,5,5,6,6) , 7,7,8,8,9,9,9-pentadecafluorononyloxymethyl) -3-ethyloxetane, 3- (3,3,4,4,5,5,6,6,7,7) , 8,8,9,9,10,10,10-heptadecafluorodecyloxymethyl) -3-methyloxetane, 3- (3,3,4 4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyloxymethyl) -3-ethyloxetane, 3- (4,4,4- Trifluorobutoxymethyl) -3-methyloxetane, 3- (4,4,4-trifluorobutoxymethyl) -3-ethyloxetane, 3- (4,4,5,5,5-pentafluoropentyloxymethyl) -3-methyloxetane, 3- (4,4,5,5,5-pentafluoropentyloxymethyl) -3-ethyloxetane, 3- (4,4,5,5,6,6,6-heptafluoro Hexyloxymethyl) -3-methyloxetane, 3- (4,4,5,5,6,6,6-heptafluorohexyloxymethyl) -3-ethyloxetane, 3- (4,4,5,5, 6, 6, 7, 7, 7- Nonafluoroheptyloxymethyl) -3-methyloxetane, 3- (4,4,5,5,6,6,7,7,7-nonafluoroheptyloxymethyl) -3-ethyloxetane, 3- (4 4,5,5,6,6,7,7,8,8,8-undecafluorooctyloxymethyl) -3-methyloxetane, 3- (4,4,5,5,6,6,7, 7,8,8,8-undecafluorooctyloxymethyl) -3-ethyloxetane, 3- (4,4,5,5,6,6,7,7,8,8,9,9,9- Tridecafluorononyloxymethyl) -3-methyloxetane, 3- (4,4,5,5,6,7,7,8,8,9,9,9-tridecafluorononyloxymethyl)- 3-ethyloxetane, 3- (4,4,5,5,6,6,7,7,8,8,9 9,10,10,10-pentadecafluorodecyloxymethyl) -3-methyloxetane, 3- (4,4,5,5,6,6,7,7,8,8,9,9,10, 10,10-pentadecafluorodecyloxymethyl) -3-ethyloxetane, 3- (4,4,5,5,6,6,7,7,8,8,9,9,10,10,11, 11,11-heptadecafluoroundecyloxymethyl) -3-methyloxetane, 3- (4,4,5,5,6,6,7,7,8,8,9,9,10,10,11) , 11,11-heptadecafluoroundecyloxymethyl) -3-ethyloxetane, 3- (2- (pentafluoroethoxy) -2,2-difluoroethoxymethyl) -3-methyloxetane, 3- (2- ( Pentafluoroethoxy) -2,2-diph Oloethoxymethyl) -3-ethyloxetane, 3- (2,2,4,4,5,5,7,7,8,8,8-undecafluoro-3,6-dioxaoctyloxymethyl)- 3-methyloxetane, 3- (2,2,4,4,5,5,7,7,8,8,8-undecafluoro-3,6-dioxaoctyloxymethyl) -3-ethyloxetane, 3- (2,2,4,4,5,5,7,7,8,8,10,10,11,11,11-pentadecafluoro-3,6,9-trioxaundecyloxymethyl) -3-methyloxetane, 3- (2,2,4,4,5,5,7,7,8,8,10,10,11,11,11-pentadecafluoro-3,6,9-trio Xaundecyloxymethyl) -3-ethyloxetane, 3- (2,2,4,4,5,5, 7,7,8,8,10,10,11,11,13,13,14,14,14-nonadecafluoro-3,6,9,12-tetraoxatetradecyloxymethyl) -3-methyloxetane , 3- (2,2,4,4,5,5,7,7,8,8,10,10,11,11,13,13,14,14,14-nonadecafluoro-3,6, 9,12-tetraoxatetradecyloxymethyl) -3-ethyloxetane, 3- (2-heptafluoropropoxy-2,3,3,3-tetrafluoropropoxymethyl) -3-methyloxetane, 3- (2- Heptafluoropropoxy-2,3,3,3-tetrafluoropropoxymethyl) -3-ethyloxetane, 3- (2,4,4,5,7,7,8,8,9,9,9-undeca) Fluoro-2,5-bis (to Fluoromethyl) -3,6-dioxanonyloxymethyl) -3-methyloxetane, 3- (2,4,4,5,7,7,8,8,9,9,9-undecafluoro-2 , 5-Bis (trifluoromethyl) -3,6-dioxanonyloxymethyl) -3-ethyloxetane, 3- (2,4,4,5,7,7,8,10,10,11,11) , 12,12,12-tetradecafluoro-2,5,8-tris (trifluoromethyl) -3,6,9-trioxadodecyloxymethyl) -3-methyloxetane, 3- (2,4,4 5,7,7,8,10,10,11,11,12,12,12-tetradecafluoro-2,5,8-tris (trifluoromethyl) -3,6,9-trioxadodecyloxy Methyl) -3-ethyloxetane and the like That.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。
なお、生成物の分析は、いずれもガスクロマトグラフィー分析(以下、「GC分析」という)によって下記条件で行った。
装置:島津製作所製GC−17A
カラム:GLサイエンス社製、キャピラリーカラムNB−5(0.32mmI.D.×30m)
検出器:水素炎イオン化検出器
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited only to these examples.
The analysis of the product was conducted by gas chromatography analysis (hereinafter referred to as “GC analysis”) under the following conditions.
Apparatus: Shimadzu GC-17A
Column: GL Science Co., Ltd., capillary column NB-5 (0.32 mm ID × 30 m)
Detector: Hydrogen flame ionization detector
実施例1 3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンの製造
温度計、撹拌装置、滴下ロートおよび冷却管を備え付けた300mLフラスコに2,2−ビス(ブロモメチル)プロパノール50.0g(0.203mol)、2,2,2−トリフルオロエタノール40.7g(0.407mol)、水10.0gを仕込み、オイルバスで内温が80℃になるまで昇温した。次いで85%水酸化カリウム40.3g(0.610mol)を水45.3gに溶解させた溶液を6時間かけて添加した後、80℃で18時間撹拌した。反応溶液を室温まで冷却した後、水40mLを添加し、よく撹拌した。分液して得られた有機層を水50mLで3回洗浄した。
有機層中の目的化合物の含有量をGC分析によって定量したところ、目的化合物の収量は29.4g、収率は78%であった。
有機層を減圧蒸留によって精製し、無色透明の油状物として3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンを26.9g得た。
GC分析の結果、蒸留精製後に得られた目的化合物の純度は99%、2,2−ビス(ブロモメチル)プロパノールに対する収率は72%であった。
Example 1 Preparation of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane 2,2-bis (bromomethyl) propanol in a 300 mL flask equipped with a thermometer, stirrer, dropping funnel and condenser 50.0 g (0.203 mol), 2,2,2-trifluoroethanol 40.7 g (0.407 mol), and water 10.0 g were charged, and the temperature was raised in an oil bath until the internal temperature reached 80 ° C. Subsequently, a solution prepared by dissolving 40.3 g (0.610 mol) of 85% potassium hydroxide in 45.3 g of water was added over 6 hours, and then stirred at 80 ° C. for 18 hours. After cooling the reaction solution to room temperature, 40 mL of water was added and stirred well. The organic layer obtained by liquid separation was washed with 50 mL of water three times.
When the content of the target compound in the organic layer was quantified by GC analysis, the yield of the target compound was 29.4 g and the yield was 78%.
The organic layer was purified by distillation under reduced pressure to obtain 26.9 g of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane as a colorless transparent oil.
As a result of GC analysis, the purity of the target compound obtained after distillation purification was 99%, and the yield based on 2,2-bis (bromomethyl) propanol was 72%.
実施例2 3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンの製造
温度計、撹拌装置、滴下ロートおよび冷却管を備え付けた300mLフラスコに2,2−ビス(ブロモメチル)プロパノール50.0g(0.203mol)、2,2,2−トリフルオロエタノール40.7g(0.407mol)、水10.0g、テトラブチルアンモニウムブロマイド3.28g(10.2mmol)を仕込み、オイルバスで内温が80℃になるまで昇温した。次いで85%水酸化カリウム40.3g(0.610mol)を水45.3gに溶解させた溶液を2時間かけて添加した後、80℃で6時間撹拌した。反応溶液を室温まで冷却した後、水40mLを添加し、よく撹拌した。分液して得られた有機層を水50mLで3回洗浄した。
有機層中の目的化合物の含有量をGC分析によって定量したところ、目的化合物の収量は32.3g、収率は86%であった。
有機層を減圧蒸留によって精製し、無色透明の油状物として3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンを28.6g得た。
GC分析の結果、蒸留精製後に得られた目的化合物の純度は99%、2,2−ビス(ブロモメチル)プロパノールに対する収率は76%であった。
Example 2 Preparation of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane 2,2-bis (bromomethyl) propanol in a 300 mL flask equipped with a thermometer, stirrer, dropping funnel and condenser 50.0 g (0.203 mol), 2,2,2-trifluoroethanol 40.7 g (0.407 mol), water 10.0 g, tetrabutylammonium bromide 3.28 g (10.2 mmol) were charged in an oil bath. The temperature was raised until the internal temperature reached 80 ° C. Subsequently, a solution prepared by dissolving 40.3 g (0.610 mol) of 85% potassium hydroxide in 45.3 g of water was added over 2 hours, and then stirred at 80 ° C. for 6 hours. After cooling the reaction solution to room temperature, 40 mL of water was added and stirred well. The organic layer obtained by liquid separation was washed with 50 mL of water three times.
When the content of the target compound in the organic layer was quantified by GC analysis, the yield of the target compound was 32.3 g and the yield was 86%.
The organic layer was purified by distillation under reduced pressure to obtain 28.6 g of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane as a colorless transparent oil.
As a result of GC analysis, the purity of the target compound obtained after distillation purification was 99%, and the yield based on 2,2-bis (bromomethyl) propanol was 76%.
実施例3 3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンの製造
温度計、撹拌装置、滴下ロートおよび冷却管を備え付けた300mLフラスコに2,2−ビス(ブロモメチル)プロパノール50.0g(0.203mol)、2,2,2−トリフルオロエタノール40.7g(0.407mol)、水10.0g、テトラブチルアンモニウムブロマイド6.55g(20.3mmol)を仕込み、オイルバスで内温が80℃になるまで昇温した。次いで85%水酸化カリウム40.3g(0.610mol)を水45.3gに溶解させた溶液を2時間かけて添加した後、80℃で3時間撹拌した。反応溶液を室温まで冷却した後、水40mLを添加し、よく撹拌した。分液して得られた有機層を水50mLで3回洗浄した。
有機層中の目的化合物の含有量をGC分析によって定量したところ、目的化合物の収量は33.5g、収率は89%であった。
有機層を減圧蒸留によって精製し、無色透明の油状物として3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンを28.5g得た。
GC分析の結果、蒸留精製後に得られた目的化合物の純度は99%、2,2−ビス(ブロモメチル)プロパノールに対する収率は76%であった。
Example 3 Preparation of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane 2,2-bis (bromomethyl) propanol in a 300 mL flask equipped with a thermometer, stirrer, dropping funnel and condenser 50.0 g (0.203 mol), 2,2,2-trifluoroethanol 40.7 g (0.407 mol), water 10.0 g, tetrabutylammonium bromide 6.55 g (20.3 mmol) were charged in an oil bath. The temperature was raised until the internal temperature reached 80 ° C. Next, a solution obtained by dissolving 40.3 g (0.610 mol) of 85% potassium hydroxide in 45.3 g of water was added over 2 hours, and then stirred at 80 ° C. for 3 hours. After cooling the reaction solution to room temperature, 40 mL of water was added and stirred well. The organic layer obtained by liquid separation was washed with 50 mL of water three times.
When the content of the target compound in the organic layer was quantified by GC analysis, the yield of the target compound was 33.5 g, and the yield was 89%.
The organic layer was purified by distillation under reduced pressure to obtain 28.5 g of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane as a colorless transparent oil.
As a result of GC analysis, the purity of the target compound obtained after distillation purification was 99%, and the yield based on 2,2-bis (bromomethyl) propanol was 76%.
実施例4 3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンの製造
温度計、撹拌装置、滴下ロートおよび冷却管を備え付けた200mLフラスコに2,2−ビス(ブロモメチル)プロパノール25.0g(0.102mol)、2,2,2−トリフルオロエタノール20.3g(0.203mol)、水5.00g、テトラエチルアンモニウムブロマイド2.14g(10.2mmol)を仕込み、オイルバスで内温が80℃になるまで昇温した。次いで85%水酸化カリウム20.1g(0.305mol)を水22.6gに溶解させた溶液を2時間かけて添加した後、80℃で6時間撹拌した。反応溶液を室温まで冷却した後、水20mLを添加し、よく撹拌した。分液して得られた有機層を水25mLで3回洗浄した。
有機層中の目的化合物の含有量をGC分析によって定量したところ、目的化合物の収量は15.8g、収率は85%であった。
有機層を減圧蒸留によって精製し、無色透明の油状物として3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンを14.1g得た。
GC分析の結果、蒸留精製後に得られた目的化合物の純度は99%、2,2−ビス(ブロモメチル)プロパノールに対する収率は75%であった。
Example 4 Preparation of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane 2,2-bis (bromomethyl) propanol in a 200 mL flask equipped with a thermometer, stirrer, dropping funnel and condenser 25.0 g (0.102 mol), 2,2,2-trifluoroethanol 20.3 g (0.203 mol), water 5.00 g, tetraethylammonium bromide 2.14 g (10.2 mmol) were charged and the oil bath was used. The temperature was raised until the temperature reached 80 ° C. Next, a solution prepared by dissolving 20.1 g (0.305 mol) of 85% potassium hydroxide in 22.6 g of water was added over 2 hours, followed by stirring at 80 ° C. for 6 hours. After the reaction solution was cooled to room temperature, 20 mL of water was added and stirred well. The organic layer obtained by liquid separation was washed 3 times with 25 mL of water.
When the content of the target compound in the organic layer was quantified by GC analysis, the yield of the target compound was 15.8 g and the yield was 85%.
The organic layer was purified by distillation under reduced pressure to obtain 14.1 g of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane as a colorless transparent oil.
As a result of GC analysis, the purity of the target compound obtained after distillation purification was 99%, and the yield based on 2,2-bis (bromomethyl) propanol was 75%.
実施例5 3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンの製造
温度計、撹拌装置、滴下ロートおよび冷却管を備え付けた200mLフラスコに2,2−ビス(ブロモメチル)プロパノール25.0g(0.102mol)、2,2,2−トリフルオロエタノール20.3g(0.203mol)、水5.00g、テトラブチルホスホニウムブロマイド1.72g(5.08mmol)を仕込み、オイルバスで内温が80℃になるまで昇温した。次いで85%水酸化カリウム20.1g(0.305mol)を水22.6gに溶解させた溶液を2時間かけて添加した後、80℃で6時間撹拌した。反応溶液を室温まで冷却した後、水20mLを添加し、よく撹拌した。分液して得られた有機層を水25mLで3回洗浄した。
有機層中の目的化合物の含有量をGC分析によって定量したところ、目的化合物の収量は15.1g、収率は80%であった。
有機層を減圧蒸留によって精製し、無色透明の油状物として3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンを13.1g得た。
GC分析の結果、蒸留精製後に得られた目的化合物の純度は99%、2,2−ビス(ブロモメチル)プロパノールに対する収率は70%であった。
Example 5 Preparation of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane 2,2-bis (bromomethyl) propanol in a 200 mL flask equipped with a thermometer, stirrer, dropping funnel and condenser 25.0 g (0.102 mol), 2,2,2-trifluoroethanol 20.3 g (0.203 mol), water 5.00 g, tetrabutylphosphonium bromide 1.72 g (5.08 mmol) were charged in an oil bath. The temperature was raised until the internal temperature reached 80 ° C. Next, a solution prepared by dissolving 20.1 g (0.305 mol) of 85% potassium hydroxide in 22.6 g of water was added over 2 hours, followed by stirring at 80 ° C. for 6 hours. After the reaction solution was cooled to room temperature, 20 mL of water was added and stirred well. The organic layer obtained by liquid separation was washed 3 times with 25 mL of water.
When the content of the target compound in the organic layer was quantified by GC analysis, the yield of the target compound was 15.1 g and the yield was 80%.
The organic layer was purified by distillation under reduced pressure to obtain 13.1 g of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane as a colorless transparent oil.
As a result of GC analysis, the purity of the target compound obtained after distillation purification was 99%, and the yield based on 2,2-bis (bromomethyl) propanol was 70%.
実施例6 3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンの製造
温度計、撹拌装置、滴下ロートおよび冷却管を備え付けた200mLフラスコに2,2−ビス(ブロモメチル)プロパノール25.0g(0.102mol)、2,2,2−トリフルオロエタノール20.3g(0.203mol)、水5.00g、18−クラウン−61.34g(5.08mmol)を仕込み、オイルバスで内温が80℃になるまで昇温した。次いで85%水酸化カリウム20.1g(0.305mol)を水22.6gに溶解させた溶液を2時間かけて添加した後、80℃で6時間撹拌した。反応溶液を室温まで冷却した後、水20mLを添加し、よく撹拌した。分液して得られた有機層を水25mLで3回洗浄した。
有機層中の目的化合物の含有量をGC分析によって定量したところ、目的化合物の収量は15.6g、収率は83%であった。
有機層を減圧蒸留によって精製し、無色透明の油状物として3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンを13.4g得た。
GC分析の結果、蒸留精製後に得られた目的化合物の純度は99%、2,2−ビス(ブロモメチル)プロパノールに対する収率は72%であった。
Example 6 Preparation of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane 2,2-bis (bromomethyl) propanol in a 200 mL flask equipped with a thermometer, stirrer, dropping funnel and condenser 25.0 g (0.102 mol), 2,2,2-trifluoroethanol 20.3 g (0.203 mol), water 5.00 g, 18-crown-61.34 g (5.08 mmol) were charged in an oil bath. The temperature was raised until the internal temperature reached 80 ° C. Next, a solution prepared by dissolving 20.1 g (0.305 mol) of 85% potassium hydroxide in 22.6 g of water was added over 2 hours, followed by stirring at 80 ° C. for 6 hours. After the reaction solution was cooled to room temperature, 20 mL of water was added and stirred well. The organic layer obtained by liquid separation was washed 3 times with 25 mL of water.
When the content of the target compound in the organic layer was quantified by GC analysis, the yield of the target compound was 15.6 g and the yield was 83%.
The organic layer was purified by distillation under reduced pressure to obtain 13.4 g of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane as a colorless transparent oil.
As a result of GC analysis, the purity of the target compound obtained after distillation purification was 99%, and the yield based on 2,2-bis (bromomethyl) propanol was 72%.
実施例7 3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンの製造
温度計、撹拌装置、滴下ロートおよび冷却管を備え付けた200mLフラスコに2,2−ビス(ブロモメチル)プロパノール25.0g(0.102mol)、2,2,2−トリフルオロエタノール20.3g(0.203mol)、水5.00g、トルエン25.0g、テトラブチルアンモニウムブロマイド3.28g(10.2mmol)を仕込み、オイルバスで内温が80℃になるまで昇温した。次いで85%水酸化カリウム20.1g(0.305mol)を水22.6gに溶解させた溶液を2時間かけて添加した後、80℃で8時間撹拌した。反応溶液を室温まで冷却した後、水20mLを添加し、よく撹拌した。分液して得られた有機層を水25mLで3回洗浄した。
有機層中の目的化合物の含有量をGC分析によって定量したところ、目的化合物の収量は15.9g、収率は85%であった。
有機層を減圧蒸留によって精製し、無色透明の油状物として3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンを13.2g得た。
GC分析の結果、蒸留精製後に得られた目的化合物の純度は99%、2,2−ビス(ブロモメチル)プロパノールに対する収率は71%であった。
Example 7 Preparation of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane 2,2-bis (bromomethyl) propanol in a 200 mL flask equipped with a thermometer, stirrer, dropping funnel and condenser 25.0 g (0.102 mol), 2,2,2-trifluoroethanol 20.3 g (0.203 mol), water 5.00 g, toluene 25.0 g, tetrabutylammonium bromide 3.28 g (10.2 mmol) The temperature was raised until the internal temperature reached 80 ° C. using an oil bath. Next, a solution prepared by dissolving 20.1 g (0.305 mol) of 85% potassium hydroxide in 22.6 g of water was added over 2 hours, and then stirred at 80 ° C. for 8 hours. After the reaction solution was cooled to room temperature, 20 mL of water was added and stirred well. The organic layer obtained by liquid separation was washed 3 times with 25 mL of water.
When the content of the target compound in the organic layer was quantified by GC analysis, the yield of the target compound was 15.9 g and the yield was 85%.
The organic layer was purified by distillation under reduced pressure to obtain 13.2 g of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane as a colorless transparent oil.
As a result of GC analysis, the purity of the target compound obtained after distillation purification was 99%, and the yield based on 2,2-bis (bromomethyl) propanol was 71%.
実施例8 3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンの製造
温度計、撹拌装置、滴下ロートおよび冷却管を備え付けた300mLフラスコに2,2−ビス(ブロモメチル)プロピルアセテート50.0g(0.174mol)、2,2,2−トリフルオロエタノール34.7g(0.347mol)、水10.0g、テトラブチルアンモニウムブロマイド2.80g(8.68mmol)を仕込み、オイルバスで内温が80℃になるまで昇温した。次いで85%水酸化カリウム45.8g(0.694mol)を水51.6gに溶解させた溶液を2時間かけて添加した後、80℃で6時間撹拌した。反応溶液を室温まで冷却した後、水50mLを添加し、よく撹拌した。分液して得られた有機層を水50mLで3回洗浄した。
有機層中の目的化合物の含有量をGC分析によって定量したところ、目的化合物の収量は26.8g、収率は84%であった。
有機層を減圧蒸留によって精製し、無色透明の油状物として3−(2,2,2−トリフルオロエトキシメチル)−3−メチルオキセタンを22.8g得た。
GC分析の結果、蒸留精製後に得られた目的化合物の純度は99%、2,2−ビス(ブロモメチル)プロピルアセテートに対する収率は71%であった。
Example 8 Preparation of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane 2,2-bis (bromomethyl) propyl in a 300 mL flask equipped with a thermometer, stirrer, dropping funnel and condenser An oil bath was charged with 50.0 g (0.174 mol) of acetate, 34.7 g (0.347 mol) of 2,2,2-trifluoroethanol, 10.0 g of water and 2.80 g (8.68 mmol) of tetrabutylammonium bromide. The temperature was raised until the internal temperature reached 80 ° C. Next, a solution prepared by dissolving 45.8 g (0.694 mol) of 85% potassium hydroxide in 51.6 g of water was added over 2 hours, followed by stirring at 80 ° C. for 6 hours. After cooling the reaction solution to room temperature, 50 mL of water was added and stirred well. The organic layer obtained by liquid separation was washed with 50 mL of water three times.
When the content of the target compound in the organic layer was quantified by GC analysis, the yield of the target compound was 26.8 g, and the yield was 84%.
The organic layer was purified by distillation under reduced pressure to obtain 22.8 g of 3- (2,2,2-trifluoroethoxymethyl) -3-methyloxetane as a colorless transparent oil.
As a result of GC analysis, the purity of the target compound obtained after distillation purification was 99%, and the yield based on 2,2-bis (bromomethyl) propyl acetate was 71%.
実施例9 3−(2,2,3,3,4,4,4−ヘプタフルオロブトキシメチル)−3−メチルオキセタンの製造
温度計、撹拌装置、滴下ロートおよび冷却管を備え付けた200mLフラスコに2,2−ビス(ブロモメチル)プロパノール25.0g(0.102mol)、2,2,3,3,4,4,4−ヘプタフルオロブタノール30.5g(0.152mol)、水5.00g、テトラブチルアンモニウムブロマイド3.28g(10.2mmol)を仕込み、オイルバスで内温が80℃になるまで昇温した。次いで85%水酸化カリウム20.1g(0.305mol)を水22.6gに溶解させた溶液を2時間かけて添加した後、80℃で4時間撹拌した。反応溶液を室温まで冷却した後、水20mLを添加し、よく撹拌した。分液して得られた有機層を水25mLで3回洗浄した。
有機層中の目的化合物の含有量をGC分析によって定量したところ、目的化合物の収量は24.7g、収率は86%であった。
有機層を減圧蒸留によって精製し、無色透明の油状物として3−(2,2,3,3,4,4,4−ヘプタフルオロブトキシメチル)−3−メチルオキセタンを21.3g得た。
GC分析の結果、蒸留精製後に得られた目的化合物の純度は99%、2,2−ビス(ブロモメチル)プロパノールに対する収率は74%であった。
Example 9 Preparation of 3- (2,2,3,3,4,4,4-heptafluorobutoxymethyl) -3-methyloxetane 2 in a 200 mL flask equipped with a thermometer, stirrer, dropping funnel and condenser. , 2-bis (bromomethyl) propanol 25.0 g (0.102 mol), 2,2,3,3,4,4,4-heptafluorobutanol 30.5 g (0.152 mol), water 5.00 g, tetrabutyl 3.28 g (10.2 mmol) of ammonium bromide was charged, and the temperature was raised with an oil bath until the internal temperature reached 80 ° C. Next, a solution prepared by dissolving 20.1 g (0.305 mol) of 85% potassium hydroxide in 22.6 g of water was added over 2 hours, and then stirred at 80 ° C. for 4 hours. After the reaction solution was cooled to room temperature, 20 mL of water was added and stirred well. The organic layer obtained by liquid separation was washed 3 times with 25 mL of water.
When the content of the target compound in the organic layer was quantified by GC analysis, the yield of the target compound was 24.7 g and the yield was 86%.
The organic layer was purified by distillation under reduced pressure to obtain 21.3 g of 3- (2,2,3,3,4,4,4-heptafluorobutoxymethyl) -3-methyloxetane as a colorless transparent oil.
As a result of GC analysis, the purity of the target compound obtained after distillation purification was 99%, and the yield based on 2,2-bis (bromomethyl) propanol was 74%.
実施例10 3−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチルオキシメチル)−3−メチルオキセタンの製造
温度計、撹拌装置、滴下ロートおよび冷却管を備え付けた200mLフラスコに2,2−ビス(ブロモメチル)プロパノール20.0g(81.3mmol)、2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクタノール48.8g(0.122mol)、水4.00g、テトラブチルアンモニウムブロマイド2.62g(8.13mmol)を仕込み、オイルバスで内温が80℃になるまで昇温した。次いで、85%水酸化カリウム16.1g(0.244mol)を水18.1gに溶解させた溶液を2時間かけて添加した後、80℃で6時間撹拌した。反応溶液を室温まで冷却した後、水16mLを添加し、よく撹拌した。分液して得られた有機層を水20mLで3回洗浄した。
有機層中の目的化合物の含有量をGC分析によって定量したところ、目的化合物の収量は32.3g、収率は82%であった。
有機層を減圧蒸留によって精製し、無色透明の油状物として3−(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8−ペンタデカフルオロオクチルオキシメチル)−3−メチルオキセタンを28.5g得た。
GC分析の結果、蒸留精製後に得られた目的化合物の純度は99%、2,2−ビス(ブロモメチル)プロパノールに対する収率は72%であった。
Example 10 Preparation of 3- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyloxymethyl) -3-methyloxetane 2200 g (81.3 mmol) of 2,2-bis (bromomethyl) propanol, 2,2,3,3,4,4,5,5 in a 200 mL flask equipped with a thermometer, stirrer, dropping funnel and condenser , 6,6,7,7,8,8,8-pentadecafluorooctanol 48.8 g (0.122 mol), water 4.00 g, tetrabutylammonium bromide 2.62 g (8.13 mmol), oil bath The temperature was raised until the internal temperature reached 80 ° C. Next, a solution prepared by dissolving 16.1 g (0.244 mol) of 85% potassium hydroxide in 18.1 g of water was added over 2 hours, and then stirred at 80 ° C. for 6 hours. After the reaction solution was cooled to room temperature, 16 mL of water was added and stirred well. The organic layer obtained by liquid separation was washed 3 times with 20 mL of water.
When the content of the target compound in the organic layer was quantified by GC analysis, the yield of the target compound was 32.3 g, and the yield was 82%.
The organic layer was purified by distillation under reduced pressure to give 3- (2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadeca as a colorless and transparent oil. 28.5 g of fluorooctyloxymethyl) -3-methyloxetane was obtained.
As a result of GC analysis, the purity of the target compound obtained after distillation purification was 99%, and the yield based on 2,2-bis (bromomethyl) propanol was 72%.
実施例11 3−(2,2,2−トリフルオロエトキシメチル)−3−エチルオキセタンの製造
温度計、撹拌装置、滴下ロートおよび冷却管を備え付けた200mLフラスコに2,2−ビス(ブロモメチル)ブタノール25.0g(96.2mmol)、2,2,2−トリフルオロエタノール19.2g(0.192mol)、水5.00g、テトラブチルアンモニウムブロマイド1.55g(4.81mmol)を仕込み、オイルバスで内温が80℃になるまで昇温した。次いで85%水酸化カリウム19.0g(0.288mol)を水21.4gに溶解させた溶液を2時間かけて添加した後、80℃で6時間撹拌した。反応溶液を室温まで冷却した後、水20mLを添加し、よく撹拌した。分液して得られた有機層を水25mLで3回洗浄した。
有機層中の目的化合物の含有量をGC分析によって定量したところ、目的化合物の収量は17.2g、収率は90%であった。
有機層を減圧蒸留によって精製し、無色透明の油状物として3−(2,2,2−トリフルオロエトキシメチル)−3−エチルオキセタンを14.7g得た。
GC分析の結果、蒸留精製後に得られた目的化合物の純度は99%、2,2−ビス(ブロモメチル)ブタノールに対する収率は77%であった。
Example 11 Preparation of 3- (2,2,2-trifluoroethoxymethyl) -3-ethyloxetane 2,2-bis (bromomethyl) butanol in a 200 mL flask equipped with a thermometer, stirrer, dropping funnel and condenser 25.0 g (96.2 mmol), 2,2,2-trifluoroethanol 19.2 g (0.192 mol), water 5.00 g, tetrabutylammonium bromide 1.55 g (4.81 mmol) were charged in an oil bath. The temperature was raised until the internal temperature reached 80 ° C. Next, a solution prepared by dissolving 19.0 g (0.288 mol) of 85% potassium hydroxide in 21.4 g of water was added over 2 hours, followed by stirring at 80 ° C. for 6 hours. After the reaction solution was cooled to room temperature, 20 mL of water was added and stirred well. The organic layer obtained by liquid separation was washed 3 times with 25 mL of water.
When the content of the target compound in the organic layer was quantified by GC analysis, the yield of the target compound was 17.2 g and the yield was 90%.
The organic layer was purified by distillation under reduced pressure to obtain 14.7 g of 3- (2,2,2-trifluoroethoxymethyl) -3-ethyloxetane as a colorless transparent oil.
As a result of GC analysis, the purity of the target compound obtained after distillation purification was 99%, and the yield based on 2,2-bis (bromomethyl) butanol was 77%.
実施例12 3−(2,2,3,3,4,4,4−ヘプタフルオロブトキシメチル)−3−エチルオキセタンの製造
温度計、撹拌装置、滴下ロートおよび冷却管を備え付けた200mLフラスコに2,2−ビス(ブロモメチル)ブタノール25.0g(96.2mmol)、2,2,3,3,4,4,4−ヘプタフルオロブタノール28.9g(0.144mol)、水5.00g、テトラブチルアンモニウムブロマイド3.10g(9.62mmol)を仕込み、オイルバスで内温が80℃になるまで昇温した。次いで85%水酸化カリウム19.0g(0.288mol)を水21.4gに溶解させた溶液を2時間かけて添加した後、80℃で4時間撹拌した。反応溶液を室温まで冷却した後、水20mLを添加し、よく撹拌した。分液して得られた有機層を水25mLで3回洗浄した。
有機層中の目的化合物の含有量をGC分析によって定量したところ、目的化合物の収量は25.0g、収率は87%であった。
有機層を減圧蒸留によって精製し、無色透明の油状物として3−(2,2,3,3,4,4,4−ヘプタフルオロブトキシメチル)−3−エチルオキセタンを21.6g得た。
GC分析の結果、蒸留精製後に得られた目的化合物の純度は99%、2,2−ビス(ブロモメチル)ブタノールに対する収率は75%であった。
Example 12 Preparation of 3- (2,2,3,3,4,4,4-heptafluorobutoxymethyl) -3-ethyloxetane 2 in a 200 mL flask equipped with a thermometer, stirrer, dropping funnel and condenser. , 2-bis (bromomethyl) butanol 25.0 g (96.2 mmol), 2,2,3,3,4,4,4-heptafluorobutanol 28.9 g (0.144 mol), water 5.00 g, tetrabutyl 3.10 g (9.62 mmol) of ammonium bromide was charged, and the temperature was raised with an oil bath until the internal temperature reached 80 ° C. Next, a solution in which 19.0 g (0.288 mol) of 85% potassium hydroxide was dissolved in 21.4 g of water was added over 2 hours, followed by stirring at 80 ° C. for 4 hours. After the reaction solution was cooled to room temperature, 20 mL of water was added and stirred well. The organic layer obtained by liquid separation was washed 3 times with 25 mL of water.
When the content of the target compound in the organic layer was quantified by GC analysis, the yield of the target compound was 25.0 g, and the yield was 87%.
The organic layer was purified by distillation under reduced pressure to obtain 21.6 g of 3- (2,2,3,3,4,4,4-heptafluorobutoxymethyl) -3-ethyloxetane as a colorless and transparent oil.
As a result of GC analysis, the purity of the target compound obtained after distillation purification was 99%, and the yield based on 2,2-bis (bromomethyl) butanol was 75%.
本発明により得られる含フッ素オキセタン化合物は、含フッ素モノマー、低屈折率樹脂組成物等の原料あるいはカチオン硬化性成分やラジカル硬化性成分として非常に有用である。 The fluorine-containing oxetane compound obtained by the present invention is very useful as a raw material for a fluorine-containing monomer and a low refractive index resin composition, or as a cationic curable component or a radical curable component.
Claims (7)
で示される2−置換−3−ハロ−2−ハロメチルプロパノール誘導体と、下記一般式(2)
で示される含フッ素アルコールとを、塩基の存在下、1ステップで分子内環化反応およびエーテル化反応させて、下記一般式(3)
で示される含フッ素オキセタン化合物を得る、含フッ素オキセタン化合物の製造方法。 The following general formula (1)
And a 2-substituted-3-halo-2-halomethylpropanol derivative represented by the following general formula (2):
In the presence of a base, the fluorinated alcohol represented by the formula (1) is subjected to an intramolecular cyclization reaction and an etherification reaction in one step.
The manufacturing method of a fluorine-containing oxetane compound which obtains the fluorine-containing oxetane compound shown by these.
The method for producing a fluorinated oxetane compound according to claim 5 or 6, wherein the phase transfer catalyst is a quaternary ammonium salt.
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