JP4104350B2 - Method for producing difluorobenzyl bromide derivative and difluorobenzyl ether derivative - Google Patents
Method for producing difluorobenzyl bromide derivative and difluorobenzyl ether derivative Download PDFInfo
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- JP4104350B2 JP4104350B2 JP2002058509A JP2002058509A JP4104350B2 JP 4104350 B2 JP4104350 B2 JP 4104350B2 JP 2002058509 A JP2002058509 A JP 2002058509A JP 2002058509 A JP2002058509 A JP 2002058509A JP 4104350 B2 JP4104350 B2 JP 4104350B2
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- RINSMVSYCNNAGC-UHFFFAOYSA-N [bromo(difluoro)methyl]benzene Chemical class FC(F)(Br)C1=CC=CC=C1 RINSMVSYCNNAGC-UHFFFAOYSA-N 0.000 title claims description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- FBVAQQANQAFFGG-UHFFFAOYSA-N [[difluoro(phenyl)methoxy]-difluoromethyl]benzene Chemical class C=1C=CC=CC=1C(F)(F)OC(F)(F)C1=CC=CC=C1 FBVAQQANQAFFGG-UHFFFAOYSA-N 0.000 title description 32
- 238000000034 method Methods 0.000 claims description 41
- 150000001555 benzenes Chemical class 0.000 claims description 40
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 40
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 34
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 125000001153 fluoro group Chemical group F* 0.000 claims description 23
- GRCDJFHYVYUNHM-UHFFFAOYSA-N bromodifluoromethane Chemical compound FC(F)Br GRCDJFHYVYUNHM-UHFFFAOYSA-N 0.000 claims description 22
- AZSZCFSOHXEJQE-UHFFFAOYSA-N dibromodifluoromethane Chemical compound FC(F)(Br)Br AZSZCFSOHXEJQE-UHFFFAOYSA-N 0.000 claims description 21
- 229910052731 fluorine Inorganic materials 0.000 claims description 19
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 150000002989 phenols Chemical class 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 9
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000004434 sulfur atom Chemical group 0.000 claims description 5
- 150000001721 carbon Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 claims description 4
- HAQZDUWRNKKMQY-UHFFFAOYSA-N ac1lapjb Chemical group F[S](F)(F)(F)F HAQZDUWRNKKMQY-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims 1
- 125000006287 difluorobenzyl group Chemical group 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- -1 butoxymethyl group Chemical group 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 40
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- 150000001875 compounds Chemical class 0.000 description 32
- 239000004973 liquid crystal related substance Substances 0.000 description 27
- 239000002585 base Substances 0.000 description 19
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical class BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000006227 byproduct Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012043 crude product Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000746 purification Methods 0.000 description 9
- 230000009257 reactivity Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000012044 organic layer Substances 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- MSYHVNATNGNOOY-UHFFFAOYSA-N 1,3-difluoro-5-(4-propylphenyl)benzene Chemical compound C1=CC(CCC)=CC=C1C1=CC(F)=CC(F)=C1 MSYHVNATNGNOOY-UHFFFAOYSA-N 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- DAKLYERWGHXWLM-UHFFFAOYSA-N CCCC1=CC=C(C=C1)C2=CC(=C(C(=C2C(F)F)F)Br)F Chemical compound CCCC1=CC=C(C=C1)C2=CC(=C(C(=C2C(F)F)F)Br)F DAKLYERWGHXWLM-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000002955 isolation Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- QSMDUZUINPQRAS-UHFFFAOYSA-N CCCC1=CC=C(C=C1)C2=CC(=C(C(=C2C(F)F)F)OC3=CC(=C(C(=C3)F)F)F)F Chemical compound CCCC1=CC=C(C=C1)C2=CC(=C(C(=C2C(F)F)F)OC3=CC(=C(C(=C3)F)F)F)F QSMDUZUINPQRAS-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 3
- 150000008046 alkali metal hydrides Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 125000006023 1-pentenyl group Chemical group 0.000 description 2
- 125000006017 1-propenyl group Chemical group 0.000 description 2
- WVSFYQJOKNIGRU-UHFFFAOYSA-N 2-bromo-1,3-difluoro-5-(4-propylphenyl)benzene Chemical compound C1=CC(CCC)=CC=C1C1=CC(F)=C(Br)C(F)=C1 WVSFYQJOKNIGRU-UHFFFAOYSA-N 0.000 description 2
- 125000005449 2-fluoro-1,4-phenylene group Chemical group [H]C1=C([*:2])C([H])=C(F)C([*:1])=C1[H] 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-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
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000006232 ethoxy propyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005446 heptyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000006233 propoxy propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- NAYIXKXYHOLMRC-UHFFFAOYSA-N 1-phenyl-4-propylbenzene Chemical compound C1=CC(CCC)=CC=C1C1=CC=CC=C1 NAYIXKXYHOLMRC-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000005450 2,3-difluoro-1,4-phenylene group Chemical group [H]C1=C([*:2])C(F)=C(F)C([*:1])=C1[H] 0.000 description 1
- 125000005732 2,6-difluoro-1,4-phenylene group Chemical group [H]C1=C(F)C([*:1])=C(F)C([H])=C1[*:2] 0.000 description 1
- 125000004777 2-fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 1
- ZRTWIJKGTUGZJY-UHFFFAOYSA-N 3,4,5-trifluorophenol Chemical compound OC1=CC(F)=C(F)C(F)=C1 ZRTWIJKGTUGZJY-UHFFFAOYSA-N 0.000 description 1
- 125000005451 3-fluoro-1,4-phenylene group Chemical group [H]C1=C([*:1])C([H])=C(F)C([*:2])=C1[H] 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- AVPMRIWGOGRNBF-UHFFFAOYSA-N [bromo(fluoro)methyl]benzene Chemical class FC(Br)C1=CC=CC=C1 AVPMRIWGOGRNBF-UHFFFAOYSA-N 0.000 description 1
- 150000004768 bromobenzenes Chemical class 0.000 description 1
- ANUZKYYBDVLEEI-UHFFFAOYSA-N butane;hexane;lithium Chemical compound [Li]CCCC.CCCCCC ANUZKYYBDVLEEI-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical class FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0466—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the linking chain being a -CF2O- chain
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明はジフルオロベンジルブロミド誘導体を簡便かつ効率的に製造する方法、およびその誘導体を中間体として、液晶材料として好適な諸物性を有するジフルオロベンジルエーテル誘導体を簡便かつ効率的に製造する方法に関する。
【０００２】
【従来の技術】
液晶表示装置は、ＯＡ機器、測定器、自動車用計器、家電製品、時計、電卓等の各種機器の表示装置として用いられている。液晶表示装置として、装置の構造・駆動方法の違いにより様々な方式が用いられているが、中でも、薄膜トランジスタ（ＴＦＴ）を用いたアクティブマトリックス方式の液晶表示装置は、コントラスト、表示容量、応答時間等の表示性能に優れるため、液晶テレビ、パソコン、携帯電話、モバイル機器、ビューファインダー等の表示装置として盛んに使用されている。近年、液晶表示装置には、さらなる小型化、低消費電力化および高速応答化が要求され、駆動電圧（しきい値電圧）が低く、粘度が低い液晶化合物または液晶組成物が要求されている。
【０００３】
液晶素子のしきい値電圧（Ｖth）は、以下の式に示されるとおり、液晶相を構成する液晶化合物の誘電率異方性値（△ε）の関数として表される（Mol.Cryst.Liq.Cryst.,12,57(1970)）。
Ｖth＝π（Ｋ／ε0 Δε）1/2 （式中、Ｋは液晶素子における液晶相の弾性定数、ε0 はその液晶相を構成する液晶化合物の真空誘電率である。）
上式より、Ｖthを低くするためには△εを大きくするか、Ｋを小さくすればよいことがわかる。しかし、現在の技術では、液晶相のＫを調整することが非常に困難であることから、Ｖthが低い液晶素子を得るためには、△εの大きな液晶化合物を使用して、液晶相の△εを大きくする必要がある。このため、△εの大きな液晶化合物が要求されている。
また、液晶表示装置の高速応答化のためには、低粘度の液晶化合物を使用して、低粘度の液晶相を調製する必要がある。
【０００４】
そこで、△εの大きな液晶化合物として、下記の式（Ａ）（特開平５−１１２７７８号公報）、式（Ｂ）（ＤＥ−１９５３１１６５Ａ１）および式（Ｃ）（ＷＯ９６／１１８９７）で表される化合物が提案されている。
【０００５】
【化３】
式（Ａ）、（Ｂ）および（Ｃ）で表される化合物は、大きな△εを示し、比較的低粘度であるため、低電圧で駆動かつ高速応答を可能にする、液晶組成物の構成成分として有用である旨記載されている。
【０００７】
これらのジフルオロベンジルエーテル誘導体の製造方法として、様々な方法が提案されており、例えば、特許公報ＤＥ−１９５３１１６５Ａ１、特開平５−２５５１６５号公報および特開２０００−９５７１５号公報に提案されている。
【０００８】
中でも特開２０００−９５７１５号公報に開示されている製造方法は、簡便な製造方法と思われる。この公報に開示されている製造方法は、下記反応式に示すとおり、式（ａ）で表されるベンゼン誘導体に塩基を作用させ、得られるカルボアニオンに式（ｂ）で表されるジフルオロメタン誘導体を作用させ、式（ｃ）で表されるベンゼン誘導体を得た後、さらに式（ｃ）で表されるベンゼン誘導体に、塩基の存在下、式（ｄ）で表されるフェノール誘導体を作用させ、式（ｅ）で表されるジフルオロベンジルエーテル誘導体を得る方法である。
【０００９】
【化４】
前記式（ａ）、（ｂ）、（ｃ）、（ｄ）および（ｅ）において、Ｒ1 は水素原子または炭素数１〜１５のアルキル基を表し、このアルキル基中の相隣接しない１個以上のメチレン基は酸素原子、硫黄原子、または−ＣＨ＝ＣＨ−で置換されていてもよく、またこのアルキル基中の任意の水素原子はフッ素原子で置換されていてもよく；Ａ1 、Ａ2 およびＡ3 はそれぞれ独立して、環を構成する１個以上のメチレン基が酸素原子または硫黄原子で置換されていてもよいトランス−１，４−シクロヘキシレン基、または１，４−フェニレン基（環上の１個以上の水素原子がフッ素原子で置換されていてもよい）を表し；Ｚ1 、Ｚ2 およびＺ3 はそれぞれ独立して単結合、−ＣＨ2 ＣＨ2 −、−（ＣＨ2 ）4 −、−ＣＨ2 Ｏ−または−ＯＣＨ2 −を表し；ｌ、ｍおよびｎはそれぞれ独立して０または１を表し；Ｘは水素原子、塩素原子、臭素原子またはヨウ素原子を表す。Ｙ1 およびＹ2 はそれぞれ独立してフッ素原子以外のハロゲン原子を表す。Ｒ2 はハロゲン原子、シアノ基、または炭素数１〜１５のアルキル基を表し、このアルキル基中の相隣接しない１個以上のメチレン基は酸素原子、硫黄原子、または−ＣＨ＝ＣＨ−で置換されていてもよく、またこのアルキル基中の１個以上の水素原子はハロゲン原子で置換されていてもよい；Ａ4 は環上の１個以上の水素原子がハロゲン原子で置換されていてもよい１，４−フェニレン基を表し；Ｚ4 は単結合、−ＣＨ2 ＣＨ2 −、−（ＣＨ2 ）4 −、−ＣＨ2 Ｏ−または−ＯＣＨ2 −を表し；Ｌ1 およびＬ2 はそれぞれ独立して水素原子またはハロゲン原子を表し；ｏは０または１である。後記の式（ｆ）においても同様である。
【００１１】
しかし、特開２０００−９５７１５号公報に記載された方法では、式（ａ）で表されるベンゼン誘導体（以下、式（ａ）で表される化合物を化合物（ａ）と記す場合がある。単に（ａ）〜（ｇ）と表記する場合も同様である。）から、ベンゼン誘導体（ｃ）を得る反応において、ハロゲン化ベンゼン誘導体（ｆ）が副生する。（ｃ）と（ｆ）との混合物から（ｃ）を単離することなく、フェノール誘導体（ｄ）を作用させることでも目的物であるジフルオロベンジルエーテル誘導体（ｅ）を得ることができる。しかし、ハロゲン化ベンゼン誘導体（ｆ）との混合物として得られるため、（ｅ）を単離するためには、高価なパラジウム炭素触媒を用いて（ｆ）をベンゼン誘導体（ｇ）に還元してから分離する必要がある。また、（ｃ）と（ｆ）との混合物から（ｃ）を単離するために複数回の再結晶処理を要する。このため、（ｃ）の単離の有無がいずれの場合であっても煩雑な処理が必要とされる。
【００１２】
【化５】
【発明が解決しようとする課題】
本発明の目的は、ジフルオロベンジルエーテル誘導体の中間体であるジフルオロベンジルブロミド誘導体を、ハロゲン化ベンゼン誘導体（ｆ）等の副生物の生成を抑制し、簡便かつ効率的に製造することができる方法を提供し、さらに、液晶材料として有用なジフルオロベンジルエーテル誘導体を、簡便かつ効率的に製造することができる方法を提供することにある。
【００１４】
【課題を解決するための手段】
前記課題を解決するため鋭意検討した結果、本発明者らは、下記式に示すとおり、式（１）で表されるベンゼン誘導体と塩基を反応させた後、ジブロモジフルオロメタン（ＣＦ2 Ｂｒ2 ）とブロモジフルオロメタン（ＣＨＦ2 Ｂｒ）の混合物とを反応させる工程を採用することにより、副生成物である式（５）で表されるブロモベンゼン誘導体の生成を抑制して、式（２）で表されるジフルオロベンジルブロミド誘導体が得られることを見出した。この反応工程において、式（１）で表されるベンゼン誘導体に塩基を作用させると、カルボアニオンが生成し、これにジブロモジフルオロメタン（ＣＦ2 Ｂｒ2 ）とブロモジフルオロメタン（ＣＨＦ2 Ｂｒ）の混合物を反応させることにより、ハロゲン化ベンゼン誘導体（ｆ）等の副生が抑制されるとともに、式（２）で表されるジフルオロベンジルブロミド誘導体が生成されると考えられる。
【００１５】
【化６】
さらに、この方法で得られた式（２）で表されるジフルオロベンジルブロミド誘導体は、１−ブロモベンゼン誘導体（５）とベンゼン誘導体（６）との混合物となる。式（２）で表されるジフルオロベンジルブロミド誘導体を単離することなく、この混合物に、通常のエーテル化反応の条件下において、式（３）で表されるフェノール誘導体を作用させることで式（４）で表されるジフルオロベンジルエーテル誘導体が生成し、反応後の混合物からも容易に単離できることを見出した。
【００１７】
【化７】
すなわち、本発明は、下記式（１）で表されるベンゼン誘導体と塩基を反応させた後、ジブロモジフルオロメタン（ＣＦ2 Ｂｒ2 ）とブロモジフルオロメタン（ＣＨＦ2 Ｂｒ）の混合物とを反応させる工程を有する、式（２）で表されるジフルオロベンジルブロミド誘導体の製造方法（以下、「第１の発明の方法」という）を提供する。
【００１９】
【化８】
さらに本発明は、第１の発明の方法により製造された、式（２）で表されるジフルオロベンジルブロミド誘導体と、式（３）で表されるフェノール誘導体とを反応させる工程を有する、式（４）で表されるジフルオロベンジルエーテル誘導体の製造方法（以下、「第２の発明の方法」という）を提供する。
【００２１】
【化９】
【発明の実施の形態】
第１の発明の方法において、出発物質として用いられるベンゼン誘導体（１）を表す式（１）および目的物質であるジフルオロベンジルブロミド誘導体（２）を表す式（２）において、Ａ1 およびＡ2 はそれぞれ独立して、１，４−フェニレン基（１個以上の水素原子がフッ素原子で置換されていてもよい）、またはトランス−１，４−シクロヘキシレン基（環を構成する１個以上のメチレン基が酸素原子または硫黄原子で置換されていてもよい）を表す。
【００２３】
Ａ1 およびＡ2 の具体例として、下記式（７）〜式（２３）で表される基が挙げられる。なお、本明細書において特に断りのない限り、環状基に結合する置換基の置換位置、特に１位および４位の位置は、式（１）および式（２）におけるＲ1 に近い方を常に４位となるように表記する。例えば、−ＰｈＦ−（式（８））は２−フルオロ−１，４−フェニレン基を示す。Ａ1 およびＡ2 として、反応性の点から、１，４−フェニレン基（式（７））が特に好ましい。
【００２４】
【化１０】
Ｒ1 は炭素数１〜８の脂肪族炭化水素基、水素原子、フッ素原子、塩素原子または臭素原子を表し、炭素数１〜８の脂肪族炭化水素基中および該基とＡ1 の間の炭素−炭素結合間に酸素原子（−Ｏ−）が挿入されていてもよく、該基中に不飽和結合および不斉炭素原子を含んでいてもよく、該基中の水素原子はフッ素原子で置換されてもよい。不飽和結合としては、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＦ−、ＣＦ2 ＝ＣＨ−、ＣＨ2 ＝ＣＨ−等が挙げられる。
【００２６】
炭素数１〜８の脂肪族炭化水素基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペントキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基、メトキシエチル基、エトキシエチル基、プロポキシエチル基、メトキシプロピル基、エトキシプロピル基、プロポキシプロピル基、ビニル基、１−プロペニル基、２−プロペニル基、１−ブテニル基、１−ペンテニル基、３−ブテニル基、３−ペンテニル基、２−フルオロエテニル基、２，２−ジフルオロエテニル基、１，２，２−トリフルオロエテニル基、４，４−ジフルオロ−３−ブテニル基、３，３−ジフルオロ−２−プロペニル基、５，５−ジフルオロ−４−ペンテニル基等が挙げられる。
Ｒ1 として、反応性の点から、プロピル基、ペンチル基、１−ブテニル基、３−ブテニル基が特に好ましい。
【００２７】
Ｚ1 およびＺ2 はそれぞれ独立して、単結合、−ＣＨ2 ＣＨ2 −、−（ＣＨ2 ）2 −、−ＣＨ2 Ｏ−、−ＯＣＨ2 −を表す。ただし、Ｚ1 またはＺ2 中の炭素−炭素結合間は不飽和結合を含んでいてもよく、該基中の水素原子はフッ素原子で置換されてもよい。不飽和結合としては、−ＣＨ＝ＣＨ−等が挙げられる。
【００２８】
不飽和結合を含む、または水素原子がフッ素原子で置換されたＺ1 およびＺ2 の具体例としては、−ＣＦ2 ＣＦ2 −、−（ＣＦ2 ）2 −、−ＣＦ＝ＣＦ−、−ＣＦ2 Ｏ−、−ＯＣＦ2 −等が挙げられる。
Ｚ1 およびＺ2 は、反応性の点から、単結合であることが特に好ましい。
また、Ｘ1 およびＸ2 は水素原子またはフッ素原子を表す。
【００２９】
Ｙは水素原子、塩素原子、臭素原子、またはヨウ素原子を表す。ただし、前記Ｘ1 およびＸ2 がともに水素原子である場合にはＹは水素原子ではない。反応性および選択性の点から、Ｘ1 およびＸ2 がともにフッ素原子であり、Ｙが水素原子であることが好ましい。
【００３０】
ｌおよびｍは、それぞれ独立して０または１を表す。反応性、反応溶媒への溶解性および最終目的物であるジフルオロベンジルエーテル誘導体（４）の単離精製のしやすさの点から、ｌとｍの合計が１であることが好ましい。
【００３１】
第１の発明の方法で特に好適に製造できるジフルオロベンジルブロミド誘導体（２）の具体例としては、下記の式（２−１) 〜式（２−３) で表される化合物が挙げられる。式中、Ｒ1 、Ａ1 、Ａ2 、Ｚ1 、Ｚ2 、Ｘ1 およびＸ2 は、式（１）または（２）について定義したとおりである。
【００３２】
【化１１】
式（２−１) で表される化合物の具体例としては、下記の式で表される化合物が好ましく挙げられる。
CH3-Ph-CF2Br
C2H5-PhF-CF2Br
C3H7-PhFF-CF2Br
C4H9-PhFF-CF2Br
C5H11-PhFF-CF2Br
C2H5-O-PhFF-CF2Br
CH3-O-CH2-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-PhFF-CF2Br
CFH2-CH2-CH2-PhFF-CF2Br
CF2=CH-CH2-CH2-PhFF-CF2Br
【００３４】
式（２−２) で表される化合物の具体例として、下記の式で表される化合物が好ましく挙げられる。
CH3-Cy-Ph-CF2Br
C2H5-Cy-PhF-CF2Br
CH3-Cy-PhFF-CF2Br
C2H5-Cy-PhFF-CF2Br
C3H7-Cy-PhFF-CF2Br
C4H9-Cy-PhFF-CF2Br
C5H11-Cy-PhFF-CF2Br
CH3-O-CH2-Cy-PhFF-CF2Br
CH2=CH-CH2-CH2-Cy-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Cy-PhFF-CF2Br
CFH2-CH2-CH2-Cy-PhFF-CF2Br
CF2=CH-CH2-CH2-Cy-PhFF-CF2Br
C2H5-Cyo-PhFF-CF2Br
C3H7-Cyoo-PhFF-CF2Br
C4H9-Cys-PhFF-CF2Br
C5H11-Cyss-PhFF-CF2Br
【００３５】
CH3-Cy-CH2-CH2-Ph-CF2Br
C2H5-Cy-CH2-CH2-CH2-CH2-PhF-CF2Br
CH3-Cy-OCH2-PhFF-CF2Br
C2H5-Cy-CH2-CH2-PhFF-CF2Br
C3H7-Cy-CH2-CH2-CH2-CH2-PhFF-CF2Br
C4H9-Cy-CH2O-PhFF-CF2Br
C5H11-Cy-CF2O-PhFF-CF2Br
CH3-O-CH2-Cy-OCF2-PhFF-CF2Br
CH2=CH-CH2-CH2-Cy-CF2-CF2-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Cy-CF2-CF2-CF2-CF2-PhFF-CF2Br
CFH2-CH2-CH2-Cy-CH2-CH2-PhFF-CF2Br
CF2=CH-CH2-CH2-Cy-CF2O-PhFF-CF2Br
【００３６】
CH3-Ph-Ph-CF2Br
C2H5-Ph-PhF-CF2Br
CH3-Ph-PhFF-CF2Br
C2H5-Ph-PhFF-CF2Br
C3H7-Ph-PhFF-CF2Br
C4H9-Ph-PhFF-CF2Br
C5H11-Ph-PhFF-CF2Br
CH3-O-CH2-Ph-PhFF-CF2Br
CH2=CH-CH2-CH2-Ph-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Ph-PhFF-CF2Br
CFH2-CH2-CH2-Ph-PhFF-CF2Br
CF2=CH-CH2-CH2-Ph-PhFF-CF2Br
【００３７】
CH3-Ph-CH2-CH2-Ph-CF2Br
C2H5-Ph-CH2-CH2-CH2-CH2-PhF-CF2Br
CH3-Ph-OCH2-PhFF-CF2Br
C2H5-Ph-CH2-CH2-PhFF-CF2Br
C3H7-Ph-CH2-CH2-CH2-CH2-PhFF-CF2Br
C4H9-Ph-CH2O-PhFF-CF2Br
C5H11-Ph-CF2O-PhFF-CF2Br
CH3-O-CH2-Ph-OCF2-PhFF-CF2Br
CH2=CH-CH2-CH2-Ph-CF2-CF2-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Ph-CF2-CF2-CF2-CF2-PhFF-CF2Br
CFH2-CH2-CH2-Ph-CH2-CH2-PhFF-CF2Br
CF2=CH-CH2-CH2-Ph-CF2O-PhFF-CF2Br
【００３８】
CH3-PhF-Ph-CF2Br
C2H5-PhFF-PhF-CF2Br
CH3-FPhFF-PhFF-CF2Br
C2H5-FPh-PhFF-CF2Br
C3H7-PhF-PhFF-CF2Br
C4H9-FPhF-PhFF-CF2Br
C5H11-PhFF-PhFF-CF2Br
C5H11-PhFF-CF2O-PhFF-CF2Br
CH3-O-CH2-FFPhF-PhFF-CF2Br
CH2=CH-CH2-CH2-PhF-CF2-CF2-PhFF-CF2Br CH3-CH=CH-CH2-CH2-PhFF-PhFF-CF2Br
CFH2-CH2-CH2-Ph-PhFF-CF2Br
CF2=CH-CH2-CH2-FFPh-CH2-CH2-PhFF-CF2Br
【００３９】
式（２−３) で表される化合物の具体例としては、下記の式で表される化合物が好ましく挙げられる。
CH3-Cy-Cy-Ph-CF2Br
C2H5-Cy-Cy-PhF-CF2Br
CH3-Cy-Cy-PhFF-CF2Br
C2H5-Cy-Cy-PhFF-CF2Br
C3H7-Cy-Cy-PhFF-CF2Br
C4H9-Cy-Cy-PhFF-CF2Br
C5H11-Cy-Cy-PhFF-CF2Br
CH3-O-CH2-Cy-Cy-PhFF-CF2Br
CH2=CH-CH2-CH2-Cy-Cy-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Cy-Cy-PhFF-CF2Br
CFH2-CH2-CH2-Cy-Cy-PhFF-CF2Br
CF2=CH-CH2-CH2-Cy-Cy-PhFF-CF2Br
C2H5-Cy-Cyss-PhFF-CF2Br
C3H7-Cy-Cys-PhFF-CF2Br
C4H9-Cy-Cyoo-PhFF-CF2Br
C5H11-Cy-Cyo-PhFF-CF2Br
【００４０】
CH3-Cy-Ph-Ph-CF2Br
C2H5-Cy-Ph-PhF-CF2Br
CH3-Cy-Ph-PhFF-CF2Br
C2H5-Cy-Ph-PhFF-CF2Br
C3H7-Cy-Ph-PhFF-CF2Br
C4H9-Cy-Ph-PhFF-CF2Br
C5H11-Cy-Ph-PhFF-CF2Br
CH3-O-CH2-Cy-Ph-PhFF-CF2Br
CH2=CH-CH2-CH2-Cy-Ph-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Cy-Ph-PhFF-CF2Br
CFH2-CH2-CH2-Cy-Ph-PhFF-CF2Br
CF2=CH-CH2-CH2-Cy-Ph-PhFF-CF2Br
C2H5-Cys-Ph-PhFF-CF2Br
C3H7-Cyss-Ph-PhFF-CF2Br
C4H9-Cyo-Ph-PhFF-CF2Br
C5H11-Cyoo-Ph-PhFF-CF2Br
【００４１】
CH3-Cy-PhF-Ph-CF2Br
C2H5-Cy-PhFF-PhF-CF2Br
CH3-Cy-PhF-PhFF-CF2Br
C2H5-Cy-FPhF-PhFF-CF2Br
C3H7-Cy-PhFF-PhFF-CF2Br
C4H9-Cy-FPh-PhFF-CF2Br
C5H11-Cy-PhF-PhFF-CF2Br
CH3-O-CH2-Cy-FPhFF-PhFF-CF2Br
CH2=CH-CH2-CH2-Cy-FFPhF-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Cy-PhF-PhFF-CF2Br
CFH2-CH2-CH2-Cy-PhF-PhFF-CF2Br
CF2=CH-CH2-CH2-Cy-PhF-PhFF-CF2Br
【００４２】
CH3-Cy-CH2-CH2-Cy-Ph-CF2Br
C2H5-Cy-CH2-CH2-Cy-PhF-CF2Br
CH3-Cy-CH2-CH2-Cy-PhFF-CF2Br
C2H5-Cy-CH2-CH2-Cy-PhFF-CF2Br
C3H7-Cy-CH2-CH2-Cy-PhFF-CF2Br
C4H9-Cy-CH2-CH2-Cy-PhFF-CF2Br
C5H11-Cy-CH2-CH2-Cy-PhFF-CF2Br
CH3-O-CH2-Cy-CH2-CH2-Cy-PhFF-CF2Br
CH2=CH-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2Br
CFH2-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2Br
CF2=CH-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2Br
【００４３】
CH3-Cy-Cy-CH2-CH2-Ph-CF2Br
C2H5-Cy-Cy-CH2-CH2-PhF-CF2Br
CH3-Cy-Cy-CH2-CH2-PhFF-CF2Br
C2H5-Cy-Cy-CH2-CH2-PhFF-CF2Br
C3H7-Cy-Cy-CH2-CH2-PhFF-CF2Br
C4H9-Cy-Cy-CH2-CH2-PhFF-CF2Br
C5H11-Cy-Cy-CH2-CH2-PhFF-CF2Br
CH3-O-CH2-Cy-Cy-CH2-CH2-PhFF-CF2Br
CH2=CH-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2Br
CFH2-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2Br
CF2=CH-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2Br
【００４４】
CH3-Cy-CH2-CH2-Ph-Ph-CF2Br
C2H5-Cy-CH2-CH2-Ph-PhF-CF2Br
CH3-Cy-CH2-CH2-PhF-PhFF-CF2Br
C2H5-Cy-CH2-CH2-PhFF-PhF-CF2Br
C3H7-Cy-CH2-CH2-Ph-PhFF-CF2Br
C4H9-Cy-CH2-CH2-PhF-PhFF-CF2Br
C5H11-Cy-CH2-CH2-PhFF-PhFF-CF2Br
CH3-O-CH2-Cy-CH2-CH2-FPhF-PhFF-CF2Br
CH2=CH-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2Br
CFH2-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2Br
CF2=CH-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2Br
【００４５】
CH3-Cy-Ph-CH2-CH2-Ph-CF2Br
C2H5-Cy-Ph-CH2-CH2-PhF-CF2Br
CH3-Cy-PhF-CH2-CH2-PhFF-CF2Br
C2H5-Cy-PhFF-CH2-CH2-PhF-CF2Br
C3H7-Cy-Ph-CH2-CH2-PhFF-CF2Br
C4H9-Cy-PhF-CH2-CH2-PhFF-CF2Br
C5H11-Cy-PhFF-CH2-CH2-PhFF-CF2Br
CH3-O-CH2-Cy-FPhF-CH2-CH2-PhFF-CF2Br
CH2=CH-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2Br
CFH2-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2Br
CF2=CH-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2Br
【００４６】
CH3-Cy-CH2O-Cy-Ph-CF2Br
C2H5-Cy-OCH2-Cy-PhF-CF2Br
CH3-Cy-CH2-CH2-CH2-CH2-Cy-PhFF-CF2Br
C2H5-Cy-CF2O-Cy-PhFF-CF2Br
C3H7-Cy-CF2-CF2-Cy-PhFF-CF2Br
C4H9-Cy-CF2-CF2-CF2-CF2-Cy-PhFF-CF2Br
C5H11-Cy-Cy-CF2O-PhFF-CF2Br
CH3-O-CH2-Cy-Cy-CH2-CH2-CH2-CH2-PhFF-CF2Br
CH2=CH-CH2-CH2-Cy-Cy-CH2O-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Cy-Cy-CF2O-PhFF-CF2Br
CFH2-CH2-CH2-Cy-CF2-CF2-Cy-PhFF-CF2Br
CF2=CH-CH2-CH2-Cy-Cy-CF2O-PhFF-CF2Br
【００４７】
CH3-Cy-CH2O-PhF-Ph-CF2Br
C2H5-Cy-OCH2-PhFF-PhF-CF2Br
CH3-Cy-CH2-CH2-CH2-CH2-PhF-PhFF-CF2Br
C2H5-Cy-CF2O-FPhF-PhFF-CF2Br
C3H7-Cy-CF2-CF2-PhFF-PhFF-CF2Br
C4H9-Cy-CF2-CF2-CF2-CF2-FPh-PhFF-CF2Br
C5H11-Cy-PhF-CF2O-PhFF-CF2Br
CH3-O-CH2-Cy-FPhFF-CH2-CH2-CH2-CH2-PhFF-CF2Br
CH2=CH-CH2-CH2-Cy-FFPhF-CH2O-PhFF-CF2Br
CH3-CH=CH-CH2-CH2-Cy-PhF-CF2O-PhFF-CF2Br
CFH2-CH2-CH2-Cy-CF2-CF2-Ph-PhFF-CF2Br
CF2=CH-CH2-CH2-Cy-PhFF-CF2O-PhFF-CF2Br
【００４８】
第２の発明の方法において、前記フェノール誘導体を表す式（３）および最終目的物質であるジフルオロベンジルエーテル誘導体を表す式（４）において、Ｒ2 は炭素数１〜８の脂肪族炭化水素基、水素原子、ハロゲン原子、５フッ化硫黄基（ＳＦ2 ）またはシアノ基を表し、炭素数１〜８の脂肪族炭化水素基は、該基中および該基とベンゼン環との間の炭素−炭素結合間に酸素原子（−Ｏ−）が挿入されていてもよく、該基中に不飽和結合および不斉炭素原子を含んでいてもよく、該基中の水素原子はハロゲン原子で置換されていてもよい。不飽和結合としては、−ＣＨ＝ＣＨ−等が挙げられる。
【００４９】
Ｒ2 の脂肪族炭化水素基の具体例としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペントキシ基、ヘキシルオキシ基、ヘプチルオキシ基、オクチルオキシ基、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基、メトキシエチル基、エトキシエチル基、プロポキシエチル基、メトキシプロピル基、エトキシプロピル基、プロポキシプロピル基、ビニル基、１−プロペニル基、２−プロペニル基、１−ブテニル基、１−ペンテニル基、３−ブテニル基、３−ペンテニル基、トリフルオロメチル基、ジフルオロメチル基、ジフルオロクロロメチル基、２，２，２−トリフルオロエチル基、２−フルオロエチル基、３−フルオロプロピル基、４−フルオロブチル基、５−フルオロペンチル基、３−クロロプロピル基、トリフルオロメトキシ基、ジフルオロメトキシ基、ジフルオロクロロメトキシ基、ペンタフルオロエトキシ基、１，１，２，２−テトラフルオロエトキシ基、ヘプタフルオロプロポキシ基、１，１，２，３，３，３−ヘキサフルオロプロポキシ基、トリフルオロメトキシメチル基、２−フルオロエテニル基、２，２−ジフルオロエテニル基、１，２，２−トリフルオロエテニル基、４，４−ジフルオロ−３−ブテニル基、３，３−ジフルオロ−２−プロペニル基、５，５−ジフルオロ−４−ペンテニル基等が挙げられる。
これらの中でも、Ｒ2 が、反応性、単離精製のしやすさの点から、フッ素原子、トリフルオロメチル基、トリフルオロメトキシ基、５フッ化硫黄基（ＳＦ5 ）、シアノ基であることが特に好ましい。
【００５０】
Ａ3 は１，４−フェニレン基であり、１個以上の水素原子がフッ素原子で置換されていてもよい。水素原子がフッ素原子で置換されたＡ3 の具体例としては、Ｒ2 に近い側を１位として、２−フルオロ−１，４−フェニレン基、３−フルオロ−１，４−フェニレン基、２，３−ジフルオロ−１，４−フェニレン基、２，６−ジフルオロ−１，４−フェニレン基、２，３，６−トリフルオロ−１，４−フェニレン基、２，３，５，６−テトラフルオロ−１，４−フェニレン基、トランス−１，４−シクロヘキシレン基等が挙げられる。反応性の点から、１，４−フェニレン基が特に好ましい。
【００５１】
Ｚ3 は単結合、−ＣＨ2 ＣＨ2 −、−（ＣＨ2 ）4 −、−ＣＨ2 Ｏ−、−ＯＣＨ2 −を表す。基中の炭素−炭素結合は不飽和結合（−ＣＨ＝ＣＨ−）であってもよく、基中の水素原子はフッ素原子で置換されてもよく、例えば、−ＣＦ2 ＣＦ2 −、−（ＣＦ2 ）4 −、−ＣＦ＝ＣＦ−、−ＣＦ2 Ｏ−、−ＯＣＦ2 −等であってもよい。反応性の点から、単結合であることが特に好ましい。
【００５２】
Ｘ3 およびＸ4 は水素原子またはハロゲン原子を表す。
Ｘ3 およびＸ4 の具体例としては、水素原子、フッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。反応性および選択性の点から、水素原子またはフッ素原子であることが好ましい。
ｎは０または１を表す。反応性、反応溶媒への溶解性および最終目的物であるジフルオロベンジルエーテル誘導体（４）の単離精製のしやすさの点から、０であることが好ましい。
なお、Ｒ1 、Ａ1 、Ａ2 、Ｚ1 、Ｚ2 、Ｘ1 、Ｘ2 、Ｙ、ｌおよびｍは前述の式（１）および式（２）の記載と同一の意味を表す。
【００５３】
第２の発明の方法によって、特に好適に製造できるジフルオロベンジルエーテル誘導体（４）の具体例としては、下記の式（４−１）〜（４−５）で表される化合物が挙げられる。
【００５４】
【化１２】
式（４−１) で表される化合物の具体例としては、下記の式で表される化合物が好ましく挙げられる。
C3H7-Ph-CF2O-Ph-F
C5H11-Ph-CF2O-PhF-F
C3H7-Ph-CF2O-PhFF-F
C3H7-PhF-CF2O-Ph-F
C5H11-PhF-CF2O-PhF-F
C3H7-PhF-CF2O-PhFF-F
C3H7-PhFF-CF2O-Ph-F
C5H11-PhFF-CF2O-PhF-F
C3H7-PhFF-CF2O-PhFF-F
C3H7-PhFF-CF2O-FPh-Cl
C5H11-PhFF-CF2O-PhF-Cl
【００５６】
C3H7-PhFF-CF2O-PhF-CN
C5H11-PhFF-CF2O-PhFF-CN
C3H7-PhFF-CF2O-PhF-CF3
C5H11-PhFF-CF2O-PhFF-CF3
C3H7-PhFF-CF2O-PhF-OCF3
C5H11-PhFF-CF2O-PhFF-OCF3
C3H7-PhFF-CF2O-PhF-SF5
C5H11-PhFF-CF2O-PhFF-SF5
C2H5-O-PhFF-CF2O-PhF-F
CH3-O-CH2-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-PhFF-CF2O-PhF-F
CFH2-CH2-CH2-PhFF-CF2O-PhFF-F
CF2=CH-CH2-CH2-PhFF-CF2O-PhFF-F
【００５７】
式（４−２）で表される化合物の具体例としては、下記の式で表される化合物が好ましく挙げられる。
C3H7-Cy-PhFF-CF2O-Ph-F
C5H11-Cy-PhFF-CF2O-PhF-F
C3H7-Cy-PhFF-CF2O-FPh-Cl
C5H11-Cy-PhFF-CF2O-PhF-Cl
C3H7-Cy-PhFF-CF2O-PhF-CN
C5H11-Cy-PhFF-CF2O-PhFF-CN
C3H7-Cy-PhFF-CF2O-PhF-CF3
C5H11-Cy-PhFF-CF2O-PhFF-CF3
C3H7-Cy-PhFF-CF2O-PhF-OCF3
C5H11-Cy-PhFF-CF2O-PhFF-OCF3
C3H7-Cy-PhFF-CF2O-PhF-SF5
C5H11-Cy-PhFF-CF2O-PhFF-SF5
CH3-Cy-Ph-CF2O-PhFF-F
C2H5-Cy-PhF-CF2O-PhFF-F
CH3-Cy-PhFF-CF2O-PhFF-F
【００５８】
C2H5-Cy-PhFF-CF2O-PhFF-F
C3H7-Cy-PhFF-CF2O-PhFF-F
C4H9-Cy-PhFF-CF2O-PhFF-F
C5H11-Cy-PhFF-CF2O-PhFF-F
CH3-O-CH2-Cy-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CF2=CH-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
C2H5-Cyo-PhFF-CF2O-PhFF-F
C3H7-Cyoo-PhFF-CF2O-PhFF-F
C4H9-Cys-PhFF-CF2O-PhFF-F
C5H11-Cyss-PhFF-CF2O-PhFF-F
【００５９】
C3H7-Cy-CH2-CH2-PhFF-CF2O-Ph-F
C5H11-Cy-CH2-CH2-PhFF-CF2O-PhF-F
C3H7-Cy-CH2-CH2-PhFF-CF2O-FPh-Cl
C5H11-Cy-CH2-CH2-PhFF-CF2O-PhF-Cl
C3H7-Cy-CH2-CH2-PhFF-CF2O-PhF-CN
C5H11-Cy-CH2-CH2-PhFF-CF2O-PhFF-CN
C3H7-Cy-CH2-CH2-PhFF-CF2O-PhF-CF3
C5H11-Cy-CH2-CH2-PhFF-CF2O-PhFF-CF3
C3H7-Cy-CH2-CH2-PhFF-CF2O-PhF-OCF3
C5H11-Cy-CH2-CH2-PhFF-CF2O-PhFF-OCF3
C3H7-Cy-CH2-CH2-PhFF-CF2O-PhF-SF5
C5H11-Cy-CH2-CH2-PhFF-CF2O-PhFF-SF5
CH3-Cy-CH2-CH2-Ph-CF2O-PhFF-F
【００６０】
C2H5-Cy-CH2-CH2-CH2-CH2-PhF-CF2O-PhFF-F
CH3-Cy-OCH2-PhFF-CF2O-PhFF-F
C2H5-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
C3H7-Cy-CH2-CH2-CH2-CH2-PhFF-CF2O-PhFF-F
C4H9-Cy-CH2O-PhFF-CF2O-PhFF-F
CH3-O-CH2-Cy-OCF2-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-Cy-CF2-CF2-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-Cy-CF2-CF2-CF2-CF2-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
【００６１】
C3H7-Ph-PhFF-CF2O-Ph-F
C5H11-Ph-PhFF-CF2O-PhF-F
C3H7-Ph-PhFF-CF2O-FPh-Cl
C5H11-Ph-PhFF-CF2O-PhF-Cl
C3H7-Ph-PhFF-CF2O-PhF-CN
C5H11-Ph-PhFF-CF2O-PhFF-CN
C3H7-Ph-PhFF-CF2O-PhF-CF3
C5H11-Ph-PhFF-CF2O-PhFF-CF3
C3H7-Ph-PhFF-CF2O-PhF-OCF3
C5H11-Ph-PhFF-CF2O-PhFF-OCF3
C3H7-Ph-PhFF-CF2O-PhF-SF5
C5H11-Ph-PhFF-CF2O-PhFF-SF5
CH3-Ph-Ph-CF2O-PhFF-F
C2H5-Ph-PhF-CF2O-PhFF-F
CH3-Ph-PhFF-CF2O-PhFF-F
C2H5-Ph-PhFF-CF2O-PhFF-F
C3H7-Ph-PhFF-CF2O-PhFF-F
【００６２】
C4H9-Ph-PhFF-CF2O-PhFF-F
C5H11-Ph-PhFF-CF2O-PhFF-F
CH3-O-CH2-Ph-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CF2=CH-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
C3H7-Ph-CH2-CH2-PhFF-CF2O-Ph-F
C5H11-Ph-CH2-CH2-PhFF-CF2O-PhF-F
C3H7-Ph-CH2-CH2-PhFF-CF2O-FPh-Cl
C5H11-Ph-CH2-CH2-PhFF-CF2O-PhF-Cl
C3H7-Ph-CH2-CH2-PhFF-CF2O-PhF-CN
C5H11-Ph-CH2-CH2-PhFF-CF2O-PhFF-CN
【００６３】
C3H7-Ph-CH2-CH2-PhFF-CF2O-PhF-CF3
C5H11-Ph-CH2-CH2-PhFF-CF2O-PhFF-CF3
C3H7-Ph-CH2-CH2-PhFF-CF2O-PhF-OCF3
C5H11-Ph-CH2-CH2-PhFF-CF2O-PhFF-OCF3
C3H7-Ph-CH2-CH2-PhFF-CF2O-PhF-SF5
C5H11-Ph-CH2-CH2-PhFF-CF2O-PhFF-SF5
CH3-Ph-CH2-CH2-Ph-CF2O-PhFF-F
C2H5-Ph-CH2-CH2-CH2-CH2-PhF-CF2O-PhFF-F
CH3-Ph-OCH2-PhFF-CF2O-PhFF-F
C2H5-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
C3H7-Ph-CH2-CH2-CH2-CH2-PhFF-CF2O-PhFF-F
C4H9-Ph-CH2O-PhFF-CF2O-PhFF-F
CH3-O-CH2-Ph-OCF2-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-Ph-CF2-CF2-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-Ph-CF2-CF2-CF2-CF2-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
【００６４】
CH3-PhF-Ph-CF2O-PhFF-F
C2H5-PhFF-PhF-CF2O-PhFF-F
CH3-FPhFF-PhFF-CF2O-PhFF-F
C2H5-FPh-PhFF-CF2O-PhFF-F
C3H7-PhF-PhFF-CF2O-PhFF-F
C4H9-FPhF-PhFF-CF2O-PhFF-F
C5H11-PhFF-PhFF-CF2O-PhFF-F
C5H11-PhFF-CF2O-PhFF-CF2O-PhFF-F
CH3-O-CH2-FFPhF-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-PhF-CF2-CF2-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-PhFF-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CF2=CH-CH2-CH2-FFPh-CH2-CH2-PhFF-CF2O-PhFF-F
【００６５】
式（４−３) で表される化合物の具体例としては、下記の式で表される化合物が好ましく挙げられる。
C3H7-Cy-Cy-PhFF-CF2O-Ph-F
C5H11-Cy-Cy-PhFF-CF2O-PhF-F
C3H7-Cy-Cy-PhFF-CF2O-FPh-Cl
C5H11-Cy-Cy-PhFF-CF2O-PhF-Cl
C3H7-Cy-Cy-PhFF-CF2O-PhF-CN
C5H11-Cy-Cy-PhFF-CF2O-PhFF-CN
C3H7-Cy-Cy-PhFF-CF2O-PhF-CF3
C5H11-Cy-Cy-PhFF-CF2O-PhFF-CF3
C3H7-Cy-Cy-PhFF-CF2O-PhF-OCF3
C5H11-Cy-Cy-PhFF-CF2O-PhFF-OCF3
C3H7-Cy-Cy-PhFF-CF2O-PhF-SF5
C5H11-Cy-Cy-PhFF-CF2O-PhFF-SF5
CH3-Cy-Cy-Ph-CF2O-PhFF-F
C2H5-Cy-Cy-PhF-CF2O-PhFF-F
CH3-Cy-Cy-PhFF-CF2O-PhFF-F
【００６６】
C2H5-Cy-Cy-PhFF-CF2O-PhFF-F
C3H7-Cy-Cy-PhFF-CF2O-PhFF-F
C4H9-Cy-Cy-PhFF-CF2O-PhFF-F
C5H11-Cy-Cy-PhFF-CF2O-PhFF-F
CH3-O-CH2-Cy-Cy-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-Cy-Cy-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-Cy-Cy-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-Cy-PhFF-CF2O-PhFF-F
CF2=CH-CH2-CH2-Cy-Cy-PhFF-CF2O-PhFF-F
C2H5-Cy-Cyo-PhFF-CF2O-PhFF-F
C3H7-Cy-Cyoo-PhFF-CF2O-PhFF-F
C4H9-Cy-Cys-PhFF-CF2O-PhFF-F
C5H11-Cy-Cyss-PhFF-CF2O-PhFF-F
C3H7-Cy-Ph-PhFF-CF2O-Ph-F
C5H11-Cy-Ph-PhFF-CF2O-PhF-F
【００６７】
C3H7-Cy-Ph-PhFF-CF2O-FPh-Cl
C5H11-Cy-Ph-PhFF-CF2O-PhF-Cl
C3H7-Cy-Ph-PhFF-CF2O-PhF-CN
C5H11-Cy-Ph-PhFF-CF2O-PhFF-CN
C3H7-Cy-Ph-PhFF-CF2O-PhF-CF3
C5H11-Cy-Ph-PhFF-CF2O-PhFF-CF3
C3H7-Cy-Ph-PhFF-CF2O-PhF-OCF3
C5H11-Cy-Ph-PhFF-CF2O-PhFF-OCF3
C3H7-Cy-Ph-PhFF-CF2O-PhF-SF5
C5H11-Cy-Ph-PhFF-CF2O-PhFF-SF5
CH3-Cy-Ph-Ph-CF2O-PhFF-F
C2H5-Cy-Ph-PhF-CF2O-PhFF-F
CH3-Cy-Ph-PhFF-CF2O-PhFF-F
C2H5-Cy-Ph-PhFF-CF2O-PhFF-F
【００６８】
C3H7-Cy-Ph-PhFF-CF2O-PhFF-F
C4H9-Cy-Ph-PhFF-CF2O-PhFF-F
C5H11-Cy-Ph-PhFF-CF2O-PhFF-F
CH3-O-CH2-Cy-Ph-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-Cy-Ph-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-Cy-Ph-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-Ph-PhFF-CF2O-PhFF-F
CF2=CH-CH2-CH2-Cy-Ph-PhFF-CF2O-PhFF-F
C2H5-Cys-Ph-PhFF-CF2O-PhFF-F
C3H7-Cyss-Ph-PhFF-CF2O-PhFF-F
C4H9-Cyo-Ph-PhFF-CF2O-PhFF-F
C5H11-Cyoo-Ph-PhFF-CF2O-PhFF-F
CH3-Cy-PhF-Ph-CF2O-PhFF-F
C2H5-Cy-PhFF-PhF-CF2O-PhFF-F
CH3-Cy-PhF-PhFF-CF2O-PhFF-F
【００６９】
C2H5-Cy-FPhF-PhFF-CF2O-PhFF-F
C3H7-Cy-PhFF-PhFF-CF2O-PhFF-F
C4H9-Cy-FPh-PhFF-CF2O-PhFF-F
C5H11-Cy-PhF-PhFF-CF2O-PhFF-F
CH3-O-CH2-Cy-FPhFF-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-Cy-FFPhF-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-Cy-PhF-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-PhF-PhFF-CF2O-PhFF-F
CF2=CH-CH2-CH2-Cy-PhF-PhFF-CF2O-PhFF-F
C3H7-Cy-CH2-CH2-Cy-PhFF-CF2O-Ph-F
C5H11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhF-F
C3H7-Cy-CH2-CH2-Cy-PhFF-CF2O-FPh-Cl
C5H11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhF-Cl
C3H7-Cy-CH2-CH2-Cy-PhFF-CF2O-PhF-CN
C5H11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-CN
C3H7-Cy-CH2-CH2-Cy-PhFF-CF2O-PhF-CF3
C5H11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-CF3
【００７０】
C3H7-Cy-CH2-CH2-Cy-PhFF-CF2O-PhF-OCF3
C5H11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-OCF3
C3H7-Cy-CH2-CH2-Cy-PhFF-CF2O-PhF-SF5
C5H11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-SF5
CH3-Cy-CH2-CH2-Cy-Ph-CF2O-PhFF-F
C2H5-Cy-CH2-CH2-Cy-PhF-CF2O-PhFF-F
CH3-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
C2H5-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
C3H7-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
C4H9-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
C5H11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CH3-O-CH2-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CF2=CH-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
【００７１】
C3H7-Cy-Cy-CH2-CH2-PhFF-CF2O-Ph-F
C5H11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhF-F
C3H7-Cy-Cy-CH2-CH2-PhFF-CF2O-FPh-Cl
C5H11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhF-Cl
C3H7-Cy-Cy-CH2-CH2-PhFF-CF2O-PhF-CN
C5H11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-CN
C3H7-Cy-Cy-CH2-CH2-PhFF-CF2O-PhF-CF3
C5H11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-CF3
C3H7-Cy-Cy-CH2-CH2-PhFF-CF2O-PhF-OCF3
C5H11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-OCF3
C3H7-Cy-Cy-CH2-CH2-PhFF-CF2O-PhF-SF5
C5H11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-SF5
CH3-Cy-Cy-CH2-CH2-Ph-CF2O-PhFF-F
【００７２】
C2H5-Cy-Cy-CH2-CH2-PhF-CF2O-PhFF-F
CH3-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
C2H5-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
C3H7-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
C4H9-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
C5H11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CH3-O-CH2-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CF2=CH-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
C3H7-Cy-CH2-CH2-Ph-PhFF-CF2O-Ph-F
C5H11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-F
C3H7-Cy-CH2-CH2-Ph-PhFF-CF2O-FPh-Cl
C5H11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-Cl
【００７３】
C3H7-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-CN
C5H11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-CN
C3H7-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-CF3
C5H11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-CF3
C3H7-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-OCF3
C5H11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-OCF3
C3H7-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-SF5
C5H11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-SF5
CH3-Cy-CH2-CH2-Ph-Ph-CF2O-PhFF-F
C2H5-Cy-CH2-CH2-Ph-PhF-CF2O-PhFF-F
CH3-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
C2H5-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
C3H7-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
C4H9-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
C5H11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CH3-O-CH2-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CF2=CH-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
【００７４】
C3H7-Cy-Ph-CH2-CH2-PhFF-CF2O-Ph-F
C5H11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhF-F
C3H7-Cy-Ph-CH2-CH2-PhFF-CF2O-FPh-Cl
C5H11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhF-Cl
C3H7-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-CN
C5H11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-CN
C3H7-Cy-Ph-CH2-CH2-PhFF-CF2O-PhF-CF3
C5H11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-CF3
C3H7-Cy-Ph-CH2-CH2-PhFF-CF2O-PhF-OCF3
C5H11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-OCF3
C3H7-Cy-Ph-CH2-CH2-PhFF-CF2O-PhF-SF5
C5H11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-SF5
CH3-Cy-Ph-CH2-CH2-Ph-CF2O-PhFF-F
【００７５】
C2H5-Cy-Ph-CH2-CH2-PhF-CF2O-PhFF-F
CH3-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
C2H5-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
C3H7-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
C4H9-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
C5H11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CH3-O-CH2-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CF2=CH-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
【００７６】
C3H7-Ph-Ph-PhFF-CF2O-Ph-F
C5H11-Ph-Ph-PhFF-CF2O-PhF-F
C3H7-Ph-Ph-PhFF-CF2O-FPh-Cl
C5H11-Ph-Ph-PhFF-CF2O-PhF-Cl
C3H7-Ph-Ph-PhFF-CF2O-PhF-CN
C5H11-Ph-Ph-PhFF-CF2O-PhFF-CN
C3H7-Ph-Ph-PhFF-CF2O-PhF-CF3
C5H11-Ph-Ph-PhFF-CF2O-PhFF-CF3
C3H7-Ph-Ph-PhFF-CF2O-PhF-OCF3
C5H11-Ph-Ph-PhFF-CF2O-PhFF-OCF3
C3H7-Ph-Ph-PhFF-CF2O-PhF-SF5
C5H11-Ph-Ph-PhFF-CF2O-PhFF-SF5
CH3-Ph-Ph-Ph-CF2O-PhFF-F
【００７７】
C2H5-Ph-Ph-PhF-CF2O-PhFF-F
CH3-Ph-Ph-PhFF-CF2O-PhFF-F
C2H5-Ph-Ph-PhFF-CF2O-PhFF-F
C3H7-Ph-Ph-PhFF-CF2O-PhFF-F
C4H9-Ph-Ph-PhFF-CF2O-PhFF-F
C5H11-Ph-Ph-PhFF-CF2O-PhFF-F
CH3-O-CH2-Ph-PhFF-CF2O-PhFF-F
CH2=CH-CH2-CH2-Ph-Ph-PhFF-CF2O-PhFF-F
CH3-CH=CH-CH2-CH2-Ph-Ph-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Ph-Ph-PhFF-CF2O-PhFF-F
CF2=CH-CH2-CH2-Ph-Ph-PhFF-CF2O-PhFF-F
C3H7-Ph-Ph-PhFF-CF2O-PhF-F
C5H11-Ph-PhFF-PhFF-CF2O-PhFF-F
C3H7-PhFF-PhFF-PhFF-CF2O-PhF-F
C5H11-PhF-PhF-PhFF-CF2O-PhFF-F
C3H7-Ph-Ph-CH2-CH2-PhFF-CF2O-PhF-F
C5H11-Ph-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
【００７８】
式（４−４) で表される化合物の具体例としては、下記の式で表される化合物が好ましく挙げられる。
C3H7-Ph-CF2O-Ph-PhF-F
C5H11-PhF-CF2O-Ph-PhFF-F
C3H7-PhFF-CF2O-Ph-PhF-F
C5H11-PhFF-CF2O-Ph-PhFF-F
C3H7-PhFF-CF2O-PhF-PhF-F
C5H11-PhFF-CF2O-PhFF-PhFF-F
C3H7-PhFF-CF2O-Ph-PhF-CN
C5H11-PhFF-CF2O-Ph-PhFF-CN
C3H7-PhFF-CF2O-Ph-PhF-CF3
C5H11-PhFF-CF2O-Ph-PhFF-CF3
C3H7-PhFF-CF2O-Ph-PhF-OCF3
C5H11-PhFF-CF2O-Ph-PhFF-OCF3
【００７９】
式（４−５) で表される化合物の具体例としては、下記の式で表される化合物が好ましく挙げられる。
C3H7-Cy-Ph-CF2O-Ph-PhF-F
C5H11-Cy-PhF-CF2O-Ph-PhFF-F
C3H7-Cy-PhFF-CF2O-Ph-PhF-F
C5H11-Cy-PhFF-CF2O-Ph-PhFF-F
C3H7-Cy-PhFF-CF2O-PhF-PhF-F
C5H11-Cy-PhFF-CF2O-PhFF-PhFF-F
C3H7-Cy-PhFF-CF2O-Ph-PhF-CN
C5H11-Cy-PhFF-CF2O-Ph-PhFF-CN
C3H7-Cy-PhFF-CF2O-Ph-PhF-CF3
C5H11-Cy-PhFF-CF2O-Ph-PhFF-CF3
C3H7-Cy-PhFF-CF2O-Ph-PhF-OCF3
C5H11-Cy-PhFF-CF2O-Ph-PhFF-OCF3
【００８０】
C3H7-Ph-Ph-CF2O-Ph-PhF-F
C5H11-Ph-PhF-CF2O-Ph-PhFF-F
C3H7-Ph-PhFF-CF2O-Ph-PhF-F
C5H11-Ph-PhFF-CF2O-Ph-PhFF-F
C3H7-Ph-PhFF-CF2O-PhF-PhF-F
C5H11-Ph-PhFF-CF2O-PhFF-PhFF-F
C3H7-Ph-PhFF-CF2O-Ph-PhF-CN
C5H11-Ph-PhFF-CF2O-Ph-PhFF-CN
C3H7-Ph-PhFF-CF2O-Ph-PhF-CF3
C5H11-Ph-PhFF-CF2O-Ph-PhFF-CF3
C3H7-Ph-PhFF-CF2O-Ph-PhF-OCF3
C5H11-Ph-PhFF-CF2O-Ph-PhFF-OCF3
【００８１】
第１の発明の方法で使用する塩基としては、アルカリ金属、アルカリ金属の水素化物、アルキルリチウム、アルカリ金属アルコラート等が挙げられる。入手の容易さ、取り扱い上の安全性、反応の高選択性の点から、アルキルリチウムが好ましく、特にｎ−ブチルリチウムが好ましい。
【００８２】
また、このベンゼン誘導体（１）と塩基の反応において、塩基の使用量は、ベンゼン誘導体（１）が、式（１）におけるＸ1 およびＸ2 がともにフッ素原子でありＹが水素原子である化合物である場合には、ベンゼン誘導体（１）の０．８〜１．３当量が好ましく、さらに高い選択性を保持しながら、タール状の副生成物を低減して最終目的物であるジフルオロベンジルエーテル誘導体（４）の単離精製を容易にし、ジフルオロベンジルエーテル誘導体（４）を高収率で得る目的から、０．９５〜１．０５当量が特に好ましい。ベンゼン誘導体（１）において、Ｙが塩素原子、臭素原子、またはヨウ素原子である化合物の場合には、塩基の使用量はベンゼン誘導体（１）の１．８〜２．５当量が好ましく、特に１．９〜２．１当量が好ましい。この場合、塩基としてはｔ−ブチルリチウムを用いることが好ましい。
【００８３】
第１の発明の方法で使用するジブロモジフルオロメタン（ＣＦ2 Ｂｒ2 ）とブロモジフルオロメタン（ＣＨＦ2 Ｂｒ）の混合物におけるＣＦ2 Ｂｒ2 ／ＣＨＦ2 Ｂｒの含有割合は、モル比で９９．９／０．１〜７５／２５の割合が好ましく、副生成物である１−ブロモベンゼン誘導体（５）の生成を抑制し、かつ反応の転化率を向上させるためには、ＣＦ2 Ｂｒ2 ／ＣＨＦ2 Ｂｒのモル比で９５／５〜８５／１５の割合が特に好ましい。ジブロモジフルオロメタン（ＣＦ2 Ｂｒ2 ）とブロモジフルオロメタン（ＣＨＦ2 Ｂｒ）の混合物におけるブロモジフルオロメタン（ＣＨＦ2 Ｂｒ）の含有率を０．１ｍｏｌ％〜２５ｍｏｌ％の間で調整することにより、副生成物である１−ブロモベンゼン誘導体（５）とベンゼン誘導体（６）の生成比を調整することができ、１−ブロモベンゼン誘導体（５）の生成量を５重量％以下に抑制することができる。また、その混合物の使用量は、ベンゼン誘導体（１）に対し、ジブロモジフルオロメタン（ＣＦ2 Ｂｒ2 ）とブロモジフルオロメタン（ＣＨＦ2 Ｂｒ）の合計で１．０〜２．０当量が好ましく、１．０〜１．３当量が特に好ましい。
【００８４】
第１の発明の方法で用いる反応溶媒としては、反応に不活性なものであれば使用でき、特に制限されない。具体例としては、ベンゼン、トルエン等の芳香族化合物、ヘキサン、ヘプタン等の脂肪族炭化水素、シクロヘキサン等の脂環式炭化水素、ジエチルエーテル、メチル−ｔ−ブチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル等の脂肪族エーテル化合物、テトラヒドロフラン、ジオキサン等の環状エーテル化合物が挙げられる。中でも、ベンゼン誘導体（１）に対する溶解度が大きい点、副生成物である１−ブロモベンゼン誘導体（５）の生成を抑制し、かつ反応の転化率を向上させる点から、トルエン、ヘキサン、テトラヒドロフランおよびこれらの混合溶媒が特に好ましい。また、その使用量は、ベンゼン誘導体（１）の重量に対して、５〜２０倍量が好ましい。
【００８５】
第１の発明の方法における反応温度は、式（１）に示すＲ1 に近い側を４位として、ベンゼン誘導体（１）の１位に高選択的にジフルオロブロモメチル基を導入するには、ベンゼン誘導体（１）と塩基の反応においては、−４０℃以下が好ましく、特に−６０〜−７５℃が好ましい。また、ジブロモジフルオロメタン（ＣＦ2 Ｂｒ2 ）とブロモジフルオロメタン（ＣＨＦ2 Ｂｒ）の混合物の反応においては、副生成物である１−ブロモベンゼン誘導体（５）の生成を抑制し、かつ反応の転化率を向上させる点で、−５０℃以下が好ましく、特に−５５〜−７０℃が好ましい。
【００８６】
【化１３】
第１の発明の方法における反応時間は、塩基を作用させる反応段階においては反応を完全に進行させるために、塩基添加後０．５〜２時間放置し熟成させることが好ましく、また、ジブロモジフルオロメタン（ＣＦ2 Ｂｒ2 ）とブロモジフルオロメタン（ＣＨＦ2 Ｂｒ）の混合物を作用させる反応においても、同様にその混合物の添加後、０．５〜２時間熟成させることが好ましい。
【００８８】
第１の発明の方法においては、ジブロモジフルオロメタン（ＣＦ2 Ｂｒ2 ）とブロモジフルオロメタン（ＣＨＦ2 Ｂｒ）の混合物を作用させる反応によって、上式に示すベンゼン誘導体（６）が若干（３５重量％以下）副生する。このとき、Ｙが水素原子であるベンゼン誘導体（１）を用いた場合には、ベンゼン誘導体（６）とベンゼン誘導体（１）は同一化合物となり、循環再使用に有効である。また、１−ブロモベンゼン誘導体（５）等の副生成物が若干（３５重量％以下）生成する。ベンゼン誘導体（６）の生成量および１−ブロモベンゼン誘導体（５）等の副生成物の生成量は反応条件により変化するが、これらの合計は３５重量％以下である。
【００８９】
第２の発明の方法において、最終目的物であるジフルオロベンジルエーテル誘導体（４）の単離精製のしやすさおよびトータル収率の観点から、１−ブロモベンゼン誘導体（５）の生成量を可能な限り抑制することが好ましい。
【００９０】
第１の発明の方法において、反応終了後、通常の有機合成で使用されている手法によって反応液から目的物を分離・精製することができる。例えば、反応液に水および抽出用の有機溶媒を加えてよく撹拌し、分取した有機層を水で洗浄する。次に、無水硫酸ナトリウム等の乾燥剤で乾燥した後、減圧下有機溶媒を除去することで、濃縮残査を得る。この濃縮残査をシリカゲルクロマトグラフィー処理、再結晶あるいは蒸留することにより、純度９５％以上の目的物を得ることができる。このとき、後記の第２の方法において、得られるジフルオロベンジルエーテル誘導体（４）の単離精製のしやすさの点から、上記第１の発明の方法において得られる反応液を精製することなく、ベンゼン誘導体（６）との混合物である濃縮残査をそのまま使用することが好ましい。
【００９１】
第２の発明の方法において、第１の発明の方法によって得られるジフルオロベンジルブロミド誘導体（２）とフェノール誘導体（３）との反応（エーテル化反応）は、塩基の存在下に行われる。使用する塩基としては、アルカリ金属、アルカリ金属水酸化物、アルカリ金属炭酸塩、アルカリ金属水素化物、アルカリ金属アルコラート等が使用できる。取り扱いが容易な点から、水酸化カリウム、水酸化ナトリウム等のアルカリ金属水酸化物、炭酸カリウム、炭酸ナトリウム等のアルカリ金属炭酸塩および油性の水素化ナトリウム等のアルカリ金属水素化物の使用が好ましい。中でも、炭酸カリウムが特に好ましい。このエーテル化反応における塩基の使用量は、使用する塩基によって異なるが、ジフルオロベンジルブロミド誘導体（２）に対して１〜２当量使用することが好ましく、１．１〜１．３当量使用することが特に好ましい。また、反応が進行しにくい場合は、反応を加速させるためには触媒量（０．０３〜０．１当量）のヨウ化カリウムを添加することが好ましい。
【００９２】
第２の発明の方法において、フルオロベンジルブロミド誘導体（２）に対して当量以上のフェノール誘導体（３）を使用すれば、問題なくジフルオロベンジルエーテル誘導体（４）が得られるが、副生成物の抑制および反応液から目的物の分離・精製を容易にする目的で、１．１〜１．２当量使用することが好ましい。
【００９３】
第２の発明の方法で使用する溶媒は、反応に不活性なものであればよく、特に制限されない。具体例としては、ベンゼン、トルエン等の芳香族化合物、ヘキサン、ヘプタン等の脂肪族炭化水素、シクロヘキサン等の脂環式炭化水素、メチル−ｔ−ブチルエーテル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル等の脂肪族エーテル化合物、テトラヒドロフラン、ジオキサン等の環状エーテル化合物、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等の脂肪族ケトン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、ヘキサメチルホスホリックトリアミド（ＨＭＰＡ）、Ｎ−メチル−２−ピロリジノン等の非プロトン性極性溶媒などが挙げられる。中でも、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）が特に好ましい。また、反応溶媒の使用量は、反応液の撹拌が良好に行え、反応が安全にかつ安定に実施できる量であれば支障がない。具体的にはフェノール誘導体（３）に対して重量で１〜１０倍量が好ましく、副生成物の抑制および反応液から目的物の分離・精製を容易であるという点から、２〜５倍量が特に好ましい。
【００９４】
第２の発明の方法において、反応温度は、ジフルオロベンジルブロミド誘導体（２）の構造にもよるが、室温から用いる溶媒の沸点までの間とすることができるが、６０〜１３０℃が好ましく、副生成物の抑制および反応時間の点で、１００〜１２０℃が特に好ましい。
【００９５】
第２の発明の方法において、反応時間は、ジフルオロベンジルブロミド誘導体（２）およびフェノール誘導体（３）の構造と量、使用する塩基の種類にもよるが、１〜６時間が好ましい。具体例としては、塩基として炭酸カリウムを使用する場合は、ジフルオロベンジルブロミド誘導体（２）、フェノール誘導体（３）、塩基および溶媒を混合し、９０〜１００℃の温度で１〜２時間程度反応させた後に１１０〜１２０℃で４〜５時間程度反応させることが好ましい。
【００９６】
第２の発明の方法において、第１の発明の方法によって得られる濃縮残査を精製することなく、ベンゼン誘導体（６）との混合物のまま使用することが好ましい。この場合、ジフルオロベンジルブロミド誘導体（２）のみが反応し、目的とするジフルオロベンジルエーテル誘導体（４）とベンゼン誘導体（６）との混合物が得られる。
【００９７】
【化１４】
第２の発明の方法において、反応液から目的物であるジフルオロベンジルエーテル誘導体（４）を分離・精製する方法は、特に制限されず、通常の有機合成で使用される手法によって行うことができる。例えば、反応液に水および抽出用の有機溶媒を加えて十分に撹拌し、不溶解物をろ過する。分取した有機層を水洗し、無水硫酸ナトリウム等の乾燥剤で乾燥した後、減圧下に有機溶媒を除去することで、濃縮残査を得る。この濃縮残査からは、シリカゲルクロマトグラフィー処理、蒸留あるいは再結晶等の既知の分離方法により、容易に純度９９％以上のジフルオロベンジルエーテル誘導体（４）を得ることができる。特に、ジフルオロベンジルエーテル誘導体（４）とベンゼン誘導体（６）は沸点の差が大きいため、蒸留による分離が容易である。
【００９９】
また、本発明において、Ｙが水素原子であるベンゼン誘導体（１）を用いてジフルオロベンジルブロミド誘導体（２）を得、これをジフルオロベンジルエーテル誘導体（４）の製造に使用する場合には、ベンゼン誘導体（６）とベンゼン誘導体（１）は同一化合物であり、出発原料であるベンゼン誘導体（１）を得ることができ、回収したベンゼン誘導体（１）を循環して再使用することができ、資材の有効利用が可能である。
【０１００】
【実施例】
以下、実施例により本発明をより詳細に説明する。
【０１０１】
（実施例１）１−ブロモジフルオロメチル−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン［C3H7-Ph-PhFF-CF2Br］の製造
撹拌機、温度計、滴下ロートおよび窒素導入管を備えた１Ｌ四つ口フラスコに、２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン５０ｇ（２１５ｍｍｏｌ）および無水テトラヒドロフラン４３０ｍＬを加え、−６５℃以下まで冷却後、同温度を維持しながらｎ−ブチルリチウムのヘキサン溶液（１．５９Ｍ）１４５ｍＬ（２２６ｍｍｏｌ）を滴下した。滴下終了後、さらに２時間、−６５℃以下を保ちながら撹拌した。
【０１０２】
次いで、ジブロモジフルオロメタン４６．１ｇ（２２０ｍｍｏｌ）とブロモジフルオロメタン８．８５ｇ（６７．６ｍｍｏｌ）をＴＨＦ２７ｍＬに溶解した溶液を−６０℃以下に保ちながら反応液に滴下し、滴下終了後、さらに２時間同温度にて撹拌した。反応液を室温まで昇温し、５％水酸化ナトリウム水溶液２１５ｍＬを添加した後、有機層と水層を分離した。水層をヘキサン２７０ｍＬで抽出処理し、抽出分と有機層を合わせて水で洗浄し、無水硫酸マグネシウムで乾燥した後、溶媒を留去して粗生成物６８．７ｇを得た。
【０１０３】
得られた粗生成物を、ガスクロマトグラフィー、 1Ｈ−ＮＭＲおよび19Ｆ−ＮＭＲで分析したところ、目的物である１−ブロモジフルオロメチル−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン（７２．５％）、１−ブロモ−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン（０．５％）、２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン（２１．８％）およびその他の不純物の混合物であった。
【０１０４】
（粗生成物の重量）×（ガスクロマトグラフィーによって測定される純度）＝目的物の重量とすると、２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼンから目的物の収率は６４％であった。粗生成物の一部をシリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）で処理した後、溶媒としてエタノールを用いて数回再結晶させることで、ガスクロマトグラフィーによって測定される純度が９９％である１−ブロモジフルオロメチル−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼンを得た。
【０１０５】
C3H7-Ph-PhFF-CF2Br
融点：室温において油状
1Ｈ−ＮＭＲ（ＣＤＣｌ3 ）δ（ｐｐｍ：ｆｒｏｍＴＭＳ）：０．９６（ｔ，３Ｈ）、１．６８（ｓｅｘｔ，２Ｈ）、２．６４（ｔ，２Ｈ）、７．１８（ｄ，２Ｈ）、７．２８（ｄ，２Ｈ）、７．４７（ｄ，２Ｈ）
19Ｆ−ＮＭＲ（ＣＤＣｌ3 ）δ（ｐｐｍ：ｆｒｏｍＣＦＣｌ3 ）：−４０．７（ｔ，２Ｆ），−１１０．３（ｔｄ，２Ｆ）
【０１０６】
C3H7-Ph-PhFF
融点：２５．５〜２７．５℃
1Ｈ−ＮＭＲ（ＣＤＣｌ3 ） δ（ｐｐｍ：ｆｒｏｍＴＭＳ）：０．９６（ｔ，３Ｈ）、１．６６（ｓｅｘｔ，２Ｈ）、２．６１（ｔ，２Ｈ）、６．７１（ｔｔ，１Ｈ）、７．０６（ｍ，２Ｈ）、７．２２（ｄ，２Ｈ）、７．４３（ｄ，２Ｈ）
19Ｆ−ＮＭＲ（ＣＤＣｌ3 ）δ（ｐｐｍ：ｆｒｏｍＣＦＣｌ3 ）：−１１０．４（ｔ，２Ｆ）
【０１０７】
（実施例２）１−（３，４，５−トリフルオロフェノキシ）ジフルオロメチル−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン［C3H7-Ph-PhFF-CF2O-PhFF-F］の製造
撹拌機、温度計、冷却管および窒素導入管を備えた３００ｍＬ四つ口フラスコに、実施例１で製造した粗生成物６６．９ｇ（１−ブロモジフルオロメチル−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン（４８．５ｇ、１３４ｍｍｏｌ、７３％）と２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン（２２％）の混合物）、３，４，５−トリフルオロフェノール２１．９ｇ（１４８ｍｍｏｌ）、炭酸カリウム２０．４ｇ（１４８ｍｍｏｌ）、およびＮ，Ｎ−ジメチルホルムアミド４４ｍＬを加え、１００℃まで加熱して１時間撹拌した後、１２０℃まで加熱して５時間撹拌した。反応液を室温まで冷却後、水１３０ｍＬおよびヘキサン１３０ｍＬを添加し、不溶解物をろ過した後、有機層を分離した。水層はヘキサンで１３０ｍＬで抽出し、抽出分と有機層を合わせて５％水酸化ナトリウム水溶液および水で洗浄し、無水硫酸マグネシウムで乾燥した後、溶媒を留去して粗生成物７０．６ｇを得た。
【０１０８】
得られた粗生成物をガスクロマトグラフィー、 1Ｈ−ＮＭＲおよび19Ｆ−ＮＭＲで分析したところ、目的物である１−（３，４，５−トリフルオロフェノキシ）ジフルオロメチル−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン（６９．５％）、１−ブロモ−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン（０．４％）、２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン（２０．０％）およびその他の不純物の混合物であった。
【０１０９】
（粗生成物の重量）×（ガスクロマトグラフィーにおける純度）＝目的物の重量とすると、１−ブロモジフルオロメチル−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼンからの目的物の収率は８５％であった。
【０１１０】
粗生成物の一部をヘキサン／エタノール＝１／４の混合溶媒を用いて３回再結晶し、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）にて精製することで、ガスクロマトグラフィーで測定される純度が９９％である１−（３，４，５−トリフルオロフェノキシ）ジフルオロメチル−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼンを得た。
【０１１１】
C3H7-Ph-PhFF-CF2O-PhFF-F
融点：４５．８〜４６．５℃
1Ｈ−ＮＭＲ（ＣＤＣｌ3 ） δ（ｐｐｍ：ｆｒｏｍＴＭＳ）：０．９７（ｔ，３Ｈ）、１．６８（ｓｅｘｔ，２Ｈ）、２．６４（ｔ，２Ｈ）、６．９８（ｔ，２Ｈ）、７．２２（ｄ，２Ｈ）、７．２８（ｄ，２Ｈ）、７．４８（ｄ，２Ｈ）
【０１１２】
19Ｆ−ＮＭＲ（ＣＤＣｌ3 ）δ（ｐｐｍ：ｆｒｏｍＣＦＣｌ3 ）：−６２．３（ｔ，２Ｆ）、−１１１．１（ｍ，２Ｆ）、−１３２．９（ｍ，２Ｆ）、−１６３．６（ｍ，１Ｆ）
【０１１３】
（比較例１）１−ブロモジフルオロメチル−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン[C3H7-Ph-PhFF-CF2Br]の製造
撹拌機、温度計、滴下ロートおよび窒素導入管を備えた１Ｌ四つ口フラスコに、２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン５０ｇ（２１５ｍｍｏｌ）、無水テトラヒドロフラン４３０ｍＬを加え、−６５℃以下まで冷却後、同温度を維持しながらｎ−ブチルリチウムヘキサン溶液（１．５９Ｍ）１４５ｍＬ（２２６ｍｍｏｌ）を滴下した。滴下終了後、さらに２時間、−６５℃以下を保ちながら撹拌した。
【０１１４】
次いで、ジブロモジフルオロメタン４５．２ｇ（２１５ｍｍｏｌ）をＴＨＦ２７ｍＬに溶解した溶液を、−６０℃以下に保ちながら滴下し、滴下終了後、さらに２時間同温度にて撹拌した。そののち、反応液を室温まで昇温し、５％水酸化ナトリウム水溶液２１５ｍＬを添加した。有機層を分離し、水層はヘキサン２７０ｍＬで抽出し、有機層を合わせて水で洗浄し、無水硫酸マグネシウムで乾燥した後、溶媒を留去して粗生成物７３．８ｇを得た。
【０１１５】
得られた粗生成物をガスクロマトグラフィー、 1Ｈ−ＮＭＲおよび19Ｆ−ＮＭＲで分析したところ、目的物である１−（３，４，５−トリフルオロフェノキシ）ジフルオロメチル−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン（７８．０％）、１−ブロモ−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン（１６．３％）、２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼン（３．８％）およびその他の不純物の混合物であった。
【０１１６】
（粗生成物の重量）×（ガスクロマトグラフィーにおける純度）＝目的物の重量とすると、１−ブロモジフルオロメチル−２，６−ジフルオロ−４−（４−プロピルフェニル）ベンゼンからの目的物の収率は７４％であった。
【０１１７】
【発明の効果】
本発明の第１の方法によれば、液晶材料の中間体として有用であるジフルオロベンジルブロミド誘導体を、ハロゲン化ベンゼン誘導体（ｆ）等の副生物の生成を抑制し、簡便かつ効率的に製造することができる。また本発明の第２の方法によれば、液晶材料として有用であるジフルオロベンジルエーテルを、簡便かつ効率的に製造できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for easily and efficiently producing a difluorobenzyl bromide derivative, and a method for easily and efficiently producing a difluorobenzyl ether derivative having various physical properties suitable as a liquid crystal material using the derivative as an intermediate.
[0002]
[Prior art]
Liquid crystal display devices are used as display devices for various devices such as office automation equipment, measuring instruments, automobile meters, home appliances, watches, and calculators. Various types of liquid crystal display devices are used depending on the structure and driving method of the device. Among them, an active matrix type liquid crystal display device using thin film transistors (TFTs) has contrast, display capacity, response time, etc. Because of its excellent display performance, it is actively used as a display device for liquid crystal televisions, personal computers, mobile phones, mobile devices, viewfinders and the like. In recent years, liquid crystal display devices are required to be further downsized, have low power consumption, and have high response speed, and have been required to be liquid crystal compounds or liquid crystal compositions having low driving voltage (threshold voltage) and low viscosity.
[0003]
The threshold voltage (Vth) of the liquid crystal element is expressed as a function of the dielectric anisotropy value (Δε) of the liquid crystal compound constituting the liquid crystal phase as shown in the following equation (Mol. Cryst. Liq .Cryst., 12, 57 (1970)).
Vth = π (K / ε0Δε)1/2(Where K is the elastic constant of the liquid crystal phase in the liquid crystal element, and ε0Is the vacuum dielectric constant of the liquid crystal compound constituting the liquid crystal phase. )
From the above equation, it can be seen that Δε should be increased or K should be decreased in order to reduce Vth. However, since it is very difficult to adjust the K of the liquid crystal phase with the current technology, in order to obtain a liquid crystal element having a low Vth, a liquid crystal compound having a large Δε is used and the Δ of the liquid crystal phase is It is necessary to increase ε. For this reason, a liquid crystal compound having a large Δε is required.
In addition, in order to increase the response speed of the liquid crystal display device, it is necessary to prepare a low viscosity liquid crystal phase using a low viscosity liquid crystal compound.
[0004]
Therefore, as a liquid crystal compound having a large Δε, a compound represented by the following formula (A) (JP-A-5-112778), formula (B) (DE-195311165A1) and formula (C) (WO 96/11897) Has been proposed.
[0005]
[Chemical Formula 3]
Since the compounds represented by the formulas (A), (B) and (C) exhibit a large Δε and have a relatively low viscosity, they can be driven at a low voltage and have a high-speed response. It is described as being useful as an ingredient.
[0007]
As a method for producing these difluorobenzyl ether derivatives, various methods have been proposed. For example, Patent Publication DE-19531165A1, JP-A-5-255165 and JP-A-2000-95715.
[0008]
Among these, the production method disclosed in Japanese Patent Application Laid-Open No. 2000-95715 seems to be a simple production method. The production method disclosed in this publication includes a difluoromethane derivative represented by the formula (b) on the carbanion obtained by allowing a base to act on the benzene derivative represented by the formula (a) as shown in the following reaction formula: To obtain a benzene derivative represented by the formula (c), and then a phenol derivative represented by the formula (d) is allowed to act on the benzene derivative represented by the formula (c) in the presence of a base. This is a method for obtaining a difluorobenzyl ether derivative represented by the formula (e).
[0009]
[Formula 4]
In the above formulas (a), (b), (c), (d) and (e), R1Represents a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group may be substituted with an oxygen atom, a sulfur atom, or —CH═CH—, Any hydrogen atom in the alkyl group may be substituted with a fluorine atom;1, A2And AThreeEach independently represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group (on the ring) in which one or more methylene groups constituting the ring may be substituted with an oxygen atom or a sulfur atom. One or more hydrogen atoms may be substituted with fluorine atoms);1, Z2And ZThreeAre each independently a single bond, —CH2CH2-,-(CH2)Four-, -CH2O- or -OCH2-Represents; l, m and n each independently represents 0 or 1; X represents a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom. Y1And Y2Each independently represents a halogen atom other than a fluorine atom. R2Represents a halogen atom, a cyano group, or an alkyl group having 1 to 15 carbon atoms, and one or more non-adjacent methylene groups in the alkyl group are substituted with an oxygen atom, a sulfur atom, or —CH═CH—. And one or more hydrogen atoms in the alkyl group may be substituted with a halogen atom;FourRepresents a 1,4-phenylene group in which one or more hydrogen atoms on the ring may be substituted with a halogen atom;FourIs a single bond, -CH2CH2-,-(CH2)Four-, -CH2O- or -OCH2-Represents L1And L2Each independently represents a hydrogen atom or a halogen atom; o is 0 or 1; The same applies to the formula (f) described later.
[0011]
However, in the method described in JP-A No. 2000-95715, a benzene derivative represented by the formula (a) (hereinafter, a compound represented by the formula (a) may be referred to as a compound (a). The same applies to the cases (a) to (g)). From the reaction of obtaining the benzene derivative (c), the halogenated benzene derivative (f) is by-produced. The target difluorobenzyl ether derivative (e) can also be obtained by reacting the phenol derivative (d) without isolating (c) from the mixture of (c) and (f). However, since it is obtained as a mixture with the halogenated benzene derivative (f), in order to isolate (e), the expensive palladium carbon catalyst is used to reduce (f) to the benzene derivative (g). Need to be separated. Further, in order to isolate (c) from the mixture of (c) and (f), a plurality of recrystallization treatments are required. For this reason, complicated processing is required regardless of whether or not (c) is isolated.
[0012]
[Chemical formula 5]
[Problems to be solved by the invention]
An object of the present invention is to provide a method capable of easily and efficiently producing a difluorobenzyl bromide derivative, which is an intermediate of a difluorobenzyl ether derivative, by suppressing the formation of by-products such as a halogenated benzene derivative (f). Furthermore, it is to provide a method capable of easily and efficiently producing a difluorobenzyl ether derivative useful as a liquid crystal material.
[0014]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors reacted dibenzenedifluoromethane (CF) after reacting the benzene derivative represented by the formula (1) with a base as shown in the following formula.2Br2) And bromodifluoromethane (CHF)2By adopting the step of reacting with the mixture of Br), the production of the bromobenzene derivative represented by the formula (5) as a by-product is suppressed, and the difluorobenzyl bromide derivative represented by the formula (2) It was found that can be obtained. In this reaction step, when a base is allowed to act on the benzene derivative represented by the formula (1), a carbanion is generated, and dibromodifluoromethane (CF2Br2) And bromodifluoromethane (CHF)2By reacting the mixture of Br), it is considered that by-products such as the halogenated benzene derivative (f) are suppressed and a difluorobenzyl bromide derivative represented by the formula (2) is generated.
[0015]
[Chemical 6]
Furthermore, the difluorobenzyl bromide derivative represented by the formula (2) obtained by this method is a mixture of the 1-bromobenzene derivative (5) and the benzene derivative (6). Without isolating the difluorobenzyl bromide derivative represented by the formula (2), the mixture is allowed to react with the phenol derivative represented by the formula (3) under the conditions of ordinary etherification reaction. It was found that the difluorobenzyl ether derivative represented by 4) was produced and could be easily isolated from the mixture after the reaction.
[0017]
[Chemical 7]
That is, in the present invention, after reacting a benzene derivative represented by the following formula (1) with a base, dibromodifluoromethane (CF2Br2) And bromodifluoromethane (CHF)2A method for producing a difluorobenzyl bromide derivative represented by the formula (2) (hereinafter referred to as “method of the first invention”), which comprises a step of reacting with a mixture of Br).
[0019]
[Chemical 8]
The present invention further comprises a step of reacting the difluorobenzyl bromide derivative represented by the formula (2) produced by the method of the first invention and the phenol derivative represented by the formula (3), 4) is provided (hereinafter referred to as “method of the second invention”).
[0021]
[Chemical 9]
DETAILED DESCRIPTION OF THE INVENTION
In the method of the first invention, in the formula (1) representing the benzene derivative (1) used as a starting material and the formula (2) representing the difluorobenzyl bromide derivative (2) which is the target substance, A1And A2Each independently represents a 1,4-phenylene group (one or more hydrogen atoms may be replaced by a fluorine atom) or a trans-1,4-cyclohexylene group (one or more constituting a ring). A methylene group may be substituted with an oxygen atom or a sulfur atom).
[0023]
A1And A2Specific examples of these include groups represented by the following formulas (7) to (23). In the present specification, unless otherwise specified, the substitution position of the substituent bonded to the cyclic group, particularly the 1-position and 4-position, is the R in formula (1) and formula (2).1The one closer to is always written in 4th place. For example, -PhF- (formula (8)) represents a 2-fluoro-1,4-phenylene group. A1And A2In view of reactivity, a 1,4-phenylene group (formula (7)) is particularly preferable.
[0024]
Embedded image
R1Represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, in the aliphatic hydrocarbon group having 1 to 8 carbon atoms and the group and A1An oxygen atom (—O—) may be inserted between the carbon-carbon bonds between these groups, and the group may contain an unsaturated bond and an asymmetric carbon atom, and the hydrogen atom in the group is It may be substituted with a fluorine atom. As the unsaturated bond, —CH═CH—, —CF═CF—, CF2= CH-, CH2= CH- and the like.
[0026]
Specific examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, methoxy group, Ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl Group, methoxypropyl group, ethoxypropyl group, propoxypropyl group, vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 1-pentenyl group, 3-butenyl group, 3-pentenyl group, 2-fluoro Ethenyl group, 2,2-difluoroethenyl group, 1,2,2-trifluoroethenyl Group, 4,4-difluoro-3-butenyl group, 3,3-difluoro-2-propenyl group, 5,5-difluoro-4-pentenyl group and the like.
R1As a reactive group, a propyl group, a pentyl group, a 1-butenyl group, and a 3-butenyl group are particularly preferable.
[0027]
Z1And Z2Each independently represents a single bond, —CH2CH2-,-(CH2)2-, -CH2O-, -OCH2-Represents. However, Z1Or Z2An unsaturated bond may be included between the carbon-carbon bonds therein, and a hydrogen atom in the group may be substituted with a fluorine atom. Examples of the unsaturated bond include —CH═CH—.
[0028]
Z containing an unsaturated bond or a hydrogen atom substituted with a fluorine atom1And Z2As a specific example, -CF2CF2-,-(CF2)2-, -CF = CF-, -CF2O-, -OCF2-Etc. are mentioned.
Z1And Z2Is particularly preferably a single bond from the viewpoint of reactivity.
X1And X2Represents a hydrogen atom or a fluorine atom.
[0029]
Y represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom. However, X1And X2When both are hydrogen atoms, Y is not a hydrogen atom. X in terms of reactivity and selectivity1And X2Are both fluorine atoms, and Y is preferably a hydrogen atom.
[0030]
l and m each independently represents 0 or 1; From the viewpoint of reactivity, solubility in the reaction solvent, and ease of isolation and purification of the final target difluorobenzyl ether derivative (4), the total of l and m is preferably 1.
[0031]
Specific examples of the difluorobenzyl bromide derivative (2) that can be particularly preferably produced by the method of the first invention include compounds represented by the following formulas (2-1) to (2-3). Where R1, A1, A2, Z1, Z2, X1And X2Is as defined for formula (1) or (2).
[0032]
Embedded image
Preferable examples of the compound represented by the formula (2-1) include compounds represented by the following formula.
CHThree-Ph-CF2Br
C2HFive-PhF-CF2Br
CThreeH7-PhFF-CF2Br
CFourH9-PhFF-CF2Br
CFiveH11-PhFF-CF2Br
C2HFive-O-PhFF-CF2Br
CHThree-O-CH2-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-PhFF-CF2Br
CFH2-CH2-CH2-PhFF-CF2Br
CF2= CH-CH2-CH2-PhFF-CF2Br
[0034]
As specific examples of the compound represented by the formula (2-2), a compound represented by the following formula is preferably exemplified.
CHThree-Cy-Ph-CF2Br
C2HFive-Cy-PhF-CF2Br
CHThree-Cy-PhFF-CF2Br
C2HFive-Cy-PhFF-CF2Br
CThreeH7-Cy-PhFF-CF2Br
CFourH9-Cy-PhFF-CF2Br
CFiveH11-Cy-PhFF-CF2Br
CHThree-O-CH2-Cy-PhFF-CF2Br
CH2= CH-CH2-CH2-Cy-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Cy-PhFF-CF2Br
CFH2-CH2-CH2-Cy-PhFF-CF2Br
CF2= CH-CH2-CH2-Cy-PhFF-CF2Br
C2HFive-Cyo-PhFF-CF2Br
CThreeH7-Cyoo-PhFF-CF2Br
CFourH9-Cys-PhFF-CF2Br
CFiveH11-Cyss-PhFF-CF2Br
[0035]
CHThree-Cy-CH2-CH2-Ph-CF2Br
C2HFive-Cy-CH2-CH2-CH2-CH2-PhF-CF2Br
CHThree-Cy-OCH2-PhFF-CF2Br
C2HFive-Cy-CH2-CH2-PhFF-CF2Br
CThreeH7-Cy-CH2-CH2-CH2-CH2-PhFF-CF2Br
CFourH9-Cy-CH2O-PhFF-CF2Br
CFiveH11-Cy-CF2O-PhFF-CF2Br
CHThree-O-CH2-Cy-OCF2-PhFF-CF2Br
CH2= CH-CH2-CH2-Cy-CF2-CF2-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Cy-CF2-CF2-CF2-CF2-PhFF-CF2Br
CFH2-CH2-CH2-Cy-CH2-CH2-PhFF-CF2Br
CF2= CH-CH2-CH2-Cy-CF2O-PhFF-CF2Br
[0036]
CHThree-Ph-Ph-CF2Br
C2HFive-Ph-PhF-CF2Br
CHThree-Ph-PhFF-CF2Br
C2HFive-Ph-PhFF-CF2Br
CThreeH7-Ph-PhFF-CF2Br
CFourH9-Ph-PhFF-CF2Br
CFiveH11-Ph-PhFF-CF2Br
CHThree-O-CH2-Ph-PhFF-CF2Br
CH2= CH-CH2-CH2-Ph-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Ph-PhFF-CF2Br
CFH2-CH2-CH2-Ph-PhFF-CF2Br
CF2= CH-CH2-CH2-Ph-PhFF-CF2Br
[0037]
CHThree-Ph-CH2-CH2-Ph-CF2Br
C2HFive-Ph-CH2-CH2-CH2-CH2-PhF-CF2Br
CHThree-Ph-OCH2-PhFF-CF2Br
C2HFive-Ph-CH2-CH2-PhFF-CF2Br
CThreeH7-Ph-CH2-CH2-CH2-CH2-PhFF-CF2Br
CFourH9-Ph-CH2O-PhFF-CF2Br
CFiveH11-Ph-CF2O-PhFF-CF2Br
CHThree-O-CH2-Ph-OCF2-PhFF-CF2Br
CH2= CH-CH2-CH2-Ph-CF2-CF2-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Ph-CF2-CF2-CF2-CF2-PhFF-CF2Br
CFH2-CH2-CH2-Ph-CH2-CH2-PhFF-CF2Br
CF2= CH-CH2-CH2-Ph-CF2O-PhFF-CF2Br
[0038]
CHThree-PhF-Ph-CF2Br
C2HFive-PhFF-PhF-CF2Br
CHThree-FPhFF-PhFF-CF2Br
C2HFive-FPh-PhFF-CF2Br
CThreeH7-PhF-PhFF-CF2Br
CFourH9-FPhF-PhFF-CF2Br
CFiveH11-PhFF-PhFF-CF2Br
CFiveH11-PhFF-CF2O-PhFF-CF2Br
CHThree-O-CH2-FFPhF-PhFF-CF2Br
CH2= CH-CH2-CH2-PhF-CF2-CF2-PhFF-CF2Br CHThree-CH = CH-CH2-CH2-PhFF-PhFF-CF2Br
CFH2-CH2-CH2-Ph-PhFF-CF2Br
CF2= CH-CH2-CH2-FFPh-CH2-CH2-PhFF-CF2Br
[0039]
As specific examples of the compound represented by the formula (2-3), a compound represented by the following formula is preferably exemplified.
CHThree-Cy-Cy-Ph-CF2Br
C2HFive-Cy-Cy-PhF-CF2Br
CHThree-Cy-Cy-PhFF-CF2Br
C2HFive-Cy-Cy-PhFF-CF2Br
CThreeH7-Cy-Cy-PhFF-CF2Br
CFourH9-Cy-Cy-PhFF-CF2Br
CFiveH11-Cy-Cy-PhFF-CF2Br
CHThree-O-CH2-Cy-Cy-PhFF-CF2Br
CH2= CH-CH2-CH2-Cy-Cy-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Cy-Cy-PhFF-CF2Br
CFH2-CH2-CH2-Cy-Cy-PhFF-CF2Br
CF2= CH-CH2-CH2-Cy-Cy-PhFF-CF2Br
C2HFive-Cy-Cyss-PhFF-CF2Br
CThreeH7-Cy-Cys-PhFF-CF2Br
CFourH9-Cy-Cyoo-PhFF-CF2Br
CFiveH11-Cy-Cyo-PhFF-CF2Br
[0040]
CHThree-Cy-Ph-Ph-CF2Br
C2HFive-Cy-Ph-PhF-CF2Br
CHThree-Cy-Ph-PhFF-CF2Br
C2HFive-Cy-Ph-PhFF-CF2Br
CThreeH7-Cy-Ph-PhFF-CF2Br
CFourH9-Cy-Ph-PhFF-CF2Br
CFiveH11-Cy-Ph-PhFF-CF2Br
CHThree-O-CH2-Cy-Ph-PhFF-CF2Br
CH2= CH-CH2-CH2-Cy-Ph-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Cy-Ph-PhFF-CF2Br
CFH2-CH2-CH2-Cy-Ph-PhFF-CF2Br
CF2= CH-CH2-CH2-Cy-Ph-PhFF-CF2Br
C2HFive-Cys-Ph-PhFF-CF2Br
CThreeH7-Cyss-Ph-PhFF-CF2Br
CFourH9-Cyo-Ph-PhFF-CF2Br
CFiveH11-Cyoo-Ph-PhFF-CF2Br
[0041]
CHThree-Cy-PhF-Ph-CF2Br
C2HFive-Cy-PhFF-PhF-CF2Br
CHThree-Cy-PhF-PhFF-CF2Br
C2HFive-Cy-FPhF-PhFF-CF2Br
CThreeH7-Cy-PhFF-PhFF-CF2Br
CFourH9-Cy-FPh-PhFF-CF2Br
CFiveH11-Cy-PhF-PhFF-CF2Br
CHThree-O-CH2-Cy-FPhFF-PhFF-CF2Br
CH2= CH-CH2-CH2-Cy-FFPhF-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Cy-PhF-PhFF-CF2Br
CFH2-CH2-CH2-Cy-PhF-PhFF-CF2Br
CF2= CH-CH2-CH2-Cy-PhF-PhFF-CF2Br
[0042]
CHThree-Cy-CH2-CH2-Cy-Ph-CF2Br
C2HFive-Cy-CH2-CH2-Cy-PhF-CF2Br
CHThree-Cy-CH2-CH2-Cy-PhFF-CF2Br
C2HFive-Cy-CH2-CH2-Cy-PhFF-CF2Br
CThreeH7-Cy-CH2-CH2-Cy-PhFF-CF2Br
CFourH9-Cy-CH2-CH2-Cy-PhFF-CF2Br
CFiveH11-Cy-CH2-CH2-Cy-PhFF-CF2Br
CHThree-O-CH2-Cy-CH2-CH2-Cy-PhFF-CF2Br
CH2= CH-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2Br
CFH2-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2Br
CF2= CH-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2Br
[0043]
CHThree-Cy-Cy-CH2-CH2-Ph-CF2Br
C2HFive-Cy-Cy-CH2-CH2-PhF-CF2Br
CHThree-Cy-Cy-CH2-CH2-PhFF-CF2Br
C2HFive-Cy-Cy-CH2-CH2-PhFF-CF2Br
CThreeH7-Cy-Cy-CH2-CH2-PhFF-CF2Br
CFourH9-Cy-Cy-CH2-CH2-PhFF-CF2Br
CFiveH11-Cy-Cy-CH2-CH2-PhFF-CF2Br
CHThree-O-CH2-Cy-Cy-CH2-CH2-PhFF-CF2Br
CH2= CH-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2Br
CFH2-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2Br
CF2= CH-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2Br
[0044]
CHThree-Cy-CH2-CH2-Ph-Ph-CF2Br
C2HFive-Cy-CH2-CH2-Ph-PhF-CF2Br
CHThree-Cy-CH2-CH2-PhF-PhFF-CF2Br
C2HFive-Cy-CH2-CH2-PhFF-PhF-CF2Br
CThreeH7-Cy-CH2-CH2-Ph-PhFF-CF2Br
CFourH9-Cy-CH2-CH2-PhF-PhFF-CF2Br
CFiveH11-Cy-CH2-CH2-PhFF-PhFF-CF2Br
CHThree-O-CH2-Cy-CH2-CH2-FPhF-PhFF-CF2Br
CH2= CH-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2Br
CFH2-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2Br
CF2= CH-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2Br
[0045]
CHThree-Cy-Ph-CH2-CH2-Ph-CF2Br
C2HFive-Cy-Ph-CH2-CH2-PhF-CF2Br
CHThree-Cy-PhF-CH2-CH2-PhFF-CF2Br
C2HFive-Cy-PhFF-CH2-CH2-PhF-CF2Br
CThreeH7-Cy-Ph-CH2-CH2-PhFF-CF2Br
CFourH9-Cy-PhF-CH2-CH2-PhFF-CF2Br
CFiveH11-Cy-PhFF-CH2-CH2-PhFF-CF2Br
CHThree-O-CH2-Cy-FPhF-CH2-CH2-PhFF-CF2Br
CH2= CH-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2Br
CFH2-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2Br
CF2= CH-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2Br
[0046]
CHThree-Cy-CH2O-Cy-Ph-CF2Br
C2HFive-Cy-OCH2-Cy-PhF-CF2Br
CHThree-Cy-CH2-CH2-CH2-CH2-Cy-PhFF-CF2Br
C2HFive-Cy-CF2O-Cy-PhFF-CF2Br
CThreeH7-Cy-CF2-CF2-Cy-PhFF-CF2Br
CFourH9-Cy-CF2-CF2-CF2-CF2-Cy-PhFF-CF2Br
CFiveH11-Cy-Cy-CF2O-PhFF-CF2Br
CHThree-O-CH2-Cy-Cy-CH2-CH2-CH2-CH2-PhFF-CF2Br
CH2= CH-CH2-CH2-Cy-Cy-CH2O-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Cy-Cy-CF2O-PhFF-CF2Br
CFH2-CH2-CH2-Cy-CF2-CF2-Cy-PhFF-CF2Br
CF2= CH-CH2-CH2-Cy-Cy-CF2O-PhFF-CF2Br
[0047]
CHThree-Cy-CH2O-PhF-Ph-CF2Br
C2HFive-Cy-OCH2-PhFF-PhF-CF2Br
CHThree-Cy-CH2-CH2-CH2-CH2-PhF-PhFF-CF2Br
C2HFive-Cy-CF2O-FPhF-PhFF-CF2Br
CThreeH7-Cy-CF2-CF2-PhFF-PhFF-CF2Br
CFourH9-Cy-CF2-CF2-CF2-CF2-FPh-PhFF-CF2Br
CFiveH11-Cy-PhF-CF2O-PhFF-CF2Br
CHThree-O-CH2-Cy-FPhFF-CH2-CH2-CH2-CH2-PhFF-CF2Br
CH2= CH-CH2-CH2-Cy-FFPhF-CH2O-PhFF-CF2Br
CHThree-CH = CH-CH2-CH2-Cy-PhF-CF2O-PhFF-CF2Br
CFH2-CH2-CH2-Cy-CF2-CF2-Ph-PhFF-CF2Br
CF2= CH-CH2-CH2-Cy-PhFF-CF2O-PhFF-CF2Br
[0048]
In the method of the second invention, in the formula (3) representing the phenol derivative and the formula (4) representing the difluorobenzyl ether derivative which is the final target substance, R2Is a C 1-8 aliphatic hydrocarbon group, hydrogen atom, halogen atom, sulfur pentafluoride group (SF2) Or a cyano group, and the aliphatic hydrocarbon group having 1 to 8 carbon atoms has an oxygen atom (—O—) inserted in the group and between the carbon-carbon bond between the group and the benzene ring. The group may contain an unsaturated bond and an asymmetric carbon atom, and the hydrogen atom in the group may be substituted with a halogen atom. Examples of the unsaturated bond include —CH═CH—.
[0049]
R2Specific examples of the aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, methoxy group, ethoxy group and propoxy group. , Butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group, methoxymethyl group, ethoxymethyl group, propoxymethyl group, butoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxypropyl group , Ethoxypropyl group, propoxypropyl group, vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 1-pentenyl group, 3-butenyl group, 3-pentenyl group, trifluoromethyl group, difluoromethyl group , Difluorochloromethyl group, 2,2,2-trifluoroethyl Group, 2-fluoroethyl group, 3-fluoropropyl group, 4-fluorobutyl group, 5-fluoropentyl group, 3-chloropropyl group, trifluoromethoxy group, difluoromethoxy group, difluorochloromethoxy group, pentafluoroethoxy group 1,1,2,2-tetrafluoroethoxy group, heptafluoropropoxy group, 1,1,2,3,3,3-hexafluoropropoxy group, trifluoromethoxymethyl group, 2-fluoroethenyl group, 2 , 2-difluoroethenyl group, 1,2,2-trifluoroethenyl group, 4,4-difluoro-3-butenyl group, 3,3-difluoro-2-propenyl group, 5,5-difluoro-4-pentenyl Groups and the like.
Among these, R2However, in terms of reactivity and ease of isolation and purification, fluorine atom, trifluoromethyl group, trifluoromethoxy group, sulfur pentafluoride group (SFFive), Particularly preferably a cyano group.
[0050]
AThreeIs a 1,4-phenylene group, and one or more hydrogen atoms may be substituted with fluorine atoms. A in which a hydrogen atom is replaced by a fluorine atomThreeAs a specific example, R21 side is the 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 2,6-difluoro-1 , 4-phenylene group, 2,3,6-trifluoro-1,4-phenylene group, 2,3,5,6-tetrafluoro-1,4-phenylene group, trans-1,4-cyclohexylene group, etc. Is mentioned. From the viewpoint of reactivity, a 1,4-phenylene group is particularly preferable.
[0051]
ZThreeIs a single bond, -CH2CH2-,-(CH2)Four-, -CH2O-, -OCH2-Represents. The carbon-carbon bond in the group may be an unsaturated bond (—CH═CH—), and the hydrogen atom in the group may be substituted with a fluorine atom, for example, —CF2CF2-,-(CF2)Four-, -CF = CF-, -CF2O-, -OCF2-Etc. may be sufficient. From the viewpoint of reactivity, a single bond is particularly preferable.
[0052]
XThreeAnd XFourRepresents a hydrogen atom or a halogen atom.
XThreeAnd XFourSpecific examples of these include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of reactivity and selectivity, a hydrogen atom or a fluorine atom is preferable.
n represents 0 or 1. From the viewpoint of reactivity, solubility in a reaction solvent, and ease of isolation and purification of the final target difluorobenzyl ether derivative (4), 0 is preferable.
R1, A1, A2, Z1, Z2, X1, X2, Y, l and m represent the same meaning as described in the above formulas (1) and (2).
[0053]
Specific examples of the difluorobenzyl ether derivative (4) that can be particularly suitably produced by the method of the second invention include compounds represented by the following formulas (4-1) to (4-5).
[0054]
Embedded image
As a specific example of the compound represented by the formula (4-1), a compound represented by the following formula is preferably exemplified.
CThreeH7-Ph-CF2O-Ph-F
CFiveH11-Ph-CF2O-PhF-F
CThreeH7-Ph-CF2O-PhFF-F
CThreeH7-PhF-CF2O-Ph-F
CFiveH11-PhF-CF2O-PhF-F
CThreeH7-PhF-CF2O-PhFF-F
CThreeH7-PhFF-CF2O-Ph-F
CFiveH11-PhFF-CF2O-PhF-F
CThreeH7-PhFF-CF2O-PhFF-F
CThreeH7-PhFF-CF2O-FPh-Cl
CFiveH11-PhFF-CF2O-PhF-Cl
[0056]
CThreeH7-PhFF-CF2O-PhF-CN
CFiveH11-PhFF-CF2O-PhFF-CN
CThreeH7-PhFF-CF2O-PhF-CFThree
CFiveH11-PhFF-CF2O-PhFF-CFThree
CThreeH7-PhFF-CF2O-PhF-OCFThree
CFiveH11-PhFF-CF2O-PhFF-OCFThree
CThreeH7-PhFF-CF2O-PhF-SFFive
CFiveH11-PhFF-CF2O-PhFF-SFFive
C2HFive-O-PhFF-CF2O-PhF-F
CHThree-O-CH2-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-PhFF-CF2O-PhF-F
CFH2-CH2-CH2-PhFF-CF2O-PhFF-F
CF2= CH-CH2-CH2-PhFF-CF2O-PhFF-F
[0057]
Preferable examples of the compound represented by the formula (4-2) include compounds represented by the following formula.
CThreeH7-Cy-PhFF-CF2O-Ph-F
CFiveH11-Cy-PhFF-CF2O-PhF-F
CThreeH7-Cy-PhFF-CF2O-FPh-Cl
CFiveH11-Cy-PhFF-CF2O-PhF-Cl
CThreeH7-Cy-PhFF-CF2O-PhF-CN
CFiveH11-Cy-PhFF-CF2O-PhFF-CN
CThreeH7-Cy-PhFF-CF2O-PhF-CFThree
CFiveH11-Cy-PhFF-CF2O-PhFF-CFThree
CThreeH7-Cy-PhFF-CF2O-PhF-OCFThree
CFiveH11-Cy-PhFF-CF2O-PhFF-OCFThree
CThreeH7-Cy-PhFF-CF2O-PhF-SFFive
CFiveH11-Cy-PhFF-CF2O-PhFF-SFFive
CHThree-Cy-Ph-CF2O-PhFF-F
C2HFive-Cy-PhF-CF2O-PhFF-F
CHThree-Cy-PhFF-CF2O-PhFF-F
[0058]
C2HFive-Cy-PhFF-CF2O-PhFF-F
CThreeH7-Cy-PhFF-CF2O-PhFF-F
CFourH9-Cy-PhFF-CF2O-PhFF-F
CFiveH11-Cy-PhFF-CF2O-PhFF-F
CHThree-O-CH2-Cy-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CF2= CH-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
C2HFive-Cyo-PhFF-CF2O-PhFF-F
CThreeH7-Cyoo-PhFF-CF2O-PhFF-F
CFourH9-Cys-PhFF-CF2O-PhFF-F
CFiveH11-Cyss-PhFF-CF2O-PhFF-F
[0059]
CThreeH7-Cy-CH2-CH2-PhFF-CF2O-Ph-F
CFiveH11-Cy-CH2-CH2-PhFF-CF2O-PhF-F
CThreeH7-Cy-CH2-CH2-PhFF-CF2O-FPh-Cl
CFiveH11-Cy-CH2-CH2-PhFF-CF2O-PhF-Cl
CThreeH7-Cy-CH2-CH2-PhFF-CF2O-PhF-CN
CFiveH11-Cy-CH2-CH2-PhFF-CF2O-PhFF-CN
CThreeH7-Cy-CH2-CH2-PhFF-CF2O-PhF-CFThree
CFiveH11-Cy-CH2-CH2-PhFF-CF2O-PhFF-CFThree
CThreeH7-Cy-CH2-CH2-PhFF-CF2O-PhF-OCFThree
CFiveH11-Cy-CH2-CH2-PhFF-CF2O-PhFF-OCFThree
CThreeH7-Cy-CH2-CH2-PhFF-CF2O-PhF-SFFive
CFiveH11-Cy-CH2-CH2-PhFF-CF2O-PhFF-SFFive
CHThree-Cy-CH2-CH2-Ph-CF2O-PhFF-F
[0060]
C2HFive-Cy-CH2-CH2-CH2-CH2-PhF-CF2O-PhFF-F
CHThree-Cy-OCH2-PhFF-CF2O-PhFF-F
C2HFive-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CThreeH7-Cy-CH2-CH2-CH2-CH2-PhFF-CF2O-PhFF-F
CFourH9-Cy-CH2O-PhFF-CF2O-PhFF-F
CHThree-O-CH2-Cy-OCF2-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-Cy-CF2-CF2-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-Cy-CF2-CF2-CF2-CF2-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
[0061]
CThreeH7-Ph-PhFF-CF2O-Ph-F
CFiveH11-Ph-PhFF-CF2O-PhF-F
CThreeH7-Ph-PhFF-CF2O-FPh-Cl
CFiveH11-Ph-PhFF-CF2O-PhF-Cl
CThreeH7-Ph-PhFF-CF2O-PhF-CN
CFiveH11-Ph-PhFF-CF2O-PhFF-CN
CThreeH7-Ph-PhFF-CF2O-PhF-CFThree
CFiveH11-Ph-PhFF-CF2O-PhFF-CFThree
CThreeH7-Ph-PhFF-CF2O-PhF-OCFThree
CFiveH11-Ph-PhFF-CF2O-PhFF-OCFThree
CThreeH7-Ph-PhFF-CF2O-PhF-SFFive
CFiveH11-Ph-PhFF-CF2O-PhFF-SFFive
CHThree-Ph-Ph-CF2O-PhFF-F
C2HFive-Ph-PhF-CF2O-PhFF-F
CHThree-Ph-PhFF-CF2O-PhFF-F
C2HFive-Ph-PhFF-CF2O-PhFF-F
CThreeH7-Ph-PhFF-CF2O-PhFF-F
[0062]
CFourH9-Ph-PhFF-CF2O-PhFF-F
CFiveH11-Ph-PhFF-CF2O-PhFF-F
CHThree-O-CH2-Ph-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CF2= CH-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CThreeH7-Ph-CH2-CH2-PhFF-CF2O-Ph-F
CFiveH11-Ph-CH2-CH2-PhFF-CF2O-PhF-F
CThreeH7-Ph-CH2-CH2-PhFF-CF2O-FPh-Cl
CFiveH11-Ph-CH2-CH2-PhFF-CF2O-PhF-Cl
CThreeH7-Ph-CH2-CH2-PhFF-CF2O-PhF-CN
CFiveH11-Ph-CH2-CH2-PhFF-CF2O-PhFF-CN
[0063]
CThreeH7-Ph-CH2-CH2-PhFF-CF2O-PhF-CFThree
CFiveH11-Ph-CH2-CH2-PhFF-CF2O-PhFF-CFThree
CThreeH7-Ph-CH2-CH2-PhFF-CF2O-PhF-OCFThree
CFiveH11-Ph-CH2-CH2-PhFF-CF2O-PhFF-OCFThree
CThreeH7-Ph-CH2-CH2-PhFF-CF2O-PhF-SFFive
CFiveH11-Ph-CH2-CH2-PhFF-CF2O-PhFF-SFFive
CHThree-Ph-CH2-CH2-Ph-CF2O-PhFF-F
C2HFive-Ph-CH2-CH2-CH2-CH2-PhF-CF2O-PhFF-F
CHThree-Ph-OCH2-PhFF-CF2O-PhFF-F
C2HFive-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CThreeH7-Ph-CH2-CH2-CH2-CH2-PhFF-CF2O-PhFF-F
CFourH9-Ph-CH2O-PhFF-CF2O-PhFF-F
CHThree-O-CH2-Ph-OCF2-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-Ph-CF2-CF2-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-Ph-CF2-CF2-CF2-CF2-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
[0064]
CHThree-PhF-Ph-CF2O-PhFF-F
C2HFive-PhFF-PhF-CF2O-PhFF-F
CHThree-FPhFF-PhFF-CF2O-PhFF-F
C2HFive-FPh-PhFF-CF2O-PhFF-F
CThreeH7-PhF-PhFF-CF2O-PhFF-F
CFourH9-FPhF-PhFF-CF2O-PhFF-F
CFiveH11-PhFF-PhFF-CF2O-PhFF-F
CFiveH11-PhFF-CF2O-PhFF-CF2O-PhFF-F
CHThree-O-CH2-FFPhF-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-PhF-CF2-CF2-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-PhFF-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CF2= CH-CH2-CH2-FFPh-CH2-CH2-PhFF-CF2O-PhFF-F
[0065]
As a specific example of the compound represented by the formula (4-3), a compound represented by the following formula is preferably exemplified.
CThreeH7-Cy-Cy-PhFF-CF2O-Ph-F
CFiveH11-Cy-Cy-PhFF-CF2O-PhF-F
CThreeH7-Cy-Cy-PhFF-CF2O-FPh-Cl
CFiveH11-Cy-Cy-PhFF-CF2O-PhF-Cl
CThreeH7-Cy-Cy-PhFF-CF2O-PhF-CN
CFiveH11-Cy-Cy-PhFF-CF2O-PhFF-CN
CThreeH7-Cy-Cy-PhFF-CF2O-PhF-CFThree
CFiveH11-Cy-Cy-PhFF-CF2O-PhFF-CFThree
CThreeH7-Cy-Cy-PhFF-CF2O-PhF-OCFThree
CFiveH11-Cy-Cy-PhFF-CF2O-PhFF-OCFThree
CThreeH7-Cy-Cy-PhFF-CF2O-PhF-SFFive
CFiveH11-Cy-Cy-PhFF-CF2O-PhFF-SFFive
CHThree-Cy-Cy-Ph-CF2O-PhFF-F
C2HFive-Cy-Cy-PhF-CF2O-PhFF-F
CHThree-Cy-Cy-PhFF-CF2O-PhFF-F
[0066]
C2HFive-Cy-Cy-PhFF-CF2O-PhFF-F
CThreeH7-Cy-Cy-PhFF-CF2O-PhFF-F
CFourH9-Cy-Cy-PhFF-CF2O-PhFF-F
CFiveH11-Cy-Cy-PhFF-CF2O-PhFF-F
CHThree-O-CH2-Cy-Cy-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-Cy-Cy-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-Cy-Cy-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-Cy-PhFF-CF2O-PhFF-F
CF2= CH-CH2-CH2-Cy-Cy-PhFF-CF2O-PhFF-F
C2HFive-Cy-Cyo-PhFF-CF2O-PhFF-F
CThreeH7-Cy-Cyoo-PhFF-CF2O-PhFF-F
CFourH9-Cy-Cys-PhFF-CF2O-PhFF-F
CFiveH11-Cy-Cyss-PhFF-CF2O-PhFF-F
CThreeH7-Cy-Ph-PhFF-CF2O-Ph-F
CFiveH11-Cy-Ph-PhFF-CF2O-PhF-F
[0067]
CThreeH7-Cy-Ph-PhFF-CF2O-FPh-Cl
CFiveH11-Cy-Ph-PhFF-CF2O-PhF-Cl
CThreeH7-Cy-Ph-PhFF-CF2O-PhF-CN
CFiveH11-Cy-Ph-PhFF-CF2O-PhFF-CN
CThreeH7-Cy-Ph-PhFF-CF2O-PhF-CFThree
CFiveH11-Cy-Ph-PhFF-CF2O-PhFF-CFThree
CThreeH7-Cy-Ph-PhFF-CF2O-PhF-OCFThree
CFiveH11-Cy-Ph-PhFF-CF2O-PhFF-OCFThree
CThreeH7-Cy-Ph-PhFF-CF2O-PhF-SFFive
CFiveH11-Cy-Ph-PhFF-CF2O-PhFF-SFFive
CHThree-Cy-Ph-Ph-CF2O-PhFF-F
C2HFive-Cy-Ph-PhF-CF2O-PhFF-F
CHThree-Cy-Ph-PhFF-CF2O-PhFF-F
C2HFive-Cy-Ph-PhFF-CF2O-PhFF-F
[0068]
CThreeH7-Cy-Ph-PhFF-CF2O-PhFF-F
CFourH9-Cy-Ph-PhFF-CF2O-PhFF-F
CFiveH11-Cy-Ph-PhFF-CF2O-PhFF-F
CHThree-O-CH2-Cy-Ph-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-Cy-Ph-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-Cy-Ph-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-Ph-PhFF-CF2O-PhFF-F
CF2= CH-CH2-CH2-Cy-Ph-PhFF-CF2O-PhFF-F
C2HFive-Cys-Ph-PhFF-CF2O-PhFF-F
CThreeH7-Cyss-Ph-PhFF-CF2O-PhFF-F
CFourH9-Cyo-Ph-PhFF-CF2O-PhFF-F
CFiveH11-Cyoo-Ph-PhFF-CF2O-PhFF-F
CHThree-Cy-PhF-Ph-CF2O-PhFF-F
C2HFive-Cy-PhFF-PhF-CF2O-PhFF-F
CHThree-Cy-PhF-PhFF-CF2O-PhFF-F
[0069]
C2HFive-Cy-FPhF-PhFF-CF2O-PhFF-F
CThreeH7-Cy-PhFF-PhFF-CF2O-PhFF-F
CFourH9-Cy-FPh-PhFF-CF2O-PhFF-F
CFiveH11-Cy-PhF-PhFF-CF2O-PhFF-F
CHThree-O-CH2-Cy-FPhFF-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-Cy-FFPhF-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-Cy-PhF-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-PhF-PhFF-CF2O-PhFF-F
CF2= CH-CH2-CH2-Cy-PhF-PhFF-CF2O-PhFF-F
CThreeH7-Cy-CH2-CH2-Cy-PhFF-CF2O-Ph-F
CFiveH11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhF-F
CThreeH7-Cy-CH2-CH2-Cy-PhFF-CF2O-FPh-Cl
CFiveH11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhF-Cl
CThreeH7-Cy-CH2-CH2-Cy-PhFF-CF2O-PhF-CN
CFiveH11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-CN
CThreeH7-Cy-CH2-CH2-Cy-PhFF-CF2O-PhF-CFThree
CFiveH11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-CFThree
[0070]
CThreeH7-Cy-CH2-CH2-Cy-PhFF-CF2O-PhF-OCFThree
CFiveH11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-OCFThree
CThreeH7-Cy-CH2-CH2-Cy-PhFF-CF2O-PhF-SFFive
CFiveH11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-SFFive
CHThree-Cy-CH2-CH2-Cy-Ph-CF2O-PhFF-F
C2HFive-Cy-CH2-CH2-Cy-PhF-CF2O-PhFF-F
CHThree-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
C2HFive-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CThreeH7-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CFourH9-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CFiveH11-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CHThree-O-CH2-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
CF2= CH-CH2-CH2-Cy-CH2-CH2-Cy-PhFF-CF2O-PhFF-F
[0071]
CThreeH7-Cy-Cy-CH2-CH2-PhFF-CF2O-Ph-F
CFiveH11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhF-F
CThreeH7-Cy-Cy-CH2-CH2-PhFF-CF2O-FPh-Cl
CFiveH11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhF-Cl
CThreeH7-Cy-Cy-CH2-CH2-PhFF-CF2O-PhF-CN
CFiveH11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-CN
CThreeH7-Cy-Cy-CH2-CH2-PhFF-CF2O-PhF-CFThree
CFiveH11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-CFThree
CThreeH7-Cy-Cy-CH2-CH2-PhFF-CF2O-PhF-OCFThree
CFiveH11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-OCFThree
CThreeH7-Cy-Cy-CH2-CH2-PhFF-CF2O-PhF-SFFive
CFiveH11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-SFFive
CHThree-Cy-Cy-CH2-CH2-Ph-CF2O-PhFF-F
[0072]
C2HFive-Cy-Cy-CH2-CH2-PhF-CF2O-PhFF-F
CHThree-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
C2HFive-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CThreeH7-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CFourH9-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CFiveH11-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CHThree-O-CH2-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CF2= CH-CH2-CH2-Cy-Cy-CH2-CH2-PhFF-CF2O-PhFF-F
CThreeH7-Cy-CH2-CH2-Ph-PhFF-CF2O-Ph-F
CFiveH11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-F
CThreeH7-Cy-CH2-CH2-Ph-PhFF-CF2O-FPh-Cl
CFiveH11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-Cl
[0073]
CThreeH7-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-CN
CFiveH11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-CN
CThreeH7-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-CFThree
CFiveH11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-CFThree
CThreeH7-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-OCFThree
CFiveH11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-OCFThree
CThreeH7-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-SFFive
CFiveH11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-SFFive
CHThree-Cy-CH2-CH2-Ph-Ph-CF2O-PhFF-F
C2HFive-Cy-CH2-CH2-Ph-PhF-CF2O-PhFF-F
CHThree-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
C2HFive-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CThreeH7-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CFourH9-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CFiveH11-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CHThree-O-CH2-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
CF2= CH-CH2-CH2-Cy-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
[0074]
CThreeH7-Cy-Ph-CH2-CH2-PhFF-CF2O-Ph-F
CFiveH11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhF-F
CThreeH7-Cy-Ph-CH2-CH2-PhFF-CF2O-FPh-Cl
CFiveH11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhF-Cl
CThreeH7-Cy-CH2-CH2-Ph-PhFF-CF2O-PhF-CN
CFiveH11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-CN
CThreeH7-Cy-Ph-CH2-CH2-PhFF-CF2O-PhF-CFThree
CFiveH11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-CFThree
CThreeH7-Cy-Ph-CH2-CH2-PhFF-CF2O-PhF-OCFThree
CFiveH11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-OCFThree
CThreeH7-Cy-Ph-CH2-CH2-PhFF-CF2O-PhF-SFFive
CFiveH11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-SFFive
CHThree-Cy-Ph-CH2-CH2-Ph-CF2O-PhFF-F
[0075]
C2HFive-Cy-Ph-CH2-CH2-PhF-CF2O-PhFF-F
CHThree-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
C2HFive-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CThreeH7-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CFourH9-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CFiveH11-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CHThree-O-CH2-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
CF2= CH-CH2-CH2-Cy-Ph-CH2-CH2-PhFF-CF2O-PhFF-F
[0076]
CThreeH7-Ph-Ph-PhFF-CF2O-Ph-F
CFiveH11-Ph-Ph-PhFF-CF2O-PhF-F
CThreeH7-Ph-Ph-PhFF-CF2O-FPh-Cl
CFiveH11-Ph-Ph-PhFF-CF2O-PhF-Cl
CThreeH7-Ph-Ph-PhFF-CF2O-PhF-CN
CFiveH11-Ph-Ph-PhFF-CF2O-PhFF-CN
CThreeH7-Ph-Ph-PhFF-CF2O-PhF-CFThree
CFiveH11-Ph-Ph-PhFF-CF2O-PhFF-CFThree
CThreeH7-Ph-Ph-PhFF-CF2O-PhF-OCFThree
CFiveH11-Ph-Ph-PhFF-CF2O-PhFF-OCFThree
CThreeH7-Ph-Ph-PhFF-CF2O-PhF-SFFive
CFiveH11-Ph-Ph-PhFF-CF2O-PhFF-SFFive
CHThree-Ph-Ph-Ph-CF2O-PhFF-F
[0077]
C2HFive-Ph-Ph-PhF-CF2O-PhFF-F
CHThree-Ph-Ph-PhFF-CF2O-PhFF-F
C2HFive-Ph-Ph-PhFF-CF2O-PhFF-F
CThreeH7-Ph-Ph-PhFF-CF2O-PhFF-F
CFourH9-Ph-Ph-PhFF-CF2O-PhFF-F
CFiveH11-Ph-Ph-PhFF-CF2O-PhFF-F
CHThree-O-CH2-Ph-PhFF-CF2O-PhFF-F
CH2= CH-CH2-CH2-Ph-Ph-PhFF-CF2O-PhFF-F
CHThree-CH = CH-CH2-CH2-Ph-Ph-PhFF-CF2O-PhFF-F
CFH2-CH2-CH2-Ph-Ph-PhFF-CF2O-PhFF-F
CF2= CH-CH2-CH2-Ph-Ph-PhFF-CF2O-PhFF-F
CThreeH7-Ph-Ph-PhFF-CF2O-PhF-F
CFiveH11-Ph-PhFF-PhFF-CF2O-PhFF-F
CThreeH7-PhFF-PhFF-PhFF-CF2O-PhF-F
CFiveH11-PhF-PhF-PhFF-CF2O-PhFF-F
CThreeH7-Ph-Ph-CH2-CH2-PhFF-CF2O-PhF-F
CFiveH11-Ph-CH2-CH2-Ph-PhFF-CF2O-PhFF-F
[0078]
Preferable examples of the compound represented by the formula (4-4) include compounds represented by the following formula.
CThreeH7-Ph-CF2O-Ph-PhF-F
CFiveH11-PhF-CF2O-Ph-PhFF-F
CThreeH7-PhFF-CF2O-Ph-PhF-F
CFiveH11-PhFF-CF2O-Ph-PhFF-F
CThreeH7-PhFF-CF2O-PhF-PhF-F
CFiveH11-PhFF-CF2O-PhFF-PhFF-F
CThreeH7-PhFF-CF2O-Ph-PhF-CN
CFiveH11-PhFF-CF2O-Ph-PhFF-CN
CThreeH7-PhFF-CF2O-Ph-PhF-CFThree
CFiveH11-PhFF-CF2O-Ph-PhFF-CFThree
CThreeH7-PhFF-CF2O-Ph-PhF-OCFThree
CFiveH11-PhFF-CF2O-Ph-PhFF-OCFThree
[0079]
As a specific example of the compound represented by the formula (4-5), a compound represented by the following formula is preferably exemplified.
CThreeH7-Cy-Ph-CF2O-Ph-PhF-F
CFiveH11-Cy-PhF-CF2O-Ph-PhFF-F
CThreeH7-Cy-PhFF-CF2O-Ph-PhF-F
CFiveH11-Cy-PhFF-CF2O-Ph-PhFF-F
CThreeH7-Cy-PhFF-CF2O-PhF-PhF-F
CFiveH11-Cy-PhFF-CF2O-PhFF-PhFF-F
CThreeH7-Cy-PhFF-CF2O-Ph-PhF-CN
CFiveH11-Cy-PhFF-CF2O-Ph-PhFF-CN
CThreeH7-Cy-PhFF-CF2O-Ph-PhF-CFThree
CFiveH11-Cy-PhFF-CF2O-Ph-PhFF-CFThree
CThreeH7-Cy-PhFF-CF2O-Ph-PhF-OCFThree
CFiveH11-Cy-PhFF-CF2O-Ph-PhFF-OCFThree
[0080]
CThreeH7-Ph-Ph-CF2O-Ph-PhF-F
CFiveH11-Ph-PhF-CF2O-Ph-PhFF-F
CThreeH7-Ph-PhFF-CF2O-Ph-PhF-F
CFiveH11-Ph-PhFF-CF2O-Ph-PhFF-F
CThreeH7-Ph-PhFF-CF2O-PhF-PhF-F
CFiveH11-Ph-PhFF-CF2O-PhFF-PhFF-F
CThreeH7-Ph-PhFF-CF2O-Ph-PhF-CN
CFiveH11-Ph-PhFF-CF2O-Ph-PhFF-CN
CThreeH7-Ph-PhFF-CF2O-Ph-PhF-CFThree
CFiveH11-Ph-PhFF-CF2O-Ph-PhFF-CFThree
CThreeH7-Ph-PhFF-CF2O-Ph-PhF-OCFThree
CFiveH11-Ph-PhFF-CF2O-Ph-PhFF-OCFThree
[0081]
Examples of the base used in the method of the first invention include alkali metals, alkali metal hydrides, alkyllithiums, alkali metal alcoholates and the like. Alkyl lithium is preferable, and n-butyl lithium is particularly preferable from the viewpoints of availability, safety in handling, and high selectivity of reaction.
[0082]
In the reaction of the benzene derivative (1) with the base, the amount of the base used is such that the benzene derivative (1) is X in the formula (1).1And X2Is a fluorine atom and Y is a hydrogen atom, 0.8 to 1.3 equivalents of the benzene derivative (1) are preferable, and a tar-like by-product is maintained while maintaining higher selectivity. In order to facilitate the isolation and purification of the final target difluorobenzyl ether derivative (4) and to obtain the difluorobenzyl ether derivative (4) in high yield, 0.95 to 1.05 equivalents Particularly preferred. In the benzene derivative (1), when Y is a chlorine atom, bromine atom, or iodine atom, the amount of base used is preferably 1.8 to 2.5 equivalents of the benzene derivative (1), particularly 1 .9 to 2.1 equivalents are preferred. In this case, t-butyl lithium is preferably used as the base.
[0083]
Dibromodifluoromethane (CF) used in the method of the first invention2Br2) And bromodifluoromethane (CHF)2CF in the mixture of Br)2Br2/ CHF2The content ratio of Br is preferably 99.9 / 0.1 to 75/25 in terms of molar ratio, suppresses the production of 1-bromobenzene derivative (5) as a by-product, and increases the conversion rate of the reaction. To improve, CF2Br2/ CHF2A ratio of 95/5 to 85/15 in terms of the molar ratio of Br is particularly preferable. Dibromodifluoromethane (CF2Br2) And bromodifluoromethane (CHF)2Bromodifluoromethane (CHF) in a mixture of Br)2By adjusting the content of Br) between 0.1 mol% and 25 mol%, the production ratio of 1-bromobenzene derivative (5) and benzene derivative (6) as by-products can be adjusted, The production amount of the 1-bromobenzene derivative (5) can be suppressed to 5% by weight or less. The amount of the mixture used is dibromodifluoromethane (CF) relative to the benzene derivative (1).2Br2) And bromodifluoromethane (CHF)2The total Br) is preferably 1.0 to 2.0 equivalents, particularly preferably 1.0 to 1.3 equivalents.
[0084]
The reaction solvent used in the method of the first invention can be used as long as it is inert to the reaction, and is not particularly limited. Specific examples include aromatic compounds such as benzene and toluene, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, diethyl ether, methyl t-butyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. Examples include aliphatic ether compounds, cyclic ether compounds such as tetrahydrofuran and dioxane. Among these, toluene, hexane, tetrahydrofuran, and these are preferable because they have high solubility in the benzene derivative (1), suppress the production of the by-product 1-bromobenzene derivative (5), and improve the conversion rate of the reaction. The mixed solvent is particularly preferred. Further, the amount used is preferably 5 to 20 times the weight of the benzene derivative (1).
[0085]
The reaction temperature in the method of the first invention is R shown in the formula (1).1In order to introduce a difluorobromomethyl group with high selectivity to the 1-position of the benzene derivative (1) with the side close to 4 being the 4-position, the reaction between the benzene derivative (1) and the base is preferably −40 ° C. or lower, In particular, -60 to -75 ° C is preferable. Dibromodifluoromethane (CF2Br2) And bromodifluoromethane (CHF)2In the reaction of the mixture of Br), −50 ° C. or less is preferable, particularly in terms of suppressing the production of the 1-bromobenzene derivative (5) as a by-product and improving the conversion rate of the reaction. -70 ° C is preferred.
[0086]
Embedded image
The reaction time in the method of the first invention is preferably left to age for 0.5 to 2 hours after the addition of the base in order to allow the reaction to proceed completely in the reaction stage in which the base is allowed to act, and dibromodifluoromethane. (CF2Br2) And bromodifluoromethane (CHF)2Similarly, in the reaction in which the mixture of Br) is allowed to act, it is preferably aged for 0.5 to 2 hours after the addition of the mixture.
[0088]
In the method of the first invention, dibromodifluoromethane (CF2Br2) And bromodifluoromethane (CHF)2The benzene derivative (6) represented by the above formula is slightly produced (35% by weight or less) as a by-product by the reaction in which the mixture of Br) is allowed to act. At this time, when the benzene derivative (1) in which Y is a hydrogen atom is used, the benzene derivative (6) and the benzene derivative (1) are the same compound, which is effective for recycling. Further, some by-products such as 1-bromobenzene derivative (5) (35% by weight or less) are produced. The production amount of the benzene derivative (6) and the production amount of by-products such as the 1-bromobenzene derivative (5) vary depending on the reaction conditions, but the total of these is 35% by weight or less.
[0089]
In the method of the second invention, the amount of 1-bromobenzene derivative (5) can be produced from the viewpoint of easy isolation and purification of the final target difluorobenzyl ether derivative (4) and the total yield. It is preferable to suppress as much as possible.
[0090]
In the method of the first invention, after completion of the reaction, the target product can be separated and purified from the reaction solution by a technique used in ordinary organic synthesis. For example, water and an organic solvent for extraction are added to the reaction solution and stirred well, and the separated organic layer is washed with water. Next, after drying with a drying agent such as anhydrous sodium sulfate, the organic solvent is removed under reduced pressure to obtain a concentrated residue. By subjecting this concentrated residue to silica gel chromatography, recrystallization or distillation, a target product having a purity of 95% or more can be obtained. At this time, in the second method described later, from the viewpoint of ease of isolation and purification of the obtained difluorobenzyl ether derivative (4), without purifying the reaction solution obtained in the method of the first invention, The concentrated residue which is a mixture with the benzene derivative (6) is preferably used as it is.
[0091]
In the method of the second invention, the reaction (etherification reaction) between the difluorobenzyl bromide derivative (2) and the phenol derivative (3) obtained by the method of the first invention is performed in the presence of a base. As the base to be used, alkali metal, alkali metal hydroxide, alkali metal carbonate, alkali metal hydride, alkali metal alcoholate and the like can be used. From the viewpoint of easy handling, it is preferable to use alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, alkali metal carbonates such as potassium carbonate and sodium carbonate, and alkali metal hydrides such as oily sodium hydride. Of these, potassium carbonate is particularly preferred. The amount of base used in this etherification reaction varies depending on the base used, but it is preferably 1 to 2 equivalents, preferably 1.1 to 1.3 equivalents, based on the difluorobenzyl bromide derivative (2). Particularly preferred. When the reaction is difficult to proceed, a catalytic amount (0.03 to 0.1 equivalent) of potassium iodide is preferably added to accelerate the reaction.
[0092]
In the method of the second invention, the difluorobenzyl ether derivative (4) can be obtained without problems if the phenol derivative (3) is used in an equivalent amount or more with respect to the fluorobenzyl bromide derivative (2). In addition, 1.1 to 1.2 equivalents are preferably used for the purpose of facilitating separation and purification of the target product from the reaction solution.
[0093]
The solvent used in the method of the second invention is not particularly limited as long as it is inert to the reaction. Specific examples include aromatic compounds such as benzene and toluene, aliphatic hydrocarbons such as hexane and heptane, alicyclic hydrocarbons such as cyclohexane, aliphatic ethers such as methyl t-butyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. Compounds, cyclic ether compounds such as tetrahydrofuran and dioxane, aliphatic ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, N, N-dimethylacetamide, N, N-dimethylformamide (DMF), hexamethylphosphoric triamide ( HMPA) and aprotic polar solvents such as N-methyl-2-pyrrolidinone. Among these, N, N-dimethylformamide (DMF) is particularly preferable. Moreover, there is no problem as long as the amount of the reaction solvent used is such that the reaction solution can be stirred well and the reaction can be carried out safely and stably. Specifically, the amount is preferably 1 to 10 times by weight with respect to the phenol derivative (3), and 2 to 5 times the amount in terms of suppression of by-products and easy separation and purification of the target product from the reaction solution. Is particularly preferred.
[0094]
In the method of the second invention, although the reaction temperature depends on the structure of the difluorobenzyl bromide derivative (2), it can be between room temperature and the boiling point of the solvent used, but is preferably 60 to 130 ° C. 100-120 degreeC is especially preferable at the point of suppression of a product and reaction time.
[0095]
In the method of the second invention, the reaction time is preferably 1 to 6 hours, although it depends on the structures and amounts of the difluorobenzyl bromide derivative (2) and phenol derivative (3) and the type of base used. As a specific example, when potassium carbonate is used as a base, the difluorobenzyl bromide derivative (2), the phenol derivative (3), a base and a solvent are mixed and reacted at a temperature of 90 to 100 ° C. for about 1 to 2 hours. After that, it is preferable to react at 110 to 120 ° C. for about 4 to 5 hours.
[0096]
In the method of the second invention, it is preferable to use the concentrated residue obtained by the method of the first invention as it is as a mixture with the benzene derivative (6) without purification. In this case, only the difluorobenzyl bromide derivative (2) reacts to obtain a mixture of the target difluorobenzyl ether derivative (4) and the benzene derivative (6).
[0097]
Embedded image
In the method of the second invention, the method for separating and purifying the target difluorobenzyl ether derivative (4) from the reaction solution is not particularly limited, and can be carried out by a method used in ordinary organic synthesis. For example, water and an organic solvent for extraction are added to the reaction solution, the mixture is sufficiently stirred, and insoluble matters are filtered. The separated organic layer is washed with water and dried with a drying agent such as anhydrous sodium sulfate, and then the organic solvent is removed under reduced pressure to obtain a concentrated residue. From this concentrated residue, the difluorobenzyl ether derivative (4) having a purity of 99% or more can be easily obtained by a known separation method such as silica gel chromatography, distillation or recrystallization. In particular, since the difference in boiling point between the difluorobenzyl ether derivative (4) and the benzene derivative (6) is large, separation by distillation is easy.
[0099]
In the present invention, when the difluorobenzyl bromide derivative (2) is obtained using the benzene derivative (1) in which Y is a hydrogen atom, and this is used for the production of the difluorobenzyl ether derivative (4), the benzene derivative (6) and the benzene derivative (1) are the same compound, the starting benzene derivative (1) can be obtained, and the recovered benzene derivative (1) can be recycled and reused. Effective use is possible.
[0100]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0101]
(Example 1) 1-bromodifluoromethyl-2,6-difluoro-4- (4-propylphenyl) benzene [CThreeH7-Ph-PhFF-CF2Of Br]
To a 1 L four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen introducing tube, 50 g (215 mmol) of 2,6-difluoro-4- (4-propylphenyl) benzene and 430 mL of anhydrous tetrahydrofuran were added, and -65 145 mL (226 mmol) of n-butyllithium hexane solution (1.59 M) was added dropwise while maintaining the same temperature after cooling to below. After completion of the dropwise addition, the mixture was further stirred for 2 hours while maintaining at -65 ° C or lower.
[0102]
Next, a solution prepared by dissolving 46.1 g (220 mmol) of dibromodifluoromethane and 8.85 g (67.6 mmol) of bromodifluoromethane in 27 mL of THF was added dropwise to the reaction solution while keeping the temperature at −60 ° C. or lower. Stir at the same temperature. The reaction solution was warmed to room temperature, 215 mL of 5% aqueous sodium hydroxide solution was added, and then the organic layer and the aqueous layer were separated. The aqueous layer was extracted with 270 mL of hexane, and the extract and the organic layer were combined, washed with water and dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 68.7 g of a crude product.
[0103]
The obtained crude product was subjected to gas chromatography,1H-NMR and19As a result of analysis by F-NMR, 1-bromodifluoromethyl-2,6-difluoro-4- (4-propylphenyl) benzene (72.5%) and 1-bromo-2,6-difluoro It was a mixture of 4- (4-propylphenyl) benzene (0.5%), 2,6-difluoro-4- (4-propylphenyl) benzene (21.8%) and other impurities.
[0104]
(Weight of crude product) × (purity measured by gas chromatography) = weight of the target product, the yield of the target product is 64% from 2,6-difluoro-4- (4-propylphenyl) benzene. Met. A part of the crude product is treated with silica gel column chromatography (developing solvent: hexane) and then recrystallized several times using ethanol as a solvent, whereby the purity measured by gas chromatography is 99%. -Bromodifluoromethyl-2,6-difluoro-4- (4-propylphenyl) benzene was obtained.
[0105]
CThreeH7-Ph-PhFF-CF2Br
Melting point: oily at room temperature
1H-NMR (CDClThree) Δ (ppm: from TMS): 0.96 (t, 3H), 1.68 (sext, 2H), 2.64 (t, 2H), 7.18 (d, 2H), 7.28 (d, 2H), 7.47 (d, 2H)
19F-NMR (CDClThree) Δ (ppm: fromCFClThree): -40.7 (t, 2F), -110.3 (td, 2F)
[0106]
CThreeH7-Ph-PhFF
Melting point: 25.5-27.5 ° C
1H-NMR (CDClThree) Δ (ppm: from TMS): 0.96 (t, 3H), 1.66 (sex, 2H), 2.61 (t, 2H), 6.71 (tt, 1H), 7.06 (m, 2H), 7.22 (d, 2H), 7.43 (d, 2H)
19F-NMR (CDClThree) Δ (ppm: fromCFClThree): -110.4 (t, 2F)
[0107]
Example 2 1- (3,4,5-trifluorophenoxy) difluoromethyl-2,6-difluoro-4- (4-propylphenyl) benzene [CThreeH7-Ph-PhFF-CF2Of O-PhFF-F]
Into a 300 mL four-necked flask equipped with a stirrer, a thermometer, a condenser tube and a nitrogen inlet tube, 66.9 g of the crude product produced in Example 1 (1-bromodifluoromethyl-2,6-difluoro-4- ( 4-propylphenyl) benzene (48.5 g, 134 mmol, 73%) and 2,6-difluoro-4- (4-propylphenyl) benzene (22%) mixture), 3,4,5-trifluorophenol 21 1.9 g (148 mmol), potassium carbonate 20.4 g (148 mmol), and N, N-dimethylformamide 44 mL were added, heated to 100 ° C. and stirred for 1 hour, then heated to 120 ° C. and stirred for 5 hours. After cooling the reaction solution to room temperature, 130 mL of water and 130 mL of hexane were added, the insoluble material was filtered off, and the organic layer was separated. The aqueous layer was extracted with 130 mL of hexane, and the extract and the organic layer were combined, washed with 5% aqueous sodium hydroxide and water, dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 70.6 g of a crude product. Got.
[0108]
The obtained crude product was subjected to gas chromatography,1H-NMR and19As a result of analysis by F-NMR, 1- (3,4,5-trifluorophenoxy) difluoromethyl-2,6-difluoro-4- (4-propylphenyl) benzene (69.5%), which is the target product, 1-bromo-2,6-difluoro-4- (4-propylphenyl) benzene (0.4%), 2,6-difluoro-4- (4-propylphenyl) benzene (20.0%) and other It was a mixture of impurities.
[0109]
(Weight of crude product) × (purity in gas chromatography) = weight of the target product, the yield of the target product from 1-bromodifluoromethyl-2,6-difluoro-4- (4-propylphenyl) benzene The rate was 85%.
[0110]
A portion of the crude product is recrystallized three times using a mixed solvent of hexane / ethanol = 1/4, and purified by silica gel column chromatography (developing solvent: hexane), and measured by gas chromatography. 1- (3,4,5-trifluorophenoxy) difluoromethyl-2,6-difluoro-4- (4-propylphenyl) benzene having a purity of 99% was obtained.
[0111]
CThreeH7-Ph-PhFF-CF2O-PhFF-F
Melting point: 45.8-46.5 ° C
1H-NMR (CDClThree) Δ (ppm: from TMS): 0.97 (t, 3H), 1.68 (sex, 2H), 2.64 (t, 2H), 6.98 (t, 2H), 7.22 (d, 2H), 7.28 (d, 2H), 7.48 (d, 2H)
[0112]
19F-NMR (CDClThree) Δ (ppm: fromCFClThree): -62.3 (t, 2F), -111.1 (m, 2F), -132.9 (m, 2F), -163.6 (m, 1F)
[0113]
Comparative Example 1 1-bromodifluoromethyl-2,6-difluoro-4- (4-propylphenyl) benzene [CThreeH7-Ph-PhFF-CF2Of Br]
To a 1 L four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a nitrogen introducing tube, 50 g (215 mmol) of 2,6-difluoro-4- (4-propylphenyl) benzene and 430 mL of anhydrous tetrahydrofuran were added, and -65 145 mL (226 mmol) of n-butyl lithium hexane solution (1.59 M) was added dropwise while maintaining the same temperature after cooling to below. After completion of the dropwise addition, the mixture was further stirred for 2 hours while maintaining at -65 ° C or lower.
[0114]
Next, a solution obtained by dissolving 45.2 g (215 mmol) of dibromodifluoromethane in 27 mL of THF was added dropwise while keeping the temperature at −60 ° C. or lower, and the mixture was further stirred at the same temperature for 2 hours after the completion of the addition. After that, the temperature of the reaction solution was raised to room temperature, and 215 mL of 5% aqueous sodium hydroxide solution was added. The organic layer was separated, and the aqueous layer was extracted with 270 mL of hexane. The organic layers were combined, washed with water and dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 73.8 g of a crude product.
[0115]
The obtained crude product was subjected to gas chromatography,1H-NMR and19As a result of F-NMR analysis, 1- (3,4,5-trifluorophenoxy) difluoromethyl-2,6-difluoro-4- (4-propylphenyl) benzene (78.0%), which is the target product, 1-bromo-2,6-difluoro-4- (4-propylphenyl) benzene (16.3%), 2,6-difluoro-4- (4-propylphenyl) benzene (3.8%) and other It was a mixture of impurities.
[0116]
(Weight of crude product) × (purity in gas chromatography) = weight of the target product, the yield of the target product from 1-bromodifluoromethyl-2,6-difluoro-4- (4-propylphenyl) benzene The rate was 74%.
[0117]
【The invention's effect】
According to the first method of the present invention, a difluorobenzyl bromide derivative that is useful as an intermediate of a liquid crystal material is produced simply and efficiently by suppressing the formation of by-products such as a halogenated benzene derivative (f). be able to. Further, according to the second method of the present invention, difluorobenzyl ether useful as a liquid crystal material can be produced simply and efficiently.
Claims (3)
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| CN102924243A (en) * | 2012-03-27 | 2013-02-13 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound containing cyclopentyl and difluorometheneoxy linking group, preparation method and applications thereof |
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| EP1813662B1 (en) * | 2006-01-27 | 2009-10-21 | MERCK PATENT GmbH | Liquid crystalline medium and liquid crystal display |
| US8030512B2 (en) * | 2008-10-20 | 2011-10-04 | Ube Industries, Ltd. | Polycyclic pentafluorosulfanylbenzene compound and process for producing the compound |
| JP5519955B2 (en) * | 2009-05-19 | 2014-06-11 | Ａｇｃセイミケミカル株式会社 | Process for producing fluorine-containing compound and intermediate |
| DE102011015813A1 (en) | 2010-04-17 | 2011-10-20 | Merck Patent Gmbh | Liquid crystalline compounds and liquid crystalline media |
| JP2013241401A (en) * | 2012-04-26 | 2013-12-05 | Agc Seimi Chemical Co Ltd | Production method of liquid crystal compound, and intermediate thereof |
| JP5850023B2 (en) | 2012-11-27 | 2016-02-03 | Jnc株式会社 | Liquid crystal compound, liquid crystal composition and liquid crystal display element having CF2OCF3 at terminal |
| CN105637066A (en) * | 2013-10-17 | 2016-06-01 | 捷恩智株式会社 | Liquid crystal composition and liquid crystal display element |
| CN110790641B (en) | 2014-03-20 | 2023-02-28 | 大金工业株式会社 | Method for producing compound having oxydifluoromethylene skeleton |
| CN109652094B (en) * | 2018-12-24 | 2020-07-14 | 西安彩晶光电科技股份有限公司 | Preparation method of difluoromethyl ether bridged liquid crystal monomer |
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| CN102924243A (en) * | 2012-03-27 | 2013-02-13 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound containing cyclopentyl and difluorometheneoxy linking group, preparation method and applications thereof |
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