JP5941338B2 - トリフルオロメチル化剤、その製造方法並びにそれを用いたトリフルオロメチル基含有化合物の製造方法 - Google Patents
トリフルオロメチル化剤、その製造方法並びにそれを用いたトリフルオロメチル基含有化合物の製造方法 Download PDFInfo
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- JP5941338B2 JP5941338B2 JP2012113898A JP2012113898A JP5941338B2 JP 5941338 B2 JP5941338 B2 JP 5941338B2 JP 2012113898 A JP2012113898 A JP 2012113898A JP 2012113898 A JP2012113898 A JP 2012113898A JP 5941338 B2 JP5941338 B2 JP 5941338B2
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- Prior art keywords
- iodide
- group
- trifluoromethyl
- general formula
- represented
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 150000001875 compounds Chemical class 0.000 title claims description 16
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 title claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 62
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 claims description 9
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical class IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Chemical group 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 238000006692 trifluoromethylation reaction Methods 0.000 claims description 2
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 claims 1
- DSWNRHCOGVRDOE-UHFFFAOYSA-N n,n-dimethylmethanimidamide Chemical compound CN(C)C=N DSWNRHCOGVRDOE-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000011701 zinc Substances 0.000 description 15
- -1 difluorocarbene Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- HSNBRDZXJMPDGH-UHFFFAOYSA-N 5-bromo-2-iodopyridine Chemical compound BrC1=CC=C(I)N=C1 HSNBRDZXJMPDGH-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- ATRQECRSCHYSNP-UHFFFAOYSA-N 2-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=CC=N1 ATRQECRSCHYSNP-UHFFFAOYSA-N 0.000 description 3
- RPFAUCIXZGMCFN-UHFFFAOYSA-N 5-bromo-2-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=C(Br)C=N1 RPFAUCIXZGMCFN-UHFFFAOYSA-N 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 3
- UAXIGXVZSSTAPU-UHFFFAOYSA-M [I-].FC(F)(F)[Zn+] Chemical compound [I-].FC(F)(F)[Zn+] UAXIGXVZSSTAPU-UHFFFAOYSA-M 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 238000010813 internal standard method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- BGVGHYOIWIALFF-UHFFFAOYSA-N 1-fluoro-2-(trifluoromethyl)benzene Chemical compound FC1=CC=CC=C1C(F)(F)F BGVGHYOIWIALFF-UHFFFAOYSA-N 0.000 description 2
- CCZWSTFVHJPCEM-UHFFFAOYSA-N 2-iodopyridine Chemical compound IC1=CC=CC=N1 CCZWSTFVHJPCEM-UHFFFAOYSA-N 0.000 description 2
- XSDMZCDURCSVFW-UHFFFAOYSA-N 3-(5-chloro-2-methoxyphenyl)-1,2-oxazol-5-amine Chemical compound COC1=CC=C(Cl)C=C1C1=NOC(N)=C1 XSDMZCDURCSVFW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 description 2
- BQLMZZVRHPZRBQ-UHFFFAOYSA-N ethyl 2-(trifluoromethyl)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1C(F)(F)F BQLMZZVRHPZRBQ-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- SYSZENVIJHPFNL-UHFFFAOYSA-N (alpha-D-mannosyl)7-beta-D-mannosyl-diacetylchitobiosyl-L-asparagine, isoform B (protein) Chemical compound COC1=CC=C(I)C=C1 SYSZENVIJHPFNL-UHFFFAOYSA-N 0.000 description 1
- KQIDHMIYXDBFHY-UHFFFAOYSA-N 1-(2-methylpropoxy)-4-(trifluoromethyl)benzene Chemical compound CC(C)COC1=CC=C(C(F)(F)F)C=C1 KQIDHMIYXDBFHY-UHFFFAOYSA-N 0.000 description 1
- POVFWAQIEYIPBL-UHFFFAOYSA-N 1-(2-methylpropyl)-4-(trifluoromethyl)benzene Chemical compound CC(C)CC1=CC=C(C(F)(F)F)C=C1 POVFWAQIEYIPBL-UHFFFAOYSA-N 0.000 description 1
- YXTJJRXJNYHJPU-UHFFFAOYSA-N 1-[(2-methylpropan-2-yl)oxy]-4-(trifluoromethyl)benzene Chemical compound CC(C)(C)OC1=CC=C(C(F)(F)F)C=C1 YXTJJRXJNYHJPU-UHFFFAOYSA-N 0.000 description 1
- RWXUNIMBRXGNEP-UHFFFAOYSA-N 1-bromo-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1Br RWXUNIMBRXGNEP-UHFFFAOYSA-N 0.000 description 1
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 1
- NNMBNYHMJRJUBC-UHFFFAOYSA-N 1-bromo-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(Br)=C1 NNMBNYHMJRJUBC-UHFFFAOYSA-N 0.000 description 1
- CTPUUDQIXKUAMO-UHFFFAOYSA-N 1-bromo-3-iodobenzene Chemical compound BrC1=CC=CC(I)=C1 CTPUUDQIXKUAMO-UHFFFAOYSA-N 0.000 description 1
- XLQSXGGDTHANLN-UHFFFAOYSA-N 1-bromo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(Br)C=C1 XLQSXGGDTHANLN-UHFFFAOYSA-N 0.000 description 1
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 description 1
- BRQXOVNAOBQYQB-UHFFFAOYSA-N 1-butoxy-4-(trifluoromethyl)benzene Chemical compound CCCCOC1=CC=C(C(F)(F)F)C=C1 BRQXOVNAOBQYQB-UHFFFAOYSA-N 0.000 description 1
- QMEHOMNBEJNMHD-UHFFFAOYSA-N 1-butoxy-4-iodobenzene Chemical compound CCCCOC1=CC=C(I)C=C1 QMEHOMNBEJNMHD-UHFFFAOYSA-N 0.000 description 1
- BYTSRLZSSBMPSN-UHFFFAOYSA-N 1-butyl-4-(trifluoromethyl)benzene Chemical compound CCCCC1=CC=C(C(F)(F)F)C=C1 BYTSRLZSSBMPSN-UHFFFAOYSA-N 0.000 description 1
- XILRUONFYBUYIE-UHFFFAOYSA-N 1-butyl-4-iodobenzene Chemical compound CCCCC1=CC=C(I)C=C1 XILRUONFYBUYIE-UHFFFAOYSA-N 0.000 description 1
- DGRVQOKCSKDWIH-UHFFFAOYSA-N 1-chloro-2-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1Cl DGRVQOKCSKDWIH-UHFFFAOYSA-N 0.000 description 1
- MPEOPBCQHNWNFB-UHFFFAOYSA-N 1-chloro-2-iodobenzene Chemical compound ClC1=CC=CC=C1I MPEOPBCQHNWNFB-UHFFFAOYSA-N 0.000 description 1
- YTCGOUNVIAWCMG-UHFFFAOYSA-N 1-chloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(Cl)=C1 YTCGOUNVIAWCMG-UHFFFAOYSA-N 0.000 description 1
- JMLWXCJXOYDXRN-UHFFFAOYSA-N 1-chloro-3-iodobenzene Chemical compound ClC1=CC=CC(I)=C1 JMLWXCJXOYDXRN-UHFFFAOYSA-N 0.000 description 1
- GWQSENYKCGJTRI-UHFFFAOYSA-N 1-chloro-4-iodobenzene Chemical compound ClC1=CC=C(I)C=C1 GWQSENYKCGJTRI-UHFFFAOYSA-N 0.000 description 1
- OXKKXADVDBJIKL-UHFFFAOYSA-N 1-cyclohexyl-4-(trifluoromethyl)benzene Chemical compound C1=CC(C(F)(F)F)=CC=C1C1CCCCC1 OXKKXADVDBJIKL-UHFFFAOYSA-N 0.000 description 1
- SXHDBSAHBVKKOF-UHFFFAOYSA-N 1-cyclohexyl-4-iodobenzene Chemical compound C1=CC(I)=CC=C1C1CCCCC1 SXHDBSAHBVKKOF-UHFFFAOYSA-N 0.000 description 1
- OELLMJAFBQUSDE-UHFFFAOYSA-N 1-cyclohexyloxy-4-(trifluoromethyl)benzene Chemical compound FC(C1=CC=C(OC2CCCCC2)C=C1)(F)F OELLMJAFBQUSDE-UHFFFAOYSA-N 0.000 description 1
- AYNLKAYCBCEOMJ-UHFFFAOYSA-N 1-cyclohexyloxy-4-iodobenzene Chemical compound C1=CC(I)=CC=C1OC1CCCCC1 AYNLKAYCBCEOMJ-UHFFFAOYSA-N 0.000 description 1
- CWCQQMOYDNXYSC-UHFFFAOYSA-N 1-cyclopentyl-4-(trifluoromethyl)benzene Chemical compound C1=CC(C(F)(F)F)=CC=C1C1CCCC1 CWCQQMOYDNXYSC-UHFFFAOYSA-N 0.000 description 1
- YVHVJKIPYIYQST-UHFFFAOYSA-N 1-cyclopentyl-4-iodobenzene Chemical compound C1=CC(I)=CC=C1C1CCCC1 YVHVJKIPYIYQST-UHFFFAOYSA-N 0.000 description 1
- FWCPJYISPKFKQG-UHFFFAOYSA-N 1-cyclopentyloxy-4-iodobenzene Chemical compound C1=CC(I)=CC=C1OC1CCCC1 FWCPJYISPKFKQG-UHFFFAOYSA-N 0.000 description 1
- WXZTZBYLSRHABZ-UHFFFAOYSA-N 1-cyclopropyl-4-(trifluoromethyl)benzene Chemical compound C1=CC(C(F)(F)F)=CC=C1C1CC1 WXZTZBYLSRHABZ-UHFFFAOYSA-N 0.000 description 1
- VHJGSLQTHIPYAC-UHFFFAOYSA-N 1-cyclopropyloxy-4-iodobenzene Chemical compound C1=CC(I)=CC=C1OC1CC1 VHJGSLQTHIPYAC-UHFFFAOYSA-N 0.000 description 1
- GINXLMPWJKEAFV-UHFFFAOYSA-N 1-ethoxy-2-(trifluoromethyl)benzene Chemical compound CCOC1=CC=CC=C1C(F)(F)F GINXLMPWJKEAFV-UHFFFAOYSA-N 0.000 description 1
- JUJREUXKABNEFA-UHFFFAOYSA-N 1-ethoxy-2-iodobenzene Chemical compound CCOC1=CC=CC=C1I JUJREUXKABNEFA-UHFFFAOYSA-N 0.000 description 1
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- UIGQMEPFSWIPHM-UHFFFAOYSA-N 1-ethoxy-3-iodobenzene Chemical compound CCOC1=CC=CC(I)=C1 UIGQMEPFSWIPHM-UHFFFAOYSA-N 0.000 description 1
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- VSIIHWOJPSSIDI-UHFFFAOYSA-N 1-ethoxy-4-iodobenzene Chemical compound CCOC1=CC=C(I)C=C1 VSIIHWOJPSSIDI-UHFFFAOYSA-N 0.000 description 1
- YEFRNUDXXWZZCS-UHFFFAOYSA-N 1-ethyl-2-(trifluoromethyl)benzene Chemical compound CCC1=CC=CC=C1C(F)(F)F YEFRNUDXXWZZCS-UHFFFAOYSA-N 0.000 description 1
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- OKXWTILSPGNEBA-UHFFFAOYSA-N 1-propyl-4-(trifluoromethyl)benzene Chemical compound CCCC1=CC=C(C(F)(F)F)C=C1 OKXWTILSPGNEBA-UHFFFAOYSA-N 0.000 description 1
- AAHQWGQDFWPRNY-UHFFFAOYSA-N 1-tert-butyl-4-(trifluoromethyl)benzene Chemical compound CC(C)(C)C1=CC=C(C(F)(F)F)C=C1 AAHQWGQDFWPRNY-UHFFFAOYSA-N 0.000 description 1
- WQVIVQDHNKQWTM-UHFFFAOYSA-N 1-tert-butyl-4-iodobenzene Chemical compound CC(C)(C)C1=CC=C(I)C=C1 WQVIVQDHNKQWTM-UHFFFAOYSA-N 0.000 description 1
- SVXYYLLSGFNYCY-UHFFFAOYSA-N C(CCCCC)OC1=CC=C(C=C1)C(F)(F)F.C1(CCCC1)OC1=CC=C(C=C1)C(F)(F)F Chemical compound C(CCCCC)OC1=CC=C(C=C1)C(F)(F)F.C1(CCCC1)OC1=CC=C(C=C1)C(F)(F)F SVXYYLLSGFNYCY-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- MHNBTKIAHHECCQ-UHFFFAOYSA-N ethyl 3-(trifluoromethyl)benzoate Chemical compound CCOC(=O)C1=CC=CC(C(F)(F)F)=C1 MHNBTKIAHHECCQ-UHFFFAOYSA-N 0.000 description 1
- POGCXCWRMMXDAQ-UHFFFAOYSA-N ethyl 3-iodobenzoate Chemical compound CCOC(=O)C1=CC=CC(I)=C1 POGCXCWRMMXDAQ-UHFFFAOYSA-N 0.000 description 1
- ZQDADDSPMCHZPX-UHFFFAOYSA-N ethyl 4-(trifluoromethyl)benzoate Chemical compound CCOC(=O)C1=CC=C(C(F)(F)F)C=C1 ZQDADDSPMCHZPX-UHFFFAOYSA-N 0.000 description 1
- YCBJOQUNPLTBGG-UHFFFAOYSA-N ethyl 4-iodobenzoate Chemical compound CCOC(=O)C1=CC=C(I)C=C1 YCBJOQUNPLTBGG-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- JLCAMDSWNZBTEE-UHFFFAOYSA-N methyl 2-(trifluoromethyl)benzoate Chemical compound COC(=O)C1=CC=CC=C1C(F)(F)F JLCAMDSWNZBTEE-UHFFFAOYSA-N 0.000 description 1
- BXXLTVBTDZXPTN-UHFFFAOYSA-N methyl 2-iodobenzoate Chemical compound COC(=O)C1=CC=CC=C1I BXXLTVBTDZXPTN-UHFFFAOYSA-N 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- QQHNNQCWKYFNAC-UHFFFAOYSA-N methyl 3-(trifluoromethyl)benzoate Chemical compound COC(=O)C1=CC=CC(C(F)(F)F)=C1 QQHNNQCWKYFNAC-UHFFFAOYSA-N 0.000 description 1
- NPXOIGSBRLCOSD-UHFFFAOYSA-N methyl 3-iodobenzoate Chemical compound COC(=O)C1=CC=CC(I)=C1 NPXOIGSBRLCOSD-UHFFFAOYSA-N 0.000 description 1
- VAZWXPJOOFSNLB-UHFFFAOYSA-N methyl 4-(trifluoromethyl)benzoate Chemical compound COC(=O)C1=CC=C(C(F)(F)F)C=C1 VAZWXPJOOFSNLB-UHFFFAOYSA-N 0.000 description 1
- DYUWQWMXZHDZOR-UHFFFAOYSA-N methyl 4-iodobenzoate Chemical compound COC(=O)C1=CC=C(I)C=C1 DYUWQWMXZHDZOR-UHFFFAOYSA-N 0.000 description 1
- QULYNCCPRWKEMF-UHFFFAOYSA-N parachlorobenzotrifluoride Chemical compound FC(F)(F)C1=CC=C(Cl)C=C1 QULYNCCPRWKEMF-UHFFFAOYSA-N 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000005226 trifluoromethylbenzenes Chemical class 0.000 description 1
Description
[1] 下記、一般式(1)
Zn(CF3)I・(DMF)n (1)
(式中、DMFはN,N−ジメチルホルムアミドを示し、nは1〜4の整数を示す)
で表されるトリフルオロメチル化剤。
[2] N,N−ジメチルホルムアミド溶剤中、亜鉛粉末とトリフルオロメチルアイオダイドを反応させた後、ろ過、濃縮することを特徴とする項1に記載の一般式(1)で表されるトリフルオロメチル化剤の製造方法。
[3] 項1に記載の一般式(1)で表されるトリフルオロメチル化剤と下記一般式(2)
で表される置換フェニルアイオダイドを、銅存在下、反応させることを特徴とする下記一般式(3)
で表されるトリフルオロメチル基含有化合物の製造方法
を提供するものである。
攪拌子を備えた20mlの2口なす型フラスコに、アルゴン雰囲気下、亜鉛粉末(654mg、10mmmol)、N,N−ジメチルホルムアミド(6ml)を仕込み、攪拌しながら−30℃に冷却した後、これにトリフルオロメチルアイオダイド(5.0g、25.5mmol)をバブリングさせながら供給した。次いで、室温まで昇温し、さらに24時間熟成を行った後、アルゴン雰囲気下、固体をろ別、減圧濃縮し淡黄色固体を得、エーテルで2回洗浄、乾燥することにより目的物を白色の固体として得た(2.85g)。
19F−NMR(282MHz,CDCl3)δ−44.3(s)、−43.1(s)ppm。
(ベンゾトリフルオライド基準:δ=−63.24ppm)
融点:80℃(分解)。
試験管にアルゴン雰囲気下、実施例1で調製したトリフルオロメチル亜鉛アイオダイド・(ジメチルホルムアミド)n錯体(600mg)、塩化銅(I)(1.9mg、0.01mmol)、1,10−フェナントロリン(1.8mg、0.01)、5−ブロモ−2−ヨードピリジン(142mg、0.5mmol)及びN,N’−ジメチルプロピレン尿素(0.4ml)を仕込み、50℃で24時間反応を行った。
実施例2と同じ反応装置を用い、5−ブロモ−2−ヨードピリジンに替えて2−ヨードピリジンを用いた以外、実施例2と同じ操作を行った。19F−NMR(ベンゾトリフルオライド内部標準法)で定量した結果、目的物2−トリフルオロメチルピリジンの収率は90%であった。
実施例2と同じ反応装置を用い、5−ブロモ−2−ヨードピリジンに替えて2−ヨード安息香酸エチルを用いた以外、実施例2と同じ操作を行った。19F−NMR(ベンゾトリフルオライド内部標準法)で定量した結果、目的物2−トリフルオロメチル安息香酸エチルの収率は90%であった。
Claims (3)
- N,N−ジメチルホルムアミド中、亜鉛粉末とトリフルオロメチルアイオダイドを反応させることを含む、CDCl 3 を溶媒とした 19 F―NMRスペクトルにおいてベンゾトリフルオライド基準(δ=−63.24ppm)でのシフト値が−44.3ppm及び−43.1ppmであるピークを有する白色固体であるトリフルオロメチル化剤の製造方法。
- 前記トリフルオロメチルアイオダイドの割合が前記亜鉛粉末に対して1.1〜5.0倍モル量であり、前記N,N−ジメチルホルムアミドの割合が前記亜鉛粉末に対して5〜200重量倍量である請求項1に記載の製造方法。
- 請求項1または2に記載の製造方法により得られるトリフルオロメチル化剤と下記一般式(2)
(式中Aは、フッ素原子、塩素原子、臭素原子、メチル基、エチル基、炭素数3〜6の直鎖、分岐若しくは環式のアルキル基、メトキシ基、エトキシ基、炭素数3〜6の直鎖、分岐若しくは環式のアルコシキ基、メトキシカルボニル基またはエトキシカルボニル基を示し、Bは炭素原子または窒素原子を示す)
で表される置換フェニルアイオダイドを、銅存在下、反応させることを特徴とする下記一般式(3)
(式中A及びBは前記に同じ)
で表されるトリフルオロメチル基含有化合物の製造方法。
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