JP5889817B2 - トリフルオロメチル化剤粉末、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粉末、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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- JP5889817B2 JP5889817B2 JP2013032699A JP2013032699A JP5889817B2 JP 5889817 B2 JP5889817 B2 JP 5889817B2 JP 2013032699 A JP2013032699 A JP 2013032699A JP 2013032699 A JP2013032699 A JP 2013032699A JP 5889817 B2 JP5889817 B2 JP 5889817B2
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- Prior art keywords
- iodide
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- general formula
- dmpu
- Prior art date
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- 239000000843 powder Substances 0.000 title claims description 19
- 239000003795 chemical substances by application Substances 0.000 title claims description 17
- 150000001875 compounds Chemical class 0.000 title claims description 16
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 title claims description 12
- 238000000034 method Methods 0.000 title description 4
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- VGGNVBNNVSIGKG-UHFFFAOYSA-N n,n,2-trimethylaziridine-1-carboxamide Chemical compound CC1CN1C(=O)N(C)C VGGNVBNNVSIGKG-UHFFFAOYSA-N 0.000 claims description 8
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 claims description 8
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical class IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 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
- 239000012141 concentrate Substances 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- UAXIGXVZSSTAPU-UHFFFAOYSA-M [I-].FC(F)(F)[Zn+] Chemical compound [I-].FC(F)(F)[Zn+] UAXIGXVZSSTAPU-UHFFFAOYSA-M 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- -1 difluorocarbene Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 2
- BGVGHYOIWIALFF-UHFFFAOYSA-N 1-fluoro-2-(trifluoromethyl)benzene Chemical compound FC1=CC=CC=C1C(F)(F)F BGVGHYOIWIALFF-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
- QHLLEZOPZRBCOY-UHFFFAOYSA-N 4-bromo-2-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC(Br)=CC=N1 QHLLEZOPZRBCOY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- 239000012043 crude product Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 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
- 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
- AFDRVFGCDMLCKR-UHFFFAOYSA-N 1-cyclopropyl-4-iodobenzene Chemical compound C1=CC(I)=CC=C1C1CC1 AFDRVFGCDMLCKR-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
- LCZDWPKGWXFANX-UHFFFAOYSA-N 1-ethoxy-3-(trifluoromethyl)benzene Chemical compound CCOC1=CC=CC(C(F)(F)F)=C1 LCZDWPKGWXFANX-UHFFFAOYSA-N 0.000 description 1
- 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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- CJNZAXGUTKBIHP-UHFFFAOYSA-N 2-iodobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1I CJNZAXGUTKBIHP-UHFFFAOYSA-N 0.000 description 1
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- 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 1
- HSNBRDZXJMPDGH-UHFFFAOYSA-N 5-bromo-2-iodopyridine Chemical compound BrC1=CC=C(I)N=C1 HSNBRDZXJMPDGH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-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
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- FNCDCENORLBNRA-UHFFFAOYSA-N FC(F)(F)S([Cu])(=O)=O Chemical compound FC(F)(F)S([Cu])(=O)=O FNCDCENORLBNRA-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
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 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
- BQLMZZVRHPZRBQ-UHFFFAOYSA-N ethyl 2-(trifluoromethyl)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1C(F)(F)F BQLMZZVRHPZRBQ-UHFFFAOYSA-N 0.000 description 1
- QOUFDDUDXYJWHV-UHFFFAOYSA-N ethyl 2-iodobenzoate Chemical compound CCOC(=O)C1=CC=CC=C1I QOUFDDUDXYJWHV-UHFFFAOYSA-N 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
- 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
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- 239000002798 polar solvent Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007086 side reaction 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000006692 trifluoromethylation reaction Methods 0.000 description 1
- 150000005226 trifluoromethylbenzenes Chemical class 0.000 description 1
Description
[1] 下記、一般式(1)
(CF3)ZnI・(DMPU)n (1)
(式中、DMPUはN,N−ジメチルプロピレンウレアを示し、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粉末。
[2] 項1の一般式(1)で表されるトリフルオロメチル化剤粉末でnが1〜4の混合物であることを特徴とするトリフルオロメチル化剤粉末。
[3] 項1の一般式(1)で表されるトリフルオロメチル化剤粉末でnが2であることを特徴とするトリフルオロメチル化剤粉末。
[4] N,N−ジメチルホルムアミド溶剤中、N,N−ジメチルプロピレンウレア、亜鉛粉末及びトリフルオロメチルヨージドを反応させた後、ろ過、濃縮することを特徴とする項1乃至項3のいずれか1項に記載の一般式(1)で表されるトリフルオロメチル化剤粉末の製造方法。
[5] 項1乃至項3のいずれか1項に記載の一般式(1)で表されるトリフルオロメチル化剤粉末及び下記一般式(2)
で表される置換フェニルヨージドを、銅(I)触媒存在下、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。
実施例1 トリフルオロメチル亜鉛ヨージド・(ジメチルプロピレンウレア) n 錯体の調製
攪拌子を備えた20mlの丸底2口フラスコに、アルゴン気流下、亜鉛粉末(Aldrich社製未活性化品、654mg、10mmol)、DMPU(2.4ml、20mmol)及びDMF(7ml)を仕込み、−20℃とした。次いでこれにトリフルオロメチルヨージド(約8.0g)をバブリグ供給した後室温に戻し、同温度で24時間反応を行った。反応終了後、アルゴン気流下、未反応の亜鉛粉末をろ別の後、減圧下濃縮し、粗製物を淡黄色の固体として得た。得られた粗製物は、アルゴン気流下、トルエンで3回洗浄することにより白色固体のトリフルオロメチル亜鉛ヨージド・(DMPU)2錯体[(CF3)ZnI・(DMPU)2]を得た。
19F−NMR(282MHz,DMF−d7)δ−42.9(s)、−44.6(s)(ベンゾトリフルオリド内部標準:−63.24)。なお、(CF3)ZnI・(DMPU)2はDMF−d7溶剤中で、下記平衡状態となり、2本のピークとして検出された。
られ、100℃以下では安定であった。
攪拌子、セプタムキャップを備えた試験管に実施例1で調製したトリフルオロメチル亜鉛ヨージド・(DMPU)2錯体(160mg、0.2mmol)及びヨウ化銅(I)(1.9mg、0.01mmol)を仕込み、アルゴン置換を3回実施した。次いで、2−ヨード安息香酸エチル(16.6μl、0.1mmol)のDMPU(0.2ml)溶液を加え、セプタムキャップをスクリューチャップに替え密封した後、50℃で24時間反応を行った。反応終了後、反応液を19F−NMR(ベンゾトリフルオライド内部標準)で定量したところ、収率80%で2−トリフルオロメチル安息香酸エチルが生成していた。
実施例2の2−ヨード安息香酸に替えて、4−ブロモ−2−ヨードピリジン(28.4mg、0.1mmol)に替えた以外、実施例2と同じ操作を行い、4−ブロモ−2−トリフルオロメチルピリジンを収率75%で得た。
Claims (3)
- 式(1)
(CF3)ZnI・(DMPU) 2 (1)
(式中、DMPUはN,N−ジメチルプロピレンウレアを示す)
で表されるトリフルオロメチル化剤粉末。 - N,N−ジメチルホルムアミド溶剤中、N,N−ジメチルプロピレンウレア、亜鉛粉末及びトリフルオロメチルヨージドを反応させた後、ろ過、濃縮することを特徴とする請求項1に記載の式(1)で表されるトリフルオロメチル化剤粉末の製造方法。
- 請求項1に記載の式(1)で表されるトリフルオロメチル化剤粉末及び下記一般式(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ヨージドを、銅(I)触媒存在下、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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