JP2012097082A - 置換または非置換のトリフルオロメチル化アリールおよびヘテロアリール化合物を製造するための銅触媒による方法 - Google Patents
置換または非置換のトリフルオロメチル化アリールおよびヘテロアリール化合物を製造するための銅触媒による方法 Download PDFInfo
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- JP2012097082A JP2012097082A JP2011234776A JP2011234776A JP2012097082A JP 2012097082 A JP2012097082 A JP 2012097082A JP 2011234776 A JP2011234776 A JP 2011234776A JP 2011234776 A JP2011234776 A JP 2011234776A JP 2012097082 A JP2012097082 A JP 2012097082A
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- Prior art keywords
- copper
- trifluoroacetate
- unsubstituted
- salt
- substituted
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000000034 method Methods 0.000 title claims abstract description 28
- -1 heteroaryl compound Chemical class 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 125000005418 aryl aryl group Chemical group 0.000 title abstract description 3
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims abstract description 12
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims abstract description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012190 activator Substances 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
- 150000001879 copper Chemical class 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001499 aryl bromides Chemical class 0.000 claims description 5
- 150000001503 aryl iodides Chemical class 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 4
- 229910001502 inorganic halide Inorganic materials 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- AHLATJUETSFVIM-UHFFFAOYSA-M rubidium fluoride Chemical compound [F-].[Rb+] AHLATJUETSFVIM-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 3
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 3
- VMVNZNXAVJHNDJ-UHFFFAOYSA-N methyl 2,2,2-trifluoroacetate Chemical compound COC(=O)C(F)(F)F VMVNZNXAVJHNDJ-UHFFFAOYSA-N 0.000 claims description 3
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- STSCVKRWJPWALQ-UHFFFAOYSA-N TRIFLUOROACETIC ACID ETHYL ESTER Chemical compound CCOC(=O)C(F)(F)F STSCVKRWJPWALQ-UHFFFAOYSA-N 0.000 claims description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 2
- RJYSYRSELCQCSO-UHFFFAOYSA-M cesium;2,2,2-trifluoroacetate Chemical compound [Cs+].[O-]C(=O)C(F)(F)F RJYSYRSELCQCSO-UHFFFAOYSA-M 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 2
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 claims description 2
- LELTVLRYLALSFG-UHFFFAOYSA-J F[Cu](F)(F)F Chemical compound F[Cu](F)(F)F LELTVLRYLALSFG-UHFFFAOYSA-J 0.000 claims 1
- VFRSADQPWYCXDG-LEUCUCNGSA-N ethyl (2s,5s)-5-methylpyrrolidine-2-carboxylate;2,2,2-trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.CCOC(=O)[C@@H]1CC[C@H](C)N1 VFRSADQPWYCXDG-LEUCUCNGSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 239000003153 chemical reaction reagent Substances 0.000 description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 229910052731 fluorine Inorganic materials 0.000 description 9
- 239000011737 fluorine Substances 0.000 description 9
- 238000006692 trifluoromethylation reaction Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 150000001502 aryl halides Chemical class 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001649 bromium compounds Chemical class 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- 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
- 0 *c1c(ccc2c(*)ccnc22)c2ncc1 Chemical compound *c1c(ccc2c(*)ccnc22)c2ncc1 0.000 description 1
- JZJWCDQGIPQBAO-UHFFFAOYSA-N 1-(4-iodophenyl)ethanone Chemical compound CC(=O)C1=CC=C(I)C=C1 JZJWCDQGIPQBAO-UHFFFAOYSA-N 0.000 description 1
- HTDQSWDEWGSAMN-UHFFFAOYSA-N 1-bromo-2-methoxybenzene Chemical compound COC1=CC=CC=C1Br HTDQSWDEWGSAMN-UHFFFAOYSA-N 0.000 description 1
- KGNQDBQYEBMPFZ-UHFFFAOYSA-N 1-fluoro-4-iodobenzene Chemical compound FC1=CC=C(I)C=C1 KGNQDBQYEBMPFZ-UHFFFAOYSA-N 0.000 description 1
- SKGRFPGOGCHDPC-UHFFFAOYSA-N 1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C=C1 SKGRFPGOGCHDPC-UHFFFAOYSA-N 0.000 description 1
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 1
- HVAPLSNCVYXFDQ-UHFFFAOYSA-N 3,3-dimethyl-1-(trifluoromethyl)-1$l^{3},2-benziodoxole Chemical compound C1=CC=C2C(C)(C)OI(C(F)(F)F)C2=C1 HVAPLSNCVYXFDQ-UHFFFAOYSA-N 0.000 description 1
- QJPJQTDYNZXKQF-UHFFFAOYSA-N 4-bromoanisole Chemical compound COC1=CC=C(Br)C=C1 QJPJQTDYNZXKQF-UHFFFAOYSA-N 0.000 description 1
- HQSCPPCMBMFJJN-UHFFFAOYSA-N 4-bromobenzonitrile Chemical compound BrC1=CC=C(C#N)C=C1 HQSCPPCMBMFJJN-UHFFFAOYSA-N 0.000 description 1
- CSFRCLYFVINMBZ-UHFFFAOYSA-N 4-iodo-1,2-dimethylbenzene Chemical compound CC1=CC=C(I)C=C1C CSFRCLYFVINMBZ-UHFFFAOYSA-N 0.000 description 1
- XOKDXPVXJWTSRM-UHFFFAOYSA-N 4-iodobenzonitrile Chemical compound IC1=CC=C(C#N)C=C1 XOKDXPVXJWTSRM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241001120493 Arene Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NPAXPTHCUCUHPT-UHFFFAOYSA-N Cc1cnc2c3ncc(C)c(C)c3ccc2c1C Chemical compound Cc1cnc2c3ncc(C)c(C)c3ccc2c1C NPAXPTHCUCUHPT-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N c(cc1)ccc1-c1ccnc(c2ncc3)c1ccc2c3-c1ccccc1 Chemical compound c(cc1)ccc1-c1ccnc(c2ncc3)c1ccc2c3-c1ccccc1 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 238000004821 distillation Methods 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012025 fluorinating agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000010814 metallic waste Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ZOUWOGOTHLRRLS-UHFFFAOYSA-N palladium;phosphane Chemical class P.[Pd] ZOUWOGOTHLRRLS-UHFFFAOYSA-N 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- QHMQWEPBXSHHLH-UHFFFAOYSA-N sulfur tetrafluoride Chemical compound FS(F)(F)F QHMQWEPBXSHHLH-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
- LSJNBGSOIVSBBR-UHFFFAOYSA-N thionyl fluoride Chemical compound FS(F)=O LSJNBGSOIVSBBR-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ZHSKFONQCREGOG-UHFFFAOYSA-N triethyl(trifluoromethyl)silane Chemical class CC[Si](CC)(CC)C(F)(F)F ZHSKFONQCREGOG-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- MWKJTNBSKNUMFN-UHFFFAOYSA-N trifluoromethyltrimethylsilane Chemical compound C[Si](C)(C)C(F)(F)F MWKJTNBSKNUMFN-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
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- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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Abstract
【解決手段】本発明は、非置換または置換のハロゲン化アリールまたはハロゲン化ヘテロアリールを、式(I)または式(II)
(式中、R1は、水素またはC1〜C5アルキル基であり、Mは、アルカリ金属またはアンモニウムイオンである)
のトリフルオロアセテートと、活性化剤化合物として無機ハロゲン化物塩またはトリフルオロ酢酸塩、および銅塩と一座、二座または三座の芳香族または脂肪族のアミンまたはピリジンのリガンドとの触媒的組合せの存在下で反応させる工程を含む、トリフルオロメチル化された非置換または置換のアリールまたはヘテロアリール化合物を製造する方法に関する。
【選択図】なし
Description
C3〜C9−アルキル、C3〜C6−シクロアルキル、アリール、ヘテロアリールの置換基で、ならびにアルコキシ、アルキルチオ、アルケニル、アルキニル、アシル、シアノ、ハロゲンおよびハロアルキルの置換基、ならびにこれらの組合せで置換された、縮合(例えば、ナフチル−、アントリル−、フェナントリル−、ビフェニル−および同等のもの)系を含む、非置換および置換のハロゲン化アリールである。ハロゲンとして、フッ素、臭素、塩素およびヨウ素が可能である。同じ置換基およびこれらの組合せは、ハロゲン化ヘテロアリールまたはハロゲン化縮合ヘテロアリールに使用できる。非置換および置換のヨウ化アリールおよび臭化アリールならびにヨウ化ヘテロアリールおよび臭化ヘテロアリールが好ましい。ヨウ化アリールおよびヨウ化ヘテロアリールが最も好ましい。
の化合物である。Mは、カリウム、ナトリウムまたはリチウムイオン、好ましくはナトリウムまたはカリウムイオンであり得る。
ガラス球またはガラス製容器において、1当量のハロゲン化アリールまたはハロゲン化ヘテロアリール、0.1から0.5当量のCu塩、0.5から2当量の活性化剤、1mmolの基質当たり1mlの溶媒および2から4当量のトリフルオロアセテートをアルゴン下で混合した。この容器は、大型の還流冷却器を備えており、混合物は、撹拌しながら160℃に16時間加熱した。この一定の期間後、反応混合物を室温に冷却した。変換率および収率は、ガスクロマトグラフィーで決定し、生成物の単離は、通常の方法(抽出、蒸留、クロマトグラフィーなど)で行った。
Claims (10)
- 前記式(I)のトリフルオロアセテートが、トリフルオロ酢酸メチルまたはトリフルオロ酢酸エチルである、請求項1に記載の方法。
- 前記式(II)のトリフルオロアセテートが、トリフルオロ酢酸ナトリウムである、請求項1に記載の方法。
- 前記銅塩が、ヨウ化銅、臭化銅、塩化銅、酢酸銅、フッ化銅(II)、四フッ化銅、硫酸銅またはトリフルオロメチルスルホン酸銅の群由来の塩である、請求項1に記載の方法。
- 前記リガンドが、エチレンジアミン、2−ジメチルアミノピリジンまたは1,10−フェナントロリンである、請求項4に記載の方法。
- 前記無機ハロゲン化物塩が、フッ化セシウム、フッ化ルビジウム、フッ化リチウム、フッ化ナトリウム、フッ化カリウム由来の塩であり、前記トリフルオロ酢酸が、トリフルオロ酢酸セシウムである、請求項1に記載の方法。
- 前記反応が、溶媒として、N,N−ジメチルホルムアミド(DMF)、N,N−ジメチルアセトアミドまたはN−メチルピロリドン中で行われる、請求項1に記載の方法。
- 前記反応が、溶媒と一緒に、または溶媒なしで、80〜250℃の温度範囲で行われる、請求項1に記載の方法。
- 前記非置換または置換のアリール化合物が、置換または非置換のヨウ化アリールまたは臭化アリールであり、前記置換または非置換のヘテロアリール化合物が、置換または非置換のヨウ化ヘテロアリールまたは臭化ヘテロアリールである、請求項1に記載の方法。
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EP10189378.2 | 2010-10-29 | ||
EP10189378A EP2447239A1 (en) | 2010-10-29 | 2010-10-29 | Copper-catalysed process for the production of substituted or unsubstituted trifluormethylated aryl and heteroaryl compounds |
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JP2014159384A (ja) * | 2013-02-19 | 2014-09-04 | Nippon Zeon Co Ltd | 1,2−ビス(パーフルオロアルキル)−パーフルオロシクロアルケンの製造方法 |
JP2020529402A (ja) * | 2017-07-28 | 2020-10-08 | ロンザ・リミテッド | 不均一コバルトの触媒反応によるアルキル化又はフルオロ、クロロ及びフルオロクロロアルキル化化合物の調製方法 |
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CN110343047B (zh) * | 2019-07-08 | 2021-03-23 | 四川大学 | 一种氨基芘类化合物的制备方法 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57139025A (en) * | 1981-02-20 | 1982-08-27 | Sagami Chem Res Center | Preparation of aromatic compound having perfluoroalkyl group |
JPS62223183A (ja) * | 1986-02-13 | 1987-10-01 | サンド・アクチエンゲゼルシヤフト | 四環式キナゾリノン類 |
JPH0413651A (ja) * | 1990-05-08 | 1992-01-17 | Daicel Chem Ind Ltd | 4―トリフルオロメチルアニリン誘導体及びその製造法 |
JPH04193856A (ja) * | 1990-11-26 | 1992-07-13 | Tosoh Corp | トリフルオロメチルフェノール誘動体の製造法 |
WO1994001383A1 (fr) * | 1992-07-10 | 1994-01-20 | Rhone Poulenc Chimie | Reactif de perfluoroalcoylation et procede utilisant ce reactif |
JP2008540466A (ja) * | 2005-05-10 | 2008-11-20 | シュトゥディエンゲゼルシャフト・コーレ・ミット・ベシュレンクテル・ハフツング | 脱炭酸反応にてカルボン酸と炭素求電子剤とをc−c結合にて結合させる方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1274838A (en) | 1985-12-12 | 1990-10-02 | Ronny W. Lin | Trifluoromethylation process |
MX2008013999A (es) | 2006-11-06 | 2008-11-12 | Sagami Chem Res | Reactivo de reaccion para trifluorometilacion. |
-
2010
- 2010-10-29 EP EP10189378A patent/EP2447239A1/en not_active Withdrawn
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2011
- 2011-10-25 EP EP11186585.3A patent/EP2447240B1/en not_active Not-in-force
- 2011-10-25 ES ES11186585.3T patent/ES2517393T3/es active Active
- 2011-10-25 PL PL11186585T patent/PL2447240T3/pl unknown
- 2011-10-26 US US13/281,646 patent/US8530666B2/en not_active Expired - Fee Related
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57139025A (en) * | 1981-02-20 | 1982-08-27 | Sagami Chem Res Center | Preparation of aromatic compound having perfluoroalkyl group |
JPS62223183A (ja) * | 1986-02-13 | 1987-10-01 | サンド・アクチエンゲゼルシヤフト | 四環式キナゾリノン類 |
JPH0413651A (ja) * | 1990-05-08 | 1992-01-17 | Daicel Chem Ind Ltd | 4―トリフルオロメチルアニリン誘導体及びその製造法 |
JPH04193856A (ja) * | 1990-11-26 | 1992-07-13 | Tosoh Corp | トリフルオロメチルフェノール誘動体の製造法 |
WO1994001383A1 (fr) * | 1992-07-10 | 1994-01-20 | Rhone Poulenc Chimie | Reactif de perfluoroalcoylation et procede utilisant ce reactif |
JP2008540466A (ja) * | 2005-05-10 | 2008-11-20 | シュトゥディエンゲゼルシャフト・コーレ・ミット・ベシュレンクテル・ハフツング | 脱炭酸反応にてカルボン酸と炭素求電子剤とをc−c結合にて結合させる方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014159384A (ja) * | 2013-02-19 | 2014-09-04 | Nippon Zeon Co Ltd | 1,2−ビス(パーフルオロアルキル)−パーフルオロシクロアルケンの製造方法 |
JP2020529402A (ja) * | 2017-07-28 | 2020-10-08 | ロンザ・リミテッド | 不均一コバルトの触媒反応によるアルキル化又はフルオロ、クロロ及びフルオロクロロアルキル化化合物の調製方法 |
JP7219752B2 (ja) | 2017-07-28 | 2023-02-08 | アークサーダ・アー・ゲー | 不均一コバルトの触媒反応によるアルキル化又はフルオロ、クロロ及びフルオロクロロアルキル化化合物の調製方法 |
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EP2447240A1 (en) | 2012-05-02 |
EP2447239A1 (en) | 2012-05-02 |
US20120245360A1 (en) | 2012-09-27 |
EP2447240B1 (en) | 2014-07-23 |
US8530666B2 (en) | 2013-09-10 |
ES2517393T3 (es) | 2014-11-03 |
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