CN115181005A - Process for producing fluorine-containing compound - Google Patents
Process for producing fluorine-containing compound Download PDFInfo
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- CN115181005A CN115181005A CN202210679598.6A CN202210679598A CN115181005A CN 115181005 A CN115181005 A CN 115181005A CN 202210679598 A CN202210679598 A CN 202210679598A CN 115181005 A CN115181005 A CN 115181005A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 108
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title abstract description 17
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title description 9
- 239000011737 fluorine Substances 0.000 title description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 34
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 23
- 125000000962 organic group Chemical group 0.000 claims abstract description 21
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 7
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 8
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011541 reaction mixture Substances 0.000 claims description 5
- 239000012860 organic pigment Chemical class 0.000 claims description 3
- -1 fluoromethylene group Chemical group 0.000 abstract description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 39
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 13
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 12
- 125000001424 substituent group Chemical group 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- RINSMVSYCNNAGC-UHFFFAOYSA-N [bromo(difluoro)methyl]benzene Chemical compound FC(F)(Br)C1=CC=CC=C1 RINSMVSYCNNAGC-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- DIIWSYPKAJVXBV-UHFFFAOYSA-N Hantzch dihydropyridine Natural products CCOC(=O)C1=CC(C(=O)OCC)=C(C)N=C1C DIIWSYPKAJVXBV-UHFFFAOYSA-N 0.000 description 6
- LJXTYJXBORAIHX-UHFFFAOYSA-N diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1 LJXTYJXBORAIHX-UHFFFAOYSA-N 0.000 description 6
- 125000001072 heteroaryl group Chemical group 0.000 description 6
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000003446 ligand Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 4
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000002252 acyl group Chemical group 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001728 carbonyl compounds Chemical class 0.000 description 4
- IRSJDVYTJUCXRV-UHFFFAOYSA-N ethyl 2-bromo-2,2-difluoroacetate Chemical compound CCOC(=O)C(F)(F)Br IRSJDVYTJUCXRV-UHFFFAOYSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical group 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- XSCHRSMBECNVNS-UHFFFAOYSA-N benzopyrazine Natural products N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- 125000006564 (C4-C8) cycloalkyl group Chemical group 0.000 description 2
- BULLJMKUVKYZDJ-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluoro-6-iodohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)I BULLJMKUVKYZDJ-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- JTYRBFORUCBNHJ-UHFFFAOYSA-N 1-bromo-1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)Br JTYRBFORUCBNHJ-UHFFFAOYSA-N 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000004593 Epoxy Substances 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 125000005279 aryl sulfonyloxy group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000001033 ether group Chemical group 0.000 description 2
- ULNDTPIRBQGESN-UHFFFAOYSA-N ethyl 2-bromo-2-fluoroacetate Chemical compound CCOC(=O)C(F)Br ULNDTPIRBQGESN-UHFFFAOYSA-N 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- WTWWXOGTJWMJHI-UHFFFAOYSA-N perflubron Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)Br WTWWXOGTJWMJHI-UHFFFAOYSA-N 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229930187593 rose bengal Natural products 0.000 description 2
- 229940081623 rose bengal Drugs 0.000 description 2
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PVPBBTJXIKFICP-UHFFFAOYSA-N (7-aminophenothiazin-3-ylidene)azanium;chloride Chemical compound [Cl-].C1=CC(=[NH2+])C=C2SC3=CC(N)=CC=C3N=C21 PVPBBTJXIKFICP-UHFFFAOYSA-N 0.000 description 1
- 125000004454 (C1-C6) alkoxycarbonyl group Chemical group 0.000 description 1
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 1
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 description 1
- FHUDAMLDXFJHJE-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-one Chemical compound CC(=O)C(F)(F)F FHUDAMLDXFJHJE-UHFFFAOYSA-N 0.000 description 1
- DOIVPHUVGVJOMX-UHFFFAOYSA-N 1,10-phenanthroline;ruthenium Chemical compound [Ru].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 DOIVPHUVGVJOMX-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000006039 1-hexenyl group Chemical group 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- 125000006076 2-ethyl-1-butenyl group Chemical group 0.000 description 1
- 125000006040 2-hexenyl group Chemical group 0.000 description 1
- 125000006020 2-methyl-1-propenyl group Chemical group 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- ZCWZXOGWEFPPNJ-UHFFFAOYSA-N 2-pyrimidin-2-ylpyrimidine ruthenium(2+) Chemical compound C1=CN=C(N=C1)C2=NC=CC=N2.C1=CN=C(N=C1)C2=NC=CC=N2.C1=CN=C(N=C1)C2=NC=CC=N2.[Ru+2] ZCWZXOGWEFPPNJ-UHFFFAOYSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- ZPSJGADGUYYRKE-UHFFFAOYSA-N 2H-pyran-2-one Chemical compound O=C1C=CC=CO1 ZPSJGADGUYYRKE-UHFFFAOYSA-N 0.000 description 1
- KKAJSJJFBSOMGS-UHFFFAOYSA-N 3,6-diamino-10-methylacridinium chloride Chemical compound [Cl-].C1=C(N)C=C2[N+](C)=C(C=C(N)C=C3)C3=CC2=C1 KKAJSJJFBSOMGS-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- 125000006041 3-hexenyl group Chemical group 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- MCFBUIIRFZBRCU-UHFFFAOYSA-N 4-[1-[5-[6-(trifluoromethyl)-1h-benzimidazol-2-yl]pyridin-2-yl]piperidin-4-yl]oxycyclohexane-1-carboxylic acid Chemical compound C1CC(C(=O)O)CCC1OC1CCN(C=2N=CC(=CC=2)C=2NC3=CC(=CC=C3N=2)C(F)(F)F)CC1 MCFBUIIRFZBRCU-UHFFFAOYSA-N 0.000 description 1
- 125000006042 4-hexenyl group Chemical group 0.000 description 1
- 125000003119 4-methyl-3-pentenyl group Chemical group [H]\C(=C(/C([H])([H])[H])C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- 125000005947 C1-C6 alkylsulfonyloxy group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FNPNRZLYTIVLNO-UHFFFAOYSA-N Cl(=O)(=O)(=O)O.C1(=C(C(=CC(=C1)C)C)C1C2=CC=CC=C2N(C=2C=CC=CC12)C)C Chemical compound Cl(=O)(=O)(=O)O.C1(=C(C(=CC(=C1)C)C)C1C2=CC=CC=C2N(C=2C=CC=CC12)C)C FNPNRZLYTIVLNO-UHFFFAOYSA-N 0.000 description 1
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
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- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- OTAFHZMPRISVEM-UHFFFAOYSA-N chromone Chemical compound C1=CC=C2C(=O)C=COC2=C1 OTAFHZMPRISVEM-UHFFFAOYSA-N 0.000 description 1
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
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- ZBQZBWKNGDEDOA-UHFFFAOYSA-N eosin B Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC([N+]([O-])=O)=C(O)C(Br)=C1OC1=C2C=C([N+]([O-])=O)C(O)=C1Br ZBQZBWKNGDEDOA-UHFFFAOYSA-N 0.000 description 1
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- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 238000002955 isolation Methods 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
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- 239000011159 matrix material Substances 0.000 description 1
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- 229910052753 mercury Inorganic materials 0.000 description 1
- LWJROJCJINYWOX-UHFFFAOYSA-L mercury dichloride Chemical compound Cl[Hg]Cl LWJROJCJINYWOX-UHFFFAOYSA-L 0.000 description 1
- 125000005948 methanesulfonyloxy group Chemical group 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 125000001715 oxadiazolyl group Chemical group 0.000 description 1
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- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
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- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004742 propyloxycarbonyl group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000002151 riboflavin Substances 0.000 description 1
- 235000019192 riboflavin Nutrition 0.000 description 1
- 229960002477 riboflavin Drugs 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000005930 sec-butyloxycarbonyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 125000001113 thiadiazolyl group Chemical group 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- PTMFUWGXPRYYMC-UHFFFAOYSA-N triethylazanium;formate Chemical compound OC=O.CCN(CC)CC PTMFUWGXPRYYMC-UHFFFAOYSA-N 0.000 description 1
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
- C07C17/275—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions of hydrocarbons and halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C22/00—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom
- C07C22/02—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings
- C07C22/04—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings
- C07C22/08—Cyclic compounds containing halogen atoms bound to an acyclic carbon atom having unsaturation in the rings containing six-membered aromatic rings containing fluorine
-
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- 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
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
- C07C43/14—Unsaturated ethers
- C07C43/17—Unsaturated ethers containing halogen
- C07C43/174—Unsaturated ethers containing halogen containing six-membered aromatic rings
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—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
- 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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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—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
- 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
- C07C67/347—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 by addition to unsaturated carbon-to-carbon bonds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
- C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds
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- C07C69/608—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a ring other than a six-membered aromatic ring in the acid moiety
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- C07C69/612—Esters of carboxylic acids having a carboxyl group bound to an acyclic carbon atom and having a six-membered aromatic ring in the acid moiety
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- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
- C07C69/675—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids of saturated hydroxy-carboxylic acids
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention addresses the problem of providing a novel method for efficiently producing a compound having a fluoromethylene group. The above object is achieved by a production method of formula (1) [ wherein R 1 Represents an organic group, R X Represents a hydrogen atom or a fluorine atom, and R 2a 、R 2b 、R 2c And R 2d The same or different, represent-Y-R 21 or-N (-R) 22 ) 2 Or R is 2b And R 2c May be linked to form a valence bond, Y represents a valence bond, an oxygen atom or a sulfur atom, R 21 Represents a hydrogen atom or an organic group, R 22 Identical or different at each occurrence and denotes a hydrogen atom or an organic group.]A process for producing a compound represented by the formula (2), or a ring-closed derivative or ring-opened derivative thereof, which comprises reacting a compound represented by the formula (2) wherein X represents a leaving group and the other symbols have the same meanings as defined above.]The compound is represented by the formula (3) [ wherein the symbols represent the same meanings as described above ] in the presence of a reducing agent and under irradiation with light.]Step A of reacting the compound shown.
Description
(divisional application of 201780016314.2 entitled "method for producing fluorine-containing Compound" filed 3/8/2017.)
Technical Field
The present invention relates to a method for producing a fluorine-containing compound, particularly a compound having a fluoromethylene group.
Background
Since a compound containing a fluoromethylene group is present as a physiologically active substance in a living body, the application of a compound having a fluoromethylene group to a pharmaceutical or the like has been actively studied.
For example, a method for producing a fluorine-containing methylene compound such as an α -fluoromethylene compound and an α -difluorohydroxyaldehyde compound, which is a carbonyl compound having 1 or more substituents selected from a fluorine atom and a perfluoroorganic group at the α -position, is highly useful (non-patent documents 1 and 2).
As a method for producing a carbonyl compound having 1 or more substituents selected from a fluorine atom and a perfluoro organic group at the α -position, there have been few reports of a method for producing a starting material of a trifluoroketone or a carbonyl compound which is a fluorine-containing carbonyl compound and which is easy to start with, and there is a demand for an efficient and simple production method using the starting material.
In non-patent document 3, the α -difluoroaldol compound is obtained from trifluoromethylacetone, but a 5-stage process is required. In addition, since thiophenol is used as a reagent, a highly toxic reagent such as mercuric chloride is required for removing sulfur from the reaction system, and the reaction operation is complicated.
In non-patent document 4, in the presence of trifluoromethanone trimethylsilylchloride, 2,2-difluoroenolsilyl ether obtained by selectively cleaving the carbon-fluorine bond in trifluoromethanone with magnesium was reacted with benzaldehyde to obtain an α -difluorohydroxyaldehyde compound, but 3 stages of reaction steps were required and a large amount of reagents were required for the reaction substrate, and thus there was room for improvement in terms of yield and the like.
In any of the above methods, since an inorganic salt is also produced as a by-product, a step for removing the inorganic salt is required, and further improvement or a novel production method is required from the viewpoints of production cost, reaction efficiency, simplicity, and the like.
Non-patent document 5 discloses an intermolecular addition reaction of a halogenated sugar group to an olefin substituted with an electron-withdrawing group, using a compound containing no fluorine as a base and an amine and Hantzsch Ester (Hantzsch Ester) as an auxiliary agent, through the medium of visible light.
On the other hand, non-patent document 6 discloses a method for producing a compound having a fluoromethylene group, using a compound containing no fluorine as a substrate.
Documents of the prior art
Non-patent document
Non-patent document 1: john T.Welch et al, tetrahedron,1987, pages 43, 14, 3123
Non-patent document 2: svante et al, J.Am.chem.Soc.,1981, page 103, 4452
Non-patent document 3: in Howa et al, synthetic Communications,1999, 29 (2), page 235
Non-patent document 4: amii et al, chem. Commun.,1999, page 1323
Non-patent document 5: andrews et al, angel, chem, int, ed, 2010, page 49, 7274
Non-patent document 6: yu et al, chem. Commun.,2014, page 50, 12884
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a novel method for efficiently producing a compound having a fluoromethylene group.
Means for solving the problems
As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by a production method of a compound represented by formula (1), or a closed ring derivative or an open ring derivative thereof [ in the present specification, it may be referred to as compound (1) ]. A production method comprising reacting a compound represented by formula (2) [ herein, the compound may be referred to as a compound (2) ]. And a compound represented by formula (3) [ in the present specification, the compound is sometimes referred to as a compound (3) ] in the presence of a reducing agent and under irradiation with light. Step a of the reaction.
Formula (1):
[ in the formula,
R 1 represents an organic group, and represents an organic group,
R X represents a hydrogen atom or a fluorine atom, and
R 2a 、R 2b 、R 2c and R 2d Identical or different, represent-Y-R 21 or-N (-R) 22 ) 2 Or R is 2b And R 2c Can be linked to form a valence bond,
y represents a bond, an oxygen atom or a sulfur atom,
R 21 represents a hydrogen atom or an organic group,
R 22 the same or different at each occurrence represents a hydrogen atom or an organic group.]
Formula (2):
[ in the formula, X represents a leaving group, and the other symbols represent the same meanings as described above. ]
Formula (3):
[ in the formula, the symbols have the same meanings as described above. ]
The present invention includes the following aspects.
Item 1.
A process for producing a compound represented by the formula (1), or a ring-closed derivative or ring-opened derivative thereof, which comprises a step A of reacting a compound represented by the formula (2) with a compound represented by the formula (3) in the presence of a reducing agent and under irradiation with light,
[ in the formula,
R 1 represents an organic group, and is a compound represented by the formula,
R X represents a hydrogen atom or a fluorine atom, and
R 2a 、R 2b 、R 2c and R 2d The same or different, represent-Y-R 21 or-N (-R) 22 ) 2 Or R is 2b And R 2c Can be linked to form a valence bond,
y represents a bond, an oxygen atom or a sulfur atom,
R 21 represents a hydrogen atom or an organic group,
R 22 the same or different at each occurrence represents a hydrogen atom or an organic group.]
Formula (2):
[ in the formula, X represents a leaving group, and the other symbols represent the same meanings as described above. ]
Formula (3):
[ in the formula, the symbols have the same meanings as described above. ]
Item 2.
The production process according to item 1, wherein R 1 Is alkyl, fluoroalkyl, alkoxycarbonyl or an aromatic group.
And (4) item 3.
The production process according to item 1 or 2, wherein R 2a Is alkyl or aryl, and R 2b 、R 2c And R 2d Is a hydrogen atom.
Item 4.
The production process according to any one of claims 1 to 3, wherein X is a bromine atom.
Item 5.
The production process according to any one of claims 1 to 4, wherein the reaction in the step A is carried out in the presence of a nitrogen-containing unsaturated heterocyclic compound having an N-H moiety.
Item 6.
The production process according to any one of the above 1 to 5, wherein,
the reducing agent is a compound represented by the formula (4),
formula (4):
[ in the formula,
R 3a 、R 3b 、R 3c and R 3d The same or different, represent an alkyl group.]
Item 7.
The production method according to any one of claims 1 to 6, wherein the reaction in the step A is carried out in the presence of a catalyst.
Item 8.
The production process according to item 7, wherein the catalyst is at least 1 kind selected from the group consisting of a transition metal complex and an organic dye compound.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a novel method for efficiently producing a compound having a fluoromethylene group can be provided.
Detailed Description
Chinese phrases
The symbols and the omission symbols in the present specification are not particularly limited, and may be understood as meaning generally used in the technical field to which the present invention belongs, from the front and the rear of the present specification, unless otherwise specified.
In this specification, the term "including" is used to include the term "essentially" and the term "consisting of \8230; constitution".
The steps, treatments, or operations described in the present specification may be performed at room temperature unless otherwise specified.
In the present specification, room temperature means a temperature in the range of 10 to 40 ℃.
In the present specification, "Cn-m" (where n and m are natural numbers, respectively) represents a carbon number of n or more and m or less as is commonly used in the field of organic chemistry.
In the present specification, "fluoromethylene group" includes, unless otherwise specified, a monofluoromethylene group and a difluoromethylene group.
In the present specification, unless otherwise specified, examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
In the present specification, unless otherwise specified, "organic group" means a group containing 1 or more carbon atoms as constituent atoms.
In the present specification, unless otherwise specified, examples of the "organic group" include a hydrocarbon group, a cyano group, a carboxyl group, an alkoxy group, an ester group, an ether group, and an acyl group.
In the present specification, unless otherwise specified, "hydrocarbon group" means a group containing 1 or more carbon atoms and 1 or more hydrogen atoms as its constituent atoms.
In the present specification, unless otherwise specified, the "hydrocarbon group" may include aliphatic hydrocarbon groups, aromatic hydrocarbon groups (aryl groups), combinations thereof, and the like.
In the present specification, unless otherwise specified, the "aliphatic hydrocarbon group" may be linear, branched, cyclic, or a combination thereof.
In the present specification, the "aliphatic hydrocarbon group" can be saturated or unsaturated unless otherwise specified.
In the present specification, unless otherwise specified, examples of the "aliphatic hydrocarbon group" include an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl group.
In the present specification, unless otherwise specified, examples of the "alkyl group" include linear or branched alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl groups.
In the present specification, a "fluoroalkyl group" is an alkyl group in which at least 1 hydrogen atom is replaced with a fluorine atom.
In the present specification, the number of fluorine atoms in the "fluoroalkyl group" may be 1 or more (for example, 1 to 3, 1 to 6, 1 to 12, 1 to the maximum number that can be substituted).
"fluoroalkyl" includes perfluoroalkyl. "perfluoroalkyl" is an alkyl group in which all hydrogen atoms have been replaced with fluorine atoms.
In the present specification, unless otherwise specified, examples of the "alkenyl group" include straight-chain or branched-chain alkenyl groups having 1 to 10 carbon atoms such as vinyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-ethyl-1-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl and 5-hexenyl groups.
In the present specification, unless otherwise specified, examples of the "alkynyl group" include straight-chain or branched alkynyl groups having 2 to 6 carbon atoms such as an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-pentynyl group, a 2-pentynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-hexynyl group, a 2-hexynyl group, a 3-hexynyl group, a 4-hexynyl group and a 5-hexynyl group.
In the present specification, unless otherwise specified, examples of the "cycloalkyl group" include cycloalkyl groups having 3 to 10 carbon atoms (preferably 4 to 10 carbon atoms) such as cyclopentyl, cyclohexyl, and cycloheptyl groups.
In the present specification, unless otherwise specified, "alkoxy" is, for example, a group represented by RO- (in the formula, R is an alkyl group).
In the present specification, unless otherwise specified, "ester group" is, for example, RCO 2 - (in the formula, R is an alkyl group).
In the present specification, unless otherwise specified, "ether group" means a group having an ether bond (-O-) and includes a polyether group. The polyether group comprises the formula: ra- (O-Rb) n- (wherein Ra represents an alkyl group, rb represents an alkylene group and n represents an integer of 1 or more, which may be the same or different at each occurrence) -. The alkylene group is a 2-valent group formed by removing 1 hydrogen atom from the above alkyl group.
In the present specification, "acyl" includes alkanoyl unless otherwise specified. In the present specification, unless otherwise specified, "alkanoyl" is, for example, a group represented by RCO- (in the formula, R is an alkyl group).
In the present specification, unless otherwise specified, "aromatic group" includes aryl and heteroaryl groups.
In the present specification, examples of the "aryl group" include C6-10 aryl groups such as phenyl and naphthyl.
In the present specification, examples of the "heteroaryl group" include a 5-to 14-membered (monocyclic, 2-ring, or 3-ring) heterocyclic group containing 1 to 4 heteroatoms selected from a nitrogen atom, a sulfur atom, and an oxygen atom in addition to carbon atoms as ring-constituting atoms.
In the present specification, specific examples of "heteroaryl" include:
(1) Monocyclic aromatic heterocyclic groups such as furyl, thienyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, and triazinyl; and
(2) Polycyclic (e.g., bicyclic) aromatic heterocyclic groups such as quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzimidazolyl, benzotriazolyl, indolyl, indazolyl, pyrrolopyrazinyl, imidazopyridinyl, imidazopyrazinyl, imidazothiazolepyrazolyl, pyrazolylthiophenyl, pyrazolotriazinyl, and the like.
Manufacturing method
The method for producing a compound represented by formula (1), or a ring-closed derivative or ring-opened derivative thereof, according to the present invention comprises a step A of reacting a compound represented by formula (2) with a compound represented by formula (3) in the presence of a reducing agent and under irradiation with light.
Formula (1):
[ in the formula,
R 1 represents an organic group, and is a compound represented by the formula,
R X represents a hydrogen atom or a fluorine atom, and
R 2a 、R 2b 、R 2c and R 2d The same or different, represent-Y-R 21 or-N (-R) 22 ) 2 Or R is 2b And R 2c Can be linked to form a valence bond,
y represents a bond, an oxygen atom or a sulfur atom,
R 21 represents a hydrogen atom or an organic group,
R 22 the same or different at each occurrence represents a hydrogen atom or an organic group.]
Formula (2):
[ in the formula, X represents a leaving group, and the other symbols represent the same meanings as described above. ]
Formula (3):
[ in the formula, the symbols have the same meanings as described above. ]
The symbols in the above chemical formulae are explained below.
R 1 Preferred examples of the "organic group" shown include alkyl groups, fluoroalkyl groups, alkoxycarbonyl groups and aromatic groups.
R 1 More preferred examples of the "organic group" shown include fluoroalkyl groups.
Examples of the above-mentioned "alkoxycarbonyl group" include C1-6 alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentabutoxycarbonyl, isopentoxycarbonyl, hexyloxycarbonyl and the like.
Preferred examples of the "aromatic group" include aryl groups, and more preferred examples include C6-10 aryl groups such as phenyl and naphthyl groups.
R X Preferably a fluorine atom.
R 2b And R 2c When a bond is formed by linkage, as is readily understood by those skilled in the art, the structure of formula (1) is a structure of the following chemical formula,
the structure of formula (3) is represented by the following chemical formula.
R 2a 、R 2b 、R 2c And R 2d 1 or more of these can be suitably electron donating groups.
In a preferred embodiment of the present invention, R is 2a 、R 2b 、R 2c And R 2d Can have more than 1 ofA hydrocarbon group having 1 or more substituents.
Examples of such substituents include:
a heteroaryl group which may have 1 or more substituent (more preferably a 5-to 18-membered heteroaryl group which may have 1 or more substituent),
A sulfide group which may have 1 or more substituent groups, and
a silazane group which may have 1 or more substituents.
Preferred examples of the "substituent" in the "heteroaryl group which may have 1 or more substituents", "sulfide group which may have 1 or more substituents" and "silazane group which may have 1 or more substituents" include a halogen atom (preferably fluorine), a cyano group, an amino group, an alkoxy group, a perfluoroorganic group (preferably a perfluoroorganic group having 1 to 8 carbon atoms, more preferably a trifluoromethyl group), and a pentafluoromercapto group (F) 5 S-)。
In a preferred embodiment of the present invention, R is 2a 、R 2b 、R 2c And R 2d At least 1 of them may be an unsubstituted hydrocarbon group (preferably a hydrocarbon group having 1 to 10 carbon atoms).
Preferred examples of the "hydrocarbon group" include alkyl groups (preferably C1-10 alkyl groups), cycloalkyl groups (preferably C3-10, preferably C4-8 cycloalkyl groups), and aryl groups (preferably C6-10 aryl groups).
In a more preferred embodiment of the present invention, R is 2a Is alkyl or aryl, and R 2b 、R 2c And R 2d Is a hydrogen atom.
Examples of the leaving group represented by X include:
halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom and iodine atom), alkylsulfonyloxy groups (e.g., C1-6 alkylsulfonyloxy groups such as methanesulfonyloxy group, trifluoromethanesulfonyloxy group and the like), and
arylsulfonyloxy (e.g., C6-10 arylsulfonyloxy such as phenylsulfonyloxy, p-toluenesulfonyloxy, etc.).
More preferred examples of X include a halogen atom.
Further preferred examples of X include a chlorine atom, a bromine atom and an iodine atom.
Still further preferred examples of X include a bromine atom.
In a preferred embodiment of the present invention,
R 1 is a fluoroalkyl, alkoxycarbonyl or aryl radical,
R X is a fluorine atom, and is a fluorine atom,
R 2a 、R 2b 、R 2c and R 2d The same or different, is an alkyl group (preferably a C1-10 alkyl group), a cycloalkyl group (preferably a C3-10 cycloalkyl group, more preferably a C4-8 cycloalkyl group), or an aryl group (preferably a C6-10 aryl group), and
x is a bromine atom.
The amount of the compound (3) used in the step a is preferably in the range of 0.5 to 10 mol, more preferably in the range of 1 to 8 mol, and still more preferably in the range of 1.2 to 6 mol, based on 1mol of the compound (2).
When the compound (3) has 1 or more carbon-carbon double bonds in addition to the carbon-carbon double bond represented by the structural formula of the formula (3), the compound (1) can be a ring-closed derivative of the compound represented by the formula (1) through a ring-closing reaction. The ring formed by this ring closure reaction can preferably be a 5-to 7-membered ring. The ring formed by the ring-closure reaction may be a heterocyclic ring containing 1 or more (preferably 1 or 2) heteroatoms selected from nitrogen atoms, sulfur atoms and oxygen atoms in addition to carbon atoms as a carbocyclic ring or a ring-constituting atom.
R 2a In the case of an epoxy group (that is, in the case where the compound (3) is an epoxy compound), the compound (1) can be a ring-opened derivative of the compound represented by the above formula (1) (that is, an epoxy ring-opened derivative) by a ring-opening reaction.
The reaction in step A is carried out in the presence of a reducing agent.
The above-mentioned reducing agent used in the present invention can be an inorganic or organic reducing agent, and examples thereof include hydrogen, formic acid, ammonium formate, sodium formate, formic acid-triethylamine, triethylsilane, tetramethyldisiloxane, polymethylhydroxysiloxane, naBH 3 CN、NHCBH3(N-heterocyclic carbene boranes:N-heterocyclic carbene boranes) and nitrogen-containing unsaturated heterocyclic compounds having N-H moieties (imino groups).
Preferred examples of the reducing agent that can be used in the present invention include nitrogen-containing unsaturated heterocyclic compounds having an N-H moiety.
Preferable examples of the "nitrogen-containing unsaturated heterocyclic compound having an N — H moiety" as the reducing agent that can be used in the present invention include compounds represented by formula (4) [ in the present specification, may be referred to as compound (4). ]
Formula (4):
[ in the formula,
R 3a 、R 3b 、R 3c and R 3d Identical or different, represents an alkyl group.]
R 3a Preferably a C1-6 alkyl group, more preferably a methyl or ethyl group.
R 3b Preferably a C1-6 alkyl group, more preferably a methyl or ethyl group.
R 3c Preferably a C1-6 alkyl group, more preferably a methyl or ethyl group.
R 3d Preferably a C1-6 alkyl group, more preferably a methyl or ethyl group.
More preferable examples of the reducing agent that can be used in the present invention include compounds of the following chemical formula. These compounds are the so-called Hantzsch esters (Hantzsch esters).
Since the halogenated alkane derivative containing the compound (2) is easily oxidized according to the common technical knowledge in the field of organic chemistry, a reducing agent such as Hantzsch Ester is directly subjected to a redox reaction with the halogenated alkane derivative, and therefore, the reaction in the step a does not proceed, and the compound (1) cannot be obtained. However, surprisingly, the reaction of step a proceeds well in the presence of compound (4) containing Hantzsch Ester (Hantzsch Ester). The results are exemplified in the examples.
These reducing agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
In the reaction in step A, an acid scavenger such as an amine can be used as desired.
When the compound (4) is used, other amines can be preferably used.
When the reducing agent is used in step a, the amount thereof is preferably in the range of 0.5 to 10 moles, more preferably in the range of 1.0 to 5.0 moles, and still more preferably in the range of 1.2 to 3.0 moles, based on 1 mole of the compound represented by formula (2) as the substrate.
The reaction in the step A can be carried out in the presence of a catalyst, or in the substantial absence or complete absence of a catalyst.
The reaction in step A is preferably carried out in the presence of a catalyst.
Examples of the above catalyst that can be used in the present invention include transition metal complexes and organic pigment compounds.
Examples of the central metal species of the transition metal complex compound that can be used in the present invention include cobalt, ruthenium, rhodium, rhenium, iridium, nickel, palladium, osmium, and platinum.
Preferred examples of the central metal species include ruthenium, iridium and palladium.
Examples of the ligand of the transition metal complex compound that can be used in the present invention include a nitrogen-containing compound, an oxygen-containing compound, and a sulfur-containing compound.
Examples of the "nitrogen-containing compound" as a ligand include diamine compounds (e.g., ethylenediamine) and nitrogen-containing heterocyclic compounds (e.g., pyridine, bipyridine, phenanthroline, pyrrole, indole, carbazole, imidazole, pyrazole, quinoline, isoquinoline, acridine, pyridazine, pyrimidine, pyrazine, phthalazine, quinazoline, and quinoxaline).
Examples of such "oxygen-containing compounds" as the ligand include diketones (e.g., ditivaloylmethane) and oxygen-containing heterocyclic compounds (e.g., furan, benzofuran, oxazole, pyran, pyrone, coumarin, and benzopyrone).
Examples of such "sulfur-containing compounds" as the ligand include sulfur-containing heterocyclic compounds (e.g., thiophene, thianaphthene, and thiazole).
In the above-mentioned transition metal complex, the number of these ligands may be 1 or more. However, the number of them is not necessarily clear.
When a catalyst is used in the reaction in step a, the amount of the catalyst used in step a is preferably in the range of 0.0001 to 0.1 mol, more preferably in the range of 0.001 to 0.05 mol, and still more preferably in the range of 0.005 to 0.02 mol, based on 1mol of the compound (2).
The organic dye compound that can be used in the present invention may be a compound containing no metal atom in the molecule.
Examples of such organic pigment compounds include rose bengal (rose bengal), erythrosine, eosin (e.g., eosin B, eosin Y), acriflavine, riboflavin, and thionine.
A preferred example of the catalyst comprises [ Ir { dF (CF) 3 )ppy} 2 (dtbpy)]PF 6 、[Ir(dtbbpy)(ppy) 2 ][PF 6 ]、Ir(ppy) 3 、Ru(bpy) 3 Cl 2 ·6H 2 O、[Ru(bpz) 3 ][PF 6 ] 2 、[Ru(bpm) 3 ][Cl] 2 、[Ru(bpy) 2 (phen-5-NH 2 )][PF 6 ] 2 、[Ru(bpy) 3 ][PF 6 ] 2 、Ru(phen) 3 Cl 2 、Cu(dap) 2 Chloride, 9-mesityl-10-methylacridine perchlorate, ir (ppy) 3 And Pd (PPh) 3 ) 4 。
These catalysts may be used alone in 1 kind, or may be used in combination of 2 or more kinds.
The catalyst used in step a is preferably a photoredox (phorodedox) catalyst.
The catalyst used in the step a may be supported on a carrier (for example, zeolite).
The reaction in step A can be carried out in the presence of a solvent or in the substantial absence or complete absence of a solvent.
The reaction of step A is preferably carried out in the presence of a solvent.
Examples of the above solvent which can be used in the present invention include Dimethylformamide (DMF), toluene, CH 3 CN, ether, tetrahydrofuran (THF), benzene, dimethyl sulfoxide (DMSO), hexane, and phenylchloroform (BTF).
These solvents may be used alone in 1 kind, also can be combined with more than 2 kinds.
At the start of the reaction in the step A, the concentration of the compound (2) in the reaction mixture is preferably in the range of 1 to 10000mM, more preferably in the range of 10 to 1000mM, and still more preferably in the range of 50 to 200 mM.
At the start of the reaction in the step A, the concentration of the compound (3) in the reaction mixture is preferably in the range of 5 to 50000mM, more preferably in the range of 50 to 5000mM, and still more preferably in the range of 250 to 1000 mM.
When a catalyst is used in the reaction in the step A, the concentration of the catalyst in the reaction mixture is preferably in the range of 0.01 to 100mM, more preferably in the range of 0.1 to 10mM, and still more preferably in the range of 0.5 to 2 mM.
The step a can be carried out by, for example, mixing the compound (2) and the compound (3), a reducing agent as desired, a catalyst as desired, and a solvent as desired.
The mixing method can be a conventional method.
The mixing may be performed by mixing all the substances at the same time, or may be performed sequentially or stepwise.
The reaction in step A is carried out under light irradiation.
The irradiation light used for the light irradiation is not particularly limited, and any light may be used as long as it causes and/or accelerates the reaction in step a. Examples of the light source include a low-pressure, medium-pressure or high-pressure mercury lamp, a tungsten lamp, and a Light Emitting Diode (LED).
The irradiation light can preferably be visible light.
The irradiation light may preferably be light including light having a wavelength of 300 to 600nm, and more preferably light including light having a wavelength of 400 to 500 nm.
The irradiation time can be preferably in the range of 1 to 24 hours, more preferably 10 to 18 hours.
The initiation of the light irradiation can be before, during, simultaneously with, or after the above-mentioned mixing.
The intensity of the light irradiation may be set to a level sufficient to supply energy for initiating and/or promoting the reaction in the step a, and these may be appropriately adjusted by adjusting the output of the light source, the distance between the light source and the reaction system in the step a, and the like, based on the technical common knowledge, for example, so that the reaction in the step a is appropriately performed.
The reaction in step A may be carried out in the presence of an inert gas. Examples of such inert gases include nitrogen and argon.
The reaction temperature in the step A is preferably in the range of 0 to 120 ℃, more preferably in the range of 10 to 80 ℃, and still more preferably in the range of 20 to 60 ℃.
If the reaction temperature is too low, the reaction in step A may be insufficient.
When the reaction temperature is too high, the cost is unfavorable, and there is a fear that an undesired reaction occurs.
The reaction time in the step A is preferably in the range of 1 to 24 hours, more preferably in the range of 5 to 18 hours, and still more preferably in the range of 10 to 15 hours.
If the reaction time is too short, the reaction in step A may be insufficient.
If the reaction time is too long, the cost is disadvantageous, and an undesirable reaction may occur.
The reaction in the step A can be suitably carried out by a batch system or a fluidized system.
The compound (1) obtained by the production method of the present invention can be purified by a known purification method such as solvent extraction, drying, filtration, distillation, concentration, or a combination thereof, as desired.
According to the production method of the present invention, the conversion of the compound (2) as a raw material can be preferably 40% or more, more preferably 60% or more, and further preferably 80% or more.
According to the production method of the present invention, the selectivity of the compound (1) can be preferably 70% or more, more preferably 80% or more.
According to the production method of the present invention, the yield of the compound (1) can be preferably 40% or more, more preferably 60% or more.
The compound (1) obtained by the production method of the present invention can be used, for example, for pharmaceutical intermediates.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the following examples, the yield is an isolated yield unless otherwise specified.
Example 1
In the vessel (1), ru (bpy) as a photo-redox catalyst was added 3 Cl 2 ·6H 2 O (7.5mg, 1mol%) and Hans ester a (380.7mg, 1.5mmol) were dissolved in DMF (5 mL), and (bromodifluoromethyl) benzene (206.6 mg, 1.0mmol), 1-octene (0.78mL, 5.0mmol) and Et were added 3 N (201.0 mg, 1.99mmol) and DMF (5 mL) were replaced with Ar, and the mixture was stirred for 12 hours under irradiation of a white lamp.
After the reaction, 40mL of a solution of EtOAc/hexane =9/1 was added to the solution, and the organic layer was washed 3 times with 20mL of pure water and 1 time with 30mL of saturated brine. After the organic layer was then dehydrated, filtered and dried, 1-difluoro-phenyl-nonane (151.6 mg, yield 63%) was obtained by silica gel column chromatography (developing solvent: hexane).
(2) The same reaction as in the above (1) was carried out, except that the photo-redox catalyst was not used.
(3) In addition, except that Et is not used 3 Except for N, the same reaction as in the above reaction (1) was carried out.
The results are shown in the table below. From this, it can be understood that when the photo-oxidation-reduction catalyst is used, the conversion rate is increased. In Et 3 In both cases of the presence and absence of N, the reaction proceeds well.
[ Table 1]
a Undecane was used as an internal standard, determined by GC
b NMR yield
(4)
Compound (1) in the following table was obtained in the same manner as in (1) above, except that compound (2) and compound (3) in the following table were used. Together with the results of (1) above, these results are shown in the following table.
[ Table 2]
a The ratio of (compound (1)/other compound) is obtained based on the isolation yield.
(5) In the reactions (1) to (4) described above, it was confirmed that, with respect to a part of the starting material compounds (the following table), in addition to the target compound a [ compound (1) ], a bromine atom-moving body b, a reduced adduct c in which an olefin 2 molecule participates, and a bromine atom-moving body d in which an olefin 2 molecule participates were obtained at the same time. In the following table, the yield and the GC area ratio of the compounds a, b, c and d are shown, respectively.
(R in each formula corresponds to R 2a 。)
[ Table 3]
Example 2
The reaction of example 1 (1) was carried out in the same manner as in example 1 (1) but under the conditions shown in the following table. The results are shown in the following table.
[ Table 4]
a Undecane was used as an internal standard, determined by GC.
Example 3
In the same manner as in example 1 (1), in a vessel were charged (bromodifluoromethyl) benzene (1.0 mmol), 1-octene (5.0 mmol), and the photoredox catalysts shown in the following table [ 1mol% or 0mol% relative to (bromodifluoromethyl) benzene ]]Hans ester a (1.5 mmol), et 3 After Ar substitution with N (2.0 mmol) and DMF (10 mL), the mixture was stirred for 12 hours while being irradiated with light from a light source shown in the following Table. As a white lamp, a white LED (5W) was used. As a fluorescent lamp, SOLARBOX 1500e (co.fo.me.gra company, xenon lamp, soda lime glass UV filter) was used.
After the reaction, 40mL of a solution of EtOAc/hexane =9/1 was added to the solution, and the organic layer was washed 3 times with 20mL of pure water and 1 time with 30mL of saturated brine. Thereafter, the organic layer was dehydrated, filtered and dried, followed by silica gel column chromatography (developing solvent: hexane) to give 1, 1-difluoro-phenylnonane.
The conversion and GC yields are shown in the table below.
[ Table 5]
a Undecane was used as an internal standard, determined by GC
Example 4
In the same manner as in example 1 (1), a vessel was charged with ethyl 2-bromo-2, 2-difluoroacetate (1.0 mmol), 1-butene (amount shown in the following table), ru (bpy) 3 Cl 2 ·6H 2 O [ 1.0mol% relative to ethyl 2-bromo-2, 2-difluoroacetate ]]Hans ester a (1.5 mmol), et 3 N (1.0 mmol) and DMF (5 mL) were replaced with Ar, followed by stirring under white light for 12 hours.
The solution after the reaction was purified by the same method as in example 1 (1), whereby compound 4A was obtained.
The yields and GC yields are shown in the following table.
[ Table 6]
Example 5
In the same manner as in example 1 (1), perfluorohexyl bromide was charged into a vessel5(1.0 mmol), 1-octene (amount in the table below), ru (bpy) 3 Cl 2 ·6H 2 O [ relative to perfluorohexyl bromide5Is 1mol%]Hans ester a (1.5 mmol), et 3 After Ar substitution of N (1.0 mmol) and DMF (5 mL), the mixture was stirred for 12 hours under irradiation with a white lamp.
The reaction solution was purified by the same method as in example 1 (1) to obtain compound 5A.
The yields and GC yields are shown in the following table.
As shown above, when the amount of 1-octene is increased from 5 molar equivalents to 20 molar equivalents, the yield of compound 5A increases, but at the same time, by-products (compound 5B, compound 5C) in which 2 molecules of 1-octene are added are produced, and the selectivity of compound 5A decreases.
[ Table 7]
Example 6
In the same manner as in example 1 (1), ethyl bromofluoroacetate (1.0 mmol), 1-octene (5, 10, or 20 molar equivalents relative to ethyl bromofluoroacetate), and Ru (bpy) were charged in a vessel 3 Cl 2 ·6H 2 O [ 1mol% relative to bromofluorinated ethyl acetate ]]Hans ester a (1.5 mmol), et 3 N (1.0 mmol) and DMF (5 mL) were replaced with Ar, and the mixture was stirred for 12 hours under irradiation with a white lamp.
The reaction solution was purified by the same method as in example 1 (1) to obtain compound 6A.
The yields and GC yields are shown in the following table
As shown above, when the amount of 1-octene was increased from 5 molar equivalents to 20 molar equivalents, the yield of compound 6A increased.
[ Table 8]
Example 7
In the same manner as in example 1 (1), perfluorohexyl iodide was charged into a vessel7(1.0 mmol), 1-octene (5.0 mmol), ru (bpy) 3 Cl 2 ·6H 2 O [ vs. perfluorohexyl iodide7Is 1.0mol%]Hans ester a (1.5 mmol), et 3 N (0, or 2.0 mmol) and DMF (5 to 10 mL) were Ar-substituted and then stirred under white lamp irradiation for 12 hours.
The solution after the reaction was purified by the same method as in example 1 (1), whereby compound 7A was obtained.
The conversion rates are all 100%.
The yields and GC yields are shown in the following table.
As shown above, compound 7A was obtained in good yield regardless of the presence of triethylamine.
[ Table 9]
Example 8
In the same manner as in example 1 (1), perfluorooctylbromide was charged into a vessel8(1.0mmol)、Ru(bpy) 3 Cl 2 ·6H 2 O [ with respect to perfluorooctylbromide8Is 1.0mol%]1-octene (20 mmol), hantzsch ester a (1.5 mmol), et 3 N (0, or 2.0 mmol) and DMF (5 to 10 mL) were replaced with Ar and stirred under white light for 12 hours.
The solution after the reaction was purified by the same method as in example 1 (1), to obtain a fluorine compound 8A.
The yields are shown in the following table.
[ Table 10]
Example 9
In the same manner as in example 1 (1), a vessel was charged with (bromodifluoromethyl) benzene (1.0 mmol), vinylnitrile (5.0 mmol), and Ru (bpy) 3 Cl 2 ·6H 2 O [ 1.0mol% relative to (bromodifluoromethyl) benzene ]]Hans ester a (1.5 mmol), et 3 N (1.0 mmol) and DMF (5 mL) were replaced with Ar, and the mixture was stirred for 12 hours under irradiation of a white lamp.
The solution after the reaction was purified by the same method as in example 1 (1) to obtain compound 8A.
The yield thereof was found to be 77%.
Example 10 (reaction in flow System 1)
In Ru (bpy) 3 Cl 2 ·6H 2 O [ 1.0mol% relative to ethyl 2-bromo-2, 2-difluoroacetate ]]Hans ester a (1.5 mmol), et 3 The reaction of ethyl 2-bromo-2, 2-difluoroacetate (1.0 mmol) with 1-octene (5.0 mmol) was carried out in a flow system in the presence of N (2.0 mmol) and DMF (10 ml) using a photo-microreactor (white lamp (white LED) irradiation) having a flow path of 1mm width, 300 μm depth and 2.35m length.
As a result, compound 10A was obtained with a retention time of 30 minutes and a yield of 56%.
Example 11 (reaction in flow System 2)
In Ru (bpy) 3 Cl 2 ·6H 2 O [ 1.0mol% relative to (bromodifluoromethyl) benzene ]]Hans ester a [ 1.5 mol equivalent (2.25 mmol) relative to (bromodifluoromethyl) benzene ]]And DMF (15 mL), using a solvent having a broad molecular weightA reaction of (bromodifluoromethyl) benzene (1.5 mmol) and 1-octene (7.5 mmol) was carried out in a flow system by irradiation with a white lamp (white LED) in a microreactor (light emitting diode) having a flow channel with a depth of 2mm, 1mm and a length of 3 m.
As a result, compound 10A was obtained with a retention time of 30 minutes and a yield of 56%.
The conversion and GC yield for each residence time are shown in the table below.
[ Table 11]
As shown above, the yield was improved as the retention time was prolonged.
The same reaction was carried out as in the reaction (12 h), whereby the GC yield of the compound 11A was 86% (yield 64%). Considering the reaction time, it was confirmed that the target compound was obtained more efficiently in the reaction of the flow system than in the batch reaction.
Example 12 (reaction in flow System 3)
The reaction in the flow system was carried out in the same manner as in example 11 except that methyl acrylate was used as the matrix in place of 1-octene.
The results are shown in the following table.
The same reaction was carried out as in the reaction (12 h), whereby the GC yield of the compound 12A was 90% (yield 72%). Considering the reaction time, it was confirmed that the target compound was obtained more efficiently in the reaction of the flow system than in the batch reaction.
[ Table 12]
Claims (8)
1. A method for producing a compound represented by the formula (1), or a closed-ring derivative or open-ring derivative thereof, characterized in that:
comprising a step A of reacting a compound represented by the formula (2) with a compound represented by the formula (3) in the presence of a reducing agent under irradiation with light,
in the formula (1), the reaction mixture is,
R 1 represents an organic group, and represents an organic group,
R X represents a hydrogen atom or a fluorine atom, and
R 2a 、R 2b 、R 2c and R 2d The same or different, represent-Y-R 21 or-N (-R) 22 ) 2 Or R is 2b And R 2c Can be linked to form a valence bond,
y represents a bond, an oxygen atom or a sulfur atom,
R 21 represents a hydrogen atom or an organic group,
R 22 identical or different at each occurrence and denotes a hydrogen atom or an organic radical,
in the formula (2), X represents a leaving group, and the other symbols represent the same meanings as described above,
the symbols in formula (3) have the same meanings as described above.
2. The manufacturing method according to claim 1, wherein:
R 1 is alkyl, fluoroalkyl, alkoxycarbonyl orAn aromatic group.
3. The manufacturing method according to claim 1 or 2, characterized in that:
R 2a is alkyl or aryl, and R 2b 、R 2c And R 2d Is a hydrogen atom.
4. The manufacturing method according to any one of claims 1 to 3, characterized in that:
x is a bromine atom.
5. The manufacturing method according to any one of claims 1 to 4, characterized in that:
the reaction in the step A is carried out in the presence of a nitrogen-containing unsaturated heterocyclic compound having an N-H moiety.
7. The manufacturing method according to any one of claims 1 to 6, characterized in that:
the reaction in the step A is carried out in the presence of a catalyst.
8. The manufacturing method according to claim 7, wherein:
the catalyst is more than 1 selected from transition metal coordination compounds and organic pigment compounds.
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