CN113651729A - Preparation method of iron-catalyzed 4-aminoalcohol - Google Patents
Preparation method of iron-catalyzed 4-aminoalcohol Download PDFInfo
- Publication number
- CN113651729A CN113651729A CN202111002401.7A CN202111002401A CN113651729A CN 113651729 A CN113651729 A CN 113651729A CN 202111002401 A CN202111002401 A CN 202111002401A CN 113651729 A CN113651729 A CN 113651729A
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- Prior art keywords
- ferric
- solvent
- ferrous
- iron
- reaction
- Prior art date
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Links
- 238000002360 preparation method Methods 0.000 title claims description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 124
- -1 azo compound Chemical class 0.000 claims abstract description 93
- 238000000034 method Methods 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 72
- 239000000047 product Substances 0.000 claims description 50
- 238000005576 amination reaction Methods 0.000 claims description 48
- 239000002904 solvent Substances 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 28
- 239000012043 crude product Substances 0.000 claims description 26
- 238000004821 distillation Methods 0.000 claims description 26
- 238000003818 flash chromatography Methods 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical class [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 22
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 18
- 150000002191 fatty alcohols Chemical class 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 150000002506 iron compounds Chemical class 0.000 claims description 14
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 9
- 235000011164 potassium chloride Nutrition 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000003863 ammonium salts Chemical class 0.000 claims description 8
- 150000002989 phenols Chemical class 0.000 claims description 8
- KFVXQDFWRLMDRW-UHFFFAOYSA-N [K].Oc1c(F)c(F)c(F)c(F)c1F Chemical compound [K].Oc1c(F)c(F)c(F)c(F)c1F KFVXQDFWRLMDRW-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- XFOWYEKVIRMOBI-UHFFFAOYSA-N 3,3-dimethylbutanenitrile Chemical compound CC(C)(C)CC#N XFOWYEKVIRMOBI-UHFFFAOYSA-N 0.000 claims description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 4
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000008282 halocarbons Chemical class 0.000 claims description 4
- 150000004677 hydrates Chemical class 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 150000003462 sulfoxides Chemical class 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- 238000010504 bond cleavage reaction Methods 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 125000005928 isopropyloxycarbonyl group Chemical group [H]C([H])([H])C([H])(OC(*)=O)C([H])([H])[H] 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 2
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 claims description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021575 Iron(II) bromide Inorganic materials 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
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- GOKIPOOTKLLKDI-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O.CC(O)=O GOKIPOOTKLLKDI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- 229960004887 ferric hydroxide Drugs 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 229940046149 ferrous bromide Drugs 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000019850 ferrous citrate Nutrition 0.000 claims description 2
- 239000011640 ferrous citrate Substances 0.000 claims description 2
- 229940076136 ferrous iodide Drugs 0.000 claims description 2
- 229940062993 ferrous oxalate Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 150000002222 fluorine compounds Chemical group 0.000 claims description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 claims description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 2
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 2
- YHGPYBQVSJBGHH-UHFFFAOYSA-H iron(3+);trisulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YHGPYBQVSJBGHH-UHFFFAOYSA-H 0.000 claims description 2
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 2
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 claims description 2
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical class CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical group C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract description 2
- 150000001414 amino alcohols Chemical class 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 88
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 52
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 26
- 238000005160 1H NMR spectroscopy Methods 0.000 description 24
- 239000011734 sodium Substances 0.000 description 22
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 5
- HQRWWHIETAKIMO-UHFFFAOYSA-N 1-phenylbutan-1-ol Chemical compound CCCC(O)C1=CC=CC=C1 HQRWWHIETAKIMO-UHFFFAOYSA-N 0.000 description 4
- LDZLXQFDGRCELX-UHFFFAOYSA-N 4-phenylbutan-1-ol Chemical compound OCCCCC1=CC=CC=C1 LDZLXQFDGRCELX-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 4
- QJQZRLXDLORINA-UHFFFAOYSA-N 2-cyclohexylethanol Chemical compound OCCC1CCCCC1 QJQZRLXDLORINA-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- OSHOQERNFGVVRH-UHFFFAOYSA-K iron(3+);trifluoromethanesulfonate Chemical compound [Fe+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F OSHOQERNFGVVRH-UHFFFAOYSA-K 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 description 2
- IBMXMCXCSPGCDQ-UHFFFAOYSA-N 3-cyclopentylpropan-1-ol Chemical compound OCCCC1CCCC1 IBMXMCXCSPGCDQ-UHFFFAOYSA-N 0.000 description 2
- HXHGULXINZUGJX-UHFFFAOYSA-N 4-chlorobutanol Chemical compound OCCCCCl HXHGULXINZUGJX-UHFFFAOYSA-N 0.000 description 2
- PCWGTDULNUVNBN-UHFFFAOYSA-N 4-methylpentan-1-ol Chemical compound CC(C)CCCO PCWGTDULNUVNBN-UHFFFAOYSA-N 0.000 description 2
- DPZMVZIQRMVBBW-UHFFFAOYSA-N 5-Phenyl-1-pentanol Chemical compound OCCCCCC1=CC=CC=C1 DPZMVZIQRMVBBW-UHFFFAOYSA-N 0.000 description 2
- HZPHQTUSOZLHKC-UHFFFAOYSA-N 6-(9H-carbazol-1-yl)hexan-1-ol Chemical compound C12=CC=CC=C2NC2=C1C=CC=C2CCCCCCO HZPHQTUSOZLHKC-UHFFFAOYSA-N 0.000 description 2
- DGUKYCANAXQEMH-UHFFFAOYSA-N 6-hydroxyhexyl acetate Chemical compound CC(=O)OCCCCCCO DGUKYCANAXQEMH-UHFFFAOYSA-N 0.000 description 2
- DUKPKQFHJQGTGU-UHFFFAOYSA-N Hexyl salicylic acid Chemical compound CCCCCCOC(=O)C1=CC=CC=C1O DUKPKQFHJQGTGU-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- PGJLOGNVZGRMGX-UHFFFAOYSA-L iron(2+);trifluoromethanesulfonate Chemical compound [Fe+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F PGJLOGNVZGRMGX-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- OEUXAZRVDHRZSV-UHFFFAOYSA-N 1-(4-methoxyphenyl)pentan-2-ol Chemical compound CCCC(O)CC1=CC=C(OC)C=C1 OEUXAZRVDHRZSV-UHFFFAOYSA-N 0.000 description 1
- ONIBHZIXCLTLNO-UHFFFAOYSA-N 4-(4-methoxyphenyl)butan-1-ol Chemical compound COC1=CC=C(CCCCO)C=C1 ONIBHZIXCLTLNO-UHFFFAOYSA-N 0.000 description 1
- KQHIAMFIAYCUNW-UHFFFAOYSA-N 6-(1H-indol-2-yl)hexan-1-ol Chemical compound N1C(=CC2=CC=CC=C12)CCCCCCO KQHIAMFIAYCUNW-UHFFFAOYSA-N 0.000 description 1
- ROMDTZBCCCGPDR-UHFFFAOYSA-N 6-[tert-butyl(dimethyl)silyl]oxyhexan-1-ol Chemical compound CC(C)(C)[Si](C)(C)OCCCCCCO ROMDTZBCCCGPDR-UHFFFAOYSA-N 0.000 description 1
- PVDHNBFKZKZOSO-UHFFFAOYSA-N 6-naphthalen-2-yloxyhexan-1-ol Chemical compound C1=CC=CC2=CC(OCCCCCCO)=CC=C21 PVDHNBFKZKZOSO-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PAWBEUGPROLMBN-UHFFFAOYSA-N adamantane;ethanol Chemical compound CCO.C1C(C2)CC3CC1CC2C3 PAWBEUGPROLMBN-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N caproic acid ethyl ester Natural products CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- HYXRUZUPCFVWAH-UHFFFAOYSA-N ethyl 6-hydroxyhexanoate Chemical compound CCOC(=O)CCCCCO HYXRUZUPCFVWAH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Natural products O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/02—Compounds containing any of the groups, e.g. carbazates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/04—Indoles; Hydrogenated indoles
- C07D209/08—Indoles; Hydrogenated indoles with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method of preparing an iron-catalyzed 4-aminoalcohol, comprising the steps of: the method has the advantages of simple reaction, simple operation, short reaction time, mild oxidation condition, high atom economy, high reaction yield, easy separation and purification of products and the like, and is suitable for synthesizing the amino alcohol-containing compound and derivatives thereof; by directly utilizing aliphatic alcohol as a raw material, the azo compound is cheap and easy to obtain, avoids using a large amount of heavy metal salt, is very attractive in industrial production, and has very large application potential in the fields of metal catalysis, chemical synthesis, drug modification and the like by utilizing cheap metal to carry out reaction.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, and particularly relates to a preparation method of iron-catalyzed 4-aminoalcohol.
Background
Amino alcohol is an important organic synthesis intermediate, and is widely applied to the fields of complex organic molecules, drug intermediates, life science, material science and the like. Selective carbon-hydrogen bond cleavage amination of fatty alcohols provides a favorable opportunity for studying molecular complexity and pharmaceutical intermediates, and makes it possible to construct nitrogen-containing compounds from inexpensive, readily available and abundant alcohols.
Remote carbon-hydrogen bond functionalization of alkanols can be achieved by the generation of oxygen radicals from fatty alcohols, followed by intramolecular 1, 5-hydrogen atom transfer. In the prior art, few reports are available for synthesizing the 4-aminoalcohol by directly using the cheap and easily obtained unprotected alcohol compounds as raw materials, mainly using silver, iridium, ruthenium, cerium and the like as metal catalysts, and the method is high in price and difficult in reaction operation and limits the synthesis development of preparing the 4-aminoalcohol compounds from alcohol.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of iron-catalyzed 4-aminoalcohol, which directly performs carbon-hydrogen bond breaking and amination reaction selectively at the 4-position of 1,2 and 3-level fatty alcohol, namely, under the promotion of an iron catalyst and an additive and the irradiation of visible light, butanol, 4-aryl butanol and 4-alkyl butanol realize amination reaction through intramolecular free radical 1, 5-hydrogen migration to generate a series of 4-aminoalcohol compounds with different substituents.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method of preparing an iron-catalyzed 4-aminoalcohol, comprising the steps of: under the action of iron compound and under the condition of providing heating temperature and/or light energy, in the presence of azo compound and additive and in organic solvent to implement selective 4-hydrocarbon bond cleavage and amination of fatty alcohol so as to obtain 4-amino alcohol compound, its reaction formula is as follows:
the structural formula of the fatty alcohol is shown asAzo compoundsThe 4-aminoalcohol compound isWherein: r, R ', R' includes hydrogen, alkyl, substituted or unsubstituted phenyl, naphthyl, pyridine, thiophene, furan, pyrrole, indole, carbazole; the substitution comprises fluorine, chlorine, bromine, iodine, hydroxyl, carboxyl, sulfydryl, amino, primary amino, secondary amino, imino, nitro, cyano, alkyl, ester group, silicon group and acyl; r1Including t-butyloxycarbonyl, isopropyloxycarbonyl, ethyloxycarbonyl and phenyl.
A preparation method of iron-catalyzed 4-aminoalcohol comprises the following reaction steps:
(1) sequentially adding an iron compound x1 mol%, an additive x2 mol%, fatty alcohol, an azo compound and an organic solvent into a dry reaction tube, stirring and dissolving the mixture in an argon atmosphere after the addition is finished, uniformly mixing the mixture, placing the reaction tube under light for irradiation and continuously stirring and/or heating the reaction tube, wherein the addition of the fatty alcohol and the organic solvent is excessive; the molar ratio of iron compound to additive is x 1: x2 ═ (0.1-10): 1;
(2) and (2) after the reaction in the step (1) is completed, removing the reaction tube from the light source, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an aminated product.
The iron compound is an iron-containing compound, including ferric iron or ferrous iron compounds; the ferric iron comprises ferric trichloride, ferric tribromide, ferric trifluoromethanesulfonate, ferric tetrafluoroborate, ferric hexafluorophosphate, ferric sulfate, ferric nitrate, ferric acetate, ferric trifluoroacetate, ferric citrate, ferric oxalate, ferric acrylate, tris (2,2,6, 6-tetramethyl-3, 5-heptanedionato) iron, ferric hydroxide, ferric acetylacetonate, ferric fluoride iron-containing compounds and hydrates thereof; the ferrous iron comprises ferrous chloride, ferrous bromide, ferrous iodide, ferrous trifluoromethanesulfonate, ferrous tetrafluoroborate, ferrous hexafluorophosphate, ferrous sulfate, ferrous nitrate, ferrous acetate, ferrous trifluoroacetate, ferrous citrate, ferrous oxalate, ferrous acrylate, ferrous bis (2,2,6, 6-tetramethyl-3, 5-heptanedionate), ferrous hydroxide, ferrous acetylacetonate, ferrous fluoride iron-containing compounds and hydrates thereof.
The organic solvent is one or more of water, hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, nitrohydrocarbon solvents, ether solvents, nitrile solvents, ester solvents, alcohol solvents, amine solvents, amide solvents, sulfone solvents and sulfoxide solvents.
The hydrocarbon solvent is one or more of benzene, toluene and saturated alkane compounds, the halogenated hydrocarbon solvent is one or more of trifluoromethylbenzene, chlorobenzene, dichloromethane, 1, 2-dichloroethane, chloroform and carbon tetrachloride, and the nitrohydrocarbon solvent is one or more of nitrobenzene and nitromethane; the ether solvent is one or more of tetrahydrofuran, 1, 4-dioxane, methyl tert-butyl ether and diethyl ether; the nitrile solvent is one or more of acetonitrile, benzonitrile and tert-butyl acetonitrile; the ester solvent is one or more of ethyl acetate, n-butyl acetate and isobutyl acetate; the alcohol solvent is one or more of methanol, ethanol, tert-butyl alcohol, n-butyl alcohol and cyclohexanol, and the amine solvent is one or more of triethylamine, diethylamine and diisopropylethylamine; the amide solvent is one or more of dimethylformamide and dimethylacetamide; the sulfoxide solvent is dimethyl sulfoxide, and can be used in any proportion in various cases.
Preferably, the solvent is acetonitrile, tert-butyl acetonitrile, ethyl acetate, dichloromethane.
The additive comprises alkali metal salts of halides, alkali metal salts of organic acid compounds, alkali metal salts of phenolic compounds, ammonium salts of halides, ammonium salts of organic acid compounds, ammonium salts of phenolic compounds, wherein the halides are fluorides, chlorides, bromides, iodides; the alkali metal salt is lithium salt, sodium salt, potassium salt or cesium salt; the organic acid compound is substituted or unsubstituted aryl carboxylic acid, substituted or unsubstituted alkyl carboxylic acid, substituted or unsubstituted aryl sulfonic acid, substituted or unsubstituted alkyl sulfonic acid, substituted or unsubstituted aryl phosphoric acid and substituted or unsubstituted alkyl phosphoric acid; the phenols are substituted or unsubstituted phenol compounds; the ammonium salt is tetramethylammonium salt, tetraethylammonium salt or tetrabutylammonium salt.
Preferably, the additive is sodium chloride, potassium chloride, tetrabutylammonium chloride and pentafluorophenol potassium salt.
The molar ratio of the iron compound to the azo compound is less than 1.
Preferably, the molar ratio of iron compound to azo compound is (0.01-0.1): 1.
preferably, the heating condition temperature is: the reacted system was placed at 25 ℃ to 100 ℃.
The illumination conditions include: the reacted system is exposed to visible light and/or monochromatic or mixed light of a wavelength of less than 500 nm.
Preferably, the system of the reaction is irradiated under light with a wavelength of 350-450 nm.
Preferably, the iron compound is ferric chloride, ferric tribromide, ferric trifluoromethanesulfonate, or ferric tetrafluoroborate.
The invention has the following beneficial effects:
the invention provides a convenient and rapid method for preparing various 4-amino alcohols, can directly use cheap and abundant fatty alcohol as a raw material, does not need to add promoters such as heavy metal salt, strong oxidant and the like, has great attraction on industrial production, simultaneously uses cheap metal for reaction, and has great application potential in the fields of metal catalysis, chemical synthesis and the like. The innovation points of the invention are as follows:
(1) the reaction only needs cheap and easily available iron catalyst.
(2) The reaction can be realized by using visible light as a light source and a blue LED lamp with the power of 1-200W.
(3) Fatty alcohol and azo compound which are widely available, cheap and easily available are used as substrates
(4) Short reaction time and high efficiency.
(5) The 4-aminoalcohol compounds with different substituents can be quickly and simply synthesized.
(6) The product is easy to separate and purify.
(7) And develops a cheap and easily-obtained methodology for selectively preparing the 4-aminoalcohol compound by 4-amination with the fatty alcohol through a one-step method, and the yield of the obtained corresponding 4-aminoalcohol compound is 26-92%.
(8) The method for providing selective amination of fatty alcohol can efficiently and quickly obtain a corresponding amination product under the catalysis of an iron compound and under the action of an additive under the condition of providing heat energy and/or light energy and/or microwaves; the reaction method has the advantages of mild conditions, neutral redox, short reaction time, safety, greenness, simple operation, no need of a large amount of high-valence metal salt, wide applicability of the substrate and great significance in industrial production.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described in the following embodiments to fully understand the objects, aspects and effects of the present invention.
Example 1
Adding ferric trichloride (0.004 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butyloxycarbonyl substituted azo compound (0.4 mmol), benzene butanol (1.2 mmol) and anhydrous acetonitrile (4 ml) into a dried reaction tube in sequence, stirring and dissolving after the addition is finished, uniformly mixing, placing the reaction tube under light (hv) with the wavelength of 390nm for irradiation and continuous stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed liquid to a flask, carrying out reduced pressure distillation to obtain a crude product, carrying out rapid column chromatography to obtain an amination product of the benzene butanol of 127.0 mg, wherein the yield is 82%, and the product is a colorless oily substance. 1H NMR (400MHz, CDCl3) delta 7.46-7.18 (m,5H, Ar-H), 6.72-5.73 (m,1H, NH), 5.59-5.00 (m,1H, CH), 3.87-3.50 (m,2H, CH2),2.39(brs,1H, OH), 2.24-1.59 (m,4H, CH 2X 2), 1.59-0.95 (m,18H, X2). 13C NMR (101MHz, CDCl3) delta 156.0,155.1,139.7,128.4,127.9,127.6,81.4,81.1,62.2,59.2,29.6,28.2,27.4. Boc IR v (neat, cm-1)3447,2369,2063,1635,1508,1255,1167,1037. HRMS (ESI +) M/z Calcd for C21H34N2O6Na + [ M + Na ] + 433.2309; found 433.2317.
Example 2
The procedure is as described in example 1, except that the amounts of reagents used are: ferric chloride (0.008 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol), 4-methoxybenzenebutanol (208 μ l, 216.7 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and heating to 60 ℃ for continuous stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 4-methoxybenzyl butanol, wherein the amination product is 117.0 mg, and the yield is 71%. 1H NMR (400MHz, CDCl3) δ 7.34-7.14 (M,2H, Ar-H),6.83(d, J ═ 8.4Hz,2H, Ar-H), 6.59-5.62 (M,1H, NH), 5.60-4.94 (M,1H, CH),3.77(s,3H, CH3), 3.78-3.53 (M,2H, CH2), 2.33-1.77 (M,5H, OH + CH2 × 2), 1.64-0.96 (M, Boc × 2), 13C NMR (101MHz, CDCl3) δ 159.0,156.1,155.1,131.8,129.1,113.7,81.1,62.2,58.8,55.2,29.6,28.2,28.1,27.5.IR (neat, cm-1)3445, 76,2931, 1700.1, 294. v. (ESI, v.8, 55.2,29.6, 29.2, 29.1, 35, 35.5. C + hrn + cd 31 + (M, cd 31 +/M); found 437.1821.
Example 3
The procedure is as described in example 1, except that the amounts of reagents used are: iron tribromide (0.012 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol), 4-chlorobutanol (240.8 mg, 1.2 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and heating to 80 ℃ for continuous stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 4-chlorobutanol, wherein the amination product is 127.5 mg, and the yield is 76%. 1H NMR (400MHz, CDCl 3). delta.7.36-7.21 (m,4H, Ar-H), 6.91-5.74 (m,1H, NH), 5.76-4.99 (m,1H, CH), 3.79-3.55 (m,2H, CH2),2.46(brs,1H, OH), 2.22-0.99 (m,22H, Boc. times.2 + CH 2. times.2). 13C NMR (101MHz, CDCl 3). delta. 156.1,155.0,138.1,133.4,130.1,129.3,128.5,128.1,81.6,81.2,80.8,62.04,58.54,29.4,28.1,28.1,27.4,26.9.IR v (neat, cm-1)3443,2067,1641,1455,1365,1278,1261.HRMS (ESI +) M/z Calcd for C14H28N2O5Na + [ M + Na ] + 327.1890; found 327.1897.
Example 4
Iron tribromide (0.0008 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), butanol (110 μ l, 89.1 mg, 1.20 mmol), anhydrous acetonitrile (4 ml) were prepared as described in example 1; placing the reaction tube under light (hv) with the wavelength of 420nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, carrying out flash column chromatography to obtain an amination product of butanol, wherein the amination product is 92.0 mg, and the yield is 75%. 1H NMR (400MHz, CDCl3) δ 6.58-6.22 (M,1H, NH),3.63(t, J ═ 6.0Hz,2H, CH2),3.45(brs,2H, CH2),2.16(brs,1H, OH), 1.68-1.54 (M,4H, CH2 × 2), 1.51-1.35 (M,18H, Boc × 2), 13C NMR (101MHz, CDCl3) δ 155.4,81.1,62.26,50.3,49.1,29.6,28.2,23.8.IR v (neat, cm-1)3443,2067,1641,1455,1365,1278,1261.HRMS (ESI +) M/z: Calcd for C14H28N2O5 + 5Na + [ 56 + ] M +327.1890 +; found 327.1897.
Example 5
Iron tribromide (0.02 mmol), sodium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), phenylpentanol (202 μ l, 197.0 mg, 1.20 mmol), anhydrous acetonitrile (4 ml) were prepared as described in example 1; placing the reaction tube under light (hv) with the wavelength of 380nm for irradiation, heating to 100 ℃, continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of the phenylpentanol, wherein the amination product is 95.1 mg, and the yield is 60%. 1H NMR (400MHz, CDCl3) delta 7.37-7.06 (M,5H, Ar-H), 6.50-5.40 (M,1H, NH), 4.77-4.15 (M,1H, CH), 3.79-3.43 (M,2H, CH2), 2.98-2.56 (M,2H, CH2),2.12(brs,1H, OH), 1.96-1.11 (M,22H, CH 2X 2+ Boc X2), 13C NMR (101MHz, CDCl3) delta 2, 81.3,80.9,62.2,60.1,57.3,39.2,29.4,28.1,28.0.IR (neat, cm-1) 43,2978,2933,2061, 1641, 3498, ESI 1,1390,1371, 35M [ 17H + CdZ ] 3+ [ 18H + 5H + (M H, 35 + Na +3 +; found 417.2368.
Example 6
The procedure is as described in example 1, except that the amounts of reagents used are: ferric triflate (0.024 mmol), sodium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol), pentanol (130 μ l, 105.3 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and heating to 60 ℃ for continuous stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an aminated product of pentanol, wherein the aminated product is 99.7 mg, and the yield is 78%. 1H NMR (400MHz, CDCl3) δ 6.46-5.97 (M,1H, NH), 4.38-3.95 (M,1H, CH), 3.73-3.47 (M,2H, CH2),2.32(brs,1H, OH), 1.79-1.23 (M,22H, Boc × 2+ CH2 × 2),1.08(d, J ═ 6.7Hz,3H, CH3), 13C NMR (101MHz, CDCl3) δ 2, 80.9,62.3,54.0,52.2,30.2,29.4,28.2,28.1,18.2.IR v (neat, cm-1)3451,3004,2367,2073,1637, 393, 1263,771,749.HRMS (ESI M/z: calc + Na 5 + [ 10 + Na ] +35 + 3+ (M +35 + 2 +); found 341.2054.
Example 7
The procedure is as described in example 1, except that the amounts of reagents used are: ferric triflate (0.028 mmol), sodium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol), 1-hexanol (151 μ l, 122.9 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); the reaction tube was irradiated with light (hv) having a wavelength of 390nm while stirring, removed from the light source after the reaction was completed, the reaction mixture was transferred to a flask, and subjected to distillation under reduced pressure to obtain a crude product, which was subjected to flash column chromatography to obtain an aminated product of 1-hexanol, 117.4 mg, in a yield of 89%. 1H NMR (400MHz, CDCl3) delta 6.60-5.96 (M,1H, NH), 4.32-3.74 (M,1H, CH), 3.72-3.45 (M,2H, CH2),2.44(brs,1H, OH), 1.91-1.15 (M,24H, Boc x 2+ CH2 x 3), 1.02-0.71 (M,3H, CH3), 13C NMR (101MHz, CDCl3) delta 156.5,155.9,155.6,81.1,80.8,62.2,60.5,58.4,29.5,28.1,26.8,25.9,25.6,11.0.IR v (neat, cm-1)3441,2367,2349,2063,1637, 393, HRMS (ESI +) M/z: Cal 16H + Na 2+ 5 + Na 2O [ 3+ 35 +35 +; found 355.2211.
Example 8
As described in example 1, iron triflate (0.036 mmol), sodium chloride (0.004 mmol), tert-butoxycarbonyl substituted azo compound (0.4 mmol), cyclohexylethanol (167 μ l, 153.5 mg, 1.20 mmol), ethyl acetate (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of the cyclohexylethanol, wherein the amination product is 80.6 mg, and the yield is 56%. 1H NMR (400MHz, CDCl3) delta 6.96-6.03 (M,1H, NH), 3.87-3.42 (M,3H, CH2+ CH), 2.67-1.81 (M,3H, OH + CH2), 1.80-1.69 (M,1H, CH), 1.68-1.51 (M,3H, CH 2X 2.5), 1.49-1.36 (M,18H, Boc X2), 1.34-1.05 (M,4H, CH 2X 2), 1.04-0.77 (M,1H, hydrogen for one methylene). 13C NMR (101MHz, CDCl 48363), 80.9,80.5,60.3,59.9,35.9,35.4,35.0,32.0,31.4,29.6,28.2, 25.25 delta 4, V.9, 80.5,60.3,59.9,35.9,35.4,35.0,32.0,31.4,29.6,28.2, 25.25 V.9, 18H + CH 3879, Na + (M, 369, 31,27, 18, 3,17, 3, 9, 3; found 381.2368.
Example 9
The procedure is as described in example 1, except that the amounts of reagents used are: ferric triflate (0.032 mmol), pentafluorophenol potassium salt (0.004 mmol), tert-butyloxycarbonyl substituted azo compound (0.4 mmol), adamantane ethanol (218.7 mg, 0.4 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of the cyclohexylethanol, wherein the amination product is 103.7 mg, and the yield is 65%. 1H NMR (400MHz, CDCl3) delta 6.33-6.21 (M,1H, NH),4.22(M,1H, CH), 3.82-3.63 (M,2H, CH2), 2.29-1.32 (M,35H, hydrogen on ring + CH2+ OH + Boc X2). 13C NMR (101MHz, CDCl3) delta 155.8,155.6,81.5,81.0,80.8,61.5,58.4,43.9,42.2,39.4,37.7,37.6,36.3,32.9,31.3,28.5,28.2,28.1,27.9.IR v (neat, cm-1)3449,2986,2365, 1270, 1637, 2083, 1257, 751, HRMS (ESI M/z: Cal 22 + Na 2O +433.2673 + [ 29H 2+ ] C2 +; found 433.2685.
Example 10
Pentafluorophenol potassium salt additive (0.004 mmol) as in example 1, tert-butoxycarbonyl substituted azo compound (0.4 mmol), 4-methylpentanol (149. mu.l, 122.3 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under light (hv) with the wavelength of 390nm for irradiation, heating the reaction tube to 80 ℃, continuously stirring the reaction tube, removing the reaction tube from a light source after the reaction is finished, transferring a reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 4-methylpentanol, wherein the amination product is 119.2 mg, and the yield is 86%. 1H NMR (400MHz, CDCl3) δ 6.47-6.34 (M,1H, NH),3.54(t, J ═ 6.5Hz,2H, CH2),2.46(brs,1H, OH), 1.99-1.84 (M,1H, hydrogen of one methylene), 1.70-1.60 (M,1H, hydrogen of one methylene), 1.59-1.31 (M,23H, Boc × 2+ CH2+ CH3), 1.27-1.14 (M,3H, CH3), 13C NMR (101MHz, CDCl3) δ 156.4,156.0,154.7,154.4,81.1,80.7,80.5,62.8,61.8,36.2,28.2,28.1,27.7,26.9,26.3.IR ν (neat, cm-1)3447,3008, 2065 + NH 5, 12517, 17 + N # 12, 17 + N # 12, 17 + (M, 17 + N # 12 + 17 + (M, 17 + N # 3+ N +; found 355.2212.
Example 11
As described in example 1, iron tetrafluoroborate (0.004 mmol), pentafluorophenol potassium salt (0.04 mmol), t-butoxycarbonyl substituted azo compound (0.4 mmol), 3-cyclopentylpropanol (156.9 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under the light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed liquid to a flask, carrying out reduced pressure distillation to obtain a crude product, carrying out flash column chromatography to obtain an amination product of 3-cyclopentyl propanol, wherein the amination product is 136.4 mg, and the yield is 92%. 1H NMR (400MHz, CDCl3) delta 6.49(s,1H, NH), 3.60-3.48 (M,2H, CH2),2.57(brs,1H, OH), 2.16-1.76 (M,4H, CH 2X 2), 1.75-1.46 (M,8H, CH 2X 4), 1.45-1.33 (M,18H, Boc X2). 13C NMR (101MHz, CDCl3) delta 2, 81.0,80.7,80.6,72.1,62.8,38.5,35.9,35.7,33.5,32.9,28.2,28.1,27.9,23.6,23.2,23.0,22.9.IR v (neat, cm-1)3353,2976,2363, ESI 3, 1615, 2063 + Na 2+ 743 + 18H + 18 +35 + HRZ 2; found381.2370.
Example 12
According to the method described in example 1, iron tetrafluoroborate (0.002 mmol), pentafluorophenol potassium salt (0.004 mmol), t-butoxycarbonyl substituted azo compound (0.4 mmol), 2-hexanol (151. mu.l, 122.9 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); the reaction tube was placed under light (hv) with a wavelength of 390nm and was continuously stirred, after the reaction was completed, the reaction tube was removed from the light source, the reaction mixture was transferred to a flask, and the crude product was obtained by distillation under reduced pressure, and flash column chromatography was carried out to obtain the aminated product of 2-hexanol in an amount of 103.3 mg with a yield of 74%. 1H NMR (400MHz, CDCl3) delta 6.82-6.04 (M,1H, NH), 4.33-3.92 (M,1H, CH), 3.85-3.58 (M,1H, CH),2.52(brs,1H, OH), 1.74-1.22 (M,22H, CH 2X 2+ Boc X2), 1.18-0.96 (M,6H, CH 3X 2).13C NMR (101MHz, CDCl3) delta 156.4,155.1,80.9,67.6,67.0,54.3,52.1,35.8,35.4,30.3,29.2,28.1,26.8,24.0,23.3,18.5,18.1.IR (neat, cm-1)3339,3320,2984, 37,1702, 1157, 1159, 29.11, 29.8, 24.0, 29.5, 29.1. V [ 17 ] NH 2+ Na + 46N 2+ (16 + NH 2 +; found 355.2211.
Example 13
According to the method described in example 1, iron tetrafluoroborate (0.0004 mmol), pentafluorophenol potassium salt (0.004 mmol), t-butoxycarbonyl substituted azo compound (0.4 mmol), ethyl 6-hydroxycaproate (191.2 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an aminated product of 6-hydroxy ethyl caproate, wherein 124.2 mg of the aminated product is obtained, and the yield is 79%. 1H NMR (400MHz, CDCl3) delta 6.57-6.09 (M,1H, NH), 4.63-4.29 (M,1H, CH), 4.17-4.00 (M,2H, CH2), 3.75-3.46 (M,2H, CH2), 2.69-2.07 (M,3H, OH + CH2), delta 1.97-1.37 (M,22H, CH 2X 2+ Boc X2), 1.27-1.15 (M,3H, CH3).13C NMR (101MHz, CDCl3) delta 173.7,171.7,156.2,155.7,155.0,81.2,64.0,62.4,61.9,60.6,60.2,55.7,54.1,37.9,34.1,32.2,29.1,28.8,28.1,25.5, 25.24.5, 24.5, 24.6, 60.2,55.7,54.1,37.9,34.1,32.2,29.1,28.8, 28.5, 24.5 v.14, 27, 27.9, 27 + Na 3+ 27, 27-1, 18 + 27, 27H, 13H, 27H, 13C NMR, 27H, 13H, 27H, 13, 27, 35, 27, 35, 27, 35, 27, 35, 27.9, 27, 27.9, 27, 35, 27, 27.1, 27.8, III; found 413.2268.
Example 14
As described in example 1, ferric trichloride (0.0012 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6- ((tert-butyldimethylsilyl) oxy) hex-1-ol (293.3 mg, 1.30 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring a reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6- ((tert-butyldimethylsilyl) oxy) hexan-1-ol, wherein the amination product is 112.4 mg, and the yield is 61%. 1H NMR (400MHz, CDCl3) delta 7.05-6.44 (M,1H, NH), 4.32-4.00 (M,1H, CH), 3.75-3.45 (M,4H, CH 2X 2),2.60(brs,1H, OH), 1.94-1.35 (M,24H, Boc X2 + CH 2X 3), 0.96-0.81 (M,9H, CH 3X 3), 0.09-0.06 (M,6H, CH 3X 2).13C NMR (101MHz, CDCl3) delta 155.7,80.7,80.4,62.8,62.5,62.0,61.4,60.8,55.9,35.6,35.2,32.6,29.4,28.7,28.2,28.1,25.9,25.7, 25.9,25.6, V # 3,2 # WO 3+ 5 + HRZ 2, 9,35.6,35.2, 2, 9, 35.6.6, 2, 9,2 # 19.6, 9,2 # 19.6, 9,2, 9, 9.6.6.6.6.6.6.6.6.6.6.6.6.7, 9, 9.8, 9, 9.6.6.6.8, 9, 9.6.6.8, 9, 9.8, 9.6.6.6.6.8, 9.8, 9, 9.6.6.6.6, 9, 9.6.6.6.8, 9, 9.6, 9, 9.6.6.6.6.6.6.6.9.9.9.9, 9, 9.6.6.9.9, 9, 9.6.6.6.6.6.6.6.6, 9, 9.9.9.9.9.9.9.9.9.9, 9, 9.9, 9, 9.9.9.9.9.9, 9.9.9, 9, 9.9.6.9.9.9.9.9.9.9.9.9.9.9.9.9.9.6, 9.9.9.6.6.6.6.6.6.8, 9.6.8, 9.9.9.; found 485.3022.
Example 15
As described in example 1, ferric trichloride (0.0016 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6-phenyloxyhex-1-ol (250.9 mg, 1.30 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6-phenyloxyhexyl-1-alcohol, wherein the amination product is 146.8 mg, and the yield is 85%. 1H NMR (400MHz, CDCl3) δ 7.20(t, J ═ 20.0Hz,2H, Ar-H), 6.99-6.67 (M,3H, Ar-H), 6.56-6.21 (M,1H, NH), 4.44-4.14 (M,2H, CH2), 4.11-3.77 (M,2H, CH2),1.96(brs,1H, OH), 1.83-1.56 (M,4H, CH2 × 2), 1.48-1.12 (M,18H Boc × 2), 13C NMR (101MHz, CDCl3) δ 158.7,158.2,156.2,155.6,129.3,120.9,120.5,114.3,80.9,66.4,65.0,62.0,55.9,32.3,32.0,29.4,28.8,28.5,28.2,28.0, 27.1249, 29.8, v ° 19.9, 18.8, 18H, C NMR (101MHz, cd 3) Δ 158.7,158.2,156.2,155.6,129.3,120.9,120.5,114.3,80.9, 18.9, 18, 18.8, 18 g, 18H, C, 2, 18H, 2, 18H, C, 2H, 18H, 2, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, 18H, 2H, ep H, 2H, ep H, 2, ep H, 2H, ep H, 2, ep H, 2, ep H, 2, ep H; found 447.2471.
Example 16
As described in example 1, iron trichloride (0.0032 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6- (naphthalen-1-yloxy) hex-1-ol (288.7 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6- (naphthalene-1-oxyl) hexan-1-ol, wherein the amination product is 124.9 mg, and the yield is 65%. 1H NMR (400MHz, CDCl3) delta 8.32-8.12 (M,1H, Ar-H), 7.88-7.73 (M,1H, Ar-H), 7.58-7.32 (M,4H, Ar-H), 6.87-6.74 (M,1H, Ar-H), 6.67-6.16 (M,1H, NH), 4.57-4.39 (M,1H, CH), 4.36-4.06 (M,2H, CH2), 3.86-3.49 (M,2H, CH2),2.22(brs,1H, OH), 2.12-1.58 (M,4H, CH 2X 2), 1.61-1.16 (M,18H, Boc X2), 13C NMR (101MHz, CDCl3) ESI 2, 81.4,80.9, 66.9, 66.32, 18, 18.9, 18, 9.32, 18, 9.8.32, 18, 9.8.8.9, 2,26,26,26,26,26,29 + (M,2,26,26,26,26,26,26,26,26,26,26,26,26,26,26,26,26,26,26,29 + (M) + [ 2,26,26,26,26,26,26,26,29 + (M,3,32 + (M,2,29 +); found 497.2623.
Example 17
As described in example 1, iron trichloride (0.0036 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6- (naphthalen-2-yloxy) hex-1-ol (293.5 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6- (naphthalene-2-yloxy) hexan-1-ol, wherein the amination product is 113.6 mg, and the yield is 60%. 1H NMR (400MHz, CDCl3) δ 7.82-7.64 (M,3H, Ar-H),7.41(t,1H J ═ 7.4Hz, Ar-H),7.31(t,1H J ═ 7.4Hz, Ar-H), 7.21-7.01 (M,2H, Ar-H), 6.84-6.43 (M,1H, NH), 4.60-3.98 (M,3H, CH + CH2), 3.81-3.46 (M,2H, CH2),2.61(brs,1H, OH), δ 2.21-1.56 (M,4H, CH2 × 2), 1.63-1.12 (M,18H, Boc × 2), 13C NMR (101MHz, CDCl 7) δ 156.7,156.1,155.7,134.4,129.2,128.8,127.5,126.7,126.2,123.4,118.9,118.5,106.8,106.3,81.3,80.9, 66.65, 62.65, 11.62, 11.9, 2 v.9, 2H, 29.9 + NH, 2,29 v.26, 29M, 29, 21 + NH, 2, 21 + 3.26, 21, 2, 29H, 13C NMR (M, 21, 11 cm, 11 cm, 9,2 cm, 9,11, 9,2, 9,2 cm, 9,2, 9,2, 9,2, 9,2, 9,2 cm, 2, 9,2, 9; found 497.2626.
Example 18
As described in example 1, ferric trichloride (0.0028 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6-hydroxyhexyl acetate (190.7 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under the light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed liquid to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6-hydroxyhexyl acetate, wherein the amination product is 120.4 mg, and the yield is 76%. 1H NMR (400MHz, CDCl3) delta 6.71-6.20 (M,1H, NH), 4.34-3.93 (M,3H, CH + CH2), 3.73-3.47 (M,2H, CH2),2.40(brs,1H, OH),2.01(s,3H, CH3), 1.90-1.27 (M,24H, CH 2X 3+ Boc X2), 13C NMR (101MHz, CDCl 5) delta 178.6,171.1,170.9,156.0,155.3,81.1,62.1,61.9,56.1,53.8,31.4,29.2,28.7,28.5,28.1,20.9.IR v (neat, cm-1)3455,2980,2941,2255,1706,1400, 3, 1253, 1369, ESIMS (740. ESI M.) + 8634H + 8678 [ CAZ ] Na + (18 + 8678 +/Na +35 +; found 413.2263.
Example 19
As described in example 1, iron tribromide (0.004 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), hexyl 6-hydroxybenzoate (276.9 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of the 6-hexyl hydroxybenzoate, wherein the amination product is 82.8 mg, and the yield is 45%. 1H NMR (400MHz, CDCl3) δ 8.02(d, J ═ 7.3Hz,2H, Ar-H),7.53(t, J ═ 7.4Hz,1H, Ar-H),7.41(t, J ═ 7.7Hz,2H, Ar-H),6.50(M,1H, NH), 4.58-4.15 (M,3H, CH + CH2), 3.79-3.53 (M,2H, CH2),2.38(brs,1H, OH), 2.08-1.56 (M,4H, CH2 × 2), 1.55-1.32 (M,18H, Boc × 2), 13C NMR (101MHz, CDCl3) δ 166.6,156.1,155.4,132.9,130.2,129.5,128.3,81.6,81.1,62.6,62.1,55.6,54.1, Boc × 2, 13C NMR (101MHz, CDCl3), δ 3876.6, 81.1,62.6,62.1, ESI, 19.0, Boc × 2, 19, v.6, 19 v. (101MHz, 35, 29, 35, 17 cm, 19M, 18H, 18 cm 2+ 19 cm 3H, 18 cm 2, 18 cm 3H, 18 cm 2, 18 cm 3H, 18 cm 3H, 18 cm 3H, 18 cm 3H, 18 cm 3H, 18 cm 3H, 18 cm 3M + (M +; found 475.2429.
Example 20
As described in example 1, iron tribromide (0.012 mmol), potassium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6-carbazolylhexan-1-ol (339.0 mg, 1.30 mmol), ethyl acetate (4 ml); placing the reaction tube under 390nm light (hv) for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6-carbazolylhexan-1-ol, wherein the amination product is 84.4 mg, and the yield is 42%. 1H NMR (400MHz, CDCl3) δ 8.08(d, J ═ 7.6Hz,2H, Ar-H), 7.73-7.34 (M,4H, Ar-H), 7.25-7.11 (M,2H, Ar-H), 6.49-5.94 (M,1H, NH), 5.13-4.60 (M,1H, CH), 4.52-4.04 (M,2H, CH2), 3.74-3.43 (M,2H, CH2),2.07(brs,1H, OH), 1.77-1.36 (M,24H, CH2 × 3+ Boc × 2), 13C NMR (101MHz, CDCl3) δ 156.0,155.6,140.3,125.5,122.8,120.2,118.7,109.0,81.9,81.5,62.3,56.7,55.2,40.9,31.5,28.9, IR 19.28, v NMR (101MHz, CDCl3) δ 156.0,155.6,140.3,125.5,122.8,120.2,118.7,109.0,81.9, 62.3,56.7,55.2, 55.9, 31.5,28.9, ESI, 28.28.3, 1656H, 19, 19.3, 17 cm (M, 17 + hrm, 17M, 35, 17, 35, 17 cm 3,17 cm 3+ (M +; found 520.2798.
Example 21
As described in example 1, ferric chloride (0.0036 mmol), tetrabutylammonium chloride (0.004 mmol), tert-butoxycarbonyl-substituted azo compound (0.4 mmol), 6-indolyhex-1-ol (260.0 mg, 1.20 mmol), ethyl acetate (4 ml); placing the reaction tube under the light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of 6-indolylhexan-1-ol, wherein the amination product is 67.2 mg, and the yield is 40%. 1H NMR (400MHz, CDCl3) δ 7.56(d, J ═ 7.9Hz,1H, Ar-H),7.31(dd, J ═ 24.2,16.0Hz,1H, Ar-H), 7.25-7.06 (M,4H, Ar-H),6.44(M,1H, NH), 5.16-4.95 (M,2H, CH2), 4.88-4.21 (M,1H, CH),4.08(t, J ═ 7.0Hz,2H, CH2),3.58(t, J ═ 6.4Hz,2H, CH2),2.10(brs,1H, OH), 1.93-1.69 (M,2H, CH2), 1.61-1.43 (M,2H, CH2), 1.45-1.04 (br, v 1H, OH), 1.93-1.69 (M,2H, CH2), 1.61-1.43 (M, ESI, 21H, 21 cm, 12 cm, 3,8 cm, 3,8 cm, 3,8 cm, 3, 9 cm, 3, 9 cm, 3,8 cm, 9 cm, 3, 9 cm, 9 +3, 9 cm 3, 9 + 11 cm 3, 9 cm 3, 9 +3, 9,3, 9 cm 3, 9,3, 9 cm 3, 9 cm 3, 9 +3, 9 cm 3, 9 +3, 9 cm 3, 9 cm 3, 9 + 9 cm 3, 9 + 9,3, 9 + 9,9 cm 3, 9 + 9,9 +3, 9 cm 3, 9,3, 9 cm 3, 9 +3, 9 +3, 9 +3, 9,2 cm 3, 9; found 442.2324.
Example 22
As described in example 1, ferric trichloride (0.004 mmol), tetrabutylammonium chloride (0.036 mmol), isopropyloxycarbonyl-substituted azo compound (79 μ l, 81.1 mg, 0.40 mmol), phenylbutanol (183 μ l, 180.1 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under the light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed liquid to a flask, carrying out reduced pressure distillation to obtain a crude product, carrying out flash column chromatography to obtain an amination product of the isopropyl oxycarbonyl substituted azo compound and the phenylbutanol, wherein the amination product is 117.9 mg, and the yield is 84%. 1H NMR (400MHz, CDCl3) delta 7.42-7.13 (M,5H, Ar-H),5.91(M,1H, NH), 5.44-5.07 (M,1H, CH), 5.05-4.29 (M,2H, CH2), 3.75-3.36 (M,2H, CH2),2.43(brs,1H, OH), 2.24-1.44 (M,4H, CH 2X 2), 1.42-0.99 (M,12H, CH 3X 4), 13C NMR (101MHz, CDCl3) delta 156.6,155.7,139.2,128.4,127.9,127.7,70.2,69.6,62.1,59.8,29.4,26.6,21.9,21.8,21.7.IR v NMR (neat, cm-1) 51,2982,2367, 343,2053, 2058. IR v (Na + (10327 + 863) Na + (863 + 863) WO 27 + Na + (863 + 3627 + Na + (9, 17 + 868); found 375.1892.
Example 23
As described in example 1, ferric chloride (0.02 mmol), tetrabutylammonium chloride (0.04 mmol), ethyloxycarbonyl-substituted azo compound (63 μ l, 69.9 mg, 0.40 mmol), phenylbutanol (183 μ l, 180.1 mg, 1.20 mmol), anhydrous acetonitrile (4 ml); placing the reaction tube under the light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed liquid to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an amination product of the ethyl oxycarbonyl substituted azo compound and the benzene butanol, wherein the amination product is 88.9 mg, and the yield is 68%. 1H NMR (400MHz, CDCl3) delta 7.45-7.19 (M,5H, Ar-H), 6.81-5.88 (M,1H, NH), 5.49-5.05 (M,1H, CH), 4.51-3.94 (M,4H, CH 2X 2), 3.79-3.43 (M,2H, CH2), 2.69-1.48 (M,5H, OH + CH 2X 2), 1.42-0.62 (M,6H, CH 3X 2), 13C NMR (101MHz, CDCl3) delta 156.8,156.1,138.9,128.4,127.9,127.8,62.5,62.0,61.9,60.5,29.4,26.6, 14.3.IR v (neat, cm-1)3449,2990,2369,2082,1641,1508, ESI 2,1271, 1421 Na 8624 + Na + (751 + Na + 3624 + 8624 + O +/3627 +; found347.1587.
Example 24
As described in example 1, iron triflate (0.04 mmol), tetrabutylammonium chloride (0.008 mmol), benzyloxycarbonyl-substituted azo compound (129.1 mg, 0.43 mmol), phenylbutanol (183 μ l, 180.1 mg, 1.20 mmol), ethyl acetate (4 ml); placing the reaction tube under the light (hv) with the wavelength of 390nm for irradiation and continuously stirring, removing the reaction tube from a light source after the reaction is finished, transferring the reaction mixed liquid to a flask, carrying out reduced pressure distillation to obtain a crude product, carrying out flash column chromatography to obtain an amination product of the benzyloxycarbonyl substituted azo compound and the benzene butanol, wherein the amination product is 51.4 mg, and the yield is 26%. 1H NMR (400MHz, CDCl3) delta 7.59-7.07 (M,15H, Ar-H), 6.96-5.99 (M,1H, NH), 5.55-4.95 (M,5H, CH + CH 2X 2), 3.84-3.32 (M,2H, CH2), 2.31-1.40 (M,5H, OH + CH 2X 2).13C NMR (101MHz, CDCl3) delta 156.6,155.9,138.7,135.7,135.4,128.5,128.3,128.1,127.9,68.2,67.7,62.2,60.5,29.5,26.6.IR v (neat, cm-1)3448,2367,2347,2069,1636,1524,1275,1260,763,750.HRMS (ESI +) M/z Calcd for C26H28N2O5Na [ M + Na ] + 471.1890; found 471.1900.
In conclusion, the method can use cheap and easily-obtained aliphatic alcohol or aromatic alcohol as a substrate to selectively aminate various organic compounds with different structures, and has the advantages of mild conditions, simple operation, short reaction time, greenness, high efficiency and wide application space.
The invention adopts the reaction condition of providing heat energy and/or light energy and/or microwaves, can realize the selective amination reaction of the fatty alcohol even under the condition of directly irradiating the blue LED lamp by one or more modes of simple heating, illumination or microwaves, does not need harsh reaction conditions such as high temperature, strong oxidant and the like or the addition of noble metal catalyst, has mild reaction conditions, is green and environment-friendly, is suitable for industrial production, and provides a new strategy for the diversity of chemical synthesis.
Claims (10)
1. A method for preparing an iron-catalyzed 4-aminoalcohol, comprising the steps of:
under the action of iron compound and under the condition of providing heating temperature and/or light energy, in the presence of azo compound and additive and in organic solvent to implement selective 4-hydrocarbon bond cleavage and amination of fatty alcohol so as to obtain 4-amino alcohol compound, its reaction formula is as follows:
the structural formula of the fatty alcohol is shown asAzo compoundsThe 4-aminoalcohol compound isWherein R, R 'and R' comprise hydrogen, alkyl, substituted or unsubstituted phenyl, naphthyl, pyridine, thiophene, furan, pyrrole, indole, carbazole; the substitution comprises fluorine, chlorine, bromine, iodine, hydroxyl, carboxyl, sulfydryl, amino, primary amino, secondary amino, imino, nitro, cyano, alkyl, ester group, silicon group and acyl; r1Including t-butyloxycarbonyl, isopropyloxycarbonyl, ethyloxycarbonyl and phenyl.
2. The method of claim 1, wherein the reaction steps are as follows:
(1) sequentially adding an iron compound x into the dried reaction tube1mol% of additive x2mol percent, fatty alcohol, azo compound and organic solvent, under argon atmosphere after the addition,stirring for dissolving, uniformly mixing, irradiating the reaction tube under light, continuously stirring and/or heating the reaction tube, wherein the addition amount of the fatty alcohol and the organic solvent is excessive;
(2) and (2) after the reaction in the step (1) is completed, removing the reaction tube from the light source, transferring the reaction mixed solution to a flask, carrying out reduced pressure distillation to obtain a crude product, and carrying out flash column chromatography to obtain an aminated product.
3. A process according to claim 1 or 2, wherein the iron compound is an iron-containing compound, including ferric or ferrous compounds; the ferric iron comprises ferric trichloride, ferric tribromide, ferric trifluoromethanesulfonate, ferric tetrafluoroborate, ferric hexafluorophosphate, ferric sulfate, ferric nitrate, ferric acetate, ferric trifluoroacetate, ferric citrate, ferric oxalate, ferric acrylate, tris (2,2,6, 6-tetramethyl-3, 5-heptanedionato) iron, ferric hydroxide, ferric acetylacetonate, ferric fluoride iron-containing compounds and hydrates thereof; the ferrous iron comprises ferrous chloride, ferrous bromide, ferrous iodide, ferrous trifluoromethanesulfonate, ferrous tetrafluoroborate, ferrous hexafluorophosphate, ferrous sulfate, ferrous nitrate, ferrous acetate, ferrous trifluoroacetate, ferrous citrate, ferrous oxalate, ferrous acrylate, ferrous bis (2,2,6, 6-tetramethyl-3, 5-heptanedionate), ferrous hydroxide, ferrous acetylacetonate, ferrous fluoride iron-containing compounds and hydrates thereof.
4. The method of claim 1 or 2, wherein the organic solvent is one or more of water, a hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, a nitrohydrocarbon solvent, an ether solvent, a nitrile solvent, an ester solvent, an alcohol solvent, an amine solvent, an amide solvent, a sulfone solvent, and a sulfoxide solvent.
5. The method of claim 4, wherein the hydrocarbon solvent is one or more of benzene, toluene and saturated alkane compounds, the halogenated hydrocarbon solvent is one or more of trifluoromethylbenzene, chlorobenzene, dichloromethane, 1, 2-dichloroethane, chloroform and carbon tetrachloride, and the nitrohydrocarbon solvent is one or more of nitrobenzene and nitromethane; the ether solvent is one or more of tetrahydrofuran, 1, 4-dioxane, methyl tert-butyl ether and diethyl ether; the nitrile solvent is one or more of acetonitrile, benzonitrile and tert-butyl acetonitrile; the ester solvent is one or more of ethyl acetate, n-butyl acetate and isobutyl acetate; the alcohol solvent is one or more of methanol, ethanol, tert-butyl alcohol, n-butyl alcohol and cyclohexanol, and the amine solvent is one or more of triethylamine, diethylamine and diisopropylethylamine; the amide solvent is one or more of dimethylformamide and dimethylacetamide; the sulfoxide solvent is dimethyl sulfoxide, and can be used in any proportion in various cases.
6. The process of claim 4, wherein the organic solvent is acetonitrile, t-butyl acetonitrile, ethyl acetate, dichloromethane.
7. A process according to claim 1 or 2, wherein the additive comprises an alkali metal salt of a halide, an alkali metal salt of an organic acid compound, an alkali metal salt of a phenolic compound, an ammonium salt of a halide, an ammonium salt of an organic acid compound, an ammonium salt of a phenolic compound, wherein the halide is fluoride, chloride, bromide, iodide; the alkali metal salt is lithium salt, sodium salt, potassium salt or cesium salt; the organic acid compound is substituted or unsubstituted aryl carboxylic acid, substituted or unsubstituted alkyl carboxylic acid, substituted or unsubstituted aryl sulfonic acid, substituted or unsubstituted alkyl sulfonic acid, substituted or unsubstituted aryl phosphoric acid and substituted or unsubstituted alkyl phosphoric acid; the phenols are substituted or unsubstituted phenol compounds; the ammonium salt is tetramethylammonium salt, tetraethylammonium salt or tetrabutylammonium salt.
8. The process according to claim 1 or 2, wherein the additive is selected from the group consisting of sodium chloride, potassium chloride, tetrabutylammonium chloride, and potassium pentafluorophenol.
9. A process for the preparation of an iron-catalyzed 4-aminoalcohol according to claim 1 or 2, wherein the molar ratio of the iron compound to the fatty alcohol is less than 1; the heating condition temperature is as follows: placing the reacted system at 25-100 ℃; the illumination conditions include: the reacted system is exposed to visible light and/or monochromatic or mixed light of a wavelength of less than 500 nm.
10. A process for the preparation of an iron-catalyzed 4-aminoalcohol according to claim 9, wherein the molar ratio of iron compound to fatty alcohol is (0.01-0.1): 1; the illumination conditions are as follows: placing the reacted system under light with the wavelength of 350-450nm for irradiation; the iron compound is ferric chloride, ferric tribromide, ferric trifluoromethanesulfonate or ferric tetrafluoroborate.
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