CN106045804A - Method for realizing asymmetric oxidation reaction of thioether under aqueous-phase catalysis of chiral Salen Ti complex catalyst based on temperature-sensitive type ionic liquid - Google Patents
Method for realizing asymmetric oxidation reaction of thioether under aqueous-phase catalysis of chiral Salen Ti complex catalyst based on temperature-sensitive type ionic liquid Download PDFInfo
- Publication number
- CN106045804A CN106045804A CN201610390141.8A CN201610390141A CN106045804A CN 106045804 A CN106045804 A CN 106045804A CN 201610390141 A CN201610390141 A CN 201610390141A CN 106045804 A CN106045804 A CN 106045804A
- Authority
- CN
- China
- Prior art keywords
- temperature
- ionic liquid
- complex catalyst
- oxidation reaction
- sensitive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 50
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 42
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000006555 catalytic reaction Methods 0.000 title abstract description 10
- 239000008346 aqueous phase Substances 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910001868 water Inorganic materials 0.000 claims abstract description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 sulfoxide compound Chemical class 0.000 claims abstract description 19
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 claims description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical group CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 230000009466 transformation Effects 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims 2
- 229920002401 polyacrylamide Polymers 0.000 claims 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- 229960000381 omeprazole Drugs 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 10
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 8
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- SUBDBMMJDZJVOS-UHFFFAOYSA-N 5-methoxy-2-{[(4-methoxy-3,5-dimethylpyridin-2-yl)methyl]sulfinyl}-1H-benzimidazole Chemical compound N=1C2=CC(OC)=CC=C2NC=1S(=O)CC1=NC=C(C)C(OC)=C1C SUBDBMMJDZJVOS-UHFFFAOYSA-N 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000010898 silica gel chromatography Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000002262 Schiff base Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JXTGICXCHWMCPM-UHFFFAOYSA-N (methylsulfinyl)benzene Chemical compound CS(=O)C1=CC=CC=C1 JXTGICXCHWMCPM-UHFFFAOYSA-N 0.000 description 2
- MPOPDYTWAYBUOD-UHFFFAOYSA-N 1-bromo-4-methylsulfinylbenzene Chemical compound CS(=O)C1=CC=C(Br)C=C1 MPOPDYTWAYBUOD-UHFFFAOYSA-N 0.000 description 2
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 2
- XSFFUNMJITWEEA-UHFFFAOYSA-N 1-methoxy-4-methylsulfinylbenzene Chemical compound COC1=CC=C(S(C)=O)C=C1 XSFFUNMJITWEEA-UHFFFAOYSA-N 0.000 description 2
- IQPSEEYGBUAQFF-SANMLTNESA-N 6-(difluoromethoxy)-2-[(s)-(3,4-dimethoxypyridin-2-yl)methylsulfinyl]-1h-benzimidazole Chemical compound COC1=CC=NC(C[S@](=O)C=2NC3=CC=C(OC(F)F)C=C3N=2)=C1OC IQPSEEYGBUAQFF-SANMLTNESA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ATTZFSUZZUNHBP-UHFFFAOYSA-N Piperonyl sulfoxide Chemical compound CCCCCCCCS(=O)C(C)CC1=CC=C2OCOC2=C1 ATTZFSUZZUNHBP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 description 1
- IWYDHOAUDWTVEP-ZETCQYMHSA-N (S)-mandelic acid Chemical compound OC(=O)[C@@H](O)C1=CC=CC=C1 IWYDHOAUDWTVEP-ZETCQYMHSA-N 0.000 description 1
- YEUYZNNBXLMFCW-UHFFFAOYSA-N 1-bromo-4-methylsulfanylbenzene Chemical compound CSC1=CC=C(Br)C=C1 YEUYZNNBXLMFCW-UHFFFAOYSA-N 0.000 description 1
- KACSTQZHMHDNKL-UHFFFAOYSA-N 1-chloro-n,n-diethylpropan-2-amine Chemical compound CCN(CC)C(C)CCl KACSTQZHMHDNKL-UHFFFAOYSA-N 0.000 description 1
- GZTOWBHKEXJZAV-UHFFFAOYSA-N 1-methoxy-2-[(2-methoxyphenyl)methylsulfinylmethyl]benzene Chemical compound COC1=CC=CC=C1CS(=O)CC1=CC=CC=C1OC GZTOWBHKEXJZAV-UHFFFAOYSA-N 0.000 description 1
- MLTFFVSGGPGNSP-UHFFFAOYSA-N 1-methylsulfinyl-4-nitrobenzene Chemical compound CS(=O)C1=CC=C([N+]([O-])=O)C=C1 MLTFFVSGGPGNSP-UHFFFAOYSA-N 0.000 description 1
- ZZTJMQPRKBNGNX-UHFFFAOYSA-N 1-nitro-4-(4-nitrophenyl)sulfanylbenzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1SC1=CC=C([N+]([O-])=O)C=C1 ZZTJMQPRKBNGNX-UHFFFAOYSA-N 0.000 description 1
- HTEFPPOWVYJBTD-UHFFFAOYSA-N 1-nitro-4-[(4-nitrophenyl)methylsulfinylmethyl]benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1CS(=O)CC1=CC=C([N+]([O-])=O)C=C1 HTEFPPOWVYJBTD-UHFFFAOYSA-N 0.000 description 1
- YFGHCGITMMYXAQ-UHFFFAOYSA-N 2-[(diphenylmethyl)sulfinyl]acetamide Chemical compound C=1C=CC=CC=1C(S(=O)CC(=O)N)C1=CC=CC=C1 YFGHCGITMMYXAQ-UHFFFAOYSA-N 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
- RRIQVLZDOZPJTH-UHFFFAOYSA-N 3,5-di-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=C(O)C(C(C)(C)C)=C1 RRIQVLZDOZPJTH-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- FUHSFUQMWWYWSZ-UHFFFAOYSA-N 5-methoxy-2-(4-methoxy-3,5-dimethylpyridin-2-yl)-1-methylsulfanylbenzimidazole Chemical compound N=1C2=CC(OC)=CC=C2N(SC)C=1C1=NC=C(C)C(OC)=C1C FUHSFUQMWWYWSZ-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical class OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 238000006202 Sharpless epoxidation reaction Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YSAVZVORKRDODB-WDSKDSINSA-N diethyl tartrate Chemical compound CCOC(=O)[C@@H](O)[C@H](O)C(=O)OCC YSAVZVORKRDODB-WDSKDSINSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- SUBDBMMJDZJVOS-DEOSSOPVSA-N esomeprazole Chemical compound C([S@](=O)C1=NC2=CC=C(C=C2N1)OC)C1=NC=C(C)C(OC)=C1C SUBDBMMJDZJVOS-DEOSSOPVSA-N 0.000 description 1
- 229960004770 esomeprazole Drugs 0.000 description 1
- LBAQSKZHMLAFHH-UHFFFAOYSA-N ethoxyethane;hydron;chloride Chemical compound Cl.CCOCC LBAQSKZHMLAFHH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229960001165 modafinil Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- HMIKWGIQTKJKOK-UHFFFAOYSA-N phenol;titanium Chemical compound [Ti].OC1=CC=CC=C1 HMIKWGIQTKJKOK-UHFFFAOYSA-N 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- MLKXDPUZXIRXEP-MFOYZWKCSA-N sulindac Chemical compound CC1=C(CC(O)=O)C2=CC(F)=CC=C2\C1=C/C1=CC=C(S(C)=O)C=C1 MLKXDPUZXIRXEP-MFOYZWKCSA-N 0.000 description 1
- 229960000894 sulindac Drugs 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
- B01J31/0297—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica the substrate being a soluble polymer, dendrimer or oligomer of characteristic microstructure of groups B01J31/061 - B01J31/068
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/46—Titanium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
Abstract
The invention discloses a method for realizing an asymmetric oxidation reaction of thioether under aqueous-phase catalysis of a chiral Salen Ti complex catalyst based on a temperature-sensitive type ionic liquid. According to the method, a chiral thioether compound and hydrogen peroxide are subjected to an asymmetric oxidation reaction under the catalytic action of the chiral Salen Ti complex catalyst based on the temperature-sensitive type ionic liquid in a water medium, and a chiral sulfoxide compound is obtained; the chiral Salen Ti complex catalyst based on the temperature-sensitive type ionic liquid also contains a chiral Salen Ti complex catalyst unit and a temperature-sensitive material unit. Compared with a conventional chiral Salen Ti catalyst, the catalyst has good water solubility, can be subjected to a catalytic reaction in the water medium and is easily recycled; the catalyst is applicable to the aqueous-phase catalytic oxidation reaction of chiral thioether and has the characteristics of high catalysis efficiency and good chiral sulfoxide selectivity.
Description
Technical Field
The invention relates to an improved chiral Salen Ti complex catalyst, in particular to a temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst and a method for catalyzing thioether asymmetric oxidation reaction based on the temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst in a water phase, and belongs to the technical field of preparation of new catalytic materials and synthesis of medical intermediates.
Background
Optically pure sulfoxide is an important chiral auxiliary, and is widely used in asymmetric synthesis reactions, such as C-C bond formation reaction, C-O bond formation reaction, asymmetric Michael addition reaction, carbonyl reduction reaction, Diels-Alder reaction, and free radical addition reaction (Chemical Communications,2009, 6129-6144). Optically pure chiral sulfoxides are active groups of many drugs and their use in the synthesis of biologically active compounds is also very broad, as some of the marketed hot-market drugs modafinil, sulindac and esomeprazole. Many biologically active molecules contain a chiral sulfinyl unit and enantiomers of different stereochemical structures have different physiological activities and metabolic actions. Meanwhile, the chiral sulfoxide can also be used as a chiral ligand to be applied to enantioselective catalytic reaction. Therefore, obtaining the sulfoxide with high enantioselectivity has important theoretical significance and practical value. During the last decades, researchers have made great efforts to develop various methods for preparing optically pure sulfoxides, mainly biological and chemical methods. The biological sulphoxide method comprises the steps of preparing chiral sulphoxide by using enzyme, microorganism and the like, and has the advantages of substrate specificity, high efficiency, greenness and the like, but the application of the biological enzyme or microorganism is limited due to the defects of poor stability, high price, narrow substrate range and the like. Chemical methods are divided into methods such as chiral auxiliary agent induction, resolution and asymmetric catalytic oxidation, and the asymmetric oxidation of thioether is the most practical method for preparing chiral sulfoxide so far. In 1984, asymmetric oxidation of thioethers was first achieved by Kagan using a modified Sharpless epoxidation catalyst (Synthesis,1984, 325-) -326; Tetrahedron Letters,1984,25, 1049-) -and after extensive and intensive research in this field, researchers developed a series of catalytic systems based on titanium, vanadium, aluminum, iron, copper, etc. (Tanaka, T.; Saito, B.; Katsuki, T.tetrahedron Letters, 2002,43,3259; Katsuki, T.J.Am.Chem.Soc.2007,129, 8940; O Maho, G.E.; Ford, A.; Maguire, A.J.Org.Chem.2012, 77,3288; Matmoto, K.; Yamaukchi, T.; Katsuki, T.1704, T.mamura.1704, T.su.su.1704, U.201muir, 201, J.Org.chem., 2008, 77,3288; Matmoto, K.; Yamaukchi, T.T.T.g.1704, T.1704, T.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.t.201mumu.t.t.t.t.t.t.t.t.t.t.t.t., conversion of highly sterically hindered, long-chain or branched substrates was successfully achieved (Dai, w.; Li, j.; Chen, b.; Li, g.; Lv, y.; Wang, l.; Gao, s.org. lett.2013,15,5658). The current literature reports that transition metal catalyzed asymmetric oxidation systems mainly comprise the following components according to chiral ligand classification: has a C2 symmetric chiral diol (phenol) -titanium catalytic system, a C3 symmetric chiral trialkanolamine-titanium and pickaxe catalytic system, a chiral porphyrin metal complex catalytic system and a chiral Schiff alkali metal complex catalytic system (Arkivoc,2011, (i), 1-110; Journal of sulfurr Chemistry,2013,34(3), 301-. However, the series of catalyst systems are carried out in a non-environment-friendly solvent of dichloromethane, and the product sulfoxide has low selectivity, which brings great difficulty to the separation and purification of the product. The existence of the problems greatly increases the synthesis cost of the chiral sulfoxide and limits the industrial production of the asymmetric oxidation reaction of the thioether.
International patents W091/12221 and W094/27988 describe the resolution of the sulphoxide compound as racemate directly into the single enantiomers, and mention is made in particular of the resolution of omeprazole into the single enantiomers. Chinese patent CN1087739, international patent applications W02006/094904, W02007/013743, etc. describe a method for obtaining levo-omeprazole by resolving omeprazole with (S) -binaphthol or tartaric acid to obtain an inclusion complex of levo-omeprazole, and then separating the inclusion complex with silica gel column or alkali to obtain levo-omeprazole. The resolution of omeprazole by the resolution method wastes half of omeprazole, causes environmental pollution and economic loss, and the resolution agent with optical activity is expensive, so the large-scale industrial application of the resolution method is limited.
International patent W096/02535, chinese patent CN1070489, discloses a process for obtaining S-omeprazole by oxidation of omeprazole thioether with a hydrogen peroxide derivative in the presence of a chiral bidentate ligand diethyl tartrate, a titanium metal complex and an alkali. International patent W003/089408 describes a process for obtaining levoomeprazole by oxidation of omeprazole thioether under catalysis of a complex of chiral monodentate (S) - (+) -mandelate with titanium or vanadium, simultaneously in the presence of a base.
Chinese patent CN200380104409.8, international patent W02004/052881, describes a process for the preparation of S-pantoprazole using a chiral pickaxel complex or a chiral hafnium complex. The method is characterized in that under the existence of (+) -or (-) -tartaric acid derivatives and alkoxy pickax or alkoxy hafnium, thioether is selectively oxidized to synthesize S-pantoprazole. CN200610023955 and CN181080803B describe a titanium-containing catalyst formed in situ by coordination of a metallic titanium reagent and a chiral diol to selectively oxidize thioether under the action of tert-butyl hydroperoxide.
International patents W096/17076 and W096/17077 describe methods for obtaining single enantiomeric sulfoxides by selective oxidation of thioethers or selective reduction of sulfones using microorganisms.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for catalyzing thioether asymmetric oxidation reaction by using a temperature-sensitive material unit and a temperature-sensitive ionic liquid chiral Salen Ti complex catalyst containing a temperature-sensitive material unit, wherein hydrophilic-hydrophobic conversion can be realized through a temperature condition.
In order to achieve the technical purpose, the invention provides a method for carrying out asymmetric oxidation reaction on thioether under the catalysis of a temperature-sensitive ionic liquid chiral Salen Ti complex catalyst in an aqueous medium, wherein a thioether compound with a structure shown in a formula 2 and hydrogen peroxide are subjected to asymmetric oxidation reaction under the catalysis of the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst with a structure shown in a formula 1, so that a chiral sulfoxide compound with a structure shown in a formula 3 is obtained:
wherein,
is a temperature sensitive unit;
X/Y is (1-100): 1.
R1、R2、R3Independently selected from hydrogen, alkyl, aryl-substituted alkyl or alkoxy;
R4is composed ofn is 0 to 3;
R5is C1～C3Alkyl or hydrogen ofAn atom;
R6and R7Independently selected from aryl, heterocyclic group, alkyl or substituted alkyl.
The preferable scheme is that R in the chiral Salen Ti complex catalyst of the temperature-sensitive ionic liquid1、R2And R3Independently selected from hydrogen, C1～C5Alkyl, phenyl, C containing phenyl substituents1～C5Alkyl or C1～C5Alkoxy group of (a); r4Is composed ofn is 0 to 2; r5Is a hydrogen atom.
In a preferred embodiment, X is in the range: 10 to 100, and Y is in the range of 1 to 10.
In the preferable scheme, X/Y in the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst is (5-50): 1.
In a preferred scheme, a temperature-sensitive unit in the temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst is an N-isopropylacrylamide unit and/or an N, N' -dimethylacrylamide unit.
Preferred embodiments, R in thioether Compounds and chiral sulfoxide Compounds6And R7Independently selected from:
c without substituents6～C12Or halogen, C1～4Alkyl radical, C1～4Alkoxy radical, C2～5C of alkoxycarbonyl, nitro or cyano substituents6～C12Aryl of (a);
or not containing substituted C1～C6Or C containing an aryl substituent1～C6Wherein the aryl substituent is preferably C having no substituent6～C12Or halogen, C1～4Alkyl radical, C1～4Alkoxy radical, C2～5Substituted by alkoxycarbonyl, nitro or cyano groupsC of radical6～C12Aryl) or C containing halogen, nitro, hydroxy or cyano substituents1～C6Alkyl groups of (a);
or a pyridine-or imidazole-containing group.
More preferred embodiment, R in thioether compounds and chiral sulfoxide compounds6And R7Independently selected from one of the following substituents:
the most preferred thioether compounds are: methyl phenyl sulfide (formula C)7H8S); 4-bromophenyl-methyl-sulfide (formula C)7H7BrS); 4-methoxy phenyl sulfide (molecular formula C)8H10OS); 4-Nitrophenyl sulfide (formula C)7H7NO2S); 2-methoxy phenyl sulfide (molecular formula C)8H10OS); omeprazole thioether (5-methoxy-2- (4-methoxy-3, 5-dimethyl-2-pyridyl) methylthio-1H-benzimidazole (molecular formula C)17H19N3O2S)。
The most preferred chiral sulfoxide compounds are: methyl phenyl sulfoxide (molecular formula C)7H8OS); 4-bromophenyl methyl sulfoxide (formula C)7H7BrOS); 4-methoxyphenyl methyl sulfoxide (formula C)8H10O2S); 4-Nitrophenyl methyl sulfoxide (formula C)7H7NO3S); 2-methoxyphenyl methyl sulfoxide (formula C)8H10O2S); omeprazole (5-methoxy-2- [ [ (4-methoxy-3, 5-dimethyl-2-pyridyl) methyl group]Sulfinyl group]-1H-benzimidazole of formula C17H19N3O3S)。
In a preferable scheme, a hydrogen peroxide solution is slowly dripped into an aqueous solution containing the thioether compound and the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst to carry out asymmetric oxidation reaction.
In a more preferable scheme, the molar ratio of the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst to the thioether compound is 1: 50-1: 1000; more preferably 1:100 to 1: 300.
In a more preferable embodiment, the molar ratio of the hydrogen peroxide to the thioether compound in the hydrogen peroxide solution is 1:1 to 2: 1; more preferably (1-1.2): 1.
In a more preferable scheme, the concentration of the hydrogen peroxide solution is 15 to 70 weight percent; more preferably 25 to 35 wt%.
In a preferable scheme, the asymmetric oxidation reaction is carried out for 0.1-5 hours at the temperature of-50 ℃. The reaction temperature is more preferably from-5 ℃ to 20 ℃. The reaction time is further preferably 1 to 1.5 hours.
According to the preferable scheme, after the asymmetric oxidation reaction is finished, the temperature of a reaction system is raised to realize hydrophilic-hydrophobic transformation of the temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst, the temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst is separated out, and the catalyst is filtered and recovered.
The preparation method of the temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst comprises the following steps:
1) performing substitution reaction on the Schiff base compound with the structure shown in the formula 4 and the imidazole compound with the structure shown in the formula 5 to obtain an ionic liquid functionalized chiral Schiff base compound with the structure shown in the formula 6;
2) carrying out coordination reaction on the ionic liquid functionalized chiral Schiff base compound and tetraisopropyl titanate to obtain an ionic liquid chiral Salen Ti complex with a structure shown in a formula 7;
3) obtaining a temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst by adopting a temperature-sensitive monomer and an ionic liquid chiral Salen Ti complex with a structure shown in a formula 7 through a controllable free radical polymerization method;
wherein,
R1、R2、R3independently selected from hydrogen, alkyl, aryl-substituted alkyl or alkoxy;
R4is composed ofn is 0 to 3;
R5is C1～C3Alkyl group or hydrogen atom of (2).
Preferred embodiment, R1、R2And R3Independently selected from hydrogen, C1～C5Alkyl, phenyl, C containing phenyl substituents1～C5Alkyl or C1～C5Alkoxy group of (a); r4Is composed ofn is 0 to 2; r5Is a hydrogen atom.
In a preferable scheme, the molar ratio of the temperature-sensitive monomer to the ionic liquid chiral Salen Ti complex is (1-100): 1; more preferably (5-50): 1.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
1) the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst adopted by the technical scheme of the invention mainly comprises a catalyst unit and a temperature-sensitive material unit, wherein the catalyst unit takes Ti as a catalytic activity central atom and chiral Salen as a ligand, the catalyst unit shows higher selectivity and high catalytic activity for the asymmetric oxidation reaction of thioether, and the yield of chiral sulfoxide is up to 85-98%. The temperature-sensitive material unit endows the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst with better water solubility, so that the asymmetric oxidation reaction of thioether is realized by taking water as a solvent, and meanwhile, the temperature-sensitive material unit has a hydrophilic-hydrophobic conversion function, can control the water solubility of the catalyst through temperature, and is favorable for recycling the catalyst.
2) The temperature-sensitive ionic liquid chiral Salen Ti complex catalyst forms a hydrophilic shell at the hydrophilic end of a temperature-sensitive material in water in the asymmetric oxidation reaction of thioether catalyzed by a water phase, hydrophobic active centers are rapidly gathered to form micelles, the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst is an ideal nano reactor, a hydrophobic thioether reaction substrate can rapidly enter a hydrophobic core after being added into an aqueous solution, and when the aqueous solution of hydrogen peroxide is taken as an oxygen source, the hydrogen peroxide can slowly enter the hydrophobic core to oxidize thioether to generate chiral sulfoxide, so that the selectivity and the reaction efficiency of chiral oxidation are greatly improved.
3) The preparation method of the temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst is simple, the process conditions are mild, the catalyst unit and the temperature-sensitive material unit in the temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst can be randomly regulated and controlled, and a series of different hydrophilic and hydrophobic materials can be obtainedProportional block polymer PNX(IS)yAnd meets different catalytic application requirements.
4) The asymmetric oxidation reaction of thioether catalyzed by the chiral Salen Ti complex catalyst based on the temperature-sensitive ionic liquid can be carried out in an aqueous medium, and the defect that the reaction needs to be carried out in an organic solvent in the prior art is overcome.
5) The temperature-sensitive ionic liquid chiral Salen Ti complex catalyst fully utilizes the hydrophobic-hydrophilic conversion performance of a temperature-sensitive material unit, has hydrophilicity at a relatively low temperature and hydrophobicity at a relatively high temperature, and can be recovered only by controlling the temperature. Overcomes the defect that the chiral Salen Ti complex catalyst is difficult to recycle in the prior art, and greatly reduces the use cost of the catalyst.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the catalyst in an aqueous solution; in the figure, b, c and e are respectively PN60(IS)2、PN68(IS)4、PN66(IS)6Transmission electron micrographs at room temperature of three representative aqueous catalyst solutions; as can be seen from FIG. 1, the catalysts can form nano-spherical particles in water, the upper right corner is an aqueous solution diagram of the three catalysts, and the three catalysts can be well dissolved in water to form micelle nanoparticles. b' is FIG. bPN60(IS)2When the temperature of the aqueous solution rises to 35 ℃, the catalyst is gathered, and as can be seen from the upper right picture, the temperature rises, the catalyst is separated out from the aqueous phase, so that the effects of high-efficiency catalysis at room temperature and simple separation at temperature rise are achieved, and the simple recovery and high-efficiency repetition of the catalyst are realized.
FIG. 2 is an infrared characterization (FT-IR) chart of several characteristic catalysts, wherein a is an infrared chart of a traditional catalyst Salen Ti, and b is a catalyst PN68(IS)4B' is catalyst PN68(IS)4Infrared images after repeated use. As can be seen from the figure, the catalyst has the characteristic peak of the traditional Salen Ti, and after the catalyst is repeatedly used, the infrared image is not changed, and the catalyst still has good catalytic effect.
Detailed Description
The invention is described in further detail below with reference to examples, which are intended to be illustrative and not limiting.
Example 1
Preparation of temperature-sensitive chiral nano reaction catalyst (R)1、R2、R3Both t-butyl), R4The ionic liquid is vinyl imidazole.
Dissolving the resolved (R, R) -cyclohexanediamine tartrate (11.2mmol) and potassium carbonate (22.5mmol) in 20mL of a mixed solvent of absolute ethyl alcohol and deionized water (5/L, V/V) at room temperature, slowly heating to 80 ℃, refluxing for 2h, placing in a refrigerator, extracting the free (R, R) -cyclohexanediamine with chloroform (4 × 5mL), combining organic phases at 0 ℃, slowly adding an ether hydrochloride solution (11.2mmol, 2mol/L), standing overnight at room temperature, dissolving the single amino protected (R, R) -cyclohexanediamine (8mmol) and 3, 5-di-tert-butylsalicylaldehyde (8mmol) in 60mL of a mixed solvent of absolute methanol and absolute ethyl alcohol (1/1, V/V), adding an active 4A molecular sieve (1g), reacting for 4h at room temperature to obtain a light yellow solid, slowly adding 20mL of a mixed solution of 3-tert-butyl-5-salicylaldehyde (8mmol) and chloromethyl triethylamine (16mmol), dropwise adding the obtained solution to the crude dichloromethane, filtering, and crystallizing to obtain a light yellow solid, and purifying the product by column chromatography, and filtering the crude product by chromatography (SiO)2Acetic acid ethyl esterN-hexane 1/5, V/V) to give CL (3.57g, 83%) as a light yellow powder. For C33H47ClN2O2:C,73.51；H,8.79；N,5.20.Found:C,73.46；H,8.91；N,5.12％.1H-NMR(CDCl3,400MHz):ppm14.29(s,1H),13.67(s,1H),8.44(s,1H),8.31 (s,1H),7.30(d,1H),7.26(d,1H),6.99(d,1H),6.89(d,1H),4.43(s,2H),3.55-3.32(m,2H),1.97-1.46(m,8H),1.40(s,9H),1.23(s,18H).FT-IR(KBr):3446,2954,2862,1629,1591,1479,1469,1439,1391,1361,1271,1252,1241,1201,1174,1144,1086,1040,981,934,879,828,803,772,731,711,644cm-1。
To 50mL of dry toluene were added equal amounts of the above solid CL (3.2mmol,1.725g) and vinylimidazole (3mmol,0.28g), N2Refluxing at 110 deg.C for 48h under protection. Distilling the solvent under reduced pressure, vacuum drying, and dissolving the product in CH at room temperature2Cl2To this was added an equimolar amount of tetraisopropyl titanate (Ti (O)iPr)43.2mmol,0.91g) at room temperature for 3h to give the yellow product IL/Ti (salen). FT-IR (KBr) < gamma >max/cm-13437,3310,3073,2973,2933,2882,1653,1540,1458,1384,1365,1263,1172,1130,1051,986,922,881,838,626,518cm-1.1H NMR(500MHz,CD3Cl3):8.11～7.65(s,2H,CH＝N),7.18～7.59(m,4H,ArH),6.05(m,1H,N-CH＝CH2)4.15(s,1H,C＝NCH),3.87(m,1H,C＝NCH),3.56(m,4H,N-CH＝CH2and-N-CH2-N-),2.36～2.65(m,2H,CH3-CH-CH3iniPrO-),1.46(m,8H,cyclohexyl-H),1.23～1.37(m,27H,H-in t-butyl),1.31(m,12H,CH3-CH-CH3iniPrO-)。
In Schlenk, temperature-sensitive materials and IL/Ti (salen) were added in different proportional amounts, dissolved in anhydrous methanol, and an initiator azobisisobutyronitrile (AIBN, 0.5mmol,0.082g) and a chain transfer agent Propanethiol (N-Propanethiol, 1mmol,0.076g), N, were added thereto2Reacting at 60 deg.C for 24 hr under protection, cooling to room temperature, distilling under reduced pressure to remove solvent, dissolving with tetrahydrofuran, precipitating with diethyl ether, and vacuum drying to obtain yellowProduct PN as a colored solidx(IS)y(x represents a polymer of a thermo-sensitive unit and y represents the degree of polymerization of an ionic liquid functionalized Salen Ti unit). x and y are obtained by nuclear magnetic characterization.
Other catalysts were prepared as described above. Four examples are listed, respectively:
PN60(IS)2:FT-IR(KBr):γmax/cm-13436,3313,3075,2971,2942,2891,1653,1542,1457,1386,1368,1263,1170,1131,1054,985,927,880,836,806,709,624,519cm-1.1H NMR(500MHz,CDCl3):6.24～6.89(m,60H,HC-NH-C＝O),6.08(m,2H,N-CH-CH2-of N-vinyl),4.18(m,2H,C＝NCH),3.99(m,60H,-CH-CH2inNIPAAm),3.88(m,2H,C＝NCH),3.67(m,8H,-CH-CH2-of N-vinyl in IL and-N-CH2-N-),3.45(m,60H,CH3-CH-CH3in NIPAAm),3.06(m,12H,-N-CH2-CH2-N-and-N-CH2-Ph-),2.84(m,2H,SH-CH2-CH2-CH3),2.64～2.73(m,4H,CH3-CH-CH3ofiPrO-in Ti(salen)),2.38(m,2H,SH-CH2-CH2-CH3),1.86～2.12 (m,120 H,-CH2-CH-in NIPAAm),1.71(s,3 H,SH-CH2-CH2-CH3),1.43(16 H,cyclohexyl-H),1.13～1.33(54H,H-int-butyl),1.09～1.16(m,384 H,CH3-CH-CH3iniPrO-and NIPAAm)；
PN68(IS)4:FT-IR(KBr):γmax/cm-13436,3302,3064,2967,2923,2867,1645,1541,1454,1382,1365,1265,1175,1128,1053,965,920,882,834,809,709,635,624,509 cm-1.1HNMR(500 MHz,CD3Cl3):8.15～7.68(m,8 H,CH＝N),7.14～7.64(m,16 H,ArH),6.24～6.89(m,68 H,HC-NH-C＝O),6.05(m,4H,N-CH-CH2-of N-vinyl),4.14(m,4 H,C＝NCH),3.99(m,68 H,-CH-CH2-in NIPAAm),3.85(m,4 H,C＝NCH),3.58(m,16 H,-CH-CH2-of N-vinyl inIL and-N-CH2-N-),3.26(m,68 H,CH3-CH-CH3in NIPAAm),2.90(m,24 H,-N-CH2-CH2-N-and-N-CH2-Ph-),2.78(m,2 H,SH-CH2-CH2-CH3),2.34～2.68(m,8 H,CH3-CH-CH3ofiPrO-inTi(salen)),2.10(m,2 H,SH-CH2-CH2-CH3),1.78～1.98(m,136 H,-CH-CH2in NIPAAm),1.73(s,3H,SH-CH2-CH2-CH3),1.47(m,32 H,cyclohexyl-H),1.21～1.38(m,108 H,H-int-butyl),1.06～1.15(m,456 H,CH3-CH-CH3iniPrO-and NIPAAm)；
PN66(IS)6:FT-IR(KBr):γmax/cm-13441,3309,3061,2974,2927,2864,1651,1530,1453,1382,1363,1266,1176,1123,1051,963,920,883,836,805,708,625,504cm-1.1H NMR(500 MHz,CD3Cl3):8.13～7.72(m,12 H,CH＝N),7.18～7.69(m,24 H,ArH),6.21～6.92(m,66 H,HC-NH-C＝O),6.16(m,6 H,N-CH-CH2-of N-vinyl),4.04(m,6H,C＝NCH),3.97(m,66 H,-CH-CH2-in NIPAAm),3.81(m,6 H,C＝NCH),3.56(m,24 H,-CH-CH2-of N-vinyl inIL and-N-CH2-N-),3.23(m,66 H,CH3-CH-CH3in NIPAAm),3.09(m,36 H,-N-CH2-CH2-N-and-N-CH2-Ph-),2.75(m,2 H,SH-CH2-CH2-CH3),2.41～2.61(m,12 H,CH3-CH-CH3ofiPrO-in Ti(salen)),2.23(m,2 H,SH-CH2-CH2-CH3),1.76～1.82(m,132 H,-CH-CH2in NIPAAm),1.75(s,3 H,SH-CH2-CH2-CH3),1.41(m,48 H,cyclohexyl-H),1.22～1.31(m,162 H,H-in t-butyl),1.01～1.12(m,469 H,CH3-CH-CH3iniPrO-and NIPAAm)；
PN64(IS)8:FT-IR(KBr):γmax/cm-13435,3302,3066,2974,2924,2860,1655,1535,1455,1380,1365,1264,1174,1125,1054,967,924,882,839,806,709,634,625,507cm-1.1HNMR(500 MHz,CD3Cl3):8.11～7.62(m,16 H,CH＝N),7.13～7.67(m,32 H,ArH),6.24～6.87(m,64 H,HC-NH-C＝O),6.22(m,8 H, N-CH-CH2-of N-vinyl),4.46(m,8H,C＝NCH),4.05(m,64H,-CH-CH2-in NIPAAm),3.78(m,8H,C＝NCH),3.58(m,32H,-CH-CH2-of N-vinylin IL and-N-CH2-N-),3.18(m,64H,CH3-CH-CH3in NIPAAm),2.86(m,48H,-N-CH2-CH2-N-and-N-CH2-Ph-),2.75(m,2H,SH-CH2-CH2-CH3),2.45～2.63(m,16H,CH3-CH-CH3ofiPrO-inTi(salen)),2.12(m,2H,SH-CH2-CH2-CH3),1.75～1.87(m,128H,-CH-CH2-in NIPAAm),1.73(s,3H,SH-CH2-CH2-CH3),1.41(m,64H,cyclohexyl-H),1.22～1.31(m,216H,H-in t-butyl),1.01～1.12(m,480H,CH3-CH-CH3iniPrO-and NIPAAm)。
according to the method, a series of catalysts are prepared by using different temperature-sensitive materials.
Example 2
The reaction conditions were optimized using methyl phenyl sulfide as a model substrate, and the results are as follows.
The reaction route is as follows:
a10 mL reaction flask was charged with 1mmol of substrate (methyl phenyl sulfide), 0.5 mmol% of catalyst PN68(IS)4，1mL H2O as solvent, slowly dropping 1.2mmol of 30% H in 15min at 25 deg.C2O2The reaction was continued for 45 min. After the reaction is finished, automatically separating out the catalyst, separating out a water phase, washing the catalyst with n-hexane, drying and reusing the catalyst, extracting the water phase with dichloromethane to obtain a product, performing gas chromatography analysis on the product to detect the conversion rate and the selectivity, performing liquid chromatography analysis to obtain an ee value, and performing column chromatographyAnd (5) when the product is obtained, calculating to obtain the yield, and determining the structure of the product by nuclear magnetic characterization.
Four comparative catalysts and a conventional Salen Ti catalyst were used to catalyze the oxidation of methyl phenyl sulfide to sulfoxide with the results shown in the following table:
[a]Yield of the isolated product.[b]Determined by HPLC.
as can be seen from the table, the proportion of the hydrophilic and hydrophobic substituents can influence the catalytic effect and show regular changes. PN (pseudo-noise)68(IS)4Is the most moderate hydrophilic-hydrophobic ratio, when the hydrophilic group is too long (PN)60(IS)2) The active center is greatly reduced, and the catalytic efficiency is lower than that of PN68(IS)4(yield was only 75%). When the ratio of hydrophilic to hydrophobic<17, the catalytic activity is also lowered, (PN)66(IS)689% of PN64(IS)886%) and the ee value also shows a regular change.
Methyl phenyl sulfoxide, white solid, silica gel column chromatography (methanol: dichloromethane ═ 20:80 (vol)) (93% yield, 98% ee).1H NMR(CDCl3,500MHz):(ppm):2.56(s,3H,Me),7.37-7.52(m,5H,ArH).13C NMR(CDCl3,125MHz):(ppm):43.8(SCH3) 123.4,129.3,131.0,145.5; the conversion and selectivity were determined by gas chromatography (Agilent Co, HP19091G-B213, column temperature 180 ℃, flow rate: 1.6mL/min),
the ee value is determined by chiral high performance liquid chromatography (column: Daicel chiralpak AD, mobile phase: isopropanol/n-hexane ═ 10:90 (volume ratio), flow rate: 1.0mL/min, wavelength: 254nm, temperature 25 ℃ C.).
Example 3
Selecting PN68(IS)4Different substrates were examined.
The reaction route is as follows:
reaction procedure and workup as in example 2 above
Catalyst PN68(IS)4And a conventional Salen Ti catalyst, for catalyzing the oxidation of the other four thioethers to sulfoxides, with the results shown in the following table:
as can be seen from the table, catalyst PN68(IS)4The catalytic effect of the catalyst is obviously superior to that of the traditional catalyst, and the catalyst has great advantages in yield and ee value.
The characterization data for the partial products are as follows:
4-bromophenyl-methyl sulfoxide, yellow solid, silica gel column chromatography (methanol: dichloromethane ═ 20:80 (vol.)) (yield 82%, ee value>99％)。1H NMR(CDCl3,500MHz):(ppm):3.07(s,3H,SCH3),7.84(d,2H,ArH),7.74(d,2H,ArH).13C NMR(CDCl3,125MHz):(ppm):44.5(SCH3) 129.0,132.7,139.5; the ee value was determined by chiral high performance liquid chromatography (column: Daicelchiralpak AD, mobile phase: isopropanol/n-hexane: 50 (volume ratio), flow rate: 1.0mL/min, wavelength: 254nm, temperature 25 ℃ C.)
4-methoxyphenyl methyl sulfoxide, colorless liquid, silica gel column chromatography separation (methanol: dichloromethane ═ 20:80 (body)Volume ratio) (yield 90%, ee 94%).1H NMR(CDCl3,500MHz):(ppm):3.01(s,3H,SCH3),3.91(s,3H,OCH3),7.04(d,2H,ArH),7.89(d,2H,ArH).13C NMR(CDCl3,125MHz):(ppm):44.9(SCH3),55.7(OCH3) 114.5,129.6,132.3,163.7; the ee value was determined by chiral high performance liquid chromatography (column: Daicelchiralpak AD, mobile phase: isopropanol/n-hexane ═ 20:80 (volume ratio), flow rate: 1.0mL/min, wavelength: 254nm, temperature 25 ℃ C.)
4-Nitrophenylmethyl sulfoxide, a yellow solid, and silica gel column chromatography (methanol: dichloromethane ═ 20:80 (by volume)) (yield 97%, ee value 88%).1H NMR(CDCl3,500MHz):(ppm):2.57(s,3H,SCH3),7.30(d,2H,ArH),8.16(d,2H,ArH).13C NMR(CDCl3,125MHz): (ppm):43.9(SCH3) 113.9,125.0,144.7,148.9; the ee value was determined by chiral high performance liquid chromatography (column: Daicel chiralpak AD, mobile phase: isopropanol/n-hexane: 30:70 (volume ratio), flow rate: 1.0mL/min, wavelength: 254nm, temperature 25 ℃ C.)
2-methoxyphenyl methyl sulfoxide (p-cresol) as a colorless liquid, which was separated by column chromatography on silica gel (methanol: dichloromethane ═ 20:80 (vol.)) (yield 88%, ee value 99%).1H NMR(CDCl3,500MHz):(ppm):2.67(s,3H,SCH3),3.78(s,3H,OCH3),6.84-7.37(m,4H,ArH).13C NMR(CDCl3,125MHz):(ppm):13C NMR(CDCl3,125MHz):(ppm):41.1(SCH3),55.7(OCH3) 118.6,121.5,124.3,132.0,154.7; the ee value was determined by chiral high performance liquid chromatography (column: Daicel chiralpak AD, mobile phase: isopropanol/n-hexane ═ 20:80 (volume ratio), flow rate: 1.0mL/min, wavelength: 254nm, temperature 25 ℃ C.)
Omeprazole, white powder, silica gel column chromatography (methanol: dichloromethane ═ 20:80 (volume ratio)) (yield 80%, ee value 87%).1H NMR (DMSO,500MHz) (ppm) 2.15(s,6H),3.65(s,3H),3.78(s,3H),4.66and 4.75(AB-system,2H),6.90(dd,1H),7.08(s,1H),7.53(d,1H),8.15(s, 1H); ee value chiral high-efficiency liquidPhase chromatography (column: Daicel chiralpak AD, mobile phase: isopropanol/n-hexane ═ 20:80 (volume ratio), flow rate: 1.0mL/min, wavelength: 254nm, temperature 25 ℃ C.)
The temperature sensitivity of the catalyst is realized in that after the reaction is finished, the catalyst is separated out from a reaction system, when the temperature is raised, the catalyst is completely separated out and separated, the catalyst is dissolved in water under the condition of room temperature, and when the temperature is raised, the catalyst is separated out from a water phase and aggregated. The specific pattern can be seen by a transmission electron microscope.
Example 4
Examination of catalyst reusability
After the solution after the reaction is heated, the catalyst can be separated out from the reaction system, and the catalyst is used in the next catalytic reaction system through the steps of filtering, washing, drying and the like, wherein the repeated use effect is shown in the following table:
[a]Yield of the isolated product.[b]Determined by HPLC.
from the above data, it can be seen that the catalyst has better reusability. The reaction system takes water as a reaction solvent, is green and environment-friendly, and provides a method for mass production of the chiral sulfoxide for enterprises.
Claims (10)
1. A method for catalyzing thioether asymmetric oxidation reaction based on a temperature-sensitive ionic liquid chiral Salen Ti complex catalyst in a water phase is characterized by comprising the following steps: in an aqueous medium, carrying out asymmetric oxidation reaction on a thioether compound with a structure shown in formula 2 and hydrogen peroxide under the catalytic action of a temperature-sensitive ionic liquid chiral Salen Ti complex catalyst with a structure shown in formula 1 to obtain a chiral sulfoxide compound with a structure shown in formula 3:
wherein,
is a temperature sensitive polymer unit;
X/Y is (1-100) 1;
R1、R2、R3independently selected from hydrogen, alkyl, aryl-substituted alkyl or alkoxy;
R4is composed ofn is 0 to 3;
R5is C1～C3Alkyl or hydrogen atom of (a);
R6and R7Independently selected from aryl, heterocyclic group, alkyl or substituted alkyl.
2. The method for catalyzing thioether asymmetric oxidation reaction based on the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst in the water phase according to claim 1, which is characterized in that: r1、R2And R3Independently selected from hydrogen, C1～C5Alkyl, phenyl, C containing phenyl substituents1～C5Alkyl or C1～C5Alkoxy group of (a); r4Is composed ofn is 0 to 2; r5Is a hydrogen atom.
3. The method for catalyzing thioether asymmetric oxidation reaction based on the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst in the water phase according to claim 1, which is characterized in that: X/Y is (5-50) 1.
4. The method for catalyzing thioether asymmetric oxidation reaction based on the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst in the water phase according to claim 1, which is characterized in that: the temperature-sensitive polymer unit is an N-isopropyl acrylamide polymer unit and/or an N, N' -dimethyl acrylamide polymer unit.
5. The method for catalyzing thioether asymmetric oxidation reaction based on the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst in the water phase according to any one of claims 1-4, which is characterized in that: r6And R7Independently selected from: c without substituents6～C12Or halogen, C1～4Alkyl radical, C1～4Alkoxy radical, C2～5C of alkoxycarbonyl, nitro or cyano substituents6～C12Aryl of (a);
or not containing substituted C1～C6Or C containing an aryl substituent1～C6Or C containing halogen, nitro, hydroxy or cyano substituents1～C6Alkyl groups of (a);
or a pyridine or imidazole-containing group.
6. The method for catalyzing thioether asymmetric oxidation reaction based on the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst in the water phase according to claim 5, which is characterized in that: r6And R7Independently selected from one of the following substituents:
7. the method for catalyzing thioether asymmetric oxidation reaction based on the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst in the water phase according to any one of claims 1-4, which is characterized in that: and slowly dripping a hydrogen peroxide solution into the aqueous solution containing the thioether compound and the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst to perform asymmetric oxidation reaction.
8. The method for catalyzing thioether asymmetric oxidation reaction based on the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst in the water phase according to claim 7, which is characterized in that: the molar ratio of the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst to the thioether compound is 1: 50-1: 1000;
the molar ratio of the hydrogen peroxide to the thioether compound in the hydrogen peroxide solution is 1: 1-2: 1;
the concentration of the hydrogen peroxide solution is 15-70 wt%.
9. The method for catalyzing thioether asymmetric oxidation reaction based on the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst in the water phase according to any one of claims 1-4, which is characterized in that: the asymmetric oxidation reaction is carried out for 0.1-5 h at the temperature of-50 ℃.
10. The method for catalyzing thioether asymmetric oxidation reaction based on the temperature-sensitive ionic liquid chiral Salen Ti complex catalyst in the water phase according to claim 9, which is characterized in that: after the asymmetric oxidation reaction is finished, raising the temperature of a reaction system to realize hydrophilic-hydrophobic transformation of the temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst, separating out the temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst, and filtering and recycling the temperature-sensitive type ionic liquid chiral Salen Ti complex catalyst for reuse.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610390141.8A CN106045804B (en) | 2016-06-03 | 2016-06-03 | A method of based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis thioether asymmetric oxidation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610390141.8A CN106045804B (en) | 2016-06-03 | 2016-06-03 | A method of based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis thioether asymmetric oxidation reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106045804A true CN106045804A (en) | 2016-10-26 |
| CN106045804B CN106045804B (en) | 2019-01-11 |
Family
ID=57170135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610390141.8A Expired - Fee Related CN106045804B (en) | 2016-06-03 | 2016-06-03 | A method of based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis thioether asymmetric oxidation reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106045804B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675626A (en) * | 2019-01-11 | 2019-04-26 | 南阳师范学院 | A kind of responsive to temperature type polyoxometallate composite catalyst and its synthetic method |
| CN111574497A (en) * | 2020-04-27 | 2020-08-25 | 湖北工程学院 | Method for preparing chiral sulfoxide drugs in water phase |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050096260A1 (en) * | 2003-10-29 | 2005-05-05 | Nagoya Industrial Science Research Institute | Metal complex-protein composite and oxidation catalyst |
| KR20120077913A (en) * | 2010-12-31 | 2012-07-10 | 제일모직주식회사 | Method for preparing aromatic carbonate from dialkyl carbonate |
| CN104117392A (en) * | 2013-04-27 | 2014-10-29 | 浙江海翔药业股份有限公司 | Supported catalyst and preparation method thereof |
-
2016
- 2016-06-03 CN CN201610390141.8A patent/CN106045804B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050096260A1 (en) * | 2003-10-29 | 2005-05-05 | Nagoya Industrial Science Research Institute | Metal complex-protein composite and oxidation catalyst |
| KR20120077913A (en) * | 2010-12-31 | 2012-07-10 | 제일모직주식회사 | Method for preparing aromatic carbonate from dialkyl carbonate |
| CN104117392A (en) * | 2013-04-27 | 2014-10-29 | 浙江海翔药业股份有限公司 | Supported catalyst and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| GUANGWU ZHAO ET AL: "Cooperative chiral salen TiIV catalysts with built-in phase-transfer capability accelerate asymmetric sulfoxidation in water", 《RSC ADVANCES》 * |
| MIN LIU ET AL: "New chiral catalytic membrane reactor created by immobilizing salen-Mn(III) onto APTES modified ceramic membrane and its performances in epoxidation of styrene", 《CATALYSIS COMMUNICATIONS》 * |
| YAOYAO ZHANG ET AL: "Asymmetric epoxidation of unfunctionalized olefins accelerated by thermoresponsive self-assemblies in aqueous systems", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
| 唐红艳等: "钛催化的不对称硫醚氧化研究进展", 《化工科技》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109675626A (en) * | 2019-01-11 | 2019-04-26 | 南阳师范学院 | A kind of responsive to temperature type polyoxometallate composite catalyst and its synthetic method |
| CN109675626B (en) * | 2019-01-11 | 2021-12-28 | 南阳师范学院 | Temperature-sensitive polyoxometallate composite catalyst and synthesis method thereof |
| CN111574497A (en) * | 2020-04-27 | 2020-08-25 | 湖北工程学院 | Method for preparing chiral sulfoxide drugs in water phase |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106045804B (en) | 2019-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105879914B (en) | A kind of temperature sensitive type ionic liquid chirality Salen Ti composition catalysts and preparation method thereof | |
| US9433926B2 (en) | Platinum/carbon nanotube catalyst, the preparation process and use thereof | |
| JP4834545B2 (en) | Method for producing optically active epoxy compound, complex used in the method, and method for producing the same | |
| US7812184B2 (en) | Production method of optically active epoxy compound, complex used for the method and production method of the complex | |
| CN109593803A (en) | (R) preparation method of -2- (2,5- difluorophenyl) pyrrolidines or its salt | |
| JP2010001443A (en) | Stereoselective alternating copolymerization of epoxide and carbon dioxide | |
| CN106045804B (en) | A method of based on temperature sensitive type ionic liquid chirality Salen Ti composition catalyst aqueous catalysis thioether asymmetric oxidation reaction | |
| CN113549062B (en) | Chiral quaternary ammonium salt phase transfer catalyst with high steric hindrance derived from cinchona alkaloid and synthesis method thereof | |
| CN102241670A (en) | Preparation method of high-purity chiral sulphoxide compound | |
| CN104744394A (en) | Method for asymmetrically synthesizing chiral quaternary carbon compound containing trifluoromethyl | |
| CN111574497A (en) | Method for preparing chiral sulfoxide drugs in water phase | |
| JP4649645B2 (en) | Process for producing optically active alcohol compounds | |
| CN109499609B (en) | SBA-15 immobilized 2-azaadamantane nitroxide free radical catalyst and preparation and application thereof | |
| CN107915653A (en) | Catalysis ester and amine carry out the method that reaction prepares acid amides | |
| CN113200954B (en) | Preparation method of cyclic carbonate | |
| CN113754605B (en) | Nitrogen-containing ligand, and preparation method and application thereof | |
| CN101844980B (en) | Method for preparing chiral alpha-hydroxy-beta-keto ester compound by utilizing chiral beta-alkoxy beta'-alkamine as catalyst | |
| CN105503673A (en) | Method for preparing chiral sulfoxide through catalysis of asymmetric oxidation of thioether | |
| CN106345526B (en) | A kind of load-type vanadium chiral catalyst and preparation method thereof for asymmetric syntheses esomeprazole | |
| CN113754604A (en) | Nitrogen-containing chiral ligand and application thereof in asymmetric oxidation reaction of thioether | |
| JP5580613B2 (en) | Production of asymmetric esters using polymer-supported gold cluster catalysts | |
| CN101891678A (en) | 4-(N,N-dimethyl) aminopyridine derivate and synthesis method thereof | |
| CN116239573B (en) | Preparation method and application of metal organic quaternary cyclic compound | |
| CN105772101B (en) | The Mn Anderson types heteropolyacid catalyst of 1 Phenethylthiourea modification, preparation method and applications | |
| CN105709826A (en) | Preparation method of axially-immobilized porphyrin-like catalyst, catalyst and application of catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190111 Termination date: 20190603 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |