CN117512615A - Method for reducing aldehyde ketone into alcohol or deuterated alcohol - Google Patents
Method for reducing aldehyde ketone into alcohol or deuterated alcohol Download PDFInfo
- Publication number
- CN117512615A CN117512615A CN202311533749.8A CN202311533749A CN117512615A CN 117512615 A CN117512615 A CN 117512615A CN 202311533749 A CN202311533749 A CN 202311533749A CN 117512615 A CN117512615 A CN 117512615A
- Authority
- CN
- China
- Prior art keywords
- alcohol
- aldehyde ketone
- deuterated
- ion
- reducing
- 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.)
- Pending
Links
- -1 aldehyde ketone Chemical class 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 150000001298 alcohols Chemical class 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 238000003487 electrochemical reaction Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 16
- 229910052718 tin Inorganic materials 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 4
- 239000010941 cobalt Substances 0.000 claims 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 4
- 239000010949 copper Substances 0.000 claims 4
- 229910052742 iron Inorganic materials 0.000 claims 4
- 239000011133 lead Substances 0.000 claims 4
- 239000011777 magnesium Substances 0.000 claims 4
- 239000011135 tin Substances 0.000 claims 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 3
- 125000000217 alkyl group Chemical group 0.000 claims 3
- 229910045601 alloy Inorganic materials 0.000 claims 3
- 239000000956 alloy Substances 0.000 claims 3
- 150000001450 anions Chemical class 0.000 claims 3
- 150000001768 cations Chemical class 0.000 claims 3
- 229910017052 cobalt Inorganic materials 0.000 claims 3
- 229910052802 copper Inorganic materials 0.000 claims 3
- 229910052749 magnesium Inorganic materials 0.000 claims 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 3
- 229910052759 nickel Inorganic materials 0.000 claims 3
- 239000010936 titanium Substances 0.000 claims 3
- 229910052719 titanium Inorganic materials 0.000 claims 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- 125000003118 aryl group Chemical group 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 239000011651 chromium Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000006260 foam Substances 0.000 claims 2
- 229910021397 glassy carbon Inorganic materials 0.000 claims 2
- 229910002804 graphite Inorganic materials 0.000 claims 2
- 239000010439 graphite Substances 0.000 claims 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 claims 2
- 239000002184 metal Substances 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 2
- 239000004332 silver Substances 0.000 claims 2
- 239000010959 steel Substances 0.000 claims 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 229910001316 Ag alloy Inorganic materials 0.000 claims 1
- 229910000838 Al alloy Inorganic materials 0.000 claims 1
- 229910000851 Alloy steel Inorganic materials 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229910000531 Co alloy Inorganic materials 0.000 claims 1
- 229910000599 Cr alloy Inorganic materials 0.000 claims 1
- 229910000881 Cu alloy Inorganic materials 0.000 claims 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims 1
- 229910000640 Fe alloy Inorganic materials 0.000 claims 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 229910000645 Hg alloy Inorganic materials 0.000 claims 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims 1
- 229910000861 Mg alloy Inorganic materials 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- 229910000990 Ni alloy Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 229910000978 Pb alloy Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims 1
- 229910001260 Pt alloy Inorganic materials 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 1
- 229910001128 Sn alloy Inorganic materials 0.000 claims 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 229910001069 Ti alloy Inorganic materials 0.000 claims 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims 1
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims 1
- 229910001297 Zn alloy Inorganic materials 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 239000010405 anode material Substances 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910001424 calcium ion Inorganic materials 0.000 claims 1
- 239000010406 cathode material Substances 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 229910001429 cobalt ion Inorganic materials 0.000 claims 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims 1
- 229910001431 copper ion Inorganic materials 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical group 0.000 claims 1
- 125000001072 heteroaryl group Chemical group 0.000 claims 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims 1
- 230000001788 irregular Effects 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 claims 1
- 229910001425 magnesium ion Inorganic materials 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 239000011572 manganese Substances 0.000 claims 1
- 229910001437 manganese ion Inorganic materials 0.000 claims 1
- 229910052753 mercury Inorganic materials 0.000 claims 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 229910001453 nickel ion Inorganic materials 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Chemical group 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Chemical group 0.000 claims 1
- 229910001414 potassium ion Inorganic materials 0.000 claims 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Chemical group 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- 125000004434 sulfur atom Chemical group 0.000 claims 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract 1
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 5
- OSOIQJGOYGSIMF-UHFFFAOYSA-N cyclopentadecanone Chemical compound O=C1CCCCCCCCCCCCCC1 OSOIQJGOYGSIMF-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- GDWRKZLROIFUML-UHFFFAOYSA-N 4-phenylbutan-2-ol Chemical compound CC(O)CCC1=CC=CC=C1 GDWRKZLROIFUML-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ORNBQBCIOKFOEO-YQUGOWONSA-N Pregnenolone Natural products O=C(C)[C@@H]1[C@@]2(C)[C@H]([C@H]3[C@@H]([C@]4(C)C(=CC3)C[C@@H](O)CC4)CC2)CC1 ORNBQBCIOKFOEO-YQUGOWONSA-N 0.000 description 2
- 241001122767 Theaceae Species 0.000 description 2
- AKGGYBADQZYZPD-UHFFFAOYSA-N benzylacetone Chemical compound CC(=O)CCC1=CC=CC=C1 AKGGYBADQZYZPD-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- ORNBQBCIOKFOEO-QGVNFLHTSA-N pregnenolone Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H](C(=O)C)[C@@]1(C)CC2 ORNBQBCIOKFOEO-QGVNFLHTSA-N 0.000 description 2
- 229960000249 pregnenolone Drugs 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 238000003612 Meerwein-Ponndorf-Verley reduction reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- GTDKXDWWMOMSFL-UHFFFAOYSA-M tetramethylazanium;fluoride Chemical compound [F-].C[N+](C)(C)C GTDKXDWWMOMSFL-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
Abstract
The invention discloses a novel method for reducing aldehyde ketone compounds into corresponding alcohols or deuterated alcohols under electrochemical conditions, and relates to the technical field of medicine and material synthesis. The synthesis method comprises the following steps: in an electrochemical reaction tank, aldehyde ketone and electrolyte are dissolved in a solvent, an electrode is connected, and the aldehyde ketone compound can be reduced into a corresponding alcohol or deuterated alcohol compound through electrifying reaction at room temperature. The method can be widely applied to large-scale, green and safe synthesis of corresponding medicaments, intermediates and materials.
Description
Technical Field
The invention relates to the technical field of medicine and material synthesis, in particular to a novel method for reducing aldehyde ketone into corresponding alcohol or deuterated alcohol under electrochemical conditions.
Background
In the history of drug synthesis, the green efficient reduction of aldehyde ketone compounds to the corresponding alcohols or deuterated alcohols is a highly valuable synthetic method, widely used in the synthesis of large amounts of drugs.
The literature reports that there are several methods currently available for reducing aldehyde ketones to alcohols or deuterated alcohols:
(1) Negative hydrogen reduction
The advantages are that: fast, simple and convenient, and better compatibility of functional groups;
disadvantages: 1. the method generally requires the use of equivalent or even excessive negative hydrogen reagent, thus causing a large amount of waste; 2. because of the strong alkalinity of negative hydrogen, the negative hydrogen can be quickly combined with acidic protons to generate hydrogen, and the negative hydrogen is inflammable and explosive; 3. the use of a large amount of negative hydrogen reagent has high cost.
(2) Meerwein-Ponndorf-Verley reduction
The advantages are that: the tolerance of the functional group is good; the safety is relatively high;
disadvantages: 1. the method needs a large amount of aluminum alkoxide, has high cost and is not suitable for large-scale production; 2. the reaction generally needs heating reflux, and the energy consumption is high; 3. the reaction is reversible and therefore generally incomplete.
(3) Catalytic hydrogenation process
The advantages are that: the yield is generally higher; the system is cleaner;
disadvantages: 1. the range of the substrate is highly limited, and unsaturated carbon-carbon double bonds or triple bonds in the molecule cannot be reserved; 2. unsafe, hydrogen and some catalysts are extremely flammable.
In summary, the existing methods for reducing aldehyde ketone into corresponding alcohol or deuterated alcohol have obvious defects and need to be improved.
Disclosure of Invention
The present invention aims to create a new green, safe, low cost method for reducing aldehyde ketones to the corresponding alcohol or deuterated alcohol compounds.
The invention relates to a method for reducing aldehyde ketone into corresponding alcohol or deuterated alcohol compound under electrochemical conditions. The method of the invention comprises the following steps: in an electrochemical reaction tank, the aldehyde ketone compound can be reduced into corresponding alcohol or deuterated alcohol compound by electrifying reaction in a solvent with electrolyte at room temperature. The specific synthesis method is as follows:
the beneficial effects of the invention are as follows: compared with the existing synthesis process, the method is green, safe, economical and simple, and does not need to use equivalent or even excessive negative hydrogen reagent; nor noble metals (e.g., palladium, platinum); high-temperature and high-pressure conditions are not needed; the cheap and easily available solvent and electrolyte are used as hydrogen or deuterium sources, so that the cost is low; the equipment is simple; the operation is simple and convenient; the reaction condition is mild; the method disclosed by the invention can be widely applied to the industrial production of medicines and new materials.
The invention provides a novel method for reducing aldehyde ketone into corresponding alcohol or deuterated alcohol compound, which is green, efficient, safe and low in consumption, and comprises the following steps:
in an electrochemical reaction tank, aldehyde ketone compound and electrolyte are dissolved in a solvent, an electrode is connected, the reaction is conducted at room temperature, the reaction progress is monitored, the stirring is stopped when the reaction is completed, the solvent is recovered by reduced pressure distillation, and the residue is subjected to column chromatography or reduced pressure distillation or recrystallization to obtain the product.
Detailed Description
The process of the present invention will be further illustrated by the following examples, but the present invention is not limited to these examples.
Example 1:
4-benzene-2-butanone (148.1 g,1.0mol,1.0 eq.) and tetrabutylammonium chloride (TBAC, 277.2g,1.0mol,1.0 eq.) were taken in a 1.0L beaker; adding CH 3 CN (300.0 mL), was dissolved by stirring; electrodes (the anode is a zinc rod or a zinc sheet, and the cathode is a tin rod or a tin sheet) are inserted into the beaker, and the beaker is electrified and subjected to 300mA constant current reaction for about 5 hours. After the completion of the reaction, the solvent was recovered by distillation, and the residue was separated by column chromatography to give the product in 95% yield.
Example 2:
cyclopentadecanone (2240.0 g,10.0mol,1.0 eq.) and tetrabutylammonium chloride (TBAC, 1386.2g,5.0mol,0.5 eq.) were taken in a 5.0L beaker; adding CH 3 CN (800.0 mL), was dissolved by stirring; electrodes (the anode is a zinc rod or a zinc sheet, and the cathode is a tin rod or a tin sheet) are inserted into the beaker, and the current is electrified, and the 4.0A constant current reaction is carried out for about 10 hours. After the completion of the reaction, the solvent was recovered by distillation, and the residue was distilled under reduced pressure to give a product in 96% yield.
Example 3:
pregnenolone (316.5 g,1.0mol,1.0 eq.) and tetrabutylammonium chloride (TBAC, 277.2g,1.0mol,1.0 eq.) were taken in a 1.0L beaker; adding CH 3 CN (300.0 mL), was dissolved by stirring; electrodes (the anode is a zinc rod or a zinc sheet, and the cathode is a tin rod or a tin sheet) are inserted into the beaker, and the beaker is electrified and subjected to 300mA constant current reaction for about 5 hours. After the completion of the reaction, the solvent was recovered by distillation, and the residue was separated by column chromatography to give the product in 90% yield.
Example 4:
4-benzene-2-butanone (148.1 g,1.0mol,1.0 eq.) and tetrabutylammonium chloride (TBAC, 277.2g,1.0mol,1.0 eq.) were taken in a 1.0L beaker; adding CD 3 CN (300.0 mL), was dissolved by stirring; electrodes (the anode is a zinc rod or a zinc sheet, and the cathode is a tin rod or a tin sheet) are inserted into the beaker, and the beaker is electrified and subjected to 300mA constant current reaction for about 5 hours. After the completion of the reaction, the solvent was recovered by distillation, and the residue was separated by column chromatography to give the product in 93% yield.
Example 5:
cyclopentadecanone (2240.0 g,10.0mol,1.0 eq.) and tetrabutylammonium chloride (TBAC, 1386.2g,5.0mol,0.5 eq.) were taken in a 5.0L beaker; adding CD 3 CN (800.0 mL), was dissolved by stirring; electrodes (the anode is a zinc rod or a zinc sheet, and the cathode is a tin rod or a tin sheet) are inserted into the beaker, and the current is electrified, and the 4.0A constant current reaction is carried out for about 10 hours. After the reaction was completed, the solvent was recovered by distillation, and the residue was distilled under reduced pressure to give a product in 95% yield.
Example 6:
pregnenolone (316.5 g,1.0mol,1.0 eq.) and tetrabutylammonium chloride (TBAC, 277.2g,1.0mol,1.0 eq.) were taken in a 1.0L beaker; adding CD 3 CN (300.0 mL), was dissolved by stirring; electrodes (the anode is a zinc rod or a zinc sheet, and the cathode is a tin rod or a tin sheet) are inserted into the beaker, and the beaker is electrified and subjected to 300mA constant current reaction for about 5 hours. After the completion of the reaction, the solvent was recovered by distillation, and the residue was separated by column chromatography to give the product in 92% yield.
Table-1A summary of the yields of the reactions (taking as an example the reduction of 4-phenyl-2-butanone to 4-phenyl-2-butanol) under various conditions (the invention is not limited to the reaction conditions listed in the Table)
And (3) table notes: the amount of ketone material in this table was 2.0 millimoles; the rod-shaped electrode has the following dimensions: the diameter is 0.8cm, and the length is 10cm; the length, width and height of the flaky electrode are as follows: 2 cm. Times.1 cm. Times.0.5 cm; TMAF is tetramethyl ammonium fluoride; TBAC is tetrabutylammonium chloride; TEAC is tetraethylammonium chloride; TBAB is tetrabutylammonium bromide; TEABF (tea-based-fiber-based) film 4 Is tetraethylammonium tetrafluoroborate; TEAPF (tea Power Filter) 6 Is tetraethylammonium hexafluorophosphate; DMF is N, N-dimethylformamide; DMSO is dimethyl sulfoxide; HFIP is hexafluoroisopropanol. [1]Under this condition, the amount of ketone was 10mol,1.48Kg scale;
appendix Table-2 the aldehyde ketones and yields examined in the present invention are selected from the list (not limited to these substrates)
And (3) table notes: the yields in this table are the isolated yields obtained with reference to the reaction conditions in the examples. When there are multiple hydroxyl groups in the product, the hydroxyl groups marked with dotted circles are newly reduced hydroxyl groups.
Claims (10)
1. A method for reducing aldehyde ketone into alcohol or deuterated alcohol is characterized in that aldehyde ketone and electrolyte are dissolved in a solvent in an electrochemical reaction tank, an electrode is connected, and electrifying reaction is carried out, so that aldehyde ketone compound can be reduced into corresponding alcohol or deuterated alcohol compound,
the electrode:
the anode material is as follows: one of zinc, magnesium, aluminum, tin, iron, manganese, nickel, copper, lead, cobalt or titanium, or an alloy of several of them; the cathode material is as follows: carbon or graphite felt or glassy carbon or zinc or magnesium or aluminum or tin or iron or manganese or nickel or copper or lead or cobalt or steel or silver or platinum or mercury or chromium or titanium or an alloy of a plurality of the materials;
the electrolyte is as follows: salts of cations with anions.
2. The method of reducing an aldehyde ketone to an alcohol or deuterated alcohol according to claim 1 wherein the electrochemical reaction cell is a divided Chi Huofei divided cell.
3. The method of reducing an aldehyde ketone to an alcohol or deuterated alcohol according to claim 1 wherein the solvent is one or a mixture of two or more of acetonitrile, dichloromethane (DCM), dichloroethane (DCE), N-Dimethylformamide (DMF), 1, 4-dioxane, acetone, methanol, ethanol, isopropanol, butanol, hexafluoroisopropanol, trifluoroethanol, chloroform, dimethyl sulfoxide, carbon tetrachloride, water, and their corresponding deuterated solvents.
4. The method for reducing aldehyde ketone to alcohol or deuterated alcohol according to claim 1, wherein the aldehyde ketone is a compound shown in the following scheme (1), and the reduction product is a compound shown in the following scheme (2):
wherein R and R' are each independently hydrogen or aryl or heteroaryl or alkyl or cycloalkyl or alkyl or aryl having halogen, oxygen, nitrogen, silicon, phosphorus, sulfur atoms attached thereto; or R and R' are joined together to form an aliphatic or aromatic ring compound.
5. The method for reducing aldehyde ketone to alcohol or deuterated alcohol according to claim 1, wherein the electrode and the anode are one or two or more of zinc, magnesium, aluminum, tin, iron, manganese, nickel, copper, lead, cobalt and titanium, or an alloy or foam metal; the cathode is carbon or graphite felt or glassy carbon or one or two or more of zinc, magnesium, aluminum, tin, iron, manganese, nickel, copper, lead, cobalt, silver, steel, platinum, mercury, chromium and titanium alloy or foam metal.
6. The method for reducing aldehyde ketone to alcohol or deuterated alcohol according to any one of claims 1 to 5 wherein the electrode is in the shape of a sheet, a block, a rod, a mesh, or an irregular shape.
7. The method of reducing an aldehyde ketone to an alcohol or deuterated alcohol according to any one of claims 1-5 wherein the electrolyte is a salt of one or more cations with one or more anions; the cations mentioned herein are lithium ion, sodium ion, potassium ion, magnesium ion, calcium ion, zinc ion, iron ion (divalent or trivalent), copper ion (monovalent or divalent), cobalt ion, titanium ion (trivalent or tetravalent), manganese ion (divalent or tetravalent), nickel ion (divalent)Ammonium radical (NH) 4 + ) Tetraalkylammonium radical (R) 4 N + ) At least one of (a) and (b); the alkyl is at least one of methyl, ethyl, propyl, isopropyl, butyl and n-hexadecyl; the anions are at least one of fluoride, chloride, bromide, iodide, perchlorate, tetrafluoroborate, hexafluorophosphate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, acetate, benzoate, carbonate, bicarbonate, nitrate, nitrite, phosphate, hydrogen phosphate, dihydrogen phosphate, sulfate, and hydrogen sulfate.
8. The method for reducing aldehyde ketone to alcohol or deuterated alcohol according to claims 1-5 wherein the electrochemical reaction is conducted in a constant current or constant voltage mode with a current intensity of 1 mA-10A; the voltage range is 2.0V-10V; the reaction temperature is 30-100 ℃ below zero.
9. The method for reducing aldehyde ketone to alcohol or deuterated alcohol according to claims 1-5 wherein the molar concentration of the electrolyte is 0.01-100 mol/L.
10. The method for electrochemically reducing an aldehyde ketone to an alcohol or deuterated alcohol according to claims 1-5 wherein the molar concentration of aldehyde ketone is from 0.01 mol/L to 100mol/L.
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