WO2018133473A1 - 一种可见光催化的饱和碳氢键直接氧化方法 - Google Patents
一种可见光催化的饱和碳氢键直接氧化方法 Download PDFInfo
- Publication number
- WO2018133473A1 WO2018133473A1 PCT/CN2017/107760 CN2017107760W WO2018133473A1 WO 2018133473 A1 WO2018133473 A1 WO 2018133473A1 CN 2017107760 W CN2017107760 W CN 2017107760W WO 2018133473 A1 WO2018133473 A1 WO 2018133473A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- visible light
- organic compound
- direct oxidation
- saturated hydrocarbon
- reaction
- Prior art date
Links
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 34
- 230000003647 oxidation Effects 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000001257 hydrogen Substances 0.000 title claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 15
- 150000001721 carbon Chemical class 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 14
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims description 25
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 21
- 230000000996 additive effect Effects 0.000 claims description 19
- 239000012327 Ruthenium complex Substances 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 230000009471 action Effects 0.000 claims description 11
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical group ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000002140 halogenating effect Effects 0.000 claims description 3
- GPQXCSVEZHPWMA-UHFFFAOYSA-N 1-fluoro-2h-pyridine Chemical compound FN1CC=CC=C1 GPQXCSVEZHPWMA-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 239000012359 Methanesulfonyl chloride Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- RILZRCJGXSFXNE-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)phenyl]ethanol Chemical class OCCC1=CC=C(OC(F)(F)F)C=C1 RILZRCJGXSFXNE-UHFFFAOYSA-N 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 4
- 150000002978 peroxides Chemical class 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 abstract description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 27
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 19
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 10
- 238000004440 column chromatography Methods 0.000 description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012267 brine Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 2-(6-amino-1h-indol-3-yl)acetonitrile Chemical compound NC1=CC=C2C(CC#N)=CNC2=C1 ZSDQQJHSRVEGTJ-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- HNBDRPTVWVGKBR-UHFFFAOYSA-N n-pentanoic acid methyl ester Natural products CCCCC(=O)OC HNBDRPTVWVGKBR-UHFFFAOYSA-N 0.000 description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 150000003303 ruthenium Chemical class 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 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 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- -1 octane bis(tetrafluoroborate) salt Chemical compound 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- GTLWADFFABIGAE-UHFFFAOYSA-N 1-chloroethylbenzene Chemical compound CC(Cl)C1=CC=CC=C1 GTLWADFFABIGAE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 0 CC(c1ccccc1)N(*)N* Chemical compound CC(c1ccccc1)N(*)N* 0.000 description 1
- 150000007960 acetonitrile Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UXXXZMDJQLPQPH-UHFFFAOYSA-N bis(2-methylpropyl) carbonate Chemical compound CC(C)COC(=O)OCC(C)C UXXXZMDJQLPQPH-UHFFFAOYSA-N 0.000 description 1
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229960001759 cerium oxalate Drugs 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- PHSMPGGNMIPKTH-UHFFFAOYSA-K cerium(3+);trifluoromethanesulfonate Chemical compound [Ce+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F PHSMPGGNMIPKTH-UHFFFAOYSA-K 0.000 description 1
- KQJQGYQIHVYKTF-UHFFFAOYSA-N cerium(3+);trinitrate;hydrate Chemical compound O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KQJQGYQIHVYKTF-UHFFFAOYSA-N 0.000 description 1
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 1
- BCBBBOXRROHVFG-UHFFFAOYSA-N cerium(4+);propan-2-olate Chemical compound [Ce+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] BCBBBOXRROHVFG-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- QLVWOKQMDLQXNN-UHFFFAOYSA-N dibutyl carbonate Chemical compound CCCCOC(=O)OCCCC QLVWOKQMDLQXNN-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- IREVRWRNACELSM-UHFFFAOYSA-J ruthenium(4+);tetrachloride Chemical compound Cl[Ru](Cl)(Cl)Cl IREVRWRNACELSM-UHFFFAOYSA-J 0.000 description 1
- NAPRBDYPCKERPN-UHFFFAOYSA-J ruthenium(4+);tetrachloride;hydrate Chemical compound O.[Cl-].[Cl-].[Cl-].[Cl-].[Ru+4] NAPRBDYPCKERPN-UHFFFAOYSA-J 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B33/00—Oxidation in general
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/14—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the side-chain of aromatic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C281/00—Derivatives of carbonic acid containing functional groups covered by groups C07C269/00 - C07C279/00 in which at least one nitrogen atom of these functional groups is further bound to another nitrogen atom not being part of a nitro or nitroso group
- C07C281/02—Compounds containing any of the groups, e.g. carbazates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
- C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
Definitions
- the invention relates to the field of organic synthesis, in particular to a visible light catalyzed method for efficiently oxidizing saturated hydrocarbon bonds in an organic compound by using a ruthenium complex.
- Visible light catalysis is a catalytic mode that utilizes the energy of visible light to activate a photocatalyst, thereby promoting organic reactions.
- visible light catalysis uses only clean light energy, low catalyst dosage and mild reaction conditions, and it is expected to develop a more efficient and environmentally friendly synthesis method.
- How to use visible light catalysis to achieve efficient saturated carbon-hydrogen bond oxidation reaction, while developing a more economical and environmentally friendly photocatalyst, in order to achieve industrial application is a great challenge.
- the method of discharge of matter is an object of the present invention to provide a catalyst and a reagent which are inexpensive and readily available under mild conditions, to achieve high-efficiency oxidation of saturated hydrocarbon bonds in an organic compound under visible light irradiation, to obtain an oxidation product in a high yield, and to reduce waste.
- the present invention provides a visible light catalyzed direct oxidation of a saturated hydrocarbon bond, characterized by comprising: the action of an organic compound and an oxidizing agent in a ruthenium complex and an additive under the condition of visible light irradiation.
- the reaction is carried out to oxidize a saturated hydrocarbon bond in the organic compound to obtain an oxidation product.
- the organic compound is a paraffin, a cycloalkane, an aromatic hydrocarbon or a saturated hydrocarbon bond Other compounds.
- the oxidizing agent is oxygen, a halogenating agent or an azo reagent.
- the halogenating agent is N-chlorosuccinimide, N-bromosuccinimide, p-toluenesulfonyl chloride, methanesulfonyl chloride, N-fluoropyridine, N-fluorodiphenyl At least one of a sulfonimide, 1-chloromethyl-4-fluoro-1,4-diazonium dicyclo 2.2.2 octane bis(tetrafluoroborate) salt and elemental iodine.
- the azo reagent is at least one of azodicarbonate, azobenzene, azoformamide and azobisisobutyronitrile.
- the metal cation of the ruthenium complex is any one of Ce 4+ and Ce 3+ , preferably ruthenium tetrachloride hydrate, ruthenium tetrachloride, ruthenium trichloride hydrate, trichlorination ⁇ , at least one of cerium nitrate hydrate, cerium triflate, cerium tetrafluoromethanesulfonate, cerium sulfate, cerium acetate, cerium oxalate and cerium tetraisopropoxide.
- the anion of the additive is any one of Cl - , Br - , preferably tetrabutylammonium chloride, tetraethylammonium chloride, tetrabutylammonium bromide, tetraethylammonium bromide, At least one of tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, sodium chloride, potassium chloride, cesium chloride, sodium bromide, potassium bromide and cesium bromide.
- the molar ratio of the organic compound to the ruthenium complex is 1:0.0000001-0.2.
- the molar ratio of the rhodium complex to the additive is 1:0.2 - 1:10.
- the reaction conditions are from room temperature to 80 °C.
- the visible light is light having a wavelength of 300-800 nm.
- the ruthenium complex functions to activate a hydrocarbon bond of an alkane under visible light irradiation to produce a highly reactive alkyl radical, and further reacts with an oxidizing reagent to obtain an oxidation product.
- the effect of the additive is to increase the catalytic efficiency of the ruthenium complex.
- the reaction of the invention only needs to be carried out at a relatively low temperature, the reaction time is short, and the reaction efficiency is high; at the same time, only visible light is required to provide the energy required for the activation reaction, which is a milder, green activation mode.
- the ruthenium catalyst used in the invention is low in cost, simple and efficient, the oxidizing agent used is more stable in nature, low in industrial use cost, and can avoid environmental pollution caused by heavy transition metals and peroxides.
- reaction raw materials ruthenium complexes, and additives in the following examples are all commercially available products.
- Ethylbenzene and p-toluenesulfonyl chloride are reacted under the action of ruthenium complexes and additives for 12 hours to oxidize the saturated carbon-hydrogen bond of ethylbenzene to obtain an oxidation product.
- the reaction equation is as follows:
- Oxygen was added to a solution of 10 mL of methyl valerate (116 mg, 1 mmol) in acetonitrile for 20 min. Oxygen saturation, adding 2 mol% ruthenium complex ruthenium trichloride (4.8 mg, 0.02 mmol) and 5 mol% of the additive tetrabutylammonium chloride (14 mg, 0.05 mmol), at room temperature (25 ° C), at ( Under the condition of blue LED lamp with wavelength of 380nm-550nm, methyl valerate and oxygen are reacted under the action of ruthenium complex and additive for 12h to oxidize the saturated carbon-hydrogen bond of methyl valerate to obtain oxidation.
- Product the reaction equation is as follows:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明提供了一种有机化合物中饱和碳氢键的直接氧化方法，其特征在于，包括：在可见光照射的条件下，使有机化合物与氧化试剂在铈复合物的存在下进行反应，使有机化合物的饱和碳氢键氧化得到氧化产物。本发明反应仅需在室温下进行，催化效率高，仅依靠可见光来提供活化反应所需的能量，是一种更加温和、绿色的活化模式；同时所用的催化剂成本低廉，所用氧化试剂性质更加稳定，在工业上利用成本低，催化体系实用性强；同时能避免重过渡金属，过氧化物等对环境的污染。
Description
本发明是有机合成领域，特别涉及一种可见光催化的，利用铈复合物高效氧化有机化合物中的饱和碳氢键的方法。
有机化合物中的碳氢键直接氧化反应一直是催化领域中的研究热点。该合成策略能够将广泛存在的碳氢键直接构建成预期的官能团(羟基，羰基，胺基等)，在合成高附加值的药物分子或其中间体中，能够使用廉价的起始原料，显著缩短合成路线，在工业上有着广泛的应用前景。由于这类碳氢键的键能较高，使得其活性较低，现有的方法通常需要贵重过渡金属催化，并使用性质不太稳定的过氧化物，也通常需要较高温度和压力。如何能在温和、绿色的条件下，仅使用廉价的催化剂和试剂，高效氧化碳氢键是化学合成领域一直追逐的目标。可见光催化是利用可见光的能量来活化光催化剂，进而促进有机反应的一种催化模式。与传统催化模式相比，可见光催化仅利用清洁的光能，催化剂的用量低，反应条件温和，有望发展出更高效，对环境更加友好的合成方法。如何利用可见光催化来实现高效的饱和碳氢键氧化反应，同时发展出更加经济环保的光催化剂，以期实现工业化应用是一个极大的挑战。
发明内容
本发明的目的是提供一种能够在温和的条件下，采用廉价易得的催化剂和试剂，在可见光照射下实现有机化合物中饱和碳氢键的高效氧化，高产率的得到氧化产物，同时减少废弃物排放的方法。
为了达到上述目的，本发明提供了一种可见光催化的饱和碳氢键直接氧化方法，其特征在于，包括：在可见光照射的条件下，使有机化合物与氧化试剂在铈的配合物及添加剂的作用下进行反应，使有机化合物中的饱和碳氢键氧化得到氧化产物。
优选地，所述的有机化合物为链烷烃、环烷烃、芳香烃或含有饱和碳氢键的
其它化合物。
优选地，所述的氧化试剂为氧气，卤代试剂或偶氮类试剂。
更优选地，所述的卤代试剂为N-氯代丁二酰亚胺，N-溴代丁二酰亚胺，对甲苯磺酰氯，甲磺酰氯，N-氟吡啶，N-氟二苯磺酰亚胺，1-氯甲基-4-氟-1,4-重氮化二环2.2.2辛烷双(四氟硼酸)盐和单质碘中的至少一种。
更优选地，所述的偶氮类试剂为偶氮二碳酸酯,偶氮苯，偶氮甲酰胺和偶氮二异丁腈中的至少一种。
优选地，所述的铈的配合物的金属阳离子为Ce4+,Ce3+中的任一种，优选四氯化铈水合物，四氯化铈，三氯化铈水合物，三氯化铈，硝酸铈水合物，三氟甲磺酸铈，四氟甲磺酸铈，硫酸铈，醋酸铈，草酸铈和四异丙醇铈中的至少一种。
优选地，所述的添加剂的阴离子为Cl-,Br-中的任一种，优选四丁基氯化铵，四乙基氯化铵，四丁基溴化铵，四乙基溴化铵，四丁基氯化磷，四丁基溴化磷，氯化钠，氯化钾，氯化铯，溴化钠，溴化钾和溴化铯中的至少一种。
优选地，所述的有机化合物与铈的配合物的摩尔比为1：0.0000001-0.2。
优选地，所述的铈的配合物与添加剂的摩尔比为1：0.2–1：10。
优选地，所述的反应条件为室温–80℃。
优选地，所述的可见光为波长为300-800nm的光。
所述的铈复合物的作用是在可见光照射下活化烷烃的碳氢键产生高活性的烷基自由基，进而和氧化试剂反应得到氧化产物。所述的添加剂的作用是提高铈复合物的催化效率。
与现有技术相比，本发明的有益效果是：
本发明反应仅需在较低温度下进行，反应时间短，反应效率高；同时仅需可见光来提供活化反应所需的能量，是一种更加温和、绿色的活化模式。本发明所用的铈催化剂成本低廉，简单高效，所用氧化试剂性质更加稳定，在工业上利用成本低，同时能避免重过渡金属，过氧化物等对环境的污染。
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之
后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
以下实施例中的各反应原料、铈的配合物以及添加剂均为市售产品。
实施例1
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向2mL乙苯(106mg,1mmol)的乙腈溶液中通入氧气20min至氧气饱和，加入1mol％铈的配合物三氯化铈(2.4mg,0.01mmol)和2mol％的添加剂四丁基氯化铵(5.5mg,0.02mmol)之后，在室温(25℃)下，在(波长为380nm-550nm的)蓝色LED灯照射的条件下，使乙苯与氧气在铈的配合物和添加剂的作用下进行反应2h，使乙苯的碳氢键氧化得到氧化产物苯乙酮，反应方程式如下：
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品苯乙酮(108mg,90％收率),核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：7.96(d,2H),7.68(t,1H),7.46(d,2H),2.50(s,3H)。
实施例2
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向2mL环己烷(85mg,1mmol)的乙腈溶液中通入氧气20min至氧气饱和，加入1mol％铈的配合物三氯化铈(2.4mg,0.01mmol)和2mol％的添加剂四丁基氯化铵(5.5mg,0.02mmol)之后，在室温(25℃)下，在(波长为380nm-550nm的)蓝色LED灯照射的条件下，使环己烷与氧气在铈的配合物和添加剂的作用下进行反应5h，使环己烷的碳氢键氧化得到氧化产物环己醇，反应方程式如下：
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品环己醇(88mg,88％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：4.80(brs,1H),3.54(m,1H),1.59(m,4H),1.45-1.5
(m,6H)。
实施例3
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向2mL环己烷(85mg,1mmol)的乙腈溶液中通入氧气20min至氧气饱和，加入2mol％铈的配合物硝酸铈(8.7mg,0.02mmol)和4mol％的添加剂四丁基溴化铵(12.9mg,0.04mmol)之后，在室温(25℃)下，在(波长为380nm-550nm的)蓝色LED灯照射的条件下，使环己烷与氧气在铈的配合物和添加剂的作用下进行反应48h，使环己烷的碳氢键氧化得到氧化产物环己酮，反应方程式如下：
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品环己酮(80mg,82％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：2.33(t,4H),1.86(m,4H),1.73(m,2H)。
实施例4
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向2mL乙苯(106mg,1mmol)的乙腈溶液中，加入对甲苯磺酰氯(286mg,1.5mmol),1mol％铈的配合物三氯化铈(2.4mg,0.01mmol)和2mol％的添加剂四丁基氯化铵(5.5mg,0.02mmol)之后，通入氩气鼓泡20min，在室温(25℃)下，在(波长为(380nm-550nm)的)蓝色LED灯照射的条件下，使乙苯和对甲苯磺酰氯在铈的配合物和添加剂的作用下进行反应12h，使乙苯的饱和碳氢键氧化得到氧化产物，反应方程式如下：
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品1-氯乙基苯(122mg,87％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：7.45-7.22(m,5H),5.07(q,1H),1.82(d,3H)。
实施例5
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向10mL乙苯(106mg,1mmol)的乙腈溶液中，加入偶联碳酸二异丁酯(0.3ml,1.5mmol),1mol％铈的配合物三氯化铈(2.4mg,0.01mmol)和5mol％的添加剂四丁基氯化铵(14mg,0.05mmol)之后，通入氩气鼓泡20min，在室温(25℃)下，在(波长为(380nm-550nm)的)蓝色LED灯照射的条件下，使乙苯和偶联碳酸二异丁酯在铈的配合物和添加剂的作用下进行反应10h,使乙苯的饱和碳氢键氧化得到氧化产物，反应方程式如下：
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品(283mg,92％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：7.36(m,5H),6.16(brs,1H),5.5(q,1H),5.0(m,2H),1.55(d,3H),1.23(d,12H)。
实施例6
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向5mL戊酸甲酯(116mg,1mmol)的乙腈溶液中，加入N-氟二苯磺酰亚胺(473mg,1.5mmol),2mol％铈的配合物三氯化铈(4.8mg,0.02mmol)和4mol％的添加剂四丁基氯化铵(11mg,0.04mmol)之后，通入氩气鼓泡20min，在室温(25℃)下，在(波长为(380nm-550nm)的)蓝色LED灯照射的条件下，使戊酸甲酯和N-氟二苯磺酰亚胺在铈的配合物和添加剂的作用下进行反应20h,使戊酸甲酯的饱和碳氢键氧化得到氧化产物，反应方程式如下：
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品(110mg,82％收率)。核磁共振氢谱表征的数据为(500MHz,氘代乙腈为溶剂)：4.72(dm,1H),3.66(s,3H),2.47-2.42(m,2H),1.95-1.84(m,2H),1.32(dd,3H)。
实施例7
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向10mL戊酸甲酯(116mg,1mmol)的乙腈溶液中溶液中通入氧气20min至
氧气饱和，加入2mol％铈的配合物三氯化铈(4.8mg,0.02mmol)和5mol％的添加剂四丁基氯化铵(14mg,0.05mmol)之后，在室温(25℃)下，在(波长为380nm-550nm的)蓝色LED灯照射的条件下，使戊酸甲酯和氧气在铈的配合物和添加剂的作用下进行反应12h,使戊酸甲酯的饱和碳氢键氧化得到氧化产物，反应方程式如下：
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品(100mg,77％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：3.64(s,3H),2.73(t,2H),2.54(t,2H),2.16(s,3H)。
实施例8
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向20mL茚满(119mg,1mmol)的乙腈溶液中溶液中通入氧气20min至氧气饱和，加入2mol％铈的配合物硝酸铈(8.7mg,0.02mmol)和4mol％的添加剂四丁基溴化铵(13mg,0.04mmol)之后，在室温(25℃)下，在(波长为380nm-550nm的)蓝色LED灯照射的条件下，使茚满和氧气在铈的配合物和添加剂的作用下进行反应2h,使茚满的饱和碳氢键氧化得到氧化产物，反应方程式如下：
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品(106mg,80％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：7.41-7.0(m,4H),2.94(t,2H),2.61(t,2H)。
实施例9
一种可见光催化的饱和碳氢键直接氧化方法，具体步骤为：
向10mL茚满(119mg,1mmol)的乙腈溶液中，加入N-溴代丁二酰亚胺(356mg,2mmol)，2mol％铈的配合物硝酸铈(8.7mg,0.02mmol)和4mol％的添加剂四丁基溴化铵(13mg,0.04mmol)之后，在室温(25℃)下，在(波长为(380nm-550nm)的)蓝色LED灯照射的条件下，使茚满和N-溴代丁二酰亚胺在铈的配合物和添
加剂的作用下进行反应12h,使茚满的饱和碳氢键氧化得到氧化产物，反应方程式如下：
停止反应后，加入二氯甲烷稀释，依次用水、饱和食盐水洗涤，干燥，柱层析分离，得产品(165mg,84％收率)。核磁共振氢谱表征的数据为(500MHz,氘代氯仿为溶剂)：7.18-7.16(m,1H),7.01-6.98(m,3H),5.33(dd,1H),2.99(m,1H),2.67(m,1H),2.39(m,2H)。
Claims (10)
- 一种可见光催化的饱和碳氢键直接氧化方法，其特征在于，包括：在可见光照射的条件下，使有机化合物与氧化试剂在铈的配合物及添加剂的作用下进行反应，使有机化合物中的饱和碳氢键氧化得到氧化产物。
- 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的有机化合物为链烷烃、环烷烃、芳香烃或含有饱和碳氢键的其它化合物。
- 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的氧化试剂为氧气，卤代试剂或偶氮类试剂。
- 如权利要求3所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的卤代试剂为N-氯代丁二酰亚胺，N-溴代丁二酰亚胺，对甲苯磺酰氯，甲磺酰氯，N-氟吡啶，N-氟二苯磺酰亚胺，1-氯甲基-4-氟-1,4-重氮化二环2.2.2辛烷双(四氟硼酸)盐和单质碘中的至少一种。
- 如权利要求3所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的偶氮类试剂为偶氮二碳酸酯,偶氮苯，偶氮甲酰胺和偶氮二异丁腈中的至少一种。
- 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的铈配合物的金属阳离子为Ce4+和Ce3+中的任一种。
- 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的添加剂的阴离子为Cl-和Br-中的任一种。
- 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的有机化合物与铈的配合物的摩尔比为1：0.0000001-0.2。
- 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的反应条件为室温–80℃。
- 如权利要求1所述的可见光催化的饱和碳氢键直接氧化方法，其特征在于，所述的可见光为波长为300-800nm的光。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP17893061.6A EP3572394A4 (en) | 2017-01-19 | 2017-10-26 | METHOD FOR THE DIRECT OXIDATION OF SATURATED CARBON HYDROGEN BONDED BY VISIBLE LIGHT |
| US16/478,476 US11008272B1 (en) | 2017-01-19 | 2017-10-26 | Visible-light-induced direct oxidation method for saturated hydrocarbon bonds |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710045228.6A CN106831387B (zh) | 2017-01-19 | 2017-01-19 | 一种可见光催化的饱和碳氢键直接氧化方法 |
| CN201710045228.6 | 2017-01-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2018133473A1 true WO2018133473A1 (zh) | 2018-07-26 |
Family
ID=59120020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2017/107760 WO2018133473A1 (zh) | 2017-01-19 | 2017-10-26 | 一种可见光催化的饱和碳氢键直接氧化方法 |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US11008272B1 (zh) |
| EP (1) | EP3572394A4 (zh) |
| CN (1) | CN106831387B (zh) |
| WO (1) | WO2018133473A1 (zh) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106831387B (zh) * | 2017-01-19 | 2020-12-29 | 上海科技大学 | 一种可见光催化的饱和碳氢键直接氧化方法 |
| CN109836307B (zh) * | 2017-11-29 | 2021-11-23 | 中国科学院大连化学物理研究所 | 一种氧化铁光催化烷烃氧化的方法 |
| CN115448830A (zh) * | 2021-06-09 | 2022-12-09 | 复旦大学 | 一种光促进含有饱和碳氢键的化合物氧化的方法 |
| CN113788742B (zh) * | 2021-10-21 | 2023-03-10 | 中国科学技术大学 | 一种光催化的苄位碳氢键氧化方法 |
| CN116354798A (zh) * | 2021-12-27 | 2023-06-30 | 复旦大学 | 一种可见光介导的环己基苯一步法制苯酚和环己酮的方法 |
| CN115110104B (zh) * | 2022-04-06 | 2023-11-28 | 齐鲁工业大学 | 一种α,α-二氯芳基酮类化合物的光电化学合成方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001025191A1 (en) * | 1999-10-06 | 2001-04-12 | Uniroyal Chemical Company, Inc. | 4-hydroxybiphenyl hydrazide derivatives |
| CN102295524A (zh) * | 2011-06-21 | 2011-12-28 | 华东理工大学 | 一种环己烷选择氧化制环己醇和环己酮的方法 |
| WO2013095699A1 (en) * | 2011-12-23 | 2013-06-27 | Dow Global Technologies, Llc | Sulfuryl chloride as chlorinating agent |
| CN106831387A (zh) * | 2017-01-19 | 2017-06-13 | 上海科技大学 | 一种可见光催化的饱和碳氢键直接氧化方法 |
-
2017
- 2017-01-19 CN CN201710045228.6A patent/CN106831387B/zh active Active
- 2017-10-26 WO PCT/CN2017/107760 patent/WO2018133473A1/zh unknown
- 2017-10-26 US US16/478,476 patent/US11008272B1/en active Active
- 2017-10-26 EP EP17893061.6A patent/EP3572394A4/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001025191A1 (en) * | 1999-10-06 | 2001-04-12 | Uniroyal Chemical Company, Inc. | 4-hydroxybiphenyl hydrazide derivatives |
| CN102295524A (zh) * | 2011-06-21 | 2011-12-28 | 华东理工大学 | 一种环己烷选择氧化制环己醇和环己酮的方法 |
| WO2013095699A1 (en) * | 2011-12-23 | 2013-06-27 | Dow Global Technologies, Llc | Sulfuryl chloride as chlorinating agent |
| CN106831387A (zh) * | 2017-01-19 | 2017-06-13 | 上海科技大学 | 一种可见光催化的饱和碳氢键直接氧化方法 |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP3572394A4 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3572394A1 (en) | 2019-11-27 |
| CN106831387B (zh) | 2020-12-29 |
| US20210130276A1 (en) | 2021-05-06 |
| US11008272B1 (en) | 2021-05-18 |
| CN106831387A (zh) | 2017-06-13 |
| EP3572394A4 (en) | 2020-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018133473A1 (zh) | 一种可见光催化的饱和碳氢键直接氧化方法 | |
| Ryu et al. | Free‐Radical Carbonylations: Then and Now | |
| CN110563571B (zh) | 一种苯甲酸类化合物的合成方法 | |
| CN104193600B (zh) | 一种以氧化铝为助催化剂空气氧化醇制备醛或酮的方法 | |
| CN103228611B (zh) | 3,4-二烷基联苯基二羧酸化合物、3,4-二烷氧羰基联苯基-3’,4’-二羧酸及相应的酸酐，及这些化合物的制备方法 | |
| Shen et al. | Enhanced catalytic performance of porphyrin cobalt (II) in the solvent-free oxidation of cycloalkanes (C5~ C8) with molecular oxygen promoted by porphyrin zinc (II) | |
| CN102126960A (zh) | 一种对硝基苯甲醛的高选择性合成方法 | |
| JP2016517846A (ja) | アセトフェノンの合成方法 | |
| CN108503545B (zh) | 一种催化氧化扁桃酸酯制备苯乙酮酸酯的方法 | |
| CN113649073A (zh) | 一种金属卟啉双金属中心2D MOFs催化氧化环烷烃的方法 | |
| CN112079706B (zh) | 一种绿色催化氧化脂肪族伯醇制备羧酸的方法 | |
| CN114891135B (zh) | 一种铁催化聚烯烃链碳氢键氧化制备含极性氧官能团聚烯烃的方法 | |
| CN102134209B (zh) | 氧化硫醚合成亚砜的方法 | |
| CN108144612B (zh) | 一种用于一锅法合成羧酸酯的钴基催化剂及其制备和应用 | |
| CN109134538B (zh) | 碘膦氧配体及其制备方法和络合物、包括该络合物的催化剂体系和用途 | |
| RU2286332C1 (ru) | Способ получения адамантанола-1 | |
| CN113788742B (zh) | 一种光催化的苄位碳氢键氧化方法 | |
| Yu et al. | Metal-organic frameworks containing N-hydroxyphthalimide as efficient heterogeneous catalysts for allylic oxidation | |
| CN116284017B (zh) | 一种利用仿酶高效催化氧化制备酰胺化合物的方法 | |
| CN111004176A (zh) | 一种2-芳氧基乙醇类化合物的合成方法 | |
| CN115340475B (zh) | 一种1-氧化二苯基二氮烯或其衍生物的制备方法 | |
| CN114805461B (zh) | 一种苯环苄位c-h键氧化成酮的方法 | |
| CN116283518B (zh) | 一种一步二氯化水解制备醛酮类化合物的方法 | |
| CN115340474B (zh) | 氢氧化锆作为催化剂催化苯胺或其衍生物制备1-氧化二苯基二氮烯或其衍生物的应用 | |
| CN115340469B (zh) | 一种二苯基二氮烯或其衍生物的制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17893061 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| ENP | Entry into the national phase |
Ref document number: 2017893061 Country of ref document: EP Effective date: 20190819 |