CN114874081B - 一种绿色高效α-官能化酮的制备方法 - Google Patents
一种绿色高效α-官能化酮的制备方法 Download PDFInfo
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- CN114874081B CN114874081B CN202210503520.9A CN202210503520A CN114874081B CN 114874081 B CN114874081 B CN 114874081B CN 202210503520 A CN202210503520 A CN 202210503520A CN 114874081 B CN114874081 B CN 114874081B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 150000002576 ketones Chemical class 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 229910052786 argon Inorganic materials 0.000 claims abstract description 24
- 239000011941 photocatalyst Substances 0.000 claims abstract description 18
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 14
- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000005286 illumination Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 71
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 56
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical group CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 31
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 28
- VHSVJTYBTJCDFL-UHFFFAOYSA-L 1,2-dimethoxyethane;nickel(2+);dibromide Chemical group Br[Ni]Br.COCCOC VHSVJTYBTJCDFL-UHFFFAOYSA-L 0.000 claims description 24
- TXNLQUKVUJITMX-UHFFFAOYSA-N 4-tert-butyl-2-(4-tert-butylpyridin-2-yl)pyridine Chemical compound CC(C)(C)C1=CC=NC(C=2N=CC=C(C=2)C(C)(C)C)=C1 TXNLQUKVUJITMX-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 description 22
- KRIOVPPHQSLHCZ-UHFFFAOYSA-N phenyl propionaldehyde Natural products CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 22
- 125000000217 alkyl group Chemical group 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 17
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 16
- MYYYZNVAUZVXBO-UHFFFAOYSA-N 1-(bromomethyl)-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(CBr)=C1 MYYYZNVAUZVXBO-UHFFFAOYSA-N 0.000 description 15
- 238000004440 column chromatography Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002390 rotary evaporation Methods 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 238000012216 screening Methods 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- -1 acetyl-substituted phenyl Chemical group 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Natural products C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 description 5
- 150000003934 aromatic aldehydes Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- KTFKRVMXIVSARW-UHFFFAOYSA-N 4-acetylbenzaldehyde Chemical compound CC(=O)C1=CC=C(C=O)C=C1 KTFKRVMXIVSARW-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 description 4
- 235000011009 potassium phosphates Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- GIGRWGTZFONRKA-UHFFFAOYSA-N 1-(bromomethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CBr)C=C1 GIGRWGTZFONRKA-UHFFFAOYSA-N 0.000 description 3
- 235000001258 Cinchona calisaya Nutrition 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000003747 Grignard reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 229960000948 quinine Drugs 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000011630 iodine Chemical group 0.000 description 2
- 229910052740 iodine Chemical group 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 2
- BTFQKIATRPGRBS-UHFFFAOYSA-N o-tolualdehyde Chemical compound CC1=CC=CC=C1C=O BTFQKIATRPGRBS-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- YGSFNCRAZOCNDJ-UHFFFAOYSA-N propan-2-one Chemical compound CC(C)=O.CC(C)=O YGSFNCRAZOCNDJ-UHFFFAOYSA-N 0.000 description 2
- LOUPRKONTZGTKE-LHHVKLHASA-N quinidine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@H]2[C@@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-LHHVKLHASA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BDHSVQLSNIGJNC-JYWFKMLOSA-N (3ar,8bs)-2-[[(3ar,8bs)-4,8b-dihydro-3ah-indeno[1,2-d][1,3]oxazol-2-yl]methyl]-4,8b-dihydro-3ah-indeno[1,2-d][1,3]oxazole Chemical compound C([C@H]1O2)C3=CC=CC=C3[C@@H]1N=C2CC1=N[C@H]2C3=CC=CC=C3C[C@H]2O1 BDHSVQLSNIGJNC-JYWFKMLOSA-N 0.000 description 1
- YFSNGZCIVOUXHS-CYBMUJFWSA-N (4S)-4-tert-butyl-2-isoquinolin-1-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(C)(C)[C@H]1COC(C=2C3=CC=CC=C3C=CN=2)=N1 YFSNGZCIVOUXHS-CYBMUJFWSA-N 0.000 description 1
- WMIQCCDZARURRI-UHFFFAOYSA-N 1,1-dichloroethane Chemical compound CC(Cl)Cl.CC(Cl)Cl WMIQCCDZARURRI-UHFFFAOYSA-N 0.000 description 1
- RZJGKPNCYQZFGR-UHFFFAOYSA-N 1-(bromomethyl)naphthalene Chemical compound C1=CC=C2C(CBr)=CC=CC2=C1 RZJGKPNCYQZFGR-UHFFFAOYSA-N 0.000 description 1
- CRRUGYDDEMGVDY-UHFFFAOYSA-N 1-bromoethylbenzene Chemical compound CC(Br)C1=CC=CC=C1 CRRUGYDDEMGVDY-UHFFFAOYSA-N 0.000 description 1
- BASMANVIUSSIIM-UHFFFAOYSA-N 1-chloro-2-(chloromethyl)benzene Chemical compound ClCC1=CC=CC=C1Cl BASMANVIUSSIIM-UHFFFAOYSA-N 0.000 description 1
- FZFGCHRSCIKKOX-UHFFFAOYSA-N 2-(bromomethyl)-4-(trifluoromethyl)furan Chemical compound FC(F)(F)C1=COC(CBr)=C1 FZFGCHRSCIKKOX-UHFFFAOYSA-N 0.000 description 1
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 1
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- DRZUOPCJWAJOAG-UHFFFAOYSA-N CC(=O)C.CC(=O)C.[Ni] Chemical compound CC(=O)C.CC(=O)C.[Ni] DRZUOPCJWAJOAG-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- DEZRYPDIMOWBDS-UHFFFAOYSA-N dcm dichloromethane Chemical compound ClCCl.ClCCl DEZRYPDIMOWBDS-UHFFFAOYSA-N 0.000 description 1
- RRSIMIHTHWYRRA-UHFFFAOYSA-L dibromonickel;1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound Br[Ni]Br.COCCOCCOC RRSIMIHTHWYRRA-UHFFFAOYSA-L 0.000 description 1
- OCMNCWNTDDVHFK-UHFFFAOYSA-L dichloronickel;1,2-dimethoxyethane Chemical compound Cl[Ni]Cl.COCCOC OCMNCWNTDDVHFK-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 1
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- GQKZBCPTCWJTAS-UHFFFAOYSA-N methoxymethylbenzene Chemical compound COCC1=CC=CC=C1 GQKZBCPTCWJTAS-UHFFFAOYSA-N 0.000 description 1
- CWMAKDYRWVQEAR-HWKANZROSA-N methyl (z)-2-(bromomethyl)but-2-enoate Chemical compound COC(=O)C(\CBr)=C\C CWMAKDYRWVQEAR-HWKANZROSA-N 0.000 description 1
- NLWBJPPMPLPZIE-UHFFFAOYSA-N methyl 4-(bromomethyl)benzoate Chemical compound COC(=O)C1=CC=C(CBr)C=C1 NLWBJPPMPLPZIE-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- YIVPTEHWMSMXGB-UHFFFAOYSA-L nickel(2+);dibromide;hexahydrate Chemical compound O.O.O.O.O.O.Br[Ni]Br YIVPTEHWMSMXGB-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical group O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 125000000168 pyrrolyl group Chemical class 0.000 description 1
- 229960001404 quinidine Drugs 0.000 description 1
- 125000003410 quininyl group Chemical group 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001544 thienyl group Chemical class 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
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Abstract
本发明公开了一种绿色高效α‑官能化酮的制备方法,包括以下步骤:
Description
技术领域
本发明属于有机合成技术领域,具体地说,涉及一种α-官能化酮的光催化合成制备方法。
背景技术
α-官能化酮是一种在天然产物、医药、香料、工业原料中常见的骨架,常作为合成各种药物骨架,如吲哚、咪唑、喹啉等杂环的关键中间体。传统的有机化学合成方法有格氏反应、氧化还原反应、氧化还原偶联等,这些反应条件都存在一些不可避免的缺陷,特别是目前工业上应用最多的格式反应,一般需要氰基、酰胺、酰氯等高氧化态的前体,同时需要使用过量的镁,反应条件苛刻、操作繁琐,并对多种官能团不耐受,不符合绿色化学的现代工业理念。
近年来,光催化反应因其对环境污染小和高效而快速发展。光催化已应用于Giese自由基反应,Minisci反应等。已有几种光催化金属协同催化偶联的策略,使用过渡金属镍或钯催化剂与四丁基铵十聚钨酸盐(TBADT)或金属铱光催化剂协同催化交叉偶联反应,其中主要为醛与芳基的偶联反应,与官能化烷基的直接偶联罕有报道。
在光催化剂方面,与以铱为基础的光催化剂相比,四丁基铵十聚钨酸盐可以从廉价的前体一步制备。镍与钯相比,价格更为低廉。因此使用镍/四丁基铵十聚钨酸盐协同催化偶联反应构建α-官能化酮骨架的方式更加经济绿色,是一种具有很高原子经济性的方法。
一直以来,技术人员致力于不断研究开发新的、更为先进合理、更加环保的α-官能化酮骨架制备方法,以便实现药物和重要价值化合物的绿色高效合成制备。
发明内容
针对上述现有技术存在的问题,本发明的目的是提供一种绿色高效α-官能化酮的制备方法。
为了实现上述目的,本发明采用的技术方案如下:
本发明提供了一种绿色高效α-官能化酮的制备方法,包括以下步骤:
将配体、过渡金属催化剂溶于溶剂中超声混匀,加入式(III)所示化合物、式(II)所示化合物、碱、光催化剂,在室温下充入氩气保护,光照反应,获得式(I)所示化合物;
所述配体、过渡金属催化剂、式(II)所示化合物、碱、光催化剂与式III所示化合物的摩尔比为(0.05~0.2):(0.05~0.2):(0.2~5.0):(1.0~5.0):(0.01~0.1):1;优选为0.1:0.1:1.5:3:0.02:1;
或,将配体、过渡金属催化剂溶于溶剂中超声混匀,加入式(III)所示化合物、式(II)所示化合物、碱、光催化剂,加入氢转移试剂,在室温下充入氩气保护,蓝色光源光照,获得式(I)所示化合物;
所述配体、过渡金属催化剂、式(II)所示化合物、碱、光催化剂、氢转移试剂与式III所示化合物的摩尔比为(0.05~0.2):(0.05~0.2):(0.2~5.0):(1.0~5.0):(0.01~0.1):(0.01~0.5):1;优选为0.1:0.1:1.5:3:0.02:0.02:1;
所述式(II)所示化合物中,R1选自氢、C1~C20直链烷基、C1~C20支链烷基、PhCH2CH2-、金刚烷基-、C3~C12环烷基、苯基、乙酰基取代苯基、硝基取代苯基、C1~C3烷氧基取代苯基、C1~C3烷基取代苯基、吡咯基、呋喃基、噻吩基、
所述式(III)所示化合物中,X选自氯、溴、碘;
R2选自氢、C1~C20直链烷基、C1~C20支链烷基;
R3选自氢、C1~C20直链烷基、C1~C20支链烷基;
R4选自
R5选自氢、C1~C20直链烷基、C1~C20支链烷基、三氟甲基、-COOCH3、C1~C20直链烷氧基、C1~C20支链烷氧基、氟、氯;
R6选自氢、C1~C20直链烷基、C1~C20支链烷基、三氟甲基、-COOCH3、C1~C20直链烷氧基、C1~C20支链烷氧基、氟、氯;
R7选自氢、C1~C20直链烷基、C1~C20支链烷基、三氟甲基、-COOCH3、C1~C20直链烷氧基、C1~C20支链烷氧基、氟、氯;
R8选自氢、C1~C20直链烷基、C1~C20支链烷基、三氟甲基、-COOCH3、C1~C20直链烷氧基、C1~C20支链烷氧基、氟、氯;
R9选自氢、C1~C20直链烷基、C1~C20支链烷基、三氟甲基、-COOCH3、C1~C20直链烷氧基、C1~C20支链烷氧基、氟、氯;
R10选自氢、C1~C20直链烷基、C1~C20支链烷基、三氟甲基、氟、氯;
较优选的,所述式(II)所示化合物中,R1选自氢、-CH2CH2CH3、PhCH2CH2-、苯基、
最优选的,所述式(II)所示化合物选自以下结构的一种:
较优选的,所述式(III)所示化合物中,X选自氯、溴、碘;
R2选自氢、甲基、乙基、正丙基、异丙基;
R3选自氢、甲基、乙基、正丙基、异丙基;
R4选自
最优选的,所述式(III)所示化合物选自以下结构的一种:
所述配体选自(1R,2R)-N,N'-二甲基-1,2-二苯基-1,2-二乙胺、2,2'-联喹啉、双((3aS,8aR)-8,8a-二氢-3aH-茚并[1,2-d]恶唑-2-基)甲烷、(S)-4-(叔丁基)-2-(异喹啉-1-基)-4,5-二氢恶唑、
R11、R12、R13、R14、R15和R16各自独立的选自叔丁基、三氟甲基、甲氧基、甲基、羧基(COOH)、酯基(COOCH3)、氰基、苄基、苯基、异丙基、Cl、H;优选为4,4'-二叔丁基-2,2'-二吡啶。
所述过渡金属催化剂选自溴化镍、溴化镍六水合物、溴化镍乙烯二醇二甲基醚络合物、溴化镍二乙二醇二甲醚复合物、氯化镍、氯化镍乙二醇二甲基醚络合物、二乙酰丙酮镍、碘化镍;优选为溴化镍乙烯二醇二甲基醚络合物。
所述溶剂选自丙酮、乙腈、二氯甲烷、水、二氯乙烷、硝基甲烷、二甲基亚砜,优选为丙酮。
所述碱选自碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、磷酸钾、三乙胺、N,N-二异丙基乙胺;优选为碳酸钠。
所述光催化剂选自四丁基铵十聚钨酸盐、十聚钨酸钠、十聚钨酸钾、蒽醌、Ir[dF(CF3)ppy]2(dtbbpy)PF6;优选为四丁基铵十聚钨酸盐。
所述氢转移试剂选自奎宁(quinuclidine)、三乙基硅烷;仅在光催化剂选自Ir[dF(CF3)ppy]2(dtbbpy)PF6时使用;优选为奎宁。
所述光照反应的波长范围为365~415纳米,优选为390纳米。
所述光照反应的时间为1~24小时,优选为3小时;温度小于40℃,优选为35℃。
所述蓝色光源光照的时间为1~24小时,优选为3小时;温度小于40℃,优选为35℃。
由于采用上述技术方案,本发明具有以下优点和有益效果:
本发明提供的绿色高效α-官能化酮的制备方法,在390纳米光照条件下,醛类化合物与卤代物反应可以以高收率制备α-官能化酮类化合物。同现有技术相比,本发明所提供的制备方法,具有高收率,如实施例5(收率92%),现有技术如对比例1和2的收率分别为62%和76%;与对比例1(20小时)和2(15小时)相比,实施例5(3小时)的反应时间大幅缩短;本发明弥补了对比例1和2均不适用于缺电子芳香醛的缺陷,如实施例11(收率57%)使用了4-乙酰基苯甲醛。本发明的基团兼容性很广,如实施例1中的三氟甲基(收率98%)、实施例5中的甲氧基(收率92%)等,还包括在无法应用Grignard反应制备的基团,如实施例8中的酯基(收率92%)、实施例11中的乙酰基(收率57%)等,本发明与Grignard反应相比更加温和绿色,操作简单安全。
具体实施方式
为了更清楚地说明本发明,下面结合优选实施例对本发明做进一步的说明。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。
实施例1
苯丙醛和1-溴甲基-3-三氟甲基苯的光催化偶联反应操作步骤:
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=19:1)得到产物28.6毫克,收率98%,淡黄色油状物。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ7.53(d,J=7.8Hz,1H),7.43(t,J=7.8Hz,1H),7.41(s,1H),7.33(d,J=7.8Hz,1H),7.28(t,J=7.3Hz,2H),7.20(t,J=7.3Hz,1H),7.13(d,J=7.3Hz,2H),3.73(s,2H),2.91(t,J=7.4Hz,2H),2.79(t,J=7.4Hz,2H);13C NMR(126MHz,CDCl3):δ206.6,141.0,135.1,133.2,131.2(q,J=32.9Hz),129.4,128.9,128.7,126.6,126.5(q,J=3.8Hz),124.3(q,J=3.8Hz),50.0,44.2,30.1.HRMS(m/z):[M+H]+calcd for C17H16F3O+293.1075,found 293.1073.
实施例2
需要加入氢转移试剂的苯丙醛和1-溴甲基-3-三氟甲基苯的光催化偶联反应操作步骤:
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、Ir[dF(CF3)ppy]2(dtbbpy)PF6(2.0μmol,2.0毫克)、奎宁(2.0μmol,1.1毫克)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,蓝色光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=19:1)得到产物25.1毫克,收率86%,淡黄色油状物。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ7.53(d,J=7.8Hz,1H),7.43(t,J=7.8Hz,1H),7.41(s,1H),7.33(d,J=7.8Hz,1H),7.28(t,J=7.3Hz,2H),7.20(t,J=7.3Hz,1H),7.13(d,J=7.3Hz,2H),3.73(s,2H),2.91(t,J=7.4Hz,2H),2.79(t,J=7.4Hz,2H);13C NMR(126MHz,CDCl3):δ206.6,141.0,135.1,133.2,131.2(q,J=32.9Hz),129.4,128.9,128.7,126.6,126.5(q,J=3.8Hz),124.3(q,J=3.8Hz),50.0,44.2,30.1.HRMS(m/z):[M+H]+calcd for C17H16F3O+293.1075,found 293.1073.
实施例3
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、4-溴甲基苯甲酸甲酯(0.10mmol,22.8毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=9:1)得到产物24.0毫克,收率85%,淡黄色油状物。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ7.98(d,J=8.3Hz,2H),7.26(d,J=14.7Hz,2H),7.22(d,J=8.3Hz,2H),7.19(t,J=7.4Hz,1H),7.13(d,J=6.8Hz,2H),3.91(s,3H),3.72(s,3H),2.88(t,J=7.5Hz,2H),2.79(t,J=7.5Hz,2H);13C NMR(126MHz,CDCl3):δ206.7,167.2,141.0,139.5,130.3,129.8,129.3,128.9,128.7,126.6,52.5,50.5,44.2,30.1.HRMS(m/z):[M+H]+calcd for C18H19O3 +283.1289,found 283.1299.
实施例4
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、2-溴甲基-4-三氟甲基呋喃(0.10mmol,22.9毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=9:1)得到产物22.0毫克,收率78%,淡黄色油状物。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ7.28(t,J=7.5Hz,2H),7.20(t,J=7.4Hz,1H),7.16(d,J=6.9Hz,2H),6.73(d,J=1.9Hz,1H),6.26(d,J=3.4Hz,1H),3.74(s,2H),2.92(t,J=7.4Hz,2H),2.82(t,J=7.2Hz,2H);13C NMR(126MHz,CDCl3):δ203.9,151.3(d,J=1.4Hz),141.7(q,J=43.1Hz),140.8,128.9,128.7,126.6,113.0(q,J=2.8Hz),109.7,44.2,42.5,29.9.HRMS(m/z):[M+Na]+calcd for C15H13F3O2Na+305.0868,found 305.0864.
实施例5
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基-4-甲氧基苯(0.10mmol,20.0毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=8:1)得到产物23.4毫克,收率92%,白色固体。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ7.26(t,J=7.2Hz,2H),7.19(t,J=7.4Hz,1H),7.14(d,J=6.8Hz,2H),7.08(d,J=8.8Hz,2H),6.86(d,J=8.8Hz,2H),3.80(s,3H),3.60(s,2H),2.87(t,J=7.3Hz,2H),2.76(t,J=7.1Hz,2H);13C NMR(126MHz,CDCl3):δ207.8,158.6,140.9,130.4,128.4,128.3,126.1,126.0,114.1,55.2,49.5,43.3,29.8.HRMS(m/z):[M+H]+calcd for C17H19O2 +255.1380,found 255.1380.
实施例6
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-氯甲基-2-氯苯(0.10mol,16.0毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=19:1)得到产物23.7毫克,收率92%,白色固体。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ7.42–7.35(m,1H),7.28(t,J=7.9Hz,2H),7.24–7.20(m,2H),7.20–7.15(m,4H),3.82(s,2H),2.93(t,J=7.5Hz,2H),2.82(t,J=7.5Hz,2H);13C NMR(126MHz,CDCl3):δ206.5,141.2,134.7,133.1,132.0,129.9,129.0,128.8,128.7,127.4,126.5,48.1,44.2,30.1.HRMS(m/z):[M+Na]+calcd forC16H15ClONa+281.0811,found 281.0812.
实施例7
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基萘(0.10mol,22.0毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=19:1)得到产物24.4毫克,收率89%,白色固体。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3)δ7.90–7.83(m,1H),7.85–7.77(m,2H),7.56–7.46(m,2H),7.43(dd,J=8.2,6.9Hz,1H),7.33(dd,J=7.0,1.2Hz,1H),7.22(t,J=7.3Hz,2H),7.19–7.12(m,1H),7.10–7.05(m,2H),4.09(s,2H),2.84(t,J=7.5Hz,2H),2.74(t,J=7.3Hz,2H);13C NMR(126MHz,CDCl3):δ208.3,141.2,134.2,132.5,131.2,129.1,128.8,128.7,128.6,128.4,126.9,126.4,126.2,125.9,124.2,49.1,43.3,30.1.HRMS(m/z):[M+H]+calcd for C20H19O+275.1358,found 275.1365.
实施例8
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、(Z)-2-(溴甲基)-2-丁烯酸甲酯(0.10mol,19.2毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=9:1)得到产物21.9毫克,收率89%,无色油状物。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ7.28(t,J=7.7Hz,2H),7.22–7.16(m,3H),7.08(q,J=7.2Hz,1H),3.71(s,3H),3.40(s,2H),2.91(t,J=7.6Hz,2H),2.81(t,J=7.6Hz,2H),1.74(d,J=7.2Hz,3H);13C NMR(126MHz,CDCl3):δ206.7,167.8,141.4,128.8,128.7,127.0,126.4,52.3,44.3,41.0,30.1,15.0.HRMS(m/z):[M+H]+calcd forC15H19O3 +247.1256,found 247.1254.
实施例9
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴乙基苯(0.10mol,18.4毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=19:1)得到产物22.9毫克,收率96%,无色油状物。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ7.34–7.28(m,2H),7.27–7.20(m,3H),7.19–7.13(m,3H),7.07(d,J=6.7Hz,2H),3.71(q,J=7.0Hz,1H),2.93–2.60(m,4H),1.38(d,J=7.0Hz,3H);13C NMR(126MHz,CDCl3):δ210.2,141.4,140.8,129.3,128.7,128.6,128.2,127.5,126.3,53.5,42.9,30.3,17.7.HRMS(m/z):[M+H]+calcd for C17H19O+239.1358,found 239.1365.
实施例10
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克)、2-甲基苯甲醛(0.15m mol,18.0毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=19:1)得到产物25.9毫克,收率93%,淡黄色油状物。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ7.74(dd,J=7.8,1.4Hz,1H),7.56–7.37(m,6H),7.33–7.24(m,2H),4.29(s,2H),2.47(s,3H);13C NMR(126MHz,CDCl3):δ200.6,139.2,137.4,135.7,133.5,132.6,132.1,131.4,129.3,129.0,126.7(q,J=3.6Hz),126.1,124.2(q,J=3.9Hz),48.1,21.8.HRMS(m/z):[M+H]+calcd for C16H14F3O+279.0918,found279.0924.
实施例11
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克)、4-乙酰基苯甲醛(0.15mmol,22.2毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=19:1)得到产物17.4毫克,收率57%,白色固体。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ8.09(d,J=8.4Hz,2H),8.05(d,J=8.2Hz,2H),7.58–7.51(m,2H),7.51–7.42(m,2H),4.39(s,2H),2.65(s,3H);13C NMR(126MHz,CDCl3):δ197.7,196.5,140.8,139.8,135.1,133.4,129.5,129.0,126.7(q,J=3.7Hz),124.4(q,J=3.3Hz),45.6,27.3.HRMS(m/z):[M+H]+calcd for C17H14F3O2 +307.0868,found307.0858.
实施例12
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克)、苯甲醛(0.15mmol,15.9毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=19:1)得到产物24.8毫克,收率94%,淡黄色油状物。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ8.05–8.00(m,2H),7.64–7.57(m,1H),7.56–7.42(m,6H),4.36(s,2H);13C NMR(126MHz,CDCl3):δ197.0,136.7,135.7,133.9,133.4,129.4,129.2,128.8,126.8(q,J=3.9Hz),124.2(q,J=3.7Hz),45.3.HRMS(m/z):[M+H]+calcd for C15H12F3O+265.0762,found 265.0764.
实施例13
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克)、正丁醛(0.15mmol,10.8毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=19:1)得到产物21.2毫克,收率92%,淡黄色油状物。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ7.53(d,J=8.5Hz,1H),7.45(t,J=8.5Hz,2H),7.38(d,J=8.5Hz,1H),3.75(s,2H),2.47(t,J=7.3Hz,2H),1.62(q,J=7.4Hz,2H),0.90(t,J=7.4Hz,3H);13C NMR(126MHz,CDCl3):δ207.6,135.5,133.2,131.4,129.4,126.6(q,J=3.8Hz),124.2(q,J=3.8Hz),49.7,44.7,17.5,14.0.HRMS(m/z):[M+H]+calcd for C12H14F3O+231.0918,found 231.0936.
实施例14
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克)、环己烷基甲醛(0.15mmol,16.8毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=19:1)得到产物25.4毫克,收率94%,淡黄色油状物。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ7.51(d,J=8.0Hz,1H),7.47–7.40(m,2H),7.36(d,J=7.4Hz,1H),3.80(s,2H),2.46(tt,J=11.4,3.4Hz,1H),1.91–1.83(m,2H),1.79(dt,J=12.4,3.4Hz,2H),1.72–1.64(m,1H),1.44–1.14(m,5H);13C NMR(126MHz,CDCl3):δ210.5,135.6,133.3,131.2(d,J=31.9Hz),129.2,126.6(q,J=3.8Hz),124.1(q,J=3.8Hz),51.0,47.4,28.8,26.1,25.9.HRMS(m/z):[M+H]+calcd for C15H18F3O+271.1231,found271.1234.
实施例15
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在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克)、(E)-2-丁烯醛(0.15mmol,10.5毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。旋蒸去除溶剂,柱层析(正己烷:乙酸乙酯=19:1)得到产物19.8毫克,收率87%,淡黄色油状物。
所得产物核磁图谱数据为:1H NMR(500MHz,CDCl3):δ7.52(d,J=7.3Hz,1H),7.48–7.42(m,2H),7.39(d,J=8.0Hz,1H),6.97(dq,J=15.5,6.7Hz,1H),6.19(dq,J=15.7,1.6Hz,1H),3.88(s,2H),1.92(dd,J=6.9,1.6Hz,3H);13C NMR(126MHz,CDCl3):δ196.6,144.6,135.7,133.3,131.4,131.3,131.1,129.4,126.6(q,J=3.8Hz),124.1(q,J=3.8Hz),47.1,18.7.HRMS(m/z):[M+H]+calcd for C12H11F3O+229.0762,found 229.0754.
实施例16
光催化剂的筛选:
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克,0.1当量)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克,0.1当量),加入2.0毫升丙酮(0.05M),超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克,3.0当量)、光催化剂及其所需的氢转移试剂(1.0~5.0μmol,0.01~0.05当量)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克,1.0当量)、苯丙醛(0.15mmol,20.1毫克,1.5当量)。在室温下,氩气保护,特定光源光照(十聚钨酸类光催化剂使用390纳米光源,Ir[dF(CF3)ppy]2(dtbbpy)PF6使用蓝色光源),风扇降温(控制温度低于40℃,约为35℃),反应3小时。
光催化剂的筛选如表1所示:
表1
光催化剂 | 用量 | 收率% |
四丁基铵十聚钨酸盐 | 2.0μmol,6.6毫克,0.02当量 | 98 |
Ir[dF(CF3)ppy]2(dtbbpy)PF6 | 2.0μmol,2.0毫克,0.02当量 | 86 |
十聚钨酸钠 | 2.0μmol,4.9毫克,0.02当量 | 91 |
四丁基铵十聚钨酸盐 | 1.0μmol,3.3毫克,0.01当量 | 76 |
四丁基铵十聚钨酸盐 | 5.0μmol,16.6毫克,0.05当量 | 88 |
使用四丁基铵十聚钨酸盐、Ir[dF(CF3)ppy]2(dtbbpy)PF6和十聚钨酸钠分别作为光催化剂,在相同用量(2.0μmol,0.02当量)下催化同一反应,使用四丁基铵十聚钨酸盐的产率最佳(98%)。降低和增加四丁基铵十聚钨酸盐的用量,都会导致产率降低(1.0μmol,0.01当量,76%;5.0μmol,0.05当量,86%)。最佳条件为四丁基铵十聚钨酸盐(2.0μmol,0.02当量)。
实施例17
过渡金属镍催化剂的筛选:
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、过渡金属镍催化剂(10μmol),加入2.0毫升丙酮(0.05M),超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。
过渡金属镍催化剂的筛选如表2所示:
表2
分别使用各种过渡金属镍催化剂,在相同用量(10μmol)下催化同一反应,使用溴化镍乙烯二醇二甲基醚络合物的产率最佳(98%),其他溴化、氯化镍类催化剂也可以使用,碘化镍的产率不佳。最佳条件为溴化镍乙烯二醇二甲基醚络合物(10μmol)。
实施例18
配体的筛选:
在4毫升干燥反应瓶中,依次加入配体(10μmol)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮(0.05M),超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。
配体的筛选如表3所示:
表3
分别使用各种配体,在相同用量(10μmol)下催化同一反应,使用4,4'-二叔丁基-2,2'-二吡啶的产率最佳(98%),其他联喹啉、联吡啶、双恶唑类等催化剂也可以使用,产率相对较低。最佳条件为4,4'-二叔丁基-2,2'-二吡啶(10μmol)。
实施例19
碱的筛选:
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入2.0毫升丙酮(0.05M),超声溶解至溶液为均一,随后依次加入碱(0.30mmol)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。
碱的筛选如表4所示:
表4
碱 | 用量 | 收率% |
碳酸钠 | 0.30mmol | 98 |
碳酸氢钠 | 0.30mmol | 94 |
碳酸钾 | 0.30mmol | 92 |
碳酸氢钾 | 0.30mmol | 82 |
磷酸钾 | 0.30mmol | 45 |
三乙胺 | 0.30mmol | 26 |
N,N-二异丙基乙胺 | 0.30mmol | 39 |
碳酸钠 | 0.11mmol | 44 |
碳酸钠 | 0.20mmol | 86 |
分别使用各种碱,在相同用量(0.30mmol)下催化同一反应,使用碳酸钠的产率最佳(98%),碳酸氢钠、碳酸钾、碳酸氢钾也可以使用,磷酸钾、三乙胺、N,N-二异丙基乙胺的产率不佳,不适合使用。降低碳酸钠的用量,会导致产率降低(0.11mmol,44%;0.20mmol,86%)。最佳条件为碳酸钠(0.30mmol)。
实施例20
溶剂的筛选:
在4毫升干燥反应瓶中,依次加入4,4'-二叔丁基-2,2'-二吡啶(10μmol,2.7毫克)、溴化镍乙烯二醇二甲基醚络合物(10μmol,3.1毫克),加入溶剂,超声溶解至溶液为均一,随后依次加入碳酸钠(0.30mmol,31.8毫克)、四丁基铵十聚钨酸盐(2.0μmol,6.6毫克)、1-溴甲基-3-三氟甲基苯(0.10mmol,23.9毫克)、苯丙醛(0.15mmol,20.1毫克)。在室温下,氩气保护,390纳米光源光照,风扇降温(控制温度低于40℃,约为35℃),反应3小时。
溶剂的筛选如表5所示:
表5
溶剂 | 浓度 | 收率% |
丙酮 | 0.05M | 98 |
乙腈 | 0.05M | <5 |
二氯甲烷 | 0.05M | 86 |
水 | 0.05M | 41 |
二氯乙烷 | 0.05M | <5 |
硝基甲烷 | 0.05M | <5 |
二甲基亚砜 | 0.05M | 29 |
丙酮 | 0.09M | 91 |
分别使用各种溶剂,在相同浓度下(0.05M)下催化同一反应,使用丙酮的产率最佳(98%),二氯甲烷也可以使用,乙腈、水、二氯乙烷、硝基甲烷、二甲基亚砜的产率不佳,不适合使用。增加反应体系的浓度,会导致产率降低(0.09M,91%)。最佳条件为丙酮(0.05M)。
对比例1
对甲氧基甲基苯(1.0mmol,5.0equiv),苯丙醛(0.2mmol,1.0equiv),NiBr2·(dtbbpy)(0.01mmol,5mol%),Ir[dF(CF3)ppy]2(dtbbpy)PF6(0.004mmol,2mol%),乙酸乙酯(4.9mL,0.04M),蓝色光源光照,室温反应20小时,产率62%。
本发明实施例5与对比例1得到相同产物,实施例5的产率为92%,与对比例1相比得到了大幅提高;光照时间由20小时减少为3小时;对比例1的底物对甲氧基甲基苯、苯丙醛的当量比为5.0:1.0,本发明实施例5的底物1-溴甲基-4-甲氧基苯、苯丙醛的当量比为1:1.5,减少了试剂浪费;对比例1不适用于缺电子芳香醛,本发明适用于各种脂肪醛和芳香醛,实施例11使用4-乙酰基苯甲醛以良好的产率得到产物(57%)。
对比例2
1-(4-甲氧基苄基)-2,4,6-三苯基吡啶四氟硼酸盐(0.7mmol,1.0equiv),苯丙醛(2.1mmol,3.0equiv),NiCl2·(dtbbpy)(0.07mmol,10mol%),磷酸钾(1.26mmol,1.8equiv),TBADT(0.035mmol,5mol%),乙腈(0.1M),390纳米光照,室温反应15小时,产率76%。
本发明实施例5与对比例2得到相同产物,实施例5的产率为92%,与对比例2相比得到了大幅提高;光照时间由15小时减少为3小时;对比例2的底物苯丙醛、1-(4-甲氧基苄基)-2,4,6-三苯基吡啶四氟硼酸盐的当量比为3.0:1.0,本发明实施例5的底物1-溴甲基-4-甲氧基苯、苯丙醛的当量比为1:1.5,减少了试剂浪费;对比例2的底物吡啶盐需要预制备,本发明使用的溴化物易于获得;与对比例2相比,本发明的原子经济性更高;对比例2不适用于缺电子芳香醛,本发明适用于各种脂肪醛和芳香醛,实施例11使用4-乙酰基苯甲醛以良好的产率得到产物(57%)。
以上所述仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭露如上,然而并非用以限定本发明,任何熟悉本专利的技术人员在不脱离本发明技术方案范围内,当可利用上述提示的技术内容作出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案的内容,依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与修饰,均仍属于本发明方案的范围内。
Claims (1)
1.一种α-官能化酮的制备方法,其特征在于,包括以下步骤:
将配体、过渡金属催化剂溶于溶剂中超声混匀,加入式(III)所示化合物、式(II)所示化合物、碱、光催化剂,在室温下充入氩气保护,光照反应,获得式(I)所示化合物;
所述配体、过渡金属催化剂、式(II)所示化合物、碱、光催化剂与式III所示化合物的摩尔比为(0.05~0.2):(0.05~0.2):(0.2~5.0):(1.0~5.0):(0.01~0.1):1;
所述式(II)所示化合物选自以下结构的一种:
所述式(III)所示化合物选自以下结构的一种:
所述配体选自4,4'-二叔丁基-2,2'-二吡啶;
所述过渡金属催化剂选自溴化镍乙烯二醇二甲基醚络合物;
所述溶剂选自丙酮;
所述碱选自碳酸钠;
所述光催化剂选自四丁基铵十聚钨酸盐。
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