CN114989112B - Method for preparing enamine compound by utilizing photocatalysis micro-channel - Google Patents
Method for preparing enamine compound by utilizing photocatalysis micro-channel Download PDFInfo
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- -1 enamine compound Chemical class 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 12
- 239000011941 photocatalyst Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000005086 pumping Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- VWNQJLIVSOOFBX-UHFFFAOYSA-L ruthenium(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.Cl[Ru]Cl VWNQJLIVSOOFBX-UHFFFAOYSA-L 0.000 claims description 4
- PRWATGACIORDEL-UHFFFAOYSA-N 2,4,5,6-tetra(carbazol-9-yl)benzene-1,3-dicarbonitrile Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=C(C#N)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C(N2C3=CC=CC=C3C3=CC=CC=C32)C(N2C3=CC=CC=C3C3=CC=CC=C32)=C1C#N PRWATGACIORDEL-UHFFFAOYSA-N 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- UEEXRMUCXBPYOV-UHFFFAOYSA-N iridium;2-phenylpyridine Chemical compound [Ir].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 UEEXRMUCXBPYOV-UHFFFAOYSA-N 0.000 claims description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FNPNRZLYTIVLNO-UHFFFAOYSA-N Cl(=O)(=O)(=O)O.C1(=C(C(=CC(=C1)C)C)C1C2=CC=CC=C2N(C=2C=CC=CC12)C)C Chemical compound Cl(=O)(=O)(=O)O.C1(=C(C(=CC(=C1)C)C)C1C2=CC=CC=C2N(C=2C=CC=CC12)C)C FNPNRZLYTIVLNO-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims 2
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 150000002081 enamines Chemical class 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 20
- 238000013508 migration Methods 0.000 description 15
- 230000005012 migration Effects 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000001072 heteroaryl group Chemical group 0.000 description 7
- 238000001819 mass spectrum Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- CGVJKUGSPAPYIC-UHFFFAOYSA-N acridin-10-ium perchlorate Chemical compound [O-]Cl(=O)(=O)=O.C1=CC=CC2=CC3=CC=CC=C3[NH+]=C21 CGVJKUGSPAPYIC-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 230000003321 amplification Effects 0.000 description 1
- ICCBZGUDUOMNOF-UHFFFAOYSA-N azidoamine Chemical class NN=[N+]=[N-] ICCBZGUDUOMNOF-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011913 photoredox catalysis Methods 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000000126 substance Substances 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/82—Nitrogen atoms
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- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/127—Sunlight; Visible light
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0231—Halogen-containing compounds
- B01J31/0232—Halogen-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0228
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
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Abstract
The invention discloses a method for preparing enamine compounds by utilizing a photocatalysis micro-channel, which comprises the following steps: (1) Dissolving an azidenols compound shown in a formula 1 and alkali in a first solvent to obtain a first reaction solution; dissolving an ethylbenzene source and a photocatalyst shown in a formula 2 in a second solvent to obtain a second reaction solution; (2) And (3) respectively and simultaneously pumping the first reaction liquid and the second reaction liquid into a micro-reaction device provided with a light source for reaction, and collecting effluent liquid to obtain the reaction liquid containing enamine compounds shown in the formula 3. The invention provides a mild and effective method for synthesizing enamine compounds, which combines a photocatalysis reaction technology and a micro-flow field reaction technology by taking azido enol compounds as substrates, and synthesizes enamine novel compounds in one step, wherein the yield is up to 90 percent.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for synthesizing a polyfunctional enamine compound by utilizing photocatalysis in a microchannel reactor, namely a synthesis method for realizing ethylphenyl by utilizing a far-end heteroaryl ipso-migration mechanism of unactivated olefin under visible light catalysis.
Background
Not only is the radical migration reaction one of the most challenging topics of basic organic chemistry, but it also represents one of the most useful and effective methods to obtain complex compounds of various structures, enabling chemists to obtain many interesting chemical processes. Since the first example of radical mediated aryl migration was developed by the Wieland group in 1911, significant progress has been made in this field, particularly in terms of radical mediated remote functional group migration. A series of interesting long-distance migration of remote aryl groups has been reported (H.Wieland, ber.Dtsch.Chem.Ges.,1911,44,2550-2556). Due to the value and popularity of heteroarenes in pharmaceutical and bioactive molecules, migration of heteroaryl groups substituted by the free radical ipso represents a highly viable remote functionalization strategy. The Zhu task group creatively achieves the difunctional of heteroaryl functional group migration in combination with unactivated systems. This protocol is then widely used for the construction of C-C bonds, C-N bonds, C-P bonds, accompanied by migration of the heteroaryl groups within the molecule under various reaction conditions, such as oxidation, photocatalysis or electrocatalysis (X.Wu, Z.Ma, T.Feng and C.Zhu, chem.Soc.Rev.,2021,50,11577-11613). However, most of these methods are limited by the range of migrating substrates and the manner in which migration occurs. For example, most heteroaryl migration reactions are limited to migration of functional groups between carbon atoms and migration between one heteroatom and two carbon atoms. Despite these advances, it is highly desirable to develop a method for synthesizing enamines that is efficient and environmentally friendly via remote C-center to N-center migration of heterocyclic groups.
Disclosure of Invention
The invention aims to provide a method for preparing enamine compounds by utilizing photocatalysis micro-channels.
In order to solve the problems, the invention discloses a method for preparing enamine compounds by utilizing a photocatalysis microchannel, which comprises the following steps:
(1) Dissolving an azidenols compound shown in a formula 1 and alkali in a first solvent to obtain a first reaction solution; dissolving an ethylbenzene source and a photocatalyst shown in a formula 2 in a second solvent to obtain a second reaction solution;
(2) Pumping the first reaction liquid and the second reaction liquid into a micro-reaction device provided with a light source respectively and simultaneously for reaction, and collecting effluent liquid to obtain reaction liquid containing enamine compounds shown in a formula 3; the micro-reaction device provided with the light source comprises a micro-reactor arranged under the irradiation of the light source;
wherein R is 1 Selected from alkyl, aryl or aryl derivatives; preferably, R 1 Mono-or polysubstituted phenyl or heterocycle which is an electron donating or withdrawing function for aryl derivatives; further preferably, R 1 Is electron-substituted or unsubstituted phenyl; still further preferably, the R 1 Phenyl substituted by halogen or alkyl, or unsubstituted phenyl; still further preferably, the R 1 Phenyl substituted by halogen or C1-C6 alkyl, or unsubstituted phenyl; still further preferably, the R 1 Phenyl substituted by chlorine, phenyl substituted by methyl, phenyl substituted by tert-butyl or phenyl substituted by unsubstituted; still further preferably, the R 1 Is benzene ring;
wherein R is 2 Selected from aryl, aryl derivatives, heterocycles or heterocyclic derivatives; preferably, R 2 Is shown as a formula II;
wherein R is 3 Selected from hydrogen or halogen; preferably, R 3 Selected from hydrogen or Br; further preferably, R 3 Is hydrogen.
Preferably, the azido enols are represented by formula 1 a;
wherein, the azido enol compound can be obtained by taking chain halogenide, phenyl acyl chloride and benzoheterocycle derivatives which are cheap and easy to obtain as raw materials through simple reaction steps.
In the step (1), the alkali is any one or a combination of several of sodium carbonate, cesium carbonate, potassium carbonate, sodium methoxide, potassium ethoxide, potassium tert-butoxide, triethylamine, diethylamine, diisopropylamine, pyridine, piperidine, N-diisopropylethylamine and 2, 6-lutidine; preferably, the base is triethylamine.
In the step (1), the ethylbenzene source shown in the formula 2 is any one of structures shown in the formulas 2 a-2 e; preferably, the ethylbenzene source represented by formula 2 is a compound of the structure represented by formula 2 a;
in the step (1), the photocatalyst is 10-methyl-9-mesityl acridine perchlorate (Mes-Acr + ) Terpyridine ruthenium dichloride hexahydrate (Ru (bpy) 3 Cl 2 ·6H 2 O), tris (2-phenylpyridine) iridium (fac-Ir (ppy) 3 ) Any one or a combination of more than one of Eosin Y (Eosin Y) and 2,4,5, 6-tetra (9H-carbazol-9-yl) isophthalic acid nitrile (4 CzIPN); preferably, the photocatalyst is tris (2-phenylpyridine) iridium (fac-Ir (ppy) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the The chemical structural formula of the photocatalyst is shown as follows:
10-methyl-9-mesityl acridine perchlorate tris (2-phenylpyridine) iridium dichloride hexahydrate terpyridine ruthenium dichloride
In the step (1), the first solvent and the second solvent are respectively and independently selected from any one or a combination of more than one of dichloromethane, 1, 2-dichloroethane, acetonitrile, methanol, ethyl acetate, 1, 4-dioxane, ethanol, benzene, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and chloroform, namely the first solvent and the second solvent can be the same or different; preferably, the first solvent and the second solvent are each independently selected from acetonitrile, tetrahydrofuran, 1, 2-dichloroethane, dichloromethane, or methanol; further preferably, the first solvent and the second solvent are both acetonitrile.
In the step (1), the concentration of the azido enol compound in the first reaction liquid is 0.1-1 mmol/mL, preferably 0.1-0.3 mmol/mL, and more preferably 0.2mmol/mL; the molar ratio of the azidenols to the base is 1:1 to 1:5, preferably 1:1 to 1:4, and more preferably 1:3.
In the step (1), the concentration of the ethylbenzene source in the second reaction solution is 0.2 to 1mmol/mL, preferably 0.3 to 0.7mmol/mL, and more preferably 0.6mmol/mL.
In the step (1), the amount of the photocatalyst is 1 to 20mol%, preferably 1 to 10mol%, and more preferably 1 to 5mol% of the azidenols; the molar ratio of the azidenols compound to the ethylbenzene source is 1:1-1:5, preferably 1:1-1:4, and more preferably 1:3.
In the step (2), the micro-reaction device provided with the light source comprises a first injector, a second injector, a first injection pump, a second injection pump, a micro-mixer, a micro-channel reactor and the light source; the first injector and the second injector are connected to the micro-mixer in a parallel manner through pipelines, the micro-mixer is connected with the micro-channel reactor in series, and the micro-channel reactor is arranged under the irradiation of a light source; the device of the invention is shown in particular in figure 1.
Wherein the first syringe pumps the reaction liquid into the micro-mixer through the first syringe pump, and the second syringe pumps the reaction liquid into the micro-reactor through the second syringe pump.
The micro-channel reactor is of a channel structure, the number of the channels is increased or reduced according to the requirement, the channel is made of polytetrafluoroethylene, the size and the inner diameter of the micro-channel reactor are 0.5-5 mm, and the length of the micro-channel reactor is 0.5-40 m.
Wherein the light source is a lamp belt or a bulb, the intensity is 6W-60W, and the wavelength is 435-577 nm; wherein, the light source is preferably 455nm blue light.
In step (2), the pump 1 rate is consistent with pump 2.
In the step (2), the temperature of the reaction is 0 to 60 ℃, preferably 20 to 50 ℃, more preferably 25 to 45 ℃, still more preferably 25 to 30 ℃.
In step (2), the residence time of the reaction is 5s to 24 hours, preferably 10s to 60 minutes, more preferably 10s to 10 minutes, most preferably 10s to 60s.
The present invention achieves distal ethylphenyl-distal functionalization of unactivated olefins via distal heteroaryl migration. This is a process of functionalization through c—c bond cleavage and recombination in combination with visible light photo-redox catalysis. This strategy provides a route to easily and flexibly obtain polyfunctional azidoamines in high yields under mild conditions.
The beneficial effects are that: compared with the prior art, the invention has the following advantages:
(1) According to the invention, visible light catalysis is utilized, azido enol compounds are used as raw materials, distal ethylenation with unactivated olefin is carried out through distal heteroaryl migration, and the enamine compounds are efficiently synthesized in one step under mild conditions.
(2) The synthesis method can realize the double-functional one-step efficient synthesis of the final novel product enamine compound by using the azido enol compound, and has the advantages of simple operation, short reaction time and reaction step, high reaction yield, simple operation, continuous and uninterrupted production, environmental protection and the like.
(3) The microchannel reaction and the photocatalysis device are simple to build, all the components are cheap and easy to obtain, and the amplification is easy.
(4) The light source is used as an energy source for chemical synthesis, accords with the concept of green chemistry, and is environment-friendly and efficient.
(5) The combination of photocatalysis and a micro-channel reactor can greatly reduce the reaction time, can reach 10s at maximum, improves the reaction yield, and is energy-saving and environment-friendly.
(6) The invention provides a mild and effective method for synthesizing enamine compounds, which combines a photocatalysis reaction technology and a micro-flow field reaction technology by taking azido enol compounds as substrates, and synthesizes the novel enamine compounds in one step, wherein the yield is up to 90 percent.
Drawings
FIG. 1 is a schematic representation of a reaction apparatus according to the present invention, which is a microchannel reactor.
FIG. 2 is a schematic diagram of a comparative example reaction object apparatus, and the reactor is a common reaction tube.
FIG. 3 is a hydrogen spectrum of the product 1 H NMR(400MHz,CDCl 3 )of 3a。
FIG. 4 is a carbon spectrum of the product 13 C NMR(100MHz,CDCl 3 )of 3a。
FIG. 5 is a mass spectrum of the product, HRMS of 3a.
FIG. 6 is a hydrogen spectrum of the product 1 H NMR(400MHz,CDCl 3 )of 3b。
FIG. 7 is a carbon spectrum of the product 13 C NMR(100MHz,CDCl 3 )of 3b。
FIG. 8 is a mass spectrum HRMS of 3b of the product.
FIG. 9 is a hydrogen spectrum of the product 1 H NMR(400MHz,CDCl 3 )of 3c。
FIG. 10 is a carbon spectrum of the product 13 C NMR(100MHz,CDCl 3 )of 3c。
FIG. 11 is a mass spectrum of the product, HRMS of 3c.
FIG. 12 is a hydrogen spectrum of the product 1 H NMR(400MHz,CDCl 3 )of 3d。
FIG. 13 is a carbon spectrum of the product 13 C NMR(100MHz,CDCl 3 )of 3d。
FIG. 14 is a mass spectrum of the product, HRMS of 3d.
FIG. 15 is a hydrogen spectrum of the product 1 H NMR(400MHz,CDCl 3 )of 3e。
FIG. 16 is a carbon spectrum of the product 13 C NMR(100MHz,CDCl 3 )of 3e。
FIG. 17 is a mass spectrum of the product, HRMS of 3e.
Detailed Description
The invention will be better understood from the following examples. However, it will be readily appreciated by those skilled in the art that the description of the embodiments is provided for illustration only and should not limit the invention as described in detail in the claims.
Example 1
1a (0.2 mmol,1 eq) was taken as Et 3 N (0.4 mmol,2 eq.) was dissolved in 1mL acetonitrile, 2a (0.6 mmol,3.0 eq.) fac-Ir (ppy) 3 (1 mol%) of 1 a) was dissolved in 1mL of acetonitrile, the above solutions were respectively introduced into syringes and pumped into a microchannel reactor by means of syringe pumps, the inflow into the reactor was 100. Mu.L/s, the inside diameter was 0.5mm, the volume was 1mL, the reaction residence time was 10s, irradiation was performed with blue light having a wavelength of 455nm of 50W, the temperature was controlled at 25℃and the yield was 90%, and 3a nuclear magnetic spectra were shown in FIGS. 3 to 5.
3a characterization data are as follows: 1 H NMR(400MHz,Chloroform-d)δ13.82(s,1H),7.86(dd,J＝7.1,1.5Hz,2H),7.66(dd,J＝8.0,3.4Hz,2H),7.47–7.32(m,5H),7.24–7.16(m,5H),6.03(s,1H),3.14–3.03(m,2H),2.74(t,J＝7.6Hz,2H),2.01(p,J＝7.7Hz,2H). 13 C NMR(101MHz,Chloroform-d)δ190.8,162.7,159.3,152.0,141.7,138.9,132.1,128.6,128.4,127.5,126.3,126.2,126.0,124.0,98.2,35.7,34.3,30.0.HRMS(ESI):C 25 H 22 N 2 OS[M+H] + :399.1526,Found:399.1526.
example 2
1b (0.2 mmol,1 eq.) pyridine (1 mmol,5 eq.) was dissolved in 1mL tetrahydrofuran, 2b (0.3 mmol,1.5 eq.) 2,4,5, 6-tetrakis (9H-carbazol-9-yl) isophthalonitrile (5 mol% of 1 b) was dissolved in 1mL tetrahydrofuran, the above solutions were each added to a syringe and pumped into a microchannel reactor by means of a syringe pump, the pump inflow was 50. Mu.L/s each with an inner diameter of 0.8mm, the volume was 1mL, the reaction residence time was 20s, irradiation was performed with blue light with a wavelength of 455nm, the control temperature was 25 ℃, the yield was 62%, and the mass spectrum of the 3b nuclear magnetic resonance spectrum was as shown in FIGS. 6 to 8.
3bCharacterization data are as follows: 1 H NMR(400MHz,Chloroform-d)δ13.78(s,1H),7.85–7.76(m,2H),7.67(dd,J＝7.7,4.5Hz,2H),7.40–7.31(m,3H),7.25–7.11(m,7H),5.97(s,1H),3.19–2.95(m,2H),2.74(t,J＝7.6Hz,2H),2.01(p,J＝7.7Hz,2H),1.51(s,2H). 13 C NMR(101MHz,Chloroform-d)δ189.3,163.3,159.2,137.3,128.9,128.8,128.6,128.4,126.3,126.0,124.1,121.6,121.1,97.8,35.7,34.3,30.0.HRMS(ESI):C 25 H 21 ClN 2 OS,[M+H] + :433.1136,Found:433.1136.
example 3
1c (0.2 mmol,1 eq.) of N, N-diisopropylethylamine (0.6 mmol,3 eq.) was dissolved in 1mL of 1, 2-dichloroethane, 2c (0.6 mmol,3 eq.) of 10-methyl-9-trimesoyl acridine perchlorate (5 mol% of 1 c) was dissolved in 1mL of 1, 2-dichloroethane, the above solutions were each fed into a syringe and pumped into a microchannel reactor by means of a syringe pump, the pump inflow was each 80. Mu.L/s reactor inner diameter 0.6mm, the volume was 1mL, the reaction residence time was 12.5s, irradiation was performed with blue light having a wavelength of 455nm, the control temperature was 30 ℃, the yield 58%, and the 3c nuclear magnetic spectrum was as shown in FIGS. 9 to 11.
The 3c characterization data are as follows: 1 H NMR(400MHz,Chloroform-d)δ13.79(s,1H),7.75–7.70(m,2H),7.67(dd,J＝8.0,4.8Hz,2H),7.56–7.49(m,2H),7.37–7.32(m,1H),7.24–7.14(m,6H),5.96(s,1H),3.11–3.01(m,2H),2.74(t,J＝7.6Hz,2H),2.01(p,J＝7.7Hz,2H),1.50(s,2H). 13 C NMR(101MHz,Chloroform-d)δ189.4,163.4,141.6,137.7,132.0,131.8,129.1,128.6,128.4,126.3,126.0,124.1,121.6,121.1,97.7,35.7,34.3,30.0.HRMS：C 25 H 21 BrN 2 OS,[M+H] + :477.0631,found:477.0633.
example 4
1d (0.2 mmol,1 eq) Et 3 N (0.6 mmol,3 eq.) was dissolved in 1mL of methylene chloride, 2d (0.6 mmol,3 eq.) of terpyridine ruthenium dichloride hexahydrate (3 mol% of 1 d) was dissolved in 1mL of methylene chloride, the above solutions were added separately to syringes and pumped into the microchannel reactor by syringe pumps, each of which had an inflow of 80. Mu.L/s, an inner diameter of 0.6mm, a volume of 2mL, a reaction residence time of 25s, irradiation with blue light having a wavelength of 477nm at a control temperature of 45℃and a yield of 61%, and 3d nuclear magnetic spectra were shown in FIGS. 12 to 14.
The 3d characterization data are as follows: 1 H NMR(400MHz,Chloroform-d)δ13.83(s,1H),7.77(d,J＝8.2Hz,2H),7.67–7.64(m,2H),7.36–7.31(m,1H),7.22(dd,J＝8.6,5.7Hz,5H),7.16–7.11(m,3H),6.02(s,1H),3.09–3.03(m,2H),2.74(t,J＝7.6Hz,2H),2.35(s,3H),2.05–1.98(m,2H). 13 C NMR(101MHz,Chloroform-d)δ190.6,162.3,152.0,142.8,141.7,131.9,129.3,128.6,126.2,126.0,123.9,121.4,121.0,98.1,35.7,34.3,30.0,29.7,21.6.HRMS(ESI):C 26 H 24 N 2 OS[M+H] + 413.1682,Found:413.1684.
example 5
1e (0.2 mmol,1 eq), 2, 6-lutidine (0.6 mmol,3 eq.) was dissolved in 1mL of methanol, 2e (0.6 mmol,3 eq.) was dissolved in 1mL of methanol, the above solutions were each added to a syringe and pumped into a microchannel reactor by means of a syringe pump, the inflow into the reactor was 80. Mu.L/s in each case with an inner diameter of 0.6mm, a volume of 5mL, a reaction residence time of 62.5s, and the reaction was irradiated with blue light with a wavelength of 455nm at 12W, the temperature was controlled at 30℃and the yield 77%, and a 3e nuclear magnetic spectrum was shown in FIGS. 15 to 17.
3e is characterized by: 1 H NMR(400MHz,Chloroform-d)δ13.83(s,1H),7.83–7.78(m,2H),7.65(dd,J＝8.3,2.9Hz,2H),7.42–7.39(m,2H),7.35–7.31(m,1H),7.25–7.11(m,7H),6.03(s,1H),3.11–2.99(m,2H),2.74(t,J＝7.6Hz,2H),2.07–1.94(m,2H),1.28(s,9H). 13 C NMR(101MHz,Chloroform-d)δ190.6,162.3,159.4,155.8,152.0,141.7,136.2,131.9,128.6,128.4,127.4,126.2,126.0,125.5,123.9,121.4,121.0,98.2,35.7,35.1,34.3,31.2,30.0.HRMS(ESI):C 29 H 30 N 2 OS,[M+H] + :455.2152,found:455.2155.
the apparatus used in each comparative example described below is shown in FIG. 2, and the reactor used in FIG. 2 is a general reaction tube, and the reactor used in each example is a microchannel reactor, as compared with each example.
Comparative example 1
1a (0.2 mmol,1 eq) was taken as Et 3 N (0.4 mmol,2 eq.) was dissolved in 1mL acetonitrile, 2a (0.6 mmol,3.0 eq.) fac-Ir (ppy) 3 (1 mol%) of 1 a) was dissolved in 1mL of acetonitrile, the above solutions were respectively introduced into syringes and pumped into ordinary reaction tubes by syringe pumps, the inflow rates of the pumps were 100. Mu.L/s, and irradiation was performed with blue light having a wavelength of 455nm at 50W, the temperature was controlled at 25℃for 24 hours, and the yield was 21%.
Comparative example 2
1b (0.2 mmol,1 eq.) pyridine (1 mmol,5 eq.) is dissolved in 1mL tetrahydrofuran, 2b (0.3 mmol,1.5 eq.) 2,4,5, 6-tetrakis (9H-carbazol-9-yl) isophthalonitrile (5 mol% of 1 b) is dissolved in 1mL tetrahydrofuran, the above solutions are added separately to syringes and pumped into a common reaction tube by means of syringe pumps, the inflow is 50. Mu.L/s, blue light with a wavelength of 455nm is used for 24H, the reaction time is controlled at 25℃and the yield is 39%.
Comparative example 3
1c (0.2 mmol,1 eq.) of N, N-diisopropylethylamine (0.6 mmol,3 eq.) was dissolved in 1mL of 1, 2-dichloroethane, 2c (0.6 mmol,3 eq.) of 10-methyl-9-trimesoyl acridine perchlorate (5 mol% of 1 a) was dissolved in 1mL of 1, 2-dichloroethane, the above solutions were respectively introduced into syringes and pumped into a common reaction tube by means of syringe pumps, the inflow was 80. Mu.L/s each, the reaction time was 24 hours, and the irradiation was carried out with 50W of blue light having a wavelength of 455nm at a control temperature of 30℃and a yield of 58%.
Comparative example 4
1d (0.2 mmol,1 eq) Et 3 N (0.6 mmol,3 eq.) was dissolved in 1mL of dichloromethane, 2d (0.6 mmol,3 eq.) of terpyridine ruthenium dichloride hexahydrate (3 mol% of 1 d) was dissolved in 1mL of dichloromethane, the above solutions were added separately to syringes and pumped into the microchannel reactor by means of syringe pumps, the pumping flows into blue light of 80. Mu.L/s, the wavelength was 477nm, irradiation was performed, the temperature was controlled at 45 ℃, the reaction time was 24h, and the yield was 11%.
Comparative example 5
1e (0.2 mmol,1 eq), 2, 6-lutidine (0.6 mmol,3 eq.) were dissolved in 1mL of methanol, 2e (0.6 mmol,3 eq.) and eosin Y (5 mol% of 1 e) were dissolved in 1mL of methanol, the above solutions were added separately to syringes and pumped into the microchannel reactor by means of syringe pumps, both of which had an inflow of 80. Mu.L/s, the reaction time period was 24 hours, irradiation was performed with blue light having a wavelength of 455nm at 12W, the temperature was controlled at 30℃and the yield was 27%.
The invention provides a method for preparing enamine compounds by utilizing photocatalysis micro-channels, and a method for realizing the technical scheme, wherein the method and the way are a plurality of preferred embodiments of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by one of ordinary skill in the art without departing from the principle of the invention, and the improvements and modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (6)
1. A method for preparing enamine compounds by using photocatalysis micro-channels, which is characterized by comprising the following steps:
(1) Dissolving an azidenols compound shown in a formula 1 and alkali in a first solvent to obtain a first reaction solution; dissolving an ethylbenzene source and a photocatalyst in a second solvent to obtain a second reaction solution;
(2) Pumping the first reaction liquid and the second reaction liquid into a micro-reaction device provided with a light source respectively and simultaneously for reaction, and collecting effluent liquid to obtain reaction liquid containing enamine compounds shown in a formula 3;
wherein R is 1 Phenyl substituted by halogen or C1-C6 alkyl, or unsubstituted phenyl;
wherein R is 2 Is shown as a formula II;
wherein R is 3 Selected from hydrogen or halogen;
the ethylbenzene source is any one of structures shown in formulas 2 a-2 d;
in the step (1), the alkali is any one or a combination of several of sodium carbonate, cesium carbonate, potassium carbonate, triethylamine, diethylamine, diisopropylamine, pyridine, piperidine, N-diisopropylethylamine and 2, 6-dimethylpyridine;
in the step (1), the first solvent and the second solvent are respectively and independently selected from any one or a combination of more than one of dichloromethane, 1, 2-dichloroethane, acetonitrile, methanol, ethyl acetate, 1, 4-dioxane, ethanol, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and chloroform;
in the step (1), the photocatalyst is any one or a combination of more than one of 10-methyl-9-mesityl acridine perchlorate, terpyridine ruthenium dichloride hexahydrate, tris (2-phenylpyridine) iridium, eosin Y and 2,4,5, 6-tetra (9H-carbazole-9-yl) isophthalonitrile;
in the step (2), the micro-reaction device provided with the light source comprises a first injector, a second injector, a first injection pump, a second injection pump, a micro-mixer, a micro-channel reactor and the light source; the first injector and the second injector are connected to the micro-mixer in a parallel manner through pipelines, the micro-mixer is connected with the micro-channel reactor in series, and the micro-channel reactor is arranged under the irradiation of a light source; the light source is a lamp band or a bulb, the intensity is 6W-60W, and the wavelength is 435-577 nm.
2. The method according to claim 1, wherein in the step (1), the concentration of the azido enols in the first reaction solution is 0.1-1 mmol/mL; the molar ratio of the azido enol compound to the alkali is 1:1-1:5.
3. The method according to claim 1, wherein in the step (1), the concentration of the ethylbenzene source in the second reaction solution is 0.2-1 mmol/mL.
4. The method according to claim 1, wherein in the step (1), the amount of the photocatalyst is 1-20 mol% of the azidenols, and the molar ratio of the azidenols to the ethylbenzene source is 1:1-1:5.
5. The method according to claim 1, wherein the microchannel reactor has a pore structure, the pore material is polytetrafluoroethylene, the size and the inner diameter of the microchannel reactor are 0.5-5 mm, and the length of the microchannel reactor is 0.5-40 m.
6. The method according to claim 1, wherein in the step (2), the reaction temperature is 0-60 ℃, and the residence time of the reaction is 5 s-24 h.
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