CN113862710B - Electrochemical synthesis method of dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound - Google Patents
Electrochemical synthesis method of dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 84
- -1 pyridine compound Chemical class 0.000 title claims abstract description 84
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000001308 synthesis method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N methylquinoline Natural products C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- FMKMKBLHMONXJM-UHFFFAOYSA-N 5-methyl-2-phenylpyrazol-3-amine Chemical compound N1=C(C)C=C(N)N1C1=CC=CC=C1 FMKMKBLHMONXJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 14
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical group CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 10
- 229940107816 ammonium iodide Drugs 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000004811 liquid chromatography Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 58
- 238000005481 NMR spectroscopy Methods 0.000 description 53
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 16
- 239000003480 eluent Substances 0.000 description 13
- 125000004159 quinolin-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C([H])C(*)=NC2=C1[H] 0.000 description 13
- 239000003208 petroleum Substances 0.000 description 10
- 229910052697 platinum Inorganic materials 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 150000003222 pyridines Chemical class 0.000 description 7
- 238000010586 diagram Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- JJPSZKIOGBRMHK-UHFFFAOYSA-N 2,6-dimethylquinoline Chemical compound N1=C(C)C=CC2=CC(C)=CC=C21 JJPSZKIOGBRMHK-UHFFFAOYSA-N 0.000 description 2
- BELFSAVWJLQIBB-UHFFFAOYSA-N 2,8-dimethylquinoline Chemical compound C1=CC=C(C)C2=NC(C)=CC=C21 BELFSAVWJLQIBB-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- SQRYQSKJZVQJAY-UHFFFAOYSA-N 6-bromo-2-methylquinoline Chemical compound C1=C(Br)C=CC2=NC(C)=CC=C21 SQRYQSKJZVQJAY-UHFFFAOYSA-N 0.000 description 1
- OCCIBGIEIBQGAJ-UHFFFAOYSA-N 6-chloro-2-methylquinoline Chemical compound C1=C(Cl)C=CC2=NC(C)=CC=C21 OCCIBGIEIBQGAJ-UHFFFAOYSA-N 0.000 description 1
- NAGJQQFMJKMXJQ-UHFFFAOYSA-N 6-methoxy-2-methylquinoline Chemical compound N1=C(C)C=CC2=CC(OC)=CC=C21 NAGJQQFMJKMXJQ-UHFFFAOYSA-N 0.000 description 1
- WQZQFYRSYLXBGP-UHFFFAOYSA-N 7-chloro-2-methylquinoline Chemical compound C1=CC(Cl)=CC2=NC(C)=CC=C21 WQZQFYRSYLXBGP-UHFFFAOYSA-N 0.000 description 1
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JXDYKVIHCLTXOP-UHFFFAOYSA-N Pseudoisatin Natural products C1=CC=C2C(=O)C(=O)NC2=C1 JXDYKVIHCLTXOP-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/09—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/14—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/05—Heterocyclic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The application discloses an electrochemical synthesis method of a dihydropyrazol [3,4-b:4',3' -e ] pyridine compound, which relates to the technical field of organic synthesis, and comprises the following steps of: (1) electrocatalytic reactions; (2) separating and purifying. According to the application, the dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound is synthesized by the 2-methylquinoline compound and the 5-amino-3-methyl-1-phenylpyrazole compound under electrochemical conditions by a one-pot method, and the method does not need the use of metal and chemical oxidants, is clean in reaction and is environment-friendly.
Description
Technical field:
the application relates to the technical field of organic synthesis, in particular to an electrochemical synthesis method of a dihydropyrazol [3,4-b:4',3' -e ] pyridine compound.
The background technology is as follows:
polysubstituted pyridine compounds are important nitrogen-containing heterocycles and widely exist in bioactive molecules and photoelectric materials. In particular to 3, 5-dimethyl-1, 7-diphenyl-4- (quinoline-2-yl) -1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compounds, the molecules of which contain a plurality of aromatic groups, which are important potential organic functional molecules. Thus, their synthesis has been the focus of research by organic chemists. However, due to the multiple chemical bond formation involved, few reports are currently being made of 3, 5-dimethyl-1, 7-diphenyl-4- (quinolin-2-yl) -1, 7-dihydro-bipyrazol [3,4-b:4',3' -e ] pyridines.
Recently, zhu task group utilized metallic Cu (OTf) 2 3, 5-dimethyl-1, 7-diphenyl was synthesized in tandem from 2-methylquinoline and 5-amino-3-methyl-1-phenylpyrazole-4- (quinolin-2-yl) -1, 7-dihydro-bipyrazole [3,4-b:4',3' -e]Pyridines (R-J.Xie, J-H.Liu, Q-Y, zhang, Y-J.Yang, L-Q.Song, T-Q, shao, K-X, liuandY-P.Zhu, org.Chem.Front,2021,8,2274.). Although the method can well realize the synthesis, the metal residues often affect the utility of the synthesized drug molecules and functional molecules and require multiple steps to remove the metal residues, the steps are complicated, and a large amount of waste liquid is discharged.
The application comprises the following steps:
the application aims to solve the technical problem of providing an electrochemical synthesis method of a dihydropyrazol [3,4-b:4',3' -e ] pyridine compound, which adopts a green electrochemical synthesis method to prepare the dihydropyrazol [3,4-b:4',3' -e ] pyridine compound in a reaction environment without adding metal and chemical oxidant so as to overcome the defects in the prior art.
The technical problems to be solved by the application are realized by adopting the following technical scheme:
an electrochemical synthesis method of a dihydropyrazol [3,4-b:4',3' -e ] pyridine compound comprises the following steps:
(1) Electrocatalytic reaction: respectively adding an electrolyte, a 2-methylquinoline compound, a 5-amino-3-methyl-1-phenylpyrazole compound and a solvent into a reaction tank, installing a catalytic electrode, and electrifying and stirring for reaction;
(2) And (3) separating and purifying: separating and purifying the solution after the electrocatalytic reaction is completed to obtain the dihydropyrazol [3,4-b:4',3' -e ] pyridine compound;
the dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound has a structure shown as follows:
wherein R is 1 Is hydrogen, C 1 ～C 5 Alkyl, C 1 ～C 5 One or more of alkoxy, halogen; r is R 2 Is phenyl or C 1 ～C 5 An alkyl group; r is R 3 Is phenyl or C 1 ～C 5 Alkyl group。
Optionally, the 2-methylquinoline compound has a structure as shown below:
wherein R is 1 Is hydrogen, C 1 ～C 5 Alkyl, C 1 ～C 5 Alkoxy, halogen.
Optionally, the 5-amino-3-methyl-1-phenylpyrazole compound has a structure as shown below:
wherein R is 2 Is phenyl or C 1 ～C 5 An alkyl group; r is R 3 Is phenyl or C 1 ～C 5 An alkyl group.
Optionally, the mass ratio of the 2-methylquinoline compound to the 5-amino-3-methyl-1-phenylpyrazole compound is 1:1-1:4.
Optionally, the initial concentration of the 2-methylquinoline compound is 0.05-0.2 mol/L.
Optionally, the electrolyte is one of tetrabutylammonium tetrafluoroborate, lithium perchlorate, ammonium iodide, potassium iodide, sodium iodide, tetramethyl ammonium iodide and tetrabutyl ammonium iodide, and the mass of the electrolyte is 30-120% of that of the 2-methylquinoline compound.
Optionally, the temperature of the stirring reaction is 0-140 ℃.
Optionally, the solvent is one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide, acetonitrile, water and 1, 2-dichloroethane.
Alternatively, the catalytic electrode is a conventional electrode material.
Optionally, the separation and purification method is one of column chromatography, liquid chromatography, distillation and recrystallization separation.
More optionally, the separation and purification method is column chromatography.
Optionally, the eluent of the column chromatography is petroleum ether/ethyl acetate. This is not a requirement of the present application to say that other eluent systems are not required, as long as reagents meeting the elution objectives can be used.
The beneficial effects of the application are as follows: the application provides an electrosynthesis method of dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compounds, which is characterized in that 2-methylquinoline compounds and 5-amino-3-methyl-1-phenylpyrazole compounds are synthesized into dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compounds by a one-pot method under electrochemical conditions, and the method does not need use of metal and chemical oxidants, has clean reaction and is environment-friendly.
Description of the drawings:
FIG. 1 shows the product of example 1 of the present application 1 H NMR；
FIG. 2 shows the product of example 1 of the present application 13 C NMR；
FIG. 3 shows the product obtained in example 2 of the present application 1 H NMR；
FIG. 4 shows the product obtained in example 2 of the present application 13 C NMR；
FIG. 5 shows the product of example 3 of the present application 1 H NMR；
FIG. 6 shows the product of example 3 of the present application 13 C NMR；
FIG. 7 shows the product obtained in example 4 of the present application 1 H NMR；
FIG. 8 shows the product obtained in example 4 of the present application 13 C NMR；
FIG. 9 shows the product obtained in example 5 of the present application 13 C NMR；
FIG. 10 shows the product obtained in example 5 of the present application 1 H NMR；
FIG. 11 shows the product of example 6 of the present application 13 C NMR；
FIG. 12 shows the product of example 6 of the present application 13 C NMR；
FIG. 13 shows the product of example 7 of the present application 1 H NMR；
FIG. 14 is a diagram of the product obtained in example 7 of the present application 13 C NMR；
FIG. 15 shows the product of example 8 of the present application 1 H NMR；
FIG. 16 shows the product of example 8 of the present application 13 C NMR。
The specific embodiment is as follows:
the application is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the application easy to understand.
An electrosynthesis method of dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound comprises the following steps:
(1) Electrocatalytic reaction: respectively adding an electrolyte, a 2-methylquinoline compound, a 5-amino-3-methyl-1-phenylpyrazole compound and a solvent into a reaction tank, installing a catalytic electrode, and electrifying and stirring for reaction;
(2) And (3) separating and purifying: separating and purifying the solution after the electrocatalytic reaction is completed to obtain the dihydropyrazol [3,4-b:4',3' -e ] pyridine compound;
the dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound synthesized by the application has the structure shown as follows:
wherein R is 1 Is hydrogen, C 1 ～C 5 Alkyl, C 1 ～C 5 One or more of alkoxy, halogen; r is R 2 Is phenyl or C 1 ～C 5 An alkyl group; r is R 3 Is phenyl or C 1 ～C 5 An alkyl group.
Specifically, in a 10mL undivided electrolytic tank, an electrode, a 2-methylquinoline compound, a 5-amino-3-methyl-1-phenylpyrazole compound, an electrolyte and a solvent are respectively added into the undivided electrolytic tank, and the mixture is electrified and stirred for reaction; the amount of the electrolyte is 30-120% of the amount of the 2-methylquinoline compound. The mass ratio of the 2-methylquinoline compound to the 5-amino-3-methyl-1-phenylpyrazole compound is 1:1-1:4. The initial concentration of the 2-methylquinoline compound is 0.05-0.2 mol/L, and the temperature of the stirring reaction is 0-140 ℃. The electrode is selected from conventional commercial electrode materials such as platinum electrode, carbon electrode, nickel electrode, copper electrode, etc.
The solution after the reaction was dried under reduced pressure, and the residue was separated by column chromatography on a silica gel column and passed through the column using a petroleum ether/ethyl acetate system as eluent. This is not a requirement of the present application to say that other eluent systems are not required, as long as reagents meeting the elution objectives can be used.
The reaction formula is:
according to the embodiment of the application, the reaction of the isatin compound and the benzoyl hydrazine compound under the electrochemical condition is realized for the first time, and the dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound is obtained with high selectivity. The method is a green and efficient method for synthesizing the dihydropyrazol [3,4-b:4',3' -e ] pyridine compound.
The 2-methylquinoline and 5-amino-3-methyl-1-phenylpyrazole compounds used in the examples were all analytically pure reagents purchased directly from Yu Annai Ji chemical, jiu Ding chemical, aladin and Aldamasc, and the solvents or eluents used were purchased from Guo nationality without further treatment.
Example 1
2-methylquinoline (0.3 mmoL,42.9 mg), 5-amino-3-methyl-1-phenylpyrazole (0.6 mmol,40.8 mg), ammonium iodide (0.3 mmol,43.5 mg), and N, N-dimethylformamide (3.0 mL) were placed in a 10mL undivided cell, and a platinum sheet electrode was used as both an anode and a cathode, and the reaction was stirred under electricity (I=10mA) at 120 ℃. After the completion of the reaction (TLC trace detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 3, 5-dimethyl-1, 7-diphenyl-4- (quinolin-2-yl) -1, 7-dihydro-bipyrazole [3,4-b:4',3' -e ] pyridine compound in 84% yield.
Subjecting the 3, 5-dimethyl-1, 7-diphenyl-4- (quinolin-2-yl) -1, 7-dihydro-bipyrazole [3,4-b:4',3' -e to a nuclear magnetic resonance spectrometer]The pyridine product was analyzed, and the results are shown in FIGS. 1-2, FIG. 1 shows 3, 5-dimethyl-1, 7-diphenyl-4- (quinolin-2-yl) -1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] provided in example 1 of the present application]Pyridine products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 2 is a schematic illustration of 3, 5-dimethyl-1, 7-diphenyl-4- (quinolin-2-yl) -1, 7-dihydro-bipyrazole [3,4-b:4',3' -e ] provided in example 1 of the present application]Pyridine products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
The obtained product is measured, and the characterization data are as follows 1 H NMR(CDCl 3 ,400MHz,ppm):δ＝8.44–8.42(m,5H),8.25(d,J＝7.2Hz,1H),8.03(d,J＝6.8Hz,1H),7.91–7.87(m,1H),7.76–7.71(m,2H),7.58–7.54(m,4H),7.33–7.29(m,2H),2.07(s,6H)； 13 C NMR(CDCl 3 ,100MHz,ppm):δ＝153.5,150.8,147.5,144.0,139.6,139.2,136.3,130.8,129.8,129.0,127.9,127.8,127.5,125.2,122.1,120.4,113.1,15.0。
The 3, 5-dimethyl-1, 7-diphenyl-4- (quinolin-2-yl) -1, 7-dihydro-pyrazolo [3,4-b:4',3' -e ] pyridine compound prepared in example 1 has the structural formula:
example 2
2, 6-dimethylquinoline (0.3 mmoL,47.1 mg), 5-amino-3-methyl-1-phenylpyrazole (0.6 mmoles, 40.8 mg), ammonium iodide (0.3 mmoles, 43.5 mg), and N, N-dimethylformamide (3.0 mL) were placed in a 10mL undivided electrolytic cell, and a platinum sheet electrode was used as both an anode and a cathode, and the reaction was performed with stirring (I=10mA) at 120 ℃. After the completion of the reaction (TLC trace detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 3, 5-dimethyl-4- (6-methylquinolin-2-yl) -1, 7-diphenyl-1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound in 74% yield.
Subjecting the 3, 5-dimethyl-4- (6-methylquinolin-2-yl) -1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e to a nuclear magnetic resonance spectrometer]The pyridine product was analyzed, and the results are shown in FIGS. 3-4, wherein FIG. 3 shows the 3, 5-dimethyl-4- (6-methylquinolin-2-yl) -1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e ] provided in example 2 of the present application]Pyridine products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 4 is a schematic illustration of 3, 5-dimethyl-4- (6-methylquinolin-2-yl) -1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e ] provided in example 2 of the present application]Pyridine products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
The obtained product is measured, and the characterization data are as follows 1 H NMR(CDCl 3 ,400MHz,ppm):δ＝8.44–8.42(m,4H),8.33(d,J＝7.6Hz,1H),8.13(d,J＝8.8Hz,1H),7.78(s,1H),7.73–7.70(m,1H),7.67(d,J＝8.4Hz,1H),7.58–7.54(m,4H),7.33–7.31(m,2H),2.65(s,3H),2.07(s,6H)； 13 C NMR(CDCl 3 ,100MHz,ppm):δ＝152.5,150.8,146.1,144.1,139.6,139.4,137.9,136.0,133.1,129.4,129.0,127.5,126.7,125.2,122.0,120.4,113.2,21.7,14.9。
The 3, 5-dimethyl-4- (6-methylquinolin-2-yl) -1, 7-diphenyl-1, 7-dihydro-pyrazolo [3,4-b:4',3' -e ] pyridine compound prepared according to example 2 has the structural formula:
example 3
6-methoxy-2-methylquinoline (0.3 mmoL,51.9 mg), 5-amino-3-methyl-1-phenylpyrazole (0.6 mmoles, 40.8 mg), ammonium iodide (0.3 mmoles, 43.5 mg), and N, N-dimethylformamide (3.0 mL) were placed in a 10mL undivided electrolytic cell, and a platinum sheet electrode was used as both an anode and a cathode, and the reaction was performed with stirring (I=10mA) at 120 ℃. After the completion of the reaction (TLC trace detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 4- (6-methoxyquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound in 40% yield.
Subjecting the 4- (6-methoxyquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e ] to a nuclear magnetic resonance spectrometer]The pyridine product was analyzed, and the results are shown in FIGS. 5-6, wherein FIG. 5 shows 4- (6-methoxyquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e ] provided in example 3 of the present application]Pyridine products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 6 is a schematic diagram of a 4- (6-methoxyquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e ] provided in example 3 of the present application]Pyridine products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
The obtained product is measured, and the characterization data are as follows 1 H NMR(CDCl 3 ,400MHz,ppm):δ＝8.44–8.42(m,4H),8.31(d,J＝7.6Hz,1H),8.13(d,J＝8.8Hz,1H),7.66(d,J＝8.4Hz,1H),7.58–7.52(m,5H),7.33–7.29(m,2H),7.27–7.26(m,1H),4.03(s,3H),2.08(s,6H)； 13 C NMR(CDCl 3 ,100MHz,ppm):δ＝158.7,150.8,150.7,144.1,143.6,139.6,139.4,134.9,131.2,129.0,128.7,125.2,123.7,122.3,120.4,113.2,105.1,55.7,14.9。
The structural formula of the 4- (6-methoxyquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound prepared in example 3 is as follows:
example 4
6-chloro-2-methylquinoline (0.3 mmoL,53.1 mg), 5-amino-3-methyl-1-phenylpyrazole (0.6 mmoles, 40.8 mg), ammonium iodide (0.3 mmoles, 43.5 mg), and N, N-dimethylformamide (3.0 mL) were placed in a 10mL undivided electrolytic cell, and a platinum sheet electrode was used as both an anode and a cathode, and the reaction was performed with stirring (I=10mA) at 120 ℃. After the completion of the reaction (TLC tracking detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 4- (6-chloroquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydropyrazol [3,4-b:4',3' -e ] pyridine compound in 83% yield.
Subjecting the 4- (6-chloroquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e to a nuclear magnetic resonance spectrometer]The pyridine product was analyzed, and the results are shown in FIG. 7-8, FIG. 7 shows that 4- (6-chloroquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e ] provided in example 4 of the present application]Pyridine products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 8 is a schematic diagram of a 4- (6-chloroquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydropyrazol [3,4-b:4',3' -e ] provided in example 4 of the present application]Pyridine products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
The obtained product is measured, and the characterization data are as follows 1 HNMR(CDCl 3 ,400MHz,ppm):δ＝8.43–8.41(m,4H),8.34(d,J＝8.0Hz,1H),8.18(d,J＝8.8Hz,1H),8.02–8.01(m,1H),7.82(dd,J＝9.2Hz,J＝2.4Hz,1H),7.74(d,J＝8.4Hz,1H),7.58–7.54(m,4H),7.34–7.29(m,2H),2.06(s,6H)； 13 C NMR(CDCl 3 ,100MHz,ppm):δ＝153.8,150.8,145.8,143.8,139.6,138.6,135.4,133.7,131.8,131.4,129.0,128.0,126.6,125.3,123.0,120.4,113.0,14.9。
The structural formula of the 4- (6-chloroquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound prepared in example 4 is shown below:
example 5
6-bromo-2-methylquinoline (0.3 mmoL,66.3 mg), 5-amino-3-methyl-1-phenylpyrazole (0.6 mmole, 40.8 mg), ammonium iodide (0.3 mmole, 43.5 mg), and N, N-dimethylformamide (3.0 mL) were placed in a 10mL undivided electrolytic cell, and a platinum sheet electrode was used as both an anode and a cathode, and the reaction was performed with stirring (I=10mA) at 120 ℃. After the completion of the reaction (TLC trace detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 4- (6-bromoquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound in 83% yield.
Subjecting the 4- (6-bromoquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e ] to a nuclear magnetic resonance spectrometer]The pyridine product was analyzed, and the results are shown in FIGS. 9-10, wherein FIG. 9 shows the 4- (6-bromoquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e ] provided in example 5 of the present application]Pyridine products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 10 is a schematic illustration of 4- (6-bromoquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydrodipyrazole [3,4-b:4',3' -e ] provided in example 5 of the present application]Pyridine products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
The obtained product is measured, and the characterization data are as follows 1 H NMR(CDCl 3 ,400MHz,ppm):δ＝8.43–8.40(m,4H),8.32(d,J＝8.0Hz,1H),8.19(d,J＝2.4Hz,1H),8.11(d,J＝9.2Hz,1H),7.95(d,J＝8.8Hz,J＝2.4Hz,1H),7.73(d,J＝8.4Hz,1H),7.58–7.53(m,4H),7.34–7.29(m,2H),2.05(s,6H)； 13 C NMR(CDCl 3 ,100MHz,ppm):δ＝153.9,150.7,146.0,143.8,139.5,138.6,135.3,134.3,131.4,129.9,129.0,128.5,125.3,123.0,121.9,120.4,112.9,14.9。
The structural formula of the 4- (6-bromoquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydropyrazolo [3,4-b:4',3' -e ] pyridine compound prepared in example 5 is as follows:
example 6
7-chloro-2-methylquinoline (0.3 mmoL,53.1 mg), 5-amino-3-methyl-1-phenylpyrazole (0.6 mmoles, 40.8 mg), ammonium iodide (0.3 mmoles, 43.5 mg), and N, N-dimethylformamide (3.0 mL) were placed in a 10mL undivided electrolytic cell, and a platinum sheet electrode was used as both an anode and a cathode, and the reaction was performed with stirring (I=10mA) at 120 ℃. After the completion of the reaction (TLC trace detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 4- (7-chloroquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydropyrazol [3,4-b:4',3' -e ] pyridine compound in 63% yield.
Subjecting the 4- (7-chloroquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e to a nuclear magnetic resonance spectrometer]The pyridine product was analyzed, and the results are shown in FIGS. 11-12, wherein FIG. 11 shows 4- (7-chloroquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydrodipyrazole [3,4-b:4',3' -e ] provided in example 6 of the present application]Pyridine products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 12 is a schematic illustration of 4- (7-chloroquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydropyrazol [3,4-b:4',3' -e ] provided in example 6 of the application]Pyridine products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
The obtained product is measured, and the characterization data are as follows 1 HNMR(CDCl 3 ,400MHz,ppm):δ＝8.43–8.40(m,5H),8.24(d,J＝2.0Hz,1H),7.97(d,J＝8.8Hz,1H),7.72–7.68(m,2H),7.58–7.54(m,4H),7.34–7.30(m,2H),2.07(s,6H)； 13 C NMR(CDCl 3 ,100MHz,ppm):δ＝154.7,150.8,147.8,143.8,139.6,138.6,136.8,136.2,129.1,129.0,129.0,128.8,125.8,125.3,122.3,120.5,113.0,14.9。
The structural formula of the 4- (7-chloroquinolin-2-yl) -3, 5-dimethyl-1, 7-diphenyl-1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound prepared in example 6 is shown below:
example 7
2, 8-dimethylquinoline (0.3 mmoL,47.1 mg), 5-amino-3-methyl-1-phenylpyrazole (0.6 mmoles, 40.8 mg), ammonium iodide (0.3 mmoles, 43.5 mg), and N, N-dimethylformamide (3.0 mL) were placed in a 10mL undivided electrolytic cell, and a platinum sheet electrode was used as both an anode and a cathode, and the reaction was performed with stirring (I=10mA) at 120 ℃. After the completion of the reaction (TLC trace detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 3, 5-dimethyl-4- (8-methylquinolin-2-yl) -1, 7-diphenyl-1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound in 69% yield.
Subjecting the 3, 5-dimethyl-4- (8-methylquinolin-2-yl) -1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e to a nuclear magnetic resonance spectrometer]The pyridine product was analyzed, and the results are shown in FIGS. 13-14, FIG. 13 shows that example 7 of the present application provides 3, 5-dimethyl-4- (8-methylquinolin-2-yl) -1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e]Pyridine products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 14 is a schematic illustration of 3, 5-dimethyl-4- (8-methylquinolin-2-yl) -1, 7-diphenyl-1, 7-dihydro-bipyrazole [3,4-b:4',3' -e ] provided in example 7 of the present application]Pyridine products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
The obtained product is measured, and the characterization data are as follows 1 H NMR(CDCl 3 ,400MHz,ppm):δ＝8.45(d,J＝7.6Hz,4H),8.35(d,J＝8.4Hz,1H),7.85(d,J＝6.4Hz,1H),7.72(d,J＝6.8Hz,1H),7.68(d,J＝8.4Hz,1H),7.62–7.55(m,5H),7.34–7.30(m,2H),2.85(s,3H),2.09(s,6H)； 13 C NMR(CDCl 3 ,100MHz,ppm):δ＝152.1,150.8,146.6,144.2,140.0,139.6,137.9,136.3,130.6,128.9,127.5,127.4,125.8,125.1,122.1,120.3,113.1,18.1,15.1。
The 3, 5-dimethyl-4- (8-methylquinolin-2-yl) -1, 7-diphenyl-1, 7-dihydro-pyrazolo [3,4-b:4',3' -e ] pyridine compound prepared according to example 7 has the structural formula:
example 8
In a 10mL undivided cell were placed 2-methylquinoline (0.3 mmoL,42.9 mg), 1, 3-dimethyl-1H-pyrazol-5-amino (0.6 mmole, 66.6 mg), ammonium iodide (0.3 mmole, 43.5 mg), and N, N-dimethylformamide (3.0 mL), and a platinum sheet electrode was used as both an anode and a cathode, and the reaction was carried out under stirring (I=10mA) at 120 ℃. After the completion of the reaction (TLC trace detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 1,3,5, 7-tetramethyl-4- (quinolin-2-yl) -1, 7-dihydro-bipyrazole [3,4-b:4',3' -e ] pyridine compound in 54% yield.
Subjecting the 1,3,5, 7-tetramethyl-4- (quinolin-2-yl) -1, 7-dihydro-dihydropyrazol [3,4-b:4',3' -e to a nuclear magnetic resonance spectrometer]The pyridine product was analyzed, and the results are shown in FIGS. 15-16, FIG. 15 shows 1,3,5, 7-tetramethyl-4- (quinolin-2-yl) -1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] provided in example 8 of the present application]Pyridine products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 16 is a diagram of 1,3,5, 7-tetramethyl-4- (quinolin-2-yl) -1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] as provided in example 8 of the present application]Pyridine products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
The obtained product is measured, and the characterization data are as follows 1 HNMR(CDCl 3 ,400MHz,ppm):δ＝8.37(d,J＝7.6Hz,1H),8.21(d,J＝7.6Hz,1H),7.99(d,J＝6.8Hz,1H),7.87–7.83(m,1H),7.71–7.67(m,1H),7.62(d,J＝8.0Hz,1H),4.10(s,6H),1.99(s,6H)； 13 C NMR(CDCl 3 ,100MHz,ppm):δ＝154.0,152.2,147.4,141.7,138.7,136.1,130.6,129.7,127.8,127.5,127.4,122.1,111.1,33.5,14.8。
The 1,3,5, 7-tetramethyl-4- (quinolin-2-yl) -1, 7-dihydro-pyrazolo [3,4-b:4',3' -e ] pyridine prepared in example 8 has the structural formula:
the energizing stirring reaction time in the embodiment of the application can be arbitrary, and 3, 5-dimethyl-1, 7-diphenyl-4- (quinoline-2-yl) -1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compounds can be prepared only by energizing, the optimal energizing time is about 15 hours, and the yield of the obtained product is highest. The 3, 5-dimethyl-1, 7-diphenyl-4- (quinolin-2-yl) -1, 7-dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound may be prepared at any other time, but the yield may be changed, the yield may be gradually increased from the start of power-on to 15 hours, and the yield may be decreased beyond 15 hours, possibly due to an excessively long power-on catalytic period, resulting in conversion of the generated product into other byproducts.
The foregoing has shown and described the basic principles and main features of the present application and the advantages of the present application. It will be understood by those skilled in the art that the present application is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present application, and various changes and modifications may be made without departing from the spirit and scope of the application, which is defined in the appended claims. The scope of the application is defined by the appended claims and equivalents thereof.
Claims (7)
1. An electrochemical synthesis method of a dihydropyrazol [3,4-b:4',3' -e ] pyridine compound is characterized by comprising the following steps:
(1) Electrocatalytic reaction: respectively adding an electrolyte, a 2-methylquinoline compound, a 5-amino-3-methyl-1-phenylpyrazole compound and a solvent into a reaction tank, installing a catalytic electrode, and electrifying and stirring for reaction;
(2) And (3) separating and purifying: separating and purifying the solution after the electrocatalytic reaction is completed to obtain the dihydropyrazol [3,4-b:4',3' -e ] pyridine compound;
the dihydro-dipyrazole [3,4-b:4',3' -e ] pyridine compound has a structure shown as follows:
wherein R is 1 Is hydrogen, C 1 ～C 5 Alkyl, C 1 ～C 5 One or more of alkoxy, halogen; r is R 2 Is phenyl or C 1 ～C 5 An alkyl group; r is R 3 Is phenyl or C 1 ～C 5 An alkyl group;
the electrolyte is ammonium iodide;
the temperature of the electrified stirring reaction is 120 ℃, and the current is 10mA;
the mass ratio of the 2-methylquinoline compound to the 5-amino-3-methyl-1-phenylpyrazole compound is 1:2.
2. The synthesis method according to claim 1, wherein: the 2-methylquinoline compound has a structure shown as follows:
wherein R is 1 Is hydrogen, C 1 ～C 5 Alkyl, C 1 ～C 5 Alkoxy, halogen.
3. The synthesis method according to claim 1, wherein: the 5-amino-3-methyl-1-phenylpyrazole compound has a structure shown as follows:
wherein R is 2 Is phenyl or C 1 ～C 5 An alkyl group; r is R 3 Is phenyl or C 1 ～C 5 An alkyl group.
4. The synthesis method according to claim 1, wherein: the initial concentration of the 2-methylquinoline compound is 0.05-0.2 mol/L.
5. The synthesis method according to claim 1, wherein: the solvent is one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide, acetonitrile, water and 1, 2-dichloroethane.
6. The synthesis method according to claim 1, wherein: the catalytic electrode is a conventional electrode material.
7. The synthesis method according to claim 1, wherein: the separation and purification method is one of column chromatography, liquid chromatography, distillation and recrystallization separation.
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