CN114507866B - Electrochemical-mediated synthesis method of 2-arylbenzofuran compound - Google Patents
Electrochemical-mediated synthesis method of 2-arylbenzofuran compound Download PDFInfo
- Publication number
- CN114507866B CN114507866B CN202210219106.5A CN202210219106A CN114507866B CN 114507866 B CN114507866 B CN 114507866B CN 202210219106 A CN202210219106 A CN 202210219106A CN 114507866 B CN114507866 B CN 114507866B
- Authority
- CN
- China
- Prior art keywords
- electrode
- electrochemical
- mediated
- synthesizing
- arylbenzofuran
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 230000001404 mediated effect Effects 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 title claims abstract description 13
- 238000001308 synthesis method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- -1 2-methoxyl benzenesulfonyl Chemical group 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 150000000475 acetylene derivatives Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 50
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 229910052697 platinum Inorganic materials 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- IANQTJSKSUMEQM-UHFFFAOYSA-N benzofuran Natural products C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- PHXQIAWFIIMOKG-UHFFFAOYSA-N NClO Chemical compound NClO PHXQIAWFIIMOKG-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- MXURFNKKQOACNL-UHFFFAOYSA-N 2-methoxybenzenesulfonohydrazide Chemical compound COC1=CC=CC=C1S(=O)(=O)NN MXURFNKKQOACNL-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 48
- HXMZLDUBSSPQIB-UHFFFAOYSA-N 2-phenyl-1-benzofuran Chemical compound O1C2=CC=CC=C2C=C1C1=CC=CC=C1 HXMZLDUBSSPQIB-UHFFFAOYSA-N 0.000 description 22
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RENYIDZOAFFNHC-UHFFFAOYSA-N 1-ethynyl-3-methylbenzene Chemical group CC1=CC=CC(C#C)=C1 RENYIDZOAFFNHC-UHFFFAOYSA-N 0.000 description 2
- 150000001907 coumarones Chemical class 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- NVBCRLXBEDANSW-UHFFFAOYSA-N 2-(3-methylphenyl)-1-benzofuran Chemical compound CC1=CC=CC(C=2OC3=CC=CC=C3C=2)=C1 NVBCRLXBEDANSW-UHFFFAOYSA-N 0.000 description 1
- 229940124125 5 Lipoxygenase inhibitor Drugs 0.000 description 1
- 208000019901 Anxiety disease Diseases 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 206010012289 Dementia Diseases 0.000 description 1
- 101100391174 Dictyostelium discoideum forC gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000000867 Lipoxygenase Inhibitor Substances 0.000 description 1
- 208000019695 Migraine disease Diseases 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002333 angiotensin II receptor antagonist Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000036436 anti-hiv Effects 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 206010027599 migraine Diseases 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 208000001072 type 2 diabetes mellitus Diseases 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/05—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- 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
- C25B3/20—Processes
- C25B3/29—Coupling reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Secondary Cells (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a synthesis method of an electrochemical-mediated 2-arylbenzofuran compound, which comprises the steps of dissolving 2-methoxyl benzenesulfonyl hydrazide, acetylene derivatives and electrolyte in an organic solvent, inserting an anode electrode and a cathode electrode into the organic solvent, and stirring and reacting under constant current to obtain the 2-arylbenzofuran compound. The invention adopts an electrochemical synthesis method, does not need to add additional metal catalyst and chemical oxidant, has the advantages of mild reaction condition, high product yield, good chemical selectivity and the like, and better accords with the aim of green sustainable development of the current society.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a synthesis method of an electrochemical-mediated 2-arylbenzofuran compound.
Background
The benzofuran and the derivatives thereof have unique structural characteristics, various biological activities and huge medicinal values, and have wide application in the fields of medicines and pesticides.
In pharmaceutical chemistry, benzofurans and derivatives thereof are widely used in natural products and synthetic drugs, and have various pharmacological actions such as antitumor property, anti-HIV property, inhibitor of protein phosphate 1B activity, 5-lipoxygenase inhibitor, angiotensin II inhibitor, antifungal property, etc. Can be used for treating cancer, cardiovascular diseases, type II diabetes, migraine, dementia, anxiety, etc. The benzofuran insecticide carbofuran and furacir is a broad-spectrum efficient and low-residue insecticide, and has wide application in the pesticide field. At present, methods for synthesizing benzofuran compounds mainly comprise two types of reactions including metal catalysis and nonmetal participation.
However, in both of these methods, some less environmentally friendly reagents are used. Therefore, it would be very valuable to develop a practical, efficient and environmentally friendly method for synthesizing such compounds.
Disclosure of Invention
The invention aims to: in order to solve the problems of environmental pollution, low product yield, poor reaction selectivity, high energy consumption and the like in the prior art, the invention provides a synthesis method of an electrochemical-mediated 2-aryl benzofuran compound.
The technical scheme is as follows: in order to achieve the above-mentioned invention problem, the technical scheme adopted by the invention is as follows:
the electrochemical mediated synthesis process of 2-aryl benzofuran compound includes dissolving 2-methoxy benzenesulfonyl hydrazine, acetylene derivative and electrolyte in organic solvent, inserting anode electrode and cathode electrode, and stirring to react under constant current to obtain 2-aryl benzofuran compound.
Taking phenylacetylene as an example, the reaction formula is as follows:
preferably, the acetylene derivative is an aryl acetylene, more preferably phenylacetylene or m-methyl phenylacetylene.
Preferably, the electrolyte is n-Bu 4 NBF 4 、n-Bu 4 NPF 6 、n-Bu 4 NClO 4 、n-Bu 4 NI、n-Bu 4 Any one or a combination of several NBr, more preferably the electrolyte is n-Bu 4 NBF 4 。
Preferably, the solvent is CH 3 CN, meOH, HFIP (hexafluoroisopropanol), H 2 O, more preferably the solvent is CH 3 A mixed solvent of CN and HFIP, wherein the volume ratio of the mixed solvent to the HFIP is 8:2;
preferably, the anode electrode is any one of a carbon electrode, a platinum electrode and a nickel electrode, and more preferably, the anode electrode is a carbon electrode;
preferably, the cathode electrode is any one of a carbon electrode, a platinum electrode, and a nickel electrode, and more preferably, the cathode electrode is a platinum electrode.
Preferably, the molar ratio of the 2-methoxybenzenesulfonyl hydrazide to the acetylene derivative is 1:1-1:3, and more preferably, the molar ratio is 1:2.
Preferably, the molar ratio of the 2-methoxybenzenesulfonyl hydrazide to the electrolyte is 10:1-2:1, more preferably the molar ratio is 5:1.
Preferably, the temperature of the reaction is 60 to 80 ℃, more preferably the reaction temperature is 70 ℃.
Preferably, the constant current in the reaction is controlled to 15-30 mA, more preferably, the current is 25mA. The specification of the adopted direct current power supply is 5A and 30V;
preferably, the reaction time is 2 to 3 hours, more preferably 2.5 hours.
The beneficial effects are that:
compared with the prior art, the invention adopts an electrochemical synthesis method, does not need to add additional metal catalyst and chemical oxidant, has the advantages of mild reaction condition, high product yield, good chemical selectivity and the like, and better accords with the aim of green sustainable development in the current society; the yield of the 2-aryl benzofuran compounds is up to about 97%.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 2-phenylbenzofuran prepared in example 1.
FIG. 2 is a nuclear magnetic resonance spectrum of 2-phenylbenzofuran prepared in example 1.
FIG. 3 is a reaction scheme of the present invention (in the case of phenylacetylene).
Detailed Description
The invention will be better understood from the following examples.
The structures, proportions, sizes, etc. shown in the drawings are shown only in connection with the disclosure of the present invention, and are not intended to limit the scope of the invention, which is defined by the claims, but rather by the terms of modification, variation of proportions, or adjustment of sizes, without affecting the efficacy or achievement of the present invention, should be understood as falling within the scope of the present invention. Also, the terms such as "upper", "lower", "front", "rear", "middle", and the like are used herein for descriptive purposes only and are not intended to limit the scope of the invention for which the invention may be practiced or for which the relative relationships may be altered or modified without materially altering the technical context.
Example 1
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Nuclear magnetic data: 1 H NMR(400MHz,CDCl3)δ7.86(dd,J＝8.4,1.2Hz,2H),7.59(d,J＝7.4Hz,1H),7.51(d,J＝8.2Hz,1H),7.45(t,J＝7.6Hz,2H),7.34(d,J＝8.0Hz,1H),7.28(d,J＝7.1Hz,1H),7.22(d,J＝7.9Hz,1H),7.01(d,J＝0.8Hz,1H). 13 C NMR(100MHz,CDCl3)δ155.94,154.93,130.51,129.26,128.82,128.58,124.95,124.28,122.94,120.93,111.21,101.31.HRMS(ESI-TOF)m/z Calcd for C 14 H 11 O[M+H] + :195.0804,found:195.0806.
example 2
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.051g of phenylacetylene, and 0.0165g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 3
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.153g of phenylacetylene, and 0.0823g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 4
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a nickel electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 5
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a platinum electrode as an anode electrode and a carbon electrode as a cathode electrode were inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 6
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a platinum electrode as an anode electrode and a nickel electrode as a cathode electrode were inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 7
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g was added2-methoxybenzenesulfonyl hydrazide, 0.102g phenylacetylene and 0.0329g n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 4 hours under a constant current of 15mA, and the product 2-phenylbenzofuran is collected.
Example 8
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2 hours under a constant current of 30mA, and the product 2-phenylbenzofuran is collected.
Example 9
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0387g of n-Bu 4 NPF 6 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 10
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0341g of n-Bu 4 NClO 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 11
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0369g of n-Bu 4 NI is dissolved in8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 12
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0321g of n-Bu 4 NBr was dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 13
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 10mL CH 3 CN, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 14
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2 lmeoh, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 15
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLH 2 O, and inserting carbon electrode as anode electrode and platinum electrode as anode electrodeIs a cathode. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 16
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 5mL CH 3 CN and 5mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode were inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 17
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 2mL CH 3 CN and 8mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode were inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 18
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under constant current of 0mA, and the product 2-phenylbenzofuran is collected.
Example 19
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 60 DEG CThe reaction was stirred at a constant current of 25mA for 2.5 hours and the product 2-phenylbenzofuran was collected.
Example 20
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.102g of phenylacetylene, and 0.0329g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 80 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-phenylbenzofuran is collected.
Example 21
In a 50mL reaction flask equipped with a tetrafluoro-magnet, 0.101g of 2-methoxybenzenesulfonyl hydrazide, 0.116g of m-tolane and 0.0329g of n-Bu 4 NBF 4 Dissolved in 8mL CH 3 CN and 2mLHFIP, and a carbon electrode as an anode electrode and a platinum electrode as a cathode electrode are inserted therein. After the electrode is connected with a direct current power supply, the reaction bottle is placed in an oil bath at 70 ℃ to be stirred and reacted for 2.5 hours under a constant current of 25mA, and the product 2-m-methylphenyl-benzofuran is collected.
Nuclear magnetic data: 1 H NMR(400MHz,CDCl 3 )δ7.63–7.56(m,2H),7.51(d,J＝7.4Hz,1H),7.43(d,J＝8.0Hz,1H),7.29–7.18(m,2H),7.18–7.11(m,1H),7.08(d,J＝7.5Hz,1H),2.36(s,3H). 13 C NMR(100MHz,CDCl 3 )δ156.15,154.87,138.46,130.43,129.40,129.28,128.73,125.57,124.18,122.92,122.18,120.86,111.15,101.22,21.53.HRMS(ESI-TOF)m/z Calcd forC 15 H 12 O[M+H] + :209.0961,found:209.0965.
examples 1 to 21 are methods for preparing 2-arylbenzofurans by electrochemical synthesis, and the main parameters and yields are shown in Table 1.A is 2-methoxy benzenesulfonyl hydrazide, B1 is phenylacetylene, and B2 is m-methyl phenylacetylene; a in the electrolyte is n-Bu 4 NBF 4 B is n-Bu 4 NPF 6 C is n-Bu 4 NClO 4 D is n-Bu 4 NI, e is n-Bu 4 NBr; c in the solvent is CH 3 CN, D is MeOH, E is HFIP (hexafluoroisopropanol), F is H 2 O。
Table 12 yields of arylbenzofurans
The present invention provides a method and a thought, and a method for realizing the technical scheme are numerous, the above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (9)
1. The electrochemical mediated synthesis process of 2-aryl benzofuran compound includes dissolving 2-methoxy benzenesulfonyl hydrazine, acetylene derivative and electrolyte in organic solvent, inserting anode electrode and cathode electrode, and stirring to react under constant current to obtain 2-aryl benzofuran compound.
2. The method for the electrochemical-mediated synthesis of 2-arylbenzofurans according to claim 1, wherein the acetylene derivative is an aryl acetylene.
3. The method for synthesizing the electrochemical-mediated 2-arylbenzofuran compound according to claim 1, wherein the electrolyte is n-Bu 4 NBF 4 、n-Bu 4 NPF 6 、n-Bu 4 NClO 4 、n-Bu 4 NI、n-Bu 4 Any one or a combination of several NBr.
4. The method for synthesizing the electrochemical-mediated 2-arylbenzofuran compound according to claim 1, wherein the organic solvent is CH 3 CN、MeOH、HFIP (hexafluoroisopropanol) or a combination of any one or more of them.
5. The method for synthesizing the electrochemical-mediated 2-arylbenzofuran compound according to claim 1, wherein the anode electrode is any one of a carbon electrode, a platinum electrode and a nickel electrode; the cathode electrode is any one of a carbon electrode, a platinum electrode and a nickel electrode.
6. The method for synthesizing the electrochemical-mediated 2-arylbenzofuran compound according to claim 1, wherein the molar ratio of the 2-methoxybenzenesulfonyl hydrazide to the acetylene derivative is 1:1-1:3; the molar ratio of the 2-methoxybenzene sulfonyl hydrazine to the electrolyte is 10:1-2:1.
7. The method for synthesizing the electrochemical-mediated 2-arylbenzofuran compound according to claim 1, wherein the constant current is controlled to be 15-30 mA.
8. The method for synthesizing the electrochemical-mediated 2-arylbenzofuran compound according to claim 1, wherein the reaction temperature is 60-80 ℃.
9. The method for synthesizing the electrochemical-mediated 2-arylbenzofuran compound according to claim 1, wherein the reaction time is 2-3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210219106.5A CN114507866B (en) | 2022-03-02 | 2022-03-02 | Electrochemical-mediated synthesis method of 2-arylbenzofuran compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210219106.5A CN114507866B (en) | 2022-03-02 | 2022-03-02 | Electrochemical-mediated synthesis method of 2-arylbenzofuran compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114507866A CN114507866A (en) | 2022-05-17 |
| CN114507866B true CN114507866B (en) | 2023-10-31 |
Family
ID=81554222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210219106.5A Active CN114507866B (en) | 2022-03-02 | 2022-03-02 | Electrochemical-mediated synthesis method of 2-arylbenzofuran compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114507866B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110067006A (en) * | 2019-06-05 | 2019-07-30 | 广西师范大学 | A kind of methods and applications of electrochemistry formated sulfonyl diazanyl Benzazole compounds |
| CN110760877A (en) * | 2019-11-07 | 2020-02-07 | 南京工业大学 | Method for continuously preparing 2-aryl-3-halogenated-benzofuran compound by using electrochemical microchannel reaction device |
| CN110791775A (en) * | 2019-11-07 | 2020-02-14 | 南京工业大学 | Method for continuously preparing 2-aryl-benzothiophene/furan compounds by using electrochemical microchannel reaction device |
-
2022
- 2022-03-02 CN CN202210219106.5A patent/CN114507866B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110067006A (en) * | 2019-06-05 | 2019-07-30 | 广西师范大学 | A kind of methods and applications of electrochemistry formated sulfonyl diazanyl Benzazole compounds |
| CN110760877A (en) * | 2019-11-07 | 2020-02-07 | 南京工业大学 | Method for continuously preparing 2-aryl-3-halogenated-benzofuran compound by using electrochemical microchannel reaction device |
| CN110791775A (en) * | 2019-11-07 | 2020-02-14 | 南京工业大学 | Method for continuously preparing 2-aryl-benzothiophene/furan compounds by using electrochemical microchannel reaction device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114507866A (en) | 2022-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Elinson et al. | General non-catalytic approach to spiroacenaphthylene heterocycles: multicomponent assembling of acenaphthenequinone, cyclic CH-acids and malononitrile | |
| CN106567104B (en) | The electrochemical method for synthesizing of 1,1 '-di-indole methyl hydride analog derivatives | |
| CN111560624B (en) | Method for continuously preparing isobenzofuran compounds by using microchannel reaction device | |
| Liu et al. | Electrosynthesis of CF3‐Substituted Polycyclic Quinazolinones via Cascade Trifluoromethylation/Cyclization of Unactivated Alkene | |
| Wang et al. | Catalyst-free, direct electrochemical trifluoromethylation/cyclization of N-arylacrylamides using TfNHNHBoc as a CF3 source | |
| Zhang et al. | Iodine-mediated electrochemical C (sp 3)–H cyclization: the synthesis of quinazolinone-fused N-heterocycles | |
| Mo et al. | Electrochemically enabled functionalization of indoles or anilines for the synthesis of hexafluoroisopropoxy indole and aniline derivatives | |
| KR20230119704A (en) | Pyridinepyrroruthenium coordination complex, preparation method thereof, and application as a catalyst for the production of hydrazine by electrocatalytic oxidation of ammonia | |
| Zhang et al. | Electrochemical oxidative cross coupling of NH-sulfoximines with disulfides | |
| Cui et al. | Electrochemically driven, cobalt–carbon bond-mediated direct intramolecular cyclic and acyclic perfluoroalkylation of (hetero) arenes using X (CF 2) 4 X | |
| CN114507866B (en) | Electrochemical-mediated synthesis method of 2-arylbenzofuran compound | |
| Liu et al. | Photocatalytic [2+ 2+ m] Cyclization of 2‐Cyanoaryl Acrylamides with 2‐Bromocarbonyls Involving C (sp3)− H Functionalization | |
| Zhang et al. | Synthesis of Selenooxazoles through Electrochemical Oxidative Selenocyclization of N‐Propargylamides | |
| CN113981477B (en) | Method for preparing pyridazine compound by one-pot two-step electrooxidation cyclization | |
| CN114438523B (en) | Green and efficient electrochemical synthesis method of benzothiophene compound | |
| CN113957463B (en) | Method for synthesizing dibenzosuberone derivative through free radical serial cyclization under electrooxidation condition | |
| Zhai et al. | Photocatalytic Markovnikov-type addition and cyclization of terminal alkynes leading to 4-sulfonyl quinoline-2 (1H)-ones | |
| CN112921346B (en) | Electrochemical synthesis method of 3-formyl indole derivative | |
| CN112853384B (en) | Method for synthesizing ibuprofen intermediate by taking halogen ions as electrocatalyst | |
| Sun et al. | Electrochemical oxidative dehydrogenative annulation of 1-(2-aminophenyl) pyrroles with cleavage of ethers to synthesize pyrrolo [1, 2-a] quinoxaline derivatives | |
| CN110714208B (en) | Method for preparing 6- (sulfonyl methyl) phenanthridine compound through electrocatalysis | |
| Yang et al. | Electricity-driven three-component reductive coupling reaction for the synthesis of diarylmethylamine | |
| Yang et al. | Neutral nickel-catalyzed dehydrosulfonylation of unactivated allylic alcohols under mild conditions | |
| Liu et al. | Electrochemical oxidation-induced diazolation of alkenes to build N, N′-ethylene-bridged bispyrazole derivatives | |
| CN113355684B (en) | Preparation method of polysubstituted isoquinoline salt derivative under electrocatalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |