CN114196973B - Method for electrochemically synthesizing aza-anthraquinone derivative - Google Patents
Method for electrochemically synthesizing aza-anthraquinone derivative Download PDFInfo
- Publication number
- CN114196973B CN114196973B CN202210048909.9A CN202210048909A CN114196973B CN 114196973 B CN114196973 B CN 114196973B CN 202210048909 A CN202210048909 A CN 202210048909A CN 114196973 B CN114196973 B CN 114196973B
- Authority
- CN
- China
- Prior art keywords
- phenyl
- amino
- naphthalene
- dione
- reaction
- 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
Images
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
- C25B3/01—Products
- C25B3/09—Nitrogen 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
- C25B3/01—Products
- C25B3/11—Halogen 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for electrochemically synthesizing aza-anthraquinone derivatives, which synthesizes aza-anthraquinone derivatives through 1, 6-eneyne electrochemical anodic oxidation. The method comprises the steps of carrying out reaction in an unseparated electrolytic cell, taking a 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-diketone compound as a raw material, dissolving the raw material and an electrolyte in a solvent, connecting a constant current in an open system, stirring for reaction, and carrying out column chromatography to obtain the quinoline derivative after the reaction is finished. Compared with the existing method, the method does not need the traditional oxidant, and synthesizes the azaanthraquinone compound with a new structure through electric reaction.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a method for electrochemically synthesizing aza-anthraquinone derivatives.
Background
The nitrogen-containing heterocyclic compound is a great research hotspot at present, is widely applied to synthesis of dyes, organic luminescent materials, medicines and the like, and is an important active structural unit of a plurality of antibacterial, antiviral and antitumor medicines because of good biological activity. Of these, azaanthraquinone derivatives are ubiquitous in natural products and drug candidates because of their considerable biological activity, including antitubercular, antileukemic, antifungal, antimycobacterial, etc. Therefore, synthetic strategies for such compounds are widely studied.
Traditionally, the preparation of azaanthraquinone compounds requires a multi-step process involving oxidation, condensation, diels-Alder, elimination, and a cascade of reactions. Currently, one of the most straightforward strategies for constructing azaanthraquinone derivatives is via transition metal catalyzed intramolecular pi-extension reactions. However, this generally requires the presence of a transition metal catalyst and an exogenous oxidant, and also produces stoichiometric waste, which is not in the direction of green chemistry. Therefore, there is a need to develop a more environmentally friendly method for constructing azaanthraquinone derivatives without the involvement of metals and exogenous oxidants.
Electrochemistry is a process of promoting oxidation reduction by using clean electric energy, and can effectively avoid the use of metal and oxidant, so that the electrochemistry is known as a green synthesis means, and the free radical cross coupling reaction is always a research hotspot. At present, the direct construction of azaanthraquinone by electrochemical anodic oxidation of 1, 6-eneyne under metal-free conditions at room temperature has not been reported.
Disclosure of Invention
The purpose of the invention is as follows: compared with the traditional quinoline synthesis method, the method provided by the invention does not need a metal catalyst and an oxidant, and the electrochemical synthesis of the quinoline compound is more environment-friendly and conforms to the green chemical synthesis direction.
In order to realize the technical purpose, the invention discloses a method for electrochemically synthesizing azaanthraquinone derivatives, which comprises the steps of adding 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-diketone compounds in a formula (I), an electrolyte and a solvent into an electrolytic cell without a diaphragm, inserting a negative electrode and a positive electrode into the electrolytic cell, switching on constant current, stirring and reacting in an open system, and after the reaction is finished, carrying out column chromatography separation to obtain the azaanthraquinone derivatives shown in the formula (II),
wherein R is 1 Is thiophene, pyridine, naphthalene ring, aliphatic hydrocarbon or substituted benzene ring, wherein the benzene ring is substituted by hydrogen, halogen, C1-C3 alkyl, phenylAny substituent of alkoxy, cyano, nitro and Boc protected amino; r 2 Is C1-C3 alkyl or halogen.
In some embodiments of the present invention, the substrate is, the 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione compound is 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 2- ((2- (p-tolylethynyl) phenyl) amino) naphthalene-1, 4-dione, 2- ((2- ((4-chlorophenyl) ethynyl) phenyl) amino) naphthalene-1, 4-dione, 2- ((4-chloro-2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione methyl 4- ((2- ((1, 4-dioxo-1, 4-dihydronaphthalen-2-yl) amino) phenyl) ethynyl) benzoate, tert-butyl 2- ((2- ((2-methoxyphenyl) ethynyl) phenyl) amino) naphthalene-1, 4-dione, (4- ((2- ((1, 4-dioxo-1, 4-dihydronaphthalen-2-yl) amino) phenyl) ethynyl) phenyl) carbamate, 2- ((2- (thien-2-ylethynyl) phenyl) amino) naphthalene-1, 4-dione, 2- ((2- (pyridin-2-ylethynyl) phenyl) amino) naphthalene-1, 4-dione Any one of diketone, 2- ((2- (naphthalene-2-ylethynyl) phenyl) amino) naphthalene-1, 4-diketone and 2- ((2- (naphthalene-2-ylethynyl) phenyl) amino) naphthalene-1, 4-diketone.
Wherein the positive electrode is any one of a carbon cloth electrode, a carbon rod electrode, a platinum electrode and an RVC electrode; the negative electrode is a platinum electrode or a carbon cloth electrode. Preferably, the positive electrode is a carbon cloth electrode and the negative electrode is a platinum electrode.
The electrolyte is any one of tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate, tetrabutylammonium acetate and tetrabutylammonium iodide. Tetrabutylammonium acetate is preferred.
The solvent is any one of acetonitrile, dimethyl sulfoxide, N-dimethylformamide, ethanol, trifluoroethanol and hexafluoroisopropanol. Preferably hexafluoroisopropanol.
The constant current for carrying out the electrochemical reaction is 5-15mA. Preferably 9-11mA.
The environment system of the electrochemical reaction is any one of nitrogen, oxygen and air. Preferably air.
The amount of electrolyte used in the electrochemical reaction is 1-3 equivalents. Of these, the amount of the electrolyte used is preferably 1 equivalent, based on 1 equivalent of (2- ((2- (phenylethynyl) phenyl) amino).
Specifically, the electrochemical reaction temperature is 0 to 40 ℃, preferably 20 to 25 ℃.
The electrochemical reaction time is 1-3h.
Has the advantages that: compared with the prior art, the nitrogen-anthraquinone compound disclosed by the invention has the advantages that the nitrogen free radicals are excited by electrochemistry, carbon-centered free radicals are formed by double-bond molecular displacement, and the nitrogen-anthraquinone compound is further obtained by serial cyclization, so that the traditional metal catalyst and oxidant are not needed, the characteristics of convenience in post-treatment, environmental friendliness and the like are realized, and the development direction of green chemical synthesis is met.
Drawings
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
FIG. 1 is a NMR chart of 2a according to the invention;
FIG. 2 is a NMR carbon spectrum of 2a in the present invention;
FIG. 3 is a NMR chart of 2b in the present invention;
FIG. 4 is a NMR carbon spectrum of 2b in the present invention;
FIG. 5 is a NMR chart of 2c according to the invention;
FIG. 6 is a NMR carbon spectrum of 2c of the present invention;
FIG. 7 is a NMR chart of 2d according to the present invention;
FIG. 8 is a NMR carbon spectrum of 2d according to the invention;
FIG. 9 is a NMR chart of 2e in accordance with the invention;
FIG. 10 is a NMR carbon spectrum of 2e in accordance with the invention;
FIG. 11 is a NMR chart of 2f according to the invention;
FIG. 12 is a NMR carbon spectrum of 2f according to the invention;
FIG. 13 is a NMR chart of 2g in accordance with the present invention;
FIG. 14 is a NMR carbon spectrum of 2g in accordance with the invention;
FIG. 15 is a NMR chart for 2h in the present invention;
FIG. 16 is a NMR carbon spectrum of 2h in accordance with the invention;
FIG. 17 is a NMR chart of 2i in the present invention;
FIG. 18 is a NMR carbon spectrum of 2i in accordance with the invention;
FIG. 19 is a NMR chart of 2j in accordance with the present invention;
FIG. 20 is a NMR carbon spectrum of 2j in accordance with the present invention;
FIG. 21 is a NMR chart of 2k in accordance with the invention;
FIG. 22 shows a 2k NMR carbon spectrum of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
0.1048g of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione (0.3mmol, 1equiv), 0.0905g of tetrabutylammonium acetate (0.3mmol, 1equiv) was dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. Washing with 100mL of saturated aqueous sodium chloride solution, separating, extracting the aqueous phase with ethyl acetate (50 mL × 3), combining the organic phases, drying with anhydrous sodium sulfate, concentrating, and separating the crude product by silica gel column chromatography with ethyl acetate/petroleum ether (petroleum ether/ethyl acetate = 3/1) as a developing agent to obtain the target product 2a with a yield of 83%.
The structure of the target product 2a is characterized as follows:
1 H NMR(400MHz,Chloroform-d)δ8.58(d,J＝8.6Hz,1H),8.50(d,J＝7.6Hz,1H),8.21(dd,J＝7.6,1.5Hz,1H),7.98(t,J＝8.0Hz,1H),7.92-7.75(m,5H),7.69(t,J＝8.5Hz,1H),7.65-7.57(m,1H),7.47(t,J＝8.3Hz,2H)；
13 C NMR(101MHz,Chloroform-d)δ194.78,181.09,180.27,148.94,148.88,146.84,135.41,134.08,133.91,133.06,132.98,132.55,132.21,131.03,129.66,128.07,127.74,127.31,126.90,125.90,125.55,123.31；
HRMS(ESI-TOF)Calcd for C 24 H 14 O 3 N[M+H] + :364.0968；found:364.0970.
fig. 1 and 2 are a nuclear magnetic resonance hydrogen spectrum and a nuclear magnetic resonance carbon spectrum of 2a, respectively.
Example 2
0.1090g (0.3mmol, 1equiv) of 2- ((2- (p-tolylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.0905g (0.3mmol, 1equiv) of tetrabutylammonium acetate, was weighed and dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. Washing with 100mL of saturated aqueous sodium chloride solution, separating, extracting the aqueous phase with ethyl acetate (50 mL × 3), combining the organic phases, drying with anhydrous sodium sulfate, concentrating, and separating the crude product by silica gel column chromatography with ethyl acetate/petroleum ether (petroleum ether/ethyl acetate = 3/1) as a developing agent to obtain the target product 2b with a yield of 80%.
The structure of the target product 2b is characterized as:
1 H NMR(400MHz,Chloroform-d)δ8.57(d,J＝8.4Hz,1H),8.50(dd,J＝7.6,1.5Hz,1H),8.21(dd,J＝7.6,1.5Hz,1H),8.0-7.94(m,1H),7.87(d,J＝1.5Hz,1H),7.84-7.76(m,2H),7.75-7.64(m,3H),7.24(d,J＝1.8Hz,2H),2.41(s,3H)；
13 C NMR(101MHz,Chloroform-d)δ194.39,181.08,180.32,149.11,148.92,146.87,144.21,134.01,133.88,133.06,132.97,132.50,132.27,130.99,129.58,128.81,127.89,127.27,126.91,125.98,125.60,123.22,20.83；
HRMS(ESI-TOF)Calcd for C 25 H 16 O 3 N[M+H] + :378.1125；found:378.1111.
fig. 3 and 4 are a nuclear magnetic resonance hydrogen spectrum and a nuclear magnetic resonance carbon spectrum of 2b, respectively.
Example 3
0.1151g (0.3mmol, 1equiv) of 2- ((2- ((4-chlorophenyl) ethynyl) phenyl) amino) naphthalene-1, 4-dione (0.0905 g, (0.3mmol, 1equiv) was weighed and dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used for the positive electrode, a platinum sheet electrode was used for the negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. Washing with 100mL of saturated aqueous sodium chloride solution, separating, extracting the aqueous phase with ethyl acetate (50 mL × 3), combining the organic phases, drying with anhydrous sodium sulfate, concentrating, and separating the crude product by silica gel column chromatography with ethyl acetate/petroleum ether (petroleum ether/ethyl acetate = 3/1) as a developing agent to obtain the target product 2c with a yield of 85%.
The structure of the target product 2c is characterized as:
1 H NMR(400MHz,Chloroform-d)δ8.58(d,J＝8.6Hz,1H),8.50(dd,J＝7.7,1.5Hz,1H),8.21(dd,J＝7.6,1.5Hz,1H),8.02-7.96(m,1H),7.82-7.86(m,1H),7.85-7.74(m,4H),7.74-7.68(m,1H),7.50-7.42(m,2H)；
13 C NMR(101MHz,Chloroform-d)δ193.55,181.15,180.13,148.99,148.17,146.82,139.59,134.20,133.96,133.84,132.98,132.66,132.10,131.13,129.81,129.02,128.48,127.37,126.89,125.66,125.36,123.31；
HRMS(ESI-TOF)Calcd for C 24 H 13 O 3 NCl[M+H] + :398.0578；found:398.0548.
fig. 5 and 6 are a nuclear magnetic resonance hydrogen spectrum and a nuclear magnetic resonance carbon spectrum of 2c, respectively.
Example 4
0.1151g (0.3mmol, 1equiv) of 2- ((4-chloro-2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione (0.0905 g, (0.3mmol, 1equiv)) was weighed and dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. Washing with 100mL of saturated aqueous sodium chloride solution, separating, extracting the aqueous phase with ethyl acetate (50 mL × 3), combining the organic phases, drying with anhydrous sodium sulfate, concentrating, and separating the crude product by silica gel column chromatography with ethyl acetate/petroleum ether (petroleum ether/ethyl acetate = 3/1) as a developing agent to obtain the target product 2d with a yield of 73%.
The structure of the target product 2d is characterized as:
1 H NMR(400MHz,Chloroform-d)δ8.53-8.44(m,2H),8.19(dd,J＝7.7,1.4Hz,1H),7.92-7.85(m,2H),7.84-7.79(m,3H),7.72(d,J＝2.3Hz,1H),7.66-7.61(m,1H),7.49(t,J＝7.7Hz,2H)；
13 C NMR(101MHz,Chloroform-d)δ195.16,181.85,180.96,148.88,148.36,147.87,137.22,136.16,135.28,135.06,134.70,134.34,133.92,133.41,133.11,129.21,128.77,128.38,128.00,127.17,125.48,124.90；
HRMS(ESI-TOF)Calcd for C 24 H 13 O 3 NCl[M+H] + :398.0578；found:398.0564.
fig. 7 and 8 are the nmr hydrogen spectrum and the nmr carbon spectrum of 2d, respectively.
Example 5
Methyl 4- ((2- ((1, 4-dioxo-1, 4-dihydronaphthalen-2-yl) amino) phenyl) ethynyl) benzoate 0.1222g, (0.3mmol, 1equiv), tetrabutylammonium acetate 0.0905g, (0.3mmol, 1equiv) was dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as the positive electrode, a platinum sheet electrode was used as the negative electrode, a constant current was controlled at 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. Washing with 100mL of saturated aqueous sodium chloride solution, separating, extracting the aqueous phase with ethyl acetate (50 mL × 3), combining the organic phases, drying with anhydrous sodium sulfate, concentrating, and separating the crude product by silica gel column chromatography with ethyl acetate/petroleum ether (petroleum ether/ethyl acetate = 3/1) as a developing solvent to obtain the target product 2e with a yield of 68%.
The structure of the target product 2e is characterized as:
1 H NMR(400MHz,Chloroform-d)δ8.56(d,J＝8.5Hz,1H),8.45(dd,J＝7.7,1.4Hz,1H),8.15(dd,J＝7.7,1.4Hz,1H),8.10(d,J＝8.5Hz,2H),8.0-7.95(m,1H),7.86(dd,J＝8.0,6.5Hz,3H),7.82-7.77(m,1H),7.75-7.67(m,2H),3.91(s,3H)；
13 C NMR(101MHz,Chloroform-d)δ195.22,182.15,181.12,166.04,149.97,149.16,147.76,139.45,135.28,135.03,134.65,133.96,133.79,133.04,132.07,130.93,130.29,128.58,128.39,127.90,126.63,126.38,124.43,52.59,31.59,22.66,14.13；
HRMS(ESI-TOF)Calcd for C 26 H 16 O 5 N[M+H] + :422.1023；found:422.1012.
fig. 9 and 10 are a nuclear magnetic resonance hydrogen spectrum and a nuclear magnetic resonance carbon spectrum of 2e, respectively.
Example 6
0.1138g, (0.3mmol, 1equiv) of 2- ((2- ((2-methoxyphenyl) ethynyl) phenyl) amino) naphthalene-1, 4-dione (0.0905 g, (0.3mmol, 1equiv) was weighed and dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used for the positive electrode, a platinum sheet electrode was used for the negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. Washing with 100mL saturated aqueous sodium chloride solution, separating, extracting the water phase with ethyl acetate (50 mL × 3), combining the organic phases, drying with anhydrous sodium sulfate, concentrating, and separating the crude product by silica gel column chromatography with ethyl acetate/petroleum ether (petroleum ether/ethyl acetate = 3/1) as a developing solvent to obtain the target product 2f with a yield of 80%.
The structure of the target product 2f is characterized as:
1 H NMR(400MHz,Chloroform-d)δ8.55-8.47(m,2H),8.37(dd,J＝7.9,1.8Hz,1H),8.24(dd,J＝7.5,1.5Hz,1H),7.96-7.90(m,1H),7.89-7.75(m,3H),7.66-7.55(m,2H),7.22(s,1H),6.85(dd,J＝8.4,0.9Hz,1H),3.17(s,3H)；
13 C NMR(101MHz,Chloroform-d)δ192.57,181.42,180.70,158.80,153.10,148.86,146.80,134.86,133.80,133.03,132.36,132.06,130.82,129.75,129.00,127.22,126.79,125.44,124.78,124.69,122.12,120.49,111.40,54.40；
HRMS(ESI-TOF)Calcd for C 25 H 16 O 4 N[M+H] + :394.1074；found:394.1068。
fig. 11 and 12 are a nuclear magnetic resonance hydrogen spectrum and a nuclear magnetic resonance carbon spectrum of 2f, respectively.
Example 7
0.1393g of tert-butyl (4- ((2- ((1, 4-dioxo-1, 4-dihydronaphthalen-2-yl) amino) phenyl) ethynyl) phenyl) carbamate, (0.3mmol, 1equiv), 0.0905g of tetrabutylammonium acetate, (0.3mmol, 1equiv) was weighed, dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as the positive electrode, a platinum sheet electrode was used as the negative electrode, a constant current was controlled at 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. Washing with 100mL of saturated aqueous sodium chloride solution, separating, extracting the aqueous phase with ethyl acetate (50 mL × 3), combining the organic phases, drying with anhydrous sodium sulfate, concentrating, and separating the crude product by silica gel column chromatography with ethyl acetate/petroleum ether (petroleum ether/ethyl acetate = 3/1) as a developing agent to obtain 2g of the target product, wherein the yield is 73%.
The structure of 2g of the target product is characterized as:
1 H NMR(400MHz,Chloroform-d)δ8.52(dd,J＝8.7,1.1Hz,1H),8.46(dd,J＝7.6,1.5Hz,1H),8.18(dd,J＝7.6,1.5Hz,1H),7.98-7.92(m,1H),7.87-7.80(m,2H),7.76(t,J＝8.3Hz,3H),7.68-7.63(m,1H),7.48-7.44(m,2H),6.96(s,1H),1.46(s,9H)；
13 C NMR(101MHz,Chloroform-d)δ194.41,182.04,181.36,152.09,150.02,149.91,147.87,143.99,135.02,134.93,133.95,133.53,133.31,131.93,131.12,130.60,130.40,128.26,127.90,127.04,126.61,124.17,117.98,81.45,28.19；
HRMS(ESI-TOF)Calcd for C 29 H 23 O 5 N 2 [M+H] + :479.1601；found:479.1585。
FIGS. 13 and 14 are the NMR hydrogen and carbon spectra of 2g, respectively.
Example 8
0.1066g (0.3mmol, 1equiv) of 2- ((2- (thien-2-ylethynyl) phenyl) amino) naphthalene-1, 4-dione (0.0905 g, (0.3mmol, 1equiv) was weighed and dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. Washing with 100mL saturated aqueous sodium chloride solution, separating, extracting the water phase with ethyl acetate (50 mL × 3), combining the organic phases, drying with anhydrous sodium sulfate, concentrating, and separating the crude product by silica gel column chromatography with ethyl acetate/petroleum ether (petroleum ether/ethyl acetate = 3/1) as a developing agent to obtain the target product for 2h, wherein the yield is 63%.
The structure of the target product 2h is characterized as:
1 H NMR(400MHz,Chloroform-d)δ8.59-8.55(m,1H),8.49(dd,J＝7.4,1.6Hz,1H),8.25(dd,J＝7.6,1.6Hz,1H),8.02-7.96(m,1H),7.93-7.90(m,1H),7.89-7.81(m,2H),7.79(dd,J＝4.9,1.2Hz,1H),7.76-7.70(m,1H),7.21(dd,J＝3.9,1.2Hz,1H),7.06(dd,J＝4.9,3.8Hz,1H)；
13 C NMR(101MHz,Chloroform-d)δ187.65,181.89,181.23,150.06,148.63,147.88,143.78,135.16,135.10,134.99,134.06,133.95,133.61,133.32,131.97,130.79,128.52,128.31,127.97,126.90,126.38,123.84；
HRMS(ESI-TOF)Calcd for C 22 H 12 O 3 NS[M+H] + :370.0532；found:370.0532。
fig. 15 and 16 are the nmr hydrogen spectrum and the nmr carbon spectrum of 2h, respectively.
Example 9
0.1051g (0.3mmol, 1equiv) of 2- ((2- (pyridin-2-ylethynyl) phenyl) amino) naphthalene-1, 4-dione (0.0905 g, (0.3mmol, 1equiv) was weighed and dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. Washing with 100mL of saturated aqueous sodium chloride solution, separating, extracting the aqueous phase with ethyl acetate (50 mL × 3), combining the organic phases, drying with anhydrous sodium sulfate, concentrating, and separating the crude product by silica gel column chromatography with ethyl acetate/petroleum ether (petroleum ether/ethyl acetate = 3/1) as a developing agent to obtain the target product 2i with a yield of 60%.
The structure of the target product 2i is characterized as:
1 H NMR(400MHz,Chloroform-d)δ8.52-8.40(m,3H),8.33-8.30(m,1H),8.09(dd,J＝7.7,1.4Hz,1H),7.99-7.94(m,1H),7.91-7.86(m,1H),7.81-7.71(m,1H),7.75-7.70(m,1H),7.68(dd,J＝8.5,1.4Hz,1H),7.63-7.57(m,1H),7.42-7.38(m,1H)；
13 C NMR(101MHz,Chloroform-d)δ196.63,182.57,181.45,153.62,151.36,149.94,149.40,147.63,137.41,135.02,134.74,134.15,133.26,133.15,132.06,130.33,128.36,127.74,127.56,126.78,125.00,122.07；
HRMS(ESI-TOF)Calcd for C 23 H 13 O 3 N 2 [M+H] + :365.0921；found:365.0912。
fig. 17 and 18 are a nuclear magnetic resonance hydrogen spectrum and a nuclear magnetic resonance carbon spectrum of 2i, respectively.
Example 10
0.1198g, (0.3mmol, 1equiv) of 2- ((2- (naphthalene-2-ylethynyl) phenyl) amino) naphthalene-1, 4-dione (0.0905 g, (0.3mmol, 1equiv) was weighed and dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. Washing with 100mL of saturated aqueous sodium chloride solution, separating, extracting the aqueous phase with ethyl acetate (50 mL × 3), combining the organic phases, drying with anhydrous sodium sulfate, concentrating, and separating the crude product by silica gel column chromatography with ethyl acetate/petroleum ether (petroleum ether/ethyl acetate = 3/1) as a developing agent to obtain the target product 2j with a yield of 70%.
The structure of the target product 2j is characterized as follows:
1 H NMR(400MHz,Chloroform-d)δ8.61(d,J＝8.5Hz,1H),8.54-8.45(m,1H),8.21-8.12(m,2H),8.07(d,J＝6.6Hz,1H),8.03-7.95(m,2H),7.92-7.88(m,1H),7.87-7.79(m,3H),7.78-7.74(m,1H),7.70-7.65(m,1H),7.50-7.46(m,1H),7.52-7.46(m,1H)；
13 C NMR(101MHz,Chloroform-d)δ195.81,182.12,181.38,150.02,147.97,136.14,135.11,134.95,134.01,133.64,133.25,132.53,132.05,131.19,130.75,129.71,129.28,129.07,128.34,127.97,127.05,126.76,124.43,123.65；
HRMS(ESI-TOF)Calcd for C 28 H 16 O 3 N[M+H] + :414.1125；found:414.1116。
fig. 19 and 20 are a nuclear magnetic resonance hydrogen spectrum and a nuclear magnetic resonance carbon spectrum of 2j, respectively.
Example 11
0.1198g (0.3mmol, 1equiv) of 2- ((2- (naphthalene-2-ylethynyl) phenyl) amino) naphthalene-1, 4-dione (0.0905 g, (0.3mmol, 1equiv) was dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as the positive electrode, a platinum sheet electrode was used as the negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. Washing with 100mL of saturated aqueous sodium chloride solution, separating, extracting the aqueous phase with ethyl acetate (50 mL × 3), combining the organic phases, drying with anhydrous sodium sulfate, concentrating, and separating the crude product by silica gel column chromatography with ethyl acetate/petroleum ether (petroleum ether/ethyl acetate = 3/1) as a developing agent to obtain the target product 2k with a yield of 71%.
The structure of the target product 2k is characterized as:
1 H NMR(400MHz,Chloroform-d)δ8.54(d,J＝8.6Hz,1H),8.52-8.48(m,1H),8.37-8.32(m,1H),8.01-7.96(m,1H),7.92-7.84(m,3H),7.82-7.76(m,1H),3.16-3.04(m,1H),2.76-2.66(m,1H),2.10-1.98(m,2H),1.14(t,J＝7.4Hz,3H)；
13 C NMR(101MHz,Chloroform-d)δ205.39,182.66,181.24,151.63,150.14,147.75,135.17,134.98,134.03,133.48,133.28,132.20,130.68,128.38,127.84,126.08,125.12,46.18,16.99,13.77；
HRMS(ESI-TOF)Calcd for C 21 H 16 O 3 N[M+H] + :330.1125；found:330.1124。
FIGS. 21 and 22 are the NMR hydrogen and carbon spectra at 2k, respectively.
Comparative example 1 (use of different electrolytes)
0.1048g (0.3mmol, 1equiv) of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.1162g (0.3mmol, 1equiv) of tetrabutylammonium hexafluorophosphate, was weighed and dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction yield was 67% at the end of the reaction, as measured using high performance liquid phase.
0.1048g (0.3mmol, 1equiv) of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.0988g (0.3mmol, 1equiv) of tetrabutylammonium tetrafluoroborate was weighed and dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction yield was 52% at the end of the reaction, as measured using high performance liquid chromatography.
0.1048g of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione (0.3mmol, 1equiv), 0.1108g of tetrabutylammonium iodide, (0.3mmol, 1equiv) was weighed and dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used for the positive electrode, a platinum sheet electrode was used for the negative electrode, a constant current was controlled at 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. And no reaction.
Comparative example 2 (use of different solvents)
0.1048g (0.3mmol, 1equiv) of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.1048g (0.3mmol, 1equiv) of tetrabutylammonium acetate was weighed and dissolved in 8mL of dimethyl sulfoxide, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction yield was 80% as determined by HPLC at the end of the reaction.
0.1048g (0.3mmol, 1equiv) of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.1048g (0.3mmol, 1equiv) of tetrabutylammonium acetate was weighed and dissolved in 8mL of N, N-dimethylformamide, a carbon cloth electrode was used for the positive electrode, a platinum sheet electrode was used for the negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction yield was determined to be 66% using HPLC at the end of the reaction.
0.1048g (0.3mmol, 1equiv) of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.1048g (0.3mmol, 1equiv) of tetrabutylammonium acetate was weighed and dissolved in 8mL of ethanol, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction yield was 28% at the end of the reaction, as measured using high performance liquid chromatography.
0.1048g (0.3mmol, 1equiv) of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.1048g (0.3mmol, 1equiv) of tetrabutylammonium acetate was dissolved in 8ml2, 2-trifluoroethanol, a carbon cloth electrode was used for the positive electrode, a platinum sheet electrode was used for the negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction yield was 42% at the end of the reaction, as measured using high performance liquid chromatography.
0.1048g (0.3mmol, 1equiv) of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.1048g (0.3mmol, 1equiv) of tetrabutylammonium acetate was weighed and dissolved in 8mL of acetonitrile, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction yield was 64% when the reaction was completed, using high performance liquid chromatography.
COMPARATIVE EXAMPLE 3 (use of different electrodes)
0.1048g (0.3mmol, 1equiv) of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.1048g (0.3mmol, 1equiv) of tetrabutylammonium acetate was weighed and dissolved in 8mL of hexafluoroisopropanol, a carbon rod electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction yield was 45% at the end of the reaction, as measured using high performance liquid chromatography.
0.1048g (0.3mmol, 1equiv) of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.1048g (0.3mmol, 1equiv) of tetrabutylammonium acetate was weighed and dissolved in 8mL of hexafluoroisopropanol, an RVC carbon electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction occurs in trace amounts.
0.1048g of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione (0.3mmol, 1equiv), 0.1048g of tetrabutylammonium acetate (0.3mmol, 1equiv) was dissolved in 8mL of hexafluoroisopropanol, a platinum sheet electrode was used for the positive electrode, a platinum sheet electrode was used for the negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction occurs in trace amounts.
0.1048g (0.3mmol, 1equiv) of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.1048g (0.3mmol, 1equiv) of tetrabutylammonium acetate was weighed and dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used for the positive electrode, a carbon cloth electrode was used for the negative electrode, a constant current was controlled to 10mA, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction did not occur.
COMPARATIVE EXAMPLE 4 (different environmental systems)
0.1048g (0.3mmol, 1equiv) of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.1048g (0.3mmol, 1equiv) of tetrabutylammonium acetate was weighed, dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, the reaction was carried out under a nitrogen atmosphere, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction yield was 30% as measured by HPLC at the end of the reaction.
0.1048g (0.3mmol, 1equiv) of 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 0.1048g (0.3mmol, 1equiv) of tetrabutylammonium acetate was dissolved in 8mL of hexafluoroisopropanol, a carbon cloth electrode was used as a positive electrode, a platinum sheet electrode was used as a negative electrode, a constant current was controlled to 10mA, the reaction was carried out in an oxygen atmosphere, and the progress of the reaction was detected by TLC (petroleum ether: ethyl acetate = 3. The reaction yield was 43% by HPLC at the end of the reaction.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention. All the components not specified in the present embodiment can be realized by the prior art.
Claims (6)
1. A method for electrochemically synthesizing aza-anthraquinone derivatives is characterized in that 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-diketone compounds in a formula (I), electrolyte and solvent are added into an electrolytic cell without a diaphragm, a negative electrode and a positive electrode are inserted into the electrolytic cell, constant current is conducted, stirring reaction is carried out in an open system, after the reaction is finished, the aza-anthraquinone derivatives shown in the formula (II) are obtained through column chromatography separation,
wherein R is 1 Thiophene, pyridine, naphthalene ring, aliphatic hydrocarbon or substituted benzene ring,wherein, the benzene ring is substituted by any substituent of hydrogen, halogen, C1-C3 alkyl, alkoxy and Boc protected amino; r is 2 Is C1-C3 alkyl or halogen; the anode is any one of a carbon cloth electrode and a carbon rod electrode; the negative electrode is a platinum electrode; the electrolyte is any one of tetrabutylammonium hexafluorophosphate, tetrabutylammonium tetrafluoroborate and tetrabutylammonium acetate; the solvent is any one or a mixture of more of acetonitrile, dimethyl sulfoxide, N-dimethylformamide, ethanol, trifluoroethanol and hexafluoroisopropanol; the constant current for electrochemical reaction is 5-15 mA; the environment system of the electrochemical reaction is any one of nitrogen, oxygen and air.
2. The method of claim 1, the 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione compound is 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, 2- ((2- (p-tolylethynyl) phenyl) amino) naphthalene-1, 4-dione, 2- ((2- ((4-chlorophenyl) ethynyl) phenyl) amino) naphthalene-1, 4-dione, 2- ((4-chloro-2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione, tert-butyl 2- ((2-methoxyphenyl) ethynyl) phenyl) amino) naphthalene-1, 4-dione, (4- ((2- ((1, 4-dioxo-1, 4-dihydronaphthalen-2-yl) amino) phenyl) ethynyl) phenyl) carbamate, 2- ((2- (thien-2-ylethynyl) phenyl) amino) naphthalene-1, 4-dione, 2- ((2- (pyridin-2-ylethynyl) phenyl) amino) naphthalene-1, 4-dione, 2- ((2- (naphthalen-2-ylethynyl) phenyl) amino) naphthalene-1, 4-dione, any one of 2- ((2- (naphthalene-2-ylethynyl) phenyl) amino) naphthalene-1, 4-dione.
3. The process according to claim 1, characterized in that 2- ((2- (phenylethynyl) phenyl) amino) naphthalene-1, 4-dione in formula (i) is replaced by methyl 4- ((2- ((1, 4-dioxo-1, 4-dihydronaphthalen-2-yl) amino) phenyl) ethynyl) benzoate to give the azaanthraquinone derivative represented by (2 e):
4. the method of claim 1, wherein the electrolyte is used in an amount of 1 to 3 equivalents in the electrochemical reaction.
5. The method of claim 1, wherein the electrochemical reaction temperature is 0-40 ℃.
6. The method of claim 1, wherein the electrochemical reaction time is 1-3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210048909.9A CN114196973B (en) | 2022-01-17 | 2022-01-17 | Method for electrochemically synthesizing aza-anthraquinone derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210048909.9A CN114196973B (en) | 2022-01-17 | 2022-01-17 | Method for electrochemically synthesizing aza-anthraquinone derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114196973A CN114196973A (en) | 2022-03-18 |
| CN114196973B true CN114196973B (en) | 2022-12-09 |
Family
ID=80658661
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210048909.9A Active CN114196973B (en) | 2022-01-17 | 2022-01-17 | Method for electrochemically synthesizing aza-anthraquinone derivative |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114196973B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054681A (en) * | 2007-02-14 | 2007-10-17 | 浙江工业大学 | Electrolytic synthesis method for 1,5-diamino-4,8-dihydroxyanthraquinone by one-step method |
| CN101070374A (en) * | 2007-04-28 | 2007-11-14 | 同济大学 | Chemical-oxidation direct preparing method for polyamino anthaquinone nano particles |
| CN101712648A (en) * | 2009-11-23 | 2010-05-26 | 南京大学 | Synthesis method of azepine anthraquinone |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090288946A1 (en) * | 2008-05-23 | 2009-11-26 | Lumimove, Inc. Dba Crosslink | Electroactivated film with layered structure |
-
2022
- 2022-01-17 CN CN202210048909.9A patent/CN114196973B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054681A (en) * | 2007-02-14 | 2007-10-17 | 浙江工业大学 | Electrolytic synthesis method for 1,5-diamino-4,8-dihydroxyanthraquinone by one-step method |
| CN101070374A (en) * | 2007-04-28 | 2007-11-14 | 同济大学 | Chemical-oxidation direct preparing method for polyamino anthaquinone nano particles |
| CN101712648A (en) * | 2009-11-23 | 2010-05-26 | 南京大学 | Synthesis method of azepine anthraquinone |
Non-Patent Citations (3)
| Title |
|---|
| Electrophilic carbocyclization reactions of 2-(2-alkynylphenyl)amino-1,4-naphthoquinones;Chang-You Sie et al.;《Organic & Biomolecular Chemistry》;20180719;第5483-5491页 * |
| Metal-Free C−C Cross Coupling: Electrosynthesis of Azaheterocycles through Anodic Oxidation Cyclization of 1,6-Enynes;Chen Cai et al.;《ACS Sustainable Chemistry & Engineering》;20220303;第3288-3294页 * |
| 间接电化学合成蒽醌等有机产品;张晋衡;《染料与染色》;19811028(第05期);第5-8页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114196973A (en) | 2022-03-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jiang et al. | Exogenous-oxidant-and catalyst-free electrochemical deoxygenative C2 sulfonylation of quinoline N-oxides | |
| CN107474047B (en) | Synthesis method of 1,2, 4-triazolo heterocyclic compound | |
| CA2995949A1 (en) | Method for the preparation of (4s)-4-(4-cyano-2-methoxyphenyl)-5-ethoxy-2,8-dimethyl-1,4-dihydro-1-6-naphthyridine-3-carboxamide and recovery of (4s)-4-(4-cyano-2-methoxyphenyl)-5-ethoxy-2,8-dimethyl-1,4-dihydro-1-6-naphthyridine-3-carboxamide by electrochemical methods | |
| Liu et al. | Electrochemical oxidation synergizing with Brønsted-acid catalysis leads to [4+ 2] annulation for the synthesis of pyrazines | |
| Liu et al. | Electrooxidative tandem cyclization of N-propargylanilines with sulfinic acids for rapid access to 3-arylsulfonylquinoline derivatives | |
| Cruz et al. | Electrochemically promoted nucleophilic aromatic substitution in room temperature ionic liquids—an environmentally benign way to functionalize nitroaromatic compounds | |
| Zhang et al. | Iodine-mediated electrochemical C (sp 3)–H cyclization: the synthesis of quinazolinone-fused N-heterocycles | |
| CN114892187A (en) | Method for electrochemically synthesizing imidazole polycyclic aromatic compounds | |
| CN111690947A (en) | Electrochemical synthesis method of trifluoromethylated aryl amide derivative | |
| CN114196973B (en) | Method for electrochemically synthesizing aza-anthraquinone derivative | |
| La-Ongthong et al. | Electrochemical trifluoromethylation of 2-isocyanobiaryls using CF 3 SO 2 Na: synthesis of 6-(trifluoromethyl) phenanthridines | |
| CN104072429B (en) | A kind of synthetic method of 1,2,4-triazole derivative | |
| Shi et al. | Electro-oxidation induced O–S cross-coupling of quinoxalinones with sodium sulfinates for synthesizing 2-sulfonyloxylated quinoxalines | |
| Zhu et al. | Synthesis of nitrocarbazole compounds and their electrocatalytic oxidation of alcohol | |
| CN113981477B (en) | Method for preparing pyridazine compound by one-pot two-step electrooxidation cyclization | |
| CN114438523A (en) | Green and efficient electrochemical synthesis method of benzothiophene compound | |
| CN111575731B (en) | Method for electrochemically synthesizing C5 and C7 dihalogenated quinoline amide derivatives | |
| CN114250479A (en) | Novel method for synthesizing alkyl-substituted nitrogen-containing heterocycle under catalysis of cerium salt | |
| CN113403635B (en) | Method for preparing N-substituted pyrrolidone derivative | |
| CN116926577A (en) | Method for electrochemically synthesizing pyridine-fused polycyclic azaaromatic compound | |
| CN110714208A (en) | Method for preparing 6- (sulfonyl methyl) phenanthridine compound through electrocatalysis | |
| CN111057058B (en) | Method for preparing 1H- [1,2,3] -triazolo [4,5-c ] quinoline compound | |
| CN113652705B (en) | Method for synthesizing fluorenone through catalytic electrolysis of N-hydroxyphthalimide | |
| CN110846675B (en) | Synthetic method of 2- (5-aryl-1, 3, 4-oxadiazole-2-yl) aniline compound | |
| CN115044923B (en) | Method for preparing 2-aryl-3-thiocyano-benzothiophene by utilizing electrochemical reaction |
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 |