CN115094447A - Method for pair-wise electrochemical synthesis of azotriazolone and oxygen-containing azotriazolone - Google Patents

Method for pair-wise electrochemical synthesis of azotriazolone and oxygen-containing azotriazolone Download PDF

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CN115094447A
CN115094447A CN202210726886.2A CN202210726886A CN115094447A CN 115094447 A CN115094447 A CN 115094447A CN 202210726886 A CN202210726886 A CN 202210726886A CN 115094447 A CN115094447 A CN 115094447A
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azotriazolone
oxygen
triazole
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戴亚堂
周天龙
王伟
蒲琳钰
巩家旭
谢明珍
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Southwest University of Science and Technology
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Abstract

The invention discloses a method for pair-wise electrochemical synthesis of azotriazolone and oxygen-containing azotriazolone, which comprises the following steps: in an electrochemical reactor, a cathode chamber and an anode chamber are separated by a diaphragm, and in a proper electrolyte and a stable reaction electrode, 3-amino-1, 2, 4-triazole-5-ketone is subjected to oxidative dehydrogenation coupling reaction in the anode chamber to generate an azotriazolone compound; 3-nitro-1, 2, 4-triazole-5-ketone is subjected to reduction reaction in a cathode chamber to generate the oxygen-containing azotriazolone. After the reaction is finished, the azotriazolone and the oxygen-containing azotriazolone compound with high purity are obtained by purifying and drying through a corresponding separation method. Compared with the traditional method, the method has the advantages of convenient operation, simple process and low cost, avoids the generation of hydrogen and oxygen, simultaneously obtains useful products of the cathode and the anode, reduces the danger during synthesis and improves the economic benefit.

Description

Method for pair-wise electrochemical synthesis of azotriazolone and oxygen-containing azotriazolone
Technical Field
The invention belongs to the technical field of electrochemical organic synthesis, and particularly relates to a method for pair-wise electrochemical synthesis of azotriazolone and oxygen-containing azotriazolone.
Background
In recent years, people pay more and more attention to environmental problems, and also in the field of high-energy materials, people pay more attention to green synthetic high-energy materials, and energetic materials can involve various environmental and ecological problems in the preparation and use processes, so that higher requirements are put forward on the synthesis of the energetic materials. The azotriazole compound is formed by connecting two originally independent high-nitrogen triazole rings through an azo group, and has higher density, heat generation and more active sites compared with an oxazole ring. However, the traditional method for synthesizing azotriazolone needs excessive oxidant and can be carried out under the heating condition; wallace et al reported an electrochemical reduction of NTO wastewater to synthesize an oxo-azotriazolone. This reaction reduces the current efficiency to some extent because the anode produces oxygen, a useless and difficult to collect oxidation product. In order to reduce the waste of reagents and environmental pollution and improve the safety and economic benefits, the invention provides a method for pair-wise electrochemically synthesizing azotriazolone and oxygen-containing azotriazolone compounds, in the method, only electrons are used as an oxidant, 3-amino-1, 2, 4-triazole-5-ketone is subjected to oxidative coupling dehydrogenation reaction in an anode chamber by controlling the concentration ratio, the type and the fine-tuning reaction voltage of an electrolyte, azotriazolone is synthesized at room temperature, and then the high-purity azotriazolone compound can be obtained by a separation method such as filtration and washing. 3-nitro-1, 2, 4-triazole-5-ketone is subjected to reduction coupling reaction in a cathode chamber, the oxygen-containing azotriazolone is synthesized at room temperature, a crude product is obtained by filtering and washing, then the pH is adjusted to be alkaline, insoluble impurities are filtered, the pH of the solution is adjusted to be acidic, and the high-purity oxygen-containing azotriazolone is obtained by filtering, washing and drying.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for paired electrochemical synthesis of azotriazolone and oxygenous azotriazolone comprising:
in a separated electrochemical reactor, applying a certain voltage, and oxidizing dehydrogenation coupling reaction is carried out on 3-amino-1, 2, 4-triazole-5-ketone in an anode chamber after electrons of the 3-amino-1, 2, 4-triazole-5-ketone are lost to generate 3, 3' -azo-1, 2, 4-triazole-5-ketone, namely, the azotriazolone is synthesized; 3-nitro-1, 2, 4-triazole-5-ketone electrons are subjected to reduction reaction in a cathode chamber to generate 3, 3' -oxygen-containing azo-1, 2, 4-triazole-5-ketone, namely the oxygen-containing azo triazolone is synthesized; 3, 3 '-azo-1, 2, 4-triazole-5-ketone and 3, 3' -oxygen-containing azo-1, 2, 4-triazole-5-ketone with high purity are obtained by corresponding separation means.
Preferably, wherein the divided electrochemical reactor is divided into a cathode chamber and an anode chamber by a diaphragm; the anode chamber is internally provided with anode chamber electrolyte, and the anode chamber electrolyte comprises 3-amino-1, 2, 4-triazole-5-ketone and alkaline electrolyte which are mixed according to a certain concentration ratio; the cathode chamber is filled with a cathode chamber electrolyte, and the cathode chamber electrolyte comprises 3-nitro-1, 2, 4-triazole-5-ketone and an acid electrolyte which are mixed according to a certain concentration ratio.
Preferably, the structural formula of the 3, 3' -azo-1, 2, 4-triazole-5-ketone is as follows:
Figure BDA0003713544420000021
the structural formula of the 3, 3' -oxygen-containing azo-1, 2, 4-triazole-5 ketone is as follows:
Figure BDA0003713544420000022
preferably, the diaphragm comprises one of an anion exchange membrane, a cation exchange membrane and a proton exchange membrane.
Preferably, the reaction electrode of the cathode chamber or the anode chamber is one of a carbon electrode and a platinum electrode.
Preferably, the constant voltage is a reaction voltage of 0 to 2V applied to the reaction electrode by a DC or pulse power supply.
Preferably, the alkaline electrolyte is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium phosphate and cesium carbonate, and the acidic electrolyte is one of hydrochloric acid and sulfuric acid.
Preferably, the separation method comprises the specific steps of filtering yellow precipitate generated after the reaction in the anode chamber, fully washing with water, and drying to obtain azotriazolone product; and (3) filtering and washing yellow precipitate generated after the reaction in the cathode chamber to obtain a crude product, then adjusting the pH value to be alkaline, then filtering impurities, then adjusting the pH value to be acidic, and then filtering, washing and drying to obtain the product of the oxazotriazolone.
Preferably, the molar ratio of the 3-amino-1, 2, 4-triazole-5-ketone to the alkaline electrolyte is 1: 1-2; the molar ratio of the 3-nitro-1, 2, 4-triazole-5-ketone to the acidic electrolyte is 1: 1 to 2.
Preferably, the reaction electrode of the anode chamber or the cathode chamber is a carbon electrode modified by nano platinum, and the preparation method of the carbon electrode modified by nano platinum comprises the following steps:
step S1, soaking and washing the 12g carbon electrode in a concentrated nitric acid solution, washing the carbon electrode with acid, and then washing and drying the carbon electrode with clean water for multiple times;
step S2, placing the carbon electrode into a mixed solution of 10-100 mM 3-aminobenzoic acid and 200mM sodium chloride in ethanol, applying a voltage of 0-2.5V at 25-35 ℃ by adopting a three-electrode system, taking the carbon electrode as a working electrode, a silver electrode as a reference electrode and a platinum sheet as a counter electrode, performing cyclic potential scanning at a sweep rate of 10-20 mV/S, washing with water and drying to obtain the precursor membrane modified carbon electrode
And step S3, dissolving 1g of chloroplatinic acid in 100ml of water to obtain a chloroplatinic acid solution, placing the carbon electrode modified by the precursor film in the chloroplatinic acid solution for constant potential deposition for 5min, wherein the potential is-0.9 VVS.SCE, so that platinum is deposited on the surface of the precursor film, and washing and drying to obtain the platinum-modified carbon electrode.
The invention at least comprises the following beneficial effects: compared with the traditional method for synthesizing azotriazolone, the method has the advantages of mild reaction conditions, simple process and convenient operation, can greatly reduce the use of potassium permanganate and other strong oxidants and the generation of byproducts, greatly improves the current efficiency and the time-space efficiency of electrosynthesis, reduces the cost, saves the electric energy and improves the electric energy efficiency compared with one-electrode electrosynthesis. Has excellent application potential in the field of energetic material synthesis.
The reaction electrode selected in the electrochemical synthesis process can also be a platinum-modified carbon electrode, and in the process of preparing the platinum-modified carbon electrode, 3-aminobenzoic acid is used as a source of a carboxyl functional group, sodium chloride is used as a supporting electrolyte to prepare a layer of mild, stable and negative charge-rich precursor film on the surface of the carbon electrode, so that a stable deposition environment is provided for subsequent platinum. Platinum is deposited on the basis of the precursor film, so that the electrocatalytic performance of the reaction electrode is greatly improved, side reactions are reduced, and the product yield of the oxygen-containing azotriazolone is improved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a schematic diagram of the synthesis principle of azotriazolone and oxygen-containing azotriazolone in an electrochemical reactor;
FIG. 2 is an infrared spectrum of a target product of the anode synthesized in example 1;
FIG. 3 is an infrared spectrum of a target product of a cathode synthesized in example 1;
FIG. 4 is a nuclear magnetic hydrogen spectrum of the target product of the anode synthesized in example 1;
fig. 5 is a nuclear magnetic hydrogen spectrum of the cathode target product synthesized in example 1.
Detailed Description
The present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
the embodiment provides a method for pair-wise electrochemical synthesis of azotriazolone and oxygen-containing azotriazolone, which comprises the following steps:
firstly, 1g of 3-amino-1, 2, 4-triazole-5-ketone and 0.8g of sodium hydroxide are dissolved in 50ml of water and put into an anode chamber of an electrochemical reactor; dissolving 1.3g of 3-nitro-1, 2, 4-triazole-5-ketone and 1.09ml of concentrated sulfuric acid in 50ml of water, and placing the solution into a cathode chamber of an electrochemical reactor; carbon electrodes are selected to be respectively used as reaction electrodes of a cathode chamber and an anode chamber, 1.2V voltage is applied to the reaction electrodes of the cathode chamber and the anode chamber, and a diaphragm is a proton exchange membrane. After the reaction is finished, directly filtering, washing and drying the reaction solution in the cathode chamber to obtain a crude product, then adding a certain amount of alkali, filtering out insoluble impurities, then adjusting the pH value of the solution to be acidic, and filtering, washing and drying to obtain the pure product of the oxygen-containing azotriazolone with the yield of 45%. The reaction solution in the anode chamber is directly adjusted to be acidic, a large amount of yellow precipitate is generated, and the azotriazolone pure product is obtained by filtering, washing and drying. The synthetic reaction principle is shown in figure 1, and 3-amino-1, 2, 4-triazole-5-ketone is subjected to oxidative dehydrogenation coupling reaction in an anode chamber to generate an azotriazolone compound; the 3-nitro-1, 2, 4-triazole-5-ketone is subjected to reduction reaction in a cathode chamber to generate the oxygen-containing azotriazolone
The tube energy group information and the molecular structure of the azotriazolone and the oxygen-containing azotriazolone prepared in the embodiment are analyzed by respectively using an infrared spectrum and a nuclear magnetic hydrogen spectrum; the infrared spectrogram and the nuclear magnetic hydrogen spectrogram of the azotriazolone prepared in the embodiment are respectively shown in fig. 2 and 4, and two peaks in fig. 4 are respectively 1 H NMR(600MHz,DMSO-d 6 ) δ 12.74(s,1H),12.44(s, 1H); the infrared spectrogram and the nuclear magnetic hydrogen spectrogram of the oxygen-containing azotriazolone prepared in the embodiment are respectively shown in fig. 3 and 5, and four peaks in fig. 5 are respectively 1 H NMR(600MHz,DMSO-d 6 )δ13.20(s,1H),12.48(s,1H),12.45(s,1H),12.08(s,1H)。
Example 2:
the present example provides a method for paired electrochemical synthesis of azotriazolone and oxaazotriazolones comprising;
firstly, 0.5g of 3-amino-1, 2, 4-triazole-5-ketone and 1g of sodium carbonate are dissolved in 50ml of water and put into an anode chamber of an electrochemical reactor; dissolving 0.65g of 3-nitro-1, 2, 4-triazole-5-ketone and 1.09ml of concentrated sulfuric acid in 50ml of water, and placing the solution into a cathode chamber of an electrochemical reactor; carbon electrodes are selected as reaction electrodes of a cathode chamber and an anode chamber respectively, 1V voltage is applied to the reaction electrodes of the cathode chamber and the anode chamber, and a diaphragm is a proton exchange membrane. After the reaction is finished, directly filtering, washing and drying the reaction solution in the cathode chamber to obtain a crude product, then adding a certain amount of alkali, filtering out insoluble impurities, then adjusting the pH value of the solution to be acidic, and filtering, washing and drying to obtain the pure product of the oxygen-containing azotriazolone with the yield of 50%. The reaction solution in the anode chamber is directly adjusted to be acidic, a large amount of yellow precipitate is generated, and the azotriazolone pure product is obtained by filtering, washing and drying.
Example 3:
the present embodiment provides a method for paired electrochemical synthesis of azotriazolone and oxaazotriazolone, comprising:
firstly, 1g of 3-amino-1, 2, 4-triazole-5-ketone and 0.8g of sodium hydroxide are dissolved in 50ml of water and put into an anode chamber of an electrochemical reactor; dissolving 1.3g of 3-nitro-1, 2, 4-triazole-5-ketone and 1.09ml of concentrated sulfuric acid in 50ml of water, and placing the solution into a cathode chamber of an electrochemical reactor; platinum modified carbon electrodes are respectively selected as reaction electrodes of a cathode chamber and an anode chamber, 1.2V voltage is applied to the reaction electrodes of the cathode chamber and the anode chamber, and a diaphragm is a proton exchange membrane. After the reaction is finished, directly filtering, washing and drying the reaction solution in the cathode chamber to obtain a crude product, then adding a certain amount of alkali to filter out insoluble impurities, then adjusting the pH value of the solution to be acidic, and filtering, washing and drying to obtain the pure product of the oxygen-containing azotriazolone with the yield of 62%. The reaction solution in the anode chamber is directly adjusted to be acidic, a large amount of yellow precipitate is generated, and the pure azotriazolone product is obtained by filtering, washing and drying.
The preparation method of the platinum modified carbon electrode comprises the following steps:
step S1, soaking and washing the 12g carbon electrode in a concentrated nitric acid solution, washing the carbon electrode with acid, and then washing and drying the carbon electrode with clean water for multiple times;
step S2, placing the carbon electrode into an ethanol mixed solution of 100mM 3-aminobenzoic acid and 200mM sodium chloride, adopting a three-electrode system, taking the carbon electrode as a working electrode, a silver electrode as a reference electrode, a platinum sheet as a counter electrode, applying 2.5V voltage at 30 ℃, performing cyclic potential scanning at a sweep rate of 20mV/S, washing with water and drying to obtain the precursor membrane modified carbon electrode
Step S3, dissolving 1g of chloroplatinic acid in 100ml of water to obtain a chloroplatinic acid solution, placing the carbon electrode modified by the precursor film in the chloroplatinic acid solution for constant potential deposition for 5min at a potential of-0.9 VVS.SCE to deposit platinum on the surface of the precursor film, and washing and drying to obtain the platinum-modified carbon electrode.
Example 4:
the embodiment provides a method for pair-wise electrochemical synthesis of azotriazolone and oxygen-containing azotriazolone, which comprises the following steps:
firstly, 1g of 3-amino-1, 2, 4-triazole-5-ketone and 0.8g of sodium hydroxide are dissolved in 50ml of water and are put into an anode chamber of an electrochemical reactor; 1.3g of 3-nitro-1, 2, 4-triazole-5-ketone and 1.09ml of concentrated sulfuric acid are dissolved in 50ml of water and are placed into a cathode chamber of an electrochemical reactor; platinum modified carbon electrodes are respectively selected as reaction electrodes of a cathode chamber and an anode chamber, 1.2V voltage is applied to the reaction electrodes of the cathode chamber and the anode chamber, and a diaphragm is a proton exchange membrane. After the reaction is finished, directly filtering, washing and drying the reaction solution in the cathode chamber to obtain a crude product, then adding a certain amount of alkali to filter out insoluble impurities, then adjusting the pH value of the solution to be acidic, and filtering, washing and drying to obtain the pure product of the oxygen-containing azotriazolone with the yield of 61%. The reaction solution in the anode chamber is directly adjusted to be acidic, a large amount of yellow precipitate is generated, and the azotriazolone pure product is obtained by filtering, washing and drying.
The preparation method of the platinum modified carbon electrode comprises the following steps:
step S1, soaking and washing the 12g carbon electrode in a concentrated nitric acid solution, washing the carbon electrode with acid, and then washing and drying the carbon electrode with clean water for multiple times;
step S2, putting the carbon electrode into ethanol mixed solution of 3-aminobenzoic acid with the concentration of 50mM and sodium chloride with the concentration of 200mM, adopting a three-electrode system, taking the carbon electrode as a working electrode, a silver electrode as a reference electrode, a platinum sheet as a counter electrode, applying 1.0V voltage at 25 ℃, performing cyclic potential scanning at the sweep rate of 10mV/S, washing with water and drying to obtain the precursor membrane modified carbon electrode
And step S3, dissolving 1g of chloroplatinic acid in 100ml of water to obtain a chloroplatinic acid solution, placing the carbon electrode modified by the precursor film in the chloroplatinic acid solution for constant potential deposition for 5min, wherein the potential is-0.9 VVS.SCE, so that platinum is deposited on the surface of the precursor film, and washing and drying to obtain the platinum-modified carbon electrode.
As can be seen from examples 1 to 4, the azotriazolone and the oxaazotriazolone with higher yield can be prepared by the method provided by the present invention, and examples 3 and 4 use the platinum modified carbon electrode as the reaction electrode, and the yield of the azotriazolone and the oxaazotriazolone is significantly higher than that of examples 1 and 2 due to the reduction of side reactions.
The number of apparatuses and the scale of the process described herein are intended to simplify the description of the present invention. Applications, modifications and variations of the present invention will be apparent to those skilled in the art.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.

Claims (10)

1. A method for pair-wise electrochemical synthesis of azotriazolone and oxygen-containing azotriazolone, which is characterized by comprising the following steps: applying a certain voltage to a separated electrochemical reactor, and leading 3-amino-1, 2, 4-triazole-5-ketone to lose electrons and generate oxidative dehydrogenation coupling reaction in an anode chamber to generate 3, 3' -azo-1, 2, 4-triazole-5-ketone, namely synthesizing to obtain azotriazolone; 3-nitro-1, 2, 4-triazole-5-ketone electrons are subjected to reduction reaction in a cathode chamber to generate 3, 3' -oxygen-containing azo-1, 2, 4-triazole-5-ketone, namely the oxygen-containing azo triazolone is synthesized; by corresponding separation means, high-purity 3, 3 '-azo-1, 2, 4-triazole-5-ketone and 3, 3' -oxygenic azo-1, 2, 4-triazole-5-ketone are obtained.
2. The paired electrochemical synthesis process of azotriazolone and azotriazolone containing oxygen according to claim 1, characterized in that said divided electrochemical reactor is divided into a cathode chamber and an anode chamber by a diaphragm; the anode chamber is internally provided with anode chamber electrolyte, and the anode chamber electrolyte comprises 3-amino-1, 2, 4-triazole-5-ketone and alkaline electrolyte which are mixed according to a certain concentration ratio; the cathode chamber is filled with electrolyte of the cathode chamber, and the electrolyte of the cathode chamber comprises 3-nitro-1, 2, 4-triazole-5-ketone and acid electrolyte which are mixed according to a certain concentration ratio.
3. The paired electrochemical synthesis method of azotriazolone and oxygen-containing azotriazolone according to claim 1, characterized in that said 3, 3' -azo-1, 2, 4-triazol-5-one has the formula:
Figure FDA0003713544410000011
the structural formula of the 3, 3' -oxygen-containing azo-1, 2, 4-triazole-5 ketone is as follows:
Figure FDA0003713544410000012
4. the paired electrochemical synthesis method of azotriazolone and azotriazolone containing oxygen according to claim 2, wherein said membrane comprises one of an anion exchange membrane, a cation exchange membrane, and a proton exchange membrane.
5. The paired electrochemical synthesis method of azotriazolone and oxygenic azotriazolone according to claim 1, characterized in that the reaction electrode in the cathode compartment or the anode compartment is one of a carbon electrode and a platinum electrode.
6. The paired electrochemical synthesis method of azotriazolone and oxygenic azotriazolone according to claim 1, wherein the certain voltage is a reaction voltage of 0-2V applied to the reaction electrode by a direct current or pulse power supply.
7. The paired electrochemical synthesis method of azotriazolone and oxygen-containing azotriazolone according to claim 2, characterized in that said basic electrolyte is at least one of sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, sodium carbonate, potassium phosphate and cesium carbonate, and said acidic electrolyte is one of hydrochloric acid and sulfuric acid.
8. The paired electrochemical synthesis process of azotriazolone and oxygenic azotriazolone as claimed in claim 1, wherein the said separation means includes filtering yellow precipitate produced after the reaction in anode chamber, water washing and drying to obtain azotriazolone product; and filtering and washing yellow precipitate generated after the reaction in the cathode chamber to obtain a crude product, then adjusting the pH value to be alkaline, then filtering impurities, then adjusting the pH value to be acidic, and then filtering, washing and drying to obtain the product of the azotriazolinone containing oxygen.
9. The paired electrochemical synthesis method of azotriazolone and oxygen-containing azotriazolone according to claim 2, characterized in that the molar ratio of 3-amino-1, 2, 4-triazol-5-one and alkaline electrolyte is 1: 1-2; the molar ratio of the 3-nitro-1, 2, 4-triazole-5-ketone to the acidic electrolyte is 1: 1 to 2.
10. The paired electrochemical synthesis method of azotriazolone and oxygenic azotriazolone according to claim 1, characterized in that the reaction electrode in the anode chamber or cathode chamber is a carbon electrode modified by nano-platinum, and the preparation method of the carbon electrode modified by nano-platinum comprises the following steps:
step S1, soaking and washing the 12g carbon electrode in a concentrated nitric acid solution, washing the carbon electrode with acid, and then washing and drying the carbon electrode with clean water for multiple times;
step S2, placing the carbon electrode into a mixed solution of 10-100 mM 3-aminobenzoic acid and 200mM sodium chloride in ethanol, applying a voltage of 0-2.5V at 25-35 ℃ by adopting a three-electrode system, taking the carbon electrode as a working electrode, a silver electrode as a reference electrode and a platinum sheet as a counter electrode, performing cyclic potential scanning at a sweep rate of 10-20 mV/S, washing with water and drying to obtain the precursor membrane modified carbon electrode
Step S3, dissolving 1g of chloroplatinic acid in 100ml of water to obtain a chloroplatinic acid solution, placing the carbon electrode modified by the precursor film in the chloroplatinic acid solution for constant potential deposition for 5min at a potential of-0.9 VVS.SCE to deposit platinum on the surface of the precursor film, and washing and drying to obtain the platinum-modified carbon electrode.
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