CN111646903B - Fully deuterated 2, 4-dinitroanisole and preparation method thereof - Google Patents
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Abstract
The invention relates to a fully deuterated 2, 4-dinitroanisole and a preparation method thereof, belonging to the technical field of synthesis of deuterated energetic materials. The invention takes deuterated anisole as the raw material, and the raw material is relatively easy to obtain; the crude product only needs one purification step, the purity of the obtained product is high, and a standard solution for analysis can be directly prepared and used as a deuterated internal standard substance for researching the metabolic process. Compared with the common 2, 4-dinitroanisole, the crystal density of the fully deuterated 2, 4-dinitroanisole is increased, and the explosive heat is also increased. The invention can be used as a insensitive fusion casting carrier explosive, and the solubility of the sample to hexogen is increased to 17g of hexogen dissolved in every 100g of fully deuterated 2, 4-dinitroanisole at 100 ℃. The method has the advantages of relatively simple operation, short reaction period, relatively high product purity and yield, realizes the preparation of the deuterium-substituted 2, 4-dinitroanisole, and provides reference for the industrial production of the deuterium-substituted 2, 4-dinitroanisole.
Description
Technical Field
The invention relates to a fully deuterated 2, 4-dinitroanisole and a preparation method thereof, belonging to the technical field of synthesis of deuterated energetic materials.
Background
2, 4-dinitroanisole is the most studied insensitive fused cast carrier explosive at present and has gained much attention since 1849. Compared with common fusion-cast explosive TNT, the 2, 4-dinitroanisole has relatively low shock wave sensitivity and thermal sensitivity, the fusion-cast explosive has relatively ideal mechanical properties, good elastic toughness and high strength, and the internal part of the fusion-cast explosive is not easy to crack. And 2, 4-dinitroanisole is also an important chemical dye intermediate for producing scarlet base RC (2-methoxy-5-nitroaniline hydrochloride). In addition, the 2, 4-dinitroanisole can be used as an insecticide with excellent performance.
Compared with 2, 4-dinitroanisole, the deuterium-substituted 2, 4-dinitroanisole has obvious mass difference between deuterium and hydrogen, so that the density of the fused cast explosive based on the deuterium-substituted 2, 4-dinitroanisole is increased, and the detonation performance is improved. In addition, the metabolic process and metabolic products of the 2, 4-dinitroanisole in the animal body can be researched by replacing the hydrogen atom in the 2, 4-dinitroanisole with a deuterium atom. Therefore, the synthesis of the deuterated 2, 4-dinitroanisole has important research significance and application value.
At present, there are many reports on the synthesis of 2, 4-dinitroanisole. 2010 summer loyalty et al synthesizes 2, 4-dinitroanisole by using 2, 4-dinitrobenzene as a raw material and benzyltriethylammonium chloride as a phase transfer catalyst; although the method obtains the 2, 4-dinitroanisole, the phase transfer catalyst is not easy to prepare and has relatively high cost, and the method is not suitable for large-scale use. Liuyan et al 2016 (synthetic chemistry, 2016,24(10):907-910) used 1-chloro-2, 4-dinitrobenzene (CDNB) as a raw material and KOH solution as a reaction medium to synthesize 2, 4-dinitroanisole in one step without using a phase transfer catalyst; the method has narrow optimal synthesis temperature range, and the product purity and yield are reduced more when the temperature deviates from the optimal temperature, thus being not beneficial to industrial operation. Patent CN1861565A discloses a process for preparing 2, 4-dinitroanisole by batch nitration of nitroanisole. The method respectively takes 4-nitrobenzyl ether, 2-nitrobenzyl ether, a mixture of 4-nitrobenzyl ether and 2-nitrobenzyl ether as raw materials, and prepares the 2, 4-dinitroanisole through batch nitration reaction, liquid-liquid separation, cooling crystallization, but the method has more complex operation and low purity of the obtained product. Patent CN106748798A discloses a method for synthesizing 2, 4-dinitroanisole. The method takes 2, 4-dinitrochlorobenzene as a raw material, uses methanol as a solvent, and reacts with sodium methoxide to synthesize 2, 4-dinitroanisole under mild conditions; the method has a long reaction period and is not beneficial to industrial production. In addition, the products obtained by the method are all non-deuterated 2, 4-dinitroanisole, and the preparation of the fully deuterated 2, 4-dinitroanisole cannot be realized by simply replacing deuterated raw materials. Therefore, a new method for efficiently preparing the deuterated 2, 4-dinitroanisole is needed to be developed.
Disclosure of Invention
The invention aims to provide a preparation method of deuterated 2, 4-dinitroanisole. The method is relatively simple to operate, short in reaction period and relatively high in product purity and yield, realizes the preparation of the deuterium-substituted 2, 4-dinitroanisole, and provides reference for the industrial production of the deuterium-substituted 2, 4-dinitroanisole.
The object of the present invention is achieved by the following steps.
A deuterated 2, 4-dinitroanisole has a structural formula:
a deuterium substituted 2, 4-dinitroanisole and a preparation method thereof comprise the following steps:
placing a pressure-resistant container filled with a substance A and carbon tetrachloride in an environment at the temperature of-5-0 ℃, dropwise adding 95-98% deuterated nitric acid into the container through a constant-pressure dropping funnel, wherein the molar ratio of the deuterated nitric acid to the substance A is (5-10): 1, mechanically stirring at the speed of 100-300 rpm while dropwise adding, maintaining the temperature of the mixed solution to be not higher than 5 ℃, and heating to 25-30 ℃ after dropwise adding to obtain a deuterated mixed acid solution B;
slowly adding deuterated anisole into the deuterated mixed acid solution B obtained in the step one in batches, wherein the molar ratio of deuterated anisole to deuterated nitric acid is 1 (15-22), then adding a substance C, wherein the mass ratio of the substance C to deuterated anisole is 1:10, sealing the reaction device, maintaining the temperature of the whole reaction system at 25-30 +/-0.5 ℃, stirring at the speed of 400-700 rpm for 4-6 hours, pouring the mixed solution into deionized water at the temperature of not higher than 5 ℃, stirring at the speed of 50-100 rpm for 0.5-1 hour, performing suction filtration, washing the filter residues with deionized water at the temperature of not higher than 5 ℃, and obtaining a deuterated 2, 4-dinitroanisole crude product until the pH value of the filtrate is neutral;
mixing deuterated ethyl acetate and deuterated n-hexane in a mass ratio of 1 (4-6) to obtain a mixed solution C, heating the solution C to 70-75 ℃, adding the deuterated 2, 4-dinitroanisole crude product obtained in the step two into the mixed solution C, wherein the mass ratio of the deuterated 2, 4-dinitroanisole crude product to the mixed solution A is 1 (10-15), sealing the reaction device, stirring at a speed of 50-80 rpm for 10-20 minutes, filtering while hot, cooling the filtrate to a temperature not higher than 5 ℃, standing for 0.5-1 hour, performing suction filtration, washing the filtrate with deionized water at a temperature not higher than 5 ℃ for 3-5 times, and performing vacuum drying at a temperature of 20-60 ℃ to obtain deuterated 2, 4-dinitroanisole crystals.
In the first step, the mass ratio of the substance A to the carbon tetrachloride is 1 (6-12).
In the first step, the substance A is one of deuterated acetic anhydride, deuterated propionic anhydride, deuterated butyric anhydride and deuterated succinic anhydride.
In the first step, the dropping rate of the deuterated nitric acid is 0.3-3 mL/min.
And a pressure-resistant container in the first step is provided with a mechanical stirring device, a constant-pressure dropping funnel and a condenser.
In the second step, the substance C is one of sodium nitrate, potassium nitrate, nickel nitrate and zinc nitrate.
Advantageous effects
(1) According to the fully deuterated 2, 4-dinitroanisole and the preparation method thereof, the deuterated anisole is used as a raw material, and the raw material is relatively easy to obtain; the crude product only needs one purification step, the purity of the obtained product is high, and a standard solution for analysis can be directly prepared and used as a deuterated internal standard substance for researching the metabolic process.
(2) Compared with the common 2, 4-dinitroanisole, the crystal density of the fully deuterated 2, 4-dinitroanisole is increased, and the explosive heat is also increased. As a insensitive fusion cast carrier explosive, the solubility of this sample to hexogen was increased to 17g of hexogen per 100g of deuterated 2, 4-dinitroanisole dissolved at 100 ℃.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Placing a pressure-resistant container with the volume of 50mL and containing 6.5g of deuterated acetic anhydride and 51g of carbon tetrachloride in a high-precision moderate-temperature circulating bath at the temperature of-5 ℃, dropwise adding 98% deuterated nitric acid into the container at the speed of 0.5mL/min through a constant-pressure dropping funnel, mechanically stirring at the speed of 150rpm while dropwise adding, maintaining the temperature of the mixed solution to be not higher than 5 ℃, and after 28 minutes, raising the temperature of the mixed solution to 30 ℃; slowly adding 2.3g of deuterated anisole into the mixed solution in 4 batches, maintaining the temperature of the mixed solution to be 30 +/-0.5 ℃ in the adding process, then adding 0.23g of sodium nitrate, sealing the reaction device after the adding is finished, increasing the stirring speed to 400rpm, pouring the mixed solution into 10mL of deionized water with the temperature of 5 ℃ after the heat preservation is carried out for 4 hours, stirring for 0.5 hour at the speed of 50rpm, carrying out suction filtration, washing the filter residue with the deionized water with the temperature of 5 ℃ until the pH value of the filtrate is neutral, and obtaining 3.9g of deuterated 2, 4-dinitroanisole crude product; adding 8g of deuterated ethyl acetate into 32g of deuterated n-hexane to obtain a uniform solution, transferring the solution into a three-port pressure-resistant device with the volume of 100mL, heating to 70 ℃, adding 3.9g of deuterated 2, 4-dinitroanisole crude product, sealing the reaction device, stirring at the speed of 50rpm for 10 minutes, filtering while hot, cooling the filtrate to 5 ℃, standing for 0.5 hour, performing suction filtration, washing the filter residue with deionized water at the temperature of 5 ℃, and performing vacuum drying at the temperature of 40 ℃ for 12 hours to obtain 3.5g of deuterated 2, 4-dinitroanisole, wherein the yield is 85.5%, and the purity is 99.7%.
The product obtained by the test has a crystal density of 1.586g/cm3And a crystal density of 2, 4-dinitroanisole (1.542 g/cm)3) Compared with the prior art, the method has the advantages that (1) the yield is increased; the explosive heat of the product was found to be 3894kJ/mol, which is likewise increased in comparison with the explosive heat of 2, 4-dinitroanisole (3856 kJ/mol). As a passive melt-cast carrier explosive, the solubility of the sample to hexogen is also increased at 100 ℃, from 14g of hexogen dissolved per 100g of 2, 4-dinitroanisole to 17g of hexogen dissolved per 100g of fully deuterated 2, 4-dinitroanisole.
Example 2
Placing a pressure-resistant container with the volume of 100mL and containing 20.5g of deuterated acetic anhydride and 175g of carbon tetrachloride in a high-precision moderate-temperature circulating bath at the temperature of-5 ℃, dropwise adding 95% deuterated nitric acid into the container at the speed of 1mL/min through a constant-pressure dropping funnel, mechanically stirring at the speed of 150rpm while dropwise adding, maintaining the temperature of the mixed solution to be not higher than 5 ℃, and after 51 minutes, heating the temperature of the mixed solution to 25 ℃; slowly adding 8.4g of deuterated anisole into the mixed solution in 6 batches, maintaining the temperature of the mixed solution to be 25 +/-0.5 ℃ in the adding process, then adding 0.84g of potassium nitrate, sealing the reaction device after the adding is finished, increasing the stirring speed to 400rpm, pouring the mixed solution into 25mL of deionized water with the temperature of 5 ℃ after the heat preservation is carried out for 4 hours, stirring for 1 hour at the speed of 50rpm, carrying out suction filtration, washing the filter residue with the deionized water with the temperature of 5 ℃ until the pH value of the filtrate is neutral, and obtaining 13.5g of deuterated 2, 4-dinitroanisole crude product; adding 27g of deuterated ethyl acetate into 108g of deuterated n-hexane to obtain a uniform solution, transferring the solution into a three-port pressure-resistant device with the volume of 200mL, heating to 70 ℃, adding 13.5g of deuterated 2, 4-dinitroanisole crude product, sealing the reaction device, stirring at the speed of 50rpm for 20 minutes, filtering while hot, cooling the filtrate to 5 ℃, standing for 0.5 hour, performing suction filtration, washing the filter residue with 5 ℃ deionized water for 3 times, and performing vacuum drying at 40 ℃ for 12 hours to obtain 11.8g of deuterated 2, 4-dinitroanisole, wherein the yield is 80.5%, and the purity is 99.5%.
The product obtained by the test had a crystal density of 1.584g/cm3And a crystal density of 2, 4-dinitroanisole (1.542 g/cm)3) Compared with the prior art, the method has the advantages that (1) the yield is increased; the explosive heat of the product was found to be 3892kJ/mol, which is likewise increased in comparison with the explosive heat of 2, 4-dinitroanisole (3856 kJ/mol). As a passive melt-cast carrier explosive, the solubility of the sample to hexogen is also increased at 100 ℃, from 14g of hexogen dissolved per 100g of 2, 4-dinitroanisole to 17g of hexogen dissolved per 100g of fully deuterated 2, 4-dinitroanisole.
Example 3
Placing a pressure-resistant container with the volume of 100mL and containing 23.5g of deuterated propionic anhydride and 190g of carbon tetrachloride in a high-precision moderate-temperature circulating bath at the temperature of-5 ℃, dropwise adding 98% deuterated nitric acid into the container at the speed of 1mL/min through a constant-pressure dropping funnel, mechanically stirring at the speed of 200rpm while dropwise adding, maintaining the temperature of the mixed solution to be not higher than 5 ℃, and after 36 minutes, raising the temperature of the mixed solution to 25 ℃; slowly adding 6.5g of deuterated anisole into the mixed solution in 5 batches, maintaining the temperature of the mixed solution to be 25 +/-0.5 ℃ in the adding process, then adding 0.654g of nickel nitrate, sealing the reaction device after the adding is finished, increasing the stirring speed to 400rpm, pouring the mixed solution into 20mL of deionized water with the temperature of 5 ℃ after the heat preservation is carried out for 5 hours, stirring for 0.5 hour at the speed of 50rpm, carrying out suction filtration, washing the filter residue with the deionized water with the temperature of 5 ℃ until the pH value of the filtrate is neutral, and obtaining 10.7g of deuterated 2, 4-dinitroanisole crude product; adding 22g of deuterated ethyl acetate into 88g of deuterated n-hexane to obtain a uniform solution, transferring the solution into a three-port pressure-resistant device with the volume of 200mL, heating to 70 ℃, adding 10.7g of deuterated 2, 4-dinitroanisole crude product, sealing the reaction device, stirring at the speed of 50rpm for 15 minutes, filtering while hot, cooling the filtrate to 5 ℃, standing for 0.5 hour, performing suction filtration, washing the filter residue with 5 ℃ deionized water for 3 times, and performing vacuum drying at 40 ℃ for 12 hours to obtain 9.6g of deuterated 2, 4-dinitroanisole, wherein the yield is 84.1%, and the purity is 99.4%.
The product obtained by the test had a crystal density of 1.582g/cm3And a crystal density of 2, 4-dinitroanisole (1.542 g/cm)3) Compared with the prior art, the method has the advantages that (1) the yield is increased; the explosive heat of the product was determined to be 3889kJ/mol, which is likewise increased in comparison with the explosive heat of 2, 4-dinitroanisole (3856 kJ/mol). As a passive melt-cast carrier explosive, the solubility of the sample to hexogen is also increased at 100 ℃, from 14g of hexogen dissolved per 100g of 2, 4-dinitroanisole to 17g of hexogen dissolved per 100g of fully deuterated 2, 4-dinitroanisole.
Example 4
Placing a pressure-resistant container with the volume of 100mL and containing 25.8g of deuterated butyric anhydride and 165g of carbon tetrachloride in a high-precision moderate-temperature circulating bath at the temperature of-5 ℃, dropwise adding 98% deuterated nitric acid into the container at the speed of 1mL/min through a constant-pressure dropping funnel, mechanically stirring at the speed of 250rpm while dropwise adding, maintaining the temperature of the mixed solution to be not higher than 5 ℃, and after 33 minutes, raising the temperature of the mixed solution to 27 ℃; slowly adding 4.3g of deuterated anisole into the mixed solution in 5 batches, maintaining the temperature of the mixed solution to be 27 +/-0.5 ℃ in the adding process, then adding 0.43g of zinc nitrate, sealing the reaction device after the adding is finished, increasing the stirring speed to 400rpm, pouring the mixed solution into 20mL of deionized water with the temperature of 5 ℃ after the heat preservation is carried out for 6 hours, stirring for 0.5 hour at the speed of 50rpm, carrying out suction filtration, washing the filter residue with the deionized water with the temperature of 5 ℃ until the pH value of the filtrate is neutral, and obtaining 7.4g of deuterated 2, 4-dinitroanisole crude product; adding 20g of deuterated ethyl acetate into 60g of deuterated n-hexane to obtain a uniform solution, transferring the solution into a three-port pressure-resistant device with the volume of 200mL, heating to 72 ℃, adding 10.7g of deuterated 2, 4-dinitroanisole crude product, sealing the reaction device, stirring at the speed of 70rpm for 20 minutes, filtering while hot, cooling the filtrate to 5 ℃, standing for 0.75 hour, performing suction filtration, washing the filter residue with 5 ℃ deionized water for 3 times, and performing vacuum drying at 40 ℃ for 12 hours to obtain 7.0g of deuterated 2, 4-dinitroanisole, wherein the yield is 91.7%, and the purity is 99.9%.
The product obtained was tested for a crystal density of 1.587g/cm3And a crystal density of 2, 4-dinitroanisole (1.542 g/cm)3) Compared with the prior art, the method has the advantages that (1) the yield is increased; the explosive heat of the product was found to be 3898kJ/mol, which is likewise increased in comparison with the explosive heat of 2, 4-dinitroanisole (3856 kJ/mol). As a passive melt-cast carrier explosive, the solubility of the sample to hexogen is also increased at 100 ℃, from 14g of hexogen dissolved per 100g of 2, 4-dinitroanisole to 17g of hexogen dissolved per 100g of fully deuterated 2, 4-dinitroanisole.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (4)
1. A preparation method of deuterium-substituted 2, 4-dinitroanisole is characterized by comprising the following steps: the method comprises the following steps:
placing a pressure-resistant container filled with a substance A and carbon tetrachloride in an environment at the temperature of-5-0 ℃, dropwise adding 95-98% deuterated nitric acid into the container through a constant-pressure dropping funnel, wherein the molar ratio of the deuterated nitric acid to the substance A is (5-10): 1, mechanically stirring at the speed of 100-300 rpm while dropwise adding, maintaining the temperature of the mixed solution to be not higher than 5 ℃, and heating to 25-30 ℃ after dropwise adding to obtain a deuterated mixed acid solution B; the substance A is one of deuterated acetic anhydride, deuterated propionic anhydride, deuterated butyric anhydride and deuterated succinic anhydride;
slowly adding deuterated anisole into the deuterated mixed acid solution B obtained in the step one in batches, wherein the molar ratio of deuterated anisole to deuterated nitric acid is 1 (15-22), then adding a substance C, wherein the mass ratio of the substance C to deuterated anisole is 1:10, sealing the reaction device, maintaining the temperature of the whole reaction system at 25-30 +/-0.5 ℃, stirring at the speed of 400-700 rpm for 4-6 hours, pouring the mixed solution into deionized water at the temperature of not higher than 5 ℃, stirring at the speed of 50-100 rpm for 0.5-1 hour, performing suction filtration, washing the filter residues with deionized water at the temperature of not higher than 5 ℃, and obtaining a deuterated 2, 4-dinitroanisole crude product until the pH value of the filtrate is neutral; the substance C is one of sodium nitrate, potassium nitrate, nickel nitrate and zinc nitrate;
mixing deuterated ethyl acetate and deuterated n-hexane in a mass ratio of 1 (4-6) to obtain a mixed solution C, heating the solution C to 70-75 ℃, adding the deuterated 2, 4-dinitroanisole crude product obtained in the step two into the mixed solution C, wherein the mass ratio of the deuterated 2, 4-dinitroanisole crude product to the mixed solution A is 1 (10-15), sealing the reaction device, stirring at a speed of 50-80 rpm for 10-20 minutes, filtering while hot, cooling the filtrate to a temperature not higher than 5 ℃, standing for 0.5-1 hour, performing suction filtration, washing the filtrate with deionized water at a temperature not higher than 5 ℃ for 3-5 times, and performing vacuum drying at a temperature of 20-60 ℃ to obtain deuterated 2, 4-dinitroanisole crystals;
the structural formula of the deuterated 2, 4-dinitroanisole is as follows:
2. the method of claim 1, wherein the method comprises the steps of: in the first step, the mass ratio of the substance A to the carbon tetrachloride is 1 (6-12).
3. The method of claim 1, wherein the method comprises the steps of: in the first step, the dropping rate of the deuterated nitric acid is 0.3-3 mL/min.
4. The method of claim 1, wherein the method comprises the steps of: and a pressure-resistant container in the first step is provided with a mechanical stirring device, a constant-pressure dropping funnel and a condenser.
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