CN111646903B - A kind of perdeuterated 2,4-dinitroanisole and preparation method thereof - Google Patents
A kind of perdeuterated 2,4-dinitroanisole and preparation method thereof Download PDFInfo
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- CVYZVNVPQRKDLW-UHFFFAOYSA-N 2,4-dinitroanisole Chemical class COC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O CVYZVNVPQRKDLW-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000012043 crude product Substances 0.000 claims abstract description 16
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 238000007789 sealing Methods 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical class CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 150000004075 acetic anhydrides Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical class CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical class CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical class O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002360 explosive Substances 0.000 abstract description 20
- XTFIVUDBNACUBN-UHFFFAOYSA-N 1,3,5-trinitro-1,3,5-triazinane Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)C1 XTFIVUDBNACUBN-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000047 product Substances 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000004060 metabolic process Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000012086 standard solution Substances 0.000 abstract description 2
- 238000005266 casting Methods 0.000 abstract 1
- 238000004880 explosion Methods 0.000 abstract 1
- -1 per-deuterated 2,4-dinitroanisole Nitroanisole Chemical class 0.000 abstract 1
- 238000004321 preservation Methods 0.000 description 4
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052805 deuterium Inorganic materials 0.000 description 3
- 239000003444 phase transfer catalyst Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ARARQWKFKMWCDL-UHFFFAOYSA-N 1-nitro-2-[(2-nitrophenyl)methoxymethyl]benzene Chemical compound [O-][N+](=O)C1=CC=CC=C1COCC1=CC=CC=C1[N+]([O-])=O ARARQWKFKMWCDL-UHFFFAOYSA-N 0.000 description 2
- VJJRVNGOHNKPHB-UHFFFAOYSA-N 1-nitro-4-[(4-nitrophenyl)methoxymethyl]benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1COCC1=CC=C([N+]([O-])=O)C=C1 VJJRVNGOHNKPHB-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 150000001975 deuterium Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- JBBNYKPRONOPHN-UHFFFAOYSA-N hydron;2-methoxy-5-nitroaniline;chloride Chemical compound Cl.COC1=CC=C([N+]([O-])=O)C=C1N JBBNYKPRONOPHN-UHFFFAOYSA-N 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008542 thermal sensitivity Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/05—Isotopically modified compounds, e.g. labelled
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种全氘代2,4‑二硝基苯甲醚及其制备方法，属于氘代含能材料的合成技术领域。本发明以氘代苯甲醚为原料，原料相对易得；粗产物仅需一步提纯步骤，所得产物纯度较高，能够直接配制分析用标准溶液，作为研究代谢过程的氘代内标物。与普通2,4‑二硝基苯甲醚相比，本发明的全氘代2,4‑二硝基苯甲醚的晶体密度增加，同时爆热也有所增加。本发明能够作为钝感熔铸载体炸药，该样品在100℃时对黑索金的溶解度增加至每100g全氘代2,4‑二硝基苯甲醚溶解17g黑索金。本发明操作相对简单，反应周期较短，产品纯度以及产率相对较高，实现对全氘代2,4‑二硝基苯甲醚的制备，为工业上生产全氘代2,4‑二硝基苯甲醚提供参考。The invention relates to a perdeuterated 2,4-dinitroanisole and a preparation method thereof, belonging to the technical field of synthesis of deuterated energetic materials. The method uses deuterated anisole as a raw material, and the raw material is relatively easy to obtain; the crude product only needs one step of purification, and the obtained product has high purity, and can directly prepare a standard solution for analysis as a deuterated internal standard for studying the metabolic process. Compared with common 2,4-dinitroanisole, the crystal density of perdeuterated 2,4-dinitroanisole of the present invention increases, and the explosion heat also increases to some extent. The present invention can be used as an insensitive casting carrier explosive, and the solubility of the sample to hexogen at 100° C. increases to dissolve 17g of hexogen per 100g of per-deuterated 2,4-dinitroanisole. The invention has relatively simple operation, short reaction period, relatively high product purity and high yield, realizes the preparation of per-deuterated 2,4-dinitroanisole, and is an industrially produced per-deuterated 2,4-dinitroanisole Nitroanisole provides a reference.
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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