阅读说明：本技术 一种全氘代三过氧化三丙酮的制备方法 (Preparation method of fully deuterated triproperoxytriacetone ) 是由 刘吉平 方祝青 于 2020-06-29 设计创作，主要内容包括：本发明涉及一种全氘代三过氧化三丙酮的制备方法,属于氘代含能材料的合成技术领域。本发明的方法是向物质A中缓慢滴加氘代丙酮,得到混合溶液B；在滴加氘代酸C,静置、洗涤等后得到全氘代三过氧化三丙酮粗品；将步骤二得到的全氘代三过氧化三丙酮粗品加入到溶剂D中,经过升温、降温、抽滤等处理后,得到全氘代三过氧化三丙酮晶体；该方法操作相对简单,反应条件温和,产品产率相对较高,实现了对全氘代三过氧化三丙酮的制备。产物全氘代三过氧化三丙酮的纯度高,化学性质稳定,可以直接配制分析用标准溶液,作为分析检测三过氧化三丙酮时的氘代内标物。(The invention relates to a preparation method of deuterated triproperoxytriacetone, belonging to the technical field of synthesis of deuterated energetic materials. Slowly dropwise adding deuterated acetone into the substance A to obtain a mixed solution B; dropping deuterated acid C, standing, washing and the like to obtain a crude product of the deuterated triproperoxytriacetone; adding the crude product of the deuterated tripropionine peroxide obtained in the step two into a solvent D, and carrying out treatment such as heating, cooling, suction filtration and the like to obtain a deuterated tripropionine peroxide crystal; the method is relatively simple to operate, mild in reaction conditions and relatively high in product yield, and the preparation of the deuterated tripropanone is realized. The product of the deuterated tripropionone trioxide has high purity and stable chemical property, and can be directly used for preparing standard solution for analysis as a deuterated internal standard substance for analyzing and detecting the tripropionone trioxide.)

1. A preparation method of deuterated triproperoxytriacetone is characterized by comprising the following steps: the method comprises the following steps:

placing a pressure-resistant container filled with a substance A in a high-precision medium-temperature circulating bath at the temperature of-15 to-5 ℃, slowly dropwise adding deuterated acetone into the substance A at a dropwise adding rate of 0.3 to 3mL/min through a constant-pressure dropping funnel, wherein the molar ratio of the substance A to the deuterated acetone is (1 to 2) to 1, starting stirring and adding a catalyst after dropwise adding is finished, wherein the mass ratio of the catalyst to the substance A is 1 (5 to 10), and stirring for 30 to 60 minutes to obtain a mixed solution B;

step two, dropping 20-40% of deuterated acid C into the mixed solution B at the speed of 0.3-3 mL/min through a constant-pressure dropping funnel, wherein the molar ratio of the deuterated acid C to the deuterated acetone is (0.5-1): 1, stirring at the speed of 50-100 rpm while dropping, maintaining the temperature of the solution at-10-0 ℃, standing the mixed solution at room temperature for 24-48 hours after dropping, performing suction filtration, and alternately washing filter residues with sodium carbonate deionized water solution and deionized water until the pH of the filtrate is neutral to obtain a crude product of the deuterated triproprione peroxide;

placing a pressure-resistant container filled with a solvent D in a high-precision medium-temperature circulating bath, adding the crude fully deuterated tripropionone peroxide obtained in the second step into the solvent D, wherein the mass ratio of the solvent D to the crude fully deuterated tripropionone peroxide is (2-5): 1, heating the reaction device to 40-60 ℃, stirring the mixture to dissolve the solid, cooling the mixture to 10-20 ℃, cooling the mixture to 1-10 ℃/min, then cooling the mixture to 0-5 ℃, cooling the mixture to 0.5-1 ℃/min, performing suction filtration, washing the filter residues with deionized water at the temperature of not higher than 5 ℃ for 3-5 times, and performing vacuum drying at the temperature of 20-40 ℃ for 12-24 hours to obtain fully deuterated tripropionone peroxide crystals;

the substance A in the first step is one of a deuterium peroxide solution with the concentration of 30-60%, deuterated dibenzoyl peroxide and deuterated methyl ethyl ketone peroxide.

2. The method of claim 1, wherein: the catalyst in the first step is one of magnesium trichloride, stannic chloride, boron trifluoride and boron trichloride.

3. The method of claim 1, wherein: the deuterated acid C in the second step is one of deuterated hydrochloric acid, deuterated sulfuric acid, deuterated nitric acid, deuterated phosphoric acid and deuterated acetic acid.

4. The method of claim 1, wherein: the solvent D in the third step is one or a mixture of more of deionized water, methanol, ethanol, glycol, propanol and glycerol.

Technical Field

The invention relates to a preparation method of deuterated triproperoxytriacetone, belonging to the synthesis technology of deuterated energetic materials.

Background

Tripropionone peroxide is a simple but powerful explosive, the molecular structure of which is formed by three acetone molecules connected together through O-O bonds. It does not contain nitrogen, can be easily detected by many explosive detectors, and the raw materials of the explosive are readily available, and therefore are often selected by terrorists, including suicide bombers. In recent years, the illegal tripropionone preparation event obtained by law enforcement departments is rare, the obtained sample needs to be detected in the law enforcement process, however, a reliable detection method needs to add a deuterated internal standard substance, but at present, no report on the synthesis of the deuterated tripropionone exists in China, and therefore the problem of synthesizing the fully deuterated tripropionone is urgently solved.

In the reported literature of the synthesis of common tripropionone peroxide at present, patent CN102584783A discloses a preparation method of tripropionone peroxide, in the method, acetone and peroxide are uniformly mixed, an acid catalyst is slowly added into the mixed solution in a dropwise manner, a large amount of white precipitate is generated by stirring reaction, and then ice water is added for washing and suction filtration, so as to obtain the tripropionone peroxide crystal. In 2011, Fitzgerald et al prepared triacetonene trioxide from acetone and hydrogen peroxide as raw materials and sulfuric acid as a catalyst. The tripropioperone crystal prepared by the method has low purity and contains a small amount of impurities such as diproponone diperoxide (Journal of Forensic Sciences,2011,56(5): 1143-1149). In addition, the products obtained by the above methods are all non-deuterated tripropionone trioxide, and if the raw materials are simply replaced by deuterated raw materials to prepare the deuterated tripropionone trioxide, the yield of the obtained products is low, the purity is not high, and the application requirements cannot be met. Therefore, it is required to develop a new method for efficiently preparing the deuterated tripropanone peroxide.

Disclosure of Invention

The invention aims to provide a preparation method of deuterated tripropanone peroxide. The method is relatively simple to operate, mild in reaction conditions and relatively high in product yield, realizes the preparation of the deuterated tripropionone and provides reference for batch preparation of the deuterated tripropionone.

The purpose of the invention is realized by the following technical scheme.

A preparation method of deuterated triproperoxytriacetone comprises the following steps:

placing a pressure-resistant container filled with a substance A in a high-precision medium-temperature circulating bath at the temperature of-15 to-5 ℃, slowly dropwise adding deuterated acetone into the substance A at a dropwise adding rate of 0.3 to 3mL/min through a constant-pressure dropping funnel, wherein the molar ratio of the substance A to the deuterated acetone is (1 to 2) to 1, starting stirring and adding a catalyst after dropwise adding is finished, wherein the mass ratio of the catalyst to the substance A is 1 (5 to 10), and stirring for 30 to 60 minutes to obtain a mixed solution B;

step two, dropping 20-40% of deuterated acid C into the mixed solution B at the speed of 0.3-3 mL/min through a constant-pressure dropping funnel, wherein the molar ratio of the deuterated acid C to the deuterated acetone is (0.5-1): 1, stirring at the speed of 50-100 rpm while dropping, maintaining the temperature of the solution at-10-0 ℃, standing the mixed solution at room temperature for 24-48 hours after dropping, performing suction filtration, and alternately washing filter residues with sodium carbonate deionized water solution and deionized water until the pH of the filtrate is neutral to obtain a crude product of the deuterated triproprione peroxide;

placing a pressure-resistant container filled with a solvent D in a high-precision medium-temperature circulating bath, adding the crude fully deuterated tripropionone peroxide obtained in the second step into the solvent D, wherein the mass ratio of the solvent D to the crude fully deuterated tripropionone peroxide is (2-5): 1, heating the reaction device to 40-60 ℃, stirring the mixture to dissolve the solid, cooling the mixture to 10-20 ℃, cooling the mixture to 1-10 ℃/min, then cooling the mixture to 0-5 ℃, cooling the mixture to 0.5-1 ℃/min, performing suction filtration, washing the filter residues with deionized water at the temperature of not higher than 5 ℃ for 3-5 times, and performing vacuum drying at the temperature of 20-40 ℃ for 12-24 hours to obtain fully deuterated tripropionone peroxide crystals;

the substance A in the first step is one of a deuterium peroxide solution with the concentration of 30-60%, deuterated dibenzoyl peroxide and deuterated methyl ethyl ketone peroxide.

The catalyst in the first step is one of magnesium trichloride, stannic chloride, boron trifluoride and boron trichloride.

And the deuterated acid C in the second step is one of deuterated hydrochloric acid, deuterated sulfuric acid, deuterated nitric acid, deuterated phosphoric acid and deuterated acetic acid.

The solvent D in the third step is one or a mixture of more of deionized water, methanol, ethanol, glycol, propanol and glycerol.

And the reaction containers in the first step, the second step and the third step are all provided with a mechanical stirring, a constant pressure dropping funnel and a condenser.

Advantageous effects

(1) The preparation method of the deuterated triproperoxytriacetone has the advantages of relatively simple operation, mild reaction conditions and relatively high product yield.

(2) The product of the deuterated tripropionone trioxide has high purity and stable chemical property, and can be directly used for preparing standard solution for analysis as a deuterated internal standard substance for analyzing and detecting the tripropionone trioxide.

(3) Compared with the common tripropionone trioxide, the impact sensitivity of the fully deuterated tripropionone trioxide is reduced, and the fully deuterated tripropionone trioxide is beneficial to the application in criminal investigation and scientific research.

Detailed Description

The present invention will be further described with reference to the following examples.