Method of synthesizing 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt

A technology of dioxodihydroxyammonium salt and bistetrazole, which is applied in the direction of organic chemistry, can solve the problems of thermal stability and mechanical stability reduction, aromatic nitro and nitramine toxicity, and increase the difficulty of post-treatment, etc., to achieve The effect of cost reduction, reduction of reaction solvent types, and shortened synthesis cycle

Inactive Publication Date: 2015-01-14
HUBEI INST OF AEROSPACE CHEMOTECHNOLOGY
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] However, these energetic compounds have some disadvantages: aromatic nitro groups and nitramines are somewhat toxic; too many ring and cage strain compounds generally have a long synthetic route (high cost); when high nitrogen compounds each ring or chain An increase in the number of nitrogen atoms on the upper surface will lead to a decrease in thermal and mechanical stability
[0017] However, this method requires multiple replacements of different solvents, especially the use of a large amount of ether, which greatly increases the risk of large-scale production, and the use of hydrogen chloride gas as a catalyst increases the difficulty of product post-processing.

Method used

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  • Method of synthesizing 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt
  • Method of synthesizing 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt
  • Method of synthesizing 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt

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Experimental program
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Embodiment 1

[0037] Add 156.0 g (1.0 mol) of dichloroglyoxime to a 2000 ml three-necked flask, and add 1000 ml of methanol solvent. After the methanol solution of dichloroglyoxime was cooled to -40°C, 65.0 g (1.0 mol) of sodium azide was added dropwise to the solution in batches, and stirring was started. After the addition was complete, the reaction was carried out for 0.5 hour and then slowly returned to room temperature. The temperature of the reaction liquid after azidation was lowered to -40° C., hydrogen chloride was passed through, and the reaction was carried out for 1 hour. After purification, the intermediate product 1,1'-dihydroxy-5,5'-bistetrazole was obtained. Dissolve 1,1'-dihydroxy-5,5'-bistetrazole in 500ml of water, add 50g of hydroxide Sodium, stirred and reacted, then 50 g of hydroxylamine hydrochloride was added for reaction to obtain 212.5 g of 5,5'-bistetrazole-1,1'-dioxydihydroxyammonium salt with a yield of 90%.

Embodiment 2

[0038]Example 2: 312.0 g (2 mol) of dichloroglyoxime was added to a 2000 ml three-necked flask, and 1000 ml of propylene glycol solvent was added. After cooling the propylene glycol solution of p-dichloroglyoxime to 0°C, add 117.0 g (1.8 mol) of sodium azide to the solution and start stirring. After the addition was complete, the reaction was carried out for 10 hours and then slowly raised to room temperature. Keep the reaction liquid after azidation at 40°C, add 1 L of 98% concentrated sulfuric acid dropwise, react for 15 hours, and obtain the intermediate product 1,1'-dihydroxy-5,5'-bistetrazole after purification. Dissolve 1,1'-dihydroxy-5,5'-bistetrazole in 1000ml of water, add 100g of sodium hydroxide, stir for reaction, then add 100g of hydroxylamine hydrochloride for reaction to obtain 5,5'-bistetrazole-1,1 401.5 g of '-dioxydihydroxyammonium salt, the yield is 85%.

Embodiment 3

[0040] Add 7.8kg (50mol) of dichloroglyoxime to a 50L reactor, and add 30L of ethanol solvent. After cooling the ethanol solution of dichloroglyoxime to 20°C, start adding 3.8kg (60mol) of sodium azide to the solution and start stirring. After the addition was complete, the reaction was carried out for 24 hours, and the temperature was slowly raised to room temperature. Cool the reaction liquid after azidation to 0°C, add 10L polystyrene sulfonic acid resin, stir for 24 hours, and purify to obtain the intermediate product 1,1'-dihydroxy-5,5'-bistetrazole , Dissolve 1,1'-dihydroxy-5,5'-bistetrazole in 20L of water, add 1kg of sodium hydroxide, stir for reaction, then add 1kg of hydroxylamine hydrochloride for reaction, and obtain 5,5'-bistetrazole-1 , 9.45kg of 1'-dioxydihydroxyammonium salt, the yield was 80%.

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Abstract

The invention discloses a method of synthesizing a 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt. The method comprises the following step: synthesizing the 5,5'-bistetrazole-1,1'-dioxodihydroxy ammonium salt by taking dichloroglyoxime, sodium azide, sodium hydroxide and hydroxylamine hydrochloride as raw materials and adopting alcohol solvents by virtue of azidation reaction, acid catalysis cyclization reaction and salt forming reaction. Compared with the prior art, the two-step reaction adopted by the method disclosed by the invention only adopts one solvent, so that not only can type of solvents be reduced, but also the after-treatment process of the azidation reaction can be cancelled. Meanwhile, the types of catalytic acids are expanded, the difficulty of the production process is lowered, the total yield of the reaction is increased, and thus, the method is an efficient and low-cost synthetic method.

Description

technical field [0001] The present invention relates to a new type of insensitive high-energy compound—5,5'-bistetrazole-1,1'-dioxydihydroxyammonium salt (molecular formula is C 2 h 8 N 10 o 4 ) new synthesis method. The energetic compound can not only achieve the goal of being a green substitute for traditional explosive RDX, but also has far better performance than RDX; at the same time, due to its high nitrogen content, it can also realize the anti-toxicity effect on gas generant components such as triaminoguanidine nitrate (TAGN) substitute. Background technique [0002] Researchers have conducted extensive research on the design of new energetic compounds, and the difference between everyone's research lies in the way of increasing internal energy. [0003] The energy of the traditional energetic materials RDX and TNT comes from the oxidation of the oxygen in the molecule to the carbon atoms of the skeleton; ring or cage strained ring compounds ONC and TNAZ further...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D257/04
CPCC07D257/04
Inventor 何金选叶丹阳卢艳华雷晴郭滢媛丁宁曹一林
Owner HUBEI INST OF AEROSPACE CHEMOTECHNOLOGY
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