阅读说明：本技术 一种1-亚硝基-3,5,7-三硝基-1,3,5,7-四氮杂环辛烷的合成方法 (A kind of synthetic method of 1- nitroso -3,5,7- trinitro- -1,3,5,7- tetraazacyclododecane octane ) 是由 罗军 张宇 候天骄 张健 于 2018-05-25 设计创作，主要内容包括：本发明公开了一种合成1-亚硝基-3,5,7-三硝基-1,3,5,7-四氮杂环辛烷的方法。其步骤为：首先是低温下3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷在甲胺盐酸盐和质量分数为96%的发烟硝酸体系中进行硝解反应、亚硝解反应；缓慢滴加水,过滤,水洗,干燥得到1-亚硝基-3,5,7-三硝基-1,3,5,7-四氮杂环辛烷。本方法避免使用硝酸铵,得到的产品纯度高,收率达到78.5%；还避免使用亚硝酸钠或四氧化二氮等,简化了生成工艺、降低了生产成本,减少对环境污染；提高生产安全。(The invention discloses a kind of methods for synthesizing 1- nitroso -3,5,7- trinitro- -1,3,5,7- tetraazacyclododecane octane.The steps include: it is that four azabicyclo [3.3.1] nonane of 3,7- dinitro -1,3,5,7- carries out nitrolysis raction, sub- nitrolysis raction in the fuming nitric aicd system that methylamine hydrochloride and mass fraction are 96% under low temperature first；Water is slowly added dropwise, filters, washing is dried to obtain 1- nitroso -3,5,7- trinitro- -1,3,5,7- tetraazacyclododecane octanes.This method avoids the product purity using ammonium nitrate, obtained high, and yield reaches 78.5%；It also avoids simplifying using sodium nitrite or dinitrogen tetroxide etc. and generating technique, reduce production cost, reduce environmental pollution；Improve production safety.)

1. a kind of 1- nitroso -3,5,7- trinitro- -1,3, the synthetic method of 5,7- tetraazacyclododecane octanes, which is characterized in that packet It includes in the presence of methylamine hydrochloride, by 3,7- dinitro -1,3, smoke of 5,7- tetra- azabicyclo [3.3.1] nonanes in 96wt% The step of nitration reaction prepares target product occurs in nitric acid system,

2. the method as described in claim 1, which is characterized in that reaction temperature is -45 DEG C~-5 DEG C.

3. the method as described in claim 1, which is characterized in that 3,7- dinitros -1,3,5,7- tetra- azabicyclo [3.3.1] nonyls The mol ratio of alkane and 96wt% fuming nitric aicd is 1:20~60.

4. the method as described in claim 1, which is characterized in that 3,7- dinitros -1,3,5,7- tetra- azabicyclo [3.3.1] nonyls Alkane and methylamine hydrochloride mol ratio are 1:1~4.

5. the method as described in claim 1, which is characterized in that the reaction time is 5min~30min.

Technical field

The present invention relates to a kind of 1- nitroso -3,5,7- trinitro- -1,3, the synthetic method of 5,7- tetraazacyclododecane octanes belongs to In energetic material preparation field.

Background technique

Octogen (1,3,5,7- tetranitro -1,3,5,7- tetraazacyclododecane octanes, abbreviation HMX) is that current obtain is advised greatly The best simple substance high energy density compound of the comprehensive performance of mould application.The industrialized production of octogen continues to use improvement substantially Bachmann method, i.e. acetic anhydride method (US2461582,1949).Using methenamine as raw material, in nitric acid-ammonium nitrate-acetic anhydride body Nitre solution is made in system.But there are many disadvantages for acetic anhydride method: (1) aceticanhydride and acetic acid usage amount are big, product yield is low, production cost It is high；(2) discharge of a large amount of spent acid, pollutes environment；(3) due to nitric acid, ammonium nitrate, aceticanhydride, vinegar in nitre solution medium in reaction process The difference of acid material ratio, the difference of feed way and temperature cause to generate many by-products, isolate and purify difficulty.Thus limit Large-scale application of the octogen in China.

Since the 1970s, new method synthesis HMX is constantly reported.Wherein, the small molecule method of China's development (is also referred to as urinated Plain method) it is that DPT then nitre solution preparation HMX is first synthesized using cheap urea and formaldehyde as raw material.Raw material cost is low for this law, It is a kind of HMX preparation method with industrial applications prospect.But the method nitre solution yield with practical application value is not More than 60%, this is also another big bottleneck for influencing small molecule method and realizing engineering.In recent years, DPT nitre solution preparation HMX is ground Studying carefully has new progress, discovery MNX be DPT nitre solution prepare HMX intermediate (Propellants.Explos.Pyrotech., 2015,40(5):645-651；Propellants.Explos.Pyrotech.,2017,42:1208-1213).However MNX system Preparation Method is less to be reported, and Wu Jiarong (explosive wastewater, 1989 (4): 1-5) is solvent with acetonitrile, and DPT is under dinitrogen tetroxide effect The yield for generating MNX is 48%, and it is lower to change method yield.Zhang Yu (Propellants.Explos.Pyrotech., 2017,42: 1208-1213；Patent 201610871430.X；Energetic material, 2018, DIO:10.11943/j.issn.1006- 9941.2018.05.000.) using DPT as raw material, fuming nitric aicd is nitrating agent, and sodium nitrite or dinitrogen tetroxide are nitrosation Agent, the yield for obtaining MNX through nitre solution, nitrous solution are 84%.But this method must be used and be difficult to handle and have explosion danger Property ammonium nitrate and enter sodium nitrite solution or dinitrogen tetroxide, processing step is cumbersome.Therefore, new MNX synthetic method is developed, It is imperative to simplify synthesis technology

Summary of the invention

The purpose of the present invention is to provide a kind of synthesis 1- nitroso -3,5,7- trinitro- -1,3,5,7- tetraazacyclododecane is pungent The new method of alkane.

The technical solution for realizing the aim of the invention is as follows: with four azabicyclo [3.3.1] of 3,7- dinitro -1,3,5,7- Nonane (DPT) is that raw material unstrings in the fuming nitric aicd and methylamine hydrochloride system that mass fraction is 96% through nitre solution-nitrous Connection reaction " treating different things alike " method synthesizes MNX.

The preparation method of above compound, preparation route are as follows:

This method comprises the following steps:

(1) under low temperature stirring, methylamine hydrochloride solid is added in the fuming nitric aicd that mass fraction is 96%, it is molten to its Xie Hou, by 3,7- dinitro -1,3,5,7- tetra- azabicyclo [3.3.1] nonanes are added portionwise, after to be dissolved, stir at such a temperature Mix a period of time；

(2) it is brilliant to be then slow added into a certain amount of elutriation, filters, washing, dry 1- nitroso -3,5,7- trinitro- - 1,3,5,7- tetraazacyclododecane octane.

Reaction temperature described in step (1) is -45 DEG C~-5 DEG C；Molar ratio 1:20~60 of DPT and fuming nitric aicd；DPT It is 1:1~4 with methylamine hydrochloride mol ratio；Reaction time is 5min~30min.

The additional amount of step (2) water is 5mL~40mL.

Compared with prior art, the present invention it is significantly a little: (1) using methylamine hydrochloride as additive, avoid making With the ammonium nitrate for being largely difficult to handle and with explosion hazard；(2) using nitric acid simultaneously as the agent of nitre solution and nitrous solution agent forerunner Body avoids the sodium nitrite or dinitrogen tetroxide very big using toxicity, reduces cost, reduces the pollution to environment, reduces to setting Standby requirement, spent acid can be recycled and be reused with existing method；(3) the method obtains product purity it is high (> 99%) and yield is still maintained at 78% or more.

Specific embodiment