CN107619394B

CN107619394B - A kind of synthetic method of 2,6- diamino -3,5- dinitro pyrazine -1- oxide

Info

Publication number: CN107619394B
Application number: CN201711105716.8A
Authority: CN
Inventors: 张蒙蒙; 李媛; 王友兵; 周杰文
Original assignee: Xian Modern Chemistry Research Institute
Current assignee: Xian Modern Chemistry Research Institute
Priority date: 2017-11-10
Filing date: 2017-11-10
Publication date: 2019-07-23
Anticipated expiration: 2037-11-10
Also published as: CN107619394A

Abstract

The present invention relates to one kind 2; 6- diamino -3; the synthetic method of 5- dinitro pyrazine -1- oxide, the method are to utilize acetic anhydride by 2,6- diamino -3; acylated 5- dinitro pyrazine is readily soluble acetylate; 2 are obtained with 2,6- diamino -3,5- dinitro pyrazine of hydrogen peroxide oxidation acetylation and hydrolysis again; 6- Diamino-3,5-dinitropyrazine-1-oxide.Method provided by the invention has the characteristics that the reaction time is short, it is simple to form without solid catalyst residue, waste liquid.The present invention is used for the synthesis of 2,6- diamino -3,5- dinitro pyrazine -1- oxide.

Description

A kind of synthetic method of 2,6- diamino -3,5- dinitro pyrazine -1- oxide

Technical field

The present invention relates to the synthetic method of one kind 2,6- Diamino-3,5-dinitropyrazine-1-oxide, belong to the material containing energy Material field.

Background technique

2,6- diamino -3,5- dinitro pyrazine -1- oxide (LLM-105) is that a kind of novel high-energy of function admirable is low Feel heat-resisting single chmical compound explosive, energy ratio TATB high 25%, be HMX 81%, DSC decomposition peak temperature up to 355 DEG C, H50=117cm is right Electrostatic spark and friction are extremely insensitive, and explosion velocity and specific impulse are respectively 8560m/s and 2122.68N.s/kg (7MPa), can be used for spy The fields such as different weapon, Insensitive booster composition, superhigh temperature petroleum perforation charge, priming system.

The synthesis of LLM-105 mainly by with 2,6- diamino -3,5- dinitro pyrazine (ANPZ) be raw material, in acetic acid Or the preparation method of hydrogen peroxide oxidation is used in trifluoroacetic acid, it is the process route generallyd use both at home and abroad.U.S. Lao Lunsi Livermore laboratory (LLNL) reported the synthesis of LLM-105 in 1997 for the first time, and was improved total synthesis method, But it is carried out in trifluoroacetic acid system always by the oxidation of ANPZ preparation LLM-105；Domestic Li Haibo is in organic chemistry, and 2007, 27 (1): 112-115 and Wang Youbing is in explosive wastewater journal, and 2013,36 (1): 38-42 reports the synthesis side of LLM-105 Method, but aoxidize link and still use trifluoroacetic acid method；For in existing method, oxidation process solvent for use trifluoroacetic acid has price The defects of high, toxicity is big, corrosion equipment, Wang Youbing etc. in Chinese patent CN 201310638137.5 using this four Formic anhydride is that catalyst obtains LLM-105 using hydrogen peroxide oxidation ANPZ in acetic acid, and purity is up to 97%, however the method exists It is reacted under heterogeneous conditions, the reaction time is long, and a large amount of solid waste are generated after reaction, and post-processing is difficult.

Current existing LLM-105 synthetic method, especially is aoxidized to obtain in LLM-105 method, there are still all by ANPZ It is mostly insufficient: CF used₃That there are solvent for use is with high costs by COOH, with strong corrosivity, to reaction and sewage treatment equipment With strict demand, wastewater treatment is difficult；Pyromellitic dianhydride usage amount reaches 50% or more of ANPZ mass, and reaction generates big Measure solid waste；Reaction carries out under heterogeneous conditions, and the reaction time is up to 5h or more.

Summary of the invention

The technical problem to be solved by the present invention is in view of the deficiencies of the prior art and defect, provide a kind of reaction time Synthesis side short, that simple 2,6- diamino -3,5- dinitro pyrazine -1- oxide is formed without solid catalyst residue, waste liquid Method.

In order to solve the above technical problems, synthetic route of the invention are as follows:

R therein is-H or-COCH₃。

Synthetic method of the invention is closed for raw material through acid catalysis with 2,6- diamino -3,5- dinitro pyrazine, acetic anhydride At readily soluble acetylation ANPZ, then through H₂O₂Oxidation, hydrolysis obtain LLM-105.

The synthetic method of the present invention 2,6- Diamino-3,5-dinitropyrazine-1-oxide, which is characterized in that 2,6- bis- The structural formula of amino -3,5- dinitro pyrazine -1- oxide is shown below:

The following steps are included:

Under stirring, 2,6- diamino -3,5- dinitro pyrazine and sulfuric acid are added in acetic anhydride, are warming up to 60 DEG C~90 DEG C, 60 DEG C are cooled to hereinafter, being slowly dropped into 50%H after reaction 0.5h solid dissolution₂O₂, 70 DEG C~90 DEG C are warming up to after adding, instead 0.5h~4h is answered, system is down to 25 DEG C, is poured into ice water and adjusts pH value 7~8, filtering with sodium bicarbonate, washing, acetone are washed Wash, dry after obtain 2,6- diamino -3,5- dinitro pyrazine -1- oxide.Wherein, 2,6- diamino -3,5- dinitro pyridine The mass volume ratio of piperazine and acetic anhydride is 1g:6mL~20.0mL, and the volume ratio of acetic anhydride and sulfuric acid is 10:0.2~2,2,6- bis- Amino -3,5- dinitro pyrazine and mass fraction 50%H₂O₂Molar ratio be 1:2~10.

The synthetic method of preferred 2,6- Diamino-3,5-dinitropyrazine-1-oxide of the invention, feature exist In including the following steps:

Under stirring, 2,6- diamino -3,5- dinitro pyrazine and sulfuric acid are added in acetic anhydride, are warming up to 75 DEG C~90 DEG C, 60 DEG C are cooled to hereinafter, being slowly dropped into 50%H after reaction 0.5h solid dissolution₂O₂, 75-85 DEG C is warming up to after adding, reaction 0.5h~2h, system are down to 25 DEG C, be poured into ice water and with sodium bicarbonate adjust pH value 7~8, filtering, washing, acetone washing, 2,6- diamino -3,5- dinitro pyrazine -1- oxide is obtained after drying.Wherein, 2,6- diamino -3,5- dinitro pyrazine with The mass volume ratio of acetic anhydride is 1g:10.0mL~20.0mL, and the volume ratio of acetic anhydride and sulfuric acid is 10:0.25~1,2,6- bis- Amino -3,5- dinitro pyrazine and mass fraction 50%H₂O₂Molar ratio be 1:2~6.

Advantages of the present invention:

The present invention provides the synthetic method of one kind 2,6- Diamino-3,5-dinitropyrazine-1-oxide, this method tools It has the advantage that and avoids using expensive CF₃COOH and required special installation, the special protective device of personnel and corrosivity Wastewater treatment；Generation without solid waste；Reaction carries out under homogeneous phase condition, and the reaction time is less than 2h.

Specific embodiment

The invention will be further described by the following examples, but the present invention is not limited by the following example.

Embodiment 1:

Under stirring, 20ml acetic acid is added in 2.0g (10mmol) 2,6- diamino -3,5- dinitro pyrazine and 0.5ml sulfuric acid In acid anhydride, 80 DEG C are warming up to, is cooled to 60 DEG C hereinafter, being slowly dropped into 1.37g (20mmol) 50%H after reacting 0.5h₂O₂, after adding 80 DEG C are warming up to, 1h is reacted, system is down to 25 DEG C, and it is poured into ice water and adjusts pH value 7~8 with sodium bicarbonate, filter, washing, 2,6- Diamino-3,5-dinitropyrazine-1-oxide, yield 85%, purity 98.3% are obtained after acetone washing, drying.

Structural Identification:

Infrared spectroscopy (KBr, cm^-1) γ: 3420,3 404,3 282,3 228,1647, l 566,1 490,923,889, 814；

¹H NMR (DMSO-d6,500MHz, ppm): 9.0469 (brs, 2H, NH ' S), 8.7709 (brs, 2H, NH ' S).On Stating the substance that Structural Identification data confirm that this step obtains is 2,6- diamino -3,5- dinitro pyrazine -1- oxide.

Embodiment 2:

Under stirring, 40ml acetic anhydride is added in 2.0g (10mmol) 2,6- diamino -3,5- dinitro pyrazine and 4ml sulfuric acid In, 75 DEG C are warming up to, is cooled to 60 DEG C hereinafter, being slowly dropped into 4.1g (60mmol) 50%H after reacting 0.5h₂O₂, heat up after adding To 75 DEG C, 2h is reacted, system is down to 25 DEG C, is poured into ice water and adjusts pH value 7~8, filtering, washing, acetone with sodium bicarbonate 2,6- Diamino-3,5-dinitropyrazine-1-oxide, yield 87%, purity 99.0% are obtained after washing, drying.

Embodiment 3:

Under stirring, 30ml acetic anhydride is added in 2.0g (10mmol) 2,6- diamino -3,5- dinitro pyrazine and 1ml sulfuric acid In, 90 DEG C are warming up to, is cooled to 60 DEG C hereinafter, being slowly dropped into 2.73g (40mmol) 50%H after reacting 0.5h₂O₂, risen after adding Temperature reacts 0.5h to 85 DEG C, and system is down to 25 DEG C, is poured into ice water and adjusts pH value 7~8 with sodium bicarbonate, filters, washing, 2,6- Diamino-3,5-dinitropyrazine-1-oxide, yield 80%, purity 98.6% are obtained after acetone washing, drying.

Claims

1. one kind 2, the synthetic method of 6- Diamino-3,5-dinitropyrazine-1-oxide, which is characterized in that 2,6- diamino- 3,5- dinitro pyrazine -1- oxide structure formula is shown below:

Under stirring, 2,6- diamino -3,5- dinitro pyrazine and sulfuric acid are added in acetic anhydride, are warming up to 60 DEG C~90 DEG C, instead 60 DEG C are cooled to hereinafter, being slowly dropped into 50%H after answering 0.5h solid to dissolve₂O₂, 70 DEG C~90 DEG C are warming up to after adding, reaction 0.5h~4h, system are down to 25 DEG C, be poured into ice water and with sodium bicarbonate adjust pH value 7~8, filtering, washing, acetone washing, 2,6- diamino -3,5- dinitro pyrazine -1- oxide is obtained after drying.Wherein, 2,6- diamino -3,5- dinitro pyrazine with The mass volume ratio of acetic anhydride is 1g:6~20.0mL, and the volume ratio of acetic anhydride and sulfuric acid is 10:0.2~2,2,6- diamino- 3,5- dinitro pyrazine and mass fraction 50%H₂O₂Molar ratio be 1:2~10.

2. the synthetic method of 2,6- Diamino-3,5-dinitropyrazine-1-oxide according to claim 1, feature It is, includes the following steps:

Under stirring, 2,6- diamino -3,5- dinitro pyrazine and sulfuric acid are added in acetic anhydride, are warming up to 75 DEG C~90 DEG C, instead 60 DEG C are cooled to hereinafter, being slowly dropped into 50%H after answering 0.5h solid to dissolve₂O₂, it is warming up to 75-85 DEG C after adding, reaction 0.5h~ 2h, system are down to 25 DEG C, are poured into ice water and adjust pH value 7~8, filtering, after washing, acetone washing, drying with sodium bicarbonate Obtain 2,6- diamino -3,5- dinitro pyrazine -1- oxide.Wherein, 2,6- diamino -3,5- dinitro pyrazine and acetic anhydride Mass volume ratio be 1g:10.0~20.0mL, the volume ratio of acetic anhydride and sulfuric acid is 10:0.25~1,2,6- diamino -3, 5- dinitro pyrazine and mass fraction 50%H₂O₂Molar ratio be 1:2~6.