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CN-121974935-A - Dinitroamino-condensed ring energetic compound and preparation method thereof

CN121974935ACN 121974935 ACN121974935 ACN 121974935ACN-121974935-A

Abstract

The invention discloses a dinitrated amino group condensed ring energetic compound which has excellent performance and high energy density. The invention also discloses a preparation method of the dinitrated amino condensed ring energetic compound, which takes the compound 3-amino-6-bromo-1, 2, 4-triazine as a raw material, firstly prepares 6-amino-7, 8-dihydro-8-hydroxytetrazolo [5,1-f ] [1,2,4] triazine, then prepares a key intermediate 6-aminotetrazolo [5,1-f ] [1,2,4] triazine by a simple solvent-free method through heating dehydration, and can realize the one-step efficient synthesis of the dinitrated amino condensed ring energetic compound by utilizing the key intermediate and fuming nitric acid to be nitrified. The method greatly simplifies the synthetic route, improves the atom economy, and opens up a new way for the efficient preparation of a series of novel high-performance energetic materials.

Inventors

  • HU LU
  • WANG YAXI
  • PANG SIPING

Assignees

  • 北京理工大学

Dates

Publication Date
20260505
Application Date
20260129

Claims (5)

  1. 1. The bisnitroamino-condensed ring energetic compound is characterized by having a structure shown in the following formula (I): (I)。
  2. 2. The method for preparing the dinitrated amino-linked fused ring energetic compound according to claim 1, which is characterized by comprising the following steps: step one, using a compound 3-amino-6-bromo-1, 2, 4-triazine as a raw material to prepare a compound 6-amino-7, 8-dihydro-8-hydroxytetrazolo [5,1-f ] [1,2,4] triazine with a structure shown in the following formula (II); (II) Step two, heating the compound 6-amino-7, 8-dihydro-8-hydroxytetrazolo [5,1-f ] [1,2,4] triazine at 135 ℃ and dehydrating to prepare the compound 6-aminotetrazolo [5,1-f ] [1,2,4] triazine with the structure shown in the following formula (III); (III) and thirdly, reacting the compound 6-aminotetrazolo [5,1-f ] [1,2,4] triazine with fuming nitric acid to synthesize the compound N, N ' - ([ 8,8' -bistetrazolo [5,1-f ] [1,2,4] triazine ] -6,6' -diyl) dinitramine shown in the formula (I).
  3. 3. The method for preparing the dinitrated amino-linked fused ring energetic compound according to claim 2, wherein the first step specifically comprises: preparing an aqueous solution of the compound 3-amino-6-bromo-1, 2, 4-triazine, adding sodium azide into the aqueous solution of the compound 3-amino-6-bromo-1, 2, 4-triazine according to the molar ratio of the compound 3-amino-6-bromo-1, 2, 4-triazine to be 10:11, heating at 100 ℃, reacting for 16 h, stopping heating, standing the reaction solution, cooling and crystallizing to obtain the compound 6-amino-7, 8-dihydro-8-hydroxytetrazolo [5,1-f ] [1,2,4] triazine.
  4. 4. The method for preparing a dinitrated amino-linked fused ring energetic compound according to claim 2, wherein the second step specifically comprises: Heating and reacting the compound 6-amino-7, 8-dihydro-8-hydroxytetrazolo [5,1-f ] [1,2,4] triazine for 1h under the condition of 135 ℃ oil bath, stopping heating, cooling to room temperature, and collecting the obtained brown solid product, namely the compound 6-aminotetrazolo [5,1-f ] [1,2,4] triazine.
  5. 5. The method for preparing a dinitrated amino-linked fused ring energetic compound according to claim 2, wherein the third step specifically comprises: adding 6-aminotetrazolo [5,1-f ] [1,2,4] triazine into fuming nitric acid in batches under the ice salt bath condition, stirring 1h after the addition is finished, and reacting to separate out a solid, namely the compound shown as the formula (I).

Description

Dinitroamino-condensed ring energetic compound and preparation method thereof Technical Field The invention relates to the technical field of energetic materials. More particularly, the invention relates to a dinitrated amino group condensed ring energetic compound and a preparation method thereof. Background The development of energetic materials continues to seek higher energy density, lower sensitivity, better environmental compatibility, and efficient synthetic methods. Among them, the high nitrogen condensed ring compound becomes an important skeleton of the new generation of energetic materials due to its high positive heat generation, abundant substitution sites and good stability. The introduction of the nitramino (-NH-NO 2) can obviously improve the oxygen balance and detonation performance of the material. Therefore, the synthesis of a compound with both a high nitrogen fused ring skeleton and a nitramino group is a current research hotspot. However, synthesis of such complex molecules often faces serious synthesis challenges. The traditional synthesis strategy generally follows the stepwise route of constructing a framework firstly and then introducing functional groups or modifying monomers firstly and then coupling the framework, and all the stepwise route face the core problems of complicated steps, low total yield, poor selectivity of key reactions, insufficient stability of sensitive intermediates or frameworks and the like. Disclosure of Invention It is an object of the present invention to provide a bisnitroamino-linked fused ring energetic compound having excellent properties and a high energy density. It is another object of the present invention to provide a process for the preparation of the intermediate 6-aminotetrazolo [5,1-f ] [1,2,4] triazine which allows the synthesis of such key intermediates by a simple solvent-free process. The invention also aims to provide a preparation method of the dinitrate amino group condensed ring energetic compound, which utilizes the key intermediate and fuming nitric acid to realize one-step efficient synthesis of the dinitrate amino group condensed ring energetic compound. To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a dinitrano-linked fused ring energetic compound having the structure of formula (I): (I)。 the invention also provides a preparation method of the dinitrated amino group condensed ring energetic compound, which comprises the following steps: step one, using a compound 3-amino-6-bromo-1, 2, 4-triazine as a raw material to prepare a compound 6-amino-7, 8-dihydro-8-hydroxytetrazolo [5,1-f ] [1,2,4] triazine with a structure shown in the following formula (II); (II) Step two, heating the compound 6-amino-7, 8-dihydro-8-hydroxytetrazolo [5,1-f ] [1,2,4] triazine at 135 ℃ and dehydrating to prepare the compound 6-aminotetrazolo [5,1-f ] [1,2,4] triazine with the structure shown in the following formula (III); (III) and thirdly, reacting the compound 6-aminotetrazolo [5,1-f ] [1,2,4] triazine with fuming nitric acid to synthesize the compound N, N ' - ([ 8,8' -bistetrazolo [5,1-f ] [1,2,4] triazine ] -6,6' -diyl) dinitramine shown in the formula (I). Preferably, the first step specifically includes: Preparing an aqueous solution of the compound 3-amino-6-bromo-1, 2, 4-triazine, adding sodium azide into the aqueous solution prepared by the compound 3-amino-6-bromo-1, 2, 4-triazine according to the mol ratio of the compound 3-amino-6-bromo-1, 2, 4-triazine to be 10:11, heating at 100 ℃, reacting for 16 h, stopping heating, standing the reaction solution, cooling and crystallizing to obtain the compound 6-amino-7, 8-dihydro-8-hydroxytetrazolo [5,1-f ] [1,2,4] triazine. Preferably, the second step specifically includes: Heating and reacting the compound 6-amino-7, 8-dihydro-8-hydroxytetrazolo [5,1-f ] [1,2,4] triazine for 1h under the condition of 135 ℃ oil bath, stopping heating, cooling to room temperature, and collecting the obtained brown solid product, namely the compound 6-aminotetrazolo [5,1-f ] [1,2,4] triazine. Preferably, the third step specifically includes: adding 6-aminotetrazolo [5,1-f ] [1,2,4] triazine into fuming nitric acid in batches under the ice salt bath condition, stirring 1h after the addition is finished, and reacting to separate out a solid, namely the compound shown as the formula (I). The invention at least comprises the following beneficial effects: The invention provides a method for efficiently constructing a dinitrate amino-condensed ring energetic compound, which adopts fuming nitric acid as a key reagent to successfully synthesize a high-energy-density target product with excellent performance. The invention breaks through the synthesis method of the key intermediate 6-amino-tetrazolo [5,1-f ] [1,2,4] triazine, can be efficiently prepared only through a simple solvent-free heating step, and lays an important foundation for the practicability o