CN113563223A

CN113563223A - Method for synthesizing nitrine nitramine by phase transfer catalysis

Info

Publication number: CN113563223A
Application number: CN202110763663.9A
Authority: CN
Inventors: 蔡春; 肖凯
Original assignee: Nanjing University of Science and Technology
Current assignee: Nanjing University of Science and Technology
Priority date: 2021-07-06
Filing date: 2021-07-06
Publication date: 2021-10-29

Abstract

The invention discloses a method for synthesizing azido nitramine by phase transfer catalysis. The compound takes 1, 5-dinitrate-3-nitryl-3-aza pentane and sodium azide as raw materials, and the diazotization reaction is carried out in an organic solvent-water two-phase system under the condition of a phase transfer catalyst to synthesize the DIANP. The method avoids the use of organic solvents such as DMSO and the like which are difficult to treat, is green and environment-friendly, and has simple and feasible synthetic route and simple product separation.

Description

Method for synthesizing nitrine nitramine by phase transfer catalysis

Technical Field

The invention relates to a method for synthesizing nitrine nitramine, and belongs to the field of synthesis of energetic materials.

Background

1, 5-diazido-3-nitro-3-aza pentane, namely nitrine nitramine (DIANP), as nitrine energetic plasticizer, has the advantages of high energy, high burning speed, low burning temperature, small relative molecular mass of fuel gas, large gas production and the like, can be used for high-energy low-ablation propellant, pyrotechnic agent and gas generating agent, and is a novel energetic plasticizer with great application prospect. The azide nitramine has good compatibility with common components of explosives and powders, particularly digestive cellulose, when the azide nitramine is used for high-energy low-ablation propellant, the detonation temperature is 200-400K lower than that of the propellant with the same energy level, the propellant power can reach 1300J/g, when the azide nitramine is used in combination with RDX, the propellant power exceeds 1400J/g, and meanwhile, higher burning speed is obtained. Use of azidatenitramines in solid propellant formulations, the combustion products being predominantly H₂、N₂And CO₂The small molecular compounds can reduce the average molecular weight of the fuel gas and the flame temperature without causing the reduction of the burning rate.

Literature (Synthesis and characterization of 1, 5-diazido-3-nitropentane of Spirodela parvifolia, lanoline, Lipura et al., [ 2 ]J]Explosive bulletin, 2008, 31 (3): 44-46.) describes a process for the synthesis of 1, 5-diazido-3-nitroheteropentane from 1, 5-dinitrate-3-nitro-3-azapentane (DINA) and NaN₃Starting with DMSO as a solvent, the DIANP was obtained by azidation, extraction with dichloromethane, decolorization, and vacuum rotary evaporation. The synthesis process has the following defects: DMSO is used as a strong polar aprotic solvent and is an ideal solvent for azide reaction, but the product azide nitramine is mutually soluble with DMSO, and because DMSO has a high boiling point, a large amount of water is used for diluting a DMSO solution in the post-treatment process of the reaction, so that the azide nitramine can be effectively separated in the extraction process. This post-treatment process results in large amounts of aqueous DMSO, which is difficult to recover and treat, and can cause severe environmental pollution, limiting the scale-up production and application of the dinp.

Disclosure of Invention

The invention aims to provide a method for synthesizing nitrine nitramine in a two-phase system. The method avoids using organic solvents which are difficult to treat, such as DMSO, and the water phase containing the phase transfer catalyst can be recycled after desalting, thereby being beneficial to realizing the large-scale production of DIANP.

The method comprises the following specific steps:

a method for synthesizing nitrine nitramine comprises the following steps: dissolving the Jina in an inert organic solvent which is not miscible with water, dissolving sodium azide in a water phase, mixing, adding into a container, adding a phase transfer catalyst at a certain temperature, stirring, separating liquid after the reaction is finished, recovering the solvent, and purifying to obtain the product, namely the azido nitramine DIANP.

Further, the feeding molar ratio of the Jina to the sodium azide is 1: 2.2 to 2.8.

Furthermore, the phase transfer catalyst is quaternary ammonium salt, and comprises any one of tetrabutylammonium bromide, tetraethylammonium bromide, benzyltriethylammonium bromide, hexadecyltrimethylammonium bromide and the like, and the dosage of the phase transfer catalyst is 0.1-0.3 equivalent of the reactant.

Further, adding a phase transfer catalyst at a certain temperature from room temperature to the boiling point of the organic solvent.

Further, the reaction time is 6-18 h.

Further, the inert and water-immiscible organic solvent is selected from any one of dichloromethane, toluene, chloroform, benzene, dichloroethane, etc.

Compared with the prior art, the invention has the advantages that:

(1) the method avoids using organic solvents such as DMSO and the like which are difficult to treat, and is green and environment-friendly;

(2 the water phase of the phase transfer catalyst can be recycled after desalting, and can be better produced in a large scale.

Drawings

FIG. 1 is a scheme of nitrine nitramine¹H-NMR spectrum.

FIG. 2 is a scheme of nitrine nitramine¹³C-NMR spectrum.

Detailed Description

The present invention will be further described with reference to specific examples;

the following are examples given by the inventors, and it should be noted that these examples are preferred examples and are mainly used for understanding the present invention, but the present invention is not limited to the examples.

The reaction formula of the nitrine nitramine is as follows:

。

example 1

A250 mL flask was charged with 2 g of Jina, followed by 50 mL of CH₂Cl₂(ii) a 1.19 g of NaN₃50 mL of water was added and dissolved with stirring, and the mixture was poured into a flask, and finally 0.4 g of tetrabutylammonium bromide was added and stirred vigorously at room temperature for 6 hours. And separating by using a separating funnel after the reaction is finished, wherein the lower layer of liquid is a dichloromethane phase, the upper layer of liquid is a water phase, and tetrabutylammonium bromide in the water phase can be recycled. The lower layer was dried over anhydrous sodium sulfate, rotary evaporated at 40 deg.C, and separated by column chromatography to give DIANP with a purity of 98.2% (HPLC, the same below).

Example 2

A250 mL flask was charged with 4 g of Jina followed by 50 mL of CH₂Cl₂(ii) a 2.38 g of NaN₃Adding 50 mL of water, stirring for dissolving, pouring into a flask together, finally adding 0.35g of tetraethylammonium bromide, introducing into a condensation reflux device at 40 ℃, and stirring vigorously for 10 hours. Separating with separating funnel after reaction, drying the lower layer liquid with anhydrous sodium sulfate, rotary evaporating at 40 deg.C, and separating by column chromatography to obtain DIANP with purity of 98.7%.

Example 3

A250 mL flask was charged with 6 g of Jiner, followed by 50 mL of CHCl₃(ii) a 3.6 g of NaN₃Adding 50 mL of water, stirring for dissolving, pouring into a flask together, finally adding 0.57 g of benzyl triethyl ammonium bromide, introducing into a condensation reflux device at 60 ℃, and stirring vigorously for 12 hours. After the reaction was completed, the mixture was separated by a separatory funnel, the lower layer was a chloroform phase, the upper layer was an aqueous phase, and the DIANP was dissolved in chloroform. Drying the lower layer liquid with anhydrous sodium sulfate, rotary evaporating at 40 deg.C for concentration, and separating by column chromatography to obtain DIANP with purity of 99.6%.

Example 4

2 g of Jina is added into a 250 mL flask, and then 40mL of toluene is added; 1.22 g of NaN₃40mL of water was added and dissolved with stirring, and the mixture was poured into a flask, and finally 0.19 g of benzyltriethylammonium bromide was added and stirred vigorously at room temperature for 8 hours. After the reaction was completed, the mixture was separated by a separatory funnel, the upper layer was toluene phase, the lower layer was aqueous phase, and DIANP was dissolved in toluene. Drying the upper layer liquid with anhydrous sodium sulfate, rotary evaporating at 40 deg.C for concentration, and separating by column chromatography to obtain DIANP with purity of 99.1%.

Example 5

4 g of Jina is added into a 250 mL flask, and then 40mL of toluene is added; 2.45 g of NaN₃40mL of water was added and dissolved with stirring, and the mixture was poured into a flask, and finally 0.85 g of tetrabutylammonium bromide was added and stirred vigorously at 80 ℃ for 16 hours. After the reaction was completed, the mixture was separated by a separatory funnel, the upper layer was toluene phase, the lower layer was aqueous phase, and DIANP was dissolved in toluene. Drying the upper layer liquid with anhydrous sodium sulfate, rotary evaporating at 40 deg.C for concentration, and separating by column chromatography to obtain DIANP with purity of 98.1%.

The DIANP structure characterization results are shown in FIGS. 1 and 2:

¹H-NMR（CDCl₃）:δ:3.72(t,2H,-CH₂NNO₂),3.97(t,2H,-CH₂N₃);¹³C-NMR (CDCl₃): δ:48.34(-CH₂NNO₂),52.04(-CH₂N₃)。

although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More specifically, the equivalents of the above-described elements, which may be directly or indirectly applied to other related arts, are all included within the scope of the present invention.

Claims

1. A method for synthesizing nitrine nitramine is characterized by comprising the following steps: dissolving 1, 5-dinitrate-3-nitro-3-aza-pentane in an inert organic solvent which is not miscible with water, dissolving sodium azide in a water phase, mixing, adding the mixture into a container, adding a phase transfer catalyst at a certain temperature, stirring, separating liquid after reaction, recovering the solvent, and purifying to obtain the 1, 5-diazide-3-nitro-3-aza-pentane.

2. The process of claim 1, wherein the molar feed ratio of 1, 5-dinitrate-3-nitro-3-azapentane to sodium azide is 1: 2.2 to 2.8.

3. The method of claim 1, wherein the phase transfer catalyst is a quaternary ammonium salt.

4. The process of claim 1 wherein the phase transfer catalyst is selected from any one of tetrabutylammonium bromide, tetraethylammonium bromide, benzyltriethylammonium bromide and cetyltrimethylammonium bromide.

5. The method of claim 1, wherein the phase transfer catalyst is used in an amount of 0.1 to 0.3 equivalents of 1, 5-dinitrate-3-nitro-3-azapentane.

6. The method of claim 1, wherein the phase transfer catalyst is added at a temperature between room temperature and the boiling point of the organic solvent.

7. The method of claim 1, wherein the reaction time is 6 to 18 hours.

8. The process according to claim 1, wherein the inert water-immiscible organic solvent is selected from any one of dichloromethane, toluene, chloroform, benzene, and dichloroethane.