CN106632357B - The method of one pot process TTBN - Google Patents

Abstract

The invention belongs to the technical field of chemistry, and specifically relates to a method for synthesizing TTBN by a one-pot method. The acidic hydrolysis of TNGU directly reacts with urotropine to synthesize TTBN in one pot. Specifically, it comprises: adding TNGU to a concentration of In a 2‑8M acidic catalyst aqueous solution, stir and hydrolyze at 15‑40°C for 30‑180 min, then add hexatropine directly, react at 30‑60°C for 30‑90 min, and synthesize TTBN in one pot. The invention simplifies the preparation process of TTBN, hydrolyzes TNGU under acidic conditions, does not undergo separation, and does not need to prepare barium salt of TNAE, but directly reacts with urotropine to synthesize TTBN in one pot.

Description

One-pot method for synthesizing TTBN

technical field

The invention belongs to the technical field of chemistry, and in particular relates to a method for synthesizing TTBN in one pot.

Background technique

Existing N-(3,6,9-trinitro-1,3,6,9-tetraazabicyclo[3.2.2]nonan-4-yl)nitroamine (N-(3,6,9 -trinitro-1,3,6,9-tetraazabicyclo[3,2,2]nonan-4-yl)nitramide, referred to as TTBN) there are few synthetic methods, the only way is: tetranitroglycoluril (TNGU) After hydrolysis in NaHCO ₃ aqueous solution, add Ba(OH) ₂ acetic acid solution to the aqueous solution to control the pH value of the reaction solution at 4-5, and white barium salt precipitates out, and the barium salt solid is obtained by filtration. Dissolve urotropine in 10% hydrochloric acid, add barium salt and stir for 5 minutes below 10°C, heat up to 50°C, first precipitate solids and then dissolve, cool and precipitate solids, and filter to obtain the product TTBN. The disadvantages of its preparation method: (1) complex process, more reagents used; (2) in the process of preparing the barium salt of tetranitroethane (TNAE), the pH value needs to be adjusted from weakly alkaline to weakly acidic, and TNAE Very sensitive to pH value, is extremely unstable between 3-8 at pH value, so causes the loss of raw material TNAE bigger; (3) product yield is low, purity is low.

Contents of the invention

The object of the present invention is to aim at the technical defect of preparing TTBN by reacting urotropine dissolved in acidic solution in advance by adjusting the pH value after TNGU is alkaline hydrolyzed to prepare the barium salt of TNAE in the prior art, and to provide a A method for synthesizing TTBN with simple operation, high yield and high purity.

The embodiment of the present invention provides a method for synthesizing TTBN by a one-pot method. The acidic hydrolysis of TNGU directly reacts with urotropine, and the one-pot synthesis of TTBN specifically includes: at room temperature, adding TNGU to a concentration of 2-8M In the acidic catalyst aqueous solution, stir and hydrolyze at 15-40°C for 30-180min, then directly add urotropine, react at 30-60°C for 30-90min, and synthesize TTBN in one pot.

Further, the acidic catalyst is hydrochloric acid, hydrobromic acid or sulfuric acid.

Further, the molar ratio of urotropine to TNGU added is 0.8:1-1.5:1, and the molar ratio of TNGU to acidic catalyst is 1:5-1:20.

Compared with prior art, the beneficial effects of the present invention are:

(1) The present invention replaces the basic hydrolysis _of NaHCO or _NaOH with HCl, HBr or _H2SO4 acidic aqueous solution when TNGU is hydrolyzed, reduces the step of alkaline hydrolysis and acidification again, makes the hydrolyzate TNAE exempt from weak base The process of separation from strong to weakly acidic process can improve the stability of TNAE, increase the yield of TNAE, and thus increase the yield of TTBN;

(2) The hydrolysis of TNGU and the synthesis reaction of TTBN are carried out in one pot, which not only saves the separation of TNAE, reduces the loss of intermediate treatment products, but also reduces the use of various raw materials such as barium hydroxide, acetic acid, and sodium bicarbonate.

(3) The synthetic steps are short, the cost is low, the yield is high, and the purity is high.

Detailed ways

The present invention will be described in detail below, but it should be noted that these embodiments do not limit the present invention, and the functions, methods, or structural equivalent transformations or substitutions made by those skilled in the art according to these embodiments belong to this invention. within the scope of protection of the invention.

This example provides a method for synthesizing TTBN in a one-pot method. The acidic hydrolysis of TNGU directly reacts with urotropine to synthesize TTBN in one pot, namely

At room temperature, add TNGU into a three-necked flask filled with _2-8M HCl, HBr or _H2SO4 aqueous solution, at 15-40°C, fully stir and hydrolyze for 30-180min, add 0.8-1.5 times the amount of TNGU ( moles) of urotropine, stirred and dissolved, heated to 30-60°C, reacted for 30-90min, filtered after the reaction, washed the filter cake with water until neutral, washed twice with dichloromethane, dried to obtain a white solid, The yield is above 73%. The method simplifies the preparation process of TTBN, and TNGU is hydrolyzed under acidic conditions without separation, and there is no need to prepare the barium salt of TNAE, but directly reacts with urotropine to synthesize TTBN in one pot.

In this embodiment, the molar ratio of urotropine to TNGU added is 0.8:1-1.5:1, and the molar ratio of TNGU to acidic catalyst is 1:5-1:20.

Specific examples:

Example 1

At room temperature, add 3.2g TNGU into a three-neck flask containing 30mL of 2M aqueous HCl solution, stir for 60min, add 2.1g of urotropine, stir to dissolve, heat up to 40°C, and react for 90min. After filtering, the filter cake was washed with water until neutral, washed twice with dichloromethane, and dried to obtain a white solid with a yield of 73% and a purity of 98%.

Example 2

At room temperature, add 3.2g TNGU into a three-necked flask containing 30mL of 3M aqueous HCl solution, stir for 120min, add 1.1g of urotropine, stir to dissolve, heat up to 60°C, and react for 30min. After filtering, the filter cake was washed with water until neutral, washed twice with dichloromethane, and dried to obtain a white solid with a yield of 76% and a purity of 98%.

Example 3

At room temperature, add 3.2g TNGU into a three-necked flask filled with 30mL of 4M HBr aqueous solution, heat to 30°C, stir for 40min, add 1.5g of urotropine, stir to dissolve, heat up to 35°C, react After 90 minutes, the reaction was filtered, the filter cake was washed with water until neutral, washed twice with dichloromethane, and dried to obtain a white solid with a yield of 82% and a purity of 98%.

Example 4

At room temperature, add 3.2g TNGU into a three-necked flask filled with 30mL of 5M _H2SO4 aqueous solution, stir for 120min, add 1.4g of urotropine, stir and dissolve, heat up to 40°C, react for 50min, after the reaction After filtering, the filter cake was washed with water until neutral, washed twice with dichloromethane, and dried to obtain a white solid with a yield of 77% and a purity of 98%.

Example 5

At room temperature, add 3.2g TNGU into a three-necked flask containing 30mL of 6M aqueous HCl solution, stir for 180min, add 1.2g of urotropine, stir to dissolve, heat up to 50°C, react for 60min, and filter after the reaction , the filter cake was washed with water until neutral, washed twice with dichloromethane, and dried to obtain a white solid with a yield of 73% and a purity of 98%.

Example 6

At room temperature, add 3.2g TNGU into a three-necked flask filled with 20mL of 3M _H2SO4 aqueous solution, stir at 40°C for 30min, add 1.5g of urotropine, stir to dissolve, heat up to 60°C, react for 30min, After the reaction was completed, the filter cake was filtered, washed with water until neutral, washed twice with dichloromethane, and dried to obtain a white solid with a yield of 79% and a purity of 98.5%.

Example 7

At room temperature, add 3.2g of TNGU into a three-necked flask filled with 30mL of 3.5M aqueous HCl solution, stir at 30°C for 60min, add 1.5g of urotropine, stir to dissolve, heat up to 40°C, and react for 50min. After the reaction was completed, the filter cake was filtered, washed with water until neutral, washed twice with dichloromethane, and dried to obtain a white solid with a yield of 86% and a purity of 99%.

Example 8

At room temperature, add 3.2g TNGU into a three-necked flask containing 30mL of 8M aqueous HCl solution, stir for 120min, add 1.5g of urotropine, stir to dissolve, heat up to 60°C, and react for 40min. After filtering, the filter cake was washed with water until neutral, washed twice with dichloromethane, and dried to obtain a white solid with a yield of 76% and a purity of 98%.

The present invention has following beneficial effect:

(1) The hydrolysis of TNGU and the synthesis of TTBN are carried out in one pot, and the synthesis process is simple. (2) When TNGU is hydrolyzed, an acidic aqueous solution is used instead of an alkaline aqueous solution for hydrolysis, which reduces the steps of alkaline hydrolysis and acidification, so that the hydrolyzed product TNAE is exempt from decomposition from weakly alkaline to weakly acidic, and improves the stability of TNAE , TNAE yield is improved, thereby TTBN yield is improved; (3) save the intermediate link of preparing TNAE barium salt, reduce the use of various raw materials such as barium hydroxide, acetic acid and sodium bicarbonate, save raw material cost.

It needs to be added that, in the implementation stage of the present invention, other alternative schemes have also been tried to synthesize TTBN, and experiments have been done respectively, including: scheme 1) TTBN can also be synthesized by directly reacting with TNAE under acidic conditions; scheme 2) TNGU is acidified after alkaline hydrolysis, and TTBN can also be synthesized in one pot by directly adding hexatropine without separation. It has been verified that the above two methods for synthesizing TTBN have serious deficiencies: adjusting the pH value in the middle will partially decompose TNAE, so the yield of the product TTBN is low, the process is complicated, and the cost is high. In addition, in the scheme 2), a large amount of salt will be produced in the acidification process, which will affect the effective progress of the reaction.

The series of detailed descriptions listed above are only specific descriptions for feasible implementations of the present invention, and they are not intended to limit the protection scope of the present invention. Any equivalent implementation or implementation that does not depart from the technical spirit of the present invention All changes should be included within the protection scope of the present invention.

It will be apparent to those skilled in the art that the invention is not limited to the details of the above-described exemplary embodiments, but that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Accordingly, the embodiments should be regarded in all points of view as exemplary and not restrictive, the scope of the invention being defined by the appended claims rather than the foregoing description, and it is therefore intended that the scope of the invention be defined by the appended claims rather than by the foregoing description. All changes within the meaning and range of equivalents of the elements are embraced in the present invention.

Claims (3)

1. a kind of method of one pot process TTBN, which is characterized in that directly reacted with methenamine by TNGU acidic hydrolysis, one Pot synthesis TTBN, specifically includes：At room temperature, TNGU is added in the acidic catalyst aqueous solution of a concentration of 2-8M, in 15- After 40 DEG C of stirring hydrolysis 30-180min, it is directly added into methenamine, 30-90min, one-pot synthesis are reacted at 30-60 DEG C TTBN。

2. the method for one pot process TTBN according to claim 1, which is characterized in that the acidic catalyst is salt Acid, hydrobromic acid or sulfuric acid.

3. the method for one pot process TTBN according to claim 2, which is characterized in that the methenamine of addition with The molar ratio of the TNGU is 0.8:1-1.5:The molar ratio of 1, the TNGU and the acidic catalyst is 1:5-1:20.