CN111471052A - Preparation method of fully deuterated C L-20 - Google Patents

Preparation method of fully deuterated C L-20 Download PDF

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CN111471052A
CN111471052A CN202010386165.2A CN202010386165A CN111471052A CN 111471052 A CN111471052 A CN 111471052A CN 202010386165 A CN202010386165 A CN 202010386165A CN 111471052 A CN111471052 A CN 111471052A
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刘吉平
方祝青
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Beijing Institute of Technology BIT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B25/00—Compositions containing a nitrated organic compound
    • C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B59/00—Introduction of isotopes of elements into organic compounds ; Labelled organic compounds per se
    • C07B59/002—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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    • C07B2200/05—Isotopically modified compounds, e.g. labelled

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Abstract

The invention relates to a preparation method of deuterium substituted C L-20, belonging to a synthesis technology of deuterium substituted energetic materials, wherein the method takes deuterium substituted N, N' -di-tert-butyl ethane-1, 2-diimine and deuterium substituted benzylamine as raw materials, takes deuterium substituted acetic acid as a catalyst to synthesize an intermediate product, namely, deuterium substituted hexa benzyl hexaazaisowurtzitane, compared with the traditional method, the yield of the deuterium substituted hexabenzyl hexaazaisowurtzitane is obviously improved, the deuterium substituted hexaacetyl hexaazaisowurtzitane is taken as a nitration precursor to be nitrated, the product does not contain impurities such as pentanitro-formacyl hexaazaisowurtzitane, and the obtained deuterium substituted C L-20 has high purity, compared with common C L-20, the detonation performance of deuterium substituted C L-20 is better, the safety is improved, and the method is more beneficial to practical application.

Description

Preparation method of fully deuterated C L-20
Technical Field
The invention relates to a preparation method of fully-deuterated C L-20, belonging to the synthesis technology of deuterated energetic materials.
Background
The hexanitrohexaazaisowurtzitane is also named C L-20, is a novel high-energy-density explosive, and is widely paid attention after being synthesized for the first time in 1987. C L-20 not only has excellent oxygen balance, but also has better detonation velocity, detonation pressure, density and the like than the current military main explosive, namely octogen (HMX), has 10% -15% higher energy output than HMX, but has higher mechanical sensitivity than HMX, and has serious restriction on development and application of C L-20 due to unsatisfactory safety.
The mass of the deuterium atom is twice of the mass of the hydrogen atom, and the density of the fully deuterated C L-20 obtained by replacing hydrogen with deuterium is higher than that of the ordinary C L-20, so that the detonation performance is better.
The TADA-20 is prepared by a TADA-20 Process (TADA-20) method, a TADA-20 method is used for preparing a penta-aza-isowurtzitane (HBIW) as a precursor, Nielsen in 1990 uses formic acid as a catalyst, benzylamine and glyoxal are reacted in an acetonitrile solvent, HBIW (Journal of Organic Chemistry,1990,55(5):1459 1466) is obtained for the first time, the acetonitrile used in the method is relatively toxic, the yield of HBIW is relatively low, and various improvements are performed in the later period, the yield is not obviously improved, the synthesis of the tetraacetyl-dibenzyl-isowurtzitane (TADD-20) performed by using HBIW as a precursor is performed by a TADA-25-20 method, a TADF method and a TATADA method, wherein TADA methods firstly acetylate is acetylated to obtain tetraacetyl-hexa-azaisowurtzitane (TADB) and subsequently performed by carrying out nitrosation and hydrogenolysis reactions to obtain C360-20 (TaDA-20 ) and finally a TADA-20 is performed by a TADA-20 method, TADA methods which is performed by replacing TADA methods, TADA methods are performed by TADA methods, TADA methods are performed by TADA methods, TADA methods are performed by a TADA methods, TADA methods are performed, TADA methods are performed, TADA methods are performed, TA.
Disclosure of Invention
The invention aims to provide a preparation method of the deuterated C L-20, which has high product purity and relatively high yield, realizes the preparation of the deuterated C L-20 and provides reference for industrial production of the deuterated C L-20.
The purpose of the invention is realized by the following technical scheme.
A preparation method of per-deuterated C L-20 comprises the following steps:
placing a three-neck flask filled with deuterated tert-butylamine in a high-precision medium-temperature circulating bath at the temperature of not higher than 25 ℃, starting stirring, dropwise adding a deuterated glyoxal solution into the deuterated tert-butylamine at a dropping rate of 1-5 m L/min through a constant-pressure dropping funnel under the stirring at the rotating speed of 200-300 rpm, wherein the molar ratio of the deuterated glyoxal to the deuterated tert-butylamine is 1 (2.3-3), continuing stirring for 30-60 minutes after the dropwise adding is finished, then adding deionized water into the mixed solution, wherein the mass ratio of the deionized water to the deuterated tert-butylamine is (4-7): 1, standing for 10 minutes, performing suction filtration on the mixture, washing precipitates on filter paper by using the deionized water in the suction filtration process until the pH value of the filtrate is neutral, and then drying the filter residue in a vacuum drying box at the temperature of 25-30 ℃ for 8-12 hours to obtain deuterated N, N' -di-tert-butylethane-1, 2-diimine;
placing a three-neck flask filled with tetrahydrofuran in a high-precision medium-temperature circulating bath at the temperature of 25-30 ℃, starting stirring, respectively adding deionized water and deuterated benzylamine into the three-neck flask under the stirring of the rotation speed of 200-300 rpm, wherein the mass ratio of tetrahydrofuran to deionized water is (4-6): 1, and the mass ratio of tetrahydrofuran to deuterated benzylamine is (7-13): 1, then adding 3-6 batches of deuterated N, N '-di-tert-butylethane-1, 2-diimine obtained in the first step into the three-neck flask, wherein the molar ratio of deuterated N, N' -di-tert-butylethane-1, 2-diimine to deuterated benzylamine is 1 (2.5-3.5), then dropwise adding deuterated acetic acid into the mixed solution at the dropping rate of 0.5-5 m L/min through a constant-pressure dropping funnel, wherein the mass of deuterated acetic acid is 1-2 times that of deuterated benzylamine, sealing the reaction system after dropwise adding, continuously stirring, performing suction filtration on the mixed solution for 3-6 hours, performing suction filtration on the filtered and drying on the filtered and the filtered six-neck flask with pH value of 5, and drying the filtered tetrahydrofuran at the temperature of 25-30 ℃, and drying the filtrate, and obtaining the filtrate;
and thirdly, dissolving the deuterated hexabenzylhexaazaisowurtzitane obtained in the second step into chloroform, wherein the mass ratio of the deuterated hexabenzylhexaazaisowurtzitane to the chloroform is 1 (10-15), transferring the mixed solution into a high-pressure reaction kettle with a stirring device after the dissolution is finished, respectively adding deuterated acetic anhydride and deuterated diacetonitrileachloropalladium into the reaction kettle, wherein the molar ratio of the deuterated hexabenzylhexaazaisowurtzitane to the deuterated acetic anhydride is 1 (3-6), the molar ratio of the deuterated diacetonitrileachloropalladium chloride to the deuterated acetic anhydride is 1 (5-10), sealing the reaction kettle, checking the sealing performance of the reaction kettle, replacing the air in the reaction kettle with nitrogen for three times, replacing the nitrogen in the reaction kettle with deuterium for three times to make the deuterium air atmosphere in the reaction kettle, then introducing deuterium into the reaction kettle for pressurizing, closing an air inlet valve when the pressure in the reaction kettle reaches 0.3-0.5 MPa, then stirring at the speed of 300-500 rpm, heating the high-pressure reaction kettle to 35 ℃, keeping the temperature for 4 hours, then introducing deuterium gas for pressurizing, performing suction filtration on the filtrate in the filtrate until the filtrate reaches 0.3-0.5 MPa, performing suction filtration on the filtrate, and drying the filtrate in the filtrate at the filtrate, wherein the filtrate A, the filtrate, performing vacuum filtration of the filtrate, and filtering on the filtrate, and drying the filtrate, and the filtrate, wherein the filtrate, and the filtrate.
And fourthly, placing the four-mouth flask filled with the deuterated nitric acid in a high-precision constant-temperature bath at the temperature of not higher than 5 ℃, stirring at the speed of 200-300 rpm, slowly adding the deuterated hexaacetylhexaazaisowurtzitane obtained in the third step into the deuterated nitric acid in batches, keeping the temperature of the mixed solution at the temperature of not higher than 5 ℃, wherein the mass ratio of the deuterated hexaacetylhexaazaisowurtzitane to the deuterated nitric acid is 1 (20-25), adding bismuth nitrate after the deuterated hexaacetylhexaazaisowurtzitane is dissolved, wherein the mass ratio of the deuterated nitric acid to the bismuth nitrate is (70-85): 1, sealing the reaction device after the bismuth nitrate is dissolved, heating to 60-80 ℃, keeping the temperature for 2-4 hours, reducing to 30-35 ℃, slowly pouring the mixture into a deionized water mixture, quickly stirring the mixture at the speed of 200-300 rpm in the pouring process, performing suction filtration, washing 3-5 times with deionized water, and drying at the temperature of 20-40 ℃ under vacuum for 12-24 hours to obtain fully substituted C-L.
In the first step, the mass fraction of the deuterated glyoxal solution is 40-60%;
advantageous effects
(1) The preparation method of the deuterated C L-20, disclosed by the invention, is characterized in that deuterated N, N' -di-tert-butyl ethane-1, 2-diimine and deuterated benzylamine are used as raw materials, and deuterated acetic acid is used as a catalyst to synthesize an intermediate product of the deuterated hexabenzylhexaazaisowurtzitane, and compared with the traditional method, the yield of the deuterated hexabenzylhexaazaisowurtzitane is obviously improved.
(2) The deuterated hexaacetylhexaazaisowurtzitane is used as a nitration precursor for nitration, the product does not contain pentanitromonoformyl hexaazaisowurtzitane and other impurities, and the obtained deuterated C L-20 has high purity.
(3) The use amount of the deuterated nitric acid is reduced in the nitration process, the use of the deuterated sulfuric acid is avoided, and the production cost is reduced.
(4) Compared with the common C L-20, the crystal density of the fully deuterated C L-20 is improved, so that the explosion velocity is higher, and meanwhile, in the aspect of restricting the sensitivity of the C L-20 application, the friction sensitivity and the impact sensitivity of the fully deuterated C L-20 are reduced, the decomposition temperature is improved, and the thermal stability is increased.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Placing a three-neck flask containing 8.4g of deuterated tert-butylamine in a high-precision medium-temperature circulating bath at the temperature of 23 ℃, starting stirring, dropwise adding a deuterated glyoxal solution with the mass fraction of 40% into the deuterated tert-butylamine at the dropping rate of 1m L/min through a constant-pressure dropping funnel under the stirring at the rotating speed of 200rpm, continuing stirring for 35 minutes after the dropwise adding is finished, then adding 33.6g of deionized water into the mixed solution, standing for 10 minutes, then carrying out suction filtration on the mixture, washing precipitates on filter paper by using the deionized water in the suction filtration process until the pH value of the filtrate is neutral, and then drying residues in a vacuum drying box at the temperature of 25 ℃ for 8 hours to obtain 7.3g of deuterated N, N' -di-tert-butyl ethane-1, 2-diimine;
placing a three-neck flask containing 79.8g of tetrahydrofuran in a high-precision moderate-temperature circulating bath at the temperature of 25 ℃, starting stirring, respectively adding 19.5g of deionized water and 11.2g of deuterated benzylamine into the three-neck flask under the stirring of the rotation speed of 200rpm, then adding 7.3g of deuterated N, N' -di-tert-butyl ethane-1, 2-diimine into the three-neck flask in 3 batches, then dropwise adding deuterated acetic acid into the mixed solution at the dropping rate of 0.7m L/min through a constant-pressure funnel, wherein the total volume of the deuterated acetic acid is 10.6m L, sealing the reaction system after the dropwise adding is finished, continuously stirring, carrying out suction filtration on the mixed solution after 3 hours, washing precipitates on the mixed solution by using 10 ℃ of tetrahydrofuran in the suction filtration process until the pH value of the filtrate is neutral, and then drying filter paper in a vacuum drying box at the temperature of 25 ℃ for 8 hours to obtain 7.8g of substituted hexabenzylhexaazaisowurtzitane;
dissolving 7.8g of deuterated hexabenzylhexaazaisowurtzitane in 77.6g of chloroform, transferring the mixed solution into a high-pressure reaction kettle with a stirring device after the dissolution is finished, respectively adding 3.8g of deuterated acetic anhydride and 1.8g of deuterated diacetonitrilchloridized palladium chloride into the reaction kettle, sealing the reaction kettle, checking the sealing property of the reaction kettle, replacing air in the kettle with nitrogen for three times, then replacing the nitrogen in the kettle with deuterium for three times to make the kettle have a deuterium atmosphere, then introducing deuterium into the kettle for pressurization, closing an air inlet valve when the pressure in the kettle reaches 0.3MPa, then stirring at the speed of 300rpm, heating the high-pressure reaction kettle to 35 ℃, keeping the temperature for 4 hours, then injecting deuterium acetyl chloride into the kettle at the speed of 0.3m L/min by a high-pressure metering pump, keeping the temperature for 9 hours, stopping stirring, performing vacuum filtration on the mixture in the kettle, using chloroform at the temperature of 5 ℃ to precipitate in a vacuum filtration tank until the filtrate is clarified, filtering the filtrate of the acetyl chloride at the temperature of 25.8 g of the iso-substituted hexaazaisowurtzitane, and drying the filtrate to obtain the iso-filtered iso-substituted acetyl-hexaazaisowurtzitane;
placing a four-neck flask filled with 90g of 95% deuterated nitric acid in a high-precision constant-temperature bath at 4 ℃, stirring at the speed of 200rpm, slowly adding 4.5g of deuterated hexaacetylhexaazaisowurtzitane into the deuterated nitric acid in batches to maintain the temperature of the mixed solution to be not higher than 5 ℃, adding 1.2g of bismuth nitrate after the deuterated hexaacetylhexaazaisowurtzitane is dissolved, sealing a reaction device after the bismuth nitrate is dissolved, heating to 60 ℃, preserving the temperature for 2 hours, reducing the temperature to 35 ℃, then slowly pouring the mixture into an ice water mixture of deionized water, rapidly stirring the ice water mixture at the speed of 300rpm in the pouring process, carrying out suction filtration, washing a filter residue with deionized water for 3 times, and carrying out vacuum drying at the temperature of 25 ℃ for 12 hours to obtain 4.2g of fully deuterated C L-20, wherein the yield is 80.8% (calculated by the deuterated hexabenzylhexaazaisowurtzitane) and the purity is 99.6%.
The crystal density of this sample was from 2.044g/cm, as compared with that of ordinary C L-203Increased to 2.069g/cm3The detonation velocity is increased to 9545m/s from 9380 m/s; at the same time, the initial decomposition temperature of the sample was 265 ℃, the friction sensitivity was 62N, and the impact sensitivity was H5031cm, the thermal stability is increased compared with the common C L-20, and the sensitivity is reduced to a certain extent.
Example 2
Placing a three-neck flask containing 21.9g of deuterated tert-butylamine in a high-precision medium-temperature circulating bath at the temperature of 24 ℃, starting stirring, dropwise adding a deuterated glyoxal solution with the mass fraction of 45% into the deuterated tert-butylamine at the dropping rate of 1.5m L/min through a constant-pressure dropping funnel under the stirring of the rotation speed of 250rpm, wherein the mass of the deuterated glyoxal solution is 13.8g, continuing stirring for 40 minutes after the dropwise adding is finished, then adding 109.4g of deionized water into the mixed solution, standing for 10 minutes, carrying out suction filtration on the mixture, washing precipitates on filter paper by using the deionized water in the suction filtration process until the pH value of the filtrate is neutral, and then drying the filter residues in a vacuum drying box at the temperature of 25 ℃ for 9 hours to obtain 17.6g of deuterated N, N' -di-tert-butyl ethane-1, 2-diimine;
placing a three-neck flask filled with 274g of tetrahydrofuran into a high-precision moderate-temperature circulating bath at the temperature of 27 ℃, starting stirring, respectively adding 60.8g of deionized water and 30.4g of deuterated benzylamine into the three-neck flask under the stirring of the rotation speed of 200rpm, then adding 17.6g of deuterated N, N' -di-tert-butyl ethane-1, 2-diimine into the three-neck flask in 4 batches, then dropwise adding deuterated acetic acid into the mixed solution at the dropping rate of 1.2m L/min through a constant-pressure dropping funnel, wherein the total volume of the deuterated acetic acid is 37.3m L, sealing the reaction system after the dropwise adding is finished, continuously stirring, carrying out suction filtration on the mixed solution after 4 hours, washing precipitates on filter paper by using tetrahydrofuran at the temperature of 8 ℃ in the suction filtration process until the pH value of the filtrate is neutral, and then drying the filtered residues in a vacuum drying box at the temperature of 25 ℃ for 10 hours to obtain 19.0g of substituted hexabenzylhexaazaisowurtzitane;
dissolving 19.0g of deuterated hexabenzylhexaazaisowurtzitane in 227.6g of chloroform, transferring the mixed solution into a high-pressure reaction kettle with a stirring device after the dissolution is finished, respectively adding 12.4g of deuterated acetic anhydride and 4.3g of deuterated diacetonitrilchloridinium chloride into the reaction kettle, sealing the reaction kettle, checking the sealing property of the reaction kettle, replacing the air in the kettle with nitrogen for three times, then replacing the nitrogen in the kettle with deuterium for three times to make the kettle have a deuterium atmosphere, then introducing deuterium into the kettle for pressurization, closing an air inlet valve when the pressure in the kettle reaches 0.35MPa, then stirring at the speed of 350rpm, heating the high-pressure reaction kettle to 40 ℃, keeping the temperature for 5 hours, then injecting deuterium acetyl chloride into the kettle at the speed of 0.8m L/min by a high-pressure metering pump, wherein the total volume of the deuterium acetyl chloride is 9.6m L, continuing to keep the temperature for 10 hours, stopping stirring, performing vacuum filtration on the mixture in the kettle, using chloroform at the temperature of 7 ℃ to precipitate in a filtrate, washing the filtrate until the filtrate is clarified, and drying the filtrate at the temperature of the filtrate of 2.8 g of the acetyl hexaazaisowurtzitane to obtain 11 g of iso-filtered and dried acetyl-substituted acetyl-2;
putting a four-neck flask filled with 246.7g of 96% deuterated nitric acid into a high-precision constant-temperature bath at 4 ℃, stirring at the speed of 200rpm, slowly adding 11.2g of deuterated hexaacetylhexaazaisowurtzitane into the deuterated nitric acid in batches to maintain the temperature of the mixed solution to be not higher than 5 ℃, adding 3.3g of bismuth nitrate after the deuterated hexaacetylhexaazaisowurtzitane is dissolved, sealing a reaction device after the bismuth nitrate is dissolved, heating to 65 ℃, keeping the temperature for 2.5 hours, reducing the temperature to 33 ℃, slowly pouring the mixture into an ice-water mixture of deionized water, quickly stirring the ice-water mixture at the speed of 250rpm during pouring, performing suction filtration, washing a filter residue with deionized water for 3 times, and performing vacuum drying at 25 ℃ for 12 hours to obtain 10.5g of fully substituted C L-20, wherein the yield is 82.2% (based on the deuterated hexaazaisowurtzitane) and the purity is 99.5%.
The crystal density of this sample was from 2.044g/cm, as compared with that of ordinary C L-203Increased to 2.069g/cm3The detonation velocity is increased to 9537m/s from 9380 m/s; at the same time, the initial decomposition temperature of the sample was 262 ℃, the friction sensitivity was 60N, and the impact sensitivity was H5031cm, the thermal stability is increased compared with the common C L-20, and the sensitivity is reduced to a certain extent.
Example 3
Placing a three-neck flask containing 34.5g of deuterated tert-butylamine in a high-precision medium-temperature circulating bath at the temperature of 24 ℃, starting stirring, dropwise adding a deuterated glyoxal solution with the mass fraction of 50% into the deuterated tert-butylamine at the dropping rate of 1.5m L/min through a constant-pressure dropping funnel under the stirring of the rotation speed of 250rpm, wherein the mass of the deuterated glyoxal solution is 17.6g, continuing stirring for 50 minutes after the dropwise adding is finished, then adding 207g of deionized water into the mixed solution, standing for 10 minutes, then carrying out suction filtration on the mixture, washing precipitates on filter paper by using the deionized water in the suction filtration process until the pH value of the filtrate is neutral, and then drying the filtrate in a vacuum drying box at the temperature of 27 ℃ for 10 hours to obtain 25.4g of deuterated N, N' -di-tert-butyl ethane-1, 2-diimine;
putting a three-neck flask filled with 516g of tetrahydrofuran into a high-precision moderate-temperature circulating bath at the temperature of 27 ℃, starting stirring, respectively adding 101.2g of deionized water and 46.9g of deuterated benzylamine into the three-neck flask under the stirring of the rotation speed of 250rpm, then adding 25.4g of deuterated N, N' -di-tert-butyl ethane-1, 2-diimine into the three-neck flask in 5 batches, then dropwise adding deuterated acetic acid into the mixed solution at the dropping rate of 2.5m L/min through a constant-pressure dropping funnel, wherein the total volume of the deuterated acetic acid is 75.3m L, sealing the reaction system after the dropwise adding is finished, continuously stirring, carrying out suction filtration on the mixed solution after 5 hours, washing precipitates on filter paper by using 5 ℃ tetrahydrofuran in the suction filtration process until the pH value of the filtrate is neutral, and then drying the filter paper in a vacuum drying box at the temperature of 27 ℃ for 11 hours to obtain 27.6g of substituted hexabenzylhexaazaisowurtzitane;
dissolving 27.6g of deuterated hexabenzylhexaazaisowurtzitane in 372.5g of chloroform, transferring the mixed solution into a high-pressure reaction kettle with a stirring device after the dissolution is finished, respectively adding 22.6g of deuterated acetic anhydride and 6.5g of deuterated diacetonitrilchloridized palladium chloride into the reaction kettle, sealing the reaction kettle, checking the sealing property of the reaction kettle, replacing air in the kettle with nitrogen for three times, then replacing the nitrogen in the kettle with deuterium for three times to make the kettle have a deuterium atmosphere, then introducing deuterium into the kettle for pressurization, closing an air inlet valve when the pressure in the kettle reaches 0.4MPa, then stirring at the speed of 400rpm, heating the high-pressure reaction kettle to 45 ℃, keeping the temperature for 6 hours, then injecting deuterium acetyl chloride into the kettle at the speed of 2.5m L/min by a high-pressure metering pump, wherein the total volume of the deuterium acetyl chloride is 16.0m L, continuing to keep the temperature for 11 hours, stopping stirring, performing vacuum filtration on the mixture in the kettle, washing the precipitate in a 5 ℃ chloroform, washing the filtrate until the filtrate is clarified, and drying the filtrate at the temperature of the filtrate of 10.7 ℃ to obtain 16.7g of deuterated hexaazaisowurtzitane;
placing a four-neck flask filled with 400.5g of deuterated nitric acid with the concentration of 97 percent in a high-precision constant-temperature bath at 4 ℃, stirring at the speed of 250rpm, slowly adding 16.7g of deuterated hexaacetylhexaazaisowurtzitane into the deuterated nitric acid in batches to maintain the temperature of the mixed solution to be not higher than 5 ℃, adding 5.0g of bismuth nitrate after the deuterated hexaacetylhexaazaisowurtzitane is dissolved, sealing a reaction device after the bismuth nitrate is dissolved, heating to 70 ℃, preserving the temperature for 3 hours, reducing the temperature to 30 ℃, slowly pouring the mixture into an ice water mixture of deionized water, quickly stirring the ice water mixture at the speed of 250rpm during pouring, performing suction filtration, washing a filter residue with deionized water for 5 times, and performing vacuum drying at 25 ℃ for 20 hours to obtain 15.7g of fully deuterated C L-20, wherein the yield is 87.4 percent (based on the deuterated hexabenzylhexaazaisowurtzitane) and the purity is 99.6 percent.
The crystal density of this sample was from 2.044g/cm, as compared with that of ordinary C L-203Increased to 2.070g/cm3The detonation velocity is increased to 9540m/s from 9380 m/s; at the same time, the initial decomposition temperature of the sample was 264 ℃, the friction sensitivity was 62N, and the impact sensitivity was H5032cm, the thermal stability is increased compared with the ordinary C L-20, and the sensitivity is reduced to a certain extent.
Example 4
Placing a three-neck flask filled with 63.9g of deuterated tert-butylamine in a high-precision medium-temperature circulating bath at the temperature of 24 ℃, starting stirring, dropwise adding a deuterated glyoxal solution with the mass fraction of 60% into the deuterated tert-butylamine at the dropping rate of 3m L/min through a constant-pressure dropping funnel under the stirring of the rotation speed of 300rpm, continuing stirring for 60 minutes after the dropwise adding is finished, then adding 447g of deionized water into the mixed solution, standing for 10 minutes, carrying out suction filtration on the mixture, washing precipitates on filter paper by using the deionized water in the suction filtration process until the pH value of the filtrate is neutral, and then drying residues in a vacuum drying box at the temperature of 30 ℃ for 12 hours to obtain 45.1g of deuterated N, N' -di-tert-butyl ethane-1, 2-diimine;
putting a three-neck flask filled with 1265g of tetrahydrofuran into a high-precision moderate-temperature circulating bath at the temperature of 30 ℃, starting stirring, respectively adding 210.8g of deionized water and 97.3g of deuterated benzylamine into the three-neck flask under the stirring of the rotation speed of 300rpm, then adding 45.1g of deuterated N, N' -di-tert-butyl ethane-1, 2-diimine into the three-neck flask in 6 batches, then dropwise adding deuterated acetic acid into the mixed solution at the dropping rate of 5m L/min through a constant-pressure funnel, wherein the total volume of the deuterated acetic acid is 179.1m L, sealing the reaction system after the dropwise adding is finished, continuously stirring, carrying out suction filtration on the mixed solution after 6 hours, washing precipitates on filter paper by using 5 ℃ of tetrahydrofuran in the suction filtration process until the pH value of the filtrate is neutral, and then drying residues in a vacuum drying box at the temperature of 30 ℃ for 12 hours to obtain 50.4g of hexabenzylhexaazaisowurtzitane;
dissolving 50.4g of deuterated hexabenzylhexaazaisowurtzitane in 753.6g of chloroform, transferring the mixed solution into a high-pressure reaction kettle with a stirring device after the dissolution is finished, respectively adding 49.1g of deuterated acetic anhydride and 12.1g of deuterated diacetonitrilchloridized palladium chloride into the reaction kettle, sealing the reaction kettle, checking the sealing property of the reaction kettle, replacing air in the kettle with nitrogen for three times, then replacing the nitrogen in the kettle with deuterium for three times to make the kettle have a deuterium atmosphere, then introducing deuterium into the kettle for pressurization, closing an air inlet valve when the pressure in the kettle reaches 0.5MPa, then stirring at the speed of 500rpm, heating the high-pressure reaction kettle to 50 ℃, keeping the temperature for 7 hours, then injecting deuterium acetyl chloride into the kettle at the speed of 2.5m L/min by a high-pressure metering pump, wherein the total volume of the deuterium acetyl chloride is 33.6m L, continuing to keep the temperature for 12 hours, stopping stirring, performing vacuum filtration on the mixture in the kettle, washing the precipitate in a 5 ℃ chloroform, and drying the clarified acetyl chloride in a vacuum filtration filter paper at the temperature of 25.12 ℃ to obtain the iso-filtered hexaazaisowurtzitane;
placing 779g of a four-neck flask containing 98% deuterated nitric acid in a high-precision constant-temperature bath at 4 ℃, stirring at the speed of 300rpm, slowly adding 31.2g of deuterated hexaacetylhexaazaisowurtzitane into the deuterated nitric acid in batches to maintain the temperature of the mixed solution to be not higher than 5 ℃, adding 9.2g of bismuth nitrate after the deuterated hexaacetylhexaazaisowurtzitane is dissolved, sealing the reaction device after the bismuth nitrate is dissolved, heating to 80 ℃, keeping the temperature for 4 hours, reducing the temperature to 30 ℃, then slowly pouring the mixture into an ice-water mixture of deionized water, rapidly stirring the ice-water mixture at the speed of 300rpm during pouring, performing suction filtration, washing a filter residue with deionized water for 5 times, and performing vacuum drying at the temperature of 25 ℃ for 20 hours to obtain 30.1g of fully deuterated C L-20, wherein the yield is 88.8% (based on the deuterated hexabenzylhexaazaisowurtzitane) and the purity is 99.8%.
The crystal density of this sample was from 2.044g/cm, as compared with that of ordinary C L-203Increased to 2.072g/cm3The detonation velocity is increased to 9549m/s from 9380 m/s; at the same time, the initial decomposition temperature of the sample was 267 ℃, the friction sensitivity was 64N, and the impact sensitivity was H5033cm, the thermal stability is increased compared with the common C L-20, and the sensitivity is reduced to a certain extent.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (2)

1. A preparation method of deuterated C L-20 is characterized by comprising the following steps:
placing a three-neck flask filled with deuterated tert-butylamine in a high-precision medium-temperature circulating bath at the temperature of not higher than 25 ℃, starting stirring, dropwise adding a deuterated glyoxal solution into the deuterated tert-butylamine at a dropping rate of 1-5 m L/min through a constant-pressure dropping funnel under the stirring at the rotating speed of 200-300 rpm, wherein the molar ratio of the deuterated glyoxal to the deuterated tert-butylamine is 1 (2.3-3), continuing stirring for 30-60 minutes after the dropwise adding is finished, then adding deionized water into the mixed solution, wherein the mass ratio of the deionized water to the deuterated tert-butylamine is (4-7): 1, standing for 10 minutes, performing suction filtration on the mixture, washing precipitates on filter paper by using the deionized water in the suction filtration process until the pH value of the filtrate is neutral, and then drying the filter residue in a vacuum drying box at the temperature of 25-30 ℃ for 8-12 hours to obtain deuterated N, N' -di-tert-butylethane-1, 2-diimine;
placing a three-neck flask filled with tetrahydrofuran in a high-precision medium-temperature circulating bath at the temperature of 25-30 ℃, starting stirring, respectively adding deionized water and deuterated benzylamine into the three-neck flask under the stirring of the rotation speed of 200-300 rpm, wherein the mass ratio of tetrahydrofuran to deionized water is (4-6): 1, and the mass ratio of tetrahydrofuran to deuterated benzylamine is (7-13): 1, then adding 3-6 batches of deuterated N, N '-di-tert-butylethane-1, 2-diimine obtained in the first step into the three-neck flask, wherein the molar ratio of deuterated N, N' -di-tert-butylethane-1, 2-diimine to deuterated benzylamine is 1 (2.5-3.5), then dropwise adding deuterated acetic acid into the mixed solution at the dropping rate of 0.5-5 m L/min through a constant-pressure dropping funnel, wherein the mass of deuterated acetic acid is 1-2 times that of deuterated benzylamine, sealing the reaction system after dropwise adding, continuously stirring, performing suction filtration on the mixed solution for 3-6 hours, performing suction filtration on the filtered and drying on the filtered and the filtered six-neck flask with pH value of 5, and drying the filtered tetrahydrofuran at the temperature of 25-30 ℃, and drying the filtrate, and obtaining the filtrate;
dissolving the deuterated hexabenzylhexaazaisowurtzitane obtained in the step two in chloroform, wherein the mass ratio of the deuterated hexabenzylhexaazaisowurtzitane to the chloroform is 1 (10-15), transferring the mixed solution into a high-pressure reaction kettle with a stirring device after the dissolution is finished, respectively adding deuterated acetic anhydride and deuterated diacetonitrileachloropalladium into the reaction kettle, wherein the molar ratio of the deuterated hexabenzylhexaazaisowurtzitane to the deuterated acetic anhydride is 1 (3-6), the molar ratio of the deuterated diacetonitrileachloropalladium chloride to the deuterated acetic anhydride is 1 (5-10), sealing the reaction kettle, checking the sealing property of the reaction kettle, replacing the air in the reaction kettle with nitrogen for three times, replacing the nitrogen in the reaction kettle with deuterium for three times to ensure that the deuterium is in a deuterium air atmosphere, introducing deuterium air into the reaction kettle for pressurizing, closing an air inlet valve when the pressure in the reaction kettle reaches 0.3-0.5 MPa, stirring at the speed of 300-500 rpm, heating the high-pressure reaction kettle to 35 ℃, keeping the temperature for 4 hours, then introducing the deuterium air for pressurizing, performing suction filtration on the filtrate until the filtrate reaches 0.3-0.5 MPa, performing suction filtration on the filtrate, and drying on the filtrate in the filtrate at the filtrate, wherein the filtrate A, the filtrate, performing vacuum filtration is performed on the filtrate until the filtrate, and the filtrate, wherein the filtrate, the filtrate is the;
and fourthly, placing the four-mouth flask filled with the deuterated nitric acid in a high-precision constant-temperature bath at the temperature of not higher than 5 ℃, stirring at the speed of 200-300 rpm, slowly adding the deuterated hexaacetylhexaazaisowurtzitane obtained in the third step into the deuterated nitric acid in batches, keeping the temperature of the mixed solution at the temperature of not higher than 5 ℃, wherein the mass ratio of the deuterated hexaacetylhexaazaisowurtzitane to the deuterated nitric acid is 1 (20-25), adding bismuth nitrate after the deuterated hexaacetylhexaazaisowurtzitane is dissolved, wherein the mass ratio of the deuterated nitric acid to the bismuth nitrate is (70-85): 1, sealing the reaction device after the bismuth nitrate is dissolved, heating to 60-80 ℃, keeping the temperature for 2-4 hours, reducing to 30-35 ℃, slowly pouring the mixture into a deionized water mixture, quickly stirring the mixture at the speed of 200-300 rpm in the pouring process, performing suction filtration, washing 3-5 times with deionized water, and drying at the temperature of 20-40 ℃ under vacuum for 12-24 hours to obtain fully substituted C-L.
2. The method of claim 1, wherein: in the first step, the mass fraction of the deuterated glyoxal solution is 40-60%.
CN202010386165.2A 2020-05-09 2020-05-09 Preparation method of fully deuterated C L-20 Pending CN111471052A (en)

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