CN113321666B - Energy-containing compound based on ring-fused framework and synthetic method thereof - Google Patents
Energy-containing compound based on ring-fused framework and synthetic method thereof Download PDFInfo
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- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
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Abstract
The invention discloses an energy-containing compound based on a ring-merging framework and a synthesis method thereof. The energetic compound is 1, 5-dinitro-4, 8-bis (methylene) diacetate-14,5,8 tetraazahydronaphthalene (2,3,6,7) benzofuroxan of the formula
Description
Technical Field
The invention belongs to the technical field of organic energetic materials, and relates to an energetic compound based on a fused ring framework and a synthesis method thereof.
Background
The energetic material is a key material basis for developing advanced weaponry, is a power energy source for completing the launching of gun and cannon shots and the propelling of rocket missiles, is a power energy source for damaging warheads, and is also a power energy source of boosting, capital adjusting and separating devices used for space delivery, space exploration and aviation lifesaving. Modern High Energy Density Materials (HEDM) have been widely used for civil and military applications. The performance of HEDM is evaluated by the burst pressure (P) and burst velocity (D), which are related to density, oxygen balance and heat of formation. The construction of the compound skeleton of the aza-condensed ring provides a thought for introducing energy-containing groups such as nitro-ammonium group and the like, the rigidity of a mother body ring is high, and the compound skeleton has the characteristics of high energy density, compact structure and the like. However, the azabicyclic compounds have not been represented to date by any prominent compound structure. However, the requirements for insensitivity and stability and the introduction of more functional groups with abundant energy are often contradictory, and the contradiction between energy, sensitivity and stability of the conventional CHNO explosive is realized, so that the problems of sensitivity, stability, environmental friendliness of the decomposed product after explosion, product cost in the explosive production and manufacturing process and the like are considered while the energy density of the compound is pursued.
Willer combines tetracyclic compounds in HNO3/TFAA or HNO3/N2O5Nitration under a nitration system to obtain a tetranitro fused ring compound, however, the structure is not stable due to the large number of nitro groups, and the tetranitro fused ring compound can only be stored at a temperature of-20 ℃ or lower basically, and cannot be practically used (Willer R L. Synthesis of 1, 4-dinitrofurazono [3,4-b ]]piperazine)。
Disclosure of Invention
The invention aims to provide an energy-containing compound based on a fused ring framework and a synthesis method thereof.
The technical solution for realizing the purpose of the invention is as follows:
the energy-containing compound based on the polycyclic skeleton is 1, 5-dinitro-4, 8-bis (methylene) diacetate-1, 4,5, 8-tetraazahydrogenated naphthalene (2,3,6,7) furoxan with the structural formula
The synthesis method of the energy-containing compound based on the polycyclic skeleton is prepared by reacting an intermediate 4, 8-diformyl-1, 4,5, 8-tetraazahydronaphthalene (2,3,6,7) and bisfurazan with a nitration system, and the reaction equation is as follows:
the method comprises the following specific steps:
slowly adding 4, 8-diformyl-1, 4,5, 8-tetraazahydronaphthalene (2,3,6,7) and difurazan into a nitration system, stirring, controlling the temperature at-10-0 ℃, after the addition is finished, keeping the temperature at-10-0 ℃ for reaction, pouring into ice water, filtering, washing, drying, and evaporating the solvent to obtain 1, 5-dinitro-4, 8-di (methylene) diacetate-1, 4,5, 8-tetraazahydronaphthalene (2,3,6,7) and difurazan.
Preferably, the nitration system is selected from nitric acid/acetic anhydride (HNO)3/Ac2O) or nitric acid/trifluoroacetic anhydride (HNO)3/TFAA), more preferably HNO3/Ac2O。
Preferably, the mass volume ratio of the 4, 8-diformyl-1, 4,5,8 tetraazahydronaphthalene (2,3,6,7) benzofuroxan to nitric acid in the nitration system is 1: 8-1: 14, g: ml; more preferably 1:8 to 1:10, g: and (3) ml.
Preferably, the mass-to-volume ratio of the 4, 8-diformyl-1, 4,5,8 tetraazahydronaphthalene (2,3,6,7) and bisfurazan to the nitration system is 1: 5-50, g: and (mL).
Preferably, the reaction time is 2 to 24 hours.
Preferably, said HNO3/Ac2In the O nitration system, HNO3Has a concentration of 98% Ac2The concentration of O was 100%.
Preferably, said HNO3HNO in the nitration System of/TFAA3The concentration of (3) was 98% and the concentration of TFAA was 100%.
Compared with the prior art, the invention has the following advantages:
the invention synthesizes energy-containing compounds based on a polycyclic framework, namely 1, 5-dinitro-4, 8-bis (methylene) diacetate-1, 4,5, 8-tetraazahydronaphthalene (2,3,6,7) furoxan for the first time. The measured density of the energetic compound is 1.725g/cm3Density of single crystal 1.721g/cm3The thermal decomposition temperature is 210.3 ℃, the actual measured impact sensitivity is 20J, the friction sensitivity is 270N, the calculated detonation velocity is 7310m/s, the detonation pressure is 20.8Gpa, the performance is superior to TNT, and the thermal decomposition is stable at room temperature. The synthetic method is simple, the yield can reach 80 percent at most, the synthetic process is safe and controllable, mass production can be realized, and the method has wide application prospect in the fields of explosive formulations and other initiating explosive devices and the like.
Detailed Description
The present invention will be described in further detail with reference to examples.
The following examples are preferred examples, and are mainly for understanding the present invention, but the present invention is not limited to the examples.
1,4,5, 8-tetraazahydronaphthalene (2,3,6,7) and Bifurazan references [ Willer R L. Synthesis of 1, 4-dinofurozano [3,4-b ] piperazine ].
Example 1
a) Synthesis of intermediate 4, 8-diformyl-1, 4,5,8 tetraaza hydronaphthalene (2,3,6,7) and bisfurazan:
1.11g (0.050mol) of 1,4,5, 8-tetraaza-hydronaphthalene (2,3,6,7) and furazan were weighed into a mixed solution of 2mL of distilled water and 5mL of formaldehyde at room temperature, and 0.02mL of 98% H was added2SO4Reacting at room temperature for 3 days, collecting the product, filtering andand (5) drying. 1.03g of a reddish brown product is obtained, which is directly taken to the next reaction without purification.
b) Synthesis of 1, 5-dinitro-4, 8-bis (methylene) diacetate-1, 4,5, 8-tetraazahydronaphthalene (2,3,6,7) and bisfurazan:
weighing 4, 8-diformyl-1, 4,5, 8-tetraaza-hydronaphthalene (2,3,6,7) and bifurazan (0.50g, 0.002mol) at 0 ℃, slowly adding the weighed materials into 6mL fuming nitric acid in batches, then reducing the temperature of the mixed solution to-10 ℃, slowly adding 6mL of 100% acetic anhydride dropwise into the mixed solution, controlling the temperature in the dropwise adding process to be below 0 ℃, slowly heating the mixed solution to-5 ℃ for reaction for half an hour after the dropwise adding is finished, and then heating the mixed solution to 0 ℃ for reaction for 2 hours. After the reaction was completed, the mixed solution was slowly poured into 30mL of ice water to quench, and a tan solid was precipitated, filtered, and washed several times with ice water to obtain 0.35g of a solid with a yield of 60%.
Decomposition temperature of final product: 210.3 ℃;1H NMR:δ＝1.95(s,2H),5.47(s,2H),7.28(s,2H)ppm；13C NMR(125MHz,DMSO-d6):δ＝20.28,63.24,139.40,147.17,169.35ppm；IR(KBr pellet):3440,2922,1609,1555,1517,1450,1328,1257,1212,1112,979,854,775,729,694cm-1；Elemental analysis of C12H12N10O10(456.07):cal C 31.59,H 2.65,N 30.70％；found C31.53,H 2.73,N 30.72％。
further, 4, 8-diformyl-1, 4,5, 8-tetraazahydronaphthalene (2,3,6,7) and difurazan were put into a nitrating agent to be nitrated at-10 to 0 ℃ for 8 hours, and the post-reaction treatment operation was the same as the above experimental procedure, while maintaining the mass-to-volume ratio of 4, 8-diformyl-1, 4,5, 8-tetraazahydronaphthalene (2,3,6,7) and difurazan to acetic anhydride at 1:12 (g: ml) while maintaining the mass-to-volume ratio of 4, 8-diformyl-1, 4,5, 8-tetraazahydronaphthalene (2,3,6,7) and difurazan to fuming nitric acid at-10 to 0 ℃. The results showed that the nitration reaction yields were 67.2% and 80.1% when the mass-to-volume ratios of 4, 8-diformyl-1, 4,5,8 tetraazahydronaphthalene (2,3,6,7) and bisfurazan and fuming nitric acid were 1:8 and 1:10, respectively, and 60.2% and 67.5% when the mass-to-volume ratios were 1:12 and 1:14, respectively. By contrast, when 4, 8-bisFormyl-1, 4,5, 8-tetraazahydronaphthalene (2,3,6,7) and bis furazan and HNO3When the mass volume ratio is 1:10, the oxidation reaction yield is the highest and reaches 80.1%.
The measured density of the obtained high-energy insensitive energetic compound is 1.725g/cm3Density of single crystal 1.721g/cm3The thermal decomposition temperature is 210.3 ℃, the measured impact sensitivity is 20J, the friction sensitivity is 270N, the calculated detonation velocity is 7310m/s, and the detonation pressure is 20.8 Gpa.
Example 2
Nitric acid/trifluoroacetic anhydride is used as a nitration system.
Weighing 4, 8-diformyl-1, 4,5, 8-tetraazahydronaphthalene (2,3,6,7) and bifurazan (0.50g, 0.002mol) at 0 ℃, slowly adding the weighed materials into 6mL fuming nitric acid in batches, then reducing the temperature of the mixed solution to-10 ℃, slowly adding 6mL of 100% trifluoroacetic anhydride dropwise into the mixed solution, controlling the temperature in the dropwise adding process to be below 0 ℃, slowly heating the mixed solution to-5 ℃ after the dropwise adding is finished, reacting for half an hour, and then heating to 0 ℃ for reacting for 2 hours. After the reaction was completed, the mixed solution was slowly poured into 30mL of ice water to quench, and a tan solid was precipitated, filtered, and washed several times with ice water to obtain 0.32g of a solid with a yield of 58%.
Comparative example 1
Nitric acid/sulfuric acid is used as a nitration system.
Weighing 4, 8-diformyl-1, 4,5, 8-tetraaza-hydronaphthalene (2,3,6,7) and bis-furazan (0.50g) at 0 ℃ and slowly adding the mixture into 6mL of 100% pure nitric acid in batches, then reducing the temperature of the mixed solution to-10 ℃, slowly adding 6mL of 98% sulfuric acid dropwise into the mixed solution, controlling the temperature below 0 ℃ in the dropwise adding process, slowly heating the mixed solution to-5 ℃ for half an hour after the dropwise adding is finished, then heating the mixed solution to 0 ℃ for reaction for 2 hours, and after the reaction is finished, slowly pouring the mixed solution into 30mL of ice water for quenching, wherein the mixed solution is less in solid, is in the shape of carbonized concentrated sulfuric acid, does not have aldol condensation space occupying reaction with formyl and cannot introduce nitro.
Claims (8)
1. Energy-containing compound based on ring-fused frameworkThe compound is characterized in that the compound is 1, 5-dinitro-4, 8-bis (methylene) diacetate-1, 4,5, 8-tetraaza-hydrogenated naphthalene (2,3,6,7) furoxan with the structural formula
。
2. The method for synthesizing the energy-containing compound based on the polycyclic skeleton according to claim 1, wherein the reaction equation is as follows:
the third step of the reaction comprises the following specific steps:
slowly adding 4, 8-dihydroxymethyl-1, 4,5, 8-tetraazahydronaphthalene (2,3,6,7) and difurazan into a nitration system, stirring, controlling the temperature at-10 to 0 ℃, after the addition is finished, keeping the temperature at-10 to 0 ℃ for reaction, pouring into ice water, filtering, washing, drying, and evaporating a solvent to obtain 1, 5-dinitro-4, 8-di (methylene) diacetate-1, 4,5, 8-tetraazahydronaphthalene (2,3,6,7) and difurazan, wherein the nitration system is selected from HNO3/Ac2O or HNO3/TFAA。
3. The synthesis method according to claim 2, wherein the mass-to-volume ratio of the 4, 8-dihydroxymethyl-1, 4,5,8 tetraazahydronaphthalene (2,3,6,7) benzofuroxan to nitric acid in the nitration system is 1: 8-1: 14, g: and (3) ml.
4. The synthesis method according to claim 2, wherein the mass-to-volume ratio of the 4, 8-dihydroxymethyl-1, 4,5,8 tetraazahydronaphthalene (2,3,6,7) benzofuroxan to nitric acid in the nitration system is 1: 8-1: 10, g: and (3) ml.
5. The synthesis method according to claim 2, wherein the mass-to-volume ratio of the 4, 8-dihydroxymethyl-1, 4,5,8 tetraazahydronaphthalene (2,3,6,7) and bisfurazan to the nitration system is 1: 5-50, g: and (mL).
6. The synthesis method according to claim 2, wherein the reaction time is 2-24 h.
7. The synthesis method according to claim 3, wherein the HNO is HNO3/Ac2In the O nitration system, HNO3Has a concentration of 98% Ac2The concentration of O was 100%.
8. The synthesis method according to claim 3, wherein the HNO is HNO3HNO in the nitration System of/TFAA3The concentration of (3) was 98% and the concentration of TFAA was 100%.
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