6, 8-dinitroquinazoline-2, 4 (1H, 3H)-diketone energetic compound and synthesis method thereof

Abstract

The invention discloses a 6, 8-dinitroquinazoline-2, 4 (1H, 3H)-diketone energetic compound and a synthesis method of the 6, 8-dinitroquinazoline-2, 4 (1H, 3H)-diketone energetic compound. The structural formula of the 6, 8-dinitroquinazoline-2, 4 (1H, 3H)-diketone is # imgabs 0 #, 4-amino-6, 8-dinitroquinazoline-2, 4-diamine is subjected to nitration reaction in a nitration reagent to generate 4-amino-6, 8-dinitroquinazoline-2 (1H)-ketone, then the 4-amino-6, 8-dinitroquinazoline-2 (1H)-ketone is dissolved in an organic solvent, an alkaline solution is added, reaction is performed to generate the 6, 8-dinitroquinazoline-2, 4 (1H, 3H)-diketone, and the 6, 8-dinitroquinazoline-2, 4 (1H, 3H)-diketone is prepared. (3H, 3H)-diketone. The 6, 8-dinitroquinazoline-2, 4 (1H, 3H)-diketone provided by the invention has good detonation performance, excellent thermal decomposition temperature, impact sensitivity and friction sensitivity, and has application potential as a heat-resistant insensitive material.

Description

Technical Field

[0001] The invention belongs to the field of energetic materials and relates to a 6,8-dinitroquinazoline-2,4(1H,3H)-dione energetic compound and a synthesis method thereof. Background Art

[0002] As a unique branch of materials science, energetic materials have developed rapidly in recent years. Energetic materials include explosives, propellants and fireworks. Among them, explosives with a thermal decomposition temperature (onset) higher than 250°C are defined as heat-resistant explosives. Traditional heat-resistant explosives include triaminotrinitrobenzene (TATB), 2,2',4,4',6,6'-hexylnitrostilbene (HNS), 3,5-dinitro-2,6-dinitroaminopyridine (PYX), 1-oxy-2,6-diamino-3,5-dinitropyrazine (LLM-105), etc. Their skeletons are mainly composed of aromatic benzene rings and six-membered nitrogen heterocycles (pyridine, pyrazine). Most of them have some defects and cannot meet the growing demand for high-performance heat-resistant explosives. For example, although HNS and PYX have higher thermal decomposition temperatures of 318°C and 360°C, respectively, their detonation performance is relatively low. Another example is the recently reported 5,5'-bis(2,4,6-trinitrophenyl)-2,2'-bis(1,3,4-oxadiazole) (TKX-55), which has relatively poor temperature resistance compared with other common heat-stable explosives. Therefore, the development of advanced heat-resistant explosives with high thermal stability and superior detonation performance remains an urgent and ongoing goal.

[0003] Condensed rings are generally considered to be polycyclic compounds formed by two or more carbon rings or heterocyclic rings with two common atoms. Condensed ring compounds may lead to higher thermal decomposition temperatures due to their larger conjugated system, which has great application potential in the field of heat-resistant materials. Based on the above advantages, in recent years, the design and synthesis of condensed ring energetic compounds with high thermal stability based on condensed ring energetic skeletons has set off a wave of research in the field. Summary of the invention

[0004] The present invention aims to provide a 6,8-dinitroquinazoline-2,4(1H,3H)-dione energetic compound and a synthesis method thereof.

[0005] The technical solution for achieving the purpose of the present invention is as follows:

[0006] 6,8-Dinitroquinazoline-2,4(1H,3H)-dione energetic compound, the structural formula is as follows:

[0007]

[0008] The synthesis method of the above 6,8-dinitroquinazoline-2,4(1H,3H)-dione energetic compound comprises the following specific steps:

[0009] (1) 6-nitroquinazoline-2,4-diamine is subjected to nitration reaction in a nitrating agent to generate 4-amino-6,8-dinitroquinazoline-2(1H)-one, wherein the nitrating agent is selected from a mixed system of fuming sulfuric acid and potassium nitrate, or a mixed system of potassium nitrate and 98% sulfuric acid, or a mixed system of nitric acid and sulfuric acid, and the reaction formula is as follows:

[0010]

[0011] (2) 4-amino-6,8-dinitroquinazoline-2(1H)-one is dissolved in an organic solvent, and an alkaline solution is added to react to generate 6,8-dinitroquinazoline-2,4(1H,3H)-dione, wherein the organic solvent is selected from acetonitrile or methanol, and the reaction formula is as follows:

[0012]

[0013] Preferably, in step (1), the mass ratio of potassium nitrate or nitric acid to 6-nitroquinazoline-2,4-diamine is (1-15):1.

[0014] Preferably, in step (1), in the mixed system of oleum and potassium nitrate, the mass ratio of oleum to potassium nitrate is (1-5):1.

[0015] Preferably, in step (1), the reaction temperature is 0 to 100° C. and the reaction time is 1 to 24 h.

[0016] Preferably, in step (2), the reaction temperature is 25°C to 100°C, and the reaction time is 1 to 24 hours.

[0017] Preferably, in step (2), the alkaline solution is selected from sodium carbonate solution, sodium hydroxide solution or sodium bicarbonate solution.

[0018] Compared with the prior art, the present invention has the following advantages:

[0019] (1) The reaction steps of the present invention are simple, the experimental process is safe and efficient, and the raw materials are cheap and easily available, the cost is low, the experimental process is safe and efficient, and the yield is high, which can reach 70%;

[0020] (2) The 6,8-dinitroquinazoline-2,4(1H,3H)-dione of the present invention has good detonation performance (D = 7908 m s -1 , P = 24.75GPa), its thermal decomposition temperature is 325℃, which is close to HNS (318℃). Its actual impact sensitivity and friction sensitivity (IS>40J, FS>360N) are greater than HNS (IS=5J, FS=240N). It has good stability and heat resistance and can be used as a heat-resistant insensitive material. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 This is the nuclear hydrogen-carbon spectrum of 4-amino-6,8-dinitroquinazolin-2(1H)-one.

[0022] Figure 2 This is the carbon NMR spectrum of 4-amino-6,8-dinitroquinazolin-2(1H)-one.

[0023] Figure 3 This is the H NMR spectrum of 6,8-dinitroquinazoline-2,4(1H,3H)-dione.

[0024] Figure 4 This is the NMR carbon spectrum of 6,8-dinitroquinazoline-2,4(1H,3H)-dione.

[0025] Figure 5 This is the DSC chart of 6,8-dinitroquinazoline-2,4(1H,3H)-dione. DETAILED DESCRIPTION

[0026] The present invention will be further described below in conjunction with specific embodiments and accompanying drawings.

[0027] In the following examples, 6-nitroquinazoline-2,4-diamine was prepared with reference to existing literature (Design, synthesis and cytotoxic evaluation of quinazoline-2,4,6-triamine and 2,6-diaminoquinazolin-4(3H)-one derivatives).

[0028] Example 1

[0029] (1) At room temperature, 6-nitroquinazoline-2,4-diamine (2.05 g, 10 mmol) was dissolved in 16 mL of fuming sulfuric acid, and KNO3 (6.634 g 65.62 mmol) was added. The reaction was carried out at 70°C for 6 h, quenched with ice water, filtered, and dried at room temperature to obtain 4-amino-6,8-dinitroquinazoline-2(1H)-one as a yellow solid (1.57 g). The yield was 62.5%.

[0030] 1 H NMR chemical shifts (300MHz, DMSO-d6, ppm): δ = 12.23 (s, 1H), 10.95 (s, 1H), 9.03 (s, 1H), 8.82 (s, 2H) ppm. 13C NMR chemical shifts (7MHz, DMSO-d6, ppm): δ = 160.15, 155.37, 148.88, 143.37, 139.13, 134.46, 124.83, 118.37ppm. IR (KBr, cm -1 ): 3174.28,3092.94,2824.41,1624.68,1495.72,1343.65,1241.35,1083.92,922.78,760.08,692.74,618.88.Elemental analysis calcd(%)for C8H5N5O5(251.16): C 38.26, H 2.01, N27.88, O 31.85., found: C 37.94, H 2.12, N 28.01, O 31.93%.

[0031] (2) 4-Amino-6,8-dinitroquinazoline-2(1H)-one (0.25 g, 1 mmol) and Na2CO3 (0.11 g, 1 mmol) were added to acetonitrile. The reaction mixture was stirred at 50°C for 1 h. The precipitate was collected by filtration and air-dried to obtain 6,8-dinitroquinazoline-2,4(1H,3H)-dione as a yellow solid (0.176 g). The yield was 70%.

[0032] 1 H NMR chemical shifts (300MHz, DMSO-d6): δ = 8.89 (s, 1H), 8.80 (s, 1H) ppm; 13 CNMR chemical shifts (75MHz, DMSO-d6): δ=160.01,155.37,148.88,143.37,140.30,134.46,126.03ppm.IR(KBr,cm -1 ): 3174.29,3092.94,2824.41,1476.00,1343.65,1270.84,1083.29,922.78,859.06,789.44,738.15,692.74.Elemental analysiscalcd(%)for C8H4N4O6 (252.14): C 38.11, H 1.60, N 22.22, O 38.07; found: C 38.26, H1.72, N22.78, O 37.24%.

[0033] Comparative Example 1

[0034] This example is basically the same as Example 1, except that the fuming sulfuric acid in step (1) is changed to 31.5 mL, and the other reaction conditions remain unchanged. After the reaction is completed, the reaction is quenched with ice water, and no solid is precipitated. After extraction with ethyl acetate, 0.247 g of yellow solid is obtained, and the yield is 9.84%.

[0035] Example 2

[0036] This example is basically the same as Example 1, except that the reaction temperature in step (1) is changed to 60°C, and the other reaction conditions remain unchanged. After the reaction is completed, the reaction is quenched with ice water to obtain 1.02 g of yellow solid, with a yield of 40.6%.

Claims

1. 6,8-Dinitroquinazoline-2,4(1H,3H)-dione energetic compound, characterized in that: The structural formula is as follows: 。 2. The method for synthesizing the 6,8-dinitroquinazoline-2,4(1H,3H)-dione energetic compound according to claim 1, characterized in that: The specific steps are as follows: (1) 6-nitroquinazoline-2,4-diamine is subjected to nitration reaction in a nitrating agent to generate 4-amino-6,8-dinitroquinazoline-2(1H)-one, wherein the nitrating agent is selected from a mixed system of fuming sulfuric acid and potassium nitrate, or a mixed system of potassium nitrate and 98% sulfuric acid, or a mixed system of nitric acid and sulfuric acid, and the reaction formula is as follows: ； (2) 4-amino-6,8-dinitroquinazoline-2(1H)-one is dissolved in an organic solvent, and an alkaline solution is added to react to generate 6,8-dinitroquinazoline-2,4(1H,3H)-dione, wherein the organic solvent is selected from acetonitrile or methanol, and the reaction formula is as follows: 。 3. The synthesis method according to claim 2, characterized in that In step (1), the mass ratio of potassium nitrate or nitric acid to 6-nitroquinazoline-2,4-diamine is (1-15):

1.

4. The synthesis method according to claim 2, characterized in that In step (1), in the mixed system of oleum and potassium nitrate, the mass ratio of oleum to potassium nitrate is (1-5):

1.

5. The synthesis method according to claim 2, characterized in that In step (1), the reaction temperature is 0-100° C. and the reaction time is 1-24 h.

6. The synthesis method according to claim 2, characterized in that In step (2), the reaction temperature is 25°C to 100°C, and the reaction time is 1 to 24 h.

7. The synthesis method according to claim 2, characterized in that In step (2), the alkaline solution is selected from sodium carbonate solution, sodium hydroxide solution or sodium bicarbonate solution.

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