3-amino-4-(5-hydroxyamino-6H-1, 2, 4-oxadiazine-3-yl)-furazan compound and synthetic method thereof

Abstract

The invention discloses a 3-amino-4-(5-hydroxyamino-6H-1, 2, 4-oxadiazine-3-yl)-furazan compound and a synthesis method thereof, the structural formula of the 3-amino-4-(5-hydroxyamino-6H-1, 2, 4-oxadiazine-3-yl)-furazan compound is as follows: # imgabs0 #, the theoretical detonation velocity of the 3-amino-4-(5-hydroxyamino-6H-1, 2, 4-oxadiazine-3-yl)-furazan compound is 7099m / s, the theoretical detonation pressure is 18.3 GPa, the molecular stability is better, the 3-amino-4-(5-hydroxyamino-6H-1, 2, 4-oxadiazine-3-yl)-furazan compound can nitryl and other high-energy groups are easily introduced; the material can be applied to composite explosives and solid propellants.

Description

Technical Field

[0001] The present invention belongs to the field of energetic materials and relates to a 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazine-3-yl)-furazan compound and a synthesis method thereof. Background Art

[0002] Furazan rings are highly strained, contain high-energy O—N and C—N bonds, and possess a π-structure, making the compound highly stable and amenable to reactions such as nitration and halogenation. Linking to other rings can further modulate its properties. 1,2,4-Oxadiazines, as important heterocyclic compounds, are commonly found in pharmaceutical molecules and exhibit promising anticancer, antiviral, antibacterial, and herbicidal activities. However, the theoretical detonation velocity of existing 1,2,4-Oxadiazines is too low to be suitable for practical applications, and their application in the field of energetic materials remains to be explored. Summary of the Invention

[0003] In view of the shortcomings of the prior art, the object of the present invention is to provide a 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazine-3-yl)-furazan compound and a synthesis method thereof, so as to solve the problem of too low detonation velocity of the 1,2,4-oxadiazine compound obtained in the prior art.

[0004] In order to solve the above technical problems, the present invention adopts the following technical solutions:

[0005] A 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furoxan compound, whose structural formula is shown in (I):

[0006]

[0007] The synthesis method of the 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazine-3-yl)-furoxan compound comprises the following steps:

[0008] Under stirring at room temperature, 3-amino-4-(5-chloromethyl-1,2,4-oxadiazol-3-yl)-furazan was added to methanol. After dissolution, hydroxylamine hydrochloride and sodium bicarbonate were poured in sequence. After the addition was completed, the reaction system was heated and reacted. Water was added to the reaction solution and stirred again. The reaction solution was filtered, washed with deionized water, and dried to obtain 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furazan.

[0009] The present invention also includes the following technical features:

[0010] Specifically, after the addition is completed, the reaction system is heated to 40-45° C. and reacted for 8 hours.

[0011] Specifically, water was added to the reaction solution and stirred for 30 min.

[0012] Specifically, the molar ratio of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazol-3-yl)-furazan, hydroxylamine hydrochloride and sodium bicarbonate is 1:2.4:3.

[0013] Compared with the prior art, the present invention has the following technical effects:

[0014] The 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazine-3-yl)-furoxan of the present invention has a new energetic compound parent structure, a theoretical detonation velocity of 7099 m / s, and a theoretical detonation pressure of 18.3 GPa.

[0015] The 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furazan of the present invention has a single crystal structure, the crystal stacking mode is a wavy layered stacking, the molecular stability is good, it can adapt to strong chemical reaction conditions to a certain extent, and high-energy groups such as nitro groups are easily introduced. DETAILED DESCRIPTION

[0016] The present invention provides a 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furazan compound and a synthesis method thereof. The structural formula of the 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furazan compound is shown in (I):

[0017]

[0018] The synthetic route of 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazine-3-yl)-furazan of the present invention is as follows:

[0019]

[0020] 3-Amino-4-(5-chloromethyl-1,2,4-oxadiazol-3-yl)-furoxan, hydroxylamine hydrochloride and sodium bicarbonate are used as raw materials and methanol is used as solvent. The reaction is carried out at 40-45°C for 8 hours to obtain 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furoxan.

[0021] The synthesis method of 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazine-3-yl)-furazan of the present invention comprises the following steps:

[0022] Under stirring at room temperature, 3-amino-4-(5-chloromethyl-1,2,4-oxadiazol-3-yl)-furazan was added to methanol at one time. After all the raw materials were dissolved, hydroxylamine hydrochloride and sodium bicarbonate were poured in one go. After the addition was completed, the reaction system was heated and reacted at 40-45° C. for 8 hours. Water was added to the reaction solution and stirred for another 30 minutes to dissolve the remaining inorganic salts. The reaction solution was filtered, washed with deionized water, and dried to obtain 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furazan, wherein the molar ratio of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazol-3-yl)-furazan, hydroxylamine hydrochloride and sodium bicarbonate was 1:2.4:3.

[0023] Specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent modifications made on the basis of the technical solution of this application fall within the protection scope of the present invention.

[0024] Example 1:

[0025] This example provides a 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furoxan compound and a synthesis method thereof. Under stirring at room temperature, 3-amino-4-(5-chloromethyl-1,2,4-oxadiazin-3-yl)-furoxan (0.52 g, 2.58 mmol) was dissolved in 10 mL of methanol, and hydroxylamine hydrochloride (0.43 g, 6.2 mmol) and sodium bicarbonate (0.65 g, 7.74 mmol) were added in sequence. After the addition was completed, the system was heated and reacted at 40-45° C. for 8 h. Water was added to the reaction solution and stirred for 30 min. The reaction solution was filtered, washed with deionized water, and dried to obtain 0.2 g of 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furoxan, with a yield of 39% and a purity of 99.8% (HPLC). The molar ratio of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazol-3-yl)-furoxan, hydroxylamine hydrochloride and sodium bicarbonate is 1:2.4:3.

[0026] The structure of 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furazan prepared in this example is identified as follows:

[0027] Crystal structure characterization: The single crystal molecular structure of 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furazan compound is shown below:

[0028]

[0029] Its crystal data and structure refinement parameters are shown in Table 1.

[0030] Table 1 Crystallographic data and structure refinement parameters of 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furoxan

[0031]

[0032]

[0033] Infrared spectrum: IR (KBr), v (cm -1 ): 3453,3415,3338,2920,1697,1631,1595,1574,1565,1545,1502,1478,1438,1370,1341,1055,997,948,917,906,865;

[0034] NMR spectroscopy: 1 HNMR(DMSO-d6,500MHz), δ:10.55(1H,s,OH),9.85(1H,s,NH),6.33(2H,s,NH2),4.48(2H,s,CH2);

[0035] 13 C NMR (DMSO-d6, 125MHz), δ: 154.87, 142.96, 138.87, 138.24, 63.54ppm.;

[0036] Elemental analysis: Molecular formula: C5H6N6O3

[0037] Theoretical values: C 30.31, H 3.05, N 42.42;

[0038] Found: C 29.63, H 3.54, N 42.34.

[0039] The substance obtained by the above preparation method was confirmed to be 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furazan.

[0040] Properties of 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furazan:

[0041] (1) Physical and chemical properties

[0042] Appearance: Colorless transparent block crystals

[0043] Solubility: Soluble in methanol, ethyl acetate, slightly soluble in water and acetic acid.

[0044] Density: 1.697g / cm 3 X-ray diffraction method friction feel (FS): 360N

[0045] Impact (IS): 40J

[0046] (2) Detonation performance

[0047] Detonation velocity: Density 1.697g / cm 3 , calculated detonation velocity is 7099.1m / s EXPLO5 6.04 Detonation pressure: density is 1.697g / cm 3 , calculated explosion pressure is 18.3GPa EXPLO5 6.04 explosion heat: density is 1.697g / cm 3 , calculated explosion heat is -4435.7 kJ / kg EXPLO5 6.04 Formation enthalpy: density is 1.697 g / cm 3 , the calculated formation enthalpy is 191.2 kJ / mol Gaussian 09 program B3LYP / 6-31G** method

[0048] Application of 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furazan:

[0049] The 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazine-3-yl)-furazan of the present invention can be used as a melt-cast explosive carrier and applied in the fields of explosives and propellants.

Claims

1. A 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furoxan compound, characterized in that: Its structural formula is shown in (I):

2. The method for synthesizing the 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furoxan compound according to claim 1, characterized in that: The following steps are involved: Under stirring at room temperature, 3-amino-4-(5-chloromethyl-1,2,4-oxadiazol-3-yl)-furazan was added to methanol. After dissolution, hydroxylamine hydrochloride and sodium bicarbonate were poured in sequence. After the addition was completed, the reaction system was heated and reacted. Water was added to the reaction solution and stirred again. The reaction solution was filtered, washed with deionized water, and dried to obtain 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furazan.

3. The method for synthesizing the 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furoxan compound according to claim 2, wherein: After the addition was completed, the reaction system was heated to 40-45°C and reacted for 8 hours.

4. The method for synthesizing the 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furoxan compound according to claim 2, wherein: Water was added to the reaction solution and stirred for another 30 min.

5. The method for synthesizing the 3-amino-4-(5-hydroxyamino-6H-1,2,4-oxadiazin-3-yl)-furoxan compound according to claim 2, wherein: The molar ratio of 3-amino-4-(5-chloromethyl-1,2,4-oxadiazol-3-yl)-furoxan, hydroxylamine hydrochloride and sodium bicarbonate is 1:2.4:3.

Images