3-azido-1-(1H-tetrazole-5-yl)-1H-1, 2, 4-triazole-5-amine and derivative and synthetic method thereof

Abstract

The invention discloses 3-azido-1-(1H-tetrazole-5-yl)-1H-1, 2, 4-triazole-5-amine as well as a derivative and a synthesis method of the 3-azido-1-(1H-tetrazole-5-yl)-1H-1, 2, 4-triazole-5-amine. The structural formula of the 3-azido-1-(1H-tetrazole-5-yl)-1H-1, 2, 4-triazole-5-amine is # imgabs 0 #, and the structural formula of the derivative of the 3-azido-1-(1H-tetrazole-5-yl)-1H-1, 2, 4-triazole-5-amine is # imgabs 1 #. The 3-azido-1-(1H-tetrazole-5-yl)-1H-1, 2, 4-triazole-5-amine and the derivative thereof disclosed by the invention have excellent detonation performance such as extremely high nitrogen content, high enthalpy of formation, high density, high detonation velocity, high initial thermal decomposition temperature and the like.

Description

Technical Field

[0001] The present invention belongs to the field of energetic materials and relates to 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HAATT), its derivatives and a synthesis method thereof. Background Art

[0002] Different from traditional energetic materials, in high-nitrogen energetic compounds, the mass percentage of nitrogen element is higher than that of carbon element, and their energy mainly comes from more high-energy N-N bonds and C-N bonds in the ring structure and greater ring strain. High-nitrogen energetic compounds generally have a high positive heat of formation, mostly do not contain nitro groups, have low sensitivity, good thermal stability, and the high-nitrogen and low-carbon-hydrogen content in the molecular structure makes it easier to achieve oxygen balance, and the combustion products are mostly environmentally friendly N. As a new type of multifunctional energetic materials, currently, research institutions at home and abroad all hope to find the fourth-generation energetic materials with high energy density and excellent safety performance, high-energy density materials, in these compounds (Yang Shiqing, Xu Songlin, Huang Hengjian, etc. High-Nitrogen Compounds and Their Energetic Materials [J]. Progress in Chemistry, 2008, 20(4): 526-537).

[0003] At present, there are many types of high-nitrogen energetic materials with excellent properties, but there are few reports on triazole-tetrazole high-nitrogen compounds. 3-Nitro-1-(2H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HANTT) synthesized by the research group of Zhou Zhiming has the structural formula Its density is 1.77 g / cm 3 , the theoretical detonation velocity is 8316 m / s, and the detonation pressure is 28.8 GPa, but its heat of formation is only 487 kJ / mol, and the nitrogen content is only 64% (Bian C, Zhang M, Li C, et al. 3-Nitro-1-(2H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HANTT) and its energetic salts: highly thermally stable energetic materials with low sensitivity [J]. Journal of Materials Chemistry A, 2014, 3(1): 163-169.). Summary of the Invention

[0004] The present invention provides 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine, its derivatives and a synthesis method thereof.

[0005] The 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine described in the present invention has the following structural formula:

[0006]

[0007] The HAATT derivative is (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azide, and its structural formula is as follows:

[0008]

[0009] The synthetic routes of the above HAATT and its derivatives are as follows:

[0010]

[0011] The synthetic method of the above HAATT is specifically as follows:

[0012] (1) Add 5-hydrazinyl-1H-tetrazole (Compound 1) to methanol or ethanol, then add cyanogen bromide. After the reaction, remove the solvent under vacuum, add water, adjust the pH of the solution to weakly alkaline, precipitate a solid, and filter and dry to obtain 3-azido-1H-1,2,4-triazol-5-amine (Compound 2);

[0013] (2) At 0 - 5 °C, dissolve 3-azido-1H-1,2,4-triazol-5-amine in an aqueous solution of potassium hydroxide, add cyanogen azide, stir at room temperature until the reaction is complete, filter and collect the filtrate, concentrate and adjust the pH to 1, precipitate a solid, and filter and dry to obtain 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HAATT, Compound 3).

[0014] The synthetic method of the above HAATT derivative is specifically as follows:

[0015] (1) Add 5-hydrazinyl-1H-tetrazole (Compound 1) to methanol or ethanol, then add cyanogen bromide. After the reaction, remove the solvent under vacuum, add water, adjust the pH of the solution to weakly alkaline, precipitate a solid, and filter and dry to obtain 3-azido-1H-1,2,4-triazol-5-amine (Compound 2);

[0016] (2) At 0 - 5 °C, dissolve 3-azido-1H-1,2,4-triazol-5-amine in an aqueous solution of potassium hydroxide, add cyanogen azide, stir at room temperature until the reaction is complete, filter and collect the filtrate, concentrate and adjust the pH to 1, precipitate a solid, and filter and dry to obtain 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HAATT, Compound 3);

[0017] (3) Dissolve 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine in hydrochloric acid. At 0-5 °C, dropwise add an aqueous solution of potassium permanganate, and heat and react at 35-50 °C. After the reaction is completed, filter and wash with ice water to obtain (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo (Compound 4).

[0018] Preferably, in step (1), the reaction temperature is 15-25 °C, the reaction time is 16 h; the pH of the weak base is 7.5-8.5, and the pH of the solution is adjusted using potassium bicarbonate or sodium bicarbonate.

[0019] Preferably, in step (2), the molar ratio of 3-azido-1H-1,2,4-triazol-5-amine to potassium hydroxide is 1:1.

[0020] Preferably, in step (2), the reaction temperature is 25-30 °C, the reaction time is 24 h; adjust the pH by adding hydrochloric acid or sulfuric acid solution.

[0021] Preferably, in step (3), the reaction temperature is 45 °C, and the heating reaction time is 4-8 h.

[0022] Compared with the prior art, the present invention has the following advantages:

[0023] (1) The 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine and its derivatives of the present invention have excellent detonation properties such as extremely high nitrogen content, high heat of formation, high density, high detonation velocity, and high initial thermal decomposition temperature.

[0024] (2) The synthesis conditions of the method of the present invention are mild, the steps are simple and highly feasible, the reaction yield is high, and the environmental pollution is small. Description of the Drawings

[0025] Figure 1 1H NMR (DMSO-d6) spectrum of 3-azido-1H-1,2,4-triazol-5-amine (Compound 2);

[0026] Figure 2 13C NMR (DMSO-d6) spectrum of 3-azido-1H-1,2,4-triazol-5-amine (Compound 2);

[0027] Figure 3 1H NMR (DMSO-d6) spectrum of 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HAATT, Compound 3);

[0028] Figure 413C NMR (DMSO-d6) spectrum of 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HAATT, Compound 3);

[0029] Figure 5 1H NMR (DMSO-d6) spectrum of (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo (Compound 4);

[0030] Figure 6 13C NMR (DMSO-d6) spectrum of (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo (Compound 4);

[0031] Figure 7 DSC spectrum of 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HAATT, Compound 3);

[0032] Figure 8 DSC spectrum of (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo (Compound 4). Detailed implementation manners

[0033] The present invention will be further described below in conjunction with specific embodiments and the accompanying drawings.

[0034] Example 1

[0035] (1) Synthesis of 3-azido-1H-1,2,4-triazol-5-amine:

[0036] At 25 °C, 5-hydrazino-1H-tetrazole (0.2 g, 2 mmol) was added to 5 mL of methanol. Cyanogen bromide (0.21 g, 2 mmol) was added to the reaction solution. After stirring for 16 h, a yellow clear solution was obtained. The solvent was removed under vacuum to obtain a yellow solid, which was dissolved in 5 mL of water. Potassium bicarbonate (0.2 g, 2 mmol) was added to adjust the pH to 8, and an off-white solid precipitated. It was filtered, washed, and dried to obtain 3-azido-1H-1,2,4-triazol-5-amine with a yield of 84.3%.

[0037] Compound structure analysis:

[0038] 1 1H NMR (500 MHz, DMSO-d6): δ 6.27 (s, 2H), 11.85 (s, 1H) ppm;

[0039] 1313C NMR (126 MHz, DMSO-d6): δ 154.5, 157.4 ppm.

[0040] (2) Synthesis of 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine:

[0041] 3-Azido-1H-1,2,4-triazol-5-amine (1.25 g, 10 mmol) was neutralized with potassium hydroxide (0.56 g, 10 mmol) in 45 mL of water at 0 °C. A solution of 20 mmol of cyanogen azide in acetonitrile was mixed with it. The mixture was stirred at 30 °C for 24 h. The by-product residue was filtered off. The filtrate was concentrated, and the pH was adjusted to 1 with hydrochloric acid. A large amount of solid precipitated out. After filtration, washing, and drying, 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine was obtained with a yield of 81.4%.

[0042] Compound structure analysis:

[0043] 1 1H NMR (500 MHz, DMSO-d6): δ 7.71 (s, 2H) ppm;

[0044] 13 13C NMR (126 MHz, DMSO-d6): δ 152.3, 156.3, 158.2 ppm.

[0045] (3) Synthesis of (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo:

[0046] 3-Azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (1.93 g, 10 mmol) was dissolved in 30 mL of concentrated hydrochloric acid. An aqueous solution of potassium permanganate (1.26 g, 8 mmol) in 30 mL was slowly added dropwise at 0 °C. After the addition was complete, the mixture was heated to 45 °C and the reaction was maintained for 6 h. After filtration, washing, and drying, (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo was obtained with a yield of 91.5%.

[0047] Compound structure analysis:

[0048] 1 1H NMR (500 MHz, DMSO-d6): δ 11.04 (s, 2H) ppm;

[0049] 13 13C NMR (126 MHz, DMSO-d6): δ 155.8, 158.68, 160.22 ppm.

[0050] Example 2

[0051] This example is substantially the same as Example 1, except that:

[0052] In step (1), the reaction time is shortened to 12 h, ethanol is used as the solvent, and the yield of the intermediate 3-azido-1H-1,2,4-triazol-5-amine is 71.6%.

[0053] Example 3

[0054] This example is substantially the same as Example 1, except that:

[0055] In step (1), the reagent used to adjust the pH to 8 is sodium bicarbonate, and the yield of the obtained intermediate 3-azido-1H-1,2,4-triazol-5-amine is 79.6%.

[0056] Example 4

[0057] This example is substantially the same as Example 1, except that:

[0058] In step (2), sulfuric acid is used for the acidification reaction, and the obtained target product 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HAATT) has a yield of 76.4%.

[0059] Example 5

[0060] This example is substantially the same as Example 1, except that:

[0061] In step (3), the reaction is heated at 35 °C for 6 h, and the obtained target product (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo has a yield of 81.4%.

[0062] Comparative Example 1

[0063] This comparative example is substantially the same as Example 1, except that:

[0064] In step (1), the selected substrate is 4H-1,2,4-triazole-3,4,5-triamine, and through nitrosation and hydrolysis rearrangement, the intermediate 3-azido-1H-1,2,4-triazol-5-amine is generated in two steps, with an overall yield of 66.7%. The synthetic route is as follows:

[0065]

[0066] Comparative Example 2

[0067] This comparative example is substantially the same as Example 1, except that:

[0068] In step (2), sodium hydroxide was selected as the base, and the target product 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HAATT) was obtained with a yield of 46.4%, which was relatively low.

[0069] Comparative Example 3

[0070] This comparative example was substantially the same as Example 1, except that:

[0071] In step (2), the reaction temperature was 15 °C and the reaction time was 24 h. The target product 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HAATT) was obtained with a yield of 55.4%, which was relatively low.

[0072] Comparative Example 4

[0073] This comparative example was substantially the same as Example 1, except that:

[0074] In step (3), the reaction was carried out at 15 °C for 6 h, and the target product (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo was obtained with a yield of 37.4%, which was relatively low.

[0075] Comparative Example 5

[0076] This example was substantially the same as Example 1, except that:

[0077] In step (3), the reaction was heated at 45 °C for 3 h, and the target product (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo was obtained with a yield of 31.5%.

[0078] Performance Characterization Example

[0079] ① Nitrogen content:

[0080] For 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine, the molecular formula is C3H3N 11 ,

[0081]

[0082] (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo, the molecular formula is C6H2N 22 ,

[0083]

[0084] ② Enthalpy of formation:

[0085] The calculation of the enthalpy of formation was carried out using the Gaussian 03 (D.01 version) program suite. All compounds were determined by the isodesmic equation as follows:

[0086]

[0087] The geometric optimization and frequency analysis of the structure were calculated using B3LYP / 6-31+G**. The calculation of the enthalpy of formation in the gas phase and the calculation of the reaction enthalpy were obtained by combining the MP2 / 6-311++G** energy difference of the reaction, the zero-point proportional energy (ZPE), the thermal correction value (HT), and other thermal factors.

[0088] The calculated enthalpy of formation of 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine: 892.069 kJ / mol;

[0089] (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo's enthalpy of formation: 2088.24 kJ / mol.

[0090] ③ Density:

[0091] The density was measured using a true density meter at room temperature.

[0092] The density of 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HAATT): 1.68 g / cm 3 ;

[0093] (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo's density: 1.75 g / cm 3 .

[0094] ④ Detonation velocity:

[0095] The detonation velocity was calculated using a detonation velocity calculation software (Explo5 v6.01).

[0096] The detonation velocity of 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HAATT): 7915 m / s,

[0097] (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo's detonation velocity: 8412 m / s.

[0098] ⑤Initial thermal decomposition temperature:

[0099] The thermal decomposition (initial) point was measured on a differential scanning calorimeter (Mettler Toledo DSC823e) at a scanning rate of 5 °C / min.

[0100] The decomposition temperature of 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine (HAATT) was: 210 °C,

[0101] The decomposition temperature of (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo was: 216 °C.

Claims

1. 3 - Azido - 1 - (1H - tetrazol - 5 - yl) - 1H - 1,2,4 - triazol - 5 - amine, characterized in that, The structural formula is as follows: 。 2. Derivatives of 3 - azido - 1 - (1H - tetrazol - 5 - yl) - 1H - 1,2,4 - triazol - 5 - amine, characterized in that, It is (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo, and the structural formula is as follows: 。 3. The synthesis method of 3 - azido - 1 - (1H - tetrazol - 5 - yl) - 1H - 1,2,4 - triazol - 5 - amine according to claim 1, characterized in that, The specific steps are as follows: (1) Add 5-hydrazino-1H-tetrazole to methanol or ethanol, then add cyanogen bromide. After the reaction, remove the solvent under vacuum, add water, adjust the pH of the solution to weakly alkaline, precipitate a solid, filter and dry to obtain 3-azido-1H-1,2,4-triazol-5-amine; (2) At 0 - 5 °C, dissolve 3-azido-1H-1,2,4-triazol-5-amine in an aqueous solution of potassium hydroxide, add cyanogen azide, stir at room temperature until the reaction is complete, filter and collect the filtrate. After concentration, adjust the pH to 1, precipitate a solid, filter and dry to obtain 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine.

4. The synthesis method of derivatives of 3 - azido - 1 - (1H - tetrazol - 5 - yl) - 1H - 1,2,4 - triazol - 5 - amine according to claim 2, characterized in that, The specific steps are as follows: (1) Add 5-hydrazino-1H-tetrazole to methanol or ethanol, then add cyanogen bromide. After the reaction, remove the solvent under vacuum, add water, adjust the pH of the solution to weakly alkaline, precipitate a solid, filter and dry to obtain 3-azido-1H-1,2,4-triazol-5-amine; (2) At 0 - 5 °C, dissolve 3-azido-1H-1,2,4-triazol-5-amine in an aqueous solution of potassium hydroxide, add cyanogen azide, stir at room temperature until the reaction is complete, filter and collect the filtrate. After concentration, adjust the pH to 1, precipitate a solid, filter and dry to obtain 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine; (3) Add 3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-amine to hydrochloric acid for dissolution. At 0 - 5 °C, dropwise add an aqueous solution of potassium permanganate, heat and react at 35 - 50 °C. After the reaction is completed, filter and wash with ice water to obtain (E)-1,2-bis(3-azido-1-(1H-tetrazol-5-yl)-1H-1,2,4-triazol-5-yl) azo.

5. The synthesis method according to claim 3 or 4, characterized in that, In step (1), the reaction temperature is 15 - 25 °C, the reaction time is 16 h; the pH of the weakly alkaline solution is 7.5 - 8.5, and the pH of the solution is adjusted with potassium bicarbonate or sodium bicarbonate.

6. The synthesis method according to claim 3 or 4, characterized in that, In step (2), the molar ratio of 3-azido-1H-1,2,4-triazol-5-amine to potassium hydroxide is 1:

1.

7. The synthesis method according to claim 3 or 4, characterized in that, In step (2), the reaction temperature is 25 - 30 °C, the reaction time is 24 h; add hydrochloric acid or sulfuric acid solution to adjust the pH.

8. The synthesis method according to claim 4, characterized in that, In step (3), the reaction temperature is 45 °C, and the heating reaction time is 4 - 8 h.

Images