Bispyrazolyl energetic compounds and preparation method thereof

A technology of bispyrazoles and bispyrazoles, which is applied in the field of bispyrazole ring energetic compounds and their preparation, and can solve problems such as poor thermal stability

Inactive Publication Date: 2014-02-26
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

If an energetic heterocyclic fragment structure can be attached to the LLM-116 molecule, it is expected to make up for its poor t

Method used

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  • Bispyrazolyl energetic compounds and preparation method thereof
  • Bispyrazolyl energetic compounds and preparation method thereof
  • Bispyrazolyl energetic compounds and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 14

[0027] Example 14 Preparation of chloro-3',5'-dinitro-1'-hydrogen-1,4'-bispyrazole (2)

[0028] Its structural formula is as follows:

[0029]

[0030] Into a 30mL thick-walled sealed glass tube, add 0.203g (1mmol) 3,4,5-trinitropyrazole, 0.102g (1mmol) 4-chloropyrazole, 0.080g (2mmol) NaOH and 2mL water in sequence, and seal Stir, heat up to 160°C, react for 20 hours, cool with 20% H 2 SO 4The solution was acidified to pH=1, filtered to obtain a yellow solid, and recrystallized from water / ethanol to obtain 0.181 g of yellow crystals, with a yield of 62%.

[0031] Melting point: 236°C (DSC, 10K min -1 ). IR(neat):3135,2377,2351,2319,1954,1618,1512,1419,1388,1354,1292,974cm -1 ; 1 H NMR (400MHz, d 6 -DMSO): δ=8.31(s, CH), 7.89(s, CH)ppm; 13 C NMR (400MHz, d 6 -DMSO):δ=147.3,140.4,131.7,112.6,110.5ppm; MS(ESI):m / z(%):257[M-H] - .

Embodiment 24

[0032] Example 2 Preparation of 4-chloro-3,3',5,5'-tetranitro-1'-hydrogen-1,4'-bispyrazole (3)

[0033] Its structural formula is as follows:

[0034]

[0035] Add 0.257g (1mmol) of compound (2) to 3.2mL of concentrated sulfuric acid in batches under ice bath, and slowly add 0.4mL of 100% HNO 3 After the addition, the solution was clear. After removing the ice bath, the temperature was raised to 100° C., and the reaction was carried out for 20 hours, and a large amount of white solid was precipitated. After cooling to room temperature, the reaction solution was slowly added dropwise into 20 mL of ice water with a straw while stirring, and a white solid was precipitated, which was filtered and dried to obtain 0.225 g, with a yield of 65%.

[0036] Melting point: 269°C, decomposition temperature: 308°C (DSC, 10K min -1 ). Density is 1.96g cm -3 . IR (neat):3260,1628,1568,1539,1486,1427,1321,1275cm -1 ; 1 H NMR (400MHz, d 6 -DMSO):δ=6.36(s,NH)ppm; 13 C NMR (400MHz, d ...

Embodiment 33

[0037] Example 33, Preparation of 3′,5,5′-tetranitro-1′-hydrogen-(1,4′-bispyrazole)-4-amine ammonium salt (4)

[0038] Its structural formula is as follows:

[0039]

[0040] Add 0.500g (1.4mmol) of compound (3) and 5mL of 25% ammonia water into a 15mL thick-walled sealed glass tube, stir in a closed chamber, heat up to 80°C, react for 20 hours, filter after cooling, and recrystallize with water to obtain 0.350g of a yellow solid. Yield 70%.

[0041] Decomposition temperature: 262°C (DSC, 10K min -1 ). Density is 1.88g cm -3 . IR(neat):3479,3333,3269,1636,1596,1573,1431,1353,1310,1270,1170cm -1 ; 1 H NMR (400MHz, d 6 -DMSO):δ=7.53(s,2H,NH 2 ), 7.06(s,4H,NH 4 + )ppm; 13 C NMR (400MHz, d 6 -DMSO):δ=150.8,143.0,131.7,130.4,109.7ppm; MS(ESI):m / z(%):328[M] - ;Elemental Analysis: C 6 h 6 N 10 o 8 (346.17) Calculated: C20.82, H1.75, N40.46; Found: C20.97, H1.72, N40.12.

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Abstract

The invention relates to bispyrazolyl energetic compounds and a preparation method thereof, and belongs to the technical field of energetic materials. The synthesis method of the compounds comprises the following steps: 1, reacting 3,4,5-trinitropyrazole with 4-chloropyrazole to obtain a compound (2), nitrating the compound (2) to obtain a compound (3), aminating to obtain a compound (4), and acidifying and aminating to obtain a neutral maternal (5) and a compound (7) respectively; 2, oxidizing the neutral maternal to obtain a compound (6); 4, mixing the neutral maternal (5) with Ba(OH)2.8H2O, reacting the obtained mixture with sulfate of a corresponding cation, filtering, and evaporating the obtained filtrate to remove a solvent in order to obtain target products (8-12); and 4, directly reacting the neutral maternal (5) with the corresponding cation, and evaporating the obtained material to remove a solvent in order to obtain target products (13-16). The referred fourteen energetic compounds have the characteristics of good thermal stability, high density, low impact sensitivity, and excellent calculated detonation performance, and are potential insensitive high explosives.

Description

technical field [0001] The invention relates to a bispyrazole ring-type energetic compound and a preparation method thereof, belonging to the technical field of energetic materials. Background technique [0002] In the past decades, various high-energy energetic materials have been reported, such as CL-20, TATB, NTO, and FOX-7, etc. TATB and FOX-7 have the similarity that the amino and nitro groups are adjacent to each other, so that there are strong hydrogen bonds in their molecules, thus showing insensitivity to external stimuli and good thermal stability. In recent years, in the field of energetic materials research, nitrogen-rich five-membered heterocyclic compounds are often used to design energetic molecules due to their positive enthalpy of formation. Moreover, the introduction of nitro groups can improve the oxygen balance and density of molecules, thereby improving the detonation performance. However, the introduction of nitro groups will reduce the thermal stabil...

Claims

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Application Information

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IPC IPC(8): C07D231/16C07D231/38C07D257/06C07C279/02C07C277/00C07C277/08C07C281/16C07C281/06C07D249/14C06B25/34
CPCC07D231/16C07D231/38C07D249/14C07D257/06
Inventor 周智明梁丽轩王凯
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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