CN103601680A - Bispyrazolyl energetic compounds and preparation method thereof - Google Patents
Bispyrazolyl energetic compounds and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
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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
The present invention relates to double pyrazole lopps energy-containing compound and preparation method thereof, belong to energetic material technical field.
Background technology
In the past few decades, reported various high-energy energetic materials, as CL-20, TATB, NTO and FOX-7 etc.TATB and FOX-7 have similarity amino and that nitryl group adjoins, make their molecular memory at stronger hydrogen bond, thereby show the immunity of stimulation to external world and good thermostability.In recent years, in energetic material research field, rich nitrogen five member ring heterocyclic compound, due to its positive Enthalpies of Formation, was often used to design containing energy molecule.And, to it, introduce nitryl group and can put forward high molecular oxygen balance and density, and then improve detonation property.But the introducing of nitro can be fallen low molecular thermostability and be increased sensitivity, and the at this moment existence of amino group is to improve one of effective ways containing energy azole compounds thermostability and sensitivity performance.Typical example is the novel insensitive high energy explosive 4-amino-3 that U.S. LLNL National Laboratory developed in calendar year 2001,5-dinitrobenzene-pyrazoles (LLM-116), and crystalline density is up to 1.90g cm
-3, there is the similar structure with TATB, and sensitivity is suitable with TATB, and energy is 1.4 times of TATB, is 90% of HMX.Yet the thermostability of LLM-116 is very not satisfactory, only promising 178 ℃ of its heat decomposition temperatures.
Conventionally also can improve by the form of salify the performance of energy-containing compound, Shreeve seminar has synthesized the rich nitrogen of a series of LLM-116 containing energy ion salt, this class salt is keeping under the characteristic of LLM-116 insensitiveness, and thermostability is almost all better than LLM-116, and wherein guanidinesalt decomposition temperature is up to 303 ℃.Another effective means is that different heterocycles is connected into a larger conjugated system with the form of covalent linkage, when improving molecule Enthalpies of Formation and density, increase its thermostability, two (1-hydrogen-5-tetrazyl) furoxans of 4-that Huanghai Sea doctor Feng of Ru Ben seminar is synthetic, this compound forms two tetrazole rings and furoxan by a large conjugated system, have high positive Enthalpies of Formation and good thermostability, Enthalpies of Formation is 728kJ mol
-1, decomposition temperature is greater than 220 ℃.This quasi-molecule that is common in bibliographical information is to be formed by two identical heterocycle structures or two kinds of different heterocycle structures.
Develop sensitivity and TATB quite and energy approaches the direction that the novel desensitized explosive of RDX or HMX becomes insensitive high energy explosive research.If can connect one containing energy heterocycle fragment structure on LLM-116 molecule, be desirably in the excellent specific property situation of inheriting LLM-116 insensitiveness high energy (IS>40J), make up the bad defect of its thermostability, form the good novel insensitiveness high energy single chmical compound explosive molecule of a kind of over-all properties.Azole containing two nitros has higher energy and lower sensitivity.If 3,5-binitropyrazole fusing point is 173 ℃, there is good thermostability and chemical stability (T
d=316 ℃), it is the structural unit of extraordinary structure energy-containing compound, therefore this fragment is chosen in the present invention's design, be connected on and on LLM-116 molecule, generated double pyrazole toroidal molecule 3,3 ', 5,5 '-tetranitro-1 ' hydrogen-(1,4 '-double pyrazole)-4-amine, and make its corresponding energy ion salt and its oxidation and ammonification derivative of containing.The performances such as this compounds thermostability, impact sensitivity, explosion velocity detonation pressure are all very outstanding, have very large potential using value.
Summary of the invention
The object of this invention is to provide double pyrazole class energy-containing compound and preparation method thereof, obtained a class and there is good thermal stability, low sensitivity and the better energetic material of detonation property.
The object of the invention is to be achieved through the following technical solutions:
Double pyrazole class energy-containing compound of the present invention, its general structure is as shown in reaction formula 1:
Reaction formula 1. double pyrazole class energy-containing compound structures
Double pyrazole class energy-containing compound of the present invention is to realize by the route shown in reaction formula 2:
Reaction formula 2. double pyrazole class energy-containing compound synthetic routes
Its concrete preparation process is as follows:
4-is chloro-3 ', 5 '-dinitrobenzene-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole (2): in heavy wall sealed glass tube, add successively 3,4,5-trinitro-pyrazoles (1), 4-chlorine pyrazoles, sodium hydroxide and water, airtight stirring, temperature reaction 20-24 hour, uses 20%H after cooling
2sO
4solution is acidified to pH=1, filters and obtains yellow solid, to obtain yellow crystals after water/ethyl alcohol recrystallization.In above-mentioned reaction, 4-chlorine pyrazoles, sodium hydroxide and (1) mol ratio are 1:2.1:1-1:2:1; Temperature of reaction 160-170 ℃, the consumption of water is 2-3mL.
4-is chloro-3,3 ', 5,5 '-tetranitro-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole (3): under ice bath, compound (2) is added in the vitriol oil in batches, slowly drip 100%HNO after adding
3, add rear solution for clarification shape, be warming up to 100 ℃ after removing ice bath, reaction 20-24 hour, separates out a large amount of white solids.Be cooled to after room temperature, while stirring reaction solution be slowly added dropwise in frozen water with suction pipe, separate out white solid, filtration drying obtains product.The vitriol oil is 3.2-3.5mL:1mmol with the amount ratio of (2), 100%HNO
3with the amount ratio of (2) be 0.4-0.5mL:1mmol, the consumption of frozen water is 20-25mL.
3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(1,4 '-double pyrazole)-4-amine ammonium salt (4): in heavy wall sealed glass tube, add compound (3) and 25% ammoniacal liquor, airtight stirring, temperature reaction 20-24 hour, cooled and filtered, water recrystallization obtains yellow solid.The amount ratio 5-7mL:1.4mmol of 25% ammoniacal liquor and (3), temperature of reaction 70-85 ℃
3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine (5): compound (4) is added in single port flask, add 20%H under stirring
2sO
4solution, until heat up and continue to stir after 2-3 hour in pH value of solution=1, cooling 1-2 hour in ice bath, filters to obtain yellow solid.Temperature of reaction is 40-55 ℃.
3,3 ', 4,5,5 '-five nitro-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole (6): under room temperature, compound (5) is dissolved in to dense H
2sO
4in, treat to dissolve completely, under ice bath, add Disodium tungstate (Na2WO4) dihydrate, then slowly drip hydrogen peroxide, dropwise and continue to stir half an hour, remove ice bath, reaction 24-48 hour, after reaction finishes, reaction solution is poured in frozen water, filtered water/ethyl alcohol recrystallization and obtain light yellow crystal.Sodium wolframate is 1.2:1-1:1 with the mol ratio of (5); In above-mentioned reaction, hydrogen peroxide concentration is 30% or 50%, and the volume ratio of the vitriol oil and hydrogen peroxide is 5:1-4:1, and hydrogen peroxide is 90:1-86:1 with the mol ratio of (5); Temperature of reaction is room temperature.
3,3 ', 5,5 '-tetranitro-1 ' hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-1 ', 4-diamines (7): under room temperature, compound (5) is dissolved in acetonitrile, waits to stir, slowly add wherein freshly prepd THA dichloromethane solution, mixed solution continues reaction 24-36 hour, after reaction finishes, revolve to steam and remove solution, then add ethyl acetate, remove by filter insolubles, filtrate is yellow, and solvent evaporated obtains solid.Crude product obtains yellow solid through post layer analysis (ethyl acetate/petroleum ether=6/1).THA is 1.5:1-1:1 with the mol ratio of (5), and temperature of reaction is room temperature.
3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine containing can ion salt the preparation of 8-12: compound 5 is dissolved in to the Ba (OH) that adds 0.5 molar equivalent after hot water
28H
2o, the reaction solution of gained stirs lower reacting by heating 2 hours, then adds in the corresponding sulfate solution of 0.5 molar equivalent, and reaction solution continues to stir lower reacting by heating 2-3 hour, remove by filter concentrated filtrate after a small amount of insolubles, gained solid water recrystallization obtains product.Temperature of reaction 60-80 ℃.
3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine contains the preparation of energy ion salt 13-16: after after compound 5 is dissolved, add wherein 3 of a molar weight equivalent, 4,5-triamino-1,2,4-triazole, the diaminourea of 1,5-diamino tetrazolium, 99% hydrazine hydrate and 0.5 molar weight equivalent.Stirring reaction 2-3 hour, after reaction solution is concentrated, thick product recrystallization obtains product.The solvent of above-mentioned reaction can be water, methyl alcohol or ethanol; Temperature of reaction 40-50 ℃.
Advantage of the present invention is:
1) obtain new double pyrazole class energy-containing compound, through DSC test good thermal stability, decomposition temperature is between 228-308 ℃, and the thermostability of majority of compounds is better than RDX (T
d=230 ℃); Density is higher after tested, between 1.67-1.96g/cm
3.
2) after tested, except compound 6 impact sensitivities are 28J, all the other compound impact sensitivities are all greater than 40J to the energy-containing compound in the present invention, and this is better than RDX (7J), and HMX (7J) or CL-20 (2J), belong to desensitized explosive.
3) its explosion velocity is between 8041-8814m/s as calculated for the energy-containing compound in the present invention, and detonation pressure is between 27.1-37.0GPa, and the explosion velocity detonation pressure performance of part of compounds is higher than RDX(EXPLO5 calculated value: 8778m/s and 35.1GPa), be insensitive high energy explosive.
4) in the present invention 4-chloro-3,3 ', 5,5 '-tetranitro-1 '-hydrogen-1,4 '-double pyrazole, 3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine ammonium salt, 3,3 ', 5, the actual measurement of 5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine is clashed into and is greater than 60J, is better than TATB (50J), and detonation property is all better than TATB, even surpass RDX, be the potential RDX surrogate of a class.
Embodiment
Embodiment 14-is chloro-3 ', the preparation of 5 '-dinitrobenzene-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole (2)
Its structural formula is as follows:
In 30mL heavy wall sealed glass tube, add successively 0.203g (1mmol) 3,4,5-trinitro-pyrazoles, 0.102g (1mmol) 4-chlorine pyrazoles, 0.080g (2mmol) NaOH and 2mL water, airtight stirring, is warming up to 160 ℃, react 20 hours, use 20%H after cooling
2sO
4solution is acidified to pH=1, filters and obtains yellow solid, to obtain yellow crystals 0.181g after water/ethyl alcohol recrystallization, productive rate 62%.
Fusing point: 236 ℃ of (DSC, 10K min
-1).IR(neat):3135,2377,2351,2319,1954,1618,1512,1419,1388,1354,1292,974cm
-1;
1H?NMR(400MHz,d
6-DMSO):δ=8.31(s,CH)，7.89(s,CH)ppm;
13C?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-is chloro-3,3 ', the preparation of 5,5 '-tetranitro-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole (3)
Its structural formula is as follows:
Under ice bath, 0.257g (1mmol) compound (2) is added in the 3.2mL vitriol oil in batches, after adding, slowly drip 0.4mL100%HNO
3, add rear solution for clarification shape, be warming up to 100 ℃ after removing ice bath, react 20 hours, separate out a large amount of white solids.Be cooled to after room temperature, while stirring reaction solution be slowly added dropwise in 20mL frozen water with suction pipe, separate out white solid, filtration drying obtains 0.225g, productive rate 65%.
Fusing point: 269 ℃, decomposition temperature: 308 ℃ of (DSC, 10K min
-1).Density is 1.96g cm
-3.IR?(neat):3260,1628,1568,1539,1486,1427,1321,1275cm
-1;
1H?NMR(400MHz,d
6-DMSO):δ=6.36(s,NH)ppm;
13C?NMR(400MHz,d
6-DMSO):δ=150.8,150.2,143.2,108.1,107.4ppm;MS(ESI):m/z(%):347.1,348.6.5(3:1)[M-H]
-。
Embodiment 33,3 ', the preparation of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine ammonium salt (4)
Its structural formula is as follows:
In 15mL heavy wall sealed glass tube, add 0.500g (1.4mmol) compound (3) and 5mL25% ammoniacal liquor, airtight stirring, is warming up to 80 ℃, reacts 20 hours, cooled and filtered, water recrystallization obtains yellow solid 0.350g, productive rate 70%.
Decomposition temperature: 262 ℃ of (DSC, 10K min
-1).Density is 1.88g cm
-3.IR (neat): 3479,3333,3269,1636,1596,1573,1431,1353,1310,1270,1170cm
-1;
1h NMR (400MHz, d
6-DMSO): δ=7.53 (s, 2H, NH
2), 7.06 (s, 4H, NH
4 +) ppm;
13c NMR (400MHz, d
6-DMSO): δ=150.8,143.0,131.7,130.4,109.7ppm; MS (ESI): m/z (%): 328[M]
-; Ultimate analysis: C
6h
6n
10o
8(346.17) calculated value: C20.82, H1.75, N40.46; Measured value: C20.97, H1.72, N40.12.
Embodiment 43,3 ', the preparation of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine (5)
Its structural formula is as follows:
0.200g (0.6mmol) compound (4) is added in 50mL single port flask, under stirring, add 20%H
2sO
4solution, until pH value of solution=1 in flask is warming up to 40 ℃, continue to stir after 2 hours, in ice bath cooling 1 hour, filters to obtain yellow solid 0.162g, productive rate 85%.
Decomposition temperature: 242 ℃ of (DSC, 10K min
-1).Density is 1.89g cm
-3.IR (neat): 3493,3378,3241,1646,1620,1555,1518,1435,1337,1312,1278,1263,1159cm
-1;
1hNMR (400MHz, d
6-DMSO): δ=11.54 (brs, 1H, NH), 7.54 (s, 2H, NH
2) ppm;
13cNMR (400MHz, d
6-DMSO): δ=150.3,143.0,131.6,130.3,109.6ppm; MS (ESI): m/z (%): 328[M-H]
-; Ultimate analysis: C
6h
3n
9o
8(329.14) calculated value: C21.89, H0.92, N38.30; Measured value: C21.99, H0.90, N38.01.
Embodiment 53,3 ', the preparation of 4,5,5 '-five nitro-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole (6)
Its structural formula is as follows:
Under room temperature, 0.300g (0.8mmol) compound (5) is dissolved in to the dense H of 30mL
2sO
4in, treat to dissolve completely, under ice bath, add 0.105g (0.3mmol) Disodium tungstate (Na2WO4) dihydrate, solution colour is thin out, then slowly drips 7mL30% hydrogen peroxide, dropwises and continues to stir half an hour, solution colour deepens gradually, then becomes yellow-green colour, removes ice bath, room temperature reaction 24 hours, has solid to separate out in process, after reaction finishes, reaction solution is poured in frozen water, filtration obtains solid 0.286g, and water/ethyl alcohol recrystallization obtains light yellow crystal 0.115g, productive rate 35%.
Fusing point: 158 ℃, decomposition temperature: 297 ℃ of (DSC, 10K min
-1).Density is 1.82g cm
-3.IR (neat): 3546,3488,1626,1591,1542,1463,1453,1405,1370,1326,1247,1200,1111,1003,905,873,836,817,792,763,690,664,587,517,469,377cm
-1;
1hNMR (400MHz, d
6-DMSO): δ=14.01 (s, 1H, NH) ppm;
13c NMR (400MHz, d
6-DMSO): δ=155.9,150.9,146.3,109.9,106.9ppm; MS (ESI): m/z (%): 358[M-H]
-; Ultimate analysis: C
6hN
9o
10(359.13) calculated value: C20.07, H0.28, N35.10; Measured value: C20.24, H0.26, N34.83.
Embodiment 63,3 ', 5,5 '-tetranitro-1 ' hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-1 ', the preparation of 4-diamines (7)
Its structural formula is as follows:
Under room temperature, by 0.346g (0.2mmol) 3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine ammonium salt is dissolved in 25mL acetonitrile, waits to stir, slowly add wherein freshly prepd THA dichloromethane solution, mixed solution continues reaction 24 hours, revolves to steam and remove solution after reaction finishes, and obtains orange/yellow solid, then add ethyl acetate, most of dissolution of solid, only has a small amount of white solid to suspend wherein, removes by filter insolubles, filtrate is yellow, and solvent evaporated obtains yellow solid.Crude product obtains yellow solid 0.196g through post layer analysis (ethyl acetate/petroleum ether=6/1), productive rate 57%.
Fusing point: 250 ℃, decomposition temperature: 284 ℃ of (DSC, 10K min
-1).Density is 1.87g cm
-3.IR (neat): 34,922,277,238,529,552,922,285,116,421,603,157,215,321,509,146,814,171,399 13641306127112181168109799892287185581676174373370965863 5604cm
-1;
1h NMR (400MHz, d
6-DMSO): δ=8.17 (s, 2H, NH
2), 7.71 (s, 2H, NH
2) ppm;
13c NMR (400MHz, d
6-DMSO): δ=144.3142.3137.1,131.7,130.3,109.8ppm; MS (ESI): m/z (%): 343[M]
-; Ultimate analysis: C
6h
4n
10o
8(344.16) calculated value: C20.94, H1.17, N40.70; Measured value: C21.16, H1.15, N40.25.
Embodiment 73,3 ', the preparation of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine guanidinesalt (8)
By 95mg (0.3mmol) Ba (OH)
28H
2o adds 197mg (0.6mmol) 3,3 ', 5, in the aqueous solution of 5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine (4.7) (50mL), at 60 ℃ of this reaction mixtures, stirring reaction is 1 hour, solid dissolves completely, then add in the aqueous solution of 0.3mmol guanidine sulfate, keep this temperature to continue to stir 2 hours, filter BaSO
4concentrated filtrate after precipitation, water recrystallization obtains product, productive rate 93%.
Its structural formula is as follows:
Decomposition temperature: 228 ℃ of (DSC, 10K min
-1).Density is 1.73g cm
-3.IR (neat): 3638,3550,3463,3353,3131,1640,1601,1578,1510,1470,1436,1414,1353,1313,1221,1173,1143,1012,985,861,843,747,680,658,637,605,445,423cm
-1;
1hNMR (400MHz, d
6-DMSO): δ=7.52 (s, 2H, NH
2), 6.90 (s, 6H, NH
2) ppm;
13c NMR (100MHz, d
6-DMSO): δ=158.4,150.8,143.0,131.8,130.4,109.6ppm; Ultimate analysis: C
7h
8n
12o
8(388.21) (%) calculated value: C21.66, H2.08, N43.30; Measured value: C21.70, H2.06, N43.03.
Embodiment 83,3 ', the preparation of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine aminoguanidine salt (9)
Condition, with embodiment 7, only changes guanidine sulfate into aminoguanidine sulfate, and productive rate is 87%.
Its structural formula is as follows:
Fusing point: 249 ℃, decomposition temperature: 272 ℃ of (DSC, 10K min
-1).Density is 1.67g cm
-3.IR (neat): 3479,3436,3363,3319,3143,1681,1657,1639,1604,1509,1473,1438,1413,1375,1314,1275,1219,1171,1136,1012,987,954,863,743,718,682,658,558,519,489cm
-1;
1h NMR (400MHz, d
6-DMSO): δ=8.55 (s, 1H, NH), 7.53 (s, 2H, NH
2), 7.25 (s, 2H, NH
2), 6.72 (s, 2H, NH
2), 4.69 (s, 2H, NH
2) ppm;
13c NMR (100MHz, d
6-DMSO): δ=159.2,150.8,143.0,131.8,130.4,109.7ppm; Ultimate analysis: C
7h
9n
13o
8(388.21) (%) calculated value: C20.85, H2.25, N45.16; Measured value: C20.88, H2.23, N44.89.
Embodiment 93,3 ', the preparation of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine diamino guanidinesalt (10)
Condition, with embodiment 7, only changes guanidine sulfate into Imidocarbonic acid dihydrazide vitriol, and productive rate is 87%.
Its structural formula is as follows:
Fusing point: 210 ℃, decomposition temperature: 272 ℃ of (DSC, 10K min
-1).Density is 1.71g cm
-3.IR (neat): 3499,3416,3374,3316,3259,3179,3143,3082,1678,1651,1600,1567,1507,1474,1358,1301,1271,1220,1169,1101,941,841,817,769,743,679,654,534,444cm
-1;
1h NMR (400MHz, d
6-DMSO): δ=8.54 (s, 2H, NH), 7.52 (s, 2H, NH
2), 7.14 (s, 2H, NH
2), 4.59 (s, 4H, NH
2) ppm;
13c NMR (100MHz, d
6-DMSO): δ=160.2,150.8,143.0,131.8,130.4,109.6ppm; Ultimate analysis: C
7h
10n
14o
8(418.24) (%) calculated value: C20.10, H2.41, N46.89; Measured value: C20.15, H2.37, N46.46.
Embodiment 103,3 ', the preparation of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine triamino guanidinesalt (11)
Condition, with embodiment 7, only changes guanidine sulfate into triaminoguanidine vitriol, and productive rate is 88%.
Its structural formula is as follows:
Fusing point: 212 ℃, decomposition temperature: 266 ℃ of (DSC, 10K min
-1).Density is 1.72g cm
-3.IR (neat): 3475,3381,3338,3282,3217,1681,1644,1594,1566,1515,1471,1430,1407,1343,1309,1287,1270,1219,1166,1127,961,864,838,818,743,710,680,639,571,512cm
-1;
1h NMR (400MHz, d
6-DMSO): δ=8.59 (s, 3H, NH), 7.53 (s, 2H, NH
2), 4.49 (s, 6H, NH
2) ppm;
13c NMR (100MHz, d
6-DMSO): δ=159.5,150.8,143.0,131.8,130.4,109.6ppm; Ultimate analysis: C
7h
11n
15o
8(433.26) (%) calculated value: C19.41, H2.56, N48.49; Measured value: C19.44, H2.54, N48.17.
Embodiment 113,3 ', the preparation of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine hydroxylammonium salt (12)
Condition, with embodiment 7, only changes guanidine sulfate into oxammonium sulfate, and productive rate is 80%.
Its structural formula is as follows:
Decomposition temperature: 259 ℃ of (DSC, 10K min
-1).Density is 1.75g cm
-3.IR (neat): 3455,3338,3216,3118,1646,1610,1581,1478,1443,1417,1401,1361,1322,1307,1279,1203,1172,1007,990,866,847,822,757,715,642,601,577,489,396cm
-1;
1h NMR (400MHz, d
6-DMSO): δ=10.09 (s, 3H, NH
3), 9.90 (s, 1H, OH), 7.54 (s, 2H, NH
2) ppm;
13c NMR (100MHz, d
6-DMSO): δ=150.8,143.0,131.8,130.4,109.7ppm; Ultimate analysis: C
6h
6n
10o
9(362.17) (%) calculated value: C19.90, H1.67, N38.67; Measured value: C19.92, H1.65, N38.26.
Embodiment 123,3 ', 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine 3,4,5-triamino-1, the preparation of 2,4-triazolium salt (13)
Its structural formula is as follows:
By 0.6mmol3,4,5-triamino-1,2,4-triazole adds 197mg (0.6mmol) 3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(1, in methyl alcohol (20mL) solution of 4 '-double pyrazole)-4-amine, stir after 2h at 50 ℃, rotary evaporation is except desolventizing, with methanol/water recrystallization solid, seasoning in gained crystal air.Productive rate: 90%.
Fusing point: 247 ℃, decomposition temperature: 297 ℃ of (DSC, 10K min
-1).Density is 1.82g cm
-3.IR (neat): 3487,3470,3354,3313,3131,1678,1637,1608,1580,1534,1510,1462,1444,1416,1390,1356,1315,1276,1220,1171,1151,1053,1014,969,910,865,844,829,800,749,715,682,661,635,603,566,436cm
-1;
1h NMR (400MHz, d
6-DMSO): δ=7.81 (br.s, 2H, NH
2), 7.52 (s, 2H, NH
2), 6.39 (br.s, 2H, NH
2), 5.59 (s, 2H, NH
2) ppm;
13c NMR (100MHz, d
6-DMSO): δ=150.8,143.0,131.8,130.4,109.7ppm; Ultimate analysis: C
8h
9n
15o
8(443.25) (%) calculated value: C21.68, H2.05, N47.40; Measured value: C21.62, H2.03, N47.12.
Embodiment 133,3 ', 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine 1, the preparation of 5-diamino tetrazolium salts (14)
Condition is with embodiment 12, and only by 3,4,5-triamino-1,2,4-triazole changes 1,5-diamino tetrazolium into, and productive rate is 86%.
Its structural formula is as follows:
Fusing point: 166 ℃, decomposition temperature: 261 ℃ of (DSC, 10K min
-1).Density is 1.72g cm
-3.IR (neat): 3494,3380,3321,3243,1646,1620,1575,1539,1519,1471,1436,1401,1314,1279,1264,1222,1194,1161,1137,1109,1073,1002,988,932,866,836,816,752,721,673,628,599cm
-1;
1h NMR (400MHz, d
6-DMSO): δ=7.36 (br, NH
2) ppm;
13c NMR (100MHz, d
6-DMSO): δ=153.6,150.4,143.2,131.8,130.4,109.7ppm; Ultimate analysis: C
7h
7n
15o
8(429.23) (%) calculated value: C19.59, H1.64, N48.95; Measured value: C19.54, H1.63, N48.66.
Embodiment 143,3 ', the preparation of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine hydrazonium salt (15)
Condition is with embodiment 12, and only by 3,4,5-triamino-1,2,4-triazole changes 99% hydrazine hydrate into, and productive rate is 91%.
Its structural formula is as follows:
Decomposition temperature: 260 ℃ of (DSC, 10K min
-1).Density is 1.80g cm
-3.IR (neat): 3424,3370,3312,3211,1637,1603,1581,1561,1504,1463,1443,1415,1396,1312,1277,1219,1174,1119,1080,1020,979,929,847,818,770,752,676,663,645,571,528,490,397,384cm
-1;
1h NMR (400MHz, d
6-DMSO): δ=8.57 (br.s, 4H, NH
2), 7.53 (s, 2H, NH
2) ppm;
13c NMR (100MHz, d
6-DMSO): δ=150.8,143.0,131.8,130.4,109.7ppm; Ultimate analysis: C
6h
7n
11o
8(361.19) (%) calculated value: C19.95, H1.95, N42.66; Measured value: C20.06, H1.93, N42.45.
The preparation of 15 couples of embodiment [3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine] diaminourea salt (16)
Condition is with embodiment 12, only by 0.6mmol3, and 4,5-triamino-1,2,4-triazole changes 0.3mmol diaminourea into, and productive rate is 85%.
Its structural formula is as follows:
Decomposition temperature: 268 ℃ of (DSC, 10K min
-1).Density is 1.78g cm
-3.IR (neat): 3493,3470,3350,3240,3197,3030,1721,1646,1608,1556,1535,1512,1472,1442,1417,1365,1310,1277,1222,1194,1166,1111,1019,989,846,829,743,719,670,665,597,538,492cm
-1;
1h NMR (400MHz, d
6-DMSO): δ=6.38 (br.s), 7.52 (s, 2H, NH
2) ppm;
13c NMR (100MHz, d
6-DMSO): δ=157.0,150.7,143.1,131.8,130.4,109.7ppm; Ultimate analysis: C
7h
9n
13o
9(419.23) (%) calculated value: C20.05, H2.16, N43.43; Measured value: C20.09, H2.15, N43.10.
Table 1 is the performance of double pyrazole class energy-containing compound involved in the present invention, decomposition temperature adopts differential calorimetric scanner (DSC) to record, density adopts Accupyc II 1340gas pycnometer Density Measuring Instrument to record, impact sensitivity and prediction detonation property, impact sensitivity adopts BAM impact sensitivity tester (BFH-10) to record, and prediction detonation property adopts Explo5 (version 5.05) to calculate and obtains.
The performance of table 1 double pyrazole class energy-containing compound
Note: the explosion velocity of compound 3 and detonation pressure are for revising nitrogen equivalent method calculated value.
Claims (10)
1. the double pyrazole class energy-containing compound that can be used for energetic material field, it has following structure:
4-according to claim 1 chloro-3,3 ', 5, the synthetic method of 5 '-tetranitro-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole, is characterized in that: under ice bath by 4-chloro-3 ', 5 '-dinitrobenzene-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole adds in the vitriol oil in batches, slowly drips 100%HNO after adding
3, add rear solution for clarification shape, be warming up to 100 ℃ after removing ice bath, reaction 20-24 hour, separates out a large amount of white solids.Be cooled to after room temperature, while stirring reaction solution be slowly added dropwise in frozen water with suction pipe, separate out white solid, filtration drying obtains product.It is characterized in that: nitrated system is 100%HNO
3and the vitriol oil, temperature of reaction is 100 ℃, the reaction times is 20-24 hour; The vitriol oil and 4-be chloro-3 ', the amount ratio of 5 '-dinitrobenzene-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole is 3.2-3.5mL:1mmol, 100%HNO
3with 4-chloro-3 ', the amount ratio of 5 '-dinitrobenzene-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole is 0.4-0.5mL:1mmol, the consumption of frozen water is 20-25mL.
According to claim 13,3 ', 5, the synthetic method of 5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine ammonium salt, is characterized in that: in heavy wall sealed glass tube, add 4-chloro-3,3 ', 5,5 '-tetranitro-1 '-hydrogen-1,4 '-double pyrazole and 25% ammoniacal liquor, airtight stirring, temperature reaction 20-24 hour, cooled and filtered, water recrystallization obtains yellow solid.It is characterized in that: the reaction times is 20-24 hour, recrystallization solvent is water, 25% ammoniacal liquor and 4-be chloro-3,3 ' and, the amount ratio 5-7mL:1.4mmol of 5,5 '-tetranitro-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole, temperature of reaction 70-85 ℃.
4. according to claim 13,3 ', the synthetic method of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine, it is characterized in that: by compound 3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(1,4 '-double pyrazole)-4-amine ammonium salt adds in single port flask, under stirring, adds 20%H
2sO
4solution, until heat up and continue to stir after 2-3 hour in pH value of solution=1, cooling 1-2 hour in ice bath, filters to obtain yellow solid.It is characterized in that: temperature of reaction is 40-55 ℃, the reaction times is 2-3 hour.
According to claim 13,3 ', the synthetic method of 4,5,5 '-five nitro-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole, is characterized in that: under room temperature by compound 3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine is dissolved in dense H
2sO
4in, treat to dissolve completely, under ice bath, add Disodium tungstate (Na2WO4) dihydrate, then slowly drip hydrogen peroxide, dropwise and continue to stir half an hour, remove ice bath, reaction 24-48 hour, after reaction finishes, pours reaction solution in frozen water into, filters water/ethyl alcohol recrystallization.Sodium wolframate and 3,3 ', the mol ratio of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine is 1.2:1-1:1; In above-mentioned reaction, hydrogen peroxide concentration is 30% or 50%, and the volume ratio of the vitriol oil and hydrogen peroxide is 5:1-4:1, hydrogen peroxide and 3,3 ' and, the mol ratio of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine is 90:1-86:1; Temperature of reaction is room temperature.
According to claim 53,3 ', the synthetic method of 4,5,5 '-five nitro-1 '-hydrogen-Isosorbide-5-Nitrae '-double pyrazole, is characterized in that: in reaction, hydrogen peroxide concentration is 30% or 50%; Reaction times is 24-48 hour; Sodium wolframate and 3,3 ', the mol ratio of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine is 1.2:1-1:1; Hydrogen peroxide and 3,3 ', the mol ratio of 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine is 90:1-86:1; Temperature of reaction is room temperature.
According to claim 13,3 ', 5,5 '-tetranitro-1 ' hydrogen-(1,4 '-double pyrazole)-1 ', the synthetic method of 4-diamines, is characterized in that: under room temperature, by 3,3 ', 4,5,5 '-five nitro-1 '-hydrogen-1,4 '-double pyrazole is dissolved in acetonitrile, waits to stir, and slowly adds wherein freshly prepd THA dichloromethane solution, mixed solution continues reaction 24-36 hour, after reaction finishes, revolve to steam and remove solution, then add ethyl acetate, remove by filter insolubles, filtrate is yellow, and solvent evaporated obtains solid.Crude product obtains yellow solid through post layer analysis (ethyl acetate/petroleum ether=6/1).THA is 1.5:1-1:1 with the mol ratio of (5), and temperature of reaction is room temperature.
8. according to claim 73,3 ', 5,5 '-tetranitro-1 ' hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-1 ', the synthetic method of 4-diamines, it is characterized in that: reaction solvent is acetonitrile, reaction times is 24-26 hour, and THA is 1.5:1-1:1 with the mol ratio of (5), and temperature of reaction is room temperature.
According to claim 13,3 ', 5,5 '-tetranitro-1 '-hydrogen-(1,4 '-double pyrazole)-4-amine, containing the synthetic method of energy ion salt, is characterized in that: (1) 3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine and half mole of Ba (OH)
28H
2o filters BaSO after reacting 2-3h with corresponding vitriol in water again after mixing
4after precipitation, concentrated filtrate obtains corresponding to energy ion salt; (2) 3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine with corresponding alkali in water, in methyl alcohol or ethanol, react steam after 2-3h desolventize and obtain corresponding to can ion salt.
10. according to claim 93,3 ', 5,5 '-tetranitro-1 '-hydrogen-(1,4 '-double pyrazole)-4-amine is containing the synthetic method of energy ion salt, it is characterized in that: while preparing ion salt by replacement(metathesis)reaction metal-salt used be 3,3 ', 5,5 '-tetranitro-1 '-hydrogen-(1,4 '-double pyrazole)-4-amine barium salt, the reaction times is 2-3h, temperature of reaction 60-80 ℃; When 3,3 ', when 5,5 '-tetranitro-1 '-hydrogen-(Isosorbide-5-Nitrae '-double pyrazole)-4-amine and alkali direct reaction, reaction solvent can be water, methyl alcohol or ethanol, and the reaction times is 2-3h, temperature of reaction 40-50 ℃.
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