CN117362232A - High-energy nitro-imitation compound for improving oxygen balance of 4-amino-3, 5-dinitropyrazole and synthesis method thereof - Google Patents
High-energy nitro-imitation compound for improving oxygen balance of 4-amino-3, 5-dinitropyrazole and synthesis method thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 18
- ZDCGXVZZNAVVFJ-UHFFFAOYSA-N 3,5-dinitro-1h-pyrazol-4-amine Chemical compound NC=1C([N+]([O-])=O)=NNC=1[N+]([O-])=O ZDCGXVZZNAVVFJ-UHFFFAOYSA-N 0.000 title abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 14
- 239000001301 oxygen Substances 0.000 title abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 14
- 238000001308 synthesis method Methods 0.000 title abstract description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- BULLHNJGPPOUOX-UHFFFAOYSA-N chloroacetone Chemical compound CC(=O)CCl BULLHNJGPPOUOX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002360 explosive Substances 0.000 claims abstract description 4
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 239000004449 solid propellant Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 239000005457 ice water Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 229940125782 compound 2 Drugs 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000010791 quenching Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 238000006396 nitration reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229940125904 compound 1 Drugs 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000002828 nitro derivatives Chemical class 0.000 claims 1
- -1 LLM-116 ammonium salt Chemical class 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000004880 explosion Methods 0.000 abstract description 3
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- MIQWEMDDUPSLRW-UHFFFAOYSA-N [O].O=C=O Chemical compound [O].O=C=O MIQWEMDDUPSLRW-UHFFFAOYSA-N 0.000 abstract description 2
- 125000001539 acetonyl group Chemical group [H]C([H])([H])C(=O)C([H])([H])* 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 238000005474 detonation Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- YLTPBDJQPIRWTQ-UHFFFAOYSA-N 3,4,5-trinitro-1h-pyrazole Chemical compound [O-][N+](=O)C1=NNC([N+]([O-])=O)=C1[N+]([O-])=O YLTPBDJQPIRWTQ-UHFFFAOYSA-N 0.000 description 2
- BADSZRMNXWLUKO-UHFFFAOYSA-N 4-chloro-1h-pyrazole Chemical compound ClC=1C=NNC=1 BADSZRMNXWLUKO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KPTSBKIDIWXFLF-UHFFFAOYSA-N 1,1,2-triaminoguanidine Chemical compound NN=C(N)N(N)N KPTSBKIDIWXFLF-UHFFFAOYSA-N 0.000 description 1
- HJRJRUMKQCMYDL-UHFFFAOYSA-N 1-chloro-2,4,6-trinitrobenzene Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C(Cl)C([N+]([O-])=O)=C1 HJRJRUMKQCMYDL-UHFFFAOYSA-N 0.000 description 1
- KEPNSIARSTUPGS-UHFFFAOYSA-N 2-n,4-n,6-n-trichloro-1,3,5-triazine-2,4,6-triamine Chemical compound ClNC1=NC(NCl)=NC(NCl)=N1 KEPNSIARSTUPGS-UHFFFAOYSA-N 0.000 description 1
- BQDDUZDJYQJMAZ-UHFFFAOYSA-N 4-chloro-3,5-dinitro-1H-pyrazole Chemical compound [O-][N+](=O)C1=NNC([N+]([O-])=O)=C1Cl BQDDUZDJYQJMAZ-UHFFFAOYSA-N 0.000 description 1
- HGVZYSPTNWIIPP-UHFFFAOYSA-N C(C(=O)C)N1N=C(C(=C1[N+](=O)[O-])N)[N+](=O)[O-] Chemical compound C(C(=O)C)N1N=C(C(=C1[N+](=O)[O-])N)[N+](=O)[O-] HGVZYSPTNWIIPP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C07D231/16—Halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/34—Compositions containing a nitrated organic compound the compound being a nitrated acyclic, alicyclic or heterocyclic amine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a high-energy nitro-imitation compound for improving the oxygen balance of 4-amino-3, 5-dinitropyrazole and a synthesis method thereof, wherein LLM-116 ammonium salt is taken as a raw material to react with chloroacetone and potassium bromide to synthesize 1-acetonyl-LLM-116; then nitrify the acetonyl group into nitro-imitation to obtain 1-nitro-imitation-LLM-116 with molecular formula of C 4 H 2 N 8 O 10 Density of 1.866g ∙ cm ‑3 The carbon dioxide oxygen balance is +4.97%, the oxygen content is 49.67%, the theoretical explosion rate is improved by about 10% compared with LLM-116, and the composite material can be used as a high-energy material in the fields of an explosive or an oxidant of a solid propellant, and the like. The method has the advantages of simple synthesis, high yield, low cost and the like, and improves the oxygen balance of LLM-116 from-32.37% to +4.97%.
Description
Technical Field
The invention relates to a high-energy nitro-simulated compound for improving the oxygen balance of 4-amino-3, 5-dinitropyrazole and a preparation method thereof, belonging to the technical field of energetic materials.
Background
4-amino-3, 5-dinitropyrazole (LLM-116) had a density of 1.9 g.cm -3 The energy of the catalyst is 90% of that of cyclotetramethylene tetranitramine (HMX), H 50 167.5cm, and detonation velocity of 8.24 km.s -1 The detonation pressure was 29.42GPa. LLM-116 was designed by the national laboratory of Lorentz Lifromo in 1993, which synthesized LLM-116 by the VNS reaction after nearly ten years. In 2007, wang Yinglei and the like of the recent chemical institute of western security studied the mechanism and influencing factors of the VNS reaction, and optimized the optimal reaction conditions (explosive and powder journal, 2007, 30:20-23). In 2010, herv et al ammoniated 3,4, 5-trinitropyrazole synthesized LLM-116 (Angew. Chem. Int. Ed.,2010, 49:3177-3181). LLM-116 was synthesized by Dalinger et al ammoniated 4-chloro-3, 5-dinitropyrazole 2012 (Synthesis, 2012, 44:2058-2064). LLM-116 has important application prospect as a high-energy low-inductance energy-containing material.
Because of the induction effect of nitro, H on pyrazole ring nitrogen in LLM-116 has certain acidity, and can form various organic amine salts with alkaline substances (such as guanidine, triaminoguanidine, carbamide amidine, etc.); forming complexes with metal ions (e.g., potassium, lead, copper, etc.). In 2009, wang Bazhou and the like of the western advanced research institute take LLM-116 as a raw material, and react with 2,4, 6-trinitrochlorobenzene and trichloromelamine to synthesize 1-bitter-4-amino-3, 5-dinitropyrazole and 2,4, 6-tris (4-amino-3, 5-dinitropyrazol-1-yl) -1,3, 5-s-triazine (energetic materials, 2009, 17:293-295). In addition, various forms of bridged bis LLM-116 compounds were synthesized. However, these compounds generally have poor oxygen balance and performance slightly below the level of LLM-116. In order to improve the energy performance of LLM-116 derivatives, their oxygen balance must be increased. The nitroimitation has high energy and good oxygen balance, but has higher sensitivity, and the patent report with the application number of 202111443058.X introduces the nitroimitation on the trinitropyrazole, so that the impact sensitivity is only 3.8J, and the application is greatly influenced by the sensitivity which is too high.
Disclosure of Invention
The invention aims to provide a high-energy nitro-imitation compound capable of improving the oxygen balance of LLM-116 and a preparation method thereof.
The technical solution for realizing the purpose of the invention is as follows:
a high-energy nitro-imitation compound with chemical formula of C 4 H 2 N 8 O 10 The structural formula is as follows:
the crystal structure of the high-energy nitro-imitation compound has the following characteristics:
and (3) crystal system: monoclinic system;
dot group: p2 1 /n；
Unit cell parameters:α＝γ＝90°，β＝98.696(3)°；
unit cell volume:
Z＝8；
density: 1.895 g.cm -3 (193K)。
The invention provides a preparation method of a high-energy nitro-imitation compound, which comprises the following steps:
(1) A step of reacting compound 1 with chloroacetone and potassium bromide in N, N-dimethylformamide to synthesize compound 2;
(2) Performing post-treatment on the compound 2 after nitration reaction under the participation of fuming nitric acid and concentrated sulfuric acid to prepare a target product;
preferably, in the step (1), the molar ratio of the compound 1 to the potassium bromide to the chloroacetone is 1:1:1.5; the reaction temperature is 60-90 ℃; the reaction time is 0.5-3 h.
Preferably, in the step (2), the volume ratio of fuming nitric acid to concentrated sulfuric acid is 1-1.5:1; the dosage ratio of fuming nitric acid to compound 2 is 8-10 mL:1g; the reaction temperature was room temperature.
Preferably, in the step (2), the compound 2 is added into concentrated sulfuric acid in batches at 15-20 ℃, fuming nitric acid is dropwise added at-5 ℃, stirring is carried out for 1h at the temperature after the completion of the dropwise addition, the reaction system is gradually restored to room temperature within 2-3 h, and then stirring is carried out for 4-8 h at the temperature.
Preferably, in the step (2), the post-treatment means: after the nitration reaction is finished, pouring the reaction solution into ice water for quenching, filtering, removing a filter cake, standing the filtrate at room temperature for more than 24 hours, and filtering to separate out a precipitate to obtain a target product.
The application of the high-energy compound as an oxidant of explosive or solid propellant in weapons and aerospace.
Compared with the prior art, the invention has the beneficial effects that:
(1) The high-energy compound has a covalent structure in which the nitro-imitation is directly connected with LLM-116, and the combination of the high-energy oxygen-enriched group and the insensitive parent ring achieves the balance of energy and stability.
(2) The high energy compounds of the present invention increase the oxygen balance of LLM-116 from-32.37% to +4.97%.
(3) The density of the high-energy compound of the present invention is 1.866 g.cm -3 Has excellent detonation performance, the calculated detonation pressure of EXPLO5 is 35.59GPa, and the detonation velocity is 9028 m.s -1 The theoretical explosion rate is improved by about 10% compared with LLM-116.
(4) In the synthesis method of the high-energy nitro-imitation compound, the intermediate LLM-116 ammonium salt for synthesizing LLM-116 is taken as a raw material, and 1-nitro-imitation-4-amino-3, 5-dinitropyrazole is prepared in two steps.
Drawings
FIG. 1 is a diagram showing the crystal structure of the 1-nitroimitation-4-amino-3, 5-dinitropyrazole of the present invention.
FIG. 2 is a unit cell stacking diagram of the 1-nitroimitation-4-amino-3, 5-dinitropyrazole of the invention.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of 1-nitroimitation-4-amino-3, 5-dinitropyrazole of the present invention (deuterated acetone as solvent).
FIG. 4 is a nuclear magnetic resonance spectrum of 1-nitromimetic-4-amino-3, 5-dinitropyrazole of the present invention (deuterated acetone as the solvent).
FIG. 5 is an infrared spectrum of the 1-nitroimitation-4-amino-3, 5-dinitropyrazole of the present invention.
FIG. 6 is a thin layer chromatogram of the product of the invention 1-nitroimitation-4-amino-3, 5-dinitropyrazole and of comparative example 2.
Detailed Description
The following examples will provide those skilled in the art with a more complete understanding of the invention, but are not intended to limit the invention in any way.
The invention introduces the nitro-imitation into the insensitive LLM-116 mother ring, not only can improve the energy of the mother ring and improve the oxygen balance of the mother ring, but also can reduce the sensitivity of the nitro-imitation, and the combination of the nitro-imitation and the mother ring can achieve the balance of energy and stability to a certain extent, thereby being an effective strategy for preparing the high-energy low-sensitivity energetic material.
According to the method, 4-chloropyrazole which is commercially available is used as a substrate, and a raw material LLM-116 ammonium salt (4-amino-3, 5-dinitropyrazole ammonium salt) is prepared through two-step reactions of nitration and ammoniation according to literature (Synthesis, 2012, 44:2058-2064).
The invention provides a preparation method of a high-energy oxidant, which comprises the following reaction equation:
the method comprises the following specific steps:
dissolving LLM-116 ammonium salt (4-amino-3, 5-dinitropyrazole ammonium salt) in N, N-dimethylformamide, adding potassium bromide into the solution, stirring at room temperature for 0.5h, heating to 60-90 ℃, dropwise adding chloroacetone at the temperature, and maintaining the temperature at 60-90 ℃ for reaction for 0.5-3 h. Cooling the reaction solution to room temperature after the reaction is finished, pouring ice water for quenching, filtering, washing with cold water for three times, and drying to obtain 1-acetonyl-LLM-116 (1-acetonyl-4-amino-3, 5-dinitropyrazole);
step two, adding 1-acetonyl-LLM-116 into 98wt% concentrated sulfuric acid in batches at 15-20 ℃, cooling to 0-5 ℃, dropwise adding fuming nitric acid, dropwise adding the fuming nitric acid, maintaining the temperature of a reaction system to be lower than 5 ℃, stirring for 1h at the temperature after the completion of the dropwise adding, gradually returning the reaction system to room temperature (15-30 ℃) within 2-3 h, stirring for reacting for 4-8 h at the temperature, pouring the reaction solution into ice water for quenching after the reaction is finished, filtering, removing filter cakes, standing filtrate for more than 24h, and separating out pale yellow solid, namely 1-nitro-LLM-116 (1-nitro-4-amino-3, 5-dinitropyrazole).
Example 1:
the raw material LLM-116 ammonium salt selected in the invention is prepared by taking commercially available 4-chloropyrazole as a substrate according to the literature (Synthesis, 2012, 44:2058-2064). LLM-116 ammonium salt (15 mmol,2.85 g) was dissolved in N, N-dimethylformamide (25 mL), potassium bromide (15 mmol,1.79 g) was added to the solution, stirred at room temperature for 0.5h, then warmed to 75℃and chloroacetone (22.5 mmol,2.08 g) was added dropwise, and reacted at 75℃for 1h, and chloroacetone was added dropwise after warming to 75℃in order to increase the reactivity of chloroacetone. After the reaction, the reaction mixture was cooled to room temperature, quenched with ice water, filtered, washed three times with cold water, and dried to give 1-acetonyl-LLM-116 (3.28 g) in a yield of 95.5%.
1-acetonyl-LLM-116 (6 mmol,1.37 g) is added into 98wt% concentrated sulfuric acid (10 mL) in batches at 15-20 ℃, the temperature is reduced to about 0 ℃, fuming nitric acid (12 mL) is added dropwise, the temperature of the reaction system is maintained to be not higher than 5 ℃, the reaction system is stirred for 1h after the completion of the dropwise addition, the reaction system is gradually restored to room temperature (25-30 ℃) within 3h, then the reaction is stirred at the temperature for 8h, the reaction solution is poured into ice water for quenching after the completion of the reaction, the filtration is carried out, the filter cake is removed, the filtrate is kept stand at the room temperature for 24h, and the light yellow solid is obtained as the pure product of 1-nitro-LLM-116 (0.85 g), and the yield is 44.1%.
1-Nitro-LLM-116 obtained in example 1 was dissolved in diethyl ether and slowly evaporated at room temperature to give pale yellow bulk single crystals, which were subjected to single crystal X-ray diffraction test, the crystal structure was as shown in FIGS. 1 and 2, and the unit cell parameters were as shown in the following Table:
table 1
The 1-nitroimitation-LLM-116 obtained in example 1 was characterized and analyzed as follows:
as shown in the nuclear magnetic hydrogen spectrogram of figure 3, 1 H NMR(C 3 D 6 O):δ8.07ppm。
as shown in the nuclear magnetic carbon spectrum of figure 4, 13 C NMR(C 3 D 6 O):δ205.47,147.81,132.24,129.75ppm。
as shown in fig. 5, IR (ATR):3674,3484,3361,2987,2901,2199,1756,1659,1633,1618,1599,1578,1539,1469,1388,1310,1265,1224,1066,1052,975,863,838,794,758,738,691,655,639,597cm -1 . Elemental analysis C 4 H 2 N 8 O 10 (322.106): found (calculated) C14.89 (14.92), H0.71 (0.63), N34.88 (34.79).
The 1-nitroimitation-LLM-116 obtained in example 1 was tested to have an impact sensitivity of 7.5J and a friction sensitivity of 120N.
For 1-nitroimitation-LLM-116 obtained in example 1, it was calculated that the carbon dioxide oxygen balance was +4.97% and the oxygen content was 49.67%.
For the 1-nitro-LLM-116 obtained in example 1, the density was 1.866 g.cm -3 Has excellent detonation performance, the calculated detonation pressure of EXPLO5 is 35.59GPa, and the detonation velocity is 9028 m.s -1 The theoretical explosion rate is improved by about 10% compared with LLM-116.
Example 2
1-acetonyl-LLM-116 (6 mmol,1.37 g) is added into 98wt% concentrated sulfuric acid (10 mL) in batches at 15-20 ℃, the temperature is reduced to about 0 ℃, fuming nitric acid (12 mL) is added dropwise, the temperature of the reaction system is maintained to be not higher than 5 ℃, the reaction system is stirred for 1h after the completion of the dropwise addition, the reaction system is gradually restored to room temperature (15-20 ℃) within 2h, then the reaction is stirred at the temperature for 8h, the reaction solution is poured into ice water for quenching after the completion of the reaction, the filtration is carried out, the filter cake is removed, the filtrate is kept stand at the room temperature for 24h, and the light yellow solid is separated out, namely, 1-nitro-LLM-116 pure product (0.67 g), and the yield is 34.8%.
Comparative example 1:
1-acetonyl-LLM-116 (6 mmol,1.37 g) is added into 98wt% concentrated sulfuric acid (10 mL) in batches at 15-20 ℃, the temperature is reduced to about 0 ℃, fuming nitric acid (12 mL) is added dropwise, the temperature of the reaction system is maintained to be not higher than 5 ℃, the reaction system is stirred for 1h at the temperature after the completion of the dropwise addition, the reaction system is quickly (10 min) warmed to room temperature (25-30 ℃), then stirred at the temperature for 8h, the reaction is finished, the reaction solution is poured into ice water for quenching, filtration is carried out, a filter cake is removed, the filtrate is kept stand at the room temperature for 24h, and the yield of the target product 1-nitroform-LLM-116 (0.25 g) is 13.0% after nuclear magnetic test.
Comparative example 2:
1-acetonyl-LLM-116 (6 mmol,1.37 g) was added in portions to 98wt% concentrated sulfuric acid (10 mL) at 15-20℃and was cooled to 0℃and fuming nitric acid (12 mL) was added dropwise, the reaction system was maintained at not higher than 5℃and stirred at this temperature for 1h after completion of the dropwise addition, the reaction system was gradually returned to room temperature (25-30 ℃) over 3h, then stirred at this temperature for 8h, the reaction mixture was poured into ice water to quench, filtered, the filter cake was removed, the filtrate was stirred rapidly at room temperature for 30min to precipitate a solid, which was filtered, dried and analyzed by thin layer chromatography (FIG. 6, the developer was ethyl acetate: petroleum ether=1:5) as a mixture of 1-nitroimitation-LLM-116 and another by-product. The mixture was eluted with ethyl acetate: petroleum ether=1:10 by column chromatography to give 0.35g (18.1% yield) of 1-nitroimitation-LLM-116 target compound, 0.58g (31.9% yield) as a by-product.
As can be seen from the implementation process, the preparation method of the 1-nitro-LLM-116 high-energy compound is different from the conventional nitration reaction method, and the temperature rising rate is too high or the stirring of filtrate can lead to the reduction of the product yield and the increase of byproducts.
Claims (8)
1. A high-energy nitro-imitation compound is characterized in that the chemical formula is C 4 H 2 N 8 O 10 The structural formula is as follows:
2. the high energy nitromimetic of claim 1 wherein the crystalline structure has the following characteristics:
and (3) crystal system: monoclinic system;
dot group: p2 1 /n；
Unit cell parameters:α＝γ＝90°，β＝98.696(3)°；
unit cell volume:
Z＝8；
density: 1.895 g.cm -3 (193K)。
3. A process for the preparation of the high energy nitromimetic compounds of claim 1 or 2, comprising:
(1) A step of reacting compound 1 with chloroacetone and potassium bromide in N, N-dimethylformamide to synthesize compound 2;
(2) Performing post-treatment on the compound 2 after nitration reaction under the participation of fuming nitric acid and concentrated sulfuric acid to prepare a target product;
4. a process according to claim 3, wherein in step (1), the molar ratio of compound 1, potassium bromide, chloroacetone is 1:1:1.5; the reaction temperature is 60-90 ℃; the reaction time is 0.5-3 h.
5. A method according to claim 3, wherein in step (2), the volume ratio of fuming nitric acid to concentrated sulfuric acid is 1-1.5:1; the dosage ratio of fuming nitric acid to compound 2 is 8-10 mL:1g.
6. A process according to claim 3, wherein in step (2), compound 2 is added to concentrated sulfuric acid in batches at 15 to 20 ℃, fuming nitric acid is added dropwise at-5 to 5 ℃, stirring is carried out for 1h at the temperature after the completion of the dropwise addition, the reaction system is gradually returned to room temperature for 2 to 3h, and then stirring is carried out for 4 to 8h at the temperature.
7. A method according to claim 3, wherein in step (2), the post-treatment means: after the nitration reaction is finished, pouring the reaction solution into ice water for quenching, filtering, removing a filter cake, standing the filtrate at room temperature for more than 24 hours, and filtering to separate out a precipitate to obtain a target product.
8. Use of a high energy nitro compound according to claim 1 as an oxidising agent for explosives or solid propellants.
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