CN109438353B - 3-gem-dinitromethyl-5-nitropyrazole hydrazine compound - Google Patents
3-gem-dinitromethyl-5-nitropyrazole hydrazine compound Download PDFInfo
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- 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
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- 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
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Abstract
The invention discloses a 3-gem-dinitromethyl-5-nitropyrazole hydrazine compound, the structural formula of which is shown as (I):
Description
Technical Field
The invention relates to an energetic material, in particular to a pyrazole hydrazine salt compound.
Background
In recent years, nitrogen-rich energetic materials show good application prospects in the fields of explosives, propellants and the like. Compared with the traditional molecular compound, the azole nitrogen-rich molecular compound has higher positive heat of formation and higher density and oxygen balance because of containing a large amount of N-N and C-N bonds. The azole nitrogen-rich energetic ionic salt has high heat of formation and high density due to the introduction of nitrogen-containing anions or cations, and simultaneously retains the high tension of a nitrogen-rich ring, thereby being a unique nitrogen-rich energetic compound. The energetic ionic salt has lower vapor pressure and low carbon hydrogen content compared with nonionic molecules, and the products after the decomposition of the nitrogen-rich energetic ionic salt are mainly N2The nitrogen-rich ions have various types and are easy to modify, and the nitrogen-rich ions have wide application prospects in the aspects of industry and military affairs as high-energy materials. Five-membered nitrogen-rich heterocycle has been the focus of research in the field of energetic materials, and azole compounds can be used as cations and anions, so that the types of energetic salts are greatly enriched, and a research basis is provided for searching energetic salts with more excellent performance.
Wanying Lei et al "research on synthesis of 3, 5-dinitropyrazole", energetic materials, 2007, 15 (6): 574-576 discloses an improved synthesis process of 3, 5-dinitropyrazole, the molecular structure of the compound is shown as (II):
the density of the compound was 1.80g/cm3The nitrogen content is 35.4%, the detonation velocity is 8150m/s, and the detonation pressure is 30.6 GPa. But the nitrogen content of the compound is lower and the energy is smaller.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide a 3-gem-dinitromethyl-5-nitropyrazole hydrazine compound with higher nitrogen content and larger energy.
The synthetic route of the 3-gem-dinitromethyl-5-nitropyrazole hydrazine compound is as follows:
using 3-formaldehyde pyrazole as raw material, firstly reacting with hydroxylamine hydrochloride to produce 3-formaldehyde oxime pyrazole, then using N2O4Carrying out nitrohydrolysis to obtain 1-nitro-3-trinitromethylpyrazole, and finally reacting with hydrazine hydrate to generate 3-gem-dinitromethyl-5-nitropyrazole hydrazine salt.
The structural formula of the 3-gem-dinitromethyl-5-nitropyrazole hydrazine compound is shown as the formula (I):
the invention discloses a method for synthesizing 3-gem-dinitromethyl-5-nitropyrazole hydrazine salt, which comprises the following steps:
(1) synthesis of 3-formaldoxime pyrazole
Adding hydroxylamine hydrochloride, sodium acetate and 3-formaldehyde pyrazole into ethanol in sequence, wherein the reaction temperature is 40-60 ℃, the reaction time is 1-2 h, after the reaction is finished, a milky turbid liquid is obtained, cooling to room temperature, filtering, evaporating the filtrate to dryness to obtain an oily viscous solid, adding water to dissolve the oily viscous solid, extracting with ethyl acetate, drying an organic phase with anhydrous sodium sulfate, filtering, and evaporating the filtrate to dryness to obtain a light yellow viscous solid, namely 3-formaldehyde oxime pyrazole. Wherein the molar ratio of the 3-formaldehyde pyrazole, the hydroxylamine hydrochloride and the sodium acetate is 1: 1-2.
(2) Synthesis of 1-nitro-3-trinitromethylpyrazole
Dissolving 3-formaldoxime pyrazole in acetonitrile, stirring for dissolving, and adding N2O4The reaction temperature is 50-70 ℃, the reaction time is 2-4 h, the reaction product is cooled to room temperature after the reaction is finished, and the residual N is removed by vigorous stirring2O4And evaporating the reaction solution to dryness, and performing column chromatography separation (eluent is dichloromethane and petroleum ether with the volume ratio of 1-3: 1) to obtain white solid 1-nitro-3-trinitromethylpyrazole. Wherein，N2O4The dosage of the compound is 0.5-2 mL per millimole of 3-formaldoxime pyrazole;
(3) synthesis of 3-gem-dinitromethyl-5-nitropyrazole hydrazine salt
Dissolving 1-nitro-3-trinitromethylpyrazole in methanol, stirring for dissolving, adding 80% hydrazine hydrate methanol solution, reacting at room temperature for 2-4 h, evaporating the reaction solution after the reaction is finished, and recrystallizing with methanol to obtain a light yellow solid 3-gem-dinitromethyl-5-nitropyrazole hydrazine salt. Wherein the molar ratio of the 1-nitro-3-trinitromethylpyrazole to the hydrazine hydrate is 1: 1-4.
The invention has the advantages that:
the 3-gem-dinitromethyl-5-nitropyrazole hydrazine compound has higher nitrogen content, the nitrogen content is 39.4 percent, and the nitrogen content of the 3, 5-dinitropyrazole in a comparison file is 35.4 percent; the 3-gem-dinitromethyl-5-nitropyrazole hydrazine compound has high energy, the detonation velocity is 8790m/s, the detonation pressure is 33.8GPa, the detonation velocity of the 3, 5-dinitropyrazole of a comparison file is 8150m/s, and the detonation pressure is 30.6 GPa.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
(1) Synthesis of 3-formaldoxime pyrazole
0.83g (12mmol) of hydroxylamine hydrochloride, 0.98g (12mmol) of sodium acetate and 40ml of ethanol are added into a 100ml three-necked flask, 0.96g (10mmol) of 3-formaldehyde pyrazole is added under stirring, the temperature is raised to 60 ℃, and the reaction is carried out for 2 h. And after the reaction is finished, obtaining milky turbid liquid, cooling to room temperature, filtering, evaporating the filtrate to dryness to obtain oily viscous solid, dissolving the oily viscous solid in 50ml of water, extracting the oily viscous solid for 3 times by using 50ml of ethyl acetate, drying an organic phase by using anhydrous sodium sulfate, filtering, evaporating the filtrate to dryness to obtain 0.93g of light yellow viscous solid, wherein the yield is 84.0%.
And (3) structural identification:
nuclear magnetic spectrum:1H NMR(600MHz,dmso):11.65,8.13,7.65,7.65,7.63,7.63,7.54,6.88,6.88,6.49,6.49；13C NMR(151MHz,dmso):172.83,170.89,144.19,142.62,140.09,138.70,133.02,132.28,109.11,103.10,60.27
elemental analysis: molecular formula C4H5N3O
Theoretical value: c43.24, H4.54, N37.82
Measured value: c43.12, H4.83, N37.65
The above structural identification data confirmed that the resulting material was indeed 3-formaldoxime pyrazole.
(2) Synthesis of 1-nitro-3-trinitromethylpyrazole
3-Methylaldoxime pyrazole (555mg, 5mmol) was added to a 50mL three-necked flask, dissolved in 20mL acetonitrile, and 5mL N was added dropwise with vigorous stirring2O4. Then the temperature is raised to 60 ℃, and the reaction is carried out for 2 hours under the condensation reflux. After the reaction is finished, the reaction solution is cooled to room temperature, and the residual N is removed by vigorous stirring2O4To obtain light yellow transparent liquid, evaporating the reaction liquid to dryness, and performing column chromatography separation (eluent is dichloromethane and petroleum ether) to obtain 245mg of white solid 1-nitro-3-trinitromethylpyrazole, wherein the yield is 18.7%.
And (3) structural identification:
infrared spectrum: IR (KBr) 3144,1655,1619,1596,1301,1259,1135,1048,816,802,771cm-1
Nuclear magnetic spectrum:1H NMR(600MHz,dmso):9.17(d,1H),7.53(d,1H)；13C NMR(151MHz,dmso)134.93(s),129.31(s),112.37(s)
elemental analysis: molecular formula C4H2N6O8
Theoretical values C18.33, H0.77, N32.07
Found C18.26, H1.01, N32.15
Mass spectrum: (ESI) M/z 261[ M-1 ]]-,216[M-46]-
The above structural identification data confirmed that the resulting substance was indeed 1-nitro-3-trinitromethylpyrazole.
(3) Synthesis of 3-gem-dinitromethyl-5-nitropyrazole hydrazine salt
1310mg of 1-nitro-3-trinitromethylpyrazole (5mmol) and 20mL of methanol were added to a 100mL three-necked flask and dissolved with stirring. 1.0mL of 80% hydrazine hydrate (15mmol) was dissolved in 20mL of methanol, and then slowly added dropwise to the reaction system. The reaction was carried out at room temperature for 4h, the reaction solution was evaporated to dryness and recrystallized from methanol to give 765mg of pale yellow solid with a yield of 61.9%.
And (3) structural identification:
infrared spectrum: IR (KBr) 3328,3194,1594,1543,1487,1463,1334,1282,1223,1185,1110,1002,952,836,759cm-1
Nuclear magnetic spectrum:1H NMR(600MHz,dmso):13.71(s,1H),8.58(s,3H),7.09(s,1H)；13CNMR(151MHz,dmso):155.58(s),137.10(s),109.83(s),102.05(s)
elemental analysis: molecular formula C4H7N7O6
Theoretical values C19.28, H2.83, N39.35
Found C19.33, H2.72, N39.47
The above structural identification data confirmed that the resulting material was indeed a 3-gem-dinitromethyl-5-nitropyrazole hydrazonium salt.
Example 2
(1) Synthesis of 3-formaldoxime pyrazole
1.04g (15mmol) of hydroxylamine hydrochloride, 1.23g (15mmol) of sodium acetate and 40ml of ethanol are added into a 100ml three-necked flask, 0.96g (10mmol) of 3-formaldehyde pyrazole is added under stirring, the temperature is raised to 60 ℃, and the reaction is carried out for 3 hours. And after the reaction is finished, obtaining milky turbid liquid, cooling to room temperature, filtering, evaporating the filtrate to dryness to obtain oily viscous solid, dissolving the oily viscous solid in 50ml of water, extracting the oily viscous solid for 3 times by using 50ml of ethyl acetate, drying an organic phase by using anhydrous sodium sulfate, filtering, evaporating the filtrate to dryness to obtain light yellow viscous solid 0.99g, wherein the yield is 89.5%.
And (3) structural identification:
nuclear magnetic spectrum:1H NMR(600MHz,dmso):11.65,8.13,7.65,7.65,7.63,7.63,7.54,6.88,6.88,6.49,6.49；13C NMR(151MHz,dmso):172.83,170.89,144.19,142.62,140.09,138.70,133.02,132.28,109.11,103.10,60.27
elemental analysis: molecular formula C4H5N3O
Theoretical value: c43.24, H4.54, N37.82
Measured value: c43.12, H4.83, N37.65
The above structural identification data confirmed that the resulting material was indeed 3-formaldoxime pyrazole.
(2) Synthesis of 1-nitro-3-trinitromethylpyrazole
3-Methylaldoxime pyrazole (555mg, 5mmol) was added to a 50mL three-necked flask, dissolved in 20mL acetonitrile, and 3mL N was added dropwise with vigorous stirring2O4. Then the temperature is raised to 60 ℃, and the reaction is carried out for 4 hours under the reflux condensation. After the reaction is finished, the reaction solution is cooled to room temperature, and the residual N is removed by vigorous stirring2O4To obtain light yellow transparent liquid, evaporating the reaction liquid to dryness, and performing column chromatography separation (eluent is dichloromethane and petroleum ether) to obtain 195mg of white solid 1-nitro-3-trinitromethylpyrazole with the yield of 14.9%.
And (3) structural identification:
infrared spectrum: IR (KBr) 3144,1655,1619,1596,1301,1259,1135,1048,816,802,771cm-1
Nuclear magnetic spectrum:1H NMR(600MHz,dmso):9.17(d,1H),7.53(d,1H)；13C NMR(151MHz,dmso)134.93(s),129.31(s),112.37(s)
elemental analysis: molecular formula C4H2N6O8
Theoretical values C18.33, H0.77, N32.07
Found C18.26, H1.01, N32.15
Mass spectrum: (ESI) M/z 261[ M-1 ]]-,216[M-46]-
The above structural identification data confirmed that the resulting substance was indeed 1-nitro-3-trinitromethylpyrazole.
(3) Synthesis of 3-gem-dinitromethyl-5-nitropyrazole hydrazine salt
1310mg of 1-nitro-3-trinitromethylpyrazole (5mmol) and 20mL of methanol were added to a 100mL three-necked flask and dissolved with stirring. 0.67mL of 80% hydrazine hydrate (10mmol) was dissolved in 20mL of methanol, and then slowly added dropwise to the reaction system. Reacting for 3h at room temperature, evaporating the reaction solution to dryness, and recrystallizing with methanol to obtain 676mg of light yellow solid with a yield of 54.7%.
And (3) structural identification:
infrared spectrum: IR (KBr) 3328,3194,1594,1543,1487,1463,1334,1282,1223,1185,1110,1002,952,836,759cm-1
Nuclear magnetic spectrum:1H NMR(600MHz,dmso):13.71(s,1H),8.58(s,3H),7.09(s,1H)；13CNMR(151MHz,dmso):155.58(s),137.10(s),109.83(s),102.05(s)
elemental analysis: molecular formula C4H7N7O6
Theoretical values C19.28, H2.83, N39.35
Found C19.33, H2.72, N39.47
The above structural identification data confirmed that the resulting material was indeed a 3-gem-dinitromethyl-5-nitropyrazole hydrazonium salt.
Properties of 3-gem-dinitromethyl-5-nitropyrazole hydrazines of the invention
(1) Physical and chemical properties
Appearance: pale yellow solid
Density: 1.80g/cm3
(2) Detonation performance
Explosion speed: the density was 1.80g/cm3And calculating the detonation velocity to be 8790m/s K-J equation
Explosion pressure: the density was 1.80g/cm3Calculating the detonation pressure to be 33.8GPa K-J equation
The invention relates to the use of 3-gem-dinitromethyl-5-nitropyrazole hydrazine salt
The 3-gem-dinitromethyl-5-nitropyrazole hydrazine salt has the characteristics of higher density, higher nitrogen content, higher energy and the like, and is expected to be used as a novel high-energy material.
Claims (1)
1. A3-gem-dinitromethyl-5-nitropyrazole hydrazine compound has a structural formula shown as the following (I):
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