CN110590670A - 1, 2-bis (3, 5-dinitropyrazolyl) ethane compound and synthetic method thereof - Google Patents

1, 2-bis (3, 5-dinitropyrazolyl) ethane compound and synthetic method thereof Download PDF

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CN110590670A
CN110590670A CN201910904684.0A CN201910904684A CN110590670A CN 110590670 A CN110590670 A CN 110590670A CN 201910904684 A CN201910904684 A CN 201910904684A CN 110590670 A CN110590670 A CN 110590670A
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bis
dinitropyrazolyl
ethane
dinitropyrazole
ethoxymethyl
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CN110590670B (en
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李辉
赵凤起
杨燕京
李娜
张建侃
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Xian Modern Chemistry Research Institute
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    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Abstract

The invention discloses a 1, 2-bis (3, 5-dinitropyrazolyl) ethane compound, and the structural formula is shown as I. The synthesis process comprises the following steps: (1) 4-methyl-3, 5-dinitropyrazole and chloromethyl ethyl ether react to obtain 1- (ethoxymethyl) -4-methyl-3, 5-dinitropyrazole; (2)1- (ethoxymethyl) -4-methyl-3, 5-dinitropyrazole is subjected to self-coupling reaction to generate 1, 2-bis (1- (ethoxymethyl) -3, 5-dinitropyrazolyl) ethane; (3)1, 2-bis (1- (ethoxymethyl) -3, 5-dinitropyrazole) ethane generates 1, 2-bis (3, 5-dinitropyrazolyl) ethane under an acidic environment. The 1, 2-bis (3, 5-dinitropyrazolyl) ethane synthesized by the method has excellent thermal stability and has potential to be used as a heat-resistant explosive.

Description

1, 2-bis (3, 5-dinitropyrazolyl) ethane compound and synthetic method thereof
Technical Field
The invention relates to 1, 2-bis (3, 5-dinitropyrazolyl) ethane and a synthesis method thereof, and belongs to the technical field of energetic materials.
Background
The heat-resistant explosive is an energetic material which can still maintain proper mechanical sensitivity and can be reliably detonated after being subjected to a high-temperature environment for a long time, and has wide application requirements in the fields of nuclear weapons, space exploration, deep well blasting and the like. In order to prevent the energetic material from decomposing or exploding early in a high-temperature environment, the energetic material is required to have a higher melting point or decomposition temperature, a lower vapor pressure and good heat resistance. The research on the thermal explosive is originally intended to meet the aerospace special requirements of high-temperature environments in the military field, such as separation of all levels of space vehicles and spaceships, for example, the mixed explosive based on Hexanitrostilbene (HNS) and Teflon is once used as a main charge in the Apollo 17 planned seismic charge in the United states.
In an oil field blasting apparatus, the perforating charge filled with RDX and HMX is a conventional perforating charge and is generally used for shallow wells and medium deep wells with the depth of less than 4000m, and the well temperature is generally not more than 220 ℃. In recent years, with the gradual depletion of petroleum resources of shallow wells and medium-deep wells, the petroleum exploitation industry at home and abroad is gradually developed from inland shallow wells or medium-deep wells to inland deep wells, ultra-deep wells and ocean deep wells. The mixed explosive of hexogen base and octogen base with the heat-resistant temperature of about 200 ℃ cannot meet the requirement, and the heat-resistant explosive which can resist higher temperature is needed. The HNS has a melting point of 300 ℃ or higher, and a perforating charge using a heat-resistant explosive such as HNS is called an ultra-high temperature perforating charge.
The HNS has a structural formula shown as II, and the HNS-based heat-resistant mixed explosive has excellent heat resistance at the temperature of 210 ℃ and 260 ℃, but the HNS has lower density and energy and the density is 1.74 g-cm-3Detonation velocity of 7600 m.s-1The energy density cannot meet the development direction of high energy of the energetic material.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art, provide 1, 2-bis (3, 5-dinitropyrazolyl) ethane which is an energetic material and has excellent thermal stability and energy level, and provide a synthesis method of 1, 2-bis (3, 5-dinitropyrazolyl) ethane.
The structural formula of the 1, 2-bis (3, 5-dinitropyrazolyl) ethane of the invention is shown as I:
the invention relates to a synthetic route of 1, 2-bis (3, 5-dinitropyrazolyl) ethane:
in order to achieve the above object, the present invention provides a method for synthesizing 1, 2-bis (3, 5-dinitropyrazolyl) ethane, comprising the steps of:
(1) adding chloromethyl ethyl ether and potassium carbonate into an acetonitrile solution of 4-methyl-3, 5-dinitropyrazole at the temperature of 20-50 ℃, reacting for 8-12 h at the temperature of 20-50 ℃, adding a proper amount of water after the reaction is finished, extracting by ethyl acetate, drying and concentrating to obtain 1- (ethoxymethyl) -4-methyl-3, 5-dinitropyrazole, wherein the molar ratio of the 4-methyl-3, 5-dinitropyrazole to the chloromethyl ethyl ether is 1: 0-1.5, and the molar ratio of the 4-methyl-3, 5-dinitropyrazole to the potassium carbonate is 1: 0-1.5;
(2) adding liquid bromine into a tetrahydrofuran solution of potassium tert-butoxide and 1- (ethoxymethyl) -4-methyl-3, 5-dinitropyrazole at 10-30 ℃, reacting for 0.5-2 h at 10-30 ℃, adding a proper amount of water after the reaction is finished to separate out solid 1, 2-bis (1- (ethoxymethyl) -3, 5-dinitropyrazolyl) ethane, wherein the molar ratio of the potassium tert-butoxide to the 1- (ethoxymethyl) -4-methyl-3, 5-dinitropyrazole is 1: 0-1.5;
(3) adding trifluoroacetic acid into a dichloromethane solution of 1, 2-bis (1- (ethoxymethyl) -3, 5-dinitropyrazolyl) ethane at 10-30 ℃, reacting for 2-10 h at 20-50 ℃, filtering and washing after the reaction is finished to obtain the 1, 2-bis (3, 5-dinitropyrazolyl) ethane.
The invention has the beneficial effects that:
the 1, 2-bis (3, 5-dinitropyrazolyl) ethane compound of the present invention has excellent thermal stability, and the initial decomposition temperature is 351 ℃, while the comparative compound HNS is 318 ℃; the 1, 2-bis (3, 5-dinitropyrazolyl) ethane compound of the present invention has relatively high density of 1.81g cm-3While the reference compound HNS was 1.74g cm-3(ii) a The 1, 2-bis (3, 5-dinitropyrazolyl) ethane compound has high detonation velocity of 8234 m.s-1While the reference compound HNS is 7600 m.s-1。
Drawings
FIG. 11, DSC curve of 2-bis (3, 5-dinitropyrazolyl) ethane compound.
Detailed Description
The infrared characterization adopts a Fourier transform infrared spectrometer model NEXUS 870 of the American thermoelectric Nippon corporation, the nuclear magnetic characterization adopts a 500MHz superconductive nuclear magnetic resonance instrument model BRUKERAV500, and the element analysis adopts an element analyzer model EXEMENTARVARIO-EL-3.
Example 1
(1) Synthesis of 1- (ethoxymethyl) -4-methyl-3, 5-dinitropyrazole
4-methyl-3, 5-dinitropyrazole (3.44g,0.02mol), chloromethyl ethyl ether (2.1g,0.02mol) and K were reacted at room temperature2CO3(3.31g,0.022mol) were added to CH separately3CN (30mL), reacted at room temperature for 8h, then 30mL of water was added, the reaction solution was extracted 3 times with ethyl acetate, each time 20mL, and the extract was dried and concentrated to give 4.35g of a white solid with a yield of 93.5%.
Characterization data:
1H NMR(400MHz,CDCl3):δ5.93(s,2H),3.60(q,2H),2.69(s,3H),1.17(t,3H).
13C NMR(100MHz,CDCl3):δ151.4,142.9,115.4,82.9,65.9,14.2,9.5.
IR(ATR,cm-1):2982,2930,1587,1519,1446,1382,1329,1301,1254,1108,1031,866,772..
elemental analysis: c7H10N4O5Theoretical values C36.53, H4.38, N24.34; measured value:C 35.99,H 4.33,N 24.03.
the above data demonstrate that the synthesized compounds are structurally correct.
(2) Synthesis of 1, 2-bis (1- (ethoxymethyl) -3, 5-dinitropyrazolyl) ethane
To a solution of potassium tert-butoxide (1.68g,0.015mol) and 1- (ethoxymethyl) -4-methyl-3, 5-dinitropyrazole (3.0 g,0.013mol) in tetrahydrofuran (45mL) was added liquid bromine (0.9mL,0.017mol) at room temperature, after 2h of reaction, 100mL of water was added to precipitate a solid, which was filtered and dried to give 2.6g of a white solid with a yield of 94.1%.
1H NMR(400MHz,CDCl3):δ5.90(s,4H),3.62(s,4H),3.51(q,4H),1.17(t,6H).
13C NMR(100MHz,CDCl3):δ151.3,143.2,116.8,83.6,66.3,22.3,14.4.
IR(ATR,cm-1):2986,1580,1516,1446,1335,1298,1248,1109,1040,864,779,699.
Elemental analysis C14H18N8O10Theoretical values C36.69, H3.96, N24.45; found C36.57, H4.01, N23.84.
The above data demonstrate that the synthesized compounds are structurally correct.
(3) Synthesis of 1, 2-bis (3, 5-dinitropyrazolyl) ethane
1, 2-bis (1- (ethoxymethyl) -3, 5-dinitropyrazolyl) ethane (2.8g,0.006mol) was dissolved in CH at room temperature2Cl2To 30mL of the reaction mixture was added trifluoroacetic acid (10mL) at room temperature, and the mixture was reacted for 5 hours at room temperature, filtered and washed with water to give 1.83g of 1, 2-bis (3, 5-dinitropyrazolyl) ethane with a yield of 87.6%.
1H NMR(400MHz,DMSO-d6):δ3.48(s,4H).
13C NMR(100MHz,DMSO-d6):δ149.3,113.9,21.3.
IR(ATR,cm-1) 3152,2953,1585,1543,1491,1447,1426,1338,1235,1166,1003,845,773. elemental analysis: c8H6N8O8Theoretical values of C28.08, H1.77, N32.75; found C27.94, H1.83, N31.94.
The above data demonstrate that the synthesized compounds are structurally correct.
Properties of 1, 2-bis (3, 5-dinitropyrazolyl) ethane
1 physical and chemical Properties
Solubility: insoluble in dichloromethane, chloroform and water, slightly soluble in ethyl acetate, ethanol, methanol, acetone, etc.;
density: 1.81g/cm3X-ray single crystal diffraction.
2 thermal Properties
1, 2-bis (3, 5-dinitropyrazolyl) ethane has no melting point, and the initial decomposition temperature is 351 ℃ (DSC 5 ℃ C. min-1)。
3 detonation behaviour
Enthalpy of formation: the density was 1.81g/cm3The enthalpy of formation was calculated to be 184.3kJ/mol (Gaussian 09 program B3LYP method).
Explosion speed: the density was 1.81g/cm3The calculated detonation velocity was 8234m/s, (EXPLO5 v 6.02).
Explosion pressure: the density was 1.81g/cm3The calculated detonation pressure was 28.6GPa (EXPLO5 v 6.02).
4. Sensitivity: impact sensitivity 10J, friction sensitivity 352N.

Claims (2)

1. A1, 2-bis (3, 5-dinitropyrazolyl) ethane compound having a structural formula shown in formula I:
2. the method of synthesizing a 1, 2-bis (3, 5-dinitropyrazolyl) ethane compound according to claim 1, wherein the synthetic route is:
the method specifically comprises the following steps:
(1) synthesis of 1- (ethoxymethyl) -4-methyl-3, 5-dinitropyrazole:
adding chloromethyl ethyl ether and potassium carbonate into an acetonitrile solution of 4-methyl-3, 5-dinitropyrazole at the temperature of 20-50 ℃, reacting for 8-12 h at the temperature of 20-50 ℃, adding a proper amount of water after the reaction is finished, extracting by ethyl acetate, drying and concentrating to obtain 1- (ethoxymethyl) -4-methyl-3, 5-dinitropyrazole, wherein the molar ratio of the 4-methyl-3, 5-dinitropyrazole to the chloromethyl ethyl ether is 1: 0-1.5, and the molar ratio of the 4-methyl-3, 5-dinitropyrazole to the potassium carbonate is 1: 0-1.5;
(2) synthesis of 1, 2-bis (1- (ethoxymethyl) -3, 5-dinitropyrazolyl) ethane:
adding liquid bromine into a tetrahydrofuran solution of potassium tert-butoxide and 1- (ethoxymethyl) -4-methyl-3, 5-dinitropyrazole at 10-30 ℃, reacting for 0.5-2 h at 10-30 ℃, adding a proper amount of water after the reaction is finished to separate out solid 1, 2-bis (1- (ethoxymethyl) -3, 5-dinitropyrazolyl) ethane, wherein the molar ratio of the potassium tert-butoxide to the 1- (ethoxymethyl) -4-methyl-3, 5-dinitropyrazole is 1: 0-1.5;
(3) synthesis of 1, 2-bis (3, 5-dinitropyrazolyl) ethane
Adding trifluoroacetic acid into a dichloromethane solution of 1, 2-bis (1- (ethoxymethyl) -3, 5-dinitropyrazolyl) ethane at 10-30 ℃, reacting for 2-10 h at 20-50 ℃, filtering and washing after the reaction is finished to obtain the 1, 2-bis (3, 5-dinitropyrazolyl) ethane compound.
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