CN110590669A - 4, 4' -bis (3, 5-dinitropyrazolyl) methane compound and synthesis method thereof - Google Patents

4, 4' -bis (3, 5-dinitropyrazolyl) methane compound and synthesis method thereof Download PDF

Info

Publication number
CN110590669A
CN110590669A CN201910904311.3A CN201910904311A CN110590669A CN 110590669 A CN110590669 A CN 110590669A CN 201910904311 A CN201910904311 A CN 201910904311A CN 110590669 A CN110590669 A CN 110590669A
Authority
CN
China
Prior art keywords
dinitropyrazolyl
bis
dipyrazolylmethane
methane
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201910904311.3A
Other languages
Chinese (zh)
Other versions
CN110590669B (en
Inventor
李辉
赵凤起
杨燕京
安亭
李娜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Modern Chemistry Research Institute
Original Assignee
Xian Modern Chemistry Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Modern Chemistry Research Institute filed Critical Xian Modern Chemistry Research Institute
Priority to CN201910904311.3A priority Critical patent/CN110590669B/en
Publication of CN110590669A publication Critical patent/CN110590669A/en
Application granted granted Critical
Publication of CN110590669B publication Critical patent/CN110590669B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

The invention discloses a 4, 4' -bis (3, 5-dinitropyrazolyl) methane compound, which has a structural formula shown in the specification. The synthesis process comprises the following steps: (1) carrying out high-temperature rearrangement reaction on the 1,1 '-dipyrazolylmethane to generate 4, 4' -dipyrazolylmethane; (2)4,4 '-di-pyrazolyl methane is subjected to nitration reaction to generate 4, 4' -bis (3, 5-dinitropyrazolyl) methane. The 4, 4' -bis (3, 5-dinitropyrazolyl) methane compound synthesized by the method has higher energy and higher density, and has potential to be used as energy-containing components of mixed explosives and propellants.

Description

4, 4' -bis (3, 5-dinitropyrazolyl) methane compound and synthesis method thereof
Technical Field
The invention relates to 4, 4' -bis (3, 5-dinitropyrazolyl) methane and a synthesis method thereof, and belongs to the technical field of energetic materials, wherein the compound can be used as energetic components of a mixed explosive and a propellant.
Background
With the innovation of weaponry and the development of military technology, energetic compounds with high energy, low sensitivity, low cost and environment-friendly synthetic process have become hot spots for researchers of energetic materials in various countries around the world. The pyrazole ring structure has high ring tension and high enthalpy of formation such as C-N bond, N-N bond and the like. The five-membered ring contains a pi electron system, electrophilic substitution reactions such as nitration, sulfonation, halogenation and the like are easy to occur, the density and the nitrogen oxygen content of the five-membered ring are increased due to introduction of the nitro group on the five-membered ring, and the five-membered ring has higher energy due to improvement of oxygen balance. Compared with triazole and tetrazole energetic materials, pyrazole energetic compounds generally show very high stability, and can endow the pyrazole energetic materials with larger structural diversity because three carbons and one nitrogen atom on a pyrazole ring can be modified through corresponding reactions.
At present, molecules in the crystal of the aza-monocyclic compound are difficult to form tight packing, the packing coefficient of the crystal is difficult to improve, the energy level is limited, and the development requirement of high energy density cannot be met, so that the connection of two or three aza-rings through proper chemical bonds becomes a commonly adopted strategy in the molecular construction of energetic materials. Such as Thomas M, an expert in the synthesis of energetic materials in germany.1, 1' -bis (3, 5-dinitropyrazolyl) methane compound disclosed in "Improving the electronic properties of dipyrazoles by designing of current concepts" European journal of organic Chemistry 2018,37(9):4125-4132, having the structural formula shown in II and having a density of 1.72g cm-3Lower density, calculated detonation velocity 7966m s-1The energy is lower.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects in the prior art, provide an energy-containing compound 4,4 '-bis (3, 5-dinitropyrazolyl) methane with higher energy and density, and provide a synthetic method of the 4, 4' -bis (3, 5-dinitropyrazolyl) methane.
The structural formula of the 4, 4' -bis (3, 5-dinitropyrazolyl) methane is shown as I:
the synthetic route of the 4, 4' -bis (3, 5-dinitropyrazolyl) methane of the invention comprises the following steps:
in order to achieve the above object, the present invention provides a method for synthesizing 4, 4' -bis (3, 5-dinitropyrazolyl) methane, comprising the steps of:
(1) synthesis of 4, 4' -dipyrazolylmethane:
adding 1,1 '-dipyrazolylmethane into a hydrobromic acid solution at the temperature of 20-50 ℃, concentrating to obtain hydrobromide of the 1, 1' -dipyrazolylmethane, and adding the hydrobromide into a sealed tube to react for 1-5 hours at the temperature of 150-200 ℃. After the reaction is finished, adding water to dissolve, adding a proper amount of sodium hydroxide solution to precipitate a product, and filtering and drying to obtain the 4, 4' -dipyrazolylmethane.
(2) Synthesis of 4, 4' -bis (3, 5-dinitropyrazolyl) methane:
adding 4, 4' -dipyrazolylmethane into fuming sulfuric acid at the temperature of 20-50 ℃, then adding fuming nitric acid, and reacting the obtained reaction liquid for 2-6 hours at the temperature of 80-120 ℃. And after the reaction is finished, pouring the reaction liquid into crushed ice to separate out a solid, and drying to obtain the 4, 4' -bis (3, 5-dinitropyrazolyl) methane. Wherein the molar ratio of the 4,4 '-dipyrazolylmethane to the oleum is 1: 20-1: 60, and the molar ratio of the 4, 4' -dipyrazolylmethane to the oleum is 1: 5-1: 20.
The invention has the beneficial effects that:
the 4, 4' -bis (3, 5-dinitropyrazolyl) methane compound of the present invention has a relatively high density of 1.81g cm-3While the comparative compound 1, 1' -bis (3, 5-dinitropyrazolyl) methane was 1.72g cm-3(ii) a 4, 4' -bis (3) of the present invention5-dinitropyrazolyl) methane compounds have high energy and the calculated detonation velocity is 8357 m.s-1Whereas the comparative compound 1, 1' -bis (3, 5-dinitropyrazolyl) methane was 7966 m.s-1
Drawings
FIG. 1 shows a crystal structure of 4, 4' -bis (3, 5-dinitropyrazolyl) methane according to the present invention.
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 4, 4' -dipyrazolylmethane
1,1 '-dipyrazolylmethane (1g, 6.7mmol) was added to an aqueous solution of hydrobromic acid (48%, 5mL) at room temperature, and after concentration, the hydrobromide salt of 1, 1' -dipyrazolylmethane was obtained and added to a sealed tube and reacted at 200 ℃ for 1 h. After the reaction, water (5mL) was added to dissolve the resulting mixture, and a 50% by mass aqueous solution of sodium hydroxide was added dropwise to a pH of 10, followed by filtration and drying to obtain 0.56g of 4, 4' -dipyrazolylmethane as a white solid in a yield of 56.0%.
1HNMR(400MHz,DMSO-d6):δ7.41(s,4H),3.61(s,2H).
13C NMR(100MHz,DMSO-d6):δ132.4,119.8,18.7.
IR(ATR,cm-1):3133,3053,2936,1505,1392,1348,1131,1045,998,955,867,812,739.
MS(ES+):149.1[M+1]+.
Elemental analysis: c7H8N4Theoretical values C56.74, H5.44, N37.81; found C55.48, H5.40, N36.75.
The above data demonstrate that the synthesized compounds are structurally correct.
(1) Synthesis of 4, 4' -bis (3, 5-dinitropyrazolyl) methane
4, 4' -dipyrazolylmethane (0.4g,2.7mmol) was added to oleum (20%, 10mL) at room temperature, followed by oleum (0.7mL), and the resulting reaction solution was warmed to 100 ℃ for reaction for 6 h. After the reaction, the reaction mixture was poured into crushed ice (50g) to precipitate a solid, which was then filtered and dried to obtain 4, 4' -bis (3, 5-dinitropyrazolyl) methane (0.45 g) in a yield of 51.1%.
Characterization data:
1HNMR(400MHz,DMSO-d6):δ4.92(s,2H).
13C NMR(100MHz,DMSO-d6):δ149.6,110.2,16.6.
IR(ATR,cm-1):3219,2873,1586,1522,1423,1338,897,833.
MS(ES-):327.0[M-1]-.
elemental analysis: c7H4N8O8Theoretical values C25.62, H1.23, N34.15; found C24.28, H1.98, N30.51.
The above data demonstrate that the synthesized compounds are structurally correct.
Properties of 4, 4' -bis (3, 5-dinitropyrazolyl) methane
1 physical and chemical Properties
Solubility: insoluble in dichloromethane, chloroform, water, ethyl acetate, acetone, etc.;
density: 1.81g/cm3X-ray single crystal diffraction.
2 thermal Properties
4, 4' -bis (3, 5-dinitropyrazolyl) methane has no melting point, and the initial decomposition temperature is 262 ℃ (DSC 5 ℃ min-1)。
3 detonation behaviour
Enthalpy of formation: the enthalpy of formation was calculated to be 224.2kJ/mol (Gaussian 09 program B3LYP method).
Explosion speed: the density was 1.81g/cm3The calculated detonation velocity was 8357m/s (EXPLO5 v 6.02).
Explosion pressure: the density was 1.81g/cm3The calculated detonation pressure was 29.7GPa (EXPLO5 v 6.02).
Sensitivity: impact sensitivity 14J, friction sensitivity 352N.

Claims (2)

1. A4, 4' -bis (3, 5-dinitropyrazolyl) methane compound, which is characterized in that the structural formula is shown as I:
2. the method for synthesizing a 4, 4' -bis (3, 5-dinitropyrazolyl) methane compound according to claim 1, which comprises the steps of,
the method specifically comprises the following steps:
(1) synthesis of 4, 4' -dipyrazolylmethane:
adding 1,1 '-dipyrazolylmethane into a hydrobromic acid solution at the temperature of 20-50 ℃, concentrating to obtain hydrobromide of the 1, 1' -dipyrazolylmethane, adding the hydrobromide into a sealed tube, and reacting for 1-5 hours at the temperature of 150-200 ℃; after the reaction is finished, adding water to dissolve, adding a proper amount of sodium hydroxide solution to precipitate a product, and filtering and drying to obtain 4, 4' -dipyrazolylmethane;
(2) synthesis of 4, 4' -bis (3, 5-dinitropyrazolyl) methane:
adding 4, 4' -dipyrazolylmethane into fuming sulfuric acid at the temperature of 20-50 ℃, then adding fuming nitric acid, and reacting the obtained reaction liquid for 2-6 hours at the temperature of 80-120 ℃; after the reaction is finished, pouring the reaction liquid into crushed ice to separate out solid, and drying to obtain 4, 4' -bis (3, 5-dinitropyrazolyl) methane; wherein the molar ratio of the 4,4 '-dipyrazolylmethane to the oleum is 1: 20-1: 60, and the molar ratio of the 4, 4' -dipyrazolylmethane to the oleum is 1: 5-1: 20.
CN201910904311.3A 2019-09-24 2019-09-24 4,4' -bis (3, 5-dinitropyrazolyl) methane compound and synthesis method thereof Active CN110590669B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910904311.3A CN110590669B (en) 2019-09-24 2019-09-24 4,4' -bis (3, 5-dinitropyrazolyl) methane compound and synthesis method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910904311.3A CN110590669B (en) 2019-09-24 2019-09-24 4,4' -bis (3, 5-dinitropyrazolyl) methane compound and synthesis method thereof

Publications (2)

Publication Number Publication Date
CN110590669A true CN110590669A (en) 2019-12-20
CN110590669B CN110590669B (en) 2023-05-12

Family

ID=68862962

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910904311.3A Active CN110590669B (en) 2019-09-24 2019-09-24 4,4' -bis (3, 5-dinitropyrazolyl) methane compound and synthesis method thereof

Country Status (1)

Country Link
CN (1) CN110590669B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2456274C1 (en) * 2011-01-11 2012-07-20 Государственное образовательное учреждение высшего профессионального образования "Алтайский государственный технический университет им. И.И. Ползунова" (АлтГТУ) Method of producing (3,5-dimethylpyrazol-4-yl)methane
CN103601680A (en) * 2013-10-28 2014-02-26 北京理工大学 Bispyrazolyl energetic compounds and preparation method thereof
CN106188009A (en) * 2016-07-05 2016-12-07 北京理工大学 3,4 dinitro 1 (1H tetrazolium 5 base) 1H pyrazoles 5 amine are containing energy ion salt preparation method and performance

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2456274C1 (en) * 2011-01-11 2012-07-20 Государственное образовательное учреждение высшего профессионального образования "Алтайский государственный технический университет им. И.И. Ползунова" (АлтГТУ) Method of producing (3,5-dimethylpyrazol-4-yl)methane
CN103601680A (en) * 2013-10-28 2014-02-26 北京理工大学 Bispyrazolyl energetic compounds and preparation method thereof
CN106188009A (en) * 2016-07-05 2016-12-07 北京理工大学 3,4 dinitro 1 (1H tetrazolium 5 base) 1H pyrazoles 5 amine are containing energy ion salt preparation method and performance

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
HUI LI等: "Molecular and Crystal Features of Thermostable Energetic Materials:Guidelines for Architecture of"Bridged"Compounds", 《ACS CENT. SCI.》 *
KOSTIANTYN V. DOMASEVITCH等: "Facile and selective polynitrations at the 4-pyrazolyl dual backbone: straightforward access to a series of high-density energetic materials", 《NEW J. CHEM.》 *
MARC F. BOLTER等: "Improving the Energetic Properties of Dinitropyrazoles by Utilization of Current Concepts", 《EUR. J. INORG. CHEM.》 *
NIAL J. WHEATE等: "Thermal Rearrangement of N-Substituted Pyrazoles to 4,4′-Dipyrazolylmethane and 1,1,2-(4,4′,4′′-Tripyrazolyl)ethane", 《AUST. J. CHEM.》 *

Also Published As

Publication number Publication date
CN110590669B (en) 2023-05-12

Similar Documents

Publication Publication Date Title
CN112661749B (en) Oxadiazole-containing cyclic gem-dinitro energetic salt and preparation method thereof
CN109096215B (en) Nitrogen-rich energetic material 3-amino-3 '-nitro-amino-5, 5' -bi-1, 2, 4-triazole and preparation method thereof
US9278984B2 (en) Method for preparation of a lead-free primary explosive
CN114605345B (en) Oxadiazole ring-containing bridged dinitromethyl energetic salt and preparation method thereof
CN114634462B (en) Furazan-containing cyclonitrate simulated energetic compound or usable salt thereof and preparation method thereof
CN110526909B (en) 5,5 '-bis (3, 5-dinitropyrazolyl) -2,2' -bis (1,3,4 oxadiazole) and synthesis method thereof
CN112574213A (en) Synthesis method of pyrazolotriazine energetic compound
CN106928161B (en) Nitramifurazan energetic potassium salt, preparation method and application thereof
CN115368272A (en) Preparation method of 4-cyano-2-methoxybenzaldehyde
CN104447762A (en) Energetic ionic salts of 7-nitryl-4-ketone-4,8-dihydro-[1,2,4] triazole [5,1-d] [1,2,3,5] tetrazine-2-oxide and preparation method of energetic ionic salt
CN110590669A (en) 4, 4' -bis (3, 5-dinitropyrazolyl) methane compound and synthesis method thereof
CN114957125A (en) Synthesis method of 4-nitro-5-nitramine pyrazole
CN114315739A (en) High-energy low-sensitivity energetic compound and preparation method thereof
CN115108990A (en) Synthesis method of 3-nitro-amino-4-nitro-2H-pyrazole energetic compound
CN115521265A (en) High nitrogen compound and synthesis method thereof
CN114014800A (en) 2-gem-dinitromethylpyridine amine salt compound, preparation method and application thereof
CN115873004B (en) Polyhedral boron hydride dodecahydrododecaboric acid bis (triethylene diamine) and synthetic method thereof
CN105646390A (en) 3,4-bis(dinitromethyl) benzofuroxan dihydrazinium salt
CN113264837B (en) Energetic ion salt of 3, 5-dihydroxy-2, 4, 6-trinitrobenzene derivative and preparation method thereof
CN115746021B (en) Synthesis method of 7-amino-6-nitrobenzofuroxan and isomer thereof
CN115611903B (en) Gem-dinitro energetic compound or salt thereof and preparation method thereof
CN105646388B (en) The synthetic method of 3 azido, 4 nitro furazan
CN115260118B (en) DNTF preparation method
WO2011162859A1 (en) Synthesis of an azido energetic alcohol
CN108586370B (en) Synthesis method of 5-nitrotetrazole sodium salt dihydrate

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant