CN108191816B - Heat-resistant energetic compound containing oxygen-bridged calixarene and preparation method thereof - Google Patents
Heat-resistant energetic compound containing oxygen-bridged calixarene and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of compound preparation, and discloses an oxygen-containing bridged calixarene heat-resistant energetic compound, which has a structural general formula shown as I, and a preparation method of the compound comprises the following steps: adding oxygen-containing bridged calixarene I, nitrate or nitric acid into concentrated sulfuric acid under the magnetic stirring of an ice-water bath; heating the reaction solution to 65 ℃ or keeping the temperature at room temperature, stirring, and reacting for 12-36 hours; and cooling after the reaction is finished, pouring the reaction liquid into an ice-water mixture, and filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound shown in the formulas I-III. Compared with common heat-resistant explosives such as TACOT and PYX, the oxygen-containing bridged calixarene heat-resistant energetic compound has better detonation performance, is insoluble in water, is environment-friendly, has higher potential industrial value, and has great significance for the research of novel heat-resistant explosives; the preparation method has the advantages of simple required equipment, simplicity, easy implementation and higher yield.
Description
Technical Field
The invention belongs to the technical field of compound preparation, and particularly relates to an oxygen-containing bridged calixarene heat-resistant energetic compound and a preparation method thereof.
Background
Precision percussion, high efficiency destructive power and high viability are goals pursued by modern weapons, and to achieve these goals, High Energy Density Materials (HEDM) as weapons energy carriers must meet the requirements of high energy, high density, low vulnerability, environmental suitability, and high thermal stability. In recent years, with the development of cosmonautic industry and the exploitation of underground resources such as petroleum and natural gas, explosive with high pressure (or low pressure) and high temperature resistance, called heat-resistant explosive for short, is more and more urgently needed. The heat-resistant explosive refers to an explosive which can maintain proper mechanical sensitivity and reliably detonate after being subjected to a high-temperature environment for a long time, and the explosive has the detonation performance of common explosives and generally needs to have a higher melting point and a higher thermal decomposition temperature (over 250 ℃). The heat-resistant explosive is firstly researched to meet the requirements of military affairs, aerospace and the like (such as space vehicles needing to withstand high-temperature environments, separation of different levels of spaceships and the like), and nowadays, the heat-resistant explosive is mainly used for blasting equipment of oil-gas well perforating bullets and is divided into heat-resistant single-substance explosives and heat-resistant mixed explosives. Meanwhile, the thermal explosive is classified into a high temperature explosive (energetic compound having a thermal decomposition temperature of 250 ℃ or more and 300 ℃ or less) and an ultra high temperature explosive (energetic compound having a thermal decomposition temperature of more than 300 ℃) according to the difference in the temperature to be endured. The heat-resistant elementary explosive can be used for filling heat-resistant detonators and heat-resistant detonating cords, and more importantly, can be used as a basic component of heat-resistant mixed explosives, such as perforating charge in petroleum technology and the like which are widely applied; on the other hand, the development of some new heat-resistant single-substance explosives is aimed at meeting special requirements of space navigation, and due to the development of rockets, missiles and space shuttles in speed, particularly the emergence of space weapons, the requirement of thermal stability is provided for the explosives. The spacecraft is influenced by aerodynamic effect, space and moon vacuum environment in the flying process, so that the spacecraft needs to be heated for disinfection and sterilization before entering space and returning to the earth, but the conventional explosive (such as cyclonite) is not stable enough under high temperature or low pressure for a long time, is easy to evaporate even under aerodynamic effect, and cannot meet the requirements. Therefore, in recent years, some countries have paid attention to research on how to improve the thermal stability of the currently developed explosives such as hexogen and octogen, and have also been developing some new heat-resistant explosives resistant to ultra-high temperature to meet special needs in terms of space navigation and the like.
Disclosure of Invention
The invention aims to provide an oxygen-containing bridged calixarene heat-resistant energetic compound which has very good thermal stability, can be used as a high-thermal-stability heat-resistant explosive and is applied to special fields of deep oil wells or space exploration and the like.
The invention also aims to provide a preparation method of the oxygen-containing bridged calixarene heat-resistant energetic compound, which has the advantages of safe raw materials, simple required equipment, simple and feasible preparation method and higher yield.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an oxygen-containing bridged calixarene heat-resistant energetic compound, which has a structural general formula shown in formula I:
wherein R is1Selected from hydrogen atoms or halogens, R2Selected from hydrogen atoms, halogens or hydroxyl groups, R3Selected from hydrogen atom, halogen, hydroxyl or methoxy.
The invention also provides an oxygen-containing bridged calixarene heat-resistant energetic compound, which has a structural formula shown as a formula II:
the invention also provides an oxygen-containing bridged calixarene heat-resistant energetic compound, which has a structural formula shown as a formula III:
the invention also provides a preparation method of the oxygen-containing bridged calixarene heat-resistant energetic compound, which comprises the following steps: adding oxygen-containing bridged calixarene I, nitrate or nitric acid into concentrated sulfuric acid under the magnetic stirring of an ice-water bath; heating the reaction solution to 65 ℃ or keeping the temperature at room temperature, stirring, and cooling after the reaction is finished; then pouring the reaction liquid into an ice water mixture, and filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound shown as the formulas I to III;
the structural formula of the oxygen-containing bridged calixarene I is shown as a formula IV:
wherein R is1Selected from hydrogen atoms or halogens, R2Selected from hydrogen atoms, halogens or hydroxyl groups, R3Selected from hydrogen atom, halogen, hydroxyl or methoxy.
Further, the molar ratio of the oxygen-containing bridged calixarene I to nitrate in nitric acid or nitrate is 1: (4.4-8).
Further, the nitrate is one of sodium nitrate, potassium nitrate, ammonium nitrate, silver nitrate, copper nitrate or manganese nitrate; the nitric acid is nitric acid with the concentration of 90-100%.
The preparation method of the oxygen-containing bridged calixarene I with the structural formula shown as the formula IV in the invention comprises the following steps: in the presence of organic alkali, carbonate or strong alkali, resorcinol or its derivative is added into organic solvent to react with 1, 5-difluoro-2, 4-dinitrobenzene or its derivative, and through cooling, the reaction liquid is poured into ice-water mixture, filtered, washed and dried to obtain oxygen-containing bridged calixarene I.
The structural general formula of the resorcinol or the derivatives thereof is shown as a formula V:
wherein R is2Selected from hydrogen atoms, halogens or hydroxyl groups, R3Selected from hydrogen atom, halogen, hydroxyl or methoxy.
The structural general formula of the 1, 5-difluoro-2, 4-dinitrobenzene or the derivative thereof is shown as a formula VI:
wherein R is1Selected from hydrogen atoms or halogens.
The organic base is triethylamine, pyridine or diisopropylethylamine; the carbonate is sodium carbonate, potassium carbonate or palladium carbonate; the strong base is potassium hydroxide or sodium hydroxide; the organic solvent is acetonitrile or N, N-dimethylformamide.
The synthesis steps of the oxygen-containing bridged calixarene heat-resistant energetic compound shown in the formulas I to III are as follows:
compared with the prior art, the invention has the beneficial effects that:
1. the thermal decomposition temperature of the oxygen-containing bridged calixarene heat-resistant energetic compound exceeds 350 ℃, the compound cannot be melted before reaching the thermal decomposition temperature, the thermal stability is very good, free energy cannot be generated due to self melting, and the high-temperature heat-resistant explosive discovered so far has no characteristics and can be used as a high-heat-stable heat-resistant explosive; the oxygen-containing bridged calixarene heat-resistant energetic compound is relatively insensitive, has an impact sensitivity value of more than or equal to 39J and a friction sensitivity of 360N, is easy to detonate (BAM determination method) compared with trinitrotriaminebenzene (TATB) and the like, and can be widely applied to special fields of deep oil wells or space detection and the like; compared with common heat-resistant explosives such as TACOT and PYX, the oxygen-containing bridged calixarene heat-resistant energetic compound has better detonation performance, is insoluble in water, is environment-friendly, has higher potential industrial value, and has great significance for the research of novel heat-resistant explosives.
2. The preparation method of the oxygen-containing bridged calixarene heat-resistant energetic compound has the advantages of safe raw materials, simple required equipment, simple and feasible preparation method and higher yield.
Drawings
FIG. 1 is a thermal decomposition curve diagram of an oxygen-containing bridged calixarene heat-resistant energetic compound prepared in the first embodiment of the invention.
FIG. 2 is a thermal decomposition graph of the oxygen-containing bridged calixarene heat-resistant energetic compound prepared in example two of the present invention.
Detailed Description
The following examples are intended to illustrate the invention, but are not intended to limit the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The test methods in the following examples are conventional methods unless otherwise specified.
Thin Layer Chromatography (Thin Layer Chromatography, TLC), also known as Thin Layer Chromatography, belongs to solid-liquid adsorption Chromatography. The invention utilizes TLC technology to detect the residual amount of the oxygen bridge connected calixarene I in the reaction kettle to judge whether the reaction is finished, and if the residual amount is 0, the reaction is finished.
The preparation method of the oxygen-containing bridged calixarene I with the structural formula shown as the formula IV in the invention comprises the following steps:in the presence of organic alkali, carbonate or strong alkali, resorcinol or its derivative is added into organic solvent to react with 1, 5-difluoro-2, 4-dinitrobenzene or its derivative, and through cooling, the reaction liquid is poured slowly into ice-water mixture, filtered, washed and dried to obtain oxygen-containing bridged calixarene I. The structural general formula of the resorcinol or the derivatives thereof is shown as a formula V, the structural general formula of the 1, 5-difluoro-2, 4-dinitrobenzene or the derivatives thereof is shown as a formula VI, and the organic base is triethylamine, pyridine or diisopropylethylamine; the carbonate is sodium carbonate, potassium carbonate or palladium carbonate; the strong base is potassium hydroxide or sodium hydroxide; the organic solvent is acetonitrile or N, N-dimethylformamide. By selecting different starting materials according to the above procedure, 1 used in the following examples can be prepared4,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons, 15,55-dichloro-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons, 15,55-dibromo-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons, 12,52-dichloro-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons, 15,55-dimethyl-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxy-1, 3,5,7(1,3) -tetraphenyl-12,52-dimethoxy-cup [4]Aromatic hydrocarbons, 15,55-dimethoxy-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxy-bridging-1, 3,5,7(1,3) -tetraphenylcalium [4 ]]Aromatic hydrocarbons, 12,32,52,72-tetrafluoro-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons, 15,55-dihydroxy-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxy-bridging-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons, 12,52-dihydroxy-15,55-dimethoxy-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons, 12,32,52,72-tetrafluoro-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons, 12,32,52,72-tetrafluoro-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons, 12,32,52,72-tetrafluoro-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]An aromatic hydrocarbon. Reference may be made in particular to Jeffrey L.Katz, Michael B.Feldman, and Recacca R.Conry.Synthesis of Functionalized Oxacalix [4 ]]arenes.Org.Lett.,2005.7,191～94。
Example one
A preparation method of an oxygen-containing bridged calixarene heat-resistant energetic compound comprises the following steps: under the magnetic stirring of ice-water bath, R is put into1、R2And R3is-H, and the structural formula is as shown in formula IV, 13.7g (namely 25mmol) of oxygen-containing bridged calixarene I (1)4,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Arene) is added into 150ml of concentrated sulfuric acid, and after the addition is finished, 15ml of nitric acid with the concentration of 90% is slowly dripped into the concentrated sulfuric acid; heating the reaction solution to 65 ℃, stirring, carrying out TLC detection to judge whether the reaction is finished or not, and cooling after the reaction is finished; then slowly pouring the reaction liquid into an ice water mixture, filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound (1) shown as the formula II4,16,34,36,54,56,74,76Octanitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons) in a yield of 93%; its nuclear magnetic resonance hydrogen spectrum is1H NMR(300MHz,DMSO-d6,TMS,ppm),δ＝8.412(s,2H),7.054(s,2H)；13C NMR(75MHz,DMSO-d6,TMS,ppm),δ＝151.911,136.983,125.437,113.433；Elemental Analysis forC24H8N8O20(728.36) calcd.C, 39.57; h, 1.10; n, 15.38; found is C, 39.58; h, 1.11; n, 15.38; o, 43.93; the thermal decomposition curve is shown in FIG. 1.
Example two
A preparation method of an oxygen-containing bridged calixarene heat-resistant energetic compound comprises the following steps: under the magnetic stirring of ice-water bath, R is put into1、R2Are all-H, R3is-Cl, and the structural formula is as shown in formula IV, 15.43g (namely 25mmol) of oxygen-containing bridged calixarene I (1)5,55-dichloro-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Arene) is added into 150ml of concentrated sulfuric acid, and after the addition is finished, 15ml of nitric acid with the concentration of 92% is slowly dripped into the concentrated sulfuric acid; keeping the reaction solution at room temperature (25 ℃), stirring, carrying out TLC detection to judge whether the reaction is finished or not, and cooling after the reaction is finished; then slowly pouring the reaction liquid into an ice water mixture, filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound (1) shown as the formula VII5,55-dichloro-14,16,34,36,54,56,74,76Octanitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbon) in 93% yield and a nuclear magnetic resonance hydrogen spectrum of1H NMR(300MHz,DMSO-d6,TMS,ppm),δ＝9.29(s,2H),7.887(s,2H),7.776(s,2H)；13C NMR(75MHz,DMSO-d6,TMS,ppm),δ＝151.309,149.593,137.948,137.638,125.685,121.181,113.794,111.186；Elemental Analysis for C24H6Cl2N8O20(797.25) calcd.C, 36.14; h, 0.76; cl, 8.88; n, 14.07; found is C, 36.16; h, 0.76; cl, 8.89; n, 14.06; o, 40.14; the thermal decomposition curve is shown in FIG. 2.
EXAMPLE III
A preparation method of an oxygen-containing bridged calixarene heat-resistant energetic compound comprises the following steps: under the magnetic stirring of ice-water bath, R is put into1、R2Are all-H, R3is-Br, and the structural formula is 17.65g (namely 25mmol) of oxygen-containing bridged calixarene I (1) shown as a formula IV5,55-dibromo-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Arene) is added into 150ml of concentrated sulfuric acid, and after the addition is finished, 15ml of nitric acid with the concentration of 95% is slowly dripped into the concentrated sulfuric acid; heating the reaction solution to 65 ℃, stirring, carrying out TLC detection to judge whether the reaction is finished or not, and cooling after the reaction is finished; then slowly pouring the reaction liquid into an ice water mixture, filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound (1) shown as the formula VIII5,55-dibromo-14,16,34,36,54,56,74,76Octanitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbon) in 89% yield and having a hydrogen nuclear magnetic resonance spectrum of1H NMR(300MHz,DMSO-d6,TMS,ppm),δ＝9.047(s,2H),7.909(s,2H)，7.705(s,2H)；13C NMR(75MHz,DMSO-d6,TMS,ppm),δ＝152.906,150.848,141.638,139.155,127.168,115.049,113.179,111.613；Elemental Analysis forC24H6Br2N8O20(886.16):calcd.C,32.51；H,0.67；Br,18.01；N,12.67；found:C,32.53；H,0.68；Br,18.03；N,12.65；O,36.11。
Example four
A preparation method of an oxygen-containing bridged calixarene heat-resistant energetic compound comprises the following steps: in ice water bathUnder stirring with force, R1、R3Are all-H, R2is-Cl, and the structural formula is as shown in formula IV, 15.43g (namely 25mmol) of oxygen-containing bridged calixarene I (1)2,52-dichloro-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Arene) is added into 150ml of concentrated sulfuric acid, and after the addition is finished, 15ml of nitric acid with the concentration of 97% is slowly dripped into the concentrated sulfuric acid; heating the reaction solution to 65 ℃, stirring, carrying out TLC detection to judge whether the reaction is finished or not, and cooling after the reaction is finished; then slowly pouring the reaction liquid into an ice water mixture, filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound (1) shown as the formula IX2,52-dichloro-14,16,34,36,54,56,74,76Octanitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons) in 87% yield and having a nmr hydrogen spectrum of1H NMR(300MHz,DMSO-d6,TMS,ppm),δ＝9.120(s,2H),9.054(s,2H),6.874(s,2H)；13C NMR(75MHz,DMSO-d6,TMS,ppm),δ＝152.244,146.778,141.874,133.794,126.649,124.350,124.008,104.225；Elemental Analysis for C24H6Cl2N8O20(797.25):calcd.C,36.17；H,0.77；Cl,8.87；N,14.05；found:C,36.16；H,0.76；Cl,8.89；N,14.06；O,40.14。
EXAMPLE five
A preparation method of an oxygen-containing bridged calixarene heat-resistant energetic compound comprises the following steps: under the magnetic stirring of ice-water bath, R is put into1is-H, R2is-COCH3，R3is-CH315.9g (25 mmol) of oxygen-containing bridged calixarene I (1) with the structural formula shown as formula IV5,55-dimethyl-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxy-1, 3,5,7(1,3) -tetraphenyl-12,52-dimethoxy-cup [4]Arene) is added into 150ml of concentrated sulfuric acid, and after the addition is finished, 15ml of nitric acid with the concentration of 100% is slowly dripped into the concentrated sulfuric acid; heating the reaction solution to 65 ℃, stirring, carrying out TLC detection to judge whether the reaction is finished or not, and cooling after the reaction is finished; then slowly pouring the reaction liquid into an ice water mixture, filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound (1) shown as the formula X5,55-dimethyl-14,16,34,36,54,56,74,76Octanitro-2, 4,6, 8-tetraoxy-1, 3,5,7(1,3) -tetraphenyl-12,52-dimethoxy-cup [4]Aromatic hydrocarbon) in 75% yield and having a hydrogen nuclear magnetic resonance spectrum of1H NMR(300MHz,DMSO-d6,TMS,ppm),δ＝8.952(s,2H),7.273(s,2H),3.537(s,6H),2.325(s,6H)；13C NMR(75MHz,DMSO-d6,TMS,ppm),δ＝152.438,152.141,142.921,142.614,141.356,133.993,125.574,105.722,63.208,13.677；Elemental Analysis for C28H16N8O22(816.04):calcd.C,41.06；H,1.72；N,13.65；found:C,41.19；H,1.98；N,13.72；O,43.11。
EXAMPLE six
A preparation method of an oxygen-containing bridged calixarene heat-resistant energetic compound comprises the following steps: under magnetic stirring in an ice-water bath, 50g of potassium nitrate and then R were added to 150ml of concentrated sulfuric acid1、R2Are all-H, R3is-COCH310.0g (i.e. 16.45mmol) of oxygen-containing bridged calixarene I (1) with the structural formula shown as formula IV5,55-dimethoxy-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxy-bridging-1, 3,5,7(1,3) -tetraphenylcalium [4 ]]Aromatic hydrocarbon) under ice water bath, stirring for 30min and stopping; keeping the reaction solution at room temperature, stirring, carrying out TLC detection to judge whether the reaction is finished or not, and cooling after the reaction is finished; the reaction was then slowly poured into a mixture of ice and waterFiltering, washing and drying to obtain 10.51g of the oxygen-containing bridged calixarene heat-resistant energetic compound (1) shown as the formula XI5,55-dimethoxy-14,16,34,36,54,56,74,76Octanitro-2, 4,6, 8-tetraoxy-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons) in a yield of 81% and a nmr hydrogen spectrum of1H NMR(300MHz,DMSO-d6,TMS,ppm),δ＝9.041(s,2H),7.777(s,2H),7.531(s,2H),4.044-4.046(d,J＝0.6Hz,6H)；13C NMR(75MHz,DMSO-d6,TMS,ppm),δ＝152.958,151.234,148.764,139.084,135.502,127.017,115.400,107.677,66.767；Elemental Analysis for C26H12N8O22(788.42):calcd.C,39.45；H,1.43；N,14.16；O,44.56；found:C,39.61；H,1.53；N,14.21；O,44.64。
EXAMPLE seven
A preparation method of an oxygen-containing bridged calixarene heat-resistant energetic compound comprises the following steps: under magnetic stirring in an ice-water bath, 50g of potassium nitrate and then R were added to 150ml of concentrated sulfuric acid1、R2Are all-F, R3is-H, the structural formula of which is shown as formula III, 15.5g (namely 25mmol) of oxygen-containing bridged calixarene I (1)2,32,52,72-tetrafluoro-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons); heating the reaction solution to 65 ℃, stirring, carrying out TLC detection to judge whether the reaction is finished or not, and cooling after the reaction is finished; then slowly pouring the reaction liquid into an ice water mixture, filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound (1) shown as the formula III2,32,52,72-tetrafluoro-14,16,34,36,54,56,74,76Octanitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbon) in 69% yield and a NMR spectrum of 69%1HNMR(300MHz,DMSO-d6,TMS,ppm),δ＝9.075(d,2H)；13C NMR(75MHz,DMSO-d6,TMS,ppm),δ＝150.211,147.653,140.797,121.649；Elemental Analysis for C24H6F4N8O20(797.25):calcd.C,35.78；H,0.55；F,9.42；N,14.05；found:C,36.02；H,0.50；F,9.50；N,14.00；O,39.98。
Example eight
A preparation method of an oxygen-containing bridged calixarene heat-resistant energetic compound comprises the following steps: under the magnetic stirring of ice-water bath, 50g of ammonium nitrate is added into 150ml of concentrated sulfuric acid, and R is added1、R2Are all-H, R3is-OH, and has a structural formula shown as formula IV of 14.50g (25 mmol) of oxygen-containing bridged calixarene I (1)5,55-dihydroxy-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxy-bridging-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons); heating the reaction solution to 65 ℃, stirring, carrying out TLC detection to judge whether the reaction is finished or not, and cooling after the reaction is finished; then slowly pouring the reaction liquid into an ice water mixture, filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound (1) shown as the formula XII5,55-dihydroxy-14,16,34,36,54,56,74,76Octanitro-2, 4,6, 8-tetraoxy-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatics) in 74% yield.
Example nine
A preparation method of an oxygen-containing bridged calixarene heat-resistant energetic compound comprises the following steps: under magnetic stirring in an ice water bath, 50g of copper nitrate was added to 150ml of concentrated sulfuric acid, and R was added1is-H, R2is-OH, R3is-OCH3The structural formula is as shown in formula IV, and the structural formula is 16.00g (namely 25 mm)ol) oxygen-containing bridged calixarenes I (1)2,52-dihydroxy-15,55-dimethoxy-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons); heating the reaction solution to 65 ℃, stirring, carrying out TLC detection to judge whether the reaction is finished or not, and cooling after the reaction is finished; then slowly pouring the reaction liquid into an ice water mixture, filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound (1) shown as the formula XIII2,52-dihydroxy-15,55-dimethoxy-14,16,34,36,54,56,74,76Octanitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatics) in 85% yield.
Example ten
A preparation method of an oxygen-containing bridged calixarene heat-resistant energetic compound comprises the following steps: under the magnetic stirring of ice-water bath, 50g of silver nitrate is added into 150ml of concentrated sulfuric acid, and R is added1、R2Are all-F, R3is-H, the structural formula of which is shown as formula III, 15.5g (namely 25mmol) of oxygen-containing bridged calixarene I (1)2,32,52,72-tetrafluoro-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons); heating the reaction solution to 65 ℃, stirring, carrying out TLC detection to judge whether the reaction is finished or not, and cooling after the reaction is finished; then slowly pouring the reaction liquid into an ice water mixture, filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound (1) shown as the formula III2,32,52,72-tetrafluoro-14,16,34,36,54,56,74,76Octanitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons) in a yield of 70%.
EXAMPLE eleven
A preparation method of an oxygen-containing bridged calixarene heat-resistant energetic compound comprises the following steps: under the magnetic stirring of ice water bath, 53g of manganese nitrate is added into 150ml of concentrated sulfuric acid, and R is added1、R2Are all-F, R3is-H, the structural formula of which is shown as formula III, 15.5g (namely 25mmol) of oxygen-containing bridged calixarene I (1)2,32,52,72-tetrafluoro-14,16,54,56-tetranitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatic hydrocarbons); heating the reaction solution to 65 ℃, stirring, carrying out TLC detection to judge whether the reaction is finished or not, and cooling after the reaction is finished; then slowly pouring the reaction liquid into an ice water mixture, filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound (1) shown as the formula III2,32,52,72-tetrafluoro-14,16,34,36,54,56,74,76Octanitro-2, 4,6, 8-tetraoxabridged-1, 3,5,7(1,3) -tetraphenyl-calix [4 ]]Aromatics) in 68% yield.
Example twelve
Detonation performance experiments were conducted on the oxygen-containing bridged calixarene heat-resistant energetic compounds prepared in examples one, two, three and seven, and compared with tetranitrodibenzo-1, 3a,4,6 a-tetraaza-pentadecene (TACOT) and 2, 6-bis (picrylamino) -3, 5-dinitropyridine (PYX), and the results are shown in the following table.
The above-mentioned embodiments are merely preferred embodiments of the present invention, which are merely illustrative and not restrictive, and it should be understood that other embodiments may be easily made by those skilled in the art by replacing or changing the technical contents disclosed in the specification, and therefore, all changes and modifications that are made on the principle of the present invention should be included in the scope of the claims of the present invention.
Claims (1)
1. An oxygen-containing bridged calixarene heat-resistant energetic compound is characterized in that the structural formula is shown as a formula III:
the preparation method of the oxygen-containing bridged calixarene heat-resistant energetic compound comprises the following steps: under magnetic stirring in an ice-water bath, 50g of potassium nitrate and then R were added to 150ml of concentrated sulfuric acid1、R2Are all-F, R3is-H, 15.5g of oxygen-containing bridged calixarene I with the structural formula shown in formula IV; heating the reaction solution to 65 ℃, stirring, carrying out TLC detection to judge whether the reaction is finished or not, and cooling after the reaction is finished; then slowly pouring the reaction liquid into an ice water mixture, filtering, washing and drying to obtain the oxygen-containing bridged calixarene heat-resistant energetic compound shown as the formula III;
the structural formula of the oxygen-containing bridged calixarene I is shown as a formula IV:
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| US3941812A (en) * | 1975-04-10 | 1976-03-02 | The United States Of America As Represented By The Secretary Of The Army | Thermally stable octanitro macrocyclic explosives |
| CN103936593A (en) * | 2014-05-16 | 2014-07-23 | 南京理工大学 | 2, 4, 6-trinitro-1, 3-bis (2', 4'-dinitrobenzene vinyl) benzene as well as preparation method and application thereof |
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| US3941812A (en) * | 1975-04-10 | 1976-03-02 | The United States Of America As Represented By The Secretary Of The Army | Thermally stable octanitro macrocyclic explosives |
| CN103936593A (en) * | 2014-05-16 | 2014-07-23 | 南京理工大学 | 2, 4, 6-trinitro-1, 3-bis (2', 4'-dinitrobenzene vinyl) benzene as well as preparation method and application thereof |
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