CN108191816A - Oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind and preparation method thereof - Google Patents
Oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to technical field of compound preparation, disclose a kind of oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, as shown in I, preparation method includes the following steps general structure：Under ice-water bath magnetic agitation, oxygen-containing bridging calixarenes I, nitrate or nitric acid are added in the concentrated sulfuric acid；Reaction solution is warming up to 65 DEG C again or keeps room temperature, stirring is reacted 12 ~ 36 hours；It cools down, reaction solution is poured into mixture of ice and water after completion of the reaction then, it is filtered, wash, be dried to obtain the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind as shown in Formulas I ~ III.The oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind of the present invention compares common heat-resistant explosive, such as TACOT and PYX, has better detonation property, not soluble in water, environmentally friendly, potential industrialization value higher is of great significance to the research of heat resistance explosive；Required equipment is simple in preparation method, simple and practicable, and yield is higher.
Description
Technical field
The invention belongs to technical field of compound preparation, and in particular to a kind of heat-resisting chemical combination containing energy of oxygen-containing bridging calixarene kind
Object and preparation method thereof.
Background technology
Precision strike, efficient Kill capability and failure-survival capability are the targets that modern weapons are pursued, and to realize these targets,
High Energy Density Materials (HEDM) as weapon energy carrier must satisfy high-energy, high density, Low vulnerability, environment and adapt to
The requirement of property and high thermal stability.In recent years, with the subterranean resource such as space travel cause and petroleum gas exploit development,
Increasingly there is an urgent need to a kind of energy high pressure resistant (or low pressure), heat safe explosive, abbreviation heat-resistant explosives.Heat-resistant explosive refers to be subjected to
Remain to keep a kind of explosive of appropriate mechanical sensitivity and reliable initiation after prolonged hot environment, this kind of explosive remove have it is general
Outside the detonation property that logical explosive is possessed, it usually should also have higher fusing point and higher heat decomposition temperature (more than 250 DEG C).
The research of heat-resistant explosive (is flown the needs of military and aerospace etc. if desired for the universe for being subjected to hot environment to meet earliest
The separation at different levels etc. of row device, airship), now, the most important purposes of heat-resistant explosive is for the explosive of perforating oil gas well bullet
In, it is divided into heat-resisting single chmical compound explosive and heat-resisting composite explosives.Meanwhile by the difference of institute's tolerable temperature, heat-resistant explosive is drawn
It is divided into high temperature resistant explosive (energy-containing compound of the heat decomposition temperature below 250 DEG C or more and 300 DEG C) and superhigh temperature resistant degree explosive
(heat decomposition temperature is more than 300 DEG C or more of energy-containing compound).Heat-resisting single chmical compound explosive can be used for filling heat-resisting detonator and resistance to thermal conductivity
In quick-fried rope, it is often more important that, it can be as the basic components of heat-resisting composite explosives, and it is in petroleum technology such as to obtain widely applied
Perforating bullet powder charge etc.；On the other hand, it is to meet cosmonautic special type to put forth effort to develop some new heat-resisting single chmical compound explosives
It needs, because the development of rocket, guided missile and space shuttle in speed, the particularly appearance of space weapon, propose explosive
The requirement of thermostability.Spaceship is in flight course since meeting is by aerodynamic effects and space and moon vacuum
The influence of environment etc., thus space vehicle is both needed to heating with sterilization before entering space and returning to the earth, but routine is fried
Medicine (such as heisuojin) is not sufficiently stable under high temperature or low pressure for a long time or even is easy to evaporate under aerodynamic effects, it is impossible to meet
Above-mentioned requirements.Thus, in recent years, some countries both focus on how research improves now developed explosive such as hexogen, Losec support
The thermostability of gold etc., and put forth effort to develop the heat-resistant explosive of some new superhigh temperature resistants to meet the special type of space travel etc.
It needs.
Invention content
The purpose of the present invention is to provide a kind of oxygen-containing heat-resisting energy-containing compounds of bridging calixarene kind, and thermal stability is very
It is good, the special dimensions such as deep oil well or space exploration can be applied to as the heat-resistant explosive of high heat stability.
Another object of the present invention is to provide a kind of preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind,
Raw materials used safety, required equipment is simple, and preparation method is simple and practicable, and yield is higher.
To achieve the above object, the present invention uses following technical scheme：
The present invention provides a kind of oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, and general structure is shown in formula I：
Wherein R1Selected from hydrogen atom or halogen, R2Selected from hydrogen atom, halogen or hydroxyl, R3Selected from hydrogen atom, halogen, hydroxyl or first
Oxygroup.
The present invention also provides a kind of oxygen-containing heat-resisting energy-containing compounds of bridging calixarene kind, and structural formula is as shown in Formula II：
The present invention also provides a kind of oxygen-containing heat-resisting energy-containing compounds of bridging calixarene kind, and structural formula is as shown in formula III：
The present invention also provides a kind of preparation method of the above-mentioned oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, including following
Step：Under ice-water bath magnetic agitation, oxygen-containing bridging calixarenes I, nitrate or nitric acid are added in the concentrated sulfuric acid；It again will reaction
Liquid is warming up to 65 DEG C or keeps room temperature, and stirring cools down after completion of the reaction；Then reaction solution is poured into mixture of ice and water, passed through
It filters, wash, being dried to obtain the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind as shown in Formulas I~III；
The structural formula of the oxygen-containing bridging calixarenes I is as shown in formula IV：
Wherein R1Selected from hydrogen atom or halogen, R2Selected from hydrogen atom, halogen or hydroxyl, R3Selected from hydrogen atom, halogen, hydroxyl or first
Oxygroup.
Further, the molar ratio of the oxygen-containing bridging calixarenes I and nitrate anion in nitric acid or nitrate is 1：(4.4~
8)。
Further, the nitrate is one in sodium nitrate, potassium nitrate, ammonium nitrate, silver nitrate, copper nitrate or manganese nitrate
Kind；The nitric acid is a concentration of 90%~100% nitric acid.
The preparation method of oxygen-containing bridging calixarenes I of the structural formula as shown in formula IV is as follows in the present invention：In organic base, carbonic acid
In the presence of salt or highly basic, resorcinol or derivatives thereof is added in organic solvent, with 1,5-, bis- fluoro- 2,4- dinitrobenzenes or
Its derivatives reaction, cooling, reaction solution is poured into mixture of ice and water, filtered, wash, be dried to obtain oxygen-containing bridging calixarenes
I。
The general structure of above-mentioned resorcinol or derivatives thereof is shown as a formula V：
Wherein R2Selected from hydrogen atom, halogen or hydroxyl, R3Selected from hydrogen atom, halogen, hydroxyl or methoxyl group.
The general structure of above-mentioned bis- fluoro- 2,4- dinitrobenzenes of 1,5- or derivatives thereof is as shown in Formula IV：
Wherein R1Selected from hydrogen atom or halogen.
Above-mentioned organic base is triethylamine, pyridine or diisopropylethylamine；Above-mentioned carbonate is sodium carbonate, potassium carbonate or carbon
Sour palladium；Above-mentioned highly basic is potassium hydroxide or sodium hydroxide；Above-mentioned organic solvent is acetonitrile or N,N-dimethylformamide.
The synthesis step of oxygen-containing bridging calixarene kind heat-resisting energy-containing compound of the present invention as shown in Formulas I~III is as follows：
Compared with prior art, the beneficial effects of the present invention are：
1. the heat decomposition temperature of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind of the present invention more than 350 DEG C, is reaching thermal decomposition
It will not be melted before temperature, thermal stability is very good, and free energy of formation will not be consumed because of the fusing of itself, this is to mesh
Before until the unexistent feature of high-temperature heat-resistance explosive that is found, can be as the heat-resistant explosive of high heat stability；The present invention is oxygen-containing
For the heat-resisting energy-containing compound of bridging calixarene kind all compared with insensitiveness, impact sensitivity value is more than or equal to 39J, friction sensitivity 360N, but
It is easy to ignite (BAM measuring methods) than trinitro- triamine benzene (TATB) etc., it is special can be widely used in deep oil well or space exploration etc.
Field；The oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind of the present invention compares common heat-resistant explosive, such as TACOT and PYX, has more
Good detonation property, not soluble in water, environmentally friendly, potential industrialization value higher have the research of heat resistance explosive
It is of great importance.
2. raw materials used safety in the oxygen-containing heat-resisting energy-containing compound preparation method of bridging calixarene kind of the present invention, required equipment
Simply, preparation method is simple and practicable, and yield is higher.
Description of the drawings
Fig. 1 is the heat decomposition curve of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind prepared by the embodiment of the present invention one
Figure.
Fig. 2 is the heat decomposition curve of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind prepared by the embodiment of the present invention two
Figure.
Specific embodiment
Following embodiment is not used to limit protection scope of the present invention for illustrating the present invention.It is unless otherwise specified, real
Apply the conventional means that technological means used in example is well known to those skilled in the art.Test method in following embodiments, such as
It is conventional method without special instruction.
Thin-layer chromatography (Thin Layer Chromatography, TLC), also known as thin-layer chromatography, belong to solid-liquid adsorption color
Spectrum.The present invention using TLC technologies detection reaction kettle include oxygen bridge connect calixarenes I surplus judge reaction whether complete, if remain
Surplus is 0, then reacts completion.
The preparation method of oxygen-containing bridging calixarenes I of the structural formula as shown in formula IV is as follows in the present invention：In organic base, carbonic acid
In the presence of salt or highly basic, resorcinol or derivatives thereof is added in organic solvent, with 1,5-, bis- fluoro- 2,4- dinitrobenzenes or
Its derivatives reaction, cooling, reaction solution is slowly poured into mixture of ice and water, filtered, wash, be dried to obtain oxygen-containing bridging cup
Aromatic hydrocarbons I.The general structure of above-mentioned resorcinol or derivatives thereof shown as a formula V, above-mentioned 1,5-, bis- fluoro- 2,4- dinitrobenzenes or its
For the general structure of derivative as shown in Formula IV, above-mentioned organic base is triethylamine, pyridine or diisopropylethylamine；Above-mentioned carbonate
For sodium carbonate, potassium carbonate or carbonate palladium；Above-mentioned highly basic is potassium hydroxide or sodium hydroxide；Above-mentioned organic solvent is acetonitrile or N, N-
Dimethylformamide.According to the method described above, select different raw materials that can be made example below is used 14,16,54,56- four nitre
Four oxygen bridges of base -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons, 15,55- two chloro- 14,16,54,56- four nitre
Four oxygen bridges of base -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons, 15,55- two bromo- 14,16,54,56- four nitre
Four oxygen bridges of base -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons, 12,52- two chloro- 14,16,54,56- four nitre
Four oxygen bridges of base -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons, 15,55Dimethyl -14,16,54,56- four nitre
Four oxygen bridges -1,3,5,7 (1,3) of base -2,4,6,8--tetraphenyl -12,52Dimethoxy-cup [4] aromatic hydrocarbons, 15,55Dimethoxy-
14,16,54,56Four oxygen bridge bases -1,3,5,7 (1,3) of tetranitro -2,4,6,8--tetraphenyl cup [4] aromatic hydrocarbons, 12,32,52,72- four
Fluoro- 14,16,54,56Four oxygen bridges of tetranitro -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons, 15,55Dihydroxy
Base -14,16,54,56Four oxygen bridge bases -1,3,5,7 (1,3) of tetranitro -2,4,6,8--tetraphenyl-cup [4] aromatic hydrocarbons, 12,52Dihydroxy
Base -15,55Dimethoxy -14,16,54,56Four oxygen bridges of tetranitro -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup [4]
Aromatic hydrocarbons, 12,32,52,72- four fluoro- 14,16,54,56Four oxygen bridges of tetranitro -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup
[4] aromatic hydrocarbons, 12,32,52,72- four fluoro- 14,16,54,56Four oxygen bridges of tetranitro -2,4,6,8- connect -1,3,5,7 (1,3)-four benzene
Base-cup [4] aromatic hydrocarbons, 12,32,52,72- four fluoro- 14,16,54,56- 1,3,5,7 (1,3) of four oxygen bridges of tetranitro -2,4,6,8- company -
Tetraphenyl-cup [4] aromatic hydrocarbons.Specifically refer to Jeffrey L.Katz, Michael B.Feldman, and Rebecca
R.Conry.Synthesis of Functionalized Oxacalix [4] arenes.Org.Lett., 2005.7,191~
94。
Embodiment one
A kind of preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, includes the following steps：It is stirred in ice-water bath magnetic force
It mixes down, by R1、R2And R3It is-H, 13.7g (i.e. 25mmol) oxygen-containing bridging calixarenes I (1 of the structural formula as shown in formula IV4,16,
54,56Four oxygen bridges of tetranitro -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons) it is added to the 150ml concentrated sulfuric acids
In, after adding slowly into the concentrated sulfuric acid be added dropwise 15ml a concentration of 90% nitric acid；Reaction solution is warming up to 65 DEG C, is stirred, is carried out
TLC detections judge whether reaction finishes, and cool down after completion of the reaction；Then reaction solution is slowly poured into mixture of ice and water, passed through
It filters, wash, being dried to obtain the heat-resisting energy-containing compound (1 of oxygen-containing bridging calixarene kind as shown in Formula II4,16,34,36,54,56,
74,76- eight nitros -2,4,6,8- tetra- oxygen bridges connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons), yield 93%；Its core
Magnetic resonance hydrogen spectrogram 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:C,39.58；H,
1.11；N,15.38；O,43.93；Its heat decomposition curve is as shown in Figure 1.
Embodiment two
A kind of preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, includes the following steps：It is stirred in ice-water bath magnetic force
It mixes down, by R1、R2It is-H, R3For-Cl, 15.43g (i.e. 25mmol) oxygen-containing bridging calixarenes I of the structural formula as shown in formula IV
(15,55- two chloro- 14,16,54,56Four oxygen bridges of tetranitro -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons)
It is added in the 150ml concentrated sulfuric acids, the nitric acid of 15ml a concentration of 92% is slowly added dropwise after adding into the concentrated sulfuric acid；Reaction solution is kept
Room temperature (25 DEG C), stirring carry out TLC detections and judge whether reaction finishes, cool down after completion of the reaction；Then reaction solution is slowly inclined
Enter in mixture of ice and water, it is filtered, wash, to be dried to obtain oxygen-containing bridging calixarene kind as shown in Formula VII heat-resisting containing can chemical combination
Object (15,55- two chloro- 14,16,34,36,54,56,74,76Four oxygen bridges of-eight nitro -2,4,6,8- connect -1,3,5,7 (1,3)-four benzene
Base-cup [4] aromatic hydrocarbons), yield 93%, hydrogen nuclear magnetic resonance spectrogram is1H 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:
C,36.16；H,0.76；Cl,8.89；N,14.06；O,40.14；Its heat decomposition curve is as shown in Figure 2.
Embodiment three
A kind of preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, includes the following steps：It is stirred in ice-water bath magnetic force
It mixes down, by R1、R2It is-H, R3For-Br, 17.65g (i.e. 25mmol) oxygen-containing bridging calixarenes I of the structural formula as shown in formula IV
(15,55- two bromo- 14,16,54,56Four oxygen bridges of tetranitro -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons)
It is added in the 150ml concentrated sulfuric acids, the nitric acid of 15ml a concentration of 95% is slowly added dropwise after adding into the concentrated sulfuric acid；Reaction solution is heated up
To 65 DEG C, stirring carries out TLC detections and judges whether reaction finishes, cools down after completion of the reaction；Then reaction solution is slowly poured into ice
It is filtered, wash, be dried to obtain the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind as shown in Formula VIII in aqueous mixtures
(15,55- two bromo- 14,16,34,36,54,56,74,76- eight nitro -2,4,6,8-, four oxygen bridges company -1,3,5,7 (1,3)-tetraphenyl -
Cup [4] aromatic hydrocarbons), yield 89%, hydrogen nuclear magnetic resonance spectrogram is1H 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 IV
A kind of preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, includes the following steps：It is stirred in ice-water bath magnetic force
It mixes down, by R1、R3It is-H, R2For-Cl, 15.43g (i.e. 25mmol) oxygen-containing bridging calixarenes I of the structural formula as shown in formula IV
(12,52- two chloro- 14,16,54,56Four oxygen bridges of tetranitro -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons)
It is added in the 150ml concentrated sulfuric acids, the nitric acid of 15ml a concentration of 97% is slowly added dropwise after adding into the concentrated sulfuric acid；Reaction solution is heated up
To 65 DEG C, stirring carries out TLC detections and judges whether reaction finishes, cools down after completion of the reaction；Then reaction solution is slowly poured into ice
It is filtered, wash, be dried to obtain the heat-resisting energy-containing compound (1 of oxygen-containing bridging calixarene kind as shown in Formula IX in aqueous mixtures2,
52- two chloro- 14,16,34,36,54,56,74,76Four oxygen bridges of-eight nitro -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup
[4] aromatic hydrocarbons), yield 87%, hydrogen nuclear magnetic resonance spectrogram is1H 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.
Embodiment five
A kind of preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, includes the following steps：It is stirred in ice-water bath magnetic force
It mixes down, by R1For-H, R2For-COCH3, R3For-CH3, the oxygen-containing bridging cup virtues of 15.9g (i.e. 25mmol) of the structural formula as shown in formula IV
Hydrocarbon I (15,55Dimethyl -14,16,54,56Four oxygen bridges -1,3,5,7 (1,3) of tetranitro -2,4,6,8--tetraphenyl -12,52- two
Methoxyl group-cup [4] aromatic hydrocarbons) it is added in the 150ml concentrated sulfuric acids, 15ml a concentration of 100% is slowly added dropwise after adding into the concentrated sulfuric acid
Nitric acid；Reaction solution is warming up to 65 DEG C, stirring carries out TLC detections and judges whether reaction finishes, cools down after completion of the reaction；So
Reaction solution is slowly poured into mixture of ice and water afterwards, it is filtered, wash, be dried to obtain oxygen-containing bridging calixarenes represented by a formula X
The heat-resisting energy-containing compound (1 of class5,55Dimethyl -14,16,34,36,54,56,74,76Four oxygen bridge -1,3 of-eight nitro -2,4,6,8-,
5,7 (1,3)-tetraphenyl -12,52Dimethoxy-cup [4] aromatic hydrocarbons), yield 75%, hydrogen nuclear magnetic resonance spectrogram is1H
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.
Embodiment six
A kind of preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, includes the following steps：It is stirred in ice-water bath magnetic force
It mixes down, 50g potassium nitrate is added in into the 150ml concentrated sulfuric acids, adds R1、R2It is-H, R3For-COCH3, structural formula such as formula IV institute
The oxygen-containing bridging calixarenes I (1 of 10.0g (i.e. 16.45mmol) shown5,55Dimethoxy -14,16,54,56Tetranitro -2,4,6,
Tetra- oxygen bridge bases -1,3 of 8-, 5,7 (1,3)-tetraphenyl cup [4] aromatic hydrocarbons), continue to stop after stirring 30min under ice-water bath；It will reaction
Liquid keeps room temperature, and stirring carries out TLC detections and judges whether reaction finishes, cools down after completion of the reaction；Then reaction solution is slowly inclined
Enter in mixture of ice and water, it is filtered, wash, to be dried to obtain oxygen-containing bridging calixarene kinds of the 10.51g as shown in Formula XI heat-resisting containing energy
Compound (15,55Dimethoxy -14,16,34,36,54,56,74,76Four oxygen bridge bases -1,3,5,7 of-eight nitro -2,4,6,8- (1,
3)-tetraphenyl-cup [4] aromatic hydrocarbons), yield 81%, hydrogen nuclear magnetic resonance spectrogram is1H 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.
Embodiment seven
A kind of preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, includes the following steps：It is stirred in ice-water bath magnetic force
It mixes down, 50g potassium nitrate is added in into the 150ml concentrated sulfuric acids, adds R1、R2It is-F, R3For-H, structural formula is as shown in formula III
The oxygen-containing bridging calixarenes I (1 of 15.5g (i.e. 25mmol)2,32,52,72- four fluoro- 14,16,54,56Four oxygen of tetranitro -2,4,6,8-
Bridging -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons)；Reaction solution is warming up to 65 DEG C, stirring carries out TLC detections and judges instead
Whether should finish, cool down after completion of the reaction；Then reaction solution is slowly poured into mixture of ice and water, it is filtered, washing, dry
To the heat-resisting energy-containing compound (1 of oxygen-containing bridging calixarene kind as shown in formula III2,32,52,72- four fluoro- 14,16,34,36,54,
56,74,76- eight nitros -2,4,6,8- tetra- oxygen bridges connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons), yield 69%,
Its hydrogen nuclear magnetic resonance spectrogram is1HNMR (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.
Embodiment eight
A kind of preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, includes the following steps：It is stirred in ice-water bath magnetic force
It mixes down, 50g ammonium nitrate is added in into the 150ml concentrated sulfuric acids, adds R1、R2It is-H, R3For-OH, structural formula is as shown in formula IV
The oxygen-containing bridging calixarenes I (1 of 14.50g (i.e. 25mmol)5,55Dihydroxy -14,16,54,56Four oxygen bridges of tetranitro -2,4,6,8-
Base -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons)；Reaction solution is warming up to 65 DEG C, stirring carries out TLC detections and judges reaction
Whether finish, cool down after completion of the reaction；Then reaction solution is slowly poured into mixture of ice and water, it is filtered, wash, be dried to obtain
The heat-resisting energy-containing compound (1 of oxygen-containing bridging calixarene kind as shown in Formula XII5,55Dihydroxy -14,16,34,36,54,56,74,
76- eight nitros -2,4,6,8- tetra- oxygen bridge bases -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons), yield 74%.
Embodiment nine
A kind of preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, includes the following steps：It is stirred in ice-water bath magnetic force
It mixes down, 50g copper nitrates is added in into the 150ml concentrated sulfuric acids, add R1For-H, R2For-OH, R3For-OCH3, structural formula such as formula IV
The shown oxygen-containing bridging calixarenes I (1 of 16.00g (i.e. 25mmol)2,52Dihydroxy -15,55Dimethoxy -14,16,54,56- four
Four oxygen bridges of nitro -2,4,6,8- connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons)；Reaction solution is warming up to 65 DEG C, is stirred,
It carries out TLC detections and judges whether reaction finishes, cool down after completion of the reaction；Then reaction solution is slowly poured into mixture of ice and water,
It is filtered, wash, be dried to obtain the heat-resisting energy-containing compound (1 of oxygen-containing bridging calixarene kind as shown in Formula XIII2,52Dihydroxy-
15,55Dimethoxy -14,16,34,36,54,56,74,76Four oxygen bridges of-eight nitro -2,4,6,8- connect -1,3,5,7 (1,3)-four benzene
Base-cup [4] aromatic hydrocarbons), yield 85%.
Embodiment ten
A kind of preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, includes the following steps：It is stirred in ice-water bath magnetic force
It mixes down, 50g silver nitrates is added in into the 150ml concentrated sulfuric acids, add R1、R2It is-F, R3For-H, structural formula is as shown in formula III
The oxygen-containing bridging calixarenes I (1 of 15.5g (i.e. 25mmol)2,32,52,72- four fluoro- 14,16,54,56Four oxygen of tetranitro -2,4,6,8-
Bridging -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons)；Reaction solution is warming up to 65 DEG C, stirring carries out TLC detections and judges instead
Whether should finish, cool down after completion of the reaction；Then reaction solution is slowly poured into mixture of ice and water, it is filtered, washing, dry
To the heat-resisting energy-containing compound (1 of oxygen-containing bridging calixarene kind as shown in formula III2,32,52,72- four fluoro- 14,16,34,36,54,
56,74,76- eight nitros -2,4,6,8- tetra- oxygen bridges connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons), yield 70%.
Embodiment 11
A kind of preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, includes the following steps：It is stirred in ice-water bath magnetic force
It mixes down, 53g manganese nitrates is added in into the 150ml concentrated sulfuric acids, add R1、R2It is-F, R3For-H, structural formula is as shown in formula III
The oxygen-containing bridging calixarenes I (1 of 15.5g (i.e. 25mmol)2,32,52,72- four fluoro- 14,16,54,56Four oxygen of tetranitro -2,4,6,8-
Bridging -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons)；Reaction solution is warming up to 65 DEG C, stirring carries out TLC detections and judges instead
Whether should finish, cool down after completion of the reaction；Then reaction solution is slowly poured into mixture of ice and water, it is filtered, washing, dry
To the heat-resisting energy-containing compound (1 of oxygen-containing bridging calixarene kind as shown in formula III2,32,52,72- four fluoro- 14,16,34,36,54,
56,74,76- eight nitros -2,4,6,8- tetra- oxygen bridges connect -1,3,5,7 (1,3)-tetraphenyl-cup [4] aromatic hydrocarbons), yield 68%.
Embodiment 12
The heat-resisting chemical combination containing energy of oxygen-containing bridging calixarene kind prepared by Example one, embodiment two, embodiment three and embodiment seven
Object carries out detonation property experiment, with tetranitro dibenzo -1,3a,-penta tower alkene (TACOT) of 4,6a- tetra- nitrogen and (the bitter ammonia of 2,6- bis-
Base) -3,5- di nitryl pyridines (PYX) are compared, and the results are shown in table below.
The embodiment of the above, only presently preferred embodiments of the present invention, is only used to explain the present invention, not limit
The scope of the present invention processed, to those of ordinary skill in the art, certainly can be according to skill disclosed in this specification
Art content makes other embodiments easily by way of replacing or changing, therefore all is made in the principle of the present invention
Changes and improvements etc. should all be included in scope of the present invention patent.
Claims (6)
1. a kind of oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, which is characterized in that its general structure is shown in formula I：
Wherein R1Selected from hydrogen atom or halogen, R2Selected from hydrogen atom, halogen or hydroxyl, R3Selected from hydrogen atom, halogen, hydroxyl or first
Oxygroup.
2. a kind of oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, which is characterized in that its structural formula is as shown in Formula II：
3. a kind of oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind, which is characterized in that its structural formula is as shown in formula III：
4. the preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind of claims 1 to 3 any one of them, feature
It is, includes the following steps：Under ice-water bath magnetic agitation, oxygen-containing bridging calixarenes I, nitrate or nitric acid are added to dense sulphur
In acid；Reaction solution is warming up to 65 DEG C again or keeps room temperature, stirring cools down after completion of the reaction；Then reaction solution is poured into ice water
It is filtered, wash, be dried to obtain the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind as shown in Formulas I~III in mixture；
The structural formula of the oxygen-containing bridging calixarenes I is as shown in formula IV：
Wherein R1Selected from hydrogen atom or halogen, R2Selected from hydrogen atom, halogen or hydroxyl, R3Selected from hydrogen atom, halogen, hydroxyl or first
Oxygroup.
5. the preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind according to claim 4, which is characterized in that
The molar ratio of the oxygen-containing bridging calixarenes I and nitrate anion in nitric acid or nitrate is 1：(4.4~8).
6. the preparation method of the oxygen-containing heat-resisting energy-containing compound of bridging calixarene kind according to claim 4, which is characterized in that
The nitrate is one kind in sodium nitrate, potassium nitrate, ammonium nitrate, silver nitrate, copper nitrate or manganese nitrate；The nitric acid is concentration
For 90%~100% nitric acid.
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| CN108997132A (en) * | 2018-09-03 | 2018-12-14 | 信阳师范学院 | A kind of fluoro- 1,3,5- triamido -4,6- dinitrobenzene of heat resistive compounds 2- and preparation method thereof |
| CN109810006A (en) * | 2019-02-21 | 2019-05-28 | 信阳师范学院 | Fluoro- 2,6- dinitroaniline of a kind of castexplosive 3,4,5- tri- and its preparation method and application |
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| CN108997132A (en) * | 2018-09-03 | 2018-12-14 | 信阳师范学院 | A kind of fluoro- 1,3,5- triamido -4,6- dinitrobenzene of heat resistive compounds 2- and preparation method thereof |
| CN109810006A (en) * | 2019-02-21 | 2019-05-28 | 信阳师范学院 | Fluoro- 2,6- dinitroaniline of a kind of castexplosive 3,4,5- tri- and its preparation method and application |
| CN109810006B (en) * | 2019-02-21 | 2021-11-23 | 信阳师范学院 | Fusion-cast explosive 3,4, 5-trifluoro-2, 6-dinitroaniline and preparation method and application thereof |
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