CN107098864A - Pentazole sodium and the triazole cocrystalization compound of 4 amino 1,2,4 and preparation method thereof - Google Patents
Pentazole sodium and the triazole cocrystalization compound of 4 amino 1,2,4 and preparation method thereof Download PDFInfo
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- CN107098864A CN107098864A CN201710335421.3A CN201710335421A CN107098864A CN 107098864 A CN107098864 A CN 107098864A CN 201710335421 A CN201710335421 A CN 201710335421A CN 107098864 A CN107098864 A CN 107098864A
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- pentazole
- sodium
- amino
- triazole
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- ANGRFWYTDAONDD-UHFFFAOYSA-N [Na].N1N=NN=N1 Chemical compound [Na].N1N=NN=N1 ANGRFWYTDAONDD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 150000001875 compounds Chemical class 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title abstract 3
- 150000003852 triazoles Chemical class 0.000 title abstract 3
- 239000013078 crystal Substances 0.000 claims abstract description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 239000012046 mixed solvent Substances 0.000 claims abstract description 18
- LJQKCYFTNDAAPC-UHFFFAOYSA-N ethanol;ethyl acetate Chemical compound CCO.CCOC(C)=O LJQKCYFTNDAAPC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 85
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical class NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 claims description 23
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 238000000108 ultra-filtration Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 5
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 claims 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- WUHLVXDDBHWHLQ-UHFFFAOYSA-N pentazole Chemical compound N=1N=NNN=1 WUHLVXDDBHWHLQ-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 4
- 210000000988 bone and bone Anatomy 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 2
- 230000003749 cleanliness Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 239000002360 explosive Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 230000008034 disappearance Effects 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 230000005496 eutectics Effects 0.000 description 5
- -1 oxazolinium ions Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B43/00—Compositions characterised by explosive or thermic constituents not provided for in groups C06B25/00 - C06B41/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D259/00—Heterocyclic compounds containing rings having more than four nitrogen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention provides a kind of pentazole sodium and the triazole cocrystalization compound of 4 amino 1,2,4 and preparation method thereof, the preparation method of cocrystalization compound of the invention comprises the following steps：Pentazole sodium is recrystallized by ethanol ethyl acetate mixed solvent, pentazole sodium crystal is obtained；It is equipped with the alcohol water mixed solution of pentazole sodium；It is equipped with the alcohol water mixed solution of the triazole of 4 amino 1,2,4；Isometric above two mixed liquor is mixed to get total mixed liquor, is statically placed in after total mixed liquor is filtered in climatic chamber, treats that solvent volatilizees, obtains cocrystalization compound.The preparation method that the present invention is provided is simply efficient, and obtained product improves its mechanical property, greatly promote its thermal stability by changing the forms of 3D back bone networks；Because its nitrogen content is high, the predominant gas produced after blast is the nitrogen of cleanliness without any pollution, therefore is a kind of energy-containing compound of environmental protection.
Description
Technical field
The invention belongs to energetic material technical field, more particularly to a kind of preparation method of high nitrogen cocrystalization compound.
Background technology
Eutectic just starts to be applied to energy-containing compound field in recent years, and it, which provides one, improves existing energetic material performance
New way, i.e. two or more explosive are combined on molecular level by intermolecular force, are imitated by space
The formation of Supramolecular Network should be influenceed with intermolecular force, microcosmic combination is assembled into supermolecule and be combined in same lattice
Thing, so as to change the Inner Constitution of explosive, utilizes intermolecular force in the case of original explosive molecules chemical constitution is not destroyed
Increase the density of explosive crystal, improve the explosion velocity of explosive.In addition, for the high explosive of mechanical sensitivity, then by with desensitized explosive
Eutectic is formed, the explosion velocity of explosive is improved, reduces its mechanical sensitivity.
Pentazole sodium (NaN5) it is the novel energetic compounds that a class contains full N structure.Five oxazolinium ions itself have higher
The enthalpy of formation and energy, with cation sodium Na+It is the energy-containing compound of excellent performance after assembling.Further, since pentazole is in dissociation
A large amount of avirulent nitrogen are produced, green non-pollution also has preferable application prospect in gas-forming agent.But five oxazolinium ions
Decomposed near 110 DEG C, cause the stability of pentazole sodium itself more general, therefore contain energy using more preferable other of heat endurance
The formed eutectic of molecule is to improve the desirable route of pentazole sodium performance.
The content of the invention
Technical problem：In order to solve the defect of prior art, the invention provides a kind of high nitrogen cocrystalization compound pentazole sodium-
Amino triazole and preparation method thereof.
Technical scheme：The invention provides the preparation of a kind of pentazole sodium and 4- amino-1,2,4-triazol cocrystalization compounds
Method, this method comprises the following steps：
(1) pentazole sodium is recrystallized in EtOH-EtOAc in the mixed solvent, obtains pentazole sodium crystal so that pentazole sodium is pure
Du Genggao；
(2) the pentazole sodium crystal of step (1) is dissolved in alcohol-water mixed solution, obtains solution A；
(3) by 4- amino -1,2,4- triazoles are dissolved in alcohol-water mixed solution, obtain solution B；Wherein, 4- amino-
Molar concentration of molar concentration of the 1,2,4- triazoles in solution B with pentazole sodium in solution A is identical；
(4) isometric solution A and solution B are mixed to get solution C, solution C is subjected to ultrasonic disperse, then crossed and filter off
Except insoluble matter；
(5) solution C for obtaining step (4) is statically placed in climatic chamber, to solvent volatilization 1/2；In climatic chamber
Design temperature is 20 DEG C~50 DEG C, and humidity is 10%~20%；
(6) temperature in climatic chamber is reduced to 10 DEG C, humidity is improved to 50%, and solvent continues to volatilize, but volatilization
It is slow than before, there is Crystallization after a period of time, produce cocrystalization compound.
Preferably：In step (1), EtOH-EtOAc in the mixed solvent, the volume ratio of ethanol and ethyl acetate
For (4~6):(4~6).
Preferably：The volume ratio of alcohol and water is (5 in alcohol-water mixed solution in step (2) and step (3)
~8):(2~5).
Preferably：In solution A in the concentration and solution B of pentazole sodium 4- amino-1,2,4-triazols concentration phase
Together, it is 0.25~0.6mol/L.
Preferably：The alcohol in alcohol-water mixed solution in step (2) and step (3) is methanol or ethanol.
Preferably：In step (4), ultrasonic power is 100~150 watts, and ultrasonic time is 10~30 minutes.
Preferably：In step (4), filtering is to use ultrafiltration membrance filter, and the aperture of milipore filter is 0.22um.
Preferably：In step (4), when solution A and solution B are mixed to get solution C, if Precipitation or molten
Liquid C becomes cloudy, and adds alcohol or deionized water to clarification.
Present invention additionally comprises the pentazole sodium being made up of any of the above-described method and 4- amino-1,2,4-triazol eutectic chemical combination
Thing.The compound obtained by the above method changes 3D back bone network forms on the basis of existing compound so that mechanical property
Improved.
Beneficial effect：The preparation method that the present invention is provided is simply efficient, the product cocrystalization compound obtained according to this method
By changing the form of 3D back bone networks, influence of the foreign impacts power to ionic structure is reduced, its mechanical property is improved, because
To have increased interionic coordination newly, greatly promote its thermal stability；The compound obtained had both remained pentazole sodium
High-power, and because add 4- amino -1,2,4- triazoles improve stability.Due to the nitrogen content of cocrystalization compound
Height, the predominant gas produced after blast is the nitrogen of cleanliness without any pollution, therefore is a kind of energy-containing compound of environmental protection.
Brief description of the drawings
Fig. 1 is the pentazole sodium of the present invention and the structural representation of 4- amino-1,2,4-triazols cocrystalization compound (100) crystal face
Figure；
Fig. 2 is the pentazole sodium of the present invention and the structural representation of 4- amino-1,2,4-triazols cocrystalization compound (001) crystal face
Figure；
Fig. 3 is the pentazole sodium of the present invention and the structural representation of 4- amino-1,2,4-triazols cocrystalization compound (010) crystal face
Figure；
Fig. 4 is pentazole sodium of the invention and 4- amino-1,2,4-triazol cocrystalization compound structure cell schematic diagrames.
Embodiment
The present invention is further illustrated with reference to embodiment.
As shown in Figure 1, Figure 2 and Figure 3, after pentazole sodium recrystallization purifying with 4- amino -1,2,4- triazoles are miscible, by molten
The method of agent cooling volatilization, is obtained with stable pentazole sodium and 4- amino -1,2,4- triazole cocrystalization compounds, the eutectic
Compound has that nitrogen content is high, stability is good, high gas generating amount, produces the characteristics such as gas cleaning, these characteristics are applicable to do new
Type green energetic material.
Pentazole sodium (NaN in the present invention5) with the preparation the equation below of 4- amino-1,2,4-triazol cocrystalization compounds
(I) represent：
Cocrystalization compound is prepared by pentazole sodium with 4- amino-1,2,4-triazols to comprise the following steps：
(1) by freshly prepd pentazole sodium (NaN5) by EtOH-EtOAc mixed solvent recrystallization, obtain pentazole sodium
Crystal；
(2) alcohol-water mixing for being equipped with the alcohol-water mixed solution and 4- amino-1,2,4-triazols of pentazole sodium is molten
Liquid, wherein pentazole sodium and 4- amino -1,2,4- triazoles concentration in above-mentioned alcohol-water mixed solution are identical, are 0.25mol/
L, wherein alcohol are methanol or ethanol；
(3) above-mentioned two parts of solution is mixed in equal volume, if there is a small amount of Precipitation immediately after mixing or become cloudy, plus alcohol
Or deionized water is extremely clarified；
(4) above-mentioned mixed solution ultrasound is disperseed for 30 minutes, then uses ultrafiltration membrance filter；
(5) solution after above-mentioned filtering is placed in climatic chamber and stood, climatic chamber setting humidity 10%~
20%, 20 DEG C~50 DEG C of temperature；Solvent quickly volatilizees, until solvent volatilization 1/2；
(6) temperature is reduced to 10 DEG C, humidity is improved to 50%, and solvent slowly volatilizees, to there is Crystallization.
The crystal of acquisition is characterized through single crystal diffraction, shown in structure below figure 1, Fig. 2, Fig. 3 and Fig. 4, and wherein Fig. 1 is (100)
Crystal face；Fig. 2 is (001) crystal face；Fig. 3 is (010) crystal face, and Fig. 4 is structure cell.
Embodiment 1
(1) by ethanol and ethyl acetate according to 4:6 volume ratio carries out being mixed to get mixed solvent, by the pentazole sodium of brand-new
Above-mentioned mixed solvent is dissolved in, configuration obtains the solution that pentazole na concn is 1mol/L, then makes the solution left standstill in 25 DEG C
Solvent volatilizees, and is recrystallized to give the crystal for the pentazole sodium that purity is 99%.
(2) methanol and water are taken respectively, and it is 8 to incite somebody to action both according to volume ratio：2 carry out being mixed to get mixed solution；Take part mixed
Solution is closed, pentazole sodium crystal made from step (1) is dissolved in wherein, the solution A that configuration pentazole na concn is 0.5mol/L；
(3) part mixed solution is taken, by 4- amino -1,2,4- triazoles are dissolved in wherein, configure 4- amino -1,2,4- tri-
Nitrogen azoles concentration is 0.5mol/L solution B；
(4) isometric solution A and solution B is taken respectively, and both, which are mixed to get after solution C, mixing, a small amount of precipitation analysis
Go out, add methanol to precipitating disappearance；Then 100 watts of ultrasonic power is set, 30 minutes time, solution C is poured into and wherein surpassed
Sound disperses, the ultrafiltration membrance filter for being then 0.22um with aperture；
(5) solution C after above-mentioned filtering is placed in climatic chamber, climatic chamber temperature 50 C, humidity is set
20%, after vaporing away 1/2 to solvent, climatic chamber is re-set as 10 DEG C of temperature, humidity 50%, solvent continues to evaporate into
There is Crystallization.
The crystal of acquisition is characterized through single crystal diffraction, shown in structure below figure 1, Fig. 2, Fig. 3 and Fig. 4, and wherein Fig. 1 is (100)
Crystal face；Fig. 2 is (001) crystal face；Fig. 3 is (010) crystal face, and Fig. 4 is structure cell, it is known that the crystal of acquisition is cocrystalization compound.
Embodiment 2
(1) by ethanol and ethyl acetate according to 6:4 volume ratio carries out being mixed to get mixed solvent, by the pentazole sodium of brand-new
Above-mentioned mixed solvent is dissolved in, configuration obtains the solution that pentazole na concn is 1mol/L, the solution then is placed in into rotary evaporation
Rotary Evaporators are set as 30 DEG C of temperature, rotating speed 100r/min is removed after half solvent, then standing makes solvent continue to wave by instrument
Hair, obtains the pentazole sodium crystal that purity is 95%.
(2) methanol and water are taken respectively, and it is 8 to incite somebody to action both according to volume ratio：2 carry out being mixed to get mixed solution；Take part mixed
Solution is closed, pentazole sodium crystal made from step (1) is dissolved in wherein, the solution A that configuration pentazole na concn is 0.6mol/L；
(3) part mixed solution is taken, by 4- amino -1,2,4- triazoles are dissolved in wherein, configure 4- amino -1,2,4- tri-
Nitrogen azoles concentration is 0.6mol/L solution B；
(4) isometric solution A and solution B is taken respectively, and both, which are mixed to get after solution C, mixing, a small amount of precipitation analysis
Go out, add deionized water to precipitating disappearance；Then 150 watts of ultrasonic power is set, 10 minutes time, solution C is poured into wherein to enter
Row ultrasonic disperse, the ultrafiltration membrance filter for being then 0.22um with aperture；
(5) solution C after being filtered in above-mentioned steps (4) is placed in climatic chamber, climatic chamber temperature is set
50 DEG C, climatic chamber after vaporing away 1/2 to solvent, is re-set as 10 DEG C of temperature, humidity 50%, solvent by humidity 20%
Continue to have evaporated into Crystallization, gained crystal is same as Example 1 by characterizing, and is cocrystalization compound.
Embodiment 3
(1) by ethanol and ethyl acetate according to 5:5 volume ratio carries out being mixed to get mixed solvent, by the pentazole sodium of brand-new
Above-mentioned mixed solvent is dissolved in, configuration obtains the solution that pentazole na concn is 1mol/L, then makes the solution left standstill in 25 DEG C
Solvent volatilizees, and is recrystallized to give the crystal for the pentazole sodium that purity is 99%.
(2) methanol and water are taken respectively, and it is 5 to incite somebody to action both according to volume ratio：5 carry out being mixed to get mixed solution；Take part mixed
Solution is closed, pentazole sodium crystal made from step (1) is dissolved in wherein, the solution A that configuration pentazole na concn is 0.6mol/L；
(3) part mixed solution is taken, by 4- amino -1,2,4- triazoles are dissolved in wherein, configure 4- amino -1,2,4- tri-
Nitrogen azoles concentration is 0.6mol/L solution B；
(4) isometric solution A and solution B is taken respectively, and both, which are mixed to get after solution C, mixing, a small amount of precipitation analysis
Go out, add deionized water to precipitating disappearance；Then 120 watts of ultrasonic power is set, 20 minutes time, solution C is poured into wherein to enter
Row ultrasonic disperse, the ultrafiltration membrance filter for being then 0.22um with aperture；
(5) solution C after being filtered in above-mentioned steps (4) is placed in climatic chamber, climatic chamber temperature is set
50 DEG C, climatic chamber after vaporing away 1/2 to solvent, is re-set as 10 DEG C of temperature, humidity 50%, solvent by humidity 15%
Continue to have evaporated into Crystallization, gained crystal is same as Example 1 by characterizing, and is cocrystalization compound.
Embodiment 4
(1) by ethanol and ethyl acetate according to 4:6 volume ratio carries out being mixed to get mixed solvent, by the pentazole sodium of brand-new
Above-mentioned mixed solvent is dissolved in, configuration obtains the solution that pentazole na concn is 1mol/L, then makes the solution left standstill in 25 DEG C
Solvent volatilizees, and is recrystallized to give the crystal for the pentazole sodium that purity is 99%.
(2) ethanol and water are taken respectively, and it is 6 to incite somebody to action both according to volume ratio：4 carry out being mixed to get mixed solution；Take part mixed
Solution is closed, pentazole sodium crystal made from step (1) is dissolved in wherein, the solution A that configuration pentazole na concn is 0.25mol/L；
(3) part mixed solution is taken, by 4- amino -1,2,4- triazoles are dissolved in wherein, configure 4- amino -1,2,4- tri-
Nitrogen azoles concentration is 0.25mol/L solution B；
(4) isometric solution A and solution B is taken respectively, and both, which are mixed to get after solution C, mixing, a small amount of precipitation analysis
Go out, add deionized water to precipitating disappearance；Then 150 watts of ultrasonic power is set, 30 minutes time, solution C is poured into wherein to enter
Row ultrasonic disperse, the ultrafiltration membrance filter for being then 0.22um with aperture；
(5) solution C after being filtered in above-mentioned steps (4) is placed in climatic chamber, climatic chamber temperature is set
50 DEG C, climatic chamber after vaporing away 1/2 to solvent, is re-set as 10 DEG C of temperature, humidity 50%, solvent by humidity 20%
Continue to have evaporated into Crystallization, gained crystal is same as Example 1 by characterizing, and is cocrystalization compound.
Embodiment 5
(1) by ethanol and ethyl acetate according to 6:4 volume ratio carries out being mixed to get mixed solvent, by the pentazole sodium of brand-new
Above-mentioned mixed solvent is dissolved in, configuration obtains the solution that pentazole na concn is 1mol/L, then makes the solution left standstill in 25 DEG C
Solvent volatilizees, and is recrystallized to give the crystal for the pentazole sodium that purity is 99%.
(2) methanol and water are taken respectively, and it is 8 to incite somebody to action both according to volume ratio：2 carry out being mixed to get mixed solution；Take part mixed
Solution is closed, pentazole sodium crystal made from step (1) is dissolved in wherein, the solution A that configuration pentazole na concn is 0.5mol/L；
(3) part mixed solution is taken, by 4- amino -1,2,4- triazoles are dissolved in wherein, configure 4- amino -1,2,4- tri-
Nitrogen azoles concentration is 0.5mol/L solution B；
(4) isometric solution A and solution B is taken respectively, and both, which are mixed to get after solution C, mixing, a small amount of precipitation analysis
Go out, add deionized water to precipitating disappearance；Then 150 watts of ultrasonic power is set, 20 minutes time, solution C is poured into wherein to enter
Row ultrasonic disperse, the ultrafiltration membrance filter for being then 0.22um with aperture；
(5) solution C after being filtered in above-mentioned steps (4) is placed in climatic chamber, climatic chamber temperature is set
30 DEG C, climatic chamber after vaporing away 1/2 to solvent, is re-set as 10 DEG C of temperature, humidity 50%, solvent by humidity 10%
Continue to have evaporated into Crystallization, gained crystal is same as Example 1 by characterizing, and is cocrystalization compound.
Embodiment 6
(1) by ethanol and ethyl acetate according to 5:5 volume ratio carries out being mixed to get mixed solvent, by the pentazole sodium of brand-new
Above-mentioned mixed solvent is dissolved in, configuration obtains the solution that pentazole na concn is 1mol/L, then makes the solution left standstill in 25 DEG C
Solvent volatilizees, and is recrystallized to give the crystal for the pentazole sodium that purity is 99%.
(2) ethanol and water are taken respectively, and it is 5 to incite somebody to action both according to volume ratio：5 carry out being mixed to get mixed solution；Take part mixed
Solution is closed, pentazole sodium crystal made from step (1) is dissolved in wherein, the solution A that configuration pentazole na concn is 0.5mol/L；
(3) part mixed solution is taken, by 4- amino -1,2,4- triazoles are dissolved in wherein, configure 4- amino -1,2,4- tri-
Nitrogen azoles concentration is 0.5mol/L solution B；
(4) isometric solution A and solution B is taken respectively, and both, which are mixed to get after solution C, mixing, a small amount of precipitation analysis
Go out, add deionized water to precipitating disappearance；Then 150 watts of ultrasonic power is set, 30 minutes time, solution C is poured into wherein to enter
Row ultrasonic disperse, the ultrafiltration membrance filter for being then 0.22um with aperture；
(5) solution C after being filtered in above-mentioned steps (4) is placed in climatic chamber, climatic chamber temperature is set
20 DEG C, climatic chamber after vaporing away 1/2 to solvent, is re-set as 10 DEG C of temperature, humidity 50%, solvent by humidity 20%
Continue to have evaporated into Crystallization, gained crystal is same as Example 1 by characterizing, and is cocrystalization compound.
Claims (9)
1. a kind of pentazole sodium and 4- amino -1,2, the preparation method of 4- triazole cocrystalization compounds, it is characterised in that including following
Step：
(1) pentazole sodium is recrystallized in EtOH-EtOAc in the mixed solvent, obtains pentazole sodium crystal；
(2) the pentazole sodium crystal of step (1) is dissolved in alcohol-water mixed solution, obtains solution A；
(3) by 4- amino -1,2,4- triazoles are dissolved in alcohol-water mixed solution, obtain solution B；Wherein, 4- amino -1,2,
Molar concentration of molar concentration of the 4- triazoles in solution B with pentazole sodium in solution A is identical；
(4) isometric solution A and solution B are mixed to get solution C, solution C is subjected to ultrasonic disperse, then filtering is removed not
Molten thing；
(5) solution C for obtaining step (4) is statically placed in climatic chamber, to solvent volatilization 1/2；Set in climatic chamber
Temperature is 20 DEG C~50 DEG C, and humidity is 10%~20%；
(6) temperature in climatic chamber is reduced to 10 DEG C, humidity is improved to 50%, and solvent continues to volatilize, and has Crystallization, i.e.,
Obtain cocrystalization compound.
2. pentazole sodium according to claim 1 and 4- amino -1,2, the preparation method of 4- triazole cocrystalization compounds, it is special
Levy and be：In step (1), EtOH-EtOAc in the mixed solvent, the volume ratio of ethanol and ethyl acetate is (4~6):(4~
6)。
3. pentazole sodium according to claim 1 and 4- amino -1,2, the preparation method of 4- triazole cocrystalization compounds, it is special
Levy and be：The volume ratio of alcohol and water is (5~8) in alcohol-water mixed solution in step (2) and step (3):(2~5).
4. pentazole sodium according to claim 1 and 4- amino -1,2, the preparation method of 4- triazole cocrystalization compounds, it is special
Levy and be：4- amino -1,2 in the concentration and solution B of pentazole sodium in solution A, the concentration of 4- triazoles is identical, be 0.25~
0.6mol/L。
5. pentazole sodium according to claim 1 and 4- amino -1,2, the preparation method of 4- triazole cocrystalization compounds, it is special
Levy and be：The alcohol in alcohol-water mixed solution in step (2) and step (3) is methanol or ethanol.
6. pentazole sodium according to claim 1 and 4- amino -1,2, the preparation method of 4- triazole cocrystalization compounds, it is special
Levy and be：In step (4), ultrasonic power is 100~150 watts, and ultrasonic time is 10~30 minutes.
7. pentazole sodium according to claim 1 and 4- amino -1,2, the preparation method of 4- triazole cocrystalization compounds, it is special
Levy and be：In step (4), filtering is to use ultrafiltration membrance filter, and the aperture of milipore filter is 0.22um.
8. pentazole sodium according to claim 1 and 4- amino -1,2, the preparation method of 4- triazole cocrystalization compounds, it is special
Levy and be：In step (4), when solution A and solution B are mixed to get solution C, if Precipitation or solution C become cloudy, add
Alcohol or deionized water are extremely clarified.
9. a kind of pentazole sodium and 4- amino -1,2,4- triazole cocrystalization compounds, it is characterised in that：It is any by claim 1-8
Method described in item claim is made.
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