CN103524444A - Synthetic method of 5, 5'-bistetrazole-1, 1'-dioxo hydroxyl ammonium salt (TKX-50) - Google Patents
Synthetic method of 5, 5'-bistetrazole-1, 1'-dioxo hydroxyl ammonium salt (TKX-50) Download PDFInfo
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- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
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Abstract
The invention provides a method for preparing 5, 5'-bistetrazole-1, 1'-dioxo hydroxyl ammonium salt (TKX-50), and belongs to the technical field of organic synthesis. The method comprises the steps as follows: step one, glyoxime is prepared, and the yield is 62%; step two, a product obtained in the step one is dissolved in water and concentrated hydrochloric acid, chlorine is introduced at the temperature of 0 DEG C for a reaction for a period of time, and dichloroglyoxime is obtained; and finally, a product obtained in the step two is dissolved in a solvent, and the product and sodium azide have a reaction at the temperature of 0 DEG C for a period of time; after that, the mixture is transferred into diethy ether, and sealed for a reaction at the room temperature overnight after HCl is introduced for a period of time; and after diethyl ether and most HCl gas are volatilized, pH of an aqueous NaOH solution is regulated to be about 8, reflux cooling is performed, filtered and separated solids are dissolved in hydroxylamine hydrochloride to have a reaction for a period of time, and TKX-50 is obtained. According to the method, glyoxal is adopted as a raw material, water is adopted as a solvent for preparation of dichloroglyoxime in the step two, and only direct filtration is required in postprocessing, so that the tedious purification process is prevented, and the cost is reduced; and besides, a target product TKX-50 is synthetized through three steps of reactions, the total yield is up to 34%, the reaction condition is mild, the operation is simple and convenient, and the industrialization is easy to realize.
Description
Technical field
The present invention relates to a kind of 5,5'-bistetrazole-1, the synthetic method of 1'-dioxy hydroxylammonium salt (TKX-50), belongs to technical field of organic synthesis.
Background technology
In civilian and military field, high energy explosive mainly belongs to ring-type and cage shape nitramine compound, as RDX, and HMX and CL-20, but they have fatal shortcoming.The strategy of modern energetic material research allows to retain or improve the detonation property of these compounds often, avoid the shortcoming of its existence: toxicity simultaneously, difficulty and expensive synthetic (HMX, CL-20), mechanical stimulus sensitivity height and spontaneous rotten (CL-20).Yet the known energetic material with the highest detonation property is due to its unprecedented energy, extremely sensitive often, and synthesis path is long and expensive, makes them not possess using value.For example, 4,4'-dinitrobenzene-3,3'-azo furoxan (DDF) and the about 10000m s of otanitrocubane (ONC) explosion velocity
-1, but both extremely sensitive, more than reagent costliness synthetic used and step reach ten steps.
In recent years, the compound of seeking the low sensitivity of high-energy of new generation is to substitute the important research direction that traditional nitro-amine compound explosive is energetic material field always.When designing new energetic material, rich nitrogen tetrazole ring is the potential blast of tool unit, and its energy comes from very high positive Enthalpies of Formation.Because tetrazole ring has the stability of aromatic structure, this compounds is easily decomposed unlike other amine or azo.Some researchs of delivering recently show, the introducing of N-oxide compound makes compound have higher density and stability, lower sensitivity and better oxygen balance.In conjunction with these principles and practical situation, consider Germany
the tetrazolium that seminar has designed and synthesized the low sensitivity of a kind of high-energy is containing can ion salt, and 5,5'-bistetrazole-1,1'-dioxy hydroxylammonium salt (TKX-50).This ion salt is carried out improving performance by bistetrazole, and it calculates explosion velocity and reaches 9698m s
-1, detonation pressure is 42.4GPa, thermally-stabilised suitable with RDX (221 ℃ start to decompose).Owing to not adopting N-NO
2form improve energy, it still maintains lower impact sensitivity (20J).Meanwhile, on azo-cycle, introduce Sauerstoffatom, not only with positively charged ion in amine formed interionic hydrogen bond system, make its density reach 1.92g cm
-3, and there is better oxygen equilibrium and also have potential using value at aspects such as rocket propellants, yet its most of performances are unknown (comprising actual measurement explosion velocity detonation pressure, friction sensitivity and consistency etc.).In view of the importance of TKX-50 and at present the defect of bibliographical information synthetic method be necessary its synthesis technique to improve, it is more suitable in suitability for industrialized production.
Summary of the invention
The object of the invention is in order to provide a kind of by synthetic 5, the 5'-of oxalic dialdehyde bistetrazole-1, the method for 1'-dioxy hydroxylammonium salt (TKX-50), the method reaction conditions is gentle, simple to operate, efficiency is high.The object of the invention is to be achieved through the following technical solutions.Concrete route is as follows:
The method is carried out according to the following steps:
1) under room temperature, NaOH is soluble in water, in this solution ice salt bath, be cooled to 0 ℃, then slowly add wherein oxammonium hydrochloride, finish, then add 40% glyoxal water solution, control temperature lower than 10 ℃, after reaction 15min, in room temperature reaction, spend the night.Filter, a small amount of frozen water washing, dries to obtain glyoxime, productive rate 62% naturally.
2), under room temperature, the glyoxime that step 1) is obtained is added to the water, and stirs, then add concentrated hydrochloric acid, treat that raw material almost all dissolves, and bathes cooling mixed liquid to 0 ℃ with cryosel, pass into chlorine, in process, dirty solution becomes clarification gradually, continues to pass into chlorine, separate out gradually white precipitate, at this time continue ventilatory response for some time, filter, a small amount of frozen water washing, naturally dry to obtain dichloroglyoxime, productive rate 45%～60%.
3) under room temperature, by step 2) dichloroglyoxime that obtains is dissolved in certain solvent.Be cooled to 0 ℃, add sodiumazide, keep temperature to be no more than 2 ℃, finish again and stir for some time.Mixture is transferred in a there-necked flask that ether is housed afterwards, cools to 0 ℃, passes into HCl(temperature control lower than 20 ℃) after for some time, sealed reaction bottle, ambient temperature overnight reaction.Wave ether and most of hydrogen chloride gas, add wherein water, then with the NaOH aqueous solution, regulate pH ≈ 8,5,5'-bistetrazole-1,1'-dihydroxyl sodium salt is separated out, and mixed solution reflux is cooling after 1 hour, filters, with frozen water, wash, until filtrate pH ≈ 7 isolates 5,5 '-bistetrazole-1,1 '-dihydroxyl sodium salt, sodium salt is dissolved in a small amount of hot water, to it, adds oxammonium hydrochloride saturated aqueous solution, continues to stir for some time, be cooled to room temperature, filter, a small amount of frozen water washing obtains TKX-50, productive rate 80%～90%.
Step 2) in, pass into the speed of chlorine for slow or rapid;
Step 2) reaction times that passes into chlorine in is 2h～4h;
In step 3), the solvent of azido reaction is DMF, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetone or N-Methyl pyrrolidone;
In step 3), ether consumption is 170～400mL:5g with the ratio of dichloroglyoxime;
The reaction times that passes into HCl in step 3) is 3h～5h;
The time that in step 3), sodium salt reacts with oxammonium hydrochloride is 1h～2h.
Advantage of the present invention is:
1) in the whole building-up process of bibliographical information TKX-50, the preparation of second step dichloroglyoxime adopts ethanol to make solvent, and reaction needs to remove under reduced pressure ethanol after finishing, and uses chloroform to wash thick product.And the present invention adopts water to make solvent, aftertreatment only needs direct filtration, without using the large chloroform of toxicity, has avoided loaded down with trivial details purification process, simple to operation, has reduced cost.
2) through the synthetic target product TKX-50 of three-step reaction, overall yield reaches 34%, and reaction conditions is gentle, easy and simple to handle, is easy to realize industrialization.
Embodiment
Embodiment 1
1) under room temperature, 165g (412.5mmol) NaOH is dissolved in 450mL water, in this solution ice salt bath, be cooled to 0 ℃, then add wherein 417g (600.1mmol) oxammonium hydrochloride, finish, then add 435g (299.8mmol) 40% glyoxal water solution, control temperature lower than 10 ℃, after reaction 15min, in room temperature reaction, spend the night.Filter, a small amount of frozen water washing, dries to obtain 174g glyoxime, productive rate 62% naturally.Fusing point: 175-177 ℃.
2) under room temperature, the glyoxime 100g (1.14mol) that step 1) is obtained adds in 2000mL water, stir, then add 500mL concentrated hydrochloric acid, treat that raw material almost all dissolves, with cryosel, bathing cooling mixed liquid to 0, ℃ (large content of starting materials is separated out again, for white casse liquid), pass into rapidly a large amount of chlorine (concentrated hydrochloric acid splashes into Manganse Dioxide and makes), in process, dirty solution becomes clarification gradually, continue to pass into fast chlorine, separate out gradually white precipitate, at this time continuing ventilatory response 4h(, to observe white precipitate more and more), filter, a small amount of frozen water washing, naturally dry to obtain 108g dichloroglyoxime, productive rate 60%.Fusing point: 195-196 ℃.
3), under room temperature, 50g (318.6mmol) dichloroglyoxime is dissolved in 637mL N-Methyl pyrrolidone (NMP).Be cooled to 0 ℃, add 45.6g (701.4mmol) sodiumazide (faint yellow turbid liquid), keep temperature to be no more than 2, ℃ finish and to stir again 1 hour.Mixture is transferred in a there-necked flask that 1700mL ether is housed afterwards, cools to 0 ℃, pass into HCl(concentrated hydrochloric acid splash in the vitriol oil make) (temperature control is lower than 20 ℃) 5h(passes in HCl gas process more and more thickness of reaction solution).Sealed reaction bottle, ambient temperature overnight reaction (guarantee HCl does not leak outside and air pressure higher than normal pressure).Wave ether and most of hydrogen chloride gas (70 degree are placed 5 hours), add wherein 500mL water, then with the 700mL NaOH aqueous solution, regulate pH ≈ 8, 5, 5'-bistetrazole-1, 1'-dihydroxyl sodium salt is separated out, mixed solution reflux is cooling after 1 hour, filter, with frozen water washing three times, until filtrate pH ≈ 7, isolate 5, 5 '-bistetrazole-1, 1 '-dihydroxyl sodium salt, sodium salt is dissolved in a small amount of hot water, to it, add 60g (863.4mmol) oxammonium hydrochloride saturated aqueous solution, continue to stir 2h, be cooled to room temperature, filter, a small amount of frozen water washing obtains 68g TKX-50, productive rate 90%.Decomposition temperature: 241 ℃ of (DSC, 10K min
-1).IR(neat):3215,3171,3071,2902,2680,2449,1574,1519,1424,1410,1350,1232,1190,1167,1044,1009,996,808,715,666,497cm
-1;
1HNMR(400MHz,d
6-DMSO):δ=10.01(brs,8H,NH
3OH)ppm;
13C?NMR(400MHz,d
6-DMSO):δ=135.2ppm;MS(ESI):m/z(%):169.1[M]
-。
Embodiment 2
With embodiment 1, the difference is that step 2) in to pass into the speed of chlorine slow, obtain 81g dichloroglyoxime, productive rate is 45%.
Embodiment 3
With embodiment 1, the difference is that step 2) in pass into chlorine reaction times be 2h, obtain 95g dichloroglyoxime, productive rate is 53%.
Embodiment 4
With embodiment 1, the difference is that step 2) in pass into chlorine reaction times be 3h, obtain 103g dichloroglyoxime, productive rate is 57%.
Embodiment 5
With embodiment 1, the difference is that the solvent of azido reaction in step 3) is DMF, obtain 64g TKX-50, productive rate is 85%.
Embodiment 6
With embodiment 1, the difference is that the solvent of azido reaction in step 3) is dimethyl sulfoxide (DMSO), obtain 61g TKX-50, productive rate is 81%.
Embodiment 7
With embodiment 1, the difference is that the solvent of azido reaction in step 3) is tetrahydrofuran (THF), obtain 60g TKX-50, productive rate is 80%.
Embodiment 8
With embodiment 1, the difference is that the solvent of azido reaction in step 3) is acetone, obtain 62gTKX-50, productive rate is 82%.
Embodiment 9
With embodiment 1, the difference is that in step 3), ether consumption is 200mL:5g with the ratio of dichloroglyoxime, obtain 68g TKX-50, productive rate is 90%.
Embodiment 10
With embodiment 1, the difference is that in step 3), ether consumption is 300mL:5g with the ratio of dichloroglyoxime, obtain 68g TKX-50, productive rate is 90%.
Embodiment 11
With embodiment 1, the difference is that in step 3), ether consumption is 300mL:5g with the ratio of dichloroglyoxime, obtain 68g TKX-50, productive rate is 90%.
Embodiment 12
With embodiment 1, the difference is that in step 3), ether consumption is 400mL:5g with the ratio of dichloroglyoxime, obtain 68g TKX-50, productive rate is 90%.
Embodiment 13
With embodiment 1, the difference is that the reaction in the reaction times that passes into HCl in step 3) is 3h, obtain 63g TKX-50, productive rate is 84%.
Embodiment 14
With embodiment 1, the difference is that the reaction in the reaction times that passes into HCl in step 3) is 3h, obtain 66g TKX-50, productive rate is 87%.
Embodiment 14
With embodiment 1, the difference is that the time that in step 3), sodium salt reacts with oxammonium hydrochloride, obtain 67g TKX-50, productive rate is 89%.
Claims (8)
1. one kind 5,5'-bistetrazole-1, the synthetic method of 1'-dioxy hydroxylammonium salt (TKX-50), concrete route is as follows:
It is characterized in that concrete steps are:
1) under room temperature, NaOH is soluble in water, in this solution ice salt bath, be cooled to 0 ℃, then slowly add wherein oxammonium hydrochloride, finish, then add 40% glyoxal water solution, control temperature lower than 10 ℃, after reaction 15min, in room temperature reaction, spend the night.Filter, a small amount of frozen water washing, dries to obtain glyoxime, productive rate 62% naturally.
2), under room temperature, the glyoxime that step 1) is obtained is added to the water, and stirs, then add concentrated hydrochloric acid, treat that raw material almost all dissolves, and bathes cooling mixed liquid to 0 ℃ with cryosel, pass into chlorine, in process, dirty solution becomes clarification gradually, continues to pass into chlorine, separate out gradually white precipitate, at this time continue ventilatory response for some time, filter, a small amount of frozen water washing, naturally dry to obtain dichloroglyoxime, productive rate 45%～60%.
3) under room temperature, by step 2) dichloroglyoxime that obtains is dissolved in certain solvent.Be cooled to 0 ℃, add sodiumazide, keep temperature to be no more than 2 ℃, finish again and stir for some time.Mixture is transferred in a there-necked flask that ether is housed afterwards, cools to 0 ℃, passes into HCl(temperature control lower than 20 ℃) after for some time, sealed reaction bottle, ambient temperature overnight reaction.Wave ether and most of hydrogen chloride gas, add wherein water, then with the NaOH aqueous solution, regulate pH ≈ 8,5,5'-bistetrazole-1,1'-dihydroxyl sodium salt is separated out, and mixed solution reflux is cooling after 1 hour, filters, with frozen water, wash, until filtrate pH ≈ 7 isolates 5,5 '-bistetrazole-1,1 '-dihydroxyl sodium salt, sodium salt is dissolved in a small amount of hot water, to it, adds oxammonium hydrochloride saturated aqueous solution, continues to stir for some time, be cooled to room temperature, filter, a small amount of frozen water washing obtains TKX-50, productive rate 80%～90%.
2. according to claim 1 a kind of 5,5'-bistetrazole-1, the synthetic method of 1'-dioxy hydroxylammonium salt (TKX-50), is characterized in that: step 2) adopt water to make solvent, aftertreatment only need be filtered washing and be obtained dichloroglyoxime.
3. according to claim 1 a kind of 5,5'-bistetrazole-1, the synthetic method of 1'-dioxy hydroxylammonium salt (TKX-50), is characterized in that: step 2) in pass into chlorine speed for slowly or rapidly.
4. according to claim 1 a kind of 5,5'-bistetrazole-1, the synthetic method of 1'-dioxy hydroxylammonium salt (TKX-50), is characterized in that: step 2) in pass into chlorine reaction times be 2h～4h.
5. according to claim 1 a kind of 5,5'-bistetrazole-1, the synthetic method of 1'-dioxy hydroxylammonium salt (TKX-50), it is characterized in that: in step 3), the solvent of azido reaction is DMF, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetone or N-Methyl pyrrolidone.
6. according to claim 1 a kind of 5,5'-bistetrazole-1, the synthetic method of 1'-dioxy hydroxylammonium salt (TKX-50), is characterized in that: in step 3), ether consumption is 170～400mL:5g with the ratio of dichloroglyoxime.
7. according to claim 1 a kind of 5,5'-bistetrazole-1, the synthetic method of 1'-dioxy hydroxylammonium salt (TKX-50), is characterized in that: the reaction times that passes into HCl in step 3) is 3h～5h.
8. according to claim 1 a kind of 5,5'-bistetrazole-1, the synthetic method of 1'-dioxy hydroxylammonium salt (TKX-50), is characterized in that: the time that in step 3), sodium salt reacts with oxammonium hydrochloride is 1h～2h.
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Cited By (17)
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| CN104151195A (en) * | 2014-07-23 | 2014-11-19 | 北京理工大学 | Synthesis method of diazidoglyoxime by one-pot process |
| CN104356080A (en) * | 2014-11-28 | 2015-02-18 | 西安近代化学研究所 | Method for preparing dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate |
| CN104829548A (en) * | 2015-03-30 | 2015-08-12 | 北京理工大学 | 5, 5 '-bistetrazole-1, 1'-dioxo hydroxylammonium salt synthetic method |
| CN105732532A (en) * | 2014-12-10 | 2016-07-06 | 湖北航天化学技术研究所 | Synthesizing method of 5, 5'-bistetrazole-1,1'-dioxygen metal salt |
| CN106045929A (en) * | 2016-06-14 | 2016-10-26 | 太原理工大学 | Synthesis process of bistetrazole hydroxyl bismuth salt |
| CN106083504A (en) * | 2016-06-01 | 2016-11-09 | 中国工程物理研究院化工材料研究所 | A kind of based on energetic compound [Mn (BTO) (H2o)2]nefficient catalytic decompose ammonium perchlorate method |
| CN108409512A (en) * | 2018-05-04 | 2018-08-17 | 北京理工大学 | A kind of method of nitroguanidine cladding TKX-50 |
| CN108456125A (en) * | 2018-03-09 | 2018-08-28 | 北京理工大学 | A kind of CL-20 and CBNT cocrystallized explosives and preparation method thereof |
| CN108558587A (en) * | 2018-05-04 | 2018-09-21 | 北京理工大学 | A kind of method that nitroguanidine fluidization spray is granulated cladding TKX-50 |
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| US11434209B2 (en) | 2018-08-21 | 2022-09-06 | Agency For Defense Development | Method for synthesis of TKX-50 using insensitive intermediate |
| KR102331642B1 (en) | 2018-08-21 | 2021-11-30 | 국방과학연구소 | Synthesis of tkx-50 using thp-dag |
| KR20200021909A (en) * | 2018-08-21 | 2020-03-02 | 국방과학연구소 | Synthesis of tkx-50 using insensitive intermediate |
| KR20200021710A (en) * | 2018-08-21 | 2020-03-02 | 국방과학연구소 | Synthesis of tkx-50 using insensitive intermediate |
| WO2020040448A1 (en) * | 2018-08-21 | 2020-02-27 | 국방과학연구소 | Method for synthesis of tkx-50 using insensitive intermediate |
| CN109824616A (en) * | 2019-04-04 | 2019-05-31 | 中国工程物理研究院化工材料研究所 | A kind of synthetic method of 5,5 '-bistetrazoles -1,1 '-dioxy disodium salt |
| CN109824616B (en) * | 2019-04-04 | 2020-06-16 | 中国工程物理研究院化工材料研究所 | Synthetic method of 5,5 '-bitetrazole-1, 1' -dioxy disodium salt |
| KR102102357B1 (en) * | 2019-10-04 | 2020-04-20 | 국방과학연구소 | Synthesis of tkx-50 using protected diazidoglyoxime |
| CN113785836A (en) * | 2021-08-26 | 2021-12-14 | 西安康诺化工有限公司 | Chitosan bactericide and preparation method thereof |
| KR102459368B1 (en) * | 2022-06-07 | 2022-10-26 | 국방과학연구소 | Method for preparing dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate, thomas klapotke explosive - 50 |
| WO2023239104A1 (en) * | 2022-06-07 | 2023-12-14 | 국방과학연구소 | Method for preparing dihydroxyammonium 5,5'-bistetrazole-1,1'-diolate |
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