CN104151195A - Synthesis method of diazidoglyoxime by one-pot process - Google Patents
Synthesis method of diazidoglyoxime by one-pot process Download PDFInfo
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- CN104151195A CN104151195A CN201410354347.6A CN201410354347A CN104151195A CN 104151195 A CN104151195 A CN 104151195A CN 201410354347 A CN201410354347 A CN 201410354347A CN 104151195 A CN104151195 A CN 104151195A
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Abstract
The invention relates to a synthesis method of diazidoglyoxime by a one-pot process, belonging to the field of organic chemical synthesis. Glyoxime, N-halogenated succimide and sodium azide used as raw materials react by a one-pot process to synthesize the diazidoglyoxime. The diazidoglyoxime is an important intermediate for synthesizing TKX-50, so the deep research into the diazidoglyoxime is beneficial to enhancing the yield of the TKX-50, lowering the synthesis cost and reducing the environmental pollution, and has important meanings for enhancing the intrinsic safety of production. By adopting the one-pot process, the method is simple, has the advantages of low pollution, high safety and high total yield (80-90%), and is easy to implement and suitable for industrial production.
Description
Technical field
The one-pot synthesis method that the present invention relates to a kind of diazido glyoxime, belongs to technical field of organic synthesis.
Background technology
1,1 '-dihydroxyl-5,5 '-bistetrazole dihydroxy amine salt (TKX-50) is a kind of novel high-energy metric density compound that the people such as Niko Fischer of 2012 Nian You Univ Munich Germanies synthesize, its density is 1.918g/cm
3, theoretical quick-fried scooter 9698m/s, and there is higher nitrogen content, positive Enthalpies of Formation, to heat and mechanical effect insensitiveness, and not halogen-containing, be a kind of high-energy, low sensitivity, economy, green, the energy-containing compound that over-all properties is splendid.In pyrotechnic composition and propelling agent field, there is fabulous application prospect.
Diazido glyoxime is the crucial synthetic intermediate of TKX-50, its synthetic original technique be by glyoxime after the dichloroglyoxime with chlorine reaction system (DCG), DCG carries out Cl-N with sodiumazide again
3replace to obtain reaction total yield only 40%.But DCG is very unstable when solid-state, is rubbed or vibrates likely and blast, and be not suitable for standing storage and transportation, and chlorine belongs to high toxic material.So the appearance of reaction dichloroglyoxime in TKX-50 synthetic route is unfavorable for the suitability for industrialized production of TKX-50.
Summary of the invention
The object of the invention is in order to solve the existing technology total yield of preparing diazido glyoxime low; Intermediate product DCG poor stability, and then there is the problem of potential safety hazard, a kind of one-pot synthesis method of diazido glyoxime is provided.
The object of the invention is to be achieved through the following technical solutions.
An one-pot synthesis method for diazido glyoxime, concrete steps are as follows:
Under step 1, room temperature, glyoxime is dissolved in organic solvent, solution is cooled to below 10 ℃, obtain glyoxime solution;
Step 2, in the glyoxime solution of step 1 gained, add N-halogenated succinimide imide in batches, obtain DCG; Be warming up to room temperature, at room temperature continue reaction until react completely, then reduce below temperature to 10 ℃; Add again azide reagent, keep low-temp reaction; After reacting completely, obtain diazido glyoxime; The mol ratio of glyoxime, N-halogenated succinimide imide and azide reagent is 1.0:2.0～3.0:1.5～3.0;
Step 3, the solution of the diazido glyoxime of step 2 gained is poured into water, standing rear filtration, seasoning, obtains diazido glyoxime.
Described in step 1, organic solvent is DMF (DMF) or methyl-sulphoxide (DMSO).
Azide reagent described described in step 2 is for participating in the compound of azide reaction; Comprise sodiumazide, potassium azide, lead azoimide, silver azide, ammonium azide;
N-halogenated succinimide imide described described in step 2 is N-chlorosuccinimide or N-bromo-succinimide;
Described in step 2, add N-halogenated succinimide imide in batches and add the temperature of sodiumazide below 10 ℃, preferred temperature is 0～5 ℃.
Described in step 2, add the temperature of reaction after N-halogenated succinimide imide to be preferably in 15～40 ℃, preferably temperature is 20～30 ℃; Add the temperature of reaction after sodiumazide to be preferably in-10～10 ℃, preferably temperature is 0～5 ℃.
Described in step 2, add the reaction times after N-halogenated succinimide imide to be preferably controlled at 1～5 hour; Add the reaction times after sodiumazide to be preferably controlled at 1～2 hour.
Reaction formula is as follows:
Wherein, the x in formula is Cl or Br
Beneficial effect
The one-pot synthesis method of a kind of diazido glyoxime of the present invention, from glyoxime simple and easy to get, adopts " one kettle way " to prepare the key intermediate of high-energy insensitive explosive TKX-50.Compare with original method, reduced the step of preparing dichloroglyoxime, thereby avoided the use of chlorine in dichloroglyoxime preparation process for the pollution of environment, got rid of the danger that dichloroglyoxime stores and the insecurity of transportation is brought for TKX-50 suitability for industrialized production simultaneously.Estimable, this synthetic method is simple, safe, it is little to pollute, and is easy to suitability for industrialized production, and yield is high, reaches 80～90%, than original method, has improved 40% left and right.
Embodiment
With specific embodiment, further illustrate below the technical scheme of invention, but the present invention is not limited to following examples.
Embodiment 1
Under room temperature, 1.00g (11.4mmol) glyoxime is dissolved in 25mL DMF, solution is cooled to below 0 ℃, add N-chlorosuccinimide 3.00g (22.8mmol) in batches, slowly rise at 10 ℃ and react 5h.Solution is cooled to 0 ℃ again, adds sodiumazide 1.48g (22.8mmol), react 1h at 0 ℃, after reaction finishes, reaction solution is poured in 200mL cold water, after standing 30min, filter seasoning.Obtain white solid 1.56g, yield 80.5%.IR(KBr)，υ(cm
-1):3222,2176,2123,1625,1366,1284,1017。
Embodiment 2
Under room temperature, 5.00g (57.0mmol) glyoxime is dissolved in 100mL DMF, solution is cooled to below 0 ℃, add N-chlorosuccinimide 15.00g (115.0mmol) in batches, rise to 20 ℃ of reaction 3h.Solution is cooled to 0 ℃ again, adds sodiumazide 11.1g (171mmol), react 2h at 0 ℃, after reaction finishes, reaction solution is poured in 300mL cold water, after standing 30min, filter seasoning.Obtain white solid 8.15g, yield 84.1%.
Embodiment 3
Under room temperature, 10.00g (114mmol) glyoxime is dissolved in 150mL DMSO, solution is cooled to below 0 ℃, add N-bromo-succinimide 40.58g (228mmol) in batches, rise to 20 ℃ of reaction 3h.Solution is cooled to 0 ℃ again, adds sodiumazide 14.8g (228mmol), react 1h at 10 ℃, after reaction finishes, reaction solution is poured in 400mL cold water, after standing 30min, filter seasoning.Obtain white solid 16.0g, yield 82.6%.
Embodiment 4
Under room temperature, 1.00g (11.4mmol) glyoxime is dissolved in 25mL DMSO, solution is cooled to below 0 ℃, add N-bromo-succinimide 4.06g (22.8mmol) in batches, rise to 20 ℃ of reaction 3h.Solution is cooled to 0 ℃ again, adds lead azoimide 2.22g (34.2mmol), react 1h at 20 ℃, after reaction finishes, reaction solution is poured in 200mL cold water, after standing 30min, filter seasoning.Obtain white solid 1.55g, yield 80.0%.
Embodiment 5
Under room temperature, 2.00g (22.8mmol) glyoxime is dissolved in 50mL DMF, solution is cooled to below 0 ℃, add N-chlorosuccinimide 9.00g (68.4mmol) in batches, rise to 20 ℃ of reaction 3h.Solution is cooled to 0 ℃ again, adds potassium azide 4.44g (68.4mmol), react 1h at 0 ℃, after reaction finishes, reaction solution is poured in 200mL cold water, after standing 30min, filter seasoning.Obtain white solid 3.34g, yield 86.0%.
Embodiment 6
Under room temperature, 8.00g (91.2mmol) glyoxime is dissolved in 150mL DMF, solution is cooled to below 0 ℃, add N-chlorosuccinimide 24.00g (182.4mmol) in batches, rise to 20 ℃ of reaction 3h.Solution is cooled to 0 ℃ again, adds silver azide 17.76g (273.6mmol), react 1h at 0 ℃, after reaction finishes, reaction solution is poured in 200mL cold water, after standing 30min, filter seasoning.Obtain white solid 13.12g, yield 84.5%.
Embodiment 7
Under room temperature, 6.00g (68.4mmol) glyoxime is dissolved in 100mL DMF, solution is cooled to below 0 ℃, add N-bromo-succinimide 6.87g (34.2mmol) in batches, rise to 20 ℃ of reaction 3h.Solution is cooled to 0 ℃ again, adds ammonium azide 13.32g (205.2mmol), react 1h at 0 ℃, after reaction finishes, reaction solution is poured in 200mL cold water, after standing 30min, filter seasoning.Obtain white solid 10.14g, yield 87.1%.
Claims (7)
1. an one-pot synthesis method for diazido glyoxime, is characterized in that: concrete steps are as follows:
Under step 1, room temperature, glyoxime is dissolved in organic solvent, solution is cooled to below 10 ℃, obtain glyoxime solution;
Step 2, in the glyoxime solution of step 1 gained, add N-halogenated succinimide imide in batches, obtain DCG; Be warming up to room temperature, at room temperature continue reaction until react completely, then reduce below temperature to 10 ℃; Add again azide reagent, keep low-temp reaction; After reacting completely, obtain diazido glyoxime; The mol ratio of glyoxime, N-halogenated succinimide imide and azide reagent is 1.0:2.0～3.0:1.5～3.0;
Step 3, the solution of the diazido glyoxime of step 2 gained is poured into water, standing rear filtration, seasoning, obtains diazido glyoxime.
2. the one-pot synthesis method of a kind of diazido glyoxime as claimed in claim 1, is characterized in that: described in step 1, organic solvent is DMF (DMF) or methyl-sulphoxide (DMSO).
3. the one-pot synthesis method of a kind of diazido glyoxime as claimed in claim 1, is characterized in that: azide reagent described described in step 2 is for participating in the compound of azide reaction; Comprise sodiumazide, potassium azide, lead azoimide, silver azide, ammonium azide.
4. the one-pot synthesis method of a kind of diazido glyoxime as claimed in claim 1, is characterized in that: N-halogenated succinimide imide described described in step 2 is N-chlorosuccinimide or N-bromo-succinimide.
5. the one-pot synthesis method of a kind of diazido glyoxime as claimed in claim 1, is characterized in that: described in step 2, add N-halogenated succinimide imide in batches and add the temperature of sodiumazide below 10 ℃, preferred temperature is 0～5 ℃.
6. the one-pot synthesis method of a kind of diazido glyoxime as claimed in claim 1, is characterized in that: described in step 2, add the temperature of reaction after N-halogenated succinimide imide to be preferably in 15～40 ℃, preferably temperature is 20～30 ℃; Add the temperature of reaction after sodiumazide to be preferably in-10～10 ℃, preferably temperature is 0～5 ℃.
7. the one-pot synthesis method of a kind of diazido glyoxime as claimed in claim 1, is characterized in that: described in step 2, add the reaction times after N-halogenated succinimide imide to be preferably controlled at 1～5 hour; Add the reaction times after sodiumazide to be preferably controlled at 1～2 hour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829549A (en) * | 2015-04-15 | 2015-08-12 | 北京理工大学 | 5,5'-bistetrazole-1,1'-dioxide metal salt and synthesis method thereof |
| CN104829548A (en) * | 2015-03-30 | 2015-08-12 | 北京理工大学 | 5, 5 '-bistetrazole-1, 1'-dioxo hydroxylammonium salt synthetic method |
| CN109232306A (en) * | 2018-11-06 | 2019-01-18 | 航天特种材料及工艺技术研究所 | A kind of preparation method of dichloroglyoxime solid |
| TWI667222B (en) * | 2018-07-31 | 2019-08-01 | 國家中山科學研究院 | Preparation method of low sensitivity and high energy explosive |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524444A (en) * | 2013-09-27 | 2014-01-22 | 北京理工大学 | Synthetic method of 5, 5'-bistetrazole-1, 1'-dioxo hydroxyl ammonium salt (TKX-50) |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524444A (en) * | 2013-09-27 | 2014-01-22 | 北京理工大学 | Synthetic method of 5, 5'-bistetrazole-1, 1'-dioxo hydroxyl ammonium salt (TKX-50) |
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| 侯党社 等: "二氯乙二肟的合成及其分析", 《西北大学学报（自然科学版）》 * |
| 薛永强 等: "《现代有机合成方法与技术》", 31 May 2003 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829548A (en) * | 2015-03-30 | 2015-08-12 | 北京理工大学 | 5, 5 '-bistetrazole-1, 1'-dioxo hydroxylammonium salt synthetic method |
| CN104829549A (en) * | 2015-04-15 | 2015-08-12 | 北京理工大学 | 5,5'-bistetrazole-1,1'-dioxide metal salt and synthesis method thereof |
| TWI667222B (en) * | 2018-07-31 | 2019-08-01 | 國家中山科學研究院 | Preparation method of low sensitivity and high energy explosive |
| CN109232306A (en) * | 2018-11-06 | 2019-01-18 | 航天特种材料及工艺技术研究所 | A kind of preparation method of dichloroglyoxime solid |
| CN109232306B (en) * | 2018-11-06 | 2021-10-29 | 航天特种材料及工艺技术研究所 | Preparation method of dichloroglyoxime solid |
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