CN104151195B - A kind of one-pot synthesis method of diazido glyoxime - Google Patents
A kind of one-pot synthesis method of diazido glyoxime Download PDFInfo
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- CN104151195B CN104151195B CN201410354347.6A CN201410354347A CN104151195B CN 104151195 B CN104151195 B CN 104151195B CN 201410354347 A CN201410354347 A CN 201410354347A CN 104151195 B CN104151195 B CN 104151195B
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Abstract
The present invention relates to the one-pot synthesis method of a kind of diazido glyoxime, the invention belongs to organic chemical synthesis field.With glyoxime, N N-halosuccinimides and Hydrazoic acid,sodium salt as raw material, diazido glyoxime is synthesized through " one kettle way ".Diazido glyoxime be synthesis TKX 50 a kind of important intermediate, to its further investigation be conducive to improve TKX 50 yield, reduce synthesis cost, reduce environmental pollution, improve produce intrinsic safety significant.The present invention uses " one kettle way " to prepare, and method is simple, pollutes low, and safety is good, and total yield reaches 80～90%, and easy to implement, is suitable for industrialized production.
Description
Technical field
The present invention relates to the one-pot synthesis method of a kind of diazido glyoxime, belong to organic synthesis technology neck
Territory.
Background technology
1,1 '-dihydroxy-5,5 '-bistetrazole dihydroxy amine salt (TKX-50) be 2012 years by Univ Munich Germany
The densification compound of a kind of novel high-energy that synthesizes of Niko Fischer et al., its density is 1.918g/cm3,
Theoretical explosion velocity is up to 9698m/s, and has higher nitrogen content, the positive enthalpy of formation, to heat and mechanism insensitiveness,
And without halogen, be a kind of high-energy, low sensitivity, economy, green, containing that combination property is splendid can chemical combination
Thing.In composite explosives and propellant field, there is fabulous application prospect.
Diazido glyoxime is the crucial synthetic intermediate of TKX-50, and original technique of its synthesis is to pass through second
Dioxime through with the dichloroglyoxime (DCG) of chlorine reaction after, DCG carries out Cl-N with Hydrazoic acid,sodium salt again3
Replace and obtain, react total yield only 40%.But DCG is highly unstable when solid-state, is rubbed or vibrated
It is likely to occur blast, is not suitable for long term storage and transport, and chlorine belongs to high toxic material.Reaction so
Dichloroglyoxime appearance in TKX-50 synthetic route is unfavorable for the industrialized production of TKX-50.
Summary of the invention
The invention aims to solve the existing technology total yield preparing diazido glyoxime low；Middle
Product DCG poor stability, and then the problem that there is potential safety hazard, it is provided that the one of a kind of diazido glyoxime
Pot method synthetic method.
It is an object of the invention to be achieved through the following technical solutions.
The one-pot synthesis method of a kind of diazido glyoxime, specifically comprises the following steps that
Under step one, room temperature, glyoxime is dissolved in organic solvent, solution is cooled to less than 10 DEG C,
To glyoxime solution；
Step 2, in the glyoxime solution of step one gained, it is dividedly in some parts N-N-halosuccinimides, obtains
DCG；Be warming up to room temperature, at room temperature continue reaction until reaction completely, then reduce temperature to 10 DEG C with
Under；Add Azide reagent, keep low-temp reaction；Diazido glyoxime is obtained after reaction completely；Second
Dioxime, N-N-halosuccinimides are 1.0:2.0～3.0:1.5～3.0 with the mol ratio of Azide reagent；
Step 3, the solution of the diazido glyoxime of step 2 gained is poured into water, filters after standing,
Natural drying, i.e. obtains diazido glyoxime.
Organic solvent described in step one is N,N-dimethylformamide (DMF) or dimethyl sulfoxide (DMSO).
Azide reagent described described in step 2 is the compound that can participate in azide reaction；Including Azide
Sodium, potassium azide, lead azide, silver azide, ammonium azide；
N-N-halosuccinimides described described in step 2 is N-chlorosuccinimide or N-bromo fourth two
Acid imide；
Be dividedly in some parts described in step 2 N-N-halosuccinimides and add Hydrazoic acid,sodium salt temperature 10 DEG C with
Under, preferred temperature is 0～5 DEG C.
Reaction temperature after addition N-N-halosuccinimides described in step 2 is preferably at 15～40 DEG C, preferably warm
Degree is 20～30 DEG C；Reaction temperature after addition Hydrazoic acid,sodium salt is preferably at-10～10 DEG C, and preferable temperature is 0～5 DEG C.
Response time after adding N-N-halosuccinimides described in step 2 is preferably controlled in 1～5 hour；Add
Entering the response time after Hydrazoic acid,sodium salt is preferably controlled in 1～2 hour.
Reaction equation 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, goes out from glyoxime simple and easy to get
Send out, use " one kettle way " to be prepared for the key intermediate of high-energy insensitive explosive TKX-50.With original method phase
Ratio, decreases the step preparing dichloroglyoxime, thus avoids chlorine in dichloroglyoxime preparation process
Use for the pollution of environment, eliminate simultaneously dichloroglyoxime store and transport insecurity for
The danger that TKX-50 industrialized production is brought.Estimable, this synthetic method is simple, safety is high,
Polluting little, it is easy to industrialized production, yield is high, reaches 80～90%, improves about 40% than original method.
Detailed description of the invention
Further illustrate the technical scheme of invention below with specific embodiment, but the present invention be not limited to
Lower embodiment.
Embodiment 1
Under room temperature, 1.00g (11.4mmol) glyoxime is dissolved in 25mL DMF, solution is cooled to 0 DEG C
Hereinafter, it is dividedly in some parts N-chlorosuccinimide 3.00g (22.8mmol), is slowly increased at 10 DEG C react 5h.
Again solution is cooled to 0 DEG C, adds Hydrazoic acid,sodium salt 1.48g (22.8mmol), at 0 DEG C, react 1h, reaction knot
Reactant liquor is poured in 200mL cold water after bundle, filter after standing 30min, natural drying.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
Less than 0 DEG C, it is dividedly in some parts N-chlorosuccinimide 15.00g (115.0mmol), rises to 20 DEG C of reaction 3h.
Again solution being cooled to 0 DEG C, add Hydrazoic acid,sodium salt 11.1g (171mmol), react 2h at 0 DEG C, reaction terminates
After reactant liquor is poured in 300mL cold water, stand and filter after 30min, natural drying.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
Less than 0 DEG C, it is dividedly in some parts N-bromo-succinimide 40.58g (228mmol), rises to 20 DEG C of reaction 3h.
Again solution is cooled to 0 DEG C, adds Hydrazoic acid,sodium salt 14.8g (228mmol), at 10 DEG C, react 1h, reaction knot
Reactant liquor is poured in 400mL cold water after bundle, filter after standing 30min, natural drying.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
Less than 0 DEG C, it is dividedly in some parts N-bromo-succinimide 4.06g (22.8mmol), rises to 20 DEG C of reaction 3h.Again
Solution being cooled to 0 DEG C, adds lead azide 2.22g (34.2mmol), react 1h at 20 DEG C, reaction terminates
After reactant liquor is poured in 200mL cold water, stand and filter after 30min, natural drying.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 0 DEG C
Hereinafter, it is dividedly in some parts N-chlorosuccinimide 9.00g (68.4mmol), rises to 20 DEG C of reaction 3h.Again will
Solution is cooled to 0 DEG C, adds potassium azide 4.44g (68.4mmol), reacts 1h, after reaction terminates at 0 DEG C
Reactant liquor is poured in 200mL cold water, filter after standing 30min, natural drying.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
Less than 0 DEG C, it is dividedly in some parts N-chlorosuccinimide 24.00g (182.4mmol), rises to 20 DEG C of reaction 3h.
Again solution is cooled to 0 DEG C, adds silver azide 17.76g (273.6mmol), at 0 DEG C, react 1h, reaction
Reactant liquor is poured in 200mL cold water after end, filter after standing 30min, natural drying.Obtain white solid
Body 13.12g, yield 84.5%.
Embodiment 7
Under room temperature, 6.00g (68.4mmol) glyoxime is dissolved in 100mL DMF, solution is cooled to
Less than 0 DEG C, it is dividedly in some parts N-bromo-succinimide 6.87g (34.2mmol), rises to 20 DEG C of reaction 3h.Again
Solution is cooled to 0 DEG C, adds ammonium azide 13.32g (205.2mmol), at 0 DEG C, react 1h, reaction knot
Reactant liquor is poured in 200mL cold water after bundle, filter after standing 30min, natural drying.Obtain white solid
10.14g, yield 87.1%.
Claims (8)
1. the one-pot synthesis method of a diazido glyoxime, it is characterised in that: specifically comprise the following steps that
Under step one, room temperature, glyoxime is dissolved in organic solvent, solution is cooled to less than 10 DEG C,
To glyoxime solution；
Step 2, in the glyoxime solution of step one gained, it is dividedly in some parts N-chlorosuccinimide, obtains
Dichloroglyoxime；It is warming up to room temperature, at room temperature continues reaction until reaction completely, then reduces temperature extremely
Less than 10 DEG C；Add Azide reagent, keep low-temp reaction；Diazido second two is obtained after reaction completely
Oxime；Glyoxime, N-chlorosuccinimide are 1.0:2.0～3.0:1.5～3.0 with the mol ratio of Azide reagent；
Step 3, the solution of the diazido glyoxime of step 2 gained is poured into water, filters after standing,
Natural drying, i.e. obtains diazido glyoxime.
The one-pot synthesis method of a kind of diazido glyoxime the most as claimed in claim 1, its feature exists
In: organic solvent described in step one is N,N-dimethylformamide or dimethyl sulfoxide.
The one-pot synthesis method of a kind of diazido glyoxime the most as claimed in claim 1, its feature exists
In: the Azide reagent described in step 2 is the compound that can participate in azide reaction；For Hydrazoic acid,sodium salt, fold
Potassium nitride, lead azide, silver azide, ammonium azide.
The one-pot synthesis method of a kind of diazido glyoxime the most as claimed in claim 1, its feature exists
In: be dividedly in some parts described in step 2 N-chlorosuccinimide and add Azide reagent temperature 10 DEG C with
Under.
5. the one-pot synthesis method of a kind of diazido glyoxime as described in claim 1 or 4, it is special
Levy and be: the temperature being dividedly in some parts N-chlorosuccinimide and addition Azide reagent described in step 2 is
0～5 DEG C.
The one-pot synthesis method of a kind of diazido glyoxime the most as claimed in claim 1, its feature exists
In: add the reaction temperature after Azide reagent described in step 2 at-10～10 DEG C.
7. the one-pot synthesis method of a kind of diazido glyoxime as described in claim 1 or 6, it is special
Levy and be: adding the reaction temperature after Azide reagent described in step 2 is 0～5 DEG C.
The one-pot synthesis method of a kind of diazido glyoxime the most as claimed in claim 1, its feature exists
In: the response time after adding N-chlorosuccinimide described in step 2 controlled at 1～5 hour；Add folded
Response time after sodium nitride controlled at 1～2 hour.
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| 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 |
| 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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| 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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| 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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| 二氯乙二肟的合成及其分析;侯党社 等;《西北大学学报（自然科学版）》;20030228;第33卷(第1期);第55-56、64页 * |
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