CN101311163A - Preparation method of diazido alkane - Google Patents
Preparation method of diazido alkane Download PDFInfo
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- CN101311163A CN101311163A CNA2007100995005A CN200710099500A CN101311163A CN 101311163 A CN101311163 A CN 101311163A CN A2007100995005 A CNA2007100995005 A CN A2007100995005A CN 200710099500 A CN200710099500 A CN 200710099500A CN 101311163 A CN101311163 A CN 101311163A
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- nitrine
- diazido
- alkane
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- octane
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Abstract
The invention relates to a preparation process for diazido alkane, which takes 1, 8-octylene glycol as the raw material and adopts the technologies such as recrystallization, column chromatographic separation, and the like, to find an economical and practical method for preparing 1, 8-diazido octane and to characterize the structure thereof. The method takes 8-octylene glycol as the raw material to synthesize 1, 8- diazido octane for the first time by two steps of esterification and azide; the 1, 8- diazido octane is initially proved to have high application value in energetic additive and organic synthesis.
Description
Technical field:
The present invention relates to 1,8-two nitrine octane compounds and preparation method thereof.Characteristics such as this compounds has good stability, and it is high to generate heat, and the combustion heat is big, and the combustion number is fast have very high using value aspect the softening agent of gas-evolution agent and solid propellant.
Background technology:
The history in existing more than 100 year so far of synthetic and research of triazo-compound, chemists have carried out a large amount of research to the aspects such as structure, performance and application of triazo-compound, have synthesized the triazo-compound that using value is much arranged very much.Since the seventies, the external especially U.S. has carried out research extensively and profoundly to the nitrine organic compound as the application of energetic material, the result shows, in energetic materials such as propelling charge, propelling agent and high explosive, use binding agent, softening agent, oxygenant and other additive that contains azido-, can not only improve energy level (each azido-can provide the Enthalpies of Formation of 356kJ/mol), can also give its many other excellent performances: improve the nitrogen content of system and do not influence its ratio of carbon-hydrogen, the free air delivery the during burning of increase system; Improve the combustionvelocity of propelling charge or propelling agent, and do not improve flame temperature; Reduce the target signature that various propulsion system produces, thereby improve the stealth of weapon.Therefore, the synthetic of the nitrine compounds that carries out in the energetic material field at present such as tackiness agent, softening agent and other additive is regarded as one of the research emphasis in this field with applied research.
Now the synthetic triazo-compound generally is divided into it nitrine polyethers, nitrine nitramine, nitrine nitro-compound, nitrine fluorine dinitro compound and nitrine alkane, nitrine ether and nitrine ester.Wherein, great majority in the nitrine hydride compounds and HMX, RDX are compatible, and good plasticising performance is arranged, and can replace inert plasticizer in the solid propellant prescription, have very wide practical value.As the azido derivant Heat stability is good of tetramethylolmethane, it is high to generate heat, and the combustion heat is big, and the burning number is fast, can be used as the softening agent of gas-evolution agent and solid propellant.At present, synthetic two nitrine alkane mainly contain 1,6-two nitrine hexanes, and for 1,8-two nitrine octanes are not seen relevant its report synthetic and performance at present as yet.
Summary of the invention:
The present invention relates to the preparation of a method of diazido alkane, and may extend into the preparation of this compounds.With 1, the 8-ethohexadiol is a raw material, by the method for easy economy, and by two reactions, and technology such as recrystallization, the separation of post layer, prepared 1, the pure product of 8-two nitrine octanes; With 1, the 8-ethohexadiol is a raw material, by esterification, azide, prepares 1 first, and 8-two nitrine octanes determine that tentatively these two nitrine alkane have good plasticising performance, are expected to have important use value aspect energetic material additive and the organic synthesis.
The method of synthetic nitrine mainly contains: produced by halogenide; Produce by pure and mild epoxy compounds; Produce by the compound that contains azido-; Produce etc. by nitrogenous compound.The method of the used method of the present invention for producing by pure and mild oxygenatedchemicals, this method also has application in the literature, but with azide reaction in adopt high temperature and absolute anhydrous condition to be prepared, separate, caused the raising of synthetic difficulty row property.And the present invention has found a most economical and gentle reaction scheme by repeatedly experiment repeatedly, for this product being applied to contain the precursor of energy additive and organic reaction.Available alkali metal azide has Lithium Azide, potassium azide and Sodium Azide, wherein preferred sodiumazide.The separation of product is carried out column chromatography for separation by silicagel column, thereby obtains the nitrine product.
Embodiment:
The specific embodiment of the invention is not limited to following embodiment.Embodiments of the invention can make the professional and technical personnel more fully understand the present invention.
Embodiment:
The preparation and the sign of 1 ethohexadiol, two p-toluenesulfonic esters
Under cryosel was bathed and stirred, methylene dichloride (20ml) solution that drips 12.6g (0.066mol) Tosyl chloride was in triethylamine (7ml) solution of 3.65g (0.025mol) ethohexadiol, and the reinforced time is 1 hour, and the adularescent solid is separated out around here.Reaction mixture reacted 4 hours under ice bath earlier, removed ice bath, reacted under room temperature 12 hours again, finished through the TLC detection reaction.This mixture is poured in 500 ml waters, cooling, the process separatory is told the organic layer of bottom, washes 3 times, uses anhydrous sodium sulfate drying, separatory, methylene dichloride is reclaimed in air distillation then, obtains light yellow oily liquid.Obtain a white solid with the anhydrous methanol recrystallization.Productive rate 73.5%.
Product analytical data is as follows:
IR(cm
-1)：1380cm
-1(-CH
3)，2959，2933cm-1(-CH
2)，1598，1455，1400cm-1(-C
6H
4)；
1H NMR (CDCl
3): δ (ppm) 7.800 (12H, four hydrogen of para-orientation benzene); 4.004 (4H, two are connected on the sulfonic group-CH
2-); 2.459 (the CH on the 6H, two phenyl ring
3); 1.614 (4H, two-CH
2-); 1.268 (4H, two-CH
2-); 1.186 (4H, two-CH
2-).Know by infrared and nmr analysis and to be target product: ethohexadiol ester p-toluenesulfonic esters.
21, the preparation and the sign of 8-two nitrine octanes
4g ethohexadiol ester p-toluenesulfonic esters is dissolved among the 20mlDMF, be heated to 60 ℃ after, stir slowly to drip down and be dissolved with 1.4gNaN
3The 3ml deionized water solution, react on 80 ℃ and reacted 72 hours down, TLC follows the tracks of reaction, after the concentration of the completely dissolve of raw material point and each product point does not change basically, reaction solution is poured in the water, the oily drop is collected in cooling, with distilled water wash for several times, the absolute ether extraction, collect extraction liquid, steaming obtains yellow oily liquid after falling solvent.Carry out column chromatography (toluene/sherwood oil, volume ratio 2.5: 1) with silicagel column, obtain yellow liquid, be product, productive rate 45.3%.
Product analytical data is as follows:
IR:2949cm-1,2872cm-1 place are the stretching vibration of C-H, and 2131cm-1,2030cm-1 are the stretching vibration of N=N, and 1312cm-1 is the stretching vibration of C-N.
1H NMR (CDCl
3): δ (ppm) 3.281 (4H, triplet, CH
2N); 1.626 (4H, multiplet ,-CH
2CH
2N); 1.307 (8H, singlet ,-CH
2CH
2CH
2N and-CH
2CH
2CH
2CH
2N).
13C-NMR (CDCl
3): the four carbon atom signal at δ (ppm) 51.25,28.82,28.63,26.44 places illustrates that four types carbon atom exists.
Through infrared and nmr analysis product is target product.
Claims (2)
1 one kinds of alkane that contain two nitrine, its structural formula are N
3CH
2(CH
2)
6CH
2N
3
The preparation method of 2 one kinds of described compounds of claim 1 is characterized in that this method comprises following each step:
1) about-5 ℃, 1,8-ethohexadiol and Tosyl chloride react, and obtain two p-toluenesulfonic esters of this compound.
2) ethohexadiol two p-toluenesulfonic esters and NaN
3Under condition of different temperatures, react, follow the tracks of reaction, find optimum reaction condition, carry out column chromatography for separation, promptly get 1,8-two nitrine octanes with silicagel column by TLC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100995005A CN101311163A (en) | 2007-05-23 | 2007-05-23 | Preparation method of diazido alkane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100995005A CN101311163A (en) | 2007-05-23 | 2007-05-23 | Preparation method of diazido alkane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101311163A true CN101311163A (en) | 2008-11-26 |
Family
ID=40100013
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100995005A Pending CN101311163A (en) | 2007-05-23 | 2007-05-23 | Preparation method of diazido alkane |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603560A (en) * | 2012-01-16 | 2012-07-25 | 新乡学院 | Tetra-azido alkane and preparation method thereof |
| CN103012194A (en) * | 2012-11-16 | 2013-04-03 | 南京理工大学 | Nitrine ester compound and synthesis method thereof |
| CN103613512A (en) * | 2013-11-04 | 2014-03-05 | 西安近代化学研究所 | 3-nitro-5-azido-3-aza amyl alcohol nitric acid ester and preparation method |
| CN104262194A (en) * | 2014-09-11 | 2015-01-07 | 黎明化工研究设计院有限责任公司 | Method of preparing 1,5-diazido-3-nitryl azapentane |
-
2007
- 2007-05-23 CN CNA2007100995005A patent/CN101311163A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102603560A (en) * | 2012-01-16 | 2012-07-25 | 新乡学院 | Tetra-azido alkane and preparation method thereof |
| CN103012194A (en) * | 2012-11-16 | 2013-04-03 | 南京理工大学 | Nitrine ester compound and synthesis method thereof |
| CN103613512A (en) * | 2013-11-04 | 2014-03-05 | 西安近代化学研究所 | 3-nitro-5-azido-3-aza amyl alcohol nitric acid ester and preparation method |
| CN103613512B (en) * | 2013-11-04 | 2015-08-12 | 西安近代化学研究所 | 3-nitro-5-azido--3-aza amyl alcohol nitric acid ester and preparation method thereof |
| CN104262194A (en) * | 2014-09-11 | 2015-01-07 | 黎明化工研究设计院有限责任公司 | Method of preparing 1,5-diazido-3-nitryl azapentane |
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Open date: 20081126 |