CN104262194A - Method of preparing 1,5-diazido-3-nitryl azapentane - Google Patents
Method of preparing 1,5-diazido-3-nitryl azapentane Download PDFInfo
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- CN104262194A CN104262194A CN201410457712.6A CN201410457712A CN104262194A CN 104262194 A CN104262194 A CN 104262194A CN 201410457712 A CN201410457712 A CN 201410457712A CN 104262194 A CN104262194 A CN 104262194A
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Abstract
The invention discloses a method of preparing 1,5-diazido-3-nitryl azapentane. The method comprises the following steps: firstly, nitrifying by virtue of a nitric acid-acetic anhydride system to synthesize an intermediate 1,5-di chlorethyl-3-nitryl azapentane (BCENA) by taking di(2-chlorethyl) amine hydrochloride as a raw material; then, synthesizing the 1,5-diazido-3-nitryl azapentane (DIANP) in an aqueous liquid in the presence of a phase transfer catalyst. According to the method, 1,5- dinitrate yl-3-nitryl azapentane is not used, so that the safety of the preparation process is greatly improved. Besides, the azidation reaction of the method is carried out in the aqueous liquid, and thus, the method is environmentally friendly.
Description
Technical field
The present invention relates to the synthetic method of novel energetic plasticiser 1,5-diazido-3-nitro aza-pentane.
Background technology
1,5-diazido-3-nitro aza-pentane (DIANP) is a kind of novel energetic plasticiser, not only has excellent plasticising performance, also has the advantages such as high energy, fast, the low combustion of high combustion is warm, combustion gas relative molecular mass is little, gas production rate is large.Because its zero pour is low, sensitivity is low, volatility is little, Heat stability is good and good with the consistency of explosive wastewater usual component especially digest cellulose, when using it in high force-low flame temperature gun propellant, quick-fried temperature 200 ~ 400K lower than co-energy level propelling charge, impetus can reach 1300J/g, with RDX with the use of, its impetus, more than 1400J/g, obtains higher burning rate simultaneously.Be used for by DIANP in solid propellant propulsion agent prescription, products of combustion is H mainly
2, N
2and CO
2deng micromolecular compound, combustion gas molecular-weight average and flame temperature can be reduced, and combustion prompt drop can not be caused low.In addition, DIANP can also be used in higher energy liquid propellant, pyrotechnics composition and gas-evolution agent, is a kind of novel energetic plasticiser having application prospect.
US4450110 reported first in 1984 with diethanolamine (DEA) for starting raw material is through the first synthetic intermediate 1 of the steps such as nitric acid nitrating, diacetyl oxide dehydration, 5-dinitric acid ester group-3-nitro aza-pentane (domestic title Ji Na, DINA), then by DINA and NaN
3reaction generates the technological process of DIANP in organic solvent.Wherein intermediate DINA belongs to explosive material, its solid is carried out to the operations such as separation and purification and there is very large danger.
In order to improve preparation security, the synthesis technique of US Patent No. in 1988 4761250 couples of DIANP improves, and proposes to add CH in DEA nitration reaction process
2cl
2solvent shifts the intermediate of generation, no longer carries out solid separation to intermediate DINA, and its purification process also carries out in a solvent, thus reduces the danger of technique, makes the synthesis technique of DIANP safer, more easily realizes suitability for industrialized production.
The synthesis and characterization [J] of the .1 such as Ji Yueping, Lan Ying, Li Purui, 5-diazido-3-nitro aza-pentane. explosive wastewater journal, 2008,31 (3): 44-46. is also with DINA and NaN
3for starting raw material, synthesize DIANP through steps such as azide, extraction, decolouring and vacuum distillings in organic solvent.
The synthesis of prior art DIANP be all with DINA be raw material in organic solvent with NaN
3reaction preparation, has following deficiency:
(1) DINA preparation process is strong heat release nitration reaction, and temperature is wayward, adds process dangerous;
(2) DINA itself is the explosive that energy is higher, is solid and sensitivity is higher, impact sensitivity H under room temperature
50=31cm (2kg drops hammer), uses at it and there is very large potential safety hazard in transfer process;
(3) DINA and NaN
3reaction carry out in the organic solvents such as DMF or DMSO, to add water precipitation product after reaction terminates, organic solvent usage quantity is more greatly and not easily reclaim.
Summary of the invention
The technical problem to be solved in the present invention is to provide the new synthetic method that one prepares 1,5-diazido-3-nitro aza-pentane.The method is avoided using DINA, and substantially increase the security of preparation technology, the method azido reaction carries out in aqueous in addition, environmentally friendly.
For background technology Problems existing, technical scheme of the present invention is: with two (2-chloroethyl) amine hydrochlorate for raw material, first through the nitrated synthetic intermediate 1 of nitric-acetic acid anhydride system, 5-Dichloroethyl-3-nitro aza-pentane (BCENA), under phase-transfer catalyst, in the aqueous solution, azido reaction synthesizes 1,5-diazido-3-nitro aza-pentane (DIANP) again.Concrete synthetic route is as follows:
Synthetic method of the present invention comprises the following steps:
(1) two (2-chloroethyl) amine hydrochlorate carries out nitration reaction, temperature of reaction 60-80 DEG C, reaction times 2-4h in the nitrated system of nitric-acetic acid anhydride, and add water phase-splitting, and organic phase washing, drying, obtain intermediate B CENA.Two (2-chloroethyl) amine hydrochlorates and the better mol ratio of nitric acid are 1: 2-4, and nitric acid and the better mol ratio of diacetyl oxide are 1: 1.05-1.2.This reaction can be carried out in a solvent or under condition of no solvent, and solvent can be the organic solvent such as ethylene dichloride, tetracol phenixin.
(2) BCENA under phase-transfer catalyst effect in the aqueous solution with reaction of sodium azide, temperature of reaction 80-100 DEG C, reaction times 6-10h, reaction terminates, cooling, extraction, washing, dry, obtains DIANP.Phase-transfer catalyst can be quarternary ammonium salt compound, and consumption is that the 0.5%-1.0% of reactant quality is better; BCENA and NaN
3mol ratio is 1: 2-4 better.
Accompanying drawing explanation
The FTIR spectrogram of Fig. 1,1,5-Dichloroethyl-3-nitro aza-pentane
Fig. 2,1,5-Dichloroethyl-3-nitro aza-pentane
1h-NMR spectrogram
The FTIR spectrogram of Fig. 3,1,5-diazido-3-nitro aza-pentane
Fig. 4,1,5-diazido-3-nitro aza-pentane
1h-NMR spectrogram
Embodiment
Following percentage ratio is massfraction.Product purity with liquid chromatography analysis,
Embodiment 1
In 500ml reaction flask, add two (2-chloroethyl) amine hydrochlorate 35.7g, 98% nitric acid 35ml, under agitation drips diacetyl oxide 86ml in reaction solution, after dripping, reacting liquid temperature is risen to 75 DEG C, and continues insulation 3h.Reaction end adds 100ml methylene dichloride and 200ml water, and organic phase is through washing-5%Na
2cO
3washing-rear anhydrous magnesium sulfate drying of washing, obtain pale yellow oily liquid body BCENA24.9g, yield 67% after concentrated organic phase, it is 97.6% that liquid phase chromatography surveys purity.
Embodiment 2
In 500ml reaction flask, add two (2-chloroethyl) amine hydrochlorate 35.7g, tetracol phenixin 50ml, 98% nitric acid 18ml, under agitation in reaction solution, drip diacetyl oxide 45ml, after dripping, reacting liquid temperature is risen to 60 DEG C, and continue insulation 2h.Reaction end adds water and carries out separatory, and organic phase is through washing-5%Na
2cO
3the rear anhydrous magnesium sulfate drying of solution washing-washing, obtain pale yellow oily liquid body BCENA24.5g, yield 66% after concentrated organic phase, it is 97.2% that liquid phase chromatography surveys purity.
Embodiment 3
In 500ml reaction flask, add two (2-chloroethyl) amine hydrochlorate 35.7g, ethylene dichloride 60ml, 98% nitric acid 26ml, under agitation drips diacetyl oxide 70ml in reaction solution, after dripping, reacting liquid temperature is risen to 80 DEG C, and continues insulation 4h.Reaction end adds water separatory, and organic phase is through washing-5%Na
2cO
3the rear anhydrous magnesium sulfate drying of solution washing-washing, obtain pale yellow oily liquid body BCENA25.2g, yield 67% after concentrated organic phase, it is 98.0% that liquid phase chromatography surveys purity.
Embodiment 4
BCENA18.7g is added, water 80ml, NaN respectively in 250ml reaction flask
320g and four butyl bromation amine 0.1g, is then warming up to 95 DEG C and insulated and stirred 8h by reaction solution.Separate out product after being cooled to room temperature after reaction terminates, with a small amount of dichloromethane extraction aqueous phase after separatory, merge organic phase and use anhydrous magnesium sulfate drying after washing 3 times, concentrated organic phase obtains DIANP16g, yield 80%, and it is 97.8% that liquid phase chromatography surveys purity.
Embodiment 5
BCENA25.0g is added respectively, water 150ml, NaN in 250ml reaction flask
330g and four butyl bromation amine 0.2g, is then warming up to 90 DEG C and insulated and stirred 6h by reaction solution.Be cooled to room temperature after reaction terminates and separate out product, with 100ml dichloromethane extraction aqueous phase after separatory, merge organic phase and use anhydrous magnesium sulfate drying after washing 3 times, concentrated organic phase obtains DIANP19.8g, yield 74%, and product purity is 97.5%.
The structural characterization result of 1,5-Dichloroethyl-3-nitro aza-pentane:
IR (KBr): 1087cm
-1for the stretching vibration peak of C-Cl, 1523cm
-1and 1268cm
-1for-NO
2stretching vibration peak, 2968cm
-1that occur is-CH
2-stretching vibration peak.
1H-NMR(CDCl
3)：δ：3.849(t，4H，-CH
2Cl)，δ：4.182(t，4H，-CH
2N-)。
The structural characterization result of 1,5-diazido-3-nitro aza-pentane:
IR (KBr): 2106cm
-1for-N
3stretching vibration peak, 1519cm
-1and 1274cm
-1for-NO
2stretching vibration peak, 2944cm
-1that occur is-CH
2-stretching vibration peak.
1H-NMR(CDCl
3)：δ：3.524(t，4H，-CH
2N
3)，δ：3.800(t，4H，-CH
2N-)。
Ultimate analysis (C
4h
8n
8o
2, %): theoretical value, C24.00, H4.03, N55.98; Measured value C24.33, H3.980, N54.69.
Claims (9)
1. prepare 1 for one kind, the method of 5-diazido-3-nitro aza-pentane, with two (2-chloroethyl) amine hydrochlorate for raw material, first through the nitrated synthetic intermediate 1 of nitric-acetic acid anhydride system, 5-Dichloroethyl-3-nitro aza-pentane (BCENA), under phase-transfer catalyst, in the aqueous solution, azido reaction synthesizes 1,5-diazido-3-nitro aza-pentane (DIANP) again.
2. the method for preparation 1,5-diazido-3-nitro aza-pentane according to claim 1, comprises the following steps:
(1) two (2-chloroethyl) amine hydrochlorate carries out nitration reaction, temperature of reaction 60-80 DEG C, reaction times 2-4h in nitric-acetic acid anhydride system, and add water phase-splitting, and organic phase washing, drying, obtain intermediate B CENA;
(2) BCENA under phase-transfer catalyst effect in the aqueous solution with reaction of sodium azide, temperature of reaction 80-100 DEG C, reaction times 6-10h, reaction terminates, cooling, extraction, washing, dry, obtains DIANP.
3. the method for preparation 1,5-diazido-3-nitro aza-pentane according to claim 2, phase-transfer catalyst is quarternary ammonium salt compound, and consumption is the 0.5%-1.0% of reactant quality.
4. the method for preparation 1,5-diazido-3-nitro aza-pentane according to claim 2, two (2-chloroethyl) amine hydrochlorates and nitric acid mol ratio are 1: 2-4, and nitric acid and diacetyl oxide mol ratio are 1: 1.05-1.2.
5. the method for preparation 1,5-diazido-3-nitro aza-pentane according to claim 2, BCENA and sodiumazide mol ratio are 1: 2-4.
6. the method for preparation 1,5-diazido-3-nitro aza-pentane according to claim 2, step (1) is carried out under condition of no solvent.
7. the method for preparation 1,5-diazido-3-nitro aza-pentane according to claim 2, step (1) is carried out having under solvent condition.
8. the method for preparation 1,5-diazido-3-nitro aza-pentane according to claim 7, described solvent refers to ethylene dichloride or tetracol phenixin.
9., according to the method for preparation 1, the 5-diazido-3-nitro aza-pentane one of claim 2-8 Suo Shu, washing step is: washing-5%Na
2cO
3solution washing-washing.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9823123B2 (en) | 2015-01-30 | 2017-11-21 | Industrial Technology Research Institute | System and method for controlling excess bias of single photon avalanche photo diode |
| CN113563223A (en) * | 2021-07-06 | 2021-10-29 | 南京理工大学 | Method for synthesizing nitrine nitramine by phase transfer catalysis |
| CN114956916A (en) * | 2022-05-23 | 2022-08-30 | 西安近代化学研究所 | Polyazido glycidyl ether compound and preparation method thereof |
| CN115385822A (en) * | 2022-08-02 | 2022-11-25 | 西安近代化学研究所 | Synthesis method of 1,5-diazido-3-nitroazapentane |
| CN115504903A (en) * | 2022-09-22 | 2022-12-23 | 西安近代化学研究所 | Preparation method of 1,5-diazido-3-nitroazapentane |
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| 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 |
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Cited By (7)
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|---|---|---|---|---|
| US9823123B2 (en) | 2015-01-30 | 2017-11-21 | Industrial Technology Research Institute | System and method for controlling excess bias of single photon avalanche photo diode |
| CN113563223A (en) * | 2021-07-06 | 2021-10-29 | 南京理工大学 | Method for synthesizing nitrine nitramine by phase transfer catalysis |
| CN114956916A (en) * | 2022-05-23 | 2022-08-30 | 西安近代化学研究所 | Polyazido glycidyl ether compound and preparation method thereof |
| CN115385822A (en) * | 2022-08-02 | 2022-11-25 | 西安近代化学研究所 | Synthesis method of 1,5-diazido-3-nitroazapentane |
| CN115385822B (en) * | 2022-08-02 | 2024-03-26 | 西安近代化学研究所 | Synthesis method of 1, 5-diazido-3-nitroazane |
| CN115504903A (en) * | 2022-09-22 | 2022-12-23 | 西安近代化学研究所 | Preparation method of 1,5-diazido-3-nitroazapentane |
| CN115504903B (en) * | 2022-09-22 | 2024-03-22 | 西安近代化学研究所 | Preparation method of 1, 5-diazido-3-nitroazane |
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