CN107619395A - A kind of synthetic method of the oxide of 2,6 diaminourea, 3,5 di nitryl pyridine 1 - Google Patents
A kind of synthetic method of the oxide of 2,6 diaminourea, 3,5 di nitryl pyridine 1 Download PDFInfo
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- CN107619395A CN107619395A CN201711106757.9A CN201711106757A CN107619395A CN 107619395 A CN107619395 A CN 107619395A CN 201711106757 A CN201711106757 A CN 201711106757A CN 107619395 A CN107619395 A CN 107619395A
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- diaminourea
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- 0 C*c1*(*)c(*=C)c(C)cc1* Chemical compound C*c1*(*)c(*=C)c(C)cc1* 0.000 description 1
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Abstract
The present invention relates to one kind 2; 6 diaminourea 3; the synthetic method of the oxide of 5 di nitryl pyridine 1, the method are to utilize acetic anhydride by 2,6 diaminourea 3; it is readily soluble acetylate that 5 di nitryl pyridines, which are acylated; again 2 are obtained with the di nitryl pyridine of 2,6 diaminourea 3,5 and hydrolysis of hydrogen peroxide oxidation acetylation; the oxide of 63,5 di nitryl pyridine of diaminourea 1.Method provided by the invention has the reaction time short, simple without solid catalyst residue, waste liquid composition.The present invention is used for the synthesis of the oxide of 2,6 diaminourea, 3,5 di nitryl pyridine 1.
Description
Technical field
The present invention relates to the synthetic method of one kind 2,6- diamino-3,5-di nitryl pyridine -1- oxides, belongs to the material containing energy
Material field.
Background technology
2,6- diaminourea -3,5- di nitryl pyridine -1- oxides (ANPyO) are a kind of low senses of novel high-energy of function admirable
Heat-resisting single chmical compound explosive, its crystalline density are 1.886g/cm3, explosion velocity and detonation pressure are respectively 7900m/s (1.84g/cm3)、28GPa
(1.84g/cm3), DSC decomposition peaks temperature is more than 350 DEG C (10 DEG C/min), impact sensitivity H50=250cm, friction sensitivity 0%, can
For fields such as special weapon, superhigh temperature petroleum perforation charge, priming systems.
ANPyO synthesis mainly by with 2,6- diamino-3,5-di nitryl pyridines (ANPy) for raw material, in acetic acid or
The preparation method of hydrogen peroxide oxidation is used in trifluoroacetic acid, is the process route generally used both at home and abroad.Ritter H,Lieht
H H etc. are in J.Heteroeyel.Chem, and 1995,32:585-590 reports ANPyO synthesis first, in ANPy oxidizing process
It is low to there is reaction yield in (reaction equation 1), acetic acid dosage is big, and particularly oxidation is difficult to thoroughly carry out, gained ANPyO impurity contents
It is higher；Afterwards, into strong grade in organic chemistry, 2008,28 (11):1943-1947 is reported with Ritter H and Lieht H H sides
Improved method based on method, process such as reaction equation 2, using sulfuric acid and niter cake as catalyst, total recovery is by original 45%
Improve to 75%, solvent load is the 1/10 of Ritter H, Lieht H H methods wherein in oxidizing process, and oxidizing process is still deposited
Only have for 85% the defects of in yield；For in existing method, oxidizing process is heterogeneous reaction, and product impurity content is high, yield
The defects of not high, Wang Hongyan etc. are in organic chemistry, 2009,29 (5):A kind of easy preparation method is reported in 780-783,
ANPyO synthesizes total recovery more than 90%, wherein oxidizing process (reaction equation 3) yield up to 97%, but this method use it is molten
Agent CF3COOH is not only expensive while has strong corrosiveness to metal, to consersion unit and the anti-nurse of operating personnel
Tool requires high, and caused severe corrosive wastewater treatment is difficult.Zhang Mengmeng et al. makes in Chinese patent CN201410479319.7
It is that catalyst obtains ANPyO acquisition yields more than 90% in acetic acid using hydrogen peroxide oxidation ANPy with this tetracarboxylic acid anhydride, it is pure
Degree up to 97%, but the method is reacted under heterogeneous conditions, reaction time length, a large amount of pyromellitic dianhydrides is produced after reaction
Solid waste, post processing are difficult.
Current existing ANPyO synthetic methods, especially are aoxidized to obtain in ANPyO methods by ANPy, still suffer from it is many not
Foot:CF used3COOH has that solvent for use is with high costs, has strong corrosivity, has to reaction and sewage treatment equipment
It is strict with, wastewater treatment is difficult；Pyromellitic dianhydride usage amount reaches more than the 50% of raw material A NPy mass, and reaction produces big
Measure solid waste；Reaction is carried out under heterogeneous conditions, and the reaction time is up to more than 5h.
The content of the invention
The technical problem to be solved in the present invention is in view of the shortcomings of the prior art and defect, there is provided a kind of reaction time
Synthesis side short, that simple 2,6- diaminourea -3,5- di nitryl pyridine -1- oxides are formed without solid catalyst residue, waste liquid
Method.
In order to solve the above technical problems, the synthetic route of the present invention is：
R therein is-H or-COCH3。
The synthetic method of the present invention is to be closed with 2,6- diamino-3,5-di nitryl pyridines, acetic anhydride for raw material through acid catalysis
Into readily soluble acetylation ANPy, then through H2O2Oxidation, hydrolysis obtain ANPYO.
The synthetic method of the present invention 2,6- diamino-3,5-di nitryl pyridine -1- oxides, it is characterised in that 2,6- bis-
The structural formula of amino -3,5- di nitryl pyridine -1- oxides is shown below：
Comprise the following steps：
Under stirring, 2,6- diamino-3,5-di nitryl pyridines and sulfuric acid are added in acetic anhydride, are warming up to 60 DEG C~90
DEG C, less than 60 DEG C are cooled to after reacting 0.5h solid dissolvings, is slowly dropped into 50%H2O2, 70 DEG C~90 DEG C are warming up to after adding, instead
0.5h~4h is answered, system is down to 25 DEG C, is poured into frozen water and adjusts pH value 7~8, filtering with sodium acid carbonate, washing, acetone are washed
Wash, obtain 2,6- diaminourea -3,5- di nitryl pyridine -1- oxides after drying.Wherein, 2,6- diaminourea -3,5- dinitro pyridine
The mass volume ratio of pyridine and acetic anhydride is 1g:The volume ratio of 6mL~20.0mL, acetic anhydride and sulfuric acid is 10:0.2~2,2,6- bis-
Amino -3,5- di nitryl pyridines and mass fraction 50%H2O2Mol ratio be 1:2~10.
The synthetic method of preferable 2, the 6- diamino-3,5-di nitryl pyridines -1- oxides of the present invention, its feature exist
In comprising the following steps：
Under stirring, 2,6- diamino-3,5-di nitryl pyridines and sulfuric acid are added in acetic anhydride, are warming up to 75 DEG C~90
DEG C, less than 60 DEG C are cooled to after reacting 0.5h solid dissolvings, is slowly dropped into 50%H2O2, 75-85 DEG C is warming up to after adding, reaction
0.5h~2h, system are down to 25 DEG C, be poured into frozen water and with sodium acid carbonate adjust pH value 7~8, filtering, washing, acetone washing,
2,6- diaminourea -3,5- di nitryl pyridine -1- oxides are obtained after drying.Wherein, 2,6- diamino-3,5-di nitryl pyridines with
The mass volume ratio of acetic anhydride is 1g:The volume ratio of 10.0mL~20.0mL, acetic anhydride and sulfuric acid is 10:0.25~1,2,6- bis-
Amino -3,5- di nitryl pyridines and mass fraction 50%H2O2Mol ratio be 1:2~6.
Advantages of the present invention：
The invention provides the synthetic method of one kind 2,6- diamino-3,5-di nitryl pyridine -1- oxides, this method tool
Have the advantage that：Avoid using expensive CF3COOH and required special installation, the special protective device of personnel and corrosivity
Wastewater treatment；Generation without solid catalyst discarded object；Reaction is carried out under homogeneous phase condition, and the reaction time is as short as within 2h.
Embodiment
The invention will be further described by the following examples, but the present invention is not limited by the following example.
Embodiment 1：
Under stirring, 2.0g (10mmol) 2,6- diamino-3,5-di nitryl pyridines and 0.5ml sulfuric acid are added into 20ml acetic acid
In acid anhydride, 80 DEG C are warming up to, less than 60 DEG C is cooled to after reacting 0.5h, is slowly dropped into 1.37g (20mmol) 50%H2O2, after adding
80 DEG C are warming up to, reacts 1h, system is down to 25 DEG C, is poured into frozen water and adjusts pH value 7~8 with sodium acid carbonate, filters, washing,
Acetone washing, obtain 2,6- diamino-3,5-di nitryl pyridine -1- oxides, yield 90%, purity 98.64% after drying.
Structural Identification：
Infrared spectrum (KBr, cm-1)γ：3451,3286,1650,1623,1490,1454,1365,1332,1280,
1232,1038,751；
1H NMR (DMSO-d6,500MHz, ppm)：9.1854(brs,2H,NH’S),8.8523(brs,2H,NH’S),
8.8027(s,1H,H-4)。
Said structure appraising datum confirms that the material that this step obtains is 2,6- diaminourea -3,5- di nitryl pyridine -1- oxygen
Compound.
Embodiment 2：
Under stirring, 2.0g (10mmol) 2,6- diamino-3,5-di nitryl pyridines and 4ml sulfuric acid are added into 40ml acetic anhydrides
In, 75 DEG C are warming up to, less than 60 DEG C is cooled to after reacting 0.5h, is slowly dropped into 4.1g (60mmol) 50%H2O2, heated up after adding
To 75 DEG C, 2h is reacted, system is down to 25 DEG C, is poured into frozen water and adjusts pH value 7~8, filtering, washing, acetone with sodium acid carbonate
Washing, obtain 2,6- diamino-3,5-di nitryl pyridine -1- oxides, yield 87%, purity 98.15% after drying.
Embodiment 3：
Under stirring, 2.0g (10mmol) 2,6- diamino-3,5-di nitryl pyridines and 1ml sulfuric acid are added into 30ml acetic anhydrides
In, 90 DEG C are warming up to, less than 60 DEG C is cooled to after reacting 0.5h, is slowly dropped into 2.73g (40mmol) 50%H2O2, risen after adding
Temperature reacts 0.5h to 85 DEG C, and system is down to 25 DEG C, is poured into frozen water and adjusts pH value 7~8 with sodium acid carbonate, filters, washing,
Acetone washing, obtain 2,6- diamino-3,5-di nitryl pyridine -1- oxides, yield 91%, purity 99.2% after drying.
Claims (2)
1. one kind 2, the synthetic method of 6- diamino-3,5-di nitryl pyridine -1- oxides, it is characterised in that 2,6- diaminourea -
3,5- di nitryl pyridine -1- oxide structure formulas are shown below：
Under stirring, 2,6- diamino-3,5-di nitryl pyridines and sulfuric acid are added in acetic anhydride, are warming up to 60 DEG C~90 DEG C, instead
Less than 60 DEG C are cooled to after answering 0.5h solid dissolvings, is slowly dropped into 50%H2O2, 70 DEG C~90 DEG C are warming up to after adding, reaction
0.5h~4h, system are down to 25 DEG C, be poured into frozen water and with sodium acid carbonate adjust pH value 7~8, filtering, washing, acetone washing,
2,6- diaminourea -3,5- di nitryl pyridine -1- oxides are obtained after drying.Wherein, 2,6- diamino-3,5-di nitryl pyridines with
The mass volume ratio of acetic anhydride is 1g:The volume ratio of 6~20.0mL, acetic anhydride and sulfuric acid is 10:0.2~2,2,6- diaminourea-
3,5- di nitryl pyridines and mass fraction 50%H2O2Mol ratio be 1:2~10.
2. the synthetic method of 2,6- diamino-3,5-di nitryl pyridines -1- oxides according to claim 1, its feature
It is, comprises the following steps：
Under stirring, 2,6- diamino-3,5-di nitryl pyridines and sulfuric acid are added in acetic anhydride, are warming up to 75 DEG C~90 DEG C, instead
Less than 60 DEG C are cooled to after answering 0.5h solid dissolvings, is slowly dropped into 50%H2O2, it is warming up to 75-85 DEG C after adding, reaction 0.5h~
2h, system are down to 25 DEG C, be poured into frozen water and with sodium acid carbonate adjust pH value 7~8, filtering, washing, acetone washing, dry after
Obtain 2,6- diaminourea -3,5- di nitryl pyridine -1- oxides.Wherein, 2,6- diamino-3,5-di nitryl pyridines and acetic anhydride
Mass volume ratio be 1g:The volume ratio of 10.0~20.0mL, acetic anhydride and sulfuric acid is 10:0.25~1,2,6- diaminourea -3,
5- di nitryl pyridines and mass fraction 50%H2O2Mol ratio be 1:2~6.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090299067A1 (en) * | 2008-05-30 | 2009-12-03 | Pagoria Philip F | New synthesis of 2,6-diamino-3,5-dinitropyrazine-1-oxide from 2,6-diaminopyrazine-1-oxide |
| CN101735147A (en) * | 2008-11-05 | 2010-06-16 | 南京理工大学 | Preparation method of high-energy insensitive explosive 2,6-diamino-3,5-dinitro pyridine-1-oxide |
| CN104262247A (en) * | 2014-09-18 | 2015-01-07 | 西安近代化学研究所 | Method for synthesizing 2,6-diamino-3,5-dinitropyridine-1-oxide |
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2017
- 2017-11-10 CN CN201711106757.9A patent/CN107619395B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090299067A1 (en) * | 2008-05-30 | 2009-12-03 | Pagoria Philip F | New synthesis of 2,6-diamino-3,5-dinitropyrazine-1-oxide from 2,6-diaminopyrazine-1-oxide |
| CN101735147A (en) * | 2008-11-05 | 2010-06-16 | 南京理工大学 | Preparation method of high-energy insensitive explosive 2,6-diamino-3,5-dinitro pyridine-1-oxide |
| CN104262247A (en) * | 2014-09-18 | 2015-01-07 | 西安近代化学研究所 | Method for synthesizing 2,6-diamino-3,5-dinitropyridine-1-oxide |
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