CN104788393A - Method for synthesizing 4,6-dinitro-5,7-diaminobenzotriazol-1-oxide - Google Patents
Method for synthesizing 4,6-dinitro-5,7-diaminobenzotriazol-1-oxide Download PDFInfo
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- CN104788393A CN104788393A CN201510219146.XA CN201510219146A CN104788393A CN 104788393 A CN104788393 A CN 104788393A CN 201510219146 A CN201510219146 A CN 201510219146A CN 104788393 A CN104788393 A CN 104788393A
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- dinitrobenzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
- C07D249/18—Benzotriazoles
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Abstract
The invention discloses a method for synthesizing 4,6-dinitro-5,7-diaminobenzotriazol-1-oxide. The method comprises the following steps of dissolving sodium bicarbonate in water at the temperature of 10-35 DEG C while stirring, adding the solution into a reaction bottle, then, adding 4,6-dinitrobenzotriazol-1-oxide, then, adding hydroxylamine hydrochloride, reacting for 4-10 hours, then, cooling to the temperature of -5 to 5 DEG C, adding a sodium hydroxide aqueous solution with the mass percentage concentration of 10.0-20.0%, reacting for 1-3 hours, then, adding hydrochloric acid with the mass percentage concentration of 20-38% to adjust the pH value of the solution to 1-3, reacting for 30-90 minutes, filtrating, washing with cold water, and drying, thereby obtaining 4,6-dinitro-5,7-diaminobenzotriazol-1-oxide, wherein the mole ratio of 4,6-dinitrobenzotriazol-1-oxide to sodium bicarbonate to hydroxylamine hydrochloride to sodium hydroxide is 1: (4-6): (3-5): (15-20), and the mass ratio of 4,6-dinitrobenzotriazol-1-oxide to water is 1: (50-100). The method is mainly used for synthesizing 4,6-dinitro-5,7-diaminobenzotriazol-1-oxide.
Description
Technical field
The present invention relates to the synthetic method that 4,6-dinitrobenzene-5,7-diamino benzo connects triazole-1-oxide compound, belong to energetic material field.
Background technology
Insensitive munitions (IM) has become one of Main way of ammunition development, and its core is research and development and the application of insensitive high explosive.In recent years, benzo connects the study hotspot that the oxide-based energy-containing compound of triazole-1-becomes energetic material.4,6-dinitrobenzene-5,7-diamino benzo connects triazole-1-oxide compound and has higher energy and lower sensitivity, and density is 1.78g/cm
3, calculating Enthalpies of Formation is 4565kJ/kg, and explosion velocity is 8022m/s, impact sensitivity 20J, friction sensitivity > 360Nm, and decomposition point is 257.0 DEG C.4,6-dinitrobenzene-5,7-diamino benzo connects triazole-1-oxide compound because of the performance of its excellence and receives the concern of energetic material domain expert.Such as, T.H.Klapotke, Carolin Pluger, Muhamed Suceska.Zwitterionic explosives based on4,6-dinitrobenzotriazol-3-ium-1-oxide.New trends in research of energetic materials, CzechRepublic, 2014,754-768 mono-literary composition discloses 4,6-dinitrobenzene-5,7-diamino benzo connects synthetic method and the partial materialization detonation property thereof of triazole-1-oxide compound, and its synthetic route is as follows:
The method connects triazole-1-oxide compound for raw material with 4,6-dinitrobenzene benzo, trimethylammonium hydrazine iodide ([Me
3nNH
2] [I]) and butyl alcohol-tert sodium (NaOtBu) be abnormal nucleophilic substitution hydrogen (VNS) reaction reagent, DMSO is solvent, react 12h under normal temperature, being then acidified to pH with concentrated hydrochloric acid is 2, obtains 4,6-dinitrobenzene-5,7-diamino benzo connects triazole-1-oxide compound crude product, finally obtains 4,6-dinitrobenzene-5 with water recrystallization, 7-diamino benzo connects triazole-1-oxide compound sterling, and yield is 64%.The method uses trimethylammonium hydrazine iodide and butyl alcohol-tert sodium as VNS reagent, expensive, wherein trimethylammonium hydrazine iodide are perishable, without commercially available, need prepare in tetrahydrofuran (THF) with unsymmetric dimethyl hydrazine and methyl iodide, and product needs just can obtain sterling with water recrystallization, the higher and complicated operation of the method cost.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, and 4,6-dinitrobenzene-5, the 7-diamino benzos providing a kind of cost lower, simple to operate connect the synthetic method of triazole-1-oxide compound.
It is as follows that 4,6-dinitrobenzene-5,7-diamino benzos of the present invention connect triazole-1-oxide compound synthetic route:
Synthetic route of the present invention connects triazole-1-oxide compound for raw material with 4,6-dinitrobenzene benzo, and oxammonium hydrochloride and sodium bicarbonate are VNS reagent, and water is solvent, and VNS is obtained by reacting 4,6-dinitrobenzene-5,7-diamino benzo and connects triazole-1-oxide compound.
4,6-dinitrobenzene-5,7-diamino benzos of the present invention connect the synthetic method of triazole-1-oxide compound, and 4,6-dinitrobenzene-5,7-diamino benzo connects triazole-1-oxide structure formula as shown in (I):
With 4, it is raw material that 6-dinitrobenzene benzo connects triazole-1-oxide compound, its structural formula is as shown in (II), comprise the following steps: temperature 10 DEG C ~ 35 DEG C under stirring, sodium bicarbonate is soluble in water and add reaction flask, then 4 are added, 6-dinitrobenzene benzo connects triazole-1-oxide compound, add oxammonium hydrochloride again, after reaction 4h ~ 10h, be cooled to-5 DEG C ~ 5 DEG C, add the aqueous sodium hydroxide solution that mass percentage concentration is 10.0% ~ 20.0%, hydrochloric acid conditioning solution pH value to 1 ~ 3 that mass percentage concentration is 20% ~ 38% are added after reaction 1h ~ 3h, reaction 30min ~ 90min, filter, cold wash, dry 4, 6-dinitrobenzene-5, 7-diamino benzo connects triazole-1-oxide compound, wherein 4, 6-dinitrobenzene benzo connects triazole-1-oxide compound, sodium bicarbonate, oxammonium hydrochloride, the mol ratio of sodium hydroxide is 1:4 ~ 6:3 ~ 5:15 ~ 20, 4, the mass ratio that 6-dinitrobenzene benzo connects triazole-1-oxide compound and water is 1:50 ~ 100.
The present invention preferred 4, 6-dinitrobenzene-5, 7-diamino benzo connects the synthetic method of triazole-1-oxide compound, comprise the following steps: temperature 20 DEG C under stirring, sodium bicarbonate is soluble in water and add reaction flask, then 4 are added, 6-dinitrobenzene benzo connects triazole-1-oxide compound, add oxammonium hydrochloride again, after reaction 6h, be cooled to-5 DEG C ~ 0 DEG C, add the aqueous sodium hydroxide solution that mass percentage concentration is 16.0%, the hydrochloric acid conditioning solution pH value to 2 that mass percentage concentration is 38% is added after reaction 2h, reaction 40min, filter, cold wash, dry 4, 6-dinitrobenzene-5, 7-diamino benzo connects triazole-1-oxide compound, wherein 4, 6-dinitrobenzene benzo connects triazole-1-oxide compound, sodium bicarbonate, oxammonium hydrochloride, the mol ratio of sodium hydroxide is 1:5:4:18, 4, the mass ratio that 6-dinitrobenzene benzo connects triazole-1-oxide compound and water is 1:67.
Advantage of the present invention:
Of the present invention 4,6-dinitrobenzene-5, it is simple to operate that 7-diamino benzo connects triazole-1-oxide synthesis, without the need to purification step can obtain that purity is more than 98.5% 4,6-dinitrobenzene-5,7-diamino benzo connects triazole-1-oxide compound, and the method in documents, operation steps is complicated, and product needs just can obtain sterling with water recrystallization; The present invention uses commercially available oxammonium hydrochloride and sodium bicarbonate as VNS reagent, needed for preparation 1.0g product, the cost of VNS reagent is 0.17 yuan, and the method in documents, use trimethylammonium hydrazine iodide and butyl alcohol-tert sodium as VNS reagent, needed for preparation 1.0g product, the cost of VNS reagent is 96.02 yuan, method of the present invention is prepared the cost that product 4,6-dinitrobenzene-5,7-diamino benzo connects triazole-1-oxide compound and is significantly reduced compared with the preparation cost of documents method.
Embodiment
Below in conjunction with embodiment, the present invention is described in further details.
Embodiment 1
Temperature 20 DEG C under stirring, 13.3mmol sodium bicarbonate is dissolved in 40mL water, then 2.66mmol 4 is added, 6-dinitrobenzene benzo connects triazole-1-oxide compound, add 10.64mmol oxammonium hydrochloride more in batches, after reaction 6h, be cooled to-5 DEG C ~ 0 DEG C, add 12mL 16.0% quality aqueous sodium hydroxide solution, after reaction 2h, add 38% quality hydrochloric acid conditioning solution pH value to 2, reaction 40min, filtration, cold wash, dry 4,6-dinitrobenzene-5, the 7-diamino benzo that obtains connect triazole-1-oxide compound 0.43g, yield 63.2%, purity is 98.7%.
Structural Identification:
Infrared spectra: IR (KBr) ν: 3362,3242,1649,1610,1536,1348,1289,1255,1233,1197,1158,1099,974,816cm
-1;
Nuclear magnetic spectrum:
1h NMR (DMSO-d
6, 500MHz), δ: 15.34 (s, NH), 9.71-10.32 (m, NH
2);
13C NMR(DMSO-d
6,125MHz),δ：149.0,146.1,145.1,131.5,114.7,111.0；
Ultimate analysis: molecular formula C
6h
5n
7o
5
Theoretical value: C 28.24, H 1.98, N 38.43
Measured value: C 28.25, H 2.02, N 37.98.
The material that said structure appraising datum proved step obtains is that 4,6-dinitrobenzene-5,7-diamino benzo connects triazole-1-oxide compound really.
Embodiment 2
Temperature 10 DEG C under stirring, 10.64mmol sodium bicarbonate is dissolved in 30mL water, then 2.66mmol 4 is added, 6-dinitrobenzene benzo connects triazole-1-oxide compound, add 7.98mmol oxammonium hydrochloride more in batches, after reaction 8h, be cooled to-5 DEG C ~ 0 DEG C, add 16mL 10.0% quality aqueous sodium hydroxide solution, after reaction 1h, add 38% quality hydrochloric acid conditioning solution pH value to 1, reaction 60min, filtration, cold wash, dry 4,6-dinitrobenzene-5, the 7-diamino benzo that obtains connect triazole-1-oxide compound 0.40g, yield 58.8%, purity is 98.5%.
Embodiment 3
Temperature 30 DEG C under stirring, 16.0mmol sodium bicarbonate is dissolved in 60mL water, then 2.66mmol 4 is added, 6-dinitrobenzene benzo connects triazole-1-oxide compound, add 13.3mmol oxammonium hydrochloride more in batches, after reaction 10h, be cooled to 0 DEG C ~ 5 DEG C, add 10.6mL 20.0% quality aqueous sodium hydroxide solution, after reaction 3h, add 20% quality hydrochloric acid conditioning solution pH value to 3, reaction 30min, filtration, cold wash, dry 4,6-dinitrobenzene-5, the 7-diamino benzo that obtains connect triazole-1-oxide compound 0.42g, yield 61.7%, purity is 98.8%.
Embodiment 4
Temperature 15 DEG C under stirring, 14.63mmol sodium bicarbonate is dissolved in 50mL water, then 2.66mmol 4 is added, 6-dinitrobenzene benzo connects triazole-1-oxide compound, add 12.0mmol oxammonium hydrochloride more in batches, after reaction 5h, be cooled to-5 DEG C ~ 0 DEG C, add 12mL 16.0% quality aqueous sodium hydroxide solution, after reaction 2h, add 25% quality hydrochloric acid conditioning solution pH value to 2, reaction 50min, filtration, cold wash, dry 4,6-dinitrobenzene-5, the 7-diamino benzo that obtains connect triazole-1-oxide compound 0.38g, yield 55.9%, purity is 98.7%.
Embodiment 5
Temperature 25 DEG C under stirring, 13.3mmol sodium bicarbonate is dissolved in 40mL water, then 2.66mmol 4 is added, 6-dinitrobenzene benzo connects triazole-1-oxide compound, add 10.64mmol oxammonium hydrochloride more in batches, after reaction 4h, be cooled to-5 DEG C ~ 0 DEG C, add 10.6mL 18.0% quality aqueous sodium hydroxide solution, after reaction 2h, add 30% quality hydrochloric acid conditioning solution pH value to 2, reaction 60min, filtration, cold wash, dry 4,6-dinitrobenzene-5, the 7-diamino benzo that obtains connect triazole-1-oxide compound 0.36g, yield 52.9%, purity is 98.6%.
Claims (2)
1. dinitrobenzene-5, a 7-diamino benzo connects the synthetic method of triazole-1-oxide compound, and 4,6-dinitrobenzene-5,7-diamino benzo connects triazole-1-oxide structure formula as shown in (I):
With 4, it is raw material that 6-dinitrobenzene benzo connects triazole-1-oxide compound, its structural formula is as shown in (II), comprise the following steps: temperature 10 DEG C ~ 35 DEG C under stirring, sodium bicarbonate is soluble in water and add reaction flask, then 4 are added, 6-dinitrobenzene benzo connects triazole-1-oxide compound, add oxammonium hydrochloride again, after reaction 4h ~ 10h, be cooled to-5 DEG C ~ 5 DEG C, add the aqueous sodium hydroxide solution that mass percentage concentration is 10.0% ~ 20.0%, hydrochloric acid conditioning solution pH value to 1 ~ 3 that mass percentage concentration is 20% ~ 38% are added after reaction 1h ~ 3h, reaction 30min ~ 90min, filter, cold wash, dry 4, 6-dinitrobenzene-5, 7-diamino benzo connects triazole-1-oxide compound, wherein 4, 6-dinitrobenzene benzo connects triazole-1-oxide compound, sodium bicarbonate, oxammonium hydrochloride, the mol ratio of sodium hydroxide is 1:4 ~ 6:3 ~ 5:15 ~ 20, 4, the mass ratio that 6-dinitrobenzene benzo connects triazole-1-oxide compound and water is 1:50 ~ 100.
2. according to claim 14, 6-dinitrobenzene-5, 7-diamino benzo connects the synthetic method of triazole-1-oxide compound, comprise the following steps: temperature 20 DEG C under stirring, sodium bicarbonate is soluble in water and add reaction flask, then 4 are added, 6-dinitrobenzene benzo connects triazole-1-oxide compound, add oxammonium hydrochloride again, after reaction 6h, be cooled to-5 DEG C ~ 0 DEG C, add the aqueous sodium hydroxide solution that mass percentage concentration is 16.0%, the hydrochloric acid conditioning solution pH value to 2 that mass percentage concentration is 38% is added after reaction 2h, reaction 40min, filter, cold wash, dry 4, 6-dinitrobenzene-5, 7-diamino benzo connects triazole-1-oxide compound, wherein 4, 6-dinitrobenzene benzo connects triazole-1-oxide compound, sodium bicarbonate, oxammonium hydrochloride, the mol ratio of sodium hydroxide is 1:5:4:18, 4, the mass ratio that 6-dinitrobenzene benzo connects triazole-1-oxide compound and water is 1:67.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153053A (en) * | 2015-09-25 | 2015-12-16 | 西安近代化学研究所 | 3-gem methyl dinitro-1,2,4-triazole compound |
-
2015
- 2015-04-30 CN CN201510219146.XA patent/CN104788393A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| ALEXANDER R. MITCHELL, ET AL.: "Advances in the chemical conversion of surplus energetic materials to higher value products", 《THERMOCHIMICA ACTA》 * |
| T. H. KLAPOTKE, ET AL.: "Zwitterionic explosives based on 4,6-dinitrobenzotriazol-3-ium-1-oxide. New trends in research of energetic materials", 《NEW TRENDS IN RESEARCH OF ENERGETIC MATERIALS,CZECH REPUBLIC》 * |
| 李海波,等.: "VNS胺化合成炸药研究进展", 《含能材料》 * |
| 王伯周,等.: "4,6-二硝基-5,7-二氨基苯并氧化呋咱(CL-14)的合成与表征", 《有机化学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153053A (en) * | 2015-09-25 | 2015-12-16 | 西安近代化学研究所 | 3-gem methyl dinitro-1,2,4-triazole compound |
| CN105153053B (en) * | 2015-09-25 | 2018-04-20 | 西安近代化学研究所 | A kind of 3 together with 1,2,4 triazole of dinitro methyl synthetic method |
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