CN104628573A - Method for synthesizing hexanitrostilbene from hexanitrobibenzil - Google Patents
Method for synthesizing hexanitrostilbene from hexanitrobibenzil Download PDFInfo
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- CN104628573A CN104628573A CN201410397175.0A CN201410397175A CN104628573A CN 104628573 A CN104628573 A CN 104628573A CN 201410397175 A CN201410397175 A CN 201410397175A CN 104628573 A CN104628573 A CN 104628573A
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Abstract
The invention relates to the technical field of preparation of energetic materials and particularly relates to a method for synthesizing hexanitrostilbene (HNS) from hexanitrobibenzil. According to the method, hexanitrobibenzil is oxidized into HNS with oxygen or air by adopting DMF, DMSO and the like as solvents and water as an accelerator in the presence of copper ammine complex as a catalyst. Oxygen or air as an oxidant is used for replacing bromine, pyridine and the like in the domestic production technology so that the process is environment-friendly; since the effective catalyst is adopted, the reaction is performed at room temperature, the energy consumption is reduced while the side effects are decreased and the product purity is improved; and an appropriate amount of water is added into the system, the reaction time is greatly shortened and the production cost is significantly reduced.
Description
Technical field
The present invention relates to energetic material preparing technical field, particularly a kind of method of being synthesized hexanitro-Stilbene by hexanitrobibenzyl.
Background technology
Hexanitro-Stilbene, hexanitrostilbene, code name HNS, chemical name 2,2 ', 4,4 ', 6,6 '-picryl sulfide base ethene, molecular formula C
14h
6o
12n
6, molecular weight 450.3, light yellow crystal, sterling fusing point about 318 DEG C, its structural formula is:
Be a kind of high temperature powder of excellent property, can be used as main charge for fields such as aerospace, deep-well petroleum exploitations, also can be used in heat-resisting explosive, can also, as nucleus during tritonal (TNT) casting dress, make the brilliant acquistion of TNT to improvement.
Abroad, the research of synthesis HNS starts from the sixties in 20th century, and main route has: (1) is by TNT one-step synthesis HNS; (2) HNS or by HNBB one-step synthesis HNS, wherein, HNBB also can be obtained by other raw material is synthesized by TNT through hexanitrobibenzyl (HNBB) two step; (3) HNS is synthesized by trinitro-benzyl chloride (TNBCl).In these three kinds of routes, be synthesize HNS with the tetrahydrofuran (THF) of TNT/methanol mixed solution and alkaline hypochlorite's reactant aqueous solution by TNT one-step synthesis HNS, these class methods are called as " Shipp method ", and be the earliest, the most basic method, cost is high, and yield is low; The method of being synthesized HNS by TNBCl employs phase-transfer catalyst, and Problems existing is that the consumption of organic bases and solvent is all very large; " two-step approach " of synthesizing HNS through HNBB by TNT is the method generally used at present.Research report around " two-step approach " is a lot, representationally mainly contains:
1975, people's methods disclosed in patent [T/9639VE-719] such as Hungary Kompolthy: take DMF as solvent, air is blasted under existing at anhydrous cupric sulfate/pyridine, potassium hydroxide/methyl alcohol and a small amount of 2-picoline/dense acetic acid, HNS is synthesized by TNT, yield 30% (by yield 55.7% during DMF/THF mixed solvent) at 55 DEG C; Take DMF as solvent, blast air at anhydrous cupric sulfate/pyridine, potassium hydroxide/methyl alcohol under existing, 50 DEG C of reaction 1h, synthesize HNS by HNBB, yield 87.1%.1980, the people such as U.S. Gilbert were in the disclosed method of patent [US 4221746]: in DMF, with bromine/pyridine for oxygenant, and 70 DEG C of reaction 4h, synthesize HNS by HNBB, yield 92%.1981, the disclosed method of patent [US 4268696] of the people such as U.S. Sollott: in solvent HMPA (HMPT), with 2, chloro-5, the 6-dicyano benzoquinones of 3-bis-are dehydrating agent, 70 DEG C of reaction 3h, HNS is synthesized, yield 89% by HNBB.These methods are all the improvement to Shipp method, all in the yield that improve HNS in varying degrees.The common problem existed is: because employ bromine, pyridine, quinones reagent etc. to the very disadvantageous raw material of environment, limits applying aborning.
1980 and 1981, the people such as Gilbert are method disclosed in patent [US 4221745] and [US 4243614]: (1) is in DMF, with 1.1 times of anhydrous cupric sulfates to HNBB (mol ratio) for dehydrating agent, ammoniacal liquor is promotor, at 25 ~ 30 DEG C, reaction 4h, synthesize HNS by HNBB, yield reaches 79%; (2) in HMPA (HMPT) solvent, with 2 times of anhydrous cupric sulfates to HNBB (mol ratio) for dehydrating agent, 70 DEG C of reaction 3h, synthesize HNS by HNBB, yield 83%.These two kinds of methods are all reaction reagent with anhydrous cupric sulfate, and the reaction times is short, but reagent dosage is large, and cost is high.
1981, the people such as Gilbert disclosed a kind of method in patent [US 4270012] again: take cupric tetramminosulfate as catalyzer, and in DMF, under room temperature, logical oxygen reaction 16h, synthesizes HNS by HNBB, yield 92%.The method both improve yield, in turn simplify reaction system, but the reaction times is oversize, and production cost is still very high.
The research of domestic synthesis HNS is from the nineties in 20th century, mainly for the further investigation that " two-step approach " carries out, most important achievement is the method that Institutes Of Technology Of Nanjing Lu Ming proposes, its process is: (1) is in ethanol-benzene mixed solvent, with aqueous sodium hypochlorite solution, TNT oxidative coupling is become HNBB, yield 72 ~ 78%, reaction conditions is: solvent: TNT: chlorine bleach liquor=8mL:1g:1.5mL, chlorine bleach liquor's concentration (available chlorine) 45 ~ 55g/L
-1, temperature of reaction 55 ~ 62 DEG C, reaction times 0.5h.(2) in pyridine-benzene mixed solvent, by bromine, HNBB oxydehydrogenation is obtained HNS crude product, yield 90 ~ 95%, reaction conditions is: solvent: bromine: HNBB=8mL:1g:1g, temperature of reaction 55 ~ 60 DEG C, reaction times 4 ~ 5h.(3) be oxidized 0.5 ~ 1h with 50 ~ 60% nitric acid of 10 ~ 15 times at 90 ~ 118 DEG C, then use 5 ~ 10 times of acetone, 55 ~ 58 DEG C of digestion 2 ~ 5h, HNS crude product is become HNS sterling.This method is that current domestic industryization produces the method adopted, but because the chemical such as bromine and pyridine is restricted the severe contamination of environment, the demand of domestic HNS mainly meets by external import.Therefore, the domestic green synthesis process needing exploitation HNS badly, to change at present because restricted situation is produced in environmental requirement.
Summary of the invention
The object of the invention is to for deficiency of the prior art, a kind of method of being synthesized hexanitro-Stilbene by hexanitrobibenzyl is provided.
The technical scheme that the present invention takes is:
Synthesized a method for hexanitro-Stilbene by hexanitrobibenzyl, it is characterized in that, comprise the following steps:
(1) hexanitrobibenzyl is joined in solvent, be stirred to dissolving;
(2) in (1) gained solution, catalyzer is added;
(3) in (2) gained solution, pass into oxygen or air, at room temperature react;
(4) by (3) gained reaction mixture filtration under diminished pressure;
(5) by (4) gained filter cake first after through methanol wash column, washing, obtain faint yellow solid, be crude product hexanitro-Stilbene;
(6) by (5) gained solid recrystallization, sterling hexanitro-Stilbene is obtained.
Further, join again in solution after adding promotor and catalyst mix in (2).
Further, (1) middle solvent is the mass ratio of DMF or DMSO, DMF or DMSO and hexanitrobibenzyl is 8 ~ 12:1;
Further, in (2), catalyzer is cupric ammine complex, and the mass ratio of cupric ammine complex and hexanitrobibenzyl is 0.02 ~ 0.08:1;
Further, cupric ammine complex is cupric tetramminosulfate;
Further, in (3), the pressure of oxygen or air is 0.01 ~ 0.08MPa, and the reaction times is 2 ~ 6 hours.
Compared with prior art, the invention has the beneficial effects as follows:
(1) have employed Green Oxidant, environmentally friendly;
(2) have employed effective catalyst, speed of response is fast, and product yield is high, and cost is low;
(3) add suitable promotor in reaction system, the reaction times is shortened greatly.
Embodiment
Present embodiments provide for a kind of method of being synthesized hexanitro-Stilbene by hexanitrobibenzyl, the method take hexanitrobibenzyl as raw material, prepares hexanitro-Stilbene via oxidizing reaction.The method has following characteristics:
(1) oxygen or air is adopted to be oxygenant, environmentally friendly;
(2) adopt cupric ammine complex to be catalyzer, catalytic efficiency is high, with low cost;
(3) while adding catalyzer, be promotor with suitable quantity of water, reaction carried out in nearly homogeneous system, accelerates speed of response, while not reducing product yield, make the reaction times shorten 3/4, production cost obviously reduces;
(4) reaction is at room temperature carried out, and side reaction is few, and product purity is high;
(5) when taking oxygen as oxygenant, react and carry out in enclosed system, oxygen consumption is almost theoretical amount, and reaction is comparatively complete, and side reaction is few.
The method comprises following process:
Under room temperature, with DMF, DMSO etc. for solvent, under cupric ammine complex catalyst action, take appropriate amount of deionized water as promotor, with oxygen or atmospheric oxidation HNBB, synthesis HNS.Concrete reaction formula is:
Here is a kind of concrete steps of being synthesized the method for hexanitro-Stilbene by hexanitrobibenzyl of the present invention:
Synthesized a method for hexanitro-Stilbene by hexanitrobibenzyl, it is characterized in that, comprise the following steps:
(1) hexanitrobibenzyl is joined in solvent, be stirred to dissolving;
(2) in (1) gained solution, catalyzer is added;
(3) in (2) gained solution, pass into oxygen or air, at room temperature react;
(4) by (3) gained reaction mixture filtration under diminished pressure;
(5) by (4) gained filter cake first after through methanol wash column, washing, obtain faint yellow solid, be crude product hexanitro-Stilbene;
(6) by (5) gained solid recrystallization, sterling hexanitro-Stilbene is obtained.
Wherein, join again in solution after adding promotor and catalyst mix in (2); Recrystallization method is crystallisation by cooling, and solvent is DMF, DMSO, NMP or nitric acid, and consumption is 10 ~ 15 times of crude product HNS, and crystallization onset temperature is 75 ~ 115 DEG C, and recrystallization solvent used is reusable after treatment.
Preferably, (1) middle solvent is the mass ratio of DMF or DMSO, DMF or DMSO and hexanitrobibenzyl is 8 ~ 12:1.
Preferably, in (2), catalyzer is cupric ammine complex, and the mass ratio of cupric ammine complex and hexanitrobibenzyl is 0.02 ~ 0.08:1.
Preferably, cupric ammine complex is cupric tetramminosulfate.
Preferably, in (3), the pressure of oxygen or air is 0.01 ~ 0.08MPa, and the reaction times is 2 ~ 6 hours, and reactor is glass or stainless steel tank vessel, and container closure during logical oxygen, during blowing air, container is not airtight.
Be below a kind of specific embodiment being synthesized hexanitro-Stilbene by hexanitrobibenzyl:
Embodiment 1
Under room temperature, 10g HNBB is dissolved in 100g DMF, adds the cupric tetramminosulfate aqueous solution 2mL of 10%, pass into 0.01MPa oxygen, confined reaction 4h.Filter, methanol wash column, washing, obtain HNS crude product 8.33g, yield 83.3%, fusing point 310 ~ 312 DEG C.Use nitric acid recrystallization, obtain HNS sterling 8.22g, yield 82.2%, fusing point 317 ~ 318 DEG C.
Embodiment 2
Under room temperature, 10g HNBB is dissolved in 100g DMF, adds the cupric tetramminosulfate aqueous solution 3mL of 10%, pass into 0.02MPa oxygen, confined reaction 5h.Filter, methanol wash column, washing, obtain HNS crude product 8.58g, yield 85.8%.
Embodiment 3
Under room temperature, 10g HNBB is dissolved in 120g DMF, adds the cupric tetramminosulfate aqueous solution 4mL of 10%, pass into 0.04MPa air, reaction 3h.Filter, methanol wash column, deionization are washed, and obtain HNS crude product 6.87g, yield 68.7%.
Embodiment 4
Under room temperature, 10g HNBB is dissolved in 100g DMSO, adds the cupric tetramminosulfate aqueous solution 4mL of 10%, pass into 0.02MPa air, reaction 4h.Filter, methanol wash column, washing, obtain HNS crude product 7.06g, yield 70.6%.
Embodiment 5
Under room temperature, 10g HNBB is dissolved in 120g DMF, then adds the cupric tetramminosulfate aqueous solution 5mL of 10%, pass into 0.03MPa oxygen, confined reaction 2h.Filter, methanol wash column, washing, obtain HNS crude product 4.53g, yield 45.3%.
Embodiment 6
Under room temperature, 10g HNBB is dissolved in 120g DMF, then adds the cupric tetramminosulfate aqueous solution 10mL of 10%, pass into 0.03MPa oxygen, confined reaction 6h.Filter, methanol wash column, washing, obtain HNS crude product 8.23g, yield 82.3%.
Embodiment 7
Under room temperature, 10g HNBB is dissolved in 120g DMSO, adds the cupric tetramminosulfate aqueous solution 4mL of 10%, pass into 0.02MPa air, reaction 4h.Filter, methanol wash column, washing, obtain HNS crude product 6.84g, yield 68.4%.
Embodiment 8
Under room temperature, 10g HNBB is dissolved in 80g DMF, adds the cupric tetramminosulfate aqueous solution 3mL of 20%, pass into 0.01MPa oxygen, confined reaction 4h.Filter, methanol wash column, washing, obtain HNS crude product 7.59g, yield 75.9%.
Embodiment 9
Under room temperature, 10g HNBB is dissolved in 100g DMSO, adds the cupric tetramminosulfate aqueous solution 5mL of 10%, pass into 0.08MPa air, reaction 4h.Filter, methanol wash column, washing, obtain HNS crude product 7.28g, yield 72.8%.
Embodiment 10
Under room temperature, 10g HNBB is dissolved in 90g DMF, adds the cupric tetramminosulfate aqueous solution 1mL of 20%, pass into 0.04MPa oxygen, confined reaction 6h.Filter, methanol wash column, washing, obtain HNS crude product 7.01g, yield 70.1%.
A series of detailed description listed is above only illustrating for feasibility embodiment of the present invention; they are also not used to limit the scope of the invention, all do not depart from the skill of the present invention equivalent implementations done of spirit or change all should be included within protection scope of the present invention.
In addition, be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should by specification sheets integrally, and the technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
Claims (7)
1. synthesized a method for hexanitro-Stilbene by hexanitrobibenzyl, it is characterized in that, comprise the following steps:
(1) hexanitrobibenzyl is joined in solvent, be stirred to dissolving;
(2) in (1) gained solution, catalyzer is added;
(3) in (2) gained solution, pass into oxygen or air, at room temperature react;
(4) by (3) gained reaction mixture filtration under diminished pressure;
(5) by (4) gained filter cake first after through methanol wash column, washing, obtain faint yellow solid, be crude product hexanitro-Stilbene;
(6) by (5) gained solid recrystallization, sterling hexanitro-Stilbene is obtained.
2. a kind of method of being synthesized hexanitro-Stilbene by hexanitrobibenzyl as claimed in claim 1, is characterized in that, join in solution after adding promotor and described catalyst mix in (2) again.
3. a kind of method of being synthesized hexanitro-Stilbene by hexanitrobibenzyl as claimed in claim 1 or 2, it is characterized in that, in (1), solvent is the mass ratio of DMF or DMSO, DMF or DMSO and hexanitrobibenzyl is 8 ~ 12:1.
4. a kind of method of being synthesized hexanitro-Stilbene by hexanitrobibenzyl as claimed in claim 1 or 2, it is characterized in that, in (2), catalyzer is cupric ammine complex, and the mass ratio of cupric ammine complex and hexanitrobibenzyl is 0.02 ~ 0.08:1.
5. a kind of method of being synthesized hexanitro-Stilbene by hexanitrobibenzyl as claimed in claim 4, it is characterized in that, described cupric ammine complex is cupric tetramminosulfate.
6. a kind of method of being synthesized hexanitro-Stilbene by hexanitrobibenzyl as claimed in claim 2, it is characterized in that, described promotor is deionized water, and the mass ratio of described deionized water and hexanitrobibenzyl is 0.1 ~ 1:1.
7. a kind of method of being synthesized hexanitro-Stilbene by hexanitrobibenzyl as claimed in claim 1 or 2, it is characterized in that, in (3), the pressure of oxygen or air is 0.01 ~ 0.08MPa, and the reaction times is 2 ~ 6 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946711A (en) * | 2017-04-10 | 2017-07-14 | 西安近代化学研究所 | A kind of hexanitro Stilbene synthetic method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4221745A (en) * | 1979-03-15 | 1980-09-09 | The United States Of America As Represented By The Secretary Of The Army | Preparation of hexanitrostilbene |
| US4243614A (en) * | 1979-08-23 | 1981-01-06 | The United States Of America As Represented By The Secretary Of The Army | Process for producing hexanitrostilbene |
| US4270012A (en) * | 1980-01-16 | 1981-05-26 | The United States Of America As Represented By The Secretary Of The Army | Preparation of HNS from HNBB using oxygen |
| CN103694122A (en) * | 2013-11-11 | 2014-04-02 | 西安近代化学研究所 | 2,2',4,4',6,6'-hexanitro diphenylethylene preparation method |
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2014
- 2014-08-13 CN CN201410397175.0A patent/CN104628573A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4221745A (en) * | 1979-03-15 | 1980-09-09 | The United States Of America As Represented By The Secretary Of The Army | Preparation of hexanitrostilbene |
| US4243614A (en) * | 1979-08-23 | 1981-01-06 | The United States Of America As Represented By The Secretary Of The Army | Process for producing hexanitrostilbene |
| US4270012A (en) * | 1980-01-16 | 1981-05-26 | The United States Of America As Represented By The Secretary Of The Army | Preparation of HNS from HNBB using oxygen |
| CN103694122A (en) * | 2013-11-11 | 2014-04-02 | 西安近代化学研究所 | 2,2',4,4',6,6'-hexanitro diphenylethylene preparation method |
Non-Patent Citations (3)
| Title |
|---|
| E.E.GILBERT: "The Preparation of Hexanitrostilbene from Hexanitrobibenzyl", 《PROPELLANTS AND EXPLOSIVES》 * |
| 史继诚，车如心: "《综合化学实验》", 28 February 2014, 北京交通大学出版社 * |
| 陆明: "两步法合成六硝基芪中溶剂对反应的影响", 《含能材料》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106946711A (en) * | 2017-04-10 | 2017-07-14 | 西安近代化学研究所 | A kind of hexanitro Stilbene synthetic method |
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Application publication date: 20150520 |