CN102702131A

CN102702131A - Method for synthesizing plasticizer 3-nitro furazan-4-methyl ether

Info

Publication number: CN102702131A
Application number: CN2012102231919A
Authority: CN
Inventors: 李树叶
Original assignee: TAICANG XINXING LIGHTINDUSTRY AUXILIARY FACTORY
Current assignee: TAICANG XINXING LIGHTINDUSTRY AUXILIARY FACTORY
Priority date: 2012-06-29
Filing date: 2012-06-29
Publication date: 2012-10-03

Abstract

The invention discloses a method for synthesizing plasticizer 3-nitro furazan-4-methyl ether. The method comprises the following steps: adding hydroxylamine under the alkaline condition by taking ethyl cyanoacetate as a starting material to form a ring, so as to obtain 3-amino furazan-4-carboxylic acid; then, reducing carboxyl group on the furazan ring to an alcoholic extract hydroxyl group by using a sodium borohydride/zinc chloride system, so as to obtain 3-amino furazan-4-methanol; then, oxidizing an amino group on the furazan ring to a nitro group by using a hydrogen peroxide/concentrated sulphuric acid system, so as to obtain 3-nitro furazan-4-methanol; in the presence of pyridine, carrying out chloride substituent on the alcoholic extract hydroxyl group by using thionyl chloride, so as to obtain 3-nitro-4-chloromethyl methyl ether furazan; and finally, reacting 3-nitro-4-chloromethyl methyl ether furazan with sodium methoxide in acetonitrile to remove NaCl so as to obtain the target compound. Compared with the traditional nitrate plasticizer, the plasticizer synthesized by using the method has higher positive enthalpies of formation and thermal stability, lower sensitivity and melting point, and has potential application prospect in the field of solid propellants.

Description

The compound method of softening agent 3-nitro furazan-4-methyl ether

Technical field

The invention belongs to the additives for plastics technical field, relate to the synthetic of a kind of softening agent, be specifically related to the compound method of a kind of softening agent 3-nitro furazan-4-methyl ether.

Background technology

The main ingredient of decision SP energy is oxygenant, tackiness agent, softening agent and fuel, and the adhesive composition that tackiness agent and softening agent are formed is the basis that SP has mechanical property and processing characteristics.Nitric ether is one of the highest softening agent of present energy density; But this compounds is all responsive to heat, mechanical effect and chemical substance; The nitrate esters SP of development all belongs to the I and II hazardous substance at present, and the dangerous phenomenon that exists present mechanism such as postponing detonation not exclusively to understand.

The furazan compounds is the comparatively popular research object in energetic material field in recent years, is that the compound that infrastructure element makes up generally has a series of good performances such as high-density, high Enthalpies of Formation with the furazan ring.According to bibliographical information, some chain furazan, two furazan also have lower fusing point, and this is the synthetic clue that provides of novel furazan class insensitiveness energetic plasticiser undoubtedly.Since nineteen sixty-eight by Coburn synthetic first obtain 3-amino-4-nitro furazan since, the furazan compounds has obtained significant progress so far, its unique biological function even come into one's own too at field of medicaments.

The structure of nitro-furazan (NF) helps forming the compound of high thermal stability and low sensitivity, has the high-energy high-density.The chemical group that connects on the furazan ring can be used for this structure of NF is carried out functionalized, thus synthesizing nitryl furazan class energetic plasticiser.People such as Ana Racoveanu have reported two kinds of compounds with this structure; Its performance shows: the compound with nitro-furazan structure has potential high-density, insensitiveness; And have the energy response that is superior to the nitrate esters softening agent, might be as the high energy softening agent of one type of new replacement nitric ether.In the new component design of SP, the furazan and the furoxan backbone that are connected to form through ehter bond not only possibly have lower melting point, and have the effect that improves structural safety performance and oxygen level.

Summary of the invention

The invention provides the compound method of a kind of softening agent 3-nitro furazan-4-methyl ether (NFME).

With the ethyl cyanacetate is starting raw material, makes its Cheng Huan through under alkaline condition, adding azanol, obtains the amino furazan of 3--4-carboxylic acid (AFCA).Use Peng Qinghuana/zinc chloride system that the carboxyl selective reduction on the furazan ring is alcoholic extract hydroxyl group again, obtain the amino furazan of 3--4-methyl alcohol (AFMA).Through the ydrogen peroxide 50/vitriol oil system amino oxygen on the furazan ring is turned to nitro then, obtain 3-nitro furazan-4-methyl alcohol (NFMA).Under pyridine catalysis, alcoholic extract hydroxyl group generation chlorine is replaced again, obtain 3-nitro-4-chloromethyl furazan (NFCM) with sulfur oxychloride.

Embodiment

The used starting material ethyl cyanacetate of the present invention, oxammonium hydrochloride, Sodium Nitrite, sodium hydroxide, Peng Qinghuana, zinc chloride, the vitriol oil, ydrogen peroxide 50, sulfur oxychloride, pyridine, sodium methylate, acetonitrile etc. are AR.

(1) AFCA's is synthetic

Get 138g (2mol) Sodium Nitrite and 1600ml zero(ppm) water wiring solution-forming, 226.4g (2mol) ethyl cyanacetate and 140ml EtOH wiring solution-forming are poured in the 2L flask.Get 80ml85%H ₃PO ₄Dropwise add stirring at room 1h.Reduce to 10 ℃ of stirred overnight.Add 16Og (4mol) NaOH, 278g (4mol) NH ₂OHHCI and 336g (6mol) KOH stirs 1h.Reflux 2h.Ice bath is cooled to envrionment temperature and transfers PH=6 with concentrated hydrochloric acid, the filtering white solid.Continue to transfer PH to separating out white solid, suction filtration, filter cake are used the zero(ppm) water recrystallization, get 118.8g (0.92mol) white crystal, productive rate 46%, purity 99.1%.

(2) AFMA's is synthetic

Flask with the bright distillation of 300ml THF is housed is got 25.4g (0.2mol) ZnCl ₂, add 16g (0.4mol) NaBH ₄, stirring at room 24h.Add the bright distillatory THF of 56g (0.4mol) AFCA and 400ml, backflow 6h.With 4N sulfuric acid cancellation reaction, Na ₂CO ₃Transfer pH=5.Suction filtration removes under the filtrate decompression and desolvates, and gets white solid, merges the back with filter cake and washs with anhydrous diethyl ether.Suction filtration, filtrating adds MgSO ₄Dewater, decompression removes down and desolvates, and gets light yellow transparent liquid 19.6g (0.17mol), productive rate 43%, purity 99.23%.

(3) NFMA's is synthetic

Getting 28ml concentration is 90%H ₂O ₂, low temperature adds the 28ml98% vitriol oil and 3.5g (0.0304mol) AFMA down.Stop up temperature and stir 1h down.Be cooled to below 10 ℃, drip 132ml zero(ppm) water, stir 30min.With 100ml * 3 extracted with diethyl ether mixed solutions, with extraction liquid with 200ml * 2 distilled water washs, MgSO ₄Drying, the rotating thin film moisture eliminator desolventizes, and gets blue liquid 4.36g (0.03mol), productive rate 99%.

(4) NFCM's is synthetic

Get 14mlSOCl ₂, 97mlCH ₂Cl ₂, low temperature adds 15.7ml pyridine and 8.4g (0.06mol) NFMA down, stirs 15min.Add distilled water diluting, the rotating thin film moisture eliminator desolventizes, and gets thickness blue-greenish colour liquid.With 40ml * 7CH ₂Cl ₂Extraction, the rotating thin film moisture eliminator desolventizes, and gets green solid 5.1g (0.032mol), productive rate 54%.

(5) NFME's is synthetic

Get 9.48g (0.06mol) NFCM, 400ml acetonitrile and 3.44g (0.06mol) sodium methylate is poured flask into, reflux 16h.Suction filtration, filtrating removes solvent, gets brown colloidal solid.Add saturated aqueous common salt, acetonitrile extraction, MgSO ₂Dewater, decompression removes down and desolvates, and gets brown viscous liquid 4.14g (0.026mol), productive rate 45%, purity 92.4%.

Claims

1. the compound method of softening agent 3-nitro furazan-4-methyl ether, it may further comprise the steps:

A, the aqueous solution that will contain the 1mol Sodium Nitrite and the EtOH solution reaction that contains the 1mo1 ethyl cyanacetate dropwise add 40ml 85%H ₃PO ₄, stirring at room 1h reduces to 10 ℃ of stirred overnight, adds 2mo1NaOH, 2mo1NH ₂OHHCI and 3mo1KOH stir 1h, and reflux 2h, ice bath are cooled to envrionment temperature and transfer PH=6 with concentrated hydrochloric acid, and the filtering white solid continues to transfer PH to separating out white solid, and suction filtration, filter cake are used the zero(ppm) water recrystallization, get the amino furazan of 3--4-carboxylic acid;

B, get 1molZnCl ₂With 2molNaBH ₄Under THF, stirring at room 24h adds the amino furazan of 2mol3--4-carboxylic acid and bright distillatory THF, and backflow 6h is with 4N sulfuric acid cancellation reaction, Na2CO ₃Transfer pH=5, suction filtration removes under the filtrate decompression and desolvates, and gets white solid, merges the back with the anhydrous diethyl ether washing with filter cake, suction filtration, filtrating adding MgSO ₄Dewater, decompression removes down and desolvates, and gets light yellow transparent liquid, obtains the amino furazan of 3--4-methyl alcohol;

C, to get 28ml concentration be 90%H ₂O ₂, low temperature adds the amino furazan of the 28ml98% vitriol oil and 0.0304mol3--4-methyl alcohol down, stops up temperature and stirs 1h down; Be cooled to below 10 ℃, drip 132ml zero(ppm) water, stir 30min; With 100ml * 3 extracted with diethyl ether mixed solutions, with extraction liquid with 200ml * 2 distilled water washs, MgSO ₄Drying, the rotating thin film moisture eliminator desolventizes, and gets blue liquid 3-nitro furazan-4-methyl alcohol;

D, get 14mlSOCl ₂, 97mlCH ₂Cl ₂, low temperature adds 15.7ml pyridine and 0.06mol3-nitro furazan-4-methyl alcohol down, stirs 15min, adds distilled water diluting, and the rotating thin film moisture eliminator desolventizes, and gets thickness blue-greenish colour liquid, with 40ml * 7CH ₂Cl ₂Extraction, the rotating thin film moisture eliminator desolventizes, and gets green solid 3-nitro-4-chloromethyl furazan;

E, get 0.06mol3-nitro-4-chloromethyl furazan, 400ml acetonitrile and 0.06mol sodium methylate are poured flask into, reflux 16h, suction filtration, filtrating removes solvent, brown colloidal solid, add saturated aqueous common salt, acetonitrile extraction, MgSO ₂Dewater, decompression removes down and desolvates, and gets brown viscous liquid 3-nitro furazan-4-methyl ether.