CN105566244A - Synthetic method for 3-(4-aminofurazan-3-radical)-4-(4-nitrofurazan-3-radical) furazan - Google Patents
Synthetic method for 3-(4-aminofurazan-3-radical)-4-(4-nitrofurazan-3-radical) furazan Download PDFInfo
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- CN105566244A CN105566244A CN201610019891.4A CN201610019891A CN105566244A CN 105566244 A CN105566244 A CN 105566244A CN 201610019891 A CN201610019891 A CN 201610019891A CN 105566244 A CN105566244 A CN 105566244A
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- furazan
- base
- amino
- radical
- aminofurazan
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/08—1,2,5-Oxadiazoles; Hydrogenated 1,2,5-oxadiazoles
Abstract
The invention provides a synthetic method for 3-(4-aminofurazan-3-radical)-4-(4-nitrofurazan-3-radical) furazan. 3-(4-aminofurazan-3-radical)-4-(4-nitrofurazan-3-radical) furazan (ANTF) is a low-melting-point (100 DEG C) explosive, is expected to replace TNT to be used in casting explosives, and is also an intermediate for synthesizing other novel explosives. An existing synthetic method of ANTF has the defects of being large in acid use amount, low in synthesis yield, strict in reaction condition and the like. 3,4-bis(3'-aminofurazan-4'-radical) furoxan (BAFF) is adopted as a raw material, 3,4-bis(3'-aminofurazan-4'-radical) furoxan (BAFF) and SnCl2.2H2O are firstly subjected to a reduction reaction to obtain 3,4-bis(aminofurazan-4-raidcal) furazan, and then 3,4-bis(aminofurazan-4-raidcal) furazan and H2O2 are subjected to an oxidizing reaction to obtain the target product 3-(4-aminofurazan-3-radical)-4-(4-nitrofurazan-3-radical) furazan. 3,4-bis(aminofurazan-4-raidcal) furazan is adopted as the raw material, H2O2 (20%-30%) is adopted as an oxidizing agent, Na2WO4 is adopted as a catalyst, and 3-(4-aminofurazan-3-radical)-4-(4-nitrofurazan-3-radical) furazan is synthesized under the acidic condition through the oxidizing reaction. The synthetic method has the advantages of being easy and convenient to operate, high in safety, controllable in process and the like.
Description
Technical field
The present invention relates to a kind of synthetic method of castexplosive, be specifically related to the synthetic method of a kind of 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan (ANTF).
Background technology
Since TNT explosive comes out, be that the castexplosive of base is widely used in all kinds of pyrotechnic composition with TNT.But with TNT be base castexplosive ubiquity below not enough: make foundry goods oil impregnate because of the low-melting impurities such as dinitrobenzene, single oil of mirbane, asymmetric trinitrobenzene containing more difficult separation, reduce dynamite charge density; TNT forms sheet coarse crystallization structure after condensation and self enbrittles, and easily produces surface of fracture; Easily crack after thermal cycling, and degree of expanding with heat and contract with cold is large.These deficiencies all result in TNT base castexplosive and in use there is larger potential safety hazard.There has been proposed some to improve one's methods: TNT high-quality, high purity for this reason; Improvement TNT crystal crystalline form; Find the surrogate of TNT.In these methods, finding novel high-energy insensitiveness castexplosive carrier replaces TNT to become widespread consensus.
Furoxan class energy-containing compound due to its low melting point be expected to replace TNT, become one of current fusion casting type single chmical compound explosive hot research, its Typical Representative 3, two (3 '-nitro furazan-4 '-Ji) furoxan (DNTF) of 4-, but DNTF deposits not enough both ways as founding carrier explosive, one be fusing point is 110 DEG C, and reached the SC service ceiling of castexplosive carrier, this brings difficulty to founding; Two are DNTF due on furoxan ring containing active coordination oxygen, there is higher mechanical sensitivity, also there is larger potential safety hazard in application process.For this reason, there has been proposed two kinds of Improving ways: one, find can with formation eutectic mixture explosive; Two, do to modify further to its structure, make it possess feature that good detonation property also possesses low sense low melting point simultaneously.At present, second method has caused people to pay much attention to, two kinds of low melting point explosives 3 have been synthesized based on this method, two (3 '-nitro furazan-4 '-Ji) furazan (BNFF-1 of 4-, fusing point 84 DEG C) and 3-(the amino furazan base of 4--3-)-4-(4-nitro furazan base-3-) furazan (ANTF, fusing point is 100 DEG C).
Show according to the research of this seminar, ANTF is a kind of oblique crystal, and spacer is P2
1/ C, crystalline density is 1.768g/cm
3, calculating explosion velocity and detonation pressure are 8.26km/s, 30.13GPa, same to TNT (ρ=1.64g/cm
3, D=6940km/s) compare, more excellent as castexplosive performance, can realize a small amount of powder charge preferably, compared with the requirement that macro-energy exports, be a kind of ideal energetic material.In addition, ANTF is upper containing amino, can also carry out azo, azide, ammonium nitrate and the reaction such as nitrated and synthesize a series of new energetic material.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of easy and simple to handle, synthesis 3-that cost is low (4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan.The structural formula of ANTF is:
The present invention is with two (3 '-amino furazan-4 '-Ji) furazan of 3,4-, through H
2sO
4/ H
2o
2/ Na
2wO
4oxidizing reaction, synthetic compound 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan.
The present invention more specifically synthetic method is as follows:
(1) synthesis of two (3 '-amino furazan-4 '-Ji) furazan of intermediate 3,4-
Under room temperature, by appropriate 3, two (3 '-amino furazan-4 '-Ji) furoxan of 4-is dissolved in anhydrous methanol, stirring and dissolving, add a certain amount of concentrated hydrochloric acid again, add stannous chloride dihydrate in batches, back flow reaction 2 ~ 5h, drying obtains two (3 '-amino furazan-4 '-Ji) furazan of faint yellow solid intermediate 3,4-
(2) synthesis of 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan
A, at 0 DEG C, sodium wolframate is joined in the vitriol oil and stirs, then slowly drip H
2o
2, in dropping process, system temperature is no more than 10 DEG C.
B, with two (3 '-amino furazan-4 '-Ji) furazan of 3,4-for raw material, at a certain temperature, according to certain mol proportion, slowly join in the oxygenant that step a configures in batches, insulation for some time, synthesize ANTF.
Reaction conditions is described below:
The first step reaction conditions:
Reaction times: 3 ~ 5h
Two (3 '-amino furazan-4 '-Ji) furoxan of raw material 3,4-: stannous chloride dihydrate: concentrated hydrochloric acid mol ratio is 1:2 ~ 4:6 ~ 8.
Second step reaction conditions:
Temperature of reaction: 10 ~ 30 DEG C;
Reaction times: 1 ~ 8h;
Intermediate 3,4-two (3 '-amino furazan-4 '-Ji) furazan, oxidation system H
2sO
4/ H
2o
2/ Na
2wO
4mol ratio is 1:1.Temperature of reaction is 15 ~ 30 DEG C, and optimal reaction temperature is 15 ~ 25 DEG C, and the reaction times is 1 ~ 8h, and optimum reacting time is 3 ~ 6h.
Compared with prior art, method of the present invention has following advantage: sit solvent with methyl alcohol, instead of acetic anhydride, and acetic anhydride belongs to easily drugs processed, and country is restricted to its use.Add catalyzer sodium wolframate, reduce the concentration of hydrogen peroxide and the usage quantity of the vitriol oil, improve security and productive rate.
Accompanying drawing explanation
Fig. 1 is 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan (ANTF) mass spectrum APCI (m/s): 219 [M-NH
2]
-.
Fig. 2 is 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan (ANTF) nuclear magnetic spectrogram.
Embodiment
Embodiment 1
(1) synthesis of two (3 '-amino furazan-4 '-Ji) furazan of intermediate 3,4-
Under room temperature, two for 3,4-(3 '-amino furazan-4 '-Ji) furoxan (10g) is dissolved in anhydrous methanol, stirring makes it dissolve, then adds concentrated hydrochloric acid (22ml), adds stannous chloride dihydrate (27g) in batches, back flow reaction 3h, cooling, has yellow solid to separate out, suction filtration, frozen water washs, vacuum-drying, obtains faint yellow solid BATF4.0g, yield 42.7%.
(2) synthesis of 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan
At 0 DEG C, sodium wolframate (2.94g) is dissolved in 98% vitriol oil (4.4ml), and stirring and dissolving, slowly drips 30%H
2o
2(10.2ml), drip process temperature and be no more than 10 DEG C, and stir.After having configured, be warming up to 20 DEG C, add two (3 '-amino furazan-4 '-Ji) furazan (2.36g) of 3,4-, insulation 3h, leave standstill for some time filtration, filtrate is joined in 30ml mixture of ice and water and separate out, filter washing, use trichloromethane recrystallization, obtain BNFF-10.75g, productive rate: 28.3%.
Embodiment 2
(1) synthesis of two (3 '-amino furazan-4 '-Ji) furazan of intermediate 3,4-
Under room temperature, two for 3,4-(3 '-amino furazan-4 '-Ji) furoxan (10g) is dissolved in anhydrous methanol, stirring makes it dissolve, then adds concentrated hydrochloric acid (22ml), adds stannous chloride dihydrate (27g) in batches, back flow reaction 3.5h, cooling, has yellow solid to separate out, suction filtration, frozen water washs, vacuum-drying, obtains faint yellow solid BATF5.8g, yield 62.0%.
(2) synthesis of 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan
At 0 DEG C, sodium wolframate (2.94g) is dissolved in 98% vitriol oil (8.1ml), and stirring and dissolving, slowly drips 25%H
2o
2(18.7ml), drip process temperature and be no more than 10 DEG C, and stir.After having configured, be warming up to 25 DEG C, add two (3 '-amino furazan-4 '-Ji) furazan (2.36g) of 3,4-, insulation 4h, leave standstill for some time filtration, filtrate is joined in 30ml mixture of ice and water and separate out, filter washing, use trichloromethane recrystallization, obtain BNFF-11.38g, productive rate: 52%.
Embodiment 3
(1) synthesis of two (3 '-amino furazan-4 '-Ji) furazan of intermediate 3,4-
Under room temperature, two for 3,4-(3 '-amino furazan-4 '-Ji) furoxan (10g) is dissolved in anhydrous methanol, stirring makes it dissolve, then adds concentrated hydrochloric acid (22ml), adds stannous chloride dihydrate (30g) in batches, back flow reaction 4.5h, cooling, has yellow solid to separate out, suction filtration, frozen water washs, vacuum-drying, obtains faint yellow solid BATF5.0g, yield 53.4%.
(2) synthesis of 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan
At 0 DEG C, sodium wolframate (2.94g) is dissolved in 98% vitriol oil (8.1ml), and stirring and dissolving, slowly drips 25%H
2o
2(18.7ml), drip process temperature and be no more than 10 DEG C, and stir.After having configured, be warming up to 25 DEG C, add two (3 '-amino furazan-4 '-Ji) furazan (2.36g) of 3,4-, insulation 4h, leave standstill for some time filtration, filtrate is joined in 30ml mixture of ice and water and separate out, filter washing, use trichloromethane recrystallization, obtain BNFF-11.38g, productive rate: 52%.
Embodiment 4
(1) synthesis of two (3 '-amino furazan-4 '-Ji) furazan of intermediate 3,4-
Under room temperature, two for 3,4-(3 '-amino furazan-4 '-Ji) furoxan (10g) is dissolved in anhydrous methanol, stirring makes it dissolve, then adds concentrated hydrochloric acid (30ml), adds stannous chloride dihydrate (27g) in batches, back flow reaction 3.5h, cooling, has yellow solid to separate out, suction filtration, frozen water washs, vacuum-drying, obtains faint yellow solid BATF4.8g, yield 51.2%.
(2) synthesis of 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan
At 0 DEG C, sodium wolframate (2.94g) is dissolved in 98% vitriol oil (8.1ml), and stirring and dissolving, slowly drips 30%H
2o
2(15.3ml), drip process temperature and be no more than 10 DEG C, and stir.After having configured, be warming up to 20 DEG C, add two (3 '-amino furazan-4 '-Ji) furazan (2.36g) of 3,4-, insulation 4h, leave standstill for some time filtration, filtrate is joined in 30ml mixture of ice and water and separate out, filter washing, use trichloromethane recrystallization, obtain BNFF-11.12g, productive rate: 42.1%.
Claims (5)
1. synthesize a method for 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan, it is characterized in that: comprise the following steps:
(1) synthesis of two (3 '-amino furazan-4 '-Ji) furazan of intermediate 3,4-
Under room temperature, by appropriate 3, two (3 '-amino furazan-4 '-Ji) furoxan of 4-is dissolved in anhydrous methanol, stirring and dissolving, then adds a certain amount of concentrated hydrochloric acid, add stannous chloride dihydrate in batches, described 3,4-two (3 '-amino furazan-4 '-Ji) furoxans, stannous chloride dihydrate, concentrated hydrochloric acid mol ratio are 1:2 ~ 4:6 ~ 8, back flow reaction 2 ~ 5h, drying obtains two (3 '-amino furazan-4 '-Ji) furazan of faint yellow solid intermediate 3,4-;
(2) synthesis of 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan
A, oxygenant configure, and under 0 DEG C of condition, sodium wolframate being added concentration is in the sulfuric acid of 98%, then slowly drips H
2o
2, control temperature is no more than 10 DEG C, and stirs;
B, with two (3 '-amino furazan-4 '-Ji) furazan of 3,4-for raw material, at a certain temperature, according to certain mol proportion, slowly join in the oxygenant that step a configures in batches, insulation for some time, synthesize ANTF.
2. the synthetic method of high energy according to claim 1 low sense explosive 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan, it is characterized in that: in step (1) 3,4-two (3 '-amino furazan-4 '-Ji) furoxans, stannous chloride dihydrate, concentrated hydrochloric acid mol ratio are 1:2.5:6.9.
3. the synthetic method of high energy according to claim 1 low sense explosive 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan, is characterized in that: the H in step (2) a
2o
2: H
2sO
4: Na
2wO
4mol ratio be 8 ~ 20:6.4 ~ 25:1.
4. the synthetic method of high energy according to claim 1 low sense explosive 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan, it is characterized in that: the mol ratio of the sodium wolframate in step (2) b 3,4-two (3 '-amino furazan-4 '-Ji) furazans and step a is 1:1.
5. the synthetic method of high energy according to claim 1 low sense explosive 3-(4-amino furazan-3-base)-4-(4-nitro furazan-3-base) furazan, it is characterized in that: described in step (2) b, temperature of reaction is 10 ~ 30 DEG C, the reaction times is 1 ~ 6h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724100A (en) * | 2019-10-28 | 2021-04-30 | 中国工程物理研究院化工材料研究所 | (5-imino-4, 5-dihydro-1, 3, 4-oxadiazol-2-yl) dinitromethane and preparation method thereof |
| CN116514737A (en) * | 2023-02-17 | 2023-08-01 | 西安近代化学研究所 | Preparation method and application of 3,3 '-dinitro-4, 4' -bifurazan |
-
2016
- 2016-01-13 CN CN201610019891.4A patent/CN105566244A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| 张君启等: "一种改进的3-氨基-4-硝基呋咱合成方法", 《含能材料》 * |
| 梁德辉等: "4-氨基-4′-硝基-[3,3′,4′,3′′]-三呋咱（ANTF）的合成及工艺研究", 《火***学报》 * |
| 葛忠学等: "3,4-二硝基呋咱的合成", 《合成化学》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724100A (en) * | 2019-10-28 | 2021-04-30 | 中国工程物理研究院化工材料研究所 | (5-imino-4, 5-dihydro-1, 3, 4-oxadiazol-2-yl) dinitromethane and preparation method thereof |
| CN112724100B (en) * | 2019-10-28 | 2022-08-16 | 中国工程物理研究院化工材料研究所 | (5-imino-4, 5-dihydro-1, 3, 4-oxadiazol-2-yl) dinitromethane and preparation method thereof |
| CN116514737A (en) * | 2023-02-17 | 2023-08-01 | 西安近代化学研究所 | Preparation method and application of 3,3 '-dinitro-4, 4' -bifurazan |
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