CN103864693B - Method for preparing low-sensitivity high-energy explosive 1-amino-2,4-dinitroimidazole - Google Patents

Method for preparing low-sensitivity high-energy explosive 1-amino-2,4-dinitroimidazole Download PDF

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CN103864693B
CN103864693B CN201410129010.5A CN201410129010A CN103864693B CN 103864693 B CN103864693 B CN 103864693B CN 201410129010 A CN201410129010 A CN 201410129010A CN 103864693 B CN103864693 B CN 103864693B
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amino
nitroimidazole
nitroimidazoles
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dinitroimidazole
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CN103864693A (en
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王军
景梅
张晓玉
马卿
李金山
黄靖伦
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/91—Nitro radicals

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Abstract

The invention discloses a method for preparing a low-sensitivity high-energy explosive 1-amino-2,4-dinitroimidazole. The method comprises the steps of firstly, preparing 2,4-dinitroimidazole potassium salt from 2,4-dinitroimidazole and solid KOH at room temperature, then, preparing a mixture of 1-amino-2,4-dinitroimidazole and trimethyl potassium benzenesulfonate from the 2,4-dinitroimidazole potassium salt and 2,4,6-trimethyl benzenesulfonyl hydroxylamine, and washing with ethyl acetate to purify, thereby obtaining a target product. According to the method, an organic toxic reagent, namely methanol, in the prior art is replaced with water, and the reaction temperature is low, so that the operating process is safer; the reaction temperature of the method is room temperature and has no need of being reduced to the temperature of 0 DEG C, and the reaction time of the method is greatly shortened to 4-5 hours, so that the operation is easier, and the efficiency is higher; in a purifying step of the method, ethyl acetate is directly used for washing, a crude target product ADNI, of which the purity reaches up to 96%, can be obtained in a manner that a filtrate resulting from filtrating is subjected to depressurized concentration and then subjected to oscillating dilution with water directly, and the purity can reach up to 99.6% after the crude target product ADNI is re-crystallized with anhydrous ethanol.

Description

The preparation method of amino-2, the 4-Nitroimidazoles of low-sensitive high explosive 1-
Technical field
Embodiments of the present invention relate to energetic material field, and more specifically, embodiments of the present invention relate to the preparation method of amino-2, the 4-Nitroimidazoles (ADNI) of a kind of novel low-sensitive high explosive 1-.
Background technology
Development of new low-sensitive high explosive, the essential safety performance promoting ammunition while strengthening ammunition power is further one of critical support technology promoting science and techniques of defence development, but difficulty is very large.The high explosive of being now on active service mainly contains TNT, RDX and HMX, and CL-20 is also in the applied basic research stage, though the U.S. has synthesized again otanitrocubane (ONC), and density 1.979g/cm 3, but its cage modle tension force is large, molecule extremely unstable, and it is hot and hydrolysis stability is all very poor, substantially without practical value.As can be seen here, at this Disciplinary Frontiers of energetic material subject, seek that energy is high, sensitivity is low, the high explosive of high comprehensive performance not yet obtains important breakthrough so far.
ADNI fusing point 171 ~ 173 DEG C, light yellow crystal, calculates explosion velocity 8500m/s.The impact sensitivity 0%(GJB772A-97 method 602.1 of our actual measurement), friction sensitivity 0%(GJB772A-97 method 601.1), H 50=104.2cm(GJB772A-97 method 601.2), 5S delayed heat blast temperature 312 DEG C (GJB772A-97 method 606.1).The low sense high energy of ADNI, thermal property is good, and high comprehensive performance, has broad prospect of application in IM ammunition.
2010, the Duddu R in AUS ARDEC research center and Dave PR(R.Duddu etal.Tetrahedron Letters, 2010,51:399-401) first reported the numerous and diverse and unpractical synthetic method of one of ADNI, point out its synthesis especially difficulty.
The synthetic method that document is introduced is as follows: first make solvent with organic reagent methyl alcohol, within 35 minutes, to synthesize obtain intermediate 2,4-Nitroimidazole sylvite with potassium hydroxide and 2,4-Nitroimidazole (2,4-DNI) 75 DEG C of back flow reaction; Then use aminating agent 2,4,6-trimethylbenzenesulfonyl azanol (MSH) and intermediate 2,4-Nitroimidazole sylvite first must react 3 hours at 0 DEG C, after rise to room temperature reaction and synthesize ADNI crude product in 20 hours; The last object that must this crude product could be separated purer by silica gel chromatographic column, total yield 45%.The organic toxic agent methyl alcohol of whole process; Require harsher to reaction temperature; Cross silica gel chromatographic column complex operation, impracticable, be unsuitable for amplifying and produce; Operating procedure is many, and potential safety hazard is given prominence to.
Summary of the invention
Instant invention overcomes the deficiencies in the prior art, the embodiment of the preparation method of amino-2, the 4-Nitroimidazoles of a kind of low-sensitive high explosive 1-is provided, efficient, safe prepare amino-2, the 4-Nitroimidazoles of explosive 1-to expect to realize.
For solving above-mentioned technical problem, one embodiment of the present invention by the following technical solutions:
The preparation method of amino-2, the 4-Nitroimidazoles of a kind of low-sensitive high explosive 1-: comprise following steps:
(1) preparation of intermediate 2,4-Nitroimidazole sylvite
Under room temperature, be dissolved in appropriate distilled water by 2,4-Nitroimidazole, add solid KOH in batches, react 1 ~ 1.5 hour, drying obtains intermediate 2, the 4-Nitroimidazole sylvite of yellow powder;
(2) preparation of amino-2, the 4-Nitroimidazoles of 1-
Under room temperature, 2,4-Nitroimidazole sylvite is dissolved in dry DMF, stirs, add the anhydrous DMF solution of 2,4,6-trimethylbenzenesulfonyl azanol, react reduced pressure concentration after 4 ~ 5 hours, obtain the mixture of 1-amino-2,4-Nitroimidazole and tri-methyl p-toluenesulfonate potassium;
(3) purification of amino-2, the 4-Nitroimidazoles of 1-
Wash the mixture of amino-2, the 4-Nitroimidazoles of 1-and tri-methyl p-toluenesulfonate potassium with ethyl acetate, separate out white precipitate, collecting by filtration filtrate, reduced pressure concentration obtains tan solid, and adding distil water concussion waters down, and separates out solid, suction filtration, drying obtains amino-2, the 4-Nitroimidazoles of light yellow 1-.
Further technical scheme is: the ratio of the weight of described 2,4-Nitroimidazoles, solid KOH is 7.5 ~ 8:3.
According to one embodiment of present invention: the ratio of the weight of described 2,4-Nitroimidazoles, solid KOH is 7.9:3.
Further technical scheme is: the ratio of the weight of described 2,4-Nitroimidazole sylvite, 2,4,6-trimethylbenzenesulfonyl azanols is 0.45 ~ 0.9:1.
According to one embodiment of present invention: the ratio of the weight of described 2,4-Nitroimidazole sylvite, 2,4,6-trimethylbenzenesulfonyl azanols is 0.46:1.
Further technical scheme is: the temperature of step (2) described reduced pressure concentration is 80 ~ 85 DEG C.
Further technical scheme is: the temperature of step (3) described reduced pressure concentration is 30 ~ 50 DEG C.
Further technical scheme is: the described light yellow 1-of step (3) amino-2,4-Nitroimidazoles absolute ethyl alcohol recrystallization is purified.
Compared with prior art, one of beneficial effect of the present invention is: the present invention is at synthetic intermediate 2, during 4-Nitroimidazole sylvite, use water instead of organic toxic agent methyl alcohol of the prior art as solvent, reaction temperature is room temperature, without the need to being heated to 75 DEG C, condition is very gentle, and operating process is safer; The present invention's intermediate 2,1-amino-2 prepared by 4-Nitroimidazole sylvite, in the process of 4-Nitroimidazole, temperature is room temperature, room temperature reaction is warming up to 20 hours after 3 hours without the need to being cooled to 0 DEG C of reaction, and the present invention significantly foreshortens to 4 ~ 5 hours this step reaction time, make operation easier, efficiency is higher; 1-of the present invention amino-2, the purification step of 4-Nitroimidazole is directly washed with acetic acid ester, directly the object ADNI crude product of high purity more than 96% is watered down to obtain with water vibration after filtering gained filtrate reduced in volume, the palpus need not introduced as document is crossed silica gel chromatographic column and could be obtained object, and after being recrystallized by absolute ethyl alcohol, purity can up to 99.6%.
Accompanying drawing explanation
Fig. 1 is the preparation flow of amino-2, the 4-Nitroimidazoles of 1-of the present invention.
Detailed description of the invention
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
(1) preparation of intermediate 2,4-Nitroimidazole sylvite
Under room temperature, 1.58g2,4-Nitroimidazole is dissolved in 30mL distilled water, adds 0.60gKOH in batches, react 1 hour under room temperature, dry, obtain yellow powder 2,4-Nitroimidazole sylvite 1.96g.
(2) preparation of amino-2, the 4-Nitroimidazoles (ADNI) of 1-
Under room temperature, by 1.96g intermediate 2,4-Nitroimidazole sylvite is dissolved in 35mL dry DMF (dimethyl formamide), stir, progressively add 4.3g2, dry DMF (40mL) solution of 4,6-trimethylbenzenesulfonyl azanol (MSH), temperature is risen to room temperature reaction 5 hours, 80 ~ 85 DEG C of decompression distillation obtain the mixture of ADNI and accessory substance tri-methyl p-toluenesulfonate potassium (MSK).
(3) purification of amino-2, the 4-Nitroimidazoles of 1-
With the mixture of ethyl acetate washing ADNI and MSK, precipitation white precipitate is accessory substance, filters, collect filtrate, 40 DEG C of decompression distillation obtain tan solid, add the vibration of 10mL water and water down, separate out solid, suction filtration, drying, obtains light yellow solid powder 1.0g, and productive rate is 57.8%, product fusing point is 168 ~ 170 DEG C, and it is 95.6% that HPLC tests purity.With absolute ethyl alcohol recrystallization, productive rate is 78.1%, and fusing point is 172 ~ 174 DEG C, and it is 99.6% that HPLC tests purity.
Embodiment 2
(1) preparation of intermediate 2,4-Nitroimidazole sylvite
Under room temperature, 79g2,4-Nitroimidazole is dissolved in 1200mL distilled water, adds 30gKOH in batches, react 1.5 hours under room temperature, dry, obtain yellow powder 2,4-Nitroimidazole sylvite 98g.
(2) preparation of amino-2, the 4-Nitroimidazoles (ADNI) of 1-
Under room temperature, 7.84g intermediate 2,4-Nitroimidazole sylvite is dissolved in 140mL dry DMF, stir, progressively add dry DMF (160mL) solution of 17.2gMSH, temperature is risen to room temperature reaction 4 hours, 80 ~ 85 DEG C of decompression distillation obtain the mixture of ADNI and accessory substance MSK.
(3) purification of amino-2, the 4-Nitroimidazoles of 1-
With the mixture of ethyl acetate washing ADNI and MSK, separate out white precipitate, filter, collect filtrate, 50 DEG C of decompression distillation obtain tan solid, add the vibration of 50mL water and water down, separate out solid, suction filtration, drying, obtains light yellow solid powder 3.84g, and productive rate is 55.8%, product fusing point is 168 ~ 170 DEG C, and it is 96.2% that HPLC tests purity.With absolute ethyl alcohol recrystallization, productive rate is 77.9%, and fusing point is 172 ~ 174 DEG C, and it is 99.4% that HPLC tests purity.
Embodiment 3
(1) preparation of intermediate 2,4-Nitroimidazole sylvite
Under room temperature, 1580g2,4-Nitroimidazole is dissolved in 25000mL distilled water, adds 600gKOH in batches, react 1 hour under room temperature, dry, obtain yellow powder 2,4-Nitroimidazole sylvite 2050g.
(2) preparation of amino-2, the 4-Nitroimidazoles (ADNI) of 1-
Under room temperature, 150g intermediate 2,4-Nitroimidazole sylvite is dissolved in 2800mL dry DMF, stir, progressively add dry DMF (3000mL) solution of 164.5gMSH, temperature is risen to room temperature reaction 5 hours, 80 ~ 85 DEG C of decompression distillation obtain the mixture of ADNI and accessory substance MSK.
(3) purification of amino-2, the 4-Nitroimidazoles of 1-
With the mixture of ethyl acetate washing ADNI and MSK, separate out white precipitate, filter, collect filtrate, 30 DEG C of decompression distillation obtain tan solid, add the vibration of 1000mL water and water down, separate out solid, suction filtration, drying, obtains light yellow solid powder 82g, and productive rate is 55%, product fusing point is 168 ~ 171.5 DEG C, and it is 96% that HPLC tests purity.With absolute ethyl alcohol recrystallization, productive rate is 77.6%, and fusing point is 172 ~ 174 DEG C, and it is 99.6% that HPLC tests purity.
Embodiment 4
(1) preparation of intermediate 2,4-Nitroimidazole sylvite
Under room temperature, 1.50g2,4-Nitroimidazole is dissolved in 30mL distilled water, adds 0.60gKOH in batches, react 1 hour under room temperature, dry, obtain yellow powder 2,4-Nitroimidazole sylvite 1.88g.
(2) preparation of amino-2, the 4-Nitroimidazoles (ADNI) of 1-
Under room temperature, by 2.60g intermediate 2,4-Nitroimidazole sylvite is dissolved in 40mL dry DMF (dimethyl formamide), stir, progressively add 4.4g2, dry DMF (45mL) solution of 4,6-trimethylbenzenesulfonyl azanol (MSH), temperature is risen to room temperature reaction 4 hours, 80 ~ 85 DEG C of decompression distillation obtain the mixture of ADNI and accessory substance tri-methyl p-toluenesulfonate potassium (MSK).
(3) purification of amino-2, the 4-Nitroimidazoles of 1-
With the mixture of ethyl acetate washing ADNI and MSK, separate out white precipitate, filter, collect filtrate, 40 DEG C of decompression distillation obtain tan solid, add the vibration of 15mL water and water down, separate out solid, suction filtration, drying, obtains light yellow solid powder 1.28g, and productive rate is 55.6%, product fusing point is 168 ~ 170 DEG C, and it is 96.1% that HPLC tests purity.With absolute ethyl alcohol recrystallization, productive rate is 78.3%, and fusing point is 172 ~ 174 DEG C, and it is 99.6% that HPLC tests purity.
Although with reference to multiple explanatory embodiment of the present invention, invention has been described here, but, should be appreciated that, those skilled in the art can design a lot of other amendment and embodiment, these amendments and embodiment will drop within spirit disclosed in the present application and spirit.More particularly, in the scope of and claim open in the application, multiple modification and improvement can be carried out to the building block of subject combination layout and/or layout.Except the modification of carrying out building block and/or layout is with except improvement, to those skilled in the art, other purposes also will be obvious.

Claims (4)

1. the preparation method of amino-2, the 4-Nitroimidazoles of low-sensitive high explosive 1-, is characterized in that: comprise following steps:
(1) preparation of intermediate 2,4-Nitroimidazole sylvite
Under room temperature, 2,4-Nitroimidazole is dissolved in appropriate distilled water, add solid KOH, the ratio of the weight of described 2,4-Nitroimidazoles, solid KOH is 7.5 ~ 8:3 in batches, react 1 ~ 1.5 hour, drying obtains intermediate 2, the 4-Nitroimidazole sylvite of yellow powder;
(2) preparation of amino-2, the 4-Nitroimidazoles of 1-
Under room temperature, 2,4-Nitroimidazole sylvite is dissolved in dry DMF, stir, add 2,4, the anhydrous DMF solution of 6-trimethylbenzenesulfonyl azanol, described 2,4-Nitroimidazole sylvite, 2,4, the ratio of the weight of 6-trimethylbenzenesulfonyl azanol is 0.46:1, react reduced pressure concentration after 4 ~ 5 hours, obtain the mixture of 1-amino-2,4-Nitroimidazole and tri-methyl p-toluenesulfonate potassium;
(3) purification of amino-2, the 4-Nitroimidazoles of 1-
With ethyl acetate washing 1-amino-2, the mixture of 4-Nitroimidazole and tri-methyl p-toluenesulfonate potassium, separate out white precipitate, collecting by filtration filtrate, reduced pressure concentration obtains tan solid, adding distil water concussion waters down, separate out solid, suction filtration, drying obtains light yellow 1-amino-2,4-Nitroimidazole, then purifies with absolute ethyl alcohol recrystallization.
2. the preparation method of amino-2, the 4-Nitroimidazoles of low-sensitive high explosive 1-according to claim 1, is characterized in that: the ratio of the weight of described 2,4-Nitroimidazoles, solid KOH is 7.9:3.
3. the preparation method of amino-2, the 4-Nitroimidazoles of low-sensitive high explosive 1-according to claim 1, is characterized in that: the temperature of step (2) described reduced pressure concentration is 80 ~ 85 DEG C.
4. the preparation method of amino-2, the 4-Nitroimidazoles of low-sensitive high explosive 1-according to claim 1, is characterized in that: the temperature of step (3) described reduced pressure concentration is 30 ~ 50 DEG C.
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CN105254636B (en) * 2015-11-04 2017-10-24 中国工程物理研究院化工材料研究所 Triazol ring ionic nitro azole compounds of 3,6,7 triamido 1,2,4 and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"N-Trinitroethylamino functionalization of nitroimidazoles: a new strategy for high performance energetic materials";Yin, Ping等;《Journal of Materials Chemistry A: Materials for Energy and Sustainability》;20131231;第1卷(第25期);第7501页SCHEME 1 *
"Synthesis of N-amino- and N-nitramino-nitroimidazoles";Raja Duddu等;《Tetrahedron Letters》;20091104;第51卷;第400页右栏1.1 *

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