CN103980199B - The preparation method of amino-3, the 5-binitropyrazoles of 1- - Google Patents
The preparation method of amino-3, the 5-binitropyrazoles of 1- Download PDFInfo
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- CN103980199B CN103980199B CN201410232058.9A CN201410232058A CN103980199B CN 103980199 B CN103980199 B CN 103980199B CN 201410232058 A CN201410232058 A CN 201410232058A CN 103980199 B CN103980199 B CN 103980199B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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
- C07D231/16—Halogen atoms or nitro radicals
Abstract
The invention discloses the preparation method of amino-3, the 5-binitropyrazoles of a kind of 1-, comprise the following steps: under room temperature, by 3,5-binitropyrazole is soluble in water, adds sodium hydroxide, stirs, dry, obtain yellow powder intermediate 3,5-binitropyrazole (3,5-DNP) sodium salt; 3,5-binitropyrazole (3,5-DNP) sodium salt is dissolved in dry DMF, stir, add 2,4, the anhydrous DMF solution of 6-trimethylbenzenesulfonyl azanol (MSH), room temperature reaction 4-5 hour, by reaction solution concentrating under reduced pressure, wash by ethyl acetate, filter, collect filtrate, underpressure distillation, obtain amino-3, the 5-binitropyrazole crude products of pale yellow powder shape 1-.The whole reaction process of this preparation method is simple to operate, and reaction conditions is gentle, and the reaction times is short, and overall yield is higher than 60%.
Description
Technical field
The invention belongs to energetic material field, be specifically related to the preparation method of amino-3, the 5-binitropyrazoles of a kind of 1-.
Background technology
The novel energetic material of exploitation high comprehensive performance, while promoting weapons and ammunitions power energetically, promote its essential safety performance is further one of critical support technology promoting science and techniques of defence development.Present explosive, the high explosive that propelling agent and firework medicament field are comparatively commonly used mainly contains TNT, TATB, PETN, AP, RDX and HMX, CL-20 is also in the applied basic research stage, though recently synthesized again otanitrocubane (ONC), its cage modle tension force is large, molecule extremely unstable, 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 shoulders heavy responsibilities, and needs long felt.
Amino-3,5-binitropyrazoles (ADNP) fusing point 111 ~ 113 DEG C of 1-, faint yellow needle-like crystal, thermolysis peak temperature 264 DEG C, actual measurement impact sensitivity 8% (GJB772A-97 method 602.1), friction sensitivity 10% (GJB772A-97 method 601.1), H
50=83.0cm (GJB772A-97 method 601.2), 5S delayed heat temperature of explosion 303.2 DEG C (GJB772A-97 method 606.1), calculates explosion velocity and is about 8600m/s.ADNP energy is high, and sensitivity is low, and thermal properties is good, and high comprehensive performance, has potential application foreground in IM ammunition.
2014, the people such as XiuxiuZhao and SipingPang of Beijing Institute of Technology (XiuxiuZhaoetal.AminationofNitroazoles – Acomparativestudyofstructuralandenergeticproperties, Molecules, 2014,19,896-910) first reported the numerous and diverse and unpractical synthetic method of one of ADNP, point out that its synthesis is very difficult.
The synthetic method that document is introduced is as follows: the ammonium salt first obtaining intermediate 3,5-binitropyrazole with poisonous molten reagent ammoniacal liquor and 3,5-binitropyrazole (3,5-DNP) Reactive Synthesis; Then react with to the ammonium salt of Methyl benzenesulfonyl azanol (THA) as aminating agent and 3,5-DNP, obtain ADNP.This process palpus normal-temperature reaction 2 days (48 hours), and aftertreatment must adopt silica gel chromatographic column separated product, yield 50%.The poisonous molten reagent of whole process, harmful; Require harsher to the reaction times, the reaction times is long, time and effort consuming; Aftertreatment must cross silica gel chromatographic column separated product, complex operation, impracticable.Whole ADNP synthesis technique is unsuitable for amplifying and produces, and operation steps is many, and potential safety hazard is given prominence to.
Summary of the invention
The object of the invention is to solve existing 1-amino-3, the generated time existed in 5-binitropyrazole synthetic method is long, noxious solvent is have employed in building-up process, the technical problem that synthetic method is loaded down with trivial details, the invention provides the preparation method of amino-3, the 5-binitropyrazoles of a kind of 1-that is efficient, environmental protection.
In order to reach above-mentioned technique effect, the present invention takes following technical scheme:
The preparation method of amino-3, the 5-binitropyrazoles of a kind of 1-, comprises the following steps:
Step one: the preparation of intermediate 3,5-binitropyrazole (3,5-DNP) sodium salt
Under room temperature, by soluble in water for 3,5-binitropyrazole, add sodium hydroxide, stir, dry, obtain yellow powder intermediate 3,5-binitropyrazole (3,5-DNP) sodium salt;
The preparation of amino-3, the 5-binitropyrazoles of step 2: 1-
3,5-binitropyrazole (3,5-DNP) sodium salt is dissolved in dry DMF (N, dinethylformamide) in, stir, add 2, the anhydrous DMF solution of 4,6-trimethylbenzenesulfonyl azanol (MSH), room temperature reaction 4-5 hour, by reaction solution concentrating under reduced pressure, with ethyl acetate washing, filter, collect filtrate, underpressure distillation, obtains amino-3, the 5-binitropyrazole crude products of pale yellow powder shape 1-.
In order to further improve 1-amino-3, the purity of 5-binitropyrazole crude product, above-mentioned preparation method also comprises the purification step of 1-amino-3,5-binitropyrazole crude product, concrete steps are that amino for 1--3,5-binitropyrazole crude product with water are carried out recrystallization.
In one embodiment of the invention, described purification step is specially 1-amino-3,5-binitropyrazole crude product is dissolved in a small amount of water, is warming up to 80 ~ 90 DEG C, then adds water to 1-amino-3,5-binitropyrazole crude product just dissolves completely, be cooled to room temperature, crystallize out, filter, washing, dry.
In one embodiment of the invention, 3,5-binitropyrazoles described in step one are 1:(1 ~ 1.2 with the ratio of the amount of substance of sodium hydroxide), in an alternative embodiment of the invention, 3,5-binitropyrazoles described in step one are 1:1 with the ratio of the amount of substance of sodium hydroxide.
In one embodiment of the invention, the ratio of 3,5-binitropyrazoles (3, the 5-DNP) sodium salt described in step 2 and the amount of substance of 2,4,6-trimethylbenzenesulfonyl azanol is 0.4:1.
In one embodiment of the invention, in the anhydrous DMF solution of 2,4,6-trimethylbenzenesulfonyl azanol (MSH), the concentration of trimethylbenzenesulfonyl azanol is 0.6 ~ 1.2mol/L; According to another embodiment of the invention, in the anhydrous DMF solution of 2,4,6-trimethylbenzenesulfonyl azanol (MSH), the concentration of trimethylbenzenesulfonyl azanol is 0.8 ~ 1.0mol/L.
The present invention compared with prior art, has following beneficial effect:
(1) intermediate 3,5-binitropyrazole sodium salt is adopted to prepare 1-amino-3,5-binitropyrazole (ADNP) in present method, the environmental protection of intermediate 3,5-binitropyrazole sodium salt; And use water as when preparing intermediate 3,5-binitropyrazole sodium salt as solvent, instead of existing noxious solvent ammoniacal liquor completely.
(2) reaction times of present method is 4-5 hour, is compared with 48 hours, obviously shortens the reaction times with the existing reaction times.
(3) adopt 2,4,6-trimethylbenzenesulfonyl azanol (MSH) as aminating agent in present method, MSH preparation method is simple and easy, easily obtains.
(4), after reaction solution of the present invention adopts ethyl acetate to be separated, can obtain amino-3, the 5-binitropyrazoles of target product 1-of high purity 96% by the method for water recrystallization, the method steps of separating-purifying is simple.
(5) the whole reaction process of this preparation method is simple to operate, and reaction conditions is gentle, and the reaction times is short, and overall yield is higher than 60%.
Accompanying drawing explanation
Fig. 1 is the synthetic route chart of amino-3, the 5-binitropyrazoles of 1-.
Embodiment
Below in conjunction with embodiments of the invention, the invention will be further elaborated.
Embodiment 1:
(1) preparation of intermediate 3,5-binitropyrazole sodium salt
3,5-binitropyrazole (1.58g, 0.01mol) and NaOH (0.40g, 0.01mol) are dissolved in 40mL distilled water, stir 1.0h under normal temperature, vacuum is spin-dried for, and obtains intermediate 3,5-binitropyrazole sodium salt [(3,5-ADNP) Na], yield 97.5%.
(2) preparation of amino-3, the 5-binitropyrazoles (ADNP) of 1-
Under condition of ice bath, by intermediate (3,5-ADNP) Na (1.44g, 0.008mol) be dissolved in 40mL dry DMF, stir, dropwise add dry DMF (25mL) solution of the MSH (4.3g, 0.02mol) prepared in advance.Then room temperature reaction 5.0h is risen to.Be target product 1-amino-3 in reacted reaction solution, 5-binitropyrazole (ADNP) and by product tri-methyl p-toluenesulfonate sodium (MSNa), by reaction solution underpressure distillation, with the washing of 150mL ethyl acetate, separate out precipitation (being precipitated as by product tri-methyl p-toluenesulfonate sodium), filter, collect filtrate, underpressure distillation, obtains pale yellow powder shape ADNP crude product 1.05g, yield 60.7%, fusing point 111-113 DEG C.
IR(KBr,cm
-1)υ:3355,3288,1690(-NH
2),3154(-NH),1508,1357(-NO
2),1556,850,728(Pyrazole),MS(ESI,m/z):172.0114[M]
+.1HNMR(DMSO-d6)δ:7.89(s,2,NH
2)；8.01(s,1H,C-H)；13CNMR(DMSO-d6)δ:101.2(s,4-C)；141.6(s,3-C)；147.2(s,5-C).Anal.CalcdforC3H3N5O4(％)C20.81,H1.75,N40.46,foundC21.02,H1.83,N40.32。
(3) purification of amino-3, the 5-binitropyrazoles (ADNP) of 1-
Get 1.0g1-amino-3,5-binitropyrazole (ADNP) crude product, add 5ml water, heat up and be heated to 90 DEG C.Continuing to add water to ADNP has only just dissolved, and shares water 12ml.This ADNP saturated solution is moved in clean beaker, room temperature naturally cooling.Faint yellow needle-like ADNP crystal is separated out.Filter, washing, dry, obtain high-quality ADNP (99.2%, HPLC) 0.82g, the recrystallization rate of recovery 82%.
Embodiment 2:
(1) preparation of intermediate 3,5-binitropyrazole sodium salt
By 3,5-binitropyrazole (12.64g, 0.08mol) with NaOH (3.20g, 0.08mol) be dissolved in 320mL distilled water, stir 1.0h under normal temperature, vacuum is spin-dried for, obtain intermediate 3,5-binitropyrazole sodium salt [(3,5-ADNP) Na], yield 98.0%.
(2) preparation of amino-3, the 5-binitropyrazoles (ADNP) of 1-
Under condition of ice bath, by intermediate (3,5-ADNP) Na (11.52g, 0.064mol) be dissolved in 160mL dry DMF, stir, dropwise add dry DMF (200mL) solution of the MSH (34.4g, 0.16mol) prepared in advance.Then room temperature reaction 5.0h is risen to.Underpressure distillation, with the washing of 1000mL ethyl acetate, separate out precipitation, filter, collect filtrate, underpressure distillation, obtains pale yellow powder shape ADNP crude product 8.42g, yield 60.8%, fusing point 111-113 DEG C.
(3) purification of amino-3, the 5-binitropyrazoles (ADNP) of 1-
Get 8.0gADNP crude product, add 40ml water, heat up and be heated to 90 DEG C.Continuing to add water to ADNP has only just dissolved, and shares water 100ml.This ADNP saturated solution is moved in clean beaker, room temperature naturally cooling.Faint yellow needle-like ADNP crystal is separated out.Filter, washing, dry, obtain high-quality ADNP (99.2%, HPLC) 6.9g, the recrystallization rate of recovery 86.3%.
Embodiment 3:
(1) preparation of intermediate 3,5-binitropyrazole sodium salt
3,5-binitropyrazole (63.2g, 0.4mol) and NaOH (16.0g, 0.4mol) are dissolved in 1500mL distilled water, stir 1.0h under normal temperature, vacuum is spin-dried for, and obtains intermediate 3,5-binitropyrazole sodium salt [(3,5-ADNP) Na], yield 96.0%.
(2) preparation of amino-3, the 5-binitropyrazoles (ADNP) of 1-
Under condition of ice bath, by intermediate (3,5-ADNP) Na (57.6g, 0.32mol) be dissolved in 1500mL dry DMF, stir, dropwise add dry DMF (1000mL) solution of the MSH (172.0g, 0.8mol) prepared in advance.Then room temperature reaction 5.0h is risen to.Underpressure distillation, with the washing of 1500mL ethyl acetate, separate out precipitation, filter, collect filtrate, underpressure distillation, obtains pale yellow powder shape ADNP crude product 43.0g, yield 62%, fusing point 111-113 DEG C.
(3) purification of amino-3, the 5-binitropyrazoles (ADNP) of 1-
Get 40.0gADNP crude product, add 200ml water, heat up and be heated to 90 DEG C.Continuing to add water to ADNP has only just dissolved, and shares water 500ml.This ADNP saturated solution is moved in clean beaker, room temperature naturally cooling.Faint yellow needle-like ADNP crystal is separated out.The recrystallization rate of recovery 85%.
Embodiment 4:
(1) preparation of intermediate 3,5-binitropyrazole sodium salt
3,5-binitropyrazole (126.4g, 0.8mol) and NaOH (32.0g, 0.8mol) are dissolved in 2000mL distilled water, stir 1.0h under normal temperature, vacuum is spin-dried for, and obtains intermediate 3,5-binitropyrazole sodium salt [(3,5-ADNP) Na], yield 98%.
(2) preparation of amino-3, the 5-binitropyrazoles (ADNP) of 1-
Under condition of ice bath, by intermediate (3,5-ADNP) Na (115.2g, 0.64mol) be dissolved in 2500mL dry DMF, stir, dropwise add dry DMF (1600mL) solution of the MSH (344.0g, 1.6mol) prepared in advance.Then room temperature reaction 5.0h is risen to.Underpressure distillation, with the washing of 2000mL ethyl acetate, separate out precipitation, filter, collect filtrate, underpressure distillation, obtains pale yellow powder shape ADNP crude product 88.2g, yield 63.7%, fusing point 111-113 DEG C.
(3) purification of amino-3, the 5-binitropyrazoles (ADNP) of 1-
Get 80.0gADNP crude product, add 400ml water, heat up and be heated to 90 DEG C.Continuing to add water to ADNP has only just dissolved, and shares water 1000ml.This ADNP saturated solution is moved in clean beaker, room temperature naturally cooling.Faint yellow needle-like ADNP crystal is separated out.Filter, washing, dry. the recrystallization rate of recovery 85%.
Although with reference to explanatory embodiment of the present invention, invention has been described here, above-described embodiment is only the present invention's preferably embodiment, embodiments of the present invention are not restricted to the described embodiments, 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.
Claims (3)
1. the preparation method of 1-amino-3, a 5-binitropyrazole, is characterized in that comprising the following steps:
Step one: the preparation of intermediate 3,5-binitropyrazole sodium salt
Under room temperature, by soluble in water for 3,5-binitropyrazole, add sodium hydroxide, stir, dry, obtain yellow powder intermediate 3,5-binitropyrazole sodium salt;
The preparation of amino-3, the 5-binitropyrazoles of step 2: 1-
3,5-binitropyrazole sodium salt is dissolved in dry DMF, stirs, add the anhydrous DMF solution of 2,4,6-trimethylbenzenesulfonyl azanol, room temperature reaction 4-5 hour, by reaction solution concentrating under reduced pressure, with ethyl acetate washing, filter, collect filtrate, underpressure distillation, obtains amino-3, the 5-binitropyrazole crude products of pale yellow powder shape 1-; In the anhydrous DMF solution of 2,4,6-trimethylbenzenesulfonyl azanol, the concentration of trimethylbenzenesulfonyl azanol is 0.6 ~ 1.2mol/L;
Also comprise 1-amino-3, the purification step of 5-binitropyrazole crude product, concrete operation step is be dissolved in a small amount of water by amino for 1--3,5-binitropyrazole crude products, be warming up to 80 ~ 90 DEG C, add water to 1-amino-3,5-binitropyrazole crude product more just to dissolve completely, be cooled to room temperature, crystallize out, filter, washing, dry.
2. the preparation method of amino-3, the 5-binitropyrazoles of 1-according to claim 1, is characterized in that 3,5-binitropyrazoles described in step one are 1:(1 ~ 1.2 with the ratio of the amount of substance of sodium hydroxide).
3. the preparation method of amino-3, the 5-binitropyrazoles of 1-according to claim 1, is characterized in that the ratio of the amount of substance of 3,5-binitropyrazole sodium salts described in step 2 and 2,4,6-trimethylbenzenesulfonyl azanol is 0.4:1.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102250007A (en) * | 2011-05-31 | 2011-11-23 | 中北大学 | Preparation method of 3,4-binitropyrazole |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102250007A (en) * | 2011-05-31 | 2011-11-23 | 中北大学 | Preparation method of 3,4-binitropyrazole |
Non-Patent Citations (3)
| Title |
|---|
| Amination of Nitroazoles - A Comparative Study of Structural and Energetic Properties;Xiuxiu Zhao et al.,;《Molecules》;20140114(第19期);第896-910页 * |
| N-Trinitroethylamino functionalization of nitroimidazoles: a new strategy for high performance energetic materials;Ping Yin， et al.,;《Journal of Materials Chemistry A》;20131231(第1期);第7500-7510页 * |
| Synthesis ofN-amino- andN-nitramino-nitroimidazoles;Raja Duddu， et al.,;《Tetrahedron Letters》;20101231(第51期);第399-401页 * |
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