CN112500357A - Synthesis method of 1, 1-diamino-2, 2-dinitroethylene (FOX-7) - Google Patents
Synthesis method of 1, 1-diamino-2, 2-dinitroethylene (FOX-7) Download PDFInfo
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- CN112500357A CN112500357A CN202011402646.4A CN202011402646A CN112500357A CN 112500357 A CN112500357 A CN 112500357A CN 202011402646 A CN202011402646 A CN 202011402646A CN 112500357 A CN112500357 A CN 112500357A
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- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
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- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
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Abstract
The invention discloses a synthesis method of 1, 1-diamino-2, 2-dinitroethylene (FOX-7), which mixes and reacts three materials, namely a concentrated sulfuric acid solution of 2-methylpyrimidine-4, 6-diketone, a mixed acid solution of concentrated sulfuric acid and fuming nitric acid and an inert solvent in a microchannel reactor 1 to generate a FOX-7 precursor; introducing cold water at the outlet of the microchannel reactor 1, and allowing the cold water and the generated FOX-7 precursor to enter the microchannel reactor 2 for hydrolysis reaction; and purifying the hydrolysate to obtain the FOX-7 product. The invention solves the problem of blockage in the microchannel reactor in the synthesis reaction process by innovatively introducing the inert solvent; under the condition that the reaction residence time is about 1 minute, the product yield is higher than 80 percent, the purity is higher than 99 percent, and the yield value is 4 to 5 percent higher than that of the prior art.
Description
Technical Field
The invention relates to a method for synthesizing energetic material 1, 1-diamino-2, 2-dinitroethylene (FOX-7), in particular to a method for continuously synthesizing FOX-7 in a microchannel reactor.
Background
1, 1-diamino-2, 2-dinitroethylene (FOX-7) is a novel energetic material with low sensitivity and high energy, has stable molecular structure and excellent comprehensive performance, has very wide application prospect as a candidate explosive of a new generation of high-energy low-sensitivity explosive formula, and becomes a key research object of various countries in the world.
The existing FOX-7 synthesis methods are all obtained by nitration of heterocyclic compounds and hydrolytic ring opening of intermediates, and mainly comprise the following three steps: 1. 2-methylimidazole is taken as a raw material, an intermediate 2- (dinitromethylene) -4, 5-imidazolidinedione is generated by nitration, and then FOX-7 is obtained by nitration reaction. The yield of the method is only 13% which is extremely low. 2. Ethylamidine hydrochloride and diethyl oxalate are used as raw materials to be condensed to generate 2-methoxy-2 methyl-4, 5-imidazolidinedione and 2 methyl-4, 5-imidazolidinedione, then methanol is used for recrystallization to obtain 2- (dinitromethylene) 4, 5-imidazolidinedione, and finally, FOX-7 is obtained through amination. The method has complex operation, time-consuming process and complicated post-treatment. 3. 2-methylpyrimidine-4, 6-diketone is taken as a raw material, is nitrified to generate an intermediate, and is hydrolyzed to open a ring to obtain FOX-7. The method has high yield and simple process.
Chinese patent CN104387280A discloses a preparation method of FOX-7, which adopts a batch reactor to complete nitration reaction by using 2-methylpyrimidine-4, 6-diketone as a raw material, wherein the nitration time is 1-3 hours, and the highest yield is 78%. From the prior art, the prior art is intermittent operation, the nitration reaction has violent heat release, the generated intermediate has poor stability, the explosion is easy to occur, the continuous production is difficult to realize, and the nitration reaction time is long and needs 3 hours.
The micro-reactor is a novel reactor taking a micro-scale channel as a basic unit, fluid in the micro-reactor is limited in a very small flow channel, has a large specific surface area and a high heat and mass transfer rate, is very suitable for synthesis of FOX-7, can greatly promote the efficiency of the reaction process, can reduce the reaction time, and improves the process safety.
However, the mixed acid nitration reaction using 2-methylpyrimidine-4, 6-diketone as the raw material is easy to generate product material blockage in the microchannel reaction process, so that the continuous, fast and safe synthesis process for solving the problem of FOX-7 in the microchannel has great significance.
Disclosure of Invention
Based on the technical background, aiming at the problems of long reaction time, severe heat release and the like in the batch reactor process, the invention provides a method for synthesizing FOX-7 by adopting a microchannel liquid-liquid continuous reaction process, which has short reaction time and high safety. Another problem to be solved by the present invention is the clogging of the nitrated product intermediates in the microchannels.
In order to achieve the purpose, the invention adopts the technical scheme that: a method for synthesizing 1, 1-diamino-2, 2-dinitroethylene (FOX-7) comprises the following steps:
(1) dissolving 2-methylpyrimidine-4, 6-diketone in concentrated sulfuric acid with the concentration of 95% -98% to prepare a reaction solution of 2-methylpyrimidine-4, 6-diketone (a concentrated sulfuric acid solution of 2-methylpyrimidine-4, 6-diketone);
(2) preparing a mixed acid solution of concentrated sulfuric acid and fuming nitric acid by using concentrated sulfuric acid with the concentration of 95% -98% and fuming nitric acid with the concentration of 98%;
(3) three materials of 2-methylpyrimidine-4, 6-diketone reaction solution (concentrated sulfuric acid solution of 2-methylpyrimidine-4, 6-diketone), mixed nitric-sulfuric acid and n-octane are continuously mixed in a microchannel reactor 1 at the same time, and are subjected to nitration reaction to obtain a FOX-7 precursor, the reaction temperature is kept between 5 ℃ and 35 ℃, and the retention time is kept between 1 minute and 10 minutes.
(4) At the outlet of the microchannel reactor 1, continuously introducing cold water with the temperature of 0-15 ℃ into the microchannel reactor 2, carrying out hydrolysis reaction with the FOX-7 precursor generated in the microchannel reactor 1, keeping the hydrolysis reaction temperature at 0-15 ℃ and the retention time at 1-5 minutes;
(5) purifying the product after the hydrolysis reaction to obtain an FOX-7 product, namely stirring the obtained hydrolysate for 5 to 20 minutes, standing overnight, and separating out a large amount of bright yellow FOX-7 crude products;
(6) filtering the bright yellow suspension after standing overnight, and washing filter cakes with cold water and cold ethanol respectively;
(7) and (3) drying the filter cake for 4-6 hours at 40-60 ℃ in vacuum to obtain the FOX-7 product.
Further, the molar ratio of the 2-methylpyrimidine-4, 6-dione to the concentrated sulfuric acid in the concentrated sulfuric acid solution of the 2-methylpyrimidine-4, 6-dione in the step (1) is 1: 7-1: 12. And (3) in the step (2), the molar ratio of fuming nitric acid to concentrated sulfuric acid in the nitric-sulfuric mixed acid of the concentrated sulfuric acid and the fuming nitric acid is 1: 1-1: 2. In the microchannel reactor 1, the molar ratio of the 2-methylpyrimidine-4, 6-diketone to the substrate 2-methylpyrimidine-4, 6-diketone in the mixed acid solution to fuming nitric acid is 1: 4.0-1: 5.2. Further, the volume flow rate of the inert solvent in the step (3) is 0.5 to 2.0 times of the sum of the volumes of the 2-methylpyrimidine-4, 6-dione reaction solution (concentrated sulfuric acid solution of 2-methylpyrimidine-4, 6-dione) and the mixed acid solution. In the step (4), in the microchannel reactor 2, the consumption of cold water is 5-20 times of the volumetric flow of the mixed acid solution.
Effects of the invention
The invention essentially relates to a continuous synthesis process for forming a reaction intermediate by continuous nitration in a microreactor and then directly hydrolyzing the intermediate in a microchannel to generate a product. Compared with the traditional batch kettle type stirring reactor, the miniaturization technology of the nitration reaction equipment is remarkable, and the nitration reaction time is shortened to 1-10 minutes from three hours. And due to the addition of the inert solvent, the problem of blockage of the reaction intermediate in the microchannel reactor is successfully solved, and the production safety is improved. Under the condition that the reaction residence time is about 1 minute, the product yield is higher than 80 percent, the purity is higher than 99 percent, and simultaneously, the yield value is 4-5 percent higher than that of the prior art.
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FIG. 1 is a schematic view of the process of the present invention;
wherein, 1-2-methylpyrimidine-4, 6-diketone reaction solution; 2-mixed acid of nitric and sulfuric acid(ii) a 3-an inert solvent; 4-stirring the mixture in a kettle; t is1-5 ℃ to 35 ℃ constant temperature water bath; t is2Water bath at constant temperature of 0-15 ℃;
FIG. 2 shows the hydrogen (FIG. a) and carbon (FIG. b) NMR spectra of 1, 1-diamino-2, 2-dinitroethylene (FOX-7).
Detailed Description
The invention is further illustrated by the following examples, but is not limited by the following specific implementations.
As shown in figure 1, 2-methylpyrimidine-4, 6-diketone reaction solution 1, mixed nitric acid and sulfuric acid 2 and inert solvent 3 enter a microchannel reactor 1 through a micro mixer to carry out nitration reaction, a generated FOX-7 precursor and cold water are subjected to hydrolysis reaction in the microchannel reactor 2, a product is placed in a stirring kettle 4 to be stirred and then stands overnight, a large amount of bright yellow solids are separated out, suspension is subjected to suction filtration, a filter cake is respectively washed by the cold water and cold ethanol, and then vacuum drying is carried out, so that bright yellow powdery solids are obtained.
The inner diameter of each micro-channel is 0.5-3 mm.
The starting materials used in the following examples are commercially available and the experimental procedures were carried out according to conventional methods and conditions.
Example 1
An advection pump is adopted as continuous conveying equipment for liquid materials, and polytetrafluoroethylene pipes with the inner diameter of 0.6mm are adopted for liquid material conveying pipelines. Weighing 10g of 2-methylpyrimidine-4, 6-diketone, dissolving in 38ml of 98% concentrated sulfuric acid, and conveying by using an advection pump 1, wherein the volume flow rate is 0.25 ml/min. Preparing mixed acid solution with the molar ratio of 1:1 by using 98% concentrated sulfuric acid and 98% fuming nitric acid, wherein the using amount of the fuming nitric acid is 16ml, and the using amount of the concentrated sulfuric acid is 18.56ml, cooling to room temperature, and conveying by using an advection pump 2, wherein the volume flow rate is 0.2 ml/min. Normal octane is used as an inert solvent, and is conveyed by an advection pump 3, and the volume flow is 0.45 ml/min. The three streams of materials are preheated to 20 ℃, and are simultaneously introduced into a micro mixer to carry out nitration reaction in a constant temperature micro-channel reactor 1 at 20 ℃, wherein the micro-channel reactor 1 is a polytetrafluoroethylene tube with the inner diameter of 2 mm. When the 2-methylpyrimidine-4, 6-diketone reaction solution and the mixed acid of nitric and sulfuric acid are subjected to nitration reaction in the microchannel reactor 1, the continuous feeding time of the 2-methylpyrimidine-4, 6-diketone reaction solution and the mixed acid of nitric and sulfuric acid is controlled to be 60 minutes. Cold water of 5 ℃ is introduced at the outlet of the microchannel reactor 1 (length 1 m) (residence time 210s), and enters the microchannel reactor 2 (the microchannel reactor 2 is a polytetrafluoroethylene tube, the length is 1m, the inner diameter is 2mm, the residence time is 80s) together with the generated FOX-7 precursor for hydrolysis, the hydrolysis temperature is 5 ℃, and the cold water flow is 2.3 ml/min. And (3) introducing the hydrolysate into a stirring kettle, stirring for 10 minutes, standing for layering to recover n-octane, and standing the water phase overnight to generate a large amount of bright yellow solid. And (3) carrying out suction filtration on the suspension, washing a filter cake for three times by using cold water and cold ethanol respectively, and carrying out vacuum drying for 5 hours at 50 ℃ to obtain 3.44g of a product with the yield of 83.9%. The purity of the product was 99.6% by liquid chromatography analysis. The samples were analyzed by nmr hydrogen and carbon spectroscopy, as shown in figure 2, consistent with literature results.
Comparative example 1
An advection pump is adopted as continuous conveying equipment for liquid materials, and polytetrafluoroethylene pipes with the inner diameter of 0.6mm are adopted for liquid material conveying pipelines. Weighing 10g of 2-methylpyrimidine-4, 6-diketone, dissolving in 38ml of 98% concentrated sulfuric acid, and conveying by using an advection pump 1, wherein the volume flow is 0.25 ml/min. Preparing mixed acid solution with the molar ratio of 1:1 by using 98% concentrated sulfuric acid and 98% fuming nitric acid, wherein the using amount of the fuming nitric acid is 16ml, and the using amount of the concentrated sulfuric acid is 18.56ml, cooling to room temperature, and conveying by using an advection pump 2, wherein the volume flow rate is 0.2 ml/min. Directly preheating a concentrated sulfuric acid solution of 2-methylpyrimidine-4, 6-diketone and a mixed acid of nitric acid and sulfuric acid to 20 ℃ without using an inert solvent, simultaneously introducing the solution into a micro mixer, and carrying out nitration reaction in a constant-temperature micro-channel reactor 1 at the temperature of 20 ℃, wherein the micro-channel reactor 1 adopts a polytetrafluoroethylene tube with the inner diameter of 2 mm. The reaction in the micro-channel reactor 1 takes about 20 minutes to cause serious blockage, and the advection pump takes place traffic jam.
Example 2
An advection pump is adopted as continuous conveying equipment for liquid materials, and polytetrafluoroethylene pipes with the inner diameter of 0.6mm are adopted for liquid material conveying pipelines. Weighing 10g of 2-methylpyrimidine-4, 6-diketone, dissolving in 38ml of 98% concentrated sulfuric acid, and conveying by using an advection pump 1, wherein the volume flow rate is 0.5 ml/min. Preparing mixed acid solution with the molar ratio of 1:1 by using 98% concentrated sulfuric acid and 98% fuming nitric acid, wherein the using amount of the fuming nitric acid is 16ml, and the using amount of the concentrated sulfuric acid is 18.56ml, cooling to room temperature, and conveying by using an advection pump 2, wherein the volume flow rate is 0.4 ml/min. Normal octane is used as an inert solvent, and is conveyed by an advection pump 3, and the volume flow is 0.9 ml/min. The three streams of materials are preheated to 20 ℃, and are simultaneously introduced into a micro mixer to carry out nitration reaction in a constant temperature micro-channel reactor 1 at 20 ℃, wherein the micro-channel reactor 1 adopts a polytetrafluoroethylene tube with the inner diameter of 2 mm. When the 2-methylpyrimidine-4, 6-diketone reaction solution and the mixed acid of nitric and sulfuric acid are subjected to nitration reaction in the microchannel reactor 1, the continuous feeding time of the 2-methylpyrimidine-4, 6-diketone reaction solution and the mixed acid of nitric and sulfuric acid is controlled to be 60 minutes. Cold water is fed into an outlet of a microchannel reactor 1 (with the length of 1 meter) (with the residence time of 104s), and enters a microchannel reactor 2 (the microchannel reactor 2 is a polytetrafluoroethylene tube, the length of the microchannel reactor is 1m, the inner diameter of the microchannel reactor is 2mm, and the residence time of the microchannel reactor is 80s) with the generated FOX-7 precursor for hydrolysis, wherein the hydrolysis temperature is 5 ℃, and the cold water flow is 4.6 ml/min. And (3) introducing the hydrolysate into a stirring kettle, stirring for 10 minutes, standing for layering to recover n-octane, and standing the water phase overnight to generate a large amount of bright yellow solid. And (3) carrying out suction filtration on the suspension, washing a filter cake for three times by using cold water and cold ethanol respectively, and carrying out vacuum drying for 5 hours at 50 ℃ to obtain 6.78g of a product with the yield of 82.7%. The purity of the product is 99.2% by liquid chromatography analysis. The samples were analyzed by nmr hydrogen and carbon spectroscopy, as shown in figure 2, consistent with literature results.
Claims (10)
1. A synthetic method of 1, 1-diamino-2, 2-dinitroethylene (FOX-7) is characterized in that a concentrated sulfuric acid solution of 2-methylpyrimidine-4, 6-diketone, a mixed acid solution of concentrated sulfuric acid and fuming nitric acid and an inert solvent are mixed and reacted in a microchannel reactor 1 to generate a FOX-7 precursor; introducing cold water at the outlet of the microchannel reactor 1, and allowing the cold water and the generated FOX-7 precursor to enter the microchannel reactor 2 for hydrolysis reaction; and purifying the product after the hydrolysis reaction to obtain the FOX-7 product.
2. The method of claim 1, wherein: the inert solvent is one of n-octane, n-heptane and n-hexane.
3. The method according to claim 1, wherein in the concentrated sulfuric acid of the 2-methylpyrimidine-4, 6-dione, the molar ratio of the 2-methylpyrimidine-4, 6-dione to sulfuric acid is 1: 7-1: 12; in the mixed acid solution of concentrated sulfuric acid and fuming nitric acid, the molar ratio of nitric acid to sulfuric acid is 1: 1-1: 2; in a microchannel reactor 1, the reaction molar ratio of 2-methylpyrimidine-4, 6-diketone to nitric acid in the mixed acid solution is 1: 4.0-1: 5.2, and the reaction temperature is 5-35 ℃; in the microchannel reactor 2, the volume flow ratio of the cold water to the mixed acid solution is 5: 1-20: 1, and the hydrolysis reaction temperature is 0-15 ℃.
4. The method of claim 1, wherein said purifying comprises: stirring the product after the hydrolysis reaction for 5-20 minutes, standing overnight, and separating out a crude FOX-7 product; and (3) carrying out suction filtration on the FOX-7 crude product, washing a filter cake with cold water and cold ethanol respectively, and then carrying out vacuum drying at 40-60 ℃ to obtain the FOX-7 product.
5. The method according to claim 1 or 2, wherein the volume flow rate of the inert solvent is 0.5 to 2.0 times of the sum of the volumes of the concentrated sulfuric acid solution and the mixed acid solution of the 2-methylpyrimidine-4, 6-dione.
6. The process according to claim 1 or 3, wherein in the microchannel reactor 1, the residence time is from 1 minute to 10 minutes; in the microchannel reactor 2, the residence time is 1 minute to 5 minutes.
7. The method according to claim 1, wherein the vacuum drying time is 4 to 6 hours.
8. The method according to claim 1, wherein the inner diameters of the microchannel reactor 1 and the microchannel reactor 2 are both 0.5-3 mm.
9. The method of claim 1 or 3, wherein the concentrated sulfuric acid is a 95% -98% concentrated sulfuric acid, and the fuming nitric acid is a 98% fuming nitric acid.
10. The method according to claim 1 or 3, wherein the cold water is cold water at a temperature of 0 ℃ to 15 ℃.
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