CN107935940A - The preparation method of 2,4,6 triamido of energy-containing compound, 5 nitro-pyrimidine, 1,3 dioxide - Google Patents
The preparation method of 2,4,6 triamido of energy-containing compound, 5 nitro-pyrimidine, 1,3 dioxide Download PDFInfo
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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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Abstract
The invention discloses a kind of preparation method of 2,4,6 triamido of energy-containing compound, 5 nitro-pyrimidine, 1,3 dioxide, include the following steps：With 2,4,6 Triaminopyrimidines and its substituent for reaction raw materials, nitration reaction is carried out；Carry out oxidation reaction；Carry out acid-base neutralization reaction；Obtain 2,4,6 triamido of required product energy-containing compound, 5 nitro-pyrimidine, 1,3 dioxide.This method has and its synthesis step is short, and raw materials used low with solvent cost and post processing is simple, to people, equipment and environmental hazard are small the advantages that；The compound synthesized using the present invention has the characteristics that high density, high-energy, to mechanical stimulus insensitiveness, has preferable market prospects in energetic material application field.
Description
Technical field
The present invention relates to energetic material synthesis technical field, and in particular to a kind of 2,4,6- triamido -5- of energy-containing compound
The preparation method of nitro-pyrimidine -1,3- dioxide.
Background technology
Energetic material is to realize power source and injure source that weapon strikes target, its energy level height directly affects weapon
The performance of system, but improving energetic material energy at the same time, its security performance often reduces.High-energy insensitive explosive contains always
The target of the energy unremitting pursuit of Material Field.But up to the present, uniquely go through and widely used high-energy insensitive explosive
There is photoacoustic spectroscopy（TATB）, but the energy of TATB is relatively low, only suitable 1,3,5,7- tetranitros -1,3, and 5,7- tetra- azepines
Cyclooctane（HMX）65%, this significantly affects its progress of miniaturization as battle injury position.Therefore, Development of Novel energy
More than TATB, the sensitivity high-energy insensitive energetic material suitable with TATB has great importance.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of energy-containing compound 2,4,6- triamido -5- nitro-pyrimidine -1,
The preparation method of 3- dioxide.
The energy-containing compound 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide preparation method of the present invention is included such as
Lower step：With 2,4,6- Triaminopyrimidines and its substituent for reaction raw materials, nitration reaction is carried out；Carry out oxidation reaction；Carry out
Acid-base neutralization reaction；Obtain required product energy-containing compound 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide；
2,4,6- Triaminopyrimidines substituent is 2,4,6- triamido -5- nitrous yl pyrimidines；
The nitrating agent of nitration reaction is that mass fraction is 90% ~ 100% nitric acid and sulfuric acid, acetic acid, trifluoroacetic acid mixed liquor, trifluoro
A kind of mixed liquor in Loprazolam, acetic anhydride, trifluoroacetic anhydride；The nitrating agent of nitration reaction is 90% ~ 100% nitric acid or four
Fluoboric acid nitryl reagent；
The temperature of nitration reaction is -10 ~ 50 DEG C；
The oxidising agent of oxidation reaction is acetic acid/hydrogen peroxide solution, trifluoromethayl sulfonic acid/hydrogen peroxide solution, trifluoro
Acetic acid/hydrogen peroxide solution, sulfuric acid/hydrogen peroxide solution；
The temperature of oxidation reaction is -10 ~ 100 DEG C；
Alkali in acid-base neutralization reaction is sodium hydroxide, in potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus
It is a kind of.
When wherein the reaction time of nitrifying process is 1 ~ 24 small.
When wherein the reaction time of oxidizing process is 1 ~ 24 small.
Wherein hydrogen peroxide refers to the aqueous hydrogen peroxide solution that mass fraction is 20% ~ 90%.
The preparation method of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide of energy-containing compound of the present invention, has
And its synthesis step is short, raw materials used low with solvent cost and post processing is simple, to people, equipment and environmental hazard are small the advantages that；
The compound synthesized using the present invention has the characteristics that high density, high-energy, to mechanical stimulus insensitiveness, is led in energetic material application
Domain has preferable market prospects.
Brief description of the drawings
Fig. 1 is the 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide of preparation method using the present invention synthesis
The NMR spectrum figure of hydrogen -1（1H NMR）.
Fig. 2 is the 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide of preparation method using the present invention synthesis
Carbon-13 nuclear magnetic resonance spectrum figure（13C NMR）.
Fig. 3 is the 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide of preparation method using the present invention synthesis
High resolution mass spectrum figure.
Embodiment
The present invention is further described in detail below with reference to the accompanying drawings and embodiments.
The structure of the 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide of preparation method synthesis using the present invention
Formula is：
Preparation method of the present invention uses following three kinds of synthetic routes：
Route one：With 2,4,6- Triaminopyrimidines for reaction raw materials, successively contain and can change through nitrifying, aoxidizing two reactions steps and be made
Compound 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide.
Under the conditions of temperature -10 ~ 50 DEG C, 2,4,6- Triaminopyrimidines are repeatedly slowly added into a certain amount of nitrification in batches and are tried
In agent, nitrating agent used is that mass fraction is 90% ~ 100% nitric acid, nitric/sulfuric acid mixed liquor, nitric acid/vinegar including mass fraction
Sour mixed liquor, nitric acid/trifluoroacetic acid mixed liquor, nitric acid/trifluoromethayl sulfonic acid mixed liquor, nitric acid/acetic anhydride mixed liquor, nitric acid/
One kind in trifluoroacetic anhydride mixed liquor or tetrafluoro boric acid nitryl reagent；The reaction was continued after adding 1 ~ 24 it is small when, then will reaction
System is poured into frozen water after cooling to room temperature, and solid filters, the nitration product of dry 2,4,6- Triaminopyrimidines, i.e., and 2,4,
6- triamido -5- nitro-pyrimidines.
Under the conditions of temperature -10 ~ 100 DEG C, 2,4,6- triamido -5- nitro-pyrimidines are dissolved in a certain amount of organic/inorganic
In acid, organic/inorganic acid used is trifluoroacetic acid, one kind in acetic acid, trifluoromethayl sulfonic acid, sulfuric acid, phosphoric acid；Then it is in batches more
It is secondary to add the aqueous hydrogen peroxide solution that enough mass fractions are 20% ~ 90%；After adding will the reaction was continued 5 ~ 24 it is small when, then will
Reaction system is poured into frozen water after cooling to room temperature, filters to obtain solid.Solid is dissolved in water, is neutral with alkali neutralization to pH, Gu
Body filters, and is drying to obtain 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide of energy-containing compound.
Route two：With 2,4,6- Triaminopyrimidines for reaction raw materials, successively oxidized, two reactions steps of nitrification are made and contain
Can compound 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide.
Under the conditions of temperature -10 ~ 100 DEG C, 2,4,6- triamido nitro-pyrimidines are dissolved in a certain amount of organic/inorganic acid
In, organic/inorganic acid used is trifluoroacetic acid, one kind in acetic acid, trifluoromethayl sulfonic acid, sulfuric acid, phosphoric acid；Then it is in batches multiple
Add the aqueous hydrogen peroxide solution that enough mass fractions are 20% ~ 90%；After adding will the reaction was continued 5 ~ 24 it is small when, then will be anti-
Answer system to be poured into after cooling to room temperature in frozen water, filter to obtain solid.Solid is dissolved in water, is neutral, solid with alkali neutralization to pH
Filter, the oxidation product of dry 2,4,6- Triaminopyrimidines, i.e., 2,4,6- Triaminopyrimidine -1,3- dioxide.
Under the conditions of temperature -10 ~ 50 DEG C, 2,4,6- Triaminopyrimidine -1,3- dioxide are repeatedly slowly added in batches
Into a certain amount of nitrating agent, nitrating agent used is that mass fraction is 90% ~ 100% nitric acid, nitric/sulfuric acid including mass fraction
Mixed liquor, nitric acid/acetic acid mixed liquor, nitric acid/trifluoroacetic acid mixed liquor, nitric acid/trifluoromethayl sulfonic acid mixed liquor, nitric acid/acetic acid
One kind in acid anhydride mixed liquor, nitric acid/trifluoroacetic anhydride mixed liquor or tetrafluoro boric acid nitryl reagent；The reaction was continued after adding 1 ~ 24
Hour, poured into after reaction system then is cooled to room temperature in frozen water, solid filters, is drying to obtain energy-containing compound 2,4,6-
Triamido -5- nitro-pyrimidine -1,3- dioxide.
Route three：It is former for reaction with 2,4,6- Triaminopyrimidine substituents, i.e., 2,4,6- triamido -5- nitrous yl pyrimidines
Material, 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide of energy-containing compound is made through a step oxidation reaction.
Under the conditions of temperature -10 ~ 100 DEG C, 2,4,6- triamido -5- nitrous yl pyrimidines are dissolved in a certain amount of organic/nothing
In machine acid, organic/inorganic acid used is trifluoroacetic acid, one kind in acetic acid, trifluoromethayl sulfonic acid, sulfuric acid, phosphoric acid；Then in batches
Repeatedly add the aqueous hydrogen peroxide solution that enough mass fractions are 20% ~ 90%；After adding will the reaction was continued 5 ~ 24 it is small when, then
Poured into after reaction system is cooled to room temperature in frozen water, filter to obtain solid.Solid is dissolved in water, is neutrality with alkali neutralization to pH,
Solid filters, is drying to obtain energy-containing compound 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide.
Embodiment 1
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route one）
（1）Under the conditions of -10 DEG C, 8ml fuming nitric aicds are slowly dropped in the 8ml concentrated sulfuric acids, 2g（16mmol）2,4,6- triamidos
Pyrimidine is repeatedly added in above-mentioned nitration mixture in batches, after adding, reaction system react at such a temperature 5 it is small when, reaction solution pours into
In frozen water, solid is filtered, it is dry, obtain 2,4,6- triamido -5- nitro-pyrimidines, yield 90%.
（2）Under the conditions of -10 DEG C, 1g（5.9 mmol）2,4,6- triamido -5- nitro-pyrimidines are dissolved in 5 ml trifluoroacetic acids
Middle stirring, is slowly added dropwise 2.5 ml aqueous hydrogen peroxide solutions（Hydrogen peroxide mass fraction：20 %）, after dripping, in this temperature
It is lower reaction 24 it is small when, filter, obtain solid.Solid is dissolved in water, and neutrality is neutralized to saturated aqueous sodium carbonate, filters solid and obtains 2,
4,6- triamido -5- nitro-pyrimidine -1,3- dioxide, yield 60%.Product analysis collection of illustrative plates is as shown in Fig. 1 ~ 3.
Embodiment 2
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route one）
（1）Under the conditions of 0 DEG C, 20 ml mass fractions are 2g in 100% nitric acid（16mmol）2,4,6- Triaminopyrimidines are in batches
Repeatedly be added to it is above-mentioned acid in, after adding, reaction system react at such a temperature 4 it is small when, reaction solution is poured into frozen water, filter
Solid, it is dry, obtain 2,4,6- triamido -5- nitro-pyrimidines, yield 92%.
（2）Under the conditions of 20 DEG C, 1g（5.9 mmol）2,4,6- triamido -5- nitro-pyrimidines are dissolved in the 10 ml concentrated sulfuric acids
Stirring, is slowly added dropwise 5 ml aqueous hydrogen peroxide solutions（Hydrogen peroxide mass fraction：27%）, after dripping, react at this temperature
12 it is small when, filter, obtain solid.Solid is dissolved in water, and neutrality is neutralized to unsaturated carbonate aqueous solutions of potassium, filters solid and obtains 2,4,6- tri-
Amino -5- nitro-pyrimidine -1,3- dioxide, yield 70%.Product analysis collection of illustrative plates is as shown in Fig. 1 ~ 3.
Embodiment 3
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route one）
（1）Under the conditions of 15 DEG C, 6ml fuming nitric aicds are slowly dropped in 6ml acetic anhydrides, 2g（16mmol）2,4,6- triamidos are phonetic
Pyridine is repeatedly added in above-mentioned nitration mixture in batches, and after adding, reaction system reacts 3 h at such a temperature, and reaction solution pours into frozen water
In, solid is filtered, it is dry, obtain 2,4,6- triamido -5- nitro-pyrimidines, yield 94%.
（2）Under the conditions of 50 DEG C, 1g（5.9 mmol）2,4,6- triamido -5- nitro-pyrimidines are dissolved in 20 ml fluoroforms
Stirred in sulfonic acid, 10 ml aqueous hydrogen peroxide solutions are slowly added dropwise（Hydrogen peroxide mass fraction：30 %）, it is warm herein after dripping
Degree 8 h of lower reaction, filter, obtain solid.Solid is dissolved in water, and neutrality is neutralized to saturated sodium bicarbonate aqueous solution, filters solid and obtains
2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide, yield 50%.Product analysis collection of illustrative plates is as shown in Fig. 1 ~ 3.
Embodiment 4
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide.（Route one）
（1）Under the conditions of 30 DEG C, 4ml fuming nitric aicds are slowly dropped in 4ml trifluoroacetic anhydride, 2 g（16mmol）2,4,6- tri-
Aminopyrimidine is repeatedly added in above-mentioned nitration mixture in batches, after adding, reaction system react at such a temperature 8 it is small when, reaction solution inclines
Pour into frozen water, filter solid, it is dry, obtain 2,4,6- triamido -5- nitro-pyrimidines, yield 75%.
（2）Under the conditions of 70 DEG C, 1g（5.9 mmol）2,4,6- triamido -5- nitro-pyrimidines, which are dissolved in 5 ml acetic acid, to be stirred
Mix, 3 ml aqueous hydrogen peroxide solutions are slowly added dropwise（Hydrogen peroxide mass fraction：50 %）, after dripping, 3 are reacted at this temperature
H, filters, obtains solid.Solid is dissolved in water, and neutrality is neutralized to saturated potassium hydrogen carbonate aqueous solution, filters solid and obtains 2,4,6- tri- ammonia
Base -5- nitro-pyrimidine -1,3- dioxide, yield 55%.Product analysis collection of illustrative plates is as shown in Fig. 1 ~ 3.
Embodiment 5
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route one）
（1）Under the conditions of 50 DEG C, 4 ml fuming nitric aicds are slowly dropped in the 4 ml concentrated sulfuric acids, 2 g（16mmol）Tri- ammonia of 2,4,6-
Yl pyrimidines are repeatedly added in above-mentioned nitration mixture in batches, after adding, reaction system react at such a temperature 0.5 it is small when, reaction solution inclines
Pour into frozen water, filter solid, it is dry, obtain 2,4,6- triamido -5- nitro-pyrimidines, 80 % of yield.
（2）Under the conditions of 100 DEG C, 1g（5.9 mmol）2,4,6- triamido -5- nitro-pyrimidines are dissolved in the 5 ml concentrated sulfuric acids
Stirring, is slowly added dropwise 1 ml aqueous hydrogen peroxide solutions（Hydrogen peroxide mass fraction：50 %）, after dripping, at this temperature instead
Answer 2 it is small when, filter, obtain solid.Solid is dissolved in water, and neutrality is neutralized to saturation sodium hydrate aqueous solution, filters solid and obtains 2,4,
6- triamido -5- nitro-pyrimidine -1,3- dioxide, yield 60%.Product analysis collection of illustrative plates is as shown in Fig. 1 ~ 3.
Embodiment 6
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route two）
（1）Under the conditions of -10 DEG C, 2g（16mmol）2,4,6- Triaminopyrimidines, which are dissolved in 10 ml acetic acid, to be stirred, and is slowly added dropwise
6ml aqueous hydrogen peroxide solutions（Hydrogen peroxide mass fraction：50%）, after dripping, when reaction 24 is small at this temperature, filters, obtain
Solid.Solid is dissolved in water, and neutrality is neutralized to saturation potassium hydroxide aqueous solution, filters solid and obtains 2,4,6- triamidos -1,3- bis-
Oxide, yield 80%.
（2）Under the conditions of -10 DEG C, 1g（6.4 mmol）2,4,6- triamido -1,3- dioxide is repeatedly added in batches
5ml mass fractions be 95% fuming nitric aicd in, after adding, reaction system react at such a temperature 10 it is small when, reaction solution pours into
In frozen water, solid is filtered, it is dry, obtain 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide, yield 75%.Product analysis
Collection of illustrative plates is as shown in Fig. 1 ~ 3.
Embodiment 7
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route two）
（1）Under the conditions of 10 DEG C, 2 g（16 mmol）2,4,6- Triaminopyrimidines, which are dissolved in 10 ml trifluoroacetic acids, to be stirred, and is delayed
It is slow that 3 ml aqueous hydrogen peroxide solutions are added dropwise（Hydrogen peroxide mass fraction：50%）, after dripping, when reaction 24 is small at this temperature,
Filter, obtain solid.Solid is dissolved in water, and neutrality is neutralized to saturated aqueous sodium carbonate, filters solid and obtains 2,4,6- triamido -1,
3- dioxide, yield 80%.
（2）Under the conditions of 0 DEG C, 1g（6.4 mmol）2,4,6- triamido -1,3- dioxide is dissolved in the 5 ml concentrated sulfuric acids
In, then 5 ml fuming nitric aicds are slowly added dropwise, after dripping, the reaction was continued 10 it is small when, reaction solution is poured into frozen water, is filtered solid
Body, it is dry, obtain 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide, yield 65%.The institute of product analysis collection of illustrative plates such as Fig. 1 ~ 3
Show.
Embodiment 8
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route two）
（1）Under the conditions of 30 DEG C, 2 g（16 mmol）2,4,6- Triaminopyrimidines, which are dissolved in 5 ml trifluoroacetic acids, to be stirred, slowly
5 ml aqueous hydrogen peroxide solutions are added dropwise（Hydrogen peroxide mass fraction：35 %）, after dripping, when reaction 12 is small at this temperature,
Filter, obtain solid.Solid is dissolved in water, and neutrality is neutralized to unsaturated carbonate aqueous solutions of potassium, filters solid and obtains 2,4,6- triamido -1,
3- dioxide, yield 80%.
（2）Under the conditions of 10 DEG C, 1g（6.4 mmol）2,4,6- triamido -1,3- dioxide is dissolved in 20 ml trifluoro second
In acid, then 10 ml fuming nitric aicds are slowly added dropwise, after dripping, the reaction was continued 15h, reaction solution is poured into frozen water, is filtered solid
Body, it is dry, obtain 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide, yield 50%.The institute of product analysis collection of illustrative plates such as Fig. 1 ~ 3
Show.
Embodiment 9
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route two）
（1）Under the conditions of 60 DEG C, 2 g（16 mmol）2,4,6- Triaminopyrimidines, which are dissolved in the 5 ml concentrated sulfuric acids, to be stirred, slowly drop
Add 5 ml aqueous hydrogen peroxide solutions（Hydrogen peroxide mass fraction：27 %）, after dripping, 6 h are reacted at this temperature, are filtered,
Obtain solid.Solid is dissolved in water, and neutrality is neutralized to saturated sodium bicarbonate aqueous solution, filters solid and obtains 2,4,6- triamidos -1,3-
Dioxide, yield 72%.
（2）Under the conditions of 30 DEG C, 1g（6.4 mmol）2,4,6- triamido -1,3- dioxide is dissolved in 20 ml acetic acid
In, then 10 ml fuming nitric aicds are slowly added dropwise, after dripping, the reaction was continued 10 it is small when, reaction solution is poured into frozen water, is filtered solid
Body, it is dry, obtain 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide, yield 53%.The institute of product analysis collection of illustrative plates such as Fig. 1 ~ 3
Show.
Embodiment 10
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route two）.
（1）Under the conditions of 100 DEG C, 2 g（16 mmol）2,4,6- Triaminopyrimidines, which are dissolved in the 5 ml concentrated sulfuric acids, to be stirred,
5 ml aqueous hydrogen peroxide solutions are slowly added dropwise（Hydrogen peroxide mass fraction：20 %）, after dripping, it is small that 2 are reacted at this temperature
When, filter, obtain solid.Solid is dissolved in water, and neutrality is neutralized to saturated potassium hydrogen carbonate aqueous solution, filters solid and obtains 2,4,6- tri- ammonia
Base -1,3- dioxide, yield 72%.
（2）Under the conditions of 50 DEG C, 1g（6.4 mmol）2,4,6- triamido -1,3- dioxide is dissolved in 10 ml acetic acid
In acid anhydride, then 10 ml fuming nitric aicds are slowly added dropwise, after dripping, the reaction was continued 3 it is small when, reaction solution is poured into frozen water, filter
Solid, it is dry, obtain 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide, yield 62%.Product analysis collection of illustrative plates such as Fig. 1 ~ 3
It is shown.
Embodiment 11
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route three）.
Under the conditions of -10 DEG C of temperature, by 1g（6.5 mmol）2,4,6- triamido -5- nitrous yl pyrimidines are dissolved in 5ml tri-
Fluoroacetic acid, is slowly added dropwise 4 ml aqueous hydrogen peroxide solutions（Hydrogen peroxide mass fraction：50 %）, after adding, reaction system is at this
At a temperature of reaction 24 it is small when, reaction solution is poured into frozen water, filter, obtain solid.Solid is dissolved in water, uses saturated aqueous sodium carbonate
Neutrality is neutralized to, solid is filtered, obtains 2,4,6- triamido -1,3- dioxide, 60 % of yield.
Embodiment 12
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route three）.
Under the conditions of 0 DEG C of temperature, by 1 g（6.5 mmol）2,4,6- triamido -5- nitrous yl pyrimidines are dissolved in 10 ml vinegar
Acid, is slowly added dropwise 10 ml aqueous hydrogen peroxide solutions（Hydrogen peroxide mass fraction：50 %）, after adding, reaction system is in the temperature
It is lower reaction 24 it is small when, reaction solution is poured into frozen water, filter, obtain solid.Solid is dissolved in water, is neutralized with unsaturated carbonate aqueous solutions of potassium
To neutrality, solid is filtered, it is dry, obtain 2,4,6- triamido -1,3- dioxide, 70 % of yield.
Embodiment 13
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route three）.
Under the conditions of 20 DEG C of temperature, by 1 g（6.5 mmol）It is dense that 2,4,6- triamido -5- nitrous yl pyrimidines are dissolved in 10 ml
Sulfuric acid, is slowly added dropwise 10 ml aqueous hydrogen peroxide solutions（Hydrogen peroxide mass fraction：35 %）, after adding, reaction system is in the temperature
When the lower reaction 15 of degree is small, reaction solution is poured into frozen water, is filtered, is obtained solid.Solid is dissolved in water, uses saturated sodium bicarbonate aqueous solution
Neutrality is neutralized to, filters solid, it is dry, obtain 2,4,6- triamido -1,3- dioxide, 65 % of yield.
Embodiment 14
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route three）.
Under the conditions of 30 DEG C of temperature, by 1 g（6.5 mmol）2,4,6- triamido -5- nitrous yl pyrimidines are dissolved in 5 ml tri-
Fluorine methanesulfonic acid, is slowly added dropwise 5 ml aqueous hydrogen peroxide solutions（Hydrogen peroxide mass fraction：27 %）, after adding, reaction system exists
When reaction 12 is small at this temperature, reaction solution is poured into frozen water, is filtered, is obtained solid.Solid is dissolved in water, with saturated potassium hydrogen carbonate water
Solution is neutralized to neutrality, filters solid, dry, obtains 2,4,6- triamido -1,3- dioxide, 53 % of yield.
Embodiment 15
The preparation of 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide（Route three）.
Under the conditions of 50 DEG C of temperature, by 1 g（6.5 mmol）It is dense that 2,4,6- triamido -5- nitrous yl pyrimidines are dissolved in 5 ml
Sulfuric acid, is slowly added dropwise 5 ml aqueous hydrogen peroxide solutions（Hydrogen peroxide mass fraction：20 %）, after adding, reaction system is in the temperature
When the lower reaction 6 of degree is small, reaction solution is poured into frozen water, is filtered, is obtained solid.Solid is dissolved in water, with saturation sodium hydrate aqueous solution
Neutrality is neutralized to, filters solid, it is dry, obtain 2,4,6- triamido -1,3- dioxide, 56 % of yield.
Claims (4)
1. energy-containing compound 2,4, the preparation method of 6- triamido -5- nitro-pyrimidine -1,3- dioxide, it is characterised in that：Institute
Preparation method is stated to include the following steps：With 2,4,6- Triaminopyrimidines and its substituent for reaction raw materials, nitration reaction is carried out；Into
Row oxidation reaction；Carry out acid-base neutralization reaction；Required product energy-containing compound 2,4,6- triamido -5- nitro-pyrimidine -1 is obtained,
3- dioxide；
2,4,6- Triaminopyrimidines substituent is 2,4,6- triamido -5- nitrous yl pyrimidines；
The nitrating agent of nitration reaction is that mass fraction is 90% ~ 100% nitric acid and sulfuric acid, acetic acid, trifluoroacetic acid mixed liquor, trifluoro
A kind of mixed liquor in Loprazolam, acetic anhydride, trifluoroacetic anhydride；The nitrating agent of nitration reaction is 90% ~ 100% nitric acid or four
Fluoboric acid nitryl reagent；
The temperature of nitration reaction is -10 ~ 50 DEG C；
The oxidising agent of oxidation reaction is acetic acid/hydrogen peroxide solution, trifluoromethayl sulfonic acid/hydrogen peroxide solution, trifluoro
Acetic acid/hydrogen peroxide solution, sulfuric acid/hydrogen peroxide solution；
The temperature of oxidation reaction is -10 ~ 100 DEG C；
Alkali in acid-base neutralization reaction is sodium hydroxide, in potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, saleratus
It is a kind of.
2. preparation method according to claim 1, it is characterised in that：Wherein the reaction time of nitrifying process is small for 1 ~ 24
When.
3. preparation method according to claim 1, it is characterised in that：Wherein the reaction time of oxidizing process is small for 1 ~ 24
When.
4. preparation method according to claim 1, it is characterised in that：Wherein hydrogen peroxide refer to mass fraction for 20% ~
90% aqueous hydrogen peroxide solution.
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Cited By (5)
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| CN108314597A (en) * | 2018-05-09 | 2018-07-24 | 中国工程物理研究院化工材料研究所 | 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide and nitric acid self-assembled crystal and preparation method thereof |
| CN108586169A (en) * | 2018-05-09 | 2018-09-28 | 中国工程物理研究院化工材料研究所 | 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide and hydrogen peroxide self-assembled crystal and preparation method |
| CN109438366A (en) * | 2018-12-03 | 2019-03-08 | 中国工程物理研究院化工材料研究所 | 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide and perchloric acid the self assembly crystalline material containing energy |
| CN110117212A (en) * | 2019-05-29 | 2019-08-13 | 中国工程物理研究院化工材料研究所 | Melamine nitrogen oxides and the crystalline material containing energy of oxidant self assembly and preparation method thereof |
| CN113354598A (en) * | 2021-07-06 | 2021-09-07 | 南京欧纳壹有机光电有限公司 | Simple and efficient nitration method of aromatic heterocyclic compound |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314597A (en) * | 2018-05-09 | 2018-07-24 | 中国工程物理研究院化工材料研究所 | 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide and nitric acid self-assembled crystal and preparation method thereof |
| CN108586169A (en) * | 2018-05-09 | 2018-09-28 | 中国工程物理研究院化工材料研究所 | 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide and hydrogen peroxide self-assembled crystal and preparation method |
| CN108586169B (en) * | 2018-05-09 | 2020-04-28 | 中国工程物理研究院化工材料研究所 | 2,4, 6-triamino-5-nitropyrimidine-1, 3-dioxide and hydrogen peroxide self-assembled crystal and preparation method thereof |
| CN109438366A (en) * | 2018-12-03 | 2019-03-08 | 中国工程物理研究院化工材料研究所 | 2,4,6- triamido -5- nitro-pyrimidine -1,3- dioxide and perchloric acid the self assembly crystalline material containing energy |
| CN110117212A (en) * | 2019-05-29 | 2019-08-13 | 中国工程物理研究院化工材料研究所 | Melamine nitrogen oxides and the crystalline material containing energy of oxidant self assembly and preparation method thereof |
| CN110117212B (en) * | 2019-05-29 | 2021-03-16 | 中国工程物理研究院化工材料研究所 | Energy-containing crystal material self-assembled by melamine nitrogen oxide and oxidant and preparation method thereof |
| CN113354598A (en) * | 2021-07-06 | 2021-09-07 | 南京欧纳壹有机光电有限公司 | Simple and efficient nitration method of aromatic heterocyclic compound |
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