CN107266376B - LLM-105 nitramine derivatives and preparation method thereof - Google Patents

LLM-105 nitramine derivatives and preparation method thereof Download PDF

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CN107266376B
CN107266376B CN201710600436.8A CN201710600436A CN107266376B CN 107266376 B CN107266376 B CN 107266376B CN 201710600436 A CN201710600436 A CN 201710600436A CN 107266376 B CN107266376 B CN 107266376B
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dimethoxypyrazine
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CN107266376A (en
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黄琪
李洪珍
聂福德
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Institute of Chemical Material of CAEP
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having 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
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Abstract

The invention discloses kinds of LLM-105 nitramine derivatives and a preparation method thereof.A LLM-105 nitramine derivative is prepared by using 2, 6-dimethoxypyrazine as a raw material through oxidation, nitration, amination and re-nitration reactions in turn. effective methods for preparing the LLM-105 nitramine derivative are provided.

Description

LLM-105 nitramine derivatives and preparation method thereof
Technical Field
The invention relates to the field of organic synthesis, in particular to LLM-105 nitramine derivatives and a preparation method thereof.
Background
The pyrazine compound has high enthalpy of formation due to a large amount of N-N and C-N contained in molecules, has higher oxygen balance and higher density compared with the traditional energetic materials TNT, RDX and HMX, is a six-membered heterocyclic compound containing two nitrogen atoms on a ring, has the nitrogen content of 35 percent, and can be used as good choices for researching high-energy-density energetic materials due to the high nitrogen content.
The 2, 6-diamino-3, 5-dinitro-1-oxopyrazine, LLM-105, was synthesized by Lorentz & Levermore national laboratory of laboratories (LLNL) in USA for the first time and attracted the attention of researchers' . LLM-105 is not sensitive to shock, spark and friction, has 15% higher capacity than TATB, is recognized to be kinds of insensitive explosives with good stability and constant energy level. numerous reports have studied the synthesis, structure and properties of LLM-105, confirming that LLM-105 is expected to be used as a passive initiator, booster, and special weapon main explosive, etc., and has a broad prospect in weapon application of . therefore, the development of pyrazine-based framework structures based on LLM-105 has important research value.
Disclosure of Invention
[ problem to be solved ]
The present invention aims at solving the problems of the prior art and providing kinds of LLM-105 nitramine derivatives and a preparation method thereof.
[ solution ]
In order to achieve the technical effects, the invention adopts the following technical scheme:
preparation method of LLM-105 nitramine derivatives, which is prepared by using 2, 6-dimethoxy pyrazine as raw material through oxidation, nitration, amination and re-nitration in turn.
According to a further embodiment of the present invention at step , the method comprises the steps of:
oxidation of A, 2, 6-dimethoxypyrazine
Preparing an oxidizing reagent solution at room temperature, and slowly dissolving 2, 6-dimethoxypyrazine in an oxidant solution; then, stirring and reacting for 2-12 hours at room temperature-80 ℃; after the reaction is finished, slowly pouring the reaction system into ice water; extracting for 3-9 times by using ethyl acetate, combining organic phases, and drying by using anhydrous magnesium sulfate; carrying out vacuum filtration, carrying out rotary evaporation under reduced pressure to remove the solvent, and drying to obtain a white solid product, namely 2, 6-dimethoxypyrazine-4-oxide;
nitration of B, 2, 6-dimethoxypyrazine-4-oxide
Slowly adding the 2, 6-dimethoxypyrazine-4-oxide prepared in the step A into sulfuric acid at the temperature of 0-10 ℃, stirring until the mixture is completely dissolved, and slowly adding a nitrating agent; continuously stirring for 30min at the temperature of 0-10 ℃, slowly heating the reaction system to room temperature, and continuously stirring for 4 h; after the reaction is finished, slowly pouring the reaction system into ice water to separate out a light yellow solid; carrying out vacuum filtration, washing by deionized water and drying to obtain a light yellow solid product, namely 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide;
preparation of C, LLM-105 alkyl derivatives
At room temperature, dissolving the 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide prepared in the step B in an organic solvent; slowly adding enough amine, stirring the reaction system at room temperature to 100 ℃ for 2-48 h, pouring the reaction system into ice water, and sequentially filtering, washing and drying to obtain the LLM-105 alkyl derivative;
nitration of D, LLM-105 alkyl derivatives
Slowly adding sufficient fuming nitric acid with the concentration of 90-100% into acid anhydride at the temperature of-10-20 ℃, and then slowly adding the LLM-105 alkyl derivative prepared in the step C; after the addition, the reaction system is stirred for 2-8 h at the temperature of-10-25 ℃; then pouring the reaction system into ice water, and sequentially filtering, washing and drying to obtain the nitramine derivative of LLM-105.
According to the technical scheme of step , in step A, the mass-to-volume ratio of the 2, 6-dimethoxypyrazine to the oxidant solution is 1g (5-20) mL, the oxidant in the oxidant solution is hydrogen peroxide or potassium hydrogen persulfate, and the oxidant solution is a solution prepared by mixing an oxidant with acetic acid, trifluoroacetic acid or sulfuric acid and the concentration of the oxidant is 10% -30%.
According to the technical scheme of step , in step B, the mass-to-volume ratio of the 2, 6-dimethoxypyrazine-4-oxide to the sulfuric acid is 1g (1-20) mL, the nitrating agent is nitric acid, fuming nitric acid, sodium nitrate or potassium nitrate, and the mass ratio of the 2, 6-dimethoxypyrazine-4-oxide to the nitrating agent is 1: 2-20.
According to the technical scheme of step , in step C, the mass-to-volume ratio of the 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide to the organic solvent is 1g (5-50) mL, the organic solvent is acetonitrile, methanol, ethanol, tetrahydrofuran, acetone or N, N-dimethylformamide, and the mass ratio of the 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide to the amine is 1: 2-8.
According to the technical scheme of step , in step D, the acid anhydride is acetic anhydride or trifluoroacetic anhydride, the fuming nitric acid is fuming nitric acid with the concentration of 95% -100%, the volume ratio of the acid anhydride to the fuming nitric acid is 1: 0.5-3, and the mass volume ratio of the LLM-105 alkyl derivative to the fuming nitric acid is 1g (2-50) mL.
According to a further embodiment of the present invention in step , in step C, the amine is methylamine, ethanolamine, methyl glycinate, methyl 3-aminopropionate or aminoacetonitrile.
the LLM-105 nitroamine derivative prepared by the above preparation method.
It has the following chemical structural formula:
wherein R is CH3、CH2CH2ONO2、CH2COOCH3、CH2CH2COOCH3Or CH2CN。
The present invention will be described in detail below.
The LLM-105 nitramine derivative is prepared by taking 2, 6-dimethoxypyrazine as a raw material and performing oxidation, nitration, amination and re-nitration respectively; the reaction for its preparation is as follows:
Figure BDA0001357006740000042
wherein, R is1Is CH3、CH2CH2OH、CH2COOCH3、CH2CH2COOCH3Or CH2CN, R is CH3、CH2CH2ONO2、CH2COOCH3、CH2CH2COOCH3Or CH2CN。
The room temperature referred to in the present invention means 25 ℃. Because the energetic material is prepared by the method, the temperature is not easy to be overhigh in the whole preparation process. Within the range of the parameters of the invention, the prepared LLM-105 nitramine derivative has higher yield and purity.
[ advantageous effects ]
Compared with the prior art, the invention has the following beneficial effects:
compared with the prior art, the invention has the advantages that modification based on the LLM-105 molecular structure is not reported, and the synthesis of the LLM-105 nitramine derivative is not reported yet, the invention provides effective methods for preparing the LLM-105 nitramine derivative, and the calculation shows that the derivative has higher detonation performance and potential application value than the precursor LLM-105, wherein the calculated detonation velocity of the LLM-105 is 8560m/s, the calculated detonation pressure is 33.4GPa, the calculated detonation velocity of the LLM-105 nitramine derivative is 7070-8940 m/s, and the calculated detonation pressure is 17.2-36.8 GPa.
Detailed Description
The invention is further illustrated and described in with reference to examples of the invention.
When R is1＝CH3；R＝CH3The preparation of LLM-105 derivatives is shown below:
Figure BDA0001357006740000051
the concrete examples are as shown in examples 1 to 3.
Example 1:
at room temperature, 20 ml of 30% hydrogen peroxide is slowly added into 20 ml of acetic acid, and then 4g of 2, 6-dimethoxypyrazine is added into the oxidant solution. After the reaction solution is dissolved, heating the reaction system to 55 ℃ and reacting for 4 hours; after the reaction is finished, cooling the reaction system to room temperature, and pouring the reaction system into ice water; extracting with ethyl acetate for 9 times, mixing organic phases, and drying with anhydrous magnesium sulfate; after filtering off the solid, the filtrate was subjected to rotary evaporation under reduced pressure to remove the solvent, to obtain a white solid product, 2, 6-dimethoxypyrazine-4-oxide, in 68% yield.
Adding 3 g of 2, 6-dimethoxypyrazine-4-oxide into 25 ml of sulfuric acid at the temperature of 5 ℃, slowly adding 8.5 g of sodium nitrate in batches after the 2, 6-dimethoxypyrazine-4-oxide is dissolved; after the addition is finished, continuously stirring for 30min at the temperature of 8 ℃; then slowly heating the reaction system to room temperature, and stirring for reaction for 4 hours; after the reaction is finished, slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake for multiple times by using deionized water, and drying to obtain a yellow solid product 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide with the yield of 61%.
2 g of 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide are dissolved in 30 ml of acetonitrile, 2 g of commercially available 40% aqueous methylamine solution are dissolved in 20 ml of acetonitrile; slowly adding the acetonitrile solution of methylamine into the acetonitrile solution of 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide; after stirring at room temperature for 36 hours, the reaction system was poured into ice water; and (3) carrying out suction filtration on the separated yellow solid under reduced pressure, washing a filter cake with deionized water, and drying to obtain the LLM-105 alkyl derivative compound 1 with the yield of 93%.
Slowly adding 10 ml of acetic anhydride into 10 ml of fuming nitric acid with the concentration of 100% at the temperature of 0 ℃, stirring for 10 minutes, and slowly adding 1g of compound 1 into the solution; after continuously stirring for 1 hour at 0 ℃, slowly heating the reaction system to 10 ℃, and continuously stirring for 4 hours; slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake by deionized water, and drying to obtain the nitramine derivative compound 2 of LLM-105 with the yield of 88%.
Example 2
Slowly adding 10 ml of 30% hydrogen peroxide into 10 ml of trifluoroacetic acid, and adding 2 g of 2, 6-dimethoxypyrazine into the oxidant solution; after the reaction solution is dissolved, heating the reaction system to 55 ℃ and reacting for 4 hours; after the reaction is finished, cooling the reaction system to room temperature, and pouring the reaction system into ice water; extracting with ethyl acetate for 8 times, mixing organic phases, and drying with anhydrous magnesium sulfate; after filtering off the solid, the filtrate was subjected to rotary evaporation under reduced pressure to remove the solvent, to obtain a white solid product, 2, 6-dimethoxypyrazine-4-oxide, with a yield of 65%.
Adding 1.5 g of 2, 6-dimethoxypyrazine-4-oxide into 10 ml of sulfuric acid at the temperature of 5 ℃, slowly adding 5 g of potassium nitrate in batches after the sulfuric acid is dissolved; after the addition is finished, continuously stirring for 30min at the temperature of 5 ℃; slowly heating the reaction system to room temperature, and stirring for reaction for 4 hours; after the reaction is finished, slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake for multiple times by using deionized water, and drying to obtain a yellow solid product 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide with the yield of 60%.
1g of 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide is dissolved in 30 ml of acetonitrile. Dissolving 1.5 grams of a commercially available 40% aqueous methylamine solution in the above solution; after stirring at room temperature for 36 hours, the reaction system was poured into ice water; and (3) carrying out suction filtration on the separated yellow solid under reduced pressure, washing a filter cake with deionized water, and drying to obtain the LLM-105 alkyl derivative compound 1 with the yield of 91%.
Slowly adding 5 ml of acetic anhydride into 8 ml of fuming nitric acid with the concentration of 98 percent at the temperature of 0 ℃; after stirring for 10 minutes, 0.5 g of compound 1 was slowly added to the above solution; after continuously stirring for 1 hour at 0 ℃, slowly heating the reaction system to 10 ℃, and continuously stirring for 4 hours; slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake with deionized water, and drying to obtain the LLM-105 nitramine derivative compound 2 with the yield of 86%.
Example 3
Slowly adding 10 ml of 30% hydrogen peroxide into 10 ml of acetic acid, and then adding 2 g of 2, 6-dimethoxypyrazine into the oxidant solution; after the reaction solution is dissolved, heating the reaction system to 55 ℃ and reacting for 6 hours; after the reaction is finished, cooling the reaction system to room temperature, and pouring the reaction system into ice water; extracting with ethyl acetate for 6 times, mixing organic phases, and drying with anhydrous magnesium sulfate; after filtering off the solid, the filtrate was subjected to rotary evaporation under reduced pressure to remove the solvent, to obtain a white solid product, 2, 6-dimethoxypyrazine-4-oxide, with a yield of 60%.
Adding 1g of 2, 6-dimethoxypyrazine-4-oxide into 10 ml of sulfuric acid at the temperature of 5 ℃, and slowly dropwise adding 8 ml of fuming nitric acid after the sulfuric acid is dissolved; after the addition is finished, continuously stirring for 30min at the temperature of 8 ℃; slowly heating the reaction system to room temperature, and stirring for reaction for 4 hours; after the reaction is finished, slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake for multiple times by using deionized water, and drying to obtain a yellow solid product 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide with the yield of 58%.
Dissolving 0.5 g of 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide in 10 ml of acetonitrile; 1g of a commercially available 40% aqueous methylamine solution is dissolved in 10 ml of acetonitrile; slowly adding the acetonitrile solution of methylamine into the acetonitrile solution of 2, 6-dimethoxypyrazine-4-oxide; heating the reaction system to 60 ℃, and stirring for 6 hours; after the reaction is finished, pouring the reaction system into ice water; and (3) carrying out vacuum filtration on the separated yellow solid, washing a filter cake by deionized water, and drying to obtain the LLM-105 alkyl derivative compound 1 with the yield of 76%.
5 ml of acetic anhydride were slowly added to 8 ml of 100% strength fuming nitric acid at 0 ℃. After stirring for 10 minutes, 0.5 g of compound 1 was slowly added to the above solution; after continuing stirring for 1 hour at 0 ℃, slowly heating the reaction system to room temperature, and continuing stirring for 2 hours; slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake with deionized water, and drying to obtain the LLM-105 nitramine derivative compound 2 with the yield of 84%.
When R is1＝CH2CH2OH；R＝CH2CH2ONO2The preparation of LLM-105 derivatives is shown below:
Figure BDA0001357006740000081
the specific examples are shown in examples 4 to 6.
Example 4:
slowly adding 20 ml of 30% hydrogen peroxide into 20 ml of acetic acid, and then adding 4g of 2, 6-dimethoxypyrazine into the oxidant solution; after it is dissolved; heating the reaction system to 55 ℃ and reacting for 2 hours; after the reaction is finished, cooling the reaction system to room temperature, and pouring the reaction system into ice water; extracting with ethyl acetate for 9 times, mixing organic phases, and drying with anhydrous magnesium sulfate; after filtering off the solid, the filtrate was subjected to rotary evaporation under reduced pressure to remove the solvent, to obtain a white solid product, 2, 6-dimethoxypyrazine-4-oxide, with a yield of 52%.
Adding 3 g of 2, 6-dimethoxypyrazine-4-oxide into 25 ml of sulfuric acid at the temperature of 5 ℃, slowly adding 8.5 g of sodium nitrate in batches after the 2, 6-dimethoxypyrazine-4-oxide is dissolved; after the addition is finished, continuously stirring for 30min at the temperature of 8 ℃; slowly heating the reaction system to room temperature, and stirring for reaction for 6 hours; after the reaction is finished, slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake for multiple times by using deionized water, and drying to obtain a yellow solid product 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide with the yield of 42%.
2 g of 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide are dissolved in 30 ml of acetonitrile. 1g hydroxyethylamine is dissolved in 20 ml acetonitrile; slowly adding the acetonitrile solution of methylamine into the acetonitrile solution of 2, 6-dimethoxypyrazine-4-oxide; after stirring at room temperature for 36 hours, the reaction system was poured into ice water; and (3) carrying out vacuum filtration on the separated yellow solid, washing a filter cake with deionized water, and drying to obtain the LLM-105 alkyl derivative compound 3 with the yield of 95%.
10 ml of acetic anhydride were slowly added to 10 ml of 100% strength fuming nitric acid at 0 ℃. After stirring for 10 minutes, 1g of compound 3 is slowly added to the above solution; after continuously stirring for 1 hour at 0 ℃, slowly heating the reaction system to 10 ℃, and continuously stirring for 4 hours; slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake with deionized water, and drying to obtain the LLM-105 nitramine derivative compound 4 with the yield of 73%.
Example 5
Slowly adding 10 ml of 30% hydrogen peroxide into 10 ml of acetic acid, and then adding 2 g of 2, 6-dimethoxypyrazine into the oxidant solution; after the reaction solution is dissolved, heating the reaction system to 45 ℃ and reacting for 4 hours; after the reaction is finished, cooling the reaction system to room temperature, and pouring the reaction system into ice water; extracting with ethyl acetate for 6 times, mixing organic phases, and drying with anhydrous magnesium sulfate; after filtering off the solid, the filtrate was subjected to rotary evaporation under reduced pressure to remove the solvent, to obtain a white solid product, 2, 6-dimethoxypyrazine-4-oxide, with a yield of 41%.
Adding 1.5 g of 2, 6-dimethoxypyrazine-4-oxide into 10 ml of sulfuric acid at the temperature of 5 ℃, slowly adding 5 g of potassium nitrate in batches after the sulfuric acid is dissolved; after the addition is finished, continuously stirring for 30min at the temperature of 5 ℃; slowly heating the reaction system to room temperature, and stirring for reaction for 2 hours; after the reaction is finished, slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake for multiple times by using deionized water, and drying to obtain a yellow solid product 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide with the yield of 41%.
1g of 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide is dissolved in 30 ml of acetonitrile; 0.8 g hydroxyethylamine was dissolved in 20 ml acetonitrile; slowly adding the acetonitrile solution of methylamine into the acetonitrile solution of 2, 6-dimethoxypyrazine-4-oxide; after stirring at room temperature for 24 hours, the reaction was poured into ice water. And (3) carrying out suction filtration on the separated yellow solid under reduced pressure, washing a filter cake with deionized water, and drying to obtain the LLM-105 alkyl derivative compound 3 with the yield of 87%.
5 ml of acetic anhydride were slowly added to 8 ml of 98% strength fuming nitric acid at 0 ℃. After stirring for 10 minutes, 0.5 g of compound 3 is slowly added to the above solution; after continuously stirring for 1 hour at 0 ℃, slowly heating the reaction system to 10 ℃, and continuously stirring for 6 hours; slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake with deionized water, and drying to obtain the LLM-105 nitramine derivative compound 4 with the yield of 85%.
Example 6
Slowly adding 10 ml of 30% hydrogen peroxide into 10 ml of acetic acid, and then adding 2 g of 2, 6-dimethoxypyrazine into the oxidant solution; after the reaction solution is dissolved, heating the reaction system to 45 ℃ and reacting for 6 hours; after the reaction is finished, cooling the reaction system to room temperature, and pouring the reaction system into ice water; extracting with ethyl acetate for 6 times, combining organic phases, drying with anhydrous magnesium sulfate, filtering off solids, and removing the solvent by performing rotary evaporation on the filtrate under reduced pressure to obtain a white solid product, namely 2, 6-dimethoxypyrazine-4-oxide, with the yield of 53%.
Adding 1g of 2, 6-dimethoxypyrazine-4-oxide into 10 ml of sulfuric acid at the temperature of 5 ℃, and slowly dropwise adding 8 ml of fuming nitric acid after the sulfuric acid is dissolved; after the addition is finished, continuously stirring for 30min at the temperature of 8 ℃; slowly heating the reaction system to 50 ℃, and stirring for reaction for 2 hours; after the reaction is finished, slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake for multiple times by using deionized water, and drying to obtain a yellow solid product 2, 6-dimethoxy-3, 5-dinitropyrazine-4 oxide with the yield of 49%.
Dissolving 0.5 g of 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide in 10 ml of acetonitrile; 0.5 g hydroxyethylamine was dissolved in 10 ml acetonitrile; slowly adding the acetonitrile solution of methylamine into the acetonitrile solution of 2, 6-dimethoxypyrazine-4-oxide; heating the reaction system to 60 ℃, and stirring for 4 hours; after the reaction is finished, pouring the reaction system into ice water; and (3) carrying out vacuum filtration on the separated yellow solid, washing a filter cake with deionized water, and drying to obtain the LLM-105 alkyl derivative compound 3 with the yield of 65%.
5 ml of acetic anhydride were slowly added to 8 ml of 100% strength fuming nitric acid at 0 ℃; after stirring for 10 minutes, 0.5 g of compound 3 is slowly added to the above solution; after continuing stirring for 1 hour at 0 ℃, slowly heating the reaction system to room temperature, and continuing stirring for 2 hours; slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake with deionized water, and drying to obtain the LLM-105 nitramine derivative compound 4 with the yield of 47%.
Example 7
When R is1＝CH2COOCH3；R＝CH2COOCH3The preparation of LLM-105 derivatives is shown below:
Figure BDA0001357006740000101
slowly adding 20 ml of 30% hydrogen peroxide into 20 ml of acetic acid, and then adding 4g of 2, 6-dimethoxypyrazine into the oxidant solution; after the reaction solution is dissolved, the temperature of the reaction system is raised to 60 ℃ and the reaction is carried out for 4 hours. After the reaction is finished, cooling the reaction system to room temperature, and pouring the reaction system into ice water; extracting with ethyl acetate for 9 times, mixing organic phases, and drying with anhydrous magnesium sulfate; after filtering off the solid, the filtrate was subjected to rotary evaporation under reduced pressure to remove the solvent, to obtain a white solid product, 2, 6-dimethoxypyrazine-4-oxide, in 66% yield.
Adding 3 g of 2, 6-dimethoxypyrazine-4-oxide into 25 ml of sulfuric acid at the temperature of 5 ℃, slowly adding 8.5 g of sodium nitrate in batches after the 2, 6-dimethoxypyrazine-4-oxide is dissolved; after the addition is finished, continuously stirring for 30min at the temperature of 10 ℃; then slowly heating the reaction system to room temperature, and stirring for reaction for 4 hours; after the reaction is finished, slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake for multiple times by using deionized water, and drying to obtain a yellow solid product 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide with the yield of 60%.
2 g of 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide is dissolved in 50 ml of acetonitrile; 1.8 g of glycine methyl ester are added in portions to the above solution; after stirring at room temperature for 36 hours, the reaction system was poured into ice water; and (3) carrying out vacuum filtration on the separated yellow solid, washing a filter cake with deionized water, and drying to obtain the LLM-105 alkyl derivative compound 5 with the yield of 90%.
Slowly adding 10 ml of acetic anhydride into 10 ml of fuming nitric acid with the concentration of 100 percent at the temperature of 0 ℃; after stirring for 10 minutes, 1g of compound 5 is slowly added to the above solution; after continuously stirring for 1 hour at 0 ℃, slowly heating the reaction system to 10 ℃, and continuously stirring for 4 hours; slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake with deionized water, and drying to obtain the nitramine derivative compound 6 of LLM-105 with the yield of 86%.
Example 8
When R is1＝CH2CH2COOCH3；R＝CH2CH2COOCH3The preparation of LLM-105 derivatives is shown below:
20 ml of 30% hydrogen peroxide is slowly added to 20 ml of acetic acid, and 4g of 2, 6-dimethoxypyrazine is added to the oxidation solution. After the reaction solution was dissolved, the reaction system was heated to 55 ℃ and reacted for 4 hours. After the reaction is finished, cooling the reaction system to room temperature, and pouring the reaction system into ice water; extracting with ethyl acetate for 6 times, mixing organic phases, and drying with anhydrous magnesium sulfate; after filtering off the solid, the filtrate was subjected to rotary evaporation under reduced pressure to remove the solvent, to obtain a white solid product, 2, 6-dimethoxypyrazine-4-oxide, with a yield of 60%.
Adding 3 g of 2, 6-dimethoxypyrazine-4-oxide into 25 ml of sulfuric acid at the temperature of 5 ℃, slowly adding 8.5 g of sodium nitrate in batches after the 2, 6-dimethoxypyrazine-4-oxide is dissolved; after the addition is finished, continuously stirring for 30min at the temperature of 5 ℃; then slowly heating the reaction system to room temperature, and stirring for reaction for 4 hours; after the reaction is finished, slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake for multiple times by using deionized water, and drying to obtain a yellow solid product 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide with the yield of 57%.
2 g of 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide are dissolved in 50 ml of acetonitrile. 2 g of methyl 3-aminopropionate are added in portions to the above solution. After stirring at room temperature for 36 hours, the reaction was poured into ice water. And (3) carrying out suction filtration on the separated yellow solid under reduced pressure, washing a filter cake with deionized water, and drying to obtain the LLM-105 alkyl derivative compound 7 with the yield of 88%.
10 ml of acetic anhydride were slowly added to 10 ml of 100% strength fuming nitric acid at 0 ℃. After stirring for 10 minutes, 1g of compound 7 is slowly added to the above solution; after stirring at 0 ℃ for 1 hour, the reaction system was slowly warmed to 20 ℃ and stirred for 2 hours. The reaction was slowly poured into ice water to precipitate a yellow solid. And (3) carrying out vacuum filtration, washing a filter cake with deionized water, and drying to obtain the nitramine derivative compound 8 of the LLM-105 with the yield of 86%.
Example 9
When R is1＝CH2CN；R＝CH2CN, LLM-105 derivatives were prepared as follows:
Figure BDA0001357006740000121
20 ml of 30% hydrogen peroxide is slowly added to 20 ml of acetic acid, and 4g of 2, 6-dimethoxypyrazine is added to the oxidation solution. After the reaction solution was dissolved, the reaction system was heated to 55 ℃ and reacted for 4 hours. After the reaction is finished, cooling the reaction system to room temperature, and pouring the reaction system into ice water; extracting with ethyl acetate for 8 times, mixing organic phases, and drying with anhydrous magnesium sulfate; after filtering off the solid, the filtrate was subjected to rotary evaporation under reduced pressure to remove the solvent, to obtain 2, 6-dimethoxypyrazine-4-oxide as a white solid product in 67% yield.
Adding 3 g of 2, 6-dimethoxypyrazine-4-oxide into 25 ml of sulfuric acid at the temperature of 8 ℃, slowly adding 8.5 g of sodium nitrate in batches after the 2, 6-dimethoxypyrazine-4-oxide is dissolved; after the addition is finished, continuously stirring for 30min at the temperature of 8 ℃; then slowly heating the reaction system to room temperature, and stirring for reaction for 4 hours; after the reaction is finished, slowly pouring the reaction system into ice water to separate out yellow solid; and (3) carrying out vacuum filtration, washing a filter cake for multiple times by using deionized water, and drying to obtain a yellow solid product 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide with the yield of 60%.
2 g of 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide are dissolved in 50 ml of acetonitrile. 1.5 g of aminoacetonitrile are added to the above solution in portions. After stirring at room temperature for 36 hours, the reaction was poured into ice water. And (3) carrying out suction filtration on the separated yellow solid under reduced pressure, washing a filter cake with deionized water, and drying to obtain the LLM-105 alkyl derivative compound 9 with the yield of 67%.
10 ml of acetic anhydride were slowly added to 10 ml of 100% strength fuming nitric acid at 0 ℃. After stirring for 10 minutes, 1g of compound 9 is slowly added to the above solution; after stirring at 0 ℃ for 1 hour, the reaction system was slowly warmed to 20 ℃ and stirred for 4 hours. The reaction was slowly poured into ice water to precipitate a yellow solid. And (3) carrying out vacuum filtration, washing a filter cake by deionized water, and drying to obtain the nitramine derivative compound 10 of the LLM-105 with the yield of 79%.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.

Claims (5)

  1. The preparation process of kinds of LLM-105 nitramine derivatives features that 2, 6-dimethoxy pyrazine as material is prepared through oxidation, nitration, amination and re-nitration successively, and includes the following steps:
    oxidation of A, 2, 6-dimethoxypyrazine
    Preparing an oxidant solution at room temperature, and slowly dissolving 2, 6-dimethoxypyrazine in the oxidant solution; then, stirring and reacting for 2-12 hours at room temperature-80 ℃; after the reaction is finished, slowly pouring the reaction system into ice water; extracting for 3-9 times by using ethyl acetate, combining organic phases, and drying by using anhydrous magnesium sulfate; carrying out vacuum filtration, carrying out rotary evaporation under reduced pressure to remove the solvent, and drying to obtain a white solid product, namely 2, 6-dimethoxypyrazine-4-oxide; the oxidant solution is obtained by slowly adding hydrogen peroxide into acetic acid or trifluoroacetic acid;
    nitration of B, 2, 6-dimethoxypyrazine-4-oxide
    Slowly adding the 2, 6-dimethoxypyrazine-4-oxide prepared in the step A into sulfuric acid at the temperature of 0-10 ℃, stirring until the mixture is completely dissolved, and slowly adding a nitrating agent; continuously stirring for 30min at the temperature of 0-10 ℃, slowly heating the reaction system to room temperature, and continuously stirring for 4 h; after the reaction is finished, slowly pouring the reaction system into ice water to separate out a light yellow solid; carrying out vacuum filtration, washing by deionized water and drying to obtain a light yellow solid product, namely 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide; the nitrating agent is fuming nitric acid, sodium nitrate or potassium nitrate;
    preparation of C, LLM-105 alkyl derivatives
    At room temperature, dissolving the 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide prepared in the step B in an organic solvent; then slowly adding enough amine, stirring the reaction system at room temperature to 100 ℃ for 2-48 h, pouring the reaction system into ice water, and sequentially filtering, washing and drying to obtain the LLM-105 alkyl derivative
    Figure FDA0002257630530000021
    R1Is CH3、CH2CH2OH、CH2COOCH3、CH2CH2COOCH3Or CH2CN; the organic solvent is acetonitrile, and the amine raw material is methylamine, ethanolamine, glycine methyl ester, 3-amino methyl propionate or aminoacetonitrile;
    nitration of D, LLM-105 alkyl derivatives
    Slowly adding sufficient fuming nitric acid with the concentration of 90-100% into acid anhydride at the temperature of 0 ℃, and then slowly adding the LLM-105 alkyl derivative prepared in the step C; after the addition, the reaction system is continuously stirred at the temperature of 0 ℃ for 2 toAfter 8 hours, slowly raising the temperature and continuing the reaction; then pouring the reaction system into ice water, filtering, washing and drying the mixture in sequence to obtain the nitramine derivative LLM-105
    Figure FDA0002257630530000022
    R is CH3、CH2CH2ONO2、CH2COOCH3、CH2CH2COOCH3Or CH2CN; the anhydride is acetic anhydride.
  2. 2. The method of claim 1 wherein in step a, the mass to volume ratio of 2, 6-dimethoxypyrazine to oxidant solution is 1 g: (5-20) mL.
  3. 3. A method of preparing LLM-105 nitramine derivative according to claim 1 wherein in step B, the mass to volume ratio of 2, 6-dimethoxypyrazine-4-oxide to sulfuric acid is 1 g: (1-20) mL; the mass ratio of the 2, 6-dimethoxypyrazine-4-oxide to the nitrating agent is 1:2 to 20.
  4. 4. The method of claim 1 wherein in step C, the mass to volume ratio of 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide to organic solvent is 1 g: (5-50) mL; the mass ratio of the 2, 6-dimethoxy-3, 5-dinitropyrazine-4-oxide to the amine is 1: 2-8.
  5. 5. A process for the preparation of LLM-105 nitramine derivative according to claim 1 wherein in step D the volume ratio of the anhydride to fuming nitric acid is 1: 0.5 to 3; the mass-volume ratio of the LLM-105 alkyl derivative to fuming nitric acid is 1 g: (2-50) mL.
CN201710600436.8A 2017-07-21 2017-07-21 LLM-105 nitramine derivatives and preparation method thereof Expired - Fee Related CN107266376B (en)

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