KR20220130413A - Method for preparing salt derivatives of 3-dinitromethyl-5-nitramino-1,2,4-triazolate(ndnt), salt derivatives of 3-dinitromethyl-5-nitramino-1,2,4-triazolate thereby - Google Patents

Abstract

A method for manufacturing a 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivative according to an embodiment of the present invention comprises the following steps: obtaining 2-(2-(2-methyl-1,3-dioxonan-2-yl)acetyl)-N'-nitrohydrazine-1-carboxyimidamide (MNCA); obtaining N-(3-((2-methyl-1,3-dioxonan-2-yl)methyl)-1hydrogen-1,2,4-triazol-5-yl)nitramide (MDTN) from the MNCA; obtaining N-(3-(2-oxopropyl)-1hydrogen-1,2,4-triazol-5-yl)nitriamide (NTNA); and obtaining the 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivative.

Description

Method for preparing 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) derivative and NDNT derivative prepared thereby 1,2,4-TRIAZOLATE(NDNT), SALT DERIVATIVES OF 3-DINITROMETHYL-5-NITRAMINO-1,2,4-TRIAZOLATE THEREBY}

The present invention relates to a method for preparing a 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) derivative and an NDNT derivative prepared thereby.

There is a continuing demand for gunpowder that can be easily made in the civilian and military fields, is safe in handling, such as storage, transport, and filling, and has excellent performance. Existing gunpowders such as TNT, RDX, HMX, and CL-20 show high performance, but there are problems in that they are toxic and very sensitive to stimuli, and that the synthesis route is complicated and long.

Recently, research on synthesizing a new high-energy material capable of securing high stability when using and transporting gunpowder while maintaining or improving the high performance of the existing gunpowder as a material that can replace such gunpowder is being conducted. Among them, many studies on C-amino-1,2,4-triazole derivatives having a triazole skeleton structure are being conducted. The C-amino-1,2,4-triazole skeleton structure is widely used in the field of research on high-energy substances, as well as in the field of synthesizing pesticides, pharmaceuticals, dyes, photographic materials, antibacterial materials, and polymers. In this framework structure, the nitrogen atom in the ring including the nitrogen of the amine group has a nucleophilic reactivity, and thus has a high reactivity with an electrophilic material. However, on the other hand, there is a problem of selectivity in the reaction with an electrophilic reagent because the reaction selectivity between each nucleophilic nitrogen atom is low. In addition, it is very necessary to develop a manufacturing method capable of minimizing these by-products because the by-product itself having a high nitrogen content generated during the synthesis process always carries the explosive risk.

Professor Shreeve's group reported on the synthesis method and physicochemical property analysis results of the new high-energy material NDNT in the Chemical A European Journal in 2017. NDNT has the advantage of generating relatively eco-friendly nitrogen by-products in the decomposition process according to the high heat of formation, ring strain, and high energy release of the triazole framework. Currently, NDNT is attracting attention as a next-generation high-energy material due to its excellent thermal stability, impact safety, and explosive performance.

Chemical A European Journal 2017, 23, 9185-9191 reported two different preparation methods as follows.

The first preparation method is ethyl 3-hydrazino-3-oxopropanoate (ethyl 2-hydrazino-2-oxopropanoate) obtained by reacting diethyl malonate (dimethyl malonate) and hydrazine hydrate (hydrazine hydrate) in ethanol; ECH) and N-methyl-N-nitroguanidine (NMNG) intermediate through a substitution reaction with ethyl 3- (2-amino (nitroimino) methyl) -hydrazine ni-3 -Oxopropanoate (ehthyl 3-(2-amino(nitroimino)mehtyl)-hydrazinyl-3-oxopropanoate) was obtained, followed by cyclization under heating conditions using sodium hydroxide and water solvent, and concentrated hydrochloric acid Through a neutralization reaction through ethyl 2- (5- (nitramino) -1 hydrogen-1,2,4-triazol-3-yl) acetate (ethyl 2- (5- (nitramino) -1H-1, 2,4-triazol-3-yl)acetate) is obtained. Thereafter, the nitration reaction was carried out under concentrated sulfuric acid and concentrated nitric acid at 0 ° C., and the chlorination reaction was carried out with a basic reagent under an ethanol solvent, followed by 3-dinitromethyl-5-nitramino-1,2,4- Energetic salt derivatives of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) are obtained.

In the second preparation method, from the intermediate of ethyl 2-(5-amino-1 hydrogen-1,2,4-triazol-3-yl)acetate, the nitration reaction is carried out under concentrated sulfuric acid and concentrated nitric acid at 0 ° C. and 3-dinitromethyl-5-nitramino-1,2,4-triazolate salt derivatives of 3-dinitromethyl-5-nitramino-1 by chlorination reaction with a basic reagent in an ethanol solvent. ,2,4-triazolate; NDNT) is obtained.

In New Journal of Chemistry 2017, 41, 3068-3072, 2-(5-amino-1 hydrogen-1,2,4-triazol-3-yl)acetic acid (2-(5-amino-1H-1) ,2,4-triazol-3-yl)acetic acid; A -1,2,4-triazole (3-trinitromethyl-5-nitramino-1H-1,2,4-triazole) intermediate was obtained, and then chlorinated with dihydrazine hydrate as a basic reagent at room temperature in a methanol solvent. to obtain a salt of dihydrazinium 3-dinitromethyl-5-nitramino-1,2,4-triazolate (dihydrazinium 3-dinitromethyl-5-nitramino-1,2,4-triazoleate) by acquire

The NDNT salt preparation method is, among the two different preparation methods presented in Chemical A European Journal 2017, 23, 9185-9191, the first preparation method is ethyl 3-hydrazino-3-oxo used as a starting material The synthetic yield of the synthesis step of propanoate (ECH) is actually very low, around 30% in the reference, and ethyl 3-(2-amino(nitroimino)methyl)-hydrazineni-3, which is an intermediate synthesized therefrom, -The overall synthesis yield up to the entire synthesis process via oxopropanonate is very low, and it is difficult to analyze, and it is very dangerous in the synthesis process because a large amount of by-products with high nitrogen content are created, which in itself poses an explosion hazard. The second preparation method has a disadvantage in that the synthesis yield of the nitration reaction and the chlorination reaction, which are the last steps of the synthesis process in the literature, is very low, within 12%. New Journal of Chemistry 2017, 41, 3068-3072 The preparation method presented in the literature is a synthetic intermediate 3-trinitromethyl-5-nitramino-1 hydrogen-1,2,4-triazole material with a large amount of nitrate. Because it has a functional group, it is a high-energy material by itself and has a risk of explosion, so it is difficult to handle in the synthesis process.

The present invention is to solve the above-described problems, and an object of the present invention is to improve the synthesis yield, prevent the risk of explosion by blocking the risk of explosion, prevent risk factors in the synthesis process, and increase the material stability of intermediates in each synthesis step when handling To provide a method for preparing a 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) derivative, which ensures stability, and an NDNT derivative prepared thereby.

However, the problems to be solved by the present invention are not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

3-dinitromethyl-5-nitramino-1,2,4-triazolate according to an embodiment of the present invention (Energetic salt derivatives of 3-dinitromethyl-5-nitramino-1,2,4-triazolate; NDNT) The method for preparing a salt derivative is ethyl 2- (2-methyl-1,3-dioxan-2-yl) acetate (ethyl 2- (2-methyl-1,3-dioxolan-) comprising the following Scheme 1 step: 2-(2-(2-methyl-1,3-dioxonane-) by synthesizing 2-yl)acetate; MDA) and N-methyl-N'-nitroguanidine (NMNG) 2-Nyl)acetyl)-N'-nitrohydrazine-1-carboxyimidamide (2-(2-(2-methyl-1,3-dioxolan-2-yl)acetyl)-N'-nitrohydrazine-1 -carboximidamide; MNCA); N- (3-((2-methyl-1,3-dioxonan-2-yl)methyl)-1 hydrogen-1,2,4-triazol-5-yl from the MNCA comprising the following Scheme 2 step ) Obtained nitramide ( N- (3-((2-methyl-1,3-dioxolan-2-yl)methyl)-1H-1,2,4-triazol-5-yl) nitramide ; MDTN) to do; N-(3-(2-oxopropyl)-1hydrogen-1,2,4-triazol-5-yl)nitramide (N-(3-(2- obtaining oxopropyl)-1H-1,2,4-triazol-5-yl)nitramide (NTNA); and N- (3-(1,1-dinitro-2-oxopropyl)-1H-1,2,4-triazol-5-yl) nitramide from the NTNA comprising the steps of Scheme 4 below 3-dinitromethyl-5-nitro via ( N- (3-(1,1-dinitro-2-oxopropyl)-1H-1,2,4-triazol-5-yl) nitramide ; DOTN) obtaining a mino-1,2,4-triazolate (NDNT) salt derivative:

[Scheme 1]

,

,

[Scheme 2]

,

,

[Scheme 3]

,

,

[Scheme 4]

,

,

In Scheme 4, X is NH ₃ or NH ₂ OH.

In one embodiment, the step of obtaining MNCA may be a substitution reaction by dropwise adding the NMNG to a mixed solution of MDA and water at room temperature and stirring for 10 to 30 minutes.

In an embodiment, the obtaining of the MNCA may include using 1 to 1.5 equivalents of NMNG based on the MDA.

In one embodiment, the step of obtaining the MNCA may be stirring at a temperature of 60 °C or higher for 6 hours to 24 hours.

In one embodiment, the step of obtaining MNCA may be to obtain MNCA in a yield of 30% or more, after cooling to room temperature, filtering and drying the resulting solid under reduced pressure.

In one embodiment, the step of obtaining MDTN is a cyclization reaction, in which an aqueous solution of sodium hydroxide is added at room temperature to an aqueous solution of MNCA in which water and MNCA are stirred at room temperature and stirred at a temperature of 100 ° C. or higher for 2 hours to 4 hours. it could be

In one embodiment, the step of obtaining the MDTN may be cooling and stirring the reaction solution after the reaction has been completed to room temperature.

In one embodiment, the step of obtaining MDTN may be to make pH 1 to 2 by dropwise adding concentrated hydrochloric acid to the reaction solution at room temperature.

In one embodiment, the step of obtaining MDTN is to obtain an organic solution through an extraction process for the reaction solution using an ethyl acetate solvent, and the extracted organic solution is magnesium sulfate (MgSO ₄ ) An anhydrous agent containing It may be to obtain MDTN in a yield of 30% or more through vacuum filtration, concentration under reduced pressure, and drying to remove the remaining water using.

In one embodiment, the step of obtaining NTNA is a deprotection reaction, MDTN may be added dropwise at room temperature in a THF solvent and stirred for 10 to 30 minutes.

In one embodiment, in the step of obtaining NTNA, 1 normal concentration aqueous hydrochloric acid solution is added dropwise at room temperature, stirred for 6 hours to 24 hours, and sodium bicarbonate (NaHCO ₃ ) until pH 6 to 8 in the reaction solution may be added dropwise and stirred, and water may be added to the reaction solution, and an aqueous solution may be obtained through an extraction process through an ethyl acetate solvent.

In one embodiment, the step of obtaining NTNA may be to add concentrated hydrochloric acid dropwise to the recovered aqueous solution until pH 1 to 2.

In one embodiment, the step of obtaining NTNA is to obtain an organic solution through an extraction process with an acidic aqueous solution using an ethyl acetate solvent, and the extracted organic solution is an anhydrous agent containing magnesium sulfate (MgSO ₄ ) may be used to remove residual water.

In one embodiment, the step of obtaining NTNA may be to obtain NTNA solid in a yield of 90% or more through vacuum filtration, concentration under reduced pressure, and drying.

In one embodiment, the step of obtaining the NDNTs, a nitration reaction step; and a chlorination step.

In one embodiment, the nitration reaction step is to put NTNA in a mixed solution of concentrated sulfuric acid and potassium nitrate (KNO ₃ ) in a reaction vessel at 0 ° C. and stir for 2 to 4 hours, the NTNA is 1 3 to 4 equivalents of potassium nitrate are used for the equivalent, and the reaction solution is to obtain an organic solution through an extraction process using an ethyl acetate solvent, and the extracted organic solution is magnesium sulfate (MgSO ₄ ) Anhydrous agent containing It may be to remove the remaining water by using it, and to obtain NDNTs through filtration under reduced pressure and concentration under reduced pressure.

In one embodiment, the chlorination reaction step, the step of obtaining the NDNT salt derivative after the nitration reaction step may be performed continuously without a purification process.

In one embodiment, in the chlorination step, the concentrate may be dissolved in a methanol solvent and stirred at 0° C. for 15 minutes to 30 minutes.

In one embodiment, in the chlorination step, a basic reagent containing nitrogen is added dropwise at 0 ° C. and stirred for 1 to 4 hours, and the basic reagent is aqueous ammonia and a methanolic amine solution. and at least one selected from the group consisting of an aqueous solution of hydroxylamine.

In one embodiment, in the chlorination step, the obtained yellow solid is stirred for 30 minutes to 1 hour under heating conditions at 80 ° C. or higher under a methanol solvent, and 1 hour to 3 hours at 0 ° C. to 5 ° C. cooling conditions under a methanol solvent It may be to obtain the NDNT salt derivative through filtration and drying using a recrystallization purification method that undergoes a cooling process to maintain.

In one embodiment, the chlorination step may be to obtain the NDNT salt derivative in a yield of 50% or more.

3-dinitromethyl-5-nitramino-1,2,4-triazolate according to another embodiment of the present invention (Energetic salt derivatives of 3-dinitromethyl-5-nitramino-1,2,4-triazolate; NDNT) salt derivatives are represented by the following formula (VII):

[Formula VII]

,

,

wherein X is NH ₃ or NH ₂ OH.

In one embodiment, the 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivative is -dinitromethyl-5 according to an embodiment of the present invention -Nitramino-1,2,4-triazolate (NDNT) may be prepared by the method for producing a salt derivative.

Gunpowder according to another embodiment of the present invention comprises a 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) derivative represented by the following formula (VII):

[Formula VII]

,

,

wherein X is NH ₃ or NH ₂ OH.

In the method for producing an NDNT derivative according to an embodiment of the present invention, as a starting material used in the initial synthesis process, it has a selective reaction site that can block the production of by-products, and is easily synthesized with a high yield of 90% or more. By using 2-(2-methyl-1,3-dioxane-2-yl)acetate (MDA), the overall synthesis yield is dramatically improved, which is excellent in terms of cost reduction. In addition, the acetyl functional group located opposite the hydrazine functional group of MDA is protected with a cyclic acetal functional group using ethylene glycol to prevent side reactions on the carbonyl functional group side, which may occur in the subsequent synthesis process. By preventing the risk of explosion of by-products with high nitrogen content at the source, it is possible to prevent risk factors in the synthesis process, and it is possible to manufacture NDNT salt derivatives that ensure stability during handling by increasing the material stability of intermediates in each synthesis step.

1 is a view showing a manufacturing process of NDNT according to an embodiment of the present invention.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes may be made to the embodiments, the scope of the patent application is not limited or limited by these embodiments. It should be understood that all modifications, equivalents and substitutes for the embodiments are included in the scope of the rights.

Terms used in the examples are used for the purpose of description only, and should not be construed as limiting. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that this does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the embodiment belongs. Terms such as those defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

In addition, in the description with reference to the accompanying drawings, the same components are assigned the same reference numerals regardless of the reference numerals, and the overlapping description thereof will be omitted. In the description of the embodiment, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the embodiment, the detailed description thereof will be omitted.

In addition, in describing the components of the embodiment, terms such as first, second, A, B, (a), (b), etc. may be used. These terms are only for distinguishing the elements from other elements, and the essence, order, or order of the elements are not limited by the terms.

Components included in one embodiment and components having a common function will be described using the same names in other embodiments. Unless otherwise stated, descriptions described in one embodiment may be applied to other embodiments as well, and detailed descriptions within the overlapping range will be omitted.

Hereinafter, the method for preparing 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) derivative of the present invention and the NDNT derivative prepared thereby will be described in detail with reference to Examples and drawings. to be explained as However, the present invention is not limited to these examples and drawings.

3-dinitromethyl-5-nitramino-1,2,4-triazolate according to an embodiment of the present invention (Energetic salt derivatives of 3-dinitromethyl-5-nitramino-1,2,4-triazolate; NDNT) The method for preparing a salt derivative is ethyl 2- (2-methyl-1,3-dioxan-2-yl) acetate (ethyl 2- (2-methyl-1,3-dioxolan-) comprising the following Scheme 1 step: 2-(2-(2-methyl-1,3-dioxonane-) by synthesizing 2-yl)acetate; MDA) and N-methyl-N'-nitroguanidine (NMNG) 2-Nyl)acetyl)-N'-nitrohydrazine-1-carboxyimidamide (2-(2-(2-methyl-1,3-dioxolan-2-yl)acetyl)-N'-nitrohydrazine-1 -carboximidamide; MNCA); N- (3-((2-methyl-1,3-dioxonan-2-yl)methyl)-1 hydrogen-1,2,4-triazol-5-yl from the MNCA comprising the following Scheme 2 step ) Obtained nitramide ( N- (3-((2-methyl-1,3-dioxolan-2-yl)methyl)-1H-1,2,4-triazol-5-yl) nitramide ; MDTN) to do; N-(3-(2-oxopropyl)-1hydrogen-1,2,4-triazol-5-yl)nitramide (N-(3-(2- obtaining oxopropyl)-1H-1,2,4-triazol-5-yl)nitramide (NTNA); and N- (3-(1,1-dinitro-2-oxopropyl)-1H-1,2,4-triazol-5-yl) nitramide from the NTNA comprising the steps of Scheme 4 below 3-dinitromethyl-5-nitro via ( N- (3-(1,1-dinitro-2-oxopropyl)-1H-1,2,4-triazol-5-yl) nitramide ; DOTN) obtaining a mino-1,2,4-triazolate (NDNT) salt derivative:

[Scheme 1]

,

,

[Scheme 2]

,

,

[Scheme 3]

,

,

[Scheme 4]

,

,

In Scheme 4, X is NH ₃ or NH ₂ OH.

In Scheme 1, Formula I is MDA, Formula II is NMNG, and Formula III is MNCA.

In Scheme 2, Chemical Formula III is MNCA, and Chemical Formula IV is MDTN.

In Scheme 3, Chemical Formula IV is MDTN, and Chemical Formula V is NTNA.

In Scheme 4, Chemical Formula V is NTNA, Chemical Formula VI is DOTN, and Chemical Formula VII is NDNT.

In one embodiment, the step of obtaining MNCA may be a substitution reaction, and stirring a mixed solution of MDA and water at room temperature.

In one embodiment, the step of obtaining the MNCA may be a substitution reaction by slowly adding the NMNG dropwise to a mixed solution of MDA and water at room temperature and stirring for 10 to 30 minutes.

In an embodiment, the obtaining of the MNCA may include using 1 to 1.5 equivalents of NMNG based on the MDA.

In one embodiment, the step of obtaining the MNCA may be stirring at a temperature of 60 °C or higher for 6 hours to 24 hours.

In one embodiment, the step of obtaining MNCA may be to obtain MNCA in a yield of 30% or more, after cooling to room temperature, filtering and drying the resulting solid under reduced pressure.

In one embodiment, the step of obtaining MDTN may be a cyclization reaction, wherein water and MNCA are stirred at room temperature.

In one embodiment, the step of obtaining MDTN is a cyclization reaction, in which an aqueous solution of sodium hydroxide is added at room temperature to an aqueous solution of MNCA in which water and MNCA are stirred at room temperature and stirred at a temperature of 100 ° C. or higher for 2 hours to 4 hours. it could be

In one embodiment, the step of obtaining the MDTN may be cooling and stirring the reaction solution after the reaction has been completed to room temperature.

In one embodiment, the step of obtaining MDTN may be to make pH 1 to 2 by dropwise adding concentrated hydrochloric acid to the reaction solution at room temperature.

In one embodiment, the step of obtaining the MDTN may be to obtain an organic solution through an extraction process for the reaction solution using an ethyl acetate solvent.

In one embodiment, the extracted organic solution is removed using an anhydrous agent containing magnesium sulfate (MgSO ₄ ), and MDTN is obtained through filtration under reduced pressure, concentration under reduced pressure, and drying.

In one embodiment, the step of obtaining the MDTN may be obtaining the MDTN with a yield of 30% or more.

In one embodiment, the step of obtaining NTNA is a deprotection reaction, MDTN may be added dropwise at room temperature in a THF solvent and stirred for 10 to 30 minutes.

In one embodiment, the step of obtaining NTNA may be to add 1 normal concentration of an aqueous hydrochloric acid solution dropwise at room temperature and stir for 6 to 24 hours.

In one embodiment, sodium bicarbonate (NaHCO ₃ ) may be added dropwise to the reaction solution until pH 6 to 8 and stirred.

In one embodiment, water may be added to the reaction solution and an aqueous solution may be obtained through an extraction process through an ethyl acetate solvent.

In one embodiment, the step of obtaining NTNA may be to slowly add concentrated hydrochloric acid dropwise to the recovered aqueous solution until pH 1 to 2.

In one embodiment, the step of obtaining NTNA may be to obtain an organic solution through an extraction process with an acidic aqueous solution using an ethyl acetate solvent.

In one embodiment, the extracted organic solution may be to remove residual water by using an anhydrous agent including magnesium sulfate (MgSO ₄ ).

In one embodiment, the step of obtaining NTNA may be to obtain a NTNA solid through vacuum filtration, concentration under reduced pressure, and drying.

In one embodiment, the step of obtaining NTNA may be to obtain a solid in a yield of 90% or more.

In one embodiment, the step of obtaining the NDNTs, a nitration reaction step; and a chlorination step.

In one embodiment, the nitration reaction step may be to stir a mixed solution of concentrated sulfuric acid and potassium nitrate (KNO ₃ ) in a reaction vessel at 0 ° C.

In one embodiment, the step of obtaining the NDNT may be to put NTNA in a mixed solution of concentrated sulfuric acid and potassium nitrate (KNO ₃ ) under 0 ° C. and stir for 2 to 4 hours.

In one embodiment, the step of obtaining the NDNT may be to use 3 to 4 equivalents of potassium nitrate per equivalent of NTNA.

In one embodiment, the step of obtaining the NDNT may be to put the reaction solution in which the reaction has been completed in ice water at 0° C. and stir for about 5 to 15 minutes.

In one embodiment, the step of obtaining NDNTs may be to obtain an organic solution through an extraction process for the reaction solution using an ethyl acetate solvent.

In one embodiment, the extracted organic solution may be obtained by removing residual water using an anhydrous agent including magnesium sulfate (MgSO ₄ ) and filtration under reduced pressure and concentration under reduced pressure to obtain NDNTs.

In one embodiment, in the chlorination reaction step, the step of obtaining the NDNT salt derivative after the nitration reaction step is to proceed with the next reaction without a purification process without using a conventional recrystallization purification method. can

In one embodiment, in the chlorination step, the concentrate may be dissolved in a methanol solvent and stirred at 0° C. for 15 minutes to 30 minutes.

In one embodiment, the chlorination step may be to add a nitrogen-containing base reagent dropwise under 0 ℃ and stirring.

In one embodiment, in the chlorination step, the basic reagent may be a basic reagent capable of forming a salt while having nitrogen, but is not limited thereto.

In one embodiment, in the chlorination step, the basic reagent may include at least one selected from the group consisting of aqueous ammonia, a methanolic amine solution, and an aqueous hydroxylamine solution. have.

In one embodiment, the chlorination step may be stirred for 1 hour to 4 hours.

In one embodiment, the chlorination reaction step in the step of obtaining the NDNT salt derivative may be filtration and drying the reaction mixture solution under reduced pressure.

In one embodiment, the chlorination reaction step in the step of obtaining the NDNT salt derivative is through a recrystallization purification method in which the obtained yellow solid is reheated in a methanol solvent and cooled, and then the NDNT salt derivative is filtered and dried. may be to obtain

In one embodiment, in the step of obtaining the NDNT salt derivative, the chlorination reaction step is stirred for 30 minutes to 1 hour under a heating condition of 80 ° C. or higher in a methanol solvent, and 1 hour to 3 hours at 0 ° C. to 5 ° C. cooling conditions It could be time keeping.

In one embodiment, the chlorination step may be to obtain the NDNT salt derivative in a yield of 50% or more.

3-dinitromethyl-5-nitramino-1,2,4-triazolate according to another embodiment of the present invention (Energetic salt derivatives of 3-dinitromethyl-5-nitramino-1,2,4-triazolate; NDNT) salt derivatives are represented by the following formula (VII):

[Formula VII]

,

,

wherein X is NH ₃ or NH ₂ OH.

In one embodiment, the 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivative is -dinitromethyl-5 according to an embodiment of the present invention -Nitramino-1,2,4-triazolate (NDNT) may be prepared by the method for producing a salt derivative.

Gunpowder according to another embodiment of the present invention comprises a 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) derivative represented by the following formula (VII):

[Formula VII]

,

,

wherein X is NH ₃ or NH ₂ OH.

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples.

However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited to the following examples.

1 is a view showing a manufacturing process of NDNT according to an embodiment of the present invention.

2-(2-(2-methyl-1,3-dioxonan-2-yl)acetyl)- N Preparation of '-nitrohydrazine-1-carboxyimidamide (2-(2-(2-methyl-1,3-dioxolan-2-yl)acetyl)-N'-nitrohydrazine-1-carboximidamide; MNCA)

Put 7.8 mL of water in a reaction vessel, add 1 equivalent of MDA (1.0 g, 6.24 mmol), and stir at room temperature. Then, 1.1 equivalents of NMNG (1.01 g, 6.87 mmol) was slowly added dropwise over 5 times. The mixture was stirred at room temperature for 10 minutes, heated to 60 °C, and stirred for 24 hours. Upon completion of the reaction, the mixture was cooled to room temperature and stirred for 20 minutes, confirming that a pale yellow solid was produced. In the separation process, 3 mL of ethanol is used, filtered under reduced pressure, washed, and dried under reduced pressure. MNCA (44 % w/w) containing 770 mg of water was obtained as a white solid.

¹ H-NMR (DMSO- d ₆ ) δ 1.39 (s, 3H), 2.48 (s, 2H), 3.87-3.94 (m, 4H), 7.55-9.82 (brs, 4H)

N -(3-((2-methyl-1,3-dioxonan-2-yl)methyl)-1 hydrogen-1,2,4-triazol-5-yl)nitramide ( N -(3-((2-methyl-1,3-dioxolan-2-yl)methyl)-1 H -1,2,4-triazol-5-yl)nitramide; MDTN) production

4.4 mL of water and the intermediate MNCA were put in a reaction vessel, and a 2 M aqueous NaOH solution (NaOH, 83.5 mg, water, 4.18 mL) prepared in advance was added while stirring, refluxed at 110 ° C., and stirred for 2 hours. In the separation step, after the reaction was completed, the reaction was cooled to room temperature, and pH 1 was prepared using 37% hydrochloric acid (concentrated hydrochloric acid 1.5 mL was used). The organic layer obtained through the extraction process using 15 mL of EA was removed using MgSO ₄ , and the organic layer was obtained by filtration under reduced pressure. The solvent was removed by distillation under reduced pressure and dried under reduced pressure to obtain MDTN as a pink solid (155 mg, yield 33%).

¹ H-NMR (DMSO- d ₆ ) δ 1.33 (s, 3H), 2.99 (s, 2H), 3.83-3.91 (m, 4H), 13.59 (s, 1H), 14.03 (s, 1H)

¹³ C{ ¹ H}-NMR (DMSO- d ₆ ) δ 24.6, 35.3, 64.8, 107.6, 147.4, 153.0.

N -(3-(2-oxopropyl)-1hydrogen-1,2,4-triazol-5-yl)nitramide ( N -(3-(2-oxopropyl)-1 H -1,2,4-triazol-5-yl)nitramide; NTNA) preparation

1.4 mL of THF was placed in a reaction vessel, 1 equivalent of synthesized MDTN (250 mg, 1.09 mmol) was added, and the mixture was stirred at room temperature. 1.4 mL of 1 N hydrochloric acid prepared in advance was added and stirred at room temperature for 24 hours. To the reaction solution, 25 mg of NaHCO ₃ was slowly added dropwise to adjust the pH to 7.

In the separation step, organic impurities (ethylene glycol, etc.) were separated by extraction three times using 15 mL of EA. 3 mL of water was added to the water layer, and 1 mL of concentrated hydrochloric acid was slowly added dropwise to adjust the pH to 1, extracted three times using 15 mL of EA, and the organic layer obtained through vacuum filtration was treated with MgSO ₄ . In the purification step, the desired NTNA was obtained in a yield of 184 mg of a brown solid, 91%, by removing the residual solvent through the separated vacuum filtration and distillation under reduced pressure and drying.

¹ H-NMR (DMSO- d ₆ ) δ 2.23 (s, 3H), 4.02 (s, 2H), 13.64-14.05 (brs, 2H)

¹³ C{ ¹ H}-NMR (DMSO- d ₆ ) δ 30.1, 63.3, 146.1, 153.2, 202.7.

Preparation of diammonium 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT)

In the nitrilation reaction, 1.5 mL of concentrated sulfuric acid and 3 equivalents of KNO ₃ (239 mg, 2.37 mmol) were added to a reaction vessel, and the mixture was stirred while maintaining 0 ℃ using an ice water bath. When the temperature was maintained, 1 equivalent of the synthesized NTNA (146 mg, 0.79 mmol) was added thereto, and the mixture was stirred at the same temperature for 2 hours. In the separation step, when the reaction was completed, 10 mL of ice water prepared in advance was slowly added dropwise to the reaction solution and stirred for 5 minutes. The organic layer was separated through the extraction process three times using 15 mL of EA, and the transfer water was removed using MgSO ₄ . After removing the residual solvent through vacuum filtration and distillation under reduced pressure to obtain a yellow liquid, it was confirmed whether the intermediate was synthesized through ¹ H-NMR analysis.

In the chlorination reaction, the reaction vessel was kept at 0 °C using an ice-water bath without further purification as a continuous reaction, and 2 mL of methanol and 152 mg of a yellow liquid intermediate were added and stirred. While maintaining the same temperature, 0.7 mL (550 mg) of 2M methanolic NH ₃ was added dropwise, and the mixture was stirred for 2 hours while gradually raising the temperature to room temperature. In the separation and purification step, when a brown solid was produced, it was filtered under reduced pressure, washed with 5 mL methanol and 2 mL diethyl ester, and dried under reduced pressure to obtain NDNT as a light yellow solid in a yield of 104 mg, 57%.

¹ H-NMR (DMSO- d ₆ ) δ 7.29 (br, NH)

¹³ C{ ¹ H}-NMR (DMSO- d ₆ ) δ 128.5, 153.0, 157.4

As a starting material used in the initial synthesis process in an embodiment of the present invention, ethyl 2-(2-methyl-1, ethyl 2-(2-methyl-1, 3-dioxane-2-yl) acetate (ethyl 2- (2-methyl-1,3-dioxolan-2-yl) acetate; MDA) was used to dramatically improve the overall synthesis yield. Therefore, not only is it excellent in terms of cost reduction, but also the side reaction of the carbonyl functional group is prevented by protecting the acetyl functional group located opposite the hydrazine functional group of MDA with a cyclic acetal functional group using ethylene glycol. It was possible to prevent the risk factors in the synthesis process by blocking the source of the explosion risk of by-products with high nitrogen content that may occur in the subsequent synthesis process. In addition, NDNT salt derivatives were prepared that ensure stability during handling by increasing the material stability of the intermediates in each synthesis step.

As described above, although the embodiments have been described with reference to the limited drawings, those skilled in the art may apply various technical modifications and variations based on the above. For example, the described techniques are performed in a different order than the described method, and/or the described components of the system, structure, apparatus, circuit, etc. are combined or combined in a different form than the described method, or other components Or substituted or substituted by equivalents may achieve an appropriate result.

Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (16)

Ethyl 2- (2-methyl-1,3-dioxan-2-yl) acetate (ethyl 2- (2-methyl-1,3-dioxolan-2-yl) acetate; MDA) comprising the following Scheme 1 step, and 2-(2-(2-methyl-1,3-dioxonan-2-yl)acetyl)-N' by synthesizing N-methyl-N'-nitroguanidine (N-methyl-N-nitroguanidine; NMNG) - Obtaining nitrohydrazine-1-carboxyimidamide (2-(2-(2-methyl-1,3-dioxolan-2-yl)acetyl)-N'-nitrohydrazine-1-carboximidamide;MNCA);
N -(3-((2-methyl-1,3-dioxonan-2-yl)methyl)-1 hydrogen-1,2,4-triazol-5-yl from the MNCA comprising the following Scheme 2 step ) Obtained nitramide ( N- (3-((2-methyl-1,3-dioxolan-2-yl)methyl)-1H-1,2,4-triazol-5-yl) nitramide ; MDTN) to do;
N-(3-(2-oxopropyl)-1 hydrogen-1,2,4-triazol-5-yl)nitramide (N-(3-(2- obtaining oxopropyl)-1H-1,2,4-triazol-5-yl)nitramide (NTNA); and
N- (3-(1,1-dinitro-2-oxopropyl)-1H-1,2,4-triazol-5-yl) nitramide ( 3-dinitromethyl-5-nitramino via N -(3-(1,1-dinitro-2-oxopropyl)-1H-1,2,4-triazol-5-yl) nitramide ; DOTN) obtaining -1,2,4-triazolate (NDNT) salt derivative;
containing,
Method for preparing 3-dinitromethyl-5-nitramino-1,2,4-triazolate (Energetic salt derivatives of 3-dinitromethyl-5-nitramino-1,2,4-triazolate; NDNT) salt derivative:
[Scheme 1]

,
[Scheme 2]

,
[Scheme 3]

,
[Scheme 4]

,
In Scheme 4, X is NH ₃ or NH ₂ OH.
According to claim 1,
The step of obtaining MNCA is a substitution reaction, adding the NMNG dropwise to a mixed solution of MDA and water at room temperature, and stirring for 10 to 30 minutes,
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
The step of obtaining the MNCA is to use 1 to 1.5 equivalents of NMNG based on the MDA,
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
The step of obtaining the MNCA is to stir for 6 hours to 24 hours at a temperature of 60 ° C. or higher,
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
The step of obtaining MNCA is, after cooling to room temperature, the resulting solid is filtered under reduced pressure and dried,
To obtain MNCA in a yield of 30% or more,
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
The step of obtaining the MDTN is a cyclization reaction, in which an aqueous solution of sodium hydroxide is added at room temperature to an aqueous solution of MNCA in which water and MNCA are stirred at room temperature and stirred at a temperature of 100 ° C. or higher for 2 to 4 hours,
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
The step of obtaining the MDTN is that the reaction solution is cooled and stirred to room temperature,
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
The step of obtaining the MDTN is to make pH 1 to 2 by dropwise adding concentrated hydrochloric acid to the reaction solution at room temperature,
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
The step of obtaining the MDTN is to obtain an organic solution through an extraction process using an ethyl acetate solvent for the reaction solution,
The extracted organic solution is removed using an anhydrous agent containing magnesium sulfate (MgSO ₄ ) to remove residual water, and MDTN is obtained in a yield of 30% or more through filtration under reduced pressure, concentration under reduced pressure, and drying.
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
The step of obtaining the NTNA is a deprotection reaction, in which MDTN is added dropwise at room temperature in a THF solvent and stirred for 10 to 30 minutes,
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
In the step of obtaining NTNA, 1 normal aqueous hydrochloric acid solution is added dropwise at room temperature and stirred for 6 to 24 hours,
Sodium bicarbonate (NaHCO ₃ ) is added dropwise to the reaction solution until pH 6 to 8 and stirred,
Putting water into the reaction solution and obtaining an aqueous solution through an extraction process through an ethyl acetate solvent,
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
In the step of obtaining the NTNA, concentrated hydrochloric acid is added dropwise to the recovered aqueous solution until pH 1 to 2,
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
The step of obtaining NTNA is to obtain an organic solution through an extraction process with an acidic aqueous solution using an ethyl acetate solvent,
The extracted organic solution is to remove the remaining water using an anhydrous agent containing magnesium sulfate (MgSO ₄ ),
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
The step of obtaining NTNA is to obtain a NTNA solid in a yield of 90% or more through reduced pressure filtration, concentration under reduced pressure, and drying,
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
According to claim 1,
The step of obtaining the NDNT comprises:
nitration reaction step; and
chlorination reaction step;
which includes,
A process for the preparation of 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) salt derivatives.
A gunpowder comprising a 3-dinitromethyl-5-nitramino-1,2,4-triazolate (NDNT) derivative represented by the following formula (VII):
[Formula VII]

,
wherein X is NH ₃ or NH ₂ OH.

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