KR102102357B1 - Synthesis of tkx-50 using protected diazidoglyoxime - Google Patents

Abstract

The present invention relates to a method for synthesizing TKX-50 using diazidoglyoxime in which a functional group is protected. More specifically, the present invention relates to a method for synthesizing TKX-50 using diazidoglyoxime in which a functional group is protected, which comprises the following steps: preparing DCG as a starting material; forming an insensitive-DAG intermediate represented by chemical formula 1 from the DCG; and synthesizing TKX-50 through the insensitive-DAG intermediate. The present invention has an advantage of being safe and easy to process by using an aqueous HCl solution instead of using HCl gas.

Description

Synthesis method of TKX-50 using diajiglyoxime with functional group protection {SYNTHESIS OF TKX-50 USING PROTECTED DIAZIDOGLYOXIME}

The present invention relates to a method for synthesizing TKX-50 using diajiglyoxime with functional group protection.

Currently, the most widely used high-energy materials for military gunpowder are RDX (1,3,5-trinitro-1,3,5-triazacyclohexane), HMX (1,3,5,7-tetranitro-1,3,5,7 -tetraazacyclooctane), CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaza-isowurtzitane), and is widely used in various fields. Recently, with the development of new weapon systems, many studies have been conducted to develop high-energy materials with higher explosive performance than previously used high-energy materials. In particular, research on materials containing ring or cage forms has been actively conducted. Became. Among these high-energy materials developed, DDF (dinitroazofuroxane) and ONC (octanitrocubane) have an explosive speed of about 10,000 m / s, but have a very high explosive performance, but have a very sensitive characteristic, which has the fatal disadvantage of threatening the safety of the handling personnel. .

In order to improve explosive performance and desensitization, recently, studies on cyclic compounds having a high nitrogen content, such as triazole, tetrazole, nitroiminotetrazole, and tetrazin, have been actively conducted, of which the tetrazole compound dihydroxylammonium 5,5'-bistetrazol-1,1'-diolate (dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate, Thomas Klapotke eXplosive-50, TKX-50) is rated as one of the promising high-energy materials I am receiving. TKX-50 is known to have higher explosive performance than conventional energy materials (RDX, HMX, CL-20), as well as insensitive sensitivity.

1 is a view for explaining the conventional synthesis method of TKX-50. Referring to Figure 1, the existing synthesis method of TKX-50 is synthesized through 5 steps of synthesis using glyoxal as a starting material. TKX-50 itself is insensitive to existing high-energy materials, but diazidoglyoxime (DAG), an intermediate obtained after azide reaction that introduces an energy group, has an explosive level (lead styphnate: impact sensitivity 2.5-5 J, friction sensitivity 1.5 N, lead azide: shock sensitivity 2.5-4 J, friction sensitivity 0.1-1 N), very sensitive sensitivity (DAG: shock sensitivity 1.5 J, friction sensitivity 5 N or less, static sensitivity 7 mJ) When synthesizing TKX-50, it not only threatens the safety of workers, but also risks accidents.

In addition, the last step of the synthesis of the previously known TKX-50 is that it is a safety hazard because it uses HCl gas, and it is difficult to apply an effective process.

The present invention is to solve the above-mentioned problems, the object of the present invention, TKX-50 is a more sensitive THP-DAG (O, O'-) rather than the sensitive intermediate chain DAG so that workers can work more safely and effectively. ditetrahydropyranyloxalohydroximoyl diazide), and provides a method for synthesizing TKX-50 using diazidoglyoxime with functional groups protected by using an aqueous HCl solution instead of HCl gas.

However, the problem to be solved by the present invention is 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.

A method for synthesizing TKX-50 using diajidoglioxime with a functional group protected according to an embodiment of the present invention includes preparing a dichloroglyoxime (DCG) as a starting material; Forming a desensitization-O, O'-ditetrahydropyranyl oxalohydroxymonyl diazide (O, O'-ditetrahydropyranyl oxalohydroximoyl diazide, desensitization-DiAzidoGlyoxime, desensitization-DAG) represented by Formula 1 below from the DCG ; And synthesizing TKX-50 through the insensitive-DAG intermediate.

[Formula 1]

(Wherein, R is Tetrahydropyranyl (THP), Methyl (Me), Methoxymethyl (MOM), Methoxythiomethyl (Methoxythiomethyl; MTM), Benzyloxymethyl (Benzyloxymethyl; BOM), 2-Methoxymethyl (MEM), 2- (trimethylsilyl) ethoxymethyl ((2- (Trimethylsilyl) ethoxymethyl); SEM), Tetrahydrofuranyl (THF), t-butyl (t -Butyl, Allyl, Benzyl, p-Methoxybenzyl, 3,4-Dimethoxybenzyl, o-Nitrobenzyl, p-Nitrobenzyl, Triphenylmethyl, Trimethylsilyl (TMS), Triethylsilyl (TES), Triisopropylsilyl (TIPS), t-butyldimethylsilyl (TPS) t-Butyldimethylsilyl (TBDMS), t-Butyldiphenylsilyl (TBDPS), Diphenylmethylsilyl (DPMS), Di-t-butylmethylsilyl (DTBMS), Acetate ( Acetate; Ac), Chloroacetate, Methoxyacetate, Triphenylmethoxyacetate, Pivaloate, Benzoate and p-Toluenesulfonate (Ts) It includes at least one selected from the group consisting of).

According to one embodiment, it may be a diazidoglyoxime (DAG) intermediate by-product.

According to one embodiment, the insensitive-DAG intermediate may have an impact sensitivity of 1.5 J to 19 J, a friction sensitivity of 5 N to 350 N, and an electrostatic sensitivity of 7 m J to 50 m J.

According to one embodiment, the step of synthesizing dichloroglyoxime (DCG); Synthesizing an R-DCG intermediate represented by Chemical Formula 2 through the DCG; Synthesizing an insensitive-DAG intermediate through the R-DCG intermediate; And synthesizing TKX-50 through the insensitive-DAG intermediate.

[Formula 2]

(Wherein, R is Tetrahydropyranyl (THP), Methyl (Me), Methoxymethyl (MOM), Methoxythiomethyl (Methoxythiomethyl; MTM), Benzyloxymethyl (Benzyloxymethyl; BOM), 2-Methoxymethyl (MEM), 2- (trimethylsilyl) ethoxymethyl ((2- (Trimethylsilyl) ethoxymethyl); SEM), Tetrahydrofuranyl (THF), t-butyl (t -Butyl, Allyl, Benzyl, p-Methoxybenzyl, 3,4-Dimethoxybenzyl, o-Nitrobenzyl, p-Nitrobenzyl, Triphenylmethyl, Trimethylsilyl (TMS), Triethylsilyl (TES), Triisopropylsilyl (TIPS), t-butyldimethylsilyl (TPS) t-Butyldimethylsilyl (TBDMS), t-Butyldiphenylsilyl (TBDPS), Diphenylmethylsilyl (DPMS), Di-t-butylmethylsilyl (DTBMS), Acetate ( Acetate; Ac), Chloroacetate, Methoxyacetate, Triphenylmethoxyacetate, Pivaloate, Benzoate and p-Toluenesulfonate (Ts) It includes at least one selected from the group consisting of).

According to one embodiment, the step of synthesizing the dichloroglyoxime (DCG) comprises: synthesizing a glyoxime; And reacting the glyoxime with N-chlorosuccinimide.

According to one embodiment, the step of synthesizing the R-DCG intermediate through the DCG, the DCG and tetrahydropyranyl (Tetrahydropyranyl; THP), methyl (Methyl; Me), methoxymethyl (Methoxymethyl; MOM), meth Methoxythiomethyl (MTM), Benzyloxymethyl (BOM), 2-Methoxymethyl (MEM), 2- (trimethylsilyl) ethoxymethyl ((2- (Trimethylsilyl) ethoxymethyl); SEM), Tetrahydrofuranyl (THF), t-Butyl, Allyl, Benzyl, p-Methoxybenzyl, 3,4-dimethoxybenzyl (3,4-Dimethoxybenzyl), o-Nitrobenzyl, p-Nitrobenzyl, Triphenylmethyl, Trimethylsilyl (TMS), Triethylsilyl (TES) ), Triisopropylsilyl (TIPS), t-Butyldimethylsilyl (TBDMS), t-Butyldiphenylsilyl (TBDPS), Diphenylmethylsilyl yl; DPMS), Di-t-butylmethylsilyl (DTBMS), Acetate (Ac), Chloroacetate, Methoxyacetate, Triphenylmethoxyacetate , Pivaloate (Pivaloate), benzoate (Benzoate) and p-toluenesulfonate (p-Toluenesulfonate; Ts) may be carried out by reacting a compound containing at least one selected from the group consisting of.

According to one embodiment, the step of synthesizing the R-DCG intermediate through the DCG may be performed under a pyridinium p-toluenesulfonate (Ppyrydinium p-toluenesulfonate, PPTS) catalyst.

According to one embodiment, the step of synthesizing the R-DCG intermediate through the DCG may be performed by stirring the DCG, the PPTS, and the compound in a molar ratio of 1: 0.1: 5, followed by reaction.

According to one embodiment, the stirring of the DCG, the PPTS and the compound may be performed at room temperature to 60 ℃.

According to one embodiment, the step of synthesizing the insensitive-DAG intermediate through the R-DCG intermediate may be performed through an azide reaction.

According to one embodiment, the step of synthesizing the insensitive-DAG intermediate through the R-DCG intermediate may be performed by reacting the R-DCG intermediate with sodium azide (NaN ₃ ).

According to one embodiment, the R-DCG intermediate and the sodium azide may be carried out by stirring at a molar ratio of 1: 2 to 4, followed by reaction.

According to one embodiment, the agitation of the R-DCG intermediate and the sodium azide may be performed at 95 ° C to 100 ° C.

According to one embodiment, the step of synthesizing TKX-50 through the desensitizing-DAG intermediate is by reacting the desensitizing-DAG intermediate with an aqueous hydrochloric acid solution to 5,5'-bistetrazol-1,1'-diol (5 , 5'-bistetrazole-1,1'-diol); And reacting the 5,5'-bistetrazol-1,1'-diol with hydroxylamine to synthesize TKX-50.

According to one embodiment, the insensitive-DAG intermediate is reacted with an aqueous hydrochloric acid solution to synthesize 5,5'-bistetrazol-1,1'-diol (5,5'-bistetrazole-1,1'-diol). The step may be performed by stirring the insensitive-DAG intermediate and the aqueous hydrochloric acid solution at room temperature.

According to one embodiment, the step of synthesizing TKX-50 by reacting the 5,5'-bistetrazol-1,1'-diol with hydroxylamine is the 5,5'-bistetrazole -1,1'-diol and the hydroxylamine may be carried out by stirring and reacting at a molar ratio of 1: 3 to 50.

According to one embodiment, the stirring of the 5,5'-bistetrazol-1,1'-diol and the hydroxylamine may be performed at 40 ° C to 60 ° C.

According to the method for synthesizing TKX-50 using diajiglyoxime with a functional group protected according to an embodiment of the present invention, instead of sensitive intermediate DAG synthesized during synthesis of TKX-50, insensitivity-DAG intermediate, which is an insensitivity improved intermediate Through, it is possible to safely work compared to the conventional synthetic method from the threat of impact, friction, static electricity explosion and fire accident. And by using an aqueous solution of HCl without using HCl gas, it has the advantage of being safe and easy to process.

1 is a view for explaining the conventional synthesis method of TKX-50.
2 is a view for explaining a method of synthesizing TKX-50 using diajiglyoxime with a functional group protected according to an embodiment of the present invention.
3 is an NMR graph of glyoxime synthesized according to Example 1 of the present invention.
4 is a NMR graph of DCG synthesized according to Example 2 of the present invention.
5 is an NMR graph of THP-DCG synthesized according to Example 3 of the present invention.
6 is a NMR graph of THP-DAG synthesized according to Example 4 of the present invention.
7 is an NMR graph of TKX-50 synthesized according to Example 5 of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, when it is determined that a detailed description of related known functions or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, terms used in the present specification are terms used to properly express a preferred embodiment of the present invention, which may vary according to a user's, operator's intention, or customs in the field to which the present invention pertains. Therefore, definitions of these terms should be made based on the contents throughout the present specification. The same reference numerals in each drawing denote the same members.

Throughout the specification, when one member is positioned "on" another member, this includes not only the case where one member is in contact with the other member but also another member between the two members.

Throughout the specification, when a part “includes” a certain component, it means that the other component may be further included instead of excluding the other component.

Hereinafter, a method for synthesizing TKX-50 using a diajiglyoxime protected with a functional group of the present invention will be described in detail with reference to examples and drawings. However, the present invention is not limited to these examples and drawings.

A method for synthesizing TKX-50 using diajidoglioxime with functional groups protected according to an embodiment of the present invention includes preparing DCG as a starting material; Forming an insensitive-DAG intermediate represented by Formula 1 below from the DCG; And synthesizing TKX-50 through the insensitive-DAG intermediate.

[Formula 1]

(Wherein, R is Tetrahydropyranyl (THP), Methyl (Me), Methoxymethyl (MOM), Methoxythiomethyl (Methoxythiomethyl; MTM), Benzyloxymethyl (Benzyloxymethyl; BOM), 2-Methoxymethyl (MEM), 2- (trimethylsilyl) ethoxymethyl ((2- (Trimethylsilyl) ethoxymethyl); SEM), Tetrahydrofuranyl (THF), t-butyl (t -Butyl, Allyl, Benzyl, p-Methoxybenzyl, 3,4-Dimethoxybenzyl, o-Nitrobenzyl, p-Nitrobenzyl, Triphenylmethyl, Trimethylsilyl (TMS), Triethylsilyl (TES), Triisopropylsilyl (TIPS), t-butyldimethylsilyl (TPS) t-Butyldimethylsilyl (TBDMS), t-Butyldiphenylsilyl (TBDPS), Diphenylmethylsilyl (DPMS), Di-t-butylmethylsilyl (DTBMS), Acetate ( Acetate; Ac), Chloroacetate, Methoxyacetate, Triphenylmethoxyacetate, Pivaloate, Benzoate and p-Toluenesulfonate (Ts) It includes at least one selected from the group consisting of).

The desensitization-DAG intermediate represented by Chemical Formula 1 has an improved desensitization property instead of DAG, a sensitive intermediate synthesized during TKX-50 synthesis. From, it can work safely compared to the conventional synthesis method.

2 is a view for explaining a method of synthesizing TKX-50 using diajiglyoxime with a functional group protected according to an embodiment of the present invention. Hereinafter, a method for synthesizing TKX-50 using a THP-DAG intermediate as an insensitive-DAG intermediate according to an embodiment of the present invention will be described with reference to FIG. 2.

A method for synthesizing TKX-50 using diajiglyoxime protected with a functional group according to an embodiment of the present invention includes preparing a dichloroglyoxime (hereinafter referred to as 'DCG') as a starting material; Forming an O, O'-ditetrahydropyranyl oxalohydroxymonyl diazide (hereinafter referred to as 'THP-DAG') intermediate from the DCG; And dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate, hereinafter referred to as 'TKX-50' through the THP-DAG intermediate. Synthesis as)).

According to one embodiment, diazidoglyoxime (hereinafter referred to as 'DAG') may be an intermediate by-product.

That is, by using a more insensitive desensitization-DAG intermediate instead of the sensitive intermediate DAG when synthesizing TKX-50, the worker can synthesize TKX-50 more safely.

According to one embodiment, the insensitive-DAG intermediate may have an impact sensitivity of 1.5 J to 19 J, a friction sensitivity of 5 N to 350 N, and an electrostatic sensitivity of 7 m J to 50 m J. The impact sensitivity, friction sensitivity, and static electricity sensitivity are not limited to the above range, and only need to be insensitive to DAG (DAG impact sensitivity 1.5 J, friction sensitivity 5 N, electrostatic sensitivity 7 mJ or more).

Table 1 is a table showing the sensitivity characteristics of the THP-DAG intermediate as an example of the DAG and the insensitive-DAG intermediate. Specifically, after THP-DAG synthesis, 5,5´-bistetrazol-1,1´-diol dihydrate (5,5´-bistetrazole-1) using a 37% HCl solution in acetonitrile solvent , 1´-diol dihydrate; 1,1'-BTO) is synthesized, the solvent is blown and reacted with hydroxyamine in one-pot, finally dihydroxyammonium 5,5'-bistetrazole -1,1'-diolate (dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate; TKX-50) was synthesized. In more detail, THP-DAG is a result of measuring impact sensitivity, friction sensitivity, and electrostatic sensitivity using BAM Fall Hammer, BAM Friction Tester, and Electrostatic Spark Sensitivity Tester.

Shock sensitivity
[J] Friction sensitivity
[N] Static sensitivity
[mJ] DAG 1.5 <5 7 THP-DAG 19.95 352.8 50

Referring to Table 1, it was confirmed that the impact sensitivity of THP-DAG was 19.95 J, the friction sensitivity was 352.8 N, and the electrostatic sensitivity was 50 mJ, which was much insensitive than DAG. In particular, the impact / friction sensitivity of THP-DAG has a much less sensitive characteristic than the high-energy materials currently in use, and when handling THP-DAG, the existing synthesis method is prevented from the threat of explosion / fire accidents due to impact / friction / electrostatics. It is possible to work more safely than using. According to one embodiment, the step of synthesizing dichloroglyoxime (DCG); Synthesizing an R-DCG intermediate represented by Chemical Formula 2 through the DCG; Synthesizing an insensitive-DAG intermediate through the R-DCG intermediate; And synthesizing TKX-50 through the insensitive-DAG intermediate.

[Formula 2]

(Wherein, R is Tetrahydropyranyl (THP), Methyl (Me), Methoxymethyl (MOM), Methoxythiomethyl (Methoxythiomethyl; MTM), Benzyloxymethyl (Benzyloxymethyl; BOM), 2-Methoxymethyl (MEM), 2- (trimethylsilyl) ethoxymethyl ((2- (Trimethylsilyl) ethoxymethyl); SEM), Tetrahydrofuranyl (THF), t-butyl (t -Butyl, Allyl, Benzyl, p-Methoxybenzyl, 3,4-Dimethoxybenzyl, o-Nitrobenzyl, p-Nitrobenzyl, Triphenylmethyl, Trimethylsilyl (TMS), Triethylsilyl (TES), Triisopropylsilyl (TIPS), t-butyldimethylsilyl (TPS) t-Butyldimethylsilyl (TBDMS), t-Butyldiphenylsilyl (TBDPS), Diphenylmethylsilyl (DPMS), Di-t-butylmethylsilyl (DTBMS), Acetate ( Acetate; Ac), Chloroacetate, Methoxyacetate, Triphenylmethoxyacetate, Pivaloate, Benzoate and p-Toluenesulfonate (Ts) It includes at least one selected from the group consisting of).

According to an embodiment, when using the THP-DCG intermediate and the THP-DAG intermediate, synthesizing a dichloroglyoxime (DCG); Synthesizing O, O'-ditetrahydropyranyl oxalohydroxymonyl dichloride (O, O'-ditetrahydropyranyl oxalohydroximoyl dichloride, hereinafter referred to as 'THP-DCG') through the DCG; Synthesizing THP-DAG through the THP-DCG; And synthesizing TKX-50 through the THP-DAG.

According to one embodiment, the step of synthesizing the dichloroglyoxime (DCG) comprises: synthesizing a glyoxime; And reacting the glyoxime with N-chlorosuccinimide.

According to one embodiment, the step of synthesizing the R-DCG intermediate through the DCG, the DCG and tetrahydropyranyl (Tetrahydropyranyl; THP), methyl (Methyl; Me), methoxymethyl (Methoxymethyl; MOM), meth Methoxythiomethyl (MTM), Benzyloxymethyl (BOM), 2-Methoxymethyl (MEM), 2- (trimethylsilyl) ethoxymethyl ((2- (Trimethylsilyl) ethoxymethyl); SEM), Tetrahydrofuranyl (THF), t-Butyl, Allyl, Benzyl, p-Methoxybenzyl, 3,4-dimethoxybenzyl (3,4-Dimethoxybenzyl), o-Nitrobenzyl, p-Nitrobenzyl, Triphenylmethyl, Trimethylsilyl (TMS), Triethylsilyl (TES) ), Triisopropylsilyl (TIPS), t-Butyldimethylsilyl (TBDMS), t-Butyldiphenylsilyl (TBDPS), Diphenylmethylsiyl lyl; DPMS), di-t-butylmethylsilyl (DTBMS), acetate (Ac), chloroacetate (Methoxyacetate), triphenylmethoxyacetate , Pivaloate (Pivaloate), benzoate (Benzoate) and p-toluenesulfonate (p-Toluenesulfonate; Ts) may be carried out by reacting a compound containing at least one selected from the group consisting of.

According to one embodiment, the step of synthesizing the R-DCG intermediate through the DCG may be performed under a pyridinium p-toluenesulfonate (Ppyrydinium p-toluenesulfonate, PPTS) catalyst. In the above, the catalyst was limited to a PPTS catalyst, but other catalysts other than PPTS may be used.

In the present invention, for example, the step of synthesizing the R-DCG intermediate through the DCG, the DCG and 3,4-dihydro-2H-pyran (3, under pyridinium p-toluenesulfonate (PPTS) catalyst) 4-dihydro-2H-pyran, DHP).

According to one embodiment, the step of synthesizing the R-DCG intermediate through the DCG may be performed by stirring the DCG and the PPTS and the compound in a molar ratio of 1: 0.1: 5, followed by reaction. Preferably, after stirring at a molar ratio of 1: 0.1: 5, it may be performed by reacting.

If it exceeds the molar ratio, there may be a problem that the yield decreases or impurities increase.

According to one embodiment, the stirring of the DCG, the PPTS and the compound may be performed at room temperature to 60 ℃. Side reactions may occur when stirring under a temperature condition outside the room temperature. Preferably, it may be carried out at 50 ℃.

As a preferred example, the step of synthesizing THP-DCG through the DCG is: 1) DCG 2.98 g (18.98 mmol), DCM 35 mL, PPTS 0.498 g (1.98 mmol), 3,4-dihydro-2H- in the reactor. After introducing pyran (3,4-dihydro-2H-pyran, DHP) 8.298 g (98.65 mmol) and stirring at 50 ° C. for 3 hours, 2) 200 mL of diethyl ether was added and the reaction solution was transferred to a separatory funnel and NaHCO was added. ₃ 150 mL of saturated solution, 150 mL of NaCl saturated solution and 150 mL of distilled water may be washed, and the solvent may be distilled under reduced pressure to obtain THP-DCG.

According to one embodiment, the step of synthesizing the insensitive-DAG intermediate through the R-DCG intermediate may be performed through an azide reaction.

According to one embodiment, the step of synthesizing the insensitive-DAG intermediate through the R-DCG intermediate may be performed by reacting the R-DCG intermediate with sodium azide (NaN ₃ ).

According to one embodiment, the R-DCG intermediate and the azide agitation may be performed by stirring the mixture at a molar ratio of 1: 2 to 4. Preferably, after stirring at a molar ratio of 1: 3, it may be performed by reacting.

If it exceeds the molar ratio, there may be a problem that the yield decreases or impurities increase.

According to one embodiment, the agitation of the R-DCG intermediate and the sodium azide may be performed at 95 ° C to 100 ° C. When stirring at a temperature condition outside 95 ° C to 100 ° C, the reaction proceeds less and the yield may decrease or a side reaction may occur.

As a preferred example, the step of synthesizing THP-DAG through THP-DCG is: 1) 5 g (15.4 mmol) of THP-DCG, 100 mL of DMF, and 3.0 g (46.2 mmol) of NaN3 are added, and the temperature inside the reactor The temperature may be increased to 100 ° C. and stirred for 2 hours, followed by cooling to room temperature, and 2) adding 100 mL of distilled water to precipitate THP-DAG and filtering to obtain THP-DAG.

According to one embodiment, the step of synthesizing TKX-50 through the desensitizing-DAG intermediate is by reacting the desensitizing-DAG intermediate with an aqueous hydrochloric acid solution to 5,5'-bistetrazol-1,1'-diol (5 , 5'-bistetrazole-1,1'-diol); And reacting the 5,5'-bistetrazol-1,1'-diol with hydroxylamine to synthesize TKX-50.

According to one embodiment, when the desensitization-DAG is reacted in an acidic aqueous solution, 5,5'-bistetrazol-1,1'-diol can be obtained with R groups separated, and in other cases, 5 with R groups attached. , 5'-bistetrazol-1,1'-protected diol (5-5'-bistetrazole-1,1'-protected diol) can be obtained. In the case of the 5,5'-bistetrazol-1,1'-protected diol with an R group, a reaction for removing the R group may be added.

According to one embodiment, the insensitive-DAG intermediate is reacted with an aqueous hydrochloric acid solution to form 5,5'-bistetrazol-1,1'-diol (5,5'-bistetrazole-1,1'-diol, 1,1). The step of synthesizing '-BTO) may be performed by stirring the insensitive-DAG intermediate and the aqueous hydrochloric acid solution under normal temperature conditions.

As a preferred example, the step of synthesizing 5,5'-bistetrazol-1,1'-diol (5,5'-bistetrazole-1,1'-diol) by reacting THP-DAG with an aqueous hydrochloric acid solution is 1 ) 0.5 g (1.47 mmol) of THP-DAG and 50 mL of acetonitrile are added to the reactor at room temperature, and then 1.0 mL (12.1 mmol) of 37% HCl solution is added. 2) The reactor is sealed and at room temperature. It may be a step of stirring for 24 hours and 3) by removing acetonitrile and HCl solution by blowing with air to precipitate 1,1'-BTO.

According to one embodiment, the step of synthesizing TKX-50 by reacting the 5,5'-bistetrazol-1,1'-diol with hydroxylamine is the 5,5'-bistetrazole The -1,1'-diol and the hydroxylamine are preferably stirred at a molar ratio of 1: 3 to 50, and then reacted. Preferably, after stirring at a molar ratio of 1:44, it may be performed by reacting.

If the weight ratio is exceeded, a problem may occur that a reaction yield decreases or impurities increase.

According to one embodiment, the stirring of the 5,5'-bistetrazol-1,1'-diol and the hydroxylamine may be performed at 40 ° C to 60 ° C. Preferably, it may be carried out at 50 ℃. When stirring under a temperature condition out of 40 ° C to 60 ° C, a reaction yield may decrease or a problem in which impurities are increased.

As a preferred example, the step of synthesizing TKX-50 by reacting the 5,5'-bistetrazol-1,1'-diol with hydroxylamine is: 1) a reactor with 1,1'-BTO 10 mL of distilled water was added to the mixture, and the temperature was increased to 50 ° C., and 4.0 mL (65.3 mmol) of NH ₂ OH (50% w / w in H ₂ O) was added. 2) After stirring for 30 minutes at 50 ° C. When cooled to TKX-50 is precipitated, and then filtered and dried may be to include the step of obtaining TKX-50.

According to the method for synthesizing TKX-50 using diajiglyoxime with a functional group protected according to an embodiment of the present invention, instead of sensitive intermediate DAG synthesized during synthesis of TKX-50, insensitivity-DAG intermediate, which is an insensitivity improved intermediate Through, it is possible to safely work compared to the conventional synthetic method from the threat of impact, friction, static electricity explosion and fire accident. And, by using an aqueous solution of HCl without using HCl gas, it has the advantage of being safe and easy to process.

Hereinafter, the present invention will be described in more detail by examples and comparative examples.

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

[Example]

Material and characterization

All chemicals were received in pure analytical grade material from Acros or Aldrich Organics. ¹ H and ¹³ C NMR spectra were found on a 400 MHz (Bruker AVANCE 400) Nuclear Magnetic Resonance Spectrometer using DMSO-d ₆ or CDCl ₃ as a solvent. Analytical thin layer chromatography (TLC) was performed with E. Merck pre-coated TLC plate, layer thickness 0.25 mm, silica gel 60F-254. High resolution mass spectra were obtained on a microTOF-QII HRMS / MS instrument (Bruker) with electrospray ionization technology. Impact sensitivity tests were performed using a BAM Fallhammer instrument (OZM) according to the STANAG 4489 revision instructions. The friction sensitivity test was performed according to the STANAG 4487 modification instruction using a BAM friction tester (OZM). Electrostatic discharge testing was performed according to STANAG 4490 using an ESD test instrument (OZM).

Example 1: Synthesis of glyoxime

NaOH 18.4 g (0.46 mol), 50 mL of distilled water was added to the reactor, cooled to 0 ° C., and 46 g (0.66 mol) of hydroammonium chloride was added to the reactor. Subsequently, 47.9 g (0.33 mol) of 40% glyoxal aqueous solution was added to the reactor while maintaining 0 to 10 ° C. The inside temperature of the reactor was maintained at 0 ° C. and stirred for 1 hour, and when a solid was formed, filtered and washed with a small amount of ice water. After drying, 24.7 g (0.28 mol, 85%) of glyoxime was obtained.

¹ H NMR (DMSO-d ₆ ): 7.73 (s, 2H, CH), 11.61 (s, 2H, OH); ¹³ C NMR (DMSO-d ₆ ): 145.82

Example 2: Synthesis of DCG via glyoxime

Glyoxime (Glyoxime) 18 g (0.20 mol), 180 mL of DMF was added to the reactor, cooled to 0 ° C., and 54.5 g (0.40 mol) of N-chlorosuccinimide (NCS) was slowly added to the reactor. Input. Thereafter, the inside of the reactor was maintained at 0 ° C and stirred for 30 minutes, and then slowly heated to 25 ° C and stirred for 1 hour. After adding 200 mL of distilled water, the reaction solution was transferred to a separatory funnel and extracted with 200 mL of EA and distilled water (150 mL x 3 times). The obtained organic layer was distilled under reduced pressure to obtain crude DCG. 100 mL of the obtained crude DCG and MC were added to the reactor, stirred at room temperature for 1 hour, and filtered. After drying, DCG 25.4 g (0.16 mol, 81%) was obtained.

¹ H NMR (DMSO-d ₆ ): 13.10 (s, 2H, OH); ¹³ C NMR (DMSO-d ₆ ): 130.86

Example 3: Synthesis of THP-DCG via DCG

To the reactor, 2.98 g (18.98 mmol) of DCG, 35 mL of DCM, 0.498 g (1.98 mmol) of PPTS, 3,3-dihydro-2H-pyran (3,4-dihydro-2H-pyran, DHP) 8.298 g (98.65 mmol) ) After stirring, the mixture was stirred at room temperature for 3 hours. Then, after adding 200 mL of diethyl ether, the reaction solution was transferred to a separatory funnel, washed with 150 mL of saturated NaHCO ₃ solution, 150 mL of NaCl saturated solution, and 150 mL of distilled water. Then, the solvent was distilled under reduced pressure to obtain 4.34 g (13.28 mmol, 70%) of THP-DCG.

¹ H NMR (CDCl ₃ ): 1.64 (m, 8H, CH ₂ ), 1.86 (m, 4H, CH ₂ ), 3.75 (m, 4H, CH ₂ ), 5.52 (m, 2H, CH); ¹³ C NMR (CDCl ₃ ): 18.80, 18.83, 25.16, 28.45, 28.47, 62.54, 62.62, 102.30, 102.36, 133.91, 133.96

Example 4: Synthesis of THP-DAG via THP-DCG

To the reactor, 5 g (15.4 mmol) of THP-DCG, 100 mL of DMF, and 3.0 g (46.2 mmol) of NaN3 were added. The temperature inside the reactor was raised to 100 ° C., stirred for 2 hours, and then cooled to room temperature. Then, 100 mL of distilled water was added to precipitate THP-DAG and filtered to obtain 4.11 g (12.166 mmol, 79%) of THP-DAG.

¹ H NMR (CDCl ₃ ): 1.63 (m, 8H, CH ₂ ), 1.80 (m, 4H, CH ₂ ), 3.75 (m, 4H, CH ₂ ), 5.34 (m, 2H, CH); ¹³ C NMR (CDCl ₃ ): 18.37, 18.45, 24.79, 28.01, 28.06, 62.10, 62.26, 101.72, 101.81, 137.80, 137.82; Impact sensitivity: 19.95 J, friction sensitivity: 352.8 N, electrostatic sensitivity: 50 mJ

Example 5: Synthesis of 1,1'-BTO via THP-DAG and TKX-50 through synthesis of 1,1'-BTO

After adding 0.5 g (1.47 mmol) of THP-DAG and 50 mL of acetonitrile to the reactor at room temperature, 1.0 mL (12.1 mmol) of a 37% HCl solution was added. After that, the reactor was sealed and stirred at room temperature for 24 hours. After the reaction, acetonitrile and HCl solution were removed by blowing with air to precipitate 1,1'-BTO. 10 mL of distilled water was added to the reactor with the precipitated 1,1'-BTO, and the temperature was raised to 50 ° C to melt. After adding NH ₂ OH (50% w / w in H ₂ O) 4.0 mL (65.3 mmol), the mixture was stirred for 2 hours while gradually lowering to room temperature. The precipitated TKX-50 was filtered and dried to obtain 0.22 g (0.931 mmol, 63.3% in two steps).

¹ H NMR (DMSO-d ₆ ): 9.74 (s, 8H, NH ₃ OH); ¹³ C NMR (DMSO-d ₆ ): 135.48

3 is an NMR graph of glyoxime synthesized according to Example 1 of the present invention. More specifically, Figure 3 (a) is a ¹ H NMR spectrum of glyoxime, Figure 3 (b) is a ¹³ C NMR spectrum of glyoxime.

3 (a) and (b), it can be seen that glyoxime was synthesized through Example 1.

4 is a NMR graph of DCG synthesized according to Example 2 of the present invention. More specifically, Fig. 4 (a) is the ¹ H NMR spectrum of DCG, and Fig. 4 (b) is the ¹³ C NMR spectrum of DCG.

Referring to Figure 4 (a) and (b), it can be seen that DCG is synthesized through Example 2.

5 is an NMR graph of THP-DCG synthesized according to Example 3 of the present invention. More specifically, Fig. 5 (a) is the ¹ H NMR spectrum of THP-DCG, and Fig. 5 (b) is the ¹³ C NMR spectrum of THP-DCG.

5 (a) and (b), it can be seen that THP-DCG was synthesized through Example 3.

6 is a NMR graph of THP-DAG synthesized according to Example 4 of the present invention. More specifically, FIG. 6 (a) is the ¹ H NMR spectrum of THP-DAG, and FIG. 6 (b) is the ¹³ C NMR spectrum of THP-DAG.

6 (a) and (b), it can be seen that THP-DAG was synthesized through Example 4.

7 is an NMR graph of TKX-50 synthesized according to Example 5 of the present invention. More specifically, Fig. 7 (a) is a ¹ H NMR spectrum of TKX-50, and Fig. 7 (b) is a ¹³ C NMR spectrum of TKX-50.

7 (a) and (b), it can be seen that TKX-50 was synthesized through Example 5.

As described above, the present invention relates to a method for synthesizing TKX-50 through THP-DAG, an intermediate insensitivity with improved insensitivity, instead of DAG, a sensitive intermediate that is synthesized during TKX-50 synthesis, explosion and fire due to impact, friction, static electricity It has the advantage of being able to work safely compared to existing synthetic methods from the threat of accidents.

As described above, although the embodiments have been described by a limited embodiment and drawings, those skilled in the art can make various modifications and variations from the above description. For example, even if the described techniques are performed in a different order than the described method, and / or the described components are combined or combined in a different form from the described method, or replaced or replaced by another component or equivalent Appropriate results can be achieved. Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

Claims (17)

Preparing dichloroglyoxime (DCG) as a starting material;
From the DCG to form an insensitive-O, O'-ditetrahydropyranyl oxalohydroxymonyl diazide (O, O'-ditetrahydropyranyl oxalohydroximoyl diazide, insensitive-DiAzidoGlyoxime, insensitive-DAG) intermediate represented by the following Chemical Formula 1 step; And
Dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate, Thomas Klapotke eXplosive-50, TKX via the insensitive-DAG intermediate -50);
Including,
Synthesizing dichloroglyoxime (DCG);
Synthesizing an R-dichloroglyoxime (R-DCG) intermediate represented by Chemical Formula 2 through DCG;
Synthesizing an insensitive-DAG intermediate through the R-DCG intermediate; And
Synthesizing TKX-50 through the insensitive-DAG intermediate;
Including,
Synthesizing the R-DCG intermediate through the DCG,
The DCG and tetrahydropyranyl (THP), methoxymethyl (MOM), tetrahydrofuranyl (THF), t-butyl (t-Butyl), p-methoxybenzyl (p-Methoxybenzyl) ), 3,4-dimethoxybenzyl, trimethylsilyl (TMS) and t-butyldimethylsilyl (t-Butyldimethylsilyl; TBDMS) at least one compound selected from the group consisting of It is carried out by reacting,
Synthesis of TKX-50 using diajiglyoxime with functional group protection:
[Formula 1]

,
[Formula 2]

(In Formula 1 and Formula 2, R is, respectively, tetrahydropyranyl (Tetrahydropyranyl; THP), methoxymethyl (Methoxymethyl; MOM), tetrahydrofuranyl (Tetrahydrofuranyl; THF), t-butyl (t-Butyl) , p-methoxybenzyl (p-Methoxybenzyl), 3,4-dimethoxybenzyl (3,4-Dimethoxybenzyl), trimethylsilyl (Trimethylsilyl; TMS) and t-butyldimethylsilyl (t-Butyldimethylsilyl; TBDMS) At least one selected from).
According to claim 1,
Diazidoglyoxime (DAG) is an intermediate by-product,
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
According to claim 1,
The insensitive-DAG intermediate,
Impact sensitivity is 1.5 J to 19 J,
Friction sensitivity is 5 N to 300 N,
The electrostatic sensitivity is 7 m J to 50 m J,
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
delete According to claim 1,
Synthesizing the dichloroglyoxime (dichloroglyoxime, DCG),
Synthesizing glyoxime; And
Reacting the glyoxime and N-chlorosuccinimide (N-chlorosuccinimide); to include,
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
delete According to claim 1,
The step of synthesizing the R-DCG intermediate through the DCG is carried out under a pyridinium p-toluenesulfonate (Pyrydinium p-toluenesulfonate, PPTS) catalyst,
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
The method of claim 7,
Synthesizing the R-DCG intermediate through the DCG,
After the DCG, the PPTS and the compound were stirred at a molar ratio of 1: 0.1: 5, and reacted,
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
The method of claim 8,
Stirring of the DCG, the PPTS and the compound is carried out at room temperature to 60 ℃,
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
According to claim 1,
Synthesizing the insensitive-DAG intermediate through the R-DCG intermediate,
It is carried out through an azide reaction,
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
The method of claim 10,
Synthesizing the insensitive-DAG intermediate through the R-DCG intermediate,
It is carried out by reacting the R-DCG intermediate with sodium azide (NaN ₃ ),
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
The method of claim 11,
It is performed by stirring the R-DCG intermediate and the sodium azide at a molar ratio of 1: 2 to 4, followed by reaction,
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
The method of claim 12,
Stirring of the R-DCG intermediate and the sodium azide is performed at 95 ° C to 100 ° C,
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
According to claim 1,
Synthesizing the TKX-50 through the insensitive-DAG intermediate,
Reacting the insensitive-DAG intermediate with an aqueous hydrochloric acid solution to synthesize 5,5'-bistetrazol-1,1'-diol (5,5'-bistetrazole-1,1'-diol); And
It comprises the step of synthesizing TKX-50 by reacting the 5,5'-bistetrazol-1,1'-diol with hydroxylamine (Hydroxylamine);
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
The method of claim 14,
The step of synthesizing 5,5'-bistetrazol-1,1'-diol (5,5'-bistetrazole-1,1'-diol) by reacting the insensitive-DAG intermediate with an aqueous hydrochloric acid solution,
Is carried out by stirring the insensitive-DAG intermediate and the aqueous hydrochloric acid solution at room temperature conditions,
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
The method of claim 14,
The step of synthesizing the TKX-50 by reacting the 5,5'-bistetrazol-1,1'-diol with hydroxylamine (Hydroxylamine),
The 5,5'-bistetrazol-1,1'-diol and the hydroxylamine are stirred at a molar ratio of 1: 3 to 50, and then reacted.
Synthesis of TKX-50 using diajiglyoxime with functional group protection.
The method of claim 16,
Stirring of the 5,5'-bistetrazol-1,1'-diol and the hydroxylamine is performed at 40 ° C to 60 ° C,
Synthesis of TKX-50 using diajiglyoxime with functional group protection.

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