KR102331641B1 - Synthesis of thp-dag intermediate - Google Patents

Abstract

The present invention relates to a method for preparing a THP-DAG intermediate, and more particularly, to a method comprising: preparing DCG as a starting material; and forming a THP-DAG intermediate from the DCG; it relates to a method for preparing a THP-DAG intermediate.

Description

THP-DAG intermediate preparation method {SYNTHESIS OF THP-DAG INTERMEDIATE}

The present invention relates to a method for preparing a THP-DAG intermediate.

Currently, the most widely used high-energy substances as 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), etc., are widely used in various fields. With the recent development of a new weapon system, many studies are being conducted to develop high-energy materials with higher explosive performance than previously used high-energy materials. became Among the high-energy materials developed in this way, DDF (dinitroazofuroxane) and ONC (octanitrocubane) have a very excellent explosive performance with an explosion speed of about 10,000 m/s, but have a very sensitive characteristic, which threatens the safety of the operator. .

In order to improve explosive performance and insensitivity, research on cyclic compounds with high nitrogen content such as triazole, tetrazole, nitroiminotetrazole, and tetrazine has been actively conducted in recent years. 5,5'-bistetrazole-1,1'-diolate (dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate, Thomas Klapotke eXplosive - 50, TKX-50) is evaluated as one of the promising high-energy materials are receiving TKX-50 is known not only to have a higher explosive performance than existing energetic materials (RDX, HMX, CL-20), but also to be less sensitive.

1 is a view for explaining a conventional synthesis method of TKX-50. Referring to FIG. 1 , in the conventional synthesis method of TKX-50, glyoxal is used as a starting material and synthesized through 5 synthesis steps. TKX-50 itself is insensitive compared to existing high-energy substances, but diazidoglyoxime (DAG), an intermediate obtained after an azide reaction that introduces an energy group, is at the level of a detonator (Lead styphnate: shock sensitivity 2.5-5 J , friction sensitivity 1.5 N, lead azide: shock sensitivity 2.5-4 J, friction sensitivity 0.1-1 N) with very sensitive sensitivity (DAG: shock sensitivity 1.5 J, friction sensitivity 5 N or less, electrostatic sensitivity 7 mJ) -50 Synthesis not only threatens the safety of workers, but also poses a risk of accidents.

The present invention is to solve the above problems, and an object of the present invention is to enable workers to work more safely when synthesizing TKX-50, instead of DAG, which is a sensitive intermediate, more insensitive THP-DAG (O,O'-ditetrahydropyranyloxalohydroximoyl diazide ) to provide a method for synthesizing

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.

A method for preparing a THP-DAG intermediate according to an embodiment of the present invention comprises the steps of preparing dichloroglyoxime (DCG) as a starting material; and forming an O,O'-ditetrahydropyranyl oxalohydroximoyl diazide (THP-DAG) intermediate from the DCG.

According to one aspect, diazidoglioxime (diazidoglyoxime, DAG) intermediate by-products-free.

According to an aspect, the THP-DAG may have an impact sensitivity of 15 J or more, a friction sensitivity of 300 N or more, and an electrostatic sensitivity of 40 m J or more.

According to one aspect, synthesizing dichloroglyoxime (dichloroglyoxime, DCG); synthesizing O,O'-ditetrahydropyranyl oxalohydroximoyl dichloride (THP-DCG) through the DCG; and synthesizing THP-DAG through the THP-DCG.

According to one aspect, the step of synthesizing the dichloroglyoxime (dichloroglyoxime, DCG) comprises the steps of synthesizing glyoxime; and reacting the glyoxime with N-chlorosuccinimide.

According to one aspect, in the step of synthesizing THP-DCG through DCG, the DCG and 3,4-dihydro-2H-pyran (3, It may be carried out by reacting 4-dihydro-2H-pyran).

According to one aspect, in the step of synthesizing THP-DCG through DCG, the DCG, the p-TsOH and the 3,4-dihydro-2H-pyran were stirred in a weight ratio of 1: 3 to 4: 1.6. After that, it may be carried out by reacting.

According to one aspect, the stirring of the DCG, the p-TsOH and the 3,4-dihydro-2H-pyran may be performed at room temperature.

According to one aspect, the step of synthesizing THP-DAG through THP-DCG may be performed through an azide reaction.

According to one aspect, the step of synthesizing THP-DAG through the THP-DCG may be performed by reacting _{the THP-DCG with sodium azide (NaN 3 ).}

According to one aspect, after stirring the THP-DCG and the sodium azide in a weight ratio of 1:0.4 to 0.8, the reaction may be carried out.

According to one aspect, the stirring of the THP-DCG and the sodium azide may be performed at 95 °C to 100 °C.

delete

delete

delete

delete

According to the present invention, by using a more insensitive THP-DAG intermediate instead of DAG, which is a sensitive intermediate, when synthesizing TKX-50, an operator can more safely synthesize TKX-50.

1 is a view for explaining a conventional synthesis method of TKX-50.
2 is a view for explaining a method for producing a THP-DAG intermediate according to an embodiment of the present invention.
3 is a view for explaining a method of manufacturing a TKX-50 according to an embodiment of the present invention.
4 is an NMR graph of glyoxime synthesized according to Example 1 of the present invention.
5 is an NMR graph of DCG synthesized according to Example 2 of the present invention.
6 is an NMR graph of THP-DCG synthesized according to Example 3 of the present invention.
7 is an NMR graph of THP-DAG synthesized according to Example 4 of the present invention.
8 is an NMR graph of 1,1'-BTO synthesized according to Example 5 of the present invention.
9 is an NMR graph of TKX-50 synthesized according to Example 6 of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. In addition, the terms used in this specification are terms used to properly express the preferred embodiment of the present invention, which may vary according to the intention of the user or operator or customs in the field to which the present invention belongs. Accordingly, definitions of these terms should be made based on the content throughout this specification. Like reference numerals in each figure indicate like elements.

Throughout the specification, when a member is said to be located “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

Throughout the specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components.

Hereinafter, the method for preparing the THP-DAG intermediate 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 preparing a THP-DAG intermediate according to an embodiment of the present invention comprises the steps of preparing DCG as a starting material; and forming a THP-DAG intermediate from the DCG.
2 is a view for explaining a method for producing a THP-DAG intermediate according to an embodiment of the present invention. Hereinafter, the present invention will be described with reference to FIG. 2 .
A method for preparing a THP-DAG intermediate according to an embodiment of the present invention comprises the steps of preparing dichloroglyoxime (hereinafter referred to as 'DCG') as a starting material; and forming an O,O'-ditetrahydropyranyl oxalohydroximoyl diazide (O,O'-ditetrahydropyranyl oxalohydroximoyl diazide, hereinafter referred to as 'THP-DAG') intermediate from the DCG; synthesizing includes ;
According to one aspect, diazidoglioxime (hereinafter referred to as 'DAG') may be an intermediate by-product-free one.
That is, by using a more insensitive THP-DAG intermediate instead of DAG, which is a sensitive intermediate, when synthesizing TKX-50, workers can synthesize TKX-50 more safely.
According to an aspect, the THP-DAG may have an impact sensitivity of 15 J or more, a friction sensitivity of 300 N or more, and an electrostatic sensitivity of 40 m J or more.
Table 1 is a table showing the sensitivity characteristics of DAG and THP-DAG. In more detail, it is the result of measuring impact sensitivity, friction sensitivity and electrostatic sensitivity of THP-DAG using BAM Fall Hammer, BAM Friction Tester, and Electrostatic Spark Sensitivity Tester.
shock sensitivity
[J] friction sensitivity
[N] Electrostatic sensitivity
[mJ] DAG 1.5 < 5 7 THP-DAG 19.95 352.8 50
Referring to Table 1, it was confirmed that the shock 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 more insensitive than the DAG. In particular, the shock/friction sensitivity of THP-DAG is much less sensitive than that of high-energy materials in use. It is safer to work than to use it. According to one aspect, the method comprises the steps of: synthesizing dichloroglyoxime (DCG); synthesizing O,O'-ditetrahydropyranyl oxalohydroxymonyl dichloride (O,O'-ditetrahydropyranyl oxalohydroximoyl dichloride, hereinafter referred to as 'THP-DCG') through the DCG; and synthesizing THP-DAG through the THP-DCG.
According to one aspect, the step of synthesizing the dichloroglyoxime (dichloroglyoxime, DCG) comprises the steps of synthesizing glyoxime; and reacting the glyoxime with N-chlorosuccinimide.
According to one aspect, in the step of synthesizing THP-DCG through DCG, the DCG and 3,4-dihydro-2H-pyran (3, It may be carried out by reacting 4-dihydro-2H-pyran).
According to one aspect, in the step of synthesizing THP-DCG through DCG, the DCG, the p-TsOH and the 3,4-dihydro-2H-pyran were stirred in a weight ratio of 1: 3 to 4: 1.6. After that, it may be carried out by reacting. Preferably, after stirring in a weight ratio of 1: 3.7: 1.6, the reaction may be carried out.
If it is out of the above weight ratio, there may be problems in that the yield is reduced or impurities are increased.
According to one aspect, the stirring of the DCG, the p-TsOH and the 3,4-dihydro-2H-pyran may be performed at room temperature. A side reaction may occur when stirring at a temperature condition outside of room temperature.
In a preferred embodiment, the step of synthesizing THP-DCG through DCG includes: 1) DCG 10 g (63.7 mmol), MC 300 mL, p-TsOH 36.7 g (191.4 mmol), 3,4-dihydro-2H in a reactor -After adding 16.1 g (191.4 mmol) of pyran, stirring at room temperature for 2 hours, 2) adding 300 mL of distilled water, transferring the reaction solution to a separatory funnel, and extracting with 200 mL of MC and distilled water (200 mL x 3 times) and 3) distilling MC under reduced pressure and purifying by column chromatography to obtain THP-DCG.
According to one aspect, the step of synthesizing THP-DAG through THP-DCG may be performed through an azide reaction.
According to one aspect, the step of synthesizing THP-DAG through the THP-DCG may be performed by reacting _{the THP-DCG with sodium azide (NaN 3 ).}
According to one aspect, after stirring the THP-DCG and the sodium azide in a weight ratio of 1: 0.4 to 0.8, the reaction may be carried out. Preferably, after stirring in a weight ratio of 1:0.6, it may be carried out by reacting.
If it is out of the above weight ratio, there may be problems in that the yield is reduced or impurities are increased.
According to one aspect, the stirring of the THP-DCG and the sodium azide may be performed at 95 °C to 100 °C. When stirring under a temperature condition outside of 95 °C to 100 °C, the reaction is less proceeded, which may cause a problem in that the yield is reduced or a side reaction proceeds.
In a preferred embodiment, the step of synthesizing THP-DAG through THP-DCG includes: 1) 5 g (15.4 mmol) of THP-DCG, 100 mL of DMF, 3.0 g (46.2 mmol) of NaN3 are added, and then the temperature inside the reactor may include a step of heating to 100 °C, stirring for 2 hours, cooling to room temperature, and 2) adding 100 mL of distilled water to precipitate THP-DAG and filtration to obtain THP-DAG.

3 is a view for explaining a method of manufacturing a TKX-50 according to an embodiment of the present invention. Hereinafter, the present invention will be described with reference to FIG. 3 .

The method for preparing a THP-DAG intermediate according to an embodiment of the present invention comprises the steps of preparing dichloroglyoxime (hereinafter referred to as 'DCG') as a starting material; forming an O,O'-ditetrahydropyranyl oxalohydroximoyl diazide (hereinafter referred to as 'THP-DAG') intermediate from the DCG; and dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate, hereinafter 'TKX-50', through the THP-DAG intermediate and synthesizing).

According to one aspect, diazidoglioxime (hereinafter referred to as 'DAG') may be an intermediate by-product-free one.

That is, by using a more insensitive THP-DAG intermediate instead of DAG, which is a sensitive intermediate, when synthesizing TKX-50, workers can synthesize TKX-50 more safely.

According to an aspect, the THP-DAG may have an impact sensitivity of 15 J or more, a friction sensitivity of 300 N or more, and an electrostatic sensitivity of 40 m J or more.

Table 2 is a table showing the sensitivity characteristics of DAG and THP-DAG. In more detail, it is the result of measuring impact sensitivity, friction sensitivity and electrostatic sensitivity of THP-DAG using BAM Fall Hammer, BAM Friction Tester, and Electrostatic Spark Sensitivity Tester.

[Table 2]

Referring to Table 2, it was confirmed that the shock 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 more insensitive than the DAG. In particular, the shock/friction sensitivity of THP-DAG is much more insensitive than that of high-energy materials in use. It's safer than using it.

According to one aspect, synthesizing dichloroglyoxime (dichloroglyoxime, DCG); synthesizing O,O'-ditetrahydropyranyl oxalohydroximoyl 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 aspect, the step of synthesizing the dichloroglyoxime (dichloroglyoxime, DCG) comprises the steps of synthesizing glyoxime; and reacting the glyoxime with N-chlorosuccinimide.

According to one aspect, in the step of synthesizing THP-DCG through DCG, the DCG and 3,4-dihydro-2H-pyran (3, It may be carried out by reacting 4-dihydro-2H-pyran).

According to one aspect, in the step of synthesizing THP-DCG through DCG, the DCG, the p-TsOH and the 3,4-dihydro-2H-pyran were stirred in a weight ratio of 1: 3 to 4: 1.6. After that, it may be carried out by reacting. Preferably, after stirring in a weight ratio of 1: 3.7: 1.6, the reaction may be carried out.

If it is out of the above weight ratio, there may be problems in that the yield is reduced or impurities are increased.

According to one aspect, the stirring of the DCG, the p-TsOH and the 3,4-dihydro-2H-pyran may be performed at room temperature. A side reaction may occur when stirring at a temperature condition outside of room temperature.

In a preferred embodiment, the step of synthesizing THP-DCG through DCG includes: 1) DCG 10 g (63.7 mmol), MC 300 mL, p-TsOH 36.7 g (191.4 mmol), 3,4-dihydro-2H in a reactor -After adding 16.1 g (191.4 mmol) of pyran, stirring at room temperature for 2 hours, 2) adding 300 mL of distilled water, transferring the reaction solution to a separatory funnel, and extracting with 200 mL of MC and distilled water (200 mL x 3 times) and 3) distilling MC under reduced pressure and purifying by column chromatography to obtain THP-DCG.

According to one aspect, the step of synthesizing THP-DAG through THP-DCG may be performed through an azide reaction.

According to one aspect, the step of synthesizing THP-DAG through the THP-DCG may be performed by reacting _{the THP-DCG with sodium azide (NaN 3 ).}

According to one aspect, after stirring the THP-DCG and the sodium azide in a weight ratio of 1: 0.4 to 0.8, the reaction may be carried out. Preferably, it may be carried out by stirring after stirring in a weight ratio of 1:0.6.

If it is out of the above weight ratio, there may be problems in that the yield is reduced or impurities are increased.

According to one aspect, the stirring of the THP-DCG and the sodium azide may be performed at 95 °C to 100 °C. When stirring under a temperature condition outside of 95 °C to 100 °C, the reaction is less proceeded, which may cause a problem in that the yield is reduced or a side reaction proceeds.

In a preferred embodiment, the step of synthesizing THP-DAG through THP-DCG includes: 1) 5 g (15.4 mmol) of THP-DCG, 100 mL of DMF, 3.0 g (46.2 mmol) of NaN3 are added, and then the temperature inside the reactor may include a step of heating to 100 °C, stirring for 2 hours, cooling to room temperature, and 2) adding 100 mL of distilled water to precipitate THP-DAG and filtration to obtain THP-DAG.

According to one aspect, in the step of synthesizing TKX-50 through THP-DAG, 5,5'-bistetrazole-1,1'-diol (5,5') by reacting the THP-DAG with hydrochloric acid gas -bistetrazole-1,1'-diol) synthesizing; and synthesizing TKX-50 by reacting the 5,5'-bistetrazole-1,1'-diol with hydroxylamine.

According to one aspect, by reacting the THP-DAG with hydrochloric acid gas, 5,5'-bistetrazole-1,1'-diol (5,5'-bistetrazole-1,1'-diol, 1,1'- The step of synthesizing BTO) may be performed by stirring the THP-DAG and the hydrochloric acid gas at room temperature.

In a preferred embodiment, the step of synthesizing 5,5'-bistetrazole-1,1'-diol by reacting the THP-DAG with hydrochloric acid gas, 1) 1.5 g (4.43 mmol) of THP-DAG and 50 mL of diethyl ether were added to the reactor, cooled to 0 °C, and HCl gas was blown in for 1 hour. 2) The reactor was sealed, and the temperature was raised to room temperature to 24 It may include a step of stirring for a period of time and 3) filtering and drying to obtain 1,1'-BTO.

According to one aspect, the step of synthesizing TKX-50 by reacting the 5,5'-bistetrazole-1,1'-diol with hydroxylamine, the 5,5'-bistetrazole- 1,1'-diol and the hydroxylamine are preferably stirred in a weight ratio of 1:0.5 to 0.7, and then reacted. Preferably, it may be carried out by stirring after stirring in a weight ratio of 1:0.64.

If it is out of the above weight ratio, there may be problems in that the reaction yield is reduced or impurities are increased.

According to one aspect, the stirring of the 5,5'-bistetrazole-1,1'-diol and the hydroxylamine may be performed at 40°C to 60°C. Preferably, it may be carried out at 50 °C. When stirring at a temperature condition outside of 40 °C to 60 °C, there may be problems in that the reaction yield is reduced or impurities are increased.

In a preferred embodiment, the step of synthesizing TKX-50 by reacting the 5,5'-bistetrazole-1,1'-diol with hydroxylamine is 1) 1,1'-BTO 1 in a reactor g (4.85 mmol), 20 mL of distilled water was added, the temperature was raised to 50 °C, and 0.64 g (9.7 mmol) of NH2OH (50% w/w in H2O) was added and 2) stirred at 50 °C for 30 min. When cooled to room temperature, TKX-50 is precipitated, and then filtered and dried to obtain TKX-50.

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.

Example 1: Synthesis of glyoxime

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

Example 2: Synthesis of DCG via glyoxime

Glyoxime 18 g (0.20 mol) and DMF 180 mL were added to the reactor, cooled to 0 °C, and 54.5 g (0.40 mol) of N-chlorosuccinimide was slowly added to the reactor. After that, the inside of the reactor was stirred for 30 minutes while maintaining the temperature at 0° C., and the temperature was slowly raised 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 was put into a reactor, stirred at room temperature for 1 hour, and then filtered. After drying, 25.4 g (0.16 mol, 81%) of DCG was obtained.

Example 3: Synthesis of THP-DCG via DCG

DCG 10 g (63.7 mmol), MC 300 mL, p-TsOH 36.7 g (191.4 mmol), and 3,4-dihydro-2H-pyran 16.1 g (191.4 mmol) were added to the reactor, followed by stirring at room temperature for 2 hours. After adding 300 mL of distilled water, the reaction solution was transferred to a separatory funnel, and extracted with 200 mL of MC and distilled water (200 mL x 3 times). Then, MC was distilled under reduced pressure and purified by column chromatography to obtain 14.9 g (45.9 mmol, 72%) of THP-DCG.

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

5 g (15.4 mmol) of THP-DCG, 100 mL of DMF, and 3.0 g (46.2 mmol) of NaN3 were added to the reactor. 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 2.81 g (8.32 mmol, 54%) of THP-DAG.

Example 5: Synthesis of 1,1'-BTO via THP-DAG

After adding 1.5 g (4.43 mmol) of THP-DAG and 50 mL of diethyl ether to the reactor, it was cooled to 0 °C, and HCl gas was blown in for 1 hour. After that, the reactor was sealed, heated to room temperature, and stirred for 24 hours. When 1,1'-BTO was precipitated, it was filtered and dried to obtain 0.6 g (2.75 mmol, 62%).

Example 6: Synthesis of TKX-50 through 1,1'-BTO

1 g (4.85 mmol) of 1,1'-BTO and 20 mL of distilled water were added to the reactor, the temperature was raised to 50 °C, and 0.64 g (9.7 mmol) of NH2OH (50% w/w in H2O) was added. After stirring at 50 °C for 30 minutes and cooling to room temperature, TKX-50 was precipitated, and then filtered and dried to obtain 0.45 g (2.23 mmol, 46%) of TKX-50.

4 is an NMR graph of glyoxime synthesized according to Example 1 of the present invention. In more detail, FIG. 4 (a) is a ¹ H NMR spectrum of glyoxime, and FIG. 3 (b) is a ¹³ C NMR spectrum of glyoxime.

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

5 is an NMR graph of DCG synthesized according to Example 2 of the present invention. In more detail, FIG. 5 (a) is a ¹ H NMR spectrum of DCG, and FIG. 5 (b) is a ¹³ C NMR spectrum of DCG.

Referring to FIGS. 5 (a) and (b), it can be seen that DCG was synthesized in Example 2.

6 is an NMR graph of THP-DCG synthesized according to Example 3 of the present invention. In more detail, FIG. 6 (a) is a ¹ H NMR spectrum of THP-DCG, and FIG. 6 (b) is a ¹³ C NMR spectrum of THP-DCG.

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

7 is an NMR graph of THP-DAG synthesized according to Example 4 of the present invention. In more detail, FIG. 7 (a) is a ¹ H NMR spectrum of THP-DAG, and FIG. 7 (b) is a ¹³ C NMR spectrum of THP-DAG.

Referring to Figures 7 (a) and (b), it can be seen that THP-DAG was synthesized in Example 4.

8 is an NMR graph of 1,1'-BTO synthesized according to Example 5 of the present invention. In more detail, FIG. 8 (a) is a ¹ H NMR spectrum of 1,1'-BTO, and FIG. 8 (b) is a ¹³ C NMR spectrum of 1,1'-BTO.

Referring to FIGS. 8 (a) and (b), it can be seen that 1,1'-BTO was synthesized in Example 5.

9 is an NMR graph of TKX-50 synthesized according to Example 6 of the present invention. In more detail, FIG. 9 (a) is a ¹ H NMR spectrum of TKX-50, and FIG. 9 (b) is a ¹³ C NMR spectrum of TKX-50.

Referring to FIGS. 9 (a) and (b), it can be seen that TKX-50 was synthesized in Example 6.

As described above, the present invention relates to a method for synthesizing TKX-50 through THP-DAG, which is an intermediate with improved insensitivity, instead of DAG, which is a sensitive intermediate synthesized during TKX-50 synthesis. It has the advantage of being able to work safely compared to the existing synthesis method from the threat of accidents.

As described above, although the embodiments have been described with reference to the limited embodiments and drawings, various modifications and variations are possible from the above description by those skilled in the art. For example, even if the described techniques are performed in an order different from the described method, and/or the described components are combined or combined in a different form from the described method, or replaced or substituted by other components or equivalents 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 (16)

Preparing dichloroglyoxime (DCG) as a starting material; and
forming an O,O'-ditetrahydropyranyl oxalohydroximoyl diazide (THP-DAG) intermediate from the DCG;
containing,
Method for preparing THP-DAG intermediate.
According to claim 1,
Diazidoglioxime (diazidoglyoxime, DAG) intermediate by-product-free,
Method for preparing THP-DAG intermediate.
According to claim 1,
The THP-DAG is,
an impact sensitivity of 15 J or more,
friction sensitivity of 300 N or more,
which has an electrostatic sensitivity of at least 40 m J,
Method for preparing THP-DAG intermediate.
According to claim 1,
synthesizing dichloroglyoxime (DCG);
synthesizing O,O'-ditetrahydropyranyl oxalohydroximoyl dichloride (THP-DCG) through the DCG; and
synthesizing THP-DAG through the THP-DCG;
containing,
Method for preparing THP-DAG intermediate.
5. The method of claim 4,
The step of synthesizing the dichloroglyoxime (DCG) is,
synthesizing glyoxime; and
Reacting the glyoxime with N-chlorosuccinimide (N-chlorosuccinimide);
Method for preparing THP-DAG intermediate.
5. The method of claim 4,
The step of synthesizing THP-DCG through DCG,
p-toluenesulfonic acid (p-toluenesulfonic acid, p-TsOH) is carried out by reacting the DCG and 3,4-dihydro-2H-pyran (3,4-dihydro-2H-pyran) under a catalyst,
Method for preparing THP-DAG intermediate.
7. The method of claim 6,
The step of synthesizing THP-DCG through DCG,
The DCG, the p-TsOH and the 3,4-dihydro-2H-pyran are stirred in a weight ratio of 1: 3 to 4: 1.6, and then reacted to perform,
Method for preparing THP-DAG intermediate.
8. The method of claim 7,
The DCG, the p-TsOH and the stirring of the 3,4-dihydro-2H-pyran is performed at room temperature,
Method for preparing THP-DAG intermediate.
5. The method of claim 4,
The step of synthesizing THP-DAG through the THP-DCG,
which is carried out through an azide reaction,
Method for preparing THP-DAG intermediate.
10. The method of claim 9,
The step of synthesizing THP-DAG through the THP-DCG,
Which is performed by reacting the THP-DCG with sodium azide (NaN _{3 ),}
Method for preparing THP-DAG intermediate.
11. The method of claim 10,
The THP-DCG and the sodium azide are stirred in a weight ratio of 1: 0.4 to 0.8, and then reacted to perform,
Method for preparing THP-DAG intermediate.
12. The method of claim 11,
The stirring of the THP-DCG and the sodium azide will be carried out at 95 ℃ to 100 ℃,
Method for preparing THP-DAG intermediate. delete delete delete delete

Images