Methods for preparing dihydroxyammonium 5,5′-bistetrazole-1,1′diolate

Patent metadata

Field	Value
Publication number	US-12258322-B2
Application number	US-202318706706-A
Country	US
Kind code	B2
Filing date	Jun 1, 2023
Priority date	Jun 7, 2022
Publication date	Mar 25, 2025
Grant date	Mar 25, 2025

Abstract

The present invention relates to a method for preparing dihydroxyammonium 5,5′-bistetrazole-1,1′-diolate. The method for preparing dihydroxyammonium 5,5′-bistetrazole-1,1′-diolate, according to one embodiment of the present invention, comprises the steps of: synthesizing 5,5′-bistetrazole-1,1′-diol dihydrate (1,1′-BTO) from ditetrahydropyranyl diazidoglyoxime (THP-DAG) by using a hydrochloric acid (HCl) solution in a first solvent; and reacting 1,1′-BTO with an amine solution so as to neutralize same and, simultaneously, obtaining dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (Thomas Klapotke explosive-50, TKX-50).

First claim

The invention claimed is:

1. A method of preparing dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate, the method comprising steps of:
synthesizing 5,5′-bistetrazole-1,1′-diol dihydrate (1,1′-BTO) from ditetrahydropyranyl diazidoglyoxime using a hydrochloric acid (HCl) solution in a first solvent; and
obtaining dihydroxylammonium 5,5′-bistetrazole-1,l′-diolate, and simultaneously, reacting and neutralizing the 1,1′-BTO and an amine solution,
wherein the step of synthesizing the 1, 1′-BTO comprises adding the ditetrahydropyranyl diazidoglyoxime and the first solvent to a reactor, adding an HCl solution with a concentration of 20% to 50%, and performing stirring in a temperature range of 30° C. to 60° C.,
wherein the step of obtaining the dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate comprises:
forming a solution by dissolving an amine solution and an HCl solution in water and then adding sodium hydroxide (NaOH), and adding water, to prepare an amine-containing solution;

adding the 1, 1′-BTO and the amine-containing solution to the first solvent;
performing stirring for 10 minutes to 40 minutes while maintaining a temperature range of 30° C. to 50° C.; raising a temperature of a reactor to a temperature of 70° C. to 90° C. and performing stirring for 20 minutes to 60 minutes; adding an amine-containing solution;
performing stirring; performing cooling by lowering a reaction temperature of a solution to a temperature of 1° C. to 10° C.; and performing a filtration, to precipitate dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate, and
wherein the first solvent comprises at least one selected from a group consisting of tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), and m-cresol.

2. The method of claim 1 , wherein the amine solution comprises at least one selected from a group consisting of hydroxylamine (NH 2 OH), ethanolamine, N-aminoethylethanolamine, diethanolamine, 2-hydroxypropylamine, N,N-bis-(2-hydroxypropyl) amine (diisopropanolamine), N,N′-bis-(2-hydroxyethyl) ethylene diamine, and neopentanolamine.

3. The method of claim 1 , further comprising, prior to the step of synthesizing the 1,1′-BTO, steps of:
synthesizing glyoxime by reacting glyoxal and hydroxylamine;
synthesizing dichloroglyoxime (DCG) from the glyoxime;
synthesizing ditetrahydropyranyl dichloroglyoxime from the DCG; and
synthesizing ditetrahydropyranyl diazidoglyoxime from the ditetrahydropyranyl dichloroglyoxime.

4. The method of claim 3 , wherein
the step of synthesizing the glyoxime comprises reacting the glyoxal and the amine solution with sodium hydroxide (NaOH) in an aqueous solution, and
the amine solution comprises at least one selected from a group consisting of hydroxylamine (NH 2 OH), ethanolamine, N-aminoethylethanolamine, diethanolamine, 2-hydroxypropylamine, N,N-bis-(2-hydroxypropyl) amine (diisopropanolamine), N,N′-bis-(2-hydroxyethyl) ethylene diamine, and neopentanolamine.

5. The method of claim 3 , wherein
the step of synthesizing the DCG comprises reacting the glyoxime with a halogenating agent under a second solvent, and
the second solvent comprises at least one organic solvent selected from a group consisting of N,N′-dimethylformamide (DMF), dimethylacetamide, N-methyl-2-pyrrolidone, tetrahydrofuran, diethyl ether, dichloromethane, chloroform, and toluene.

6. The method of claim 5 , wherein the halogenating agent comprises at least one selected from a group consisting of N-chlorosuccinimide, N-bromosuccinimide, and N-iodosuccinimide.

7. The method of claim 3 , wherein
the step of synthesizing the ditetrahydropyranyl dichloroglyoxime is performed by using p-toluenesulfonic acid (p-TsOH) as a catalyst under a third solvent and reacting the DCG with 3,4-dihydro-2H-pyran, and
the third solvent comprises at least one halogenated organic solvent selected from a group consisting of dichloromethane (DCM), chloroform, and dichloroethane.

8. The method of claim 7 , wherein
after a reaction of the DCG, the p-TsOH, and the 3,4-dihydro-2H-pyran, the first solvent and water are added and reacted at a temperature of 50° C. to 80° C. for 1 hour to 3 hours, and
a reaction temperature is lowered to room temperature, acetone is added, and cooling is performed by lowering a temperature to a temperature of 1° C. to 10° C. to precipitate a solid, and a filtration and washing are performed, to precipitate ditetrahydropyranyl dichloroglyoxime.

9. The method of claim 3 , wherein the step of synthesizing the ditetrahydropyranyl diazidoglyoxime comprises reacting the ditetrahydropyranyl dichloroglyoxime with an azide salt under N,N′-dimethylformamide (DMF).

10. The method of claim 9 , wherein
the ditetrahydropyranyl dichloroglyoxime, the DMF, and the azide salt are stirred at a temperature of 90° C. to 120° C. for 1 hour to 3 hours and then cooled to a temperature of 60° C. to 80° C., and
distilled water is added, and cooling is performed by lowering a temperature to a temperature of 1° C. to 10° C. to precipitate a solid, to precipitate ditetrahydropyranyl diazidoglyoxime.

11. The method of claim 9 , wherein the azide salt comprises at least one selected from a group consisting of sodium azide (NaN 3 ), potassium azide (KN 3 ), and lithium azide (LiN 3 ).

Assignees

• Agency Defense Dev

Inventors

• Kwon Kuk Tae
• Yoo Hae Wook
• Kim Seung Hee
• Lee So Jung

Classifications

• C07D309/12

  only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers · CPC title

• C07C249/12

  by reactions not involving the formation of oxyimino groups · CPC title

• C07C249/08

  by reaction of hydroxylamines with carbonyl compounds · CPC title

• C07C259/20

  with at least one nitrogen atom of hydroxamidine groups bound to another nitrogen atom · CPC title

• C07C259/02

  with replacement of the other oxygen atom of the carboxyl group by halogen atoms · CPC title