KR101264166B1 - Method for preparing 1,2-bis(5-aminotetrazol-1-yl)ethane - Google Patents

Abstract

PURPOSE: A manufacturing method of 1,2-bis(5-aminotetrazole-1-yl)ethane is provided to reduce the generation of harmful materials and to obtain a mass production process with low carbon, high nitrogen, and environmentally friendly nitroaminotetrazole classes. CONSTITUTION: 1,2-bis(5-aminotetrazole-1-yl)ethane is manufactured from an ethane derivative represented by chemical formula (I) and 5-aminotetrazole hydrate through a nucleophilic substitution reaction which uses water as a solvent under the presence of hydroxide of an alkali metal. The 1,2-bis(5-aminotetrazole-1-yl)ethane is manufactured from a 5-aminotetrazole derivative represented by chemical formula (II) and 5-aminotetrazole hydrate through a nucleophilic substitution reaction which uses water as a solvent under the presence of hydroxide of an alkali metal. The 1,2-bis(5-aminotetrazole-1-yl)ethane is separated by filtering at 80-100 deg. Celsius after the nucleophilic substitution reaction. The hydroxide of alkali metal is selected from NaOH(sodium hydroxide) or potassium hydroxide.

Description

Method for preparing 1,2-bis (5-aminotetrazol-1-yl) ethane {Method for preparing 1,2-bis (5-aminotetrazol-1-yl) ethane}

The present invention relates to a method for preparing 1,2-bis (5-aminotetrazol-1-yl) ethane, a low-carbon, high-nitrogen-containing high-energy substance, from a 5-aminotetrazole hydrate and an ethane derivative through a nucleophilic substitution reaction. will be.

The present invention also provides 1,2-bis (5-aminotetrazol-1-yl) ethane, a low-carbon, high-nitrogen-containing, high-energy substance from 5-aminotetrazole hydrate and 5-aminotetrazole derivatives through nucleophilic substitution reactions. It relates to a method of manufacturing.

Tetrazole derivatives with high nitrogen content are of interest as heterocyclic materials that can be applied to various high energy high density materials (HEDM). In particular, aminotetrazole-based energy materials are in the limelight because of their high thermal stability, high heat generation, low sensitivity, very strong explosion and less pollutants.

In the known methods, it is common to synthesize 1,2-bis (5-aminotetrazol-1-yl) ethane, which is one of tetrazole derivatives, with the cyanogen azide and 1,2-diaminoethane as the toxic reagents. to be.

)와 1,2-다이아미노에탄 (

)의 고리화 반응에 의하며 그 반응식은 아래와 같다.This conventional synthesis method uses cyanogen azide (

) And 1,2-diaminoethane (

) By the cyclization reaction, and the reaction formula is as follows.

Cyanogen azide is not commercially available and can be obtained by, for example, reacting cyanogen bromide with sodium azide as follows.

However, cyanogen bromide is not produced in Korea and has a problem that it is expensive and expensive to purchase as it has a lot of import restrictions.

On the other hand, the conventional synthesis method is a disadvantage that the cyanogen bromide or cyanogen azide is exposed to the air can come out toxic gas. On small laboratory scales, working in the hood is not a problem, but a safer and improved synthesis method is required because it can involve dangerous processes in mass production applications.

Barmin et al. Russ . J. Appl . Chem . 2001 , 74 , 1156 disclose that 1,2-bisbromoethane and sodium 5-aminotetrazolate are reacted at a high temperature of 130 ° C. to produce 1,2-bis ( Although a method of synthesizing 5-aminotetrazol-1-yl) ethane has been reported, dimethylformamide, which is an environmental problem, is used as a solvent, and a separation process for the resulting isomer is not disclosed. In addition, the melting or decomposition temperatures of the isomers are reported significantly differently.

1,2-bis (5-aminotetrazol-1-yl) ethane as a low carbon high nitrogen-containing high energy substance was synthesized in a safe and economical manner, 1,2-bis (5-aminotezol-1-yl There is a need to develop a method for selectively separating only 1,2-bis (5-aminotetrazol-1-yl) ethane from isomers produced simultaneously in the synthesis of ethane.

An object of the present invention is a 1,2-bis (5-aminotetrazole-1) which is a low-carbon, high-nitrogen-containing high energy substance from 5-aminotetrazole hydrate and ethane derivative or 5-aminotetrazole derivative through nucleophilic substitution reaction. To provide a safer and more economical way of producing ethane.

One embodiment of the present invention for achieving the above object is from a 5-aminotetrazole hydrate and an ethane derivative represented by the following formula (I) through a nucleophilic substitution reaction using water as a solvent in the presence of an alkali metal hydroxide And 1,2-bis (5-aminotetrazol-1-yl) ethane.

Formula (I)

R is a leaving group which is separated by a nucleophilic substitution reaction.

The present invention relates to the synthesis of 1,2-bis (5-aminotetrazol-1-yl) ethane, the structure of which is as follows.

In the present invention, 5-aminotetrazole may be used as a raw material, and nucleophilic substitution may be applied to prepare / separate pure 1,2-bis (5-aminotetrazol-1-yl) ethane. 5-aminotetrazole used as a raw material can be mass-produced without restriction of the supply, and the present invention is pointed out as a problem of the conventional synthesis method in the reaction of 1,2-bis (5-aminotetrazol-1-yl) ethane. The reaction can be terminated without the formation of lethal toxic gases generated from cyanogen azide and its decomposition products.

5-aminotetrazole used as a reactant in the present invention is a material that is being applied to a variety of high energy materials due to the high nitrogen content, thermal stability and high generated heat. Recently, it is used as a raw material in the manufacture of pharmaceuticals and LCDs, and domestic demand is increasing, so the production cost per ton is low and it is known as a material that can be supplied in Korea.

In the nucleophilic substitution reaction of the present invention, water is used as a solvent, and after the nucleophilic substitution reaction of 5-amino tetrazolate, 1,2-bis (5-aminotetrazol-1-yl) is subjected to a high temperature filtration process. Ethane can be separated from the other two isomers.

In the method for preparing 1,2-bis (5-aminotetrazol-1-yl) ethane of the present invention, only water is used as a solvent, whereby 1,2-bis (5-aminotetrazol-1-environmentally friendly is used. It is possible to secure a synthetic process that can safely produce large quantities of ethane.

One embodiment of a method for preparing 1,2-bis (5-aminotetrazol-1-yl) ethane according to one embodiment of the present invention is shown in Scheme I below.

Scheme I:

After the nucleophilic substitution reaction of the present invention, in addition to 1,2-bis (5-aminotetrazol-1-yl) ethane, which is a product of interest in the present invention, two isomers may be generated as a secondary product. These two isomers are 1- (5-aminotetrazol-1-yl) -2- (5-aminotetrazol-2-yl) ethane and 1,2-bis (5-aminotetrazol-2-yl, respectively. In ethane, the chemical formula is:

: 1- (5-aminotetrazol-1-yl) -2- (5-aminotetrazol-2-yl) ethane

: 1,2-bis (5-aminotetrazol-2-yl) ethane

The nucleophilic substitution reaction of the present invention is carried out in the presence of an alkali metal hydroxide, the metal ion of the alkali metal hydroxide reacts with 5-aminotetrazole to form an alkali metal 5-aminotetrazole salt, and 5-aminotetrazole It is anionic and acts to increase nucleophilicity.

The hydroxide of the alkali metal may be preferably sodium hydroxide or potassium hydroxide, but is not limited thereto.

In the ethane derivative represented by the formula (I), R is a leaving group separated by a nucleophilic substitution reaction, preferably halogen, benzosulfonyl or tosyl group. More preferably, R may be Br or I.

Method for producing 1,2-bis (5-aminotetrazol-1-yl) ethane of the present invention is filtered after the nucleophilic substitution reaction at 80 ~ 100 ℃ to 1,2-bis (5-aminotetrazole- 1-yl) ethane may be further included. Preferably, the method may further include separating 1,2-bis (5-aminotetrazol-1-yl) ethane by filtration at 85˜100 ° C. after the nucleophilic substitution reaction. More preferably, the method may further include separating 1,2-bis (5-aminotetrazol-1-yl) ethane by filtration at 85˜90 ° C. after the nucleophilic substitution reaction.

In the method for preparing 1,2-bis (5-aminotetrazol-1-yl) ethane of the present invention, the separation step through high temperature filtration after the nucleophilic substitution reaction is 80-100 ° C., preferably 85-100. It may be carried out two or more times by further adding water of 85 ℃, more preferably 85 ~ 90 ℃.

Through the nucleophilic substitution reaction of the present invention, 1- (5-aminotetrazol-1-yl) -2- (5-aminotetrazol together with 1,2-bis (5-aminotetrazol-1-yl) ethane The isomers of 2-yl) ethane and 1,2-bis (5-aminotetrazol-2-yl) ethane are also synthesized and present in the form of a mixture. Therefore, to obtain 1,2-bis (5-aminotetrazol-1-yl) ethane, which is the object of the present invention, 1,2-bis (5-aminotetrazol-1-yl) ethane is separated from these mixtures. May be required. Since the three isomers show a difference in solubility in water according to temperature, 1,2-bis (5-aminotetrazol-1-yl) ethane obtained in the present invention is obtained by adopting a high temperature filtration method using the same. can do. Thus, hot filtration can be made at a temperature of 80 ° C. to 100 ° C. to selectively separate only 1,2-bis (5-aminotetrazol-1-yl) ethane, preferably 85 ° C. to 100 ° C., more Specifically, it may be made at a temperature of 85 ℃ to 90 ℃.

Another embodiment of the present invention for achieving the above object is a 5-aminotetrazole hydrate and 5- represented by the following formula (II) through a nucleophilic substitution reaction using water as a solvent in the presence of an alkali metal hydroxide A method for preparing 1,2-bis (5-aminotetrazol-1-yl) ethane from aminotetrazole derivatives.

(II)

R is a leaving group which is separated by a nucleophilic substitution reaction.

As in the nucleophilic substitution reaction using the ethane derivative, the nucleophilic substitution reaction of the present invention using the 5-aminotetrazole derivative is also filtered using high temperature after the nucleophilic substitution reaction of 5-amino tetrazolate using water as a solvent. The process can be applied to separate 1,2-bis (5-aminotetrazol-1-yl) ethane from the concomitant isomers.

One embodiment of a method for preparing 1,2-bis (5-aminotetrazol-1-yl) ethane according to one embodiment of the present invention is shown in Scheme II below.

Scheme II:

After the nucleophilic substitution reaction of the present invention using the 5-aminotetrazole derivative, 1- (5-aminotetra in addition to 1,2-bis (5-aminotetrazol-1-yl) ethane, which is a product of interest in the present invention. Isomers of zol-1-yl) -2- (5-aminotetrazol-2-yl) ethane may be subsequently synthesized, and the chemical formula is as follows.

: 1- (5-aminotetrazol-1-yl) -2- (5-aminotetrazol-2-yl) ethane

The nucleophilic substitution reaction of the present invention using the 5-aminotetrazole derivative is also carried out in the presence of an alkali metal hydroxide, and the metal ion of the alkali metal hydroxide reacts with 5-aminotetrazole to give an alkali metal 5-aminotetrazole salt. Is formed, 5-aminotetrazole is anionic and serves to increase the nucleophilicity.

Hydroxide of the alkali metal may preferably be sodium hydroxide or potassium hydroxide, but is not limited thereto.

In the 5-aminotetrazole derivative represented by the formula (II), R is a leaving group separated by a nucleophilic substitution reaction, preferably halogen, benzosulfonyl or tosyl group. More preferably, R may be Br or I.

Method for producing 1,2-bis (5-aminotetrazol-1-yl) ethane of the present invention using the 5-aminotetrazole derivative is filtered at 80 to 100 ° C after the nucleophilic substitution reaction to obtain 1,2 The method may further include separating -bis (5-aminotetrazol-1-yl) ethane. Preferably, the method may further include separating 1,2-bis (5-aminotetrazol-1-yl) ethane by filtration at 85˜100 ° C. after the nucleophilic substitution reaction. More preferably, the method may further include separating 1,2-bis (5-aminotetrazol-1-yl) ethane by filtration at 85˜90 ° C. after the nucleophilic substitution reaction.

In the method for preparing 1,2-bis (5-aminotetrazol-1-yl) ethane of the present invention, the separation step through high temperature filtration after the nucleophilic substitution reaction is 80-100 ° C., preferably 85-100. It may be carried out two or more times by further adding water of 85 ℃, more preferably 85 ~ 90 ℃.

1- (5-aminotetrazol-1-yl) together with 1,2-bis (5-aminotetrazol-1-yl) ethane through the nucleophilic substitution reaction of the present invention using the 5-aminotetrazole derivative The 2- (5-aminotetrazol-2-yl) ethane isomer is also synthesized to be present in the mixture. Therefore, in order to obtain 1,2-bis (5-aminotetrazol-1-yl) ethane, which is the object of the present invention, a step of separating these mixtures may be required. Since the two isomers show a difference in solubility in water according to temperature, 1,2-bis (5-aminotetrazol-1-yl) ethane obtained in the present invention is obtained by adopting a high temperature filtration method using the same. can do. Thus, hot filtration can be made at a temperature of 80 ° C. to 100 ° C. to selectively separate only 1,2-bis (5-aminotetrazol-1-yl) ethane, preferably 85 ° C. to 100 ° C., more Specifically, it may be made at a temperature of 85 ℃ to 90 ℃.

An object of the present invention is a 1,2-bis (5-aminotetrazole-1) which is a low-carbon, high-nitrogen-containing high energy substance from 5-aminotetrazole hydrate and ethane derivative or 5-aminotetrazole derivative through nucleophilic substitution reaction. To provide a safer and more economical way of producing ethane.

That is, the method for preparing 1,2-bis (5-aminotetrazol-1-yl) ethane of the present invention does not use cyanogen azide, which is a highly toxic reagent used in the prior art. Cyanogen azide is a material that can react with water in the air and produce toxic gases, so it is not a big problem on a laboratory scale, but it is dangerous in mass production. Therefore, according to the production method of 1,2-bis (5-aminotetrazol-1-yl) ethane of the present invention, which does not use cyanogen azide, it excludes the potential risk for human injury that may occur in the production process. can do.

On the other hand, 5-aminotetrazole hydrate used as a raw material in the production method of 2-bis (5-aminotetrazol-1-yl) ethane of the present invention is a compound produced domestically, so it is easy to purchase, so that the localization of raw materials It can secure the stability of domestic supply and demand and the reduction of production cost.

In addition, the production method of 1,2-bis (5-aminotetrazol-1-yl) ethane of the present invention is simple, environmentally friendly by using water as a solvent, and enables mass production. As a result, it is possible to secure a low-carbon, high-nitrogen-friendly, nitroiminotetrazole-based mass production process while reducing the generation of harmful substances.

1 shows NMR data of 1,2-bis (5-aminotetrazol-1-yl) ethane prepared / separated through the preparation method of Example 1. FIG.
2 shows NMR data of 1,2-bis (5-aminotetrazol-1-yl) ethane prepared / isolated through the preparation method of Example 2. FIG.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

One. Example  1: 1,2- Of bis (5-aminotetrazol-1-yl) ethane  Synthesis and Separation

Dibromoethane (BrCH ₂ CH ₂ Br) used Sigma-Aldrich reagent. 5-aminotetrazole (CH ₃ N ₅ ) hydrate was purchased from Penisula El & S Inc., sodium hydroxide (NaOH) and dimethyl sulfoxide (DMSO) were purchased from Samjeon Reagent. The water used for the separation of the isomers was a laboratory tap water.

206 g (2.00 mol) 5-aminotetrazole hydrate was suspended with 350 mL of water, and then 80.0 g (2.00 mol) sodium hydroxide dissolved in 150 mL of water was added slowly with stirring. 187 g (1.00 mol) 1,2-dibromoethane was added and refluxed for 18 hours. The solid produced after the reaction was filtered quickly while boiling and the filtered solid (24.5 g) was washed twice with water. Precipitation began slowly in the remaining solution after filtration and the resulting solid was filtered after 1 hour. 100 mL of water was added again and the mixture was boiled and filtered. The solid (7.12 g) obtained after one more repeat of this method was collected. The total yield of 1,2-bis (5-aminotetrazol-1-yl) ethane was 16% (31.6 g, 0.161 mol).

NMR analysis results:

¹ H NMR (DMSO-d ₆ ): 4.50 (s, 4H, CH ₂ ), 6.72 (s, 4H, NH ₂ ); ¹³ C NMR (DMSO-d ₆ ): 43.0, 155.5.

2. Example  2: 1,2- Of bis (5-aminotetrazol-1-yl) ethane  Synthesis and Separation

1- (2-chloroethyl) 5-aminotetrazole was synthesized according to the method described in Einberg, F. J. Org . Chem . 1970 , 35 , 3978-3980.

13.2 g (0.128 mol) 5-aminotetrazole hydrate was suspended with 100 mL of water, and then 5.14 g (0.128 mol) sodium hydroxide dissolved in 50 mL of water was stirred while slowly pouring the aqueous solution. 15.8 g (0.107 mol) of 1- (2-chloroethyl) 5-aminotetrazole was synthesized and refluxed for 18 hours. After the reaction, the resulting solid was quickly filtered while boiling and the filtered solid was washed three times with water. The total yield of 1,2-bis (5-aminotetrazol-1-yl) ethane was 14% (3.04 g, 15.5 mmol).

NMR analysis results:

¹ H NMR (DMSO-d ₆ ): 4.50 (s, 4H, CH ₂ ), 6.72 (s, 4H, NH ₂ ); ¹³ C NMR (DMSO-d ₆ ): 42.9, 155.4.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (5)

1,2-bis (5-aminotetrazole-1) from a 5-aminotetrazole hydrate and an ethane derivative represented by the following formula (I) through a nucleophilic substitution reaction using water as a solvent in the presence of an alkali metal hydroxide How to prepare ethane:
(I)

Here, R is a leaving group separated by a nucleophilic substitution reaction and is selected from halogen, benzylsulfonyl, tosyl group. 1,2-bis (5-amino from 5-aminotetrazole hydrate and 5-aminotetrazole derivative represented by the following formula (II) through a nucleophilic substitution reaction using water as a solvent in the presence of an alkali metal hydroxide How to prepare tetrazol-1-yl) ethane:
(II)

Here, R is a leaving group separated by a nucleophilic substitution reaction and is selected from halogen, benzylsulfonyl, tosyl group. delete The method of claim 1 or 2, further comprising the step of separating the 1,2-bis (5-aminotetrazol-1-yl) ethane by filtration at 80 ° C to 100 ° C after the nucleophilic substitution reaction. How. The method according to claim 1 or 2, wherein the hydroxide of the alkali metal is selected from sodium hydroxide or potassium hydroxide.

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