KR102605033B1 - A method of preparing 5-alkyltetrazole - Google Patents

Abstract

The present invention relates to a method for producing 5-alkyltetrazole, which includes a) reacting an alkyl imidate of Formula 1 with a1) hydrazine to obtain a compound of Formula 2, and reacting the compound of Formula 2 with a nitrous acid compound and an acid. , a2) obtaining a reaction mixture by reacting with an azide compound and an acid; and b) reacting the reaction mixture with a base to obtain 5-alkyltetrazole of Chemical Formula 3.

Description

Method for producing 5-alkyltetrazole {A METHOD OF PREPARING 5-ALKYLTETRAZOLE}

The present invention relates to a method for producing 5-alkyltetrazole, which can be produced at low cost.

The microcircuit manufacturing process for liquid crystal displays or semiconductor devices involves uniformly applying photoresist to a conductive metal film such as copper or copper alloy film or an insulating film such as silicon oxide or silicon nitride film formed on a substrate, and selectively exposing and developing the photoresist. After processing to form a photoresist pattern, the conductive metal film or insulating film is wet or dry etched using the patterned photoresist film as a mask to transfer the fine circuit pattern to the photoresist lower layer, and then peeling off the unnecessary photoresist layer. It proceeds with a process of removing it with a liquid.

At this time, the etchant composition required when etching a metal film or insulating film is a cyclic amine compound that controls the etching speed and plays an etching inhibitory role in reducing pattern CD loss to increase process margins. This is included. At this time, 5-methyltetrazole, a 5-alkyltetrazole compound, is mainly used because it performs the above role and has the effect of controlling the initial inclination angle of the etching reaction to be constant without increasing even as the number of treated sheets is accumulated.

The method for producing 5-methyltetrazole includes using acetonitrile as a starting material [Applied Organometallic Chemistry, vol.29, nb.11, p.730-735; Synthesis (Germany), vol. 46, nb. 15, p. 2065-2070; Journal of Organic Chemistry, vol.76, nb. 21, p. 9090-9095; Synthesis (Germany), nb. 13, p. 2175-2178; Chemical Communications, vol. 50, nb. 85, p. 12847-12850; Tetrahedron Letters, vol. 54, nb. 1, p. 106-109; Synthesis (Germany), vol. 46, nb. 6, p. 781-786; Canadian Journal of Chemistry, vol. 65, p. 166-169; Journal of Materials Chemistry, vol. 22, nb. 33, p. 17227-17235; RSC Advances, vol. 5, nb. 124, p. 102134-102142; Journal of Organic Chemistry, vol. 75, nb. 19, p. 6468-6476; Journal of Organic Chemistry, vol. 15, p. 1082-1092; Synthesis (Germany), vol. 47, nb. 4, p. 507-510] and a method using thioacetamide as a starting material [German Patent No. 1954-00014582] are known, but these methods have a high reaction temperature and require the use of a high-pressure reactor, leading to the problem of increased manufacturing costs. there is.

German Patent No. 1954-00014582 (April 25, 1957, Dr. Egon Wiberg)

Applied Organometallic Chemistry, vol. 29, nb. 11, p. 730-735 Synthesis (Germany), vol. 46, nb. 15, p. 2065-2070 Journal of Organic Chemistry, vol. 76, nb. 21, p. 9090-9095 Synthesis (Germany), nb. 13, p. 2175-2178 Chemical Communications, vol. 50, nb. 85, p. 12847-12850 Tetrahedron Letters, vol. 54, nb. 1, p. 106-109 Synthesis (Germany), vol. 46, nb. 6, p. 781-786 Canadian Journal of Chemistry, vol. 65, p. 166-169 Journal of Materials Chemistry, vol. 22, nb. 33, p. 17227-17235 RSC Advances, vol. 5, nb. 124, p. 102134-102142 Journal of Organic Chemistry, vol. 75, nb. 19, p. 6468-6476 Journal of Organic Chemistry, vol. 15, p. 1082-1092 Synthesis (Germany), vol. 47, nb. 4, p. 507-510

The present invention is intended to solve the above problems, and its purpose is to provide a production method that can reduce the production cost of 5-alkyltetrazole.

The method for producing 5-alkyltetrazole according to the present invention to achieve the above object is

a) an alkyl imidate of the formula 1 below,

a1) react with hydrazine to obtain a compound of formula 2 below, and react the compound of formula 2 with a nitrite compound and acid, or

a2) obtaining a reaction mixture by reacting with an azide compound and an acid; and

b) reacting the reaction mixture with a base to obtain 5-alkyltetrazole of the following formula (3).

[Formula 1]

(In Formula 1 above,

R ₁ is a C1 to C4 alkyl group,

R ₂ is an alkyl group of C1 to C5.)

[Formula 2]

(In Formula 2 above,

R ₁ is the same as in Formula 1 above.)

[Formula 3]

(In Formula 3 above,

R ₁ is the same as in Formula 1 above.)

The method for producing 5-alkyltetrazole according to the present invention has the effect of reducing the manufacturing cost.

In the present invention, when a part "includes" a certain component, this means that it may further include other components rather than excluding other components, unless specifically stated to the contrary.

Hereinafter, preferred embodiments of the present invention will be described in detail.

The method for producing 5-alkyltetrazole according to one aspect of the present invention includes an alkyl imidate of the following formula (1) as a reaction starting material, and includes the following reaction steps.

a) an alkyl imidate of the formula 1 below,

a1) react with hydrazine to obtain a compound of formula 2 below, and react the compound of formula 2 with a nitrite compound and acid, or

a2) obtaining a reaction mixture by reacting with an azide compound and an acid;

b) reacting the reaction mixture with a base to obtain 5-alkyltetrazole of the following formula (3).

[Formula 1]

(In Formula 1 above,

R ₁ is a C1 to C4 alkyl group,

R ₂ is an alkyl group of C1 to C5.)

[Formula 2]

(In Formula 2 above,

R ₁ is the same as in Formula 1 above.)

[Formula 3]

(In Formula 3 above,

R ₁ is the same as in Formula 1 above.)

5-alkyltetrazole produced through the above reaction steps is capable of low-temperature reaction, which has the effect of lowering the production cost by not using a high-pressure reactor.

The alkyl group refers to a straight-chain or branched-chain hydrocarbon radical that consists only of carbon and hydrogen atoms, has no degree of unsaturation, and is bonded to the rest of the molecule by a single bond. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, etc.

The alkyl imidate in step (a) can be prepared using synthetic methods known in the art, such as (i) mixing C1 to C5 alcohol and an acid catalyst to form a mixture, and (ii) It can be prepared by reacting a C1 to C4 alkylnitrile with the mixture to obtain an alkylimidate of the formula (1). The alcohol may specifically include methanol, ethanol, propanol, butanol, etc. The acid catalyst is not particularly limited as long as it is used in the art, and specific examples include acetyl chloride, hydrochloric acid, and thionyl chloride. The alkylnitrile specifically includes acetonitrile, propionitrile, butyronitrile, and valeronitrile.

Step (a1) includes reacting the alkyl imidate of Formula 1 with hydrazine to obtain the compound of Formula 2. At this time, the reaction may be performed, for example, in an environment of -10 to -15°C for a reaction time of 1 to 2 hours. Additionally, step (a1) includes reacting the compound of Formula 2 with a nitrous oxide compound in the presence of an acid to obtain a reaction mixture. At this time, the reaction may be performed, for example, under an environment of 5°C or lower for a reaction time of 30 minutes to 1 hour. The nitrous oxide compound reacts with the compound of Formula 2 in the presence of acid, and specifically, alkali metal salts such as sodium salt and potassium salt; Alkaline earth metal salts such as magnesium salts, calcium salts, and barium salts; It may include salts such as silver salts, aluminum salts, zinc salts, and other metal salts, but is not limited thereto. From the viewpoint of reducing manufacturing costs, it is preferable to include an alkali metal salt.

In step (a2), the alkyl imidate of Formula 1 is reacted with an azide compound in the presence of acid. At this time, the reaction may be performed, for example, at a temperature of 5°C to room temperature for a reaction time of 1 to 2 hours. The azide compound includes alkali metal salts such as sodium salts and potassium salts; Alkaline earth metal salts such as magnesium salts, calcium salts, and barium salts; It may include salts such as silver salts, aluminum salts, zinc salts, and other metal salts, but is not limited thereto. From the viewpoint of reducing manufacturing costs, it is preferable to include an alkali metal salt.

The acid used in steps (a1) and (a2) is used to adjust pH in the reaction step, and is not particularly limited as long as it is used in the industry. For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, citric acid, oxalic acid, benzenesulfonic acid, etc. can be used, and hydrochloric acid is preferably used.

In step (b), the reaction mixture produced in steps (a1) to (a2) is reacted with a base to obtain 5-alkyltetrazole of Formula 3. At this time, the reaction may be performed, for example, in an environment where air is refluxed, for a reaction time of 1 to 2 hours. The base used is added to facilitate purification of 5-alkyltetrazole produced during the reaction process. The base may be an organic or inorganic base commonly used in the art. Specifically, it may be selected from the group consisting of ammonium hydroxide, alkali metal or alkaline earth metal hydroxide, alcoholate, acetate, fluoride, phosphate, carbonate, and hydrogen carbonate, and may also include trimethylamine, triethylamine, Tributylamine, N,N-dimethylaniline, N,N-dimethylbenzylamine, tertiary amines such as pyridine, alkylpyridines such as 2-methyl-5-ethylpyridine, N-methyl piperidine, N-methyl p. It may be selected from the group consisting of rolidone, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN), and diazabicycloundecene (DBU), and mixtures thereof, but is not limited thereto. no. It is preferred to use ammonium hydroxide.

The protic polar solvent used in the present invention is not particularly limited as long as it is used in the art, but considering that the temperature condition in which the reaction occurs is 80°C or higher, one with a boiling point of 80 to 100°C can be used, preferably It is preferable to use an alcoholic solvent such as ethanol, butanol, pentanol, ethylene glycol, or water, and more preferably, it is more preferable to use water. When water with a boiling point of 100°C is used as a solvent, it has the advantage of remaining in the water without evaporating easily even under the temperature conditions under which the reaction takes place, thereby fully functioning as a solvent during the reaction.

Hereinafter, preferred embodiments are presented to aid understanding of the present invention. However, the following examples are merely illustrative of the present invention, and it is clear to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the attached patent claims. In the following examples and comparative examples, “%” and “part” indicating content are based on weight, unless otherwise specified.

Example 1 to 2: 5 - of methyltetrazole synthesis

Example 1.

Under a nitrogen atmosphere, 58.4 mL (1.0 mol) of anhydrous ethanol was added to a 100 mL three-necked round flask, cooled to 5°C, and then 35.6 mL (0.5 mol) of acetyl chloride was slowly added dropwise and stirred at the same temperature for 30 minutes to form a mixed solution. manufacture. Add 13.06 mL (0.25 mole) of acetonitrile to the mixed solution and stir at 35°C for 16 hours. Afterwards, 14.59 mL (0.25 mol) of anhydrous ethanol is added and the temperature of the mixed solution is cooled to -10°C to -15°C to synthesize ethyl acetimidate.

15.65 g of hydrazine monohydrate 80% was slowly added dropwise to the cooled ethyl acetimidate, stirred at -10°C to -15°C for 1 to 2 hours, and then an aqueous solution of 21.57g of NaNO ₂ dissolved in 50 mL of water was slowly added dropwise. do. After stirring for 30 minutes at 5°C or lower, completion of the reaction is confirmed by high-performance liquid chromatography (HPLC), and the pH of the solution is adjusted to 4.5 to 5.5 with an aqueous NaOH solution and refluxed for 2 hours to prepare a mixed solution. All of the solvents, ethanol and water, are removed from the mixed solution under vacuum, 100 mL of acetone is added, stirred for 30 minutes, and then filtered. At this time, the resulting filtrate is removed again under vacuum to obtain 15.8 g of 5-methyltetrazole. The production result of 5-methyltetrazole was confirmed through ¹ H-NMR.

¹ H-NMR (δ) (Acetone-d ⁶ ) ; 2.60(s, CH ₃ ), 10.3(NH)

Example 2.

Under a nitrogen atmosphere, add 29.5 mL (0.5 mol) of anhydrous ethanol to a 100 mL three-necked round flask, cool to 5°C, slowly add 17.8 mL (0.25 mol) of acetyl chloride dropwise, and stir at the same temperature for 30 minutes to prepare a mixed solution. do. Add 13.06 mL (0.25 mole) of acetonitrile to the mixed solution and stir at 35°C for 16 hours to synthesize ethyl acetimidate.

The ethyl acetimidate was cooled to 5°C or lower, and an aqueous solution of 20.32 g (0.25 mol) of NaN ₃ dissolved in 35 mL of water was slowly added dropwise, the temperature was raised to room temperature, stirred for 1 hour, and refluxed for 2 hours. Completion of the reaction is confirmed by high-performance liquid chromatography (HPLC), the pH of the solution is adjusted to 4.5 to 5.5 with NaOH aqueous solution, and refluxed for 2 hours to prepare a mixed solution. All ethanol and water are removed from the mixed solution by vacuum, and 100 mL of acetone is added, stirred for 30 minutes, and filtered. At this time, the resulting filtrate is removed again under vacuum to obtain 14.3 g of 5-methyltetrazole. The production result of 5-methyltetrazole was confirmed through ¹ H-NMR.

¹ H-NMR (δ) (Acetone-d ⁶ ) ; 2.60(s, CH ₃ ), 10.3(NH)

Claims (8)

a) an alkyl imidate of the formula 1 below,
a2) obtaining a reaction mixture by reacting with an azide compound and an acid; and
b) A method for producing 5-alkyltetrazole, comprising the step of reacting the reaction mixture with a base to obtain 5-alkyltetrazole of the following formula (3).
[Formula 1]

(In Formula 1 above,
R ₁ is a C1 to C4 alkyl group,
R ₂ is an alkyl group of C1 to C5.)
[Formula 3]

(In Formula 3 above,
R ₁ is the same as in Formula 1 above.) According to paragraph 1,
The alkyl imidate of Formula 1 is
i) mixing C1 to C5 alcohol and an acid catalyst to form a mixture; and
ii) reacting the mixture with a C1 to C4 alkylnitrile to obtain an alkylimidate of the formula (1). delete According to paragraph 1,
A method for producing 5-alkyltetrazole, wherein the azide compound includes an alkali metal azide salt. According to paragraph 1,
The method for producing 5-alkyltetrazole is characterized in that it includes a protic polar solvent as a reaction solvent. According to clause 5,
A method for producing 5-alkyltetrazole, wherein the protic polar solvent is water. According to paragraph 1,
A method for producing 5-alkyltetrazole, wherein the acid contains hydrochloric acid. According to paragraph 1,
A method for producing 5-alkyltetrazole, wherein the base contains ammonium hydroxide.