JPH07278121A - Method for producing 1H-1,2,3-triazole - Google Patents

Abstract

(57) [Summary] [Purpose] To a mixed solution of glyoxal and ammonia,
Provided is a method for producing a safe and convenient 1H-1,2,3-triazole by adding a sulfonylhydrazine compound and reacting it. A method for producing 1H-1,2,3-triazole, which comprises reacting a sulfonylhydrazine compound in a mixed solution of glyoxal and ammonia.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel method for producing 1H-1,2,3-triazole. 1H-1, 2,
3-Triazole is useful as a raw material compound for antifungal agents and agricultural fungicides containing 1H-1,2,3-triazole as a partial structure. The method of using such antifungal agent and agricultural fungicide as a raw material is, for example, 1H-1,
A method for synthesizing a 2-substituted oxetane derivative using 2,3-triazole is described on pages 23 to 24 of JP-A-5-170763.

[0002]

2. Description of the Related Art The applicant of the present invention uses glyoxal to obtain 1
As a method for producing H-1,2,3-triazole,
Japanese Patent Application No. 5-268840 discloses that glyoxal monooxime hydrazone is produced by reacting an aqueous solution of glyoxal in a reaction solution of a salt of hydroxylamine and hydrazine monohydrate. -2
In Japanese Patent No. 38779, there has been proposed a method for obtaining 1H-1,2,3-triazole by carrying out a cyclization reaction using the above glyoxal monooxime hydrazone and a condensing agent such as phosphorus pentachloride.

This method requires the synthesis of glyoxal monooxime hydrazone, and requires a condensing agent in the cyclization reaction, so that 1H-1,2,3-
Since two steps are required to obtain triazole, it is not necessarily a production method that is industrially satisfactory.

[0004]

DISCLOSURE OF THE INVENTION According to the present invention, a sulfonylhydrazine compound is added to a mixed solution containing glyoxal and ammonia for reaction, and 1H-in one step.
It is an object of the present invention to provide an industrial production method for obtaining 1,2,3-triazole.

[0005]

The present invention is directed to glyoxa-
Of the general formula (I)

[0006]

[Chemical 2]

(Wherein R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may have a substituent), a sulfonylhydrazine compound represented by the formula 1H-1, It relates to a method for producing 2,3-triazole.

The present invention includes, for example, the reaction formula (I) shown below.
Can be expressed as Reaction formula (I)

[0009]

[Chemical 3]

In the sulfonylhydrazine compound represented by the general formula (I) used in the present invention, R represents an alkyl group or an optionally substituted phenyl group, and the optionally substituted phenyl group means a phenyl group, Represents a substituted phenyl group.

The alkyl group is, for example, a linear or branched alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group and t-butyl group. Can be mentioned,

Examples of the substituted phenyl group include o-tolyl group, m-tolyl group, p-tolyl group and 2,3
-Xylyl group, 2,4-xylyl group, o-cumenyl group,
1 to 2 carbon atoms such as m-cumenyl group and p-cumenyl group
Substituted with a halogen atom such as a phenyl group substituted with the above alkyl group, o-chlorobenzene, m-chlorobenzene, p-chlorobenzene, o-bromobenzene, m-bromobenzene, p-bromobenzene There is a phenyl group.

R is preferably methyl group, ethyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, p-fluorophenyl group, p-chlorophenyl group,
It is a p-bromophenyl group, more preferably a methyl group, a p-tolyl group, and a p-chlorophenyl group, and most preferably a p-tolyl group.

Specific examples of the sulfonylhydrazine compound include methylsulfonylhydrazine, ethylsulfonylhydrazine, propylsulfonylhydrazine, i-propylsulfonylhydrazine, butylsulfonylhydrazine, i-butylsulfonylhydrazine and t-butylsulfonylhydrazine. Carbon number 1
˜4 linear or branched alkylsulfonylhydrazines substituted with an alkyl group having 1 to 4 carbon atoms,

O-toluenesulfonylhydrazine, m-
Such as toluenesulfonylhydrazine, p-toluenesulfonylhydrazine, 2,3-xylylsulfonylhydrazine, 2,4-xylylsulfonylhydrazine, o-cumenylsulfonylhydrazine, m-cumenylsulfonylhydrazine, p-cumenylsulfonylhydrazine. Alkyl-substituted phenylsulfonylhydrazines, o-chlorobenzenesulfonylhydrazine, m-chlorobenzenesulfonylhydrazine, p-chlorobenzenesulfonylhydrazine, o-bromobenzenesulfonylhydrazine, m-bromobenzenesulfonylhydrazine, p-bromobenzenesulfonylhydrazine, etc. Halogen-substituted phenylsulfonylhydrazines, benzenesulfonylhydrazine can be mentioned,

Alkylsulfonylhydrazines substituted with an alkyl group having 1 to 2 carbon atoms, tolyl-substituted sulfonylhydrazines, chloro-substituted phenylsulfonylhydrazines and benzenesulfonylhydrazine are preferable, and benzenesulfonylhydrazine is more preferable.
P-toluenesulfonylhydrazine and p-chlorobenzenesulfonylhydrazine are preferred, and p-toluenesulfonylhydrazine is most preferred in view of availability.

As the sulfonyl hydrazine compound, a commercially available compound may be used, but as the compound other than the commercially available product, for example, organic synthesis (ORGANIC SYNTH) is used.
ESES, Vol. 40, 93-95, 1960). That is, the corresponding sulfonyl chloride (RSO ₂ Cl) was dissolved in tetrahydrofuran, cooled to 10 ° C., and then an aqueous solution of hydrazine was added,
A tetrahydrofuran solution is added at such a rate that the temperature of the tetrahydrofuran solution is kept at 10 to 15 ° C. to obtain a reaction solution. The organic layer obtained by separating from the obtained reaction solution is washed twice with saturated saline and then dried to obtain the desired sulfonylhydrazine compound.

The glyoxal used in the present invention is usually a 40% aqueous solution. The amount of glyoxal used is usually 1 to 50 times mol, preferably 1 to 10 times mol, per mol of the sulfonylhydrazine compound.

Ammonia used in the present invention is
It can also be used as ammonia gas, liquid ammonia, aqueous ammonia solution or ammonia dissolved in an organic solvent. Ammonia dissolved in an organic solvent can be produced, for example, by a usual method of blowing ammonia gas into ice-cooled methanol. The amount of ammonia used is usually 2 to 200 times mol, preferably 5 to 50 times mol, relative to 1 mol of the sulfonylhydrazine compound.

In the present invention, when a liquid substance such as liquid ammonia is used, it is not always necessary to add a reaction solvent, but in other cases, a reaction solvent is added. In that case, as the reaction solvent to be used,
There is no particular limitation as long as it is a reaction solvent which dissolves a necessary amount of sulfonylhydrazine compound, glyoxal, and ammonia without participating in the reaction.

As the reaction solvent, for example, water or an organic solvent can be mentioned, and the object compound (1H-
Since 1,2,3-triazol) has high water solubility, an organic solvent is preferable in terms of separation method after the reaction. In this case, it is preferable that the organic solvent used as the reaction solvent and the organic solvent that dissolves the raw material compound are the same.

Examples of the organic solvent include lower alcohol solvents such as methanol, ethanol, propanol and isopropanol, methyl ether, ethyl ether,
There may be mentioned ether solvents such as propyl ether, dimethyl sulfoxide, dimethylformamide, aprotic polar solvents such as acetonitrile, preferably methanol, ethanol, and ethanol in the point of efficiently dissolving ammonia. Lower alcohol solvents such as propanol and isopropanol are more preferable, and methanol and ethanol are more preferable in view of low azeotropic temperature, and methanol is particularly preferable. The amount of organic solvent used is
Although not particularly limited, it is usually a sulfonylhydrazine compound 1
The amount is 50 to 500 times mol, preferably 1
The molar amount is from 00 to 500 times.

The reaction temperature in the present invention is generally -3.
It is 0 to 150 ° C, preferably 0 to 120 ° C.
If it is lower than this range, there is a drawback that temperature control becomes difficult, and if it is higher than this range, there is a drawback that thermal decomposition or the like occurs and the yield remarkably decreases.

In the present invention, the reaction time is the reaction temperature,
It is usually 1 to 150 hours, preferably 1 to 60 hours, though it depends on the amount of the raw material charged. If the reaction time is too long, the yield does not improve, and if it is too short, the reaction does not proceed sufficiently.

The present invention can be carried out usually under normal pressure or under pressure, but it is preferable to carry out under pressure because the yield is improved. In this case, set the reaction temperature to 7 in a closed container.
A natural pressure method by raising the temperature to 0 to 150 ° C can be used.

The present invention will be described in more detail below. For example, when liquid ammonia is used, there can be mentioned a method in which glyoxal is dropped into liquid ammonia in a closed container, and then a sulfonylhydrazine compound is dropped and mixed and stirred. In this case, glyoxal may be dissolved in the above organic solvent and added dropwise to liquid ammonia, and then the sulfonylhydrazine compound may be dissolved in the above organic solvent, which may be added dropwise and then mixed and stirred.

When an aqueous ammonia solution or an ammonia solution dissolved in an organic solvent is used, glyoxal is dropped into the ammonia solution, and then a sulfonylhydrazine compound is added and dissolved by stirring to obtain a uniform solution. After that, the reaction may be performed under normal pressure or increased pressure. In this case, the glyoxal and sulfonylhydrazine compounds dissolved in the above organic solvent may be used.

In the present invention, an ammonia solution dissolved in an organic solvent as ammonia is added to a solution of 40 glyoxal.
% Glyoxal aqueous solution dissolved in an organic solvent is added, and then a sulfonylhydrazine solution prepared by dissolving a sulfonylhydrazine compound as an sulfonylhydrazine compound in an organic solvent is added, followed by reacting by stirring. Is preferred. In this case, the reaction conditions such as the addition amount of the raw material may follow the above reaction conditions.

After the reaction is completed, unreacted ammonia, an organic solvent and water are distilled off, the residue is dissolved in methylene chloride or chloroform, and the undissolved material is filtered to obtain a filtrate. From the obtained filtrate, 1H-1,2,3-triazole can be easily obtained by concentrating and then distilling or separating by column chromatography.

[0030]

Industrial Applicability As in the present invention, a sulfonylhydrazine compound is added to a mixed solution containing glyoxal and ammonia and reacted to produce 1H-in one step.
1,2,3-triazole can be obtained. That is, since the 1H-1,2,3-triazole can be obtained in one step by using a safe compound having less explosive properties, the present invention is a safe, simple and industrially usable 1H. It can be said that this is a method for producing -1,2,3-triazole.

[0031]

EXAMPLES Examples will be shown below. The yield in the examples is p-
1H- based on toluenesulfonidohydrazine (mol)
This is the yield of 1,2,3-triazole (mol).

Example 1 A 200 ml three-neck round bottom flask was charged with ammonia.
Methanol mixed solution [ammonia: methanol = 1: 3
(Weight ratio); 590 mmol as ammonia] 40 g
Was added. To the mixed solution, a solution of 4.35 g of a 40% aqueous glyoxal solution (30 mmol as glyoxal) dissolved in 5 ml of methanol was added dropwise to the mixed solution, and the mixture was further stirred for 30 minutes, and then p-toluenesulfonide 5.58 g (30 mmol) of hydrazine was added to 20 ml of methanol.
The solution dissolved in was added to obtain a mixed solution. The mixed liquid was reacted at room temperature for 48 hours while stirring to obtain a reaction liquid. Excess ammonia was distilled off from the obtained reaction solution, and a part of the remaining reaction solution was sampled and quantified by gas chromatography-internal standard method, whereby 1H-1,2,3-triazole was 0. It was found that 0.65 g (yield: 31.5%) was produced.

The residue obtained by distilling off methanol from the reaction solution was used as a developing solvent, ethyl acetate: hexane = 7:
As a result of silica gel column chromatography treatment using No. 3, 0.57 g of 1H-1,2,3-triazole was obtained as a product. The NMR analysis results of the product are shown in Journal of Chemical Society (B).
(J. Chem. Soc. (B), 516 (196).
7)) and IR analysis are described in Journal of Chemical Society (B) (J. Chem. So.
c. (B), 307 (1969)).

Example 2 The amount of p-toluenesulfonidohydrazine added was 1.8.
The same operation as in Example 1 was carried out except that the amount was 6 g (10 mmol), and 1H-1,2,3-triazole 0.28 g
Was obtained (yield: 40.6%). The NMR analysis results of the product are shown in the Journal of Chemical Society.
(B) (J. Chem. Soc. (B), 516 (19)
67)) and the IR analysis
Chemical Society (B) (J. Chem. So
c. (B), 307 (1969)).

Example 3 The reaction container was a sealed container of 200 ml and the reaction temperature was 90.
The same operation as in Example 1 was carried out except that the temperature was 15 ° C. and the reaction time was 15 hours. 1H-1,2,3-triazole 1.00
g was obtained (yield: 48.3%). The NMR analysis results of the product are shown in the Journal of Chemical Society.
(B) (J. Chem. Soc. (B), 516 (19)
67)) and the IR analysis
Chemical Society (B) (J. Chem. So
c. (B), 307 (1969)).

Example 4 The reaction vessel was a sealed vessel of 200 ml and the reaction temperature was 90%.
The same operation as in Example 2 was carried out except that the temperature was 15 ° C. and the reaction time was 15 hours. 1H-1,2,3-triazole 0.40
g was obtained (yield: 58.3%). The NMR analysis results of the product are shown in the Journal of Chemical Society.
(B) (J. Chem. Soc. (B), 516 (19)
67)) and the IR analysis
Chemical Society (B) (J. Chem. So
c. (B), 307 (1969)).

The preferred embodiments of the present invention are as follows.

1. The sulfonylhydrazine compound is represented by the general formula (I)

[0039]

[Chemical 4]

(In the formula, R represents an alkyl group having 1 to 2 carbon atoms, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, p-chlorophenyl group, p-bromophenyl group) The method for producing 1H-1,2,3-triazole according to claim 1, which is a sulfonylhydrazine compound represented by:

2. The 1H-1,2,3-triazo-group according to claim 1, wherein the sulfonylhydrazine compound is a sulfonylhydrazine compound represented by the general formula (I) in which R is a phenyl group, a p-tolyl group or a p-chlorophenyl group. How to make le.

3. The sulfonylhydrazine compound is R
1H-1, according to claim 1, which is a sulfonylhydrazine compound represented by the general formula (I), wherein is a p-tolyl group.
A method for producing 2,3-triazole.

4. The method for producing 1H-1,2,3-triazole according to claim 1, wherein the solution of the mixed solution is an organic solvent.

5. The method for producing 1H-1,2,3-triazole according to claim 1, wherein the solution of the mixed solution is a lower alcohol.

6. The method for producing 1H-1,2,3-triazole according to claim 1, wherein the solution of the mixed solution is methanol.

7. The solution of the mixed solution is an organic solvent, and R is an alkyl group having 1 to 2 carbon atoms, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, p-chlorophenyl group. 1H-1,2 according to claim 1, which is a sulfonylhydrazine compound represented by the general formula (I), which is a p-bromophenyl group.
A method for producing 3-triazole.

8. The solution of the mixed solution is an organic solvent, the sulfonylhydrazine compound is R, phenyl group, p
-Tolyl group, p-chlorophenyl group of the general formula (I)
A sulfonylhydrazine compound represented by:
The method for producing 1H-1,2,3-triazole according to 1.

9. The 1H-1, 2, 3 according to claim 1, wherein the solution of the mixed solution is an organic solvent, and the sulfonylhydrazine compound is a sulfonylhydrazine compound represented by the general formula (I) in which R is a p-tolyl group. -Method for producing triazole.

10. The solution of the mixed solution is a lower alcohol, and R is an alkyl group having 1 to 2 carbon atoms, phenyl group, o-tolyl group, m
-Tolyl group, p-tolyl group, p-chlorophenyl group, p
The 1H- according to claim 1, which is a sulfonylhydrazine compound represented by the general formula (I) which is a -bromophenyl group.
A method for producing 1,2,3-triazole.

11. The solution of the mixed solution is a lower alcohol, and the sulfonylhydrazine compound is a sulfonylhydrazine compound represented by the general formula (I) in which R is a phenyl group, a p-tolyl group or a p-chlorophenyl group. The method for producing 1H-1,2,3-triazole according to 1.

12. The 1H-1,2 according to claim 1, wherein the solution of the mixed solution is a lower alcohol, and the sulfonylhydrazine compound is a sulfonylhydrazine compound represented by the general formula (I) in which R is a p-tolyl group. , 3-
Method for manufacturing triazole.

13. The solution of the mixed solution is methanol, and the sulfonylhydrazine compound has R having 1 carbon atom.
~ 2 alkyl groups, phenyl group, o-tolyl group, m-
Tolyl group, p-tolyl group, p-chlorophenyl group, p-
The 1H- according to claim 1, which is a sulfonylhydrazine compound represented by the general formula (I) which is a bromophenyl group.
A method for producing 1,2,3-triazole.

14. The solution of the mixed solution is methanol, and the sulfonylhydrazine compound is a sulfonylhydrazine compound represented by the general formula (I) in which R is a phenyl group, a p-tolyl group or a p-chlorophenyl group. A process for producing the described 1H-1,2,3-triazole.

15. The 1H-1, 2, according to claim 1, wherein the solution of the mixed solution is methanol, and the sulfonylhydrazine compound is a sulfonylhydrazine compound represented by the general formula (I) in which R is a p-tolyl group. A method for producing 3-triazole.

Claims (1)

[Claims] 1. In a mixed solution containing glyoxal and ammonia, a compound represented by the general formula (I): (In the formula, R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may have a substituent), and a sulfonylhydrazine compound represented by the formula 1H-
A method for producing 1,2,3-triazole.