DE2442685A1 - PROCESS FOR THE PREPARATION OF 2-PHENYL4-HYDROXY-1,2,3-TRIAZOL-1-OXIDES - Google Patents

Description

CLBA-GEIGY AG. CH-4002 Brsol

Dr. F. Zumstein Sr. - Dr. E. Assmann Dr. R.Koenigsberger - Dipl. Phys. R. Holzbauer "

Dr. F. Zumstein jun. 0 UL 2 β 8

P α t β η J α η wa I te 44HiUUd

8 Mönchen 2, Brauhautstrasse 4 / III

5-8968 / E Germany

Process for the preparation of 2-pheayl-4-hydroxy-i, 2,3-

triazole-1-oxides

The present invention relates to a process for the preparation of 2-phenyl-4-hydroxy-1,2,3-triazole-1,2 oxides.

From the German patent specification 1,168,437 it is known that by reacting diazotized Azo compounds obtainable with methazonic acid arylamine the formula

HC CH — NO ₂

N-aryl

which are also called oxime hydrazones of the formula HC C — NO

Il Il.

/ NN \
H (K ^X NH ~ aryl

can be understood, in aqueous-alkaline medium in the presence of acid anhydrides or acid halides at temperatures between 0 ° +50 ⁰ C to 2-aryl-4-nitro- ·

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1,2,3-triazoles can close in a ring.

It has now surprisingly been found that 2-phenyl-4-hydroxy ~ l, 2,3-triazole ~ loxides can be obtained in a simple manner of formula I.

HC Cf-OH _%

Il Il

• ·· o / ^N \ _N / ^N

in which R denotes a substituted or unsubstituted phenyl radical, can arrive if one is an oxime hydrazone of formula II

HC C-NO

NH-R

H (T

in which R has the meaning given unter.Formel has I, in the presence of a lower aliphatic carboxylic acid at temperatures between 15 and 100 ⁰ C.

As lower aliphatic carboxylic acids are those having 1 to 5 carbon atoms, for example formic acid, propionic acid, butyric acid and preferably acetic acid into consideration. It is expedient to use mixtures of these acids with water, the water content of which is 1 to 25%, preferably 5-10 % . The reaction is preferably carried out at temperatures from 20 to 30 ⁰ C. The reaction time is 1 to 24 hours.

• The substituates on the phenyl radical R include, for example, 1 or more identical or different fluorine, chlorine, bromine and / or iodine atoms, alkyl, haloalkyl, cyano, alkoxy, nitro, alkoxycarbonyl, alkylthio, alkylsulfonyl ,

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Alkylsulfinyl, acetylamino, amino, monoalkylamino, dialkylamino, Phenoxy and / or phenylsulfonyl groups are suitable. As or in the substituents on the phenyl radical occurring alkyl groups can have 1 to 5 carbon atoms.

The oxime hydrazones of the formula II used as starting compounds can be obtained in a simple manner by coupling a diazotized aromatic amine derived from the radical R with methazonic acid. For this purpose, the prepared solution of the diazonium salt in the conventional manner at 0 to 10 ⁰ C in an acetic acid, sodium acetate will integrate containing aqueous Methazonsäurelösung. Methazonic acid itself can be obtained, for example, by the method described in Journal ftlr Praxis Chemie [2], Volume 81, Page 203 [1910].

The 2-phenyl-4-hydroxy-1,2,3-triazole-1-oxides which can be prepared according to the invention can easily in the presence of glacial acetic acid by means of zinc dust to the corresponding 2-phenyl-4-hydroxy-1,2,3-triazoles be reduced. This reduction can advantageously take place immediately after the ring closure made v / ground in the reaction mixture.

The 2-phenyl-4-hydroxy-1,2,3-triazole-1-oxides of the formula I which can be prepared according to the invention and the 2-phenyl-4-hydroxy-1,2,3-triazoles obtainable therefrom by reduction can also be chlorinated or brominated in the 5-position. This chlorination or bromination may be either chlorine or bromine, with elemental or by the action of N-chlorosuccinimide or N-bromosuccinimide, in inert solvents to these agents, such as halogenated hydrocarbons, _/ preferably be performed carbon tetrachloride.

The 2-phenyl-4-hydroxy-1,2,3-triazole-1-oxides which can be prepared according to the invention and the secondary products of the obtainable therefrom by reduction and / or by halogenation Forrrel Ia

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Y-C C-OH

I 'ii

ft N

in which Y denotes hydrogen, chlorine or bromine and η denotes 0 or 1 and R denotes the meaning given under formula I. has insecticidal, fungicidal, bactericidal and nematocidal effects. Also, these are connections valuable starting materials for the production of phosphoric acid esters with an insecticidal effect. Such Phosphoric acid esters are described, for example, in our patent application no. 012961/73.

As can be seen from the above, the process according to the invention also provides easy access to the corresponding 2-phenyl-4- hydroxy-1,2,3-triazoles. Of this class of substances, only 2-phenyl-4-hydroxy-1,2,3-triazole, which is unsubstituted in the phenyl radical, is known. To prepare it, glyoxal was first converted into glyoxal-diphenylhydrazone by reaction with phenylhydrazine and this was condensed in the presence of copper sulfate to give 2-phenyl-1,2,3-triazole (see JL Riebsomer, J. Org. Chem 13 , (1948 ), 815). This was then converted into 2-phenyl-3-methyl-1,2,3-triazolium fluorine-sulfonate with fluorosulphide methyl ester, which by treatment with N-bromosuccinimide and sodium hydroxide solution, 2-phenyl-3-methyl-1,2 , 3-triazolin-4-one provides (cf. M. Begtrup et al, Acta Chem. Scand, 25. »(1971), 2087). The latter compound is then converted into 2-phenyl-4-benzoyloxy-1,2,3-triazole by reaction with benzoyl chloride, which gives 2-phenyl-4-hydroxy-1,2,3-triazole on alkaline hydrolysis (cf. . M. Begtrup, Acta Chem. Scand. 26, 1972 715) '.

Although in principle also the im Phenyl radical substituted 2-phenyl-4-hydroxy-1,2,3-triazoles

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and it should be possible to prepare the corresponding 1-oxides on the basis of these, this process is hardly considered in practice, as it is very cumbersome on the one hand and the desired end products only in a yield of less than 10 ° L of theory based on the starting materials on the other hand Glyoxal and. Phenylhydrazine supplies. The present invention thus provides for the first time a process which enables the production of 2-phenyl-4-hydroxy-1,2,3-triazole-loxides and the corresponding 2-phenyl-4-hydroxy-1,2i 3- ^:. ^. · Enables triazoles in a simple and economical manner.

The present invention is illustrated in more detail by the following examples.

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2U2685

example 1

2-phenyl-4-hydroxy-l, 2,3-triazole-l-oxide (according to formula I)

A prepared in the usual manner Diazoliumsalzlösung of 2 moles of aniline is allowed under stirring at 0 ° to 10 ⁰ C in an acetic acid containing sodium acetate aqueous Methazonsäurelösung which are obtained from 244 g of nitromethane (4 moles) is prepared enter.

The yellow oxime hydrazone of the formula II (R = phenyl) separates out as a thick suspension.

The precipitate is digested while still moist (water content: approx. 60%) at room temperature in 3000 ml of glacial acetic acid. After a short time a clear, dark solution forms with the escape of nitrous gases, which is stirred overnight and then evaporated to dryness. The solid residue is washed with ether, filtered off with suction and dried, Recrystallization of the end product from acetonitrile. Yield: 210 g = 59% based on nitromethane .Smp. 155-156 ° C dec.

Analysis: C. 3 H 95 N 7th 0 1 ber .: 54, 0 3, 9 23, 3 18 5 found : 54, 3, 23, 18

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Example 2

2- (3,4-Dichlorpher.yl) -4-hydroxy-l, 2, 3-triazole-l-oxide (according to formula i)

The still moist oxime hydrazone (corresponding to formula II; R = 3,4-dichlorophenyl) prepared in a known manner from 1 mol of diazotized 3,4-dichloroaniline and methazonic acid analogous to Example 1 is digested in 2000 ml of glacial acetic acid at room temperature. After a few hours, a clear, dark solution results with the formation of nitrous gases. A short time later, the product begins to precipitate. After 24 hours, it is suctioned off and dried.

Yield: 172 g (70% of theory based on nitromethane) mp 183-184 ⁰ C dec..

Analysis: C. , 0 H 0 Cl , 9 N 1 0 0 ber .: 39 , 3 2, 0 28 , 3 17, 6th 13, 8th found : 39 2, 29 16, 12,

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Example 3 2- (2-chlorophenyl) -4-hydroxy-1,2,3-triazole-1-oxide

100 g of the oxime hydrazone II (R = 2-chlorophenyl), made from diazotized 2-chloroaniline and methazonic acid, Earth in 1000 ml of 90% acetic acid at room temperature touched. After a short time nitrous gases form and a dark, clear solution is created. After 10 Hours is evaporated to TiDckne and the residue in Aether digested, filtered off and dried.

Yield: 45 g = 52% of theory

M.p. 161-163 ° C dec.

Analysis: C H Cl N calc .: 45.4 2.8 16.8 19.85 found: 44.8 2.9 16.4 19.3

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Example 4

2- (4-Carbaethoxyphenyl) -4-hydroxy-1,2,3-triazole-1-oxide

280 g of the oxime-hydrazone II (R = Carbaethoxyphenyl) made of diazotized 4-amino-benzoic acid ethyl ester and Me thazonsäure be FTIR in 2000 ml of acetic acid for 10 hours at 60 ⁰ C stirred. It is then cooled, the precipitate is suctioned off, washed well with water and again suctioned off.

Yield: 130 g = 52% of theory
M.p .: 186 ° C

Analysis: CH N calc .: 53.0 4.4 16.9 found:. 53.0 4.3 16.65

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Example 5 2-Phenyl-4-hydroxy-1,2,3-triazole

88.5 g of 2-phenyl-4-hydroxy-1,2,3-triazole-1-oxide of the formula I (R =? Phenyl) are dissolved in 1000 ml of glacial acetic acid Stirred under ice cooling with 75 g zinc dust. To The end of the reaction is filtered off and the filtrate is evaporated to dryness. The residue is in Water digests; Sucked off, washed with water and sucked off again.

Yield: 70 g = 87% of theory

Analysis: C. 6th H 35 N. 1 0 95 Ber:: 59, 5 4, 4th 26, 8th 9, 1 found : 59, 4, 25, 10,

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Example 6

2- phenyl-4-hydroxy-5-bromo - l ₎ 2 _> 3-triazole

32.2 g of 2-phenyl-4-hydroxy-1,2,3-triazole vierden in 400 ml of chloroform with 32 g of bromine at room temperature for 16 hours. After evaporation of the solvent the residue is digested in petroleum ether and filtered off with suction,

analysis C. H 5 Br 3 N , 5 ber .: 40.0 2, 6th 33, 0 17th , 4 found : 40.8 2, 35, 17th

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I ·

• I · III

• t · lit

Example 7

40.25 g of 2-phenyl-4-hydroxy-1,2,3-triazole are placed in 500 ml of chloroform. Be at room temperature then slowly passed in 17.8 g of chlorine, and stirred for 12 hours.

The reaction mixture is then completely evaporated, the residue digested with petroleum ether and filtered off with suction.

After recrystallisation from ligroin 44 g of 2-phenyl-4-hydroxy-5-chloro-l, 2,3-triazol obtained (90% of theory) of mp. 135-14O ^C C.

Analysis: C. 1 H 1 Cl 15th N 5 ber .: 49, 1 3, 3 18 1 21 0 found : 50, 3, 17, 22

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• I

Example 8

The following compounds of the formula I were prepared analogously to Examples 1-4.

M.p.

o-tolyl 128-132 ° C m-tolyl 114-116 ° C p-tolyl 155-157 ° C 3-chlorophenyl 166-168 ° C 4-chlorophenyl 173-174 ° C 2-methoxyphenyl 149-152 ° C 4-methoxyphenyl 122-123 ° C 2,5-dichlorophenyl 153-155 ° C 3,5-dichlorophenyl 168 ° C 4-bromophenyl 175-177 ° C 4-fluorophenyl 182-184 ° C 3-trifluoromethyl-phenyl 139-142 ° C 3-chloro-4-fluorophenyl 170-172 ° C 2-chloro-5-trifluoromethyl-phenyl 164-167 ° C

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Claims (13)

Claims 1. Process for the preparation of 2-phenyl-4-hydroxy-1,2,3-triazole-1-oxides of formula I. HC C-OH (I) in which R denotes a substituted or unsubstituted phenyl radical, characterized in that an oxime hydrazone of the formula II HCi JS N _x HCK> NH-R in which R has the meaning given under formula I has, in the presence of a lower aliphatic carboxylic acid at temperatures between 15 and 100 ⁰ C. 2. The method according to claim 1, characterized in that the lower aliphatic carboxylic acids those with 1 to 5 carbon atoms are used. 3. The method according to claim 1, characterized in that the lower aliphatic carboxylic acid Acetic acid used. 4. The method according to claim 1, characterized in that the reaction medium is a mixture of a lower carboxylic acid and water used in which 509811/1155 the water content is 5-25 "L. 5. The method according to claim 1, characterized in that the reaction temperature is 20-30 ⁰ C. 6. The method according to claim 1, characterized in that the compounds of formula I in Presence of glacial acetic acid reduced to the corresponding 2-phenyl-4-hydroxy-1,2,3-triazoles by means of zinc dust. 7. The method according to claim 6, characterized in that the reduction immediately after the ring closure is carried out in the reaction mixture. 8. The method according to claim 1, characterized in that that the compounds of the formula I and the 2-phenyl-4-hydroxy-1,2,3-triazoles which can be obtained from them by reduction be chlorinated or brominated in the 5-position. 9. The method according to claim 8, characterized in that one als.Halogenierungsmittel elemental chlorine or bromine is used. 10. Method according to claim b _? characterized in that one succinimide as the halogenating agent is N-chloro- or N-bromosuccinimide. 11. The method according to claims 8 to 10, characterized in that the halogenation is carried out in inert solvents such as halogenating hydrocarbons carries out. 12. The method according to claim ll, characterized in that the inert solvent used is carbon tetrachloride. . \ 509811/1155 13. 4-Hydroxy-1,2,3-triazole derivatives of the formula la Y-C Ό - OH Il in which R is a substituted or unsubstituted phenyl radical, Y is hydrogen, chlorine or bromine and η is 0 or 1 denotes, with the exception of the compound in which R denotes phenyl, Y denotes hydrogen and η denotes 0. 509811/1155