CH586011A5 - 1-(Carbamoyloxy-trichloro-ethyl)-1,2,4-triazole derivs - prepd. e.g. by reacting 1-(hydroxy-trichloro ethyl)-cpd. with carbamoyl halide - Google Patents

Abstract

Triazole derivs. of formula (I): (where R1 is H, 1-3C alkyl or 1-3C alkoxy and R2 is 1-6C alkyl or 3-4C alkenyl opt. substd. by CN, halogen, NO2, 1-3C alkoxy or 1-3C alkylthio, or is 3-8C cycloalkyl or cycloalkenyl opt. substd. by 1-3C alkyl), e.g. 1-/1-(N-n-propylcarbamoyloxy)-2,2,2-trichloroethyl/-1,2,4-triazol- e, are new cpds. which may be prepd. by reacting 1-(1-hydroxy-2,2,2-trichloroethyl)-1,2,4-triazole (II) with Hal-CO-NR1R2 (III) (where Hal is halogen) in the presence of an acid-binding agent or (to give (I; R1 = H)) with R2NCO (IV). Some cpds. (I) are active against phytopathogenic bacteria on various crop plants and others are selective herbicides. However, (I) are particularly useful as systemic fungicides.

Description

  

  
 



   The present invention relates to pesticidal agents containing as at least one active component a 1- (1 'carbamoyloxy-2', 2 ', 2'-trichloroethyl) -1, 2,4-triazole derivative of the formula
EMI1.1
 wherein
R1 C1-C3 alkyl or C1-C3 alkoxy and
R2 denotes C16 alkyl or C3-C4 alkenyl optionally substituted by cyano, halogen, nitro, C1-C3 alkoxy or C1-C3 alkylthio or C3-C8 cycloalkyl or cycloalkenyl optionally substituted by C13 alkyl.



   A particularly interesting group of compounds of the formula I are those in which R2 is a C14 alkyl group.



   Also of interest are compounds of the formula I in which R2 is cyclohexyl.



   Under alkyl are depending on the number of carbon atoms specified z. B. to understand the following groups: methyl, ethyl, propyl, butyl or hexyl and their isomers such as. B.



  iso-propyl, iso-, sec- or tert-butyl, l-methylbutyl, etc.



   The following groups are to be understood by alkenyl; Allyl and butenyl and its isomers.



   As C3-C8 cycloalkyl or cycloalkenyl, for. B.



  the following groups in question; Cyclopropyl, Cyclopentyl, Cyclohexyl, Cyclohexenyl, Cycloheptyl, Cycloheptenyl, Cyclooctyl, etc.



   The halogens optionally present as substituents are fluorine, chlorine, bromine or iodine.



   The alkoxy and alkylthio groups that may be present as substituents have methyl, ethyl, n-propyl or i-propyl as the alkyl part.



   The compounds of the formula I can be prepared by adding a compound of the formula II
EMI1.2
 a) with a compound of the formula III
EMI1.3
 in the presence of an acid-binding agent, where in formula III R1 and R2 have the meanings given under formula I and Hal stands for halogen, preferably chlorine or bromine.



   The compound of formula II is prepared in a manner known per se, such as. B. by reacting 1,2,4 triazole with chloral. This compound is new and has some bactericidal activity.



   The reactions can be carried out in anhydrous solvents or diluents which are inert towards the reactants, such as aliphatic, aromatic and / or halogenated hydrocarbons such as. B. benzene, toluene or chloroform; in ethers such as B. diethyl ether, dioxane, tetrahydrofuran; in ketones such as B. acetone, methyl ethyl ketone; in nitriles such as B. acetonitrile; in esters, such as B. acetic acid esters and mixtures of such solvents can be made.



   In the reactions, as acid-binding agents, preferably equimolar amounts of tertiary amines such. B.



  Triethylamine can be used.



   In the reactions, as acid-binding agents, preferably equimolar amounts of tertiary amines such. B.



  Triethylamine can be used.



   The reactions are carried out at temperatures between -20 and + 120 ° C., preferably between + 10 and 40 ° C., and at normal pressure.



   Some of the compounds of the formula I are suitable for combating phytopathogenic bacteria on cereals, maize, potatoes, rice, vegetables, vines, ornamental plants, fruits and other crops.



   As phytopathogenic bacteria, representatives of the order Pseudomonas z. B. Pseudomonas tomato, Pseudomonas lachrymans and Pseudomonas phaseolicola, Xanthomonas z. B. Xanthomonas oryzae, Xanthomonas vesicatoria and Xanthomonas phaseoli as well as Erwinia and Corynebacterium can be mentioned.



   Some compounds of the formula I show selective herbicidal activity against weeds in certain crops of useful plants.



   However, the action of the compounds of the formula I against phytopathogenic fungi should be emphasized. So they work z. B. against Phycomycetes such as Phytophthora infestans, Ascomycetes such as Erysiphe graminis and against fungi imperfecti such as Piricularia oryzae, Fusarium oxysporum and Verticillium albo-atrum.



   A particular property of the compounds of the formula is their systemic action, i. H. their ability to be transported in a plant to a source of infection that is remote from the site of application. After treating the soil, such a compound can be absorbed by the roots of a plant and transported to the source of the disease.



   The compounds of the formula I can be applied to all parts of the plant in the form of the compositions according to the invention. The compounds of the formula I can of course be used together with other suitable pesticidal or plant growth-promoting active ingredients in order to broaden their spectrum of action, in the compositions according to the invention.



   According to the invention, the compounds of the formula I are used together with suitable carriers and / or other additives. Suitable carriers and additives can be solid or liquid and correspond to the substances customary in formulation technology such as. B. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.



  Such agents are produced in a manner known per se by intimately mixing and grinding the constituents.



   For application, the compounds of the formula I can be in the following working-up forms: Solid working-up forms:
Dusts, grit, grains, granules, coating granules, impregnation granules and homogeneous granules.



  Liquid processing forms: a) Active substance concentrates dispersible in water:
Wettable powders, pastes, emulsions; b) Solutions, aerosols.



   The content of active ingredient in the compositions described above is between 0.1 and 95 percent by weight. The active ingredients of the formula I can be formulated as follows, for example: Dusts:
The following substances are used to produce a) 5% and b) 2% dusts: a) 5 parts of active ingredient,
95 parts of talc; b) 2 parts of active ingredient,
1 part of highly dispersed silica,
97 parts of talc.



   The active ingredients are mixed and ground with the carrier substances.



  Granules:
The following substances are used to produce 5% granules:
5 parts active ingredient,
0.25 parts epichlorohydrin,
0.25 part of cetyl polyglycol ether,
3.50 parts of polyethylene glycol,
91 parts of kaolin (grain size 0.3-0.8 mm).



   The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto kaolin, and the acetone is then evaporated in vacuo.



  Wettable powder:
The following ingredients are used to produce a) 40%, b) and c) 25%, d) 10% wettable powder: a) 40 parts of active ingredient,
5 parts of lignin sulfonic acid sodium salt,
1 part dibutylnaphthalenesulfonic acid sodium salt,
54 parts of silica; b) 25 parts of active ingredient,
4.5 parts calcium lignosulfonate,
1.9 parts of champagne chalk / hydroxyethyl cellulose
Mixture (1: 1),
1.5 parts of sodium dibutyl naphthalene sulfonate,
19.5 parts of silica,
19.5 parts of champagne chalk,
28.1 parts of kaolin; c) 25 parts of active ingredient,
2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol,
1.7 parts of champagne chalk / hydroxyethyl cellulose
Mixture (1: 1),
8.3 parts sodium aluminum silicate,
16.5 parts kieselguhr,
46 parts of kaolin;

   d) 10 parts of active ingredient,
3 parts mixture of the sodium salts of saturated
Fatty alcohol sulfates,
5 parts of naphthalenesulfonic acid / formaldehyde condensate,
82 parts of kaolin.



   The active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to form suspensions of the desired concentration.



  Emulsifiable concentrates:
The following substances are used to produce a 25% emulsifiable concentrate: a) 25 parts of active ingredient,
2.5 parts epoxidized vegetable oil,
10 parts of an alkylarylsulfonate / fatty alcohol poly glycol ether mixture,
5 parts of dimethylformamide,
57.5 parts of xylene.



   Emulsions of the desired concentration can be prepared from such concentrates by diluting them with water.



   The following examples serve to explain the invention in more detail without restricting it. The temperature data relate to degrees Celsius.



   Manufacturing example
Preparation of 1- [1 (N-methoxy-N-methylcarb amoyl- oxy) -2 ', 2', 2 '-trichloroethyl] -1, 2,4-triazole of the formula
EMI2.1

To a slurry of 21.7 g of 1- (1'-hydroxy 2 ', 2', 2'-trichloroethyl) -1,2,4-triazole in 40 ml of chloroform, 13.6 g of methoxymethylcarbamoyl chloride were added simultaneously with thorough stirring at room temperature in 20 ml of benzene and 11 g of triethylamine in 20 ml of benzene were added dropwise within one hour. After stirring for twelve hours, the reaction mixture was washed twice with water to remove the triethylamine hydrochloride, dried over sodium sulfate, and the solution was evaporated to dryness and crystallized with petroleum ether.

  After recrystallization from diethyl ether, the white crystals of compound I melt between 78-80 C.



   1- [1 '- (N, N-dimethylcarbamoyloxy) -2', 2 ', 2'-trichloroethyl] -1,2,4-triazole melting point 118 to 119 "C was prepared in an analogous manner (compound 2 ).



   Biological examples
A. Action against Erysiphe graminis on Hordeum vulgare
A spray mixture prepared from wettable powder of the active ingredient was poured into barley plants about 8 cm high (0.01% active ingredient based on the volume of the soil).



  Care was taken to ensure that the spray mixture did not come into contact with the above-ground parts of the plant. After 48 hours, the treated plants were dusted with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22 ° C. and the fungal attack was assessed after 10 days.



   Compound No. 2 showed a good effect (i.e.



  Plants less than 20% infected, compared to untreated but infected control plants).



   B. Action against Fusarium oxysporum
Solanum lycopersicum
After 3 weeks of cultivation, tomato plants were injured at the roots and infected with a spore suspension of the wilt pathogen. After 24 hours, the plants were sprayed with a spray mixture prepared from a wettable powder of the active ingredient (0.18% active ingredient). After 14 days of incubation in a greenhouse at about 22 ° C., the degree of wilting of the infected tomato plants was determined. Compound No. 1 showed a good effect (i.e. plants less than 20% infected compared to untreated but infected control plants).

 

   PATENT CLAIM 1
Pesticidal compositions containing as at least one active component a 1- (1'-carbamoyloxy-2 ', 2', 2'-trichloroethyl) -1,2,4-triazole derivative of the formula

** WARNING ** End of DESC field could overlap beginning of CLMS **.



   

 

Claims (1)

** WARNING ** Beginning of CLMS field could overlap end of DESC **. of formula I can for example be formulated as follows: Dusts: The following substances are used to produce a) 5% and b) 2% dusts: a) 5 parts of active ingredient, 95 parts of talc; b) 2 parts of active ingredient, 1 part of highly dispersed silica, 97 parts of talc. The active ingredients are mixed and ground with the carrier substances. Granules: The following substances are used to produce 5% granules: 5 parts active ingredient, 0.25 parts epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin (grain size 0.3-0.8 mm). The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto kaolin, and the acetone is then evaporated in vacuo. Wettable powder: The following ingredients are used to produce a) 40%, b) and c) 25%, d) 10% wettable powder: a) 40 parts of active ingredient, 5 parts of lignin sulfonic acid sodium salt, 1 part dibutylnaphthalenesulfonic acid sodium salt, 54 parts of silica; b) 25 parts of active ingredient, 4.5 parts calcium lignosulfonate, 1.9 parts of champagne chalk / hydroxyethyl cellulose Mixture (1: 1), 1.5 parts of sodium dibutyl naphthalene sulfonate, 19.5 parts of silica, 19.5 parts of champagne chalk, 28.1 parts of kaolin; c) 25 parts of active ingredient, 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of champagne chalk / hydroxyethyl cellulose Mixture (1: 1), 8.3 parts sodium aluminum silicate, 16.5 parts kieselguhr, 46 parts of kaolin; d) 10 parts of active ingredient, 3 parts mixture of the sodium salts of saturated Fatty alcohol sulfates, 5 parts of naphthalenesulfonic acid / formaldehyde condensate, 82 parts of kaolin. The active ingredients are intimately mixed with the additives in suitable mixers and ground on appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to form suspensions of the desired concentration. Emulsifiable concentrates: The following substances are used to produce a 25% emulsifiable concentrate: a) 25 parts of active ingredient, 2.5 parts epoxidized vegetable oil, 10 parts of an alkylarylsulfonate / fatty alcohol poly glycol ether mixture, 5 parts of dimethylformamide, 57.5 parts of xylene. Emulsions of the desired concentration can be prepared from such concentrates by diluting them with water. The following examples serve to explain the invention in more detail without restricting it. The temperature data relate to degrees Celsius. Manufacturing example Preparation of 1- [1 (N-methoxy-N-methylcarb amoyl- oxy) -2 ', 2', 2 '-trichloroethyl] -1, 2,4-triazole of the formula EMI2.1 To a slurry of 21.7 g of 1- (1'-hydroxy 2 ', 2', 2'-trichloroethyl) -1,2,4-triazole in 40 ml of chloroform, 13.6 g of methoxymethylcarbamoyl chloride were added simultaneously with thorough stirring at room temperature in 20 ml of benzene and 11 g of triethylamine in 20 ml of benzene were added dropwise within one hour. After stirring for twelve hours, the reaction mixture was washed twice with water to remove the triethylamine hydrochloride, dried over sodium sulfate, and the solution was evaporated to dryness and crystallized with petroleum ether. After recrystallization from diethyl ether, the white crystals of compound I melt between 78-80 C. 1- [1 '- (N, N-dimethylcarbamoyloxy) -2', 2 ', 2'-trichloroethyl] -1,2,4-triazole melting point 118 to 119 "C was prepared in an analogous manner (compound 2 ). Biological examples A. Action against Erysiphe graminis on Hordeum vulgare A spray mixture prepared from wettable powder of the active ingredient was poured into barley plants about 8 cm high (0.01% active ingredient based on the volume of the soil). Care was taken to ensure that the spray mixture did not come into contact with the above-ground parts of the plant. After 48 hours, the treated plants were dusted with conidia of the fungus. The infected barley plants were placed in a greenhouse at about 22 ° C. and the fungal attack was assessed after 10 days. Compound No. 2 showed a good effect (i.e. Plants less than 20% infected, compared to untreated but infected control plants). B. Action against Fusarium oxysporum Solanum lycopersicum After 3 weeks of cultivation, tomato plants were injured at the roots and infected with a spore suspension of the wilt pathogen. After 24 hours, the plants were sprayed with a spray mixture prepared from a wettable powder of the active ingredient (0.18% active ingredient). After 14 days of incubation in a greenhouse at about 22 ° C., the degree of wilting of the infected tomato plants was determined. Compound No. 1 showed a good effect (i.e. plants less than 20% infected compared to untreated but infected control plants). PATENT CLAIM 1 Pesticidal compositions containing as at least one active component a 1- (1'-carbamoyloxy-2 ', 2', 2'-trichloroethyl) -1,2,4-triazole derivative of the formula EMI3.1 wherein R1 C1-C3 alkyl or C13 alkoxy and R2 optionally substituted by cyano, halogen, nitro, C1 C3 alkoxy or C1-C3 alkylthio C1-C6 alkyl or C34 alkenyl or optionally by C1-C3 Alkyl is substituted C3-C8 cycloalkyl or cycloalkenyl. SUBCLAIMS 1. Agent according to claim I, containing 1- [1 '- (N, N-dimethylcarbamoyloxy) -2', 2 ', 2'-trichloroethyl] -1,2,4-triazole as the active component. 2. Means according to claim 1. containing as active component 1- [1 '- (N-methoxy-N-methyl-carbamoyloxy) - 2 ', 2', 2'-trichloroethyl-1 2,4-triazole. PATENT CLAIM II Use of an agent according to claim I for Control of phytopathogenic fungi.