CS214809B2 - Fungicide means and method of making the active substance - Google Patents

Abstract

Novel microbicidal compounds of the formula I <IMAGE> Wherein: R1 is tertbutyl or phenyl optionally substituted by halogen R2 is phenyl or diphenyl optionally substituted by 1 to 3 halogen atoms, C1-2 alkyl, methoxy, cyano, nitro, and/or phenoxy and A is <IMAGE> wherein R3 to R6 are hydrogen, C1-6 alkyl, C1-6 alkoxy methyl or phenoxy methyl or R3 and R4 together are tetramethylene and X is CH or N.

Description

The present invention relates to a fungicidal composition comprising, as active ingredient, novel azolyl ketals of the general formula I,

in which it means

R 1 is a tert-butyl group or an optionally mono- or double-substituted phenyl group and a

R 2 is optionally 1 to 3 halogen atoms, C 1 -C 2 alkyl, methoxy, cyano, nitro and / or phenoxy substituted phenyl or diphenyl, and

A group —GH — GH—

R3 R4 or. --CH2 --C - CH2 -;

R5 Rg in which

R 3, R ₄ , R 5 and R ₆ are each independently hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxymethyl or phenoxymethyl, or

R 3 and R 4 together represent a tetramethylene group, and

X is CH or N, including their salt-tolerated salts with inorganic or organic acids and metal complexes.

The alkyl or alkyl moieties of other substituents refer to the following groups according to the number of carbon atoms indicated: methyl, ethyl, propyl, butyl, pentyl, hexyl, as well as their isomers (such as isopropyl, isobutyl, sec-butyl, tert-butyl). butyl, isopentyl, etc.).

Halogen means fluorine, chlorine, bromine or iodine.

Examples of salt-forming acids include hydrochloric, hydrobromic, hydrogen, sulfuric, phosphoric, nitric, acetic, trifluoroacetic, trichloroacetic, oxalic, benzenesulfonic, methanesulfonic acid.

The complex compounds of the formula I with metals consist of a basic organic molecule and an inorganic or organic metal salt, such as halides, nitrates, sulphates, phosphates, tartrates etc. of copper, manganese, iron, zinc and other metals. In this case, the metal cations can be present in the various states which are appropriate to them.

However, this list is not intended to be limited to the examples.

The compounds of the formula I are very valuable active compounds against phytopathogenic microorganisms.

A preferred subgroup of active fungicides are the compounds of formula I in which they are

R 1 is a tert-butyl group or, optionally, one or two fluorine or chlorine substituted phenyl groups,

R _{2 is} optionally substituted phenyl or biphenyl by 1 to 2 halogen atoms,

A —CH — CH—

Rb R4 or -CH ₂ -C-CH ₂ -, / \

R ₅ R ₆ in which>

R _3, R _{Z1, R5} and _phi are independently hydrogen, alkyl of 1-3 carbon atoms, methoxymethyl or phenoxymethyl, or ·

R ₃ and R ₄ together represent a tetramethylene group, and

X is CH or N.

Another subgroup of active fungicides are the compounds of formula (I) in which they are

R1 t-butyl or 2,4-dichlorophenyl,

R ₂ optionally substituted by methyl, chloro, methoxy, cyano or phenoxy substituted phenyl and

R ₃ and R ₄ together represent a tetramethylene group.

Another subgroup of active fungicides are the compounds of formula (I) in which they are

Rx t-butyl or 2,4-dichlorophenyl,

R ₂ optionally substituted by methyl, chloro, methoxy, cyano or phenoxy substituted phenyl, and

A is —CH (R ₃ ) —CH (RJ), wherein R ₃ is hydrogen and R _{4 is} C 1 -C 6 alkoxymethyl, with alkoxymethyl groups of 1 to 3 carbon atoms being preferred among possible alkoxymethyl side chains in the alkoxy moiety.

A preferred sub-group of active fungicides comprises compounds of formula I in which they are

R, t-butyl or 2,4-dichlorophenyl,

R _{2 is} one or two substituted phenyl radical;

And optionally C1 -C3 alkyl or methoxymethyl substituted ethylene and

X is CH or N.

However, those fungicides which contain, as active ingredient, a compound of the formula I in which

Rj is a tert-butyl group,

R ₂ once or twice · chlorine-substituted phenyl,

And an ethylene group and

X is CH or N.

Particularly preferred are the following individual compounds:

2-tert-butyl-2- [1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl)] methyl-1,3-dioxolane,

2-tert-Butyl 1-2- [1- (4-chlorophenoxy) -1- (imidazol-1-yl)] methyl-1,3-dioxolane,

2-tert-butyl-2- [1- (phenoxy) -1- (1,2,4-triazol-1-yl)] methyl-1,3-dioxolane,

2-tert-butyl-2- [1- (4-fluorophenoxy) -1- (1,2,4-triazol-1-yl)] methyl-1,3-dioxolane,

2- [2,4-dichlorophenyl) -2- (1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl)] methyl-1,3-dioxolane,

2-tert-Butyl 1-2- [1- (2,4-dichlorophenoxy) -1- (1,2,4-triazol-1-yl)] methyl-1,3-dioxolane.

The compounds of the formula I according to the invention are produced by reacting a compound of the formula II,

in which

R _b R ₂ and A are as defined in formula Ia

Hal represents halogen, preferably chlorine or bromine, with a compound of the formula

III,

(lil) in which

X is as defined in formula I and Me is hydrogen or a metal cation, preferably an alkali metal or alkaline earth metal cation, for example sodium or potassium.

This process is optionally carried out in the presence of aprotic polar solvents which are inert to the components of the reaction mixture. Examples of such solvents include acetonitrile, dimethylsulfoxide, dvmethylformamide, dimethylacetamide, hexamethylphosphoric triamide or sulfolane.

In the case where in formula III the symbol Me is hydrogen, the procedure is carried out in the presence of a base. Examples of such bases include inorganic bases such as alkali and alkaline earth metal oxides, hydroxides, hydrides, carbonates and acid carbonates, as well as tertiary amines such as triethylamine, triethylenediamine, pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine and diazabicyclooctane.

The process is carried out at temperatures between 0 and 150 ° C and at atmospheric pressure.

The starting ketals of formula II are prepared by: a) compounds of formula IV,

O

II

R 1 —C — CH ₂ O — R ₂ (IV) wherein

R1 and R2 are as defined above, in reaction with a diol of formula V,

НО — А — ОН (V) in which

A is as defined above, in the presence of a

(b) the ketal of formula VI thus obtained, in which:

R _b R ₂ and A are as defined above, halogenated.

Solvents which are inert to the components of the reaction mixture are used, such as for example a) hydrocarbons such as benzene, toluene and halogenated hydrocarbons (carbon tetrachloride, chloroform, methylene chloride, dichloroethane, etc.), or for reaction b) halogenated hydrocarbons (carbon tetrachloride, chloroform, methylene chloride, etc.), diethyl ether, tetrahydrofuran, dioxane, etc.

Suitable acids for process (a) are, for example, mineral acids such as hydrobromic, hydrochloric and sulfuric acids, as well as p-toluenesulfonic acid and boron trifluoride etherate.

Suitable halogenating agents in process b) are, for example, chlorine, sulfuryl chloride, bromine or N-bromosuccinimide, and catalysts such as light, peroxide such as dibenzoyl peroxide or -a can be used when N-bromosuccinimide or chlorine are used, and - azoisobutyronitrile.

The reaction temperatures in step a) are from 40 to 150 ° C, preferably using a water separator. In process b), the reaction temperatures are from 0 ° C to 100 ° C, preferably 35 to 70 ° C. Steps a) and b) ketalization and halogenation of pinacoline ether of formula IV (R 1 - tert -butyl) to intermediates of formulas VI and II represent a separate further aspect of the invention. This aspect is also an independent method for preparing pinacolinetherketals of formula VI and halogenated ketals of formula II.

The ketols which form the basis of the ketals of the formula I are, in individual cases, substances known from DOS 2 325 156, 2 705 676, DAS 2 201 063 and DOS 2 705 678. However, these compounds cannot be used as starting materials for procedure outlined here.

The following examples serve to illustrate the invention in further detail without restricting it. Temperatures are given in degrees Celsius, pressure data are in Pa. Percentages and parts refer to weight.

Examples illustrating a process for the preparation of active substances.

Example 1

Preparation of 2-tert-butyl 1-2- [1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl)] methyl-1,3-dioxolane of formula

(VI)

(Compound No. 18)

a) Preparation of 2-tert-butyl-2- [1- (4-chlorophenoxy)], methyl 1-1,3-dioxolane of formula

g of 4-chlorophenoxypinacoline is heated with 17 g of ethylene glycol with the addition of 0.2 g of .beta.-p-toluenesulfonic acid in 300 ml of toluene for 30 minutes at reflux using a water trap. The cooled toluene solution was washed successively with dilute acidic carbonate solution and water, dried over sodium sulfate, filtered, and concentrated in vacuo. The crystals thus obtained were recrystallized from petroleum ether to give 35 g of an intermediate, m.p. 68-70 ° C.

b) Preparation of 2-tert-butyl-2- 1- (4-chlorophenoxy) -1-bromo] methyl-1,3-dioxolane of formula

NO. 1

C / ^ - C -'сКн-о- ^ У-ы

CH 2 Br g of 4-chlorophenoxypinacoline-ethylene ketal from step a) was dissolved in 150 ml of carbon tetrachloride. At 40-50 ° C, about 16 g of bromine is slowly added dropwise. After stirring at this temperature for 15 hours, bromine was consumed. After cooling, the carbon tetrachloride solution was washed with dilute acidic carbonate solution, dried and evaporated. The residue yielded 18 g of product from petroleum ether, m.p. 118-120 ° C.

(c) End product:

3 g of 1,2,4-triazole and 2 g of a 55% suspension of sodium hydride in paraffin oil are brought into contact with each other in absolute dimethylformamide. After completion of hydrogen evolution, the reaction mixture is stirred at 80-100 ° C for 1 hour. Then, 11 g of 2-tert-butyl-2- [1- (4-chlorophenoxy) -1-bromo] methyl-1,3-dioxolane in dimethylformamide was added dropwise, and the reaction mixture was stirred for 18 hours at a temperature. 100-120 ° C. The solvent is removed in vacuo and the oily residue is taken up in ether, washed with water, dried, filtered and evaporated. After evaporation, 8 g of a viscous oil are obtained from the ether solution, which is purified by chromatography on a silica gel column. In this way, colorless crystals of compound 18 are obtained with a melting point of 103-105 ° C.

Example 2

Preparation of 2-tert-butyl-2- [1- (4-chlorophenoxy) -1- (imidazolyl-yl)] methyl-1,3-dioxolane of formula

CH. I CHrC- ⁵ I ^CH 5

Cl (Compound # 1)

Reaction product:

g of imidazole and 2 g of a 55% suspension of sodium hydride in paraffin oil were contacted in absolute dimethylformamide. After the hydrogen evolution had ceased, the reaction mixture was stirred at 80-100 ° C for 1 hour. 11 g of 2-tert-butyl-2- [1- (4-chlorophenoxy) 1-bromo] methyl-1,3-dioxolane in dimethylformamide were then added dropwise and the reaction mixture was stirred at 100-120 for 18 hours. Deň: 32 ° C. The solvent is removed in vacuo and the oily residue is taken up in ether, the ether solution is washed with water, dried, filtered and evaporated. 9 g of a viscous oil are obtained from the ether solution after evaporation of the solvent, which, after recrystallization from hexane, yields colorless crystals of compound 1. Melting point 102-104 ° C.

Example 1 a d 3

Preparation of 2- (2,4-dichlorophenyl) -2- [1- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) methyl-1,3,3-dioxolane of formula

(Compound No. 35)

a) Preparation of 2- (2,4 (101110 (phenyl) -2- (1- (4-chlorophenoxy)) methyl-1,3-dioxolane)

A mixture of 54 g of .alpha .- (p-chlorophenoxy) -2,4-dichloroacetophenone, 20 ml of ethylene glycol and 2-.gamma.-toluenesulfonic acid in 400 ml of tolue214809 nu is heated to reflux using a water trap. An additional 10 ml of ethylene glycol was added after 10 hours of reaction time. After 50 hours, the reaction mixture is cooled to room temperature, washed once with sodium bicarbonate solution and twice with water, the toluene phase is separated, dried over sodium sulphate and concentrated. 61 g of a pale yellow, viscous oil are obtained.

b) Preparation of 2- (2,4-dichlorophenyl) -2- [1- (4-chlorophenoxy) -1-bromo] methyl-1,3-dioxolane of formula [Compound No. 26]

a) Preparation of 2-tert-butyl-2- [1- (2,4-dichlorophenoxy)] methyl-1,3-dioxolane of the formula

Cl

100 g of 2- (2,4-dichlorophenyl) -2- [1- (4-chlorophenoxy)] methyl-1,3-dioxolane are dissolved in 400 ml of absolute dioxane and kept at 70 ° C for this solution. C dropwise 46 g (15 ml) of bromine with stirring. After a reaction time of 5 hours, the reaction mixture is cooled to room temperature and then poured into 2 l of ice water containing 20 g of sodium bicarbonate. The precipitated oil is extracted with dichloromethane, the organic phase is washed with aqueous sodium bicarbonate solution and dried over sodium sulphate. 130 g of a brown oil are obtained, which is taken up in 500 ml of hexane. 78 g of beige-colored crystals, m.p. 100 DEG-104 DEG C., are precipitated from this solution.

(c) End product:

To a solution of 77 g of 2- (2,4-dichlorophenyl) -2- (1- [4-chlorophenoxy) -1-bromo] methyl-1,3-dioxolane in 500 ml of absolute dimethylformamide is added 37 g of potassium salt 1, 2,4-triazole and the reaction mixture was stirred at 100 ° C for 15 hours. After removal of dimethylformamide in vacuo, the brown residue was extracted with water and a mixture of hexane and dichloromethane (8: 2 by volume). The organic extracts were dried over sodium sulfate and concentrated. 62 g of a dark brown oil are obtained which, after purification on a column of 30 g of alumina (activity 2 to 3), gives a yellowish crystalline mass of compound 35 with a melting point of 104 to 107 ° C.

Example 1 a d 4

Preparation of 2-tert-butyl-2- [1- (2,4-dichlorophenoxy) -1- (1,2,4-thiazol-4-yl)] methyl-1 H -dioxolane of formula g 2,4-dichlorophenoxypinacoline was heated with 20 g of ethylene glycol and 0.5 g of p-toluenesulfonic acid in 300 ml of toluene under reflux for 24 hours using a water trap. The solution cooled to room temperature was washed with aqueous sodium bicarbonate solution and then with water, dried over sodium sulfate and concentrated in vacuo. 55 g of colorless crystals, mp 61-63 C. ³

b) Preparation of 2-tert-butyl-2- [1- (2,4-dichlorophenoxy) -1-bromo] methyl-1,3-dioxolane of formula

200 g of 2,4-dichlorophenoxypinacolinethylene ketal prepared in (a) are dissolved in 900 ml of absolute dioxane and 105 g of bromine are added dropwise at 40 to 50 ° C with stirring. After stirring for 4 hours, bromine is consumed. The reaction mixture is stirred for a further 1 hour and then poured into 5 liters of ice water containing 50 g of sodium bicarbonate. The precipitated crystals are filtered off, dried and recrystallized from hexane. 130 g of colorless crystals are obtained, m.p. 99-102 ° C.

(c) End product:

Solution of 15 g of potassium salt of 1,2,4-triazole in

250 ml of dimethylsulfoxide were stirred together

With 38.5 g of 2-tert-butyl-2- [1- (2,4-dichlorophenoxy) -1-bromo] methyl 1-1,3-dioxolane at 100 ° C for 15 hours. The reaction solution was then cooled to room temperature and poured into water. The resulting brown oil was extracted with diethyl ether, dried over sodium sulfate and purified on a silica gel column. 17 g of a viscous oil are obtained, which is crystallized by the addition of petroleum ether. The precipitated crystals of Compound (26) are recrystallized from hexane / diethyl ether and have a melting point of 106-108 ° C.

The following compounds of formula I can be prepared in an analogous manner:

кт К

X ο-

Гч а

Ю й

ЗГ Сч U Ж со ω

hy <hyí ЬН НЧ М-Ч НМ нм НМ НМ НМ НМ * -М

i /

Table II (X = CH; A = -OH2-C-CH2-) ^R 5 ^R 6

compound no. R ^R 2 ^R 5 R _c physical constants 15 Dec tert-butyl —C6H4 — Cl (4) H H 16 - ₃ C 6 H ^ - ^ 12 (2.4) —C ₆ H ₄ —C1 (4) CH3 CH3 mp 82-84 ° C 17 —C ₆ H4 — F (4) -СбЩ-С1 (3) CH3 CH3 mp 150-151 ° C

compound R _t R ₂ R ₃ R ₄ physical constants no

O CD O CD CD O O 0 O O O Ю what Ю ° Ф O Φ oo O O) i — 1 CM CM O tH г — 1 tH CD O t — 1 O t — 1 > N > N > N > N 'X > N > N CD CD Honors * g CD C N CD WHAT Ю O О Ю Ю Ό what O CD г — 1 CD Λί r-i Λ3 O t — 1 г-1 rH . cn i — 1 СЛ vH 4-J > 4-J 4— * -w 4—> 4— ' 4-J

'ω _o Ф о? о? см с ooo

Ό Ю Ю Ό CD

Xi Xi CM wp, 23 ¹ ► ** и · * и>4_>

X) X) X) X3 X3 rQ ХЭ , Q Go X) Ά X) X! x> rá ώ CJ CJ 6 CJ * CJ O CJ CJ * CJ * ω CJ CJ CJ CJ Γ-4 ř-i ř-i ř-l t4 ÍH f-4 ÍH f-l ř- < í-4 ř-l ř-4 Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Ф Ф Ф Ф 4-J 4-J 4-J 4-J 4-J 4-J 4-J 4-J 4-J 4-J 4-J 4-J ^4-1

OOCDOrHCMOO ^ LOCOC ^ COCDO ^ HCMOOXftlOCOt ^ OO гЧг-НСМСМСМСМСМСМСМСМСМСМГОООООСОООСОСООООСО

AND

Table IV (X = N; A = -CH ₂ —C — CH ₂ -) / \

R5 ^ 6

compound no. R1 Rs R _S R ₆ physical constants 39 tert-butyl -C ₆ H ₄ -C 1 (4) CH, CH3.HCl viscous oil '40 target, butyl _-C6 H, -C1 (4) H H mp 55-57 ° C 41 —C ₆ H ₃ —Cl ₂ (2,4) C _C Hz-C1 (4) CH, CH ₃ mp 128-131 ° C 42 —C ₆ H ₄ —F (4) —C _G H ₄ —Cl (4) CH, CH ₃ mp 134-138 ° C

The compounds of formula I may be used alone or together with suitable carriers and / or other additives. Suitable carriers and additives may be solid or liquid and correspond to those commonly used in the preparation of such compositions, such as natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers. The active compounds of the formula I can also be used in admixture, for example with pesticidal agents or with plant growth promoters.

The active compound content of the commercially available formulations ranges from 0.0001 to 90%.

For application, the compounds of formula I may exist in the following processing forms:

Solid forms of processing

Dusts and spreading agents generally contain up to 10% of the active ingredient. For example, a 5% dust may consist of 5 parts of the active ingredient and 95 parts of an additive such as talc. The 2% dust may consist of 2 parts of active ingredient, 1 part of highly disperse silicic acid and 97 parts of talc. In addition, further mixtures are possible with such and other carriers and additives useful in the preparation of such compositions. In the manufacture of these dusts, the active compounds are mixed with these carriers and additives and the mixtures are ground. In this form they can then be applied by dusting.

Granules, such as coated granules, impregnated granules, homogeneous granules and pellets (grains) usually contain 1 to 80% of the active ingredient. Thus, 5%; the granulate may consist, for example, of 5 parts of active ingredient, 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether, 3.50 parts of polyethylene glycol and 91 parts of kaolin (with a preferred particle size of 0.3 to 0.8 mm). The following steps can be taken to produce the granulate:

The active ingredient is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone, followed by addition of polyethylene glycol and cetyl polyglycol. The solution thus obtained is sprayed onto kaolin and then the acetone is evaporated in vacuo. Such microgranules are preferably used to combat soil fungi.

Liquid forms of processing

Generally, a distinction is made between active ingredient concentrates which are water dispersible or soluble and aerosols. Active substance concentrates which are dispersible in water include, for example, wettable powders and pastes which usually contain from 25 to 90% of the active ingredient in a commercial package and from 0.01 to 15% of the active ingredient in ready-to-use solutions. The emulsion concentrates contain 10 to 50% and the concentrated solutions contain 0.0001 to 20% active ingredient in a ready-to-use solution. Thus, a 70% wettable powder may consist, for example, of 70 parts of the active ingredient, 5 parts of sodium dibutylnaphthylsulfonate, 3 parts of a naphthalenesulfonic acid condensation product, phenosulfonic acids and formaldehyde (3: 2: 1 ratio), 10 parts of kaolin and 12 parts of chalk. Champagne). For example, a 40% wettable powder may consist of the following components: 40 parts of active ingredient, 5 parts of sodium ligninsulfonic acid, 1 part of dibutylnaphthalenesulfonic acid sodium and 54 parts of diatomaceous earth. The production of 25% wettable powder can be carried out in various ways. Thus, it may consist, for example, of the following components: 25 parts of active ingredient, 4.5 parts of lignin sulphonic acid calcium salt, 1.9 parts of chalk (provenance Champagne) and hydroxyethylene cellulose (1: 1), 1.5 parts of sodium dibutylnaphthalenesulfonate, 5 parts of silicic acid, 19.5 parts of chalk (provenance of Champagne) and 28.1 parts of kaolin, 25% wettable powder may also consist, for example, of 25 parts of active ingredient, 2.5 parts of isooctylphenoxypolyoxyethyleneethanol, 1.7 parts of chalk mixture (provenance) Champagne) and hydroxyethylcellulose (1: 1), 8.3 parts of sodium silicate, 16.5 parts of diatomaceous earth and 46 parts of kaolin. A 10% wettable powder can be made, for example, from 10 parts of active ingredient, 3 parts of a mixture of sodium salts of saturated sulfonated fatty alcohols, 5 parts of a naphthalenesulfonic acid-formaldehyde condensation product and 82 parts of kao214809 liner. Other wettable powders may be mixtures. composed of 5 to 30% active ingredient together with 5 parts absorbent carrier material such as silicic acid, 55 to 80 parts carrier material such as kaolin, and a dispersant mixture consisting of 6 parts sodium aryl sulfonate and 5 parts alkylaryl polyglycolpther. The 25% emulsion concentrate may contain, for example, the following emulsifiable substances: 25 parts of active ingredient, 2.5 parts of epoxidized vegetable oil, 10 parts of an alkylarylsulfonate mixture, and. a polyglycol ether of a fatty alcohol, 5 parts of dimethylformamide and 57.5 parts of xylene.

Emulsions of the desired active compound concentration, which are particularly suitable for application to plant leaves, can be prepared from such concentrates by dilution with water. In addition, other wettable powders can be produced with others. relative to each other or with. other carriers and additives useful in the preparation of such compositions. The active ingredients are intimately mixed in suitable mixing with the mentioned ingredients and the resulting mixtures are ground in appropriate mills and rollers. A wettable powder having excellent wettability and suspendability is obtained, which can be diluted with water to suspensions of the desired concentration which can be used in particular for application to plant leaves. Such compositions are also within the scope of this invention.

Surprisingly, it has been found that the compounds of formula I have a very favorable spectrum of microbicidal effects for the protection of crop plants for practical requirements. The crop plants within the scope of the invention are, for example: cereals (wheat, barley, rye, oats, rice); beet (sugar beet and fodder beet); fruit trees with fruits that have stones, kernels, and berries (apple, pear, plum, peach; almond, cherry, strawberry, raspberry, blackberry); legumes (beans, lentils, peas, soybeans); oilseeds (rape, mustard, poppy, olive, sunflower, coconut, castor oil, cacao, groundnut); cucurbits (gourd, cucumbers, melons); fibrous plants (cotton, flax, hemp, jute); citrus plants (orange, lemon, biggest lemon, tangerine); various vegetables (spinach, lettuce, asparagus, different types of brassica, carrots, onions, tomatoes, potatoes, peppers) or plants such as corn, tobacco, walnuts, coffee trees, tea trees, sugar cane, grapevine, hops, banana trees and rubber trees, as well as ornamental plants.

The active compounds of the formula I can destroy or suppress the occurring fungi on the plants or on parts of plants (fruits, flowers, leaves, stems, tubers, roots) of the abovementioned and related crop plants, while remaining protected from such fungi and later grown parts plant. The active substances are active against phytopathogenic fungi belonging to the following classes:

Ascomycetes (e.g., Erysiphaceae, Fusarium, Ilelminthosporium, Venturia, Podosphaera); Basidiomycetes, such as in particular rust fungi (e.g. Puccinia, Tilletia, Hemileia); Fungi imperfecti (for example Moniliales et al., Cercospora, as well as Botrytis and Verticillium) and Oomycetes belonging to the Phycomycetes class.

In addition, the compounds of formula I act systemically. They can also be used as mordants for the treatment of seed (fruits, tubers, grains) and plant seedlings to protect against fungal infections as well as against phytopathogenic fungi that occur in the soil.

The invention furthermore relates to the use of the compounds of the formula I for combating phytopathogenic microorganisms and possibly for preventing plant infestations.

Examples illustrating biological activity

Example 5

Action against mildew (Erysiphe graminis) on barley

a) Residual - protective effect

About 8 cm high barley plants are sprayed with a suspension of the active ingredient which has been prepared from a wettable. powder, and which contained 0.02% active ingredient. After 3-4 hours, the treated plants are dusted with conidia of the fungus. Infected barley plants are placed in a greenhouse at a temperature of about 22 ° C and after 10 days the fungal infestation is assessed.

b) Systemic effect

Barley plants of about 8 cm in height are covered with a suspension prepared from a wettable powder containing 0.006% of active ingredient by volume of soil. Care is taken that the suspension does not come into contact with the aerial parts of the plants. After 48 hours, the treated plants are dusted with conidia of the fungus. Infected barley plants are placed in a greenhouse at about 22 ° C and after 10 days the fungal infestation is assessed.

The compounds shown in Tables I to IV show good fungicidal activity against Erysiphe in the above experiments. Thus, among other things, compounds # 1, 3, 7, 8, 10, 11, 13, 17, 18, 19, 20, 21, 22, 24, 25, 26, 28, 29, 30, 31, 32, 33, 34, 35, 36, 39, 40, and 42 infestation at: 0 to 20% / o and compound number 1 *, 3 *, 7 *, 8 *, 10 *, 11, 13 *, 16, 18 * 19 *, 20 *, 11 *, 12 *, 24 *, 15 *, 26 *, 28 *, 19 *, 10 *, 31 *, 32 *, 33 *, 14 *, 15 *, 36 *, 19 * , 10 * and 42 to 0 to 5 ° / o, with the compounds marked (*) · completely suppressing fungal attack also at the test concentration of 0.02 ·%. Untreated, however, compounds labeled with (*) suppress infected control plants show fungal infestation of 100%.

Example 6

Effect against rust (Puccinia graminis) on wheat and (Residual - protective effect

Wheat plants take 6 days. after sowing, they spray a suspension made of wettable powder containing 0.06. %' active substance. After 24 hours, the treated plants are infected with a fungal uredospore suspension. After incubation for 48 hours at 95-100% relative humidity and about 20 ° C, the infected plants are placed in a greenhouse at about 22 ° C. Assessment of rust development is performed 12 days after infection.

b] Systemic effect

Wheat plants are flooded 5 days after sowing with an active ingredient suspension prepared from wettable powder in an amount corresponding to 0.006% active ingredient based on soil volume. After 48 hours, the treated plants are infected with a fungal uredospore suspension. After incubation for 48 hours at 95 to 100% relative humidity and about 20 ° C, the infected plants are placed in a greenhouse where they are stored at about 22 ° C. An assessment of rust development is made 12 days after infection.

The compounds shown in Tables I to IV exhibit the above. described experiments good fungicidal activity against the fungus Puccinia. Thus, among other things, compounds No. 1, 3, 7, 8, 10, 11, 13, 18, 19, 20, 21, 22, .24, 25, 26, 28, 29, 30, 31, 32, 34, 35, 36, 39, and 40 suppress fungal infestation to 0-20% and compounds 1 *, 3 *, 7 *, 8 *, 10, 13 *, respectively. 18, 19 *, 20, 21, 22, 24, 16 *, 28 *, 30 *, 31, 34 *, 35 *, 36, 19 *, and 40 * to 0 to 5%, respectively. marked (* j) also completely suppress fungal infestation at a test concentration of 0.02%. Treated but infected control plants show 100% fungal infestation.

Example 1 a d 7

Activity against Cercospora arachidicola on groundnut plants

Residual protective effect

Peanuts about 10 to 15 cm high are sprayed with an active ingredient suspension prepared from a wettable powder and containing 0.02% active ingredient. After 48 hours, the plants are infected with a conidia suspension of the fungus. The infected plants are then incubated for 72 hours at a temperature of about 21 ° C and at high relative humidity and then. are placed in a greenhouse where they are kept until the typical spots on the leaves. Assessment of the fungicidal effect is performed 12 days after infection and is based on the number and size of the spots occurring.

The compounds of Tables I to IV exhibit good fungicidal activity against Cercospora as described above. Thus, compounds 1 *, 7 *, 8, 18, 10 *, 22, 16 * and 15 * cause, among other things, suppression of 0-20% malignancy and compounds 1, 7, 18, 20, 22, 26 and 35 suppress fungal infestation to 0 to 5%, with the compounds labeled (*) also showing this effect at a test concentration of 0.006%. Untreated but infected control plants show fungal infestation 100%.

Example 8

Effect against apple scab (Venturia inaequalis) on apple tree

Residual protective effect

Apple seedlings with about 5 leaves developed are sprayed with an active ingredient suspension prepared from a wettable powder and containing 0.06% active ingredient. After 24 hours, the treated plants are infected with a conidia suspension of the fungus. . The plants are then incubated for 5 days at 90-100% relative humidity and then placed in a greenhouse at 20-24 ° C for a further 10 days. Scab infestation is evaluated 15 days after infection.

The compounds of Tables I to IV exhibit anti-fungal activity in the above-described experiment. Venturia good fungicidal effect. Thus, compounds 1, 3, 7, 10, 16, 19, 22, 26, 28, 29, 30, 31, 32, 33, 34, 35, 36, 39, and 41 cause fungal infestation to 0 ^: up to 20% and compounds No. 1, 1 *, 1 *, 10, 16 *, 19 *, 29, 30, 32 and 15 * to 0 to 5%, with compounds marked with (*) completely suppressing fungal infestation even when test concentration 0.02%. Untreated but infected control plants show 100% infestation.

Claims (2)

A fungicidal composition, characterized in that it contains at least one compound of the formula I as active ingredient. - C - in which it means R 1 is a tert-butyl group or an optionally mono- or double-substituted phenyl group and a R _{2 is} optionally 1 to 3 halogen atoms, C 1 -C 2 alkyl, methoxy, cyano, nitro and / or phenoxy substituted phenyl or diphenyl, and A is -CH-CH- R3 is R * or a group -CH ₂ -C-CH ₂ -, Rs Re in which R 3, R 4, R 5 and R ₆ are each independently hydrogen, (C 1 -C 6) alkyl, (C 1 -C 6) alkoxymethyl, or phenoxymethyl; or R 3 and R 4 together represent a tetramethylene group, and X is CH or N, or a plant-tolerable salt thereof with inorganic or organic acids, or a complex thereof with metals, together with one or more carriers. 2. A process for the preparation of an active ingredient according to claim 1, which comprises: C-CH-OR 2 H 2 ^O XaZ (II I in which R b R 2 and A are as defined in formula Ia Hal is halogen, reacts with a compound of formula III, (III) wherein X is as defined in formula I and Me is hydrogen or a metal cation.