DD152901A5 - AZOLYLKETALS AS MICROBICIDES - Google Patents

Abstract

Novel compounds of formula I defined herein are described which have valuable microbicidal properties. They can be used to combat phytopathogenic microorganisms, in particular against phytopathogenic fungi. Thus, the compounds of formula I have a very favorable for practical needs curative and preventive Wirkg.zum to protect Kulturpfl, without affecting them by unwanted side effects. They can be used in practice alone or in the form of pesticides.

Description

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Azoljrlketals as microbicides

Field of application of the invention

The invention relates to the use of new Azolylketale as microbicides and processes for their preparation.

Characteristic of the known technical solution

There are a number of known Hikrobiziden. However, these always have the risk of resistance after a certain period of use.

Object of the invention

Because of the emerging resistance to microbicides, new substances with microbicidal properties are constantly being sought. The aim of the invention is therefore the search for new microbial substances and processes in their production,

Loan of the invention

The present invention "relates Azolylketale of formula I.

, · = 11

(D

including their plant tolerated salts with inorganic or organic acids and metal complexes,

wherein R-j tertiary butyl or optionally mono- or di-substituted by halogen phenyl and

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R? optionally substituted by 1 to 3 halogen atoms, C.-C ₂ alkyl, methoxy, cyano, HITRO and / or phenoxy-substituted phenyl or biphenyl, and

A stands for -CH CH- or - CHg- -Ρς · -CH ₂ -,

• 3 4 5 6

in which R, R, R ₁ and R 'independently of one another are hydrogen,

0, -Cg-alkyl, C ^ -Cg-alkoxymethyl or phenoxymethyl or

Ro and R, together denote tetramethylene and j 4 ·

X stands for CH or IJ »

Alkyl or alkyl moiety of another substituent, depending on the number of carbon atoms given, are understood as meaning the following groups: methyl, ethyl, propyl, butyl, pentyl or hexyl and their isomers (such as isopropyl, isobutyl, sec, butyl, tert. Butyl, iso-pentyl, etc.)

Halogen is eluor, chlorine, bromine or iodine.

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

Metal complexes of formula I consist of the underlying organic molecule and an inorganic Lietall salt, z, B, halides, nitrates, sulfates, phosphates, tartrates, etc. of copper, hangans, iron, zinc and other metals present to them. - "?: ..:

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Hit these various exemplary lists is not limited.

Compounds of the formula I are very valuable active substances against plant-derived hog microorganisms.

A preferred subgroup of active fungicides are those compounds of formula I wherein R is tertiarybutyl or optionally phenyl mono- or di-substituted by fluorine or chlorine and R _{2 is} optionally phenyl or diphenyl substituted by 1 to 2 halogen atoms and A is -CH - GH - or -OH ₀ - ^ It-CH ₀ - stands,

3 4 -56

in which R, R, R, and R independently of one another are hydrogen, C 1 -C 4 -alkyl, methoxymethyl or phenoxymethyl or R 1 and R 2 together are tetramethylene and X is GH or IT »

Another subgroup of active fungicides are those compounds of the formula I in which R 1 is tert-butyl or 2,4-dichlorophenyl, R p is a phenyl radical which is unsubstituted or substituted by methyl, chlorine, llethoxy, cyano or phenoxy, and R 1 and R 2. together form a tetramethylene bridge

A further subgroup,.: Effective fungicides are those compounds of the formula I in which R- is tert-butyl or 2,4-dichlorophenyl, Rp represents a phenyl radical which is optionally substituted by methyl, chlorine, hethoxy, cyano or phenoxy, and A is GH (R ₃ ) -CH (R 1) - where R _{5 is} hydrogen and R is C 1 -C 4 alkoxyethyl or phenoxymethyl

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among the possible alkoxymethyl side chains, the G-j-C 1-4 alkoxymethyl groups are preferred

A preferred subset of effective fungicides consists of those compounds of formula I in which IL is tertiary butyl or 2,4-dichlorophenyl, IU is a phenyl radical mono- or di-chloro-substituted, A is optionally C-, -G. Forms alkylene or hethoxymethyl substituted ethylene bridge and X is G ¹ H or 1.

However, particular preference is given to those fungicides which obey the formula I in which R is tert-butyl, Rp is a phenyl radical which is monosubstituted or disubstituted by chlorine, A is an ethylene bridge and X is CH or IT,

The following individual compounds are particularly preferred:

2-tert-butyl-2-ri- (4-chlorophenoxy) -l- (l, 2,4 ~ triazol-l-YLJ-methyl-1,3-dioxolane

2-Tertiarybutyl-2- [1- (4-chlorophenoxy) -l- (imidasol-1-yl) J -methyl-1,3-diosolan

2-tertiarybutyl ~ 2- Γΐ- (phenoxy) -1- (1, 2 _K 4-triazol-1-yl) j -methyl- "1,3-dioxolane

2-Ethylbutyl-2- [1- (4-fluorophenoxy) -1- (1,2,4-triazol-1-yl) -methyl-1,3-dioxolane

2- (2,4-Diclilo-phenyl) -2-Ll- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) -methoxy-1,3-dioxolane

2-tert-butyl-2- [l- (2,4-dichlorophenoxy) -1- (1,2,4-triazol-lyl) J-methyl ~ 1,3-diozola.n,

The compounds of the formula I are prepared according to a further subject of the present invention by a

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Compound of the formula II

C CH-O-R

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(II)

with a compound of formula III

where R 1, Rp, X and A have the meanings given under formula I, Hal is halogen, preferably chlorine or bromine and Me is hydrogen or a metal cation, preferably an alkali metal or alkaline earth metal cation (eg potassium or sodium) stand.

If appropriate, the process is carried out in the presence of aprotic polar solvents which are inert toward the reactants. Examples of such solvents are acetonitrile, dimethylsulfoxide, dimethylformamide, dimethylacetamide, hexaethylethylphosphoric triamide or sulfolanes

In the cases where v / o in the formula (HI) He is hydrogen, the process is carried out in the presence of a base. Examples of such bases are inorganic bases such as the oxides, hydroxides, hydrides, carbonates and hydrogen carbonates of alkali and alkaline earth metals and z , B. tert amines such as triethylamine, triethylenediamine, pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine and diazabicyclooctane

The process is carried out at temperatures between O and 150 C and at IJorraaldruck.

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The starting ketals of formula II are prepared by

a) a compound of formula IV

(IV)

with a diol of the formula V.

HO-A-OH (V)

in the presence of an acid and.

b) the ketal of the formula VI thus obtained. ,

R is -C-CH ₀ -O-IU (VI)

¹ / \ ^{2 2} 0 0

halogenated.

Inert solvents are used with the reactants, such as, for example, hydrocarbons such as benzene, toluene, and halogenated hydrocarbons (carbon tetrachloride, chloroform, dichloromethane, dichloroethane, etc.) or halogenated hydrocarbons (carbon tetrachloride, chloroform, for reaction b) , Methylene chloride, etc.), diethyl ether, tetrahydrofuran, dioxane, etc.

As acids in the process a) come z. B. Llineralsäuren such as HBr, IiCl and H ₉ SO. and p-toluenesulfonic acid and boron trifluoride etherate in question,

Suitable halogenating agents in process b) are, for example, chlorine, sulfuryl chloride, bromine or IT brorosuccinimide, it being possible to use H-bromosuccinimide or chlorine,

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Catalysts (ζ. Β. Light, "peroxide such as dibenzoyl peroxide or Q & ," θ £ "'-Azoiso-butyronitrile) can be used.

The reaction temperatures are in sub-step a) to 150 C, which is advantageously carried out with a water. In the process b), the reaction temperatures range from 0 ° to 100 ⁰ C, preferably 35 ° to 70 ⁰ C. The traversing · ensschritte a) and b) of the ketalization and the halogenation of the pinacolin ether IV (R, = tert-butyl ) to intermediates of the formulas VI and II represent an independent further aspect of the present invention. This aspect is also an independent method for the preparation of Pinakolinätherketalen of formula VI and of halogenated ketals of formula II,

The ketones of formula I formally underlying ketones are in some cases by De-OS 2,325,156; 2,705,676; DE-AS 2,201,063 and DE-OS 2,705,678 become known. However, they can not be used as starting materials for the process steps described here.

The following examples serve to illustrate the invention in more detail without restricting it. Temperatures are given in degrees Centigrade, pressures in millibars. Percentages and parts are by weight

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EMBODIMENT EXAMPLE 1 Example 1;

Preparation of 2-tert-butyl-2-il- (4-chlorophenoxy) -1- (1,2,4-triazol-1-yl) J-methyl-1,3-dioxolane of the formula

CH ₃ CH - C - V - CH - O - f. O ^ - - ^oil (Verb.Hr.18)

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

CH ₃ OO 'y

CH, - C - ^N C ^ CHp-O- ^ O

40 g of 4-chlorophenoxypinacoline were refluxed with 17 g of ethylene glycol with the addition of 0.2 g of p-toluenesulfonic acid in 300 ml of toluene over 30 hours on a water separator. The cooled toluene solution was washed successively with dilute bicarbonate solution and water, dried with sodium sulfate, filtered and concentrated in vacuo. The crystals thus obtained were crystallized from petroleum ether to give 35 · g of the intermediate product, mp. 68 - 70 ⁰ C.

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

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CH ₃

- ο ¥ - CH -0- · '* - *. -Cl

CH ₃ Br> v ~ /

24 g of 4-Chlorphenoxypinakolin-äthylenketals of step a) were dissolved in 150 ml of carbon tetrachloride · At 40 - - '50 C was slowly added dropwise about 16 g of bromine. ITach 15 hours of stirring at this temperature, the bromine was consumed, laughing cooling, the carbon tetrachloride solution was washed with dilute bicarbonate solution, dried and concentrated · The residue from petroleum ether 18 g of product of mp. 118 - 120 ⁰ C.

c) end product.

3 g of 1,2,4-triazole and 2 g of 55 % ITatriumhydridsuspension in paraffin oil were combined in absolute dimethylformamide. After completion of the hydrogen evolution was continued for 1 hour at 80 - 10.0 ⁰ C stirred. (4-chlorophenoxy) -1-bromJ-methyl-1,3-dioxolane are added dropwise in dimethylformamide and the reaction mixture for 18 hours at 100 - - then 11g), 2-tert-butyl-2- [1 stirred 120 ⁰ C · The solvent. was removed in vacuo and the oily residue taken up in ether, washed with water, dried, filtered and evaporated. After evaporation, 8 g of a viscous oil were obtained from the ether solution, which was purified by chromatography on a silica gel column. In this way, colorless crystals of compound ITr were obtained. 18 with mp 103-105 ⁰ C.

Example 2:

Preparation of 2-tertiary-butyl-2- [1- (4-chloro-plienosyl) -1- (imidasol-1-yl) -J-methyl-1,3-dioxolane of the forms!

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Ch ₃ ο o. y \

G --Λο <CH- 0 - .. ^ O \ -Cl (Verb.Hr.1)

f! Il

Final product.,

3 g of imidazole and 2 g of 55% ITatriumhydridsuspension in paraffin oil were combined in absolute dimethylformamide lach ended hydrogen evolution was stirred for 1 hr. At 80 - 100 ⁰ C stirred. Then 11 g of 2-tert-butyl-2-ΊΊ - (4-chlorophenoxy) -l-bromo-methyl-1,3-dioxolane in dimethylformamide were added dropwise and the reaction mixture was stirred for 18 hrs. At 100-120 ⁰ C The solvent was removed in vacuo and the oily residue was taken up in ether, washed with water, dried, filtered and evaporated. From the ether solution after evaporation, 9 g of a viscous oil were obtained, which after recrystallization from hexane led to colorless crystals of compound No. 1. Snip, 102-104 ⁰ C.

example 3:

Preparation of 2- (2,4-dichlorophenyl) -2- [i- (4-chlorophenoxy) -1- (1j2,4-triazol-1-yl) J-methyl-1,3-dioxolane of the formula

.-. ^x O ~ J

"Il

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a) Preparation of 2- (2,4-dichlorophenyl) -2- [i- (4-chloro-phenoxy) J-methyl-1,3-dioxolane of the formula

Gl ί 1 · - ·

A mixture of 54 g of α- (p-chlorophenoxy) -2,4-dichloroacetophenone, 20 ml of ethylene glycol and 2 g of p-toluenesulfonic acid in 400 ml of toluene was refluxed on a water separator. After 10 hours, the reaction mixture was cooled to room temperature, washed once with ITatriumbicarbonatlösung and twice with water, the toluene phase separated, dried over sodium sulfate and concentrated. 61 g of a pale yellow, viscous oil were obtained.

b) Preparation of 2- (2,4-dichlorophenyl) -2 - ([1- (4-chlorophenoxy) -1-bromo-methyl-1,3-diol: olane of the formula

-f \ -Cl

100 g of 2- (2,4-dichlorophenyl) -2- |] l- (4-chlorophenoxy) J-niethyl-1,3 ~ dioxolan vairden in 400 ml of absolute dioxane and allowed 46 g (70 ⁰ G 15 ml) add bromine while stirring. After 5 hours, the reaction mixture was cooled to room temperature and poured into 2 liters of ice-water, the latter containing 20 g of IT sodium bicarbonate.

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extracted with dichloromethane, the organic phase washed with aqueous sodium bicarbonate solution and dried over sodium sulfate. This gave 130 g of a brown oil which was taken up in 500 ml of hexane. From this solution, 73 g of beige-colored crystals differed from the mp. .100 - 104 ⁰ G from.

c) end product *

To a solution of 77 g of 2- (2,4-dichlorophenyl) -2-di- (4-chlorophenosyl) -1-bromo-methyl-1,3-dioxolane in 500 ml of absolute dimethylformamide, 37 g of 1.2 g were obtained, 4-triasol potassium was added and the reaction mixture was stirred at 100 ° C for 15 hours. · Kach Removal of the dimethylformamide in vacuo, the brown residue was extracted with water and hexane / dichloromethane (8: 2 parts by volume). The organic extracts were dried over sodium sulfate and concentrated to give 62 g of a dark brown oil which, after purification with an alumina (activity 2-3) column, gave 30 g of a yellowish crystalline mass of compound Hr, 35 of mp 104. 107 ⁰ G revealed

Example 4 t, -.- .. '

Preparation of 2-tert-butyl-2-yl- (2,4-dichlorophenoxy) -1- (T, 2, 4-triazol-1-yl) J-methyl-1,3-dioxolane of the formula '

GH ₃ OO Cl

OH ₃ / Ϊ _Ν

Ν (Verb.lTr.26)

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a) Preparation of 2-tert-butyl-2- | i- (2,4-dichloropheno: xy)] ~ methyl-1,3-dioxolane of the formula

Cl

CH ₂ -O-Γ, -Cl

50 g of 2,4-Dichlorphenoxypinakolin were heated with 20 g of ethylene glycol and 0.5 g of p-toluenesulfonic acid in 300 ml of toluene for 24 hours am.Wasserabscheider under reflux. The cooled to room temperature solution was washed with aqueous sodium bicarbonate solution and then with water, with Dried sodium sulfate and concentrated in vacuo · There were obtained 55 g of colorless crystals of Smt>, 61-63 ⁰ C.

b) Preparation of 2-tertiarybutyl-2- | i- (2,4-dichlorophenoxy) -1-bromo-methyl-1,3-diosolan the Pormel

O ο ¹ CH - - O- • - .-Cl \. I Br N = / G -

V3 C -

CHO

200 g of the 2,4-Dichlorphenoxypinakoldnethylenketals prepared according to a) were dissolved in 900 ml of absolute dioxane and treated at 40 - 50 ⁰ C dropwise with 105 g of bromine with stirring. Each 4 hours of stirring, the bromine was consumed. The mixture was stirred for a further 1 hour and then entered the reaction solution in 5 liters of ice water, the latter containing 50 g of sodium bicarbonate. The precipitated crystals were filtered off with suction, dried and recrystallized from hexane.

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sierto

This gave 130 g of colorless crystals of mp. 99-102 ° C.

c) end product ·

A solution of 15 g of 1,2,4-triazole potassium in 250 ml of dimethyl sulfoxide was treated with 38.5S 2-tert-butyl-2- | j- (2,4-dichloropienoxy) -1-bromo-1-methyl-1 , 3-dioxolane and stirred at 100 ⁰ C for 15 hours. Then, the reaction solution was cooled to room temperature and poured into water. The resulting brown oil was extracted with diethyl ether, dried over sodium sulfate and purified with a silica gel column. This gave 17g of a sawing oil, which could be crystallized by the addition of Petrolather. The resulting crystals of the connection Hr. 26 were recrystallized from hexane / diethyl ether and had a mp. From 106 to 108 ⁰ C.

In an analogous manner, the following compounds of the formula I can be prepared:

(D

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Table I R ₁ ^R 1 ? 3 (X = CH; A = -CH - .lh ^E 4 Phys vise • Konst « - 84 ⁰ C -151 ^0G t-butyl t-butyl 15 t -butyl 16 -Cx-H, -CI ₀ oj 2 17 -Cz-H ₄ -F (A R ₂ ^R 3 H m.p. H. 1/2 CuSO ₄ 102-104 ° Verb, t-butyl -C ₆ H ₄ -GK ₄ ) -C ₆ H ₄ -ClU) H H CH ₃ , oil 1 2 t-butyl -C ₆ H ₄ -ClU) CH ₃ C ₃ H ₇ (n) 3 t-butyl -C ₆ H ₄ -CK ₄ ) H -CHgOCH ₃ • 4 t-butyl -C ₆ H ₄ -ClU) H -Chg-GHG-GH, VJL t-butyl -C ₆ H ₄ -GK ₄ ) -CIIg H β t-butyl ο 3 2 , 4) H C ₂ H ₅ vise 7 t-butyl , 4) H .CH ₂ OGH ₃ vise .8th t-butyl -OgH ₃ -Cl ₂ (2, , 4) H H resin • oil 9 t-butyl H C ₂ H ₅ , oil 10 ₆ H ₃ Clg (2 diphenyl H C ₃ H ₇ (n) H 11 6 ^ , 4) -C ₆ H ₄ -GK ₄ ) -C ₆ H ₄ -ClU) - H H H 12 -C 13 -C Table II -Γ ¹ TT -CL ( ? Ο 3 2 , 4) H GH ₉ -) 14 -C (X = CH, A = -CH ₀ -  6 Verb * ur. R ₅ R ^R 5 ^R 6 'Phys. Konst, * 2. H . H CH ₃ CH ₃ CH ₃ CH ₃ Smp ", 82 Smp.150 -C ₆ H ₄ -C 1 (4) (2,4) -O ₆ H ₄ -ClU)) -G ₆ H ₄ -CK 4)

587

Table III (S = IT, A = -CH-CH-)

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Verb.

ITr.

Phys.Ko-nst.

18 't-butyl - -C ₆ H ₄ -ClU) 4). H H. Srnp.1O3-1O5 ^c 19 t-butyl -C ₆ H ₄ -ClC ₄ ) 4) H H. 1 / 2CuSO ₄ Mp. 195-1930 20 t-butyl -C ₆ H, -ClU) 4) H C ₂ H ₅ Smp ₄ 110-115 ^G 21 t-butyl 4) H C ₃ H ₇ Cn) Mp * 90-92 ° 22   t-butyl Γ \ TT / "t * 1 f A \ CH ₃ CH ₃ vise. oil 23 t-butyl -C ₆ H ₄ -Cl (4) H -CH ₂ -O-GH ₃ ^α ηρ 24 t-butyl -G ₆ H ₄ -C 1 C ₄ ) -CH 2-CII ₂ -GII ₂ -CII ₂ - 11 5-1 2CP 25 t-butyl -G ₆ H ₄ -G1C4) 4) H -GH ₂ -OC ₆ H ₅ vise.Öl 26 t-butyl -C ₆ H ₃ -Cl ₂ C ₂ , • Η H M.p., 106- 108 ° 27 t-butyl -C ₆ H ₃ -Cl ₂ C ₂ , H H.1 / 2Mn (N0 ₃ H 28 t-butyl , 4) ο 3 2 - 4) H -C ₂ H ₅ vise. oil 29 t-butyl , 4) -C ₆ H ₃ -Cl ₂ C ₂ , H -CH ₂ -O-GH ₃ resin 30 t-butyl · , 4) - ^C 6 ^H 5 H H vise.Öl 31 t-butyl , 4). -C ₆ H ₄ -FU) H H vise.Öl 32 t-butyl diphenyl H C ₂ H ₅ visc.Öl 33 - ° 6 ^H 5 -C ₆ H ₃ -Cl ₂ C ₂ , H H Mp.129-132 ° 34 -C ₆ H ₄ -P (4) -C ₆ H ₄ -GlU) H H Srap.115-116 ° 35 -C ₆ H ₃ -Gl ₂ (2 -C ₆ H ₄ -ClU) H H Mp.104-107 36 . -O ₆ H ₃ -Cl ₂ (2 -G ₆ H ₃ -Cl ₂ C ₂ , H H Srap.94-97 ° 37 -C ₆ H ₃ -Cl ₂ C ₂ -G ₆ H ₄ -Cl (4) H -GH ₂ -O-CH ₃ 38 -G ₆ H-Gl ₂ C ₂ -C ₆ H ₄ -ClU) H G ₃ H ₇ Cn)

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TableV (X = IT, A = -CH,

4 \

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Verb,

Mr.

Phys.Konst.

39 t-butyl 40. · t-butyl

41 -O ₆ H ₃ -C 1 ₂ (2,4)

42 -C ₆ H ₄ -P (4)

-Cl (4)

-C / -Η. - C 1 (4) v ^ XJ-o vy ± x-j

-C ₆ H ₄ -C 1 (4) HH

CH 1 CH,

.HCl vise. oil

CH ₃ CH

Smp, 128-131 Smp.134-138 ^c

The compounds of the formula I can be used alone or together with suitable carriers and / or other additives. Suitable carriers and adjuvants can be solid or liquid and correspond to the substances customary in formulation technology, such as, for example, natural or regenerated mineral substances, solvents, dispersants, adhesives, adhesives, thickeners, binders or fertilizers. Active ingredients de2 * formula I can also be used in a mixture with z. B. pesticidal or plant v / uchsverbessernden preparations ·

The content of active substance in marketable agents is between 0.0001 to 90 %.

For application, the compounds of the formula I can be present in the following work-up forms:

Fixed processing fields;

Dust and solids 1. Generally contain up to 10 fj of the active ingredient. For example, a 5% dust may contain

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consist of 5 parts of the active ingredient "and 95 parts of an additive such as talc" or consist of 2 parts of active ingredient, 1 part of fumed silica and 97 parts of talc. In addition, further mixtures with such and other carrier materials and additives commonly used in formulation technology are conceivable. In the production of these dusts, the active ingredients "mixed with the carriers and additives and milled and can be dusted in this form"

Granules such as coating granules, impregnating granules, homogeneous granules and pellets (= grains) usually contain from 1 to 80 % of the active ingredient. Thus, a 5 / iger granules z. B _e from 5 parts of the active ingredient, 0.25 parts of epichlorohydrin, 0.25 parts Cetylpolyglykoläther, 3 »50 parts of polyethylene glycol and 91 parts of kaolin (preferred grain size 0.3-0.8 mm) put together. The following procedure can be followed during the production of the granulate:

The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, then Polyäthyleiiglykol and Cetylpolyglykoläther added. The resulting solution is sprayed on kaolin, and then the acetone is evaporated in vacuo. Such microgranules are advantageously used to control soil fungi.

Liquid workup forms;

A distinction is generally made between active substance concentrates which are dispersible or soluble in water and aerosols. To the water-dispersible active substance concentrates. count z. For example, j5pritζp_uIver (wettable powders) and pastes, commonly used in retail packs 25-90 % and in

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Ready- to-use solutions contain 0.01 to 15 % of the active ingredient, emulsion concentrates contain 10 to 50 % and solution concentrates contain 0.0001 to 20 % of active substance in the ready-to-use solution. So can a 70 pounds Jiges spray powder z. B. from 70 parts of the active ingredient, 5 parts Itfatriumdibutylnaphthylsulfonat, to 3 parts of naphthalenesulfonic - phenolsulfonic - pox-maldehyde condensate (in the mixing ratio 3: 2: 1), 10 parts of kaolin and 12 parts of Champagne chalk be composed. A 40% spray powder can, for. B, consisting of the following substances: 40 parts of active substance, 5 parts of lignosulphonic acid sodium salt, 1 part of dibutylnaphthalenesulphonic acid sodium salt and 54 parts of silicic acid. The preparation of a 25% spattering powder may be carried out in different ways. So this can be z. B. composed of: 25 parts of the active ingredient, 4 »5 parts calcium lignosulfonate, 1.9 parts of chalk chalk / Hydroxyäthylencellulöse mixture 1: 1, 1.5 parts of sodium dibutylnaphthalenesulfonate, 19.5 parts of silica, 19.5 parts of Champagne Chalk and 28.1 parts of kaolin. A 25/5 spray powder can, for example, also be ordered from 25 parts of active ingredient, 2.5 parts of isooctylphenoxy-polyoxyethylene-etlianol, 1.7 parts of 1: 1 Champagne chalk / hydroxyethylcellulose mixture, 8.3 parts of ITatriumsilikat, 16.5 parts Diatomaceous earth and 46 parts kaolin. A 10biges spray powder can be z. B. from 10 parts of Y / irkstoifes, 3 parts of a. Mixture of sodium salts of saturated fatty alcohol sulfonates, 5 parts ITaphthalene sulfonic acid / Pormaldehyd condensate and 82 parts of kaolin. Other fuel powders know mixtures represent from 5 to 30 % of AktivQubstanz together with 5 parts of an absorbent carrier material such as silica, 55 to 80 parts of a carrier material such as kaolin and a Dispersiermittelgemisches consisting of 5 parts iiat.riumarylsulfonates and 5 parts of a Alkylarylpolyglykoläthers. A 25% emulsion formulation

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centrate can z. For example, the following emulsifiable materials include 25 parts of the active ingredient, 2.5 parts of epoxidized vegetable oil, 10 parts of an alkylaryl sulfonate / fatty alcohol polyglycolate mixture. 5 parts of dimethylformamide and 57 parts of xylene.

From such concentrations, emulsions of the desired application concentration which are particularly suitable for foliar application can be prepared by dilution with water. In addition, further wettable powders with different mixing ratios or other carrier materials and additives customary in formulation technology can be prepared. The active ingredients are intimately mixed in appropriate mixers with the additives mentioned and ground on appropriate mills and rollers. This gives wettable powders of excellent wettability and suspension, which can be diluted with water to give suspensions of the desired concentration and can be used in particular for foliar application. Such agents are also part of the invention

It has surprisingly been found that compounds of the structure of the formula I have a very favorable for practical needs Mikrobisid spectrum for the protection of crops. Crop plants are in the context of the present invention, for example:

Cereals: (wheat, barley, rye, oats, rice); Beets: (sugar and fodder beets); Pome, stone and berry fruits: (apple, pears, plums, peaches, almonds, cherries, peanuts, cranberries and blackberries); Legumes: (beans, lentils, peas, soya); Oil crops: (oilseed rape, mustard, sneeze, olives, sunflower, coconut, castor, cocoa, peanuts); Cucumber plants:

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(Pumpkin, cirrus, love); Fiber plants: (cotton, flax, hemp, jute); Citrus fruits: (oranges, lemons, grapefruit, mandarins); Vegetables: (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, peppers) or plants such as corn ,. Tobacco, mead, coffee, tea, sugar cane, vines, hops, banana and Uaturkautschukgewächse and ornamental plants.

With the active compounds of the formula I, the fungi which occur can be contained or destroyed on plants or parts of plants (fruits, flowers, foliage, stems, tubers, roots) of this and related culture, whereby even later-growing parts of plants are spared from such fungi. The active substances are active against the phytopathogenic fungi belonging to the following classes: Ascomycetes (eg Erysiphaseae, Fusarium, Helminthosporium, Venturia, Podosphaera); Basidiomycetes such as, in particular, rust fungi (z, B. Puccinia, Tilletia, Hemileia); Fungi imperfecti (eg lioniiiales and others, Cercospora and Botrytis and Verticillium) and the Phycomycetes belonging to the class of Oomycetes, Moreover, the compounds of formula I systemically. They can also be used as a dressing for the treatment of Fattgut (fruits, .Nuts, grains) and plant cuttings to protect against fungal infections and against occurring in the soil phytopathogenic fungi.

The invention thus further relates to the use of the compounds of the formula I for controlling phytopathogenic Liikroorganismen or for the preventive prevention of infestation of plants.

• Biological examples

587

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Example 5:

Effect g e ^ s Erysi phe graminis f au barley

^a ) Re-Aidual Protective Effect

Barley plants about 8 cm high were sprayed with a spray mixture of active ingredient (0.02 % active ingredient). The treated plants were dusted with conidia of the fungus for 3-4 hours. The infected barley plants were sprayed in a greenhouse at approx. 22 judged.

placed at about 22 ⁰ G and the fungal infection after 10 days

b) Systemic effect

To about «8 cm high barley plants was prepared from a wettable powder of the active ingredient sprayed (0.006 % active substance based on the volume of the earth)» It was ensured that the spray mixture did not come into contact with the above-ground parts of plants, ITach 48 hours were the treated Plants pollinated with conidia of the fungus. The infected barley plants were assessed in a greenhouse at about 22 ⁰ C ι

ca * 22 ⁰ C and the fungal attack after 10 days

Example 6:

Action against Puccinia__ graminis on wheat

a) Re sidual-protective effect

6 days after sowing, wheat plants were sprayed with a spray mixture (0.06 active substance) prepared from spray powder of the active substance. After 24 hours, the treated plants were infected with a uredospore suspension of the fungus. After incubation for 48 hours at 95-100 %

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relative humidity and about 20 ⁰ C, the infected plants were placed in a greenhouse at ca, 22 ⁰ C. The assessment of rust pustule development was made 12 days after infection.

b) Systemic effect

For 5 days after sowing, a spray mixture prepared from wettable powder of the active substance was poured (0.006 % of active substance in relation to the volume of the soil) to seed lances. Efach 43 hours, the treated plants were infected with a Uredosporensuspension of the fungus. After incubation for 48 hours at 95-100 % relative humidity and ca, 20 G, the infected plants were placed in a greenhouse at about 22 ⁰ C. The assessment of rust pustule development was made 12 days after infection.

Example 7: Cercospora arachidicola has an effect on peanut plants Residual-protective effect;

10-15 cm high peanut plants were sprayed with a spray liquor prepared from active ingredient spray (0.02 % active ingredient) and infected 43 hours later with a conidia suspension of the Pilses. The infected plants were \ incubated 7ährend 72 hours at about 21 ⁰ C and high humidity and then placed until the typical leaf spots in a greenhouse · The assessment of the 'fungicidal action is made 12 days after infection based on the number and the magnitude of blecken.

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Example 8:

Wirkun ^ j ^ ay Ve nt uria inaequalis on apple trees Kesidual protective action

Apple seedlings with about 5 developed leaves were sprayed with a syringe made of spray powder of the active ingredient. broth '(0.06 % active substance) sprayed. After 24 hours, the treated plants were infected with a conidia suspension of the fungus. The plants were then incubated for 5 days at 90-100 % relative humidity and placed for 10 additional days in a greenhouse at 20-24 C. Scab infestation was assessed 15 days after infection.

The compounds of formula .1 according to the invention generally showed a good fungicidal activity in the experiments described above. Among other things, the compounds listed below caused an inhibition of infestation to less than 20 % in comparison with untreated but infected (= 100 % infestation) control plants:

In Puccinia graminis: Verb.ITr. 1, 3, 11, 13, 18, 19, 20, 21,

  22, 24, 26, 28, 29, 30, 31, 32, 34, 35, 39.

In Cercospora arachidicola: Verb.ITr. 1, 18, 20, 22, 26, 32, -

35. '

In Erysiphe graminis: Verb.ITr. 1, 3, 11, 13, 17, 18, 19, 20,

21, 22, 24, 25, 26, 28, 29, 30, 31, 32, 33, 34, 35, 36, 39.

21 6 567

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For Venturia inaequalis: Verb.Nr * 1, 3, 13, 18, 19, 20, 21,

22, 25, 26, 28, 29, 30, 31, 32, 33,

34, 35, 39 ·

An inhibition of the infestation to 5 % and less caused the following compounds of the formula I in the above experiments:

For Puccinia graminis: Verb.Hr. 1, 3, 13, 18, 19, 20, 22,

, 26, 28, 29, 30, 31, 35, 39.

In Cercospora arachidicola: Verb.Hr. 1, 18, 20, 22, 26,

For Erysiphe graminis: Verb.Hr. 1, 3, 13 »18, 19, 20, 21, 22,

25, 26, 28, "29, 30, 31, 32, 33, 34, 35, 39.

At Venturia inaequalis: Verb.Hr. 1, 18, 22, 26, 29, 30, 31,

35, 39 ·

Claims (6)

-26- 15.2.1980 AP C 07 D / 216 587 56 395/11 invention claim 1. Pesticides for controlling phytopathogenic microorganisms, characterized in that -es as at least one active component, a compound of formula I. . = IT R ₁ - C - CH - IT I (I) ¹ / VA \ X =. V ^R 2. -. including their plant-compatible salts with inorganic or organic acids and metal complexes, in which R is tert-butyl or optionally mono- or di-substituted by halogen, and Rp is optionally substituted by 1 to 3 halogen atoms, C 1 -C 6 -alkyl, methoxy, cyano, IT-nitro and / or phenoxy substituted phenyl or diphenyl, and represents -CH CH- or -CH ₀ -C CH ₀ -, / V 3 4 5 6 R-, Ή. _Λ Rc π. / · wherein R ^ j R. »Rc and Rr are independently hydrogen, C ₁ -Cg -AllCyI, Cj ^ -Cg alkoxymethyl or Phenoxymetiiyl or R and R together are tetraethylene and X is CH or IT, together with one or more carriers. 2. According to Punlct 1, dadtirch that it is a Verbindimg the Pormel I, wherein R-tert-butyl or optionally once or twice by fluorine or chlorine 216,587 -27- 15.2.1980 AP C 07 D / 21 β 587 56 395/11 substituted phenyl and R _{2 are} optionally substituted by 1 or 2 halogen atoms substituted phenyl or diphenyl, and : .- A is -CH CH- or -CH C ₀ CH ₀ - stands, it 2. / κ έ R-3 R. π ρ ). 3 4 R ₅ R ₆ wherein R ^ i R>, R _r and R ^ - is independently hydrogen, C.-Cο alkyl, methoxymethyl or phenoxymethyl, or R and R together represent tetramethylene and X is CH or N, which contains · 3 · Composition according to item 1, characterized in that it represents a compound of the formula I in which'R _{1 is} tert-butyl or 2,4-chlorophenyl, Rp represents an optionally methyl, chlorine, methoxy, cyano or phenoxy-substituted phenyl radical and R and R together represent a tetramethylene bridge,   , 4 · Composition according to item 1, characterized in that it represents a compound of the formula I in which R- represents tert-butyl or 2,4-dichlorophenyl, R _{0 represents} a phenyl radical which is unsubstituted or substituted by methyl, chlorine, methoxy, cyano or phenoxy, and A represents -CH (R ₃ ) -CH (R.) -, where R is hydrogen and R is C, -C, - alkoxyethyl or phenoxymethyl, contains » Composition according to item 1, characterized in that it is a compound of the formula I in which R 1 is tert-butyl or 2,4-dichlorophenyl, R _{0 is} a phenyl radical which is monosubstituted or disubstituted by chlorine, A is an alkyl radical which is unsubstituted or substituted by , -Cj-alkyl or!. Lethoxymethyl forms substituted ethylene bridge and X is CH or 1Γ contains. - • ar- 2 U 587 β ", means according to item 1, characterized in that it is a compound of formula I according to point 5» wherein R _{1 is} tert-butyl, PL · represents a mono- or di-chloro-substituted phenyl radical, Λ forms an ethylene bridge, and X, CH or IT means j efttfiti. 7. Composition according to item 1, characterized in that it 2 ~ tert-butyl-2- [i- (4-chlorophenoxy) -1- (1, 2,4, -triazol-1-yl) J ~ methyl-1, 3 contains dioxolane. 8. Composition according to item 1, characterized in that it comprises 2-tertiarybutyl-2- [i -] (4-chlorophenosyl) -1- (imidazo1-yl) -1-methyl-1,3-d Contains .ioxolan. 9. Composition according to item 1, characterized in that it contains 2-tert-butyl-2- [i- (phenoxy) -1 - (1,2,4-triazol-1-yl)] methyl-1,3-dioxolane , 10, composition according to item 1, characterized in that it comprises 2-tert-butyl-2-one - (4-fluorophenoxy) -1- (1,2,4-triazol-1-yl) 3-methyl-1,3 contains dioxolane. 11 "Composition according to item 1, characterized in that it contains 2- (2,4-chloro-phenyl) -2- [i- (4-chlorophenyl) -1- (1, 2,4-triazol-1-yl) -j- methyl-1, 3-dioxolane. 12. Composition according to item 1, characterized in that it is 2-tert-butyl-2-L1- (2,4-dichlorophenoxy) -1- (1,2,4-triazol-1-yl) J-methyl-1,3 contains dioxolane, iy _Q Use of compounds of the formula I according to item 1, characterized in that it is used for the control and / or preventive prevention of infestation of phytopathogenic microorganisms. , , 4ty \ use of compounds of. Pormel I after point marked by the fact that connections according to points 2 to 12 are used «