DD259344A5 - MICROBICIDE MEDIUM - Google Patents

Abstract

According to the invention are used as active ingredient in the novel microbicidal agents novel heterocyclic organosilyl compounds of the general formula (I), in which R 1 is hydrogen, C 1 -C 10 -alkyl, C 3 -C 7 -cycloalkyl, phenyl or trimethylsilyl; R 2 is hydrogen or C 1 -C 4 alkyl, or R 1 and R 2 together form a saturated or unsatured ring of 6 carbon atoms; R 3 and R 4 independently of one another are hydrogen, C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy and furthermore R 4 is C 3 -C 7 -cycloalkyl; R5-R12 independently of one another represent hydrogen or C1-C4-alkyl, it also being possible for R8 and R9 together to form a saturated or unsatured ring having 6 carbon atoms; X represents CH 2, oxygen or sulfur, and n and Z independently of one another denote zero or 1, and in the event that Z denotes zero, include their acid addition salts. The new active substances have microbicidal properties and are particularly suitable for controlling phytopathogenic microorganisms. Formula (I)

Description

Field of application of the invention

The present application relates to microbiological agents containing novel heterocyclic organosilyl compounds of formula I below and their acid addition salts. The invention further relates to the preparation of these substances and the use of the active ingredients for controlling harmful microorganisms, in particular phytopathogenic fungi.

Characteristic of the known state of the art

Processes for the preparation of heterocyclic organosilyl compounds having fungicidal activity are described in DE-OS 3215409 and in European Patent Application 148026. However, the fungicidal activity of these compounds has not always proved to be fully satisfactory, particularly when using low concentrations.

Object of the invention

The aim of the invention is the provision of new agents with a favorable microbicide spectrum, which are suitable for controlling fungi and bacteria, in particular pnytopathogenic fungi.

Explanation of the essence of the invention

The invention has for its object to find new compounds which are suitable as active ingredient in microbicidal agents having the desired properties.

According to the invention as active ingredient in the new microbicidal agents compounds of the formula I.

V ^R 12

V ₃ -

fs.

CH - Si - CH - N

O R O I

R ₂ (0) _z 8

applied in which

R _{1 is} hydrogen, C ₁ -C ₁₃ -alkyl, C ₃ -Cr -cycloalkyl, phenyl or trimethylsilyl and R _{2 is} hydrogen or C ₁ -C ₄ -alkyl or

R ₁ and R ₂ together form a saturated or unsaturated ring of 6 carbon atoms; R ₃ and R ₄ independently of one another are hydrogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy and furthermore R _{4 is} Cs-Cr-cycloalkyl; Rs-R ₁₂

independently of one another represent hydrogen or C ₁ -C ₄ -alkyl, where also.

R ₈ and R ₉ together can form a saturated or unsaturated ring of 6 carbon atoms; XfUrCH ₂ , oxygen or sulfur, and η and Z are independently zero or 1, and when Z is zero, include their acid addition salts.

The term alkyl as an independent substituent or as part of a substituent depending on the number of carbon atoms specified, for example, the following groups are to be understood: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl and their isomers such as , As isopropyl, isobutyl, tert-butyl, sec-butyl or isopentyl. C3-C7 cycloalkyl is optionally cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl. As salt formers with compounds of the formula I in which Z is equal to zero, all organic and inorganic acids come into question, provided that they form plant physiologically acceptable salts.

Examples of hydrochloric acids are inorganic acids: hydrohalic acid such as hydrofluoric acid, hydrochloric acid, hydrobromic acid and sulfuric acid, phosphoric acid, phosphoric acid, nitric acid and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, tartaric acid, glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid , Cinnamic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid or 2-acetoxybenzoic acid. These acids are added according to methods known per se to the relevant free compounds of the formula I.

The compounds of the formula I are stable at room temperature. They can be de · on. Agricultural sector or related areas use preventively and curatively for controlling plant-damaging microorganisms, the active compounds of formula I according to the invention are characterized in wide application concentrations by a very good fungicidal action and easy application

 The compounds of the formula I

9-R12

have several centers of asymmetry (*), which can affect the Si atom in addition to the labeled C atoms, depending on the substitution. Due to the chiral groupings, the compounds can be obtained in different stereoisomeric forms which have enantiomeric or diastereomeric structures.

In general, in the preparation of these compounds, a mixture of diastereomers or enantiomers is formed. This can be in the usual way, for. B. split by fractional crystallization of salts with optically active strong acids in the pure optical antipodes. However, it is also possible to produce pure diastereomeric or enantiomeric forms by targeted synthesis. The pure diastereomers and enantiomers may have different biological effects, such as. B. in one form a foliar fungicidal and in the other a soil fungicidal effect in the foreground.

In addition, a gradual difference in activity can occur with the same spectrum of activity.

The present invention relates to all pure enantiomers or diastereomers and their mixtures with one another.

A narrower scope of the invention are compounds of formula Γ

R ₁ -

in which

R _{1 is} hydrogen, C ₁ -C ₁₀ -alkyl, C ₃ -C ₇ -cycloalkyl, phenyl or trimethylsilyl and R _{2 is} hydrogen or C 1 -C ₄ -alkyl or

Ri and R ₂ together form a saturated or unsaturated ring of 6 carbon atoms; R ₃ ', R ₄ ' and R ₅ -R 12 independently represent hydrogen or C ₁ -C ₄ -A ^ yI, wherein also R ₈ and Rg together can form a saturated or unsaturated ring having 6 carbon atoms; X is CH ₂ , oxygen or sulfur and

η and Z are independently zero or 1,

and when Z is zero, include their acid addition salts.

Due to their pronounced microbicidal activity, the following substance groups, including their acid addition salts, are preferred.

Group la:

Compounds of the formula Γ in which

R _{1 is} Cy-C ₄ -alkyl or trimethylsilyl,

R _{2 is} hydrogen, methyl or ethyl, or

R ₁ and R ₂ together form a phenyl ring fused in 3,4-position,

R ₃ 'and R ₄ ' independently of one another are methyl or ethyl,

R ₅ , R ₆ , R ₇ and R ₈ independently of one another are hydrogen, methyl or ethyl,

R9-R12 represent hydrogen, or

R ₈ and R ₉ together in the 3,4-position form a fused hexane or phenyl ring, X is CH ₂ , oxygen or sulfur,

η is 1 or zero, and

Z is zero.

Group Ib:

Compounds of the formula Γ in which R _{1 is} isopropyl, tert. Butyl or trimethylsilyl, R _{2 is} hydrogen, or R ₁ and R ₂ together form a phenyl ring fused in the 3,4-position, R ₃ 'and R ₄ ' are methyl,

R ₅ , R ₆ and R ₉ -R ₁₂ are each hydrogen, methyl or R ₃ and R ₉ together in the 3,4-position form a fused hexane or phenyl ring, X is CH ₂ , R ₇ and R _{3 are} independently Oxygen or sulfur, η is 1 or zero and Z is zero.

Group Ic:

Compounds of the formula Γ in which R _{1 is} isopropyl, tert. Butyl or trimethylsilyl, R _{2 is} hydrogen, or R ₁ and R ₂ together form a 3,4-fused phenylene ring, R ₃ 'and R ₄ ' independently of one another methyl, R ₅ , R ₆ and R ₉ -R ₁₂ hydrogen, R ₇ and R ₈ independently of one another represent hydrogen or methyl, or R ₈ and R ₉ together in the 3,4-position form a fused hexane or phenyl ring, X represents CH ₂ , oxygen or sulfur, n 1, and

Z is zero.

Peerid:

Compounds of the formula I in which R _{1 is} C ₁ -C ₄ -alkyl or trimethylsilyl, R _{2 is} hydrogen, methyl or ethyl, or R ₁ and R ₂ together form a phenyl ring fused in the 3,4-position, R ₃ and R ₄ independently of one another represent hydrogen, methyl, ethyl, methoxy or cyclohexyl, R ₅ , R ₆ , R ₇ and R ₈ independently of one another represent hydrogen, methyl or ethyl, R ₉ -Ri _{2 represent} hydrogen, or R ₈ and R ₉ together in 3 , 4-position form a fused hexane or phenyl ring, X is CH ₂ , oxygen or sulfur, η is 1 or zero, and Z is zero.

Preferred individual compounds are:

Group A:

Dimethyl 4-tert-butylbenzyl-2,6-dimethylrnorpholin-4-ylmethyl-silane (Comp.1.1); Dimethyl 4-tert-butylbenzyl-morpholin-4-ylmethyl-silane (Comp 1.5); Dimethyl 4-tert-butylbenzyl-N-piperidinylmethylsilane (Comp.1.6); Dimethyl 4-trimethylsilylbenzyl-N-piperidinylmethyl-silane (Comp.1.15); Dimethyl 4-trirnethylsilylbenzyl-morpholin-4-ylmethyl-silane (Comp.116); Dimethyl 4-trimethylsilylbenzyl-2,6-dimethylmorpholin- (4) ylmethylsilane (Comp 1.17); Dimethyl 4-tert-butylbenzyltetrahydro-1,4-thiazine (4) ylmethylsilane (Comp 1.28); Dimethyl 4-isopropylbenzyltetrahydro-1,4-thiazine-4-ylmethyl-silane (Comp.129); Dimethyl 4-tert-butylbenzyl-N-pyrrolidinylmethyl-silane (Comp 1.30); Dimethyl 4-trimethylsilylbenzyltetrahydro-i, 4-thiazine-4-ylmethylsilane (Comp 1.33); Dimethyl-tert-butylbenzyl-cyclohexane-piperidine-filylmethyl-silane (Comp 2.4); Dimethyl 4-tert-butylbenzyl-benzo [cis -piperidin-1-ylmethyl-silane (Comp 2.5); Dimethyl 4-trimethylsilylbenzylcyclohexa [c] piperidin-1-ylmethylsilane (Comp 2.14); Dimethyl-naphthyl- (2) ylmethyl-2,6-dimethylmorpholin- (4) -ylmethylsilane (Compound 3.1); Dimethyl-naphthyl- (2) ylmethylcyclohexa [c] piperidin-1-ylmethylsilane (Comp.3.8): j

Group B:

cis-dimethyl-4-tert-butylbenzyl-2,6-dimethylmorpholin-4-ylmethylsilane (Comp.137); cis -cyclohexyl-4-tert-butylbenzyl-2,6-dimethylmorpholin-4-ylmethylsilane (Comp 1.44); cis-methoxycyclohexyl- (4-tert-butylbenzyl) -2,6-dimethylmorpholine-4) yl-silane (Comp.146). The novel compounds of the formula I are prepared by reacting 1) in a multistage process a) a compound of the formula II

i :,

Ri 1 \ CH-Hal- (II),

with an alkaline earth metal, preferably magnesium, react and the resulting organometallic compound of the formula

_Rl ζ ^ _CH _ _M _ _Hal , "

* Currently * I

Rs b) with a halosilane compound of formula IV

Ra Ru • Cl-Si-OH-Hal (IV)

and the compound V thus obtained

Ri '(\ CH-Si-CH-

R ₁ ^ ρ CH-Si-CH-Hal (V)

Rs Pw Rs

c) with a heterocyclic amine of formula VI

, y

if appropriate in the presence of an auxiliary base, to give a compound of the formula Ia

R9-R12, R ₇

_CHCH __ / \ _(x) ·

react and this compound, if desired,

d) by oxidation with an oxidizing agent, e.g. H2O2 or peracids, in the compound Ib

R9-R12

_Rl _. / \ R _H - $ i-ΓΗ-NT Vx) (Ib),

transferred;

2) an organometallic compound of formula VII

R · - () -M shark < ^VII >

with a Si-org.anischen compound of formula VIII

Hai-CH-CH $ i

implements.

In the above formulas Il-VIII, the radicals R 1 -R 12 and the symbols η and Z have the meanings given for formula I, M is an alkaline earth metal atom, preferably magnesium, and Hal is halogen, preferably chlorine, bromine or iodine.

The reaction temperatures in process (1) are in the stage (1 a) -80 ° to 8O ⁰ C, preferably -20 ° to 8O ⁰ C, in the stage (1 b) -20 ° to 100 ⁰ C, preferably 0 ° to 40 ° C, in the step (1c) 0 ° to 18O ⁰ C, preferably 20-15O ⁰ C, and in the step (1d) 0 ° to 100 ° C, preferably 0 to 50 ° C. In the method (2) are the reaction temperature at -20 ° to 80 ⁰ C, preferably at 0 to 60 "C. The Verfahrensst'jfen (1 a) and (1 b) may conveniently be carried out in one pot, so that the insulation and purification of the product of formula V is unnecessary.

The auxiliary bases which can be used in process stage (1c) serve as acid acceptors. For this purpose, all customary acid binders, such as tertiary amines, as well as alkali and alkaline earth compounds can be used. Examples of these include the hydroxides, oxides and carbonates de: lithium, sodium, potassium, magnesium, calcium and barium, further basic compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, tribenzylamine, tricyclohexylamine, triamylamine, trihexylamine, ιΝ, Ν-dimethylaniline , N, N-dimethyltoluidine, Ν, Ν-dimethyl-p-aminopyridine, N-methylpyrrolidine, N-methyl-piperidine, N-methylpyrrolidine, N-methylimidazole, N-methyl-pyrrole, N-methylmorpholine, N Methylhexamethyleneimine, pyridine, quinoline, alpha-picoline, β-picoline, isoquinoline, pyrimidine, acridine, Ν, Ν, Ν ', Ν'-tetramethylethylenediamine, Ν, Ν, Ν', Ν'-tetraethylethylenediamine, quinoxaline, N-propyldiisopropylamine , Ν, Ν-dimethylcyclohexylamine, 2,6-lutidine, 2,4-lutidine, triethylenediamine.

It is expedient to use the acid acceptor in an excess or deficit of up to 20%, based on the starting material.

In the process according to the invention, inert solvents and diluents are used in adaptation to the particular reaction conditions. As examples are:

Halogenated hydrocarbons, in particular chlorohydrocarbons, such as tetrachlorethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, chloronaphthalene, dichloromapthalene, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, difluorobenzene, 1,2-dichloroethane, 1,1'-dichloroethane, 1,2-cis Dichloroethylene, chlorobenzene, fluorobenzene, bromobenzene, iodobenzene, dichlorobenzene, dibromobenzene, chlorotoluene, trichlorobenzene; Ethers, such as ethyl propyl ether, methyl tert-butyl ether, n-butyl ethyl ether, di-n-butyl ether, diisobutyl ether, diisomethyl ether, diisopropyl ether, anisole, phenetole, cyclohexylmethyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, thioanisole, dichlorodiethyl ether; Nitrohydrocarbons, such as nitromethane, nitroethane, nitrobenzene, chloronitrobenzene, o-nitrotoluene; Nitriles such as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile, m-chlorobenzonitrile; aliphatic or cycloaliphatic hydrocarbons, such as heptane, pinane, nonane, cymene, gasoline fractions within a boiling point interval of 70 to 19O ⁰ C, cyclohexane, methylcyclohexane, decalin, petroleum ether, hexane, ligroin, trimethylpentane, trimethylpentane, 2,3,3-trimethylpentane, octane ; Esters such as ethyl acetate, acetoacetic ester, isobutyl acetate; Amides, eg formamide, methylformamide, dimethylformamide; Ketones, such as acetone, methyl ethyl ketone, optionally also water. Mixtures of the solvents and diluents mentioned are also suitable.

The salts of the compounds of the formula I where Z is zero are obtained by combining the free amines with the relevant acids, if appropriate in an inert solvent, then removing the solvent by distillation and optionally recrystallizing the residue formed.

It has surprisingly been found that compounds of the formula I have a very favorable for practical needs microbicidal spectrum against fungi and bacteria, especially against phytopathogenic fungi and bacteria. They have very beneficial curative, systemic and especially preventive properties and can be used to protect numerous crops. With the active compounds of the formula I, the occurring pests can be contained or destroyed on plants or on parts of plants (fruits, flowers, foliage, stems, tuberous roots) of different crops, whereby later-growing parts of plants are protected from phytopathogenic microorganisms, such as. As mushrooms, spared. '

As microbicides, the active ingredients of the formula I z. B. against the phytopathogenic fungi belonging to the following classes: Fungi imperfect! (e.g., Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora, and Alternaria); Basidiomycetes (eg the genera Hemileia, Rhizocotonia, Puccinia); In particular, they act against the class of Ascomycetes (eg Venturia, Podosphaera, Erysiphe,

Monilinia, Uncinula). Moreover, the compounds of formula I act systemically. They can also be used as a seed dressing for the treatment of seeds (fruits, tubers, grains) and plant cuttings for the protection of fungal infections and against occurring in the soil phytopathogenic fungi.

The invention thus also relates to pesticides, in particular microbicidal agents, as well as their use in the agricultural sector or related fields.

In addition, the present invention also includes the preparation of these agents, which is characterized by the intimate mixing of the active substance with one or more substances or substance groups described herein. Also included is a method for the treatment of plants which is distinguished by the application of the compounds of the formula I or of the novel agents.

As target cultures for the microbicidal use disclosed herein, for example, the following plant species apply within the scope of this invention: cereals (wheat, barley, rye, oats, rice, sorghum and relatives); Beets (sugar and fodder beets); Pome, stone and berry fruits (apples, pears, plums, peaches, almonds, cherries, peanuts, cranberries and blackberries); Legumes (beans, lentils, peas, soybeans); Oil crops (rape, mustard, poppy, olives, sunflowers, coconut, castor, cocoa, peanuts); Cucumbers (squash, cucumbers, melons); Fiber plants: (cotton, flax, hemp, jute); Citrus fruits (oranges, lemons, grapefruit, mandarins); Vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers); Laurel family (avocado, cinnamonium, camphor) and other plants such as corn, tobacco, nuts, coffee, sugar cane, tea, vines, hops, banana and natural rubber plants and ornamental plants (composites). Active ingredients of the formula I are usually used in the form of compositions and can be added to the surface or plant to be treated simultaneously or successively with further active ingredients. These additional active ingredients may be fertilizers, trace element mediators or other preparations which influence plant growth. However, they may also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, together with optionally further customary in formulation technology excipients, surfactants or other application-promoting additives.

Suitable carriers and additives may be solid or liquid and correspond to the substances useful in formulation technology, such as. As natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

A preferred method for applying an active ingredient of the formula I or an agrochemical agent containing at least one of these active ingredients, in the application to the foliage (foliar application). The number of applications and the application rate depend on the infestation pressure for the corresponding pathogen (mushroom strain). The active compounds of the formula I can also enter the plant via the soil through the root system (systemic action) by tinging the location of the plant with a liquid preparation or introducing the substances into the soil in solid form, eg. B. in the form of granules (soil application). However, the compounds of the formula I can also be applied to seed grains (coating) by either impregnating the grains with a liquid preparation of the active ingredient or coating them with a solid preparation. In addition, other types of application are possible in special cases, such. As the targeted treatment of plant stems or buds.

The compounds of the formula I are used in unchanged form or preferably together with the auxiliaries customary in the formulation formulation. They are z. As to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, by encapsulation in z. B. polymeric substances processed in a known manner. The application methods such as spraying, misting, dusting, scattering, brushing or pouring are chosen in the same way as the type of means according to the desired goals and the given conditions. Cheap application rates are generally at 50g to 5kg of active ingredient (aa) per ha; preferably 100g to 2kg AS / ha, especially at 200g to 600g AS / ha.

The formulations, i. the active substance of formula I and optionally a solid or liquid additive containing agent, preparations or compositions are prepared in a known manner, for. B. by intimately mixing and / or grinding the active compounds with extenders, such as. As with solvents, solid carriers, and optionally surface-active compounds (surfactants).

Suitable solvents are: Aromatic hydrocarbons, preferably fractions C ₃ to C ₁₂ , such as xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or Dioctylphthalat, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as Ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as expoxydated coconut oil or soybean oil; or water.

As solid carriers, z. As for dusts and dispersible powders, natural minerals are generally used, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. As granular, adsorptive granule carriers are porous types such. Pumice, broken brick, sepiolite or bentonite and, as nonsorptive carrier materials z. As calcite or sand in question. In addition, a variety of pre-granulated materials of inorganic or organic nature, such as' in particular dolomite or crushed plant residues, can be used. Particularly advantageous, application-promoting additives, which can lead to a strong reduction in the application rate, are also natural (animal or vegetable) or synthetic phospholipids from the series of cephalins and lecithins, which can be obtained, for example, from soybeans.

Depending on the nature of the active compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also surfactant mixtures.

Suitable anionic surfactants may be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

As soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C10-C22), such as. The Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures, e.g. can be obtained from coconut or tallow oil, called. Furthermore, the fatty acid Methyllaurinsalze be mentioned.

Frequently, however, so-called synthetic surfactants are used, in particular alkanesulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkyl sulfonates.

The fatty alcohol sulfonates or sulfates are generally present as alkali metal, alkaline earth metal or optionally substituted ammonium salts and have an alkyl radical having 8 to 22 carbon atoms, wherein alkyl also includes the alkyl moiety of acyl radicals, for. As the Na or Ca salt of lignin, the Dodecylschwefelsäureesters or a fatty alcohol sulfate mixture prepared from natural fatty acids. This subheading also covers the salts of sulfuric acid esters and sulfonic acids of fatty alcohol ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid residue having 8-22 C atoms. Alkylarylsulfonates are z. As the Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid-formaldehyde condensation product.

Furthermore, corresponding phosphates, e.g. Salts of the phosphoric acid ester of a p-nonylphenol (4-14) -Ethylenoxyd adduct in question. ,

Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols ,

Further suitable nonionic surfactants are the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups of polypropylene glycol, ethylene diaminopolypropylene glycol and alkylpropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol units.

Nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethyleneethanol, polyethylene glycol and octylphenoxypolyethoxyethanol may be mentioned as examples of nonionic surfactants.

Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as the polyoxyethylene sorbitan trioleate.

The cationic surfactants are, above all, quaternary ammonium salts which contain as N-substituents at least one alkyl radical having 8 to 22 C atoms and contain, as further substituents, lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. The stearyltrimethylammonium chloride or the benzyldi (2-chloroethyl) ethylammonium bromide.

Further surfactants commonly used in formulation technology are known to the person skilled in the art or can be used in the relevant,

Specialist literature be taken.

The agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight of active compound of the formula I, from 99.9 to 1% by weight, in particular from 99.8 to 5% by weight. % of a solid or liquid additive and 0 to 25% by weight, especially 0.1 to 25% by weight, of a surfactant.

While merchandise is more likely to be concentrated, the end user typically uses diluted funds.

The compositions may also contain other additives such as stabilizers, defoamers, Viskositätsregul.atoren, binders, adhesives and fertilizers or other agents to achieve special effects.

Agrochemical compositions which contain compounds of the formula I as active component likewise form part of the present invention.

embodiment

The following examples serve to illustrate the invention in more detail; without limiting it. 1. Production Examples Example 1.1: Preparation of

CH,

f ^H 3

J M-CH- - Si - CH- - N C- CH_ - C -if ^N } - CH ₀ - Si - CH ₀ - N

³ ι \ __ / ² I ² \ /

CH ₃ * - 'CH ₃ * - _N

CH,

Dimethyl-4-tert.butylbenzyi-2,6-dimethylmorpholine (4) ylmethylsilan

7.6 g (0.03 M) of dimethyl-4-tert-butylbenzyl-chloromethylsilane are stirred together with 20 ml of 2,6-dimethylmorpholine at 150 ° C overnight. After cooling, the reaction mixture is dissolved in 100 ml of methylene chloride and washed 3 times with water and once with saturated potassium carbonate solution. After drying over sodium sulfate, filtration and concentration, the crude product is distilled under high vacuum. This gives 2.7 g of the title compound with a bp 100-102 ° C / 1.3Pa.

Production of the intermediate

CH ₇ CH,

ι ο. ο

jc j

CH, -C - // ^ j - CH ₀ - Si - CH ₀ Cl

³ ι W ² I ²

CH ₃ CH ₃

Dimethyl-4-tert.butylbenzyl-chloromethyl-silane

1.2 g (0.05 mol) of magnesium turnings are introduced into 20 ml of diethyl ether and admixed with about 1 ml of 4-tert-butylbenzene; It is then heated to boiling, and some iodine crystals are added. After the onset of the reaction, the residual amount of 4-tert-butylbenzyl chloride (totally 10 g [0.055 M] in 80 ml of diethyl ether) is added dropwise so that the temperature is maintained at 25-3O ⁰ C. The reaction mixture is stirred for a further 2 hours at room temperature. Then 7.2 g (0.05M) of chloromethyldimethylchlorosilane in 20 ml of diethyl ether are added dropwise at room temperature and stirring is continued overnight at room temperature. 100 ml of a saturated ammonium chloride solution are added, the organic phase is separated off, diluted with ethyl acetate and washed 3 times with water. The crude intermediate obtained after drying over sodium sulfate, filtering and concentrating on a water-jet vacuum is cooled to 0 ° C. and filtered. This gives 11.2 g (88% dT) of the desired intermediate as a filtrate. For further purification, the product can be distilled on a water jet vacuum (bp 149-150 ° C / 2000 Pa).

As described in the preceding example or according to one of the illustrated methods for the synthesis of the compounds of formula I, the following compounds can be prepared:

Table 1

.1:

R ₁

CH-Si-CH

.R ₇

\ _e

No. Ri R ₂ R ₃ Ru Rs re R ₇ R ₈ X Physics. dates 1.1 1.2 CnH ₉ Ct) C ₁₁ H ₉ Ct) ^; HH CH ₃ C ₂ H ₅ CH ₃ C ₂ H ₅ H H H H CH ₃ CH ₃ CH ₃ CH ₃ O O Sdp.l00-102 ° C (1.3 Pa) 1.3 CuHoCt) H CH ₃ CH ₃ CH ₃ H CH ₃ CH ₃ O 1.4 C ₁ H ₉ Ct) H CH ₃ CH ₃ H CH ₃ CH ₃ CH ₃ O 1.5 1.6 1.7 C ₁ HoCt) C _M H ₉ (t) CuH ₀ Ct) H H H CK ₃ CH ₃ C ₂ Hs CH ₃ CH ₃ C ₂ H ₅ H H Ή H H H K H H H H H O CH ₂ CH ₂ Sdp.lO7-lo8 ° C (4.0 Pa) bp. 92-95 ⁰ C (0.7 Pa). 1.3 CH ₃ CH ₃ CH ₃ CH ₃ H H CH ₃ CH ₃ O 1.9 C ₂ H ₇ Ci) H CH ₃ CH ₃ H H CH ₃ CH ₃ O 1.10 C ₃ H ₇ Ci) H CH ₃ CH ₃ H H H H O 1.11 C ₃ H ₇ Ci) H CH ₃ 'CH ₃ H H H H CH ₂ 1.12 C ₃ H ₇ Ci) H CH ₃ CH ₃ CH ₃ H CH ₃ CH ₃ O 1.13 C ₂ Hs H CH ₃ CH ₃ H H CH ₃ CH ₃ O 1.14 C ₂ H ₅ H CH ₃ CH ₃ H H H H CH ₂ 1.15 1.16 CCHiJ) ₃ Si-CCH ₃ ) 3Si H H CH ₃ CH ₃ CH ₃ CH ₃ H H H H H H H H CH ₂ O Bp. 96-98 ° C (1.3 Pa) Sdp.104-108 ⁰ C (2.6 Pa) 1.17. 1.18 CCH ₃ ) ₃ Si (CH ₃ ) ₃ Si H H CH ₃ C ₂ H ₅ CH ₃ C ₂ H ₅ H H H H CH ₃ CH ₃ CH ₃ CH ₃ O O Sdp.100-102 ⁰ C (2.6 Pa) 1.19 (CHa) ₃ Si H CH ₃ CH ₃ CH ₃ H CH ₃ CH ₃ O 1.20 CuH ₉ Ct) H CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ O 1.21 C ₃ H ₇ Ci) H CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ CH ₃ O 1.22 C ₃ H ₇ Ci) H CH ₃ CH ₃ CH ₃ CH ₃ H H CH ₂ 1.23 CuH ₉ Ct) H CH ₃ CH ₃ CH ₃ CH ₃ H H CH ₂ 1.24 * \ • - / » H CH ₃ CH ₃ H H CH ₃ CH ₃ O

Continuation Table 1

No. Ri • * = · R ₂ R ₁ Ru R ₅ R ₆ R? re X Physics. dates 1.25 CuH ₉ (OC ₃ H ₇ (i) H CH ₃ CH ₃ H H H H CH ₂ 1.26 CuH ₉ Ct) C ₃ H ₇ Ci) H CH ₃ CH ₃ H H CH ₃ CH ₃ 0 1.27 (CH ₃ J ₃ Si H CH ₃ CH ₃ H H H H CH ₂ 1.23 1.29 (CHj) ₃ Si CuH ₉ Ct) H H CH ₃ CH ₃ CH ₃ CH ₃ H H H H H H H H S S Bp.127-13O ° C (.1.3 Pa) 1.30 1.31 CuH, (t) H H CH ₃ CH ₃ CH ₃ CH ₃ H H H H H H H H Bp 88-90 ° C (2.7 Pa) 1:32 CH ₉ (O H CH ₃ CH ₃ H H H H - 1.33 1.34 CuHoCt) H H CH ₃ C ₂ H ₅ CH ₃ C ₂ H ₅ H H · H H H . H H H S S Sdp.120-128 ⁰ C (3.0 Pa) 1:35 (CHi) ₃ Si H C ₂ H ₅ C ₂ H ₅ ' H . H H H 0 1:36 CuH ₉ Ct) H C ₂ H ₅ C ₂ H ₅ H H H H - 1:37 CuH ₉ Ct) H CH ₃ CH ₃ H H CH ₃ * CH ₃ * 0 Bp 120-125 ° C '(11.7 Pa) 1:33 CuH ₉ Ct) K CH ₃ CH ₃ H H CH ₃ * CH ₃ * 0 1:39 CuH ₉ Ct) H H CH ₃ H H CH ₃ CH ₃ 0 1:40 CuH ₉ Ct) H H CH ₃ H H H H CH ₂ 1:41 CuH ₉ Ct) H H CH ₃ H H CH ₃ * CH ₃ - 0 1:42 H H t / \ j H I H H H H CH ₂ 1:43 H H j H j 'v /' H H CH ₃ CH ₃ '0 1:44 H H j H j H H CH ₃ * CH ₃ * 0

Continuation Table 1

No. Ri R ₂ Rb R ₁ , H R ₅ R ₇ R ₃ X Physics. dates 1:45 CuH ₉ Ct) H OCH _{3 t} / \ ί HI t · H H CH ₃ CH ₃ 0 1:46 CuH ₉ Ct) μ OCH ₃ 1 HI • * H H CH ₃ * CH ₃ * 0 1:47 Ci ₁ H ₉ Ct) H OCH ₃ OCH ₃ H H CH ₃ CH ₃ 0 1:48 CuH ^ Ct) H OCH ₃ OCH ₃ H H CH ₃ * CH ₃ * 0 1:49 CuH ₉ Ct) H OCH ₃ OCH ₃ H K H CH ₂

^ CIS isomer

CJ ο O .- ^ CJ CJ Ζ ^ 4 Oil Ό " 33 I 0 <^ * s ι O .-- v U  - · O CJ - * Cu -Ι Γ3 I CJ tr - · ^ _: r- CU. I , -I  30 PL,  ο ι u: • -ι OJ I O , ι ,, οι ο  x _ ^ ι ^ c Oil O < I O I LO CJ I I Cj · * -Ι LO ι-I "^^ LO - LO ι OJ co f- <CM CJ i r ^ Oj OJ O) 33 > dp. I CO dp. * ~ ^ 33 Cu VO CO CO CJ 33 -ι I ro ro C ¹ J CJ CJ CJ "Γ * I ¹ - ' ro I <r -; ro OJ O C ~) CJ P- 1 - 33 ci ₌ •H ₌ ro 33 ^ - |] CJ ο " CJ O) - CJ LJ I I CJ I P ' " ro ro. O-I O 33 'Ο, CJ - 33 OJ O) 53 O 53 - / ^ CJ 33 ι • Η 33 33 = 3 I ο. <Τ ^ [ 33 ro ro OJ CJ I 33 33 CJ CJ ro - I m ο, ro O) CJ CJ U U = 3 -Γ- - · j: = 33 OJ CJ CJ cj: OJ •H q ci ^. I s_ ^ - rs 33 CO I I • 1-1 33 rc ⁼ CO CO ^^ oi ro γ · * = 3 CJ = ρ " CJ CJ = OJ ₌ Ε3 Oil OO qs = OJ Oil = 33 U OJ CSJ ro CJ Oil ο, r ^ ci CJ CJ CJ OJ ΓΟ α JT α CJ CJ ₌ XJ 33 23 y. 33 33 33 U JT CJ CO O CJ OJ <! LO OJ OJ

O N

Il

cj:

C-Jl

Hi CCt

El

Ml ti

YY • Η j *. as ** - G I G I CJ O • -x -T P-! ^ O co ·. <r ei , -ι- • α "C 1 ro : I as SS I I J- -a- I ο ι ro G I CO • G I co egg ,,   ο G I as CJ O. O. CJ - ro CJ CM G I CO -O ο: a: CJ CJ CJ I 3-CII 3-Cll (1.1) ro = υ I co I co I CO I co I co ro G I CM Ό = I ro G I CJ I I ro ro c: ns as I • CO ro O. ^ _- CJ α Ό CJ as Oi CJ I co ₌ ro CJ ro as cj: cj: ro G = ro G ro o ro vn έ as as CJ CJ I co G ro I co CO ro ro ro O O OIL = ro ₌ CM CJ as O CJ CJ CJ CJ ro G Ld Cl U as as CJ ro ro u i ro 2S CJ ro G , - · ro ₌ CJ CJ C-] CJ • CJ ro as G as ro U • HCO ro ΓΟ jj JJ = U ro ro OO co CJ CJ JJ jj as a? U CJ ro ΓΟ jj JJ tr * CJ U No. a: CJ 2.14 (CI fj- CJ CJ σ. a? O CJ co CN <r CM rH , -I -H CO ro O I-CM CM CM C-J CM ro • HCO ro CNl CJ O CNI C-J CM G ro JJ JJ r-H CNl CM r-I CM (CI CM co CM α i-l CX5-I CNl CN)

(D I!

cj:

Table 3

r ^H _3: -OiCH ₂ -R

: h ₃

Verb no. R • - / CH ₃ . " • - CH ₃ ^ • - CH ₃ ⁷ - / • - i \ * / ^N ._. Phys ik. dates ° C / 2.6 Pa 3.1 • - • - • - / '"\ \ /' • - * Bp. 144-150 • - - · ^X CH ₃ ⁰ C / 1.3 Pa • - t CH ₃ / H ₃ Bp. 138-140 ⁰ C / ..2,6 Pa 3.3 • - - 0 ice Bp. 158-162 • - ^N CH ₃ ⁰ C / 1.3 Pa 3.4 t - Bp. 138-142 ⁰ C / 2.6 Pa 3.5 Bp. 134-137 ⁰ C / 2.6 Pa 3.6 Bp. 138-140 ⁰ C / 7.8 Pa 3.7 3.8 Bp. 184-188 3.9 3.10

2. Formulation Examples for Liquid Active Ingredients of the Formula 1 (% = wt .-%)

2.1 Emulsion Concentrates a) b) O Active ingredient from Tables 1-3 25% 40% 50 ° / Calcium dodecylbenzenesulfonate 5% 8th% 6 ° / Castor oil polyethylene glycol ether 5% - - (36 moles of ethylene oxide) Tributylphenoyl polyethylene glycol ether - 12% 4 ° / (30 moles of ethylene oxide) cyclohexanone - 15% 20 ° / xylenes 65% 25% 20 ⁰ A

From such concentrates, emulsions of any desired concentration can be prepared by dilution with water. ;

2.2 solutions a) b) c) d) Foodstuffs Tables 1-3 80% 10% 5% 95 ° -; Ethylene glycol monomethyl ether 20% - _ - Polyethylene glycol MG 400 - 70% - - N-methyl-2-pyrrolidone - 20% - - Epoxidized coconut oil - - 1% 5 ° / Gasoline (boiling limit 160-190 ⁰ C) - - 94% - (MW = molecular weight) The solutions are for use in shape, smallest drop suitable. 2.3 Granules a) b) Active substance from Tables 1-3 ^N 5% 10% kaolin 94% - Highly dispersed silicic acid 1% - Atta pu Ig it - 90%

The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated in vacuo.

2.4 Dusts a) b) Active substance in Tables 1-3 2% 5%

Highly disperse silica 1% 5%

Talc 97% -

Kaolin - 90%

Intimately mixing the excipients with the active ingredient gives ready-to-use dusts. Formulation Examples of Solid Active Ingredients of Formula I (% = Wt.%)

2.5 wettable powder a) b) O Active ingredient from Tables 1-3 25% 50% 75 ° / < Na ligninsulfonate 5% 5% Na lauryl sulfate 3% - 5 ° λ Na Diisobutylnaphthalinsulfonat - 6% 1Q ° / ₍ octylphenol polyethylene glycol ether - 2% - (7-8 moles of ethylene oxide) Highly dispersed silicic acid 5% 10% 10% kaolin 62% 27%

The active ingredient is well mixed with the additives and ground well in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

2.6 Emulsion Concentrate

Active substance from Tables 1-3 10%

Octylphenol polyethylene glycol ether 3%

(4-5 moles of ethylene oxide)

Ca-dodecylbenzenesulfonate 3%

Castor oil polyglycol ether (35 mol 4%

ethylene oxide)

Cyclohexanone 30%

Xylene mixture 50%

From this concentrate emulsions of any desired concentration can be prepared by dilution with water.

a) b) 5% 8 ° / ί 95%

2.7 dusts

Active ingredient from Tables 1-3

talc

Kaolin - 92%

Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding on a suitable mill.

2.8 extruder granules

Active ingredient from Tables 1-3 10%. ,

Na lignosulfonate. 2%

Carboxymethylcellulose 1%

Kaolin 87%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in a stream of air.

2.9 Serving Granules

Active ingredient from Tables 1-3 3%

Polyethylene glycol (MG200) 3%

Kaolin 94%

(MW = molecular weight)

The finely ground active ingredient is applied evenly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

2.10 suspension concentrate 40% Active ingredient from Tables 1-3 10% ethylene glycol 6% nonylphenol (15 moles of ethylene oxide) 10% N-lignin sulfonate 1% Carboxymethylcellulose · 0.2 ° / 37% aqueous formaldehyde solution 0.8 7 < Silicone oil in the form of a 75% aqueous emulsion 32% water

The finely ground active substance is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

3. Biological examples: '

Example 3.1: Action against Puccinia graminis on wheat

a) Residual-protective action

Wheat plants are sprayed 6 days after sowing with a spray mixture prepared from wettable powder of the active ingredient (0.02% active substance). After 24 hours, the treated plants are infected with a Uredosporensuspension of the fungus. 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. The assessment of rust pustule development takes place 12 days after the infection.

b) Systemic effect

For wheat plants, a spray mixture prepared from wettable powder of the active ingredient is poured 5 days after sowing (0.006% of active substance based on the volume of the soil). After 48 hours, the treated plants are infected with a Uredosporensuspension of the fungus. After incubation for 48 hours at 95-100% relative humidity and about 20 ⁰ C, the infected plants are placed in a greenhouse at about 22 ° C. The assessment of rust pustule development is 12 days after infection. ;

Compounds from the tables show good activity against Puccinia fungi. On the other hand, untreated but infected control plants have a Puccinia infestation of 100%. To reduce z. B. Compounds No. 1.1; 1.6; 1.17; 1.28; 2.3; 2.4; 3.3; the Puccinia infestation to a remainder of less than 20%.

Example 3.2: Action against Cercospora arachidicola on peanut plants Residual-protective action

10-15 cm high peanut plants are sprayed with a spray liquor prepared from active ingredient spray (0.02% active ingredient) and infected 48 hours later with a conidia suspension of the fungus. The infected plants are incubated for 72 hours at about 21 ⁰ C and high humidity and then placed until the appearance of the typical leaf spots in a greenhouse. The evaluation of the fungicidal effect takes place 12 days after the infection based on the number and size of the spots occurring.

- 18 - 259

Compared to untreated but infected control plants (number and size of spots = 100%), peanut plants treated with active ingredients from the tables show greatly reduced Cercospora infestation. To prevent z. B. the compounds' no. 1.1; 1.5; 1.6; 1.16; 1.17; 2.3; 2.4; 2.14; 3.5 in the above experiment, the appearance of stains almost completely (0-10%).

Example 3.3: Action against Erysiphae graminis on barley

a) Residual-protective action

Barley plants about 8 cm high are sprayed with a spray mixture (0.02% active substance) prepared from the spray powder of the active substance. After 3-4 hours, the treated plants are pollinated with conidia of the fungus. The infected barley plants are placed in a greenhouse at about 22 ³ C and assessed the fungal infection after 10 days.

b) Systemic effect

To about 8cm high barley plants, a spray mixture prepared from wettable powder of the active ingredient is poured (0.006% active substance based on the volume of the earth). Care was taken to ensure that the spray mixture did not come into contact with the aboveground plant parts. After 48 hours, the treated plants are pollinated with conidia of the fungus. The infected barley plants are placed in a greenhouse at about 22 ° C. and the fungal infestation is assessed after 10 days Compounds from the tables show good activity against Erysiphe mushrooms, whereas untreated but infected control plants have an Erysiphe infestation of 100%. For example, the compounds Nos. 1.1, 1.5, 1.6, 1.15, 1.16, 1.17, 1.28, 1.30, 1.33, 2.1, 2.3, 2.4, 2.5, 2.14, 3.1, 3.5, 3.6, 3.8 inhibit fungal attack on barley to 0 to 5 %.

Example 3.4: Action against Botrytis cinerea on apple fruits

Artificially wounded apes! are treated by dropping a spray mixture prepared from spray powder of the active substance on the injury sites. The treated fruits are then inoculated with a spore suspension of Botrytis cinerea and incubated for one week at high humidity and about 20 ° C.

In the evaluation, the rotted injury sites are counted and derived from the fungicidal action of the test substance. Inter alia, Compound No. 1.1 inhibits; 1.5; 1.16; 1.17; 1.28; 2.4; 2.14; 3.9 the fungal infection (0-5%) compared to untreated control fruit almost completely.

Example 3.5: Action against Pyricularia oryzae on rice plants

a) Residual-protective action

Rice plants are sprayed after two weeks of cultivation with a spray liquor prepared from wettable powder of the active ingredient (0.05% active substance). After 48 hours, the treated plants are infected with a conidia suspension of the fungus. After 5 days incubation at 95-100% relative humidity and 24 ⁰ C, the fungal infection is assessed.

b) Systemic effect

Rice plants growing from flower powders of the active ingredient are sprayed with rice plants growing to two weeks old in conventional flower pots (0.006% active substance based on the volume of the soil). Then the pots are filled with water to the extent that the lowest stem parts of the rice plants are in the water. After 48 hours, the treated rice plants are infected with a conidia suspension of the fungus. After incubation of the infected plants for 5 days at 95-100% relative humidity and about 24 ⁰ C, the fungal infection is assessed.

Compounds from the tables show good activity against the Pyriculariapilz. On the other hand, untreated but infected control plants have a Pyricularia infestation of 100%. Thus, e.g. the compounds 1.16; 2.3 the fungal infection up to 0 to 5%.

Example 3.6: Action against Rhizoctonia solani (soil fungus on rice plants)

a) Protective-Iokale soil application

12 day old rice plants are sprayed with a formulation of the active ingredient prepared spray mixture (0.006% active ingredient) without contaminating aboveground plant parts. To infect the treated plants, a suspension of mycelium and sclerotia of R. solani is added to the soil surface. After 6 days incubation at 27 ⁰ C (day), or 23 ⁰ C (night) and 100% rel. Humidity (wet box) in the climate chamber, the fungal attack on leaf sheath, leaves and stems is assessed.

b) Protective-Iocal Leaf Application

12-day-old rice plants are sprayed with a spray mixture prepared from a formulation of the active ingredients. One day later, the treated plants are infected with a suspension of mycelium and sclerotia of R. solani. After 6 days incubation at 27 ° C (day), or 23 ° C (night) and 100% rel. Humidity (wet box) in the climate chamber, the fungal attack on leaf sheath, leaves and stems is assessed.

Compounds from the tables show good activity by inhibiting the Rhizoctonia infestation. On the other hand, untreated but infected control plants show an infection of 100%. To inhibit z. B. the compounds 1.1; 1.15; 1.16; 1.17; 1.28; 1:33; 2.1; 2.3; 2.4; 2.14; 3.1; 3.3 the fungal infection down to 0 to 5%.

Claims (11)

1. A microbicidal agent for controlling or preventing an infestation by microorganisms, characterized in that in addition to conventional additives as active component at least one compound of formula I. contains, in which R _{1 is} hydrogen, C ₁ -C ₁₀ -alkyl, C ₃ -C ₇ -cycloalkyl, phenyl! ortrimethylsilyl and R _{2 are} hydrogen or C ₁ -C ₄ -alkyl, or R ₁ and R ₂ together form a saturated or unsaturated ring of 6 carbon atoms; R ₃ and R ₄ independently of one another are hydrogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkoxy and furthermore R ₄ C ₃ -C 7 -cycloalkyl, R ₅ -R _{12 are} independently hydrogen or C ₁ -C ₄ -A ^ yI, wherein also R ₈ and R _{9 may} together form a saturated or unsaturated ring having 6 carbon atoms; X is CH ₂ , oxygen or sulfur and η and Z are independently zero or 1, and, if Z is zero, including their acid addition salts. Composition according to claim 1, characterized in that it compounds of formula Γ contains, in which R _{1 is} hydrogen, C ₁ -C ₁₀ -alkyl, C ₃ -C ₇ -cycloalkyl, phenyl or trimethylsilyl and R _{2 is} hydrogen or C ₁ -C ₄ -alkyl or R ₁ and R ₂ together form a saturated or unsaturated ring of 6 carbon atoms; R ₃ ', R ₄ ' and R ₅ -RI ₂ independently of one another represent hydrogen or C ₁ -C ₄ -alkyl, in which case R ₈ and R _{9 can} together form a saturated or unsaturated ring having 6 carbon atoms, X is CH ₂ , oxygen or sulfur and
η and Z are independently zero or 1,
and, if Z is zero, including their acid addition salts. 3. Composition according to claim 1, characterized in that it contains compounds of the formula I, in which R _{1 is} C ₁ -C ₄ -alkyl or trimethylsilyl,
R _{2 is} hydrogen, methyl or ethyl, or Ri and R ₂ together form a phenyl ring fused in 3,4-position, R ₃ and R ₄ independently of one another hydrogen, methyl, ethyl, methoxy or cyclohexyl, Rs, R ₆ / R ₇ and R ₈ independently of one another hydrogen, methyl or ethyl, R ₉ -R _{12 represent} hydrogen, or R ₈ and R ₉ together in the 3,4-position form a fused hexane or phenyl ring, X is CH ₂ , oxygen or sulfur,
η is 1 or zero, and
ZNullist. 4. Composition according to claim 1, characterized in that it contains compounds of the formula I ', in which R _{1 is} C ₁ -C ₄ -alkyl or trimethylsilyl, R _{2 is} hydrogen, methyl or ethyl, or · R ₁ and R ₂ together form a phenyl ring fused in the 3,4-position, R ₃ 'and R ₄ ' independently of one another are methyl or ethyl, R5 / R6 / R7 ^and d Rs independently of one another represent hydrogen, methyl or ethyl, R ₉ -R _{12 represent} hydrogen, or R ₈ and R ₉ together in the 3,4-position form a fused hexane or phenyl ring, X for CH ₂ , oxygen or sulfur, η is 1 or zero, and Z is zero. i 5. Composition according to claim 1, characterized in that it contains compounds of the formula,, in which R ₁ isopropyl, tert. Butyl or trimethylsilyl, R _{2 is} hydrogen, or R ₁ and R ₂ together form a 3,4-fused in the phenyl ring, R ₃ 'and R ₄ ' is methyl, R ₅ , R ₆ and R ₉ -R _{12 is} hydrogen, R ₇ and R ₈ independently of one another represent hydrogen or methyl, or R ₈ and R ₉ together in the 3,4-position form a fused-on hexane or phenyl ring, X is CH ₂ , oxygen or sulfur, η is 1 or zero and Z is zero is. 6. Composition according to claim 1, characterized in that it contains compounds of the formula I ', in which R ₁ isopropyl, tert. Butyl or trimethylsilyl, R _{2 is} hydrogen, or R ₁ and R ₂ together form a phenyl ring fused in the 3,4-position, R ₃ 'and R ₄ ' are methyl, R ₅ , R ₆ and R ₉ -R _{12 are} hydrogen, R ₇ and R ₈ independently of one another, form hydrogen or methyl, or R ₈ and R ₉ together in the 3,4-position form a fused hexane or phenyl ring, X is CH ₂ , Oxygen or sulfur, n1 means, and
Z is zero. · 7. Composition according to claim 1, characterized in that it contains a compound of formula I ', selected from the group dimethyl-4-tert-butylbenzyl-2,6-dimethylmorpho! In (4) ylmethyl-silane; Dimethyl-4-tert.butylbenzyl-morpholine (4) ylmethyl-silane; Dimethyl-4-tert. butyl benzyl-N-piperidinylmethylsilane; Dimethyl-4-trirnethylsilylbenzyl-N-piperidinylmethyl-silane; Dimethyl-4-trimethylsilylbenzyl-morpholine (4) ylmethyl-silane; Dimethyl-4-trimethylsilylbenzyl-2,6-dimethylmorpholine (4) ylmethylsilan; Dimethyl-4-tert.butylbenzyl-tetrahydro-1,4-thiazine (4) ylmethylsilan; Dimethyl-4-isopropylbenzyl-tetraydro-1,4-thiazine (4) ylmethyl-silane; Dimethyl-4-tert.butylbenzyl-N-pyrrolidinylmethyl-silane; Dimethyl-4-trimethylsilylbenzyl-tetrahydro-1,4-thiazine (4) ylmethylsilan; Dimethyl ^ -tert.butylbenzyl-cyclohexatcjN-piperidinylmethyl-silane; Dimethyl ^ -tert.butylbenzyl-benzotclN-piperidinylmethyl-silane; Dimethyl ^ -trimethylsilylbenzyl-cyclohexatclN-piperidinylmethyl-silane; ! Dimethy naphthyl (2) ylmethyl -2,6-dimethylmorpholine (4) ylmethylsilan!; Dimethyl-naphthyl- (2) ylmethyl-cyclohexa [c] piperidine (1) ylmethyl-silane. 8. Composition according to claim 1, characterized in that it contains the compound of formula I 'cis-dimethyl-4-tert-butylbenzyl-2,6-dimethylmorpholin-4-ylmethyl-silane. 9. Composition according to claim 1, characterized in that it contains the compounds of formula I cis-cyclohexyl-4-tert-butylbenzyl-2,6-dimethylmorpholin-4-ylmethyl-silane or cis-methoxy-cyclohexyl- (4-tert-butyl benzyl) -2,6-dimethylmorpholine-4) yl-silane. 10. Composition according to one of claims 1 to 9, characterized in that it contains 0.1 to 99 wt .-% of an active ingredient of the formula I or Γ, 99.9 to 1 wt .-% of a solid or liquid additive and 0 to 25Gew. contains -% of a surfactant. 11. A process for preparing an agrochemical composition, characterized in that at least one compound of formula I or I 'intimately mixed with suitable solid or liquid additives and surfactants. 12. Method for controlling or preventing infestation by cultivated plants by phytopathogenic microorganisms, characterized in that a compound of the formula I or I 'is applied to the plant or its location.