DD296279A5 - MICROBICIDAL - Google Patents

Abstract

Compounds of the formula I and their acid addition salts are valuable microbicides and can be used in the form of crop protection agents for the prevention and control of microorganism infestation. In the formula: X is oxygen or sulfur, Het is a 5- or 6-membered heterocycle, having one to three identical or different heteroatoms selected from nitrogen, oxygen and sulfur, which is unsubstituted or with the same or different substituents selected from halogen, cyano, nitro , C1-C4-alkyl, C3-C6-cycloalkyl, C1-C4-alkoxy, C1-C3-haloalkoxy and trifluoromethyl mono-, di- or trisubstituted, BCH2CH (R2) CH2 or CH {microbicidal; Pesticides; Microorganism infestation; combating; Prevention}

Description

H-NZ (V)

wherein the substituents R ₁ , R ₃ , R ₄ , B, X, Het and Z and η have the meanings given under formula I; or

c) if B is the chain -CH ₂ -C (R ₂ ) = CH- or -CH ₂ -CH (R ₂ ) -CH ₂ -, by reaction of an aldehyde of the formula Vl

^HnX "(VO

CHO

at -25 ° C to +300 ⁰ C, with an amine of formula V to give a compound of formula VII

Het-X / T \

^^ (VII)

within the scope of the formula I and, if desired, subsequent hydrogenation of the double bond, where the substituents R ₁ , R ₂ , R ₃ , R ₄ , X, Het, η and Z have the meanings given under formula I; optionally further oxidation of the compounds of the formula I thus obtained with m = 0 to obtain the corresponding N-oxides (m = 1) of the formula I.

28. A microbicidal composition containing as at least one active ingredient a compound of formula I according to claim 1, together with a suitable carrier material.

29. A composition according to claim 28 containing as active ingredient a compound according to any one of claims 2 to 26.

30. Use of compounds of the formula I according to any one of claims 1 to 26 for the control or prevention of infestation of phytopathogenic microorganisms.

31. A method for controlling or preventing infestation of plants by phytopathogenic microorganisms, characterized in that applying a compound of formula I according to any one of claims 1 to 26 to the plant, plant parts or their location.

32. The method according to claim 31, wherein the plant parts are the seed.

The present invention relates to aminoaliphatic heterocyclyl phenyl ethers of the following formula I and their acid addition salts. The invention further relates to the preparation of these substances and microbicidal agents which contain as active ingredient at least one of these compounds. The invention also relates to the use of the active compounds for controlling harmful microorganisms, in particular phytopathogenic fungi.

The compounds of the invention have the formula

/} - ^{B N}

/ Τλ Hci-X

in which mean:

X oxygen or sulfur,

Het a 5- or 6-membered heterocycle, having one to three identical or different heteroatoms selected from nitrogen, oxygen and sulfur, which is unsubstituted or with the same or different substituents selected from halogen, cyano, nitro, Ci-C ₄ alkyl, Q- Ce-cycloalkyl, Ci-C ₄ -alkoxy, C ₁ -C ₃ -HaIOaIkOXy and trifluoromethyl mono-, di- or trisubstituted,

B is -CH ₂ -CH (R ₂ ) -CH ₂ -or-CH = C (R ₂ ) -CH ₂ -or-CH ₂ -C (R ₂ ) = CH-, R _{1 is} halogen, C ₁ -C ₄ -A ^ yI, C ₁ -C ₄ -alkoxy, η O to 2, m Ooderi,

R _{2 is} hydrogen, C ₁ -C ₄ -alkyl, R _{3 is} hydrogen, C ₁ -C ₃ -alkyl, R _{4 is} hydrogen, hydroxyl, C ₁ -C ₃ -alkoxy or else C ₁ -C ₄ -alkyl which is unsubstituted or substituted by hydroxy or C ₁ -C ₃ -alkoxy,

Z is oxygen, sulfur or -CH ₂ ;

including the acid addition salts of these compounds.

The term alkyl itself or as part of another substituent such as alkoxy or haloalkoxy, etc., depending on the number of carbon atoms given, for example, the following straight-chain or branched groups to understand: methyl, ethyl, propyl, butyl and their isomers, such as. As isopropyl, isobutyl, tert-butyl, etc. Halogen and halo are fluorine, chlorine, bromine or iodine. Haloalkoxy thus stands for a simple to perhalogenated alkoxy, such as. OCHCl ₂ , OCH ₂ F, OCCl ₃ , OCH ₂ Cl, OCHF ₂ , OCHFCH ₃ , OCH ₂ CH ₂ Br, OC ₂ Cl ₅ , OCH ₂ Br, OCHBrCl, etc. C ₃ -C ₆ cycloalkyl is optionally for Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

As a 5- or 6-membered heterocycle having one, two or three identical or different heteroatoms N, O and / or S come z. B. in question:

Pyridine, pyrimidine, pyrazine, pyridazine, triazine, thiazole, oxazole, thiadiazole, oxadiazole, triazole, imidazole, furan, thiophene and corresponding hydrogenated or partially hydrogenated heterocycles such. As piperidine, morpholine, thiomorpholine, pyran, tetrahydrofuran and others. This list is not limiting.

Examples of salt-forming acids are inorganic acids: hydrohalic acid such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic 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 free compounds of the formula I. The compounds of the formula I are stable at room temperature. They can be used preventatively and curatively for controlling plant-damaging microorganisms in the agricultural sector or related fields. The active compounds of the formula I according to the invention are distinguished in wide application concentrations by a very good fungicidal action and problem-free application.

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

Compounds of the subgroup of formula I, wherein the 5- or 6-membered heterocycle Het contains at least one N atom, R _{1 is} halogen, methyl or methoxy, η is O or 1, m is O and R ₂ and R _{3 are} independently hydrogen or Mean methyl. (Subgroup 1 a)

Within subgroup 1 a, preference is given to those compounds in which X is oxygen and R _{4 is} hydrogen, hydroxyl, methyl, methoxy, hydroxymethyl, hydroxyethyl, methoxymethyl or methoxyethyl. (Subgroup 1 aa) An important class of compounds are those of subgroup 1 aa, wherein Het is an unsubstituted or substituted pyridyl radical. (Subgroup 1 b)

Preferred among these compounds are those in which B is the chain -CH ₂ -CH (CHa) -CH ₂ - or -CH = C (CH ₃ ) -CH ₂ -, and the pyridyl radical is unsubstituted or by at most two of the substituents halogen, NO ₂ , -OCHF ₂ and CF _{3 is the} same or different substituted. (Subgroup 1 bb)

Among the latter compounds, preferred are those wherein Z represents oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning of hydrogen or methyl. Another important class of compounds is that of subgroup 1 aa, wherein Het is an unsubstituted or substituted pyrimidinyl radical. (Subgroup 1 c)

Among these compounds 1c, those are preferred in which B is the chain -CH ₂ -CH (CH ₃ ) -CH ₂ - or -CH = C (CH ₃ ) -CH ₂ -, and the pyrimidinyl radical is unsubstituted or halogen, Ci-C ₄ alkyl, cyclopropyl is the same or different monosubstituted to trisubstituted. (Subgroup 1 cc)

Among the latter compounds, preferred are those wherein Z represents oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning of hydrogen or methyl.

Another important class of compounds is that of subgroup 1 aa, wherein Het is an unsubstituted or substituted pyrazinyl radical. (Subgroup 1 d)

Preferred among these compounds 1 d are those wherein B is KeHe-CH ₂ -CH (CH ₃ I-CH ₂ - or -CH = C (CH ₃ ) -CH ₂ - and the pyrazinyl radical is unsubstituted or C 1 -C ₄ (Subgroup 1 dd) Among the latter compounds, preferred are those wherein Z represents oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both are the same Meaning hydrogen or methyl.

Another important class of compounds is that of subgroup 1 aa, wherein Het is unsubstituted or substituted 1,3,5-triazinyl. (Subgroup 1 e)

Among the compounds 1 e those are preferred wherein B is the chain -CH ₂ -CH (CH ₃ J-CH ₂ - or -CH = C (CH ₃ J-CH ₂ -) and the 1,3,5-triazinyl radical is unsubstituted (Subgroup 1 ee) Among the latter compounds, preferred are those wherein Z represents oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning of hydrogen or methyl.

Another important class of compounds within subgroup 1 aa are those in which Het is an unsubstituted or substituted thiazolyl radical. (Subgroup 1 f)

Among the compounds If, preferred are those wherein B is the chain -CH ₂ -CH (CH ₃ J-CH ₂ -or-CH = C (CH ₃ I-CH ₂ -) and the thiazolyl is unsubstituted or by NO ₂ or halogen (subgroup 1 ff) Among the latter compounds, preferred are those wherein Z represents oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning of hydrogen or methyl.

Another important class of compounds within subgroup 1 aa are those in which Het is an oxazolyl radical (= subgroup 1g), especially those in which Z is oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl.

Another important class of compounds within subgroup 1 aa are compounds wherein Het is an unsubstituted or substituted by C ₁ -C ₄ -A ^ yI 1,2,4-triazolyl (= subgroup 1 h), especially those in which Z is oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl.

Another important class of compounds within subgroup 1 aa are compounds in which Het is an unsubstituted or C 1 -C ₄ -alkyl-substituted 1,2,4-imidazolyl radical (= subgroup 1 i), especially those in which Z is oxygen or CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl.

Another important class of compounds within subgroup 1 aa are compounds in which Het is an oxadiazole radical (= subgroup 1 j), especially those in which Z represents oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl.

Another important class of compounds within subgroup 1 aa are compounds in which Het is a thiadiazole radical (= subgroup 1 k), especially those in which Z is oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl.

Another important subgroup of compounds are those of formula I, wherein Het is an unsubstituted or by halogen or Ci-C ₄ alkyl is identical or different at most twice doubly substituted thienyl. (Subgroup 1m) Among the compounds 1m, preferred are those wherein X is oxygen, η is O or 1, m is O, R _{1 is} halogen, methyl or methoxy, R _{2 is} hydrogen or methyl and R _{3 is} hydrogen or methyl and R _{4 is} hydrogen, methyl, hydroxy, methoxy, hydroxymethyl or methoxymethyl. (Subgroup 1 mm) Among the latter compounds, preferred are those wherein Z is oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning of hydrogen or methyl.

The new compounds of the formula I can be prepared, if m = O, by

a) reaction of an amine of the formula II

fv + y

A ₁ ^R 4

with a heterocycle of the formula III

Het-A ₂ (III)

wherein one of A ₁ and A _{2 is} a nucleofugic leaving group and the other is the group -XMe in which Me is hydrogen or preferably a metal cation.

Preferably IStA ₁ = XMe. Metal cations Me are, for example, alkali metal, ζ. As lithium, sodium or potassium cations, or alkaline earth metal, for example, magnesium, calcium, strontium or barium cations.

Nucleofuge leaving groups are, for example, reactive esterified hydroxy groups which are reacted with a hydrohalic acid, eg. With fluoro, chloro, bromo or hydroiodic acid, or with a lower alkanesulfonic acid, or esterified with an optionally substituted benzene or halosulfonic acid; for example, with methane, ethane, benzene, p-toluene or fluorosulfonic esterified hydroxy groups.

Compounds of formula II in which A, OH or SH are partially known or can be prepared by methods known in the art (e.g., EP-A 262870).

The substituents R ₁ , R ₃ , R ₄ , B, X and Z and η have the meanings given under formula I.

The reaction is preferably carried out in a relatively polar but reaction-inert organic solvent, e.g. B.

Ν, Ν-dimethylformamide, N, N-dimethalyetamide, dimethyl sulfoxide, acetonitrile, benzonitrile and others. Such solvents may be used in combination with other reaction inert solvents such as aliphatic or aromatic hydrocarbons, e.g. Benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene, and the like. be used.

Elevated temperatures of 0 ⁰ C to 220 ⁰ C, preferably 120-170 ⁰ C, are advantageous.

Suitably, the reaction mixture is heated to reflux.

The compounds of the formula I where m = 0 can also be prepared by

b) condensation of a heterocyclic diphenyl ether of the formula IV

wherein C represents a nucleofugic leaving group, with an amine of the formula V ^R 3

H-NZ (V)

R ₄

The reaction can be carried out without solvent or in the presence of solvents at 0 ^° C. to 120 ^° C.

As the solvent, if necessary, ethers (eg, diethyl ether, tetrahydrofuran, dioxane), alcohols (eg, ethylene glycol, methanol, ethanol), Ν, Ν-dimethylformamide, Ν, Ν-dimethylacetamide, dimethylsulfoxide, etc. may be used, but also excess amine of formula V.

c) Compounds of the formula I in which m = 0 and B are the chain -CH ₂ -C (R ₂ ) = CH-OdBr-CH ₂ -CH (R ₂ I-CH ₂ - meaning, can also be obtained by reaction an aldehyde of formula Vl

Het-X ·

(VI) • CHO

with an amine of the formula V to give a compound of the formula VII

Hot-X -

(VII)

in the scope of the formula I and, if desired, then hydrogenation of the double bond.

The reaction of an aldehyde of formula VI with an amine of formula V is carried out at temperatures of -25 ° C to +300 ⁰ C, preferably at + 1O ⁰ C to 200 ⁰ C, suitably using an inert solvent. As such, aliphatic and aromatic hydrocarbons, including chlorinated hydrocarbons, in question, for example, petroleum ether, hexane, toluene, xylene, benzene, chlorobenzene, methylene chloride, chloroform, dichloroethane, dibromomethane; furthermore, ethers such as diethyl ether, methyl tert-butyl ether, dioxane, tetrahydrofuran (THF); furthermore alcohols such as methanol, ethanol, ethylene glycol, glycerol or esters such as methyl acetate or ethyl acetate.

The presence of dehydrating agents is advantageous. For example, anhydrous Na ₂ SO ₄ , MgSO ₄ , CaCl ₂ , silica gel, Al ₂ O ₃ or molecular sieve can be used.

Acid catalysts accelerate the reaction, e.g. Hydrogen chloride, hydrogen bromide, sulfuric acid, nitric acid, acetic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid and. a.

If the unsaturated enamines of the formula VII (in the scope of the invention of the present invention) are to be hydrogenated to saturated compounds, metal hydrides can be used as reducing agents for this reaction, e.g. Sodium, potassium or lithium borohydride.

As suitable solvents or solvent mixtures with one another, it is possible to use the abovementioned alcohols, ethers, esters and aromatic hydrocarbons, and also also acetic acid or water.

Suitable reducing agents are also aluminum hydrides, such as lithium aluminum hydride or aluminum diisobutyl hydride, which are advantageously used in the stated ethers or hydrocarbons or mixtures of these solvents. The hydrogenation takes place in the temperature range from -6O ⁰ C to +200 ⁰ C, preferably -20 ⁰ C to +120 ⁰ C as the reducing agent is also formic acid in question, and the reaction is preferably carried out in the absence of a solvent. The formic acid is added dropwise to the enamine at a temperature of 0 ⁰ C to 100 ⁰ C, preferably 50-70 ⁰ C, if necessary with cooling.

Compounds of formula VII can also be catalytically. Particularly suitable catalysts are noble metal catalysts, such as, for example, platinum, palladium, if appropriate co-precipitated on carbon, and Raney nickel. Preference is given to palladium on carbon.

Suitable inert solvents are hydrocarbons such as benzene, toluene or xylene and alcohols such as methanol or ethanol. Preference is given to toluene. As the reaction temperature is advantageously an interval between 0 ° C and +50 ⁰ C, preferably room temperature selected.

From the above according to a), b) or c) obtained compounds of formula I with m = 0 can, if desired, by oxidation, the corresponding N-oxides (m = 1) of the formula I win.

As the oxidizing agent, u.a. Hydrogen peroxide, perbenzoic acid, peracetic acid, m-chloroperbenzoic acid.

The reaction is carried out in a temperature range from -20 ⁰ C to 200 ⁰ C, preferably from 0 ⁰ C to 120 ⁰ C, carried out in an inert solvent. Examples of solvents are chlorinated hydrocarbons (eg chloroform, dichloromethane, dichloroethane alcohols (eg methanol, ethanol, ethylene glycol), ethers (ζ Β. Diethyl ether, THF, dioxanes), Ν, Ν-dimethylformamide, Ν, Lösungsmittel-dimethylacetamide, dimethylsulfoxide, etc. These solvents may be used alone or in combination All of the above-described processes a), b) and c), together with their variants and the optionally used reaction step, are subject to postoxidation (to obtain N-oxides) present invention. The compounds of the formulas IV and VI are novel, but can be prepared by the customary methods of preparative organic chemistry, for example analogously to the processes described in DE-OS 2752135.

1 he: ropanMeerivateder3ormel 6 have in BM! PositionL if? _B Ylkyl bedeutetL always present an asymmetric * C atom and can therefore exist in two enantiomeric forms. In general, in the preparation of these substances, a mixture of both enantiomers. This can be in the usual way, for. B. by fractional crystallization of salts with optically active strong acids, split into the pure optical antipodes. Both enantiomers can have different biological activities. As soon as cis / trans isomerism occurs due to a double bond in the 2-position, the same considerations apply.

The present invention relates to all pure enantiomers or diastereomers and their mixtures with one another. It has surprisingly been found that compounds of the formula I have a very favorable for practical needs microbicidal spectrum against fungi and bacteria. They have very beneficial curative, preventive and systemic properties and can be used to protect crops. With the compounds of the formula I plants or parts of plants (fruits, flowers, foliage, stems, tubers, roots) of different crops, the microorganisms occurring can be contained or destroyed, with even later growing plant parts are spared by such microorganisms.

The active substances are active against the phytopathogenic fungi belonging to the following classes: Ascomycetes (eg Venturia, Podosphaera, Erysiphe, Monilinia, Pyrenophora, Uncinula); Basidiomycetes (e.g., the genera Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti (e.g., Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora, Colletotrichum, RhynchosporiurTvPseudocercosporella and Alternaria). 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 to protect against fungal infections and against occurring in the soil phytopathogenic fungi. The active compounds according to the invention are distinguished by particularly good plant tolerance.

The invention thus also relates to microbicidal agents and to the use of the compounds of the formula I for controlling pathogenic microorganisms, in particular plant-damaging fungi, or for the preventive prevention of infestation with plants.

As target cultures for the indication areas disclosed herein, within the scope of this invention z. The following plant species: 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, strawberries, raspberries and blackberries); Legumes: (beans, lentils, peas, soya); Oil crops: (rapeseed, mustard, poppy, olives, sunflowers, coconut, castor, cocoa, peanuts); Cucumber plants: (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, cinnamonum, camphor) or plants such as corn, tobacco, nuts, coffee, sugar cane, tea, vines, hops, banana and natural rubber plants and ornamental plants (flowers, shrubs, deciduous trees and conifers). This list is not a limitation.

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 further 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.

The compounds of the formula I are used in unchanged form or preferably together with the usual auxiliaries in formulation technology and are therefore used, for. B. to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts,

Granules, by encapsulation in ζ. B. polymeric substances processed in a known manner. The methods of application, like the type of means, are chosen according to the aims and the circumstances. In the agricultural sector are low application rates generally at 50g to 5 kg of active ingredient (aa) per ha; preferably 100g to 2 kg ai / ha, especially at 150g to 800g.

Suitable solvents are: Aromatic hydrocarbons, preferably the fraction C ₈ -C ₁₂ , such as

Xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, 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 epoxidized coconut oil or soybean oil; or water.

Particularly advantageous, application-promoting additives that can lead to a large reduction in the application rate, are also natural (animal or plant) or synthetic phospholipids from the series of cephalins and lecithins, such as. As phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol or lysolecithin.

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.

The surfactants commonly used in formulation technology are i.a. described in the following publications:

Mc Cutcheon's Detergents and Emulsifiers Annual

BC Publishing Corp., Ringwood New Jersey, 1981;

Helmut Stäche "Tensid-Taschenbuch" Carl Hanser-Verlag

Munich / Vienna 1981.

M. and J. Ash. "Encyclopedia of Surfactants", Vol. Ill., Chemical Publishing Co., New York, 1980-1981.

The agrochemical preparations generally contain 0.1 to 99%, in particular 0.1 to 95% active ingredient of the formula 1.99.9 to 1%, in particular 99.8 to 5% of a solid or liquid extender and 0 to 25% , in particular 0.1 to 25% of a surfactant.

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

The following examples serve to illustrate the invention without limiting it. Temperatures are given in degrees centigrade. Percentages and parts are by weight.

Preparation Examples

Example 1: Preparation of

CH ₃

CH ₂ -CH-CH ₂ -NO

CH ₃

CH ₃

To a solution of 3.6 g of 4- [3- (3-hydroxyphenyl) -2-methylpropyl] -2,6-dimethylmorpholine in 40 ml of absolute methanol is added at room temperature 2.7 g of 30% sodium methylate. The mixture is heated at reflux for half an hour, then methanol is removed on a rotary evaporator and the crystalline sodium salt is mixed with 50 ml of absolute dimethylformamide. 2.0 g of 2-chloro-5-trifluoromethylpyridine and 0.3 g of catalytically active potassium iodide are added. The mixture is then stirred for 18 hours at 100 ⁰ C, then cooled to room temperature, poured the reaction mixture to 150 ml of water and extracted three times with 50 ml of ethyl acetate. The combined organic phases are washed twice with 100 ml of water, dried over sodium sulfate, filtered and freed from the solvent by evaporation. The brown oily residue is purified by hexane / ethyl acetate (2: 1) over a silica gel column. Chromatography The title compound is obtained as a yellow oil; n ": 1.5012.

Example 2: Preparation of

CH ₃

Cl is CH ₂ -CH-CH ₂ -NO

(/y_o <yJ CH₃

Cl 4- [3- {3 - ((2,5-dichloro-3-pyridyloxy) phenyl} -2-methylpropyl] -2,6-dimethylmorpholine

To a solution of 3.6 g of 4- [3- (3-hydroxyphenyl) -2-methylpropyl] -2,6-dimethylmorpholine in 40 ml of absolute methanol is added 0.8 g of solid sodium methylate and the mixture is refluxed for 30 minutes. The methanol is then removed on a rotary evaporator and the crystalline sodium salt is mixed with 50 ml of absolute dimethylacetamide, 2.5 g of 2,5-dichloro-3-fluoropyridine and 0.3 g of potassium iodide. This mixture is stirred at 120 ° C for 20 hours, then cooled to room temperature and poured onto 250 ml of water. After three extractions with 100 ml of ethyl acetate, the organic phases are combined, washed twice with 150 ml of water, dried over sodium sulfate, filtered and freed from the solvent on a rotary evaporator. The dark oily residue is chromatographed on hexane / ethyl acetate (2: 1) over silica gel column for purification. After evaporation of the mobile phase mixture, a yellow oil is obtained; ng ³ : 1,5508. Synthesis of intermediates

Example 3: Preparation of

CH ₃

CH = C - CHO

3- (3-benzyloxyphenyl) -2-methacrolein

31.8 g of 3-benzyloxybenzaldehyde are dissolved in 200 ml of methanol, treated with 0.5 g of powdered potassium hydroxide and heated to 45 ⁰ C. At this temperature (± 5 ° C) within 1 hour 26.0g propionaldehyde are added dropwise and the mixture is stirred for 4 hours at 40-45 ° C. The solvent is then evaporated on a rotary evaporator, the oily residue is poured into 500 ml of water, and extracted 3 times with 150 ml of diethyl ether. The organic phases are combined, washed 2 × with 200 ml of water, dried over sodium sulfate, filtered and concentrated. The title compound is obtained as a yellow oil, ng ⁰ : 1.6217.

Example 4: Preparation of

CH ₃

- CH-CH ₂ OH

3- (3-benzyloxyphenyl) -2-methyl-propanol

10.0 g of lithium aluminum hydride are heated under nitrogen in 350 ml of absolute tetrahydrofuran at reflux. For this purpose, within 2 hours at reflux 44.2 g of the obtained under Example 3 3- (3-benzyloxyphenyl) -2-methyl-acrolein, dissolved in 70 ml of absolute tetrahydrofuran, added dropwise and heated for a further 3 hours at reflux.

It is then cooled to room temperature, and while cooling carefully 250 ml of ice water are added dropwise. Then the reaction mixture is mixed with 300 ml of diethyl ether and filtered with suction through Hyflo. From the filtrate, the organic phase is separated and the aqueous phase extracted 2x with 250 ml of ether. The organic phases are combined, washed 3 times with 250 ml of water, dried over sodium sulfate, filtered and the solvent is removed by evaporation. For purification, the oily residue is chromatographed on hexane / ethyl acetate (3: 1) over a silica gel column. After evaporation of the mobile phase mixture, a yellow oil is obtained; ng ² : 1.5624.

Example 5: Preparation of

CH ₃

CH ₂ --CH- CH ₂ OSO ₂

1- (p-tosyloxy) -2-methyl-3- (3-benzyloxyphenyl) propane

21.0 g of 3- (3-benzyloxyphenyl) -2-methyl-propanol are introduced into 80 ml of pyridine and cooled to -5 ° C. At -5 'C to ⁰ ° C. 17.2 g of p-toluenesulfonyl chloride are added portionwise within 1 hour were added and the mixture stirred at 0 ⁰ C for 4 hours. The reaction mixture is poured onto 300 ml of ice water and extracted 3 times with 200 ml of diethyl ether. The organic phases are combined, washed twice each with 150 ml of 2N hydrochloric acid and 3 times with 200 ml of water, dried over sodium sulfate and filtered, then the solvent is evaporated off.

The oily residue is chromatographed with hexane / ethyl acetate (1: 1) over a silica gel. The title compound is obtained as a yellow oil, ng ² : 1.5667.

Example 6: Preparation of

CH,

CH ₂ --CH- CH ₂ N

CH ₃

4- [3- (3-Benzyloxyphenyl) -2-methylpropyl] -2,6-dimethylmorpholine 8.7 g of the 1- (p-tosyloxy) -2-methyl-3- (3-benzyloxyphenyl) propane obtained in Example 5 and 5.6 g of dimethylmorpholine are stirred for 2.2 hours at 100 ⁰ C, then cooled to room temperature and treated with 50 ml of water and 50 ml of ethyl acetate. The organic phase is separated, the aqueous phase extracted 2x with 50 ml of ethyl acetate. The organic phases are combined, washed 3x with 150 ml of water, dried over sodium sulfate, filtered and concentrated. The oily residue is chromatographed on a silica gel column for purification with hexane / ethyl acetate (2: 1). After evaporation of the mobile phase mixture, a yellow oil is obtained; n§ ² : 1.5381.

Example 7: Preparation of

CH ₂ --CH- CH ₂ N

HO

- / Λ

CH-,

CHO

CHQ

4- [3- (3-Hydroxyphenyl) -2-methylpropyl] -2,6-dimethylmorpholine 10.0 g of the 4- [3- (3-benzyloxyphenyl) -2-methylpropyl] -2,6-dimethylmorpholine obtained in Example 6 are hydrogenated in 70 ml of ethyl acetate in the presence of 1.0 palladium-carbon (5%) at room temperature within 19 hours. Subsequently, the catalyst is separated by filtration and the solvent removed on a rotary evaporator. The title compound is obtained as a viscous oil of yellow color; ns ⁶ : 1.5109.

The following compounds are prepared in this way or in the manner of one of the methods given above. In the following mean

Morph

Pip. = N)

CHQ

CH,

DMP = -Ν \ CiS-DMP:

CH ₃

cis-DM M =

- ^N , P trans-DMM = - ^N. P

CH-,

CHQ

trans-DMP =

 N

CH-,

table

CH ₂ CH CH ₂ A

X phys.

dates

DMM

cis-DMP

trans-DMP

: 1.5012

: 1.5083: 1.5088

1.3. 2,5-dichloro-3-pyridyl

Pip. Pip.

1.5. 2-thienyl V Morph O 1.6. 2-pyridyl DMM O 1.7. CF ₃ - / thiomorpholine O

No. Q

1.8. 2-pyrimidinyl

1.9. 2-thiazolyl

CU _x

1.10.

1.12.

1.15.

1.13. 2-pyrazinyl

1.14. ^CF 3

16.1. 2,5-dichloro-3-pyridyl 1.17.

pyridyl

1.18. 2-pyridyl

19.1. 2-thienyl

CH-,

-N

Pip.

DMM

Morph

DMM

Pip.

cis-DMM

trans-DMM O Pip. O ΜΟ _Φ Η S Pip. O DMM O

phys. data

O n £ j ^J : 1.5066

No. Q

phys. data

20.1. 3,5-dichloro-2-pyridyl

1-21- O ₀ N-

-N DMM

1.22.

pyridyl DMM

.25

: 1.5352

23.1. 5-chloro-2-pyridyl

1.24.

Cl

Cl DMM

1.25. ^CF 3

26.1. 2-pyrimidinyl

1.27. 5-bromo-2-pyridyl

1.28.

= N

1.29. 2-thienyl

DMM O · $ 1.5090 Pip. O Mp. 148 ⁰ C] cis-DMM O [Nitrate: Pid. O

No. Q

30.1. 3-chloro-2-pyridyl

CH ₃

1.31.

CH ₃

phys. data

-N

Pip.

CH-,

CH ₃ -CH ₂ Cl

1:32.

DMM

1:33. 2-thiazolyl 1.34. 1.35.

1.36.

1.37.

1.38.

CP, -JX

pyridyl

pyridyl 2-pyrimidinyl

Cl

CF,

DMM

DMP

cis-DMM

Pip.

trans-DMM O

O r £ ^u : 1.5314

[Nitrate: mp 128 ° C]

Thiomorpolin S

No. Q

1.39. 2,5-dichloro-3-pyridyl

1:40. 2-pyridyl 1.41. 3,5-dichloro-2-pyridyl

1:42.

1:43. 5-chloro-2-pyridyl

1:44. 3-chloro-2-pyridyl

1:45. 2,5-dichloro-3-pyridyl

1:46. 2-pyrazinyl

1.47.

1:48. 1:49.

1:50.

2-thienyl 2-thienyl

X - 15- phys. 296 279 n ^ ⁵ : 1,5508 A dates O DMM O Morph O Pip.

Morph

DMM

CH ₂ OH

cis-DMM trans-DMM

DMM

thiomorpholine

O O

1:51. 5-Bromo-2-pyridyl DMM

: 1.5483

No. Q

1:52.

Cl

CH ₃ CH ₂ Cl

1:53.

f /

 Ν

1.54. 2-pyridyl

1.55. 5-chloro-2-pyridyl

1:56. 4-pyrimidinyl

1.57. ^CF 3

1:58. 2-pyrimidinyl

1:59. 2,5-dichloro-3-pyridyl

1.60.

Cfo

Morph

Pip.

DMM

-N

DMM

cis-DMP

Morph Morph

O O

O O

N) -CH ₃ ο

phys. data

No. Q

phys

 dates

1.61.

DMP

1.5320

1.62. 2-thienyl 1.63. 3,5-dichloro-2-pyridyl 1.64. 3-Chloro-2-pyridyl 1.65. 5-chloro-2-thienyl 1.66. 2-pyrazinyl 1.67. 5-chloro-2-pyridyl 1.68. 3-thienyl

DMM S DMP O DMM O Pip. O DMM O DMP O Pip. O

1.69.

1.70.

Moiph

1.71. 3,5-dichloro-2-pyridyl

Morph

1.72. ^CF 3

1.73. 2,5-dichloro-3-pyridyl

Pip.

cis-DMM

1.5428

1.74. 2,5-dichloro-3-pyridyl

trans-DMM

No. Q

1.75.

CH-,

1.76. 4,6-dimethyl-2-pyrimidinyl

1.77. 2-thienyl

1.78. 2-pyrimidinyl

1 79 ^CF 3 - '' ^ 1.80.

1.81.

1.82. 3,5-dichloro-2-pyridyl

1.83. 2,5-dichloro-3-pyridyl 1.84. 5-chloro-2-pyridyl 1.85. 5-chloro-2-thienyl

Pip.

cis-DMM

Ochi

-N

cis-DMM

DMM

DMP

CH ₂ OCH ₃

- N

DMM O

CH ₂ OH

DMM

-N

CH ₂ OCH ₃

phys. data

.34

: 1.5288

: 1.5458

1.86. 3-chloro-2-pyridyl

DMP

No. Q

phys. data

CH ₇

1.87.

Pip.

CH ₃ CH ₂ Cl

1.88.

DMP

1.89. 6-methoxy-2-pyridyl pip.

1.90.

Cl

1.91.

Cl

cis-DMP

CH-,

1.92. 3-nitro-2-pyridyl

Pip.

1.93.

DMM

1.94.

Pip.

Cl

1.95.

CF ₃

Pip.

1.96. 5-chloro-2-thienyl

DMM

No. Q

phys. data

1.97. 5-bromo-2-pyridyl

1.98. 4-pyrimidinyl

1.99. 5-nitro-2-thiazolyl

trans-DMM O Pip. O DMM O

1100. 4-pyridyl

1101.

Pip.

1110. N

Cl

OH

• Ν

Pip.

1102. 5-chloro-2-pyridyl Morph O 1103. 2-pyrazinyl DMP O 1104. 3,5-dichloro-2-pyridyl trans-DMM O 1105. 3,5-dichloro-2-pyridyl cis-DMM O n ^ ⁹ : 1.5454 [Nitrate: mp. 146 ° C] 1106. 5-chloro-2-thienyl DMP O 1107. 3-thienyl DMM O 1108. 3-chloro-2-pyridyl Pip. O 1109. 5-nitro-2-pyridyl DMM O Cl

1111. 3-pyridyl

DMM

1112.

DMM

No. Q

1113.

CHOCH ₉ Cl

1114. 5-chloro-2-pyridyl

1115. 4-methyl-2-pyridyl

CH ₃

1116.

1.117 5-chloro-2-thienyl 1,118. 5-bromo-2-pyridyl

1119.

CHO

1120.

CH ₃

1121. 4-pyridyl

1122. 3,5-dichloro-2-pyridyl

cis-DMM

DMM Pip.

O O

Thiomorpholine O

Morph

N) CH ₃

cis-DMP

DMM

DMM

-N

CH ₂ OCH ₃

phys. data

1123. 4-methyl-2-pyridyl DMM

No. Q

phys. data

1124. CH _3n I Cl / Y- 1125. J 1126.

cis-DMM

trans-DMM

Pip.

1127. 5-chloro-2-thienyl

cis-DMP

1128. 5-pyrimidinyl

DMM

1129. 3,5-dichloro-2-pyridyl

-N

CH ₃

1.130 5-pyrimidinyl

Pip.

1131. 4-pyrimidinyl

1132.

1133. 3-Chloro-2-pyridyl 1,134. 3-nitro-2-pyridyl 1,135. 3,5-dichloro-2-pyridyl 1,136. 5-chloro-2-thienyl

1137. 5-chloro-2-pyridyl

DMP CH ₃ O -O DMM O DMM S cis-DMP O DMM O cis-DMM S O

: 1.5375

No. Q

1138. 5-chloro-2-pyridyl

CH _3> Cl

1139. /

-N

1140.

1142.

1143. 3-pyridyl

1144. 5-chloro-2-pyridyl

1145. 5-chloro-2-thienyl

1146. 5-chloro-2-thienyl

1147. 5-bromo-2-pyridyl

1148. 4-pyridyl

CH ₃ CH ₂ Cl

1149. / \

trans-DMM O

DMM

Pip.

1141. 6-methoxy-2-pyridyl DMM

DMM CH ₂ OH O Pip. -Ö O trans-DMM cis-DMM O O O

DMP

trans-DMM O

phys. data

No. Q

phys. data

1150. 5-chloro-2-pyridyl

- N

CH ₂ OCH ₃

1151. 3-chloro-2-pyridyl cis-DMM

1152.

1153.

N N

F ₃ C-

DMM

DMM

1154. CH,

N N

Il! I

Pip.

1155.

CH ₃

1156. CH-,

DMM

DMM

1157. CH,

N N

Il

DMM

CFa

 N

1158.

CF ₃ .

1159.

CH ₃

-N

I H

DMM

DMM

No. Q

1160.

N N

1161. N

1162.

1163.

CH ₁

CH ₃ -N.

: N

: N

CH ₃ O,

1164.

1165.

1166.

CH ₃

-N

VI CH ₃

N N

NI CH ₃

N N

NI CH ₃

1167. N

Pip.

DMM

DMM DMM

DMM

DMM

DMM

DMM

0 0

0 0

phys

 dates

OCHFCl

1168.

1169.

1170. N

Hi

cis-DMM

cis-DMM

cis-DMM

40

.40

: 1.5245

: 1.5632

: l, 5318

table

3

^CH 2 " ^CH - ^CH 2- ^A

⁵ T ⁶

No. -X-Q

phys. data

Ι-Ο-Π

DMM

2.2.

egg

Morph

2.3.

4-F

DMM

2.4.

2-O

Pip.

2.5.

Cl

3 - ο

4-α

DMP pip.

Cl CH ₂ CH ₃

t-o_ / \

N = DMM

No. -X-Q

phys. data

CI

2.8.

Pip.

2.9. 4 ο-I

DMM

2.10.

4 - <

2-C1 Pip.

11.2.

(3-

4-Cl DMM

Cl

² · ¹² ·

13.2.

3

DMM

Pip.

N =

2.14. 3 ο-1 ^ / i-Cl

4-Cl DMM

Cl

2.15.

4-ο

DMM

Cl

2.16

3 - ο

Pip.

2.17. 4 ο-U

-Cl DMM

No. -X-Q

phys. data

Cl

2.18. 3- ° - / /

Cl

4-F Pip ·

2.19.

N =

DMM

20.2. 4 _o // \

2-Cl DMM

Cl

2.21.

4_o- ^

Cl

Pip.

Cl V-N

3-Ο / Λ DMP

2.23. 2-o

DMM

4-CH ₃ Pip.

2.25.

4-ο

CH-, DMM

No. -X-Q

phys. data

2.26.

2.27.

3 - Pip.

DMM

2.28.

Pip.

2.29.

3 o-4

egg

4-Cl Pip.

2.30.

3

Cl \ N

trans-DMM

Cl

2.31

3 -

cis-DMM

Cl

2.32. 3-ο - / \

V = N

Cl

DMM

Pip.

No. -X-Q

phys. data

CH-,

2.34.

3-ο

CH-, DMM

Cl

2.35.

3-ο

4-C1 Pip.

2.36. 4 o

Pip.

2.37.

DMM

2.39. ⁴ - ^:

DMM

2:40.

χ -o- /

Pip.

2.41.

3-ο

/ Λ

4-OCH ₃ DMM

No. -X-Q

phys. data

2.42. 4 o-J

Pip.

2.43.

DMM

4 O-

2.44.

DMM

2.45. 4-ο-

Pip.

2.46. ο _η _ / ~ Λ

4-CH-, DMM

Cl CH ₂ CH ₃

2.47.

Λ = / DMM

Cl

2.48.

3 - <

Cl

2.49.

3 - <

cis-DMM

trans-DMM

Cl

2:50.

3

4-Cl Pip.

No. -X-Q

phys. data

Cl

2.51. ⁴ - ⁽

Cl DMM

2.52.

3-ο- / \ ί

CH ₃ Pip.

2.53.

N N

3-o-O

DMM

2.54. 4

-yy /%

DMM

2.55. 4 Ο-

4-C1

Pip.

DMM

2.57.

3-O

Cl \ N

DMM

Cl

2.58. 4-ο ~ / ^)

Cl

DMM

2.59. 4 o

NO, DMM

No. -X-Q

2.60.

3- <

-33 - 296 279 phys. dates

^CF 3 4-OCH ₃ Pip.

2.61. A _ _ J ~ \

4-s- ('>>) - α

N ^: DMM

2.62. 4 o-

N-

Il

-NOo

2.63.

3

CI Pip.

DMM

2-64. ₄ _ _Ο __ / Λ_ _α

trans-DMM

2.65.

cis-DMM

4-Cl

DMM

2.67.

DMM

2.68. 4 <

DMM

No. -X-Q

phys. data

Cl

2.69.

3- S- / ^) = N

2.70.

4-ο

DMM DMM

2.71. 4 Ο

DMM

2.72.

3 o

Pip.

N N

2.73.

I CH ₃ DMM

table

3.3.

3.6. 3.7.3.8.

Y-CHO-A

No. Q

-Ο- / Λ

3.1. ^CF 3

3.2. 3-pyridazinyl

3.4. 2,5-dichloro-3-pyridyl

3.5. ^CF 3

2-pyrimidinyl 3,5-dichloro-2-pyridyl

phys. data

-CH ₂

CH ₃

-CH ₂ -CH-CH ₃

I -CH = C-

CH ₂ CH ₃

-CH ₂ -CH-

DMM

Pip.

DMM

Pip.

-CH = CH-DMM

CH ₃ -CH = C-

Pip.

-CH ₂ CH ₂ - DMM

CH ₃

-CH = C-

Morph

No. Q

3.9. 3,5-dichloro-2-pyridyl

phys. data

CH ₁

-CH = C-

DMM

10.3.

Cl

11.3. 5-chloro-2-thiazolyl 3.12. 2,5-dichloro-3-pyridyl

3.13. 2-pyrazinyl 3.14.

3.15. 5-chloro-2-pyridyl

16.3.

3.17. 5-chloro-2-pyridyl

CH ₃

-CH = C-

CH ₃

I -CH = C-

CH ₂ CH ₃

-CH ₂ -CH-

CH ₃ -CH = C-

CH ₃

-CH = C-

CH ₃ -CH = C-

CH ₃ -CH = C-

CH ₃ -CH = C-

Pip.

DMM DMM

DMM DMM

Pip.

DMM

DMM

2-oxazolyl

CH-,

-CH ₂ -CH-

DMM

phys. data

N N

NI CH ₃

CH ₃

-CH ₂ -CH-CH ₃

-CH ₂ -CH-DMM Pip.

N N

CH ₃

-CH ₂ -CH pip.

Formulation Examples of Active Ingredients of the Formula I.

F1. solutions

a)

d)

Active ingredient from the tables 80% 107 < Ethylene glycol monomethyl ether 20% - Polyethylene glycol MG 400 - 70 ° / N-methyl-2-pyrrolidone - 20 7 < Epoxidized coconut oil - - Gasoline (boiling limit 160-190 ⁰ C) - - (MW = molecular weight)

The solutions are suitable for use in the form of very small drops.

F2. Granules a) b)

Active ingredient from the tables 5% kaolin 94% Highly dispersed silicic acid 1% attapulgite -

95%

5%

94%

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

F3. dusts a) b) Active ingredient from the tables 2% 5% Highly dispersed silicic acid 1% 5% talc 97% - kaolin _ 90%

Intimately mixing the excipients with the active ingredient gives ready-to-use dusts.

F4. Spray powder a) b) c)

Active ingredient from the tables 25% 50% 75% Na ligninsulfonate 5% 5% - Na lauryl sulfate 3% - 5% Na Diisobutylnaphthalinsulfonat - 6% 10% 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.

F5. Emulsion concentrate

Active substance from the tables 10%

Octylphenol polyethylene glycol ether 3%

(4-5 moles of ethylene oxide)

Ca-dodecylbenzenesulfonate 3%

Castor oil polyglycol ether 4%

(35 moles of ethylene oxide)

Cyclohexanone 30%

Xylene mixture 50%

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

F6. Coating granules active substance from the tables 3%

Polyethylene glycol KMG 200) 3%

Kaolin 94%

(MW = molecular weight)

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

Biological examples: Example B1 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 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.

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 2O ⁰ C, the infected plants are placed in a greenhouse at about 22 ⁰ C. The assessment of rust pustule development is 12 days after infection.

Untreated but infected control plants showed a Puccinia infestation of 100%. Compounds from the tables showed a good action against Puccinia fungi (5-20% infestation). Compounds Nos. 1.1, 1.2a, 1.2b, 1.10, 1.11, 4.1, 4.1, 8.1, 9.1, 3.1, 6.1, 4.1, 12, 5.1, 9.1, 6.1, 16, 1.11, 16.7, 9.1, 9.1, 16.10, 1.16, 1.11, and others inhibited the infestation to 0-5%.

Example B2 Action against Cercospora arachidicola on peanut plants

a) 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 ° C and high humidity and then placed until the appearance of the typical leaf spots in a greenhouse. The evaluation of the fungicidal activity takes place 12 days after the infection based on the number and size of the spots occurring.

b) Systemic effect

To 10-15cm high peanut plants, a spray mixture prepared from wettable powder of the active ingredient is poured (0.06% active substance based on the volume of soil). After 48 hours, the treated plants are infected with a conidia suspension of the fungus and incubated for 72 hours at about 21 ° C. and high humidity, then the plants are placed in the greenhouse and after 11 days the fungal infestation is assessed.

Compared to untreated but infected control plants (number and size of spots = 100%), peanut plants treated with active ingredients from the tables show a greatly reduced Cercospora infestation. Thus, the compounds Nos. 1.1,1.6,1.10,1,12,1,13,1,14,1.22,1.2,1,1,14,1,2,14,1,31,1.32,1.33,1.36,1.39,1,40,1.42,1.43, 1.51,1.57,1.58,1.61, 1.75,1.82,1.87,1.91,1.105,1.113,1.124,1.126,1.140,1.143,1.151,1.168,1.169,1.170, 2.1, 2.2, 2.17,2.62, 2.70,2.71 and 3.2 in the above experiments the appearance of spots almost completely (0-10%).

Example B 3

Effect against Erysiphae graminis on barley

a) Residual-protective action

Approximately 8 cm high barley plants are sprayed with a spray mixture of active ingredient prepared from spray powder (0.02% active ingredient). 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 ° C, and the fungal infection is assessed after 10 days.

b) Systemic effect

To a barley plants about 8 cm high, a spray mixture prepared from wettable powder of the active ingredient is poured (0.006% active substance based on the volume of the soil). Care is taken to ensure that the spray mixture does 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 assessed the fungal infection after 10 days. Compounds of the formula I showed a good activity against Erysiphae fungi. Untreated but infected control plants showed an Erysiphae infestation of 100%. Among other compounds in the Tables, compounds Nos. 1.1, 1.2a, 1.2b, 1.6,1.14, 1, 2, 4.1, 4.1, 7.1, 8.1, 9.1, 6.1, 6.1, 8.1, 6.1, 6.1, 6.1, 16, 12, 16, 16, 16, 16, 16, 16, 16, 16, 18, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 16, 18, 16, 16, 16, 16, 16, 18, 16, 16, 16, 16, 18, 16, 18, 18, 18, 18, 18, 16, 18, 18, 18, 18, 18, 18, 18, 18, 18, 18, 18, 18, 18, 18, 16 , 2.13, 2.14, 2.15,2.20, 2.24,2.41, 2.42,3.1,3.2,3.19 the fungus infestation in barley to 0 to 5%.

Example B4 Residual-protective action against Venturia inaequalis on apple shoots

Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture of active ingredient prepared spray powder (60.06% active substance). 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 placed for 10 more days in a greenhouse at 20-24X. Scab infestation is assessed 15 days after infection. Compounds from the tables caused a marked inhibition of disease infestation. Thus, the compounds 1.1, 1.2a, 1.2b, 1.24, 1.28, 1.40, 1.14, 1.16, 1.68, 1.12, 5.2, 20.20, 2.24 and 3.2 inhibited fungal infestation almost completely (0.5%). Untreated but infected shoots showed 100% Venturia infestation.

Example B 5 Action against botrytis cinerea on beans Residual protective effect

Approximately 10 cm high bean plants are sprayed with a spray mixture of active ingredient produced from spray powder (0.02% active ingredient). After 48 hours, the treated plants are infected with a conidia suspension of the fungus. After incubation of the infected plants for 3 days at 95-100% relative humidity and 21 ⁰ C, the assessment of fungal infestation takes place.

Botrytis infestation of untreated but infected bean plants was 100%. The infestation after treatment with one of the compounds of formula I was <20%; when treated with the compounds Nos. 1.1,1.2,1.10,1.14,1.19,1.22,1.24,1.26, 1.28,1.32,1.39,1.51,1.66,1.78,1.82,1.93,1.99,1.120,1.124,1.152,1.157,1.158 , 1.163,1.165,1.168,1.170,2.1,2.9,2.14,2.25,2.53, 2.59,3.3,3,14 and others no infestation occurred (0-5%).

Example B 6 Action against Rhizoctonia solani (soil fungus on rice plants)

a) Protective-Iokale soil application

12 day old rice plants are cast with a spray mixture prepared from a formulation of the active ingredient (0.006% active ingredient) without wetting 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 ° 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.

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 showed good activity by inhibiting the Rhizoctonia infestation. So inhibited z. B. the compounds 1.1,1.14.1.16.1.17,1.22,1.28,1.39,1.82,1.168,2.1,2.3,2.4, 2.14,2.17,3.1,3.3 the fungal infection to 0 to 5%. By contrast, untreated but infected control plants showed an infestation of 100%.

Claims (27)

(O) _n , in which mean: X oxygen or sulfur, Het a 5-or 6-membered heterocycle having one to three identical or different heteroatoms selected from nitrogen, oxygen and sulfur, which is unsubstituted or having the same or different substituents selected from halogen, cyano, nitro, C ₁ -C ₄ -alkyl, C ₃ - C ₆ -CyClOalkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₃ -HaIOalkoxy and trifluoromethyl mono-, di- or trisubstituted, B is -CH 2 -CH (R 2) -CH 2 or -CH = C (R ₂ ) -CH 2 or -CH ₂ -C (R ₂ ) = CH-, R _{1 is} halogen, C ₁ -C ₄ -alkyl, C ₁ -C _4- alkoxy, η 0bis2, m o or 1, R _{2 is} hydrogen, C ₁ -C ₄ -alkyl, R _{3 is} hydrogen, C ₁ -C ₃ -alkyl, R _{4 is} hydrogen, hydroxyl, C ₁ -C ₃ -alkoxy or else C ₁ -C ₄ -alkyl which is unsubstituted or substituted by hydroxyl or C ₁ -C ₃ -alkoxy, Z is oxygen, sulfur or -CH ₂ -; including the acid addition salts of these compounds. 2. Compounds according to claim 1, wherein the 5- or 6-membered heterocycle Het contains at least one N atom, R _{1 is} halogen, methyl or methoxy, η is O or 1, m is O and R ₂ and R _{3 are} independently hydrogen or Mean methyl. 3. Compounds according to 2, wherein X is oxygen and R _{4 is} hydrogen, hydroxy, methyl, methoxy, hydroxymethyl, hydroxyethyl, methoxymethyl or methoxyethyl. 4. Compounds according to claim 3, wherein Het represents an unsubstituted or substituted pyridyl radical. 5. Compounds according to claim 4, wherein B is the chain -CH ₂ -CH (CH ₃ ) -CH ₂ - or -CH = C (CH ₃ ) -CH ₂ - means, and the pyridyl unsubstituted or by a maximum of two of the substituents halogen , NO ₂ , -OCHF ₂ and CF _{3 is the} same or different substituted. 6. Compounds according to claim 5, wherein Z is oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl. 7. Compounds according to claim 3, wherein Het represents an unsubstituted or substituted pyrimidinyl radical. 8. Compounds according to claim 7, wherein B is the chain -CH ₂ -CH (CH ₃ J-CH ₂ - or -CH = C (CH ₃ ) -CH ₂ - means, and the pyrimidinyl radical is unsubstituted or by halogen, C ₁ C ₄ alkyl, cyclopropyl is the same or different monosubstituted to trisubstituted. 9. Compounds according to claim 8, wherein Z represents oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl. 10. Compounds according to claim 3, wherein Het represents an unsubstituted or substituted pyrazinyl radical. Compounds according to claim 10, in whichB is -CH ₂ -CH (CH ₃ ) -CH ₂ -or-CH = C (CH ₃ ) -CH ₂ - and the pyrazinyl radical is unsubstituted or by C ₁ -C ₄ -alkyl and / or Halogen is substituted at most twice. 12. Compounds according to claim 11, wherein Z is oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl. 13. Compounds according to claim 3, wherein Het is an unsubstituted or substituted 1,3,5-triazinyl radical. 14. Compounds according to claim 13, wherein B is the chain -CH 2 -CH (CH ₃ ) -CH 2 - or -CH = C (CH ₃ ) -CH 2 - and the 1,3,5-triazinyl unsubstituted, alkyl and / or is halogen-substituted. 15. Compounds according to claim 14, wherein Z is oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl. 16. Compounds according to claim 3, wherein Het represents an unsubstituted or substituted thiazolyl radical. 17. Compounds according to claim 16, wherein B is the chain -CH 2 -CH (CH ₃ ) -CH 2 - or -CH = C (CH ₃ ) -CH 2 -, and the thiazolyl radical is unsubstituted or monosubstituted by NO ₂ or halogen. 18. Compounds according to claim 17, wherein Z is oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl. 19. Compounds according to claim 3, wherein Het is an oxazolyl radical, Z is oxygen or -CH ₂ -darstellt and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl. 20. Compounds according to claim 3, wherein Het is an unsubstituted or C 1 -C ₄ alkyl substituted 1,2,4-triazolyl radical, Z is oxygen or -CH ₂ - and R ₃ and R _{4 are} the two adjacent to Z. Occupy positions and both have the same meaning hydrogen or methyl. 21. Compounds according to claim 3, in which Het is an unsubstituted or C 1 -C ₄ -alkyl-substituted 1,2,4-imidazolyl radical, Z is oxygen or -CH ₂ - and R ₃ and R _{4 are} the two adjacent to Z. Occupy positions and both have the same meaning hydrogen or methyl. 22. Compounds according to claim 3, wherein Het is an oxadiazole radical, Z is oxygen or -CH ₂ -darstellt and R ₃ and R ₄ occupy the two adjacent to Z positions and both have the same meaning hydrogen or methyl. 23. Compounds according to claim 3, wherein Het is a thiadiazole radical, Z is oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl. 24. A compound according to claim 1, wherein Het is an unsubstituted or by halogen, or C ₁ -C ₄ -AIkYl the same or different at most doubly substituted thienyl radical. 25. A compound according to claim 24, wherein X is oxygen, η is OobeM, m is OiStR _{1 is} halogen, methyl or methoxy, R _{2 is} hydrogen or methyl and R _{3 is} hydrogen or methyl, and R _{4 is} hydrogen, methyl, hydroxy, methoxy, Represents hydroxymethyl or methoxymethyl. 26. Compounds according to claim 25, wherein Z represents oxygen or -CH ₂ - and R ₃ and R ₄ occupy the two positions adjacent to Z and both have the same meaning hydrogen or methyl. 27. A process for the preparation of compounds of the formula I according to claim 1, characterized a) by reaction of an amine of the formula II (ID A ₁ R4 at 0 ⁰ C to 220 ⁰ C with a heterocycle of the formula III Het-A ₂ (III) wherein one of the radicals A ₁ and A _{2 is} a nucleofugic leaving group and the other the group -XMe, in which Me is hydrogen or a metal cation, while the substituents R ₁ , R ₃ , R ₄ , B, X and Z and η that under formula I have meanings given; or b) by condensation of a heterocyclic diphenyl ether of the formula IV (Ri) B-C Sf // HCI X ' wherein C represents a nucleofugic leaving group, at 0 ⁰ C to 120 ⁰ C with an amine of formula V