DE19540970A1 - p-Hydroxy aniline derivs useful as fungicides - Google Patents

Abstract

An agent for the control of harmful fungi contains p-hydroxy-aniline derivs. of formula (I) and conventional additives. R<1> = H, 1-8C alkyl (opt. partially or completely halogenated and/or opt. mono- or di-substd. with 1-4C alkoxy, 1-4C haloalkoxy, 1-4C alkylthio, 3-7C cycloalkyl, 5-7C cycloalkenyl (the cyclic gps. themselves opt. mono-, di- or tri-substd. with halogen, 1-3C alkyl and/or 1-3C alkoxy) and aryl ( opt. partially or completely halogenated and/or opt. mono-, di- or tri-substd. with NO2, CN, 1-4C alkyl, 1-4C haloalkyl, 1-4C alkoxy, 1-4C haloalkoxy or 1-4C alkylthio)), 6-15C bicycloalkyl or 7-15C bicycloalkenyl (these last 2 gps. opt. partially or completely halogenated and/or opt. mono-, di- or tri-substd. with 1-4C alkyl, 1-4C haloalkyl, 1-4C alkoxy, 1-4C haloalkoxy and aryl (opt. partially or completely halogenated and opt. mono-, di- or tri-substd. with NO2, CN, 1-4C alkyl, 1-4C haloalkyl, 1-4C alkoxy, 1-4C haloalkoxy or 1-4C alkylthio)); R<2> and R<3> = each halogen, 1-4C alkyl, 1-4C haloalkyl, 1-4C alkoxy or 1-4C haloalkoxy).

Description

The present invention relates to a to combat harm mushrooms suitable agent, containing common additives and an effective amount of a p-hydroxyaniline derivative of the general NEN Formula I

in which the residues have the following meaning:
R¹ is hydrogen, C₁-C₈-alkyl, which can be partially or completely halogenated and / or carry one or two of the following groups: C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio, C₃-C₇-cycloalkyl , C₅-C₇-cycloalkenyl, where the cyclic groups in turn can carry one to three halogen atoms, C₁-C₃-alkyl groups and / or C₁-C₃-alkoxy groups and aryl, which may be partially or completely halogenated and / or one to three of the following substituents can wear: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and C₁-C₄-alkylthio, C₆-C₁₅-bicycloalkyl or C₇-C₁₅-bicycloalkenyl, where these radicals can be partially or completely halogenated and / or can carry one to five of the following groups: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-halogen alkoxy and aryl, which is partially or completely be halogenated and / or one to three of the can carry the following substituents: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-halogeno alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and C₁-C₄-alkylthio;
R² and R³ independently of one another halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy.

The invention also relates to the use of the compounds I. and the agents for controlling harmful fungi containing them and the use of the compounds I for the preparation of Medium.  

From the literature, alkyl carboxylic acid anilides are fungicidal Effect known (US-A 3 849 478, US-A 3 958 006, EP-A 293 718 and JP-A 345 751/93).

4-hydroxyanilides are also known from EP-A 339 418, which, however, are not yet in terms of their fungicidal activity to satisfy.

The present invention has agents with improved effects against a broader spectrum of harmful fungi as a task reasons.

Accordingly, the agents defined at the outset were found.

In addition, the use of these funds and the verbin found I to combat harmful fungi and Ver Use of the compounds I for the preparation of the agents.

The compounds of general formula I and their preparation are known from EP-A 653 417 and EP-A 653 418. The Compounds are there as intermediates for fungicidal O-acy lated p-hydroxyaniline derivatives wrote.

The hydroxyaniline derivatives of the general formula I are obtained, by using a p-hydroxyaniline of the formula II known per se Manner (cf. DE-A 32 02 100; EP-A 339 418) in an inert orga African solvent and optionally in the presence of a base reacted with a carbonyl derivative of the formula III.

The variable X in formula III stands for halogen, in particular Chlorine, bromine and iodine or another in acylation reactions common leaving group, e.g. B. R¹-CO-O.

The reaction is usually carried out at temperatures from -70 to 140, preferably 0 to 110 ° C.  

Suitable solvents are aliphatic hydrocarbons such as Pentane, hexane, cyclohexane and petroleum ether, aromatic coal water materials such as toluene, o-, m- and p-xylene, halogenated coal water substances such as methylene chloride, chloroform and chlorobenzene, ether such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and Propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, as well as dimethyl sulfoxide and dimethyl formamide.

Mixtures of the solvents mentioned can also be used will.

Preferred solvents are dioxane, tetrahydrofuran and Dimethylformamide, alone or in a mixture.

Possible bases are: alkali metal and alkaline earth metal hydroxides, e.g. B. lithium hydroxide, sodium hydroxide, potassium hydroxide, Calcium hydroxide; Alkali metal and alkaline earth metal oxides, e.g. B. Lithium oxide, sodium oxide, calcium oxide, magnesium oxide; Alkali metallamides, e.g. B. lithium amide, sodium amide, potassium amide; Alkali metal and alkaline earth metal carbonates, e.g. B. lithium carbonate, Calcium carbonate; Alkali metal bicarbonates, e.g. B. sodium hydrogen carbonate; Alkali metal and alkaline earth metal alcoholates, e.g. B. sodium methoxide, sodium ethanolate, potassium ethanolate, Potassium tert-butanolate, dimethoxymagnesium; organic bases, e.g. B. tertiary amines such as trimethylamine, triethylamine, tri-isopro pylethylamine and N-methylpiperidine, pyridine Pyridines such as collidine, lutidine and 4-dimethylaminopyridine as well bicyclic amines.

Alkali metal carbonates and alcoholates are particularly preferred or tertiary amines used.

The bases are generally used in equimolar amounts, but they can also in excess or as a solvent be used.

The starting materials are generally together in equimolar amounts the implemented. It can be advantageous for the yield that Carbonyl derivative III in an excess or deficit based on to use the p-hydroxyaniline II.

The starting materials II and III required for the implementation are known from the literature (II: J. Chem. Soc. PT I, 1, 1 (1973); Houben-Weyl, vol. 10/1, p. 1140 f .; ibid. Vol. 6 / 1c, pp. 85-101; III: Houben-Weyl, E5, Part 1, p. 587; Can. J. Chem. 71,  S. 1099-1105 (1993)) or can according to the literature cited getting produced.

The reaction mixtures are worked up in a conventional manner, e.g. B. by mixing with water, separation of the phases and given if chromatographic purification of the raw products. The products fall z. T. in the form of colorless or slightly brownish, viscous oils at under reduced pressure and at moderately elevated Volatile components can be freed or cleaned of temperature can. If the intermediate and end products as solids cleaning can also be maintained by recrystallization or digesting.

The compounds I can ent or one or more centers of asymmetry hold and are in the form of Obtained mixtures of enantiomers or diastereomers. The quantities Relationships can vary depending on the groups be different. These mixtures can, if necessary, according to the usual metho which are separated. The compounds I can both as pure Isomers or as mixtures of isomers are used.

In the definitions of the compounds I given at the beginning, the collective terms were used which are generally representative of the following substituents:
Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: straight-chain or branched alkyl groups with 1 to 3, 4, 6 or 8 carbon atoms, e.g. B. C₁-C₆-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methyl-propyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1 , 2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2 Trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl;
Haloalkyl or partially or fully halogenated alkyl: straight-chain or branched alkyl groups having 1 to 4, 6 or 8 carbon atoms as mentioned above, where in these groups the hydrogen atoms can be replaced partially or completely by halogen atoms as mentioned above, for. B. C₁-C₂-haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2nd - chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
Alkoxy: straight-chain or branched alkoxy groups having 1 to 3 or 4 carbon atoms, such as methyloxy, ethyloxy, propyloxy, 1-methylethyloxy, butyloxy, 1-methyl-propyloxy, 2-methylpropyloxy and 1,1-dimethylethyloxy;
Haloalkoxy: straight-chain or branched partially or fully halogenated alkyl groups with 1 to 4 carbon atoms as mentioned above, these groups being bonded to the structure via an oxygen atom (-O-);
Alkylthio: straight-chain or branched alkyl groups with 1 to 4 carbon atoms as mentioned above, which are bonded to the structure via a sulfur atom (-S-);
Cycloalkyl: monocyclic alkyl groups with 3 to 7 carbon ring members: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cycloheptyl;
Cycloalkenyl: monocyclic alkenyl groups with 5 to 7 carbon ring members and one or two double bonds: 1-cyclopentyl, 2-cyclopentenyl, 3-cyclopentenyl, 1,3-cyclopentadienyl, 1,4-cyclopentadienyl, 1-cyclohexenyl, 2-cyclohexenyl, 3 -Cyclohexenyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,5-cyclohexadienyl, 2,4-cyclohexadienyl, 1-cycloheptenyl, 2-cycloheptenyl, 3-cycloheptenyl, 4-cycloheptenyl, 1,3-cycloheptadienyl , 1,4-cycloheptadienyl, 1,5-cycloheptadienyl, 1,6-cycloheptadienyl, 2,4-cycloheptadienyl, 2,5-cycloheptadienyl, 2,6-cycloheptadienyl and 3,5-cycloheptadienyl;
Bicycloalkyl: bicyclic alkyl groups with 6 to 15 carbon ring members, e.g. B. Bicyclo- [2.1.1] -hex-5-yl, Bicyclo- [2.2.1] -hept-2-yl, Bicyclo- [2.2.2] oct-2-yl, Bicyclo- [3.2.1] -oct-6-yl, bicyclo- [3.2.2] -non-6-yl, bicyclo- [4.2.2] -dec-7-yl, bicyclo- [3.1.0] -hex-1-yl, bicyclo - [4.1.0] -hept-1-yl, bicyclo- [4.3.0] -non-1-yl, bicyclo- [4.4.0] -dec-1-yl, particularly preferably 5-methyl-bi cyclo- [2.1.1] -hex-5-yl, 2-methyl-bicyclo- [2.2.1] -hept-2-yl, 2-methyl-bicyclo- [2.2.2] -oct-2-yl, 6th -Methyl-bicyclo- [3.2.1] -oct-6-yl, 6-methyl-bicyclo- [3.2.2] -non-6-yl, 7-methyl-bicyclo- [4.2.2] -dec- 7-yl, 1-methyl-bicyclo- [3.1.0] -hex-1-yl, 1-methyl-bicyclo- [4.1.0] -hept-1-yl, 1-methyl-bicyclo- [4.3 .0] -non-1-yl, 1-methyl-bicyclo- [4.4.0] -dec-1-yl, 2-methyl-bicyclo- [3.1.0] -hex-1-yl, 2-methyl -bi cyclo- [4.1.0] -hept-1-yl, 2-methyl-bicyclo- [4.3.0] -non-1-yl, 2-methyl-bicyclo- [4.4.0] -dec-1 -yl;
Bicycloalkenyl: bicyclic alkenyl groups with 7 to 15 carbon ring members, e.g. B. Bicyclo- [2.2.1] -hept-2-en-5-yl, Bicyclo- [2.2.2] -oct-2-en-5-yl, Bicyclo- [4.2.2] -dec-7- en-2-yl, bicyclo- [4.3.0] -non-7-en-1-yl, bicyclo- [4.4.0] -dec-3-en-1-yl, bicyclo- [4.1.0] - hept-3-en-1-yl, 5-methyl-bicyclo- [2.2.1] - hept-2-en-5-yl, 5-methyl-bicyclo- [2.2.2] -oct-2-en- 5-yl, 2-methyl-bicyclo- [4.2.2] -dec-7-en-2-yl, 2-methyl-bicyclo- [4.3.0] - non-7-en-1-yl, 2- Methyl-bicyclo- [4.4.0] -dec-3-en-1-yl, 2-methyl-bicyclo- [4.1.0] -hept-3-en-1-yl;
Aryl: phenyl or naphthyl.

The statement "partially or completely halogenated" is intended to end bring pressure that in the groups so characterized the Hydrogen atoms partially or completely by the same or various halogen atoms as mentioned above can be replaced can.

With regard to their biological action against harmful fungi Preferred compounds of the formula I

• - in which R¹ for a branched or substi in the 1-position tuiert alkyl group, preferred as substituents are: halogen, C₁-C₄ alkoxy and aryl, which is partial or be completely halogenated and / or one to three of the fol the following residues can carry: nitro, cyano, C₁-C₄-alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy and C₁-C₄ alkylthio,
• - in which R¹ for 2-methyl-bicyclo- [2.2.1] -hept-2-yl, 2-methyl bicyclo- [2.2.2] oct-2-yl, bicyclo- [4.1.0] -hept-1-yl, 1-Me thyl-bicyclo- [4.3.0] -non-1-yl, 1-methyl-bi cyclo- [4.4.0] -dec-1-yl, 1-methyl-bicyclo- [4.1.0] -hept-1-yl, 2-methyl-bicyclo- [4.3.0] - non-1-yl, 2-methyl-bicyclo- [4.4.0] -dec-1-yl, 5-methyl-bi cyclo- [2.2.1] -hept-2-yl, 5-methyl-bi cyclo- [2.2.2] oct-2-en-5-yl, 2-methyl-bi cyclo- [4.4.0] -dec-3-en-1-yl, or 2-methyl-bi cyclo- [4.1.0] -hept-3-en-1-yl,
• - in which R² represents halogen, alkyl or alkoxy,
• in which R² is alkyl, in particular methyl,  
• - in which R² represents fluorine or chlorine,
• - in which R³ is alkyl, haloalkyl, alkoxy or halogen alkoxy stands,
• - in which R³ is halogen, alkyl, haloalkyl or halogen alkoxy stands and / or
• - in which R³ is fluorine, chlorine, methyl or trifluoromethyl stands.

In particular, those compounds I are preferred in which R1 for 1,1-dimethylethyl, 1,1-dimethylpropyl, 1-methyl-1-ethyl propyl, 2-chloro-1,1-dimethylethyl and 2-fluoro-1,1-dimethylethyl stands.

Are very particularly preferred with regard to their use for Control of harmful fungi as shown in the following tables 1 to 18 compiled connections.

Table 1

Compounds of the general formula I.1, in which the combination the substituents R² and R³ for a compound each one Row of table A stands

Table 2

Compounds of the general formula I.2, in which the combination the substituents R² and R³ for a compound each one Row of table A stands

Table 3

Compounds of the general formula I.3, in which the combination the substituents R² and R³ for a compound each one Row of table A stands

Table 4

Compounds of the general formula I.4, in which the combination the substituents R² and R³ for a compound each one Row of table A stands

Table 5

Compounds of the general formula I.5, in which the combination the substituents R² and R³ for a compound each one Row of table A stands

Table 6

Compounds of the general formula I.6, in which the combination the substituents R² and R³ for a compound each one Row of table A stands

Table 7

Compounds of the general formula I.7, in which the combination the substituents R² and R³ for a compound each one Row of table A stands

Table 8

Compounds of the general formula I.8, in which the combination the substituents R² and R³ for a compound each one Row of table A stands

Table 9

Compounds of the general formula I.9, in which the combination the substituents R² and R³ for a compound each one Row of table A stands

Table 10

Compounds of the general formula I.10, in which the Kombina tion of the substituents R² and R³ for one compound each Row of table A stands

Table 11

Compounds of the general formula I.11, in which the Kombina tion of the substituents R² and R³ for one compound each Row of table A stands

Table 12

Compounds of the general formula I.12, in which the Kombina tion of the substituents R² and R³ for one compound each Row of table A stands

Table 13

Compounds of the general formula I.13, in which the Kombina tion of the substituents R² and R³ for one compound each Row of table A stands

Table 14

Compounds of the general formula I.14, in which the Kombina tion of the substituents R² and R³ for one compound each Row of table A stands

Table 15

Compounds of the general formula I.15, in which the Kombina tion of the substituents R² and R³ for one compound each Row of table A stands

Table 16

Compounds of the general formula I.16, in which the Kombina tion of the substituents R² and R³ for one compound each Row of table A stands

Table 17

Compounds of the general formula I.17, in which the Kombina tion of the substituents R² and R³ for one compound each Row of table A stands

Table 18

Compounds of the general formula I.18, in which the Kombina tion of the substituents R² and R³ for one compound each Row of table A stands

Table A

The new compounds of formula I are suitable as fungicides.

The new compounds or the compositions containing them can for example in the form of directly sprayable solutions, pul vern, suspensions, also high-proof aqueous, oily or other suspensions or dispersions, emulsions, oil dispersers sions, pastes, dusts, sprinkles or granules Spraying, atomizing, dusting, scattering or pouring be applied. The application forms depend on the uses purposes; in any case, they should be the finest Ensure distribution of the active ingredients according to the invention.

The plants are usually sprayed with the active ingredients or pollinated or the seeds of the plants with the active ingredients treated.

The formulations are prepared in a known manner, e.g. B. by stretching the active ingredient with solvents and / or Carriers, if desired using emulsifier agents and dispersants, where in the case of water as Ver other organic solvents as auxiliary solvents can be used. As auxiliary agents come there for essentially: solvents such as aromatics (e.g. Xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. Petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g.  Cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and Water; Carriers such as natural rock powder (e.g. kaolins, Clays, talc, chalk) and synthetic stone powder (e.g. finely divided silica, silicates), emulsifiers like not ionogenic and anionic emulsifiers (e.g. polyoxyethylene fatty al alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants agents such as lignin sulfite liquor and methyl cellulose.

The alkali, alkaline earth, Ammonium salts of aromatic sulfonic acids, e.g. B. lignin, Phenolic, naphthalene and dibutylnaphthalenesulfonic acid, as well as from Fatty acids, alkyl and alkyl aryl sulfonates, alkyl and lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ethers, condensates products of sulfonated naphthalene and its derivatives Formaldehyde, condensation products of naphthalene or Naphthalenesulfonic acids with phenol and formaldehyde, polyoxy ethylenoctylphenol ether, ethoxylated isooctyl, octyl or Nonylphenol, alkylphenol, tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethyleno xid condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulfite liquor or methyl cellulose.

Powders, materials for spreading and dusts can be mixed or joint grinding of the active substances with a solid Carrier are manufactured.

Granules, e.g. B. coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers be put. Solid carriers are mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, lime stone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, Calcium and magnesium sulfate, magnesium oxide, ground art substances, fertilizers, such as ammonium sulfate, ammonium phosphate, Ammonium nitrate, ureas and herbal products, such as Cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

Examples of such preparations are (the active ingredients used substances are labeled in accordance with Table B):

• I. a solution of 90 parts by weight of compound no. 1 and 10 Parts by weight of N-methyl-α-pyrrolidone for use in The shape of the smallest drops is suitable;  
• II. A mixture of 20 parts by weight of compound no. 1, 80 parts by weight of xylene, 10 parts by weight of the add-on pro product of 8 to 10 moles of ethylene oxide with 1 mole of oleic acid-N-mono ethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesul fonic acid, 5 parts by weight of the adduct of 40 mol Ethylene oxide on 1 mole of castor oil; by finely distributing the Solution in water gives a dispersion.
• III. an aqueous dispersion of 20 parts by weight of the compound
  No. 1, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutane nol, 20 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil;
• IV. An aqueous dispersion of 20 parts by weight of the compound No. 2, 25 parts by weight of cyclohexanol, 65 parts by weight of a Mi. mineral oil fraction from boiling point 210 to 280 ° C and 10 Parts by weight of the adduct of 40 mol of ethylene oxide to 1 mol castor oil;
• V. a mixture of 80 ground in a hammer mill Parts by weight of compound no. 2, 3 parts by weight of sodium salt of diisobutylnaphthalene-a-sulfonic acid, 10 parts by weight the sodium salt of a lignin sulfonic acid from a sulfite blue and 7 parts by weight of powdered silica gel; by finely distributing the mixture in water, egg is obtained ne spray liquor;
• VI. an intimate mixture of 3 parts by weight of compound no. 2 and 97 parts by weight of finely divided kaolin; this dusts contains 3% by weight of active ingredient;
• VII. An intimate mixture of 30 parts by weight of the compound No. 3, 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil on the surface of this Silica gel was sprayed; this preparation gives the Active ingredient good adhesion;
• VIII. A stable aqueous dispersion of 40 parts by weight of Ver Binding No. 3, 10 parts by weight of the sodium salt one Phenolsulfonic acid-urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, the can be further diluted;
• IX. a stable oily dispersion of 20 parts by weight of the verbin 3, 2 parts by weight of the calcium salt of dodecylbene bolsulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid  Urea-formaldehyde condensate and 68 parts by weight of a paraffin mineral oil.

The compounds I and the agents according to the invention stand out due to its excellent effectiveness against a wide range of phytopathogenic fungi, in particular from the class of Ascomycetes, Basidiomycetes, Deuteromycetes and Phycomycetes. Some of them are systemically effective and can be used as leaf and Soil fungicides are used.

They are particularly important for combating a large number of mushrooms on various crops such as wheat, rye, Barley, oats, rice, corn, grass, cotton, soy, coffee, sugar pipe, wine, fruit and ornamental plants and vegetables such as cucumbers, Beans and pumpkin plants and on the seeds of these plants.

The compounds I and the agents according to the invention are listed applies by looking at the harmful fungi, their habitat or the Fungal attack on protected seeds, plants, surfaces, materia lien or rooms with a fungicidally effective amount of the active ingredient fe I or the agent treated.

The application takes place before or after the infection of the seeds, Materials or plants through the mushrooms.

The compounds I and those according to the invention are particularly suitable Means to control the following plant diseases:

Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichora cearum and Sphaerotheca fuliginea on pumpkin family, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species on cotton and lawn, Ustilago Species of cereals and sugar cane, Venturia inaequalis (scab) Apples, Helminthosporium species on cereals, Septoria nodorum Wheat, botrytis cinerea (gray mold) on strawberries, vines, Ornamental plants and vegetables, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, pyricula ria oryzae on rice, Phytophthora infestans on potatoes and Tomatoes, Fusarium and Verticillium species on different Plants, Plasmopara viticola on vines, Alternaria species Vegetables and fruit.

Combating botrytis by means of the Compounds I or the agent according to the invention.  

The compounds I and the agents according to the invention can also used in material protection (wood protection), e.g. B. against Pae cilomyces variotii.

The agents according to the invention generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.

The application rates depend on the type of effect desired between 0.01 and 2.0 kg of active ingredient per ha.

When treating seeds, amounts of active ingredient are generally used from 0.001 to 50 g, preferably 0.01 to 10 g per kilogram of seed well needed.

The agents according to the invention can also be used together with others Active substances are present, e.g. B. with herbicides, insecticides, awake regulators, fungicides or also with fertilizers.

When mixed with other fungicides you get in vie len cases an increase in the fungicidal spectrum of activity.

The following list of fungicidal active ingredients with which he compounds according to the invention can be used together, should explain the possible combinations, but not one restrict:

Sulfur, dithiocarbamates and their derivatives, such as ferridimethyl dithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithio carbamate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylene diamine-bis-dithiocarbamate, tetramethylthiuram disulfide, zinc ammonium, ammonia-bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) ammonium bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) and ammonium bis (ammonia) bis (ammonia) bis (ammonia) bis (n) - complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis (thio carbamoyl) disulfide;
Nitroderivatives, such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl-iso-propyl carbonate, 5 -Nitro-iso-phthalic acid di-iso-propyl ester;
heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl phthalimidophosphonothioate, 5-amino-1- [bis- (dimethylamino ) - phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo [4,5-b] quinoxaline, 1 - (Butylcarbamoyl) -2-benzimidazole carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1,1,2,2 Tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimide,
N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanemethylthiobenzothiazole, 1,4-dichloro-2,5- dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl- 1,4-oxathiin, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide, 2-methyl-5,6-di hydro-4H-pyran-3-carboxylic acid -anilide, 2-methyl-furan-3-carbonsäu reanilide, 2,5-dimethyl-furan-3-carbonsäureanilide, 2,4,5-trimethyl-furan-3-carbonsäureanilide, 2,5-dimethyl-furan-3 -carbon acid cyclohexylamide, N-cyclohexyl-N-methoxy-2,5-dimethyl furan-3-carboxamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine-2, 2,2-trichloroethyl acetal, piperazine-1,4-diylbis- (1- (2,2,2-trichloroethyl) formamide, 1- (3,4-dichloroanilino) -1-formylamino-2,2,2 - trichloroethane,
2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methylpropyl ] -cis-2,6-dimethylmorpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-1 , 3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan- 2-yl -ethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazol-yl-urea, 1- (4-chlorophenoxy ) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5-pyrimidine-methanol, 5 -Butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridinomethanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) benzene, 1 , 2-bis-3-methoxycarbonyl-2-thioureido) benzene, [2- (4-chlorophenyl) ethyl] - (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol as well
various fungicides, such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl)] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethylphenyl) - N-furoyl (2) alaninate, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl -D, L-2-aminobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2.4 -dioxo-1,3-oxazolidine, 3- [3,5-dichlorophenyl (-5-methyl-5-methoxymethyl] -1,3-oxazolidin-2,4-dione, 3- (3,5-dichlorhenyl) -1-iso-propylcarbamoylhy dantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-difluoro-α- (1H-1,2,4-triazolyl-1-methyl) -benzhydryl alcohol, N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1 - ((bis- (4-fluorophenyl) methyl silyl) methyl ) -1H-1,2,4-triazole.

Strobilurins such as methyl-E-methoximino- [α- (o-tolyloxy) -o- tolyl] acetate, methyl E-2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, methyl-E-methoxy mino- [α- (2-phenoxyphenyl)] acetamide, methyl E methoxy mino- [α- (2,5-dimethyloxy) -o-tolyl] acetamide.

Anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- (4-methyl- 6-cyclopropyl-pyrimidin-2-yl) aniline.

Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole- 3-carbonitrile.

Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acrylic acid morpholide.

(2RS, 3SR) -1 [3- (2-chlorophenyl) -2,3-epoxy-2- (4-fluor phenyl) propyl] -1H-1,2,4-triazole.

Synthesis examples

The regulation given in the synthesis example below to produce the compounds Ia can be modified by Starting compounds for obtaining further representatives of the Connections I are used. Examples made accordingly are in the following table B with physical data given.

3-chloro-2,2-dimethylpropane carboxylic acid N- (2,3-dichloro-4- hydroxyphenyl) amide (Compound 1 in Table B)

To a solution of 1.93 g (0.011 mol) of 4-amino-2,3-dichlorophenol in 30 ml of tetrahydrofuran at 0 ° C 1.55 g (0.01 mol) of chlorpi dripped valinic acid chloride and stirred at 25 ° C until thin-layer chromatography no more starting compound could be pointed. Then the reaction mixture added to water and three times with 20 ml of extra methylene chloride here. The combined organic phases were washed twice with Was  water washed, dried and concentrated. The backlog was on Chromatographed silica gel (eluent: cyclohexane: vinegar ester = 2: 1; Yield: 0.75 g, mp 115 ° C).

Table B

Examples of use Botrytis cinera

Pepper seedlings of the "Neusiedler Ideal Elite" variety with 4-5 good developed leaves were treated with an aqueous active substance suspension sion sprayed soaking wet. After the spray coating has dried on the plants were exposed to a conidia of the fungus Sprayed botrytis cinera. After 5 days at 22 ° C-24 ° C and higher The fungus infestation of the leaves was assessed in air humidity.

Claims (5)

1. Suitable for controlling harmful fungi, containing conventional additives and an effective amount of a p-hydro xyanilinderivates of the general formula I. in which the residues have the following meaning:
R¹ is hydrogen, C₁-C₈-alkyl, which can be partially or completely halogenated and / or carry one or two of the following groups: C₁-C₄-alkoxy, C₁-C₄-halogen alkoxy, C₁-C₄-alkylthio, C₃- C₇-Cycloalkyl, C₅-C₇-Cyclo alkenyl, where the cyclic groups in turn can carry one to three halogen atoms, C₁-C₃-alkyl groups and / or C₁-C₃-alkoxy groups and aryl, which may be partially or completely halogenated and / or one can carry up to three of the following substituents: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C-C₄-alkoxy, C₁-C₄-haloalkoxy and C₁-C₄-alkylthio, C₆-C₁₅-bicycloalkyl or C₇- C₁₅-bicycloalkenyl, these radicals being partially or completely halogenated and / or bearing one to five of the following groups: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C--haloalkoxy and aryl which are partially or fully halogenated and / or one to three d it can carry the following substituents: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and C₁-C₄-alkylthio;
R² and R³ independently of one another halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy or C₁-C₄-haloalkoxy. 2. Use of the compounds of general formula I according to Claim 1 for combating harmful fungi. 3. Use of the agent according to claim 1 for combating Harmful fungi.   4. Use of the compounds of general formula I according to Claim 1 for the production of for controlling harmful fungi appropriate means. 5. A method of combating harmful fungi, characterized records that the harmful fungi, their habitat or the seeds, plants, surfaces, mate to be kept free of them rialien or spaces with an effective amount of a compound of the general formula I according to claim 1 or an agent treated according to claim 1.