DE19504599A1 - 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 for combating Agent suitable for harmful fungi, containing conventional additives and an effective amount of a p-hydroxyaniline derivative 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-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, these radicals being partially or completely halogenated and / or carrying one to five of the following groups: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and aryl, which can be partially or completely halogenated and / or can carry one to three of 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.

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 underlying.

Accordingly, the agents defined at the outset were found.

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

The compounds of general formula I and their preparation are from the older German applications P 43 38 469.2 or P 43 38 512.5 known. The connections are there as an intermediate products for fungicidal O-acylated p-hydroxyaniline derivatives be 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 manner organic solvents and optionally in the presence of a Base reacted with a carbonyl derivative of formula III.

The variable X in formula III stands for halogen, in particular Chlorine, bromine and iodine, or one 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 Hydrocarbons such as toluene, o-, m- and p-xylene, halogenated Hydrocarbons such as methylene chloride, chloroform and Chlorobenzene, ethers 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, and Dimethyl sulfoxide and dimethylformamide.

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 metal amides, 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 bicarbonate; Alkali metal and Alkaline earth metal alcoholates, e.g. B. sodium methoxide, Sodium ethanolate, potassium ethanolate, potassium tert-butoxide, Dimethoxy magnesium; organic bases, e.g. B. tertiary amines such as Trimethylamine, triethylamine, tri-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, Lutidine and 4-dimethylaminopyridine and 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 in equimolar amounts implemented with each other. It may be advantageous for the yield the carbonyl derivative III related in an excess or deficit 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, ES, 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 optionally chromatographic purification of the raw products. The Products fall e.g. T. in the form of colorless or slightly brownish, viscous oils on under reduced pressure and at moderately increased Volatile components can be freed or cleaned of temperature can. If the intermediate and end products as solids cleaning can also be obtained by recrystallization or digesting.

The compounds I can have one or more centers of asymmetry contained and are in the form of Obtained mixtures of enantiomers or diastereomers. The Quantity ratios can depend on the groups be different. These mixtures can, if necessary, according to the usual Methods are separated. The compounds I can both as pure isomers or as mixtures of isomers for use come.

In the definitions of the compounds I given at the outset, 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 completely halogenated alkyl: straight-chain or branched alkyl groups having 1 to 4, 6 or 8 carbon atoms as mentioned above, wherein 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, 2- 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 completely 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-cyclopentenyl, 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 preferred
5-methyl-bicyclo- [2.1.1] hex-5-yl,
2-methyl-bicyclo- [2.2.1] hept-2-yl,
2-methyl-bicyclo- [2.2.2] oct-2-yl,
6-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-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;
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 fully halogenated" is intended to Express 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 in the 1-position or substituted alkyl group, being as a substituent preferred are: halogen, C₁-C₄ alkoxy and aryl, which be partially or fully halogenated and / or one to can carry three of the following residues: nitro, cyano, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄ haloalkoxy and C₁-C₄ alkylthio,
• - in which R¹ is 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-methyl-bicyclo- [4.3.0] -non-1-yl, 1-methyl-bicyclo- [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-bicyclo- [2.2.1] -hept-2-yl, 5-methyl-bicyclo- [2.2.2] oct-2-en-5-yl, 2-methyl-bicyclo- [4.4.0] -dec-3-en-1-yl, or 2-methyl-bicyclo- [4.1.0] -hept-3-en-1-yl,
• - in which R² represents halogen, alkyl or alkoxy, in which R² represents alkyl, in particular methyl,
• - in which R² represents fluorine or chlorine,
• - in which R³ is alkyl, haloalkyl, alkoxy or Halogenalkoxy stands,
• - in which R³ is halogen, alkyl, haloalkyl or Halogenalkoxy 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.

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 of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 2

Compounds of the general formula I.2, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 3

Compounds of the general formula I.3, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 4

Compounds of the general formula 1.4 in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 5

Compounds of the general formula I.5, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 6

Compounds of the general formula I.6, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 7

Compounds of the general formula I.7, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 8

Compounds of the general formula I.8, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 9

Compounds of the general formula I.9, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 10

Compounds of the general formula I.10, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 11

Compounds of the general formula I.11, in which the combination of the substituents R² and R³ represents a compound in each case one line of Table A.

Table 12

Compounds of the general formula I.12, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 13

Compounds of the general formula I.13, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 14

Compounds of the general formula I.14, in which the combination of the substituents R² and R³ represents a compound in each case one line of Table A.

Table 15

Compounds of the general formula I.15, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 16

Compounds of the general formula I.16, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 17

Compounds of the general formula I.17, in which the combination of the substituents R² and R³ represents a compound in each case one row of Table A.

Table 18

Compounds of the general formula I.18, in which the combination of the substituents R² and R³ represents a compound in each case one line of Table A.

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, Powders, suspensions, including high-proof aqueous, oily or other suspensions or dispersions, emulsions, Oil dispersions, pastes, dusts, spreading agents or Granules by spraying, atomizing, dusting, scattering or pouring can be applied. The application forms are directed according to the uses; in any case, they should be as possible the finest distribution of the active ingredients according to the invention guarantee.  

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 Emulsifiers and dispersants, being in the case of water as a diluent other organic solvents than Auxiliary solvents can be used. As auxiliary substances are essentially considered: 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 like natural Rock flour (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, Silicates), emulsifiers such as nonionic and anionic Emulsifiers (e.g. polyoxyethylene fatty alcohol ether, Alkyl sulfonates and aryl sulfonates) and dispersants 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 ether, Condensation products of sulfonated naphthalene and its Derivatives with formaldehyde, condensation products of naphthalene or the naphthalenesulfonic acids with phenol and formaldehyde, Polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol, tributylphenyl polyglycol ether, Alkylaryl polyether alcohols, isotridecyl alcohol, Fatty alcohol ethylene oxide condensates, ethoxylated castor oil, Polyoxyethylene alkyl ether or polyoxypropylene, Lauryl alcohol polyglycol ether acetate, sorbitol ester, Lignin liquor or methyl cellulose into consideration.

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 prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth,
Calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

Examples of such preparations are (the ones used Active substances have the designation according to 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 Addition product of 8 to 10 moles of ethylene oxide with 1 mole Oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt Dodecylbenzenesulfonic acid, 5 parts by weight of the Addition product of 40 moles of ethylene oxide with 1 mole Castor oil; by finely distributing the solution in water you get 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 Isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole 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 one 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 of the sodium salt of a lignosulfonic acid a sulfite waste liquor and 7 parts by weight of powder Silica gel; by finely distributing the mixture in Water is obtained from a 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 Compound No. 3, 10 parts by weight of the sodium salt of 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 Compound No. 3, 2 parts by weight of the calcium salt of Dodecylbenzenesulfonic acid, 8 parts by weight 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 one paraffinic 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 cane, 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 applied by the harmful fungi, their habitat or the Seeds, plants, surfaces to be protected from fungal attack Materials or rooms with a fungicidally effective amount of Active ingredients 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 the agents according to the invention are particularly suitable for controlling the following plant diseases:
Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species on cotton and turf, Ustilago sugar species on cereals, Ustilago sugar on cereals, Ustilago varieties on cereals, Ustilago sugar varieties on cereals, Ustilago varieties on cereals, Ustilago varieties inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (gray mold) on strawberries, vines, ornamental plants and vegetables, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Reisicularophyte oryzaza infestans on potatoes and tomatoes, Fusarium and Verticillium species on various plants, Plasmopara viticola on vines, Alternaria species on vegetables and fruits.

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 Paecilomyces 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 Seed needed.

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

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

The following list of fungicidal active ingredients with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:
Sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylenediamine-bis-dithiocarbamate,
Tetramethylthiuram disulfide, ammonia complex of zinc (N, N-ethylene-bis-dithiocarbamate), ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis) -dithiocarbamate), N, N'-polypropylene bis (thiocarbamoyl) 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-phenyl-sulfuric acid dia. Mid, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanmethylthiobenzothiazole, 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-dihydro-4H-pyran-3-carboxylic acid anilide , 2-methyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,4,5-trimethyl-furan-3-carboxylic acid anilide, 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, Piperazin-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-pyridine-methanol, 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, 1- [3- (2-chlorophenyl) -1- (4-fluorophenyl) oxiran-2-yl-methyl] -1H-1,2,4-triazole and
various fungicides, such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl)] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N- furoyl (2) -alaninate, DL-N- (2,6-dimethyl-phenyl) -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-oxazolidine-2,4-dione, 3- (3,5-dichlorophenyl) -1-iso -propylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboxylic acid im id, 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- (3rd -Chlor-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1 - ((bis- (4-fluorophenyl) methylsilyl) 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-methoximino- [α- (2-phenoxyphenyl)] acetamide, Methyl-E-methoximino- [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.  

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 Table B below with physical data specified.

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) Chlorpivalinsäurechlorid dropped and at 25 ° C so long stirred until none by thin layer chromatography Initial connection could be detected more. Subsequently the reaction mixture was added to water and three times with Extracted 20 ml methylene chloride. The united organic Phases were washed twice with water, dried and constricted. The residue was chromatographed on silica gel (Mobile phase: cyclohexane, ethyl acetate = 2: 1. Yield: 0.75 g, Mp 115 ° C.

Table B

Botrytis cinera

Pepper seedlings of the "Neusiedler Ideal Elite" variety with 4-5 good developed leaves were washed with an aqueous Active ingredient suspension sprayed to runoff. After drying the The plants were sprayed with conidia  sprayed of the botrytis cinera mushroom. After 5 days at 22 ° C-24 ° C and high humidity became the fungal attack on the leaves judged.

Claims (5)

1. Suitable for controlling harmful fungi, containing conventional additives and an effective amount of a p-hydroxyaniline derivative 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-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, these radicals being partially or completely halogenated and / or carrying one to five of the following groups: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy and aryl, which can be partially or completely halogenated and / or can carry one to three of 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. Process for combating harmful fungi, thereby characterized in that the harmful fungi, their habitat or the seeds, plants, areas, Materials or spaces with an effective amount of one Compound of general formula I according to claim 1 or of an agent treated according to claim 1.