DD293115A5 - NEW 2-ANILINO-PYRIMIDINE DERIVATIVES - Google Patents

Abstract

The invention relates to 2-anilino-pyrimidine derivatives of the formula in which R1 and R2 independently of one another are hydrogen, halogen, C1-C3-alkyl, C1-C2-haloalkyl, C1-C3-alkoxy or C1-C3- haloalkoxy; R 3 is C 3 -C 6 -cycloalkyl or C 3 -C 6 -cycloalkyl substituted by methyl or halogen up to three times identically or differently; R4 is halogen, thiocyano, OR5, SR5, NR5R6, wherein R5 and R6 are as defined herein, are novel agents for preventing microbial attack on plants. The compounds may be used as such or as suitable agents as microbicides. The invention further relates to processes for the preparation of said compounds and pesticides. Formula {2-anilino-pyrimidine derivatives; microbicides; Method; manufacture; Prevention of microorganism infestation; Plants}

Description

Field of application of the invention

The present invention relates to processes for the preparation of 2-anilino-pyrimidine derivatives of the following formula I and to agrochemical compositions which contain as active ingredient at least one of these compounds. The invention also relates to the preparation of said agents and the use of the active substances or the agents for controlling pests, especially plant-damaging microorganisms, preferably fungi.

Characteristic of the known state of the art

Publications which underlie the present invention as prior art are currently unknown.

Object of the invention

By the method according to the invention new compounds are provided which can be used in microbicidal agents.

Explanation of the essence of the invention

The present invention has for its object to produce microbicidally active compounds.

According to the invention, processes for the preparation of novel 2-anilino-pyrimidine derivatives of the general formula I are made available,

(D

in which mean:

R ₁ and R ₂ independently of one another are hydrogen, halogen, C ₁ -C ₃ -alkyl, C ₁ -C -haloalkyl, C ₁ -C ₃ -alkoxy or C ₁ -C ₃ -haloalkoxy;

R _{3 is} C ₃ -C ₆ -cycloalkyl or up to three times identically by methyl or halogen or represents C ₃ -C ₆ cycloalkyl; R _{4 is} halogen, thiocyano (-SCN), - OR ₅ , -SR ₅ , -NR ₅ R ₆ , wherein R _{5 is} a) hydrogen, unsubstituted C ₁ -C ₈ alkyl, or a Ci-C-alkyl group represented by halogen, hydroxy, cyano, C ₁ -C ₄ -alkoxy, dd-alkylamino, bis (C ₁ -C ₄ -alkyl) amino, C ₃ -C ₆ -cycloalkyl, or by substituted or unsubstituted phenyl or by CO-OC ₁ -C ₃ alkyl substituted; or

b) unsubstituted or methyl-substituted C ₃ -C 6 -cycloalkyl; or

c) unsubstituted or halogen-substituted Cs-Ce-alkenyl; or

d) unsubstituted or halogen-substituted C ₃ -C ₆ alkynyl; or

e) phenyl which is unsubstituted or substituted by halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, nitro; or

f) an unsubstituted or substituted by halogen, C ₁ -C ₃ -A ^ yI, C ₁ -C ₃ -alkoxy, nitro-substituted 5-membered or 6-membered optionally via -CH ₂ - bonded heterocyclic radical having one to three heteroatoms N, O or S. represents; or

g) represents an acyl I-rest-CO-R ', wherein R' is unsubstituted or C ₁ -C ₆ -alkyl substituted by halogen, C ₁ -C ₃ -alkoxy; unsubstituted or halogen-substituted C ₃ -C ₆ alkenyl; unsubstituted or substituted by halogen, C ₁ -C ₃ -AlkYl, C ₁ -C ₃ alkoxy, nitro-substituted phenyl; or

h) represents a carbamoyl-CO-NH-R "or an oxycarbonyl-CO-OR" in which R "represents an aliphatic or cycloaliphatic radical of at most 6 C-atoms, which is unsubstituted or halogen-substituted, or wherein R" is a phenyl or benzyl radical which is in each case unsubstituted or substituted in the aromatic ring by HaIOgCn ₁ C ₁ -C ₃ -alkyl-C ₁ -C ₃ -alkoxy, nitro; and in which

R _{6 is} hydrogen, unsubstituted C ₁ -C ₈ -alkyl or else C ₁ -C ₄ -alkyl which is substituted by halogen, hydroxy, cyano, C ₁ -C ₄ -alkoxy; or wherein R _{6 is} unsubstituted or methyl-substituted C ₃ -C ₆ -cycloalkyl; each unsubstituted or halogen-substituted Cs-Ce-alkenyl or C ₃ -C ₆ -alkyl; or unsubstituted or substituted by halogen, C ₁ -C ₃ -AlkYl, C ₁ -C ₃ -alkoxy, nitro-substituted phenyl; wherein in the case of R ₄ = NR ₅ R _6, the substituents R ₅ and R ₆ together with the N-atom may also together form an aziridine ring or a 5- or 6-membered heterocyclic radical which in addition to the N-atom nor one or two heteroatoms N, O or S may be included and alkyl substituted.

Under alkyl itself or under alkyl as a constituent of another substituent, such as haloalkyl, alkoxy or haloalkoxy, depending on the number of named carbon atoms, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and their isomers, such as. As isopropyl, isobutyl, isoamyl, tert-butyl or sec-butyl to understand.

By an aliphatic radical is meant, optionally, an alkyl, alkenyl or alkynyl group. Accordingly, a cycloaliphatic radical is understood as meaning a saturated or unsaturated cyclic hydrocarbon radical. C ₃ -C ₆ alkenyl represents an aliphatic radical having a double bond, e.g. Allyl, methallyl, crotyl, butenyl, pentenyl, etc. A C ₃ -C ₆ -AlkJnYlTeSt contains a triple bond, such. Propargyl, propyn-1-yl, butynyl, etc. Halogen is fluorine, chlorine, bromine or iodine.

-7- Z.ÜÖ I

Haloalkyl and haloalkoxy simply refer to perhalogenated radicals, such as. B. CHCl ₂ , CH ₂ F, CCI ₃ , CH ₂ Cl, CHF ₂ , CF ₃ , CH ₂ CH ₂ Br, C ₂ Cl ₅ , CHBr, CHBrCl etc., preferably CF ₃ and CHF ₂ .

Cycloalkyl is depending on the number of carbon atoms mentioned z. As for cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

In a substituted phenyl ring, 1 to 5, preferably 1 to 3, identical or different substituents selected from halogen, C, -C ₃ alkyl, C ₁ -C ₃ -alkoxy and nitro, it being understood by those skilled in the art, that a substituent tending to decay such as nitro and spatially bulky substituents such as isopropyl or iodine can be present at most three times.

Examples of heterocycles of the group NR ₅ R ₆ are imidazole, oxazole, thiazole, 1,2,4-triazole, pyrrole, pyrrolidone, piperidine, morpholine, thiomorpholine, 2,6-dimethylmorpholine and others

Further examples according to the definition of R ₅ alone are the abovementioned heterocycles which are also bonded via carbon, and furan, tetrahydrofuran (= THF), thiophene, pyridine, picoline, pyrazine, triazine, oxazine, dioxane and the like

N-pyrimidinylaniline compounds are already known. Thus, in EP-A-0224339 and DD 151404, compounds having an N-2-pyrimidinyl structure are described as being effective against plant-damaging fungi. However, the known compounds have not been able to satisfy the demands made on them in practice. The compounds of the formula I according to the invention differed characteristically from the known compounds by the introduction of specific substituents R ₃ and R ₄ and their combination into the anilinopyrimidine structure, whereby an unexpectedly high microbicidal activity is achieved in the novel compounds.

The compounds of formula I are stable at room temperature oils, resins or solids. They can be used preventatively and curatively in the agricultural sector or related areas to combat plant-damaging microorganisms. The active compounds of the formula I according to the invention are not only distinguished by excellent fungicidal activity at low application concentrations, but also by particularly good plant tolerance.

An important group are those of formula I wherein R ₁ and R _{2 are} independently hydrogen or fluorine.

A particular group is represented by the following compounds of the formula I in which R 1 and R _2, independently of one another, are hydrogen, halogen, C ₁ -C ₃ -alkyl, C ₁ -C 4 -haloalkyl, C ₁ -C ₃ -alkoxy or C ₁ -C -haloalkoxy; R _{3 is} C ₃ -C ₄ cycloalkyl which is unsubstituted or monosubstituted by methyl or halogen; R _{4 is} halogen, -OR ₅ ; -NR ₅ R ₆ , where

R _{5 has} the meanings a), b), c), d) or g), and

R _{6 represents} hydrogen or an alkyl, alkenyl or alkynyl radical which is optionally unsubstituted or halogen-substituted; or where

R ₅ and R ₆ together with the common N atom represent an aziridine ring, or an optionally unsubstituted or methyl-substituted piperidine or morpholine ring (= linking group Ib).

Among the aforementioned compounds, preferred are those in which R ₁ and R _{2 are} independently hydrogen or fluorine (= compound group I bb).

Another important group are those compounds of formula I, wherein

R ₁ and R ₂ independently of one another are hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy;

R _{3 is} cyclopropyl or cyclopropyl mono- or di-identical or differently substituted by methyl or halogen; R _{4 is} halogen, -SR ₅ , -OR ₅ , -NR ₅ R ₆ ; and

R ₄ represents alkyl ₅ is hydrogen or a C-C, which are unsubstituted or substituted by halogen, hydroxy, C ₁ -C ₄ -alkoxy, Ci-C ₄ alkylamino, bis (C ₁ -C ₄ alkyl) amino, cyclopropyl, or is substituted by -COOC ₁ -C ₃ -AlkVl; or wherein R _{5 represents} QH ^ -alkenyl or C ₃ -C ₄ -alkynyl or represents an unsubstituted or halogen, methyl, or methoxy-substituted phenyl group or an acyl radical corresponding to the meaning g); and

R ₆ represents hydrogen or a C ^ C ^ alkyl group unsubstituted or substituted by halogen, hydroxy, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ alkylamino or substituted bis ^ Ct-AlkyOamino or wherein R ₆ is C ₃ -C ₄ alkenyl or C 3 C ₄ alkynyl represents (= compound group Ic).

Among these compounds of the formula Ic, preference is given to those in which

R ₁ and R _{2 are} hydrogen, fluorine or difluoromethoxy,

R _{3 represents} cyclopropyl,

R _{4 is} halogen, -OR ₅ or -NR ₅ R ₆ , and

R _{5 is} hydrogen or R ₆ , and

R _{6 is} C ₁ -C ₃ alkyl which is unsubstituted or monosubstituted by C ₁ -C ₄ alkoxy or cyclopropyl or substituted by halogen up to five times; or C ₃ -C ₄ alkenyl or alkynyl (= linking group I d).

Among the latter, those compounds are preferred in which R ₁ and R _{2 are} independently hydrogen, 3-fluoro, 4-fluoro, 5-fluoro (= linking group Idd).

Another preferred group are the following compounds of the formula I in which R ₁ and R _2, independently of one another, are hydrogen, halogen, C ₁ -C ₃ -alkyl, C ₁ -C 4 -haloalkyl, C ₁ -C ₃ -alkoxy or C ₁ - C ₃ haloalkoxy;

R _{3 is} C ₃ -C ₄ cycloalkyl which is unsubstituted or monosubstituted by methyl or halogen; R _{4 is} halogen (compound group Ie).

Among the aforementioned compounds, those are preferred in which R ₁ and R ₂ independently of one another are hydrogen or fluorine (= linking group lee). Particularly preferred are those in which Ri and R _{2 are} independently hydrogen, 3-fluoro, 4-fluoro, 5-fluoro.

The compounds of formula I are prepared by reacting 1 a) a phenylguanidine salt of formula Ha

-NH-C

NHo

(Ha)

or the underlying guanidine of formula lib

NH

-NH-C

(Lib)

with a β-ketoester of the formula III,

0 0

(Hl)

R ₃ CCH ₂ COR ₇

in which R ₁ , R ₂ , R ₃ have the meaning given for the formula I and R _{7 is} C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkyl, unsubstituted or substituted by halogen and / or C ₁ -C ₃ alkyl-substituted benzyl or C ₁ -C ₈ -alkyl mean, without solvent or in a solvent, preferably in a protic solvent, at temperatures from 6O ⁰ C to 160 ⁰ C, preferably from 6O ⁰ C to 11O ⁰ C, to give the compound la:

(La)

and, if desired, the OH group exchanged for halogen and to give compounds of formula I b

(Ib)

and, if desired, further replacement of the halogen atom with one of the other groups mentioned for R ₄ , as explained below. · · ... , · · .. · '. ,

1 b) According to a further process variant, the compound I a can also be obtained in a multistage process by reacting an isothiuronium salt of the formula IV

H ₂ N,

H ₂ N

SRs

.Θ

(IV)

where A® is any anion such as chloride, sulfate, phosphate and the like, and R _{8 is} C ₁ -C ₈ -alkyl or unsubstituted or substituted by halogen and / or C ₁ -C ₄ -Alkyl benzyl, with a ß-ketoester of Formula Hl, preferably in a solvent, at temperatures of 40 ⁰ C to 140 ⁰ C, preferably at 6O ⁰ C to 100 ⁰ C brings to react, wherein the thiopyrimidine V forms.

(V)

The compound of formula V thus obtained is treated with an oxidizing agent, ζ. With a peracid, to the pyrimidine compound of formula VI

R ₈ SO ₂ -

(Vl)

OH

oxidized and this with a formylaniline of the formula VII

-NHCHCO

(VII)

in an inert solvent in the presence of a base as a proton acceptor at temperatures between -30 ⁰ C to +120 ⁰ C to give a compound of formula VIII

(VIII)

implemented. The resulting compound VIII is subjected to hydrolysis in the presence of a base, for example, alkali metal hydroxide, or an acid, e.g. As hydrohalic acid or sulfuric acid, in water or aqueous solvent mixtures, such as aqueous alcohols or dimethylformamide, at temperatures of 10 ⁰ C to 110 ⁰ C, preferably 3O ⁰ C to 60 ⁰ C, subjected and then provides the compound of formula la

 Compound Ib is obtained when, in conjunction with la, hydroxyl is replaced by halogen:

(Ib)

This is done with halogen compounds of drej- or pentavalent phosphorus in the presence or absence of a proton acceptor such. BTbiethylanilin, wherein the Phosphoroxyhalogenide are preferably used. The reactions are performed in an inert solvent or without solvent at temperatures between 60 ⁰ C to 14O ⁰ C, preferably 70 ⁰ C to 120 ° C is performed.

To the other compounds of the formula I, in which R _{4 has} a meaning other than -OH or halogen, is obtained by reacting a compound of the formula Ib with a compound

HOR ₅ HSR ₅ H ₂ NR ₅ HNR ₅ R ₆

(IX)

(X)

(XI)

(XII).

These reactions can be carried out in an inert solvent. If the reactants are alcohols, they can be used as solvents. In the compounds IX and X proton acceptors are necessary, including z. As alkali metal or alkaline earth metal hydroxides, the alkali or alkaline earth metal salt of IX or X, or metal hydrides are used.

When Xl or XII is used, an excess of the corresponding amine may also be used as the proton acceptor

The reactions are carried out at -30 ⁰ C to + 140 ⁰ C, preferably at -10 ⁰ C to +110 ⁰ C.

Is in the formula I

R ₅ = -CR ¹ , »

so are preferred for the reactions acid halides XIII

(XIII) Hal-C-R '

or acid anhydrides XIV used.

R'-C

P (XIV)

R ¹ -C

Is in the formula I

ο o

R ₅ = -C-NH-R "or -COR"

so get either isocyanates XV

R "NCO (XV),

Formic Acid Halides XVI or Formic Acid Anhydrides XVII For Reaction:

(XVI)

Hal-COR "

R ¹¹ OC

Q (XVII)

R ¹¹ OC

The production methods described, including all sub-steps, form part of the present invention. Surprisingly, it has now been found that compounds of the formula I have a very favorable biocidal spectrum for practical purposes for controlling insects and phytopathogenic microorganisms, in particular fungi. They have very beneficial curative, preventive and in particular systemic properties and are used for the protection of numerous crops. With the active compounds of the formula I, the occurring pests can be contained or destroyed in plants or parts of plants (fruits, flowers, foliage, stems, tubers, roots) of different crops, whereby later growing plant parts z. B. spared from phytopathogenic microorganisms.

Compounds of the formula I are z. B. against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (especially Botrytis, also Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetes (eg Rhizoctonia, Hemileia, Puccinia). In addition, they are active against the class of Ascomycetes (e.g., Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and the Oomycetes (e.g., Phytophthora, Pythium, Plasmopara). The

Compounds of the formula I can also be used as seed dressers for the treatment of seeds (fruits, tubers, grains) and plant cuttings for the protection of fungal infections and against phytopathogenic fungi occurring in the soil.

The invention also relates to the compositions containing as active ingredient component compounds of formula I, in particular plant protection agents, and their use in the agricultural sector or related fields.

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

As target crops for the plant protection use disclosed herein, for example, the following plant species apply in the context of this invention: cereals (wheat, barley, rye, oats, corn, sorghum and related species); Beets (sugar and fodder beets); Pome, stone and berry fruits (apples, pears, plums, peaches, almonds, cherries, peanuts, cranberries and blackberries); Legumes (beans, lentils, peas, soybeans); Oil crops (rape, mustard, poppy, olives, sunflowers, coconut, castor, cocoa, peanuts); Cucumbers (squash, cucumbers, melons); Fiber plants (cotton, flax, hemp, jute); Citrus fruits (oranges, lemons, grapefruit, mandarins); Vegetables (spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers); Laurel family (avocado, cinnamonium, camphor) or plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, banana and natural rubber plants and ornamental plants. 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. It is also possible to use selective herbicides and also insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations together with optionally further excipients customary in formulation technology, surfactants or other application-promoting additives.

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

A preferred method of applying an active ingredient of the formula I or of an agrochemical composition containing at least one of these active ingredients is application to the foliage (foliar application). Application frequency and application rate depend on the infestation pressure of the relevant pathogen. However, the active substances of the formula I can also enter the plant via the soil through the root system (systemic action) by impregnating the location of the plant with a liquid preparation or introducing the substances into the soil in solid form, e.g. in the form of granules (soil application). In water rice crops, such granules can be added to the flooded rice field. However, the compounds of the formula I can also be applied to seed grains (coating) by either soaking the grains in a liquid preparation of the active ingredient or coating them with a solid preparation. The compounds of the formula I are used here in unchanged form or preferably together with the auxiliaries customary in formulation technology. For this they are expediently, e.g. To emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, by encapsulation in z. B. polymeric substances processed in a known manner. The application methods such as spraying, misting, dusting, scattering, brushing or pouring are chosen in the same way as the type of means according to the desired goals and the given conditions. Cheap application rates are generally 50 g to 5 kg of active ingredient (ai) per ha, preferably 100 g to 2 kg ai / ha, in particular from 200 g to 600 g ai / ha.

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

Suitable solvents are: Aromatic hydrocarbons, preferably the fractions C ₈ to C 12, such as Xyiolgemische or substituted naphthalenes, phthalic acid esters such as dibutyl or Dioctylphthalat, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, Ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

As solid carriers, for. As for dusts and dispersible powders, natural minerals are generally used, such as calcite, talc, kaolin, montmorilonite or attapulgite. To improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. As granular, adsorptive granules are porous types such. As pumice, broken brick, sepiolite or bentonite, as non-sorptive support materials, eg. As calcite or sand, in question. In addition, a variety of vorgranulierten materials of inorganic nature, in particular dolomite or crushed plant residues can be used. Depending on the nature of the active compound of the formula I to be formulated, suitable surface-active compounds are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also surfactant mixtures.

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

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

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

The cationic surfactants are, above all, quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N-substituent and lower, optionally halogenated, alkyl, benzyl or lower hydroxyalkyl radicals as further substituents.

Further surfactants commonly used in formulation technology are known to the person skilled in the art or can be found in the relevant specialist literature. The agrochemical preparations generally contain from 0.1 to 99%, in particular from 0.1 to 95%, of the active ingredient of the formula from 1.99.9 to 1%, in particular from 99.8 to 5%, of a solid or liquid additive and from 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 compositions may also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.

embodiments

The following examples serve to illustrate the invention without limiting it. Preparation Examples

Example 1: Preparation of Z-phenylamino-1-hydroxy-e-cyclopropyl-pyrimidine of the formula

OH

(Verb no. 2.1)

19.7 g (0.1 mol) of phenylguanidine hydrogencarbonate and 15.6 g (0.1 mol) of ethyl S-cyclopropyl-S-oxopropionate in 100 ml of ethanol are refluxed under stirring for 16 hours, forming a reddish-colored solution to form carbon dioxide , After cooling to room temperature is treated with charcoal, filtered and the filtrate mixed with 400 ml of water. The precipitated gray powder is purified by column chromatography on silica gel (methanol / chloroform 1: 1). After evaporation of the mobile phase mixture, a white crystal powder remains; Mp 234-235 ° C. Yield 16.6 g (73 mmol, 73% of theory).

Example 2: Preparation of 2-phenylamino-4-chloro-6-cyclopropylpyrimidine of the formula

N:

(Verb NM.1)

19.6 g (86.3 mmol) of 2-phenylamino-4-hydroxy-6-cyclopropylpyrimidine are added to 50 ml (0.55 mol) of phosphorus oxychloride with stirring at 75 ° C. within half an hour and then heated under reflux for one hour. After completion of evolution of hydrogen chloride, the cooled to room temperature reaction mixture is added with vigorous stirring in 200 ml of water, the temperature is maintained by the addition of ice to about 50 ° C. By slow dropwise addition of 220 ml of 30% aqueous sodium hydroxide solution, the approximately 400 ml of the light brown suspension are brought to pH 7 and extracted three times with 150 ml of ethyl acetate. The combined extracts are washed twice with 100 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The 20.7 g light brown powders are treated with 400 ml diethyl ether and filtered from the insoluble. After evaporation of the diethyl ether, the residue is recrystallized from diisopropyl ether. The yellowish crystals melt at 127-128 ⁰ C. Yield 17.7 g (72.1 mmol;. 83.5% of theory.).

Example 3: Preparation of 2-phenylamino-4-methoxy-6-cyclopropylpyrimidine of the formula

OCH ₃ y

N:

-NH (\ /) (verb # 2.3)

To 5.8 g (32.2 mmol) of sodium methylate in 10 mM abs. Methanol are added dropwise within half an hour with stirring at room temperature 6.87 g (28 mmol) of 2-phenylamino-4-chloro-6-cyclopropyl-pyrimidine in 25 ml of dioxane and then heated to 50 ° C for 6 hours. To complete the reaction nor 0.76 g (4.2 mmol) of sodium methylate are added and heated to 50 ⁰ C for a further 20 hours. After evaporation of the solvent, the residue is mixed with 300 ml of diethyl ether, the suspension washed twice with 100 ml of water, then dried over sodium sulfate, filtered and the diethyl ether evaporated. 6.7 g residual yellow oil are purified by column chromatography on silica gel with toluene as eluent. After evaporation of the toluene, a light yellow oil with refractive index nD25: 1.6225 remains. Yield: 5.8 g (24mMii, 86% of theory).

Example 4: Preparation of 2-phenylamino-4-dimethylamino-6-cyclopropylpyrimidine of the formula

N (CH ₃ ) ₂

N:

(Verb no.3.1)

To 9.8 g (40 μmol) of 2-phenylamino-4-chloro-6-cyclopropyl-pyrimidine in 20 ml abs. Ethanol at room temperature with stirring within 10 minutes 17.9ml 33% (10OmMoI) abs. ethanolic dimethylamine solution is added dropwise, and the resulting yellow suspension is heated at 50 ⁰ C for one hour, then for a further hour under reflux. After evaporation of the solvent, the residue is taken up in 200 ml of methylene chloride, washed twice with 100 ml of water, dried over sodium sulfate, filtered and freed by evaporation of methylene chloride. The remaining 10.2 g of a yellow oil are purified by column chromatography on silica gel with methylene chloride as the eluent. After evaporation of the methylene chloride, a pale yellow oil remains, which crystallizes after a few hours. The light yellow crystals melt at 90-91 ⁰ C. Yield: 8.9 g (35 mmol; 87.5% of theory.).

 In this way or according to one of the methods mentioned above, the following compounds are obtained.

Table 1: Compounds of the formula

Verb no. Ri R ₂ R ₃ 1.1 H H Cl 1.2 4-F H Cl 1.3 3-F H Cl 1.4 H H -SCH ₃ 1.5 H H br 1.6 H H SCN 1.7 H H -SC ₂ H ₅ 1.8 H H F 1.9 3-F 5-F Cl 1.10 3-F H F 1.11 3-F H br 1.12 ' 4-F H F 1.13 H H J 1.14 4-F H br

Physical constant

Mp 127-128 ° C, mp 142-144 ° C, mp 133-134 ° C, mp 99-100 ° C. Mp. 132-133 ° C mp. 104-105 ⁰ C.

Mp 123-124 ° C

Mp. 144.5-147 ° C mp 137-139 ° C mp 151-153'C mp 141-144-C mp 142-145 ° C

Table 2: Compounds of the formula

Verb. rl R ₂ R ₄ No 2.1 H H -OH 2.2 4-F H -OCH ₃ 2.3 H H -OCH ₃ 2.4 H H -OCHF ₂ 2.5 3-F H -OCH ₃ 2.6 H H -OCH ₂ -C ^ CH 2.7 H H -OCH ₂ CH ₃ 2.8 H H -0-CCH ₃ Il Il 2.9 H H -OCH ₂ CH ₂ N (CH ₃ ) 2 2.10 H H -OCH ₂ CH = CH-CH ₃ 2.11 4-CH ₃ H -OCH ₃ 2.12 H H -OCNHCH ₃ Il Il 2.13 H H -OCF ₂ CHF ₂ 2.14 4-F H -OH 2.15 4-OCHF ₂ H -OCH ₃ 2.16 H H -OCH ₂ CH ₂ OCH ₃ 2.17 4-CF ₃ H -OCH ₃

Physical constant

Mp 234-235 ° C Mp. 91.5-93 "C OeI: n _D ²⁵ : 1, 6225 mp 55-57 ° C

Mp. 84-85 ° C Mp. 62.5-63 ° C

oil; n _D ²⁰ : 1.5977 OeI; n _D ²⁰ : 1, 6079

Mp. 233-236

Mp. 72-74 ° C m.p.> 250 ° C

Mp 91-92 ° C OeI; n _D ²⁰ : 1, 6278

Table 2 (continued)

2.19

H -OCF ₂ CCIFCF ₂ CHCIf

Mp. 40-41 ⁰ C

2.20 4-FH -OCCH ₃

- O-CH ₂

OCH ₃

2.22 J. Λ. H H -OCHCH ₂ CH ₃ I I CH ₃ 2.23 H H -OCHCH ₂ OCH ₃ I I CH ₃ 2.24 4-OCH ₃ H -OCH ₃ 2.25 H H -OCOCH, η Il 0 2.26 H H -OCH ₂ CF ₃ 0 Μ 2.27 H H M -OCCH ₂ Cl 2.28 H H -OC ₃ H ₇ -I 0 'Μ 2.29 H H Il -OCCH ₂ OCH ₃ 30.2 3-OCHF ₂ H -OCH ₃ 2.31 3-F 5-F -OCH ₃ . 2:32 H H -OCF ₂ CHClF 2:33 3-F H -OH

Mp 140-141 ⁰ C oil. n _D ²⁰ : 1.5 902

oil; n _D ²⁰ : 1.5 90 8

oil; n _D ²⁰ : 1.60 05 mp 89-90 ° C

oil; n _D ³⁰ : 1.5 971

Mp 37-39 ° C m.p. 179-185 ° C

Table 3: Compounds of the formula

Verb. ^R l R ₂ R ₄ No 3.1 H H -N (CH ₃ ) ₂ 3.2 H H -NH ₂ 3.3 H H -NHC ₂ H ₅ O Η 3.4 H H Il -NHCCH ₂ Cl

Physical constant

Mp. 90-91 ° C j

Mp 114-115 ° C '

oil; n _D ³⁰ : 1, 63 60

- N

3.11 3.12

Mp 142-143 ° C

3.6 H H -NHCH ₂ CH ₂ OH tough mass 6478 3.7 H H -NHCH ₃ oil; n _D ²⁰ : 1, 3.8 3-F H -N (CH ₃ ) ₂ 5 ° C 3.9 H H NH ^ J Smp.100,5-101 3.10 H H -N (CH ₂ CH ₂ OH) ₂ Mp 94-95 ° C

-HN C

- NHCH ₂ -

oil; n _D ⁵⁰ : 1.6437

Table 3 (continued)

3.13

3.26

3.27

-HN C

H H Cl -NHCH ₂ CH ₂ CH ₃ oil; n _D ²⁰ : 1, 62 94 3.14 H H -NH (CH ₂ J ₇ CH ₃ oil; n _D ²⁰ : 1.5881 3.15 4-F H -N (CH ₃ ) ₂ 3.16 O H H H Il-NHCH ₂ COC ₂ H ₅ Mp. 113-115'C 3.17 H H -NHCH ₂ CH ₂ OCH ₃ Mp. 109.5-lll ° C 3.18 H H -NHCHCH ₂ OH oil; n _D ⁵⁰ : 1.6173 3.19 CH ₃ 3-F H -N (CH ₂ CH = CH ₂ ) ₂ 3.20 H H -N-CH ₂ CH ₂ CN Mp. 143-147 ° C 3.21 CH ₃ H H -NH (CH ₂ ) ₃ N (CH ₃ ) ₂ oil; n _D ²⁰ : 1, 6160 3.22 H H _ _N _CH2 ^ fA Mp. 120-121 ⁰ C 3.23 CH ₃ \ / H . , H -NH (CH ₂ -CH = CH ₂ ) 3.24 H H -NH-CH ₂ CH-C ₂ H ₅ tough Dimensions 3.25

CH ₃

_{H is} -NHCH ₂ CH-CH ₂

I i

OH OH

Mp 151-153 ° C

Mp 185-186 ° C

Table 3 (continued)

3.28 H

3.34 H

3.35 H

3.36 H

3.37 H

3.38 H

3.29 H H 3.30 H H 3.31 H H 3:32 H H 3:33 H H

-NHCH ₂ -C = CH NH- / H

NH

/ = N

-N

CH

CH,

- N

I is CH ₂ CH ₂ OH

oil; n _D ⁵⁰ : 1.6255

Mp. 114-116'C

-NH (CH ₂ ) ₂ N (C ₄ H ₉ -n) ₂ viscous mass -NHCH ₂ -

oil; n _D ²⁰ : 1, 6476 mp 104-105 ° C

oil; n _D ⁵⁰ : 1.6103

Mp 119-120 ° C, mp 202-203 ° C

Mp. 209-210 ⁰ C

Mp 117-118 ° C

Table 3 (continued)

3.39 H

3.40 H

3.41 3.42 3.43 3.44

3-F

4-F

3-F

H H

H H H 4-F

-NHCH ₂ CH ₂ N (C ₂ Hs) ₂ -NH (CH ₂ ) 3 OCH 3

-N

-N

- N 'tough mass, mp 80-83 ⁰ C

Mp 92-95 ° C

-N

3:45

3-F

5-F

-N '

3 .46 H H -NH-CO-NH-CH ₃ Mp. 164-166 "C. 3 .47 H H -NH-COOCH ₃ Mp. 216-217 ° c

Table 4: Compounds of the formula

Verb no.

R ₃

R ₄

Physical constant

3-F

ι-CH,

Mp 124-127 ° C

4.3 H H cyclobutyl Cl -OCH ₃ mp , 146-149 ° C 4.4 H H cyclohexyl Cl / T-CH ₃ -OCH ₃ 4.5 4-F H cl " 4.6 H H -4 Cl , oil; nn ²⁵ : 1.6232 4.7 H H cyclobutyl / T-CH ₃ 4.8 H H - <

4.10

4-F

4-F

Cl

-OCH ₃

-OCH ₃ Mp. 85-88 ° C

4 .11 4-F H cyclobutyl -CH ₃ -OCH ₃ 4 .12 H H cyclohexyl -OCH ₃ / 4 .13 3-F H < -OCH ₃

Table 4 (continued)

4.14

4.15

4.16

4:17

3-F H

3-F H

Cl

-OCH ₃

-OCH ₃

-N (CH ₃ ) ₂ m.p. 88-91 ° C

-N (CH ₃ )

4.18 H H / j- ^CH 3 a) 25% 5% 5% 65% -N (CH ₃ ) 2 Λ 4.19 4-F H cyclobutyl -N (CH ₃ ) 2 4.20 H H cyclohexyl -N (CH ₃ ) 2 4.21 H H 2. Formulation examples of liquid active ingredients of the formula -N (CH ₃ ) 2 2.1. Emulsion concentrates Active ingredient from the table Ca-Dodecylbenzenesulphonate Castor oil polyethylene glycol ether (36 mol ethylene oxide) Tributylphenoyl polyethylene glycol ether (30 mol ethylene oxide) Cyclohexanone Xylene mixture I% = wt .-%) b) c) 40% 50 ° / <8% 6 ° / <12% 4 ° / <15% · 20% 25% 20%

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

2, 2. Solutions .

Active ingredient from the table. · Ethylene glycol monomethyl ether, polyethylene glycol MG 400 N-methyl-2-pyrrolidone epoxidised coconut petrol (boiling limits 160-190 ⁰ C) (MW = molecular weight)

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

2.3. granules

Active ingredient from the table Kaolin

Highly dispersed silica attapulgite

a): - • b) O. % d).   80% 10% '. , ul  .-; _ 95% 20%   - - - _ 70% - - - 20% - % - - - 1 % 5% _ 94 _

a) b) 5% 10 ° / 94% - 1%

90%

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

2.4. Dust Active substance from the table Fumed silica talc

Kaolin - 90%

a) b) 2% 5% 1% 5% 97% _

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

2.5. wettable powder a) b) c) Active ingredient from the table 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.

2.6. Emulsion concentrate 10% Active ingredient from the table 3% octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3% Calcium dodecylbenzenesulfonate 4% castor oil polyglycol (35 moles of ethylene oxide) 34% cyclohexanone 50% xylenes

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

2.7. Dusts a) b)

Active ingredient from the table 5% 8%

Talc 95%

Kaolin - 92%

Ready-to-use dusts are obtained by milling the active ingredient mixed with the carrier on a suitable mill.

2.8. Extruder granules

Active substance from the table 10%

N-lignosulfonate 2%

Carboxymethylcellulose 1%

Kaolin 87%

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

2.9. Coated granules

Active ingredient from the table 3%

Polyethylene glycol (MG200) 3%

Kaolin 94%

(MW = molecular weight)

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

2.10. Suspension concentrate 40% Active ingredient from the table 10% ethylene glycol 6% nonylphenol (15 moles of ethylene oxide) 10% N-lignin sulfonate 1% carboxymethylcellulose 0.2 ° / 37% aqueous formaldehyde solution 0.8 ° / Silicone oil in the form of a 75% aqueous emulsion 32% water

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

3. Biological examples

Example 3.1: Action against Venturia inaequalis on apple shoots. Residual-protective effect Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture prepared from spray powder of the active ingredient (0.006% 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 20-24 ⁰ C. Scab infestation is assessed 15 days after infection. Compounds from Tables 1 to 4 show good activity against Venturia (infestation: less than 20%). For example, z. For example, Compounds Nos. 1,1,1,13 and 2.2 reduce Venturia infestation to 0 to 5%. By contrast, untreated but infected control plants had a Venturia infestation of 100%.

Example 3.2: Action against Botrytis cinerea on apple fruits. Residual-protective effect

Artificially injured apples are treated by dropping a spray mixture (0.002% of active substance) prepared from the active ingredient of the active substance onto the injury sites. The treated fruits are then inoculated with a spore suspension of the fungus and incubated for one week at high humidity and about 20 ⁰ C. In the evaluation, the rotted injury sites are counted and derived from the fungicidal action of the test substance. Compounds from the tables show good activity against Botrytis (infestation: less than 20%). For example, compounds Nos. 1.1, 2.1, 1.1, 1.1, 4.1, 4.1, 4.1, 4.1, 4.1, 4.1, 4.2, 2.2, 3.2, 2.2, 13, 21, 28, 13, 31, , 4.16 and others the botrytis infestation to 0 to 10%. By contrast, untreated but infected control plants showed Botrytis infestation of 100%.

Example 3.3: Action against Erysiphae graminis on barley a) Residual-protective action

Approximately 8 cm high barley plants are sprayed with a spray mixture of active ingredient (0.006% active substance) prepared from spray powder of the 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 assessed the fungal infection after 10 days. Compounds from the tables show good activity against Erysiphae (infestation: less than 20%). By contrast, untreated but infected control plants have an Erysiphae infestation of 100%.

Example 3.4: Action against Helminthosporium gramineum

Wheat grains are contaminated with a spore suspension of the fungus and dried again. The contaminated grains are pickled with a suspension of the test substance prepared from spray powder (600 ppm active ingredient based on the weight of the seeds). After two days, the grains are placed on suitable agar dishes and after another four days the development of the fungal colonies around the grains is assessed. The number and size of the fungal colonies are used to assess the test substance. The compounds of Tables 1 to 4 largely prevent fungal infection (Obis 10% fungal infestation).

Example 3.5: Action against Colletotrichum lagenarium on cucumbers

Cucumber plants are sprayed after 2 weeks of cultivation with a spray prepared from wettable powder of the active ingredient (concentration 0.002%). After 2 days the plants are inoculated with a spore suspension (1.5 χ 10 ⁶ spores / ml) of the fungus and incubated C and high atmospheric humidity for 36 hours at 23 ^0th The incubation is then continued at normal atmospheric humidity and about 22-23 ° C. The occurred fungal attack is assessed 8 days after the infection. Untreated but infected control plants have a fungal infection of 100%.

Compounds of the formula I from the tables show good activity and prevent the spread of disease infestation. The fungal infection is pushed back to 20% or less.

Claims (24)

1. A process for the preparation of 2-anilino-pyrimidine derivatives of the formula I. in which mean: R ₁ and R ₂ are independently hydrogen, halogen, Ci-C ₃ -alkyl, ^^ - haloalkyl, C ₁ -C ₃ alkoxy or Ci-Cs-haloalkoxy; R ₃ C 3 -C ₆ -cycloalkyl or up to three times identically by methyl or halogen or represents C ₃ -C ₆ cycloalkyl; R _{4 is} halogen, thiocyano (-SCN), -OR ₅ , -SR ₅ , -NR ₅ R ₆ , wherein R _{5 is} a) - hydrogen, unsubstituted C ₁ -C ₈ alkyl, or a Ci-Cj-alkyl group represented by halogen, hydroxy, cyano, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, bis-C ₁ -C ₄ -alkylamino, C ₃ -C ₆ -cycloalkyl, or by substituted or unsubstituted phenyl or by CO-OC ₁ -C ₃ alkyl substituted; or b) is unsubstituted or methyl substituted C ₃ -C ₆ cycloalkyl; or c) unsubstituted or halogen-substituted C ₃ -C ₆ alkenyl; or d) unsubstituted or halogen-substituted C ₃ -C ₆ alkynyl; or e) phenyl which is unsubstituted or substituted by halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, nitro; or f) an unsubstituted or substituted by halogen, C ₁ -C ₃ -AlkYl, Ci-C ₃ -alkoxy, nitro substituted 5-membered or 6-membered optionally via -CHr bonded heterocyclic radical having one to three heteroatoms N, O or S; or g) represents an acyl radical-CO-R ', where R' is unsubstituted or substituted by halogen, C ₁ -C ₃ -alkoxy Ci-Cö-alkyl; unsubstituted or halogen-substituted C ₃ -C ₆ alkenyl; unsubstituted or substituted by halogen, C- | -C ₃ alkyl, C ₁ -C ₃ -alkoxy, nitro-substituted phenyl; or h) represents a carbamoyl-CO-NH-R "or an oxycarbonyl-CO-OR" in which R "represents an aliphatic or cycloaliphatic radical of at most 6 C-atoms, which is unsubstituted or halogen-substituted, or wherein R" is a phenyl - or benzyl radical which is unsubstituted or substituted in the aromatic ring by halogen, C ₁ -C ₃ -AlkYl, C ₁ -C ₃ alkoxy, nitro; and in which R ₆ is hydrogen, unsubstituted C ₈ alkyl or C | -C ₄ alkyl which is substituted by halogen, hydroxy, cyano, Ci-C ₄ -alkoxy; or wherein R _{6 is} unsubstituted or methyl-substituted C ₃ -C ₆ -cycloalkyl; each unsubstituted or halogen-substituted C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkylene; or phenyl which is unsubstituted or substituted by halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, or nitro; wherein in the case of R ₄ = NR ₅ R _6, the substituents R ₅ and R ₆ together with the N-atom may also together form an aziridine ring or a 5- or 6-membered heterocyclic radical which in addition to the N-atom nor one or two heteroatoms Contain N, O or S and may be alkyl-substituted, characterized in that a) a phenylguanidine salt of the formula Ha wherein Α ^{θ is} any anion or the underlying guanidine of the formula II b NH-C NH (Nb) NH, with a β-keto ester of the formula
0 0 CH ₂ COR ₇ in which R 1, R ₂ , R ₃ have the meaning given for the formula I, and R ₇ denotes C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, unsubstituted or -substituted with halogen and / or C 1 -C ₃ -alkyl Benzyl or C 1 -C ₈ -alkyl, without solvent or in a solvent, at temperatures of 6O ⁰ C to 160 ⁰ C, to the compound Ia; and, if desired, the OH group acylated, carbamoylated or carbonylated, or replaced with halogen to obtain compounds of the formula I b, and, if desired, further replacement of the halogen atom with one of the other groups mentioned for R ₄ or shark (La) b) that is an isothiuronium salt of the formula IV H ₀ N (Ib) where A ^{e is} any anion and R _{8 is} C ₁ -C ₈ -alkyl or unsubstituted or substituted by halogen and / or C -] - C ₄ alkyl benzyl, with a ß-keto ester of the formula III at temperatures of 40 ⁰ C. bring to 140 ⁰ C to the reaction, wherein dasThiopyrimidin V forms, R. with an oxidizing agent to the pyrimidine compound of the formula Vl (Vl) is oxidized and this with a formylaniline of the formula ViI Yv__NHCHCO (VII) ^R l R ₂ in an inert solvent in the presence of a base at temperatures between -30 ⁰ C to + 120 ⁰ C to give a compound of formula VIII (VIII) is reacted, whereupon the resulting compound VIII is subjected to hydrolysis in the presence of a base or acid at temperatures of 10 ⁰ C to 110 ° C, to obtain compounds of formula I a, and, if desired, replacement of the OH group to halogen for obtaining compounds of the formula I b, and, if desired, further exchange of the halogen for one of the other groups mentioned for R ₄ . 2. The method according to claim 1, characterized in that compounds of formula I are prepared in which R ₁ and R _{2 are} independently hydrogen or fluorine. 3. The method according to claim 1, characterized in that compounds of formula I are prepared in which R ₁ and R ₂ independently of one another are hydrogen, halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₂ -haloalkyl, C ₁ - C ₃ -alkoxy or C 1 -C -haloalkoxy; R _{3 is} C ₃ -C ₄ cycloalkyl which is unsubstituted or monosubstituted by methyl or halogen; R _{4 is} halogen, -OR ₅ , -NR ₅ R ₆ , where R _{5 has} the meanings a), b), c), d) or g), and R _{6 is} hydrogen or an alkyl, alkenyl or alkynyl radical which optionally unsubstituted or is halogen-substituted; orthe R ₅ and R ₆ together with the common N atom represent an aziridine ring, or an optionally unsubstituted or methyl-substituted piperidine or morpholine ring. 4. The method according to claim 3, characterized in that compounds of formula I are prepared in which R ₁ and R _{2 are} independently hydrogen or fluorine. 5. The method according to claim 1, characterized in that compounds of formula I are prepared, in which mean: R 1 and R ₂ independently of one another are hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, Methoxy, ethoxy or difluoromethoxy; R _{3 is} cyclopropyl or by methyl or halogen once or twice the same or different substituted cyclopropyl; R _{4 is} halogen, -SR ₅ , -OR ₅ , -NR ₅ R ₆ ; and R _{5 is} hydrogen or a C ₁ -C ₄ alkyl group which is unsubstituted or substituted by halogen, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylamino, bis (C ₁ - C ₄ alkyl) amino, cyclopropyl or by-C00C- | substituted -C ₃ alkyl; or wherein R _{5 represents} C ₃ -C ₄ alkenyl or C ₃ -C ₄ alkynyl or represents an unsubstituted or halogen, methyl or methoxy-substituted phenyl group or an acyl radical corresponding to the meaning g); and R _{6 is} hydrogen or a C ₁ -C 12 alkyl group which is unsubstituted or substituted by halo, hydroxy, C ₁ -C ₄ alkoxy, C 1-12 alkylamino or B 1-8 alkylamino or R ₆ is C ₁ -C 12 alkenyl or C ₃ -C ₄ alkynyl. 6. The method according to claim 5, characterized in that compounds of formula I are prepared in which Ri and R _{2 are} hydrogen, fluorine or difluoromethoxy, R _{3 is} cyclopropyl, R _{4 is} halogen, -OR ₅ or -NR ₅ R ₆ , and R _{5 is} hydrogen or R ₆ , and R _{6 is} C ₁ -C ₃ alkyl which is unsubstituted or monosubstituted by C ₁ -C ₄ alkoxy or cyclopropyl or substituted by halogen up to five times; or Cs-C ₄ alkenyl or Alkynyl means. 7. The method according to claim 6, characterized in that compounds of formula I are prepared, in which R ₁ and R _{2 are} independently hydrogen, 3-fluoro, 4-fluoro, 5-fluoro. 8. The method according to claim 1, characterized in that compounds of formula I are prepared in which R ₁ and R ₂ are independently hydrogen, halogen, C ₁ -C ₃ -alkyl, C ^ C ^ haloalkyl, C ₁ -C ₃ alkoxy-C or Cr ₃ haloalkoxy; R _{3 is} C ₃ -C ₄ -cycloalkyl which is unsubstituted or monosubstituted by methyl or halogen and R _{4 is} halogen. 9. The method according to claim 8, characterized in that compounds of formula I are prepared in which R ₁ and R _{2 are} independently hydrogen or fluorine. 10. The method according to claim 9, characterized in that compounds of formula I are prepared, in which R ₁ and R _{2 are} independently hydrogen, 3-fluoro, 4-fluoro, 5-fluoro. 11. Microbicidal agent, characterized in that it contains, in addition to the usual carrier material as active component, a compound of the formula I according to one of claims 1 to 7. 12. Composition according to claim 11, characterized in that the active component is a compound of the formula I according to one of claims 8 to 10. 13. A method for controlling or preventing an infestation of crops by phytopathogenic microorganisms, characterized in that as the active ingredient is applied a compound of formula I according to any one of claims 1 to 7 on the plant, on plant parts or their location. 14. The method according to claim 13, characterized in that one applies a compound of formula I according to any one of claims 8 to 10. 15. Compounds of the formula I in which mean: R ₁ and R ₂ independently of one another are hydrogen, halogen, C ₁ -C ₃ -alkyl, C 1 -C 4 -haloalkyl, C 1 -C ₃ Alkoxy or C-i-Qs-haloalkoxy; R ₃ C ₃ -C ₆ -CyClOaIkYl or by methyl or halogen up to three times the same or different substituted C ₃ -C ₆ -cycloalkyl; R ₄ halogen, thiocyaho hSCN), - OR ₅ , -SR ₅ , -NR ₅ R ₆ , where R _{5 is} a) -hydrogen, unsubstituted C ₁ -C ₄ -alkyl, or else a C ₁ -C ₄ -alkyl group which is represented by halogen, hydroxyl, cyano, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, bis ( C 1 -C ₄ -alkyl) amino, C ₃ -C ₆ -cycloalkyl, or by substituted or unsubstituted phenyl or by -CO-OC ₁ -C ₃ -alkyl is substituted; or b) unsubstituted or methyl-substituted C ₃ -C ₆ -cycloalkyl; or c) represents unsubstituted or halogen-substituted C 1 -C 6 alkenyl; or d) unsubstituted or halogen-substituted C ₃ -C ₆ alkynyl; or e) phenyl which is unsubstituted or substituted by halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, nitro; or f) an unsubstituted or substituted by halogen, C ₁ -C ₃ -AlkYl, C ₁ -C ₃ -alkoxy, nitro-substituted 5-membered or 6-membered optionally via-CH ₂ - bonded heterocyclic radical having one to three heteroatoms N, O or S; or g) represents an Acy I rest -CO-R ', wherein R' is unsubstituted or C ₁ -C ₆ -alkyl substituted by halogen, C ₁ -C ₃ -alkoxy; unsubstituted or halogen-substituted C ₃ -C ₆ alkenyl; unsubstituted or substituted by halogen, C ₁ -C ₃ -AlkYl, C ₁ -C ₃ -alkoxy, nitro-substituted phenyl; or h) represents a C rbamoy I rest-CO-NH-R "or an oxycarbonyl-CO-OR", in which R "is an aliphatic or cycloaliphatic radical having a maximum of 6 C-atoms, which is unsubstituted or halogen-substituted, or wherein R "represents a phenyl or benzyl radical which is each unsubstituted or substituted in the aromatic ring by halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₃ -alkoxy, nitro; and in which R _{6 is} hydrogen, unsubstituted C ₁ -C ₈ -A! ^! or is C ₁ -C ₄ -alkyl which is substituted by halogen, hydroxy, cyano, C ₁ -C ₄ -alkoxy; or wherein R _{6 is} unsubstituted or methyl substituted Cs-Ce-cycloalkyl; each unsubstituted or halogen-substituted C ₃ -C ₆ alkenyl or C ₃ -C ₆ alkylene; represents or unsubstituted or substituted by halogen, Ci-C ₃ -alkyl, C ₁ -C ₃ -alkoxy, nitro; wherein in the case of R ₄ = NR ₅ R _6, the substituents R ₅ and R ₆ together with the N-atom may also together form an aziridine ring or a 5- or 6-membered heterocyclic radical which in addition to the N-atom nor one or two heteroatoms N, O or S may be included and alkyl substituted. 16. Compounds according to claim 15, wherein R ₁ and R _{2 are} independently hydrogen or fluorine. 17. Compounds according to claim 15, wherein Ri and R ₂ are independently hydrogen, halogen, C ₁ -C ₃ -alkyl, Ci-C ₂ haloalkyl, C ₁ -C ₃ -alkoxy or C ₃ haloalkoxy; R _{3 is} Cs-C 1-5 cycloalkyl which is unsubstituted or monosubstituted by methyl or by halogen; R _{4 is} halogen, -OR ₅ , -NR ₅ R ₆ , where R _{5 has} the meanings a), b), c), d) or g), and R _{6 represents} hydrogen or an alkyl, alkenyl or alkynyl radical which is optionally unsubstituted or halogen-substituted; or where R ₅ and R ₆ together with the common N atom represent an aziridine ring, or an optionally unsubstituted or methyl-substituted piperidine or morpholine ring. 18. Compounds according to claim 17, wherein R ₁ and R _{2 are} independently hydrogen or fluorine. 19. Compounds according to claim 15, wherein R- and R ₂ independently of one another are hydrogen, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy or difluoromethoxy; R _{3 is} cyclopropyl or cyclopropyl mono- or di-identical or differently substituted by methyl or halogen; R _{4 is} halogen, -SR ₅ , -OR ₅ , -NR ₅ R ₆ ; and R ₄ represents alkyl ₅ is hydrogen or a C-C, which are unsubstituted or substituted by halogen, hydroxy, _Ci-C4 alkoxy, _C1-C4 alkylamino, BisfC iQ AlkyOamino, cyclopropyl or-COOC ₁ -C _3- alkyl substituted; or wherein R _{5 represents} C ₃ -C ₄ alkenyl or C ₃ -C ₄ alkynyl or represents an unsubstituted or halogen, methyl or methoxy-substituted phenyl group or an acyl radical corresponding to the meaning g); and R _{6 is} hydrogen or a C ₁ -C ₄ alkyl group which is unsubstituted or substituted by halo, hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylamino or BisfC d -alkylamino, or in which R _{6 is} C ₃ -C ₄ alkenyl or C ₃ -C ₄ alkynyl. 20. Compounds according to claim 19, in which R ₁ and R _{2 are} hydrogen, fluorine or difluoromethoxy, R _{3 is} cyclopropyl, R _{4 is} halogen, -OR ₅ or -NR ₅ R ₆ , and R _{5 is} hydrogen or R ₆ , and R _{6 is} C ₁ -C ₃ alkyl which is unsubstituted or monosubstituted by C ₁ -C ₄ alkoxy or cyclopropyl or substituted by halogen up to five times; or C ₃ -C ₄ -AlkCnYl or alkynyl. 21. Compounds according to claim 20, in which Ri and R ₂ independently of one another are hydrogen, 3-fluoro, 4-fluoro, 5-fluoro. 22. Compounds according to claim 15, wherein R- and R ₂ independently of one another are hydrogen, halogen, C ₁ -C ₃ -alkyl, C ₁ -C ₂ -haloalkyl, C ₁ -C ₃ -alkoxy or C ₁ -C ₃ -haloalkoxy; R _{3 is} C ₃ -C ₄ -cycloalkyl which is unsubstituted or monosubstituted by methyl or halogen and R _{4 is} halogen. 23. Compounds according to claim 22, wherein R ₁ and R _{2 are} independently hydrogen or fluorine. 24. Compounds according to claim 23, in which R ₁ and R ₂ independently of one another are hydrogen, 3-fluoro, 4-fluoro, 5-fluoro.