IE910652A1 - Microbicides - Google Patents

Abstract

Compounds of the formula in which R1 and R2 independently of one another are hydrogen, C1-C4-alkyl or cyclopropyl, including the acid addition salts of the compounds, have valuable fungicidal properties. The novel active substances can be used in crop protection for preventing crop plants from being attacked by phytopathogenic fungi, and for controlling these pests.

Description

The present invention relates to novel N-(2,6-dinitro-3-chloro-4-trifluoromethylphenyl)4-amino-6-fluoropyrimidine derivatives of formula I below. It relates also to the preparation of those compounds and to agrochemical compositions that contain at least one of those compounds as active ingredient. The invention relates also to the preparation of the said compositions and to the use of the compounds or the compositions for controlling or preventing an attack on plants by phytopathogenic fungi.

The compounds according to the invention have the general formula I wherein R1 and R2 independently of each other are hydrogen, C1-C4alkyl or cyclopropyl; including the acid addition salts of the compounds of formula I.

Depending on the number of carbon atoms indicated, alkyl shall be understood as being, for example, the following straight-chain or branched groups: methyl, ethyl, propyl, butyl and also the isomers thereof, for example isopropyl, isobutyl, sec-butyl or tert-butyl.

The compounds of formula I are solids at room temperature and are distinguished by very valuable phytofungicidal properties. They can therefore be used in the agricultural sector or related fields for controlling phytopathogenic fungi.

The invention relates both to the free compounds of formula I and to their addition salts with inorganic and organic acids. -2Salts according to the invention are especially addition salts with, according to the intended use, biocompatible inorganic or organic acids, for example hydrohalic acids, e.g. hydrochloric, hydrobromic or hydriodic acid, and also sulfuric acid, phosphoric acid, phosphorous acid, nitric acid, unsubstituted or halogenated fatty acids, such as acetic acid, trichloroacetic acid and oxalic acid, or sulfonic acids, such as benzenesulfonic acid and methanesulfonic acid, or alternatively addition salts with suitable salts, for example magnesium chloride or calcium chloride.

The compounds of formula I are novel and as such represent a selection of products from the general descriptions of European Patent Applications No. 139613, No. 248 348 and No. 248 349. The compounds disclosed in the above-mentioned publications are described as pesticides, in some cases also as fungicides, but those compounds do not always meet the requirements made of them in practice, especially when used against certain pests.

By contrast, the novel compounds of formula I prove to be effective especially against specific genera of the following classes of fungus: Fungi imperfecti (e.g. Cercospora), Basidiomycetes (e.g. Puccinia), Ascomycetes (e.g. Erysiphe and Venturia) and Oomycetes (e.g. Plasmopara and Phytophthora). They therefore represent a valuable addition to the compositions available in crop protection for controlling phytopathogenic fungi. For practical field application purposes, they have, advantageously, curative, preventive and also systemic properties and can be used for protecting numerous cultivated plants. With the compounds of formula I it is possible to inhibit or destroy the pests which occur on plants or on parts of plants (fruit, blossoms, leaves, stems, tubers, roots) in different crops of useful plants, while at the same time the parts of plants which grow later are also protected from attack e.g. by phytopathogenic fungi. The compounds of formula I can also be used as dressing agents for protecting seeds (fruits, tubers, grains) and plant cuttings against fungus infections as well as against phytopathogenic fungi which occur in the soil.

The following compounds of formula I are preferred in respect of their mode of action: N-(2',6'-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(2,5-diethyl-6-fluoro)pyrimidine; N-(2',6'-dinitro-3'-chloro-4,-trifluoromethylphenyl)-4-amino-(5-ethyl-6-fluoro)pyrimidine; N-(2',6'-dinitro-3,-chloro-4'-trifluoromethylphenyl)-4-amino-(2-ethyl-5-methyl-6-fluoro)pyrimidine; -3N-(2',6'-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(2-cyclopropyl-6-fluoro) pyrimidine; N-(2',6'-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(2-n-propyl-6-fluoro)pyrimidine; N-(2',6'-dinitro-3,-chloro-4,-trifluoromethylphenyl)-4-amino-(2-isopropyl-6-fluoro)pyrimidine; N-(2,,6'-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(5-ethyl-6-fluoro)pyrimidine; N-(2’,6,-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(2-cyclopropyl-6-fluoro) pyrimidine; N-(2,,6'-dinitro-3'-chloro-4,-trifluoromethylphenyl)-4-ainino-(2,5-dimethyl-6-fluoro)pyrimidine; N-(2',6,-dinitro-3,-chloro-4,-trifluoromethylphenyl)-4-amino-(2-methyl-5-n-propyl-6fluoro)-pyrimidine; N-(2',6'-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(2-methyl-5-isopropyl-6 fluoro)-pyrimidine.

Of those compounds, the following compound is to be regarded as especially advantageous: N-(2',6'-dinitro-3,-chloro-4,-trifluoromethylphenyl)-4-aniino-(2,5-diethyl-6-fluoro)pyrimidine.

The compounds of formula I are prepared by reacting: a compound of formula II NO. (Π) Cl no2 with a pyrimidine derivative of formula ΠΙ wherein the substituents Rj and R2 are as defined under formula I and Z and Y are NH2, halogen or SO2R in which R is C1-C4alkyl or aryl, with the proviso that, when Z is halogen or SO2R, Y is NH2, and when Z is NH2, Y is halogen or SO2R, if desired in solvents that are inert towards the reactants, at temperatures of from -80°C to +150°C, preferably at from -50°C to +30°C, and, if desired, advantageously in the presence of acid-binding agents.

Suitable acid-binding agents are organic and inorganic bases, for example tertiary amines, such as trialkylamines (trimethylamine, triethylamine, tripropylamine, etc.), pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidylaminopyridine, etc.), oxides and hydroxides, carbonates and hydrogen carbonates of alkali metals and alkaline earth metals, and also alkali metal acetates.

Examples of suitable inert solvents or diluents are aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylenes, petroleum ether, halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ethers (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.), anisole, dioxane, tetrahydrofuran; nitriles, such as acetonitrile, propionitrile; Ν,Ν-dialkylated amides, such as dimethylformamide; dimethyl sulfoxide; ketones, such as acetone, diethyl ketone, methyl ethyl ketone, and mixtures of such solvents with one another.

The reaction of the compound of formula (II) with the compound of formula (ΠΙ) may also be carried out in an aqueous two-phase system in accordance with the generally known principle of phase transfer catalysis.

The following solvents, for example, are suitable as the organic, water-immiscible phase: aliphatic and aromatic hydrocarbons, such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylenes, etc., halogenated hydrocarbons, such as dichloromethane, chloroform, carbon tetrachloride, ethylene dichloride, 1,2-dichloroethane, -5tetrachloroethylene, etc., or aliphatic ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc. Examples of suitable phase transfer catalysts are: tetraalkylammonium halide, tetraalkylammonium hydrogen sulfates or tetraalkylammonium hydroxide, such as tetrabutylammonium chloride, bromide or iodide; triethylbenzylammonium chloride or bromide; cetyltrimethylammonium chloride, bromide or iodide, etc. Phosphonium salts are also suitable phase transfer catalysts. The reaction temperatures are generally from -30° to 130°C, or the boiling point of the solvent or solvent mixture.

Some of the compounds of formulae Π and ΠΙ are known, or they can be prepared in accordance with known processes [Ser. Khim. Nauk. 1973 (6) 81-85 (CA: 80/59913), Yakugaku Zasshi 87 (11), 1315-1321 (1967) (CA: 68/114540) andD.J. Brown; The Chemistry of Heterocyclic Compounds, The Pyrimidines Supplement Π 1985, 167].

The invention also relates to compositions that contain compounds of formula I as active ingredient, especially crop protection compositions, and to their use in the agricultural sector or related fields.

The present invention further embraces the preparation of those compositions, which comprises homogeneously mixing the active ingredient with one or more compounds or groups of compounds described herein. The invention furthermore relates to a method of treating plants, which comprises applying thereto the novel compounds of formula I or the novel compositions.

Target crops to be protected within the scope of the present invention comprise e.g. the following species of plants: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related crops); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (cucumber, marrows, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocados, cinnamon, camphor), or plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals. -6The compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds. These compounds can be fertilisers or micronutrient donors or other preparations that influence plant growth. They can also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology.

Suitable carriers and adjuvants can be solid or liquid and correspond to the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers.

A preferred method of applying a compound of formula I, or an agrochemical composition which contains at least one of said compounds, is foliar application. The number of applications and the rate of application depend on the risk of infestation by the corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) if the locus of the plant is impregnated with a liquid formulation, or if the compounds are applied in solid form to the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field. The compounds of formula I may, however, also be applied to seeds (coating) either by impregnating the seeds with a liquid formulation containing a compound of formula I, or by coating them with a solid formulation.

The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are for this purpose advantageously formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application are normally from 10 g to 5 kg of active ingredient (a.i.) per hectare, preferably from 50 g to 1 kg a.i./ha, most preferably from 200 g to 600 g a.i./ha. -Ί The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methy 1-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term surfactants will also be understood as comprising mixtures of surfactants.

Both so-called water-soluble soaps and also water-soluble synthetic surface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tallow oil. Mention may also be made of fatty acid methyllaurin salts. -8More frequently, however, so-called synthetic surfactants are used, especially alkanesulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylsulfonates.

The fatty alcohol sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a C8-C22alkyl radical, which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.

Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethyleneethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants. -9Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C8-C22alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ammonium bromide.

Further surfactants customarily employed in formulation technology are known to the person skilled in the art or can be taken from the relevant specialist literature.

The agrochemical compositions usually contain 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula 1,99.9 to 1 %, preferably 99.9 to 5 %, of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also contain further auxiliaries such as stabilisers, antifoams, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for obtaining special effects.

The following Examples serve to illustrate the invention in greater detail, but do not constitute a limitation thereof. 1. Preparation Examples: 1.1 Preparation of N- (2',6'-dinitro-3 ,-chloro-4'-trifluoromethylphenvl)-4-amino(2,5-diethvl-6-fluoro)-pyrimidine (comp. no. 3) A solution of 7.2 g of potassium tert-butoxide in 50 ml of tetrahydrofuran is added dropwise at -45°C, within a period of half an hour, to a suspension of 5.1 g of 2,5-diethyl4-amino-6-fluoropyrimidine and 10.1 gof l,3-dinitro-2,4-dichloro-5-trifluoromethylbenzene in 60 ml of tetrahydrofuran. When the addition is complete, the tempera ture of the red-coloured reaction mixture is slowly allowed to rise to room temperature. After stirring for 12 hours at room temperature, the solvent is evaporated off under reduced pressure and the residue is taken up in 100 ml of ethyl acetate. The organic phase is washed with 2 x 150 ml of water, with 3 x 150 ml of 10 % acetic acid and with a further -102 x 100 ml of water, dried over sodium sulfate and filtered, and the solvent is evaporated off in vacuo. The residue is purified by chromatography over a silica gel column using hexane/ethyl acetate (4:1), yielding the title compound in the form of white crystals; m.p. 111-112°C.

The following compounds can be prepared analogously. - 11 Table 1: Cl N02 R2 No.Ri r2 physical data 1 H ch3 2 ch3 H 3 ch2ch3 CH2CH3 m.p. 111-112°C 4 5 C4H9-I1 C(CH3)4 6 CH(CH3)CH2CH3 C3H7-i m.p. 148-150°C 7 ch3 ch3 8 H C4Hg-n 9 ch2ch3 H m.p. 79-80°C 10 “kl CH2CH3 11 ch2ch2ch3 H 12 C4H9-t C4H9-n 13 C3H7-i CH(CH3)CH2CH3 14 CH2CH3 C4H^-n 15 H H 16 ch3 CH2CH3 m.p. 98-99°C 17 X] H 18 C4H9-I1 C4H9-11 m.p. 69-71°C 19 H m.p. 136-138°C 20 ch3 C3H7-n m.p. 82-86°C -12Table 1: (continuation) No. Ri r2 physical data 21 ch3 22 ch2ch3 C3H7-i 23 C4Hg*t CH(CH3)CH2CH3 24 ch2ch2ch3 ch2ch3 m.p. 79-82°C 25 C3H7-i 26 ch3 C3H7-i 27 H C4H^-t 28 CH2CH3 C3H7-n m.p. 83-85°C 29 μ C4Hg-t 30 CH(CH3)CH2CH3 C3H7-n 31 C3H7-i ch3 m.p. 98-100°C 32 C4H9-n H 33 ch3 QHg-n 34 H ch3 35 CH2CH3 X] m.p. 132-134°C 36 C3H7-n 37 ch2ch2ch3 “K1 38 CJH^-t C4H^-t 39 ch2ch3 ch3 m.p. 118-121°C 40 ch3 CH2CH(CH3)2 41 H C3H7-n m.p. 130-132°C 42 X] C3H7-i 43 CH(CH3)CH2CH3 H 44 CJHg-n CH(CH3)CH2CH3 -13Table 1: (continuation) No.Ri r2 physical data 45 ch2ch3 CH2CH(CH3)2 46 H C3H7-i m.p. 128-129°C 47 ch3 m.p.111-113°C 48 ch2ch2ch3 C3H7-n 49 C4Hg-n 50 C4H9-t CH2CH(CH3)2 51 C3H7-i C4Hg-t 52 C4H9-n 53 ch3 CH(CH3)CH2CH3 54 H CH2CH(CH3)2 55 ch2ch3 C(ch3)4 56 CH(CH3)CH2CH3 ch3 57 CH2CH(CH3)2 58 ch2ch2ch3 CH(CH3)2 59 C4H^-t C3H7-n 60 C3H7-i CH2CH(CH3)2 61 CH2CH(CH3)2 H 62 H CH(CH3)CH2CH3 63 CH3 C4H9-n 64 C4H9-n CH2CH(CH3)2 65 CH2CH(CH3)2 ch2ch3 66 ch2ch3 CH(CH3)CH2CH3 67 C4H^-t C3H7-i 68 ch2ch2ch3 C4H9-n -14Table 1: (continuation) No. Ri r2 physical data 69 C3H7-i C4Hg-n 70 o CH(CH3)CH2CH3 71 CH(CH3)CH2CH3 72 C4H^-t 73 ch2ch2ch3 ch3 m.p. 95-97°C 74 CH(CH3)CH2CH3 C^Hg-n 75 C4Hg-n C3H7-i 76 C3H7-i C3H7-i 77 C4H^-t ch3 78 CH2CH(CH3)2 C3H7-n 79 CH(CH3)CH2CH3 CH(CH3)CH2CH3 80 C4H^-n C3H7-n 81 CH2CH(CH3)2 C3H7-i 82 ch2ch2ch3 CH2CH(CH3)2 83 C3H7-i C3H7-n 84 CH2CH(CH3)2 C4Hg-n 85 C4H^-t ch2ch3 86 CH2CH(CH3)2 CH2CH(CH3)2 87 CH2CH(CH3)2 C^Hg-t 88 ch2ch2ch3 CH(CH3)CH2CH3 89 C4Hg-n ch3 m.p. 130-132°C 90 CH(CH3)CH2CH3 C4Hg-t 91 CH2CH(CH3)2 92 C3H7-i ch2ch3 Table 1: (continuation) No.Ri r2 physical data 93 CH2CH(CH3)2 CH(CH3)CH2CH3 94 C4H^-t H 95 ch2ch2ch3 C4H^-t 96 CH(CH3)CH2CH3 CH2CH(CH3)2 97 C4H9-n ch2ch3 98 CH(CH3)CH2CH3 ch2ch3 99 C3H7-i H 100 CH2CH(CH3)2 ch3 2. Formulation Examples for solid active ingredients of formula I (throughout, percentages are by weight) 2.1. Wettable powders a compound of Table 1 sodium lignosulfonate sodium lauryl sulfate 3 % sodium diisobutylnaphthalenesulfonate octylphenol polyethylene glycol ether (7-8 mol of ethylene oxide) highly dispersed silicic acid kaolin a) b) c) % 50 % 75 % % 5 % - 5 % % 10 % 2% 5 % 10 % 10 % 62% 27% The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration. 2.2. Emulsifiable concentrate a compound of Table 1 % - 16octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3 % calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide) 4 % cyclohexanone 30 % xylene mixture 50 % Emulsions of any required concentration can be obtained from this concentrate by dilution with water. 2.3. Dusts a compound of Table 1 talcum kaolin a) b) % 8 % % 92% Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. 2.4. Extruder granules a compound of Table 1 10 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % kaolin 87 % The active ingredient is mixed and ground with the adjuvants, and the mixture is subsequently moistened with water. The mixture is extruded and then dried in a stream of air. 2.5. Coated granules a compound of Table 1 3 % polyethylene glycol (mol. wt. 200) 3 % kaolin 94 % The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. - 172.6. Suspension concentrate a compound of Table 1 ethylene glycol nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % sodium lignosulfonate 10 % carboxymethylcellulose % aqueous formaldehyde solution silicone oil in the form of a 75 % aqueous emulsion water 40% % % % 0.2% 0.8% 32% The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water. 3. Biological Examples Example 3.1: Action against Puccinia graminis on wheat a) Residual-protective action Wheat plants are sprayed 6 days after sowing with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are incubated for 48 hours at 95-100 % relative humidity and about 20°C and then stood in a greenhouse at about 22°C. Evaluation of rust pustule development is made 12 days after infection. b) Systemic action Wheat plants are watered 5 days after sowing with a spray mixture (0.006 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound. After 48 hours the treated plants are infected with a uredospore suspension of the fungus. The infected plants are then incubated for 48 hours at 95-100 % relative humidity and about 20°C and then stood in a greenhouse at about 22°C. Evaluation of rust pustule development is made 12 days after infection. - 18jE 91652 Compounds of Table 1 exhibit very good activity against Puccinia fungi. Compound no. 46, inter alia, inhibits Puccinia infestation to 0 to 5 %. On the other hand, Puccinia infestation is 100 % on untreated and infected control plants.

Example 3.2: Action against Cercospora arachidicola on groundnut plants Residual-protective action Groundnut plants 10-15 cm in height are sprayed with a spray mixture (0.006 % active ingredient) prepared from a wettable powder formulation of the test compound, and infected 48 hours later with a conidia suspension of the fungus. The infected plants are incubated for 72 hours at about 21 °C and high humidity and then stood in a greenhouse until the typical leaf specks occur. Evaluation of the fungicidal action is made 12 days after infection and is based on the number and size of the specks.

Compared with untreated and infected control plants (number and size of the specks = 100 %), Cercospora infestation on groundnut plants treated with compounds of Table 1 is substantially reduced. Thus compounds nos. 3,9, 16, 19 and 46 inhibit the occurrence of specks almost completely (0 to 10 %) in the above test.

Example 3.3: Action against Erysiphae graminis on barley a) Residual-protective action Barley plants about 8 cm in height are sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. The treated plants are dusted with conidia of the fungus after 3 to 4 hours. The infected barley plants are stood in a greenhouse at about 22°C. The fungus infestation is evaluated after 10 days. b) Systemic action A spray mixture (0.006 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound is used to water barley plants about 8 cm in height. Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. The treated plants are dusted 48 hours later with conidia of the fungus. The infected barley plants are then stood in a greenhouse at about 22°C and evaluation of fungus infestation is made after 10 days.

Compounds of Table 1 exhibit good activity against Erysiphae fungi. Thus compounds nos. 3,16 and 46 inhibit fungus infestation on barley to less than 10 %. On the other hand, -19Erysiphae infestation is 100 % on untreated and infected control plants.

Example 3.4: Residual-protective action against Venturia inaequalis on apple shoots Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.006 % a.i.) prepared from a wettable powder formulation of the test compound. The treated plants are infected 24 hours later with a conidia suspension of the fungus. The plants are then incubated for 5 days at 90-100 % relative humidity and stood in a greenhouse for a further 10 days at 20-24°C. Scab infestation is evaluated 15 days after infection. With compounds of Table 1, infestation is substantially reduced. Thus compounds nos. 3,9,16,19,41 and 46 inhibit Venturia infestation to 5 %. On the other hand, infestation is 100 % on untreated and infected control shoots.

Example 3.5: Action against Botrytis cinerea on beans Residual-protective action Bean plants about 10 cm in height are sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. After 48 hours the treated plants are infected with a conidia suspension of the fungus. The infected plants are incubated for 3 days at 95-100 % relative humidity and 21°C and then evaluated for fungus infestation. Compounds of Table 1 inhibit fungus infestation very strongly. On the other hand, Botrytis infestation is 100 % on untreated and infected bean plants.

Example 3.6: Action against Phytophthora infestans on tomato plants a) Residual-protective action After a cultivation period of 3 weeks, tomato plants are sprayed with a spray mixture (0.02 % active ingredient) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants are infected with a sporangia suspension of the fungus. The infected plants are then incubated for 5 days at 90-100 % relative humidity and 20°C and then evaluated for fungus infestation. b) Systemic action After a cultivation period of 3 weeks, a spray mixture (0.006 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound is used to water tomato plants. Care is taken that the spray mixture does not come into contact with the parts of the plants above the soil. The treated plants are infected 48 hours later with a sporangia suspension of the fungus. The infected plants are then incubated for -205 days at 90-100 % relative humidity and 20°C and then evaluated for fungus infestation.

Compounds of Table 1 exhibit very good activity against Phytophthora in the above tests. Compared with untreated and infected control plants in which infestation is 100 %, compounds nos. 3,9,19,41 and 49 inhibit fungus infestation almost completely (0 to 10 %).

Example 3.7: Action against Plasmopara viticola on vines a) Residual-protective action Vine seedlings in the 4-5 leaf stage are sprayed with a spray mixture (0.02 % a.i.) prepared from a wettable powder formulation of the test compound. After 24 hours the treated plants are infected with a sporangia suspension of the fungus. Fungus infestation is evaluated after incubation for 6 days at 95-100 % relative humidity and 20°C. b) Residual-curative action Vine seedlings in the 4-5 leaf stage are infected with a sporangia suspension of the fungus. After incubation for 24 hours in a humidity chamber at 95-100 % relative humidity and 20°C, the infected plants are dried and sprayed with a spray mixture (0.006 % active ingredient) prepared from a wettable powder formulation of the test compound. After the spray coating has dried, the treated plants are again placed in the humidity chamber. Evaluation of fungus infestation is made 6 days after infection.

Compounds of Table 1 exhibit very good activity against Plasmopara viticola on vines; in particular, compounds nos. 9,19,41 and 46 inhibit fungus infestation completely (0 to 5 %).

Claims (15)

What is claimed is:

1. A compound of formula I wherein Rj and R 2 independently of each other are hydrogen, C 1 -C 4 alkyl or cyclopropyl; or an acid addition salt of a compound of formula I.

2. A compound of formula I according to claim 1 from the group: N-(2',6'-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(2,5-diethyl-6-fluoro)pyrimidine; N-(2',6'-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(5-ethyl-6-fluoro)pyrimidine; N-(2',6'-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(2-ethyl-5-methyl-6-fluoro)pyrimidine; N-(2',6'-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(2-cyclopropyl-6-fluoro)pyrimidine; N-(2',6'-dinitro-3 , -chloro-4'-trifluoromethylphenyl)-4-amino-(2-n-propyl-6-fluoro)pyrimidine; N-(2',6’-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(2-isopropyl-6-fluoro)pyrimidine; N-(2',6'-dinitro-3'-chloro-4’-trifluoromethylphenyl)-4-amino-(5-ethyl-6-fluoro)pyrimidine; N-(2',6 , -dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(2-cyclopropyi-6-fluoro)pyrimidine; N-(2',6'-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(2,5-dimethyl-6-fluoro)pyrimidine; N-(2',6'-dinitro-3 , -chloro-4'-trifluoromethylphenyl)-4-amino-(2-methyl-5-n-propyl-6-22- fluoro)-pyrimidine; N-(2 , ,6'-dinitro-3'-chloro-4'-trifluoromethylphenyl)-4-amino-(2-methyl-5-isopropyl-6fluoro)-pyrimidine.

3. N-(2',6'-Dinitro-3 , -chloro-4'-trifluoromethylphenyl)-4-amino- (2,5-diethyl-6-fluoro)pyrimidine.

4. A process for the preparation of a compound of formula I according to claim 1, which comprises reacting a compound of formula II with a pyrimidine derivative of formula ΠΙ wherein the substituents Rj and R 2 are as defined under formula I and Z and Y are NH 2 , halogen or SO 2 R in which R is Q-C4alkyl or aryl, with the proviso that, when Z is halogen or SO 2 R, Y is NH 2 , and when Z is NH 2 , Y is halogen or SO 2 R, at temperatures of from-80°C to+150°C.

5. A composition for controlling or preventing an attack on plants by phytopathogenic fungi, which contains as active ingredient at least one compound of formula I according to claim 1, together with a suitable carrier.

6. A composition according to claim 5, which contains as active ingredient at least one ΙΕ 91652 -23compound of formula I according to claim 2.

7. A composition according to claim 5, which contains as active ingredient at least one compound of formula I according to claim 3.

8. A method of controlling or preventing an attack on cultivated plants by phytopathogenic fungi, which comprises applying a compound of formula I according to claim 1 as active ingredient to the plant, to parts of the plant or to the locus thereof.

9. A method according to claim 8, wherein a compound as claimed in claim 2 or claim 3 is applied as active ingredient.

10. A process for the preparation of an agrochemical composition as claimed in claim 5, which comprises homogeneously mixing at least one compound of formula I according to claim 1 with suitable solid or liquid adjuvants and/or surfactants. -2411. A compound according to claim 1, substantially as hereinbefore described and exemplified.

11. 12. A process for the preparation of a compound according to claim 1, substantially as hereinbefore described and exemplified.

12. 13. A compound according to claim 1, whenever prepared by a process claimed in claim 4 or 12.

13. 14. A composition according to claim 5, substantially as hereinbefore described and exemplified.

14.

15. A method according to claim 8, substantially as hereinbefore described and exemplified.