IE62436B1

IE62436B1 - Microbicides

Info

Publication number: IE62436B1
Application number: IE175988A
Authority: IE
Inventors: Adolf Hubele
Original assignee: Ciba Geigy Ag
Priority date: 1987-06-11
Filing date: 1988-06-10
Publication date: 1995-02-08
Also published as: FI882709A0; PL272950A1; PT87707A; BG49923A3; JP2632187B2; ZW7588A1; HU208961B; KR890000436A; CA1305483C; KR970001478B1; FI98912C; FI882709A; DK317588D0; JPS63316774A; FI98912B; DK167975B1; CZ281586B6; PL154960B1; IL86666A0; AU1760688A

Abstract

Novel compounds of the formula in which: R1 and R2 independently of one another represent hydrogen, halogen, C1-C3-alkyl, C1-C2-haloalkyl, C1-C3-alkoxy or C1-C3-haloalkoxy; R3 represents hydrogen, C1-C4-alkyl; C1-C2-alkyl which is substituted by halogen or hydroxyl, or represents cyclopropyl or cyclopropyl which is substituted by halogen and/or methyl; R4 represents C1-C8-alkyl; C2-C6-alkyl which is substituted by halogen, hydroxyl, cyano, C1-C4-alkoxy, C3-C4-alkoxyalkoxy or C1-C3-alkylthio; C3-C6-alkenyl; C3-C6-alkynyl; C3-C7-cycloalkyl or C3-C7-cycloalkyl which is substituted by methyl; and X represents oxygen or sulphur. Compounds of the formula I are valuable preparations for controlling microorganisms, especially in the agrochemical sector, and harmful insects.

Description

Microbicides The present invention relates to novel 2-anilinopyrimidine derivatives of formula I below. It relates also to the preparation of these substances and to agrochemical compositions that contain as active ingredient at least one of these compounds. The invention relates also to the preparation of the mentioned compositions and to the use of the active ingredients or of the compositions for controlling pests, especially harmful insects and plant-destructive microorganisms, preferably fungi.

The compounds according to the invention correspond to the general formula I Ri -Ra \ / NH—· (I) •N· CH2XR4 in which: Rj and R2 independently of one another are hydrogen, halogen, C1-C3alkyl, Ci-C2-haloalkyl, Ci-Ca-alkoxy or Ci-C3~haloalkoxy; R3 is hydrogen; Ci-Ci»-alkyl; Ci-C2-alkyl substituted by halogen or by hydroxy; cyclopropyl; or cyclopropyl substituted by halogen and/or by methyl; Ri* is Ci-Ce-alkyl; Ca-Ce-alkyl substituted by halogen, hydroxy, cyano, C1-Ci*-alkoxy, C3-Cu-alkoxyalkoxy or by Cj-C3-alkylthio; C3-Ce-alkenyl; C3-C6-alkynyl; C3-C7-cycloalkyl; or C3-C7-cycloalkyl substituted by methyl; and X is oxygen or sulphur.

Depending on the number of carbon atoms indicated, alkyl by itself or as a component of another substituent, such as haloalkyl, alkoxy or haloalkoxy, is to be understood as meaning, for example: methyl, ethyl, - 2 propyl, butyl, pentyl, hexyl, heptyl and octyl and their isomers, such as, for example, isopropyl, isobutyl, tert.-butyl, isopentyl etc..

Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl and haloalkoxy are mono- to per-halogenated radicals, such as, for example, CHC12, CHZF, CC13, CH2C1, CHF2, CH2CH2Br, C2C15, CHBr, CHBrCl etc., preferably CFj. Alkenyl is, for example, propen-l-yl, allyl, buten-l-yl, buten-2-yl or buten-3-yl, and also chains having several double bonds. Alkynyl is, for example, propyn-2-yl, butyn-l-yl, butyn-2-yl, pentyn-4-yl etc., preferably propargyl. Depending on the number of carbon atoms indicated, cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

Compounds having an N-pyrimidylaniline structure are already known. For example, in published Japanese Patent Application Sho 56-65804 and in GDR Patent Specification 151404, compounds that have this basic structure are described as being effective against plant pests. 2-Nitroanilinopyrimidines are further known from EP-A-264348, EP-A-135472 and from EP-A-172786. However, the known compounds have hitherto been unable fully to meet the demands made of them in practice. The characteristic difference between the compounds of formula I according to the invention and the known compounds is the introduction of specific substituents and their combination into the anilinopyrimidine structure, as a result of which an unexpectedly high fungicidal activity and insecticidal action is obtained with the novel compounds .

The compounds of formula I are oils, resins or solids that are stable at room temperature and that are distinguished by valuable microbicidal properties. They can be used preventively and curatively in the agricultural sector or related fields for controlling plant-destructive microorganisms. The compounds of formula I according to the invention are distinguished in low application concentrations not only by excellent insecticidal and fungicidal action but also by the fact that they are especially well tolerated by plants.

An important group of phytofungicides is formed by those of the formula I in which Ri and R2 are hydrogen. - 3 A special group of anilinopyrimidine derivatives is formed by compounds of formula I in which Ri and R2 independently of one another are hydrogen, halogen, C1-C3alkyl, Ci~C2-haloalkyl, Ci-C3~alkoxy or Ci-C3~haloalkoxy; R3 is hydrogen, Ci-Ci,-alkyl or cyclopropyl; Ru is Ci-Ce-alkyl; Cj-Ce-alkyl substituted by halogen, hydroxy, cyano, Cι-Cu-alkoxy, C3-Ci,-alkoxyalkoxy or by Ci-Cs-alkylthio; C3-C6-alkenyl; C3-C6~alkynyl; Cs-Cj-cycloalkyl; or Cs-C7-cycloalkyl substituted by methyl; and X is oxygen or sulphur.

The following groups of active ingredients are preferred because of their pronounced biocidal, especially phytofungicidal, activity: Group la: Compounds of formula I in which: Ri and R2 independently of one another are hydrogen, fluorine, chlorine, bromine, Ci-C3-alkyl, Ci-C2-haloalkyl, Ci-C3-alkoxy or Ci-C2-haloalkoxy; R3 is hydrogen, Ci-C3-alkyl or cyclopropyl; Ri« is Ci-Cg-alkyl; C2~Ci,-alkyl substituted by halogen, hydroxy, cyano, Ci-C3-alkoxy, C3-Cu-alkoxyalkoxy or by Ci-C2-alkylthio; C3~alkenyl; C3~alkynyl; or C6-C7-cycloalkyl that is unsubstituted or substituted by methyl; and X is oxygen or sulphur.

Of the above-mentioned compounds, an especially preferred group is formed by those in which Ri = R2 = hydrogen (= Group laa).

Group lb: Compounds of formula I in which: Ri and R2 independently of one another are hydrogen, fluorine, chlorine, bromine, Ci-C3-alkyl, Ci-C3-alkoxy, trifluoromethyl, -OCHF2, -OCF2CHF2, -OCF2CHCIF, -OCF2CHCI2 or -OCF2CCI2F; R3 is hydrogen, methyl, ethyl or n-propyl; - 4 Ru is Ci-C^-alkyl; Cj-Ca-alkyl substituted by halogen, hydroxy, cyano, Ci-C2~alkoxy or by Cj-Cz-alkylthio; Ca-Cg-alkenyl; Ca-Cj-alkynyl; or cyclohexyl; and X is oxygen or sulphur.

Of the above-mentioned compounds, an especially preferred group is formed by those in which Ri = R2 = hydrogen (= Group lbb).

Group lc: Compounds of formula I in which: Ri and R2 independently of one another are hydrogen, fluorine, chlorine, bromine, Ci-C2-alkyl, Ci-C2-alkoxy, trifluoromethyl, -OCHF2, -OCF3, -OCF2CHF2 or -OCF2CHCIF; R3 is hydrogen or Ci-C2-alkyl; Ry is Ci-C3-alkyl; C2~alkyl substituted by halogen, hydroxy, cyano, Ci-C2-alkoxy or by Ci-C2~alkylthio; C3-Ci,-alkenyl; or C3-Cu-alkynyl; and X is oxygen or sulphur.

Of the above-mentioned compounds, an especially preferred group is formed by those in which Ri = R2 = hydrogen and X is oxygen (= Group lcc).

Group Id: Compounds of formula I in which: Ri and R2 independently of one another are hydrogen, fluorine, chlorine, bromine, Ci-C2-alkyl, Ci-C2-alkoxy, trifluoromethyl or -OCHF2; R3 is methyl; Ri, is Ci-C2-alkyl; C2-alkyl substituted by fluorine, chlorine, bromine, cyano, Ci-Cj-alkoxy or by methylthio; allyl; or propargyl; and X is oxygen or sulphur.

Of the above-mentioned compounds, an especially preferred group is formed by those in which Ri = R2 = hydrogen and X is oxygen (= Group ldd).

Group 2a: Compounds of formula I in which: Ri and R2 independently of one another are hydrogen, halogen, Ci~C2alkyl, halomethyl, Ci-C2-alkoxy or Ci-C2-haloalkoxy; R3 is hydrogen; Ci-C3-alkyl; Ci-C2-alkyl substituted by halogen or by hydroxy; cyclopropyl; or cyclopropyl mono- to tri-substituted by the same or different substituents selected from the group consisting of halogen and methyl; Ri* is Ci-Ci*-alkyl; C2-C3-alkyl substituted by halogen, cyano, Ci-C2alkoxy or by Ci-C2-alkylthio; C3-C6~alkenyl; C3-C6-alkynyl; or C3-C7cycloalkyl; and X is oxygen or sulphur.

Of the above-mentioned compounds, an especially preferred group is formed by those in which Ri = R2 = hydrogen ( = Group 2aa).

Group 2b: Compounds of formula I in which: Ri and R2 independently of one another are hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or difluoromethoxy; R3 is hydrogen; Ci-C3-alkyl; Ci-C2-alkyl substituted by halogen or by hydroxy; cyclopropyl; or cyclopropyl mono- to tri-substituted by the same or different substituents selected from the group consisting of halogen and methyl; Ri* is Ci-C3-alkyl; C2-C3~alkyl substituted by fluorine, chlorine or by Ci-C2-alkoxy; C3-C6~alkenyl; C3-C6~alkynyl; or C3-C6~cycloalkyl; and X is oxygen or sulphur.

Of the above-mentioned compounds, an especially preferred group is formed by those in which Ri = R2 = hydrogen (= Group 2bb).

Group 2c: Compounds of formula I in which: Ri and R2 independently of one another are hydrogen, fluorine, chlorine, methyl, trifluoromethyl, methoxy or difluoromethoxy; - 6 R3 is Ci-C3-alkyl; methyl substituted by halogen or by hydroxy; cyclopropyl; or cyclopropyl mono- to tri-substituted by halogen or by methyl; Ru is Ci-C3-alkyl; C2-C3-alkyl substituted by fluorine, chlorine or by methoxy; C3-Cu-alkenyl; C3-Ci»-alkynyl; cyclopropyl; or cyclohexyl; and X is oxygen.

Of the above-mentioned compounds, an especially preferred group is formed by those in which Ri = R2 = hydrogen (= Group 2cc).

Group 2d: Compounds of formula I in which: Ri and R2 are hydrogen; R3 is Ci-C3-alkyl; methyl substituted by fluorine, chlorine or by bromine; cyclopropyl; or cyclopropyl substituted by chlorine or by methyl; Ru is Ci-C3-alkyl, 2-chloroethyl, 2,2,2-trifluoroethyl, allyl or propargyl; and X is oxygen.

Individual substances that are especially preferred are, for example: 2-phenylamino-4-methyl-6-methoxymethylpyrimidine (comp. no. 1); 2-phenylamino-4-cyclopropyl-6-methoxymethylpyrimidine (comp. no. 10).

The compounds of formula I are prepared as follows: 1. a phenylguanidine salt of formula Ila \ _ / (Ha) or the free guanidine base of formula lib \ Z NH (lib) is reacted with a diketone of formula III - 7 Rj :—CH CH2XRu (III) without solvents or in an aprotic solvent, but preferably in a protic solvent, at temperatures of from 60°C to 160°C, preferably from 60°C to 110°C, or 2. in a multi-stage process: 2.1 urea of formula IV NH; o=c: ,/ (IV) is reacted with a diketone of formula III ,-UU :—CH2XRu (III) in the presence of an acid in an inert solvent at temperatures of from 20°C to 140°C, preferably from 40°C to 100°C, and is then cyclised at the reflux temperature of the solvent used to give a pyrimidine compound of formula V Rj HO— (V) CH2XRu and 2.2 the resulting compound of formula V is reacted further with excess POCI3, without solvents or in a solvent that is inert towards POCI3, at temperatures of from 50°C to 110°C, preferably at the reflux temperature of POCI3, to give the compound of formula VI and Cl—· / XCH2XRu (VI) 2.3 the resulting compound of formula VI is reacted further with an aniline compound of formula VII (VII) depending on the reaction conditions either a) in the presence of a proton acceptor, such as an excess of the aniline compound of formula VII or an inorganic base, without solvents or in a protic or aprotic solvent, or b) in the presence of an acid in an inert solvent, in each case at temperatures of from 60°C to 120°C, preferably from 80°C to 100°C; or 3. in a two-stage process: 3.1 a guanidinium salt of formula VIII h2n—c: ,nh2 '''ΝΗς is cyclised with a diketone of formula III Ra—$—CH2— :—CH2XRu .Θ (VIII) (III) a) without solvents, at temperatures of from 100°C to 160°C, preferably from 120°C to 150°C, or b) in a protic or aprotic solvent or a mixture of protic and aprotic solvents, at temperatures of from 30°C to 140°C, preferably from 60°C to 120°C, to give a pyrimidine compound of formula IX H2N—· / \h2XRi* and (IX) - 9 3.2 the resulting compound of formula IX is reacted with a compound of formula X in the presence of a proton acceptor in aprotic solvents at temperatures of from 30°C to 140°C, preferably from 60°C to 120°C, to remove HY, the substituents Ri to Ri, and X in the formulae II to X being as defined for formula I, Αθ being an acid anion and Y being halogen.

In the processes described above, in the case of compounds of formulae Ila and VIII containing the acid anion Αθ, the following salts, for example, are suitable: carbonate, hydrogen carbonate, nitrate, halide, sulphate and hydrogen sulphate. Halide is to be understood as meaning fluoride, chloride, bromide or iodide, preferably chloride or bromide.

The acids used are especially inorganic acids, such as, for example, hydrohalic acids, for example hydrofluoric acid, hydrochloric acid or hydrobromic acid, and also sulphuric acid, phosphoric acid or nitric acid; however, suitable organic acids may also be used.

As proton acceptors there are used, for example, inorganic bases, such as, for example, alkali metal or alkaline earth metal compounds, for example the hydroxides, oxides or carbonates of lithium, sodium, potassium, magnesium, calcium, strontium and barium, or also hydrides, such as, for example, sodium hydride.

In the processes described above, for example, the following solvents may be used, depending on the particular reaction conditions: Halogenated hydrocarbons, especially chlorinated hydrocarbons, such as tetrachloroethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, chloronaphthalene, carbon tetrachloride, trichloroethane, trichloroethylene, pentachloroethane, difluorobenzene, 1,2-dichloroethane, 1,1-dichloroethane, 1,2-cis-dichloroethylene, chlorobenzene, fluorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, chlorotoluene, trichlorotoluene; ethers, such as ethyl propyl ether, methyl tert.-butyl ether, n-butyl ethyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, diisopropyl ether, anisole, cyclohexyl methyl ether, diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxan, thioanisole, dichlorodiethyl ether; nitro-hydrocarbons, such as nitromethane, nitroethane, nitrobenzene, chloronitrobenzene, o-nitrotoluene; nitriles, such as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile, m-chlorobenzonitrile; aliphatic or cycloaliphatic hydrocarbons, such as heptane, hexane, octane, nonane, cymol, petroleum fractions within a boiling point range of from 70°C to 190°C, cyclohexane, methylcyclohexane, Decalin, petroleum ether, ligroin, trimethylpentane, such as 2,3,3-trimethylpentane; esters, such as ethyl acetate, ethyl acetoacetate, isobutyl acetate; amides, for example formamide, methylformamide, dimethylformamide; ketones, such as acetone, methyl ethyl ketone; alcohols, especially lower aliphatic alcohols, such as, for example, methanol, ethanol, n-propanol, isopropanol and the butanols; and, where appropriate, also water. Also suitable are mixtures of the mentioned solvents and diluents.

Methods of synthesis that are analogous to the above-described preparation processes have been published in the literature in the following references: Process 1: A. Kreutzberger and J. Gillessen, J. Heterocyclic Chem. 22, 101 (1985).

Process 2, Stage 2.1: 0. Stark, Ber. Dtsch. Chem. Ges. 42, 699 (1909); J. Hale, J. Am. Chem. Soc. 36, 104 (1914); G.M. Kosolapoff, J. Org.

Chem. 26, 1895 (1961). Stage 2.2: St. Angerstein, Ber. Dtsch. Chem.

Ges. 34, 3956 (1901); G.M. Kosolapoff, J. Org. Chem. 26, 1895 (1961). Stage 2.3: M.P.V. Boarland and J.F.W. McOmie, J. Chem. Soc. 1951, 1218; T. Matsukawa and K. Shirakuwa, J. Pharm. Soc. Japan 71, 933 (1951); Chem.

Abstr. 46, 4549 (1952).

Process 3: A. Combes and C. Combes, Bull. Soc. Chem. (3), 2» 791 (1892); W.J. Hale and F.C. Vibrans, J. Am. Chem. Soc. 40, 1046 (1918).

The described preparation processes, including all partial steps, form part of the present invention.

Surprisingly, it has been found that the compounds of formula I have, for practical field application purposes, a very advantageous biocidal spectrum against insects and phytopathogenic microorganisms, especially fungi. Compounds of formula I have very advantageous curative, preventive and, in particular, 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 in plants or in 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, for example, from attack by phytopathogenic microorganisms.

The compounds of formula I are effective against the phytopathogenic fungi belonging to the following classes: Fungi imperfecti (e.g.

Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora, Alternaria); Basidiomycetes (e.g. the genera Hemileia, Rhizoctonia, Puccinia); and Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula). They are also effective against Oomycetes (Perenosporales, Phytophthora, Plasmopara, Pythium). They can also be used as dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against fungus infections as well as against phytopathogenic fungi which occur in the soil. In addition, compounds of formula I are effective against insect pests, for example against pests on cereals such as rice.

The invention also relates to compositions containing as active ingredient compounds of formula I, especially plant-protecting 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 inven- 12 tion 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.

The 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 application-promoting adjuvants customarily employed in the art of formulation.

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. - 13 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 granulates may be applied in metered amounts to the flooded rice field. The compounds of formula I may, however, also be applied to seeds (coating) by impregnating the seeds either with a liquid formulation containing a compound of formula I, or 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 the art of formulation, 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, granulates, 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 50 g to 5 kg of active ingredient (a.i.) per hectare, preferably from 100 g to 2 kg a.i./ha, most preferably from 200 g to 600 g a.i./ha.

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, surfaceactive compounds (surfactants). - 14 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-methyl-2-pyrrolidone, dimethyl sulphoxide 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. Particularly advantageous application-promoting adjuvants which are able to reduce substantially the rate of application are also natural (animal or vegetable) or synthetic phospholipids of the series of the cephalins and lecithins, which can be obtained e.g. from soybeans.

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.

More frequently, however, so-called synthetic surfactants are used, especially alkanesulphonates, fatty alcohol sulphates, sulphonated benzimidazole derivatives or alkylsulphonates.

The fatty alcohol sulphonates or sulphates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain a Ce~C22-alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulphonic acid, of dodecylsulphate or of a mixture of fatty alcohol sulphates obtained from natural fatty acids. These compounds also comprise the salts of sulphated and sulphonated fatty alcohol/ethylene oxide adducts. The sulphonated benzimidazole derivatives preferably contain 2 sulphonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulphonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulphonic acid, dibutylnaphthalenesulphonic acid, or of a condensate of naphthalenesulphonic 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 moles of ethylene oxide.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or 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.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one Ce-C22-alkyl 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, methylsulphates or ethylsulphates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ammonium bromide.

Further surfactants customarily employed in the art of formulation 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 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula I, 99.9 to 1 % by weight, preferably 99.8 to 5 % by weight, of a solid or liquid adjuvant, and 0 to 25 % by weight, preferably 0.1 to 25 % by weight, 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, without limiting it.

Example 1: Preparation of 2-phenylamino-4-methyl-6-roethoxymethylpyrimidine CH; (Comp. no. 1) CH2OCH3 A mixture of 7.5 g of phenylguanidine hydrogen carbonate and 7.4 g of methoxyacetylacetone is heated at 100°C for four hours with stirring, the evolution of carbon dioxide which occurs subsiding as the reaction progresses. After the brown emulsion has been cooled to room temperature, ml of diethyl ether are added and the whole is then washed three times with 20 ml of water each time, dried over sodium sulphate and filtered, and the solvent is evaporated. The 10.5 g of oily residue are dissolved in 140 ml of diethyl ether, and then 4.4 g of 65 % nitric acid are added thereto with stirring. The suspension of the resulting nitrate salt is stirred for a further 20 minutes and is then filtered and washed with 100 ml of diethyl ether. 6 g of 30 % sodium hydroxide solution are added with stirring to a mixture consisting of 11 g of the nitrate salt, 80 ml of diethyl ether and 60 ml of water, the organic phase is separated off, washed twice with 40 ml of water each time, dried over sodium sulphate and filtered, and the solvent is evaporated. The 8.7 g of light-brown oily residue are crystallised with 100 ml of petroleum ether (b.p. 5O-7O°C), filtered and dried. The 8 g of pale, beige-coloured crystalline powder melt at 59-60°C; yield: 92 % of the theoretical yield, relative to phenylguanidine hydrogen carbonate. - 18 Cl—NH— Z Example 2: Preparation of 2-(p-chlorophenylamino)-4-methyl-6-methoxymethylpyrimidine zch3z« (Comp. no. 70) \h2och3 A solution of 6.4 g of 4-chloroaniline and 8.6 g of 2-chloro-4-methyl-65 methoxymethylpyrimidine is adjusted to pH 1 with 5 ml of concentrated hydrochloric acid with stirring, and is then heated under reflux for 20 hours. After cooling to room temperature, the brown emulsion is rendered alkaline with 12 ml of 30 % ammonia, poured onto 100 ml of icewater and extracted three times with 50 ml of ethyl acetate each time.

IQ The combined extracts are washed with 50 ml of water, dried over sodium sulphate and filtered, and the solvent is evaporated. The 11.8 g of red oil are chromatographed over a 30 cm long silica gel column using dichloromethane/diethyl ether (3:2). After evaporation of the eluant, the initially oily residue is crystallised by trituration with petroleum -] 5 ether. Recrystallisation from diisopropyl ether/petroleum ether (5O-7O°C) gives 9.8 g of beige-coloured crystalline powder which melts at 57-59°C; yield: 74 % of the theoretical yield.

Table: Compunds of the formula Ra X / \„ / X ·=· N=· Rz \ CH2XRi, Comp.No. Ri Rz Ra X Ri» Physical data 1 H H ch3 0 -ch3 m.p. 59-6OuC 2 H H ch3 0 -ch2ch=ch2 oil n“ 1.6013 3 H H ch3 0 -c2h5 oil η“ 1.5975 4 H H CuHg-tert. 0 -ch3 m.p. 71,5-73°C 5 H H ch3 0 -CHz-CsCH oil njj* 1.6106 6 H H ch3 0 -C3H7-n 1.5880 7 H H ch3 S -CH3 oil n“ 1.6452 8 H H CuHg-tert. 0 -C2H5 viscous composition n“ 1.5717 9 3-C1 5-C1 ch3 0 -CH2-CsCH m.p. 88-91°C Comp.No. Ri Rz Rj X Rm Physical data 10 H H cyclopropyl 0 -ch3 m.p. 79-8O°C 11 H H ch3 0 -C3H7-i oil nJ* 1.5919 12 4-OCH3 H ch3 0 -CHj m.p. 57-59°C 13 3-OC2H5 4-OC2H5 CHj 0 -c2h5 red oil nJ* 1.5936 14 H H ch3 0 -CuHg-n 15 H H ch3 0 CHj -chc2h5 oil n“ 1.5788 16 H H ch3 0 CHj -ch2-C»ch2 17 3-OC2H5 4-OC2H5 ch3 0 -CHj m.p. 54-57°C 18 H H ch3 0 -CHj -CH2CH CHj oil nJ* 1.5813 19 3-C1 5-C1 ch3 0 -c2h5 oil nJ* 1.5963 20 H H ch3 s -C2Hs 1' Comp. No. Ri Rz Ri X Ru Physical data 21 3-C1 5-Cl CH3 0 -ch2ch=ch2 oil ηθ 1.6078 22 4-OCHj H cyclopropyl 0 -CHj viscous composition n^ 1.6109 23 H H ch3 0 -C(CHj)j 24 H H CHj 0 -CH2CH2OCHj oil 1.6011 25 3-C1 5-Cl CHj 0 -CHj viscous composition n2^ 1.6180 26 H H CHj 0 -(CH2)uCH3 27 4-OCHj H CHj 0 -c2h5 oil ηθ* 1.5838 28 H H CHj 0 CHj -CH-C=CH 29 3-OC2H5 4-OC2H5 cyclopropyl 0 -CHj black oil 30 H H CHj 0 CHj -CH-CjH7-n 31 3-OC2H5 4-OC2H5 CHj 0 -CH2CH=CH2 black oil Comp.No. Ri Rz R3 X Rn Physical data 32 H H CHj 0 -CH2CH2OC2H5 33 H H CHj 0 CHj -CH2CH-C2H5 34 3-C1 5-C1 cyclopropyl 0 -CHj viscous composition ηθ1* 1.6228 35 4-OCH3 H CHj 0 CHj -CHC2H5 oil ηθ* 1.5760 36 H H CHj 0 CHj -6-ch=ch2 CHj 37 3-C1 5-C1 CHj 0 CHj -0H-C2Hs viscous composition 1.5879 38 H H c2h5 0 -CHj m.p. 35,5-37°C 39 H H ch3 0 CHj -CH2CH2CHCH3 40 H H CHj 0 -CH2CFj oil n“ : 1.6205 41 3-OC2H5 4-OC2H5 CHj 0 CHj -CHC2H5 dark red oil n“ 1.6205 42 H H ch3 0 CHj -CH2CH2-C=CH2 Comp.No. Ri Rz Ra X Ru Physical data 43 H H CHj 0 CHj- -CH2CH2OCHCHj 44 4-OCHj H CuHg-tert. 0 -C2H5 viscous composition n“ 1.5662 45 H H ch3 0 CHj -CH2-C-CHj CHj 46 H H CHj 0 -CH2CH2O(CH2)jCHj 47 4-OCHj H CHj 0 -CH2CsCH oil n^ 1.6059 48 H H CHj 0 CHj -c-c2h5 ch3 49 3-OCzH5 4-OCzHs CHj 0 -ch2-c=ch m.p. 63-65°C 50 H H CHj S CHj -CHCH2CHj 51 H H C2Hs 0 -CzHs 52 H H CHj 0 cyclopentyl 53 3-C1 5-Cl CuHe-tert. 0 -c2h5 oil n2)* 1.5848 Corap.No. Ri Rz tl Ri X Ru Physical data 54 3-OC2H5 4-OC2H5 CuHg-tert. 0 -C2H5 black oil 55 H H CHj 0 ch3 ch3 -Ch—ch—ch3 56 H H ch3 0 -ch2ch2cn 57 H H ch3 0 cyclohexyl 58 H H ch3 0 -CH2CH2O(CH2)2OCH3 59 H H cyclopropyl 0 -C2Hs m.p. 54-57°C 60 H H ch3 0 -(CH2)5CH3 61 H H C2H5 0 -CH2-CH=CH2 62 3-OC2H5 4-OC2H5 CuHg-tert. 0 -CH3 viscous composition 63 H H ch3 0 ch3 -CH2CH-C3H7-n 64 H H ch3 0 -CH2CH20H 65 H H ch3 0 cycloheptyl 66 H H ch3 0 CHj -c-ch3 CN Comp.No. Ri Ra Rj X Ru Physical data 67 H H cyclopropyl 0 -ch2-ch=ch2 68 H H ch3 0 OaHs -ch2ch-c2h5 69 4-OCH3 H CuHg-tert. 0 -ch3 m.p. 1O4-1O6°C 70 4-C1 H CH3 0 -ch3 m.p. 57- 59°C 71 H H ch3 0 ch3 ch3 -ch-ch2-Ch-ch3 72 4-C1 H CHj 0 -c2h5 73 H H C3H7-1 0 -ch2ch2oh 74 H H ch3 0 2-methylcyclohexyl 75 H H ch3 0 -(ch2)6oh 76 H H ch3 0 -(ch2)6ch3 77 H H cyclopropyl 0 cyclohexyl 78 H H ch3 S -(ch2)5ch3 79 H H C3H7-i 0 -ch2ch2oc2hs 'J Comp.No. Ri Rz Ra X Rm Physical data 80 H H CHj 0 CHj -ch(ch2).,ch3 81 H H CHj 0 5N -CH-CHj 82 H H CHj 0 -CH2CH2SCHj 83 H H CHj 0 -ch2^h-ch3 84 4-C1 H CHj 0 -ch2ch=ch2 85 H H C2Hs 0 CHj -ch2-c=ch2 86 H H CjH7-n 0 -CH2-C=CH 87 H H CHj 0 CzHs -CH-(CH2)jCHj 88 H H CHj S CHj -CH-CHj 89 H H CjH7-1 0 -CH2CH2OCHj 90 H H CHj 0 -ch2ch2ci 91 H H CjH7-1 0 -ch2-c=ch Comp.No. Ri Rz Ri X Ru Physical data 92 H H CHj 0 CjH7-n -CH-CH2CH2CHj 93 4-C1 H CHj 0 -CH2OCH2CH2OCHj 94 H H CHj S -ch2-ch=ch2 95 H H c2h5 0 -CH2-C=CH 96 H H CHj 0 -(CH2)jC1 97 4-C1 H CHj 0 -CH2CF3 98 H H CHj 0 -(CH2)7CHj 99 4-C1 H c2h5 0 -CH3 100 3-C1 H CHj 0 -CHj m.p. 49-51uC 101 H H CHj S CHj -CH2-CH-CH3 102 4-C1 H H 0 -CH3 103 H H C3H7-I 0 -ch2-ch=ch2 104 4-Br H CHj 0 -CHj m.p. 76-78°C Comp.No. Ri Rz Ra X Ru Physical data 105 H H ch3 0 ch3 -Ch(ch2)5ch3 106 4-C1 H ch3 0 -CH2-CECH 107 H H c2h5 0 cyclohexyl 108 H H ch3 0 -(CH2)mC1 109 4-Br H ch3 0 -c2h5 110 H H C3H7-i 0 -ch2ch2ci 111 4-Br H ch3 0 -ch2cf3 112 H H ch3 0 CH2C1 -C^ CHjCl 113 H H cyclopropyl 0 -CH2CH2OC2H5 114 H H C3H7-1 0 -(CH2)i»CH3 115 H H c3h7-i 0 -ch2cf3 116 H H c2h5 0 -ch2ch2och3 117 4-Br H ch3 0 -ch2ch2och3 118 H H C3H7-i s -ch3 Comp.No. Ri Rz Rj X Ru Physical data 119 H H CHj 0 CHj -ch-ch2ci 120 3-C1 H CHj 0 -C2Hs 121 H H CHj 0 -CH2CC1j 122 H H C3H7-i 0 CHj -CHC2H5 123 H H H S -CHj 124 H H C2H5 0 -CH2CH2OC2H5 125 4-Br H CHj 0 -CH2CsCH 126 H H Ci,H9-n 0 -CHj oil 1.5823 127 H H CHj 0 -CH2CH2Br 128 H H C3H7-i 0_C2Hs 129 4-Br H C2H5 0 -CHj 130 H H CHj 0 -2)3Br 131 3-C1 H CHj 0 -CH2CFj 132 H H H ° -CH2CH2CN Corop.No. Ri r2 Ri X 5¼ Physical data 133 3-C1 H CHj 0 -CH2CH2OCHj 134 3-C1 H CHj 0 -CH2-CH=CH2 135 H H CjH7-i 0 -CHj oil ηθ* 1.5883 136 H H ΟΐιΗθ—n 0 -C2Hs 137 H H H 0 -CH2CH2C1 138 4-F H CHj 0 -CHj m.p. 62-65°C 139 H H C2Hs 0 -CH2CH2OH 140 3-C1 H CHj 0 -CH2-C=CH 141 H H CijHg—n CHj -CHC2H5 142 H H CjH7-i s -CHj 143 3-C1 4-C1 CHj 0 -CHj 144 H H CuHj-n 0 -CHzCH2C1 145 H H H 0 -CHzCH20H 146 H H c2h5 0 -CH2CH2C1 Comp.No. Ri Rz Ra X Rm Physical data 147 3-CFj 4-C1 CHj 0 -CHj m.p. 86-88°C 148 H H CuHg-n 0 -CH2CFj 149 3-C1 4-C1 ch3 0 -c2h5 150 H H C3H7-11 0 -ch2ch2cn 151 3-C1 4-C1 CHj 0 -ch2-c=ch 152 H H Η 0 -CH2CH2OCHj 153 4-CHj H CHj 0 -CHj m.p. 58-60°C 154 H H c2h5 0 -CH2CFj 155 3-CFj 4-C1 CHj 0 -c2h5 156 H H H 0 -CH2CH2OC2Hs 157 3-C1 4-C1 CHj 0 -CH2CFj 158 H H H 0 cyclohexyl 159 H H CjH7-n 0 -CH2CFj 160 H H cyclopropyl 0 -CH2CH2OCHj 161 3-CFj 4-C1 CHj 0 -ch2c=ch Comp.No. Ri Rz Rj X Ru Physical data 162 H H C2H5 0 -CH2CH2CN 163 4-OCHF2 H CHj 0 -ch3 164 H H C14H9—n 0 -CH2-C=CH 165 4-CH3 H CH3 0 -C2H5 166 4-CH3 H ch3 0 -CH2CsCH 167 H H C3H7-n 0 -CH2CH2CI 168 H H H 0 -CH2CsCH 169 4-OCHFz H ch3 0 -C2H5 170 H H cyclopropyl 0 -CHzCH20H 171 H H c2h5 S -ch3 172 4-CH3 H CHj 0 -ch2cf3 173 4-F H ch3 0 -C2H5 174 4-F H ch3 0 -ch2cf3 175 H H C3H7-n 0 -ch3 oil ηθ* 1.5913 176 H H H 0 -ch2-ch=ch2 Comp. No. Ri Ra Rl X Ru Physical data 177 H H cyclopropyl 0 -CH2CH2C1 178 H H C3H7-n 0 -CH2CH2OH 179 4-OCHF2 H CHi 0 CHj -CHCHj 180 4-F H CHj 0 -CHjCsCH 181 H H C jH7-n 0 -c2h5 182 H H H 0 -c2h5 183 4-OC2H5 H CHj 0 -ch3 184 H H H 0 ch3 -c-ch3 185 H H C3H7-n 0 -ch2-ch=ch2 186 H H cyclopropyl 0 -ch2cf3 187 2-C1 H CH3 0 -ch3 188 H H C 3H7-n 0 -CH2CH2OC2H5 189 4-OCzHs H ch3 0 -c2h5 190 H H C3H7-n 0 CHj -ch2-c=ch2 Comp. No. Ri Ra Ri X Ru Physical data 191 4-OC2H5 H CH3 0 -CH2CFj 192 2-C1 H ch3 0 -C2Hs 193 H H cyclopropyl 0 -CHz-CsCH 194 4-OC2H5 H ch3 0 -CHzOCH2CH2OCHj ri : 1.6128 195 H H H 0 -CHj 196 H H C3H7-n 0 -CH2CH2OCHj 197 2-C1 H CHj 0 -CH2CFj 198 H H CFj 0 -CHj m.p. 63-65°C 199 2-F H CH3 0 -ch3 200 3-F 4-CH3 ch3 0 -CHj 201 4-OCF2CHF2 H CHj 0 -ch3 202 2-C1 4-C1 CHj 0 -ch3 203 H HH”r/j —\l • 0 -CHj m.p. 51-53°C 204 2-OCH3 5-CHj CHj 0 -ch3 Comp.No. Ri Rz R3 X Rit Physical data 205 3-F H ch3 0 -CHj m.p. 50-51°C 206 2-F 4-F ch3 0 -CHj 207 2-CF3 H ch3 0 -ch3 m.p. 101-103°C 208 2-Br 4-CH 3 ch3 0 -ch3 209 4-OCF2CHClF H ch3 0 -ch3 210 H H W \l • 0 -ch3 m.p. 76-78°C 211 3-C1 4-OCH3 ch3 0 -CHj 212 3-OC2H5 H ch3 0 -ch3 213 H H -Ri • 0 -ch3 214 4-OCF3 H ch3 0 -CHj 215 2-C3H7-i H CHj 0 -CHj 216 H H -CFjCl 0 -CHj m.p. 59-60°C 217 H H ch3 0 -ch3 218 4-C3H7-l H ch3 0 -ch3 Comp. No. Ri Rz Ri X Ru Physical data 219 2-C1 6-CH3 CH3 0 -CHj 220 H H -cf2cf3 0 -CHj m.p. 63-65°C 221 4-OCF2CHCl2 H CHj 0 -CHj 222 3-C1 4-CHa CH3 0 -ch3 223 2-OCH3 H CH3 0 -CHj 224 2-C1 4-CH3 CH3 0 -c2h5 225 2-CH3 3-C1 CH3 0 -CHj 226 H H CHj -CHC2Hs 0 -ch3 oil ηθ1* : 1.5791 227 2-C1 5-CH 3 CHj 0 -ch3 228 H H /C1 • 0 -CHj 229 3-OCH3 H ch3 0 -ch3 230 3-C2H5 H CHj 0 -CHj 231 H H /j-CHz -\l • 0 -CHj oil ηθ* : 1.6169 Comp.No. Ri Rz Ra X Ru Physical data 232 3-F 5-F ch3 0 -CHj 233 4-0C3H7-i H CHj 0 -CHj 234 2-CHj 5-F CHj 0 -CHj 235 4-C2H5 H ch3 0 -CHj 236 2-C1 4-0CHF2 CHj 0 -CHj m.p. 65-67°C 237 2-CH3 4-OCH3 CHj 0 -CHj 238 2-CFa H CHj 0 -c2h5 239 2-C2H5 H CHj 0 -CHj 240 2-C1 4-Br CHj 0 -CHj 241 2-OCHF2 H CHj 0 -CHj 242 3-CFs 5-CF3 CHj 0 -CHj 243 2-CH3 4-0CHF2 CHj 0 -CHj oil : 1.5493 244 2-OCHj 5-C1 CHj 0 -CHj 245 2-CF3 4-C1 CHj 0 -CHj Comp.No. Ri r2 Ri X Ru Physical data 246 3-C1 4-F CH3 0 -CHj 247 2-CH3 4-Br ch3 0 -CHj 248 4-CFj Η ch3 0 -CHj m.p. 75-78°C 249 3-CH3 4-Br ch3 0 -CHj 250 3-CF3 H ch3 0 -CHj m.p. 101-103°C 251 H H -CH2OH 0 -CHj oil n“ : 1.6236 252 3-CH3 H CH3 0 -CHj oil njj* : 1.5902 253 2-C1 5-CF3 CHj 0 -CHj 254 2-CH3 6-CH3 CHj 0 -ch3 255 2-CH3 4-C1 CHj 0 -CHj 256 H H -CH2C1 0 CHj oil : 1.6188 257 2-F 3-F CHj 0 -CHj 258 4-J H CHj 0 -CHj 259 H H -CHCI2 0 -CHj I U) oo I Comp.No. Ri Rz Rj X Ru Physical data 260 3-CHj 5-CH3 CHj 0 -CHj 261 2-CHj 5-C1 ch3 0 -CHj 262 H H -ch2f 0 -ch3 oil ηθ* : 1.6173 263 2-CH3 3-F ch3 0 -ch3 264 H H -CHzOH 0 -c2h5 265 2-CHj H ch3 0 -CHj 266 2-Br 4-Br CHj 0 -CHj 267 H H • 0 -CHj 268 H H -CH2Br 0 -ch3 oil n“ : 1.6204 269 H H -CCl 3 0 -CHj 270 3-Br H CHj 0 -CHj 271 2-Br 5-Br CHj 0 -CHj 272 H H F/j-™3 -\l • 0 -CHj Comp.No. Ri Rz Ra X Rm Physical data 273 H H CHj 0 cyclopropyl 274 H H -CHzCl 0 -c2h5 275 2-C1 3-C1 CHj 0 -ch3 276 H H fe 1 a — · \ / • 1 0 -ch3 oil nJ* : 1.6098 277 H H Hj^.-C! —\l • 0 -CHj 278 2-Br H CHj 0 -CHj 279 H H - 0 -CHj 280 2-CHj 3-CHj CHj 0 -CHj 281 H H CHj 0 cyclobutyl 282 H H -CH2F 0 -c2h5 283 2-C1 5-C1 ch3 0 -CH3 284 2-OCH3 4-OCH3 CH3 0 -CHj 285 H H - 0 -CHj Comp.No. Ri Rs Ri X Ru Physical data 286 2-C1 6-C1 ch3 0 -ch3 287 H H /C1 • 0 -ch3 288 2-CHj 4-CH3 CHi 0 -ch3 289 H Hzch3 -^C„, « 0 -CHj 290 3-CH3 4-CH3 CH3 0 - CHj 291 H H —CH2Br 0 -c2h5 292 2-F 5-F ch3 0 -ch3 293 H Hzch3 —φοκ, • 0 -ch3 294 2-CH3 5-CH3 ch3 0 -ch3 295 3-OCH3 4-CH3 CHi 0 -ch3 296 3-F 4-F CHi 0 -ch3 297 2-F 6-F CHi 0 -ch3 Comp. No. Ri Rz Ra X Ri* Physical data 298 H H - 0 -ch3 299 H H —> 0 —CHj 300 3-CF3 H ch3 0 -C2Hs 301 H H ZC1 - 0 -CHj 302 4-CFj H ch3 0 • - 303 H H jXj'cH, 0 -CHj 304 4-OCFj H ch3 0 -CzHs 305 H H Haf/j-Br • 0 -CHj 306 2-F H CHj 0 -C2H5 307 4-CFj H ch3 0 -CzHs Comp. No. Ri Rz Ri X Ru Physical data 308 H H Z' - 0 -CH3 309 2-Br 6-Br ch3 0 -CHj 310 H H /»* H4z< —ch3 • 0 -CHj 311 H Hzch3H3Vzi\ —\J CHj • 0 -CHj 312 2-OCH3 5-OCH3 CHj 0 -CHj 313 H H zcl • 0 -CHj 314 3-OCH3 5-OCH3 CHj 0 -CHj 315 H H zBr • 0 -CHj ι co I Comp.No. Ri Rz Ri X Ru Physical data 316 2-CF3 H ch3 0 • - 317 H HzCH3 • 0 -ch3 I 2. Formulation Examples for liquid active ingredients of formula I (throughout, percentages are by weight) 2.1. Emulsifiable concentrates a) b) c) a compound of the Table 25 % 40 % 50 % calcium dodecylbenzenesulphonate 5 % 8 % 6 % castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5 % - - tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) — 12 % 4 % cyclohexanone - 15 % 20 % xylene mixture 65 % 25 % 20 % Emulsions of any desired concentration can be produced from such concen trates by dilution with water. 2.2. Solutions a) b) c) d) a compound of the Table 80 % 10 % 5 % 95 % ethylene glycol monomethyl ether 20 % - - - polyethylene glycol (mol. wt. 400) - 70 % - - N-wethyl-2-pyrrolidone - 20 % - - epoxidised coconut oil - - 1 % 5 % ligroin (boiling range 160-190°C) - - 94 % - These solutions are suitable for application in the form of micro-drops 2.3. Granulates a) b) a compound of the Table 5 % 10 % kaolin 94 % - highly dispersed silicic acid 1 % attapulgite - 90 % The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo. 2.4. Dusts a compound of the Table highly dispersed silicic acid talcum kaolin a) b) % 5 % % 5 % % % Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.

Formulation Examples for solid active ingredients of formula I (throughout, percentages are by weight) 2.5. Wettable powders a compound of the Table sodium lignosulphonate sodium laurylsulphate sodium diisobutylnaphthalenesulphonate octylphenol polyethylene glycol ether (7-8 moles of ethylene oxide) highly dispersed silicic acid kaolin a) % % 3 % % % b) % % % % % 27 % c) % % % % 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. 2.6. Emulsifiable concentrate a compound of the Table 10 % octylphenol polyethylene glycol ether (4-5 moles of ethylene oxide) 3 % calcium dodecylbenzenesulphonate 3 % castor oil polyglycol ether (35 moles of ethylene oxide) 4 % cyclohexanone 30 % xylene mixture 30 % - 47 Emulsions of any required concentration can be obtained from this concentrate by dilution with water. 2.7. Dusts a) b) a compound of the Table 5 % 8 % talcum 95 % - kaolin — 92 % Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. 2.8. Extruder granulate a compound of the Table 10 % sodium lignosulphonate 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. 2.9. Coated granulate a compound of the Table 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 granulates are obtained in this manner. 2.10. Suspension concentrate a compound of the Table 40 % ethylene glycol 10 % nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6 % sodium lignosulphonate 10 % carboxymethylcellulose 1 % % aqueous formaldehyde solution 0.2 % silicone oil in the form of a 75 % aqueous emulsion 0.8 % water 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 treated 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 treated 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.

Compounds of the Table exhibit good activity against Puccinia fungi (less than 20 % attack). On the other hand, Puccinia attack is 100 % on untreated and infected control plants. - 49 Example 3.2: Action against Phytophthora on tomato plants a) Residual protective action After a cultivation period of three 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. Evaluation of fungus attack is made after incubation of the infected plants for 5 days at 90-100 % relative humidity and 20°C. b) Residual curative action After a cultivation period of three weeks, tomato plants are infected with a sporangia suspension of the fungus. The infected plants are then incubated for 22 hours in a humidity chamber at 90-100 % relative humidity and 20°C and are then dried and sprayed with a spray mixture (0.02 % 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 attack is made 5 days after infection. c) Systemic action After a cultivation period of three weeks, a spray mixture (0.002 % active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the test compound is poured onto 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. Evaluation of fungus attack is made after incubation of the infected plants for 5 days at 90-100 % relative humidity and 20°C.

Compounds of the Table exhibit good activity against Phytophthora (less than 20 % attack). On the other hand, Phytophthora attack is 100 % on untreated and infected control plants.

Example 3.3: Action against Plasmopara viticola on vines Residual protective action Vine seedlings in the 4-5 leaf stage 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. Fungus attack is evaluated after incubation for 6 days at 95-100 % relative humidity and 20°C.

Compounds of the Table exhibit good activity against Plasmopara. On the other hand, Plasmopara attack is 100 % on untreated and infected control plants.

Example 3.4: Action against Cercospora arachidicola on groundnut plants Residual protective action Groundnut plants 10-15 cm in height are sprayed with a spray mixture (0.02 % 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 appear. Evaluation of the fungicidal action is made 12 days after infection and is based on the number and size of the specks.

Compounds of the Table exhibit good activity against Cercospora (less than 20 % attack). On the other hand, Cercospora attack is 100 % on untreated and infected control plants.

Example 3.5: Action against Venturia inaequalis on apple shoots Residual protective action Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray mixture (0.02 % active ingredient) 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.

Compounds of the Table exhibit good activity against Venturia; thus e.g. compounds nos. 1, 10, 38, 59, 231, 262 and 276 reduce Venturia attack to less than 10 %. On the other hand, Venturia attack is 100 % in untreated and infected control plants.

Example 3.6: Action against Botrytis cinerea on apple fruits Residual protective action Artificially damaged apples are treated by the dropwise application to the damaged sites of a spray mixture (0.002 % active ingredient) prepared from a wettable powder formulation of the test compound. The treated fruits are then inoculated with a spore suspension of the fungus and incubated for one week at high humidity and about 20°C. Evaluation is made by counting the rotted damaged sites and deriving the fungicidal activity of the test compound therefrom.

Compounds of the Table exhibit good activity against Botrytis (less than 20 % attack). Thus e.g. compounds nos. 1, 3, 7, 10, 38, 59, 231, 256, 262, 268 and 276 reduce Botrytis attack to 0 to 5 7«. On the other hand, Botrytis attack is 100 % on untreated and infected control plants.

Example 3.7: Action against Erysiphe graminis on barley 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 attack is evaluated after 10 days.

Compounds of the Table exhibit good activity against Erysiphe; thus e.g. compounds nos. 1, 5, 6, 10, 38, 59, 135, 175, 231 and 262 reduce Erysiphe attack to less than 20 %. On the other hand, Erysiphe attack is 100 % on untreated and infected control plants.

Example 3.8: Action against Helminthosporium gramineum Wheat grains are contaminated with a spore suspension of the fungus and dried. The contaminated grains are dressed with a suspension of the test compound prepared from a wettable powder (600 ppm of active ingredient, based on the weight of the seeds). Two days later the grains are placed in suitable agar dishes and the development of fungus colonies around the grains is assessed after another 4 days. The effectiveness of the test compounds is evaluated on the basis of the number and size of the colonies. The compounds of the Table substantially prevent fungus attack (0 to 10 %).

Example 3.9: Action against Fusarium nivale Wheat grains are contaminated with a spore suspension of the fungus and dried. The contaminated grains are dressed with a suspension of the test compound prepared from a wettable powder (600 ppm of active ingredient, based on the weight of the seeds). Two days later the grains are placed in suitable agar dishes and the development of fungus colonies around the grains is assessed after another 4 days. The effectiveness of the test compounds is evaluated on the basis of the number and size of the colonies.

In the case of grains treated with a wettable powder containing as active ingredient a compound of the Table, the development of the fungus colonies was inhibited almost completely (0 to 5 %).

Example 3.10: Action against Tilletia caries Barley grains are contaminated with a spore suspension of the fungus and dried. The contaminated grains are dressed with a suspension of the test compound prepared from a wettable powder (600 ppm of active ingredient, based on the weight of the seeds). Two days later the grains are placed in suitable agar dishes and the development of fungus colonies around the grains is assessed after another 4 days. The effectiveness of the test compounds is evaluated on the basis of the number and size of the colonies. The compounds of the Table substantially inhibit fungus attack (0 to 10 %). - 53 Example 3.11: Action against Colletotrichum lagenariutn on cucumbers (Cucumis sativus L.) After a cultivation period of two weeks, cucumber plants are sprayed with a spray mixture (concentration 0.02 %) prepared from a wettable powder formulation of the test compound. After two days the plants are infected with a spore suspension (1.5 x 10$ spores/ml) of the fungus and incubated for 36 hours in the dark at 23°C and high humidity. Incubation is then continued at normal humidity and about 22-23°C. Evaluation of fungus attack is made 8 days after infection. Fungus attack is 100 % on untreated and infected control plants.

Compounds of the Table exhibit good activity and inhibit the spread of the disease. Fungus attack is reduced to 20 % or less.

Example 3.12 Action against Septoria nodorum on wheat Residual protective action 7-day-old wheat plants are sprayed with a spray mixture (concentration 0.02 %) prepared from the formulated test compound and two days later are infected with a conidia suspension (400,000 conidia/ml, with the addition of 0.1 % Tween 20 as wetting agent) of Septoria nodorum. After an incubation phase of two days in a greenhouse compartment at 20uC and 95-100 % relative humidity, the test plants are placed uncovered in a greenhouse compartment at 21 °C and 60 % relative humidity until the end of the test. Evaluation of fungus attack is made 7 to 10 days after infection.

While untreated and infected plants exhibit 100 % attack, plants treated with compounds of the Table exhibit fungus attack of less than 20 %.

Example 3.13: Action against Alternaria solani on tomatoes Residual protective action 3-week-old tomato plants are sprayed with a spray mixture (concentration 0.02 %) prepared from the formulated test compound and 2 days later are infected on both sides with a conidia suspension (20,000 conidia/ml) of Alternaria solani. In order to prevent the fine drops of the spray coating from being washed off, the infected plants are covered with closemeshed nets in a first incubation phase of 3 days in a greenhouse com- 54 partment at 20bC and 100 % relative humidity. The plants are then placed in a greenhouse compartment at 24°C until the end of the test. Evaluation of fungus attack is made 4 days after infection.

While untreated and infected control plants exhibit 100 % attack, plants treated with compounds of the Table exhibit fungus attack of less than 20 %.

Example 3.14: a) Insecticidal contact action against Nephotettix cincticeps and Nilaparvata lugens (nymphs) The test is carried out with growing rice plants. For this purpose 4 plants (14-20 days old) about 15 cm in height are planted into each of a number of pots (diameter 5.5 cm).

The plants in each pot are sprayed on a rotary table with 100 ml of an aqueous emulsion preparation containing 400 ppm of the test compound. After the spray coating has dried, each plant is populated with 20 nymphs of the test organisms in the third stage. To prevent the cicadas from escaping, a glass cylinder which is open at both ends is slipped over each of the plants and sealed with a gauze top. The nymphs are kept on the treated plants for 6 days until they have reached the adult stage. An evaluation is made on the basis of percentage mortality 6 days after population of the plants. The test is carried out at about 27°C and 60 % relative humidity. The plants are exposed to light for a period of 16 hours per day. b) Systemic insecticidal action against Nilaparvata lugens (in water) Rice plants about 10 days old (about 10 cm high) are placed in a plastics beaker which contains 150 ml of an aqueous emulsion preparation of the test compound in a concentration of 100 ppm and is closed by a perforated plastics lid. The roots of each of the rice plants are pushed through a hole in the plastics lid into the aqueous test preparation. Then the rice plants are populated with 20 nymphs of Nilaparvata lugens in the N2 to N3 stage and covered with a plastics cylinder. The test is carried out at about 26°C and 60 % relative humidity, and the plants are exposed to light for a period of 16 hours per day. After five days the number of dead test organisms is assessed in comparison with untreated controls. It is thus established whether the test substance absorbed via the roots kills the test organisms at the upper parts of the plants.

Compounds of the Table are more than 80 % effective against the mentioned rice pests both in the contact test and in the systemic test.

Claims

1. Patent Claims

1. Compounds of formula I CH 2 XRu in vhich: Ri and R 2 independently of one another are hydrogen, halogen, C1-C3alkyl, Ci-C 2 -haloalkyl, Ci-C 3 -alkoxy or Ci-C 3 -haloalkoxy; Ra is hydrogen; Ci-Cu-alkyl; Ci-C 2 -alkyl substituted by halogen or by hydroxy; cyclopropyl; or cyclopropyl substituted by halogen and/or by methyl; Ru is Ci-Ce-alkyl; C 2 -C6-alkyl substituted by halogen, hydroxy, cyano, C1-Ci,-alkoxy, C 3 -Cu-alkoxyalkoxy or by Ci-C3-alkylthio; C 3 -C6-alkenyl; C 3 -C6-alkynyl; C 3 -C7-cycloalkyl; or C 3 -C7-cycloalkyl substituted by methyl; and X is oxygen or sulphur.

2. Compounds of formula I according to claim 1 in which R 3 , Ru and X have the meanings given and Ri and R 2 are hydrogen.

3. Compounds of formula I according to claim 1 in which: Ri and R 2 independently of one another are hydrogen, halogen, C1-C3alkyl, Ci-C 2 -haloalkyl, Ci-C 3 -alkoxy or Ci-C 3 -haloalkoxy; R 3 is hydrogen, C1-C1,-alkyl or cyclopropyl; Ru is Ci-Ce-alkyl; C 2 -Ce-alkyl substituted by halogen, hydroxy, cyano, Ci-Cu~alkoxy, C 3 -Cu-alkoxyalkoxy or by Ci-C 3 -alkylthio; C 3 -C6 _ alkenyl; C3—C6-alkynyl; C5-C 7 -cycloalkyl; or Cs-C7-cycloalkyl substituted by methyl; and X is oxygen or sulphur.

4. Compounds of formula 1 according to claim 3 in which: Ri and R 2 independently of one another are hydrogen, fluorine, chlorine, bromine, Ci-C 3 -alkyl, Ci-C 2 -haloalkyl, Ci-C 3 -alkoxy or Ci-C 2 -haloalkoxy; R 3 is hydrogen, Ci-C 3 -alkyl or cyclopropyl; Ri, is Ci-C6~alkyl; C2-Ci»-alkyl substituted by halogen, hydroxy, cyano, Ci-Cj-alkoxy, Cj-Cu-alkoxyalkoxy or by Ci-C 2 -alkylthio; C3~alkenyl; Cj-alkynyl; or C6 - C7-cycloalkyl that is unsubstituted or substituted by methyl; and X is oxygen or sulphur.

5. Compounds of formula I according to claim 3 in vhich: Ri and R 2 independently of one another are hydrogen, fluorine, chlorine, bromine, Ci-Cj-alkyl, Cj-Cj-alkoxy, trifluoromethyl, -OCHF 2 , -OCF2CHF2, -OCF2CHCIF, -OCF 2 CHC1 2 or -OCF2CCI2F; R3 is hydrogen, methyl, ethyl or n-propyl; Ru is Ci-Cu-alkyl; C 2 -C3-alkyl substituted by halogen, hydroxy, cyano, Ci-C 2 -alkoxy or by Ci-C 2 -alkylthio; Cj-Ce-alkenyl; C3-Ce-alkynyl; or cyclohexyl; and X is oxygen or sulphur.

6. Compounds of formula I according to claim 4 in which: Ri and R 2 independently of one another are hydrogen, fluorine, chlorine, bromine, Ci-C 2 -alkyl, Ci-C 2 -alkoxy, trifluoromethyl, -OCHF 2 , -OCF3, -OCF 2 CHF 2 or -OCF 2 CHC1F; R3 is hydrogen or Ci-C 2 -alkyl; Ri, is Ci-C 3 -alkyl; C 2 -alkyl substituted by halogen, hydroxy, cyano, Ci-C 2 -alkoxy or by Ci-C 2 -alkylthio; C3 —Ci,-alkenyl; or C3-Ci,-alkynyl; and X is oxygen or sulphur.

7. Compounds of formula I according to claim 6 in which: Ri and R 2 independently of one another are hydrogen, fluorine, chlorine, bromine, Ci-C 2 -alkyl, Ci~C 2 -alkoxy, trifluoromethyl or -OCHF 2 ; R3 is methyl; Ri, is Ci-C2~alkyl; C 2 -alkyl substituted by fluorine, chlorine, bromine, cyano, Ci-C 2 -alkoxy or by methylthio; allyl; or propargyl; and X is oxygen or sulphur.

8. Compounds of formula I according to claim 1 in which: Ri and R 2 independently of one another are hydrogen, halogen, Ci-C 2 alkyl, halomethyl, Ci-C 2 -alkoxy or Ci-C 2 -haloalkoxy; 58 R 3 is hydrogen; Ci-C 3 -alkyl; Ci-C 2 -alkyl substituted by halogen or by hydroxy; cyclopropyl; or cyclopropyl mono- to tri-substituted by the same or different substituents selected from the group consisting of halogen and methyl; 5 Ri» is Ci-C«-alkyl; C 2 -C 3 -alkyl substituted by halogen, cyano, Ci-C 2 alkoxy or by Ci-C 2 -alkylthio; C3-C6-alkenyl; C 3 -C6~alkynyl; or C3-C7cycloalkyl; and X is oxygen or sulphur.

9. Compounds of formula I according to claim 8 in which: 10. Ri and R 2 independently of one another are hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or difluoromethoxy; R3 is hydrogen; Ci-C 3 -alkyl; Ci-C 2 -alkyl substituted by halogen or by hydroxy; cyclopropyl; or cyclopropyl mono- to tri-substituted by the same or different substituents selected from the group consisting of halogen 15 and methyl; Ri» is Ci-C 3 -alkyl; C 2 -C 3 -alkyl substituted by fluorine, chlorine or by Ci-C 2 -alkoxy; C 3 -C6 _ alkenyl; C 3 -C6-alkynyl; or C 3 -C6~cycloalkyl; and X is oxygen or sulphur.

10. Compounds of formula I according to claim 9 in which: 2Q Ri and R 2 independently of one another are hydrogen, fluorine, chlorine, methyl, trifluoromethyl, methoxy or difluoromethoxy; R 3 is Ci-C 3 -alkyl; methyl substituted by halogen or by hydroxy; cyclopropyl; or cyclopropyl mono- to tri-substituted by halogen or by methyl; Ri» is Ci-C 3 -alkyl; C 2 -C 3 -alkyl substituted by fluorine, chlorine or by 25 methoxy; C 3 -Ci»-alkenyl; C 3 -Ci»-alkynyl; cyclopropyl; or cyclohexyl; and X is oxygen.

11. Compounds of formula I according to claim 10 in which: Ri and R 2 are hydrogen; R 3 is Ci-C 3 -alkyl; methyl substituted by fluorine, chlorine or by 30 bromine; cyclopropyl; or cyclopropyl substituted by chlorine or by methyl; 59 Ru is Ci-C3-alkyl, 2-chloroethyl, 2,2,2-trifluoroethyl, allyl or propargyl; and X is oxygen.

12. A compound of formula I according to claim 3 selected from 2-phenylamino-4-methyl-6-methoxymethylpyr imidine; 2-pheny lamino-4-cyclopropyl-6-methoxymethylpyrimidine.

13. A process for the preparation of compounds of formula I according to claim 1, characterised in that 1. a phenylguanidine salt of formula Ila (Ha) or the free guanidine base of formula lib • .NH —NH—c/ (Hb) is reacted with a diketone of formula III R3—C—CH 2 —C—CH 2 XRu (III) without solvents or in an aprotic solvent, but preferably in a protic solvent, at temperatures of from 60°C to 160°C, or 2. in a multi-stage process: 2.1 urea is reacted with a diketone of formula III (III) in the presence of an acid in an inert solvent at temperatures of from 20°C to 140°C and is then cyclised at the reflux temperature of the solvent used to give a pyrimidine compound of formula V - 60 (V) HO— Ν— \=· / X CH 2 XRi, and 2.2 the resulting compound of formula V is reacted further with excess POCI3, without solvents or in a solvent that is inert towards POCI3, at temperatures of from 50°C to 110°C, to give the compound of formula VI Λ /N—C ci—( ;· (vi) NOHjXRi, and 2.3 the resulting compound of formula VI is reacted further with an aniline compound of formula VII (VII) depending on the reaction conditions either a) in the presence of a proton acceptor, without solvents or in a protic or aprotic solvent, or b) in the presence of an acid in an inert solvent, in each case at temperatures of from 60°C to 120°C, or 3. in a two-stage process: 3.1 a guanidine salt of formula VIII H Z N—Ci /«3 \h 2 .© is cyclised with a diketone of formula III XU r 3 i 2 —c—ch 2 xr., (III) (VIII) a) without solvents, at temperatures of from 100°C to 160°C, or b) in a protic or aprotic solvent or a mixture of protic and aprotic solvents, at temperatures of from 30°C to 140°C, to give a pyrimidine compound of formula IX H Z N/ \ v< (IX) CH 2 XR·, and 3.2 the resulting compound of formula IX is reacted with a compound of formula X 10 in the presence of a proton acceptor in aprotic solvents at temperatures of from 30°C to 140°C to remove HY, the substituents Ri to Ru and X in the formulae II to X being as defined for formula 1, Αθ being an acid anion and Y being halogen.

14. A composition for controlling or preventing an attack by insect pests or microorganisms, characterised in that it contains as at least one active component a compound of formula I according to claim 1.

15. A composition according to claim 14, characterised in that it contains as at least one active component a compound of formula I according to claim 2.

16. A composition according to claim 14, characterised in that tains as at least one active component a compound of formula I to claim 3.

17. A composition according to claim 14, tains as at least one active component a to any one of claims 4 to 12. it conaccording it conaccording characterised in that compound of formula I - 62

18. A composition according to claim 14, characterised in that it contains from 0.1 to 99 % by weight of a compound of formula I, from 99.9 to 1 % by weight of a solid or liquid adjuvant and from 0 to 25 % by weight of a surfactant.

19. A process for the preparation of an agrochemical composition as defined in claim 14, characterised in that at least one compound of formula I as defined in claim 1 is intimately mixed with suitable solid or liquid adjuvants and surfactants.

20. A method of controlling or preventing an attack of cultivated plants by insect pests or phytopathogenic microorganisms, characterised in that a compound of formula I as defined in claim 1 is applied to the plant or its locus.

21. The use of compounds of formula I according to claim 1 for controlling and/or preventing an attack by harmful microorganisms.

22. The use according to claim 21, characterised in that the microorganisms are phytopathogenic fungi.

23. The use according to claim 22 against fungi of the class Fungi imperfect!.

24. The use according to claim 23 against Botrytis attack.

25. A compound of the formula I given and defined In claim 1, which Is any one of those specifically hereinbefore mentioned other than a compound as claimed In claim 12.

26. A process for the preparation of a compound of the formula I given and defined In claim 1, substantially as hereinbefore described with particular reference to the accompanying Preparation Examples.

27. A compound of the formula I given and defined In claim 1, whenever prepared by a process claimed In claim 13 or 26.

28. A composition according to claim 14 for controlling or preventing an attack by Insect pests or microorganisms, substantially as hereinbefore described with particular reference to the accompanying Formulation Examples.

29. A process according to claim 19 for the preparation of an agrochemical composition, substantially as hereinbefore described with particular reference to the accompanying Formulation Examples.

30. An agrochemical composition, whenever prepared by a process claimed In claim 19 or 29.

31. A method according to claim 20 of controlling or preventing an attack of cultivated plants by Insect pests or phytopathogenic microorganisms, substantially as hereinbefore described with particular reference to the accompanying Biological Examples.