DK167975B1 - 2-ANILINO-PYRIMIDINE DERIVATIVES AND THEIR PREPARATION AND USE AS FUNGICIDE OR INSECTICIDE - Google Patents

Description

DK 167975 B1

The present invention relates to novel 2-anino-pyrimidine derivatives of the general formula I. The invention also relates to the preparation of these compounds as well as agrochemical insecticides or fungicides containing as at least one of these compounds. In addition, the invention relates to a method for controlling or protecting against infestation of pest insects or phytopathogenic fungi on 10 culture plants.

The compounds of the invention have the general formula: JR · 3 · N = +

OH2XIU

wherein R 1 and R 2 are each independently hydrogen, halogen, C (1-3) alkyl, C (1-2) haloalkyl, C (1-3) alkoxy or C (1-3) halogenalkoxy, R3 means hydrogen, C (1-4) alkyl, with halogen or hydroxy substituted C (1-2) alkyl, cyclopropyl or with halogen and / or methyl substituted cyclopropyl, R4 means C (1-8) alkyl, with halogen , hydroxy, cyano, C (1-4) alkoxy, C (3-4) alkoxyalkoxy or C (1-3) alkylthio substituted C (2-6) alkyl, C (3-6) alkenyl , C (3-6) -alkynyl, C (3-7) -cycloalkyl or methyl substituted C (3-7) -cycloalkyl, and X means oxygen or sulfur.

By alkyl itself or as a constituent of another substituent such as haloalkyl, alkoxy or haloalkoxy, depending on the number of carbon atoms mentioned, is meant, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and their isomers, such as isopropyl, isobutyl, tert-butyl and isopentyl.

Halogen means fluorine, chlorine, bromine or iodine. Halo-2 DK 167975 B1 alkyl and haloalkoxy denote mono- to perhalogenated groups, such as e.g. CHCl2, CH2F, CCl3, CH2Cl, CHF2, CH2CH2Br, C2Cl5, CHBr and CHBrCl, preferably CF3. Alkenyl 5 means, for example, propenyl- (1), allyl, butenyl- (1), butenyl- (2) or butenyl- (3) and several double bond chains. Alkynyl means e.g. propynyl (2), butynyl (1), butynyl (2) or pentynyl (4), preferably propargyl. Cycloalkyl means, depending on the number of the 10 carbon atoms listed, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

Compounds having an N-pyrimidylaniline structure are known.

From the specification for JP patent application Sho 56-65804 and from DD patent specification 151,404, compounds having this basic structure and with effect against plant damage organisms are known. However, the known compounds have not been able to fully satisfy the conditions set in practice in a satisfactory manner. The compounds of the invention of formula I characteristically differ from the 20 known compounds by containing an aliphatoxymethyl or aliphatthiomethyl group at the 4-position of the pyrimidine ring. Thereby, the novel compounds of the invention achieve a surprisingly high fungicidal and insecticidal activity, which is further illustrated in the following.

The compounds of formula I are at room temperature stable oils, resins or solids which are characterized by valuable microbicidal properties. They can be used preventively and curatively in the agricultural sector and related areas to control plant harmful microorganisms. The active substances according to the invention of formula I are distinguished by low application concentrations not only by excellent insecticide and fungicide effect but also by very good plant compatibility.

An important group of plant fungicides are compounds of formula I wherein Εχ and R 2 represent hydrogen.

3 DK 167975 B1. A particular group of anilino-pyrimidine derivatives are compounds of Formula I wherein and R 2 are each independently hydrogen, halogen, C (1-3) -alkyl, C (1-2) -haloalkyl, 5C (1-3) -alkoxy or C (1-3) haloalkoxy, R3 means hydrogen, C (1-4) alkyl or cyclopropyl, R4 means C (1-8) alkyl, with halogen, hydroxy, cyano, C (1-4) ) -alkoxy, C (3-4) -alkoxyalkoxy, C (1-3) -alkylthio substituted C (2-6) -alkyl, C (3-6) -alkenyl, C (3-6) -alkynyl, 10 C (5-7) -cycloalkyl or methyl-substituted C (5-7) -cycloalkyl, and X means oxygen or sulfur.

The following groups of active substances are preferred because of their pronounced biocidal activity, especially plant fungicidal activity: Group 1a:

Compounds of Formula I wherein R 1 and R 2 each represent hydrogen, fluoro, chloro, bromo, C (1-3) alkyl, C (1-2) haloalkyl, C (1-3) alkoxy or C (1-2) halo-alkoxy, R3 means hydrogen, C (1-3) alkyl or cyclopropyl, R4 represents C1-C6 alkyl, with halogen, hydroxy, cyano, C (1-3) -alkoxy, C (3-4) -alkoxyalkoxy or C (1-2) -alkylthio substituted C (2-4) -alkyl, C3-alkenyl, C3-alkynyl or unsubstituted or methyl-substituted C (6-7) - cycloalkyl, and X is oxygen or sulfur.

Among the compounds listed above, a particularly preferred group is those wherein R 1 and R 2 are hydrogen (group 1 a).

Group 1b: Compounds of formula I wherein R 1 and R 2 are each independently hydrogen, fluoro, chloro, bromo, C (1-3) -alkyl, C (1-3) -alkoxy, trifluoromethyl, -OCHF 2 - OCF2CHF2, -OCF2CHC1F, -OCF2CHCl2 or -OCF2CCl2F, R3 means hydr, methyl, ethyl or n-propyl, R4 means C (1-4) alkyl, with halogen, hydroxy, cyano, C (1) -2) alkoxy or C (1-2) alkylthio substituted C (2-3) alkyl, 5 C (3-6) -alkenyl, C (3-6) -alkynyl or cyclohexyl, and X means oxygen or sulfur.

Of these compounds, a particularly preferred group is those wherein R 1 and R 2 are hydrogen (group 1bb).

Group lc;

Compounds of formula I wherein R 1 and R 2 are each independently hydrogen, fluorine, chlorine, bromine, C (1-2) alkyl, C (1-2) alkoxy, trifluoromethyl, -OCHF2, -OCF3, -OCF2CHF2, or -OCF2CHCIF, R3 means hydrogen or C (1-2) alkyl, R4 means C (1-3) alkyl, with halogen, hydroxy, cyano, C (1-2) alkoxy or C (1-2) ) -alkylthio is substituted C2-alkyl, C (3-4) -alkenyl or C (3-4) -alkynyl, and X is oxygen or sulfur.

Of the compounds listed above, 20 are particularly preferred, wherein R 1 and R 2 are hydrogen and X is oxygen (group 1 cc).

Group ld:

Compounds of formula I wherein R 1 and R 2 are each independently hydrogen, fluoro, chloro, bromo, C 1 -C 2 alkyl, C 1 -C 2 alkoxy, trifluoromethyl or -OCHF 2, R 3 is methyl, R 4 represents C (1-2) alkyl, with fluoro, chloro, bromo,. cyano, C (1-2) alkoxy or methylthio substituted C2 alkyl, allyl or propargyl, and X is oxygen or sulfur.

Among these compounds, particularly preferred are those wherein R 1 and R 2 are hydrogen and X is oxygen (group .ldd).

5 DK 167975 B1

Group 2a:

Compounds of formula I wherein and R 2 are each independently hydrogen, halogen, C 1 -C 2 alkyl, halo-methyl, 5 C (1-2) alkoxy or C (1-2) -haloalkoxy, R 3 is hydrogen, C (1-3) alkyl, with halogen or hydroxy substituted C (1-2) alkyl, cyclopropyl or with halogen and / or methyl one to three times the same or differently substituted cyclopropyl, R4 means C (1-4) - alkyl, with halogen, cyano, C (1-2) alkoxy or C (1-2) alkylthio substituted C (2-3) alkyl, C (3-6) -alkenyl, C (3-6) -alkynyl or C (3-7) -cycloalkyl, and X means oxygen or sulfur.

Of the above-mentioned compounds, especially those in which R 1 and R 2 are hydrogen (group 2aa) are preferred.

Group 2b:

Compounds of Formula I wherein R 1 and R 2 are each hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy or difluoromethoxy, R 3 is hydrogen, C 1 -C 3 alkyl, with halogen or hydroxy substituted C (1-2) alkyl, cyclopropyl, or with halogen and / or methyl one to three times the same or differently substituted cyclopropyl, R 4 represents C (1-3) alkyl, with fluoro, chloro or C ( 1-2-alkoxy substituted C (2-3) -alkyl, C (3-6) -alkenyl, C (3-6) -alkynyl or C (3-6) -cycloalkyl, and X is oxygen or sulfur .

Among the compounds listed above are particularly preferred, wherein R 1 and R 2 are hydrogen (group 2bb).

Group 2c: Compounds of formula X wherein R 1 and R 2 are each independently hydrogen, fluoro, chloro, methyl, trifluoromethyl, B1 methoxy or difluoromethoxy, R 3 is C (1-3) alkyl, with halogen or hydroxy substituted methyl, cyclopropyl or with halogen or methyl mono- to trisubstituted cyclopropyl, R 4 is C 1 -C 3 alkyl, with fluoro, chloro or methoxy substituted C (2-3) -alkyl, C (3-4) -alkenyl, C (3-4) -alkynyl, cyclopropyl or cyclohexyl, and X is oxygen.

Among the compounds listed above, a particularly preferred group is those wherein R 1 and R 2 are hydrogen (group 2cc).

Group 2d:

Compounds of Formula I wherein R 1 and R 2 are hydrogen, R 3 is C (1-3) alkyl, with fluoro, chloro or bromo substituted methyl, cyclopropyl or with chloro or methyl substituted cyclopropyl, R 4 is C (1-3) ) -alkyl, 2-chloroethyl, 2,2,2-trifluoroethyl, allyl or propargyl, and X is oxygen.

Examples of particularly preferred compounds may be mentioned 2-phenylamino-4-methyl-6-methoxymethyl-pyrimidine (compound # 1) and 2-phenylamino-4-cyclopropyl-6-methoxymethyl-pyrimidine (compound # 10).

The process of the invention for the preparation of the compounds of formula I is characterized by the reaction of a phenylguanidine salt of the formula

Rj. «TU ® 2 A® (n.) ΉΗ2 or the basic guanidine of the formula

Vw "kh2 7 with a diketone of the formula O 0

In a non-solvent or aprotic solvent, preferably, however, in a protic solvent at temperatures of 60 to 160 ° C, preferably 60 to 110 ° C, or 2. a multistage process: 2.1 2.1 reacting urea of formula NH 2 O = C 2 (IV) NH 2 with a ketone of formula 15 0 0

li II

R3-C-CH2-C-CH2XR4 (III) in the presence of an acid in an inert solvent at temperatures from 20 to 140 ° C, preferably from 40 to 100 ° C, and then at the reflux temperature of the solvent used, cyclizes to a pyrimidine feed. compound of formula / 3H0 - (). (V) N - * \ CH 2 X R 1 and 2.2 react the compound of formula V with 25 excess of POCl 3 without solvent or a solvent inert to POCl 3 at temperatures from 50 to 110 ° C, preferably at the reflux temperature of 8 DK 167975 B1 POCl 3, to form a compound of the formula / R 3 ·, N - (ci - (; · (vi) N =.

and 2 2.3 react the formed compound of formula VI with an aniline compound of formula xR1

Y-V

HZN + (VII) = =, / R2 depending on the process conditions either a) in the presence of a proton acceptor such as excess of the aniline compound of formula VII or an inorganic base, without solvent or in a protic or aprotic solvent or b) in the presence of an acid in an inert solvent at temperatures from 60 to 120 ° C, preferably from 80 to 100 ° C, or 3. In a two-step process 3.1, a guanidinium salt of the formula NH2® H2N-Αθ (VIII) 20 cycles. NH2 with a diketone of the formula

ISLAND ISLAND

l> H

R3-C-ch2-c-ch2xr4 (III) 9 a) without solvent at temperatures from 100 to 160 ° C, preferably from 120 to 150 ° C, or b) in a protic or aprotic solvent or a mixture of protic and aprotic solvents at temperatures from 30 to 140 ° C / preferably from 60 to 120 ° C, to form a pyrimidine compound of formula Μ- / 'H2N - * \ / * (IX) N = \ CH2XRi.

10 and 3.2, the compound of formula IX formed is reacted with a compound of formula y - (? <3!) · = Decomposing HY in the presence of a proton acceptor 15 in aprotic solvents at temperatures from 30 to. 140 ° C, preferably from 60 to 120 ° C, where the substituents R 1 to R 4 and X in formulas II to X have the meanings given under formula I, A® means an acid anion and Y means halogen.

In the above-described methods, as an acid. For example, the anion A® in the compounds of formulas 11a and VIII uses the following salts: carbonate, hydrogen carbonate, nitrate, halide, sulfate or hydrogen sulfate. Halide is meant fluoride, chloride, bromide or iodide, preferably chloride or bromide.

Preferably as acids are used inorganic acids such as e.g. hydrogen halide acids, for example hydrogen fluoric acid, hydrochloric acid or hydrogen bromic acid, as well as sulfuric acid, phosphoric acid or nitric acid. However, suitable organic acids may also be used.

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

For example, in the methods described above, the following solvents may be used, for example: , 1,2-dichloroethane, 1,1-dichloroethane, 1,2-cis-dichloroethylene, chlorobenzene,. fluorobenzene, bromobenzene, dichlorobenzene, dibromobenzene, chlorotoluene or trichlorotoluene, ethers such as ethyl propyl ether, methyl tert-butyl ether, n-butyl ethyl ether, di-n-butyl ether, di-isobutyl ether, diisoamyl ether, diisopropyl ether, anisole, anisole, anisole diethyl ether, ethyl englycol dimethyl ether, tetrahydrofuran, dioxane ,. thioanisole or dichlorodiethyl ether, nitrocarbon hydrides such as nitromethane, nitroethane, nitrobenzene, chloro nitrobenzene or o-nitrotoluene, nitriles such as acetonitrile, butyronitrile, isobutyronitrile, benzonitrile or m-chlorobenzonitrile, aliphatic or aliphatic, aliphatic, gasoline fractions within a boiling range of 70 to 190 ° C, cyclohexane, methylcyclohexane, decalin, petroleum ether, ligroin, trimethylpentane, such as 2,3,3-trimethyl ester, esters, such as ethyl acetate, acetate acetic acid and isobutyl acetate, amides, e.g. formamide, methylformamide and dimethylformamide, ketones such as acetone and methylethyl ketone, alcohols, especially lower aliphatic alcohols such as e.g. methanol, ethanol, n-propanol, iso-propanol and butanol, and optionally also water. Mixtures of said solvents and diluents may also be used.

Synthetic methods analogous to the methods described above are described in the following literature:

Procedure 1: A. Kreutzberger and J. Gillessen, J.

Heterocyclic Chem. 22, 101 (1985).

Procedure 2: Step 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). Step 2.2:

St. Angerstein, Ber.Dtsch.Chem.Ges. 34, 3956 (1901), G.M. Kosolapoff, J.Org.Chem. 26, 1895 (1961). Step 2.3: M.P.V.

20 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).

Procedure 3: A. Combes and C. Combes, Bull.Soc.Chem.

(3), 7, 791 (1892), W.J. Hale and F.C. Vibrans, J.Am.Chem.

Soc. 40, 1046 (1918).

Surprisingly, it has been found that compounds of formula I have a very favorable biocidal spectrum for controlling insects and phytopathogenic microorganisms, especially fungi, for practical purposes. The compounds of formula I 30 have very advantageous curative, preventive and especially systemic properties and are used for the protection of numerous cultural plants. With the active substances of formula I

In particular, harmful organisms that occur on plants or plant parts (fruits, flowers, foliage, stems, tubers, roots) of various crops can be inhibited or eradicated, since later growing plant parts are also protected against, for example, phytopathogenic microorganisms.

Compounds of formula I are effective against phytopathogenic fungi, which belong, for example, to the following classes: Fungi imperfecti (especially Botrytis, Helminthosporium, Fusarium, Sept. 10, Cercospora and Alternaria), basidiomycetes (e.g. the genera Hemileia, Rhizoctonia, Puccinia), and ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia and Uncinula). They are also effective against oomycetes (Perenosporales, Phytophthora, Plasmopara and Pythium). The 15 can also be used as a dressing agent for the treatment of plant propagating material (fruits, tubers, grains) and plant cuttings for protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. In addition, compounds of formula I are effective against insect pests, e.g. against pest insects in cereals, such as rice.

The agent according to the invention for controlling or protecting against attacks of harmful insects or fungi is characterized in that it contains as at least one active component a 2-anilino-pyrimidine derivative according to the invention.

The method of the invention for controlling or protecting against an attack by pest insects or phytopathogenic fungi is characterized by applying a 2-aniline no-pyrimidine derivative to the plants or their habitat or habitat.

As target cultures for the plant protection efforts described herein, for example, the following plant species may be mentioned: cereals (wheat, barley, rye, 13 oats, rice, maize, sorghum and related species), beets (sugar beet and fodder beet), kernel -, stone and berry fruits (apple, pears, plums, peaches, almonds, cherries, strawberries, 5 raspberries and blackberries), legumes (beans, lentils, peas, soy), oil cultures (rapeseed, mustard, poppy, olive, sunflower, coconut, castor, cocoa, peanut), cucumber (pumpkin, cucumber, melon), fiber (cotton, flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit and 10 mandarins), vegetable varieties (spinach, main salad, asparagus, cabbage) carrots, onions, tomatoes, potatoes, peppers), laurel plants (avocado, cinnamon, camphor) or plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, grapes, hops, banana and natural rubber plants and ornamental plants.

Active substances of formula I are usually used in the form of preparations and can be applied to the areas or plants to be treated, at the same time as other active substances or thereafter. These other active substances may be fertilizers, trace elements or other preparations which affect plant growth. Selective herbicides as well as insecticides, fungicides, bactericides, nematodicides, molluscicides or mixtures of several of these compositions may also be used together with any other carriers, surfactants or other application-promoting additives commonly used in the formulation technique.

Suitable carriers and additives may be solid or liquid and correspond to the appropriate substances in the formulation technique, such as e.g. natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickeners, binders or fertilizers.

A preferred method of applying an active substance of formula I or an agent containing at least one of these active substances is application to the foliage (leaf application). The frequency of application and the amount of application depends on the severity of the attack with the 5 pathogen in question. However, the active substances of formula I can also reach the plants via the soil through the root network (systemic effect), by watering the plant's growing site with a liquid preparation or introducing the substances in solid form into the soil, e.g. in the form 10 of granules (soil application). In rice cultivation such granules can be added to the rice field which is under water. However, the compounds of formula I may also be applied to seed (coating) by either wetting the grains in a liquid composition with the active substance or coating them with a solid composition.

The compounds of formula I can be used in unchanged form, or preferably together with the auxiliaries commonly used in the formulation technique. For this purpose they are conveniently processed e.g. for '20 emulsion concentrates, iron-ready pastes, direct sprayable or dilute solutions, diluted emulsions, spray powders, soluble powders, powder preparations, granules or by encapsulation in e.g. polymer substances in known manner. The methods of application such as spraying, misting, powdering, scattering, laying or pouring as well as the nature of the agent are selected according to the objectives and conditions given. Favorable amounts of application usually range from 50 g to 5 kg of active substance (AS) per day. ha, preferably from 100 g 30 to 2 kg AS / ha, especially from 200-600 g AS / ha.

The formulations, ie. the agents containing the active substance of formula I and optionally a solid or liquid additive, the compositions or compositions are prepared in known manner, e.g. by intimate mixing 35 and / or grinding the active substances with excipients such as e.g. solvents, solid carriers and optional surfactants (surfactants).

As solvents, aromatic hydrocarbons, preferably fractions C (8-12), such as e.g. xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl 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 10 cyclohexanone, highly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and optionally epoxidized plant oils such as epoxidized coconut oil or soybean oil, or water.

As solid carriers, e.g. for powder preparations and. dispersion powders are generally used in natural stone flour such as calcite, talc, kaolin, montmorillonite or atta pulgite. To improve the physical properties, high-dispersion silicic acid or high-dispersion absorbent polymerisers can also be added. Porous types can be used as granular adsorptive granular carriers, e.g. pumice, crushed bricks, sepiolite or bentonite, and as non-sorptive carriers e.g. calcite or sand. In addition, a large number of pre-granulated materials of inorganic nature, such as dolomite in particular, or finely divided plant residues can be used. Particularly advantageous application promoting additives which can lead to a sharp reduction in the use are also natural (animal or vegetable) or synthetic phospholipids selected from the kephalinerae and the lecithins which can be obtained, for example, from soybeans.

As surfactants, depending on the nature of the active substance of formula I to be formulated, nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties can be used. Surfactants also include surfactant mixtures.

Suitable anionic surfactants may be so-called water-soluble soaps as well as water-soluble synthetic surfactants.

As soaps, mention may be made of alkali metal, alkaline earth metal and optionally substituted ammonium salts of higher fatty acids (C (10-22)), such as e.g. The Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures which can be extracted, for example, by coconut or tallow oil. Furthermore, fatty acid methyl laurine salts can also be used.

More often, however, so-called synthetic surfactants are used, especially alkanesulfonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkyl sulfonates.

The fatty alcohol sulphonates or sulphates are usually present as alkali metal, alkaline earth metal or optionally substituted ammonium salts and contain an alkyl group of 8-22 carbon atoms, the alkyl also comprising the alkyl portion of acyl residues, e.g. The Na or Ca salt of lignin sulfonic acid, of dodecyl sulfuric acid ester or of a fatty alcohol sulfate mixture made from natural fatty acids. These include the salts of sulfuric acid ester and sulfonic acids of fatty alcohol-ethylene oxide addition products. The sulfonated benzimidazole derivatives preferably contain two sulfonic acid groups and a fatty acid residue of 8-22 carbon atoms. Alkylarylsulfonates are e.g. Reach-,

The Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid formaldehyde condensation product.

Further, similar phosphates may also be used, e.g. salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxide addition product.

17 DK 167975 B1

As nonionic surfactants, poly-glycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkyl phenols which may contain 3-30 glycol ether groups and 8-20 carbon atoms in the (aliphatic) hydrocarbon group and 6-18 are used primarily. carbon atoms in the alkyl group of the alkyl phenols.

Other suitable nonionic surfactants are water-soluble, 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups containing polyethylene oxide addition products with polypropylene glycol, ethylene diamino polypropylene glycol and alkyl polypropylene glycol having 1-10 carbon atoms in the alkyl chain. The said compounds usually contain from 1 to 5 ethyl eng lycol units per liter.

15 propylene glycol unit.

Examples of nonionic surfactants include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene polyethylene oxide addition products, tributylphenoxypolyethyleneethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Furthermore, fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate can also be used.

The cationic surfactants are primarily quaternary ammonium salts containing as N-substituent at least one alkyl group of 8-22 carbon atoms and as additional substituents low, optionally halogenated alkyl, benzyl or low hydroxyalkyl groups. The salts are preferably present as halides, methyl sulfates or ethyl sulfates, e.g. the stearyl trimethylammonium chloride or the benzyldi (2-chloroethyl) ammonium bromide.

Other surfactants commonly used in the formulation technique are well known to those skilled in the art or are described in the art literature.

18 DK 167975 B1

The agents generally contain 0.1-99%, especially 0.1-95%, active substance of formula I, 99.9-1%, especially 99.8-5%, solid and liquid additives and 0-25%, especially 0.1-25%, ten-sid.

While as a commodity prefer concentrated funds, the end consumer usually uses diluted funds.

The agents may also contain other additives, such as stabilizers, antifoaming agents, viscosity regulators, binders, adhesives, and fertilizers or other active substances to achieve particular effects.

The invention is further illustrated in the following examples.

Example 1

Preparation of 2-phenylamino-4-methyl-6-methoxymethyl-pyrimidine / Η3 \ τ = · (Compound No. 1) XCH20CHa 4 hours to 100 ° C, whereby the occurrence of carbon dioxide evolution becomes weaker, the longer the reaction proceeds. After cooling to room temperature, 60 ml of diethyl ether are added to the brown emulsion, which is washed with 3 x 20 ml of water, dried with sodium sulfate, filtered and the solvent evaporated. 10.5 g of oily residue are obtained, which is dissolved in 140 ml of diethyl ether, and with stirring 4.4 g of 65% nitric acid is added. The suspension 5 of the precipitated nitrate salt is stirred for an additional 20 minutes, then filtered and washed with 100 ml of diethyl ether. To a mixture consisting of 11 g of the nitrate salt, 80 ml of diethyl ether and 60 ml of water is added with stirring 6 g of 30% sodium hydroxide solution, whereupon the organic phase is isolated, washed with 2 x 40 ml of water, dried with sodium sulfate, filtered and the solvent is evaporated. 8.7 g of light brown oily residue are obtained which are crystallized with 100 ml of petroleum ether (boiling range 50-70 ° C), filtered and dried. There are 15 g of light, beige colored crystal powder with m.p. Yield: 92% of theory, based on the phenylguanidine hydrogen carbonate.

Example 2

Preparation of 2- (p-chlorophenylamino) -4-methyl-6-20 methoxymethyl 1-pyrimidine / CH 3

C— NH NH—— forb (Compound No. 70) CH₂OCH3

A solution of 6.4 g of 4-chloro aniline and 8.6 g of 2-chloro-4-methyl 1-6-methoxymethyl-pyrimidine is stirred with 5 ml of concentrated hydrochloric acid at pH 1, then heated for 20 hours. under reflux. After cooling to room temperature, the brown emulsion is made basic with 12 ml of 30% ammonia, then poured into 100 ml of ice water and extracted with 3 x 50 ml of ethyl acetate. The combined extracts are washed with 50 ml of water, dried with 30% sodium sulfate and filtered and the solvent is evaporated.

20 DK 167975 B1

11.8 g of red oil are obtained which are chromatographed on a 30 cm silica column using dichloromethane / diethyl ether (3: 2). After evaporation of the eluent, the initially oily residue is crystallized by rubbing off with petroleum ether. After recrystallization from diisopropyl ether / petroleum ether (50-70 ° C), 9.8 g of beige colored crystal powder melting at 57-59 ° C is obtained: 74% of theory.

21 DK 167975 B1

ISLAND ISLAND

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

5 2.4 Powder Preparation a) b)

Active substance from the table 2% 5% High-dispersion silicic acid 1% 5%

Talc 97% -

Kaolin - 90% 10 Ready-made powder formulations are prepared by intimate mixing of carriers with the active substance.

Formulation examples of solid active substances with the fontile I (% = wt%) 2.5 Spray tea powder a) b) c) 15 Active substance from the table 25% 50% 75%

Na-lignin sulfonate 5% 5%

Na-Lauryl Sulfate 3% - 5%

Na-Diisobutylnaphthalenesulfonate - 6% 10%

Octylphenol polyethylene glycol ether 20 (7-8 moles of ethylene oxide) - 2% - High-dispersed silicic acid 5% 10% 10%

Kaolin 62% 27%

The active substance is thoroughly mixed with the additives and grinding is performed on a suitable mill. 25 syringes of powder are obtained, which can be diluted with water to suspensions of any desired concentration.

2 ♦ 6 Emulsion Concentrate

Active substance from table 10%

Octylphenol polyethylene glycol ether 30 (4-5 moles of ethylene oxide) 3% 47 2. Formulation examples for liquid active substances of formula I (% = wt%) 2.1 Emulsion concentrates a) b) c) Active substance from table 25% 40% 50 %

Ca-Dodecylbenzenesulfonate 5% 8% 6%

Castor oil polyethylene glycol ether (36 moles of ethylene oxide) 5%

Tributylphenoy1-polyethylene glycol ether (30 moles of ethylene oxide) - 12% 4%

Cyclohexanone - 15% 20%

Xylene blend 65% 25% 20%

By dilution with water, emulsions of any desired concentration can be prepared from such concentrates.

2.2 Solutions a) b) c) d)

Active substance from the table 80% 10% 5% 95%

Ethylene glycol monomethyl ether 20% - - -

Polyethylene Glycol 400 - 70% 20 N-Methyl-2-pyrrolidone - 20%

Epoxidized Coconut Oil - 1% 5%

Gasoline (boiling range 160-190 ° C) - - 94%

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

2.3 Granules a) b)

Active substance from the table 5% 10%

Kaolin 94% High-dispersion silicic acid 1%

Attapulgit - 90% 49 DK 167975 B1

Ca-Dodecylbenzenesulfonate 3%

Castor oil polyglycol ether (35 moles of ethylene oxide) 4% Cyclohexanone 34%

Xylene Mixture 50%

By dilution with water, emulsions of any desired concentration can be prepared from this concentrate.

2.7 Powder Preparation a) b)

Active substance from the table 5% 8%

Talc 95%

Kaolin - 92%

Ready powder preparations are obtained by mixing the active substance with the carrier and grinding the mixture on a suitable grinding apparatus.

2.8 Extruder granules

Active substance from table 10%

Na-lignin sulfonate 2% Carboxymethyl cellulose 1%

Kaolin 87%

The active substance is mixed with the additives, the mixture is ground and wetted with water. Then the mixture is extruded, which is eventually dried in an air stream.

25 2 ♦ 9 Envelope granules

Active substance from table 3%

Polyethylene glycol (200) 3%

Kaolin 94% 50 DK 167975 B1

The finely ground active ingredient is uniformly applied in a kaolin wetting apparatus wetted with polyethylene glycol. In this way, dust-free casing granules are obtained.

2.10 Suspension concentrate

Active substance from the table 40%

Ethylene glycol 10%

Nonylphenol polyethylene glycol ether (15 moles of ethylene oxide) 6% Na-lignin sulfonate 10%

Carboxymethyl cellulose 1% 37% aqueous formaldehyde solution 0.2%

Silicone oil in the form of a 75% aqueous emulsion 0.8% Water 32%

The finely ground active substance is thoroughly mixed with the additives. In this way, a suspension concentrate is obtained from which, by dilution with water, suspensions of any desired concentration can be prepared.

3. Biological examples

Example 3.1: Effect against Puccinia graminis on wheat a) Residual protective effect

Wheat plants are sprayed 6 days after sowing with a 25 spray liquid (0.02% active substance) prepared from a spray powder containing the active substance. After 24 hours, the treated plants are infected with an uredospores suspension of the fungus. After an incubation period of 48 hours at a relative humidity of 95-100% and approx.

At 20 ° C, the infected plants are placed in a greenhouse at approx.

22 ° C. The assessment of rust development is carried out 12 days after infection, b) Systemic effect

For wheat plants, 5 days after sowing, a 5 spray liquid (0.006% active substance, calculated on the soil volume) is poured from a spray powder containing the active substance. After 48 hours, the treated plants are infected with an uredospores suspension of the fungus. After an incubation period of 48 hours at a relative humidity of 95-100% and approx. At 20 ° C, the infected plants are placed in a greenhouse at approx. 22 ° C. Assessment of rust development is done 12 days after infection.

Compounds from the table show good effect against Puccinia (attack: <20%). Untreated but infected control plants, on the other hand, exhibit a 100% Puccinia attack.

Example 3.2: Effect against Phytophthora on tomato plants a) Residual protective effect

After 3 weeks of cultivation, tomato plants are sprayed with a spray liquid (0.02% active substance) prepared from 20 from a spray powder containing the active substance. After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. The fungal attack is assessed after a 5-day incubation period for the infected plants at a relative humidity of 90-100% 25 and 20 ° C.

b) Residual curative effect

After 3 weeks of cultivation, tomato plants are infected with a sporangia suspension of the fungus. After an incubation time of 22 hours in a humidity chamber at a relative humidity of 90-100% and 20 ° C, the infected plants are dried and sprayed with a spray liquid (0.02% active substance) prepared from a spray powder containing the active substance. After drying the spray coating, the treated plants are placed back in the humidity chamber. The assessment of the fungal attack is made 5 days after the infection.

c) Systemic effect

For tomato plants, after 3 weeks of cultivation, a 10 spray liquid (0.002% active substance, based on soil volume) is poured, which is made from a spray powder containing the active substance. Care is taken to ensure that the spray liquid does not come into contact with the plants' soil. After 48 hours, the treated 15 plants are infected with a sporangia suspension of the fungus. The fungal attack is assessed after a 5-day incubation period for the infected plants with a relative humidity of 90-100% and 20 ° C.

Compounds from the table show good effect against 20 Phytophthora (attack: <20%). Untreated but infected control plants, on the other hand, show a Phyphthora attack of 100%.

Example 3.3: Effect against Plasmopara viticola on grapes

Residual protective effect 25 4-5 leaf stage vine plants are sprayed with a spray liquid (0.02% active substance) prepared from a spray powder containing the active substance. After 24 hours, the treated plants are infected with a sporangia suspension of the fungus. After an incubation period of 6 days 30 at a relative humidity of 95-100% and 20 ° C is evaluated. fungus attack.

53 DK 167975 B1

Compounds from the table show good effect against Plasmopara. Untreated with infected control plants, on the other hand, exhibit a 100% Plasmopara attack.

Example 3.4: Effect against Cercospora arachidicola on peanut plants

Residual protective effect

Peanut plants with a height of 10-15 cm are sprayed with a spray liquid (0.02% active substance) made out of 10 from a spray powder containing the active substance, and 48 hours later the plants are infected with a conidial suspension of the fungus. The infected plants are incubated for 72 hours at 21 ° C and high humidity, then placed in a greenhouse until typical leaf spots appear.

The fungicidal effect is assessed 12 days after infection and is based on the number and size of the spots occurring.

Compounds from the table show good effect against

Cercospora (attack: <20%). Untreated but infected control plants, on the other hand, exhibit a 100% Cercospora attack.

Example 3.5: Effect against Venturis inaequalis on apple shoots

Residual-protective effect Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray liquid (0.02% active substance), which is made from a spray powder containing the active substance. After . Within 24 hours, the treated plants are infected with a conidial suspension of the fungus. The plants are then incubated for 5 days at a relative humidity of 90-100% and then placed for an additional 10 days in a greenhouse at 20-24 ° C. The scab attack is assessed 15 days after the infection.

54 DK 167975 B1

Compounds from the table show good effect against Venturia. For example, compounds Nos. 1, 10, 38, 59, 231, 262 and 276 reduce the Venturia attack to less than 5 10%. Untreated but infected control plants, on the other hand, exhibit a 100% Venturia attack.

Example 3.6: Effect against Botrytis cinerae on apple fruit

Residual Protective Effect 10 Artificially damaged apples are treated by grafting at the damaged sites with a spray liquid (0.002% active ingredient) prepared from a spray powder containing the active substance. The treated fruits are then inoculated with a spore suspension of the fungus, whereupon they are incubated for a week at high humidity and ca. 20 ° C. In the assessment, the damaged places where advice occurs are counted and from this result the fungicidal effect of the test compound is calculated.

. Compounds from the table show good effect against Botrytis 20 (attack: <20%). For example, Compound Nos. 1, 3, 7, 10, 38, 59, 231, 256, 262, 268 and 276 Botrytis infestation are reduced to 0-5%. Untreated but infected control plants, on the other hand, exhibit a 100% Botrytis attack.

Example 3.7: Effect against Erysiphe graminis on barley 25 Residual protective effect

Barley plants with a height of approx. 8 cm is sprayed with a spray liquid (0.02% active substance) prepared from a spray powder containing the active substance. After 3-4 hours, the treated plants are pollinated with conidia of the 30 fungus. The infected barley plants are placed in a greenhouse at approx. 22 ° C and the fungal attack is assessed after 10 days.

55 DK 167975 B1

Compounds from the table show good effect against Erysiphe. Thus, for example, compounds Nos. 1, 5, 6, 10, 38, 59, 135, 175, 231 and 262 reduce the Erysiphe attack to 5 less than 20%. Untreated but infected control plants, on the other hand, exhibit a 100% Erysiphe attack.

Example 3.8: Effect against Helminthosporium gramineum

Wheat grains are contaminated with a spore suspension of the fungus and dried. The contaminated grains are stained with a suspension of the test compound prepared from a spray powder (600 ppm active substance, based on the weight of the grains). After 2 days the grains are laid on suitable agar dishes and after a further 4 days the development of fungal colonies around the grains is evaluated. The number and size of the fungal colonies 15 are used to evaluate the test compound. The compounds from the table largely prevent the fungal attack (0-10%).

Example 3.9: Effect against Fusarium levels

Wheat grains are contaminated with a spore suspension of the sponge, after which the grains are again dried. Contaminated grains are stained with a suspension of the test compound made from a spray powder (600 ppm active substance, based on the weight of the grains). After 2 days, the grains are laid on suitable agar dishes, and after a further 4 days the development of 25 fungal colonies around the grains is assessed. Number and size of the fungal colonies are used to evaluate the test compound.

In the cereals that have been treated with a spray powder containing as an active substance a compound from the table, the development of the fungal colonies is almost completely suppressed (0-5%).

Example 3.10: Effect against Tilletia caries 56 DK 167975 B1

Barley is contaminated with a spore suspension of the sponge, after which the grains are again dried. The contaminated grains are stained with a suspension of the test compound prepared from spray powder (600 ppm active substance, based on the weight of the grains). After 2 days, the grains are laid on suitable agar dishes and after a further 4 days the development of fungal colonies around the grains is assessed. The number and size of the fungal colonies are used to evaluate the test compound.

• The compounds from the table largely prevent the fungal attack (0-10%).

Example 3.11: Effect against Colletotrichum lagenarium on cucumbers (Cucumis sativus L.) 15 · After 2 weeks of cultivation, cucumber plants are sprayed with a spray liquid (concentration 0.02%) prepared from a spray powder containing the active substance. After 2 days, the plants are infected with a spore suspension (1.5 x 10 5 spores / ml) of the fungus and incubated for 36 20 hours in the dark at 23 ° C and high humidity. Then the incubation is carried out at normal humidity and approx.

22-23eC. The fungal attack that occurs is assessed 8 days after infection. Untreated but infected control plants exhibit a 100% fungal attack.

25 Compounds from the table show good effect and prevent the spread of the disease attack. The fungal attack is fought to 20% or less.

Example 3.12: Effect against Septoria nodorum on wheat

Residual Protective Effect 30 7-day-old wheat plants are sprayed with a spray liquid (concentration 0.02%) prepared from the formulated test compound, and 2 days later infested with a conidial suspension (400,000 conidia / ml with the addition of 0, 1% "Tween" ®20 as a wetting agent) of Septoria 5 nodorum. After a 2-day incubation period in a greenhouse cabin at 20 ° C and a relative humidity of 95-100%, the experimental plants are placed uncovered in a greenhouse cabin at 21 ° C and a relative humidity of 60% until the end of the experiment. The assessment of the 10 fungal infestation is done 7-10 days after the infection.

While untreated but infected control plants are completely infected, plants treated with compounds from the table exhibit a fungal attack of less than 20%.

Example 3.13: Effect against Alternaria solani on tomatoes 15 Residual-protective effect 3-week-old tomato plants are sprayed with a spray liquid (concentration 0.02%) prepared from an agent containing the active substance, and two days later infections from both pages with a conidia suspension 20 (20,000 conidia / ml) of Alternaria solani. To prevent washing of the spray coating in the form of fine droplets, the infected plants are covered in a first 3 day incubation phase in a greenhouse at 20 ° C and climate humidification with fine mesh. Then, the plants are placed until the end of the experiment in a greenhouse at 24 ° C. The assessment of the fungal attack is done 4 days after the infection.

While untreated but infected control plants are completely infected, plants treated with compounds from the table exhibit a fungal attack of less than 20%.

Example 3.14: 58 DK 167975 B1 a) Insecticidal contact action against Nephotettix cincticeps and Nilaparvata hatch (nymphs) 5 The experiment is carried out on growing rice plants. For each experiment 4 plants (14-20 days old) with a height of approx. 15 cm in pots (5.5 cm diameter).

The plants are sprayed onto a turntable with 100 ml of aqueous emulsion preparation containing 400 ppm of the 10 test compound. After drying the spray coating, each plant is infested with 20 nymphs of the third-stage experimental animal. To prevent the cicadas from evading, the occupied plants are placed in a glass cylinder which is open at both ends and closed with a gauze cover. To reach the adult stage, the nymphs are kept for 6 days on the treated plants. The percentage mortality is assessed 6 days after the herd. The experiment is carried out at approx. 27 ° C and a relative humidity of 60% and an illumination period of 16 hours.

B) Systemic insecticidal action against the Nilaparvata hatch (in water)

Ca. 10 day old rice plants (height about 10 cm) are placed in a plastic beaker containing 150 ml of emulsion preparation of the test compound at a concentration of 100 ppm and which is closed with a plastic lid provided with several holes. The root of the rice plant is pushed through a hole in the plastic lid into the aqueous test preparation. Then, the rice plant is filled with 20 nymphs of the Nilaparvata lugens in the N 2- to N-3 state, and then covered with a plastic cylinder. Experiment 30 is performed at ca. 26 ° C and a relative humidity of 60% with an illumination period of 16 hours. After 5 days, the number of test animals is counted, which is compared to untreated controls. It is hereby ascertained.

DK 167975 ΒΊ 59 on the active substance absorbed over the roots kills the test animals on the upper plant parts.

Compounds from the table show an effect of more than 80% against the rice damage organisms used in both contact experiment 5 and systemic experiment.

In the following, comparative experiments with a known comparative compound of DD Patent No. 151,404 with Formula X and 10 below are made representative of the compounds of General Formula I. Formula and No. of the test compounds used are listed below.

Compound Formula ch3

x rv-M

\ = / N = / CH3 (known) CHg 0 "" ø ch2-och3 ch3 2 fy \ = / N = \ ch2-och2ch = ch2 60 DK 167975 B1 CH3 5 O—

CH 2 OCH 2 C? CH

ch3 7 \ == z / N = / ch2-s-ch3 10 / \ NH— / \ \ = / \ = / ch2-och3 c2h5 38 / \ —nh — ζ \ = S Ν == ζ \ ch2-och3 ch3 138 F i \ NH— ^ \ • v == / N = / ch2-och3 ch3 231 ^ \ NH- ^ \ \ = / N = / ch2-och3 DK 167975 B1 61 ch2-ci 256 f \ -NH- In the biological experiments below, the compounds are used in the form of dilute aqueous solutions of spray powders. Untreated but infected control plants exhibit a 5% attack of 100%.

Example 3.15:

Residual protective effect against Venturia inaequalis on apple shoots Apple cuttings with 10-20 long fresh shoots are sprayed with a 10 spray liquid (0.002% active ingredient), which is made from a spray powder containing the active substance. After 24 hours, the treated plants are infected with a conidial suspension of the fungus. The plants are then incubated for 5 days at a relative humidity of 90-100%, after which they are placed for an additional 10 days in a greenhouse at 20-24 ° C. The scab attack is assessed 15 days after the infection.

Compounds Nos. 1, 2, 5, 7, 10, 38, 138, 231 and 256 reduce the scab grip to 0-10%.

Comparison compound X reduces the attack to 20 .10-20%.

Example 3.16: 62 DK 167975 B1

Effect against Botrytis cinera on apple fruit Residual protective effect 5 Artificially damaged apples are treated by grafting at the damaged sites with a spray liquid (0.002% active substance) prepared from a spray powder containing the active substance. The treated fruits are then inoculated with a spore suspension of the fungus, whereupon they are incubated for 1 week at high humidity and a temperature of approx. 20 ° C. In the assessment, the damaged places where advice occurs are counted and from this result the fungicidal effect of the test compounds is calculated.

Compounds Nos. 1, 2, 5, 7, 10, 38, 138, 231 and 256 15 reduce the Botrytis attack to 0%.

Comparative compound X reduces the attack to 20-40%.

Example 3.17:

Effect against Erysiphae graminis on barley 20 Residual protective effect

Ca. 8 cm tall barley plants are sprayed with a spray liquid (0.006% active ingredient), which is made from a spray powder containing the active substance. After 3-4 hours, the treated plants are pollinated with conidia of the fungus. The 25 infected barley plants are placed in a greenhouse at approx. 22 ° C and the fungal attack is evaluated after 10 days.

Compounds Nos. 1, 2, 5, 10, 38 and 231 reduce the attack with real mildew to 10-20%.

Comparative compound X reduces the attack to 20-40%.

Example 3.18: 63 DK 167975 B1

Effect against Septoria nodorum on wheat Residual protective effect 5 7-day-old wheat plants are sprayed with a spray liquid (concentration 0.02%) prepared from the formulated test compound, and after 2 days infection is done with a conidial suspension (400,000 conidia / ml with the addition of 0.1% "Tween" (as a wetting agent) of Septoria nodorum. After an incubation period of 2 days in a greenhouse chamber at 20 ° C and a relative humidity of 95-100%, the experimental plants are placed uncovered in a greenhouse chamber at 21 ° C and a relative humidity of 60% until the end of the experiment. The assessment of the 15 fungal attack is done 7-10 days after the infection.

Compounds Nos. 1, 7, 10, 38 and 138 reduce the fungal attack to 20-40%.

Comparative compound X practically does not reduce the attack (to 50-100%).

Claims (10)

Compounds according to claim 1, characterized in that R 1 and R 2 are hydrogen. Compounds according to claim 1, characterized in that R 3 is hydrogen, C 1 -C 4 alkyl or cyclopropyl, and R 4 is C 1 -C 8 alkyl, with halogen, hydroxy, cyano, C (1- 4) alkoxy, C (3-4) alkoxyalkoxy or C (1-3) alkylthio substituted C (2-6) alkyl, C (3-6) alkenyl, C (3-6) alkynyl yl, C (5-7) -cycloalkyl or methyl substituted C (5-7) -cycloalkyl. Compounds according to claim 3, characterized in that and R 2 are each independently hydrogen, fluorine, chlorine, bromine, C (1-3) -alkyl, C (1-3) -alkoxy, trifluoromethyl, -OCHF2, -0CF2CHF2, -CF2CHC1F, -OCF2CHCl2 or -OCF2CCl2F, R3 represents hydrogen, methyl, ethyl or n-propyl, and R4 represents C 1 -C 4 alkyl, with halogen, hydroxy, cyano, C ( 1- (2) -alkoxy or C (1-2) -alkylthio substituted C (2-3) -alkyl, C (3-6) -alkenyl, C (3-6) -alkynyl or cyclohexyl. Compounds according to claim 3, characterized in that and R 2 are each independently hydrogen, fluorine, chlorine, bromine, C (1-2) -alkyl, C (1-2) alkoxy, trifluoromethyl, -OCHF 2, -OFC 3 , -OCF2CHF2, or -OCF2CHC1F, R3 means hydrogen or C (1-2) alkyl, and R4 means C (1-3) alkyl, with halogen, hydroxy, cyano, C (1-2) alkoxy or C (1-2) alkylthio substituted ethyl, C (3-4) -alkenyl or C (3-4) -alkylene. Compound according to claim 3, characterized in that it is 2-phenylamino-4-methyl-6-methoxymethyl-pyrimidine or 2-phenylamino-4-cyclopropyl-6-methoxymethyl-pyrimidine. Process for the preparation of 2-anilino-pyrimidine derivatives according to claim 1, characterized in that: 1. a phenylguanidine salt of the formula R 1 - v β 2 ° \ A (IIa) or the basic guanidine of the formula is reacted RlV ~ \ J ** 2 · *; NH-cf "<IIb) Y" h2 DK 167975 B1 having a dike ton of the formula 0 0 H II R3-C-CH2-C-CH2XR4 (III) 5 without solvent or in an aprotic, preferably in a protic solvent at temperatures of 60 to 160 ° C, or 2. In a few steps: 2.1 reactes urea with a ketone of the formula 10 0 0 r 3 - (ϋ-ch 2 - CH 2 X R 4 (III) in the presence of an acid in an inert solvent at temperatures of 20 to 140 ° C, and then cyclizes at the reflux temperature of the solvent used to form a pyrimidine compound of the formula / ΝΝ \ HO -. (> (V) N =. CH 2 X R formed compound of formula V with 20 excess of POC13 without solvent or in a solvent inert to POC13 at temperatures of 50 to 110 ° C to form a compound of formula ^ - <R1 C1 ~ v> XCHzXRi, DK 167975 B1 and 2.3 react the formed compound of formula VI with an aniline compound of formula a-j / R1 5 h2n - (will) R2 depending on the process conditions either a) in the presence of a proton-free solvent or in a protic or aprotic solvent or b) in the presence of an acid in an inert solvent at temperatures from 60 to 120 ° C, or 3. In a two-step process 3.1, a guanidine salt of formula NH2® cycles (A) without solvent at temperatures of 100 to 160 ° C / or b) in a protic or aprotic solvent. 15 H2N-A® (VIII) NH2 with a diketone of the formula OO II II R3-C-ch2-C-CH2XR4 (III) or a mixture of protic and aprotic solvents at temperatures of 30 to 140 ° C, 25 to a pyrimidine compound of formula DK 167975 B1 / * »/ N ~ * \ h2n -. (). (IX) * <CH2XRu and 3.2, the compound of formula IX formed with a compound of formula .-- / 1 * - <_ in (x) Rz under decomposition of HY in the presence of a proton acceptor in aprotic solvents at temperatures from 30 to 140 ° C, wherein the substituents R 1 to R 4 and X of formulas II 10 to X have the meanings given in claim 1, A® means an acid anion and Y means halogen. A means for controlling or protecting against attacks of harmful insects or fungi, characterized in that it contains as at least one active component a 2-ani-15-lino-pyrimidine derivative according to claim 1. Agent according to claim 8, characterized in that it contains as at least one active component a 2-anilino-pyrimidine derivative according to claim 2. Agent according to claim 8, characterized in that it contains at least one active component a 2-anilino-pyrimidine derivative according to claim 3. An agent according to claim 8, characterized in that it contains as at least one active component a 2-anilino-pyrimidine derivative according to one of claims 4-6. DK 167975 B1 '12. A method of controlling or protecting against an attack of insect pests or phytopathogenic fungi on cultured plants, characterized in that a 2-anilino-pyrimidine derivative according to claim 1 is applied to the plants or their growing site or habitat.