CA2068338A1 - Pyridine derivatives, process for making them, agents containing them and their use as fungicides - Google Patents

Abstract

Abstract of the disclosure Pyridine derivatives, process for their preparation, agents containing them and their use as fungicides Compounds of the formula I

Description

2~8338 .iOECHST AKTI~NGES2LLSCHAF~ ~OE 89/F 359 ~e~criptio7a ?yridine derivatives, process for their preparation, ~gents containing them and their use as fungicides The present invention relates to novel pyridine deriva-ti-~es, a process for their prepara~ion, agents containing them and their use as fungicides.

Pyridine derivatives are already known as acti~e components in fungicidal agents (cf. EP-A-270,362, EP-A 278,610, EP-A-259,139, EP-A 234,104). However, the action of these cornpounds is not always satisfactory, in particular at low application rates.

Novel pyridine derivatives have now been found which have advantageous effects in the control of a wide spectrum of phytopathogenic fungi, in particular at low dosages.

The present inven~ion therefore relates to the compounds of the formula I, ~5 ~ ~` R9 R~R 2 ~ 8 in which R1, R2, R3 and R4 are independently of one another, hydrogen, halogen, nitro, (C~-C4)alkyl, (Cl-C4~alkoxy, (cl-c4)alkylthio~ (Cl-C4)haloalkoxy or (C1 -C4 ) haloalkyl, R5, R6 and R7 are independently of one another hydrogen, (C1 C6)alkyl or phenyl, it being possible for the phenyl radical to be monosubstituted to 2~33~

trisubstituted by halogen, nitro, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4 ) haloalkyl, or (Cl-C4)haloalkoxy, R8 and R9 are independently of one another hydrogen, (C1-C6)alkyl, ( C3-C7 ) cycloalkyl, ( C3-C7 ) cycloalkyl-(C,-C4)alkyl, it being possible for the ~wo last-mentioned radicals to be monosu~stituted to trisubstituted in the cycloalkyl moiety by (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy, (Cl-C4)alkylthio, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkylthio-(C1-C4)alkyl, halogen, (C2-C6)al-kenyl, (C2-C6)alkynyl, phenyl, phenoxy, phenoxy-(C1-C4)alkyl, phenylmercapto-(Cl-C4)alkyl, phenyl-mercapto, phenyl-(C1-C4)alkoxy or phenyl-(C1-C4)alkylthio, it being po~sible for the seven last-mentioned radical to be monosubstituted to trisubstituted in the phenyl moiety by halogen, nitro, cyano, (C1-C4)alkyl, (Cl-C4)alkoxy, (C1 C4)alkylthio, (Cl-C4)haloalkyl or (C1-C4)haloalkoxy, or (c2-c4)alkenyloxy~
~C2-C4)alkynyloxy, (Cl-C4)haloalkoxy, (Cl-C4)alkoxy-(Cl-C4)alkoxy or (C1-C4)alkylthio-(C1-C4)alkylthio, Rl is hydrogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C2-C6)-alkenyloxy, (C2-C6)alkynyloxy, (C1-C4)alkylthio, halogen, phenyl, it beinq possible for the phenyl radical to be monosubstituted to trisubstituted by halogen, nitro, cyano, (C1-C4)alkyl, (Cl-C4)alk-oxy, (C1-C4)alkylthio, (Cl-C4)haloalkyl or (Cl-C4)haloalkoxy, or 30 R8 and R10 together form a polymethylene chain of the formula -(CH2) m- where m = 3 - 4, Rl1 and R12 are independently of one another hydrogen or (C1-C4)alkyl, Y is N or -CRl and n is 1-3, and their acid addition salts.

The alkyl, alkenyl or alkynyl radicals here can be both straight-~hain and branched. Halogen is F, Cl, Br and I, preferably F, Cl and Br. The prefix "halo~' in the 2~833~

description of a substituent here and in the following means that this substituent can occur once or several times with the s~ne or a different meaning. The prefix 'halo" comprises fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine. Examples of haloalkyl which may be mentioned are: CF3, CF2CHF2, CF2CF3, CC13, CC12F, CFzCF2CF3~ CF2CHFCF3 and (CF2)3CF3- ExampleS of haloalkoxy are OCF3, OCF2CHF2 or OCF2CF2CF3.

Preferred compounds of the formula I are those in which Rl, R2, R3 and R4 are independently of one another hydro-qen, halogen, (C1-C2)haloalkyl or (C1-C3)alkyl, R5 and R6 are independently of one another hydrogen, ~C1-C3)alkyl or phenyl, it being possible for the phenyl radical to be monosubstituted to trisub-stituted by halogen or (C1-C4)alkyl, R7 is hydrogen, R3 and R9 are independently of one another hydrogen, (Cl-C6)alkyl, (C3-C6jcycloalkyl, (Cs-C6)cycloalkyl-(C1-C3~alkyl, halogen, phenyl which can be mono-substituted to tri~ubstituted by halogen, (C1-C4)alkyl or (Cl-C4)alkoxy, or (C2-C4)alkenyloxy, (C2-C4)alkynyloxy, ( C~-C4 ) haloalkoxy or ( Cl-c4 ) alk-oxy-(C1-C4)alkoxy R10 is hydrogen, (C1-C4)alkyl, halogen, phenyl, it being possible for the phenyl radical to be monosubstituted to trisubstituted by halogen or (Cl-C3)alkyl, or (C1 C3 ) alkoxy or R3 and R10 together form a polymethylene chain of the formula -(CH2) m~ where m - 3 - 4, Rl1 and Rl2 are hydrogen, Y is N or -CR10 and n = 1, and their acid addition salts.

The following acids are suitable for the preparation of the acid addition salts of the compounds of the formula I:
hydrohalic acid such as hydrochloric acid or hydrobromic 20~8338 acid, and in addition phosphoric acid, nitric acid, sulfuric acid, mono or bifunctional carboxylic acids and hydroxycarboxylic acids such as ~cetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid or lactic acid, and sulfonic acids such as p-toluenesulfonic acid or 1,5-naphthalene-disulfonic acid. The acid addition salts of the compounds of the formula I can be obtained in a simple manner by customary salt formation methods, for example by dis-solving a compound of the formula I in a suitable organic solvent and adding the acid and are isolated in a known manner, for example by filtering off, and, if desired, purified by washing with an inert organic solvent.

The present invention also relates to a process for the preparation of the compounds of the formula I.

These compounds can be prepared by the following variants:

1~ Pyridine derivatives of the formula I where R9 = H
and Y = -CR10 can be obtained by reductive dehalogen-ation of appropriate halopyrimidines of the formula I in which R9 - halogen (for example Cl, Br, or I) and the remaining substituents are as defined in formula I.

The dehalogenation can be carried out with hydrogen in the presence of catalysts (for example palladium/carbon) in an inert solvent, for example water, lower alcohol (such as methanol and ethanol), ethyl acetate or toluene or mixtures thereof. The addition of base~ such as alkali metal hydroxides or alkali metal carbonates or alkaline earth metal hydroxides or alkaline earth metal carbonates is advantageous. The reaction i~ carried out in the range 15-60C under a pressure of 1 to 5 bar.

2) Pyridine derivatives of the -formula I, in which R9 2~83~

is (C~-C4)alkoxy, (Cl-C4)alkylthio, phenoxy, phenyl-mercapto,phenyl-(C1-C4)alkoxyorphenyl-(Cl-C4)alkyl thio, it being possible for the 4 last-mentioned radicals in the phenyl moiety to be mono~ubstituted to trisubstituted by halogen, nitro, cyano, (Cl-C4)alkyl, (Cl-C4)alkoxy, (C1-C4)alkylthio, (Cl-4)haloalkylor(C1-C4)haloalkoxy,or(C2-C4)alkenyl-oxy (C2-C4)alkynyloxy, ( C~-C4 ) haloalkoxy, (C1-C4)alk-oxy-(Cl-C4)alkoxy or(C1-C4)alkylthio-(C1-C4)alkylthio and Y is -CRl, can be prepared by reaction of the appropriate halopyrimidines I (R9 = halogen) with an alkali metal compound of the formula II RaM (II), in which R9 has the abovementioned meaning and M is an alkali metal (for example Li, Na or K).

The reaction can be carried out between 0~C and 130C in the course of 0.5 h to 72 h. The alkali metal compound (II) can be employed in amounts of 1 to 2 mol equivalents relative to 1 equivalent of the halopyrimidine (I) (R9 = halo~en). The reaction is usually carried out in the presence of a solvent.

In the cases in which an alkali metal compound R9M
is employed in which R9 is (Cl-C4)alkoxy, phenyl-(C1-C4)alkoxy, (C2~C4)alkenyloxyl (C2-C4)-alkynyloxy, (C1-C4)haloalkoxy or (C1-C4)alkoxy-(Cl-C4)alkoxy, the corresponding alcohol R9OH or an ether (for example diethyl ether, dioxane or tetrahydrofuran) or a mixture thereof is used as the solvent.

In the cases in which an alkali metal compound is employed in which R9 is (Cl-C4)alkylthio, phenoxy, phenylmercapto, phenyl-(Cl-C4)alkoxy or phenyl-(C1-C4)alkylthio, an ether (for example diethyl ether, dioxane or tetrahydrofuran), a nitrile (for example acetonitrile), an aromatic hydrocar~on (for example toluene or xylene) or a mixture thereof is used as the solvent.

~g338 3) Pyridlne derivatives of the formula I, in which R9 is (Cl-C6)alkyl, ( C3-c7 ) cycloalkyl, 1 C3-C7 ) cycloalkyl-(cl-c4)alkyl~(cl~c4)alkoxy-(cl-c4)alkylr(cl-c4)alkyl-thio-(Cl-C4)alkyl or phenyl, it being possible for the last-mentioned radical to be monosubstituted to trisubstituted by (Cl-C4)alkyl or (Cl-C4)alkoxy, and Y is -CR10, can be obtained by reaction of appropri-ate halopyrimidines I (R9 = halogen) with Grignard compounds R9MgX (III), where R9 is defined a~ indi-cated above and X is halogen (Cl, Br or I), in the presence of nickel-phosphine complexes such as, for example, 1,2-bi~(diphenylphosphino)ethane-nickel(II) chloride or 1,3-bis(diphenylphosphino)propane-nickel(II) chloride (cf. Chem. Pharm. Bull. 26, 2160 (1978)).

The reaction can be carried out in the course of 2 - 48 h between 0C and 80C or at the boiling point of the solvent. The Grignard compound R9MgX is in this case employed in amounts of 1-2.5 mol equivalents relative to 1 equivalent of halo-pyrimidine (I). Suitable solvents are ethers such as, for example, diethyl ether, THF, dioxane and dime~hoxyethane.

The halopyrimidines I (R9 = halogen) can be obtained by reaction of the appropriate hydroxypyrimidines (I), in which R9 is the radical OH and the other substituents have the meanings as in formula I, with halogenating agents. Halogenating agents which can be employed are, for example, thionyl chloride, phosgene, phosphorus oxychloride, phosphorus pen-tachloride, phosphorus oxybromide or phosphorus tribromide. The reactions can be carried out in a solvent, but also without solvent. The halogenating agent is employed in amounts of 1 to ~ equivalents relative to 1 equivalent of the hydroxypyrimidine lI) (R9 = 0~). The reactions can be carried out in a temperature range from 25 to 160C. Solvents used ~0~833~

are, for example, aromatic hydrocarbons (for example benzene or toluene, inter alia) or halogenated hydrocarbons (for example chlorobenzene).

The hydroxypyrimidines (I) (R9 = OH) can be prepared by condensation of the amidine derivatives (IV) with ~-oxocarboxylates V
; - _7 .. I `

;.; ~R
' - _ 3 ? ^ 2 :~3 :~
. ~
I~ V
in which Rl-R8, R10-Rl2 and n are as defined in formula I, X is halogen (for example chlorine, bromine or iodine) and Rl3 is lower alkyl radicals such as methyl, ethyl and propyl.

The reactions are carried out in the temperature range from 20 to 110C within the course of 2 - 72 h. The ~-oxocarboxylate (V) can be employed in amounts of 1 - 1.5 equivalents relative to 1 equivalent of amidine derivative (IV). The reaction is carried out in the presence of a base and of a solvent. Bases used can be, for example, inorganic bases such as alkali metal hydroxide6 and carbonates or organic ba~es such as ~odium alkoxides, trialkylamines and N,N-dialkylanilines. Solvents used are lower alcohols (such as methanol and ethanol), cyclic ethers (such as dioxane and THF), pyridine, N,N-dimethylformamide, water or mixtures thereof. The amidine derivatives t~V) and the ~oxocarboxy:Late~ can be prepared by proces6es known per se (cf. J. Org. Chem. 32, 1591 (1967) and ~8~3~

S~-~nthesis 1982, 451 and Organikum 1986, 516 et seq.).

4) Pyridine derivatives of the formula (I), in which R~
= R9 and is (Cl-C4)alkyl, phenyl-(C1-C4)alkyl or phenyl, it being possible for the two last-mentioned radicals to be monosubstituted to trisubstituted in the phenyl moiety by halogen, nitro, [lacuna]
(C1-C4)alkyl, (Cl-C4)alkoxy, (Cl-C4)alkylthio, (Cl-C4)haloalkyl or (C1-C4)haloalkoxy, and Y is N, can be prepared by reaction of the amidine derivatives IV with an imidate derivative of the formula VI in which R9 [sic]

?~ C~ 3 (VI), has the abovementioned meaning and R13 is as defined in formula v (cf. also JOC 27, 3608 (1962~).

lS The reaction can be carried out in the presence of a solvent or, alternatively, without solvent.
Suitable solvents are lower alcohols such as methanol and ethanol. The reaction is carried out in the temperature range from 10C to 100C. The imidate derivative (VI) can be employed in amounts of 2 to 5 equivalents relative to 1 equivalent of amidine derivative IV.

The compounds of the formula (I) according to the inven-tion are distinguished by an excellent fungicidal action.
Causative organisms of fungal disease which have already penetrated into the plant tissue can be successfully controlled in a curative manner~ This is particularly important and advantageous in those fungal diseases which, after infection has occurred, can no longer be controlled effectively with the otherwise customary ~68338 funaicides. The spectrum of action of the compounds claimed includes a plurality of various economically important phytopathogenic fungi, such as, for example, Piricularla oryzae, Venturia inaequalis, Cercospora beticola, powdery mildew species, Fusarium species, Plasmopora viticola, Pseudoperonospra cubensis [sic], Leptosphaeria nodorum, Drechslera, various rust fungi and Pseudocercosporella herpotrichoides. Benzimidazole- and dicarboximide- sensitive and -resistant Boytritis cinerea [sic] strains are particularly well controlled.

The compounds according to the invention are in addition also suitable for use in industrial fields, for example as wood preservatives, as preservatives in paints, in cooling lubricants for metal processing or as preserva-tives in drilling and cutting oils.

The invention also relates to agents which contain thecompounds of the formula I in addition to suitable formulation auxiliaries.

The agents according to the invention in general contain the active compounds of the formula I in amounts of 1 to 95% by weight.

They can be variously formulated, depending on how it is prespecified by the biological and/or physicochemical parameters. Suita~le formulation possibilities are therefore:

Wettable powders (WP), emulsifiable concentrates (EC), aqueous solutions ~SC), emulsions, sprayable solutions, dispersions having an oil or water base (SC), ~uspo-emulsions (SC), dusting agents (DP), seed dressings, granules in the form of micro-, spray, absorption and adsorption granules, water-dispersible granules (WG), ULV
formulations, microcapsules, waxes or baits.

These individual formulation types are known in principle 2~833~

and are described, for example, in: Winnacker-Kuchler, "Chemische Technologie" (Chemical Technology), Volume 7, C- Hauser Verlag Munich, 4th Ed. 1986; van Falkenburg, "Pesticides Formulations", Marcel Dekker N.Y., 2nd Ed.
1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed.
1979, G. Goodwin Ltd. London.

The formulation auxiliaries required such as inert materials, surfactants, solvents and other additives are likewise known and are described, for example, in:
Watkins, "Handbook of Insecticide Dust Diluents and Carriers , 2nd Ed., Darland Books, Caldwell N.J.; H.Y.
Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y.; Marschen [sic], "Solvents Guide", 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964;
Schonfeldt, "Grenzflachenaktive Athylenoxidaddukte"
(Surface-active ethylene oxide adducts), Wiss.
Verlagsgesell., Stuttgart 1976; Winnacker-Kuchler, "Chemische Technologie~ (Chemical Technology), Volume /, C. ~auser Verlag Munich, 4th Ed. 1986.

On the basis of these formulations, combinations with other pesticidally active substances, fertilizers and/or gro~th regulators can also be prepared, for example in the form of a finished formulation or as a tank mix.

Wettable powders are preparations which can be uniformly dispersed in water and, apart from the active compound and a diluent or inert substance, additionally contain wetting agents, for example polyoxyethylated alkyl-phenols, polyoxyethylated fatty alcohols, alkyl- or alkylphenolsulfonates and dispersing agents, for example sodium ligninsulfonate, sodium 2,2'-dinaphthylmethane-6r6'-disulfonate, sodium dibutylnaphthalenesulfonate or, alternatively, sodium oleylmethyltaurate. Emulsifiable ; concentrates are prepared by dissolving the active 2~3C~8 compound in an organic solvent, ~or example butanol, cyclohexanone, dimethylformamide, xylene or, alter-natively, higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. Examples of emulsifiers which can be used are.
alkylarylsulfonic acid calcium salts such as Ca dodecyl-benzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl pol~glycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide [lacuna] sorbitan fatty acid esters, polyoxy-ethylene sorbitan fatty acid esters or polyoxyethylene sorbitol e~ters.

Dusting agents are obtained by grinding the active compound with finely divided solid substances, for example talc, natural clays such as kaolin, bentonite, poryphillite [sic] or diatomaceous earth. Granules can either be prepared by spraying the active compound onto adsorptive granulated inert material or by applying active compound concentrates by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or, alternatively, mineral oils, to the surface of support substances such as sand or kaolinites or of granulated inert material. Suitable active compounds can also be granulated in the customary manner for the pre~aration of fertilizer granules - if desired mixed with fertilizers.

In wettable powders the active compound concentration is, ~or exarnple, about 10 to 90% by weight, the remainder to 100~ by weight is composed of customary formulat.ion com-ponents. In the case of emulsifiable concentrates, the active compound concentration can be about 5 to 80% by weight. Dust-like formulations contain mostly 5 to 20~ by weight of active compound, sprayable solutions about 2 to 20~ by weight of active compound. In the case of granules, the active compound content partially depends on whether the active compound is liquid or solid and which granulation auxiliaries, fillers etc. are used.

20~8~3~

In addition, said active compound formulations optionally contain the adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, filler~ or support substances customary in each ca~e.

For application, the concentrates present in commercial form are optionally diluted in a customary manner, for example by means of water in the case of wettable pow^
ders, emulsifiable concentrates, dispersions and some-times even in the case of microgranulates. Dust-like and granulated preparations, and sprayable solutions are customarily not diluted further with other inert substan-ces before application.

The application rate required varies with the external conditions such as temperature, humidity and the like. It can vary within wide limits, for example between 0.005 and 10.0 kg/ha or more of active substance, but it is preferably between 0.01 and 5 k~/ha.

The active compounds according to the invention in their commercial formulations can be applied either alone or in combination with other fungicides known from the litera-ture.

Examples of fungicides known from the literature which, according to the invention, can be combined with the compounds of the formula I are the following products:
imazalil, prochloraz, fenapanil, SSF 105, triflumizol, PP 969, flutriafol, BAY-ME~ 6401, propiconazole, etaconazole, diclobutrazol, bitertanol, triadimefon, triadimenol, fluotrimazole, tridemorph, dodemorph, fenpropimorph, falimorph, S-32165, chlobenzthiazone, parinol, buthio~ate, fenpropidin, triforine, fenarimol, nuarimol, triarimol, ethirimol, dimethirimol, bupirimate, rabenzazole, tricyclazole, fluobenzimine, pyroxyfur, NK-483, PP~389, pyroquilon, hymexazole, fenitropan, UHF-8227, cymoxanil, dichlorunanid [sic], captafol, captan, folpet, tolylfluanid, chlorothaloni], 2~3~8 etridiazole, iprodione ~formula II), procymidone, vinclozolin, metomeclan, myclozolin, dichlozolinate, fluorimide, drazoxolan, quinomethionate, nitrothal-i~opropyl, dithianon, dinocap, binapacryl, fentin acetate, fentin hydroxide, carboxin, oxycarboxin, pyracarbolid, methfuroxam, ~enfura [sic], furmecyclox, benodanil, mebenil, mepronil, flutalanil, fuberidazole, thiabendazole, carbendazim, benomyl, thiofante [sic], thiofanate-methyl [sic], CGD-94340 F, IKF-1216, mancozeb, maneb, zineb, nabam, thiram, probineb, prothiocarb, propamocarb, dodine, guazatine, dicloran, quintozene, chloroneb, tecnazene, biphenyl, ~nilazlne, 2-phenylphenol, copper compounds such as Cu oxychloride, oxine Cu, Cu oxides, sulfur, fosetylaluminum [sic], sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium C13/C15 alcohol ether sulfonate, sodium cetostearylphosphate ester, dioctyl sodium sulfosuccinate, sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfcnate, cetyltrimethylammonium chloride, Salts of long-chain primary, secondary or tertiary amines, alkylpropylenamines, laurylpyridinium bromide, ethoxylated quaternized fatty amines, alkyldimethyl-benzylammonium chloride and 1-hydroxyethyl-2-alkylimid-azoline.

The abovementioned combination components are known active compounds, many of which are described in CH [sic].~. Worthing, U. [sic]S.B. Walker, ~The Pesticide Manual", 7th Edition (1983), British Crop Protection Council.

The active compounds according to the invention, in particular those of the examples mentioned, can in addition be present in their commercial formulations and 3 3 ~

in the application forms prepared from these formulations mixed with other active compounds, such as insecticides, attractants, sterilants, acaricides, nematicides, fun gicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin cornpounds, substances produced by microorganisms and the like. Preferred mixture components are:

1. from the phosphoric acid ester group azinphos-2 ethyl, azinphos-2 methyl, 1-(4-chloro-phenyl)-4-(O-ethyl, S-propyl)phosphoryl-oxypyrazole (TIA-230), chlorpyrifos, coumaphos, demeton, demeton-S-methyl, diazinon, dichlorvo~, dimethoate, ethoprophos, etrimfos, fenitrothion, fenthion, heptenophos, parathion, parathion-methyl, phosalone, pirimiphos-ethyl, pirimiphos-methyl, profenof GS, prothiofos, sulprofos, triazophos or trichlorophon.

2. from the carbamate group aldicarb, bendiocarb, BPMC (2-(1-methylpropyl)-phenylmethyl carbamate), butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl, oxamyl, primicarb[sic], promecarb, propoxur or thiodicarb.

3. from the carboxylic acid ester group . 25 allethrin, alphamethrin, bioallethrin, : bioresmethrin, cycloprothrin, cyfluthrin, . cyhalothrin, cypermethrin, deltamethrin, alpha-cyano-3-phenyl-2-methylbenzyl 2,2-dimethyl-3-(2-chloro-2-trifluoromethylvinyl)-cyclopropanecarboxy-late (FMC 54800), fenpropathrin, fenfluthrin, fen-valerate, flucythrinate, flumethrin, fluvalinate, permethrin, resmethrin or tralomethrin.

4. from the formamidine group amitraz or chlordimeform 2 ~ 3 ~

5. from the tin compound group azocyclotin, cyhexatin and fenbutatin oxide 6. Miscellaneous abamektin, Bacillus thuringiensis, bensultap, binapacryl, bromopropylate, buprofecin, camphechlor, cartap, chlorobenzialate [sic], chlorfluazuron, 2-(4-chlorophenyl)-4,5-diphenylthiophene (UBI-T 930), chlofentezine, 2-naphthylmethyl cyclopropanecar-boxylate (Ro 12-0470), cyromacin, DDT, dicofol, N-(3,5-dichloro-4-(1,1,2,2-tetrafluoroethoxy)phenyl-amino)carbonyl)-2,6-difluorobenzamide (XRD 473), diflubenzuron, N-(2,3-dihydro-3-methyl-1,2-thiazol-2-ylidene)-2,4-xylidine, dinobuton, dinocap, endo-sulfan, fenoxycarb, fenthiocarb [sic], flubenzimine, flufenoxuron, gamma-HCH, hexythiazox, hydramethylnon (AC 217 300),ivermectin,2-nitromethyl-4,5-dihydro-6H-thiazine (SD 52618), 2-nitromethyl-3,4-dihydro-thiaz~le(SD 35651),2-nitromethylene-1,3-thiazinan-3-yl-carbamaldehyde [sic] (WL 108 477), propargite, teflubenzuron, tetradifon, tetrasul, thiocyclam, triflumaron, core polyhedrosis and granulosis viruses.

The active compound content of the application forms prepared from the cornmercial formulations can vary within wide ranges, and the active compound concentration of the application forms can be from 0.0001 up to 100% by weight of active compound, preferably between 0.001 and 1% by weight. Application is carried out in one of the custom-ary ways 6uited to the application forms.

The following examples serve to illustrate the invention.

A. Formulation example~

a) A dusting agent is obtained by mixing 10 parts by weight of active compound and 90 parts by weight of talc as the inert substance and comminuting the 2~g33~

mixture in a hammer mill.

b) A wettable powder which is e~sily dispersible in water is obtained by mixing 25 part by weight of active compound, 64 parts by weight of kaolin-containing quartz as the inert sub~tance, 10 parts by weight of potas~ium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurate as the wetting agent and dispersant and grinding the mixture in a pinned disk mill.

c) A dispersion concentrate which is easily dispersible in water is obtained by mixing 40 parts by weight of active compound with 7 part~ by weight of a sul-fosuccinic acid half-ester, 2 parts by weiyht of a sodium ligninsulfonate and 51 parts by weight of water and grinding the mixture in a friction ball mill to a fineness o less than 5 microns.

d) An emulsifiable concentrate can be prepared from 15 parts by weight of active compound, 75 parts by weight of cyclohexanone as the solvent and 10 parts by weight of oxyethylated nonylphenol (10 E0) as the - emulsifier.

e) Granules can be prepared from 2 to 15 parts by weight of active compound and an inert granulate support material such as attapulgite, pumice ; 25 granules and/or quartz sand. Expediently, a ~uspen-sion of the wettable powder from Example b) having a solid~ content of 30% is used and this is sprayed onto the surface of attapulgite granules, dried and mixed intimately. The weight content of the wettable powder here i8 about 5% and that of the inert support material is about 95% of the finished granules.

2~33~

B. Chemical exa~ples 2-(6-Benzylpyridin-2-yl)-4-propylpyrimidine (Example No.: 1.2) 0.2 g of 5% palladium/carbon is added to a solution of 3.24 g (0.01 mol) of 2-(6-benzylpyridin-2-yl)-6-chloro-4-propylpyrimidine in 50 ml of ethanol. ~his mixture is brought into contact with hydrogen under a pressure of 3 bar and at a temperature of 60C with vigorous stirring for 2 h. The catalyst is then filtered off and the filtrate is concentrated in vacuo. The residue is taken up in water, saturated with sodium bicarbonate and extracted with CH2Cl2. The organic phase is dried over Na2S04 and concentrated. 2.85 g (98.6%) of a yellowish oil are obtained.

2-(6-benzylpyridin-2-yl)-4-methoxy-6-phenylpyrimidine (Example No.: 1.15) A sodium methylate solution is prepared by dissolving 0.184 g (0.008 mol) of sodium in 40 ml of abs. methanol.
1.79 g (0.005 mol) of 2-(6-benzylpyridin-2-yl)-4~chloro-6-phenylpyrimidine is added to this solution and the mixture is boiled under reflux for 3 h. It is then concentrated, water is added to the residue and the mixture is extracted with methylene chloride. The organic phase i5 dried using Na2S04 and concentrated. After crystallization from diisopropyl ether, 1.49 g (84.3%) of a colorless solid are obtained.
Melting point: 128 - 129C

2-(5-benzylpyridin-2-yl)-4,6-dimethyl-1,3,5-triazine (Example No. 2.L) 2.47 g (0,01 mol) of 6-benzyl-2-picolinamidine hydrochlo-ride are stirred together with 3048 g (0.04 mol) of ethyl acekimidate at 60c for 2 h. The reacticn mixture is then taken up in water and extracted with CHCl3. The organic 20~833~
~ 18 -phase is washed with water, dried over Na2SO4 and con centrated. The residue is subjected to column chromatog-- raphy (eluent: methylene chloride). 1.62 g (58.7%) of a colorless oil are obtained.

The compounds of Table A can be prepared analogously to these examples.

3 3 ~

,,.~ r,~
r~ ~ r,~
r~ O r~ r~ i~,q J ~ _ ~ ~3 ~ ~ r~
rrJ r~ r~ V d' '~ ~`
~ 3 . ~ _ 3 ~ r.~
_~ r~
ra ,r~ ~ ~ r,~
-1 '-- N ~ r~ L'l ~ N ~D ~ O
ui . rD ~ r~ rJ~ z N r.~ r ~
r . = r,~o r,~ r~ o` ~ r;o r~ ~D r.~J o ~ L _ ~ ~a rE ~ ~ ~1 ~ E

._ _ _ 'J r ) V

r~ _ _ O
-V J V
~_~Z ~ __ N
.2 v,~ 3~

~ n L'7 3 T :C
U U r~-) r.~ r,~ N
C;l :C 3 T
V V J

.

Z ~ ~1 ~8~3~

C~ _ [,, ~ C _ _-U~ ~ ~ r.\l J~ r,~l r~ I
~ ~ 1~ !` r~,~ Z r~ r.~ r~ r ~r" Z rD ~ Z
,~ ~ w~ ~) r~ O ~ 7r~ O :~ D 1` -- -- -~ EU~ ~ ~ ~ ~ E (l~ ~ ~ ~ ~~; ~ ~, ..

::- r_, ~J ~ U ~

-I! = U~
r) 11l _ 0 ~
;:~ r = ~
O 0 0 ~7 ~J J _ O

rl ,~ r~
~ ~ ~ ~ _ = _ _ r~
~ ~ r ) ~ r~ r~ r~
r~ _ ~ r ~ = ~ = _ ~D~

,r~
E~

O Lr~ L'l L')L'') L') L'') Lr~ L'~
c O ~D `D `D `D ~O ~ ~D
.~ r~) r~) r~ C,) ~ r~ ) r~ ) r~
~a ~ r~l r,~ r~\~ r,~l r X ~. 3 X

. r~
O O ~ Lr~ 0 rJ~
~ æ . . ...
~ r~ ~ ~ r~ ~1 ~ ~

206~3~$

r ~ o r~ ~_ r I' ) r~
~~ ~ C ~ r~
rr~
~) I ~ r~
~ ~ (~ C' r~
e~ E ~ a ~ J J ~) ~) ~ rJ

' L'~

'J~ ' ~ ~r , N ~,` "~
O ~,') = O O~? _-- -- ~ t/? O _) ~ V

LJ J J ~J
_ I ~ I I
~ ~ L') Lrl L~ L'~ ~ ~ ~ ~ L'l L~ L') L') L^
'~ '_, -- '`~D ~) ~D ~O ~` ? ~ ? '~ ? ~i? \~
_~ ~J r,, r ~ rJ rJ 'J rJ rJ rJ rJ U V C.) j I
2 2 2 2 2 _ _ _ = _ Lr) U~
r~ ,r.~ 2r~ =
_ _ ~ 3: 2 5 ~ 2 Ti 5 ~ J ~r rJ _ =
L~l L^ ~ X 1 5 X 5 2 2 t ) V J 5 5 $~ -- V
r¢
Q) _~

E~ ~ ~
L'~ L')L~l Lr~ Lr~ L') L') U) L'l L'~
O L'~ L' l ~ D 5 X 5 5 5 :r: 5 -- X V U ~ ? ~ r.) V V
~D \D I I t.) V ~) ~ ) rJ ~ r~ ) O t ) V r.~l r,~ r~ r,~ r,~
~ N T ~ V 3 ~ ~-- ~r 5, 5 X X ~V V V

.~
~ N r~) ~ Ll~ ~r~ O~ O ~1 ~ ~) ~ Lr~
~ 1 r\~ r~ ~r ~ r~ r~ J
O O I
r~ r~~ r~~ lr-~ ~1 ~ ~ r-l ~ ~--1 2~83~

-- 2 2 -- ~V ?,1 .. . .

.~ --I~V r'^~
_~ ~ ~
r~a ~ C
~n I ~ .
~ :~ r. ~ C~
_ ~ ~ ~;
L"
Ll~ L'~ ? I
`5 5 ~) ~
8 - = ~ = = V 'J V CJ o o 'J '~) ' ) ' V O O V V O 'J ' ) !

=
J
=
r rJ
_ rJ ! ) L~ L'l ?~l ? l ~_~ ?') =
-- _ ?`~
'^' ' rJ ;j ~ ) r ~ r~) ~ V r ) V ----. O O r ) O O _ ~) O r~l) ~ O _ ' _ r.~

_ ? ~ r\~
J r' , ~ -- ., N
r ~ ?~ r~ ?
= _ ~ r~ ) r~) r,~l r.~ r~ ~ ?~
_. l ~ - ~-) r`) v ,.`-, d' _ -- = = -- r ~ -- r.
'', y y O O O V V V r~ r ) V O V t,) _, __ _ _ _ ~ 2 2 _ 2 ~
L'`) ~rv S '~~ 2 ~ ~ 2 ~ -- 2 2 ~I
u~ 1:
-- C~
Lr)V5 :~ I ~ X 2 ~ 2 ~ :~: 2 a) v '~) l l r~?~ ~r~
L ~
, ~ L" L~ 2 ~r ~--1 r~ r7 r~ '~ _ ., L'') L'`) 5 5 O ~ v 2 X Ll ) Lr) U-) Ul V V
~r~r ~ V V 5`S) ~ ~ L~
C x ~ ~ I I ~.) V ~ 2 2 u-O ~v `5 5 N N I I ~_) V ~ ~v 2 V V tJ ~ 2 ?~ r~)r,~ ?~ r~ r~r~ r~) r~) V ~D
2 ~ r 2 2 f~l N N N ?~ N N V ~ ) V ~_) V ~_) V N
::1 -- -- X -- -- ~ 2 = 2 2 ~ X ~
V'~ ) O O V C~ U V C) O V V V V
J~
C: 0 vn~ O r~~ ('\1 ?~ r~ Lr) ~D 1~ 0 v~ O r'~ N
O ?~ N r~ r~) r~) r~ r~) r.~ r~ r~r) r~
~'~ O~ , ............ .

20~83'~8 _ 23 --r~ 't~ r7 C? ~ r O o O~? Or.7 0 r.7 O ~ r~
t ,, ~ rr~_ r~ ~ ~ ~ ~ r r~ I r7 ~ ~?r7 ~1i?r7 ~ r? ~ ~r,? ~7 ~ ~ ~7 ~ ~ .J
¦rJ r.~ L?_) ~r~O ~(? ~ C) ~ r~ _) L") ~D --~ I a ~D r.7 a ~ , a ~ Lr) a ~ .n a ~D rJ a ~r? r.7 Lr~
'~ I ~ U~ V ~ V u~ ~ ~ V V V U~
r~?~ ~ ~ ~ ~ c~ rV
G ~ O ~ ~O ~~ C~ r~
Z r\l L') Z rl O Z~1 0Z r~ O ~r Z N ~r ~ Z c~
? ~ r~? ~ ~rl? ~D ~1 ~ rl? ~
? ,1 ~? ~? ,1 ~ J? ~ ~r~ ~? ~ ,1 ~ ~? ~ ~ ~ ~ _ r,_~ ~J
r7 r7 _ J
~L?
r7 r~ r~ '~
_ ~ ~- r~
G~ r ~ r~_)rJ r~
,~ o rJ? rJ~ O

~1 L'~
~ ~ ~ ~r r~
~ ~ ,,, r~ _ rw L~ L'') Lr) C:~ ~,) r~ ~.) O r~ O
r_ r,~ ~ -- :C X

~D
~ ~ 3 U
~Y :~ X 3 r~

r~
L_l O L-) L.n L~ L~
O ~? ~? ~ L?
r~ r~ r~ r~ r.~ r~

.~ ~ r~
C O ~ d' d' O æ~

~0~8~3~

r~ r,~
~`, O Lr~
_ '~ r J
~O ~ ` ' "~ '^ ~,!
~ C _) g~) r~-) r~
~ ~ O
~0 ,, ~ ~ ~ ~ ~n D
t~ C r~ C
Z ~`i ,~
r,~ ~`
~ ~ E

r~
.~ = x ~ ~ m ~ o ~ -r~
X
-- _-__, 1 r~) r~) r~ _ L'~ ~ O 1~
r~ ~ r~) r~') r~ T ,_, r~) ~ -- _ -- T r") r.~ D

D ~
r~ ~ . X~ X X _ X ~ ~ X ~ ~ = ~ = _ ~ --~ XX X ~ X ~ -- X ~ ~ X ~

ta _ ~
E~

Lr~ Lr)Lt ~ Ln Lr~ _ _ O ~ ~ ~ X X~ D ~D ~ D ~ D ~D ~ J
1~ r ~I ~N N N N N N N N N N N N N t~ `
C: -- X~ XXXXX ~'_--,--,~
.,.1 O OC`~ L~ L~ O ~ N r C" -'`

2~833~
-- ~5 _ O ~D

~ a . ~

I Z ~ o CO
~, ~ ~ O ~ ~ O ~) ~
~ o t~ U ~

~ , o o ~ _ -- ~

_ C~
5 0t` L~) L~l ~ L') tJ ~ u t~ ) v c~ u u u c~ u u r Ll-)L~l T ~
~D ~ C 3 1 -- ~ t-) U ~ r ~ X ~ ~ X ~ T T X

N
L'~ X X ~ X ~ 1 2 ~ :: 3 T ~ ~:C rq X :C ~ _ r~ ~ ~ U ~r a) _ . ~ r,q O ~q ~q U
_I U O O L~ U t ) .4~,) U t) U d' d' Il~ Ul Lrl 11~ Lt~ ~ 1~ t~ O I O C~ I --~ d~ ~r ~ r~ r~ q tq r1 ~ r.~ ~ ~ ~ ~ d' N
O ~ d' ~ d' ~ r~ r~ rq ~q ~q ~q ~ ~ ~ ~ ~ d' d' r'~
~ T T X ~r X S T T ~ S X ~ 3 X X 3: T
O O U ~ U ~ ~ U U U C~ C~
N N N N ~ N ~ N ~ ~ N ~ t~ N N N N N N N N N

O U o ~ O U ~ ~X X X 3~ ~3 T X _ C
~D t~ rD 0~ O ~ N F) ~ O 1` r D C~ O ~ N rq ~ L~
C O ~ r ~ ~ rD rD r~q r~ rD

2068~3~
-~; L î
.. _ ..
r, = C ~ ~ r7 o 3 r~ ~ t~ r~ o . r~J .

~, ~ z r~ r^, r) ~ o ~, _ ~ ~ c~ _ r^ r~ c~ --r~ ~ E
a~

Z Z Z Z Z Z Z Z Z Z Z Z ' r~ ~
r, u) r1 --_ ~ = , ~ j c~
ct~
c ~ ~A r,r, r r-- ' L î e'` `~ C

^~

L, r, --c-~r r, ~ ~ ~
r, -- --r~ r~ r _ ' ~ L ' C r~l c~ -, , = ~ = _ = _ _ ~ = . , = _ ~V ~ T ~ _ = r~

L^

_I I L^
r~
E~ U cq z O U- Lr~ Lr) L~ 3 r O
~-l - ~ -r~ r~ r~ ~ r~ r~ r~ r~ r~ ~ r~
11~ 3 r ~ S 3 ~ T
._ ~: ~1 r~ D ~ O ~ r~
c~ z I r.~ ~ ~ r~ r~l r~l r~l r~l r~ r~; r~;

- 27 - 2~;8338 .~

P~

Z Z Z

_ r~,) ~ o C~ ~
_ _ _ a~ ~ r~_ _5 r_~ C

~ Ln ~
~ U ~ U
~ _ _ _ r _ ~ ~_ _~
E~
d~
O u~ ~ ,r C T T ~r ~ U ~J
C~
= ~ _ .
Z r 2~8338 - ~8 -C. Biological Examples Example 1 Rice plants of the "Ballila" type about 5 weeks old were treated with the concentration of the claimed compounds indicated below after prespraying with 0.05~ strength gelatine solution. After the spray coating had dried on, the plants were uniformly inoculated with a spore suspen-sion of Piricularia oryzae and placed for 48 h in a climatic chamber, which was kept dark, having a tempera-ture of 25C and 100% relative atmospheric humidity. The rice plants were then cultivated further in a greenhouse having a temperature of 25C and 80~ relative atmospheric humidity. Evaluation of attack was carried out after 5 days. The degree of attack was expressed in % of attacked leaf surface in comparison to untreated infected controlplants. The results are collated in Table lo T~ble 1 Compound Leaf surface attacked with Piricularia according oryzae in % at mg of active compound/
to Bxample liter of spray liquor . _ 1.3 0 1.2 1.5 0 2.1 0 1.43 0 1.11 0 1.44 0 1.10 0 1.46 o . _ _ untreated infected plants 100 Exa~ple 2 Barley plants were heavily inoculated in the 2-leaf stage with barley mildew conidia (Erysiphe graminis hordei) and cultivated further in a greenhouse at 20C and a relative atmospheric humidity of about 50%. 1 day after inocula-tion, the plants were we~ted uniformly with the compounds listed in Table 2 at the active compound concentration indicated. After an incubation time of 7-9 days, the plants were examined for attack by barley mildew. The degree of attack is expressed in ~ of attacked leaf surface, relative to untreated infected control plants (=
100% attack). The result is summarized in Table 2.

Table 2 Compound Leaf surface attacked with barley according mildew in % at mg of active compound/
to Example liter of spray liquor .. . ....

1.2 0 1.43 0 1.10 0 1.~6 0 .: -untreated infected plants 100 Example 3 Wheat of the "Jubilar" type was treated in the 2-leaf stage with aqueous suspensions of the claimed compounds until dripping wet. After the spray coating had dried on, the plants were inoculated with an aqueous spore sus-pension of Puccinia recondita. The plants were placed dripping wet in a climatic chamber at 20C and about 100%

2~833~

relative atmospheric humidity for about 16 hours. The infected plants were then cultivated further in a green~
house at a temperature of 22-25C and 50-70% relative atmospheric humidity.

After an incubation time of about 2 weeks, the fungi sporulates onto the entire leaf surface of the untreated control plants such that an evaluation of attack of the test plants can be carried out. The degree of attack was expressed in % of attacked leaf surface in comparison to untreated infected control plants and iY reproduced in Table 3.

Table 3 Compound Leaf surface attacked with Puccinia re-according condita in % at mg of active compound/
to Example liter of spray liquor .
1.3 0 1.2 0 untreated infected plants 100 ~ample 4 Wheat plants of the "Jubilar" type were treated in the 2-leaf stage with aqueous suspensions o~ the preparations given in Table 4 until dripping wet.

After the spray coating had dried on, the plants were inoculated with an aqueous pyknospore suspension of Leptosphaeria nodorum and incubated at 100% relative atmospheric humidity in a climatic chamber for several hours. Until expression of symptoms, the plants were further cultivated in a greenhouse at about 9Q% relative atmospheric humidity.

- 31 - 2~83~
The degree of action is expressed as a percentage of the untreated infected control and is reproduced in Table 4.

Table 4 Compound Leaf surface attacked with Leptosphaeria according nodorum in % at mg of actlve compound~
to Example liter of spray liquor 1.43 0 1.11 0 1.44 0 1.46 o 1.14 0 1.5 0 1.4 0 1.3 0 1.2 0 untreated infected plants 103 ~xample 5 Broad beans of the "Herz Freya" or "Frank's Ackerperle"
type about 14 days old were treated with aqueous suspensions of the claimed compounds until dropping wet.

After the spray coating had dried on, the plants were inoculated with a spore suspension (1.5 million spores/ml) of Botrytis cinerea. The plants were cul-tivated further in a climatic chamber at 20-22C and about 99% relative atmospheric humidity. The infection of the plants is manifested by the formation of black spots on the leaves ancl stalks. Evaluation of the tests was carried out 1 week after inoculation.

The degree of action of the test substances was assessed 3 ~ ~

as a percentage of the untreated infected control and is reproduced in Ta~le 5.

Table 5 Compound Leaf surface attacked with ~otrytis according cinerea in % at mg of active compound/
to Example liter of spray liquor 2.1 0 untreated infected plants 100

Claims (6)

Patent claims

1. A compound of the formula I

(I), in which R1, R2, R3 and R4 are independently of one another, hydrogen, halogen, nitro, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)haloalkoxy or (C1-C4) haloalkyl, R5, R6 and R7 are independently of one another hydrogen, (C1-C6)alkyl or phenyl, it being possible for the phenyl radical to be monosubstituted to trisub-stituted by halogen, nitro, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4) haloalkyl, or (C1-C4)haloalkoxy, R8 and R9 are independently of one another hydrogen, (C1-C6)alkyl, (C3-C7) cycloalkyl, (C3-C7) cycloalkyl-(C1-C4)alkyl, it being possible for the two last-mentioned radicals to be monosubstituted to trisubstituted in the cycloalkyl moiety by (C1-C4)alkyl, (C1-C4)haloalkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)alkoxy-(C1-C4)alkyl, (C1-C4)alkylthio-(C1-C4)alkyl, halogen, (C2-C6)al-kenyl, (C2-C6)alkynyl, phenyl, phenoxy, phenoxy-(C1-C4)alkyl, phenylmercapto-(C1-C4)alkyl, phenyl-mercapto, phenyl-(C1-C4)alkoxy or phenyl-(C1-C4)alkylthio, it being possible for the seven last-mentioned radicals to be monosubstituted to trisubstituted in the phenyl moiety by halogen, nitro, cyano, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)haloalkyl or (C1-C4)halo-alkoxy, or (C2-C4)alkenyloxy, (C2-C4)alkynyloxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy or (C1-C4)alkylthio-(C1-C4)alkylthio, R10 is hydrogen, (C1-C4)alkyl, (C1-C4)alkoxy, (C2-C6)-alkenyloxy, (C2-C6)alkynyloxy, (C1-C4)alkylthio, halogen, phenyl, it being possible for the phenyl radical to be monosubstituted to trisubstituted by halogen, nitro, cyano, (C1-C4)alkyl, (C1-C4)alk-oxy, (C1-C4)alkylthio, (C1-C4)haloalkyl or (C1-4)haloalkoxy, or R8 and R10 together form a polymethylene chain of the formula -(CH2)m- where m = 3 - 4, R11 and R12 are independently of one another hydrogen or (C1-C4)alkyl, Y is N or -CR10 and n is 1-3, and their acid addition salts.

2. A compound of the formula I of claim 1, in which R1, R2, R3 and R4 are independently of one another hydro-gen, halogen, (C1-C2)haloalkyl or (C1-C3)alkyl, R5 and R6 are independently of one another hydrogen, (C1-C3)alkyl or phenyl, it being possible for the phenyl rddical to be monosubstituted to trisub-stituted by haloqen or (C1-C4)alkyl, R7 is hydrogen, R8 and R9 are independently of one another hydrogen, (C1-C6)alkyl, (C3-C6)cycloalkyl, (C5-C6)cycloalkyl-(C1-C3)alkyl, halogen, phenyl which can be mono-substituted to trisubstituted by halogen, (C1-C4)alkyl or (C1-C4) alkoxy, or (C2-C4)alkenyl-oxy, (C2-C4)alkynyloxy, (C1-C4)haloalkoxy or (C1-C4)alkoxy-(C1-C4)alkoxy, R10 is hydrogen, (C1-C4)alkyl, halogen, phenyl, it being possible for the phenyl radical to be monosubstituted to trisubstituted by halogen or (C1-C3)alkyl, or (C1-C3)alkoxy or R8 and R10 together form a polymethylene chain of the formula -(CH2)m- where m = 3 - 4, R11 and R12 are hydrogen, Y is N or -CR10 and n = 1, and their acid addition salts.

3. A process for the preparation of compounds of the formula I as claimed in claim 1 or 2, which comprises a) for compounds I where R9 = H, Y = -CR10 and the remaining substituents have the meanings of the formula I, reductively dehalogenating an appropriate halopyrimidine I in which R9 = halogen, or b) for compounds I in which R9 is (C1-C4)alkoxy, (C1-C4)alkylthio, phenoxy, phenylmercapto, phenyl-(C1-C4)alkoxy or phenyl-(C1-C4)alkylthio, it being possible for the 4 last-mentioned radicals in the phenyl moiety to be monosubstituted to trisubstitu-ted by halogen, nitro, cyano, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)haloalkyl or (C1-C4)haloalkoxy, or (C2-C4) alkenyloxy, (C2-C4)alkynyl-oxy, (C1-C4)haloalkoxy, (C1-C4)alkoxy-(C1-C4)alkoxy or (C1-C4)alkylthio-(C1-C4)alkylthio and Y is -CR10, reacting an appropriate halopyrimidine I in which R9 = halogen with a compound of the formula II

R9M (II), where R9 has the abovementioned meaning and M is an alkali metal, or c) for compounds of the formula I in which R9 is (C1-C6)alkyl, (C3-C7)cycloalkyl, (C3-C7)cycloalkyl-(C1-C4)alkyl,(C1-C4)alkoxy-(C1-C4)alkyl,(C1-C4)alkyl-thio-(C1-C4)alkyl or phenyl, it being possible for the last-mentioned radical to be monosubstituted to trisubstituted by (C1-C4)alkyl or (C1-C4)alkoxy, and Y is -CR10 reacting an appropriate halopyrimidine I
where R9 = halogen with a Grignard compound III
R9 MgX (III), where R9 has the abovementioned meaning and X is halogen, in the presence of nickel-phosphine com-plexes, or d) for compounds o the formula I in which R3 = R9 and is (C1-C4)alkyl, phenyl-(C1-C4)alkyl or phenyl, it being possible for the two last-mentioned radicals to be monosubstituted to trisubstituted in the phenyl moiety by halogen, nitro, cyano, (C1-C4)alkyl, (C1-C4)alkoxy, (C1-C4)alkylthio, (C1-C4)haloalkyl or (C1-C4)haloalkoxy, and Y is N, reacting an amidine derivative of the formula IV

(IV), in which R1-R7, R11-R12 and n have the meaning indicated in formula I and X is halogen, with an imidate derivative of the formula VI

(VI), where R9 has the abovementioned meaning and R13 is (C1-C3)alkyl.

4. A fungicidal agent which contains an effective amount of a compound of the formula I as claimed in claim 1 or 2.

5. The use of compounds of the formula I as claimed in claim 1 or 2 for controlling harmful fungi.

6. A method for controlling harmful fungi which com-prises applying an effective amount of a compound of the formula I as claimed in claim 1 or 2 to the plants, surfaces or substrates attacked by them.