WO2001034576A2

WO2001034576A2 - Use of pyrimidinone derivatives for controlling undesired microorganisms

Info

Publication number: WO2001034576A2
Application number: PCT/EP2000/010623
Authority: WO
Inventors: Qinghong Tang; Liang Chen; Jin Cao; Ernst Rudolf F. Gesing; Gerd Hänssler; Karl-Heinz Kuck
Original assignee: Bayer Aktiengesellschaft
Priority date: 1999-11-09
Filing date: 2000-10-27
Publication date: 2001-05-17
Also published as: AU1697701A; CN1294852A; WO2001034576A3

Abstract

Pyrimidinone derivatives of the formula (I) in which R1 represents alkoxy, R2 represents hydrogen or alkyl, R3 represents alkyl or phenyl and R4 represents optionally substituted aryl, optionally substituted heteroaryl or optionally substituted heteroarylalkyl, are very suitable for controlling undesired microorganisms. New pyrimidinone derivatives of formula (Ia) in which R?1, R2 and R3¿ have the above-mentioned meanings and R6 has the meanings mentioned in the specification, and a process of the preparation of the new compounds.

Description

Use of pyrimidinone derivatives for controlling undesired microorganisms

The present invention relates to the new use of pyrimidinone derivatives for controlling undesired microorganisms. Further, the invention relates to new pyrimidinone derivatives and to a process for their preparation.

Certain 2-arylamino-pyrimidinone derivatives are already known (cf. EP-A 0 636 615). However, only herbicidal and plant-growth regulating properties of these compounds have hitherto been described.

It has also been disclosed already that various 2-dialkylamino-pyrimidinone derivatives can be employed for the control of plant diseases (cf. IP- A 190 670-1989 and JP-A 112 566-1988). The activity of these previously known compounds, however, is not always completely satisfactory, if the compounds are applied at low dosages.

It has now been found that the pyrimidinone derivatives of the formula

in which

R¹ represents alkoxy,

R² represents hydrogen or alkyl,

R³ represents alkyl or phenyl and R⁴ represents optionally substituted aryl, optionally substituted heteroaryl or optionally substituted heteroarylalkyl,

are very suitable for controlling undesired microorganisms.

Surprisingly, the compounds according to the invention show markedly better microbicidal activity than the constitutionally most similar prior art compounds of the same indication.

Formula (I) provides a general definition of the pyrimidinone derivatives which can be used according to the invention.

R¹ preferably represents straight-chain or branched alkoxy having 1 to 6 carbon atoms.

R² preferably represents hydrogen or straight-chain or branched alkyl having 1 to 6 carbon atoms.

R³ preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms or represents phenyl.

R⁴ preferably represents aryl having 6 to 10 carbon atoms, wherein each of these groups may be mono- to tri-substituted by identical or different radicals selected from the group consisting of halogen, nitro, cyano, alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxy having 1 to 6 carbon atoms, halogeno- alkoxy having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 8 carbon atoms, phenyl and phenoxy, or

R⁴ preferably represents 5- or 6-membered heteroaryl having 1 to 3 heteroatoms, such as nitrogen, sulphur and or oxygen, wherein each of the heterocyclic groups may be mono- to tri-substituted by identical or different radicals selected from the group consisting of halogen, nitro, alkoxycarbonyl comprising 1 to 6 carbon atoms in the alkoxy group, cyano, alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxy having 1 to 6 carbon atoms, halogeno- alkoxy having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 8 carbon atoms, phenyl and phenoxy, or

R⁴ preferably represents 5- or 6-membered heteroarylalkyl having 1 to 6 carbon atoms in the alkyl group and 1 to 3 heteroatoms, such as nitrogen, sulphur and/or oxygen, in the heteroaryl group, wherein each of the heterocyclic groups may be mono- to tri-substituted by identical or different radicals selected from the group consisting of halogen, nitro, alkoxycarbonyl comprising 1 to 6 carbon atoms in the alkoxy group, cyano, alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxy having 1 to 6 carbon atoms, halogeno- alkoxy having 1 to 6 carbon atoms and 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to 8 carbon atoms, phenyl and phenoxy.

Particularly preferred are pyrimidinone derivatives of the formula (I), in which

R¹ represents straight-chain or branched alkoxy having 1 to 4 carbon atoms,

R² represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms,

R³ represents straight-chain or branched alkyl having 1 to 4 carbon atoms or represents phenyl and

R⁴ represents phenyl or naphthyl, each of which may be mono- to tri-substituted by identical or different radicals selected from the group consisting of fluorine, chlorine, bromine, nitro, cyano, alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl and phenoxy, or

R⁴ represents 5- to 6-membered heteroaryl having 1 to 3 heteroatoms, such as nitrogen, sulphur and/or oxygen, wherein each of the heterocyclic groups may be mono- to tri-substituted by identical or different radicals selected from the group consisting of fluorine, chlorine, bromine, nitro, alkoxycarbonyl comprising 1 to 4 carbon atoms in the alkoxy group, cyano, alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl and phenoxy, or

R⁴ represents 5- or 6-membered heteroarylalkyl having 1 to 4 carbon atoms in the alkyl group and 1 to 3 heteroatoms, such as nitrogen, sulphur and/or oxygen, in the heteroaryl group, wherein each of the heterocyclic groups may be mono- to tri-substituted by identical or different radicals selected from the group consisting of fluorine, chlorine, bromine, nitro, alkoxycarbonyl comprising 1 to 4 carbon atoms in the alkoxy group, cyano, alkyl having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 fluorine, chlorine and/or bromine atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl and phenoxy.

Nery particularly preferred are pyrimidinone derivatives of the formula (I), in which R¹ represents methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, iso-butoxy, sec- butoxy or tert-butoxy,

R² represents hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso- butyl or tert-butyl,

R³ represents methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, iso-butyl, tert- butyl or phenyl and

R⁴ represents phenyl or naphthyl, each of which may be mono- to tri-substituted by identical or different radicals selected from the group consisting of fluorine, chlorine, bromine, nitro, cyano, methyl, ethyl, propyl, isopropyl, n- butyl, iso-butyl, sec. -butyl, tert-butyl, trifluoromethyl, trichloromethyl, chloro-difluoromethyl, methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, trifluoromethoxy, chloro-difluoro- methoxy, trichloromethoxy, cyclopropyl, cyclopentyl, cyclohexyl, cyclo- heptyl, phenyl and phenoxy, or

R⁴ represents thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, isothia- zolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, 1,2,3-triazinyl, 1,2,4- triazinyl, 1,3,4-triazinyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl, wherein each of these heterocyclic groups may be mono- to tri-substituted by identical or different radicals selected from the group consisting of fluorine, chlorine, bromine, nitro, methoxycarbonyl, ethoxycarbonyl, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec. -butyl, tert-butyl, trifluoromethyl, trichloromethyl, chloro-difluoromethyl, methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, trifluoromethoxy, chloro-difluoromethoxy, trichloromethoxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl and phenoxy, or

R⁴ represents a group of the formula -A-R⁵, wherein A represents straight-chain or branched alkylene having 1 to 4 carbon atoms and

R⁵ represents thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl, 1,2,3- triazinyl, 1,2,4-triazinyl, 1,3,4-triazinyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl, wherein each of these heterocyclic groups may be mono- to tri-substituted by identical or different radicals selected from the group consisting of fluorine, chlorine, bromine, nitro, methoxycarbonyl, ethoxycarbonyl, cyano, methyl, ethyl, propyl, isopropyl, n-butyl, iso-butyl, sec. -butyl, tert-butyl, trifluoromethyl, trichloromethyl, chloro-difluoromethyl, methoxy, ethoxy, propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, trifluoro- methoxy, chloro-difluoromethoxy, trichloromethoxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, phenyl and phenoxy.

The above-mentioned substituent definitions can be combined among each other. Additionally, individual definitions may be redundant.

The pyrimidinone derivatives of the formula (I), which can be used according to the invention are known in some cases (cf. EP-A 0 636 615).

New pyrimidinone derivatives are those compounds of the formula

in which R¹ represents alkoxy,

R² represents hydrogen or alkyl,

R³ represents alkyl or phenyl and

R⁶ represents a group of the formula

The pyπmidmone deπvatives of the formula (la) can be prepared by reacting methylthio-pyrimidinones of the formula

R¹, R² and R³ have the above-mentioned meanings,

with amines of the formula

H₇N-R⁶ (HI),

in which

R⁶ has the above-mentioned meanings,

if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.

The already-known pyrimidinone derivatives of the formula (I) can be prepared in the same manner.

Formula (la) provides a general definition of the new pyrimidinone derivatives. Preferred are the compounds of the formula (la), in which

R¹, R² and R³ have the meanings, which have already been mentioned as preferred for these radicals, and

R⁶ has the above-mentioned meanings.

Particularly preferred are the compounds of the formula (la), in which

R¹, R² and R³ have the meanings, which have already been mentioned as particularly preferred for these radicals, and

R⁶ has the above-mentioned meanings. Very particularly preferred are the compounds of the formula (la), in which

R¹, R² and R³ have the meanings, which have already been mentioned as very particularly preferred for these radicals, and

R⁶ has the above-mentioned meanings.

If 2-methylthio-3-methyl-6-methoxy-pyrimidin-4-one and 2-methoxycarbonyl-3- amino-4-methyl-thiophen are used as starting materials, the course of the reaction of the process according to the invention can be illustrated by the following formula scheme:

Formula (II) provides a general definition of the methylthio-pyrimidinones required as starting materials for carrying out the process according to the invention. In this formula, R¹, R² and R³ preferably have those meanings which have already been mentioned as being preferred for these radicals.

The methylthio-pyrimidinones of the formula (II) are known or can be prepared by known methods (cf. EP-A 0 636 615). Formula (III) provides a general definition of the amines required as reaction components for carrying out the process according to the invention. In this formula, R⁶ has those meanings which have already been mentioned above for this radical.

The amines of the formula (III) are known or can be prepared by known methods (cf. EP-A 0 636 615).

Upon carrying out the process according to the invention, the amines of the formula (III) can also be replaced by formyl-substituted amines of the formula

NH— R⁶

CHO <^IV>^*

in which

R⁶ has the above-mentioned meanings.

The formyl-substituted amines of the formula (IV) are also known or can be prepared by known methods.

The process according to the invention is preferably carried out in the presence of an acid binder. Suitable acid binders are all customary inorganic and organic bases. Preference is given to using alkaline earth metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as, for example, sodium hydride, sodium amide, sodium methoxide, sodium ethoxide, potassium tert- butoxide, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate or sodium bicarbonate, further ammonium compounds, such as ammonium hydroxide, ammonium acetate or ammonium carbonate, and furthermore tertiary amines, such as trimethylamine, triethylamine, tributyla ine, N,N- dimethylaniline, N,N-dimethylbenzylamine, pyridine, N-methylpiperidine, N- methylmorpholine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

Suitable diluents for carrying out the process according to the invention are all customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimeth- oxyethane, 1 ,2-diethoxyethane or anisol; ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; nitriles, such as acetonitrile, propionitrile, n- or i- butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N- dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethyl- phosphoric triamide; esters such as methyl acetate or ethyl acetate; suphoxides, such as dimethyl sulphoxide; sulphones, such as sulpholane, or amines, such as pyridine.

When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the reaction is carried out at temperatures between 0°C and 150°C, preferably at temperatures between 20°C and

140°C.

The process according to the invention is generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.

When carrying out the process according to the invention, the methylthiopy- rimidinones of the formula (II) and the amines of the formula (III) generally are employed at approximately equimolar amounts. However, it is also possible to use an excess of one of the two components. Work-up is carried out by customary methods. In general, the reaction mixture is diluted with water and then extracted with an organic solvent which is only sparingly miscible with water, the combined organic phases are dned and concentrated under reduced pressure The product that remains can be freed of any impunties that may still be present using customary methods, such as chromatography or recrystalhzation

The compounds according to the invention have a potent microbicidal activity and can be employed for controlling undesirable microorganisms, such as fungi and bactena, in crop protection and in the protection of matenals The compounds are suitable for the direct control of undesired microorganisms as well as for generating resistance in plants against attack by undesired microorganisms

Fungicides are employed in crop protection for controlling Plasmodiophoromycetes, Oomycetes, Chytndiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes

Bactencides are employed in crop protection for controlling Pseudomonadaceae,

Rhizobiaceae, Enterobacteπaceae, Corynebactenaceae and Streptomycetaceae

Some pathogens causing fungal and bactenal diseases which come under the genenc names listed above are mentioned as examples, but not by way of limitation

Xanthomonas species, such as, for example, Xanthomonas campestns pv oryzae,

Pseudomonas species, such as, for example Pseudomonas syπngae pv lachrymans,

Erwinia species, such as, for example, Erwinia amylovora,

Pythium species, such as, for example, Pythium ultimum, Phytophthora species, such as, for example, Phytophthora infestans,

Pseudoperonospora species, such as, for example, Pseudoperonospora humu or

Pseudoperonospora cubensis,

Plasmopara species, such as, for example, Plasmopara viticola,

Bremia species, such as, for example, Bremia lactucae, Peronospora species, such as, for example, Peronospora ptsi or P brassicae,

Erysiphe species, such as, for example, Erysiphe graminis, Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus

(conidia form: Drechslera, Syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita; Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

Tilletia species, such as for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;

Pellicularia species, such as for example, Pellicularia sasakii;

Pyricularia species, such as for example, Pyricularia oryzae; Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens; Alternaria species, such as, for example, Alternaria brassicae; and

Pseudocercosporella species, such as, for example, Pseudocercosporella herpotri- choides.

The good corp safety of the active compounds at the concentrations necessary for controlling plant diseases permits a treatment of above-ground parts of plants, and also a treatment of vegetative propagation stock and seed and of the soil.

The active compounds according to the invention can be used here particularly successfully for controlling cereal diseases, such as, for example, against Erysiphe species, or of diseases in viticulture and in fruit and vegetable growing, such as, for example, against Plasmopara or Venturia species, or of rice diseases, such as, for example, against Pyricularia species.

The active compounds according to the invention are also suitable for increasing the harvest yield. Additionally, they have reduced toxicity and good crop safety.

The active compounds according to the invention additionally have a strong resistance- inducing action in plants. They are therefore suitable for producing resistance in plants to attack by undesired microorganisms.

Resistant-inducing substances are understood in the present context as meaning those substances which on the one hand, when acting directly on the undesired microorganisms, only exhibit a low activity, but are able to stimulate the defense system of plants such that the treated plants, when subsequently inoculated with undesired microorganisms, display extensive resistance to these microorganisms.

Undesired microorganisms are to be understood in the present case as meaning phytophatogenic fungi, bacteriae and viruses. The substances according to the invention can thus be employed in order to produce resistance in plants within a certain period of time after treatment to attack by the harmful causative organisms mentioned.

The period of time within which resistance is produced in general extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.

In the protection of materials, the compounds according to the invention can be employed for protecting industrial materials against infection with, and destruction by, undesired microorganisms.

Industrial materials in the present context are understood as meaning non-living materials which have been prepared for use in industry. For example, industrial materials which are intended to be protected by active compounds according to the invention from microbial change or destruction can be adhesives, sizes, paper and board, textiles, leather, wood , paints and plastic articles, cooling lubricants and other materials which can be infected with, or destroyed by, microorganisms. Parts of production plants, for example cooling-water circuits, which may be impaired by the proliferation of microorganisms may also be mentioned within the scope of the materials to be protected. Industrial materials which may be mentioned within the scope of the present invention are preferably adhesives, sizes, papers and boards, leather, wood, paints, cooling lubricants and heat-transfer liquids, particularly preferably wood.

Microorganisms capable of degrading or changing the industrial materials which may be mentioned are, for example, bacteria, fungi, yeast, algae and slime or organisms. The active compounds according to the invention preferably act against fungi, in particular moulds, wood-discolouring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

Microorganisms of the following genera may be mentioned as examples:

Alternaria, such as Alternaria tenuis, Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniephora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum, Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus, Depending on their particular physical and/or chemical properties, the active compounds can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and micro- encapsulations in polymeric substances and in coating compositions for seeds, and

ULV cool and warm fogging formulations.

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam formers. If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkyl- naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide or dimethyl sulphoxide, or else water. Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at standard temperature and under atmospheric pressure, for example aerosol propellants such as halogenated hydrocarbons, or else butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as highly disperse silica, alumina and silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. Suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxycthylcnc fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates. Suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations. Other possible additives are mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations also mixed with known fungicides, bactericides, acaricides, nematicides or insecticides in order thus, for example, to widen the spectrum of action or to prevent development of resistance. In many cases, synergistic effects are achieved, i.e. the activity of the mixture exceeds the activity of the individual components. Examples of co-components in mixtures are the following compounds:

Fungicides: aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin, benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl, bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate, calcium polysulphide, capsimycin, captafol, captan, carbendazim, carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chloro- thalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram, debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, drazoxolon, edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole, famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover, fluoromide, fluquinconazole, flu rimidol, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole- cis, furmecyclox, guazatine, hexachlorobenzene, hexaconazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP), iprodione, irumamycin, isoprothiolane, isovaledione, kasugamycin, kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulphate, copper oxide, oxine-copper and Bordeaux mixture. mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram, metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim, oxyfenthiin, paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine-sodium, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quinconazole, quintozene (PCNB), quinoyfen sulphur and sulphur preparations, tebuconazole, tecloftalam, tecnazene, tetcyclasis, tetraconazole, thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, trichlamide, tricyclazole, tridemoφh, triflumizole, triforine, triticonazole, uniconazole, validamycin A, vinclozolin, viniconazole, zarilamide, zineb, ziram and also Dagger G, OK-8705,

OK-8801, -( 1 , 1 -dimethylethyl)-β-(2-phenoxyethyl)- 1 H- 1 ,2,4-triazole- 1 -ethanol, α-(2,4-dichlorophenyl)-β-fluoro-β-propyl- 1 H- 1 ,2,4-triazole- 1 -ethanol, α-(2,4-dichlorophenyl)-β-methoxy-α-methyl- 1 H- 1 ,2,4-triazole- 1 -ethanol, α-(5-methyl-l,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-lH-l,2,4- triazole-1 -ethanol,

(5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-( 1 H- 1 ,2,4-triazol- 1 -yl)-3-octanone, (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide, isopropyl {2-methyl- 1 -[[[1 -(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl } - carbamate,

1 -(2,4-dichlorophenyl)-2-( 1 H- 1 ,2,4-triazol- 1 -yl)-ethanone-O-(phenylmethy 1 )-oxime. 1 -(2 -methyl- 1 -naphthalenyl)- 1 H-pyrrole-2,5-dione, l-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione, l-[(diiodomethyl)-sulphonyl]-4-methyl-benzene, l-[[2-(2,4-dichlorophenyl)-l,3-dioxolan-2-yl]-methyl]-lH-imidazole, l-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-lH-l,2,4-triazole, l-[l-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-lH-imidazole, l-methyl-5-nonyl-2-(phenylmethyl)-3-pynolidinole,

2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-l,3-thiazole-5- carboxanilide, 2,2-dichloro-N-[ 1 -(4-chlorophenyl)-ethyl]- 1 -ethyl-3-methy 1- cyclopropanecarboxamide,

2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate, 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, 2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide, 2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,

2-[(l-methylethyl)-sulphonyl]-5-(trichloromethyl)-l,3,4-thiadiazole, 2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4- methoxy-lH-pyrrolo[2,3-d]pyrimidine-5-carbonitrile, 2-aminobutane, 2-bromo-2-(bromomethyl)-pentanedinitrile,

2-chloro-N-(2,3-dihydro-l,l,3-trimethyl-lH-inden-4-yl)-3-pyridinecarboxamide, 2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide, 2-phenylphenol (OPP),

3,4-dichloro-l-[4-(difluoromethoxy)-phenyl]-lH-pyrrole-2,5-dione, 3,5-dichloro-N-[cyano-[(l-methyl-2-propinyl)-oxy]-methyl]-benzamide,

3-(l,l -dimethylpropyl-l-oxo-lH-indene-2-carbonitrile, 3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,

4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-l H-imidazole-l -sulphonamide, 4-methyl-tetrazolo[ 1 ,5-a]quinazolin-5(4H)-one, 8-(l,l -dimethylethyl)-N-ethyl-N-propyl-l ,4-dioxaspιro[4.5]decane-2-methaneamine,

8-hydroxyquιnolιnc sulphate. 9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide, bis-(l-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedi- carboxylate, cis- 1 -(4-chlorophenyl)-2-( 1 H- 1 ,2,4-triazol- 1 -yl)-cycloheptanol, cis-4-[3-[4-(l , l-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl- morpholinehydrochloride, ethyl [(4-chlorophenyl)-azo]-cyanoacetate, potassium hydrogen carbonate, methanetetrathiol sodium salt, methyl 1 -(2,3-dihydro-2,2-dimethyl- 1 H-inden- 1 -yl)- 1 H-imidazole-5-carboxylate, methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate, methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,

N-(2,3-dichloro-4-hydroxyphenyl)-l-methyl-cyclohexanecarboxamide,

N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide, N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,

N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,

N-(4-cyclohexylphenyl)- 1 ,4,5,6-tetrahydro-2-pyrimidineamine,

N-(4-hexylphenyl)-l,4,5,6-tetrahydro-2-pyrimidineamine,

N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide, N-(6-methoxy)-3 -pyridinyl)-cyclopropanecarboxamide,

N-[2,2,2-trichloro- 1 -[(chloroacetyl)-amino]-ethyl]-benzamide,

N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N'-methoxy-methaneimidamide,

N-formyl-N-hydroxy-DL-alanine-sodium salt,

O,O-diethyl [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate, O-methyl S-phenyl phenylpropylphosphoramidothioate,

S-methyl 1 ,2,3-benzothiadiazole-7-carbothioate, spiro[2H]-l -benzopyrane-2, 1 '(3'H)-isobenzofuran]-3'-one. Bactericides: bromopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.

Insecticides/Acaricides/Nematicides: abamectin, acephate, acrinathrin, alanycarb, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin,

Bacillus thuringiensis, 4-bromo-2-(4-chlorophenyl)-l -(ethoxymethyl)-5-(trifluoro- methyl)-lH-pynole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxin, butylpyridaben, cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, N-[(6-chloro-3-pyridinyl)-methyl]-N'-cyano-N-methyl-ethaneimidamide, chlor- pyrifos, chloφyrifos M, cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton M, demeton S, demeton S-methyl, diafenthiuron, diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox, ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, HCH, heptenophos, hexaflumuron, hexythiazox, imidacloprid, isazophos, isofenphos, isoprocarb, isoxathion, ivermectin, lambda-cyhalothrin, lufenuron. malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde, methacrifos, methamidophos, methidathion, methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin, naled, NC 184, nitenpyram, omethoate, oxamyl, oxydemethon M, oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate, pymetrozin, pyrachlophos, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen, quinalphos, salithion, sebufos, silafluofen, sulfotep, sulprofos, tebufenozide, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiamethoxam, thiodicarb, thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin, triarathen, triazophos, triazuron, trichlorfon, triflumuron, trimethacarb, vamidothion, XMC, xylylcarb, zetamethrin.

It is also possible to admix other known active compounds, such as herbicides, or else fertilizers and growth-promoting substances.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by pouring, spraying, atomizing, spreading, dusting, foaming, brushing on and the like. It is further possible to apply the active compounds by the ultra-low volume method or to inject the active compound formulation, or the active compound itself, into the soil. The seed of the plants can also be treated.

When using the active compounds according to the invention for controlling microorganisms, the application rates can be varied within a relatively wide range, depending on the kind of application. When treating parts of plants, the actn c compound application rates are generally between 0.1 and 10,000 g/ha, preferably between 10 and 1000 g/ha. When treating seed, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. When treating the soil, the active compound application rates are generally between 0.1 and 10,000 g ha, preferably between 1 and 5000 g/ha.

The compositions used for the protection of industrial materials generally comprise an amount of from 1 to 95%, preferably from 10 to 75%, of the active compounds.

The use concentrations of the active compounds according to the invention depend on the species and the occurrence of the microorganisms to be controlled and on the composition of the material to be protected. The optimal rate of application can be determined by test series. In general, the use concentrations are in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight, based on the material to be protected.

It is possible to increase the activity and the activity spectrum of the active compounds which are to be used according to the invention in the protection of materials, or of the compositions, concentrates or quite generally formulations which can be prepared from these, by adding, if appropriate, other compounds having antimicrobial action, fungicides, bactericides, herbicides, insecticides or other active compounds for increasing the activity spectrum or for obtaining special effects such as, for example, additional protection against insects. These mixtures may have a wider activity spectrum than the compounds according to the invention.

The preparation and the use of the compounds according to the invention are illustrated by the examples below. Preparation Examples

Example 1

0.6 g of sodium hydride (95%) were added to a solution of 2.74 g (16 mmol) of 2- methoxycarbonyl-3-amino-4-methyl-thiophen in 10 ml of dimethylformamide. After stirring the mixture for 10 minutes at room temperature, 3.73 g (mmol) of 3-methyl- 2-methylthio-6-methoxy-pyrimidin-4-one were added. The resulting mixture was then stirred for 8 hours at 120°C. Ice water was added to the reaction mixture, and the resulting mixture was then extracted with ethyl acetate. The combined organic phases were successively washed with water and a saturated aqueous sodium chloride solution. The organic phase was then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue (4.0 g) was crystallized by treatment with hexane. The crystalline solid was filtered off and washed with hexane so as to obtain 1.43 g of the compound of the formula shown above. The organic filtrate was concentrated and the remaining product was purified by chromatography over a silica gel column with hexane/acetone = 2:1. After concentrating the eluate, 0.12 g of the compound of the above-mentioned formula were obtained in the form of a solid product having a melting point of 180-182°C. The total yield of the compound was 1.55 g (=31.3 % of theory). Example 2

0.5 g of sodium hydride (95%) were added to a solution of 1.45 g (8 mmol) of N- formyl-2,4-dimethoxy-aniline in 20 ml of dimethylformamide. After stirring the mixture for 10 minutes at room temperature, 2.14 g (10 mmol) of 2-methylthio-3- methyl-6-isopropoxy-pyrimidin-4-one were added. The reaction mixture was stirred for 7 hours at 100°C. Ice water was added to the reaction mixture, and the resulting mixture was extracted with ethyl acetate. The combined organic phases were successively washed with water and a saturated aqueous sodium chloride solution. The organic phase was then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue (1.5 g) was purified by chromatography over a silica gel column with hexane/acetone = 2:1. After concentrating the eluate, 0.70 g (= 27.4% of theory) of the compound of the formula shown above were obtained in the form of a crystalline solid having a melting point of 140-142°C.

The compounds shown in the following Table 1 were also prepared by the above- mentioned methods.

Table 1

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Preparation of starting materials

Example 47

4.4 g (36 mmol) of potassium carbonate were added to a solution of 10.0 g (58 mmol) of 3-methyl-2-methylthio-6-hydroxy-pyrimidin-4-one in 100 ml of dimethylformamide. Whilst stirring this mixture at room temperature, 7.5 g (61 mmol) of isopropyl bromide were added dropwise. After stirring this mixture at 60°C for 3 hours, water was added thereto. The resulting mixture was then extracted with ethyl acetate. The combined organic phases were successively washed with water and a saturated aqueous sodium chloride solution, and then dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure. 3.9 g (= 31.4% of theory) of 3-methyl-2-methylthio-6-isopropoxy-pyrimidin-4-one were obtained in the form of a solid product having a melting point of 79 - 80°C.

Example 48

4.4 g (36 mmol) of potassium carbonate were added to a solution of 13.57 g (58 mmol) of 2-methylthio-3-phenyl-5-methyl-6-hydroxy-pyrimidin-4-one in 100 ml of dimethylformamide. Whilst stirring this mixture at room temperature, 8.7 g (61 mmol) of methyl iodide were added dropwise. After stirring this mixture at 60°C for 3 hours, water was added, and the resulting mixture was extracted with ethyl acetate. The combined organic phases were successively washed with water and a saturated aqueous sodium chloride solution, and then dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure and the residue (12.5 g) was purified by chromatography over a silical gel column with hexane/acetone = 2: 1. After concentrating the eluate under reduced pressure, 2.50 g (= 17.4% of theory) of 2-methylthio-3-phenyl-5-methyl-6-methoxy-pyrimidin-4-one were obtained in the form of a solid product having a melting point of 149 - 152°C.

The compounds of the formula (II) shown in the following Table 2 were also prepared according to the methods described in Example Nos. 47 and 48.

Table 2

The compounds shown in the following Tables can also be prepared according to the methods described above.

Table 3

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

Table 3 (continued)

In Table 3 above, the radicals Q¹ - Q⁹ have the following meanings:

Table 4

Use Example

Example A

Erysiphe test (barley)/induction of resistance

Solvent: 50 parts by weight of N,N-dimethylformamide

Emulsifier: 1.17 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with water and the stated amount of emulsifier to the desired concentration.

To test for resistance-inducing activity, young barley plants are sprayed with the preparation of active compound at the stated rate of application. 4 days after the treatment, the plants are inoculated with an aqueous spore suspension of Erysiphe graminis f. sp.hordei. The plants are subsequently placed in a greenhouse at 70% relative atmospheric humidity and 18°C.

The test is evaluated 2 days after the inoculation. 0% means an efficacy which coπesponds to that of the control while an efficacy of 100% means that no disease is observed.

The active compounds, active compound concentrations and results can be seen from the following table: Table A

Erysiphe test (barley )/induction of resistance

Claims

Patent Claims

1. Use of pyrimidinone derivatives of the formula

in which

R¹ represents alkoxy,

R² represents hydrogen or alkyl,

R³ represents alkyl or phenyl and

R⁴ represents optionally substituted aryl, optionally substituted heteroaryl or optionally substituted heteroarylalkyl,

for controlling undesired microorganisms.

2. Method for controlling undesired microorganisms, characterized in that pyrimidinone derivatives to the formula (I), according to claim 1 are applied to the microorganisms or to their habitat.

3. Pyrimidinone derivatives of the formula

in which

R¹ represents alkoxy,

R² represents hydrogen or alkyl,

R³ represents alkyl or phenyl and

R⁶ represents a group of the formula

4. Process for the preparation of pyrimidinone derivatives of the formula (la) according to claim 3, characterized in that methylthio-pyrimidinones of the formula

in which

R¹, R² and R³ have the above-mentioned meanings,

are reacted with amines of the formula

H₂N -R⁶ (III)

in which

R⁶ has the above-mentioned meanings,

Microbicidal compositions, characterized by comprising at least one pyrimidinone derivative of the formula (la) according to claim 3 in admixture with extenders and/or surface active agents.

6. Process for the preparation of microbicidal compositions, characterized in that pyrimidinone derivatives of the formula (la) according to claim 3 are mixed with extenders and/or surface-active agents.