WO2013156324A1

WO2013156324A1 - Use of compounds for the control of cereal diseases

Info

Publication number: WO2013156324A1
Application number: PCT/EP2013/057194
Authority: WO
Inventors: Clemens Lamberth; Renaud Beaudegnies; Fiona Murphy Kessabi; Laura Quaranta; Guillaume Berthon; Stephan Trah
Original assignee: Syngenta Participations Ag
Priority date: 2012-04-16
Filing date: 2013-04-05
Publication date: 2013-10-24
Also published as: UY34739A; AR090680A1; TW201402011A

Abstract

The present invention relates to the use of compounds of the general formula (I) wherein the substituents are as defined in claim 1, for the control of at least one cereal disease.

Description

Use of compounds for the control of cereal diseases

This invention relates to the use of certain carboxylic acid amides for the control of cereal diseases, in particular leaf spot diseases of cereals, especially Septoria diseases of wheat.

Cereal diseases caused by fungi may provoke serious yield losses and constitute a major limiting factor to cereals production. Accordingly, there is a constant need for efficient means for controlling these diseases. The present invention fulfills this goal and produces further advantages.

Certain carboxylic acid amide derivatives and their use as fungicides are disclosed, for example, in WO09/030467 and WO09/030469. The invention thus relates to the use of a compound of the general formula (I) for the control of at least one cereal disease:

wherein

R¹ is ethyl or methylthio;

R² is CR³R⁴R⁵;

R³ and R⁴, together, are hydrogen or methyl; and

R⁵ is methyl, ethyl or vinyl;

or a salt or a N-oxide thereof.

The compounds of general formula (I) contain at least one asymmetric carbon atom and therefore may exist as enantiomers, as pairs of diastereoisomers or as mixtures of such. Compounds of general formula (I) can therefore exist as racemates, diastereoisomers, or single enantiomers, and the invention includes all possible isomers or isomer mixtures in all proportions. The salts which the compounds of the formula (I) can form are preferably those formed by interaction of these compounds with acids. The term "acid" comprises mineral acids such as hydrogen halides, sulphuric acid, phosphoric acid etc. as well as organic acids, preferably the commonly used alkanoic acids, for example formic acid, acetic acid and propionic acid.

N-oxides are preferably compounds of the formula (I) with an oxygen atom at the nitrogen atom of the quinoline ring. Preferably, R³ and R⁴ together are hydrogen.

R⁵ is preferably methyl or ethyl.

In a particularly preferred group of compounds of the formula (I), R¹ is ethyl, R³ and R⁴ together are hydrogen and R⁵ is methyl.

In another preferred group of compounds of formula (I), R¹ is ethyl, R³ and R⁴ together are hydrogen and R⁵ is ethyl. In a particularly preferred group of compounds of the formula (I), R¹ is methylthio, R³ and R⁴ together are hydrogen and R⁵ is methyl.

In another preferred group of compounds of formula (I), R¹ is methylthio, R³ and R⁴ together are hydrogen and R⁵ is ethyl.

Compounds that can be used according to the invention are illustrated in Table 1 below.

Compounds of the formula (I):

Table 1 The compounds of Table 1 are of the general formula (I) where R¹, R³, R⁴ and R⁵ have the values given in the table.

The compounds of formula (I) may be prepared in an analogous manner as outlined in WO09/030467 and WO09/049716 by chemical reactions known in the art.

As mentioned above a cereal disease according to the invention is caused by one or more fungus. As a consequence, the terms "control of a cereal disease" and "control of a fungus" are equally used and mean the use of a compound of formula (I) to control a cereal disease caused by one or more fungus.

Preferably, the compounds of formula (I) are used to control at least one fungus selected in the group comprising Blumeria graminis sp. (powdery mildew of wheat and barley), Drechslera tritici-repentis (tan spot of wheat), Fusarium spp. (head blight of wheat), including Fusarium culmorum, Gaeumannomyces graminis (take-all of wheat), Magnaporthe grisea (rice blast), Monographella nivalis (snow mould of wheat),

Mycosphaerella graminicola (leaf blotch of wheat), Oculimacula spp. (eye spot of wheat), Phaeosphaeria nodorum (glume blotch of wheat), Puccinia recondita (brown rust of wheat), Pyrenophora teres (net blotch of barley), Ramularia collo-cygni (leaf spot of barley), Rhizoctonia solani (sheath blight of r\ce),Rhynchosporium secalis (scald of barley), and mixtures thereof.

In particular the compound of formula (I) proved to be appropriate for the control of leaf spot disease of cereals, caused by at least one fungus selected in the group comprising Drechslera tritici-repentis (tan spot of wheat), Magnaporthe grisea (rice blast), Mycosphaerella graminicola (leaf blotch of wheat), Phaeosphaeria nodorum (glume blotch of wheat), Pyrenophora teres (net blotch of barley), Ramularia collo-cygni (leaf spot of barley), Rhizoctonia solani (sheath blight of r\ce),Rhynchosporium secalis (scald of barley) and mixtures thereof.

The compound of formula (I) are especially well-suited for the control of Septoria disease of wheat, caused by Mycosphaerella graminicola (leaf blotch) and, or

Phaeosphaeria nodorum (glume blotch). Preferably, the cereal is selected in the group comprising wheat, barley, rye and rice, and is preferably wheat.

A compound of formula (I) may move acropetally, basipetally or locally in plant tissue to be active against one or more fungi. Moreover, a compound of formula (I) may be volatile enough to be active in the vapour phase against one or more fungi on the plant.

According to the invention "use" of a compound of formula (I) means applying said compound to a cereal. A compound of formula (I) may be applied by any of the known means of applying fungicidal compounds. For example, it may be applied, formulated or unformulated, to a plant, which means any part of the plant, including the foliage, stems, branches or roots, to the seed, and plant propagation materials before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapour or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water-soluble bag) in soil or an aqueous environment.

The invention therefore provides a method for combating or controlling a cereal disease which comprises applying a fungicidally effective amount of a compound of formula (I) to a plant, to a seed of a plant, to the locus of the plant or seed or to soil or any other plant growth medium, said seed or said plant being a cereal.

Applying a compound of formula (I) also means injecting into plants or spraying onto vegetation using electrodynamic spraying techniques or other low volume methods, or applying by land or aerial irrigation systems. According to the invention, "controlling" includes controlling, preventing and treating a cereal disease or, in other words, using or applying a compound of formula (I) as a protectant, prophylactic, curative, systemic, eradicant and/or antisporulant treatment against a cereal disease.

As a matter of example, controlling means reducing any undesired effect or risk of undesirable effect such as:

fungi infestation or fungi attack of, and

- phytopathogenic damage due to fungi on, a plant, part of a plant or seed to such a level that an improvement is observed over a like plant, part of a plant or seed without treatment by the compound of formula (I).

The term "plant" as used herein includes seedlings and bushes. The term "plant" as used herein also includes crops of useful plants in which the compositions according to the invention can be used and includes especially cereals, in particular wheat, barley, rye and rice.

The term "crops" is to be understood as also including crops that have been rendered tolerant to herbicides or classes of herbicides (for example ALS, GS, EPSPS, PPO and HPPD inhibitors) as a result of conventional methods of breeding or genetic engineering.

The compounds of formula (I) are preferably used for agricultural and horticultural purposes in the form of a composition.

In order to use a compound of formula (I) according to the invention, a compound of formula (I) is usually formulated into a composition which includes, in addition to a fungicidally effective amount of a compound of formula (I), a suitable inert diluent or carrier and, optionally, a further fungicidal compound, and/or a surface active agent (SFA). SFAs are chemicals that are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%, of a compound of formula (I). The composition is generally used for the control of fungi such that a compound of formula (I) is applied at a rate of from 0.1 g to 10kg per hectare, preferably from 1 g to 6kg per hectare, more preferably from 1 g to 1 kg per hectare.

When used in a seed dressing, a compound of formula (I) is used at a rate of 0.0001 g to 10g (for example 0.001 g or 0.05g), preferably 0.005g to 10g, more preferably 0.005g to 4g, per kilogram of seed.

In a still further aspect the invention provides a method of combating or controlling fungi at a locus, which comprises treating the fungi, or the locus of the fungi with a fungicidally effective amount of a compound of formula (I), wherein said fungus is selected in the group comprising Blumeria graminis sp., Drechslera tritici-repentis, Fusarium sp., Gaeumannomyces graminis, Magnaporthe grisea, Monographella nivalis,

Mycosphaerella graminicola, Oculimacula sp., Phaeosphaeria nodorum, Puccinia recondita, Pyrenophora teres, Ramularia collo-cygni, Rhizoctonia solani,

Rhynchosporium secalis and mixtures thereof.

If the compound of formula (I) used according to the invention is formulated in a composition, said composition can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro-emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of formula (I).

Dustable powders (DP) may be prepared by mixing a compound of formula (I) with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder. Soluble powders (SP) may be prepared by mixing a compound of formula (I) with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulphate) or one or more water-soluble organic solids (such as a

polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of formula (I) with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of a compound of formula (I) and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of formula (I) (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of formula (I) (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulphates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compound of formula (I) in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallisation in a spray tank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of formula (I) in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).

Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone), alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), /V-alkylpyrrolidones (such as /V-methylpyrrolidone or /V-octyl- pyrrolidone), dimethyl amides of fatty acids (such as C₈-Ci₀ fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of formula (I) either as a liquid (if it is not a liquid at ambient temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents that have a low solubility in water. Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of formula (I) is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in ECs or in EWs. An ME may be either an oil-in-water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion. Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula (I). SCs may be prepared by ball or bead milling the solid compound of formula (I) in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.

Alternatively, a compound of formula (I) may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.

Aerosol formulations comprise a compound of formula (I) and a suitable propellant (for example n-butane). A compound of formula (I) may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non-pressurised, hand-actuated spray pumps.

A compound of formula (I) may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.

Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerisation stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of formula (I) and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of formula (I) and they may be used for seed treatment. A compound of formula (I) may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.

A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of formula (I)). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of formula (I)).

A compound of formula (I) may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).

Wetting agents, dispersing agents and emulsifying agents may be SFAs of the cationic, anionic, amphoteric or non-ionic type. Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.

Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, calcium dodecylbenzenesulphonate, butylnaphthalene sulphonate and mixtures of sodium di- /^'sopropyl- and tri-/^'sopropyl-naphthalene sulphonates), ether sulphates, alcohol ether sulphates (for example sodium laureth-3-sulphate), ether carboxylates (for example sodium laureth-3-carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulphosuccinamates, paraffin or olefin sulphonates, taurates and lignosulphonates. Suitable SFAs of the amphoteric type include betaines, propionates and glycinates. Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as

octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide); alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).

Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs, SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of formula (I) (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.

A compound of formula (I) may be used in mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers). Suitable formulation types include granules of fertiliser. The mixtures suitably contain up to 25% by weight of the compound of formula (I).

The invention therefore also provides the use of a compound of formula (I) in

combination with a fertiliser composition comprising a fertiliser.

The compositions used according to this invention may contain other compounds having biological activity, for example micronutrients or compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.

By including another fungicide, the resulting composition may have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone. Further, the other fungicide may have a synergistic effect on the fungicidal activity of the compound of formula (I).

The compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergise the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of formula (I); or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition.

Examples of further fungicidal compounds which may be included in the composition of the invention are AC 382042 (/V-(1 -cyano-1 ,2-dimethylpropyl)-2-(2,4-dichlorophenoxy) propionamide), acibenzolar-S-methyl, alanycarb, aldimorph, anilazine, azaconazole, azafenidin, azoxystrobin, benalaxyl, benomyl, benthiavalicarb, biloxazol, bitertanol, blasticidin S, boscalid (new name for nicobifen), bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA 41396, CGA 41397, chinomethionate, chlorbenzthiazone, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate, and Bordeaux mixture,

cyamidazosulfamid, cyazofamid (IKF-916), cyflufenamid, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide 1 ,1 '-dioxide, dichlofluanid, diclocymet, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, 0,0-di-/so-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethirimol, dimethomorph, dimoxystrobin, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethaboxam, ethirimol, ethyl (Z)-/V-benzyl-/V([methyl(methyl-thioethylideneaminooxy- carbonyl)amino]thio)-p-alaninate, etridiazole, famoxadone, fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil (AC 382042), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluoroimide, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb, isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY21 1795, LY 248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metalaxyl M, metconazole, metiram, metiram-zinc, metominostrobin, metrafenone, MON65500 (/V-allyl-4,5-dimethyl-2- trimethylsilylthiophene-3-carboxamide), myclobutanil, NTN0301 , neoasozin, nickel dimethyldithiocarbamate, nitrothale-isopropyl, nuarimol, ofurace, organomercury compounds, orysastrobin, oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosphorus acids, phthalide, picoxystrobin, polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, propionic acid, proquinazid, prothioconazole, pyraclostrobin, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, silthiofam (MON 65500), S-imazalil, simeconazole, sipconazole, sodium pentachlorophenate, spiroxamine, streptomycin, sulphur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamide, 2-(thiocyano- methylthio)benzothiazole, thiophanate-methyl, thiram, tiadinil, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole, validamycin A, vapam, vinclozolin, XRD-563, zineb, ziram, zoxamide and the compounds of the formulae:

The compounds of formula (I) may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.

Some mixtures may comprise active ingredients, which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.

The invention is illustrated by the following non-limiting examples in which the following abbreviations are used:

ml = millilitres DMF = dimethylformamide

g = grammes NMR = nuclear magnetic resonance ppm = parts per million HPLC = high performance liquid

M⁺ = mass ion chromatography

s = singlet q = quartet

d = doublet m = multiplet

bs = broad singlet t = triplet

EDCI = 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide

HOAT = 1-hydroxy-7-azabenzotriazole

Example 1 : This example illustrates the preparation of 2-(3-ethynyl-8-methyl-quinolin-6- yloxy)-2-methyl-sulfanyl-N-propyl-acetamide (Compound No. 5)

To a solution of 2-(3-ethynyl-8-methyl-6-quinolyloxy)-2-methylsulfanyl-acetic acid (0.29 g, 1.0 mmol) in 5 ml of DMF was sequentially added triethylamine (0.1 g, 1.0 mmol), EDCI (0.19 g, 1 .0 mmol), HOAT (0.14 g, 1.0 mmol) and n-propylamine (0.06 g, 1 .0 mmol). The reaction was stirred for 16 h at room temperature, subsequently taken up in ethyl acetate and diluted with water. After separation of the phases, the organic layer was washed with brine, dried over magnesium sulfate, filtered and evaporated. The crude product was purified by column chromatography over silica gel (ethyl acetate / heptane 1 :1 ) to yield 2-(3-ethynyl-8-methyl-quinolin-6-yloxy)-2-methyl-sulfanyl-N-propyl- acetamide (Compound 5) as an off-white solid. M.p. 127 - 130 °C. ¹H-NMR (400 MHz, CDCI₃): δ = 0.96 (t, 3H), 1.61 (q, 2H), 2.20 (s, 3H), 2.78 (s, 3H), 3.31 - 3.44 (m, 2H), 5.72 (s, 1 H), 6.73 (bs, 1 H), 7.04 (d, 1 H), 7.32 (d, 1 H), 8.17 (d, 1 H), 8.83 (d, 1 H). MS: m/z = 329 [M+1 ]⁺.

Throughout this description, temperatures are given in degrees Celsius and "m.p." means melting point. LC/MS means Liquid Chromatography Mass Spectroscopy and the description of the apparatus and the method is: (HP 1 100 HPLC from Agilent,

Phenomenex Gemini C18, 3 m particle size, 110 Angstrom, 30 x 3 mm column, 1 .7mL/min., 60 °C, H₂0 + 0.05% HCOOH (95%) / CH₃CN/MeOH 4:1 + 0.04% HCOOH (5%) - 2 min. - CH₃CN/MeOH 4:1 + 0.04% HCOOH (5%) - 0.8 min., ZQ Mass

Spectrometer from Waters, ionization method: electrospray (ESI), Polarity: positive ions, Capillary (kV) 3.00, Cone (V) 30.00, Extractor (V) 2.00, Source Temperature (°C) 100, Desolvation Temperature (°C) 250, Cone Gas Flow (L/Hr) 50, Desolvation Gas Flow (L/Hr) 400)).

Table 2

This table gives analytical data (melting point) for compounds of Table 1.

Table 3

This table gives analytical data (LC/MS) for compounds of Table 1.

Compound Structural formula Compound LC/MS No.

3 N-(1 ,1-dimethyl- Rt = 1.14 propyl)-2-(3- min; MS: ethynyl-8-methyl- m/z = 339 quinolin-6-yloxy)- (M+1 butyramide

Example 2

This Example illustrates the fungicidal properties of compounds of formula (I). Compounds were tested in DMSO solutions or as IF and EC formulations against a set of standard screening pathosystems as exemplified below.

Liquid culture tests:

Mycelia fragments or conidia suspensions of a fungus, prepared either freshly from liquid cultures of the fungus or from cryogenic storage, are directly mixed into nutrient broth. DMSO solutions of the test compound (max. 10 mg/ml) is diluted with 0.025% Tween20 by factor 50 and 10 μ I of this solution is pipetted into a microtiter plate (96-well format) and the nutrient broth containing the fungal spores/mycelia fragments is then added to give an end concentration of the tested compound. The test plates are incubated at 24 °C and 96% rH in the dark. The inhibition of fungal growth is determined photometrically after 2 - 6 days and antifungal activity is calculated.

Whole plant tests:

Active ingredient is formulated as IF or EC and just before spraying the formulations are mixed with water and ultrasonically agitated in order to achieve homogeneous distribution. Spray solutions are made up in water. Foliar application is at 500 L/ha in an application device providing coverage of both upper and lower leaf surfaces (placed on turntable, air assisted spraying from 2 nozzles). Preventative tests are performed as 1 or 2 day preventative applications, i.e. plants are treated with the compounds 1 or 2 days prior to artificial inoculation with fungal spores, whereas for curative tests the inoculation is carried out prior to application. A single evaluation of disease level is made 2 to 19 days after inoculation, depending on the pathosystem. Disease control relative to the untreated check plants is then calculated.

Blumeria qraminis f. sp. tritici (Erysiphe qraminis f. sp. tritici) I wheat / leaf disc preventative (Powdery mildew on wheat)

Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated by shaking powdery mildew infected plants above the test plates 1 day after application. The inoculated leaf disks are incubated at 20°C and 60% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check leaf segments (6 - 8 days after application). Compounds 1 , 2, 3, 5, 6, 7, 8, 9 and 1 1 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Blumeria qraminis f. sp. tritici (Erysiphe qraminis f. sp. tritici) I wheat / preventative (Powdery mildew on wheat)

1 -week old wheat plants cv. Arina are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spreading powdery mildew spores over them in an inoculation chamber two days after application. The inoculated test plants are incubated at 20° C / 18°C (day/night) and 60% rh in a greenhouse and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (7 - 9 days after application).

Compounds 2, 6 and 7 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Fusarium culmorum I wheat / spikelet preventative (Head blight):

Wheat spikelets cv. Monsun are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The spikelets are inoculated with a spore suspension of the fungus 1 day after application. The inoculated spikelets are incubated at 20°C and 60% rh under a light regime of 72 h semi darkness followed by 12 h light / 12 h darkness in a climate chamber and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check spikelets (6 - 8 days after application). Compounds 1 , 5, 6, 7, 8, 9 and 1 1 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %. Gaeumannomyces qraminis I liquid culture (Take-all of cereals) Mycelial fragments of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores iss added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.

Compounds 1 , 2, 6, 7, 8, 9 and 1 1 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Maanaporthe grisea (Pyricularia oryzae) I rice / leaf disc preventative (Rice Blast)

Rice leaf segments cv. Ballila are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segments are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 22°C and 80% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application).

Compounds 5, 6, 8 and 1 1 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Maanaporthe grisea (Pyricularia oryzae) I rice / preventative (Rice blast)

3-week old rice plants cv. Koshihikari are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spraying them with a spore suspension two days after application. The inoculated test plants are incubated at 25° C and 95% rh and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (7 - 9 days after application).

Compounds 1 , 2, 5, 7, 8, 9 and 1 1 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Monographella nivalis (Microdochium nivale) / liquid culture (foot rot cereals)

Conidia of the fungus from cryogenic storage are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound into a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 4-5 days after application.

Compounds 1 , 2, 3, 5, 6, 7, 8, 9 and 1 1 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Mycosphaerella graminicola (Septoria tritici) I liquid culture (Septoria blotch)

Mycosphaerella graminicola (Septoria tritici) / wheat / preventative (Septoria tritici leaf spot on wheat)

2-week old wheat plants cv. Riband are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spraying a spore suspension on them one day after application. After an incubation period of 1 day at 22°C / 21 °C (day / night) and 95% rh, the inoculated test plants are kept at 22°C / 21 °C (day / night) and 70% rh in a greenhouse. Efficacy is assessed directly when an appropriate level of disease appears on untreated check plants (16 - 19 days after application). Compounds 1 , 2, 5, 6, 7, 8, 9 and 1 1 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Mycosphaerella qraminicola (Septoria tritici) I wheat / curative (Septoria tritici leaf spot on wheat)

2-week old wheat plants cv. Riband are inoculated by spraying them with a spore suspension. After an incubation period of 2 days at 22°C / 21 °C (day / night) and 95% rh, the test plants are kept at 22°C / 21 °C (day / night) and 70% rh in a climate chamber. The inoculated test plants are sprayed 5 days after inoculation in a spray chamber with the formulated test compound diluted in water. The percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (1 1 - 14 days after application).

Compounds 1 , 2, 5, 6, 7 and 1 1 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Phaeosphaeria nodorum (Septoria nodorum) / wheat / leaf disc preventative (Glume blotch)

Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated test leaf disks are incubated at 20°C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).

Compounds 1 , 2, 3, 5, 6, 7, 8, 9 and 1 1 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %. Puccinia recondita f. sp. tritici I wheat / leaf disc preventative (Brown rust)

Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf segments are incubated at 19°C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (7 - 9 days after application). Compounds 1 , 2, 3, 5, 6, 7, 8, 9 and 1 1 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %. Puccinia recondita f. sp. tritici / wheat / preventative (Brown rust on wheat)

2-week old wheat plants cv. Arina are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spraying them with a spore suspension one day after application. After an incubation period of 1 day at 20° C and 95% rh, the inoculated test plants are kept at 20° C / 18° C (day/night) and 60% rh in a greenhouse. The percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (12 - 14 days after application).

Compounds 1 , 6 and 8 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Pyrenophora teres I barley / leaf disc preventative (Net blotch)

Barley leaf segments cv. Hasso are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf segmens are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf segments are incubated at 20°C and 65% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf segments (5 - 7 days after application). Compounds 5, 6, 7, 8, 9 and 1 1 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Pyrenophora teres (Helminthosporium teres) I barley / preventative (Net blotch on barley)

1 -week old barley plants cv. Regina are sprayed in a spray chamber with the formulated test compound diluted in water. The test plants are inoculated by spraying them with a spore suspension 2 days after application. The inoculated test plants are incubated at 20° C and 95% rh and the percentage leaf area covered by disease is assessed when an appropriate level of disease appears on untreated check plants (5 - 7 days after application). Compounds 1 , 6, 7, 8 and 9 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Rhizoctonia solani I liquid culture (foot rot, damping-off)

Mycelia fragments of a newly grown liquid culture of the fungus are directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format), the nutrient broth containing the fungal material is added. The test plates are incubated at 24°C and the inhibition of growth is determined photometrically 3-4 days after application.

Compounds 3, 5, 6, 7, 8 and 1 1 from Tables 2 and 3 according to the invention at 200 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions untreated control plants are infected by the phytopathogenic fungi to over 80 %.

Comparative examples: Table 4

This table gives analytical data (¹H-NMR) for compounds disclosed in WO 2009/087098.

Compound Structural formula Compound ¹ H-NMR

No. (CDCIs, ppm)

Cereal diseases:

Mycosphaerella qraminicola (Septoria tritici) I liquid culture (Septoria blotch)

Compounds 1 and 2 from Tables 2 and 3 according to the invention at 60 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions compounds 48 and 154 from Table 4 at 60 ppm showed an efficacy lower than 30 %. Phaeosphaeria nodorum (Septoria nodorum) / wheat / leaf disc preventative (Glume blotch)

Wheat leaf segments cv. Kanzler are placed on agar in a multiwell plate (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated test leaf disks are incubated at 20°C and 75% rh under a light regime of 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application). Compounds 1 and 2 from Tables 2 and 3 according to the invention at 60 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions compounds 48 and 154 from Table 4 at 60 ppm showed an efficacy lower than 30 %.

Non-cereal diseases:

Alternaria solani I tomato / leaf disc (early blight)

Tomato leaf disks cv. Baby are placed on agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 2 days after application. The inoculated leaf disks are incubated at 23 °C / 21°C (day/night) and 80% rh under a light regime of 12/12 h (light/dark) in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears on untreated check disk leaf disks (5 - 7 days after application).

Compounds 48 and 154 from Table 4 at 60 ppm inhibit fungal infestation in this test to at least 80 %, while under the same conditions compounds 1 and 2 from Tables 2 and 3 according to the invention at 60 ppm showed an efficacy lower than 30 %.

Phytophthora infestans I tomato / leaf disc preventative (late blight)

Tomato leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks are inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf disks are incubated at 16°C and 75% rh under a light regime of 24 h darkness followed by 12 h light / 12 h darkness in a climate cabinet and the activity of a compound is assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (5 - 7 days after application).

Compounds 48 and 154 from Table 4 at 200 ppm inhibit fungal infestation in this test to at least 60 %, while under the same conditions compounds 1 and 2 from Tables 2 and 3 according to the invention showed an efficacy lower than 30 %.

Claims

1. Use of a compound of the general formula (I) for the control of at least one cereal disease:

Wherein,

R¹ is ethyl or methylthio;

R² is CR³R⁴R⁵;

R³ and R⁴, together, are hydrogen or methyl; and

R⁵ is methyl, ethyl or vinyl;

or a salt or a N-oxide thereof.

2. Use according to claim 1 , wherein R³ and R⁴ together are hydrogen.

3. Use according to claim 1 , wherein R⁵ is ethyl.

4. Use according to claim 1 , wherein R¹ is ethyl, R³ and R⁴ together are hydrogen and R⁵ is methyl or ethyl.

5. Use according to claim 1 , wherein R¹ is methylthio, R³ and R⁴ together are hydrogen and R⁵ is methyl or ethyl.

6. Use according to claim 1 , wherein the cereal disease is leaf spot disease.

7. Use according to claim 1 , wherein the cereal disease is Septoria disease of wheat.

8. Use according to claim 1 wherein the cereal is selected in the group comprising wheat, barley, rye and rice.

9. Use according to claim 1 wherein said compound of formula (I) is formulated in a composition comprising:

- a fungicidally effective amount of a compound of formula (I)

- a suitable carrier or diluent therefore, and optionally,

- a further fungicidal compound.

10. A method for combating or controlling a cereal disease which comprises applying a fungicidally effective amount of a compound of formula (I) according to claim 1 to a plant, to a seed of a plant, to the locus of the plant or seed or to soil or any other plant growth medium, said seed or said plant being a cereal.

1 1. A method of combating or controlling fungus at a locus, which comprises treating the fungi, or the locus of the fungi with a fungicidally effective amount of a compound of formula (I) according to claim 1 , wherein said fungus is selected in the group comprising Blumeria graminis sp., Drechslera tritici-repentis, Fusarium sp., Gaeumannomyces graminis, Magnaporthe grisea, Monographella nivalis, Mycosphaerella graminicola, Oculimacula sp., Phaeosphaeria nodorum, Puccinia recondita, Pyrenophora teres, Ramularia collo-cygni, Rhizoctonia solani, Rhynchosporium secalis and mixtures therof.