GB2081709A - Fungicidal and plant growth regulating imidazole and triazole derivatives - Google Patents

Abstract

Compounds of formula: <IMAGE> and isomers thereof, wherein R<1> and R<2> are unsubstituted or halo- substituted alkyl, unsubstituted or alkyl-substituted cycloalkyl, optionally substituted phenyl, alkoxy-alkyl, furyl, or thienyl provided that at least one of them is alkoxyalkyl, furyl or thienyl, Y is =N- or =CN- and Z<1> and Z<2> are carbonyl (or a derivative thereof) or CHOH, and salts, ethers, esters and metal complexes thereof having fungicidal and plant growth regulating activity.

Description

SPECIFICATION Fungicidal compounds This invention relates to imidazole and triazole compounds useful as fungicides and plant growth regulating agents, to processes for preparing them, to fungicidal and plant growth regulating compositions containing them, to a method of combating fungal infections in plants using them and to a method of regulating the growth of plants using them.

The present invention provides a compound having the general formula (I)

or a stereoisomer thereof, wherein R1 and R2, which may be the same or different, are unsubstituted or alkyl-substituted cyclo-alkyl, unsubstituted or halo-substituted alkyl, or u nsubstituted or substituted phenyl, alkoxyalkyl, furyl, or thienyl, provided that at least one of R1 and R2 is alkoxyalkyl, furyl or thienyl; Y is N- or =CH- and Z1 and Z2, which may be the same or different, are C=O or a derivative thereof (e.g. an imine, oxime, ketai, hydrazone or semicarbazone) or-CH(OH); and esters, ethers, acid addition salts and metal complexes thereof.

The compounds of the invention contain chiral centres. The compounds are generally obtained in the form of racemic mixtures. However, these and other mixtures can be separated into the individual isomers by methods known in the art e.g. chromatography. In many cases, the compounds can be prepared stereospecifically in the form of a single diastereoisomer. These diastereoisomers and other isomers, form part of the present invention.

When R1 and R2 are alkyl groups these can be straight or branched chain and preferably have 1 to 5 carbon atoms; examples are methyl, ethyl, propyl (n- ori-propyl) and butyl (n-, i- or t-butyl).

When R1 and R2 are phenyl suitable substituents for the phenyl group are halogen, C14 alkyl [e.g.

methyl, ethyl, propyl (n- or i-propyl) and butyl (n-, i- or t-butyl)i, halo(C14 alkyl) (e.g. chloro- or bromomethyl), hydroxy (C14 alkyl) (e.g. hydroxymethyl), phenyl, halophenyl (e.g. chlorophenyl), cycloalkyl, nitro, cyano, C14 alkoxy (e.g. methoxy, ethoxy, propoxy or butoxy), C24 alkenyloxy (e.g. allyloxy). (C14 alkylene)dioxy (e.g. methylenedioxy), (C1-4 alkoxy) (C14 alkyl) [e.g. methoxy- or ethoxy- methyl or 2methoxy- or ethoxy-ethyl], mercapto, (C14 alkyl)thio [e.g. methyl- or ethyl-thio], (Cl-4 alkyl)sulphonyl [e.g. methyl- or ethyl-sulphonyl], (C14 haloalkyl)sulphonyl [e.g. trifluoromethylsulphonyl], phenylsulphonyl, unsubstituted or mono- or di-(C1~4 alkyl) substituted sulphamoyl or carbamoyl, 1pyrrolidinylsulphonyl, carboxy, (C14 alkoxy)carbonyl [e.g. methoxy- or ethoxy- carbonyl], hydroxy, C16 alkanoyloxy, benzoyloxy, carboxy (C14 alkyl)oxy (e.g. carboxymethoxy or 1-carboxyethoxy), unsubstituted or mono- or di-(C1~4 alkyl) substituted amino, (C16 alkanoyl)amino, N-(C1~4 alkyl)-N-(C1~6 alkanoyl)amino, formylamino, N-(C1~4 alkyl) formylamino, phenylethyl, methylenedioxyphenyl, phenoxy or benzyloxy. A suitable alkanoyl is acetyl or propionyl.The phenyl group can have more than one substituent; examples of polysubstituted groups are those substituted with up to the maximum possible number (especially 1, 2 or 3) of for example halogen (particularly chlorine) atoms and/or nitro, methyl or methoxy groups.

Examples of suitable phenyl groups for R1 and R2 are phenyl itself, chlorophenyl (for example o-, m- or p-chlorophenyl), dichlorophenyl (e.g. 3,4-, 2,4- 3,5- or 2,6-dichlorophenyl), trichlorophenyl (e.g.

2,3,6- or 2,4,5-trichlorophenyl), tetrachlorophenyl, pentachlorophenyl, bromophenyl (e.g. o-, m- or pbromophenyl), dibromophenyl (e.g. 2,4-dibromophenyl, fluorophenyl (e.g. o-, m- or I p-fluorophenyl), difluorophenyl (e.g. 2,4-or 3,4-difluorophenyl, pentafluorophenyl, iodophenyl (e.g. o-iodophenyl), aminophenyl (e.g. p-aminophenyl), methylphenyl (e.g. o-, m- or p-methylphenyl), dimethylphenyl (e.g.

2,6-, 2,5- or 3,4-dimethylphenyl), ethylphenyl (e.g. p-ethylphenyl), propylphenyl (e.g. p-i-propylphenyl), butylphenyl (e.g. p-t-butylphenyl), cyanophenyl (e.g. o-, m- or p-cyanophenyl), nitrophenyl (e.g. o-, m- or p-nitrophenyl), dinitrophenyl (e.g. 2,4-dinitrophenyl), cyanochlorophenyl (e.g. 3-cyano-4-chlorophenyl or 4-cyano-3-chlorophenyl), methylsulphonylphenyl (e.g. p-methylsulphonylphenyl), sulphamoylphenyl (e.g. p-sulphamoylphenyl), N,N-dimethylsulphamoylphenyl [e.g. p-(N,N-dimethylsulphamoyl)phenylj, pyrollid in- 1 -ylsulphonylphenyl (e.g. p-pyrollidin- 1 -ylsulphonylphenyl), trifluoromethylsulphonylphenyl (e.g. p-trifluoromethylsulphonylphenyl), methylthiophenyl (e.g. p-methylthiophenyl), (chloromethyl)phenyl [e.g. o-, m- or p-(chloromethyl)phenylj, (bromomethyl)phenyl [e.g. o-, m- or p (bromomethyl)phenyl], (hydroxymethyl)phenyl [e.g. o-, m- or p-(hydroxymethyl)phenylj, (methoxymethyl)phenyl [e.g. o-, m- or p-(methoxymethyl)phenyl], carboxyphenyl (e.g. o-, m- or pcarboxyphenyl), methoxycarbonylphenyl (e.g. o-, m- or p-methoxycarbonylphenyi), N,Ndimethylcarbamoylphenyl [e.g. o-, m- or p-(N,N-dimethylcarbamoyl)phenyl], N,N-dimethylaminophenyl [e.g. o-, m- or p-(N,N-dimethylamino)phenyl], hydroxyphenyl (e.g. o-, m- or p-hydroxyphenyl), acetoxyphenyl (e.g. o-, m- or p-acetoxyphenyl), benzoyloxyphenyl (e.g. o-, m- or p-benzoyloxyphenyl), (trifluoromethyl)phenyl [e.g. o-, m- or p-(trifluoromethyl)phenyl], methoxyphenyl (e.g. o-, m- or pmethoxyphenyl), dimethoxyphenyl (e.g. 2,4-, 3,4for 3,5-dimethoxyphenyl), ethoxyphenyl (e.g. o-, m- or p-ethoxyphenyl), propoxyphenyl (e.g. p-i-propoxyphenyl or p-n-propoxyphenyl), butoxyphenyl (e.g. o-.

m- or p-i-butoxyphenyl), allyloxyphenyl (e.g. o-, m- or p-allyloxyphenyl), carboxymethoxyphenyl (e.g. o-, m- or p-carboxymethoxyphenyl), 1 -carboxyethylphenyl [e.g. o-, m- or p-( 1 -carboxyethyl)phenyl], chloronitrophenyl (e.g. 3-nitro-4- chlorophenyl), fluoronitrophenyl (e.g. 2-nitro-4-fluorophenyl), ch lorofluorophenyl (e.g. 2-fluoro-4-chlorophenyl, 2-chloro-6-fluorophenyl or 2-chloro-4-fluorophenyl), fluorobromophenyl (e.g. 2-fluoro-4-bromophenyl), methylenedioxychlorophenyl (e.g. 2-chloro-4,5methylenedioxyphenyl), methoxychlorophenyl (e.g. 3-chloro-4-methoxyphenyl), methoxybromophenyl (e.g. 2-methoxy-5-bromophenyl or 3-bromo-4-methoxyphenyl), methoxynitrophenyl (e.g. 2-methoxy-5nitrophenyl or 4-methoxy-3-nitrophenyl), ethoxynitrophenyl (e.g. 4-ethoxy-3-nitrophenyl).

ethoxychlorophenyl (e.g. 4-ethoxy-3-chlorophenyl), ethoxybromophenyl (e.g. 4-ethoxy-3-bromophenyl), benzyloxyphenyl (e.g. p-benzyloxyphenyl), phenylphenyl (e.g. p-phenylphenyl) or methylenedioxyphenylphenyl (e.g. 3,4-methylenedioxyphenylphenyl).

When R1 and R2 are cycloalkyl the cycloalkyl group suitably has 3 to 6 carbon atoms; preferably it is cyclopropyl, cyclopentyl, cyclohexyl or methylcyclohexyl.

When R1 and R2 are haloalkyl, preferably the haloalkyl group contains 1 to 3 halogen atoms; examples are 2-ch loroethyl, trifluoromethyl or trichloromethyl.

Preferred alkoxyalkyl groups are those containing from 2 to 8 carbon atoms and a particularly preferred group is:

The halogen can be fluorine, chlorine, bromine or iodine.

Suitable salts are salts with inorganic acids, e.g. hydrochloric, nitric, sulphuric, toluenesulphonic, acetic or oxalic acid. The esters are suitably alkanoates (e.g. acetates) and the ethers are suitably alkyl (e.g. methyl or ethyl), aryl (e.g. phenyl) or aralkyl (e.g. benzyl) ethers.

The metal complex is suitably one including copper, zinc, manganese or iron. It preferably has the general formula:

wherein Y, R1, R2, Z1 and Z2 are as defined above, M is a metal, A is an anion (e.g. a chloride, bromide, iodide, nitrate, sulphate or phosphate anion), n is 2 or 4 and y is O or an integer of 1 to 12.

Examples of the triazole compounds of general formula (I) are given in Table I.

TABLE I

Melting Compound R' R Point No. F1 R2 Z Z2 (CC) /CH3 /OCH3 1 -C-CH3 -C-CH C=0 CHOH 108-111 CH2 OCH3 (mixture Oil (Mixture of 2 -C(CH3)2 -C - CH1 CHOH CO diastereo isomers) CH2 3 -C(CH3)3 t3 1] CHOH C=O 110 4 -CH(CH3)2 (iso) 1 CHOH C=O 153-155 5 o-CH3O-C6H4 t3 CHOH C=O 168-169 6 2$diCl2.C6H ) CHOH C=O 125-127 70CH3 7 -C-CH3 t-C4H, C=O C=O Oil CH3 8 t-C4H9 j C=O CO 118-119 TABLE I contd.

Me Iting Comound Point No. R' RZ Z' z' ("c) 1Q pCH3OC6H4 -C-O 0-0 184-185 11 i-C3H, U c-a 0-a 121-123 12 oOCH3.06H4 U 0-0 88-89 H 13 o-CI.C,H, .C6H4 Q c o 104-1 06 14 U II 06H5 0-0 CsO 203-206 15 U o,pd10l06H3 0=0 0-0 104-105 16 U U 0-0 0-0 198-197 TABLE I contd.

Melting Compound R' R2 Z Point No. R1 R2 ZI Z2 ("c) /OCH3 17 -r/ CH, t-C,H, CHOHCHOH 107-109 CH3 CH3 18 t-C4H9 i CHOH CHOH 108-109 The triazole compounds of the general formula I wherein Z' and Z2 are both carbonyl may be made by reacting 1 2,4-triazole, or a salt or metal complex thereof, and,the appropriate b-diketone, by any of the methods set out in the literature.Thus 1 ,2,4-triazole can be reacted with a compound (e.g. a - diketone) of general formula (II) R' 9'--CH=CH 2~R2 (formula II) wherein Ra, R2, Z1 and Z2 are as defined above.

This process may be carried out merely by heating the reactants together in the absence of a solvent or diluent, but preferably a solvent is present. Suitable solvents are high-boiling hydrncarbor solvents such as benzene, toluene or a xylene.

The process is generally performed by dissolving the reactants in a solvent and, after allowing reaction to occur, isolating the product by removing the solvent in vacuo. Any untreated triazole can be removed by extraction with a suitable solvent and the extract can then be washed with water.

Crystallisation or other purification procedures may then be carried out, if desired.

The -diketone starting material may be made by methods set out in the literature.

The compounds, salts and complexes of the invention wherein, in the general formula I, one of Z' and Z2 is carbonyl and the other is CH(OH) may be made by selectively reducing a diketone of general formula (III):

(formula Ill) wherein Y, R' and R2 are as defined above, or a salt or metal complex thereof, with for example a metal hydride reducing agent (e.g. lithium aluminium hydride or sodium borohydride) in an inert polar solvent (e.g. diethyl ether, water or ethanol).

The diketone starting materials may be made by reacting imidazole or 1,2,4-triazole or a salt thereof with the appropriate unsaturated y-diketone in a high boiling hydro-carbon solvent (e.g. toluene or xylene) at refluxing temperatures. Thus for example 1 2,4-triazole may be reacted with a compound of general formula (IV):

(formula IV) where R' and R2 are as defined above.

The reduction of the diketone generally involves dissolving the reactants in a solvent such as diethyl ether or tetrahydrofuran (for lithium aluminium hydride reduction) or water (for sodium borohydride reduction). The temperature at which the reaction may be carried out will depend on the reactants and solvent but generally the reaction mixture is heated under reflux. The reaction product is then isolated by, for example, extraction into a convenient solvent after acidification with a dilute mineral acid. After removal of the solvent in vacuo, the product may be crystallised from a convenient solvent.

The compounds of general formula (IV) may be made by any of the methods set out in the literature.

The salts, metal complexes, ethers, esters and silyl ethers of the compounds of general formula Ill can be prepared from the latter in known manner. For example, the complexes can be made by reacting the uncomplexed compound with a metal salt in a suitable solvent. The substituent on the phenyl group in the compound of general formula (I) can often be changed by methods known in the art. For example, a compound wherein for example F1 is phenyl substituted with carboxy can be prepared from the corresponding compound wherein R, is phenyl substituted with alkoxycarbonyl, and vice-versa.

The compounds of the invention wherein, in general formula I, Z' and Z2 are both CHOH may be made by reducing (preferably at 0 to 1000C and for 1 to 12 hours) a diketone or ketoalcohol of general formula (V)

formula (V) wherein Y, RT and R2 are as defined above, and either both the groups Z' and Z2 are 0=0 or one is 0=0 and the other is CHOH, or a salt or metal complex thereof, with, for example, a metal hydride reducing agent (e.g. lithium aluminium hydride, sodium borohydride or aluminium isopropoxide) in an inert polar solvent (e.g. water or ethanol).

The diketones wherein Y is N- are the subject of British Patent Specification No. 1 51 1956, the disclosure of which document is incorporated herein by reference. The ketoalcohols wherein Y is =N- are the subject of German Offenlegungschrift No. 28198797, the disclosure of which document is incorporated herein by reference.

The starting materials for the process may be made by reacting imidazole or 1 2,4-triazole or a salt thereof with the appropriate y-diketone or ketoalcohol in a high boiling hydrocarbon solvent (e.g.

toluene or xylene) at refluxing temperatures. Thus for example 1 ,2,4-triazole may be reacted with a compound of general formula (VI): F1-Z1-CH=CH-Z2-F2 (formula VI) where Rr, R2, Z1 and Z2 are as defined hereinabove.

The reduction generally involves dissolving the reactants in a solvent such as diethyl ether or tetrahydrofuran (for lithium aluminium hydride reduction) or a hydroxylic solvent (for sodium borohydride reduction). The temperature at which the reaction may be carried out will depend on the reactants and solvent but generally the reaction mixture is heated under reflux. The reaction product is then isolated by extraction into a convenient solvent after acidification with dilute mineral acid. After removal of the solvent in vacuo, the product may be crystallised from a convenient solvent.

The compounds of general formula (VI) may be made by any of the methods set out in literature.

The salts, metal complexes, ethers and esters of the compounds of general formula (V) can be prepared from the latter in known manner. For example, the complexes can be made by reacting the uncomplexed compound with a metal salt in a suitable solvent.

The compounds of the invention are active fungicides, particularly against the diseases: Pyricularia oryzae on rice Puccinia recondita, Puccinia strfiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts e.g. coffee, apples, vegetables and ornamental plants Plasmopara viticola on vines Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildews on various hosts such as Helminthosporium spp. on cereals, Sphaerotheca fuliginea on cucurbits (e.g. cucumber), Podosphaera leucotricha on apples and Uncinula necator on vines Cercospora arachidicola on peanuts and other Cercospora species on for example sugar beet, bananas and soya beans Botrytis cinerea (grey mould) on tomatoes, strawberries, vines and other hosts Phytophthora in fes tans (blight) on tomatoes and potatoes Venturia inaequalis (scab) on apples Some of the compounds have also shown a broad range of activities against fungi in vitro. They have activity against various post-harvest diseases on fruit (e.g. Penicillium digitatum and italicum on oranges and Gloeosporium musarum on bananas).Further some of the compounds are active as seed dressings against: Fusarium spp., Septoria spp., Tllletia spp. (i.e. bunt, a seed borne disease of wheat), Ustilago spp., Helminthosporium spp. on cereals, Rhizoctonia solani on cotton and Corticium sasakii on rice.

The compounds also have plant growth regulating activities.

The plant growth regulating effects of the compounds are manifested as for example a stunting or dwarfing effect on the vegetative growth of woody and herbaceous mono- and di-cotyiedonous plants.

Such stunting or dwarfing may be useful, for example, in peanuts, cereals and soya bean where reduction in stem growth may reduce the risk of lodging and may also permit increased amounts of fertiliser to be applied. The stunting of woody species is useful in controlling the growth of undergrowth under power lines etc. Compounds which induce stunting or dwarfing may also be useful in modifying the stem growth of sugar cane thereby increasing the concentration of sugar in the cane at harvest; in sugar cane, the flowering and ripening may be controllable by applying the compounds. Stunting of peanuts can assist in harvesting. Growth retardation of grasses can help maintenance of grass swards.

Examples of suitable grasses are Stenotaphrum secundatum (St. Augustine grass), Cynosurus cristatus, Lolium multiflorum and perenne, Agrostis tenuis, Cynodon dactylon (Bermuda grass), Dactyls glomerata, Festuca spp. (e.g. Festuca rubra) and Poa spp. (e.g. Poa pratense). The compounds may stunt grasses without significant phytotoxic effects and without deleteriously affecting the appearance (particularly the colour) of the grass; this makes such compounds attractive for use on ornamental lawns and on grass verges. They may also have an effect on flower head emergence in for example grasses.

The compounds can also stunt weed species present in the grasses; examples ot such weed species are sedges (e.g. Cyperus spp.) and dicotyledonous weeds (e.g. daisy, plantain, knotweed, speedwell, thistle, docks and ragwort). The growth of non-crop vegetation (e.g. weeds or cover vegetation) can be retarded thus assisting in the maintenance of plantation and field crops. In fruit orchards, particularly orchards subject to soil erosion, the presence of grass cover is important. However excessive grass growth requires substantial maintenance. The compounds of the invention could be useful in this situation as they could restrict growth without killing the plants which would lead to soil erosion; at the same time the degree of competition for nutrients and water by the grass would be reduced and this could result in an increased yield of fruit.In some cases, one grass species may be stunted more than another grass species; this selectivity could be useful for example for improving the quality of a sward by preferential suppression of the growth of undesirable species.

The dwarfing may also be useful in miniaturising ornamental, household, garden and nursery plants (e.g. poinsettias, chrysanthemums, carnations, tulips and daffodils).

As indicated above, the compounds can also be used to stunt woody species. This property can be used to control hedgerows or to shape fruit trees (e.g. apples). Some coniferous treet are not significantly stunted by the compounds so the compounds could be useful in controlling undesirable vegetation in conifer nurseries.

The plant growth regulating effect may (as implied above) manifest itself in an increase in crop yield.

In the potato, vine control in the field and inhibition of sprouting in the store may be possible.

Other plant growth regulating effects caused by the compounds include alteration of leaf angle and promotion of tillering in monocotyledonous plants. The former effect may be useful for example in altering the leaf orientation of, for example, potato crops thereby letting more light into the crops and inducing an increase in photosynthesis and tuber weight. By increasing tillering in monocotyledonous crops (e.g. rice), the number of flowering shoots per unit area may be increased thereby increasing the overall grain yield of such crops. In grass swards an increase in tillering could lead to a denser sward which may result in increased.resilience in wear.

The treatment of plants with the compounds can lead to the leaves developing a darker green colour.

The compounds may inhibit, or at least delay, the flowering of sugar beet and thereby may increase sugar yield. They may also reduce the size of sugar beet without reducing significantly the sugar yield thereby enabling an increase in planting density to be made. Similarly in other root crops (e.g. turnip, swede, mangold, parsnip, beetroot, yam and cassava) it may be possible to increase the planting density.

The compounds could be useful in restricting the vegatative growth of cotton thereby leading to an increase in cotton yield.

The compounds may be useful in rendering plants resistant to stress since the compounds can delay the emergence of plants grown from seed, shorten stem height and delay flowering; these properties could be useful in preventing frost damage in countries where there is significant snow cover in the winter since then the treated plants would remain below the snow cover during the cold weather.

Further the compounds may cause drought or cold resistance in certain plants.

When applied as seed treatments at low rates the compounds can have a growth stimulating effect on plants.

In carrying out the plant growth regulating method of the invention, the amount of compound to be applied to regulate the growth of plants will depend upon a number of factors, for example the particular compound selected for use, and the identity of the plant species whose growth is to be regulated. However, in general an application rate of 0.1 to 15, preferably 0.1 to 5, kg per hectare is used. However, on certain plants even application rates within these ranges may give undesired phytotoxic effects. Routine tests may be necessary to determine the best rate of application of a specific compound for any specific purpose for which it is suitable.

The compounds may be used as such for fungicidal or plant growth regulating purposes but are more conveniently formulated into c6qmpositions for such usage. The invention thus provides also a fungicidal or plant growth regulating composition comprising a compound of general formula (I) or a salt, complex, ether or ester thereof as hereinbefore defined, and a carrier or diluent.

The invention also provides a method of combating fungal diseases in a plant, which method comprises applying to the plant, to seed of the plant or to the locus of the plant or seed a compound or salt, complex, ether or ester thereof as hereinbefore defined.

It also provides a method of regulating the growth of a plant, which method comprises applying to the plant, to seed of the plant or to the locus of the plant or seed a compound or salt, complex, ether or ester thereof as hereinbefore defined.

The compounds, salts, complexes, ethers and esters can be applied in a number of ways, for example they can be applied, formulated or unformulated, directly to the foliage of a plant or they can be applied also to bushes and trees, to seeds or to other medium in which plants, bushes or trees are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation, or they can be applied as a vapour. Application can be to any part of the plant, bush or tree, for example to the foliage, stems, branches or roots, or to soil surrounding the roots, or to the seed before it is planted.

The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes preventative, protectant, prophylactic and eradicant treatment.

The compounds are preferably used for agricultural and horticultural purposes in the form of a composition. The type of composition used in any instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dusting powders or granules comprising the active ingredient and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay. Such granules can be preformed granules suitable for application to the soil without further treatment. These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler.

Compositions for dressing seed, for example, may comprise an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed; alternatively the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example N-methyl-pyrrolidone or dimethylformamide).

The compositions may also be in the form of dispersible powders, granules or grains comprising a wetting agent to facilitate the dispersion in liquids of the powder or grains which may contain also fillers and suspending agents.

The aqueous dispersions of emulsions may be prepared by dissolving the active ingredient(s) in an organic solvent optionally containing wetting, dispersing or emulsifying agent(s) and then adding the mixture to water which may also contain wetting, dispersing or emulsifying agent(s). Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes, trichloroethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol, and glycol ethers (e.g. 2-ethoxyethanol and 2-butoxyethanol).

The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant, e.g.

fluorotrichloromethane or dichlorodifluoromethane.

The compounds can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating in enclosed spaces a smoke containing the compounds.

Alternatively, the compounds may be used in a microencapsulated form.

By including suitable additives, for example additives for improving the distribution, adhesive power and resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities.

The compounds can be used as mixtures with fertilisers (e.g. nitrogen-, potassium- or phosphoruscontaining fertilisers). Compositions comprising only granules of fertiliser incorporating, for example coated with, the compound, are preferred. Such granules suitably contain up to 25% by weight of the compound. The invention therefore also provides a fertiliser composition comprising the compound of general formula (I) or a salt, metal complex, ether or ester complex thereof.

The compositions may also be in the form of liquid preparations for use as dips or sprays which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surfactants e.g. wetting agent(s), dispersing agent(s), emulsifying agent(s) or suspending agent(s).

These agents can be cationic, anionic or non-ionic agents. Suitable cationic agents are quaternary ammonium compounds, for example cetyltrimethylammonium bromide.

Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesu Iphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulpRonate, and a mixture of sodium diisopropyl- and triisopropyl-naphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonyl- phenol and octylcresol. Other nonionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose), and the vegetable gums (for example gum acacia and gum tragacanth).

The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient(s), the concentrate to be diluted with water before use. These concentrates often should be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain up to 95%, suitably 1085%, for example 2560%, by weight of the active ingredient(s). These concentrates suitably contain organic acids (e.g.

alkaryl or aryl sulphonic acids such as xylene-sulphonic acid or dodecylbenzenesulphonic acid) since the presence of such acids can increase the solubility of the active ingredient(s) in the polar solvents often used in the concentrates. The concentrates suitably contain also a high proportion of surfactants so that sufficiently stable emulsions in water can be obtained. After dilution to form aqueous preparations, such preparations may contain varying amounts of the active ingredient(s) depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of active ingredient(s) may be used.

The compositions of this invention can comprise also other compound(s) having biological activity, e.g. compounds having similar or complementary fungicidal or plant growth regulating activity or compounds having herbicidal or insecticidal activity.

The other fungicidal compound can be for example one which is capable of combating ear diseases of cereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporium spp., seed and soil borne diseases and downy and powdery mildews on grapes and powdery mildew and scab on apple etc.

These mixtures of fungicides can have a broader spectrum of activity than the compound of general formula (I) alone; further the other fungicide can have a synergistic effect on the fungicidal activity of the compound of general formula (I). Examples of the other fungicidal compound are imazalil, benomyl, carbendazim (BCM), thiophanate-methyl, captafol, captan, sulphur, dithiocarbamates, carbathins.

copper oxychloride, triforine, dodemorph, tridemorph, dithianon, pyrazophos, binapacryl, quinomethionate, panoctine, furalaxyl, aluminium tris(ethylphosphonate) DPX32 1 7, ethirimol, dimethirimol, bupirimate, chlorothalonil and metaxanine.

Suitable insecticides are pirimor, croneton, dimethoate, metasystox and formothion.

The other plant growth regulating compound can be one which controls weeds or seedhead formation, improves the level or longevity of the plant growth regulating activity of the compounds of general formula (I), selectively controls the growth of the less desirable plants (e.g. grasses) or causes the compound of general formula (I) to act faster or slower as a plant growth regulating agent. Some of these other agents will be herbicides. Examples of suitable agents are the gibberellins (e.g. GA3, GA4 or GA7), the auxins (e.g. indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (e.g. kinetin, diphenylurea, benzimidazole, benzyladenine or BAP), phenoxyacetic acids (e.g. 2,4-D or MCPA), substituted benzoic acids (e.g.TIBA), morphactins (e.g. chlorfluorecol), maleic hydrazide, glyphosate, glyphosine, long chain fatty alcohols and acids (e.g. Off Shoot O or Off Shoot T), dikegulac, Sustar, Embark, substituted quaternary ammonium and phosphonium compounds (e.g. CCC or Phosfon-D), Ethrel, carbetamide, Racuza, Alar, asulam, abscissic acid, isopyrimol, RH531, hydroxybenzonitriles (e.g. bromoxynil), Avenge, Suffix or Lontrel.

The following Examples illustrate the invention; the temperatures are given in degrees Centigrade (CC).

EXAMPLE 1 This Example illustrates the preparation of the compound 5-(1 ,2,4-triazol-1 -yl)-2-methoxy-2,7,7 trimethyl-octan-3-ol-6-one having the structure:

Stage 1 Methoxy2isoprnpyl methyl ketone (58 parts) was stirred in methanol (1000 ml) at room temperature and bromine (80 parts) added dropwise. The solution was warmed at SOC for four hours during which time the solution became pale yellow. The methanol was removed in vacuo and the orange oil poured into water (200 ml), extracted with chloroform (300 ml). After washing with water (3 x 200 ml), and drying over anhydrous magnesium sulphate, the chloroform was removed in vacuo to give an orange oil.Distillation at the water pump gave methoxy-isopropyl bromomethyl ketone (90%) as a pale yellow liquid b.p. 100-1 02C/24 mmHg.

Stage 2 Methoxy-isopropyl bromomethyl ketone (29 parts) was added dropwise to a solution of triphenyl phosphine (40 parts) in toluene (300 ml) at room temperature. After stirring at room temperature for 30 minutes the solution was refluxed for 2 hours, cooled to room temperature and the solid filtered off. After washing with petrol and toluene the phosphonium salt (45 parts) was dissolved in ethanol (100 ml) and added dropwise to a solution of sodium methoxide (5.5 parts) in methanol (500 ml) at room temperature. After the complete addition the solution was stirred at room temperature for 10 hours. Removal of the solvent gave a brown oil which was dissolved in chloroform (600 ml), washed with water (2 x 200 ml), and dried over anhydrous sodium sulphate.Evaporation of the solvent gave a brown solid which recrystallised from petrol/chloroform to give the phosphorane (80%) m.p. 1 045C.

Stage 3 The phosphorane (15 parts) and freshly distilled t-butyl glyoxal (4.5 parts) were stirred in sodium-dried toluene (100 ml) at room temperature for 12 hours. After this time the solvent was removed in vacuo and the oil triturated with ether (50 ml). The insoluble triphenyl phosphine oxide was filtered off and the solution eluted down a silica column eluted with toluene to give 2-methoxy-2,7,7trimethyl-oct-4-en-3,6-dione (60%) as a pale yellow oit.

Stage 4 2-methoxy-2,7,7-trimethyl-oct-4-en-3,6-dione (4 parts) and 1,2,4-triazole (1.5 parts) were refluxed together in toluene (100 ml) in the presence of benzyl-trimethylammonium hydroxide (4 drops) for 16 hours. After cooling to room temperature the mixture was poured into water (100 ml), washed with water (2 x 100 ml) and dried over anhydrous sodium sulphate. Removal of the solvent gave an oil which was purified by column chromatography (silica eluted with 1:1 60-80 petroleum ether/ethyl acetate) to give 2-methoxy-2,7,7-trimethyl-5-triazol-l -yl-octan-3,6-dione.

Stage 5 5-(1 ,2,4-triazol-1 -yl)-2-methoxy-2,7,7-trimethyl-octan-3,6-dione (3 parts) was stirred in methanol (20 ml) at OC and sodium borohydride (0.1 parts) added portionwise. After stirring at OC for 4 hours the solution was poured into water and carefully neutralised with 2N HCI. The solution was extracted with chloroform (100 ml), washed with water (3 x 100 ml) and dried over anhydrous sodium sulphate. Removal of the solvent gave a viscous oil which recrystallised from petroleum ether/dichloromethane to give the title compound as a white crystalline solid m.p. 108-111 .

EXAMPLE 2 This Example illustrates the preparation of 2,2-dimethyl-4-( 1 ,2,4-triazol-1 -yl)-5-(2'-furoyl) pentan-3-ol having the structure:-

Stage 1 The preparation of 2,2-dimethyl-5-(2'-furoyl)-pent-4-ene-3-one of the structure:

Triphenylphosphonium bromide (3.56 parts), derived from bromopinacolone and triphenylphosphine, was added with stirring at 5 to a suspension of potassium t-butoxide (0.9 parts) in tetrahydrofuran (50 ml). The reaction mixture was slowly allowed to warm up to room temperature and stirred at this temperature for 1.5 hours.The mixture was cooled to 5 and 2-furylglyoxal (1.0 part) in tetrahydrofuran (20 ml) was added dropwise with stirring and left at room temperature overnight. The reaction mixture was filtered, the solvent was removed from the filtrate and ether (30 ml) was added. The resulting solid was filtered off, washed twice with ether and the solvent was removed from the filterate. The resulting yellow solid was crystallised twice from ether. The title compound was obtained with a slight contamination with triphenylphosphine oxide. This was used without further purification.

Stage 2 The preparation of 2,2-dimethyl-5-(2'-furoyl)-4-( 1 ,2,4-triazol-1 -yl)-pentan-3-one of the structure:

To a solution containing 2,2-dimethyl-5-(2'-furoyl)-pent-4-ene-3-one (4.45 parts) in toluene (50 ml) was added 1,2,4-triazole (1.64 parts), triton B (4 drops) and refluxed for six hours and left at room temperature overnight. Toluene was removed in vacuo andwater (50 mix was added. The solid that came out was filtered off, washed with water and dried. Recrystallisation from ether gave the title compound as a white crystalline solid, m.p. 11 8-11 9C Spectral evidence suggests that the triazole group is located next to the t-butyl ketone group.

Stage 3 To a solution of 2,2-dimethyl-5-(2-furoyl)-4-( 1 ,2,4-triazol-l -yl)-pentan-3-one (1.37 parts) in methanol (25 ml) at OC was added sodium borohydride (0.05 g) and the mixture was stirred for three hours at this temperature and then for an additional three hours at room temperature. The solvent was removed in vacuo, water (25 ml) was added, and the mixture neutralised with dilute hydrochloric acid.

The mixture was then extracted with methylene chloride, the organic layer washed with water and then dried (MgSO4), whereupon the solvent was removed. The resulting oily solid was carefully crystallised from ethyl acetate/petrol (60-80 ). 2.2-Dirmethyl-4-(1,2,4-triazol-1-yl)-5-(2-furoyl)-pentan-3-ol) was obtained as a single diastereoisomer, m.p. 1 100.

EXAMPLE 3 This Example illustrates the preparation of 2-methyl-5-(2'-furoyl)-4-( 1 ,2,4-triazol-1 -yl)-pentan-3- ol having the structure:

Stage 1 The preparation of 2-methyl-5-(2'-furoyl)-pent-4-ene-3-one of the structure:

This compound was made in a similar manner as described in Example 2, Stage 1, using 2-furylglyoxal and the appropriate phosphonium bromide. The product was purified by chromatography over silica gel (230 400 mesh) using ethyl acetate-petrol (60-80 ), 1:1 as the eluent. Recrystailisation from toluene gave the pure title compound, m.p. 6061 .

Stage 2 The preparation of 2-methyl-5-(2'-furoyl)-4-(1,2,4-trlzol-1 -yl)-pentan-3-one having the structure:

This compound was made in a similar manner described in Example 2, Stage 2. The product was obtained as an off-white powdery solid, m.p. 120-121 .

Stage 3 The above-mentioned dione was reduced in a similar manner to that described in Example 2, Stage 3 and the ketol was obtained as a light yellow solid, m.p. 146-163 .

EXAMPLE 4 This Example illustrates the preparation of 1 -(2'-methoxyphenyl)-2-(1 ,2,4-triazol-1 -yl)-3-(2' furoyl)-propane-1 -ol having the structure:

(Compound 5 of Table I) Stage 1 The preparation of 1 -(2'-methoxybenzoyl)-2-(2'-furoyl)-ethylene having the structure:

This was made in a similar manner as described in Example 2, Stage 1 using 2-furylglyoxal and the required phosphonium bromide. The title compound was obtained as a white crystalline solid with no contamination with triphenylphosphine oxide, m.p. 86-87 C, Stage 2 The preparation of 1-(2'-methoxyphenyl)-2-(1,2,4-trlazol-1-yl)-3-(2'-furoyl)-propane-1-one having the structure:

This was made in a similar manner as described in Example 2, Stage 2.The title compound was obtained as a crystalline solid, m.p. 8889C.

Stage 3 Reduction of the keto-group next to the triazole in the above-mentioned diketone was carried out as described in Example 2, Stage 3 using the required amount of sodium borohydride. The hydroxy ketone was obtained as a crystalline solid, m.p. 1 68-1 69C.

EXAMPLE 5 An emulsifiable concentrate was made up by mixing the ingredients, and stirring the mixture until all the constituents were dissolved.

Compound of Example 1 10% Ethylene dichloride 40% Calcium dodecylbenzenesulphate 5% "Lubrol" L 10% "Aromasol" H 35% EXAMPLE 6 A composition in the form of grains readily dispersible in a liquid, e.g. water, was prepared by grinding together the first three ingredients in the presence of added water and then mixing in the sodium acetate. The resultant mixture was dried and passed through a British Standard mesh sieve, size 44-100, to obtain the desired size of grains.

Compound of Example 2 50% "Dispersol" T 25% "Lubrol" APN 5 1.5% Sodium acetate 23.5% EXAMPLE 7 The ingredients were all ground together to produce a powder formulation readily dispersible in liquids.

Compound-of Example 3 45% "Dispersol" T 5% "Lissapol" NX 0.5% "Cellofas" B600 2% Sodium acetate 47.5% EXAMPLE 8 The active ingredient was dissolved in a solvent and the resultant liquid was sprayed on to the granules of China clay. The solvent was then allowed to evaporate to produce a granular composition.

Compound of Example 4 5% China clay granules 95% EXAMPLE 9 A composition suitable for use as a seed dressing was prepared by mixing the three ingredients.

Compound of Example 1 50% Mineral oil 2% China clay 48% EXAMPLE 10 A dusting powder was prepared by mixing the active ingredient with talc.

Compound of Example 2 5% Talc 95% EXAMPLE 11 A Col formulation was prepared by ball-milling the constituents set out below and then forming an aqueous suspension of the ground mixture with water.

Compound of Example 3 40% "Dispersol" T 10% "Lubrol" APNS 1% Water EXAMPLE 12 A dispersible powder formulation was made by mixing together the ingredients set out below and then grinding the mixture until all were thoroughly mixed.

Compound of Example 4 25% "Aerosol" OT/B 2% "Dispersol" A.C. 5% China clay 28% Silica 40% EXAMPLE 13 This Example illustrates the preparation of a dispersible powder formulation. The ingredients were mixed and the mixture then ground in a comminution mill.

Compound of Example 1 25% "Perminal" BX 1% "Dispersol" T 5% Polyvinylpyrrolidone 10% Silica 25% China clay 34% EXAMPLE 14 The ingredients set out below were formulated into a dispersible powder by mixing then grinding the ingredents.

Compound of Example 2 25% "Aerosol" OT/B 2% "Dispersol" A 5% China clay 68% In Examples 5 to 14 the proportions of the ingredients given are by weight.

there now follows an explanation of the compositions or substances represented by the various Trade Marks and Trade Names mentioned above.

LUBROL L: a condensate of nonyl phenol (1 mole) with ethylene oxide (13 moles) AROMASOL H: a solvent mixture of alkylbenzenes DISPERSOL T g AC: a mixture of sodium sulphate and a condensate of formaldehyde with sodium naphthale sulphonate LUBROL APNS: a condensate of nonyl phenol (1 mole) with naphthalene oxide (5.5 moles) CELLOFAS B600: a sodium carboxymethyl cellulose thickener LISSAPOL NX: a condensate of nonyl phenol (1 mole) with ethylene oxide (8 moles) AEROSOL OT/B: dioctyl sodium sulphosuccinate PERMINAL BX: a sodium alkyl naphthalene sulphonate EXAMPLE 15 The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No. 1, or Seed, as appropriate) in 4 cm diameter mini-pots. A layer of fine sand was placed at the bottom of the pot to facilitate uptake of test compound by the roots.

The test compounds were formulated either by bead-milling with aqueous Dispersol T or as a solution in acetone/ethanol which was diluted to the required concentration immediately before use. For the foliage diseases, 100 p.p.m. a.i. suspensions were sprayed on to the foliage and applied to the roots of the same plant via the soil. (Sprays were applied to maximum retention, and root drenches to a final concentration equivalent to approximately 40 ppm a.i./dry soil). Tween 20, to give a final concentration of 0.1%, was added when the sprays were applied to the cereals.

For most of the tests, the test compound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inoculated with the diseases. An exception was the test on Erysiphe graminis, in which the plants were inoculated 24 hours before treatment. After inoculation, the plants were put into an appropriate environment to allow infection to take place and then incubated until the disease was ready for assessment. The period between inoculation and assessment varied from 4 to 14 days according to the disease and environment.

The disease control was recorded by the following grading: 4=No disease U - 3=0-5% 2 =625% 1 = 2660% 0-80 The results are shown in Table II.

TABLE II

puccinia Erysiphe Piricularia Plasmopara Plasmopara Phytophthora Botrytls Cercospora Venturla Compound recondita graminis oryzae viticola viticola intestans cinerea arachidicola inequalls number (wheat) (barley) (rice) (vine) (vine) (tomato) (tomato) (peanut) (apple) 1 4 4 3 0 0 2 4 4 2 4 4 1 0 0 1 4 4 3 4 4 0 0 0 0 3 4 4 0 4 0 1 0 0 3 4 5 0 4 0 0 0 0 3 2 6 0 2 0 0 0 0 2 7 0 4 0 0 0 0 4 4 8 3 4 3 1 0 1 4 4 9 0 4 0 0 0 4 0 0 10 0 4 3 0 0 0 0 0 11 0 4 0 0 0 0 4 2 12 0 4 2 0 0 0 1 1 13 0 4 0 4 0 1 3 3 14 0 3 0 2 0 0 0 2 15 0 0 0 0 0 0 0 16 0 4 2 0 0 0 0 0 17 4 4 0 0 1 4 4 18 3 4 0 1 0 1 3 4

Claims (11)

1. The compound having the general formula (I)

formula (I) or a stereoisomer thereof, wherein R1 and R2, which may be the same or different, are unsubstituted or alkyl-substituted cyclo-alkyl, unsubstituted or halo-substituted alkyl, or unsubstituted or substituted phenyl, alkoxyalkyl, furyl, or thienyl, provided that at least one of R and R alkoxyalkyl, furyl or thlenyl; Y Is=N-or=CH-and Z and Z, which may be the same or different, are C=O or a derlvatlve thereof (e.g. an imine, oxime, ketal, hydrazone or semicarbazone) or-CH(OH); and esters, ethers, acid addition salts and metal complexes thereof.

2. A compound according to claim 1 wherein R' or R2 is an alkyl group which is a straight or branched chain and preferably one having from 1 to 5 carbon atoms; and is optionally substituted with halogen.

3. A compound according to claim 1 wherein R or R2 is phenyl or phenyl substituted with halogen C1-4 alkyl [e.g. methyl, ethyl, propyl, (n-or/-propyl) and butyl (n-, i- or t-butyl)], halo(C1-4alkyl) (e.g.

chloro-or bromo- methyl), hydroxy (c1-4 alkyl) (e.g. hydroxymethyl), phenyl, halophenyl (e.g.

chlorophenyl), cycloalkyl, nitro, cyano, C1-4 alkoxy (e.g. methoxy, ethoxy, propoxy or butoxy), C24 alkenyloxy (e.g. allyloxy), (C14 alkylene)dioxy (e.g. methylenedioxy), (C1-4 alkoxy) (C1-4 alkyl) [e.g.

methoxy- or ethoxymethyl or 2-methoxy- or ethoxy-ethyli, mercapto, (C1-4 alkyl) thio [e.g. methyl- or ethyl-thio], (C14 alkyl) sulphonyl [e.g. methyl- or ethyl-sulphonyl], (C14 haloalkyl)sulphonyl [e.g.

trifluoromethylsulphonylj, phenylsulphonyl, unsubstituted or mono- or di-(C1~4 alkyl) substituted sulphamoyl or carbamoyl, 1 -pyrrolidinylsulphonyl, carboxy, (C14 alkoxy)carbonyl [e.g. methoxy- or ethoxy- carbonyl], hydroxy, C1-8 alkanoyloxy, benzoyloxy, carboxy (C1-4 alkyl)oxy (e.g. carboxymethoxy or 1 carboxyethoxy), unsubstituted or mono- or di-(C1-4 alkyl) substituted amino, (C1-6 alkanoyl)amino, N-(C1-4 alkyl)-N-(C1-4 alkanoyl)-amino, formylamino, N-(C1-4 alkyl) formylamino, phenylethyl, methylenedioxyphenyl, phenoxy or benzyloxy,

4. A compound according to claim 1 wherein R or R is cycloalkyl preferably having from 3 to 6 carbon atoms.

5. A compound wherein R or R is an alkoxyalkyl group containing from 2 to 8 carbon atoms; and particularly is:

6. A process for preparing the compounds defined in claim 1 wherein Z' and Z2 are both carbonyl which comprises reacting 1,2,4-triazole, or a salt or metal complex thereof, with a #-diketone of general formula (II) R-Z-CH=CH-Z-R (formula II) wherein R' and R are as defined above in claim 1.

7. A process for preparing the compounds defined in claim 1 wherein one of Z1 and Z2 is carbonyl and the other is CH(OH) which comprises selectively reducing a diketone of general formula (III):

(formula III) wherein Y, R; and R2 are as defined in claim 1, or a salt or metal complex thereof, with, for example, a metal hydride reducing agent (e.g. lithium aluminium hydride or sodium borohydride) in an inert polar solvent (e.g. diethyl ether, water or ethanol).

8. A process for preparing compounds defined in claim 1 wherein, Z1 and Z2 are both CHOH, which comprises reducing (preferably at O to 1000C and for 1 to 12 hours) a diketone or ketoalcohol of general formula (V)

formula (V) wherein Y, R1 and R2 are as defined above, and either both the groups1 and Z2 are 0=0 Or one is 0=0 and the other is CHOH, or a salt or metal complex thereof, with, for example, a metal hydride reducing agent (e.g. lithium aluminium hydride, sodium borohydride or aluminium isopropoxide) in an inert polar solvent (e.g. water or ethanol).

9. A fungicidal or plant growth regulating composition comprising as an active ingredient a compound according to any of claims 1 to 5, or a salt, metal complex, ether or ester thereof, together with a carrier or diluent therefor.

10. A method of combating fungal diseases in a plant, which method comprises applying to the plant, to seed of the plant or to the locus of the plant or seed a compound, or a salt, metal complex, ether or ester thereof, as defined in any of claims 1 to 5; or a composition as claimed in claim 9.

11. A method of regulating the growth of a plant, which method comprises applying to the plant, to seed of the plant or to the locus of the plant or seed a compound, or a salt, metal complex, ether or ester thereof as defined in any of claims 1 to 5: or a composition as claimed in claim 9.