GB2143523A - Heterocyclic compounds - Google Patents

Abstract

Compounds of formula: <IMAGE> and stereoisomers thereof. wherein W is N or CH; R is an optionally substituted aryl (especially phenyl), alkyl, cycloalkyl, or an optionally substituted aralkyl group. or a hydrogen atom; and A and B, which may be the same or different, are hydrogen or halogen atoms, or alkyl, alkoxy, haloalkoxy. phenyl, or phenoxy groups, possess fungicidal and plant-growth regulating activity. Several novel intermediates are also disclosed.

Description

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

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

and stereoisomers thereof, wherein W is N or CH; R is an optionally substituted aryl (especially phenyl), alkyl, cycloalkyl, or an optionally substituted aralkyl group, or a hydrogen atom; and A and B, which may be the same or different, are hydrogen or halogen atoms, or alkyl, alkoxy, haloalkoxy, phenyl, or phenoxy groups; and acid salts and metal complexes thereof.

Preferred alkyl groups contain from 1 to 6 carbon atoms. Preferred cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups.

The compounds of the invention contain at least one chiral centre, and are generally obtained in the form of racemic mixtures. However, these mixtures can be methods known in the art, and this invention embraces such isomers.

Examples of suitable substituents for the group R when it is aryl (especially phenyl) or aralkyl are halogen, alkyl, alkoxy, haloalkyl, optionally substituted phenyl, and optionally substituted phenoxy; the alkyl and alkoxy groups preferably contain 1 to 4 carbon atoms.

When R is an aryl, especially phenyl, group it may be unsubstituted or substituted with 1, 2 or 3 ring substituents, which may be the same or different, as defined above. Specific examples for the group R are phenyl, 2-, 3- or 4-chlorophenyl, 2,4- or 2,6-dichlorophenyl, 2,4- or 2,6difluorophenyl, 2-, 3- or 44luorophenyl, 2-, 3- or 4-bromophenyl, 2-, 3- or 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-fluoro-4-chlorophenyl, 2-chloro-4-fluorophe- nyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-trifluoromethylphenyl, 4phenylphenyl (4-biphenylyl), 2-chloro-4-methoxyphenyl, 2-fluoro-4-methoxyphenyl, 2-chloro-4methylphenyl, 2-fluoro-4-methylphenyl, 4-isopropylphenyl, 2-methyl-4-chlorophenyl or 2-methyl 4-fluorophenyl.

When R is alkyl it can be a straight or branched chain alkyl group having 1 to 6, eg. 1 to 4 carbon atoms; examples are methyl, ethyl, propyl (n or ispropyl) and butyl (n, sec, iso or tbutyl).

The moiety W is preferably N, ie. The preferred compounds are triazoles.

The salts can be salts with inorganic or organic acids eg. hydrochloric, nitric, sulphuric, acetic, 4-toluenesulphonic or oxalic acid.

Suitably the metal complex is one including, as the metal, copper, zinc, manganese, or iron. It preferably has the formula:

wherein R, W, A and B are as defined above, E is a metal, Q is an anion (eg. a chloride, bromide, iodide, nitrate, sulphate, or phosphate anion), n is 2 or 4, F is zero or an integer of 1 to 1 2, and m is an integer consistent with valency.

Examples of the compounds of the invention are shown in Table I. These conform to formula (l') TABLE I

COMPOUND R X W Melting NO Point (C) | 1 4-Cl-C6H4 H N Oil 2 4-F-C6H4 H N 120-121 3 n-C4Hg H N Oil 4 n-C4Hg H CE Oil 5 cyclohexyl H N | Oil 6 4-F-C6H4 Cl N Oil 7 n-C4H9 Cl N 85-86 The compounds of the invention having the general formula (I) can be prepared from protected olefinic alcohols of general formula (IV) by the steps shown in Scheme I.

Scheme I

Throughout Scheme I the terms R, W, A and B are as defined above, Z is a halogen atom (such as a bromine, iodine or chlorine atom) or a sulphonate group (such as a CH3SO20- or 4-CH3-C6H4-SO20- group), and Y is a protecting group (such as a trityl or acyl group) for a hydroxyl function.

Thus compounds of general formula (I) can be prepared by treatment of compounds of general formula (II) either with 1 ,2,4-triazole or with imidazole, each in the presence of an acidbinding agent or in the form of one of its alkali metal salts, in a convenient solvent (such as dimethylformamide or acetonitrile) and at a convenient temperature (such as 60 to 1 60 C).

Compounds of general formula (II) in which Z is a halogen atom can be prepared by treatment of olefinic alcohols of general formula (III) with a halogen (such as bromine or iodine) in the presence of an acid-binding agent (such as pyridine or triethylamine) in a convenient solvent (such as dichloromethane) (see, for example, I. Monkovic, Y.G. Perron, R. Martel, W.J. Simpson and J.A. Gylyls, J. Med. Chem., 1973, 16, 403; H. Wong, J. Chapuis and l.Monkovic, J.Org.Chem.,1974, 39, 1042).

Olefinic alcohols of general formula (III) can be prepared from protected olefinic alcohols of general formula (IV) under reaction conditions which depend upon the nature of the protecting group Y. If, for example, Y is a trityl group, deprotection can be accomplished under mildly acidic conditions; if Y is an acyl group, deprotection can be accomplished using aqueous hydroxide. Other protecting groups may also be used, and removed under appropriate conditions.

Protected olefinic alcohols of general formula (IV) can be prepared by the routes shown in Schemes II and Ill.

Scheme II

Scheme III

Throughout Schemes II and Ill the terms R, A, B and Y are as defined above.

Thus, protected olefinic alcohols of general formula (IV) can be prepared by dehydration of alcohols of general formula (V). Heating the neat alcohol (V) with a catalytic quantity of iodine is one of several possible methods for accomplishing this dehydration.

Alcohols of general formula (V) can be prepared by selectively protecting the primary hydroxyl group of diols of general formula (Vl) using, for example, trityl chloride or an acyl chloride, each in the presence of a suitable base (such as triethylamine or pyridine). The primary hydroxyl group can also be protected with other groups using appropriate reagents and conditions.

Diols of general formula (Vl) can be prepared by reduction of lactones of general formula (VII) using, for example, lithium aluminium hydride in a suitable solvent such as diethyl ether or tetrahydrofuran.

Lactones of general formula (VII) can be prepared by treatment of compounds of general formulae (VIII) or (IX) with an excess of organometallic reagents of general formulae RM or CH3M respectively, where R is as defined above, and M is a metal atom (such as a lithium atom) or a metal atom plus an associated halogen atom (such as Mgl, Mg Br, or MgCl), followed by lactonisation of the resulting hydroxy acids under acidic conditions.

Alternatively, protected olefinic alcohols of general formula (IV) can be prepared by methylenation of ketones of general formula (X) using, for example, methylenetriphenylphosphorane in a suitable solvent (such as dimethylsulphoxide, diethyl ether, or tetrahydrofuran) (see, for example, R. Greenwald, M. Chaykovsky, and E.J.Corey, J. Org. Chem., 1963, 28, 1128).

Ketones of general formula (X) can be prepared by oxidation of alcohols of general formula (Xl) using, for example, pyridinium dichromate in dimethylformamide (see, for example, E.J.Corey and G.Schmidt, Tetrahedron Letters, 1979, 399).

Alcohols of general formula (XI) can be prepared by selectively protecting one hydroxyl group of diols of general formula (XII) using, for example, trityl chloride or an acyl chloride, each in the presence of a suitable base (such as triethylamine or pyridine). The hydroxyl group can also be protected with other groups using appropriate reagents and conditions.

Diols of general formula (Xll) can be prepared by treatment of compounds of general formula (XV) with an excess of organometallic reagents of general formula RM, where R and M are as defined above, in a suitable solvent such as diethyl ether or tetrahydrofuran.

Alternatively, diols of general formula (XII) can be prepared by reduction of lactones of general formula (XIII) using, for example, lithium aluminium hydride in a suitable solvent such as diethyl ether or tetrahydrofuran.

Lactones of general formula (XIII) can be prepared by treatment of compounds of general formula (XIV) with an excess of organometallic reagents of general formula RM, where R and M are as defined above, in a suitable solvent such as diethyl ether or tetrahydrofuran, followed by lactonisation of the resulting hydroxy acids under acid conditions.

The compounds of general formulae (VEIL), (IX), (XIV) and (XV) may exist as the ring-closed species illustrated, or as the corresponding ring-opened species, or in the form of equilibrium mixtures of ring-closed and ring-opened species. Each of these compounds can be prepared by standard methods described in the chemical literature.

The compounds, salts and metal complexes are active fungicides, particularly against the diseases: Piricularia oryzeae on rice Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts eg. coffee, apples, 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 Sphaerotheca fuliginea on cucurbits (eg. cucumber), Podosphaera leucotricha on apples and Uncinula necator on vines Helminthosporium spp., Rhynchosporium spp. and Pseudocercosporella herpotrichoides on cereals 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 infestans (late blight) on tomatoes 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 (eg. Penicillium digatatum anditalicum on oranges and Gloeosporium musarum on bananas). Further some of the compounds are active as seed dressings against: Fusarium spp., Septoria spp., Tilletia spp. (ie.

bunt, a seed borne disease of wheat), Ustilago spp., Helminthosporium spp. on cereals, Ahizoctonia solani on cotton and Corticium sasakii on rice.

The compounds can move acropetally in the plant tissue. Moreover, the compounds can be volatile enough to be active in the vapour phase against fungi on the plant.

They may also be useful as industrial (as opposed to agricultural) fungicides, eg, in the prevention of fungal attack on wood, hides, leather and especially paint films.

The compounds are also useful for the treatment of candidiasis and human dermatophyte infections.

The compounds, and their derivatives as defined above, 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 dicotyledonous plants. Such stunting or dwarfing may be useful, for example, in peanuts, cereals such as wheat and barley, oil seed rape, field beans, sunflowers, potatoes and soya bean where reduction in stem height, with or without further advantageous effects such as stem strengthening, thickening and shortening, internode shortening, increased buttress root formation and more erect stem and leaf orientation, 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), Dactylis glomerata, Festuca spp. (eg. Festuca rubra) and Poa spp. (eg. 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 of such weed species are sedges (eg. Cyperus spp.) and dicotyledonous weeds (eg. daisy, plantain, knotweed, speedwell, thistle, docks and ragwort).The growth of non-crop vegetation (eg. 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 (eg. 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 or reduce the need for pruning, of fruit trees (eg.

apples, pears, cherries, peaches, vines etc). Some coniferous trees 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 itselt in an increase in crop yield; or in an ability in orchards and other crops to increase fruit set, pod set and grain set.

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 changes in leaf morphology (both of which may permit increased light interception and utilization) and promotion of tillering in monocotyledonous plants. Improved light interception is of value in all major world crops, eg. wheat, barley, rice, maize, soya, sugarbeet, potatoes, plantation crops and orchard crops. The leaf angle effect may be useful for example in altering the leaf orientation of, for example, potato crops thereby letting rnore light into the crops and inducing an increase in photosynthesis and tuber weight. By increasing tillering in monocotyledonous crops (eg. rice), the number of flowering shoots per unit area may be increased thereby increasing the overall grain yield of such crops.In addition better control and modification of hierarchical relationships is possible both in vegetative and reproductive stages of monocotyledonous and dicotyledenous plant growth, especially in cereals such as wheat, barley, rice and maize, whereby the number of flowering shoots per unit area may be increased and the size distribution of grains within the ear may be modified in such a way as to increase yield. In the treatment of rice plants, or rice crops the invention compounds can be applied, eg.

as granules or a granular formulation, for example as slow release granules, to nursery boxes, paddy water and other like cultivation loci and media. In grass swards, especially amenity grass, an increase in tillering could lead to a denser sward which may result in increased resilience in wear; and to increased yields and better quality of forage grass, eg. improved digestability and palatability.

The treatment of plants with the compounds can lead to the leaves developing a darker green colour. In dicotyledonous plants such as soyabean and cotton, there may be promotion of sideshooting.

The compounds may inhibit, or at least delay, the flowering of sugar beet (and thereby may increase sugar yield) or otherwise modify the flowering patterns in many other crops. 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 (eg. 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 vegetative growth of cotton thereby leading to an increase in cotton yield. Crop yields may also be increased by improvement of the harvest index (ie. the harvested yield as a proportion of the total dry matter produced) by altering dry matter partitioning. This applies to all the aforements root, pod cereal, tree, plantation and orchard crops.

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 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. With the use of biodegradable polymeric slow release granules rates of 1 to 10g per hectare are feasible; whilst electrodynamic spraying techniques may also deploy lower rates of application. 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 compositions for such usage. The invention thus provides a fungicidal or plant growth regulating composition comprising a compound of general formula (I) as hereinbefore defined, or a salt, metal complex, ether or ester thereof; and, optionally, a carrier or diluent.

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

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

The compounds, salts, metal complexes, ethers and esters can be applied in a number of ways, for example they can be applied, formulated or unformuiated, 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; or as slow releast granules. 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; or to the soil generally, to paddy water or to hydrophonic culture systems. The invention compounds may also be injected into plants or trees and they may also be sprayed onto vegetation using electrodynamic spraying techniques.

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-methylpyrrolidone 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 or emulsions may be prepared by dissolving the active ingredient(s) in an oganic 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 (eg. 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, eg.

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 micro-encapsulated form. They may also be formulated in biodegradable polymeric formulations to obtain a slow, controlled release of the active substance.

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 (eg. nitrogen-, potassium- or phosphorus-containing fertilisers). Compositions comprising only granules of fertiliser incorporat ing, for example coated with, the compound are preferred. Such granules suitable 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 or metal 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 eg. wetting agent(s), dispersing agent(s), emulsifying agent(s) or suspending agent(s); or which are spray formulations of the kind suitable for use in electrodynamic spraying techniques. The foregoing 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 dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropylnaphthalene 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 non-ionic 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), and the concentrate is 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 and electrodynamic spray equipment. The concentrates may conveniently contain up to 95%, suitably 10-85%, for example 25-60%, by weight of the active ingredient(s).These concentrates suitably contain organic acids (eg. alkaryl or aryl sulphonic acids such as xylenesulphonic acid or dodecylbenesulphonic 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, eg. compounds having similar or complementary fungicidal or plant growth activity or compounds having plant growth regulating, herbicidal or insecticidal activity.

The other fungicial compound can be, for example, one which is capable of combating ear diseases of cereals (eg. 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, thiophanate-methyl, captafol, captan, sulphur, triforine, dodemorph, tridemorph, pyrazophos, furalaxyl, ethirimol, tecnazene, dimethirimol, bupirimate, chlorothalonil, vinclozolin, procymidone, iprodione, metalaxyl, forsetyl-aluminium, carboxin, oxycarboxin, fenarimol, nuarimol, fenfuram, methfuroxan, nitrotal-isopropyl, triadimefon, thiabendazole, etridiazole, triadimenol, biloxazol, dithianon, binapacryl, quinomethionate, guazitine, dodine, fentin acetate, fentin hydroxide, dinocap, folpet, dichlofluanid, ditalimphos, kitazin, cycloheximide, dichlobutrazol, a dithiocarbamate, a copper compound, a mercury compound, 1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea, fenapanil, ofurace, propiconazole, etaconazole and fenpropemorph.

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

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 (eg.

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 plant growth regulating compounds, which can display synergy in admixture, or use, with the invention compounds are the gibberellins (eg. GA3, GA4 or GA7), the auxins (eg. indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (eg. kinetin, diphenylurea, benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids (eg. 2,4-D or MCPA), substituted benzoic acids (eg. triiodobenzoic acid), morphactins (eg. chlorofluorecol), maleic hydrazide, glyphosate, glyphosine, long chain fatty alcohols and acids, dikegulac, fluoridamid, mefluidide, substituted quaternary ammonium and phosphonium compounds (eg. chlommequat chlorphonium or mepiquatchloride), ethephon, carbetamide, methyl-3,6-dichloroanisate, daminozide asulam, abscisic acid, isopyrimol, 1-(4 chlorophenyl)-4, 6-dimethyl-2-oxo- 1 , 2-dihydropyridine-3-carboxylic acid, hydroxybenzonitriles (eg. bromoxynil), difenzoquat, benzoylprop-ethyl 3,6-dichloropicolinic acid, and tecnazene.

Synergy will be most likely to occur with those of the foregoing which are quaternary ammonium compounds in particular those marks with an asterisk.

The use of the compounds of general formula (I) in conjunction with gibberellins can be useful where it is desired to reduce the plant growth regulating effects of the compounds (eg. where they are to be used as fungicides). Where the compounds are being applied to the soil surrounding the plants or to the roots of the plant, the plant growth regulating effects of the compounds may possibly be reduced by using also certain types of phenoxybenzoic acids and their derivatives.

The following Examples illustrate the invention. Throughout these Examples magnesium sulphate was used to dry solutions, and the abbreviations shown below are used: THF : tetrahydrofuran DMF : dimethylformamide DMSO : dimethylsulphoxide s : singlet t : triplet m : multiplet d : doublet q : quartet EXAMPLE 1 This Example illustrates the preparation of 1 -(4-chlorophenyl) 1 -(1,2, 4-triazol- 1 -ylmethyl)- 1,3- dihydroisobenzofuran (Compound No 1 of Table I).

A solution of 2-(4-chlorobenzoyl)benzoic acid (26.059) in dry diethyl ether (400ml) was added dropwise to a stirred solution of methylmagnesium iodide [from methyl iodide (31.25g) and magnesium (5.309)1 in dry diethyl ether (1 30ml) at about 1 5 C. A thick precipitate formed, making stirring difficult. The mixture was allowed to stand overnight, then aqueous ammonium chloride was added (precipitate dissolved) and the mixture was acidifed with concentrated hydrochloric acid.Ethyl acetate extracts of this mixture were washed successively with aqueous sodium bicarbonate ( X 3) and water, then dried and concentrated to give 3-(4-chlorophenyl)-3methyl-1,3-dihydro-1-oxoisobenzofuran (12.269, 47%) as a viscous oil, u max. (film) 1760cm-1, 1H n.m.r. (CDCI3): S 2.02 (3H,s).

A solution of 3-(4-chlorophenyl)-3-methyl-l ,3-dihydro-l -oxoisobenzofuran (7.309) in dry TH F (75ml) was added dropwise to a stirred suspension of lithium aluminium hydride (1.1 0g) in dry THF (50ml). The mixture was stirred at room temperature for 2 hours then poured carefully into ice and aqueous ammonium chloride and extracted with ether. The extracts were washed with water, treated with magnesium sulphate and charcoal, then filtered and concentrated to give 1 (4-chlorophenyl)-1-(2-hydroxymethylphenyl)ethanol (6.659, 90%) as a viscous oil which slowly crystallised to give a solid, melting point 110-111"C, 1H n.m.r. (CDCl3): 8 1.83 (3H,s), 4.09 (2H,s).

A mixture of 1 -(4-chlorophenyl)-1 -(2-hydroxymethylphenyl)ethanol (6.659), benzoyl chloride (3.919) and pyridine (2.409) was stirred at room temperature for 48 hours. The mixture was diluted with water and extracted with ether. The extracts were washed with water, dried, concentrated, and chromatographed on a column of silica gel using 20% diethyl ether in petrol to give 1 -(4-chlorophenyl)-1 -(2-benzoyloxymethylphenyl)ethanol (4.439, 48%) as a white solid, melting point 105-109 C, 1H n.m.r. (CDCl3): 81.92 (3H,s), 4.89 (1H, d J 14Hz), 5.34 (1H, d J 14Hz).

1-(4-Chlorophenyl)-1-(2-benzoyloxymethylphenyl)-ethanol (4.249) was heated at 1 30 C with a catalytic quantity of iodine for 1 hour. The resulting mixture was dissolved in ethyl acetate, dried, and concentrated to give 1 -(4-chlorophenyl)- 1 -(2-benzoyloxymethylphenyl)ethylene (3.859, 96%) as a yellow oil which crystallised on standing to give a solid, melting point 75-76 C, 1H n.m.r. (CDC13): 8 5.22 (2H,s), 5.32 (1 H, s), 5.85 (1 H, s).

A stirred mixture of 1 -(4-chlorophenyl)- 1 -(2-benzoyloxymethylphenyl)ethylene (3.609) and sodium hydroxide (0.459) in THF (80ml) methanol (1 5ml) and water (5 my) was warmed gently in a stream of hot air until thin-layer chromatography indicated that hydrolysis was complete.

The mixture was diluted with water and extracted with ether. The extracts were washed with water then dried and concentrated to give a yellow oil (3.149) containing 1-(4-chlorophenyl)-1 (2-hydroxymethylphenyl)ethylene.

Pyridine (0.85ml) and bromine (0.53ml) were added successively to a stirred solution of the crude 1 -(4-chlorophenyl)-l -(2-hydroxymethylphenyl)ethylene (3.1 4g) in dichloromethane (50ml) at 5 C. The reaction mixture was stirred at this temperature for 0.5 hours then washed successively with water, dilute hydrochloric acid, and water, then dried and concentrated to give an orange oil (3.739) containing 1 -(bromomethyl)-i -(4-chlorophenyl)- 1 ,3-dihydroisobenzofuran and none of the initial olefinic alcohol.Part of this oil (3.34g) was added to a solution of sodium 1 ,2,4-triazole [from 1 2,4-triazole (1.089) and sodium hydride (0.379)] in DMF (60ml), and the mixture was heated at 1 60 C for 4 hours. The mixture was poured into water and extracted with ethyl acetate. The extracts were washed with water, dried, concentrated, and chromatographed on a column of silica gel using ethyl acetate as eluant to give the title compound [0.779, 25% from 1-(4-chlorophenyl)-1-(2-benzoyloxymethylphenyl)ethylene] as a viscous oil, H n.m.r.

(CDCI3): 8 4.83 (2H, s), 5.07 (2H, tight AB q, J 1 2Hz), 7.08-7.56 (8H, m), 7.72 (1 H, s), 8.08 (1H, s).

EXAMPLE 2 This Example illustrates the preparation of I-(but-l-yl)-l-(l ,2,4-triazol-l -yl-ylmethyl)-l ,8dihy- droisobenzofuran (Compound No 3 of Table I).

A solution of 2-carboxybenzaldehyde (16.169) in dry THF (50ml) was added dropwise to a paddle-stirred solution of butylmagnesium bromide [from 1-bromobutane (31.09) and magnesium (5.94g)] in dry diethyl ether (1 70ml). The addition was exothermic and a thick precipitate formed. After 2 hours, ice was added to the reaction mixture and it was acidifed with concentrated hydrochloric acid (precipitate dissolved) then stirred at room temperature for 48 hours. The organic and aqueous layers were separated and the latter was extracted with ether.

The combined organic layers were washed successively with aqueous sodium bicarbonate and water, then dried and concentrated to give almost pure 3-but-1-yl-1,3-dihydro-1-oxoisobenzofu- ran (15.649, 76%) as a yellow liquid, v max (film) : 1760cm-1.

A solution of 3-but-1-yl-1,3-dihydro-1-oxoisobenzofuran (15.649) in dry THF (150ml) was added dropwise to a stirred suspension of lithium aluminium hydride (3.1 2g) in dry THF (100ml). The resulting mixture was stirred at room temperature for 2 hours, then poured into a mixture of ice and aqueous ammonium chloride and extracted with ether. The extracts were washed with water, dried, and concentrated to give 1-(2-hydroxymethylphenyl)butan-1-ol (14.259, 89%) as a viscous oil, 'H n.m.r. (CDCl3) : 8 4.62 (2H, AB q, CH20H), 4.83 [1 H, t J 7a,CH(OH)(CH2)3CH3].

A mixture of 1-(2-hydroxymethylphenyl)butan-1-ol (12.1 8g), triphenylmethyl chloride (19.149), triethylamine (11 .37g) and 4-pyrrolidinopyridine (0.309) in dichloromethane (250ml) was stirred overnight at room temperature. The resulting solution was washed successively with water, dilute hydrochloric acid, and water, then dried and concentrated to give a thick red oil (29.19) containing 1 -(2-triphenylmethoxymethylphenyl)butan-1 -ol.

A solution of all of this red oil in dry DMF (200ml) was stirred with pyridinium dichromate (50.1g) at room temperature for 6.5 hours. The resulting mixture was poured into water and extracted with ether. The extracts were washed with water, dried and concentrated to give an oily solid (23.29). Trituration, then concentration of the washings and further trituration, gave o (triphenylmethoxymethyl)valerophenone [1 8.96g, 70% from 1 -(2-hydroxymethylphenyl)butan-l - ol) as a cream-coloured solid, melting point 98-99 C, 'H n.m.r. (CDCI3) : 8 2.73 (2H, t J8Hz), 4.40 (2H, s). A sample crystallised from 80-100 C petrol had a melting point of 99-100"C.

A suspension of sodium hydride (1.249) in dry DMSO (80ml) was stirred at about 50'C for 2 hours and then allowed to cool to room temperature. A solution of methyltriphenylphosphonium bromide (18.479) in dry DMSO (90ml) was added, and the resulting mixture was stirred at room temperature for 15 minutes to allow the ylide to form. A solution of oQtriphenylmethoxy- methyl)valerophenone (15.009) in dry DMSO (80ml) was then added dropwise to the ylide (exothermic) and the mixture was stirred at room temperature for 2 hours, then diluted with water and extracted with ethyl acetate.The extracts were washed with water, dried, concentrated, and chromatographed on a column of silica gel using ether as eluant to give 1-but-1-yl-1- (2-triphenylmethoxymethylphenyl)ethylene (1 3.42g, 90%) as a viscous oil, 1H n.m.r. (CDCl3) : 8 4.22 (2H, s), 4.78 and 5.01 (each 1 H, d J ca. 1Hz).

A mixture of l-but-l-yl-l -(2-triphenylmethoxymethylphenyl)ethylen (13.009) and ptoluene- sulphonic acid (0.5g) in dry methanol (1 50ml) was stirred at room temperature for 2 hours then poured into water and extracted with ether. The extracts were washed successively with water, aqueous sodium bicarbonate, and water, then dried, concentrated and chromatographed on a column of silica gel using 10% diethyl ether in petrol as eluant to give (-but-1-yl-1-(2- hydroxymethylphenyl)ethylene (5.029, 88%) as a pale yellow oil, 'H n.m.r. (CDCl3): S 4.71 (2H, s), 4.96 and 5.25 (each 1 H, d J ca.1 Hz).

l-But-l-yl-l -(2-hydroxymethylphenyl)ethylene was converted into the title compound in 2 steps (30% yield) by the method described in Example 1 for the conversion of 1-(4 chlorophenyl)-l -(2-hydroxymethyl)ethylene into 1 -(4-chlorophenyl)-1-( -(1,2, 4-triazol- 1 -ylmethyl)1,3-dihydroisobenzofuran. The product, a viscous oil, showed 1H n.m.r. (CDCl3) : 8 4.59 (2H, s), 5.08 (2H, AB q J 1 3Hz).

EXAMPLE 3 This Example illustrates the preparation of 5-chloro-1-(4-fluorophenyl)-1-(1,2,4-triazol-1-ylme- thyl)-1,3-dihydroisobenzofuran (compound number 6 of Table 1).

r > Butyl-lithium (73 ml of 1.5 M solution in rphexane) was added dropwise to a stirred solution of 2-(4-chlorophenyl)-4, 4-dimethyl-2-oxazoline (20.9 g, prepared from 4-chlorobenzoyl chloride by the method of A. I. Meyers et al., J. Org. Chem., 1974, 39, 2787) in dry diethyl ether (300 ml) at O to 5 C. The resulting red solution was stirred at ca. 5 C for 1 hour, then a suspension of paraformaldehyde (3.33 g) in dry ether (130 ml) was added in one portion. The reaction mixture was allowed to warm to room temperature, stirred for 3 hours, poured into iced water, and extracted with ether.The extracts were washed with water, then dried and concentrated to give almost pure 2-(2-hydroxymethyl-4-chlorophenyl)-4,4-dimethyl-2-oxazoline (24.0 g, quantitative) as an orange oil, 1H n.m.r. (CDCl3) : # 1.41 (6H,s), 4.16 (2H,s), 4.65 (2H, broad s).

A mixture of 2-(2-hydroxymethyl-4-chlorophenyl)-4,4-dimethyl-2-oxazoline (18.64 g) and 4.5 M hydrochloric acid (400 ml) was heated at 140'C (bath temperature) for 1 hour. The solid that precipitated was filtered off, washed with water and dried to give 5-chloro-1,3-dihydro-1- oxoisobenzofuran (8.49 g, 66%) as a fawn solid, melting point 151-152'C, "max (nujol) 1745 cm-1, H n.m.r. (CDCI3) : 8 5.32 (2H,5).

Di-isobutylaluminium hydride (62.4 ml of 1 M solution in hexane) was added dropwise to a stirred solution of 5-chloro-1,3-dihydro-1-oxoisobenzofuran (8.49 g) in dry diethyl ether at between - 70 and - 60'C. The resulting mixture was stirred at ca. - 70"C for 1 hour, then poured into a mixture of ice and water. The ether layer was separated, washed with water, dried and concentrated to give 5-chloro-1,3-dihydro-1-hydroxyisobenzofuran (5.11g, 60%) as a solid, melting point 80-81 C; its infrared spectrum (nujol mull) showed hydroxyl (3370 cm-1) but no carbonyl absorption, while its 'H n.m.r. spectrum (CDCl3) indicated that some formyl component is present in solution (8 10.14).

A solution of 5-chloro-1,3-dihydro-1-hydroxyisobenzofuran (3.54 g) in dry diethyl ether (40 ml) was added dropwide to a stirred solution of 4-fluorophenylmagnesium bromide [from 4bromofluorobenzene (7.80 g) and magnesium (1.21 g)l in diethyl ether (10 ml). The resulting mixture was stirred for 2 hours, then dilute hydrochloric acid was added carefully. The organic and aqueous layers were separated and the latter was extracted with ether. The combined organic layers were washed with water, dried, concentrated, and chromatographed on a column of silica gel using diethyl ether/petrol (1:1) as eluant to give (4-fluorophenyl)(4-chloro-2hydroxymethylphenyl)-methanol (3.079, 56 %), 1H n.m.r. (CDCl3) : 8 4.56 (2H, AB q J 1 3 Hz), 6.07 (1H,s).

(4-Fluorophenyl)(4-chloro-2-hydroxymethylphenyl)methanol was converted into the title compound in 6 steps (6% overall yield) by the method described in Example 2 for the conversion of 1 -(2-hydroxymethylphenyl)butan- 1 -ol into 1-but-1-yl)-1,2,4-triazol-1 -ylmethyl)- 1 , 3-dihydroisoben- zofuran. The product, a viscous oil, had 'H n.m.r. (CDCI3) : 8 4.81 (2H, AB q J 17Hz), 5.01 (2H, AB q J 11Hz).

EXAMPLE 4 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 5 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" APN5 1 1.58 Sodium acetate 23.5% EXAMPLE 6 The ingredients were all ground together to produce a powder formulation readily dispersible in liquids.

Compound of Example 3 45% "Dispersol" T 5% "tissapol" NX 0.5% "Cellofas" B600 2% Sodium acetate 47.5% EXAMPLE 7 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 1 5% China clay granules 95% EXAMPLE 8 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 9 A dusting powder was prepared by mixing the active ingredient with talc.

Compound of Example 2 5% Tale 95% EXAMPLE 10 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" APN5 1% Water 49% EXAMPLE 14 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 1 25% "Aerosol" OT/B 2% "Dispersol" A.C. SI China clay 28% Silica 40% EXAMPLE 12 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 13 The ingredients set out below were formulated into a dispersible powder by mixing then griding the ingredients.

Compound of Example 2 25% "Aerosol" OT/B 2% "Dispersol" A 5* China clay 68% In Examples 4 to 1 3 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 a AC: a mixture of sodium sulphate and a condensate of formaldehyde with sodium naphthalene sulphonate LUBROL APN5: 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 14 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 2) in 4 cm diameter minipots.

A layer of fine sand was placed at the bottom of the pots containing the dicotyledonous plants 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 or acetone/ethanol which was diluted to the required concentration immediately before use. For the foliage diseases, suspensions (100 ppm active ingredient) were sprayed on to the soil. Exceptions to this were the tests on Botrytis cinerea, plasmopara viticola and Venturia inaequalis. The sprays were applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a.i./dry soil. Tween 20, to give a final concentration of 0.05%, was added when the sprays were applied to cereals.

For most of the tests the compound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inocluated with the diseases. An exception was the test of 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 four to fourteen days according to the disease and environment.

The disease control was recorded by the following grading:4 = no disease 3 = trace-5% of disease on untreated plants 2 = 6-25% of disease on untreated plants 1 = 26-59% of disease on untreated plants 0 = 60 = 100% of disease on untreated plants TABLE II

COMPOUND PUCCINIA ERYSIPHE PIRICULARIA PLASMOPARA PHYTOPHTHORA BOTRYTIS CERCOSPORA VENTURIA NUMBER RECONDITA GRAMINIS ORYZAE INFESTANS CINEREA CINERA ARACHIDICOLA INAEQUALIS (WHEAT) (BARLEY) (RICE) (VINE) (TOMATO) (GRAPE OR (PEANUT) (APPLE) TOMATO) 1 4 4 3 0 - 2 0 4 2 3 4 4 0 - 4 4 4 3 4 4 4 1 - 0 4 4 4 3 4 0 0 - 0 4 4 5 4 4 3 0 - 0 4 4 6 4 4 4 4 - - 4 4 7 - - - - - - - 4 The results are shown in Table II. A dash in the table thus "-" signifies that no test against the disease was conducted.

EXAMPLE 15 This Example illustrates the plant growth regulating properties of the compounds. The compounds were applied as an overall spray of an emulsifiable concentrate diluted to give the concentrations shown in Table Ill The plants were grown in 3" pots in peat compost and sprayed at the 2 leaf stage. Plant growth regulating effects were assessed 12 days after application of the compounds. Retardation of growth was scored on a 0-3 scale where: 1 = 0-30% retardation 2 = 31-75% retardation 3 = 75% retardation Additional plant growth regulating properties are indicated as follows: G = darker green leaf colour A = apical effect T = tillering effect The results are shown in Table Ill. If no figure is given, the compound was substantially inactive as a stunting agent.

TABLE III

COMPOUND DAT RATE AT CC DA LT SB TO fly CT HZ W BR NUMBER (ppm) 1 19 4000 - - - 2 2G 3AGT 2G 2GT - - 2 - - - 2G 2G 10 20 10 2GT 1GT 3 - - - 3 2G ICT 1 3AGT 3G 4 - - 1 1 1 - 2TA G 10 1 5 1G 1G 1G 1G 1G Key to test species in Table Ill SY Glycine max CT Gossypium hirsutum SB Beta vulgaris AT Agrostis tenuis CC Cynosurus cristatus DA Dactylis glomerata WW Triticum aestivum BR Hordeum vulgare MZ Zea mays LT Lactuca sativa TO Lycopersicon esculentum

Claims (14)

1. A compound having the general formula (I):

and stereoisomers thereof, wherein W is N or CH; R is an optionally substituted aryl (especially phenyl), alkyl, cycloalkyl, or an optionally substituted aralkyl group, or a hydrogen atom; and A and B, which may be the same or different, are hydrogen or halogen atoms, or alkyl, alkoxy, haloalkoxy, phenyl, or phenoxy groups; and acid salts and metal complexes thereof.

2. A compound as claimed in claim 1 wherein R is phenyl or phenyl substituted with alkyl, alkoxy, haloalkyl, phenyl or phenoxy or is alkyl having from 1 to 6 carbon atoms or cycloalkyl having from 3 to 6 carbon atoms; and A and B, which may be the same or different, are hydrogen or halogen.

3. A compound as claimed in claim 1 or 2 wherein R is phenyl, 2-, 3- or 4-chlorophenyl, 2,4- or 2,6-dichlorophenyl, 2,4- or 2,6-difluoropenyl, 2-, 3- or 4-fluorophenyl, 2-, 3- or 4bromophenyl, 2-, 3- or 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2fluoro-4-chlorophenyl, 2-chloro-4-fluorophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-trifluoromethylphenyl, 4-phenylphenyl (4-biphenylyl), 2-chloro-4-methoxyphenyl, 2fluoro-4-methoxyphenyl, 2-chloro-4-methoxyphenyl, 2-fluoro-4-methylphenyl, 4-isopropylphenyl, 2-methyl-4-chlorophenyl or 2-methyl-4-fluorophenyl, or is methyl, ethyl, n-propyl, propyl, r- butyl, sbutyl, butyl, or t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

4. A compound as claimed in any of claims 1 to 3 wherein W is -N- and A is hydrogen and B is hydrogen or chlorine.

5. The compound having the structure:

6. A process for preparing compounds as claimed in claims 1 to 5 which comprises bringing into reaction a compound having the general formula:

where A, B and R are as defined and Z is a hydrogen atom or a sulphonate group, with 1 ,2,4- triazole or imidazole, each in the presence of an acid binding agent or in the form of one of its alkali metal salts, in a solvent, and, if necessary, applying heat.

7. A process as claimed in claim 6 wherein the compounds of formula:

are prepared by bringing into reaction olefinic alcohols of formula:

with a halogen in the presence of an acid binding agent in a solvent.

8. Reaction scheme I as hereinbefore defined, or any part or stage thereof.

9. Reaction scheme II as hereinbefore defined, or any part or stage thereof.

10. Reaction scheme Ill as hereinbefore defined, or any part or stage thereof.

11. A fungicidal or plant growth regulating composition comprising a compound of general formula (I) as claimed in any of claims 1 to 5 or a salt or metal complex thereof, together with a carrier or diluent therefor.

1 2. A method of combating fungi, which comprises applying to a plant, to seed of a plant, or to the locus of the plant or seed, a compound, or salt or metal complex thereof, as defined in any of claims 1 to 5 or a composition as claimed in claim 11.

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

14. The novel intermediates of formulae (if), (III), (IV), (V), (Vl) and (VII) as hereinbefore described.