GB1595696A - Triazoles and imidazoles useful as plant fungicides and growth regulating agents - Google Patents

Description

(54) TRAIZOLES AND IMIDAZOLES USEFUL AS PLANT FUNGICIDES AND GROWTH REGULATING AGENTS (71) We, IMPERIAL CHEMICAL INDUSTRIES LIMITED, Imperial Chemical House, Millbank, London SWIP 3JF, a British Company do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to heterocyclic compounds which are imidazole or 1,2,4triazole compounds, to a process for preparing them, to compositions comprising them, to a method of combating fungal diseases in plants using them, and to a method of regulating the growth of plants using them.

The invention provides a compound of general formula (I):

wherein R, is alkenyl, alkynyl or optionally substituted aralkyl, Y is =N-- or =CH--, R2 is cycloalkyl, alkyl or haloalkyl, and R3 is hydrogen, methyl or alkenyl, or a carboxylic acid ester, an ether, an acid addition salt or a metal complex thereof.

The compounds of the invention contain chiral centres. The compounds are generally obtained in the form of racemic mixtures. However these or 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.

The alkyl groups, which can be straight or branched chain, preferably have 1 to 5 carbon atoms; examples are methyl, ethyl, propyl (n- or i-propyl) and butyl (n-, i- or t-butyl). Suitable alkenyl and alkynyl groups (which can also be straight or branched chain) are those having up to 7, preferably up to 4, carbon atoms; examples are allyl and propargyl.

The aralkyl group suitably contains 7 to 12 carbon atoms. The aralkyl (e.g. benzyl) group can be substituted in its alkyl (e.g. CH2 and/or aryl (e.g. phenyl) moieties. Suitable substituents on its aryl (e.g. phenyl) moiety are halogen, C14 alkyl [e.g. methyl, ethyl, propyl (n- or i- propyl) and butyl (n-, i-, or t-butyl)], halo (C1-4 alkyl), phenyl, halophenyl (e.g. chlorophenyl), cycloalkyl, nitro, cyano, C1-4 alkoxy (e.g. methoxy or ethyl), (C1-4 alkylene)- dioxy (e.g. methylenedioxy), (C1-4 alkoxy) (C1-4 alkyl) [e.g. 2-methoxy- or ethoxy-ethyl], mercapto, (C1-4 alkyl) thio [e.g. methyl- or ethyl-thio], (C1-4 alkyl) sulphonyl [e.g. methyl- or ethyl-sulphonyl], (C1-4 haloalkyl)sulphonyl [e.g. trifluoromethylsulphonyl], phenyl-sulphonyl, unsubstituted or mono- or di-(C1-4 alkyl) substituted sulphamoyl or carbamoyl, carboxy, (C1-4 alkoxy)-carbonyl [e.g. methoxy or ethoxy-carbonyl], unsubstituted. or mono- or di (C,~4 alkyl) substituted amino, (C16 alkanoyl)amino, N-(C14alkyl)-substituted (C 1-6 alkanoyl)-amino, formylamino, N-(C14 alkyl)-substituted formylamino, phenylethyl, phenoxy or benzyloxy. A suitable alkanoyl is acetyl or propionyl. The aralkyl group can have more than one ring 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. Suitable substituents on the alkyl moiety of the aralkyl (e.g. benzyl) group are halogen, C1-4 alkyl (e.g. methyl), phenyl or benzyl, both latter groups being optionally substituted as indicated above for aryl, cyano, (C1-4 alkoxy)carbonyl [e.g. methoxy or ethoxy-carbonyl] or trihalomethyl (e.g. trifluoro methyl).

Examples of suitable aralkyl groups are benzyl itself, a-methylbenzyl, amethylchlorobenzyl (e.g. a - methyl - p - chlorobenzyl), a-methyldichlorobenzyl (e.g. a - methyl - 2,4 - dichlorobenzyl), a-methylfluorobenzyl [e.g. a - methyl p - fluorobenzyl], chlorobenzyl (for example o-, m- or p - chloro - benzyl), dichlorobenzyl (e.g. 3,4- 2,4- or 2,6-dichlorobenzyl), trichlorobenzyl (e.g. 2,3,6- or 2,4,5-trichlorobenzyl), tetrachlorobenzyl, pentachlorobenzyl, bromobenzyl (e.g. om- or p-bromobenzyl), dibromobenzyl (e.g. 2,4-dibromobenzyl), fluorobenzyl (e.g. o-, m- or p-fluorobenzyl), difluorobenzyl (e.g. 2,4-difluorobenzyl) pentafluorobenzyl, methylbenzyl (e.g. o-, m- or p-methylbenzyl), dimethylbenzyl (e.g. 2,5-dimethylbenzyl), cyanobenzyl (e.g. p-cyanobenzyl), nitro-benzyl (e.g. pnitrobenzyl), (trifluoromethyl)benzyl [e.g. m-(trifluoromethyl)benzyll, methoxybenzyl (e.g. o-, m- or p-methoxybenzyl), chloronitrobenzyl (e.g. 3 - nitro 4 - chlorobenzyl), chlorofluorobenzyl (e.g. 2 - chloro - 4 - fluorobenzyl), fluorobromobenzyl (e.g. 2 - fluoro - 4 - bromo - benzyl), methoxybromobenzyl (e.g. 2 - methoxy - 5 - bromobenzyl), phenylbenzyl (e.g. p - phenylbenzyl), phenylethyl (e.g. 2-phenylethyl) or naphthylmethyl.

The cycloalkyl group suitably has 3 to 6 carbon atoms; preferably it is cyclopropyl, cyclopentyl or cyclohexyl.

Preferably the haloalkyl group contains 1 to 3 halogen atoms; examples are 2chloroethyl, trifluoromethyl or trichloromethyl.

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

A preferred class of compounds are those wherein R, is benzyl, m- methylbenzyl, a - methylchlorobenzyl, a - methyldichlorobenzyl, a methylfluorobenzyl, chlorobenzyl, dichlorobenzyl, trichlorobenzyl, tetrachlorobenzyl, penta-chlorobenzyl, bromobenzyl, dibromobenzyl, fluorobenzyl, difluorobenzyl, pentafluorobenzyl, methylbenzyl, dimethyl-benzyl, cyanobenzyl, nitrobenzyl, trifluoromethylbenzyl, methoxybenzyl, chloronitrobenzyl, chlorofluorobenzyl, fluorobromobenzyl, methoxybromobenzyl, phenylbenzyl, phenylethyl or naphthylmethyl, Y is =N-, R2 is propyl or butyl and R3 is hydrogen or methyl. Also preferred are the corresponding compounds where Y is =CH Particularly preferred are those compounds wherein R, is allyl, benzyl, cu - methyl - p - chlorobenzyl, a - methyl - 2,4-dichlorobenzyl, a - methyl - p fluorobenzyl, o-, m- or p-chlorobenzyl, 2,4-, 3,4- or 2,6-dichlorobenzyl, 2,4,5- or 2,3,6-trichlorobenzyl, pentachlorobenzyl, m- or p-bromobenzyl, 2,4dibromobenzyl, o-, m- or p-fluorobenzyl, 2,4-difluorobenzyl, o- or p-methylbenzyl, 2,5 - dimethyl - benzyl, p-nitrobenzyl, m-(trifluoromethyl)benzyl, o- or pmethoxybenzyl, 3 - nitro - 4 - chlorobenzyl, 2 - chloro - 4 - fluorobenzyl, 2 fluoro - 4 - bromobenzyl, or 2 - methoxy - 5 - bromobenzyl, Y is =N-, R2 is ipropyl or t-butyl, and R3 is hydrogen or methyl. Also particularly preferred are those compounds wherein R, is benzyl, o-chlorobenzyl, 2,4-dichlorobenzyl, o- or pfluorobenzyl, p-bromobenzyl, or 2 - chloro - 4 - fluorobenzyl, Y is =CH-, R2 is tbutyl and R3 is hydrogen or methyl.

Suitable salts are salts with inorganic or organic 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 and R3 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 I to 12.

Specific examples of the compounds are given in Table I.

TABLE I

Melting (or Boiling) No. R1 R2 R3 Y 1* p-Cl-C6H4CH2- t-Bu H =N- 162-164 2 C6H5CH2- t-Bu H =N- 91-93 3 p-F-C6H4CH2- t-Bu H =N- 137-142 4 p-F-C6H4CH2- t-Bu Me =N- 152-153 5* p-Cl-C6H4CH2- t-Bu H =N- 133-134 6 p-Cl-C6H4CH2- t-Bu Me =N- 176-178 7 p-Cl-C6H4CH2- t-Bu H =CH- 179-181 8 p-NO2-C6H4CH2- t-Bu H =N- 157-159 9 3,4-diCl-C6H3CH2- t-Bu H =N- 186-188 10 p-F-C6H4CH2- t-Bu H =N- 100-102 11 2,4-diCl-C6H3CH2- t-Bu H =N- 140-143 12 CH2CH=CH2- t-Bu H =N- (110-120 / 0.1 mm) 13 m-CF3-C6H4CH2- t-Bu H =N- 71-73 14 3-NO2-4-Cl-C6H3CH2- t-Bu H =N- 177-178 15 o-Cl-C6H4CH2- t-Bu H =N- 100-102 16 p-Br-C6H4CH2- t-Bu H =N- 181-183 17 m-F-C6H4CH2- t-Bu H =N- 110-113 18 m-Br-C6H4CH2- t-Bu H =N- 133-136 19 2,4-diCl-C6H3CH2- i-Pr H =N- 127-130 20 p-CI-C6H4CH2- i-Pr H N- 100-103 21+ p-Cl-C6H4CH2- t-Bu H =N- 138-140 22 o-F-C6H4CH2- i-Pr H NM 74-78 23 2,6-diCl-C6H3CH2- t-Bu H =N- 151-154 24 2-Cl,-4-F-C6H3CH2- t-Bu H =N- 137-140 25 o-Cl-C6H4CH2- i-Pr H =N- 122-127 26 C6H5CH2- t-Bu H =N- 173-175 27 2,4-triCl-C6H2CH2- t-Bu H =N- 188-192 28 2,3-triCl-C6H2CH2- t-Bu H =N- 168-172 29x p-Cl-C6H3CH2- t-Bu H =N- 125-128 30 2-Cl-4-C6H3CH2- t-Bu Me =N- 153-154 TABLE I CONTINUED

Melting (or Boiling) No. R R2 R3 Y Point C 31 2,4-diF-C6H3CH2- t-Bu H =N- 111-114 32 p-F-C6H4CH(Me)- t-Bu H =N- 197-201 33 2,4-diCl-C6H3CH(Me)- t-Bu H =N- 145-147 34 p-Cl-C6H4CH(Me)- t-Bu H =N- 182-185 35 2-F-4-Br-C6H3CH2- t-Bu H =N- 171-174 36 2,4-diBr-C6H3CH2- t-Bu H =N- 157-160 37 o-MeO-C6H4CH2- t-Bu H =N- 141-144 38 o-Me-C6H4CH2- t-Bu H =N- 123-125 39 p-Me-C6H4CH2- t-Bu H =N- 144-146 40 2,5-diMe-C6H3CH2- t-Bu H =N- 141-117 41 2,4-diCl-C6H3CH2- t-Bu H =CH- 191-193 42 C6H5CH2- t-Bu H =CH- 167-169 43 2-Cl-4-C6H3CH2- t-Bu H =CH- 162-164 44 o-Cl-C6H4CH2- t-Bu H =CH- 167-169 45 o-F-C6H4CH2- t-Bu H =CH- 164-165 46 p-F-C6H4CH2- t-Bu H =CH- 164-166 47 p-Cl-C6H4CH2- t-Bu H =CH- 199-201 48 o-F-C6H4CH2- t-Bu H =CH- 146-149 49 p-Br-C6H4CH2- t-Bu Me =CH- 188-192 50 m-Cl-C6H4CH2- t-Bu H N- 127-129 51 p-MeO-C6H4CH2- t-Bu H =N 52 2-MeO-5-Br-C6H3CH2- t-Bu H =N- 184-186 *Compounds 1 and 5 are diastereoisomers of each other.

XThis compound is in the form of the acetate and was obtained in an impure form.

+ This compound is in the form of a copper complex believed to have the structure

Nuclear magnetic resonance studies have shown that Compounds 22, 24, 25 and 33 are each in the form of a mixture of stereoisomers. The weight ratios of the two isomers in each case are as follows: Compound Weight ratio 22 9:1 24 7:1 25 4:1 33 1.5:1 The compounds of general formula (I) wherein R3 is hydrogen, or a salt thereof, can be prepared by reducing, preferably at 0 to 1000C and for l to 12 hours, a compound of general formula (II):

wherein Y, R, and R2 are as defined above, or a salt thereof. Suitable reducing agents are sodium borohydride, lithium aluminium hydride or aluminium isopropoxide. If desired, catalytic hydrogenation using a suitable metal catalyst can be used. When the compound of general formula (II) is a sterically hindered ketone, a Grignard reagent, for example butylmagnesium halide (e.g. bromide or iodide) can be used as the reducing agent; when a reagent such as a butylmagnesium halide is used, single diastereoisomers are often produced.

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

The compounds of general formula (I) wherein R3 is methyl or alkenyl, or a salt thereof, can be prepared by reacting, preferably at 15 to 800C and for 6 to 12 hours, a compound of general formula (II) or a salt thereof with the appropriate Grignard reagent e.g. a methy or alkenyl magnesium halide such as methyl or allyl magnesium bromide or iodide. This reaction can be performed by methods known in the art.

The starting compound of general formula (II) may be made by reacting imidazole or 1,2,4-triazole, or a salt thereof, with a a-haloketone of general formula (III):

wherein X is halogen, preferably bromine or chlorine, and R, and R2 are as defined above. This process may be carried out by heating the reactants together in the absence of a solvent or diluent, but preferably a solvent is present.

Suitable solvents are non-hydroxylic solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, sulpholane and tetrahydrofuran.

Hydroxylated solvents, for example, methanol and ethanol, may be used in certain circumstances when the presence of the hydroxyl group does not interfere with the reaction. The process can be carried out in the presence of a base such as sodium hydride, sodium ethoxide, excess imidazole or triazole, or an alkali metal carbonate (e.g. potassium carbonate). The reaction temperature will depend upon the choice of reactants, solvents and base, but generally the reaction mixture is heated under reflux. The process generally consists of dissolving the reactants in a solvent and then isolating the product by removal of the reactant solvent in vacuo. Unreacted imidazole or triazole can be removed by extraction of the product with a suitable solvent which is then washed with water. A crystallisation or other purification procedure may then be carried out if desired.

The a-halo ketones may be made by known methods.

The a-haloketones wherein X is halogen, Rl is optionally substituted benzyl and R2 is t-butyl are novel compounds and are the subject of Patent Application No 8005534. (Serial No. 1,595,699).

The compounds of general formula (II) or a salt thereof may also be made by alkenylating, alkynylating or aralkylating a compound of general formula (IV);

wherein Y and R2 are as defined above. Further details of this reaction can be found in British Patent Specification No. 1,533,706.

The salts, metal complexes, ethers and esters of the compounds of general formula (I) 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 are active fungicides, particularly against the diseases: Piricularia oryzae on rice Puccinia recondita, Puccinia stritformis and other rusts on wheat, Puccinia horde 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 Sphaerotheca fuliginea on cucurbits (e.g. cucumber), Podosphaera leucotriche 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 infestans (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 (e.g.

Penicillium digatatum and italicum on oranges and Gloeosporium musarum on bananas). Further some of the compounds are active as seed dressings against: Fusarium spp., Septoria spp., Tilletia spp. (i.e. bunt, a seed borne disease of wheat), Ustilago spp., and Pyrenophora spp. on cereals.

They can also be used as industrial (as opposed to agricultural) fungicides, e.g. as paint film fungicides.

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-cotyledonous plants. Such stunting or dwarfing may be useful, for example, in cereals and soya bean where reduction in stem growth may reduce the risk of lodging. Compounds which induce stunting or dwarfing may also be useful in modifying the growth of sugar cane thereby increasing the concentration of sugar in the cane at harvest. 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, Loltum multiflorum, and perenne, Agrotis tenuis, Cynodon dactylon (Bermuda grass), Dactylis glomerata, Festuca spp. (e.g. Festuca rubra) and Poa spp. (e.g. Poa pratense). At least some of the compounds will 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. The compounds can also stunt weed species present in the grasses; examples of such weed species are sedges (e.g. Cyperus spp.) and dicotyledonous weeds. 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. The plant growth regulating effect may manifest itself in an increase in crop yield.

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

Further the compounds may inhibit 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.

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. l to 15, preferably 0. l to 5, kg per hectare is used.

However, on certain plants even application rates within these ranges may give undesired phytoxic 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 also have algicidal, anti-bacterial and anti-viral activities as well as herbicidal activity.

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 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 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, kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay.

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 organic solvent optionally containing wetting, dispersing or emulsifying agents(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 2butoxyethanol).

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 phosphorus-containing 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 wetting agents(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 dodecylbenzenesulphonate, sodium, calcium or ammonium ligninosulphonate, butylnaphthalene sulphonate, 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 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), 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%, suitablyle85%, for example 2540%, by weight of the active ingredient(s). When diluted 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. other growth stimulating substances such as the gibberellins (e.g. GA3, GA4 or GA7), the auxins (e.g. indoleactic or indolebutyric acid) and the cytokinins (e.g. kinetin, diphenylurea, benzimidazole and benzyladenine) and other compounds having complementary fungicidal or insecticidal activity], as well as stabilising agent(s), for example epoxides (e.g. epichlorhydrin). The other fungicidal compound can be one which is capable of combating ear diseases of cereals (e.g. wheat) such as Septoria, Gibberella, Helminthosporium and the sooty mould complex; examples of such compounds are benomyl, carbendazole (BCM) and captafol.

Alternatively, it can be one which is capable of combating seed- and soil-borne diseases; examples of such compounds are Maneb and Captan.

The following Ex solution was washed with saturated aqueous sodium bicarbonate and with water, dried (magnesium sulphate), and concentrated in vacuo to afford, as a white crystalline solid, crude l - (4' - chlorophenyl) - 2 - bromo - 4,4 dimethylpentan - 3 - one, m.p. 4850 .

Stage IV. The product (0.69 g) of Stage III and 1,2,4-triazole (0.17 g) were mixed with potassium carbonate (0.52 g) in acetone (l0 ml) and the mixture refluxed for 2 hours. After cooling to room temperature the inorganic material was filtered off and the filtrate concentrated in vacuo to afford crude a - p - chlorobenzyl - a 1,2,4 - triazol - I - yl pinacolone.

Using the same techniques l - (2,4 - dichlorophenyl) - 4,4' - dimethyl - 2 (1,2,4 - triazol - l - yl)pentan - 3 - one was prepared.

Example 2.

1 - t - Butyl - 2 - (1,2,4 - triazol - I - yl) - 2 - benzylethanol (Compound 2) Stage I. Pinacolone (10 g) in dry diethyl ether (30 ml) was added slowly to a suspension of sodamide (4.1 g) in dry diethyl ether (15 ml). The mixture was then stirred overnight at room temperature and then stirred and refluxed for 16 hours (the mixture was by this time orange-coloured). Benzyl chloride (13.2 g) was then added dropwise and the mixture refluxed for 24 hours. Water (100 ml) was added and the ethereal layer separated, and washed with water, dilute hydrochloric acid and again with water; it was then dried (sodium sulphate). The ether was evaporated under reduced pressure and then the residue was distilled to give benzylpinacolone, b.p.

78-80 /0.06 mm Hg.

Stage II. Bromine (1.4 ml) was added dropwise to a-benzylpinacolone (5.2 g) in diethyl ether (80 ml) at about 10 . The solution was then stirred for l hour at room temperature and the ether was evaporated in vacuo to give a red liquid which was distilled in a bulb to give, as a slightly coloured liquid a - bromo - a - benzyl pinacolone, b.p. 100 /0.1 mm Hg.

Stage 111. 1,2,4-Triazole (0.28 g) in dimethyl formamide (5 ml) was added dropwise to a suspension of sodium hydride (0.1 g of 100%) in dimethyl formamide (2 ml).

The reaction mixture was stirred for 2 hours and the a - bromo - a - benzyl pinacolone (1.0 g) in dimethylformamide (5 ml) was added. The reaction mixture was stirred at room temperature overnight and then poured into water (75 ml) to give, as a white crystalline solid, a - (1,2,4 - triazol - 1- yl) - a - benzyl pinacolone, m.p. 6971 .

Stage IV. a - 1,2,4 - Triazol - 1 - yl - a - benzylpinacolone (2.0 g) in methanol (20 ml) was treated portionwise with sodium borohydride (0.26 g). The mixture was then refluxed for one hour. The solvent was removed in vacuo and hydrochloric acid (1 N; 40 ml) was added to the residue. The white precipitate was filtered off, washed with water, dried and crystallised from aqueous ethanol to give the title compound as a white crystalline solid.

Example 3.

I - (1,2,4 - Triazol - 1 - yl) - I - p -fluorobenzyl - 2 - t - butyl - propan - 2 - ol (Compound 4) An ethereal solution of methylmagnesium iodide [prepared by reacting methyl iodide (6.2 g) with magnesium (1.1) in dry diethyl ether] was treated dropwise with α - 1,2,4 - triazol - 1 - yl - α - p - fluorobenzyl - pinacolone (4.0 g) in dry diethyl ether (30 ml). The mixture was then refluxed for one hour, cooled and treated with 10% sulphuric acid (20 ml). The insoluble material was filtered off, washed with dilute hydrochloric acid and water and then dried to give, after crystallisation from aqueous ethanol, the title compound.

Example 4.

I - t - Butyl - 2 - (1,2,4 - triazol - 1 -yl) -2 -p - chlorobenzylethanol (Compound 5) A solution of butylmagnesium bromide [prepared from butyl bromide (5.63 g) and magnesium (1.0 g) in dry diethyl ether] was treacted dropwise with a-(1,2,4-triazol- 1 - yl) - a - p - chlorobenzylpinacolone (4.0 g) in diethyl ether (30 ml) and the mixture was refluxed for one hour. The reaction mixture was treated with dilute sulphuric acid (20 ml) and the ethereal layer was separated, washed with water and dried (sodium sulphate). Removal of solvent in vacuo gave a white solid which was crystallised from diethyl ether/petrol (6080 ) to give the title compound.

Example 5.

The copper complex of Compound 1. (Compound 21) Cupric chloride (0.9 g; 0.005 mole) dissolved in water (4 ml) was added dropwise to a solution of Compound 1(2.9 g; 0.01 mole) in ethanol (60 ml) and the resulting green solution stirred for half an hour. The volume of solvent was then reduced by about 30 ml and water (30 ml) added. A green oil separated out. The aqueous phase was decanted off and the organic phase was stirred for 30 minutes with iso-propanol (50 ml). The resultant green solid was then filtered off and dried to give, after recrystallisation from ethanol/water, the copper complex (1.6 g).

Example 6.

1 - t - Butyl - 2 - (1,2,4 - triazol - I - yl) - 2 - (2' - 4' - dichlorobenzyl) ethanol (Compound 11).

1 - (2',4' - Dichlorophenyl) - 4,4' - dimethyl - 2 - (1,2,4 - triazol - l - yl) - pentan - 3 - one (4.0 g) in methanol (40 ml) was treated with sodium borohydride (0.46 g). After the initial exothermic reaction had subsided the solution was refluxed on a steam bath for 1 hour. The solvent was removed in vacuo and 1Nhydrochloric acid (40 ml) was added to the residue to give a white crystalline solid, which was filtered off, washed with water and dried. Crystallisation from ethyl acetate-petroleum ether (680") gave the title compound as a white crystalline solid, m.p. 14043 .

Example 7.

This Example lists a number of compositions of the invention.

(1) Dispersible Powder Compound 1 50% wt/wt Aerosol OT 2% Polyfon H 5% China Clay 43% (2) Emulsifiable Concentrate Compound 1 lOog/litre Amine dodecylbenzene sulphonate 400 litre 2-n-Butoxyethanol to l litre (3) Aqueous Suspension Compound l 250 g/litre Polyfon H 25 g/litre Bentonite 15 Polysaccharide 0.75 Water to 1 litre (4) Dust Compound 1 5% wt/wt China clay 95% (5) Granules Compound 1 5% wt/wt Starch 5% China clay 90% (6) Solvent solution Compound 1 200 g/litre Dimethylformamide to 1 litre Example 8.

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 4cm 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 ("Dispersol" is a Registered Trade Mark) 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 ("Tween" is a Registered Trade Mark) 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 3 =05% 2 = 625% 1 = 26-60% O = > 60% The results are shown in Table II.

TABLE II

DISEASE CONTROL Puccinia Phytophthora Plasmopara Piricularia Cercospora Botrytis Erysiphe Compound recondita infestans viticola oryzae arachidicola cinerea graminis No. in wheat in tomato in vines in rice in peanuts in tomato in barley 1 4+ 0 3 4 3 4 2 4 0 0 1-2 3 4 3 4 0 0 3 1-2 4 4 4 0 0 3 0 4 5 4+ 0 3-4 0-1 3 4 6 2 0 3 0 1-2 4 7 4 0 0 0 3-4 4 8 4 0 0-1 0 0-2 4 9 4 0 0 0 0-1 4 10 4 0 2-3 2-3 0-2 4 11* 4 0 0-1 1 2-3 4 12 4 0 0-3 1 0 4 13 4 0 0 1-2 0 4 14 2 0 0 1-2 4 15 4 0 - 3 3 4 16 4 0 0 3 4 4 TABLE II CONTINUED

DISEASE CONTROL Puccinia Phytophthora Plasmopara Piricularia Cercospora Botrytis Erysiphe Compound recondita infestans infestans oryzae arachidicola cinerea graminis No. in wheat in tomato in vines in rice in peanuts in tomato in barley 17 3 4 P P 0 3 18 3 0 - 0 1-2 4 19 1 0 0 0 2-3 0 20 1 0 0 0 2-3 21 3 3-4 3 3 4 22 4 0 0 1 0 4 23 4 0 0 2-3 1-2 4 24 4 0 0 2-3 1-2 3 25 3 0 0 1 0-1 4 26 0-1 0 0 2 0-1 3-4 27 0-1 0 0 0 2-3 3-4 28 3 0 0 0-1 2-3 4 30 1-2 2-3 0 0 1-2 3 31 3 0 4 3 3 2 2-3 32 4 0 0-1 0-1 3-4 3 4 33 4 0 0 0 1-2 2 4 34 3-4 0 0 0 2 2-3 4 TABLE II CONTINUED

DISEASE CONTROL Puccinia Phytophthora Plasmopara Piricularia Cercospora Botrytis Erysiphe Compound recondita infestans viticola oryzae arachidicola cinerea graminis No. in wheat in tomato in vines in rice in peanuts in tomato in barley 35 4 0 0 0 3 1-2 3 36 4 0 0 0-1 0 0-1 4 37 4 0 0 1-2 3-4 3 4 38 3 0 0 0 4 3-4 4 39 3 0 0 0 4 3-4 4 40 4 0 0 1 0 4 41 1-2 0 0 0-1 1-2 4 42 3 0 0 0 0 4 43 3 0-1 0 0-1 0 4 44 1 0 0-1 1 4 45 0 0 0 2-3 4 46 3 0 0 0-1 0 2 4 47 3 0 0 0 0 3 4 48 0-1 0-1 0 3 4-3 49 0-3 0 0 3-4 4-3 50 1 1-2 0 51 52 53 Notes for Table II.

* This compound is of interest because it has a weaker stunting effect on vegatative growth of monocotyledonous plants (e.g. wheat and barley) than the mono (chloro and fluoro-) compounds.

+ At lower concentrations, Compound 1 is more active than its diastereoisomer Compound 5.

P = Compound phytotoxic.

Example 9.

This Example illustrates the protectant activity (at 50 ppm) of the compounds against various fruit fungal diseases.

The activity of the compounds against apple powdery mildew (Podosphera leucorricha) and vine powdery mildew (Uncinula necator) was determined as follows.

Small apple (Jonathan) and vine plants about 3 weeks old and growing in mini pots (diameter: 3 cm) were sprayed first with the solution or suspension of the test compound, allowed to dry overnight in a growth room and then infected on the following day with spores of the disease by placing them in an enclosed space and allowing spores of the disease blown into the still space to settle upon them over four to six hours.

Assessment was made of the percentage amount of disease on the leaves of the plants (after 8 days for apples and 9 to 10 days for vines).

The tests against apple scab (Venturia inaequalis) were performed as follows.

Venturia inaequalis was treated as an obligate parasite, the spores of the fungus being transferred from plant to plant by-passing agar plate culture which ensures a very pathogenic fungus.

Infected leaves were removed from stock plants 13 days after inoculation. The spores were removed from the leaves by agitation in a small volume of deionised water, counted and then adjusted to 100,000 spores/ml. This suspension was sprayed onto the undersides of apple seedling leaves of one of three susceptible varieties, i.e. Jonathan, Granny Smith and Red Delicious. The inoculated seedlings were immediately placed in a high humidity cabinet at 190C and left therein for 48 hours. After this incubation period the plants were placed in growth room conducive to disease development. The disease was easily assessed 12 or 13 days after inoculation.

The test compound was applied 24 hours after inoculation.

The grading system used is the same as for Table II. Table III shows the results. TABLE III

DISEASE CONTROL Podosphaera Uncinula Venturia Compound leuchotricha necator inaequalis No. on apples on vines on apples 1 4 3 3 2 4 4 0-4 3 4. 4' 0 4 | 0 | 4 5 4 4 0 6 C 2 7 0 1 0 8 4 4 9 0 4 0 10 1 0 0 11 3 4 0-2 12 0 0 0 13 0 1 0 14' 0 0 15 1 0 16 2 4 4 17 2 4 0 18 0 4 19 2 4 1 20 0 4 0 21 4 4 2 22 1 2 0 23 0 4 0 24 2 4 1 25 0 2 0 26 27 0 1 0 28 0 3 1 30 1 0 0 31 2 4 2 TABLE l[l CONTINUED

DISEASE CONTROL Podosphaera Uncinula Venturia Compound leuchotricha necator inaequalis No. on apples on vines on apples 32 4 4 1 33 4 4 4 34 4 4' 4 35 36 3 4 2 37 2 1 1 38 4 4 3 39 4 4 4 40 0 2 0 41 0 0 42 0 1 0 43 1 1 0 Example 10.

The compounds were tested at 50 ppm and as a protectant dip against Penicillium digitatum on oranges and Gloeosporium musarum on bananas.

The oranges were scrubbed and then wiped over with industrial methylated spirit. The peel was then removed and cut into discs with a No. 6 cork borer. The peel discs were then dipped into a solution (containing 0.1% Tween 20 as a wetting agent) of the test compound. They were then put outer side uppermost in Repli dishes. The discs were allowed to dry and were then sprayed with a spore suspension of Penicillium digitatum at a concentration of l x 106 spores/ml. The dishes were then stored in a moist environment at l9 C for 13 days.

The tests on bananas were performed in a similar fashion using discs ofbanana peel.

The discs were then assessed using the grading system used for Table II. Table IV shows the results.

TABLE [V

DISEASE CONTROL Compound P. digitatum G. musarum No. on oranges on bananas 1 4 4 2 4 0 3 1 3 4 5 1 2 6 7 8 9 10 3 3 11 1 1 12 13 0 1 14 15 0 4 16 4 0 17 18 19 20 21 4 22 23 24 1 25 26 27 28 30 31 4 32 Example 11.

This Example illustrates the plant growth regulating properties of the compounds. The compounds were applied in the form of a 5000 p.p.m. solution in distilled water and the solution was then applied to the foliage of young seedlings of wheat, barley, maize, rice, Lolium rye grass, soya, cotton, groundnut, lettuce, tomato, Mung bean and French bean. The experiments were replicated twice.

After 21 days from treatment, the plants were assessed for plant growth regulating effects and phytotoxic symptoms.

Table V shows the stunting effect of the compounds on the vegetative growth using the following grading: 0 = # 20% retardation I = 21-40% retardation 2=41-60% retardation 3 = 6180% retardation If no figure is given, the compound was substantially inactive as a stunting agent.

Additional plant growth regulating properties are indicated as follows: G = darker green leaf colour A = apical effect T = tillering effect The symbol "-" is used to indicate that the compound has not been tested on that particular crop.

The asterisk (*) indicates that the compound was applied at 4000 p.p.m.

TABLE V

Lolium Rye Ground Mung French Compound Wheat Barley Maize Rice Grass Soya Cotton Nut Lettuce Tomato Bean Bean 1 1G 1G 0 G 1GA 0 1 2G 1G 1A GA 2 1 2G 0 G 1GA 0 3 2G 2GAT 2GA 1GA 3 2G 3G 1 1G 1G 1 3 3GA 2GA 1GA 1GA 4 5 1G 1G 0 G 1G 1 3 3GA 2A 2A 1GA 6. 2GA 1 - A 0 1A 7 - - - - - - - - - - - 8 1G 1G 0 0 1GA G GA A 2A 9 1GA G GA 2G 10 1GT G 2A 1G A 0 2GA 11 2GA 2 GA 1GA 12 - 1GA 1GA 2G 2 2GA 13 1 0 2 2GA G A GA 2A 14 1GA 0 GA 15 0 1GA 1G GA GA A 1GA 16 1G 1G 0 1G 2GA G GA G A 3GA 17 1G 1 0 0 2GAT 1G G A 3A 18 TABLE V CONTINUED

Lolium Rye Ground Mung French Compound Wheat Barley Maize Rice Grass Soya Cotton Nut Lettuce Tomato Bean Bean 19 1 1 - 2A 2 20 2 2 1 - 2GA 2GA 3A - 2G 21 0 0 G 1GAT T GA 1GA 22* - 23* - 3G 1GA 1 3GA - 3GA 24* 2T 1 1G - 3GA A 1A 3GA - 3GA 25* - 3GA 2A 3GA 26* - 27* - 28* 2 1G - 2A 3GA 30* - 2GA 2A A 2G 31 - - - - - - - - - - - 32* - 33 - - - - - - - - - - - 34* - 35* 2GT 2G 1 - 3GA 1 2G - 2GA 36 37* - TABLE V CONTINUED

Lolium Rye Ground Mung French Compound Wheat Barley Maize Rice Grass Soya Cotton Nut Lettuce Tomato Bean Bean 38* 2GT 2GT - 3GA 1A 2G - 3GA 39* 2 1 - 2 1A 1A 1 - 1G 40 41* - In Patent Application No. 8005524 (Serial No. 1,596,697) there is claimed 1 t - butyl - 2 - (1,2,4 - triazol - 1 - yl) - 2 - p - chlorobenzylethanol and in Patent Application No. 8005529 (Serial No 1,595,698) there is claimed 1 - t - butyl - 2 (1,2,4 - triazol - 1 - yl) - 2 - (2',4' - dichlorobenzyl)ethanol. In this Specification, we make no claim to either 1 - t - butyl - 2 - (1,2,4 - triazol - 1 - yl) - 2 - p chlorobenzylethanol per se or 1 - t - butyl - 2 - (1,2,4 - triazol - 1 - yl) - 2 (2',4' - dichlorobenzyl) ethanol per se.

Claims (50)

1. Subject to the foregoing disclaimers, WHAT WE CLAIM IS:1. A compound of the general formula (I):

   wherein R, is alkenyl alkynyl or optionally substituted aralkyl, Y is N- or =CH-, R2 is cycloalkyl, alkyl or haloaikyl, and R3 is hydrogen, methyl or alkenyl, or a carboxylic acid ester, an ether, an acid addition salt or a metal complex thereof.
2. 2. A compound according to claim I wherein R, is optionally substituted aralkyl, R2 is alkyl, and R3 is hydrogen, or an acid addition salt thereof.
3. 3. A compound according to claim 1 wherein R2 is alkyl, and R3 is methyl, or an acid addition salt or a metal complex thereof.
4. 4. A compound according to claim 1 wherein R2 is C38 cycloalkyl or C1-5 alkyl or haloalkyl.
5. 5. A compound according to claim 1 wherein R2 is propyl or butyl.
6. 6. A compound according to claim 5 wherein R2 is i-propyl or t-butyl.
7. 7. A compound according to any one of claims l and 4 to 6 wherein R3 is hydrogen, methyl or C14 alkenyl.
8. 8. A compound according to claim 7 wherein R3 is hydrogen, methyl or allyl.
9. 9. A compound according to any one of claims 1 and 4 to 8 wherein R, is alkenyl or alkynyl having up to four carbon atoms, or R, is benzyl optionally ring substituted with halogen, C14 alkyl, halo (C,~4 alkyl), phenyl, halophenyl, C36 cycloalkyl, nitro, cyano, C14 alkoxy, (C1-4 alkylene)dioxy, (C1-4 alkoxy) (C14 alkyl), mercapto, (C14 alkyl)thio, (C14 alkyl) sulphonyl, C14 haloalkyl)sulphonyl, phenylsulphonyl, unsubstituted or mono- or di- (C,~4 alkyl) substituted sulphamoyl or carbamoyl, carboxy, (C1-4 alkoxy)carbonyl, unsubstituted or mono- or di-(C,~4 alkyl) substituted amino, (C26 alkanoyl)amino, N-(C1-4 alkyl)-substituted (C2-6 alkanoyl)amino, formylamino, N-(C1-4 alkyl)-substituted fomylamino, phenylethyl, phenoxy or benzyloxy, the number of ring substituents being 1,2 or 3, and/or optionally substituted on the a-carbon atom with one phenyl or benzyl optionally substituted as recited above for benzyl, halogen, C1-4 alkyl, cyano, (C1-4 alkoxy)carbonyl or trihalomethyl.
10. 10. A compound according to claim l wherein R, is allyl, benzyl, amethylbenzyl, a-methylchlorobenzyl, a-methyldichlorobenzyl, a-methylfluorobenzyl, chlorobenzyl, dichlorobenzyl, trichlorobenzyl, tetrachlorobenzyl, pentachlorobenzyl, bromobenzyl, dibromobenzyl, fluorobenzyl, difluorobenzyl, pentafluorobenzyl, methylbenzyl, dimethylbenzyl, cyanobenzyl, nitrobenzyl, trifluoromethylbenzyl, methoxybenzyl, chloronitrobenzyl, chlorofluorobenzyl, fluorobromobenzyl, methoxybromobenzyl, phenylbenzyl, phenylethyl or naphthylmethyl, the substituents other than the a-methyl substituents being all ring substituents.
11. 11. A compound according to claim 10 wherein R, is allyl, benzyl, a - methyl p - chlorobenzyl, a - methyl - 2,4-dichlorobenzyl, a - methyl - p - fluorobenzyl,' o-, m- or p-chlorobenzyl,, 2,4-, 3,4- or 2,6-dichlorobenzyl, 2,4,5- or 2,3,6trichlorobenzyl, pentachlorobenzyl, m- or p-bromobenzyl, 2,4-dibromobenzyl, om-, or p-fluorobenzyl, 2,4-difluorobenzyl, o- or p-methylbenzyl, 2,5dimethylbenzyl, p-nitrobenzyl, m-(trifluoromethyl)-benzyl, o- or p-methoxybenzyl, 3-nitro-4-chlorobenzyl, 2- chloro - 4- fluorobenzyl, 2 - fluoro - 4 bromobenzyl, or 2 - methoxy - 5 - bromobenzyl, and Y is N-.
12. 12. A compound according to claim 10 wherein R, is benzyl, o-chlorobenzyl, 2,4-dichlorobenzyl, o- or p-fluorobenzyl, p-bromobenzyl, or 2 - chloro - 4 fluorobenzyl, and Y is =CH-.
13. 13. A compound according to any one of claims l and 4 to 12 which is in the form of an alkanoate ester.
14. 14. A compound according to claim 13 which is in the form of an acetate ester.
15. 15. A compound according to any one of claims 1 and 4 to 12 which is in the form of alkyl, aryl or aralkyl ether.
16. 16. A compound according to any one of claims l to 4 to 12 which is in the form of an acid addition salt with hydrochloric, nitric, sulphuric, toluenesulphonic, acetic or oxalic acid.
17. 17. A compound according to any one of claims 1 and 4 to 12 which is in the form of a complex with copper, zinc, manganese or iron.
18. 18. 1 - t - Butyl - 2 - (1,2,4 - triazol - I - yl) - 2 - p - chlorobenzylethanol in the form of a diastereoisomer and in the form of a copper complex, the diastereisomer having, in the uncomplexed form, a melting point of 162-164 C.
19. 19. 1 - t - Butyl - 2 - (1,2,4 - triazol - 1 - yl) - 2 - benzylethanol.
20. 20. 1 - t - Butyl - 2 - (1,2,4 - triazol - 1 - yl) - 2 - p - fluorobenzylethanol.
21. 21. 1 - t - Butyl - 2 - (1,2,4 - triazol - 1 - yl) - 2 - p - bromobenzylethanol.
22. 22. 1 - t - Butyl - 2 - (1,2,4 - triazol - I - yl) - 2 - (2' - chloro - 4' fluorobenzyl)ethanol.
23. 23. 1 -t - Butyl -2 -(1,2,4 - triazol - l - yl) - 2 -o - methoxybenzylethanol.
24. 24. 1 - t - Butyl - 2 - (1,2,4 - triazol - I - yl) - 2 - o - methylbenzylethanol.
25. 25. 1 - t - Butyl - 2 - (1,2,4 - triazol - I - yl) - 2 - p - methylbenzylethanol.
26. 26. A compound according to claim l which is any one of Compounds 4, 6 to 10 and 12 to 14 of Table I hereinbefore.
27. 27. A compound according to claim l which is any one of Compounds 15, 17 to 20 and 22 to 25 of Table I hereinbefore.
28. 28. A compound according to claim l which is any one of Compounds 26 to 28 and 30 to 32 of Table I hereinbefore.
29. 29. A compound according to claim l which is any one of Compounds 33 to 36 and 40 to 51 of Table I hereinbefore.
30. 30. A process for preparing a compound or an ester, ether, salt or metal complex thereof, according to any one of the preceding claims, the process comprising (1), when a compound of general formula (I) wherein R3 is hydrogen is required, reducing a compound of general formula (II):

    wherein Y, R, and R2 are as defined in claim 1, or a salt thereof; or (2), when a compound of general formula (I) wherein R3 is methyl or alkenyl is required, reacting with an appropriate Grignard reagent a compound of general formula (II) or a salt thereof; and if desired or required reacting in known manner the compound of general formula (I) so produced to give an ester, ari ether, an acid addition salt or metal complex thereof.
31. 31. A process according to claim 30 wherein a-p-chlorobenzyl, a-1,2,4-triazol- 1 - ylpinacolone is reduced to give l - t - butyl - 2 - (1,2,4 - triazol - 1 - yl) - 2 - p - chlorobenzylethanol in the form of a diastereoisomer having a melting point of 162--164"C.
32. 32. A process according to claim 30 wherein a - (2',4' - dichlorobenzyl) - a 1,2,4 - triazol - I - ylpinacolone is reduced to give l - t - butyl - 2 - (1,2,4 triazol - I - yl) - 2 - (2',4' - dichlorobenzyl)ethanol.
33. 33. A process according to claim 30 substantially as described in any one of Examples I to 6.
34. 34. A compound of general formula (I) or an ester, an ether, an acid addition salt or a metal complex thereof, prepared by a process according to claim 30 or 33.
35. 35. 1 - t - butyl - 2 - 1,2,4 - triazol - I - yl - 2 - p - chlorobenzylethanol prepared by a process according to claim 31.
36. 36. 1 - t - butyl - 2 - 1,2,4 - triazol - I - yl - 2 - (2',4' - dichlorobenzyl) ethanol prepared by a process according to claim 32.
37. 37. A fungicidal composition comprising, as active ingredient, a compound or salt according to claim 2 or 35 and a carrier for the active ingredient.
38. 38. A fungicidal or plant growth regulating composition comprising, as active ingredient, a compound, salt or metal complex according to any one of claims 3, 18 to 20, 26 and 36, and a carrier for the active ingredient.
39. 39. A fungicidal or plant growth regulating composition comprising, as active ingredient, a compound according to claims 21 or 27, and a carrier for the active ingredient.
40. 40. A fungicidal or plant growth regulating composition comprising, as active ingredient, a compound according to claim 22 or 28, and a carrier for the active ingredient.
41. 41. A fungicidal or plant growth regulating composition comprising, as active ingredient, a compound, ester, ether, salt or metal complex according to any one of claims l, 5 to 17, 23 to 25, 29 and 34, and a carrier for the active ingredient.
42. 42. A fungicidal or plant growth regulating composition according to claim 40 substantially as described in example 7.
43. 43. A fungicidal or plant growth regulating composition according to claim 41 substantially as described herein.
44. 44. A method of combating fungal diseases in a plant, the method comprising applying to the plant, to seed of the plant or to the locus of the plant or seed, a compound or salt according to claim 2 or 35.
45. 45. A method of regulating the growth of a plant, the method comprising applying to the plant, to seed of the plant or to the locus of the plant or seed, a compound or salt according to claim 2 or 35.
46. 46. A method of combating fungal diseases in, or regulating the growth of, a plant, the method comprising applying to the plant, to seed of the plant or to the locus of the plant or seed, a compound, salt or metal complex according to any one of claims 3, 18 to 20, 26 and 36.
47. 47. A method of combating fungal diseases in, or regulating the growth of, a plant, the method comprising applying to the plant, to seed of the plant or to the locus of the plant or seed, a compound according to claim 21 or 27.
48. 48. A method of combating fungal diseases in, or regulating the growth of, a plant, the method comprising applying to the plant, to seed of the plant or to the locus of the plant or seed, a compound according to claim 22 or 28.
49. 49. A method of combating fungal diseases in, or regulating the growth of, a plant, the method comprising applying to the plant, to seed of the plant or to the locus of the plant or seed, a compound, ester, ether, salt or metal complex according to any one of claims 1, 5 to 17, 23 to 25, 29 and 34.
50. 50. A method according to claim 49 substantially as described herein.