NZ208654A - Certain 2-(1,2,4-triazol-1-yl)-1-butyl-1-halophenylethanols - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £08654 2086 54 Priority Date^s): I 0_0 - OI Complete Specification Filed: Class- ../.."fivjy.teJtft.............

Publication Date: ....a P.O. Journal, No: ' Under the provisions of Regift latlon 23 (I) the Specification has been ante-dated initials HO DRAWIKGS NEW ZEALAND PATENTS ACT, 1953 Divided from No. 198085 No.: Date: COMPLETE SPECIFICATION HETEROCYCLIC COMPOUNDS k'i^ ' K/We, IMPERIAL CHEMICAL INDUSTRIES ■LIMITED uf Imperial Chemical House, •j^l^lMillbank, London SW1P 3JF» England, a British Company, fix N.Z. PATENT OFFICE 25JUN1984 RECEIVED hereby declare the invention for which >1 / we pray that a patent may be granted to rrJe/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - 208654 This invention relates to triazole compounds useful as fungicides and plant growth regulating agents, to a process for preparing them, to fungicidal compositions containing them, and to a method of combating fungi, especially fungal infections in plants, using them.

Our New Zealand Patent Specification No. 198,085 describes and claims a method of regulating plant growth which comprises applying to a plant, to seed of a plant, or to the locus of the plant or seed a sufficient amount to produce a plant growth regulating effect of a compound of general formula (I): OH N N CH2 C R2 R1 (I) wherein R^ is Gj-g alkyl, or cycloalkyl having up to 6 carbon atoms or phenyl, and R2 is phenyl or benzyl; the phenyl of r! and the phenyl or phenyl moiety of the benzyl of R2 being optionally substituted with from one to three halogen, C]_5 alkyl, C]_4 alkoxy, halo-C[_4 alkyl, halo-C]_4 alkoxy, nitro, phenyl, phenoxy, benzyl, benzyloxy, halobenzyloxy, Cj_2 alkylenedioxy, halo-Cj_2 alkylenedioxy, amino, mono- or di-C]_4 alkylamino, hydroxy, morpholino or carboxy or an alkyl ester thereof, and/or the alkyl moiety of the benzyl is optionally substituted with one C]__4 alkyl; or an acid addition salt, ether, ester or metal complex thereof as therein defined.

In one aspect of the method as defined above R^ is Oj_4 alkyl and R2 is optionally substituted phenyl, especially halophenyl and particularly chlorophenyl.

When r! is alkyl it can be a straight or branched chain group having 1 to 6, e.g. 1 to 4, carbon atoms; examples are methyl, ethyl, propyl (&- or iso-propyl), butyl (r-, sec-, iso- or i-butyl), pentyl (e.g. n-pentyl) and hexyl (e.g. n-hexyl). It is preferably butyl, especially i-butyl, and especially so when R2 is chlorophenyl. 208654 The compounds of formula (I) can contain chiral centres. Such compounds are generally obtained in the form of racemic mixtures. However, these and other mixtures can be separated into the individual isomers by methods known in the art.

The present invention provides a racemic compound of formula (IA) "OH n- n chit (IA) n R and stereoisomers thereof, wherein R^ is ji-butyl and R^ is 2,4-dichlorophenyl or R^ is i-butyl and R2 is p-chlorophenyl, and acid addition salts, ethers, esters and metal complexes thereof.

The salts of the novel compounds can be salts with inorganic or organic acids e.g. hydrochloric, nitric, sulphuric, acetic, p-toluenesulphonic or oxalic acid.

Suitably the metal complex is one including, as the metal, copper, zinc, manganese or iron. It preferably has the general formula: M V-yn 2° 4 £654 wherein R.1 and R2 are as defined for formula (IA), M is a metal, A is an anion (e.g. a chloride, bromide, iodide, nitrate, sulphate or phosphate anion), n is 2 or 4, y is 0 or an integer of 1 to 12, and m is an integer consistent with valency,.

The coirpounds of the invention are shown in Table I.

TABLE 1 COMPOUND NO. R1 R2 MELTING POINT (°C) 1 n-Bu 2,4-diCl-CgH3- 106-108° 2 t-Bu p-Cl-CgH4- 70-73° The coirpounds of general formula (IA) may be produced by reacting a compound of general formula (II) or (III): (II) (III) 2086 54 in which and R2 are as defined for formula (IA) and X is a halogen atom (preferably a chlorine or bromine atom), with 1,2,4-triazole either in the presence of an acid-binding agent or in the form of one of its alkali metal salts in a convenient solvent. Suitably the compound of general formula (II) or (III) is reacted at 20-100°C with the sodium salt of 1,2,4-triazole (the salt can be prepared by adding either sodium hydride or sodium methoxide to 1,2,4-triazole) in a convenient solvent such as acetonitrile, methanol, ethanol or dimethylformamide. The product can be isolated by pouring the reaction mixture into water and recrystallising the solid formed from a convenient solvent.

The compounds of general formula (II) and (III) can be prepared by reacting a compound of general formula (IVa) or (IVb): o O x—ch2— c—r1 X- CH2 C R2 (IVa) (IVb) wherein R^, R2 and X are as defined above with, respectively, a Grignard compound of general formula (Va) or (Vb): Y Mg — R2 Y Mg r1 (Va) (Vb) 6 203654 wherein and r2 are as defined above and Y is a halogen (preferably chlorine, bromine or iodine) in a convenient solvent such as diethyl ether or tetrahydrofuran. Generally a mixture of the coirpounds of general formula (II) and (III) are obtained. When a compound of general formula (IVa) wherein is butyl is reacted, the compound of formula (II) generally predominates in the mixture.

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

The coirpounds of general formula (II) can also be produced by reacting a |3-hydroxy selenide compound formula (VII) R1 CH3 —Se —CH2 C —OH R2 (VII) wherein R^ and R^ are as defined above, with methyl iodide in potassium t-butoxide according to the method of Van Ende, Dumont and Krief, Angew. Chem. Int. Ed., 1975, 14, 700.

The {Z -hydroxy selenide compound can be prepared by treating the diselenide with the appropriate ketone in the presence of butyl lithium.

Our New Zealand Patent Specification No. 208653 describes and claims the catpounds having the foxntulae: CH2— C R1 R2 Formula (II) 208654 and OH X CH2 C R1 Formula (III) R2 (III) wherein and R^ are as defined for formula (IA) and X is a halogen atom, especially chlorine.

The acid addition salts and metal complexes of the coirpounds of general formula (IA) 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 coirpounds of general formula (IA) are generally prepared by the above reactions in the form of racemic mixtures. The resolution of these mixtures into the constituent enantiomers can be performed by known methods. Examples of these methods are (1) forming the diastereoisomeric salts or esters of the compound of general formula (IA) with an optically active acid (e.g. a camphor sulphonic acid), separating the isomeric salts or esters and converting the separated isomeric salts or esters into the enantiomers of the compound of general formula (IA); (2) forming the diastereoisomeric carbamates of the compound of general formula (IA) by reacting a halo-formate (e.g. chloroformate) of the latter with an optically active amine (e.g. 0<-methyl-benzylamine), separating the isomeric carbamates, and converting the separated isomeric carbamates into the enantiomers of the compound of general formula (IA), (3) reacting the hemiphthate with an optically active amine (e.g. c<-methylbenzylamine) to give a salt of the hemiphthate, separating the isomeric t salts and converting the separated salts into the enantiomers of the compound of general formula (IA); or (4) resolving the mixtures using 8 208654 enantio-selective crystallisation techniques (Leigh, Chemistry and Industry, 1970, pages 1016-1017, and ibid. 1977, page 36). The separation of the diastereoisomeric salts, esters and carbamates can be achieved by for example crystallisation techniques or by high pressure liquid chromatography (HPLC). Alternatively, the enantiomers can be prepared directly from the compound of general formula (II) by stereospecific reduction, for example by biochemical reduction (using for example yeast or Aspergillus nicer) or by hydrogenation using chiral catalysts (e.g. a Wilkinson's catalyst) or by reduction with borohydride/amino acid complexes.

The compounds of general formula (IA), salts, ethers, esters and metal complexes thereof, are active fungicides, particularly against the diseases Piricularia orvzae on rice Puccjnia recondita. Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts e.g. coffee, apples, vegetables and ornamental plants Plasmooara viticola on vines Erysiphe grarninis (powdery mildew) on barley and wheat and other powdery mildews on various hosts such as Sphaerotheca fuliginea on cucurbits (e.g. cucumber), Phodosohaera leucotricha on apples and Uncinula necator on vines Helminthosporium spp. and Rhvnchosporium spp. on cereals Cercospora arachidicola on peanuts and other Cercospora species on for example suggar beet, bananas and soya beans Botrytis cinerea (grey mould) on tomatoes, strawberries, vines and other hosts Phvtophthora infestans (late blight) on tomatoes Venturia inaecrualis (scab) on apples.

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 diqatatum and italicum on oranges and *654 Gloeosporium musarun on bananas). Further 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., Helminthosporium spp. on cereals, Rhizoctonia 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, e.g. in the prevention of fungal attack on wood, hides, leather and especially paint films.

The compounds can 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 peanuts, cereals and soya bean where reduction in stem growth may reduce the risk of lodging and may also permit increased amounts of fertiliser to be applied. The stunting of woody species is useful in controlling the growth of undergrowth under power lines etc. Compounds which induce stunting or dwarfing may also be useful in modifying the stem growth of sugar cane thereby increasing the concentration of sugar in the cane at harvest; in sugar cane, the flowering and ripening may be controllable by applying the compounds. Stunting of peanuts can assist in harvesting. Growth retardation of grasses can help maintenance of grass swards. Examples of suitable grasses are Stenotaphrum secundatum (St. Augustine grass), Cynosurus cristatus, Lolium multiflorum and perenne, Agrostis tenuis, Cynodon dactylon (Bermuda grass), Dactylis 208654 gloraerata, Festuca spp. (e.g. Festuca rubra) and Poa spp. (e.g. Poa pratense) . The compounds may stunt grasses without significant phytotoxic effects and v/ithout deleteriously affecting the appearance (particularly the 5 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 10 species are sedges (e.g. Cyperus spp.) and dicotyledonous weeds (e.g. daisy, plantain, knotweed, speedwell, thistle, docks and ragwort). The growth of non-crop vegetation (e.g. weeds or cover vegetation) can be retarded thus assisting in the maintenance of plantation and field 15 crops. In fruit orchards, particularly orchards subject to soil erosion, the presence of grass cover is important. However excessive grass grov/th requires substantial maintenance. The compounds of the invention could be useful in this situation as they could restrict growth 20 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 25 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 30 ornamental, household, garden and nursery plants (e.g. poinsettias, chrysanthemums, carnations, tulips and daffodils) .

As indicated above, the compounds can also be used to stunt woody species. This property can be used to control 35 hedgerows or to shape fruit trees (e.g. apples). Some 11 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) 5 above) manifest itself in an increase in crop yield.

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

Other plant growth regulating effects caused by the compounds include alteration of leaf angle and promotion 10 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 phytosynthesis and tuber weight. By increasing tillering 15 in monocotyledonous crops (e.g. rice), the number of flowering shoots per unit area may be increased thereby increasing the overall grain yield of such crops. In grass swards an increase in tillering could lead to a denser sward which may result in increased resilience in 20 wear.

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

The compounds may inhibit, or at least delay, the flowering of sugar beet and thereby may increase sugar 25 yield. They may also reduce the size of sugar beet without reducing significantly the sugar yield thereby enabling an increase in planting density to be made. Similarly in other root crops (e.g. turnip, swede, mangold, parsnip, beetroot, yam and cassava) it may be 30 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.

The compounds may be useful in rendering plants 35 resistant to stress since the compounds can delay the 208654- 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 coirpounds can have a growth stimulating effect on plants.

In carrying out the plant growth regulating treatment, 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. Hcwever, 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.

Our New Zealand Patent Specification No. 198085 describes and claims a method of regulating plant growth which comprises applying to a plant, to seed of a plant or to the locus of a plant or seed a compound of the present invention or an ester, ether, salt or metal complex thereof.

The compounds may be used as such for fungicidal purposes but are more conveniently formulated into compositions for such usage. The invention thus provides also a fungicidal composition comprising a compound of the invention or an ester, ether, salt or metal complex thereof, and 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 a plant or seed, a compound of the invention or an ester, ether, salt or metal complex thereof. 2 086 5 4 13 The compounds can be applied in a number of ways, for example they can be formulated or unformulated, directly to the foliage of a plant, to seeds or to other medium in which plants 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 be1 applied as a vapour. Application can be to any part of the plant, bush or tree, for example to the foliage, stems, branches or roots, or to soil surrounding the roots, or to the seed before it is planted.

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

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

The compositions may be in the form of dusting powders or granules comprising the active ingredient and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay. Such granules can be preformed granules suitable for application to the soil without further treatment. These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler. Compositions for dressing seed, for example, may comprise an agent (for example a mineral oil) for assisting the 2086 5 14 adhesion of the composition to the seed; alternatively the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example N-methyl-pyrrolidone or dimethylformamide) .

The compositions may also be in the form of dispersible powders, granules or grains comprising a wetting agent to facilitate the disperion 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 agent(s) and then adding the mixture to water which may also contain wetting, dispersing or emulsifying 15 agent(s). Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, a. methylnaphthalene, the xylenes, trichloroethylene, furfuryl alcohol, tetrahydro-furfuryl alcohol, and glycol ethers (e.g. 2-ethoxyethanol 20 and 2-butoxyethanol).

The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant, e.g. fluorotrichloromethane or dichlorodif luoromethane. 25 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-30 encapsulated 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. 35 The compounds can be used as mixtures with 2 OSS 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 a compound as hereinbefore defined.

The compositions may also be in the form of liquid preparations for use as dips or sprays which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surfactants e.g. wetting agent(s), dispersing agent(s), emulsifying agent(s) or suspending agent(s). These.agents can be cationic, anionic or non-anionic 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 dodecylbenzene— sulphonate, sodium, calcium or ammonium lignosulphonate, 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 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 2086 16 . 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 5 withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogenous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently 10 contain up to 95%, suitably 10-85%, for example 25-60%, by weight of the active ingredient(s). These concentrates suitably contain organic acids (e.g. alkaryl or aryl sulphonic acids such as xylene-sulphonic acid or dodecyl-benzenesulphonic acid) since the presence of such acids 15 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 pre-20 parations, 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. 2 5 The compositions of this invention can comprise also other compound(s) having biological activity, e.g. compounds having similar or complementary fungicidal or plant growth regulating activity or compounds having herbicidal or insecticidal activity.

The other fungicidal compound can be for example one which is capable of combating ear diseases of cereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporium spp., seed and soil borne diseases and downy and powdery mildews on grapes and powdery mildew and 35 scab on apple etc. These mixtures of fungicides can have 208654 17 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 5 other fungicidal compound are imazalil, benomyl, carbendazim, thiophanate-rnethyl, captafol, captan, sulphur, triforine, dodemorph, tridemorph, pyrazophos, furalaxyl, ethirimol, dimethirimol, bupirimate, chlorothalonil, vinclozolin, procymidone, iprodione, 10 metalaxyl, carboxin, oxycarboxin, fenarimol, nuarimol, fenfuram, methfuroxam, nitrothal-isopropyl, triadimefon, thiabendazole, etridiazole, triadimenol, biloxazol, dithianon, binapacryl, quinomethionate, guazatine, dodine, fentin acetate, fentin 15 hydroxide, dinocap, folpet, diclofluanid, ditalimphos, kitazin, fenpropemorph , cycloheximide, a dithiocarbamate, a copper compound, a mercury compound, DPX 3217, RH 2161, Chevron RE 20615, CGA 64250 and CGA 64251.

The compounds of general (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 forraothion.

The other plant growth regulating compound can be one which controls weeds or seedhead formation, improves the level or longevity of the plant growth regulating activity of the compounds of general formula (I), selectively controls the growth of the less desirable plants (e.g. grasses) or causes the compound of general formula (I) to act faster or slower as a plant growth regulating agent. Some of these other agents will be herbicides. Examples of suitable agents are the gibberellins (e.g. GA^, GA^ or GA-^) , the auxins (e.g. an indoleacetic acid, an indolebutyric acid, a naphthoxy- 2086 18 acetic acid or a naphthylacetic acid), the cytokinins (e.g. kinetin, a diphenylurea, a benzyladenine or BAP), phenoxyacetic acids (e.g. 2,4-D or MCPA), substituted benzoic acids (e.g. TIBA), morphactins, maleic hydrazide, glyphosate, glyphosine, dikegulac, Sustar, Embark, substituted quaternary ammonium and phosphonium compounds (e.g. CCC or Phosfon-D), Ethrel, carbetamide, Racuza, Alar, asulam, abscissic acid, isopyrimol, RH531, hydroxy-benzonitriles (e.g. bromoxynil), Avenge, Suffix, Lontrel or thiocarbamates (e.g. Eptam).

The following Examples illustrate the invention; the temperatures are given in degrees Centigrade (°). 19 208G54- EXAMPLE 1 This Example illustrates the preparation of: 1-fl; 2-r-4—Triazol-l-^vB—2—f 4—chlorophenvl) —3 ,3-dimethyl-butart-2—ol--(Compound - No 2-:of-.-Table--I ) Stage-1. Trimethyl acetonitrile (0.1 mol) in dry tetrahydrofur:an(50 ml) was added dropwise with stirring to the Grignard reagent prepared from 4-chloro-iodobenzene (0.11 mol) and magnesium turnings (0.11 g atoms) in sodium dry ether (50 ml) at such a rate as to retain gentle reflux. The solution was reluxed for 4 hours, cooled to room temperature, and water (40 ml) added carefully. 2N H2SO4 (50 ml) was added and the ether solution washed with water (3 x 100 ml) and dried over anhydrous magnesium sulphate. Removal of the solvent gave a yellow oil which was distilled at the water pump to give tertiary butyl 4-chlorophenyl ketone (40%) as a colourless liquid b.p. 116-128°/15 mm Hg.

Stage--2. A solution of dimethyl oxosulphonium rnethylide was prepared under nitrogen from sodium hydride (0.03 mol) and powdered trimethyl oxosulphonium iodide (0.03 mol) in dry dimethyl sulphoxide (40 ml). A solution of 4-chlorophenyl tertiary butyl ketone (0.025 mol) in dry dimethyl sulphoxide (10 ml) was added dropwise at rocm terrperature and the solution heated at 50°C for 2.5 hours. After cooling to room temperature the solution was extracted with ether (150 ml), washed with water and dried over anhydrous sodium sulphate. Removal of the solvent gave 1-(4-chlorophenyl)-1-t-butyl-ethylene oxide (95%) as a colourless liquid. 208654 Stage-3. 1,2,4-Triazole (0.04 mol) was added portionwise to sodium hydride (0.04 mol) in dimethyl formamide (40 ml) and the solution stirred at room temperature until the effervescence ceased. 1-(4-chlorophenyl)-1-t-butyl-ethylene oxide (0.02 mol) in dimethyl formamide (10 ml) was added dropwise and the solution stirred at 60° for 3 hours. The solution was poured into water and triturated with petroleum ether to give a white solid which recrystallised from 60/80 petroleum ether gave the title compound (65%) m.p. 70-3°. 2086s 21 - EXAMPLE 2 I An emulsifiatole 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 3 A composition in the form of grains readily dis-persible 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 1 50% "Dispersol" T 25% "Lubrol" APN5 1.5% Sodium acetate 23.5% EXAMPLE 4 The ingredients were all ground together to produce, a powder formulation readily dispersible in liquids.

Compound of Example 1 "Dispersol" T 45% 5% 208654 22 "Lissapol" NX 0.5% "Cellofas" B 600 2% Sodium acetate 47.5% EXAMPLE 5 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 6 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 7 A dusting powder was prepared by mixing the active ingredient with talc.

Compound of Example 1 5% Talc 95% 20865 23 EXAMPLE 8 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 1 40% "Dispersol" T 10% "Lubrol" APN5 .1% Water EXAMPLE 9 A dispersible powder formulation was made by mixing 10 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. 5% China clay 28% Silica 40% EXAMPLE 10 This Example illustrates the preparation of a ■ dispersible powder formulation. The ingredients were mixed 20 and the mixture then ground in a comminution mill.

Compound of Example 1 25% "Perminal" BX 1% "Dispersol" T 5% Polyvinylpyrrolidone 10% 208654 24 Silica China clay % EXAMPLE 11 The ingredients set out below were formulated into a dispersible powder by mixing then grinding the ingredients . ' Compound of Example 1 "Aerosol" OT/B "Dispersol" A 10 China clay % 2% 5% 68% In Examples 2 to 11 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 15 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 & 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) 20865 a sodium carboxymethyl cellulose thickener a condensate of nonyl phenol (1 mole) with ethylene oxide (8 moles) dioctyl sodium sulphosuccinate a sodium alkyl naphthalene sulphonate EXAMPLE 12 f 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 20 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 25 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 30 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.

CELLOFAS B600 : LISSAPOL NX : AEROSOL OT/B : PERMINAL BX : 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 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 four to fourteen days according to the disease and environment.

The disease control was recorded by the following grading no disease trace - 5% of disease on untreated plants 6-25% of disease on untreated plants 26-59% of disease on untreated plants 60=100% of disease on untreated plants The results are shown in Table II. A dash in the table thus "-" signifies that no test against the disease was conducted. :—— 4 = 3 = 2 = 1 = 0 = I • TABLE II compound puccinia erysiphe piricularia plasmopara phytophthora botrytis cercospora venturia number recondita graminis oryzae viticola infestans cinerea arachidicola inaequalis (wheat) (barley) (rice) (vine) (tomato) (grape) (peanut) (apple) 1 4 4 - 2 0 4 4 4 2 4 4 - • 0 0 4 4 4 ro •^i Is) O 00 o Ul 2 28 EXAMPLE 13 This Example illustrates the plant growth regulating properties of the compounds. The compounds were applied in the form of a 4000 ppm solution in distilled water and the solution was then applied to the foliage of young seedlings of various plants. The experiments were replicated twice. After 12 or 13 days from treatment the plants were assessed for plant growth regulating effects and phytotoxic symptoms.

Table III shows the stunting effect of a compound on the"vegetative growth using the following grading : 0-30% retardation 31-75% retardation 75% retardation If no figure is given, the compound was substantially inactive as a stunting agent. Additional plant growth regulating properties are indicated as follows : darker green leaf colour apical effect tillering effect. 1 = 2 = 3 = G = A = T = •# TABLE III compound sugar agrostis cynodon dactylis number soya cotton beet tenuis dactylon glomerata wheat barley maize tomato 2 2G 3G 3G 1 1G 1G 1 3GA NJ O 00 ON

Claims (11)

WHAT WE CLAIM IS: 30 208654

1. A racemic compound of general formula (IA)

OH and stereoisomers thereof, wherein R-*- is n-butyl and is 2,4-dichlorophenyl or is i-butyl and is ]>-chlorophenyl, and acid addition salts, ethers, esters and metal complexes thereof. 2. The compound: oh CI

3. The compound: oh N -n ch2 — c '// \ CI n ck3— c— ch3 ch- 31. 2.0S654-

4. A process for preparing a compound, salt or metal complex according to any of the preceding claims, characterised by comprising reacting a compound of the general formula (II) or (III) >0 OH ch2— c R -ch. (II) (III) 1 2 wherein R and R are as defined in claun 1 and X is halogen, with 1,2,4—triazole in the presence of an acid binding agent or with an alkali metal salt of 1,2,4-triazole in a convenient solvent.

5. A process according to claim 4 wherein X is chlorine.

6. A process according to claim 4 or claim 5 wherein a compound of formula II or III is brought into reaction with the sodium salt of 1,2,4-triazole at a terrperature of from 20 to 100°C.

7. A process according to any of claims 4, 5 and 6 wherein the reaction is carried out using acetonitrile, methanol, ethanol or dimethylformamide as a solvent.

8. A process according to any of claims 4, 5, 6 and 7 wherein a compound of general formula II or III is prepared by reacting a compound of general formula IVa or IVb 208654 32. 0 X — CH2 — C — R 0 X — CH2 — C (IVa) (ivy 1 2 wherein R , R and X are as defined in claim 4 with, respectively, a Grignard compound of formula (Va) or(Vb): - Mg- — R (Va) Mg — R (Vb) 1 2 wherein R and R are as defined above and Y is a halogen in a convenient solvent such as diethyl ether or tetrahydrofuran.

9. A process according to claim 8 wherein Y is chlorine, bromine or iodine.

10. A fungicidal composition characterised in that it comprises, as an active ingredient, a compound, or salt, ester, ether, or metal complex thereof, as defined in any of claims 1 to 3, together with a carrier or diluent.

11. A method of combating fungi, especially 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, salt,ester, ether, or metal complex thereof according to any one of the claims 1 to 3 or a composition as claimed in claim 10. (See next page -33^--) A. J. PA FE* I* "b S agents f©* the afhjcawts - 33A - 208654 Reference has been directed,in pursuance of Section 16(1) of the Patents Act 1953, to patent no. 192962. # :. BURTON Assisfe^rfit Commissioner of Patents m *