GB2224278A - I-triazole-ethanols as fungicides - Google Patents

Description

W 2224278 4, - 1 HETEROCYCLIC COMPOUNDS This invention relates to triazole

compounds which are useful as fungicides and plant growth regulating agents, to processes for preparing them, to fungicidal compositions containing them, and to method of combating fungi, especially fungal infections in plants.

The present invention provides triazole derivatives having the general formula (I):

YR5 R' R2 1 1 3 N-N-CH-C LC--R 11 1:,,1 14 ,N R and stereoisomers thereof, wherein R is phenyl optionally substituted with halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, nitro, halomethylenedioxy, amino, mono- or di-alkylamino, hydroxy, morpholino or alkoxYcarbonyl, or phenyl, phenoxy, benzyl or benzyloxy all optionally substituted with halogen; R', R2 and R3 are independently hydrogen, halogen, alkyl, trialkylsilyl; R4 is hydrogen or alkyl; R5 is hydrogen, alkyl, cycloalkylr alkenyl, alkynyl, optionally substituted benzyl or alkylcarbonyl (providing the carbon atom adjacent to the oxygen atom is not involved in any unsaturation); and acid addition salts and metal complexes thereof; provided that Rl, R2,, R3 and R4 are not all hydrogen, and that when R1 and R2 are both hydrogen then R3 is not alkyl.

i k, : the invention can contain The compounds olL geometric isomers about the double bond in the general formula (I). Mixtures containing these isomers can be separated into the individual isomers by methods known in the literature. Such isomers and mixtures thereof in all proportions constitute a part of the present invention.

The compounds of the invention contain one or more chiral centres. Such compounds are generally obtained in the form of racemic mixtures. However, these and other mixtures can be separated into individual isomers by methods known in the art. Such isomers and mixtures thereof in all proportions constitute a part of the present invention.

Alkyl groups and alkyl moieties of mono- or dialkylamino, alkylcarbonyl, alkoxycarbonyl, haloalkyl, haloalkoxy and alkoxy, contain 1 to 6, preferably 1 to 4, carbon atoms and are either straight or branched chain groups, for example methyl, ethyl, propyl (n or iso-propyl), butyl (n, sec, iso, or tbutyl), pentyl (for example n-pentyl) and hexyl (for example n-hexyl).

Halogen includes fluorine, chlorine, bromine and iodine atoms, and is preferably chlorine or bromine.

An alkenyl group contains 3 to 6 carbon atoms and is preferably allyl.

An alkynyl group contains 3 to 6 carbon atoms and is preferably propargyl.

A cycloalkyl group contains 3 to 8, preferably 3 to 6, carbon atoms and is for example cyclopropyl cyclobutyl, cyclopentyl or cyclohexyl. Examples of substituents on an optionally substituted benzyl moiety are halogen, alkoxy and alkyl. 35 An example of halomethylenedioxy is difluoromethylenedioxy.

-Q 1 1 3 - In another aspect the invention provides triazole derivatives having the general formula (I):

ORS R' R2 1 1 3 N-N-CH-C-C----J-R 11 1 14 1 R R and stereoisomers thereof, wherein R is phenyl, or phenyl substituted with halogen, Cl-5 alkyl, Cl-4 alkoxy, halo(C1-4)alkyl, halo(C1-4)alkoxy, nitro, halomethylenedioxy, amino, mono- or di-Cl-4 alkylamino, hydroxy, morpholino or C1-4 alkoxYcarbonyl, or R is phenyl substituted by phenyl, phenoxy, benzyl or benzyloxy all of which may be substituted by halogen; R', R2, R3 are hydroqen, halogen, Cl-6 alkyl, trialkylsilyl (where the alkyl chains may be straight or branched having 1 to 6 carbon atoms) or a straiqht or branched chain alkyl group having 1 to 6 carbon atoms; R4 is hydrogen or Cl-6 alkyl, provided that R', R2, R3 and R4 are not all hydrogen and that when R1 and R2 are both hydrogen then R3 is not a straight or branched chain alkyl group having 1 to 6 carbon atoms; R5 is hydrogen or Cl-6 alkyl, C3-6 alkenyl, C3-6 alkynyl, optionally substituted benzyl or Cl-4 alkylcarbonyl (provided that the carbon atoms adjacent to the oxygen atom is not involved in any unsaturation); and acid addition salts and metal complexes thereof.

In a further aspect the invention provides triazole derivatives wherein R is phenyl or a substituted phenyl which is 2-, 3- or 4-chlorophenyl, 2..4or 2,5-dichlorophenyl, 2-, 3- or 4- fluorophenyl, c 2,4- or 2,6-difluorophenyl, -j-, 3- or 4-bromophenyl, 2-chloro-4- fluorophenyl, 2-fluoro-4-chlorophenyl,2chloro-6-fluorophenyl, 2-, 3- or 4methoxyphenyl, 2,3dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4nitrophenyl, 2-chloro-4-nitrophenyl, 2-chloro-5nitrophenyl, 2-, 3- or 4trifluoromethoxyphenyl, 2-, 3- or 4-(1,2,2,2-tetrafluoroethoxy)phenyl, 2-, 3-or 4-methylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4butylphenyl, 2,3(difluoromethylenedioxy)phenyl, 2- fluoro-4-methoxyphenyl, 2-methoxy-4-fluorophenyl, 2methoxy-4-chlorophenyl, 2-chloro-4-methoxyphenyl, 2-, 3- or 4-phenoxy-phenyl, 2-, 3 or 4-phenylphenyl (2-, 3- or 4-biphenylyl), 2-, 3- or 4-benzylphenyl, 2-, 3- or 4benzyloxyphenyl, 2-, 3- or 4-(4-chloroor 4-fluorobenzyloxy)phenyl, 2-, 3or 4aminophenyl, 2-, 3- or 4-(N,Ndimethylamino)phenyl, 2-, 3- or 4hydroxyphenyl, 2-, 3- or 4(methoxycarbonyl)phenyl or 2-, 3- or 4morpholinophenyl.

In a still further aspect the invention provides triazole derivatives having the general formula (I):

OR5 R' R2 1 1 1 N-N-CH --C-(.j-R R4 R (I) and stereoisomers thereof, wherein R is phenyl optionally substituted with fluorine, chlorine, Cl-4 alkyl or Cl-4 alkoxy; Rl, R2 and R3 are independentl y 25 chlorine, bromine, hydrogen, Cl-4 alkyl or trimethylsilyl; R4 is hydrogen or Cl-4 alkyl; R5 is hydrogen, Cl-4 alkyl, Cl-4 alkylcarbonyl, allyl, propargyl or benzyl optionally substituted with C chlorine; and acid addition salts and metal complexes thereof; provided that R', R2, R3 and R4 are not all hydrogen and that when R' and R2 are both hydrogen then R3 is not Cl-4 alkyl.

In another aspect the invention provides triazole derivatives having the general formula (I):

OR5 R1 2 1 3 1 14 N%; R and stereoisomers thereof, wherein R is phenyl, 4chlorophenyl or 2,4- dichlorophenyl; R', R2 and R3 are independently hydrogen, chlorine, bromine, methyl or -imethylsilyl; R4 is hydrogen; R5 is hydrogen, methyl or acetyl; and acid addition salts and metal complexes thereof; provided that when R' and R2 are hydrogen then R3 is not hydrogen or methyl.

In a further aspect the invention provides the 15 compounds (Compound 6 of Table I) 0 H C H 3 1 1 N-N-CHf-C-C H 2 c---Cl 1 cC l OH CH 1 1 3 NN-CH2-C-C===:CH2 -N cl (Compound 5 of Table I) and their stereoisomers metal complexes thereof.

The invention is illustrated by the following specific compounds set out in Table I below. These conform to the general formula (I):

and acid addition salts and R4 ORS R' R2 1 1 1 1 N N-CH - C - CC - R 1 1 W." R (I) In Table I the significance of the abbreviations is as follows:

Me represents methyl Et represents ethyl nPr represents normal propyl nBu represents normal butyl tBu represents tertiary butyl W 9 1 1 TABLE 1

Compound R R' R2 R3 R4 R5 Olefin No stereo- chemistry cl Br Br H H cis -b-CI 2 cl Br Br H H trans 3 cl cl cl H H H cis --b- c 1 r 4 cl cl cl H H H trans -b-CI i 1 A 1 MP1,c 162-164 138-141 1 -11 1 159-162 131-133 1 TABLE I (cont/d) Compound No R R' Me Me R R R 2 H H Me Me R4 H H H H R5 H a H 11 R3 Olef in stereochemistry MPI OC 1 6 7 cl' Q cl - 1 cl cl 0 cl --)-Cl i H 88-90 H 112-115 Me 111114 8 Me f 1 co 1 105-106 1 1 1 1 TABLE 1 (cont/d) Compound R R' R 2 R 3 R 4 R5 Olefin mplC No stereo chemistry 9 cl Me Me H H H cis:trans oil 0 F:3 - cl Me Me H H cis:trans oil 0 1-:2 - 11 cl Me Me H H H cis:trans oil Y-Cl mixture 12 Me H 11 H H 84-86 1 kD 1 I^ TABLE 1 (cont/d) Compound R R' R2 R3 R4 RS Olefin mploc No stereochemistry 13 cl Me 3 si R H H H trans 112-115 14 cl Me H H H Me - semi solid cl Me H 11 H W - 111-113 C-Me -- -ci ---fl 1 F, 0 1 1, 1 TABLE I (cont/d) R Et Et n Pr n Pr R 2 H H H H R3 H H H H p R4 R5 H R H Compound No 16 R cl 17 cl 0 cl --o-ci cl 0 Olef in stereochemistry H 18 H H 19 H H 1 l_i F 1 TABLE I (cont/d) R5 H Compound R R' R 2 R3 R4 No cl nBu H H H -b- cl 21 cl nBu H H H Q 1 22 cl Me Et H H "I, - &Cl 23 cl Me Et H H 1 Olefin mp/lc stereochemistry trans trans H H H 1 1 F m 1 11 1 1 1 TABLE 1 (cont/d) Compound No 24 R cl --b-cl R' Me Me Me Me Ck P 26 cl --b-CI 11 'i 27 cl k? R2 Et Et n Pr n Pr 1 R3 R4 Otefin stereochemistr mp loc trans trans 1 W 9 TABLE 1 (cont/d) Compound No R R' Me Me Me R2 R3 n Pr H n Pr H Me Me Me Me 1 R4 28 cl H H H H 1 1 - F' Mploc 1 1 R5 Olefin stereo chemistry H cis R cis H R 29 cl -b-ci cl t? 31 1 l_i A.

1 1 1 TABLE I (cont/d) R5 H cis H cis H H Olef in stereochemistry t rans trans Compound R R' R2 R3 R4 No 32 cl Me Me Et R -b-CI 33 c 1 Me Et Me R Q 34 c 1 11 Et Me R -b- cl c 1 R Me Et H t 1 Iul 1 TABLE I (cont/d) r p r Compound R R' R2 R3 R4 R5 Olefin No stereo- chemistry 36 cl R Et Et R H -b- cl 37 cl H Et Et H H - 0 38 c Et Et Me H H cis d 1 39 cl Et Et Me H H trans 1 0, - 1 1-- 1 MPIC 11 1 1 F m 1 1 1 1^ TABLE I (cont/d) Compound No R R' R 2 R3 R 4 R5 Olefin mpl"C stereo chemistry Me Me R H Et S-Cl cl Me Et H H Et 0 Me Me H H C H 2 C -==-C H cis C 1 Me Me H H C H 2 C -==-r- H trans cl -b- 41 42 43 1 b-A 1 TABLE 1 (cont/d) Compound R R' R2 R3 R 4 R5 Olefin MPPIC No stereo chemistry 44 cl 0 Me H H H CR 2 C =;--C H cl t? Me 11 H H CH 2CH=CH2 - 46 cl Me H H H $ - b cl 47 cl Me 3S' H H H -b- cl 11 TABLE 1 (cont/d) Compound R RI R2 R3 R4 R5 Olefin mploc No stereochemistry! 48 cl H Me Me 3S' H H 0- 49 MeO Me H H H H - so c Me H 11 H H - a 51 C6-CH3 Et H H H H - - llk TABLE 1 (cont/d) Compound R R' R 2 R3 R4 R5 Olefin No stereo- chemistry 52 S-OCH3 n Pr R H H H 53 Et Me H H H 54 cl Me Me H H H -Me cl Me Me H HH b-Et R - 1 w- - mp /()c 1 t,l 0 1 O_ TABLE I (cont/d) Compound R. R' R 2 R3 R 4 R5 Olefin mploc No stereo- chemistry 1 56 Et Me Me H H H b-Cl 57 Et Me Me H H H 1 58 nPr Me Me H H H 0 - 1 m 1 TABLE I (cont/d) Compound R R' R 2 R3 R4 R5 Olefin i mploc No stereo chemistry 59 tBu Me Me H H H 0 tBu Me Me Me H H - 0 1 t,.) 1 1 1) can be The compounds of general formula ( prepared by reacting a compound of the general formula (II) or (III):

0 R' R2 3 C R 1 R4 R (ii) OH R -L X - CH - C R2 1 c 3 - C C -R R4 R (III) or wherein R, R', R2, R3 and R4 are defined above, R5 is hydrogen and X is a halogen atom (preferably a chlorine or a bromine atom), with 1,2,4triazole 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 20-1000C 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, ethanoll iso-propanol or NtN-dimethylformamide. The product can be isolated by pouring the reaction mixture into water and extracting with ethyl acetate. A-fter drying with a suitable agent such as magnesium sulphate or sodium sulphate and chromatography on silica gel the solid or gum obtained can be (re)-crystallised from a convenient solvent.

24 - The compounds of general formula (II) and (III) can be prepared by reacting a compound of general formula (IVa) or (IVb) - 0 R' R2 11 1 1 3 X-CH-C- C C- R R 0 11 X- CH - C -R 4 1 4 R (IVa) (IVb) wherein R, R', R2, R3 and R4 are as defined above and X is a halogen atom, with, respectively, a Grignard compound of the general formula (Va) or (Vb) R' R2 Y-Mg-R 1 1 - 3 Y-Mg_ C C R (Va) (Vb) wherein R, Rl, R2 and R3 are as defined above and Y is a halogen (preferably chlorine, bromine or iodine), in a convenient solvent such as diethyl ethyl or tetrahydrofuran. Generally, a mixture of the compounds of the general formula (II) and (III) are obtained.

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

The compounds of general formula (II), wherein R, Rl, R2 and R3 are as defined above, can also be prepared by reacting the appropriate ketone compound of general formula (VI):

0 R ' R 2 1 R wherein R, R11 R2, and R3 are as defined above, with dimethyl sulphonium methylide or diphenylethyl sulphonium methylide (Corey & Chaykovsky, J. Am. Chem. Soc., 1962, 84, 3782) using methods set out in the 5 literature.

Compounds of general formula (VIII):

0 H i N-N- CH - C 1 4 1 ' N ---j R R X X 1 1 C C H (VI I I) wherein R and R4 are as defined above and X is halogen, which are examples of compounds of general formula (I) wherein R' and R2 are halogen and R3 and R5 are hydrogen, can be produced by reacting a compound of general formula (VII):

OH N- N - CH --- -C CH , M;lli R4 1 R (VII) wherein R and R4 are as defined above, whose preparation is described in EP 97426 (USP 4,634,466), with a halogen, such as chlorine or bromine, in the presence of light, 15 in a suitable solvent, such as chloroform, at 200C to 1000C, but preferably at room temperature. This 1 procedure normally provides a mixture of geometric isomers.

Compounds of general formula (XI):

OH R H N-N- C H -R 3 i.N.i A4 A (M) wherein R3 is trialkylsilyl and R4 and R are as defined above, can be prepared by reacting a compound of general formula (IX):

OH t N ---- N-CH ME -----=C H 11 1 14 1 N R R (IX) wherein R and R4 are as defined above, with a suitable alkyllithium base, such as methyllithium or nbutyllithium, in a suitable solvent, such as tetrahydrofuran, at a suitable temperature, for example -780C, followed by treatment with a chlorotrialkylsilane to give a compound of general formula M:

OH 1 3 N-N-Ch-(--CC 11 1 14 (X) wherein R and R4 are as defined above and R3 is trialkylsilyl. Compounds of general formula (X) can be reduced to the trans-olefinic compounds (M) using a suitable reducing agent, for example a toluene solution of sodium bis(2-methoxyethoxy) aluminium hydride, in a - 27 suitable solvent, such as tetrahydrofuran, and at a suitable temperature for example in the range of -100C to 250C preferably OOC.

The compounds of general formula (I) wherein R5 is other than hydrogen and alkyl carbonyl can be prepared by treating the compound of general formula (I), wherein R5 is hydrogen, with a suitable base, such as sodium hydride, in a suitable solvent, such as a tetrahydrofuran with a compound of formula (XII):

R S-L (XI I) wherein R5 is as defined above, but is not hydrogen, and L is halogen (for example chlorine or bromine) or a sulphonate group (for example a mesylate, tosylate or benzene sulphonate group).

The compounds of general formula (I) wherein R5 is an alkylcarbonyl group can be prepared by treating the compounds of general formula (I), wherein R5 is hydrogen, with a suitable base, for example sodium hydride, in a suitable solvent, for example tetrahydrofuran, with a compound of formula (XIII):

alkyl-L (XIII) wherein L is bromine or chlorine.

The compounds of general formula (I), wherein R5 is other than hydrogent can also be prepared by etherifying or esterifying compounds of general formula (1), wherein RS is hydrogen, by standard techniques well known in the literature.

The salts and metal complexes of the compounds of general formula (I) can be prepared by standard techniques well known in the literature. For example, the complexes can be made by reacting the 28 uncomplexed compound with a metal salt in a suitable solvent.

The compounds of general formula (I) 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 in the art. Examples of such methods are:- (1) Forming the diastereomeric salts or esters of the compound of general formula (I) with an optically active acid (eg camphor sulfonic acid) separating the isomeric salts or esters and converting the separated isomeric salts or esters into the enantiomers of the compound of general formula (I).

is (2) Forming the diastereomeric carbamates of the compound of general formula (I) by reacting an haloformate (eg chloroformate) of the latter with an optically active amine (eg alpha-methyl benzylamine), separating the isomeric carbamates and converting the separated isomeric carbamates into the enantiomers of the compound of general formula (I).

(3) Forming the hemiphthalate ester of the compound of general formula (I), reacting the hemiphthalate with an optically active amine (eg alphamethylbenzylamine) to give a salt of the hemiphthalate, separating the isomeric salts and converting the separated salts into the enantiomers of the compound of general formula (I) or 29 - Resolving the mixtures using enantio-selective crystallisation techniques (Leigh, "Chemistry and.Industry (London), 1970, 1016-1017 and ibid., 1977, 36. The separation of the diastereomeric salts, esters and carbamates can be achieved by, for example, crystallisation techniques or by high performance liquid chromatography.

The compounds, and their acid addition salts, metal complexes and Noxides are active fungicides, particularly against the following diseases: Puccinia 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.

Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildews on various hosts such as Sphaerotheca fuliqinea on cucurbits (e.g. cucimber), Podosphaera leucotricha on apples and Uncinula necator on vines.

Helminthosporium spp., eg. Pyrenophora teres, Rhynchosporium spp., Pseudocercosporella herpotrichoides, Septoria spp., and Rhizoctonia spp. 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.

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 disease s on fruit (e.g. Penicillium diqatatum and italicum on oranges, Gloeosporium musarum on bananas and Botrytis cinerea on - C4- 4 grapes). Further, some of the compounds are a tive as seed dressings against: Fusarium spp., Septoria spp., Tilletia spp. (i.e. bunt, a seed borne disease of wheat), Ustilaqo spp., Helminthosporium spp. and Pseudocercosporella herpotrichoides on cereals, Rhizoctonia solani on cotton.

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

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. Some of the compounds of the invention exhibit plant growth regulating activity and may be deployed for this purpose at appropriate rates of application.

The compounds may be used as such for fungicidal or plant growth regulating purposes but are more conveniently formulated into compositions for such usages. The invention thus provides a fungicidal or plant growth regulating composition comprising a compound of general formula (I) as hereinbefore defined, an acid addition salt or a metal complex thereof, and, optionally, a carrier or diluent.

The invention also provides a method of combating fungi or regulating plant growth, which comprises applying to a plant, to seed of a plant, or to the locus 30. of the plant or seed, a compound, an acid addition salt or a metal complex thereof, as hereinbefore defined.

The compounds, their acid addition salts and metal complexes can be applied in a number of ways, for example they can be applied, formulated or unformulated, 1 - 31 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 release granules. Application can be to any part of the plant, bush or tree. for example to the foliager 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 hydroponic culture systems. The invention compounds, their acid addition salts or metal complexes 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 their acid addition salts and metal complexes 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 5 solvent (for example N-methylpyrrolidone or N,Ndimethylformamide).

The compositions may also be in the form of dispersible powders, granules or grains comprising a wetting agent to facilitate the dispersion in liquids o f 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 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 their acid addition salts and metal complexes 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 their acid addition salts and metal complexes 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 incorporating, for example coated with,'the compound are preferred. Such granules suitably contain up to 25% by weiqht of the compound. The invention therefore also provides a fertiliser is composition comprising the compound of general formula (I) or a salt thereof.

The compositions may also be in the form of liquid preparations for use as dips or sprays which are genera lly 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)i 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 1 k - 34 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 dodecyl benzenesulphonic 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 - R r, - 0.0005% or 0.01% to 10% by weiqht 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 activity or compounds having plant growth regulating, herbicidal or insecticidal activity.

The other fungicidal 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 carbendazim, benomyl, thiophanate-methylr thiabendazole, fuberidazole, etridazole, dichlofluanid, cymoxanil, oxadixyl, ofurace, metalaxyl, furalaxyl, benalaxyl, fosetyl aluminium, fenarimol, iprodione, procymidione, vinclozolin, penconazole, myclobutanil, systhane, S3308r pyrazophos, ethirimol, ditalimfos, tridemorph, triforine, nuarimol, triazbutyl, guazatine, propiconazole, prochloraz, flutriafol, triadimefon,triadimenol, diclobutrazolf hexaconazole, furconazole, cis-furconazole, bromoconazole, cyproconazole, flusilazole, tebuconazole, dimethomorph, fenpropimorph, fenpropidin, chlorozolinate, diniconazol, imazalilf fenfuram, carboxinj oxycarboxin, methfuroxam, dodemorph, bitertanol, bupirimate, etaconazole,.

streptomycin, cypofuram, biloxazol, quinomethionate, dimethirimol, 1-(2cyano-2-methoxyimino-acetyl)-3-ethy1 urea, 4-chloro-N(cyano(ethoxy)methyl) benzamide, 36 - fenaponil, tolclofos-methyl, pyroxyfur, polyram, maneb, mancozeb, captafol, chlorothalonil, anilazine, thiram, captan, folpet, zineb, propineb, sulphur, dinocap, binapacryl, nitrothalisopropyl, dodine, dithianon, fentin hydroxide, fentin acetate, tecnazene, quintozene, dichloran, tetraconazole, fenpiclonil, difenoconazole, copper containing compounds such as copper oxychloride, copper sulphate and Bordeaux mixture, and organomercury compounds.

The compounds of general formula (I), and acid addition salts or metal complexes thereof, 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 which may be incorporated in the composition of the invention include pirimicarb, dimethoate, demeton-s-methyl, formothion, carbaryl, isopro.carb, XMC, BPMC, carbofuran, carbosulfan, diazinon, fenthion, fenitrothion, phenthoate, chlorpyrifos, isoxathion, propaphos, monocrotophos, buprofezin, ethroproxyfen and cycloprothrin.

Plant growth regulating compounds for use in the invention compositions are compounds which control weeds or seedhead formation, or selectively control the growth of less desirable plants (e.g. grasses).

Examples of suitable plant growth regulating compounds for use with the invention compositions are the gibberellins (e.g. GA3, GA4 or GA7), the auxins (e.g. indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (e.g. kinetin, diphenylurea, benzimidazole, benzyladenine or benzylaminopurine), phenoxyacetic acids (e.g. 2,4-D or MCPA), substituted benzoic acids (e.g. triiodobenzoic acid), morphactins (e.g.

chlorfluoroecol), maleic hydrazide, glyphosatei i 1 glyphosine, lonq chain fatty alcohols and acids, dikegulac, paclobutrazol, flurprimidol, fluoridamid, mefluidide, substituted quaternary ammonium and phosphonium compounds (e.g. chloromequat chlorphonium or 5 mepiquatchloride), ethephon, carbetamide, methyl-3,6dichloroanisate, daminozide, asulam, abscisic acid, isopyrimil, 1-(4-chlorophenyl)-4,6dimethyl-2-oxo-1,2dihydropyridine-3-carboxylic acid, hydroxybenzonitriles (e.g. bromoxynil), difenzoquat benzoylprop-ethyl 3,610 dichloropicolinic acid, fenpentezol, inabenfide, triapenthenol and tecnazene.

The following Examples illustrate the invention; the temperatures are given in degrees Centigrade (OC), and reactions involving water-sensitive intermediates 15 were performed under atmospheres of nitrogen.

In the Examples selected proton NMR data are given for certain compounds. Where this data is given chemical shifts are in ppm from tetramethylsilane and deuterochloroform was used as a solvent. The NMR were 20 all run at 270 MHz.

The molecular ion peak from a chemical ionisation mass spectrum is given for certain compounds.

In the Examples the following abbreviations are used:

S = singlet d = doublet q = quartet THF= tetrahydrofuran DMF= N,N-dimethylformamide HPLC = High Performance Liquid Chromatography br = broad dd = doublet of doublet m = multiplet "DISPERSOL"I "TWEENII and "RED ALI' are Trade or Service Marks.

EXAMPLE 1

This example illustrates the preparation of compounds 1 and 2 of Table I. The reaction can be expressed schematically as follows:- cl 9 cl c - \ i/ 1 CH2 OH 1-1 N-N N Light = 100 W Tungsten lamp 91 cl cl Br2/CHC13 light cl OH H i -C- c- cc 1 1 CH2 Br Br 1 N-N L J V4 cis form 1 Z 1 - Form (compound 1 of Table I) cl OH 1 C- L -=-- CH 1 1 CH2 Br i Br N- N 111-,' J N trans form E' - Form (compound 2 of Table I) - 39 3-Hydroxy-3-(2,4-dichlorophenyl)-4-(1,2,4triazol-l-yl)but-l-yne (0.99g), whose preparation is described in EP 97426, was slurried in chloroform (Sml) and a few drops of bromine in chloroform were added.

The mixture was irradiated with a 100 Watt Tungsten lamp. After 10 minutes some decolourisation took place. The remainder of the bromine in chloroform (total of 0.56g bromine in 5m1 chloroform) was added and the stirring and irradiation continued for 1.5 hours. The mixture was then poured into very dilute aqueous sodium hydroxide, shaken and the aqueous layer was discarded. The chloroform solution was dried over magnesium sulphate and filtered. The filtrate was evaporated in vacuo to give a white foam (1.669). This crude product was then purified by HPLC using t-butyl methyl ether: methanol (99:1 v/v) as eluant to give the pure E-isomer (0.7569) and pure Z-isomer (0.33g).

Z-isomer Melting Point 162-164IC; Proton NMR: 5.01 (1H,d), 5.35 (1H,d), 5.32 (1H,s), 6.92 (1H,s) 7.11 (1H, dd), 7.40 (1H,d) 7.52 (1H,dd), 7.81 (1H,s), 7.96 (1H,s) E-isomer Melting Point 138-141OC; Proton NMR 4.95 (1H,d), 4.98 (1HrS)r 5.24 (1H,d), 6.80 (1H,s), 7.12 (1H,dd), 7.36 (1Hrd), 7.40 (1H,d), 7.83 (1H,s), 7.87 (1H,s) EXAMPLE 2

This example illustrates the preparation of compounds 3 and 4 of Table I. The reaction can be expressed schematically by the following equation:- cl OH cl OH C12/CHC13 1 Light cl C- C ===:C H 1 1 cl C - C:-E-- C H. A cl cl CH 2 CH2 1 N- N N- N N JI N' cis form 'Z'-Form (compound 3 of Table I) light = 10OW Tungsten lamp C1 OH cl 1 1 cl C -IC CH R I - CH2 cl 1 N- N N) trans form EI-Form (compound 4 of Table I) 41 3-Hydroxy-3-(2,4-dichlorophenyl)-4-(1,2,4-triazol-lyl)but-l-yne (0.999) was slurried in chloroform (5m1) and about lml of a solution of chlorine dissolved in chloroform was added to the stirred slurry. The mixture was irradiated with a 100 Watt tungsten lamp. After 10 minutes the remainder of the chlorine in chloroform solution (total being 0.259 chlorine in 5m1 chloroform) was added and the stirring and irradiation were continued. After 30 minutes all the solid had gone into solution. After a further hour the reaction was poured into very dilute aqueous sodium hydroxide. The organic layer was extracted with ethyl acetate (20m1) and then discarded. The organic layers were combined, washed with water (10m1), dried over magnesium sulphate and filtered. The filtrate was evaporated in vacuo to give a white foam (1.28g). This crude product was then purifie-l by HPLC using L-butyl methyl ether: methanol (99:1 v/v) as eluant to give the pure Z-isomer (0. 53g) and the pure E-isomer (0.27g).

Z-Isomer Melting Point - 159-162OC; Proton NMR:

4.96 (1H,d), 5.35 (1H,d), 5.36 (1H,s), 6.40 (1H,s), 7.21 (1H,dd), 7.40 (1Hfd)y 7.53 (1H,d), 7.81 (1H,s), 7.95 (1HyS).

E-Isomer Melting Point - 131-133C; Proton NMR:

H 4.90 (1H,d), 5.10 (1H,s), 5.24 (1H,d), 6.40 (1H,S), 7.11 (1H,dd), 7.30 (1H#d), 7.36 (1H,dd), 7.81 (1H#S), 7.83 (1H,S).

- 42 EXAMPLE 3

This example demonstrates the preparation of compound 5 of Table I. Staqe 1 Preparation of the Grignard Reagent. To a stirred mixture of magnesium turnings (1.19) in dry tetrahydrofuran (10m1) was added a small amount of a solution of 2-bromoprop-l-ene (5g) in dry THF (40m1) to initiate the formation of the Grignard reagent. Once the formation started the remainder of the solution of 2-bromoprop-l-ene in dry THF was added in dropwise fashion. The reaction mixture was then refluxed for 30 minutes.

Staqe 2 The preparation of compounds:

OH CH3 1 1 Br- CH2-C-C-=-ZH2 cl and f 43 - CH3 i >-,-' 1 1 -11 cl 4-Chlorophenacyl bromide (7.5g) in dry THF (50m1) was added to the Grignard reagentr produced in Stage 1, drop by drop at 0-50C. After 15 minutes stirring at OOC the reaction was quenched by adding saturated aqueous brine to the reaction mixture and the pH-adjusted to pH 5 (pH paper) using 2 M dilute aqueous hydrochloric acid. This mixture was quickly extracted with diethyl ether (3 x 100m1) and the combined ethereal extracts dried over sodium sulphate. Filtration followed by evaporation in vacuo of ethereal solution afforded a pale yellow mobile liquid. The proton NMR and IR indicated that the product was a mixture of the chlorohydrin and the epoxide both shown above. This mixture was used in Stage 3 without purification.

Staqe 3 The preparation of the compound:

44 OH CH3 N -N- CH2- C -C ====CH2 I 'I _1 i:;1 i cl Sodium hydride (50% dispersion in oil, 3.5g) was pre-washed with hexane to remove the oil and then suspended in dry DMF (100m1). A solution of 1, 2,4triazole (5g) dissolved in dry DMF (50m1) was added to the sodium hydride with stirring at OOC and stirred at room temperature for 1 hour after the addition was complete. To the reaction mixture was added a solution of the mixture of epoxide and bromohydrin (produced in Stage 2) in dry DMF (50m1) over 15 minutes. After the addition was complete, the reaction mixture was heated at 1000C for 2 hours. The reaction mixture was poured into water (200m1) and the pH of the solution adjusted to pH 6 (pH paper) using 2M hydrochloric acid.

The aqueous mixture was extracted with ethyl acetate (3 x 200m1) and the combined ethyl acetate extracts were dried over sodium sulphate, filtered and evaporated in vacuo to afford a brown gum. The gum was subjected to column chromatography on flash silica using ethyl acetate:hexanes (9:1 v/v) as eluant. The fractions containing pure product were combined and evaporated in vacuo to afford a gum that crystallised on standing. The solid was recrystallised from dichloromethane/hexane to afford white crystals - (melting point 88-90IC) (2.19, 24.7%).

Proton NMR:

1.67 (3H,s), 4.61, 4.72 (2H,AB), J 8HZ) 5.05 (1H,s), 5.10 (1H,s), 4.2-5.3 (1H,br), 7.3 (4H, complex), 7.85 (1H1s)p 7.89 (1H,s).

M/Z 263 (M+) The following compounds were prepared in a manner similar to that described in Example 3:

Compound 6 of Table I, using 2-bromoprop-l-ene (59), magnesium turnings (0.9g), 1,2,4-triazole (4.76g) and sodium hydride (55%; 1.519). This gave 1.0229 of a solid that melted at 112-1150C.

Proton NMR:

M/Z 297 (M+) 1.72 (3H,s), 4.70 (1H,d), 4.72 (1H,s), 4.97 (1H,s), 5.14 (1H,s), 5.46 (1H, d), 7.13 (1H,dd), 7.32 (1H,dd), 7.78 (1H,s), 7.89 (1H,s).

Compound 7 of Table I. This is a solid with a melting point of 111-1141C.

Proton NMR:

M/Z 277 (M+) 1.46 (3H,s), 1.73 (3H,S), 3.8 (1H,s, OH) 4.2 (1H,d), 4.37 (1H,d), 5.7 (1H, br s), 7.33 (4H, AA1 BBI), 7.88 (1HrS)r 7.91 (1Hts).

- 46 iii) Compound 8 of Table I, was obtained as pale green solid with a melting point of 105-1061C.

Proton NMR: 1.42 (3H,s), 1.72 (3H,S), 4.18 (1H, br S-OH), 5.68 (2H, AB q), 5.72 (1H, br s), 7.18 (1H,dd), 7.37 (1H,dd), 7.71 (JH,d), 7.83 (1H,s), 7.97 (1H,s).

M/Z 311 (M+) iv) Compounds 9 and 10 of Table I were obtained as oils both of which were mixtures of isomers.

trans isomer Proton NMR: 1.47 (3H,d), 1.78 (3H,d), 4.30 (1H,br), 4.60 and 4.72 (2H, AB q), 5.55 (1H, br s), 7.24 (4H, AA1 BB'), 7.83 (1H,s), 7.87 (1H,s).

cis isomer Proton NMR:

1.52 (3H,d), 1.65 (3H,d), 4.30 (1H,br), 4.62 and 4.70 (2H, AB q) 5.68 (1H, q), 7.24 (4H, AA' BB'), 7.86 (1H,s), 7.90 (1H,S).

v) Compound 11 of Table I was obtained as an oil.

Proton NMR: 1.40 (3Htd), 1.95 (3H,S), 4.40 (1H,s), 4.84 (2H,dd), 5.50 (1H, m), 7.05 (1H,m), 7.35 (2H,m), 7.75 (1Hrs)f 7.78 (1H,s).

vi) Compound 1.2 of Table I was purified by using crystallisation, (a diethylether - hexane mixt-,re of solvents) rather than by column using chromatography. The crystalline product had a melting point of 84-660C.

Proton NMR:

M/Z 229 (M+) 1.66 (3H,S), 4.45 (1H, br s), 5.12, 4.67 and 4.75 (2H, AB q), 5.04 (1H, br s), 5.12 (1H, br s), 7.27.42 (5H, complex), 7.83 (1H,s), 7.88 (1H,s) EXAMPLE 4

Preparation of compound number 13 of Table I:

OH H N - N - CH 1 SiMe3 . N j 2 - C - C A_ 1 0 Cl H 1 3-Hydroxy-3-(2,4-dichlorophenyl)-4-(1,2,4-triazol-lyl)but-l-yne (1.383g) was dissolved in dry THF (100M1), kept under an atmosphere of dry nitrogen and cooled to -780C using a solid carbon dioxide and acetone cold bath. N-butyllithium (1.6M in hexanes; 6.13m1) was added to this solution drop by drop at such a rate that the temperature of the reaction was maintained below -700C The reaction mixture was then stirred for 10 20 minutes. Neat trimethylsilyl chloride (1.4m1; 1.179) was added drop by drop to the reaction mixture and when the addition was complete the cooling bath was removed and the reaction mixture was allowed to warm to room temperature and stirred for a further 20 minutes.

- 48 Dilute aqueous hydrochloric acid (2M,10mj) and methanol (10m1) were added to.the reaction mixture with stirring. The reaction was monitored by tlc (using ether:hexane 3:1 v/v as eluant) until all the highest Rf triazole 5 containing material (as determined using a chloroplatinic acid spray) had disappeared. The reaction mixture was poured quickly into saturated brine and extracted with ethyl acetate (3 x 100m1). The combined ethyl acetate layers were dried over sodium sulphate, filtered and the volatile solvents removed by distillation under reduced pressures to leave an orange oil. The oil was subjected to column chromatography on silica gel using a diethyl ether:hexanes (3:1 v/v) solvent mixture as eluant. The fractions containing the triazoyl silyl acetylene were combined and evaporated in vacup. The residue was crystallised from diethyl ether, to yield 1-trimethylsilyl-3hydroxy-3-(2,4dichlorophenyl)-4-(1,2,4-triazol-l-yl)but-l-yne (0.2589) as a white solid with a melting point of 140-1431C.

Some starting material was recovered from the chromatography column with the aid of ethyl acetate as eluant.

Proton NMR: 0.13 (9H,s), 4.63 and 4.89 (2H,AB q), 4.6 (1H,s), 7.25 (1H, dd), 7.44 (1H,d), 7.78 (1H,d)r 7.93 (1H,s), 8.12 (1H,s).

M/Z 338 (M-Me)+ - 49 A solution of sodium bis(2-methoxyethoxy)alluininium hydride in toluene (Red-Al sold by the Aldrich Chemical Co Ltd.,) (3.4M; 0.86m1) was dissolved in dry THP (100m1) and cooled to OOC with the aid of an ice with salt cold-bath. To this was added, drop by drop, a solution of 1trimethylsilyl-3-hydroxy-3(2,4dichlorophenyl)-4-(1,2,4-triazol-l-yl)but-lyne (0.258g) in dry THF (10m1) with stirring under dry nitrogen at OOC. When the addition was complete, the cooling bath was removed and the reaction mixture allowed to warm to ambient temperature. The reaction mixture was then stirred for a further 3 hours. It was then carefully poured into water (to avoid over-vigourous frothing) and the products extracted into ethyl acetate (3 x 100m1).

The combined ethyl acetate layers were dried (Na2S04), filtered and the filtrate evaporated under reduced pressure. The resulting gum was purified by column chromatography on silica gel using ethyl acetate:hexanes (3:1 v/v) as eluant. The chromatography fractions containing vinyl silanes were combined and evaporated in vacuo. The resulting semi-solid was crystallised using a diethyl ether and hexane mixture of solvents to afford trans 1-trimethylsilyl-3-hydroxy-3-(2, 4dichlorophenyl)-4-(1,2,4-triazol-l-yl)but-l-ene (0.1389) as a crystalline solid with a melting point of 1121150C.

Proton NMR:

M/Z 340 (M-Me+) 0.01 (9H,s), 4.53 (1H, br s), 4.71 and 5.1 (2H, AB q), 6.12 and 6.60 (2H, AB q,j 14Hz), 7.23 (1H,dd), 7.40 (1H,d), 7. 72 (1Hrd), 7.89 (1H,s), 8.05 (1H,s).

- EXAMPLE 5

Preparation of compound number 14 of Table I:

0Me N--CH --C-C 2 0 c 1 cl "_,CH3 11 CH2 Sodium hydride (55% dispersion in mineral oil; 0.176g) was washed twice with dry hexane to remove the mineral oil, and was suspended in dry THF (50m1). 2-Methyl-3 hydroxy-3-(2,4-dichlorophenyl)-4-(1,2,4-triazol-l- yl)but-l-ene (0.8g) (compound 6 of Table I) was added slowly to the suspension of sodium hydride. There was effervescence during the addition. The mixture was stirred and heated to reflux for 30 minutes under a dry inert atmosphere, cooled to room temperature and methyl iodide (0.769g) added. The mixture was stirred and slowly brought to reflux over 30 minutes. It was refluxed for 3 hours under a dry inert atmosphere. The reaction mixture was then cooled to room temperature, poured into water and extracted into ethyl acetate (3 x 100m1). The combined ethyl acetate layers were dried (Na2S04), filtered and the filtrate evaporated in vacuo to leave an oil. This was subjected to column chromatography on silica gel using ethyl acetate as eluant. 2-Methyl-3-methoxy-3-(2,4-dichlorophenyl)-4(1,2,4-triazol-l-yl)but-l-ene (0.412g) was obtained as a yellow oil.

f - 51 Proton NMR: 1.50 (3H,s), 3.41 (3H,s), 4.88 and 5. (2H, AB q), 5.8 (1H,s), 5.43 (1H,S), 7.08 (1H,dd), 7.37 (1H,d), 7.40 (1H,d) 7.59 (1H,s), 7.70 (1H, s), M/Z 280 (M-OMe)+ EXAMPLE 6

Preparation of compound number 15 of Table I 0 =C - CH3 0/ 1 N-N- CH2-C-C , N 0).l 0 cl cl H3 CH2 Sodium hydride (55% dispersion, 0.11g), washed with dry hexane to remove the mineral oils, was suspended in dry THF (50m1). Finely powdered 2- methyl-3-hydroxy-3-(2,4dichlorophenyl)-4-(1,2,4-triazol-l-yl)but-l-ene (0.5g) (compound 6 of Table I) was added, with stirring, to the sodium hydride. There was effervescence during the addition. The mixture was heated to reflux for 40 minutes under a dry inert atmosphere and cooled to room temperature. Acetyl chloride (0.267g) in THF (5m1) was added to the reaction mixture and the mixture was slowly brought to reflux and kept refluxing for 3 hours. The reaction mixture was then poured into water and extracted with 1 ethyl acetate (3 x 100m1). The combined ethyl acetate extracts were dried (Na2S04), filtered, and the filtrate evaporated in vacuo to leave a brown gum. The brown gum was purified by HPLC using ethyl acetate: hexane (3:1 v/v) as eluant. The desired fractions were evaporated in vacuo to leave a residue which was crystallised from a diethyl ether hexane mixture of solvents to give [2methyl-3-(2,4-dichlorophenyl)-4-(1,2,4-triazol-lyl)but1-en-3-yllacetate as a solid with a melting point of 111-1130C.

Proton NMR:

1.60 (3H,S), 2.15 (3H,S), 5.03 (1H,s), 5.22 (1H,S), 5.34 and 5.50 (2H,AB q), 7.22 (1H,dd), 7.38 (1H,d), 7.41 (1H,d), 7.77 (1H,S), 7.82 (1H,S).

M/Z 339 (M+) EXAMPLE 7

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

Compound of Example 1 Ethylene dichloride Calcium dodecylbenzenesulphate 11Lubroll' L 11Aromasoll' H 10% 40% 5% 10% 35% 53 - EXAMPLE 8

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 resulta.. 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 (E form) I'Dispersol" T 11Lubroll' APN5 Sodium acetate EXAMPLE 9

50% 25% 1.5% 23.5% The ingredients were all ground together to produce a powder formulation readily dispersible in liquids.

Compound of Example 1 I'Dispersoll' T I'Lissapol" NX 11Cellofas11 B600 Sodium acetate EXAMPLE 10

45% 5% 0.5% 2% 47.5% The active ingredient was dissolved in a solvent and 20 the resultant liquid was sprayed on to the granules of 1 - 54 China clay. The solvent was then allowed to evaporat to produce a granular composition.

Compound of Example 1 China clay granules EXAMPLE 11

5% 95% A composition suitable for use as a seed dressing was prepared by mixing the three ingredients.

Compound of Example 1 mineral oil China clay EXAMPLE 12

50% 2% 48% A dusting powder was prepared by mixing the active ingredient with talc.

Compound of Example 1 Talc EXAMPLE 13

5% 95% 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 "Dispersoll' T "Lubrol" APN5 Water 40% 10% 1 % 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 "Aerosol" OT/B I'Dispersol" A.C. China clay Silica 25% 2% 5% 28% 40% EXAMPLE 15

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 "Perminal" BX I'Dispersoll' T Polyvinylpyrrolidone Silica 25% 1% 5% 10% 25% 1 - 56 China clay 3 4.

EXAMPLE 16

The ingredients set out below were formulated into a dispersible powder by mixing then grinding the ingredients.

Compound of Example 1 "Aerosol" OT/B I'Dispersoll' AC China clay 25% 2% 5% 68% In Examples 7 to 16 the proportions of the ingredients given are by weight.

The compounds set out in Table 1 and numbered 2 to 15 can be similarly formulated as specifically described in Examples 7 to 16.

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

LUBROL L:

AROMASOL H:

DISPERSOL T & AC:

LUBROL APN5 a condensate of nonyl phenol 1 mole) with ethylene oxide (13 moles) a solvent mixture of alkylbenzenes a mixture of sodium sulphate and a condensate of formaldehyde with sodium naphthalene sulphonate a condensate of nonyl phenol (lmole) with naphthalene oxide 1 1 (5.5 moles) CELLOFAS B600 LISSAPOL NX AEROSOL OT/B PERMINAL BX:

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 17

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. The test compounds were formulated either by bead milling with aqueous I'Dispersoll' T or as a solution in acetone or acetone/ethanol which was diluted to the required concentration immediately before use. For the foliage diseases, the formulations (100 ppm active ingredient) were sprayed on to the foliage and applied to the roots of the plants in the soil. The sprays were applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a.i./dry soil. 11Tweenll 20, to give a final concentration of 0.05%, was added when the sprays were applied to cereals.

58 - 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 disease. An exception was the test on Erysiphe graminis in which the plants were inoculated 24 hours before treatment. Foliar pathogens were applied by spray as spore suspensions onto the leaves of test plants. After inoculation, the plants were put into an appropriate environment to allow infection to proceed 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 The results are shown in Table II.

EXAMPLE 18

Some compounds from Table 1 were tested for plant growth regulator activity against four species for various growth effects relevant to plant growth 25 regulation.

Methodoloqy The plant species used in this screen are presented 1 59 - in Table III with the leaf stage at which they were sprayed. Each chemical was applied at 4000 ppm (4 kg/ha in a 1000 1/ha field volume) using a tracksprayer. After spray the plants were grown in a glasshouse 5 with 250C day/220C night temperatures and supplementary lighting was supplied when necessary (from mercury vapour lamps), to provide a 16 hour photoperiod. The exception to this were the temperature cereals, wheat and barley which were grown in 161C day/130C night temperatures.

After 2-6 weeks in the glasshouse, depending on the time of Year, the plants were visually assessed for morphological characteristics. Formulation blanks were used as controls to assess the plants. The results are 15 presented in Table IV.

1 TABLE II

COMPOUND PUCCINIA ERYSIPHE VENTURIA CERCOSPORA NUMBER RECONDITA GRAMINIS INAEQUALIS ARACHIDICOLA (WHEAT) (BARLEY) (APPLES) (PEANUTS) 1 4 4 4 4 2 4 4 4 4 3 4 4 4 4 4 4 4 4 4 4 4 4 4 6 4 4 4 7 4 4 4 4 8 4 4 4 4 9 4 4 4 4 4 4 4 - 11 3 4 4 4 12 4 2 4 4 13 4 1 4 4 14 4 4 4 4 3 1 4 4 - No result P34982 MAIN FiT/maa AA025 11 AugUSt 1989 TABLE III

PLANT MATERIAL USED FOR WHOLE PLANT SCREEN SPECIES CODE VARIETY GROWTH STAGE NO PLANTS at TREATMENT per 7.5cm pot Barley BR Atem 1-1.5 leaves 3 Wheat WW Rapier 1-1.5 leaves 3 Maize MZ Earliking 241 leaves I Tomato TO Alisa Craig 21 leaves 1 For compound 1 there were 4 plants per pot For compound 1 the variety used was Timmo 9 m b1 TABLE IV

SPECIES BR ww mz TO COMPOUND EFFECT 1 y 1 2 3 3 L 1 2 3 3 D 1 2 3 3 G 1 1 2 R 1 E 1 3 Q 3 2 y 2 1 D 1 1 B 2 G 2 E 1 Q 1 3 y 1 D 2 E 2 G 1 2 L 1 1 1 TABLE IV CONTINUED SPECIES BR ww mz 1 TO COMPOUND EFFECT 4 y 1 2 D 1 2 L 2 E 3 G 3 B 2 Q 3 R 1 y 1 1 L 2 1 E 1 R 2 G 1 S 1 1 6 R 1 y 2 3 L 3 3 D 3 B 3 E 3 Q 3 S 2 G 1 1 TABLE IV CONTINUED 1 SPECIES BR WW M TO COMPOUND EFFECT 9 Y L D E R Y L E R 2 Key Y = Whole plant retardation L = Shorter internodes D = Smaller leaf area 9 = Darker green R = Increased number of side shoots E = Morphogenic effects (on leaves) Q = Apical effects B = Less leaves S = Decreased number of side shoots All effects are scored visually on a 1-3 basis wher 1 = 10-30% 2 = 31-60% 3 = 61-100% Blank means less than 10% effect or not tested.

f r - 6.5 -

Claims (10)

1. Triazole d (I):

erivatives having the general formula R5 R' R2 3 N----N -C H - -R 14 1 R (I) and stereoisomers thereof, wherein R is phenyl optionally substituted with halogen, alkyl, alkoxy, haloalkyl, haloalkoxy, nitro, halomethylenedioxy, amino, mono- or dialkylamino, hydroxyr morpholino or alkoxycarbonyl, or phenyl, phenoxy, benzyl or benzyloxy all optionally substituted with halogen; R', R2 and R3 are independently hydrogen, halogen, alkyl or trialkylsilyl; R4 is hydrogen or alkyl; R5 is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, optionally substituted benzyl or alkylcarbonyl (providing the carbon atom adjacent to the oxygen atom is not involved in any unsaturation); and acid addition salts and metal complexes thereof; provided that R'p R2, R3 and R4 are not all hydrogen, and that when R1 and R2 are both hydrogen then R3 is not alkyl.

- 6C

2. Triazole derivatives having the general -formula (I):

OR5 R' R2 1 i l-N-CH-C.-. 3 C C-R 14 R (I) is and stereoisomers thereof, wherein R is phenyl, or phenyl substituted with halogen, Cl_5 alkyl, Cl-4 alkoxy, halo(C1-4)alkyl, halo(C1-4)alkoxy, nitro, halomethylenedioxy, amino, mono- or diCl-4 alkylamino, hydroxy, morpholino or Cl-4 alkoxycarbonyl, or R is phenyl substituted by phenyl, phenoxy, benzyl or benzyloxy all of which may be substituted by halogen; R', R2, R3 are hydrogen, halogent Cl-6 alkyl, trialkylsilyl (where the alkyl chains may be straight or branched having 1 to 6 carbon atoms) or a straight or branched chain alkyl group having 1 to 6 carbon atoms; R4 is hydrogen or Cl-6 alkyl, provided that R', R2, R3 and R4 are not all hydrogen and that when R1 and R2 are both hydrogen then R3 is not a straight or branched chain alkyl group having 1 to 6 carbon atoms; RS is hydrogen or Cl-6 alkyl, C3-6 alkenyl, C3-6 alkynyl, optionally substituted benzyl or Cl-4 alkylcarbonyl (provided that the carbon atom adjacent to the oxygen atom is not involved in any unsaturation); and acid addition salts and metal complexes thereof.

3. Triazole derivatives as claimed in any of the preceeding claims wherein, when R is phenyl or a substituted phenyl which is 2-, 3- or

4 chlorophenyl, 2,4- or 2,5-dichlorophenyl, 2-, 3- or 4-fluorophenyl 2,4- or 2,6 difluorophenyl, 2-, 3- or 4-bromophenyl, 2 chloro-4-fluorophenyl, 2-fluoro-4 chlorophenyl, 2-chloro-6-fluorophenyl, 2-, 3- or 4-methoxyphenyl, 2,3 dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-nitrophenyl, 2 chloro-4-nitrophenyl, 2-chloro-5-nitrophenyl, 2-, 3- or 4-trifluoromethoxyphenyl, 2-, 3- or 4 (1,2,2,2-tetrafluoroethoxy)phenyl, 2-, 3- or 4 methylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4 butylphenyl, 2,3-(difluoromethylenedioxy)phenyl, 2-fluoro-4-methoxyphenyl, 2-methoxy-4 fluorophenylf 2-methoxy-4-chlorophenyl, 2 chloro-4-methoxyphenyl, 2-, 3or 4-phenoxy phenyl, 2-, 3- or 4-phenyl-phenyl (2-, 3- or 4 biphenylyl), 2-, 3- or 4-benzylphenyl, 2-, 3 or 4-benzyloxyphenyl, 2-, 3- or 4-(4-chloro- or 4-fluorobenzyloxy)phenyl, 2-, 3- or 4 aminophenyl, 2-, 3or 4-(N,N-dimethylamino) phenyl, 2-, 3- or 4-hydroxyphenyli 2-, 3- or 4 (methoxycarbonyl)phenyl or 2-, 3- or 4 morpholinophenyl.

Triazole derivatives as claimed in any of the preceeding claims and having the general formula (I):

N-N- CH 14 k,N,") R OR5 R' R2 r 1 1 3 C - C C R i R (I) f r and stereoisomers thereof, wherein R is phenyl optionally substituted with fluorine, chlorine, Cl-4 alkyl or Cl-4 alkoxy; R', R2 and R3 are independently chlorine, bromine, hydrogen, Cl-4 alkyl or

5 trimethylsilyl; R4 is hydrogen or Cl-4 alkyl; R is hydrogen, Cl-4 alkyl, Cl-4 alkylcarbonyl, allyl, propargyl or benzyl optionally substituted with chlorine; and acid addition salts and metal complexes thereof; provided that R', R2, R3 and R4 are not all hydrogen and that when R1 and R2 are both hydrogen then R3 is not Cl-4 alkyl.

Triazole derivatives as claimed in any of the preceeding claims and having the general formula (I):

OR5 R' R2 1 1 -R 3 NL-N - C tl ---C- C I-NA A4 A and stereoisomers thereof, wherein R is phenyl, 4-chlorophenyl or 2,4- dichlorophenyl; R', R2 and R3 are independently hydrogen, chlorine, bromine, methyl or trimethylsilyl; R4 is hydrogen; R5 is hydrogen, methyl or acetyl; and acid addition salts and metal complexes thereof; provided that when R1 and R2 are hydrogen R3 is not hydrogen or methyl.

f 1

6 9 - 6. The compounds:

OH CH3 N-N-CH 11 --N:O%w) 2 2 cl cl (Compound 6 of Table I) OH CH 3 N-N-CH2- 11 1"12 N (Compound 5 of Table I) and their stereoisomers; and acid addition salts and metal complexes thereof.

7. A process for preparing the triazole derivatives claimed in any of claims 1 to 6 which comprises reacting a compound having the general formula (II) or (III):

-7o - 0 R' 1 R4 X (II) R2 J I_ 3 cR OH R' R2 1 1 1 - 3 X-CH2-k' C ===C R 1 (III) wherein R, R', R2, R3 and R4 are as defined in claim 1 and X is halogen (preferably a chlorine or bromine atom), with 1,2,4-triazole either in the presence of a acid binding agent or in the form of one of its alkali metal salts in a convenient solvent.

8. A process for preparing triazole derivatives having the general formula (VIII):

OH R' R2 1 jj N-N-CH-C-C- H it ' R R 14 1 (VIII) wherein R, and R4 are as defined in claim 1, and R1 and R2 are the same halogen atom, which comprises reacting a compound having the general formula (VII):

4 - 71 OH N-N-CH-J-CCH 11 " 1 1 4 1 N R R (VII) with a halogen (preferably chlorine or bromine) in the presence of light in a suitable solvent.

A process for preparing triazole derivatives of general formula:

OH 1 1 t 3 N-N -Ch -C-C ----L-R 14 1. N-,'-3 R A H H (M) wherein R and R4 are defined in claim 1 and R3 is tri(C1-6)alkylsilyl, which comprises reacting a compound of general formula (IX):

OH 1 N- N-CH-C --- -C-H A4 j R (IX) wherein R4 and R are as defined in claim 1, with an alkyllithium (preferably methyllithium or nbutyllithium) in a suitable dry ethereal solvent followed by treatment with trialkylsilyl halide to afford a compound having the general formula (X):

OH 1 3 N-N-k-ii-L-CC 4 i R (X) wherein R and R4 are as defined in claim 1 and R3 is tri(C1-6)alkylsilyl, which is then reduced with an aluminium hydride reducing agent (preferably sodium bis(2-methoxyethoxy)aluminium hydride) in a suitable solvent.

10. A fungicidal or plant growth regulating composition comprising as an active ingredient a compound as in claim 1 or a stereoisomer, acid addition salt or metal complex thereof, and, optionally, a carrier or diluent therefor.

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, as claimed in claim 1 or a stereoisomer, acid addition salt, or metal complex thereof, or a composition as claimed in claim 10.

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 compound, as claimed in claim 1 or a stereoisomeri acid addition salt. or metal complex thereof or a composition as claimed in claim 10.

Pubhshed 1990atThe Patent Office, State House, 86f71 High Ho1borajondonWCIR4TP. Further copies maybe obtainea fromIne FaTlenLviuaeSales Branch. St Mary Cray, Orpington, Kent BR5 3RD. Printed by Multiplex techniques ltd, St Mary Cray, Kent. Con. 1187