IE43937B1 - 1,2,4-triazole compounds and their use as pesticides - Google Patents

Abstract

Compounds of the formula: wherein Y is = N- or =C(R)-, each of R, R1, and R2 is hydrogen, halogen nitro or alkyl; R3 and R4 is hydrogen or hydrocarbyl; R5 is hydroxy hydrocarbyl, hydrocarbyloxy, or amino optionally substituted with amino or hydrocarbyl, and X is O or S or a ketal, hydrazone, semicarbazone, imine or oxime derivative. They are useful as plant furgicides.

Description

pCJENCE REFERENCE LIBRARY j PATENT APPLICATION BY (71) IMPERIAL CHEMICAL INDUSTRIES LIMITED, A BRITISH COMPANY OF IMPERIAL CHEMICAL HOUSE, MILLBANK, LONDON SWlP 3JF, ENGLAND.

Prttt 12{p 43S37 This invention relates to heterocyclic compounds which are I,2,4-triazole compounds, to a process for preparing them, to compositions containing them and to methods of combating pests (particularly fungal pests) using them.

The compounds of the invention have the general formula (I): wherein each of R, R^ and Rg, which may IQ be the same or different, is hydrogen, halogen, nitro or alkyl (e.g. methyl, ethyl, propyl or butyl); each of Rg and R4, which may be the same or different, is hydrogen or substituted or unsubstituted hydrocarbyl, provided that when R^ is phenyl then Rg is hydrogen; Rg is hydroxy, substituted or unsubstituted hydrocarbyloxy or amino or substituted or unsubstituted hydrocarbyl other than substituted or unsubstituted phenyl; and Z is C = 0 or C = S or a functional derivative of said C = 0; or a salt of such a compound.

The compounds can contain chiral centres(s). Normally the compounds are prepared in the form of racemic mixtures. However these and other mixtures can be separated into the individual isomers by methods known in the art. <38 37 The halogen can be fluorine, chlorine, bromine or iodine.

The amino group can be substituted with amino (i.e. it is hydrazino) or with one or two substituted or unsubstituted hydrocarbyl groups.

The hydrocarbyl and hydrocarbyloxy groups may be saturated or unsaturated, straight or branched chain or cyclic or acyclic. Examples are alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, aralkenyl or alkaryl, and their θ hydrocarbyloxy equivalents.

When a hydrocarbyl or hydrocarbyloxy group is, or contains, a phenyl group, the latter can be substituted by halogen, alkyl, nitro, trifluoromethyl, cyano, alkoxy or alkylenedioxy (e.g. methylenedioxy).

’ Suitable C = 0 functional derivatives are ketals, hydrazones, semicarbazones, imines and oximes.

Rj and R^ are preferably cj__gz e.g. ci-7' hydrocarbyl; examples are methyl, ethyl, propyl (n or i-propyl), butyl (η-, i- or t-butyl), amyl (e.g. isopentyl), hexyl (e.g. 3,35 dimethylbutyl), heptyl, allyl, propynyl (e.g. propargyl), phenyl, tolyl (e.g. m-tolyl), 3-phenylallyl, benzyl, 2-, 3or 4-fluorobenzyl, 4-chlorobenzyl, 2-bromobenzyl-, 3,4-, 2,6- or 2,4-dichlorobenzyl, ci-methylbenzyl, 4-cyanobenzyl, 2-, 3- or 4-nitrobenzyl, 3-methylbenzyl, a-methyl-4-chlorobenzyl, 3-trifluoromethylbenzyl, 3-nitro-4-chlorobenzyl, 2methoxy-5-nitrobenzyl, 2-ohloro-4,5-methylenedioxybenzyl, or n-dodecyl. 43S37 Rg can be one of,the hydrocarbyl groups listed above for R4 (with the exception of substituted or unsubstituted phenyl). Thus Rg can be substituted or unsubstituted aralkyl, cycloalkyl or branched chain alkyl. Suitable aralkyl groups are benzyl optionally substituted with halogen (e.g. fluorine, chlorine, bromine or iodine) or alkyl (e.g. methyl or ethyl). Examples of suitable cycloalkyl groups are cyclohexyl and cyclopentyl which can, if desired, be alkyl-substituted. Rg can also be C-L_? hydrocarbyloxy for example methoxy, ethoxy, propoxy (e.g. i-propoxy), butoxy (e.g. n- or t-butoxy), allyloxy, -OC(CH3)2C2Hg, -OCH2C(CH3)g, 0 (CHg) 2C (CH3) g, benzyloxy, p-chlorobenzyloxy, cyclopentyloxy, phenoxy or p-chlorophenoxy. Other examples of suitable Rg groups are phenylamino, n- or t-butylamino, 1,1- or 2,2-dimethylpropy1-5 lamino, amino, hydrazino, benzylamino, o- or p-chlorophenylamino, p-tolylamino, m-chloro-p-tolylamino, p-nitrophenylamino, -NHCH2C(CHg)3,m-chloro-p-nitrophenylamino, or m-trifluoromethy Iphenylamino .

A preferred class of triazole compounds are those wherein R , R? and Rg are hydrogen, R4 is hydrogen, C-j^g alkyl, alkenyl or alkynyl having up to 4 carbon atoms, phenylallyl, phenyl, benzyl optionally ring-substituted with halogen, 0χ_4 alkyl or alkoxy, nitro, trifluoromethyl, cyano or methylene dioxy, or a-(C1_4 alkyl) benzyl optionally !5 ring-substituted with halogen, and Rg is hydroxy, alkyl or alkoxy, amino, hydrazino, phenylamino optionally ring4 43837 substituted with alkyl, halogen, nitro or trifluoromethyl, (C^_g alkyl) amino, phenyloxy optionally substituted with halogen, benzylamino, benzyloxy, cycloalkoxy or cycloalkyl, and Z is C ? 0 or C = NH, or a salt of such a compound.

The salts of the compounds can be salts of organic or inorganic acids e.g. hydrochloric, sulphuric, acetic or oxalic acid, or, when Rg is hydroxy, salts with alkali metals, for example lithium, sodium or potassium, alkaline earth metals, for example calcium and magnesium, ammonia and primary, secondary or tertiary amines, for example mono-, di- or tri-(C1_g aliphatic amines.

Examples of suitable triazole compounds are shown in Table I.

TABLE ο ζ Η Ο U JO Ζ Η HOf< 9 0)0 J Η Η Β Ο a ο cm 0 . in ί <*) VD rH ό \ 0 VD CM *-4 Ο σι 03 I co co rH ο °Ο co I ~ CO g Γ» κ 0 Η r—t c4 1 Ο rH r-l | Thick Oil* r-1 ό °o CM r—1 0 co —CM r4 I H CM «-Ι Ν Ο ii υ te }S II ο ο 1! Ο ο II ο ο II ο o II u o n cj o II o ιη ίϋ 3 η Ρ ο a ο »-Μ Ο +1 W ο a S ζ ri CQ 1 π t te te 3 a 1 +> o w a z νρ Ρί a a 3 m β Μ CM 1 •rl ΰ b 3 a « & £ d CQ 1 q <η Ρί a Β Β a te a K a ' CM Ρί 0 § ρΓ EC a a a a te a a COMPOUND NO «Η CM ΓΠ in VD r- co TABLE I CONTINUED ( if MELTING (OR BOILING) POINT °C * ι—1 •H O 3ί ϋ cn •r-l Ch H 122-123° 0 in CM rd 1 CQ CM rd H ό °O CQ rd Thick Oil* 124-126° 69-70° rd 6 •χ °o M· r-l 0 VO VO 1 «Μ* VO o O o o O O O o o N Ii II II II II II Ii ll il cj u o u CJ CJ Q υ U cQ H £ B ft y »2 a 04 2 CM 2 CM 3 in Di ic 0 M CQ I B CJ Iki! CQ 1 CM m tf) 1 ΊΓ +J § +J sc 35 4J y •2 o a a a o CQ r-l CM u B Π a Jd CJ 3 2 2 l y w P|) CM II n ffl ¢14 tf) Di 1 β 1 •H B CJ 1 β 1 2 CM ffl 1 2 CM « CM O SC o B o υ 1 CQ Pi a B B tf! B B B B as CM Pi a § « B B B B B B K B rd « Q_ o o σ» O rd . CM . CQ *3* . m VO f** a a rd rd t—1 H rd rd rd H O o 43837 TABLE I CONTINUED MELTING (OR BOILING) POINT C 85-87° 140-2° 0 co VO cn 0 o Γ— 1 co vo 0 VO VO r—1 N* VO H a a VO O \ 0 VO O rH *3* O rH Ι- Ο \ 0 VO cn I *3· 0\ VO O \ 0 CN m r-i 1 o cn «Η - j Oil* (not pure) CM O II a o 11 a o II o o II o O il o o II o o II u o II o o II y in ma Cl ΝΒθαι3 V ra l fi cn a u a 2 3 a 4> CN o $ g a ra I ri 1 o CU 1 H I o P o fi ra 5 ri ra ra Oi fi m l a 05 o 13 Q a o M ft 1 •H cn 0° CN ra a ra β ra 1 Λ a ra 1 a fi ra 1 fi a ft m Pi a a a a a a ra a a cn 05 Q Z rH 05 K a a a a a a a a . COMPOUND NO co K σ» rH o CN cH CN CN CN m CM *3* CN m CN VO CN 43837 TABLE I CONTINUED 43837 TABLE I CONTINUED i.

TABLE I CONTINUED MELTING (OR BOILING) POINT °C j 100-102° 49-50° 127-129° 0 CTl co ID CO 0 co ΟΊ 1 ID σι Oil* 104-106° tsi O II u O II o O II O o II o o II o o II Ό O II ϋ in tf fi tf 1 4J fi tf I +1 a fi tf CN O ' 53 .0 u a a£o a a O’ tf CN r-l .fi tf S3 ϋ tl w o CN tf D Cl __ a a 1 co a o a o n-Bu « 1 fi 3 tf fi n tf a a ' a a a a a' CN tf Q £ H tf a a a a H tf a COMPOUND NO in in in VO in in co m cn in o ID 43037 TABLE I CONTINUED MELTING (OR BOILING) POINT °C * H . •r4 o- 121-123° 0 r* 1 H f- 117-119° 0 o CO 1 CO o ba o II o o II o o II o O II CJ o II CJ o II CJ in 33 CM n U m 33 1 33 CJ— O — CJ 33 S3 u P< •Hl ft •Hl H 34 •Hl έ! •Hl 0 tf 3 rt CN o $ CM S3 CJ fw Φ CM 33 p s 9 CM 33 CJ Cl CH2-£&-C1 H O Φ CM 33 □ ‘ m tf w S3 33 33 33 33 CN tf Q § rd tf S3 33 33 l-M K 33 COMPOUND NO <0 m ko M3 in KO KO KO 43837 TABLE Τ CONTINUED MELTING (OR BOILING) POINT °C 143-146° 200-202° O 11 o C=0 oi fi ra I P CN O ra Φ ra ra Pi fH o ra ra u—.Q M ft 1 •H m oi a a Rx AND Rg a a --—,—, COMPOUND ] NO Γ- ΙΟ CO io The indicated structures of these compounds were confirmed by NMR and mass spectrographic analysis.

The compounds may be made by reacting an optionally substituted 1,2,4-triazole or a salt thereof with the appropriate activated halo compound (for example an wherein R^ and R2 are as defined above, or a salt thereof, can be reacted with a compound of general formula (III):*4 ί ς wherein X is halogen, preferably bromine or chlorine, and Rg, R^, Rg and Z are as defined above.

Alternatively, the compounds wherein Rg and/or R^ are hydrocarbyl are made by hydrocarbylating (e.g. with an appro15 priately substituted alkylating· or aralkylating agent) a compound of general formula (IV):15 43337 R -Z-R wherein Z, y^ R^, R2 and Rg are as defined above, or a salt thereof, suitably in the presence of a base in a hydroxylie or non-hydroxylic solvent using methods set out in the literature.

These processes may in some cases be carried out by heating the reactants together in the absence of a solvent or diluent, but preferably a solvent is present. Suitable solvents are non-hydroxylic solvents such as acetonitrile (which is preferred), dimethylformamide, dimethyl sulphoxide, sulpholane and tetrahydrofuran. Hydroxylated solvents, for example methanol and ethanol, may be used in certain circumstances when the presence of the hydroxyl group does not interfere with the progress of the reaction. The processes may also be carried out in the presence of a base, but preferably excess triazole is present to remove liberated HX from the reaction. Other suitable bases are sodium hydride (although not when a hydroxylated solvent or diluent is used), alkali metal carbonates (such as potassium carbonate) and alkali metal hydroxides (such as potassium hydroxide). The reaction temperature depends upon the choice of reactants, solvent and base, but generally the reaction mixture is refluxed.

The processes generally involve dissolving the reactants in a solvent and, after allowing reaction to occur, isolating the product by removal of the reactant solvent in vacuo.

The unreacted triazole is removed by extraction of the product with a suitable solvent and the extract is washed with water. A crystallisation or other f purification procedure may. then be carried out if desired.

The activated halo compounds may be made by any of the methods set out in the literature.

The compounds wherein Z is a derivative of C = 0 may be made from the respective carbonyl compound using any of the . standard techniques set out in the literature.

The compounds are active fungicides, particularly against the following diseases :Piricularia oryzae on rice Puccinia recondita and other rusts on wheat and rusts on I-ζ other hosts Plasmopara viticola on vines Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildews on various hosts such as Sphaarotheca fulginea on cucumbers, Podosphaera leucotricha on apples and Unclnula necator on vines Botrytis cinerea (grey mould) on tomatoes, strawberries, vines and other hosts Gleosporiun musarum on bananas and Penicillium digitatum on oranges (Compounds 8 and 19 show activity against these latter two) Some of the -compounds are active in the form of seed dressings against: Pusarium spp., Septoria spp., Tilletia spp., and Pyrenophora spp. on cereals.

The compounds also have certain anti-bacterial and anti-viral activities.

They may be used as such for anti-fungal purposes but are more conveniently formulated into compositions for such usage.

The invention therefore also provides a fungicidal composition comprising, as an active ingredient, triazole compound or salt thereof, and a carrier for the active ingredient.

The invention also provides a method for combating pests, which are fungi, viruses or bacteria, which method comprises treating plants, seeds or trees with triazole compound or salt thereof as hereinbefore defined The compounds can be used to combat plant pests and treat plants or seeds in a number of ways, for example they can be applied, formulated or unformulated, directly to the foliage of a plant which is infected or likely to become infected, 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.

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.

The term treating as used herein refers to all these 1< modes of application and the term plant includes seedlings, bushes and trees. Furthermore, the method of the invention includes preventative, protectant, prophylactic and eradicant treatment.

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

,,- The compositions may be in the form of dusting powders or granules comprising the active ingredient and a solid diluent or carrier, for example, kaolin, bentonite,' kie'selguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's, earth, gypsum, Hewitt's earth, diatomaceous earth and China clay. Compositions for dressing seed, for example, may comprise an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed. 43037 The compositions may also be in the form of dispersible powders or grains comprising a wetting agent to facilitate the dispersion in liquids of the powder or grains which may contain also fillers and suspending agents.

The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient(s) in an organic solvent optionally containing wetting, dispersing or emulsifying agent(s) and then adding the mixture to water which may also contain wetting, dispersing or emulsifying agent(s).

Suitable solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes and trichloroethylene .

The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane. 3y including suitable additives, for example additives for improving the distribution, adhesive power and resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities.

The compounds can be used as mixtures with fertilisers (e.g. nitrogen - or phosphorus - containing fertilisers). Compositions comprising only granules of fertiliser incorporating, for example coated with, the triazole ft Χ’ compound, are preferred. The invention therefore also provides a fertiliser composition comprising the •triazole compound..

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

Suitable cationic agents are quaternary ammonium compounds for example, cetyltrimethylammonium bromide.

Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropyl-naphthalene sulphonates). Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octylphenol, nonylphenol 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. 439 37 Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose), and the vegetable gums (for example gum acacia and gum tragacanth}.

The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient (s)', the concentrate to be diluted with water before use. These concentrates often should be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain 10-85%, generally 2560%, by weight of the active ingredient(s). When diluted to form aqueous preparations, such preparations may contain varying amounts of the active ingredient(s) depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of active ingredient(s) may be used.

The compositions of this invention can comprise also other compound(s) having biological activity, as well as stabilising agent(s), for example epoxides (e.g. epichlorhydrin).

The following Examples illustrate the invention; the temperatures are given in degrees Centigrade (°C). 22 EXAMPLE 1 ft 1,2,4-Triazole (33.4 g) and sodium ethoxide rom sodium (11.6 g) and ethyl alcohol (250 ml) .7 were refluxed for 1 hour. To this solution at the reflux temperature was added bromopinacolone (87 g), and the mixture was then heated for 2 hours.. It was then cooled to ambient temperature and filtered to remove the precipitated sodium bromide; the solvent was removed in vacuo. The residue was extracted with chloroform (100 ml). The extract was washed with water (4 x 15 ml), dried (sodium sulphate) and filtered. Petroleum ether (50 ml; b.p. 60-80°) was added and the solution concentrated to give oC-l,2,4-'triazol-4-yl-pinacolone, m.p. 176°. Further concentration of the solution gave the title compound, m.p. 63-65°. ; EXAMPLE 2 j l-Imlno-2-(l.,2,4-triagol-,l-yl)ethyl methyl ether (Compound 2) J J 1,2,4-Triazole (3.45 g) was added to a sodium methoxide in methanol /(prepared from sodium (1.15 g) and methanol (40 X· ml}/7, and the mixture was refluxed for 1 hour, and cooled to 25°C; chloroacetonitrile (3.78 g) was then added and the | ! ί i 3937 mixture was refluxed, for a further 6 hours.· The solution was filtered and the solvent removed in vacuo. The resultant mixture was dissolved in petroleum ether (50 ml; b.p. 4060°C) and the solution filtered to remove unreacted 1,2,45 triazole. Removal of the solvent in vacuo gave a residue which on distillation gave the title compound.

EXAMPLE 3 i Ethyl c<-l,2,4-tria2ol-l-yl isovalerate. (Compound 4) Ethyl EXAMPLE 4 ¢1-1,2,4-Triagol-l-yl caproanilide.. (Compound 5) Stage 1 ; Ethyl c(_-brcmocaproate (4.5 g) in dimethylformamide was added to the sodium salt of 1,2,4-triazole 43037 /“prepared by reacting 1,2,4-triazole (3 g) with sodium hydride (1.8 gj 50% dispersion in oil)J7 in dimethylformamide (20 ml). The reaction mixture was maintained at 50°C for 5 hours, the solvent removed in vacuo and the residue extracted - with ether (100 ml). The ethereal phase was washed with water (2 x 50 ml) and dried (sodium sulphate), the solvent removed in vacuo and the residue extracted with ether (100 ml). The ethereal phase was washed with water (2 x 50 ml), and dried (sodium sulphate)? the solvent was removed in . vacuo. Distillation of the residue gave a liquid, b.p. 86.90°/0.2 mm. To this liquid (12 g) was added potassium hydroxide (6.5 g) in water (50 ml) and the mixture stirred for 15 minutes. The mixture was washed with ether (2 x 20 ml) and then acidified to pH 2 (concentrated hydrochloric acid).

The white solid so obtained was washed with cold water (50 mis) and dried. Recrystallisation of this solid gave <<-l,2,4~triazol-l-ylcaproic acid, m.p. 141-143°. < Stage 2 : et-l,2,4-Triazol-l-yloaprOic acid (1.83 g) and thionyl chloride (1.5 ml) were refluxed for 30 minutes.

Excess thionyl chloride was removed in vacuo and the resultant gum extracted with methylene chloride (10 ml); the extract was added to aniline (2.83 g) in methylene chloride (10 ml) at 10-15°. The mixture was stirred for 30 minutes, washed with water (50 ml) and then dried (magnesium sulphate) Removal of the solvent in vacuo gave a solid which on recrystallisation from toluene gave the title compound.

Alternatively this compound can be made starting from oL-bromocapranilide as described in Example 1 using the sodium salt of the triazole.

EXAMPLE 5 et·-1,2,4-Triazol-1-y1-isovaleroylhydrazine.

(Compound 11) .0 Stage 1 : To a solution of the sodium salt of 1,2,4triazole (1.81 g) (prepared as described in Example 4) in dimethylformamide (30 ml) was added ethyl cL-bromoisovalerate (5.0 g) dropwise with stirring and the mixture kept at 5560° for five hours. The bulk of the solvent was removed in vacuo, and the residue was diluted with water and extracted with ether. The ethereal layer was Washed with water and dried (magnesium sulphate), and the solvent was distilled off to give ot-1,2,4-triazol-l-yl iso-valerate as a clear liquid.

D Stage 2 : A solution of the above compound and hydrazine hydrate (3 ml) in ethanol (15 ml) was refluxed for two hours. Removal of solvent gave a white solid which was recrystallised from ethyl acetate to give the title compound. 43837 EXAMPLE 6 cZ. -p-Chlorobenzyl- 01-1,2,4-triazol-l-yl-pinacolone (Compound 10) ©t-l,2,4-Triazol-l-yl-pinacolone (3.3 g) in dimethy15 formamide (20 ml) was .added dropwise to a suspension of sodium hydride (0.48 g;. 100%) in dimethylformamide (10 ml) at room temperature with stirring. After stirring for two hours, p-chlorobenzyl chloride (3.2 g) in dimethylformamide (2-3 ml) was added dropwise and the reaction mixture was kept at 5-10° for two hours. The solvent was removed in vacuo and water was added to the residue. The aqueous solution was extracted with methylene chloride, the organic layer was washed with water and dried (magnesium sulphate). The solvent was removed to give a yellow solid which was crystallised to give the title compound.

EXAMPLE 7 —1,2,4-Triazol-l-yIcaproamide. (Compound 8) Ethyl 0C-l,2,4-triazol-l-ylcaproate (3. 0 g) was added to liquid ammonia (0.880, 15 ml) and the mixture was shaken well for a few minutes and then left overnight at room • temperature. The white solid was filtered and washed with water to give, after recrystallisation from water, the title compound.

EXAMPLE 9 The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No. 1, or Seed, as appropriate) in 4 cm diameter mini-pots.

A layer of fine sand was placed at the bottom of the pot to facilitate uptake of test compound by the roots. Vermiculite was used to cover the seed in the soil tests.

The test compounds were formulated either by beadmilling with aqueous Dispersol T (Dispersol11 is a Trade Mark) or as a solution in acetone/ethanol which was diluted to the required concentration immediately before use. For the foliage diseases, 100 ppm a.i. suspensions were sprayed on to the foliage and applied to the roots of the same plant via the soil. (Sprays were applied to maximum retention, and root drenches to a final concentration 43837 equivalent to approximately 40 ppm a.i./dry soil). Tween 20 (Tween is a Trade Mark), to give a final concentration of 0.1%, was added when the sprays were applied to the cereals.

For most of the tests, the test compound was applied to the soil and foliage 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 3 to 10 days according to the disease and environment.

The disease control was recorded by the following grading: = No disease = 0-5% = 6-25% 1 = 26-60% = > 60% The results are shown in Table II.

Claims (14)

1. A compound of general formula (I): wherein each of R^ and Rg, which may be the same or different, is hydrogen, halogen, nitro or alkyl, each of Rg and R^, which may be the same or different, is hydrogen or substituted or unsubstituted hydrocarbyl, provided that when R^ is phenyl then Rg is hydrogen? R^ is hydroxy, substituted or unsubstituted hydrocarbyloxy or amino, or substituted or unsubstituted hydrocarbyl other than substituted or unsubstituted phenyl, and Z is C=OorC=Sora functional derivative of said C = 0, or a salt of such a compound.

2. A compound according to claim 1 wherein each of Rg and R^, which may be the same or different, is hydrogen or halo-substituted or unsubstituted hydrocarbyl, provided that when R^ is phenyl then Rg is hydrogen; Rg is hydroxy, halo-substituted or unsubstituted hydrocarbyloxy mono- or di- alkyl or aryl-substituted or unsubstituted amino or halo-substituted or unsubstituted hydrocarbyl other than halo-substituted or unsubstituted phenyl, and Z is C = 0 or C = S or a functional derivative of said 5 C = 0, or a salt of such a compound.

3. A compound according to claim 1 wherein Rg, Rg and Rg are hydrogen, R 4 is hydrogen; Cg_g alkyl,* alkenyl or alkynyl having up to 4 carbon atoms; phenyl-allyl; phenyl; benzyl optionally ring-substituted with halogen, 10 c i-4 alkyl or alkoxy, nitro, trifluoromethyl, cyano or methylenedioxy; or ec-(Cg_ 4 alkyl)benzyl optionally rihgsubstituted with halogen; and Rg is hydroxy; Cg_g alkyl or alkoxy; amino; hydrazino; phenylamino optionally ring-substituted with Cg_ 4 alkyl, halogen, nitro or tri15 fluoromethyl; (Cg_g alkyl)amino; phenyloxy optionally substituted with halogen; benzylamino; benzyloxy; cycloalkyloxy or cycloalkyl; and Z is C = 0 or C = NH; R^ being other than hydrogen, phenyl or Cg_ 6 alkyl when Rg is cycloalkyl or Cg_g alkyl and Z is C = 0, and 20 Rg being other than cycloalkyl or Cg_g alkyl when R^ is hydrogen, phenyl or Cg_g alkyl and Z is C = 0; or a salt of such a compound.

4. A compound according to claim 1 which is any one of compounds 1, 2 and 4 to 18 of Table I hereinbefore. 4 3 9 3 7

5. A compound according to claim 1 which is any one of compounds 3 or 19 to 60 of Table I hereinbefore.

6. A compound according to claim 1 which is any one of compounds 61 to 68 of Table I hereinbefore. 5

7. A process for preparing a compound or a salt thereof according to any one of the preceding claims, the process comprising reacting a compound of general formula (II): wherein Rg and Rg are as defined in claim 1,. 3 or a salt thereof, with a compound, of general formula (III): wherein Rg, R^, Rg and Z are as defined in claim 1, and X is halogen. - 38 4 39 3 7

8. A process for preparing a compound or a salt thereof according to any one of claims 1 to 6 wherein Rg and/or R 4 is substituted or unsubstituted hydrocarbyl, the process comprising hydrocarbylating a compound or a salt 5 thereof according to any one of claims 1 to 6 wherein Rg and/or R^ is hydrogen.

9. A process according to claim 7 and 8 substantially as described in any one of Examples 1 to 7.

10. A compound of general formula (I) according to claim 1 or 10 2 or a salt thereof prepared by a process according to any one of claims 7 to 9.

11. A fungicidal composition comprising, as active ingredient, a compound or salt according to any one of claims 1, 3, 6 and 10 and a carrier for the active ingredient. 15

12. A fungicidal composition comprising, as active ingredient, a compound or salt according to claim 2 or 4, and a carrier for the active ingredient.

13. A method of combating fungal diseases in a plant, which method comprises applying to theplant, or to the locus of 20 the plant, a compound or salt according to any one of claims 1, 3, 6 and 10.

14. A method'of combating fungal diseases in a plant, which method comprises applying to the plant, or to the locus of the plant, a compound or salt according to claim 2 or 4. 439 37