AZOLE DERIVATIVE HERBICIDES AND FUNGICIDES

Abstract: Herbicidal compounds of formula (I) where: Az is imidazol-1-yl or 1,2,4-triazol-1-yl; each X represents halogen, carboxy, nitro, cyano, a group COR<5>, COOR<5> or S(O)pR<5>, or an optionally substituted alkyl, alkoxy, aryl or heteroaryl group; or two adjacent groups X together form a fused benzo group; R<1> represents a group CN, COR<5>, COOR<5>, or S(O)pR<5>; R<2> represents a group CN, COR<5>, COOR<5>, S(O)pR<5>, SO2N(R<5>)2, P(O)(OR<5>)2, nitro, aryl, heteroaryl or aralkyl; R<3> and R<4>, which may be the same or different, each represent hydrogen, or an optionally substituted alkyl, aryl or heteroaryl group; R<5> represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group; or hydrogen (but only when p=0); n is 0 to 4; and p is 0 to 2.

Description: Title; Azole Derivative Herbicides and Fungicides Field of the invention This invention concerns new azole derivatives having herbicidal/fungicidal activity, processes for their preparation, and compositions containing them. Description Ir. one aspect, the invention provides the compounds of the formula: where: Az is imidazol-1-yl or 1,2,4-triazol-l-yl; each X represents halogen, carboxy, nitro, cyano, a group COR 5 , COOR 5 or S(0) p R 5 , or an optionally substituted alkyl, alkoxy, aryl or heteroaryl group; or two adjacent groups X- together form a fused benzo group; R 1 represents a group CN, COR 5 , COOR 5 or S(0) p R 5 ; R 2 represents a group CN, COR 5 , COOR 5 , S(0) p R 5 , S0 2 N(R 5 ) 2 , P(O) (OR 5 ) 2 , nitro, aryl, heteroaryl or aralkyl; R 3 and R 4 , which may be the same or different, each represent hydrogen, or an optionally substituted alkyl, aryl or heteroaryl group; R 5 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group; or hydrogen (but only when p is 0) ; n is 0 to 4; and p is 0 to 2. Any alkyl group present in the molecule is preferably of 1 to 8, especially of 1 to 4, carbon atoms, eg methyl, ethyl, n-propyl, isopropyl or t-butyl. Where such a group is substituted, the substituent groups may, for example, include halogen, alkoxy of 1 to 4 carbon atoms (eg methoxy or ethoxy) , or aryl (eg phenyl) . Any alkenyl or alkynyl group present in the molecule is preferably of 2 to 6 carbon atoms, eg vinyl, allyl or propargy1. Any cycloalkyl group present in the molecule is preferably of 3 to 7 carbon atoms, eg cyclopentyl or cyclohexyl. ' Any aryl moiety present in the molecule is preferably a phenyl moiety. Where such a group is substituted, the substituent groups may, for example, include halogen, alkyl of 1 to 4 carbon atoms (eg methyl) , alkoxy of 1 to 4 carbon atoms (eg methoxy or ethoxy) , nitro, or a further phenyl group. Any heteroaryl group present in the molecule is preferably thienyl, furyl or pyridyl. R 1 is preferably a group -COOR 5*1 (particularly where R 5*1 is alkyl of 1 to 8 carbon atoms, allyl, phenyl or benzyl) , and especially such a group where R-" is methyl, ethyl, n-propyl, iso-propyl or n-butyl. R 2 is preferably cyano, optionally substituted phenyl, benzoyl, optionally substituted phenylthio, -COOR 5*1 (particularly where R 51 is alkyl of 1 to 8 carbon atoms, methoxyethyl, cyclopentyl, allyl or benzyl, and especially methyl, ethyl, n-propyl, iso-propyl or n-butyl) , or -S0 2 R 5b (where R 5b is-alkyl of 1 to 4 carbon atoms, phenyl, pyridyl or benzyl, especially phenyl) . In a particularly preferred group of compounds of formula I, R 1 and R 2 are identical and each represents -COOR 5 or phenylthio, or one represents -COOR * ' and the other represents phenylsulphonyl. R 3 and R 4 are each preferably hydrogen. Az is preferably 1,2,4-triazol-l-yl. n is preferably 1 or 2. X n preferably represents substitution in the 2- position, or disubstitution in the 2,4- or 2 ,5-positions on the phenyl ring. Preferred substituent groups which X may represent include chloro, bromo, methoxy, methoxycarbonyl and nitro. Specific preferred substitution patterns are 2-methoxy, 2-carboxymethyl, 2- chloro, 2,4-dichloro, 2,4-dimethoxy, 2-nitro-4-chloro, 2- methoxy-5-chloro and 2-methoxy-5-bromo. Specific preferred compounds are those of the Examples provided hereinafter. Particular mention may be made, however, of di-n-propyl (2, 4-dichlorophenyl) [ (1H- l,2,4-triazol-l-yl)methyl]malonate, ethyl 2- (2,4- dichlorophenyl) -2-(phenylsulfonyl) -3- (1H-1,2,4-triazol-l- yl)propionate and n-propyl 2-(2 , 4-dichlorophenyl) -2- (phenylsulfonyl) -3- (1H-1,2 ,4-triazol-l-yl)propionate. The compounds of the invention may be prepared by a process in which a compound of the formula: where R 1 , R 2 , X and n are as defined hereinbefore is reacted with a compound of the formula: R 3 I Z - C - Az (III) R 4 where R 3 and R 4 are as defined hereinbefore, and Z represents a leaving group (especially chlorine) , in the presence of a strong base (eg sodium hydride) . The reaction is preferably effected in a suitable inert solvent medium, eg dimeth lformamide. The compounds of formulae II and III are themselves either known compounds or may be made by processes analogous to those used for the preparation of similar known compounds. The compounds of the invention have activity as herbicides where they exhibit activity against a number of weed species when applied both pre- and post- emergence. The compounds are also comparatively safe to certain crop species, and may thus be of use as selective herbicides, particularly in the control of a range of weeds in cereals or other crops, eg wheat, barley, maize, soya beans, oilseed rape, cotton, sugar beet or, especially, rice, where their control of barnyardgrass is particularly useful. The compounds of the invention also have activity as fungicides, where their activity is manifested particularly against fungal diseases of plants, eg barley powdery mildew (Ervsiphe graminis) . They are also active against vine downy mildew (Plasmopara viticola) as well as being active against diseases such as rice blast fPyricularia oryzae) , wheat brown rust (Puccinia recondita) and potato blight (Phytophthora infestans) . Accordingly, the invention also provides a method of combating weeds and/or fungi at a locus infested or liable to be infested therewith, which comprises applying thereto an effective amount of one or more compounds of formula I. In addition, the invention provides a herbicidal and/or fungicidal composition which comprises one or more compounds of formula I in association with a suitable carrier and/or surface active agent. The compositions of the invention usually contain from 0.01 to 99% by weight of the present compounds, and are normally produced initially as concentrates containing from 0.5 to 99%, preferably from 0.5 to 85%, and especially from 10 to 50% by weight thereof. Such concentrates are diluted if necessary before application - to the locus to be treated such that the active ingredient comprises from 0.01 to 5% by weight of the formulation applied. The carrier may be water, in which case an organic solvent may also be present, though this is not usually employed. A flowable suspension concentrate may be formed by grinding the compound with water, a wetting agent and a suspending agent, eg xanthan gum. The carrier may alternatively be a water immiscible organic solvent, eg a hydrocarbon which boils within the range 130-270C, eg xylene, in which the compound is dissolved or suspended. An e ulsifiable concentrate containing a water immiscible solvent may be formed with a surface active agent so that the concentrate acts as a self-emulsifiable oil on admixture with water. The carrier may alternatively be a water-miscible organic solvent eg 2-methoxy ethanol, methanol, propylene glycol, diethylene glycol, diethylene glycol monoethyl ether, methylformamide or di ethylformamide. The carrier may alternatively be a solid, which may be finely divided or granular. Examples of suitable solids are limestone, clays, sand, mica, chalk, attapulgite, diatomite, perlite, sepiolite, silicas, silicates, lignosulfonates and solid fertilizers. The carrier can be of natural or synthetic origin or can be modified natural material. Wettable powders soluble or dispersible in water may be formed by admixing the compound in particulate form with a particulate carrier or spraying molten compound on to the carrier, admixing a wetting agent and a dispersing agent and finely grinding the whole powder mixture. An aerosol composition may be formed by admixing the compound with a propellant, eg a polyhalogenated alkane such as dichlorofluoromethane, and suitably also with a solvent. The term --surface active agent' is used in the broad sense to include materials variously called emulsifying agents, dispersing agents and wetting agents. Such agents are well known in the art. The surface active agents used may comprise anionic surface active agents, for example mono- or di-esters of phosphoric acid with a fatty alcohol ethoxylate, or salts of such esters, fatty alcohol sul ates such as sodium dodecyl sulfate, ethoxylated fatty alcohol sulfates, ethoxylated alkylphenol sulfates, lignin sulfates, petroleum sulfonates, alkylaryl sulfonates such as -alkyl-benzene sulfonates or lower alkylnaphthalene sulfonates, salts of sulfonated naphthaleneformaldehyde condensates, salts of sulfonated phenolformaldehyde condensates, or more complex sulfonates such as the amide sulfonates, eg the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulfosuccinates eg the sodium sulfonate of dioctyl succinate. The surface active agents may also comprise non-ionic agents, for example condensation products or fatty aeid esters, fatty alcohols, fatty acid amides or alkyl-substitutedphenols with ethylene oxide, fatty esters of polyhydric alcohol ethers eg sorbitan fatty acid esters, condensation products of such esters with ethylene oxide eg polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl-5- decyn-4,7-diol, or ethoxylated acetylenic glycols. The surface active agents may also comprise cationic agents, for example alkyl- and/or aryl-substituted quaternary ammonium compounds such as cetyl trimethylammonium bromide, or ethoxylated tertiary fatty amines. Preferred surface active agents include ethoxylated fatty alcohol sulfates, lignin sulfonates, alkyl-aryl sulfonates,salts of sulfonated naphthalenefor aldehyde condensates, salts of sulfonated phenolformaldehyde condensates, sodium oleoyl N-methyltauride, dialkyl sulfosuccinates, alkyl phenol ethoxylates, and fatty alkyl ethoxylates. The present active compounds may be admixed with another pesticide, eg a herbicide, fungicide or insecticide, or a plant growth regulator, particularly another herbicide. Suitable further herbicides include trietazine, linuron, MCPA, dichlorprop, isoxaben, diflufenican, etolachlor, fluometuron, oxyfluorfen, fo esafen, bentazone, prometryne, norflurazon, chlomazone, EPTC, i azaquin, and especially isoproturon, methabenzthiazuron, trifluralin, ioxynil, bro oxynil, benazolin, mecoprop, fluroxypyr, alachlor, acifluorfen, lactofen, metribuzin, pendimethalin, ethofumesate, benfuresate, phenmedipham, benzophenap, butachlor, chlomethoxyfen, dimepiperate, mefenacet, molinate, naproanilide, oxadiazon, piperophos, prometryne, pyrazoxyfen, pyrazosulfuron-ethyl, bensulfuron, si etryne, pyrazolate, pretilachlor, thiobencarb and pyributicarb. Suitable further fungicides include fenpropimorph, propiconazole, triadimefon, triadimenol, diclobutrazol, prochloraz (and metal complexes of this eg the manganese chloride complex) , and guazatine. The present compound may be applied to plants, the soil, land or aquatic areas, and particularly to a locus at which a crop is growing. Examples The invention is illustrated by the following Examples, in which Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Ph = phenyl, Cypent = cyclopentyl, Bz = benzyl, Im = imidazol-1-yl, Py = pyrimidin-2-yl, and Tr = 1,2,4-triazol-l-yl: Example 1 Dipropyl (2 ,4-dichlorophenyl) f(1H-1--2.4-triazol-l- yl)methyl " !malonate (a) Propyl (2 ,4-dichlorophenyl)acetate A solution of (2,4-dichlorophenyl)acetic acid (50g) , propanol (300ml) and concentrated sulfuric acid (20 drops) was heated at reflux for 7 hrs. After cooling, the solution was concentrated in.vacuo and ethyl acetate (500ml) and aqueous sodium bicarbonate (200ml) were added to the residue. The organic layer was separated, dried with magnesium sulfate and evaporated. The resulting liquid was distilled to give 47.7 g of propyl (2,4- dichlorophenyl)acetate, bp 112°C at 0.1 mmHg. (b) Dipropyl (2 .4-dichlorophenyl)malonate Propyl (2,4-dichlorophenyl)acetate (24.7g) was added to a stirred solution of lithium di-iso-propylamide (0.1 M) in dry tetrahydrofuran (250ml) at -78°C. After 90 minutes propyl * chloroformate (12.3g) was added dropwise and the resulting solution was stirred for a further 60 minutes and finally for 16 hours at room temperature. 5% Hydrochloric acid (30ml) was added and the mixture was partially evaporated in vacuo to remove most of the tetrahydrof ran. The residual liquid was extracted with ether (3 x 100ml) , dried with magnesium sulfate and concentrated in vacuo. Fractional distillation of the residual " liquid afforded 10.4 g of dipropyl (2,4- dichlorophenyl) alonate as a colourless liquid, bp 142°C at 0.4 mmHg. (c) Dipropyl (2.4-dichlorophenyl) r flH-l.2 , 4-triazol-l- yD ethyllmalonate Sodium hydride (0.9 g, 80% in mineral oil) was added portionwise and with stirring to a solution of dipropyl (2,4-dichlorophenyl)malonate (9.9g) in 1,2- di ethoxyethane (120ml) . The mixture was stirred for 30 minutes at room temperature and sodium iodide (0.4g) and l-chloromethyl-lH-l,2,4-triazole (3.6g) were added. The mixture was heated at reflux for 30 minutes, cooled with ice, and water (100ml) added. The solvent was removed by concentration in vacuo and dichloromethane (100ml) was added to the residue. The organic. layer was separated and the aqueous layer was further extracted with dichloromethane (2 x 100ml) . The organic extracts were combined, washed with water (50ml) and dried with magnesium sulfate. Concentration of the organic extracts in vacuo gave an oil which solidified on standing. This was recrystallised from a hexane/diisopropyl ether mixture to give 3.7 g of the desired compound as a white solid, mp 62-4°C. Example 2 Ethyl 2-(2 ,4-dichlorophenyl) -2- (phenylsulfonyl) -3- (1H- 1,2 ,4-tr"-εzol-l-yl)propionate (a) Ethyl ( 2 ,4-dichlorophenyl) (phenylthio) acetate Benzenethiol (3.86g) was added to a solution of potassium hydroxide (1.9g) in ethanol (100ml) and the mixture was stirred for 30 minutes. Ethyl bromo(2,4- dichlorophenyl) acetate (9.4g) was added dropwise and the mixture was then heated at reflux for 4 hours. After cooling, the mixture was concentrated in vacuo and the residue partitioned between dichloromethane (100ml) and water (100ml) . The organic layer was separated and the aqueous solution extracted further with dichloromethane (2 x 100ml) . The organic extracts were combined, dried with magnesium sulfate and concentrated in vacuo. The resulting liquid was distilled to give 8.5g of the desired compound, bp 128-45°C at 0.1 mmHg. (b) Ethyl (2,4-dichlorophenyl) (phenylsulfonyl)acetate A mixture of ethyl (2,4-dichlorophenyl)- (phenylthio)acetate (3.4g) and m-chloroperbenzoic acid (4.97 g, 90%) in chloroform (30ml) was heated at reflux for 16 hours. After cooling, dichloromethane (30ml) was added and the mixture was filtered. The filtrate was washed with sodium bicarbonate solution (25ml) , dried with magnesium sulfate and concentrated in vacuo. The resulting solid was recrystallised from diisopropylether to give 1.8 g of the desired compound as a white solid, p 86-8°C. (c) Ethyl 2-f2,4-dichlorophenyl)-2-(phenylsulfonyl)-3- flH-1,2.4-triazol-l-yl)propionate Sodium hydride (0.81 g; 80% in mineral oil) was added portionwise and with stirring to a solution of ethyl (2,4-dichlorophenyl) (phenylsulfonyl)acetate (lOg) in 1,2-dimethoxyethane (80ml) and dimethylformamide (20ml) . The mixture was stirred at room temperature for 30 minutes before adding sodium iodide (O.lg) followed by 1-chloromethyl-lH-l,2,4-triazole (3.15g) . This mixture was heated at reflux for 1 hour, cooled with ice, and water (100ml) was added. The solvent was removed in vacuo, and ethyl acetate (100ml) and water (100ml) were added. The organic layer was separated and the aqueous solution was extracted with ethyl acetate (2 x 100ml) . The combined organic extracts were dried with magnesium sulfate and concentrated in vacuo. The resulting oil was flash chromatographed on silica using 3% methanol in ■dichloromethane at eluent to obtain 2.3 g of the desired compound as a yellow solid, mp 74°C. Examples 3-116 The following compounds of formula I where R 3 and R 4 are both hydrogen, and Az is 1,2,4-triazol-l-yl except Az la Im Im Im 35 2,3-benzo 36 2,4-diCl 37 2,4-diCl 38 4-C1 39 2,4-diCl 40 2,4-diMe 41 4-C1 42 2,4-diCl 43 2,4-diCl 44 2,4-diCl 45 2,4-diCl 46 2,4-diCl 47 2,4-diCl 48 2-OMe 49 2-N0 2 50 2-Me 51 3-C1 52 2-CF 3 53 2-OMe 54 2,4-diCl 55 3-OMe 56 2,4-diCl 57 2-COOMe 58 2,4-diCl 59 2,6-diCl 60 2,4-diCl 61 2,4-diCl 62 2,4-diCl 63 2,4-diF 64 2,4-diOMe 65 2,4-diCl 66 2,4-diCl 67 2-SMe 8 2-OEt 103 2,4-diCl 104 2,6-diF 105 H 106 H 107 4-Cl,2-N0 2 108 2,4-diCl 109 2,4-diCl 110 2,4-diCl 1112,4-diCl 112 2,4-diCl 113 5-Cl,2-OMe 114 2,4-diCl 115 2-OMe The following compound of formula I in which Az is 1,2,4-triazol-l-yl, R 4 is hydrogen, and R 3 is methyl, was prepared by methods analogous to those described in Examples 1 and 2: 116 2,4-diCl COOEt COOEt Oil HERBICIDAL EXAMPLE A (Pre-Emerσence) Seeds of the test species listed below were each sown in 8.5cm square pots filled to within 2cm of the top with sterile loam, and were covered with a 2-5mm layer of loam. The pot ' s were watered, and then treated by application to the soil surface in a spray cabinet with the compounds of the Examples listed below formulated as a solution/suspension in 3:1 by volume of acetone and the wetting agent polyoxyethylene (20 moIs) monolaurate solution (10 g per litre) . The concentration of each test compound and volume of application were calculated to give the desired rate of application of the compound in 200 litres per hectare. After 3 to 4 weeks growth in a glasshouse (minimum temperature 16°C for temperate species, 21°C for non- temperate species, 16 hours per day photoperiod) the plants were visually assessed for any herbicidal response. All differences from an untreated control were scored accordingly to an index where 0 = no effect, 1 = 1-24% effect, 2 = 25-69% effect, 3 = 70-89% effect and 4 = 90-100% effect. In the table below, the following letters are used to denote the plant species: a - Triticum aestivu (wheat) b - Hordeum vulqare (barley) c - Beta vulqaris (sugar beet) d - Brassica napus (rape) e - Alopecurus mvosuroides (blackgrass) f - Avena fatua (wild oat) g - Elymus repens (couch) h - Bro us sterilis (barren brome) i - Viola arvensis (field pansy) j - Stellaria media (chickweed) k - Galium aparine (cleavers) 1 - Matricaria inodora (scentless mayweed) m - Polyαonum lapathifoliu (Pale persicaria) n - Veronica persicae (Buxbaum's speedwell) . The results obtained were as follows: 0 0 1 4 2 1 3 1 4 2 2 1 3 2 2 3 2 4 0 0 0 2 3 0 4 2 4 0 2 0 3 2 0 2 2 4 0 0 1 1 2 0 2 1 3 0 3 2 2 1 0 3 2 3 0 0 0 3 1 0 2 2 3 0 2 1 2 2 0 2 2 2 1 4 3 3 2 0 4 2 4 0 2 2 1 0 1 3 1 3 0 1 2 1 2 0 3 1 3 0 2 2 3 0 2 3 2 4 0 3 0 3 1 0 3 0 1 1 3 3 3 2 2 4 2 4 0 1 1 3 1 2 3 2 4 0 1 2 2 2 0 3 2 4 1 2 1 2 2 1 3 2 4 2 2 2 2 2 2 4 2 4 1 1 1 2 2 1 2 1 4 0 0 2 2 1 1 4 2 4 2 2 3 3 2 2 4 2 4 1 2 2 2 1 2 4 2 4 0 2 0 3 0 0 3 1 4 HERBICIDAL EXAMPLE B fPost-Emercrence) The plant species listed below were grown in 8.5cm square pots containing sterile loam in a glasshouse (minimum temperature 16 °C for temperate species, 21°C for non-temperate species, 16 hours per day photoperiod) , and were treated in a spray cabinet at the 2-3 leaf stage with the compounds of the Examples listed below formulated as a solution/ suspension in 3:1 by volume of acetone and the wetting agent polyoxyethylene (20 mols) monolaurate solution (10 g per litre) . The concentration of each test compound and volume of application were calculated to give the desired rate of application of the compound in 200 litres per hectare. After 3-4 weeks, the plants were visually assessed for any herbicidal response. All differences from an untreated control were scored according to an index where 0 = no effect, 1 = 1-24% effect, 2 = 25-69% effect, 3 = 70-89% effect and 4 = 90-100% effect. In the table below, the letters used denote the same plant species as in Herbicidal Example A: The results obtained were as follows: Ex Kσ/ha a b c d e f. g h _i j k l. m ri 2 0.25 1 0 2 2 1 0 0 0 2 2 2 3 48 2.0 3 2 2 2 3 2 3 2 3 2 3 3 2 4 49 2.0 1 0 2 2 1 0 0 0 2 2 3 2 1 3 50 1.0 2 2 2 2 1 0 1 0 2 0 3 2 1 3 57 2.0 3 3 2 2 3 2 3 4 3 2 3 3 3 4 58 1.0 0 1 2 3 1 1 0 2 3 2 3 2 2 4 60 1.0 1 2 2 2 2 1 2 2 3 2 3 2 2 3 61 2.0 0 1 2 2 0 1 0 0 3 1 3 2 0 4 63 2.0 0 1 2 2 1 1 0 0 2 1 3 0 0 4 64 1.0 1 1 2 2 2 1 2 1 3 1 2 2 2 4 68 1.0 0 1 1 2 0 0 0 2 2 0 2 2 0 4 70 1.0 0 0 2 2 1 0 0 0 3 1 3 3 2 4 72 1.0 2 2 2 2 2 0 1 2 2 0 2 3 0 4 73 2.0 2 2 2 2 2 2 2 2 2 2 3 2 2 4 78 2.0 1 1 2 2 2 1 1 2 3 1 3 2 2 4 88 1.0 1 1 3 2 2 1 2 1 3 2 3 2 4 4 89 1.0 2 2 2 2 2 2 3 2 2 1 3 2 2 4 96 1.0 2 2 2 2 2 1 1 2 3 2 3 2 2 4 100 1.0 3 3 2 2 2 2 2 2 3 2 3 3 2 4 102 1.0 2 2 2 2 2 1 1 2 2 0 3 2 2 4 109 1.0 1 1 2 2 0 0 1 0 3 2 3 3 2 4

Claims: CLAIMS 1. The compounds of the formula: where: Az is imidazol-1-yl or 1,2,4-triazol-l-yl; each X represents halogen, carboxy, nitro, cyano, a group COR 5 , COOR 5 or S(0) p R 5 , or an optionally substituted alkyl, alkoxy, aryl or heteroaryl group; or two adjacent groups X together form a fused benzo group; R 1 represents a group CN, COR 5 , COOR 5 or S(0) p R 5 ; R 2 represents a group CN, COR 5 , COOR 5 , S(0) p R 5 , S0 2 N(R 5 ) 2 , P(O) (OR 5 ) 2 nitro, aryl, heteroaryl or aralkyl; R 3 and R 4 , which may be the same or different, each represent hydrogen, or an optionally substituted alkyl, aryl or heteroaryl group; R 5 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group; or hydrogen (but only when p=0) ; n is 0 to 4; and p is 0 to 2. 2. The compounds according to claim 1 where R 1 is COOR 5*1 (where R 51 is alkyl of 1 to 8 carbon atoms, allyl, phenyl, phenylthio, benzyl or cyano) . 3. The compounds according to claim 2 where .R 5a is methyl, ethyl, n-propyl, iso-propyl or n-butyl. 4. The compounds according to any of claims 1 to 3 where R 2 is cyano, optionally substituted phenyl, benzoyl, optionally substituted phenylthio, COOR 5 " (where R 5ϊ is alkyl of 1 to 8 carbon atoms, methoxyeth 1, cyclopentyl, allyl or benzyl) , or S0 2 R 5b (where R 5b is alkyl of 1 to 4 carbon atoms, phenyl, pyridyl or benzyl) . 5. The compounds according to claim 4 where R 2 is COOR 5 " (where R 5s is methyl, ethyl, n-propyl, iso-propyl or n-butyl) or S0 2 R 5b (where R 5b is phenyl) . 6. The compounds according to any of claims 1 to 5 where R 3 and R 4 are each hydrogen. 7. The compounds according to any of claims 1 to 6 where each group X represents chloro, bro o, methoxy, etnoxycarbonyl or nitro. 8. The compounds according to any of claims 1 to 7 where X. represents mono-substitution in the 2-position, or disubstitution in the 2,4- or 2,5-positions on the phenyl ring. 9. A compound selected from: di-n-propyl (2,4-dichlorophenyl) [ (1H-1,2,4-triazol-l- yl)methyl]malonate; ethyl 2-(2,4-dichlorophenyl)-2-(phenylsulfonyl) -3- (lH-l,2,4-triazol-l-yl)propionate; and n-propyl 2-(2,4-dichlorophenyl)-2-(phenylsulfonyl)-3- (1H-1,2,4-triazol-l-yl)propionate. 10. A herbicidal and/or fungicidal composition which comprises one or more compounds according to any of claims 1 to 9, in association with a suitable carrier and/or surface active agent. AM----NDED CLAIMS [received by the International Bureau on 14 April 1993 (14.04.93) original claim 1 amended ; other claims unchanged (2 pages) ] 1. The compounds of the formula: where : Az is imidazol-1-yl or 1,2,4-triazol-l-yl; each X represents halogen, carboxy, nitro, cyano, a group COR 5 , COOR 5 -or S(0) p R 5 , or an optionally substituted alkyl, alkoxy, aryl or heteroaryl group; R 1 represents a group COR 5 , COOR 5 , SH or S.(0) p R 5 ; R 2 represents a group CN, COR 5 , COOR 5 , SH, S(0) p R 5 , S0 2 N(R 5 ) 2 , P(O) (OR 5 ),, nitro, aryl, heteroaryl or aralkyl; R 3 and R 4 , which may be the same or different, each represent hydrogen, or an optionally substituted alkyl, aryl or heteroaryl group; R *1 represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl or heteroaryl group; n is 0 to 4; and p is 0 to 2; with the proviso that R l and R 2 do not simultaneously represent groups of formula S(0) p R 5 where R 5 is in each case alkyl or alkenyl. 2. The compounds according to claim 1 where R 1 is COOR 5 " (where R 5a is alkyl of 1 to 8 carbon atoms, allyl, phenyl, phenylthio, benzyl or cyano) . 3. The compounds according to claim 2 where R 5a is methyl, ethyl, n-propyl, iso-propyl or n-butyl. 4. The compounds according to any of claims 1 to 3 where R 2 is cyano, optionally substituted phenyl, benzoyl, optionally substituted phenylthio, COOR- * - 1 (where R 5a is alkyl of 1 to 8 carbon atoms, methoxyethyl, cyclopentyl, allyl or benzyl) , or S0 2 R 5b (where R *)b is alkyl of 1 to 4 carbon atoms, phenyl, pyridyl or benzyl) . 5. The compounds according to claim 4 where R 2 is COOR 5a (where R * " * is methyl, ethyl, n-propyl, iso-propyl or n-butyl) or S0 2 R 5b (where R 5b is phenyl) . 6. The compounds according to any of claims 1 to 5 where R 3 and R 4 are each hydrogen. 7. The compounds according to any of claims 1 to 6 where each group X represents chloro, bro o, methoxy, methoxycarbonyl or nitro. 8. The compounds according to any of claims 1 to 7 where X n represents mono-substitution in the 2- position, or disubstitution in the 2,4- or 2,5- positions on the phenyl ring. 9. A compound selected from: di-n-propyl (2 , 4-dichlorophenyl) [ (1H-1, 2 , 4-triazol- 1-yl)methyl] alonate; ethyl 2-(2, 4-dichlorophenyl) -2- (phenylsulfonyl) -3- (1H-1,2,4-triazol-l-yl)propionate; and n-propyl 2-(2,4-dichlorophenyl) -2- (phenylsulfonyl) - 3-(1H-1,2,4-triazol-l-yl) propionate. 10. A herbicidal and/or fungicidal composition which comprises one or more compounds according to any of claims 1 to 9, in association with a suitable carrier and/or surface active agent. STATEMENT UNDER ARTICLE 19 Claim 1 of the above application has been amended (a) to exclude the possibility that R 1 can be CN, (b) to add a proviso that R 1 and R 2 do not simultaneously represent groups of formula S(O) p R 5 where R 5 is in each case alkyl or alkenyl, (c) to exclude the possibility that two adjacent groups X may together form a fused benzo group, and (d) to insert SH as an explicit designation for R τ and R 2 , and remove the equivalent designation of hydrogen for the group R 5 . Amendment (a) is made to overcome citations EP 61840, EP 251775, US 4073921 , and US 4167576. Amendment (b) is made to overcome citation EP 61794. Amendment (c) is made to overcome citation EP 1 6587.

Inventors: BRIGGS GEOFFREY GOWER, BUEHMANN ULRICH, CORNELL CLIVE LEONARD, WEST PETER JOHN, BRIGGS, GEOFFREY, GOWER, BUEHMANN, ULRICH, CORNELL, CLIVE, LEONARD, WEST, PETER, JOHN
Applicants: SCHERING AGROCHEMICALS LTD, SCHERING AGROCHEMICALS LIMITED
Application year: 1992
Main classification: C07D249
IPC codes: A01N43, C07D233, C07D249, C07D401, C07D521, C07F9