GB2314080A - Fungicidal cyclic boron compounds - Google Patents

Abstract

Compounds of formula (I): wherein A 1 and A 2 are, independently, alkyl, phenyl, furyl or thienyl each optionally substituted by halogen, C 1-4 alkyl, C 1-4 alkoxy, C 1-4 alkyilhio, C 1-4 haloalkyl, C 1-4 haloalkoxy or C 1-4 haloalkylthio; M is O, SO 2 or CR 3 R 4 ; R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are, independently, hydrogen, halogen, hydroxy, C 1-4 alkyl, C 1-4 haloalkyl or benzyl (optionally substituted by halogen, C 1-4 alkyl or C 1-4 haloalkyl); R 1 and R 2 or R 3 and R 4 may together form =O or =CR 7 R 8 ; R 2 and R 3 or R 4 and R 5 may together form a double bond; R 2 and R 3 or R 1 and R 4 or R 3 and R 5 or R 4 and R 6 may join together to form a methylene bridge; R 7 and R 8 are, independently, hydrogen, halogen or C 1-4 alkyl; and R 9 is hydrogen or halogen are useful as plant fungicides.

Description

CHEMICAL COMPOUNDS The present invention relates to novel fungicidal organoborons, to processes for preparing them, to fungicidal compositions containing them and to methods of using them to combat fungi, especially fungal infections of plants.

The invention provides a compound of formula (I):

wherein A' and A2 are, independently, alkyl, phenyl, furyl or thienyl each optionally substituted by halogen, C1-4 alkyl, CIA alkoxy, CIA alkylthio, C1-4 haloalkyl, CIA haloalkoxy or CIA haloalkylthio; M is O, SO2 or CR3R4;R1,R2,R3,R4,R5 and R6 are, independently, hydrogen, halogen, hydroxy, C1-4 alkyl, CIA haloalllyl or benzyl (optionally substituted by halogen, CIA alkyl or CIA haloalkyl); Rl and R2 or R3 and R4 may together form =0 or =CR7R8; R2 and R3 or R4 and R5 may together form a double bond; R2 and R3 or R' and R4 or R3 and R5 or R4 and R6 may join together to form a methylene bridge; R7 and R8 are, independently, hydrogen, halogen or C1.4 alkyl; and R9 is hydrogen or halogen.

The compounds of formula (I) exist as stereoisomers. This invention covers all stereoisomers (enantiomers and diastereoisomers) and mixtures thereof in all proportions.

Alkyl moieties are straight or branched chain. Alkyl is, for example, methyl, ethyl, npropyl, iso-propyl, n-butyl or tert-butyl.

Alkoxy is, for example, methoxy or ethoxy.

Alkylthio is, for example, methylthio or ethylthio.

Halogen is preferably fluorine or chlorine.

Haloalkyl moieties are preferably fluoroalkyl or chloroalkyl moieties. Haloalkyl is, for example, trifluoromethyl; and haloalkoxy is, for example, trifluoromethoxy.

In one particular aspect the present invention provides a compound of formula (I) wherein A' and A2 are, independently, alkyl, phenyl, furyl or thienyl each optionally substituted by halogen, C1-4 alkyl, CIA alkoxy, CiA alkylthio, C,A haloalkyl, Cla,'haloalkoxy or or CIA haloalkylthio; M is O, SO2 or CR3R4;R1,R2,R3, R4, R5 and R6 are, independently, hydrogen, halogen, hydroxy, C1-4 alkyl, C1-4 haloalkyl or benzyl (optionally substituted by halogen, 1-4 alkyl or C1-4 haloalkyl); Rl and R2 or R3 and R4 may together form =0 or =CR7R8; R2 and R3or R4 and R5 may together form a double bond; R2 and R3 or R1 and R4 or R3 and R5 or R4 and R6 may join together to form a methylene bridge; R7 and R8 are, independently, hydrogen, halogen or C1-4 alkyl; and R9 is hydrogen.

In another aspect the present invention provides a compound of formula (I) wherein A' and A2 are, independently, C-6 alkyl or phenyl optionally substituted by C1-4 alkoxy.

In yet another aspect the present invention provides a compound of formula (I) wherein A' and A2 are, independently, C1.6 alkyl or phenyl optionally substituted by halogen, C1-4 alkyl or C1-4 haloalkyl.

In a further aspect the present invention provides a compound of formula (I) wherein A' and A2 are both unsubstituted phenyl.

In an additional aspect the present invention provides a compound of formula (I) wherein M is CR3R4.

In a further aspect the present invention provides a compound of formula (I) wherein R1,R2, R5 and R6 are, independently, hydrogen or CiA alkyl; and R9 is hydrogen.

In a still further aspect the present invention provides a compound of formula (II):

wherein Al and A2 are, independently, C1-4 alkyl (especially methyl) or phenyl optionally substituted by CiA alkoxy (especially methoxy); R', R2, R5 and R6 are, independently, hydrogen or C1-4 alkyl (especially methyl); R3 and R4 are, independently, hydrogen, halogen, hydroxy or C1A alkyl (especially methyl) or R3 and R4 together form =0 or =CH2; R2 and R3 may together form a double bond or a methylene bridge; and R9 is hydrogen or halogen (especially fluorine).

In another aspect the present invention provides a compound of formula (II): wherein Al and A2 are, independently, CIAalkyl (especially methyl) or phenyl optionally substituted by C1-4 alkoxy (especially methoxy); Rl, R2, R5 and R6 are, independently, hydrogen or C1-4 alkyl (especially methyl); R3 and R4 are, independently, hydrogen, halogen, hydroxy or C1-4 alkyl (especially methyl) or R3 and R4 together form =0 or =CH2; R2 and R3 may together form a double bond or a methylene bridge; and R9 is hydrogen.

Examples of compounds of formula (11) are provided in Table I.

TABLE I

Compound No. R1 R2 R3 R4 R5 R6 R9 A1 A2 1 H H H H H H H C6H5 C6H5 2 H H H F H H H C6H5 C6H5 3 H H F H H H H C6H5 C6H5 4 H H CH3 H H H H C6H5 C6H5 5 H H H CH3 H H H C6H5 C6H5 6 H H F F H H H C6H5 C6H5 7 H H =O H H H C6H5 C6H5 8 H H =CH2 H H H C6H5 C6H5 9 H = H H H H C6H5 C6H5 10 H = CH3 H H H C6H5 C6H5 11 H CH3 H H H H H C6H5 C6H5 12 CH3 H H H H H H C6H5 C6H5 13 H H H H CH3 H H C6H5 C6H5 14 H H H H H CH3 H C6H5 C6H5 TABLE I (continued)

Compound No. R1 R2 R3 R4 R5 R6 R9 A1 A2 15 H H H H H H H CH3 C6H5 16 H H H F H H H CH3 C6H5 17 H H F H H H H CH3 C6H5 18 H H CH3 H H H H CH3 C6H5 19 H H H CH3 H H H CH3 C6H5 20 H H F F H H H CH3 C6H5 21 H H =O H H H CH3 C6H5 22 H H =CH2 H H H CH3 C6H5 23 H = H H H H CH3 C6H5 24 H = CH3 H H H CH3 C6H5 25 H CH3 H H H H H CH3 C6H5 26 CH3 H H H H H H CH3 C6H5 27 H H H H CH3 H H CH3 C6H5 28 H H H H H CH3 H CH3 C6H5 TABLE I (continued)

Compound No. R1 R2 R3 R4 R5 R6 R9 A1 A2 29 H H H H H H H C6H5 CH3 30 H H H F H H H C6H5 CH3 31 H H F H H H H C6H5 CH3 32 H H CH3 H H H H C6H5 CH3 33 H H H CH3 H H H C6H5 CH3 34 H H F F H H H C6H5 CH3 35 H H =O H H H C6H5 CH3 36 H H =CH2 H H H C6H5 CH3 37 H = H H H H C6H5 CH3 38 H = CH3 H H H C6H5 CH3 39 H CH3 H H H H H C6H5 CH3 40 CH3 H H H H H H C6H5 CH3 41 H H H H CH3 H H C6H5 CH3 42 H H H H H CH3 H C6H5 CH3 TABLE I (continued)

Compound No. R1 R2 R3 R4 R5 R6 R9 A1 A2 43 H H H H H H H 4-CH3OC6H4 4-CH3OC6H4 44 H H H F H H H 4-CH3OC6H4 4-CH3OC6H4 45 H H F H H H H 4-CH3OC6H4 4-CH3OC6H4 46 H H CH3 H H H H 4-CH3OC6H4 4-CH3OC6H4 47 H H H CH3 H H H 4-CH3OC6H4 4-CH3OC6H4 48 H H F F H H H 4-CH3OC6H4 4-CH3OC6H4 49 H H =O H H H 4-CH3OC6H4 4-CH3OC6H4 50 H H =CH2 H H H 4-CH3OC6H4 4-CH3OC6H4 51 H = H H H H 4-CH3OC6H4 4-CH3OC6H4 52 H = CH3 H H H 4-CH3OC6H4 4-CH3OC6H4 53 H CH3 H H H H H 4-CH3OC6H4 4-CH3OC6H4 54 CH3 H H H H H H 4-CH3OC6H4 4-CH3OC6H4 55 H H H H CH3 H H 4-CH3OC6H4 4-CH3OC6H4 56 H H H H H CH3 H 4-CH3OC6H4 4-CH3OC6H4 TABLE I (continued)

Compound No. R1 R2 R3 R4 R5 R6 R9 A1 A2 57 H H H H H H F C6H5 C6H5 58 H H H F H H F C6H5 C6H5 59 H H F H H H F C6H5 C6H5 60 H H CH3 H H H F C6H5 C6H5 61 H H H CH3 H H F C6H5 C6H5 62 H H F F H H F C6H5 C6H5 63 H H =O H H F C6H5 C6H5 64 H H =CH2 H H F C6H5 C6H5 65 H = H H H F C6H5 C6H5 66 H = CH3 H H F C6H5 C6H5 67 H CH3 H H H H F C6H5 C6H5 68 CH3 H H H H H F C6H5 C6H5 69 H H H H CH3 H F C6H5 C6H5 70 H H H H H CH3 F C6H5 C6H5 TABLE I (continued)

Compound No. R1 R2 R3 R4 R5 R6 R9 A1 A2 71 H H H H H H F CH3 C6H5 72 H H H F H H F CH3 C6H5 73 H H F H H H F CH3 C6H5 74 H H CH3 H H H F CH3 C6H5 75 H H H CH3 H H F CH3 C6H5 76 H H F F H H F CH3 C6H5 77 H H =O H H F CH3 C6H5 78 H H =CH2 H H F CH3 C6H5 79 H = H H H F CH3 C6H5 80 H = CH3 H H F CH3 C6H5 81 H CH3 H H H H F CH3 C6H5 82 CH3 H H H H H F CH3 C6H5 83 H H H H CH3 H F CH3 C6H5 84 H H H H H CH3 F CH3 C6H5 TABLE I (continued)

Compound No. R1 R2 R3 R4 R5 R6 R9 A1 A2 85 H H H H H H F C6H5 CH3 86 H H H F H H F C6H5 CH3 87 H H F H H H F C6H5 CH3 88 H H CH3 H H H F C6H5 CH3 89 H H H CH3 H H F C6H5 CH3 90 H H F F H H F C6H5 CH3 91 H H =O H H F C6H5 CH3 92 H H =CH2 H H F C6H5 CH3 93 H = H H H F C6H5 CH3 94 H = CH3 H H F C6H5 CH3 95 H CH3 H H H H F C6H5 CH3 96 CH3 H H H H H F C6H5 CH3 97 H H H H CH3 H F C6H5 CH3 98 H H H H H CH3 F C6H5 CH3 TABLE I (continued)

Compound No. R1 R2 R3 R4 R5 R6 R9 A1 A2 99 H H H H H H F 4-CH3OC6H4 4-CH3OC6H4 100 H H H F H H F 4-CH3OC6H4 4-CH3OC6H4 101 H H F H H H F 4-CH3OC6H4 4-CH3OC6H4 102 H H CH3 H H H F 4-CH3OC6H4 4-CH3OC6H4 103 H H H CH3 H H F 4-CH3OC6H4 4-CH3OC6H4 104 H H F F H H F 4-CH3OC6H4 4-CH3OC6H4 105 H H =O H H F 4-CH3OC6H4 4-CH3OC6H4 106 H H =CH2 H H F 4-CH3OC6H4 4-CH3OC6H4 107 H = H H H F 4-CH3OC6H4 4-CH3OC6H4 108 H = CH3 H H F 4-CH3OC6H4 4-CH3OC6H4 109 H CH3 H H H H F 4-CH3OC6H4 4-CH3OC6H4 110 CH3 H H H H H F 4-CH3OC6H4 4-CH3OC6H4 111 H H H H CH3 H F 4-CH3OC6H4 4-CH3OC6H4 112 H H H H H CH3 F 4-CH3OC6H4 4-CH3OC6H4 A compound of formula (I) can be prepared by reacting a compound of formula (IV):

or an anhydride thereof, wherein A' and A2 are as defined above, with a compound of formula (nI):

wherein R', R2 R5, R6, R9 and M are as defined above. It is preferred that this process is carried out at room temperature and in the presence of a suitable solvent (such as a chlorinated solvent, for example, dichloromethane or an ether, for example tetrahydrofuran or diethylether).

Compounds of formula (I) can be purified using standard techniques (such as crystallisation or trituration).

Compounds of formulae (m) and (IV) can be obtained by methods described in the literature.

In a further aspect the present invention provides a process, as hereinbefore described, for preparing compounds of formula (I).

The compounds of formula (I) are active fungicides and may be used to control one or more of the following pathogens: Pyricularia oryzae on rice and wheat and other Pyricularia spp. on other hosts; Puccinia recondita, Puccinia striifonnis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts e.g. turf, rye, coffee, pears, apples, peanuts, sugar beet, vegetables and ornamental plants; Erysiphe graminis (powdery mildew) on barley, wheat, rye and turf and other powdery mildews on various hosts such as Sphaerotheca macularis on hops, Sphaerotheca fuliginea on cucurbits (for example cucumber), Podosphaera leucotricha on apple and Uncinula necator on vines; Cochliobolus spp., Helminthosporium spp., Drechslera spp. (Pyrenophora spp.), Rhynchosporium spp., Septoria spp. (including Mycosphaerella graminicola and Leptosphaeria nodorum), Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals (for example wheat, barley, rye), turf and other hosts; Cercospora arachidicola and Cercosporidium personatum on peanuts and other Cercospora species on other hosts, for example, sugar beet, bananas, soya beans and rice; Botrytis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrytis spp. on other hosts; Alternaria spp. on vegetables (for example cucumber), oil-seed rape, apples, tomatoes, cereals (for example wheat) and other hosts; Venturia spp. (including Venturia inaequalis (scab)) on apples, pears, stone fruit, tree nuts and other hosts; Cladosporium spp. on a range of hosts including cereals (for example wheat); Monilinia spp. on stone fruit, tree nuts and other hosts; Didymella spp. on tomatoes, turf, wheat and other hosts; Phoma spp. on oil-seed rape, turf, rice, potatoes, wheat and other hosts; Aspergillus spp. and Aureobasidium spp. on wheat, lumber and other hosts; Ascochyta spp. on peas, wheat, barley and other hosts; Plasmopara viticola on vines; other downy mildews such as Bremia lactucae on lettuce, Peronospora spp. on soybeans, tobacco, onions and other hosts, Pseudoperonospora humuli on hops and Pseudoperonospora cubensis on cucurbits; Pythiurn spp. (including Pythium ultimum) on turf and other hosts; Phytophthora infestans on potatoes and tomatoes and other Phytophthora spp. on vegetables, strawberries, avocado, pepper, ornamentals, tobacco, cocoa and other hosts; Thanatephorus cucumeris on rice and turf and other Rhizoctonia species on various hosts such as wheat and barley, vegetables, cotton and turf; Sclerotinia spp. on turf, peanuts, oil-seed rape and other hosts; Sclerotium spp. on turf, peanuts and other hosts; Colletotrichum spp. on a range of hosts including turf, coffee and vegetables; Laetisaria fuciformis on turf; Mycosphaerella spp. on banana, peanut, citrus, pecan, papaya and other hosts; Diaporthe spp. on citrus, soybean, melon, pear, lupin and other hosts; Elsinoe spp. on citrus, vines, olives, pecans, roses and other hosts; Pyrenopeziza spp. on oil-seed rape and other hosts; Oncobasidium theobromae on cocoa causing vascular streak dieback; Fusarium spp., Typhula spp., Microdochium nivale, Ustilago spp., Urocystis spp., Tilletia spp., and Claviceps purpurea on a variety of hosts but particularly wheat, barley, turf and maize; Ramularia spp. on sugar beet and other hosts; post-harvest diseases particularly of fruit (for example Penicillium digitatum and P. italicum and Trichoderna viride on oranges, Colletotrichum musae and Gloeosporium musarum on bananas and Botrytis cinerea on grapes); other pathogens on vines, notably Eutypa lata, Guignardia bidwellii, Phellinus igniarus, Phomopsis viticola, Pseudopezicula tracheiphila and Stereum hirsutum; other pathogens on lumber, notably Cephaloascusfragrans, Ceratocystis spp., Ophiostoma piceae, Penicillium spp., Trichodenna pseudokoningii, Trichodenna viride, Trichodenna harzianum, Aspergillus niger, Leptographium lindbergi and Aureobasidium pullulans; add fungal vectors of viral diseases for example Polymyxa gram in is on cereals as the vector of barley yellow mosaic virus (BYMV).

Further, some of the compounds may be useful as seed dressings against pathogens including Fusarium spp., Septoria spp., Tilletia spp., (for example bunt, a seed-borne disease of wheat), Ustilago spp. and Helminthosporium spp. on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on rice.

The compounds may move acropetally/locally in plant tissue. Moreover, the compounds may be volatile enough to be active in the vapour phase against fungi on the plant.

The invention therefore provides a method of combating fungi which comprises applying to a plant, to a seed of a plant or to the locus of the plant or seed a fungicidally effective amount of a compound as hereinbefore defined, or a composition containing the same.

The compounds may be used directly for agricultural purposes butare more conveniently formulated into compositions using a carrier or diluent, The invention thus provides fungicidal compositions comprising rooinpound as hereinbefore defined and an acceptable carrier or diluent therefor. It is preferred that all compositions, both solid and liquid formulations, comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 1 t 25% or 25 to 60%, of a compound as hereinbefore defined.

When applied to the foliage of plants, the compounds of the invention are applied at rates of 0. it to 10keg, preferably ig to 8kg, more preferably lOg to 4keg, of active ingredient (invention compound) per hectare.

When used as seed dressings, the compounds of the invention are used at rates of 0.OOOlg to lOg (for example 0.OOlg or 0.05g), preferably 0.005g to 8g, more preferably 0.005g to 4g, of active ingredient (invention compound) per kilogram of seed.

The compounds can be applied in a number of ways. For example, they can be applied, formulated or unformulated, directly to the foliage of a plant, to seeds or to other medium in which plants are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation, or they can be applied as a vapour or as slow release granules.

Application can be to any part of the plant including the foliage, 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 may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.

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

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 dustable powders or granules comprising an active ingredient (invention compound) and a solid diluent or carrier, for example, a filler such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, diatomaceous earth or 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 pelieting a mixture of the active ingredient and powdered filler. Compositions for dressing seed may include an agent (for example, a mineral oil) for assisting the adhesion of the composition to the seed; alternatively the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example, N-methylpyrrolidone, propylene glycol or N,N-dimethyl- formamide). The compositions may also be in the form of water dispersible powders or water dispersible granules optionally comprising one or more wetting agents, one or more dispersing agents or a mixture of said agents to facilitate the dispersion in liquids. The powders and granules may also contain fillers and antisettting agents.

The compositions may also be in the form of soluble powders or granules, or in the form of solutions in polar solvents.

Soluble powders may be prepared by mixing an active ingredient with a water-soluble salt such as sodium bicarbonate, sodium carbonate, magnesium sulphate or a polysaccharide, and optionally one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water dispersibility/solubility. The mixture may then be ground to a fine powder. Similar compositions may also be granulated to form water-soluble granules.

Solutions may be prepared by dissolving the active ingredient in polar solvents such as ketones, alcohols and glycol ethers. These solutions may contain surface active agents to improve water dilution and prevent crystallisation in a spray tank.

Emulsifiable concentrates or emulsions may be prepared by dissolving an active ingredient in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents) and, for an emulsion, subsequently adding the mixture to water (which may contain one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents are aromatic solvents such as allrylbenzenes and alkylnaphthalenes, ketones such as cyclohexanone and methylcyclohexanone, chlorinated hydrocarbons such as chlorobenzene and trichloroethane, and alcohols such as benzyl alcohol, furfuryl alcohol, butanol and glycol ethers.

Aqueous suspension concentrates of largely insoluble solids may be prepared by ball or bead milling with a dispersing agent with an antisettling agent included to stop the insoluble solid settling.

Compositions to be used as sprays may be in the form of aerosols wherein the formulation is held in a container under pressure of a suitable propellant.

The invention compounds can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating in enclosed spaces a smoke containing the compounds.

Alternatively, the invention compounds may be used in 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 uptake, distribution, adhesive power or resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities. Other additives may be included to improve the biological efficacy of the various formulations. Such additives can be surface active materials to improve the wetting or retention on surfaces treated with the formulation or the uptake or mobility of the active material, or additionally can include oil based spray additives, for example, certain mineral oil and natural plant oil (such as soya bean and rape seed oil) additives, or blends of them with other bio-enhancing adjuvants.

The invention compounds can be used as mixtures with fertilisers (for example nitrogen-, potassium- or phosphorus-containing fertilisers), such as granules of fertiliser comprising a compound of formula (I). Such granules suitably contain up to 25% by weight of the compound. The invention therefore also provides a fertiliser composition comprising a fertiliser and the compound of formula (I).

Water dispersible powders, emulsifiable concentrates and suspension concentrates optionally contain a surfactant (for example one or more wetting agents, one or more dispersing agents, or one or more emulsifying agents or a mixture of said agents, in which each agent can be, independently, cationic, anionic or non-ionic) and optionally contains one or more anti settling 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 triisopropylnaphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, alkyl glucosides, polysaccharides and the lecithins and the condensation products of the said partial esters with ethylene oxide. Suitable suspending agents are hydrophilic colloids (for example, polyvinylpyrrolidone and sodium carboxymethylcellulose), and swelling clays such as bentonite or attapulgite.

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, the concentrate being diluted with water before use. These concentrates should preferably be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain up to 95%, suitably 1-85%, for example 1-25% or 25-60%, by weight of the active ingredient. After dilution to form aqueous preparations, such preparations may contain varying amounts of the active ingredient depending upon the intended purpose, but an aqueous preparation containing 0.0001 to 10%, for example 0.005 to 10%, by weight of active ingredient may be used.

The compositions of this invention may contain other compounds having biological activity, for example compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal or insecticidal activity.

By including another fungicide, the resulting composition can have a broader spectrum of activity or a greater level of intrinsic activity than the compound of formula (I) alone.

Further the other fungicide can have a synergistic effect on the fungicidal activity of the compound of formula (I). Examples of fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-(2-phenoxyphenyl)-2 methoxyiminoacetamide, (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxyiminoacetamide, (RS)- 1 -aminopropylphosphonic acid, (RS)4-(4-chlorophenyl )- -2-phenyl-2-( I H- 1 ,2,4-triazol- 1 -ylmethyl)butyronitrile, (Z)-N-but-2-enyloxymethyl- -2-chloro-2' ,6'-diethylacetanilide, 1 -(2cyano-2-methoxyiminoacetyl)- 3-ethyl urea, 4-(2,2-difluoro- 1 ,3-benzodioxol4-yl)pyrrole-3carbonitrile, 4-bromo-2-cyano-N,N-dimethyl -6-trifluoromethylbenzimidazole- 1 -sulphonamide, 5-ethyl-5,8-dihydro-8-oxo( 1,3)-dioxol- (4,5-g)quinoline-7carboxylic acid, a-[N-(3-chloro-2,6-xylyl)-2-methoxy acetamido] -y-butyrolactone, N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, alanycarb, aldimorph, ampropylfos, anilazine, azaconazole, azoxystrobin, BAS 490F, benalaxyl, benomyl, biloxazol, binapacryl, bitertanol, blasticidin S, bromuconazole, bupirimate, butenachlor, buthiobate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, CGA 245704, chinomethionate, chlorbenzthiazone, chloroneb, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulphate, copper tallate, and Bordeaux mixture, cycloheximide, cymoxanil, cyproconazole, cyprodinyl, cyprofuram, debacarb, di-2-pyridyl disulphide l,l'-dioxide, dichiofluanid, dichlone, diclobutrazol, diclomezine, dicloran, didecyl dimethyl ammonium chloride, diethofencarb, difenoconazole, O,O-di-iso-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, etaconazole, ethirimol, ethoxyquin, ethyl (Z)-N-benzyl-N-(Emethyl(methyl-thioethylideneamino- oxycarbonyl)amino]thio)-p-alaninate, etridiazole, famoxadone, fenaminosulph, fenapanil, fenarimol, fenbuconazole, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, ipconazole, iprobenfos, iprodione, isopropanyl butyl carbamate, isoprothiolane, kasugamycin, mancozeb, maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methfuroxam, metiram, metiram-zinc, metsulfovax, myclobutanil, NTN0301, neoasozin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxolinic acid, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al, phosphorus acids, phthalide, polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propamocarb hydrochloride, propiconazole, propineb, propionic acid, prothiocarb, pyracarbolid, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinconazole, quinomethionate, quintozene, rabenazole, sodium pentachlorophenate, streptomycin, sulphur, tebuconazole, techlofthalam, tecnazene, tetraconazole, thiabendazole, thicyofen, thifluzamide, 2-(thiocyanomethylthio)benzothiazole, thiophanatemethyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triacetate salt of 1,1'-iminodi(octamethylene)diguanidine, triadimefon, triadimenol, triazbutyl, triazoxide, tricyclazole, tridemorph, triforine, triflumizole, triticonazole, validamycin A, vapam, vinclozolin, XRD-563, zineb and ziram. The compounds of formula (I) can be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.

The following Examples illustrate the invention. The following abbreviations are used throughout the Examples: mp = melting point q = quartet s = singlet dd = doublet of doublets d = doublet m = multiplet t = triplet EXAMPLE 1 Preparation of 3,3-diphenyl-5-oxo-2-azonia-3-borata-4-oxabicyclo[4.3.0]nonane (Compound No. 1 in Table I).

A solution of diphenylborinic anhydride (1.0g, 2.9mmol) and cis-2aminocyclopentanecarboxylic acid (712mg, 5.52mmol) in dry diethyl ether (soil) was stirred at ambient temperature for 2.5 hours. The precipitated solid was filtered off and partitioned between ethyl acetate and water. The organic phase was separated, dried and evaporated to leave a cream solid, which was washed with diethyl ether to yield the title compound (541mg; mp 247-249"C).

'H NMR (CD30D): 6 7.46 (4H, m), 7.15 (6H, m), 3.49 (1H, m), 2.69 (1H, q), 2.09 (1H, m), 2.00 (2H, m), 1.72 (2H, m), 1.40 (1H, m) ppm.

EXAMPLE 2 Alternative preparation of 3,3-diphenyl-5-oxo-2-azonia-3-borata-4- oxabicyclo[4.3.0]nonane (Compound No. 1 in Table I).

2N Hydrochloric acid (20ml) was added to a stirred solution of 2aminoethyldiphenylborinate (lOg, 44mmol) in ethanol (100ml). The mixture was heated at reflux for 2 hours, then cooled and extracted with ethyl acetate. The combined organic extracts were washed with water, dried and evaporated to provide a solid. This material was dissolved in chloroform, and the resulting solution washed repeatedly with water, then dried and evaporated to provide diphenylborinic acid as an orange oil which slowly solidified to a yellow solid.

H NMR (CDCI3): 6 7.87 (1H, dd), 7.78 (1H, dd), 7.62 (2H, m), 7.40 (6H, m) ppm.

A solution of diphenylborinic acid (282mg, 1.55mmol) and cis-2aminocyclopentanecarboxylic acid (200mg, 1.55mmol) in dry diethyl ether (20ml) was stirred at ambient temperature under nitrogen for 5 hours and then allowed to stand overnight. The precipitated solid was filtered off and partitioned between ethyl acetate and water. The organic phase was separated, dried and evaporated to yield the title compound as a white solid (173mg).

Compounds 43 of Table I and 57 of Table I were prepared using a process analogous to that described in Example 2.

Compound 43 (Table I) 'H NMR (CDCl3): 7.30 (4H,m), 6.86 (2H,d), 6.78 (2H,d), 5.22 (lH,m), 3.90 (1H,m), 3.79 (3H,s), 3,73 (3H,s), 3.55 (lH,m), 2.72 (lH,dd), 2.18-1.35 (6H,m) ppm.

Compound 57 (Table I) 'H NMR (CD3SOCD3): 6 7.48-7.20 (7H,m), 7.20-6.98 (4H,m), 6.76 (1 H,t), 3.45-3.20 (1H,m), 2.27-1.47 (6H,m)ppm.

A 44:56 mixture of compounds 15 and 29 of Table I was also prepared using a process analogous to that described in Example 2. This mixture decomposed between 210 C-217 "C.

EXAMPLE 3 Preparation of 3,3-diphenyl-8-methylene-5-oxo-2-azonia-3-borata4- oxabicyclo[4.3.0]nonane (Compound No. 8 in Table I) Diphenylborinic anhydride (203mg, 0.56mmol) was added to a stirred suspension of cis-2-amino-4-methylenecyclopentanecarboxylic acid (156mg, 1.12mmol) in dry tetrahydrofuran (12ml), and the resulting mixture stirred at ambient temperature for 19 hours.

The mixture was then filtered and the filtrate evaporated to leave a white solid, which was crystallised from ethyl acetate/hexane to provide the title compound as a white solid (192 mg; mp 243-245 0C).

'H NMR (CD3SOCD3): 6 7.4-7.0 (10H, m), 7.26 (1H, m), 6.50 (1H, m), 4.75 (2H, m), 3.40 (lH, m), 2.8-2.3 (5H, m) ppm.

EXAMPLE 4 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 Dispersol T or as a solution in acetone or acetone/ethanol which was diluted to the required concentration immediately before use. The formulations (100 ppm active ingredient) were sprayed on to the foliage of the plants to maximum retention. Tween 20 was adad to give a final concentration of Tween 20 of 0. 0.1% by volume when the sprays were applied to cereals.

The compounds were applied to the foliage (by spraying) one or two days before the plant was inoculated with the disease. Foliar pathogens were applied by spray as zoosporangial 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 level present (i.e. leaf area covered by actively sporulating disease) on each of the treated plants was recorded using the following assessment scale: 0 = 0% disease present 20 = 10.1-20% disease present 1 = 0.1 - 1% disease present 30 = 20.1-30% disease present 3 = 1.1-3% disease present 60 = 30.1-60% disease present 5 = 3.1-5% disease present 90 = 60.1-100% disease present 10 = 5.1-10% disease present Each assessment was then expressed as a percentage of the level of disease present on the untreated control plants. This calculated value is referred to as a POCO (Percentage of Control) value. An example of a typical calculation is as follows: Disease level on untreated control = 90 Disese level on treated plant = 30 POCO = disease level on treated plant x 100 = 30 x 100 = 33.3 disease level on untreated control 90 This calculated POCO value is then rounded to the nearest of the values in the 9-point assessment scale shown above. In this particular example, the POCO value would be rounded to 30. If the calculated POCO falls exactly mid-way between two of the points, it is rounded to the lower of the two values.

The POCO results are shown in Table II.

TABLE II

Compound No (Table No) LEPTNO PUCCRT PLASVI PHYTIN VENTIN 1 (I) 0 0 0 0 0 8 (I) 90 0 0 0 15/29 (I)1 20 90 90 90 60 43 (I) 60 60 60 90 30 57 (I) 90 30 90 90 144:56 mixture of these compounds.

Key to Diseases LEPTNO Septoria nodorum PLASVI Plasmopara viticola PUCCRT Puccinia recondita PHYTIN Phytophthora infestans VENTIN Venturia inaequalis lycopersici

Claims (9)

1. CLAIMS 1. A compound of formula (I):

   wherein Al and A2 are, independently, alkyl, phenyl, furyl or thienyl each optionally substituted by halogen, C1-4 alkyl, C,4 alkoxy, C14 alkylthio, C,4 haloalkyl, C1-4 haloalkoxy or C14 haloalkylthio; M is 0, SO2 or CR3R4; R1, R2, R3, R4, R5 and R6 are, independently, hydrogen, halogen, hydroxy, C14 alkyl, C1-4 haloalkyl or benzyl (optionally substituted by halogen, C,4 alkyl or C1-4 haloalkyl); R1 and R2 or R3 and R4 may together form =0 or =CR7RS; R2 and R3 or R4 and RS may together form a double bond; R2 and R3 or R' and R4 or R3 and RS or R4 and R6 may join together to form a methylene bridge; R7 and R8 are, independently, hydrogen, halogen or C14 alkyl; and R9 is hydrogen or halogen.
2. 2. A compound as claimed in claim 1 wherein A1 and A2 are, independently, C,6 alkyl or phenyl optionally substituted by C14 alkoxy.
3. 3. A compound as claimed in claim 1 wherein A' and A2 are, independently, C1-6 alkyl or phenyl optionally substituted by halogen, C14 alkyl or C14 haloalkyl.
4. 4. A compound as claimed in claim 1, 2 or 3 wherein M is CR3R4.
5. 5. A compound as claimed in claim 1, 2, 3 or 4 wherein R', R2, R5 and R6 are, independently, hydrogen or C14 alkyl; and R9 is hydrogen.
6. 6. A compound of formula (II):

   wherein A1 and A2 are, independently, C1-4 alkyl or phenyl optionally substituted by C1-4 alkoxy; Rl, R2, R5 and R6 are, independently, hydrogen or C1-4 alkyl; R3 and R4 are, independently, hydrogen, halogen, hydroxy or CIA alkyl or R3 and R4 together form =0 or =CH2; R2 and R3 may together form a double bond or a methylene bridge; and R9 is hydrogen or halogen.
7. 7. A process for preparing a compound as claimed in claim 1 by reacting a compound of formula (IV):

   or an anhydride thereof, wherein Al and A2 are as claimed in claim 1, with a compound of formula (m):

   wherein R', R2 , RS, R6, R9 and Mare as defined in claim 1.
8. 8. A fungicidal composition comprising a fungicidally effective amount of a compound according to claim 1 and a fungicidally acceptable carrier or diluent therefor.
9. 9. A method of combating fungi which comprises applying to plants, to the seeds of plants or to the locus of the plants or seeds, a compound according to claim 1 or a composition according to claim 8.