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WO1997011951A1 - Fongicides - Google Patents

Fongicides Download PDF

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Publication number
WO1997011951A1
WO1997011951A1 PCT/GB1996/002228 GB9602228W WO9711951A1 WO 1997011951 A1 WO1997011951 A1 WO 1997011951A1 GB 9602228 W GB9602228 W GB 9602228W WO 9711951 A1 WO9711951 A1 WO 9711951A1
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WO
WIPO (PCT)
Prior art keywords
thienyl
compound
furanyl
alkyl
formula
Prior art date
Application number
PCT/GB1996/002228
Other languages
English (en)
Inventor
Kevin Robert Lawson
William Roderick Mound
William Guy Whittingham
Original Assignee
Zeneca Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zeneca Limited filed Critical Zeneca Limited
Priority to AU69354/96A priority Critical patent/AU6935496A/en
Publication of WO1997011951A1 publication Critical patent/WO1997011951A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/08—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing boron

Definitions

  • FUNGICIDES The present invention provides pyrimidinylborane derivatives of formula (I), processes for their preparation, compositions comprising them and methods of using them to combat fungi (especially fungal infections of plants), insects, acarine pests, nematodes, mites or micro-organisims.
  • the present invention provides a compound of formula (I)
  • a 1 and A 2 are, independently, phenyl, furyl or thienyl each optionally substituted by halogen, CM alkyl, CM alkoxy, CM alkylthio, C haloalkyl, C haloalkoxy or C M haloalkylthio;
  • R is C M alkyl, C M haloalkyl, C 2 -4 alkenyl, C 2 ⁇ haloalkenyl, C 3-7 cycloalkyl, C 3 .7 cycloalkyl(C M )alkyl, benzyl or phenyl, wherein benzyl and phenyl are optionally substituted by halogen, C alkyl, C haloalkyl, C M alkoxy or C haloalkoxy; and R'and R : are, independently, hydrogen, Ci-g alkyl, C ⁇ -g haloalkyl, C ⁇ - 8 alkoxy, Ci.g haloalk
  • R 1 and R 2 join together to form ring, the ring being optionally subsututed by halogen, C M alkyl, C haloalkyl, alkoxy, C haloalkoxy or nitro; and R s , R 6 and R 7 are independently hydrogen or C M alkyl.
  • Alkyl, alkoxy and alkylthio groups are straight or branched chain and are, for example, methyl, ethyl, ⁇ -propyl, zjo-propyl, n-butyl or tert-butyl.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Alkenyl is, for example, vinyl or allyl.
  • Cycloalkyl is, for example, cyclopropyl, cyclopentyl or cyclohexyl.
  • the present invention provides a compound of formula (I) wherein A 1 and A 2 are, independently, phenyl optionally substituted by halogen, CM alkyl, or C haloalkyl.
  • the present invention provides a compound of formula (I) wherein A 1 and A 2 are both unsubstituted phenyl.
  • the present invention provides a compound of formula (I) wherein R is C alkyl (especially methyl).
  • R 1 and R 2 join to form a ring, the ring formed is carbocyclic or heterocyclic
  • the ring is preferably a 5- or 6-membered ring.
  • R 1 and R 2 together with the ring to which they are attached, may join to form a benzene, cyclohexene, pyridine or imidazole ring.
  • the present invention provides a compound of formula (I) wherein
  • R'and R 2 are independently, hydrogen, C
  • the present invention provides a compound of formula (I) wherein R is C M alkyl (especially methyl or ethyl), C 2 ⁇ alkenyl (especially vinyl), C 3- ⁇ cycloalkyl
  • R 1 and R 2 are, independently, hydrogen, C alkyl (especially methyl), phenyl, C x ⁇ alkoxy (especially methoxy), NH 2 , halogen (especially bromine) or COR 7 (wherein R 7 is C M alkyl (especially methyl or tert-butyl)); or R 1 and R 2 join to form a ring (R 1 and R 2 preferably join to form CHCHCHCH, CHCHCFCH, CHCHCC1CH, CH 2 CH 2 CH 2 CH 2 or NCHNH).
  • the present invention provides a compound of formula (I) wherein R is C alkyl (especially methyl); A 1 and A 2 are both unsubstituted phenyl; R 1 is hydrogen, C M alkyl (especially methyl), phenyl or COR 7 ; R 2 is hydrogen, C alkyl (especially methyl), halogen (especially bromine), phenyl or COR 7 ; and R 7 is C alkyl (especially methyl).
  • a compound of formula (I) can be prepared by reacting a compound of formula (II):
  • a 1 and A 2 are as defined above, with a Grignard reagent of formula R Mg X, wherein R is as defined above and X is chlorine, bromine or iodine, and reacting the product formed with a compound of formula (DI):
  • R'and R 2 are as defined above. It is preferred that the reaction of RMgX with a compound of formula (II) is carried out at a temperature in the range -30 to 20°C (such as about O°C). It is preferred that this preparation is carried out in a suitable solvent, such as an ether (for example tetrahydrofuran or diethyl ether). Alternatively a compound of formula (I) can be prepared by reacting a compound of formula (IV):
  • R, A 1 and A 2 are as defined above, with a compound of formula (IH) as defined above. It is preferred that this process is carried out at room temperature and in the presence of a solvent (such as an ether, for example diethyl ether).
  • a solvent such as an ether, for example diethyl ether.
  • R, A and A are as defined above, with a compound of formula (D3) (as hereinbefore described) in a suitable solvent (such as a chlorinated solvent, for example dichloromethane) and at a suitable temperature (for example ambient temperature).
  • a suitable solvent such as a chlorinated solvent, for example dichloromethane
  • a compound of formula (V) can be prepared by reacting a compound of formula (II) (as hereinbefore described) with a Grignard reagent of formula RMgX (as hereinbefore described), and reacting the product formed with ammonia and ammonium chloride solution sequentially.
  • R wherein A 1 and A 2 are as defined above and R* is C alkoxy, with a Grignard reagent of formula RMgX (as hereinbefore described), and reacting the product formed with a compound of fo ⁇ nula (IE) (as hereinbefore described).
  • a Grignard reagent of formula RMgX (as hereinbefore described)
  • IE fo ⁇ nula
  • the reaction of RMgX with a compound of formula (VI) is carried out at a temperature in the range -30 to 20°C (such as about O°C). It is preferred that this preparation is carried out in a suitable solvent, such as an ether (for example tetrahydrofuran or diethyl ether).
  • a compound of formula (VI) can be prepared by reacting a tri(C alkyl)borate with a Grignard reagent A'MgX or sequential addition of Grignard reagents A'MgX and A 2 MgX, wherein A 1 , A 2 and X are as defined above. It is preferred that this reaction is carried out at a temperature in the range -30 to 20°C (such as 0°C) and in a suitable solvent, such as an ether (for example tetrahydrofuran or diethyl ether).
  • a suitable solvent such as an ether (for example tetrahydrofuran or diethyl ether).
  • a compound of formula (VI) can be prepared by deprotonating a suitable phenyl, thiophene or furan compound using an alkyl lithium (such as n-butyl lithium), and reacting the product with a tri(C
  • an alkyl lithium such as n-butyl lithium
  • -4 alkyl)borate it is preferred that this reaction is carried out at a temperature in the range -80 to 10°C (especially -80 to 0°C), and that it is conducted in a suitable solvent (such as tetrahydrofuran).
  • the present invention provides processes, as hereinbefore described, for preparing the compounds of formula (I).
  • the compounds of formula (I) are active fungicides and may be used to control one or more ofthe following pathogens: Pyricularia oryzae on rice and wheat and other Pyricularia spp. on other hosts; Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts e.g.
  • Leptosphaeria nodorum Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals (e.g. 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; Botryiis cinerea (grey mould) on tomatoes, strawberries, vegetables, vines and other hosts and other Botrytis spp. on other hosts; Altemaria spp. on vegetables (e.g. cucumber), oil-seed rape, apples, tomatoes, cereals (e.g.
  • 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 (e.g. 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.
  • Ramularia spp. on sugar beet and other hosts post-harvest diseases particularly of fruit (e.g. Pencillium digitatum and P. italicum and Trichoderma 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 Cephaloascus fragrans, Ceratocystis spp., Ophiostoma piceae, Penicillium spp., Trichoderma pseudokoningii, Trichoderma viride, Trichoderma harzianum, Aspergillus niger, Leptographium lindbergi and
  • Polymyxa graminis on cereals as the vector of barley yellow mosaic virus (BYMV).
  • BYMV barley yellow mosaic virus
  • some of the compounds may be useful as seed dressings against pathogens including Fusarium spp., Septoria spp., Tilletia spp., (e.g. bunt, a seed-borne disease of wheat), Ustilago spp. and Helminthosporium spp. on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on rice.
  • some of the compounds show good eradicant activity against Pythium ultimum.
  • the compounds may move acropetally/locally in plant tissue.
  • 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 but are more conveniently formulated into compositions using a carrier or diluent.
  • the invention thus provides fungicidal compositions comprising a compound as hereinbefore defined and an acceptable carrier or diluent therefor. It is preferred that all compositions, both solid and liquid formulations, comprise 0.0001 to 95%, more preferably 1 to 85%, for example 1 to 25% or 25 to 60%, of a compound as hereinbefore defined.
  • the compounds of the invention When applied to the foliage of plants, the compounds of the invention are applied at rates of O.lg to 10kg, preferably lg to 8kg, more preferably lOg to 4kg, of active ingredient (invention compound) per hectare. When used as seed dressings, the compounds of the invention are used at rates of
  • O.OOOlg (for example O.OOlg or 0.05g) to lOg, 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.
  • Apphcation 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.
  • plant as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method ofthe 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.
  • compositions may be in the form of dustable powders or granules comprising the active ingredient (invention compound) and a sohd diluent or carrier, for example, fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fuller's earth, gypsum, diatomaceous earth and china clay.
  • a sohd diluent or carrier for example, fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, fuller's earth, gypsum, diatomaceous earth and china clay.
  • Such granules can be preformed granules suitable for apphcation to the soil without further treatment.
  • These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdere
  • compositions for dressing seed may include an agent (for example, a mineral oil) for assisting the adhesion of the composition to the seed; altematively the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example, N-methylpyrrolidone, propylene glycol or NN-dimethylformamide).
  • the compositions may also be in the form of water dispersible powders or water dispersible granules comprising wetting or dispersing agents to facilitate the dispersion in liquids.
  • the powders and granules may also contain fillers and suspending agents.
  • compositions may also be in the form of soluble powders or granules, or in the fo ⁇ n of solutions in polar solvents.
  • Soluble powders may be prepared by mixing the active ingredient with a water-soluble salt such as sodium bicarbonate, sodium carbonate, magnesium sulphate or a polysaccharide, and a wetting or dispersing agent 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 the active ingredient in an organic solvent optionally containing a wetting or emulsifying agent and then adding the mixture to water which may also contain a wetting or emulsifying agent.
  • organic solvents are aromatic solvents such as alkylbenzenes and alkylnaphthalenes, ketones such as cyclohexanone and methylcyclohexanone, chlorinated hydrocarbons such as chlorobenzene and trichlorethane, 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 a suspending agent included to stop the 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 propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.
  • a propellant e.g. fluorotrichloromethane or dichlorodifluoromethane.
  • 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.
  • the 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.
  • suitable additives for example additives for improving the uptake, distribution, adhesive power and 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 ofthe various formulations.
  • Such additives can be surface active materials to improve the wetting and retention on surfaces treated with the formulation and also the uptake and 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 adjuvants.
  • the invention compounds can be used as mixtures with fertilisers (e.g. nitrogen-, potassium- or phosphorus-containing fertilisers).
  • fertilisers e.g. nitrogen-, potassium- or phosphorus-containing fertilisers.
  • Compositions comprising only granules of fertiliser inco ⁇ orating, for example coated with, a compound of fo ⁇ nula (I) are preferred. 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 general formula (I) or a salt or metal complex thereof.
  • Water dispersible powders, emulsifiable concentrates and suspension concentrates will normally contain surfactants, e.g. a wetting agent, dispersing agent, emulsifying agent or suspending agent. These agents can be cationic, anionic or non-ionic agents.
  • Suitable cationic agents are quaternary ammonium compounds, for example, cetyltrimethylammonium bromide.
  • Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example, sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example, sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropylnaphthaiene 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, polyvinylpy ⁇ olidone 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.
  • compositions of this invention may contain other compounds having biological activity, e.g. compounds having similar or complementary fungicidal activity or which possess plant growth regulating, herbicidal or insecticidal activity.
  • the resulting composition can have a broader spectrum of activity or a greater level of intrinsic activity than the compound of general formula (I) alone. Further the other fungicide can have a synergistic effect on the fungicidal activity of the compound of general formula (I).
  • fungicidal compounds which may be included in the composition of the invention are (RS)-l-aminopropylphosphonic acid, (RS)- 4-(4-chlorophenyI)-2-phenyl-2-( IH- 1 ,2,4-triazol- 1 -ylmethyl)butyronitrile, (Z)-N-but-2- enyloxymethyl-2-chloro-2',6'-diethylacetanilide, l-(2-cyano-2-methoxyiminoacetyl)-3-ethyI urea, 4-(2,2-difluoro- 1 ,3-benzodioxol-4-yl)pyr ⁇ ole-3-carbonitrile, 4-bromo-2-cyano-NN- -.-ime yl-6-trifluoromethylbenzi.n idazole- 1 -sulphonamide, 5-ethyl-5,8-dihydro-8-oxo ( 1 ,3)-
  • the compounds of general formula (I) can be mixed with soil, peat or other rooting media for the protection of plants against seed-bome, soil-borne or foliar fungal diseases.
  • the compounds of formula (I) may also be used to combat and control infestations of insect pests and also other invertebrate pests, for example, acarine pests.
  • insect and acarine pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, forestry, the storage of products of vegetable origin, such as fruit, grain and timber, and also those pests associated with the transmission of diseases of man and animals.
  • compositions which include in addition to the insecticidally active ingredient or ingredients of formula (I) suitable inert diluent or carrier materials, and/or surface active agents.
  • suitable inert diluent or carrier materials and/or surface active agents.
  • the compositions may also comprise another pesticidal material, for example another insecticide or acaricide, or a fungicide, or may also comprise an insecticide synergist, such as for example dodecyl imidazole, safroxan, or piperonyl butoxide.
  • compositions may be in the form of dusting powders wherein the active ingredient is mixed with a sohd diluent or carrier, for example kaolin, bentonite, kieselguhr, or talc, or they may be in the form of granules, wherein the active ingredient is absorbed in a porous granular material for example pumice.
  • a sohd diluent or carrier for example kaolin, bentonite, kieselguhr, or talc
  • compositions may be in the form of baits wherein the active ingredient is mixed with a nutrient carrier for example sucrose, yeast, malt extract, cereal or cereal products and optionally an attractant such as a pheromone or pheromone analogue.
  • a nutrient carrier for example sucrose, yeast, malt extract, cereal or cereal products
  • an attractant such as a pheromone or pheromone analogue.
  • compositions may be in the form of liquid preparations to be used as dips or sprays, which are generally aqueous dispersions or emulsions ofthe active ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifying agents (surface active agents) of the type described above for the fungicidal compositions.
  • the insecticidal compositions may be prepared by dissolving the active ingredient in a suitable solvent, for example, a ketonic solvent such as diacetone alcohol, or an aromatic solvent such as trimethylbenzene and adding the mixture so obtained to water which may contain one or more known wetting, dispersing or emulsifying agents.
  • Suitable organic solvents are dimethyl formamide, ethylene dichloride, isopropyl alcohol, propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, white oil, methylnaphthalene, xylenes and trichloroethylene, N-methyl-2- pyrrolidone and tetrahydrofurfuryl alcohol (THFA).
  • the insecticidal compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion ofthe active ingredient or ingredients, the said concentrate to be diluted with water before use.
  • These concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • the concentrates may contain 10-85% by weight ofthe active ingredient or ingredients.
  • When diluted to form aqueous preparations such preparations may contain varying amounts of the active ingredient depending upon the pu ⁇ ose for which they are to be used.
  • insecticidal compositions are applied to the pests, to the locus of the pests, to the habitat of the pests, to growing plants liable to infestation by the pests, or, where there is systemic uptake by plants, to the soil surrounding plants liable to infestation, by any of the known means of applying pesticidal compositions, for example, by dusting or spraying.
  • the compounds of the invention may be the sole active ingredient of the insecticidal composition or they may be admixed with one or more additional active ingredients such as insecticides, insecticide synergists, herbicides, fungicides or plant growth regulators where appropriate.
  • Suitable additional active ingredients for inclusion in admixture with the compounds of the invention may be compounds which will broaden the spectrum of activity of the compounds of the invention or increase their persistence in the location of the pest. They may synergise the activity of the compound of the invention or complement the activity for example by increasing the speed of effect, improving knockdown or overcoming repellency.
  • multi-component mixtures of this type may help to overcome or prevent the development of resistance to individual components.
  • insecticide insecticide, herbicide or fungicide included in the mixture will depend upon its intended utility and the type of complementary action required.
  • suitable insecticides include the following:
  • Pyrethroids such as permethrin, esfenvalerate, deltamethrin, cyhalothrin in particular lambda-cyhalothrin, cypermethrin, alpha cypermethrin, bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids for example ethofenprox, natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin, or
  • Organophosphates such as profenofos, sulprofos, methyl parathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon, fenamiphos, monocrotophos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chloropyrifos, phosalone, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, fenitrothion or diazinon; • Carbamates (including aryl carbamates) such as pirimicarb, cloethocarb, carbofuran, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur or oxamyl;
  • Benzoyl ureas such as triflumuron, or chlorfluazuron
  • Organic tin compounds such as cyhexatin, fenbutatin oxide, or azocyclotin
  • Macrolides such as avermectins or milbemycins, for example such as abamectin, ivermectin, and milbemycin;
  • Hormones such as pheromones
  • Organochlorine compounds such as benzene hexachloride, DDT, chlordane or dieldri ⁇ ; or • Amidines, such as chlordimeform or amitraz.
  • insecticides having particular targets may be employed in the mixture if appropriate for the intended utility of the mixture.
  • selective insecticides for particular crops for example stemborer specific insecticides for use in rice such as cartap or buprofezin can be employed.
  • Altematively insecticides specific for particular insect species/stages for example ovo-larvicides such as clofentezine, flubenzimine, hexythiazox and tetradifon, acaricides such as dicofol, propargite, bromopropylate, chlorobenzilate, or growth regulators such as hydramethylnon, cyromazine, methoprene, hydroprene, chlorfluazuron and diflubenzuron may also be included in the compositions.
  • suitable insecticide synergists for use in the compositions include piperonyl butoxide, sesamex, and dodecyl imidazole.
  • Suitable herbicides, fungicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
  • An example of a rice selective herbicide which can be included is propanil, an example of a plant growth regulator for use in cotton is "Pix", and examples of fungicides for use in rice include blasticides such as blasticidin-S.
  • the ratio of the compound of the invention to the other active ingredient in the composition will depend upon a number of factors including type of target, effect required from the mixture etc. However in general, the additional active ingredient of the composition will be applied at about the rate as it is usually employed, or at a slightly lower rate if synergism occurs.
  • the compounds of formula (I) and insecticidal compositions comprising them may also be active against organophosphate, pyrethroid or cyclodiene (for example lindane or dieldrin) resistant strains of public and animal health pests. They may be effective in combating both susceptible and resistant strains ofthe pests in their adult and immature stages of growth, and may be applied to the infested host animal by topical, oral or parenteral administration.
  • the compounds of formula (I) can be used to control one or more of the following micro-organisms: Aspergillus niger, Aureobasidium pullulans, Candida albicans, Gliocladium roseum, Pencillium pinophylum, Bacillus subtilis, Escherichia coli, Pseudomonas aeruginose or Staphylococcus aureus.
  • Systems in which micro-organisms cause problems include hquid, particularly aqueous, systems such as cooling water liquors, paper mill liquors, metal working fluids, geological drilling lubricants, polymer emulsions and especially surface coating compositions such as paints, varnishes and lacquers and more especially sohd materials such as wood, plastics materials and leather.
  • the compounds of formula (I) can be used as disinfectants (especially for solid surfaces).
  • a compound of formula (I) can be included in such materials to provide an anti-microbial effect.
  • the amount ofthe compound is typically in the range of 0.00001 to 2.0% preferably from 0.0001 to 1% and especially from 0.0002 to 0.5% by weight of the compound relative to the system to which it is added.
  • the invention therefore provides a method of combating the growth of micro ⁇ organisms which comprises applying a compound of formula (I) to a surface or providing a compound of formula (I) to the locus of a surface, said surface being susceptible to micro ⁇ organism growth.
  • a compound of formula (I) When used to control micro-organisms, a compound of formula (I) may be used directly or formulated in a composition comprising a carrier or diluent.
  • the carrier is generally selected so that the composition is compatible with the medium to be protected.
  • the carrier is preferably a solvent especially a non-polar solvent such as white spirits.
  • the carrier is preferably a plasticiser or stabiliser typically used in the fabrication of plastics articles such as dioctylphthalate, dioctyladipate or epoxidised soya bean oil.
  • the carrier is preferably water or a water-miscible organic solvent or mixture thereof.
  • suitable water-miscible organic solvents are acetic acid, NN- dimethylformamide, dimethylsulphoxide, N-methyl-2-pyrrolidine, alcohols (such as ethanol or a glycol (such as ethylene glycol, propylene glycol or dipropylene glycol)) or lower C ⁇ alkyl caibitols (such as methyl carbitol). If the carrier is a solid, the composition may be a dry solid.
  • a compound of formula (I) is formulated in a composition including a carrier which is a plasticiser or stabiliser.
  • a biocidal composition comprising a biocidally effective amount of a compound of formula (I) and a biocidally acceptable carrier or diluent therefor. If the biocide composition is in the form of a suspension or emulsion, it preferably also contains a surface active agent to produce a stable dispersion or to maintain the non-continuous phase uniformly distributed throughout the continuous phase.
  • any surface active agent which does not adversely affect the biocidal activity of the compound of formula (I) may be used, such as those hereinbefore recited, for example alkylene oxide adducts of fatty alcohols, alkyl phenols, amines such as ethylene diamine or anionic surfactants such as adducts of naphthol sulphonates and formaldehyde.
  • the concentration of the compound of formula (I) in the biocide composition is preferably up to a level at which the biocide composition is stable under the conditions of storage or transportation and is preferably from 1 to 50%, especially from 5 to 30% and more especially from 10 to 20% by weight relative to the total weight of the biocide composition.
  • the compound of formula (I) may be the only antimicrobial compound used to protect the medium or it may be used together with other compounds having antimicrobial activity.
  • a mixture of anti-microbial compounds hereinafter referred to as a "biocide mixture” often has a broader anti-microbial spectrum and hence is more generally effective than the components of the mixture.
  • the other antimicrobial compound or compounds may possess antibacterial, anti-fungal, anti-algal or other antimicrobial activity.
  • the biocide mixmre typically contains from 1 to 99% by weight, and preferably from 40 to 60% by weight, of a compound of fo ⁇ nula (I) relative to the total weight of an antimicrobially active compound, in the biocide mixture.
  • antimicrobial compounds which may be used, together with the compound of formula (I) are: quaternary ammonium compounds such as N,N-dimethyl-N- dodecyl-N-benzylammonium chloride, NN-dimethyl-N-octadecyl-N-(dimethylbenzyl)- ammonium chloride, NN-dimethyl-N-N-didecylammonium chloride, N,N-dimethyl-N,N- didodecylammonium chloride, N,N,N-trimethyl-N-tetradecylammonium chloride, N-benzyl- NN-d-imethyl-N(C ⁇ 2 -Ci ⁇ -alkyl)ammonium chloride, N-(dichlorobenzyl)-N,N- ⁇ iimethyl-N- dodecylammonium chloride, N-hexadecylpyridinium chloride; N-hexadecy
  • Methylmagnesium bromide (3.0 M solution in diethyl ether; 20 ml, 60 mmol) was added dropwise to a solution of diphenylborinic acid ethanolamine ester (4.5 g, 20 mmol) in tetrahydrofuran (60 ml) at ambient temperature. The resulting solution was stirred at ambient temperature under nitrogen for 2 hours. 4-Phenylpyrimidine (6.24 g, 40 mmol) was added and the reaction mixture stirred under nitrogen at ambient temperature for 20 hours. The solution was acidified by the addition of dilute hydrochloric acid, and the phases separated. The aqueous phase was extracted with ethyl acetate and the combined organic phases dried and evaporated to leave an orange oil. Hexane was added and the resulting mixture filtered to yield the title compound as a pale orange solid (2.93 g). mp 112-116 °C.
  • Methyimagnesium bromide (3.0 M solution in diethyl ether; 20 ml, 60 mmol) was added dropwise to a solution of diphenylborinic acid ethanolamine ester (4.5 g, 20 mmol) in tetrahydrofuran (60 ml) at ambient temperature.
  • Methylmagnesium bromide 49.8ml of a 2.7M solution in diethyl ether was added to a stirred solution of diphenylborinic acid ethanolamine ester ( lO.Og) in dry tetrahydrofuran (150ml) at room temperature. A water bath was used to maintain the temperature at approximately room temperature. The resulting solution was stirred at room temperature for 2 hours. Ammonia gas was then bubbled into the solution, with vigorous stirring, for about 1.75 hours. The reaction mixture was allowed to stand for 4 days.
  • EXAMPLE 6 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 or applied to the roots of the plants in the soil.
  • the sprays were applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a.i. in dry soil.
  • TWEEN 20 was added to give a final concentration of 0.05% when the sprays were applied to cereals.
  • the compounds were applied to the soil (roots) or 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:
  • 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 compounds were tested against a variety of micro-organisms.
  • the technique employed was as follows.
  • a bacterial inoculum consisted of 24 hour cultures of the organisms grown in Oxoid Nutrient broth, subcultured daily and incubated at 37°C. Spore suspensions of each of the test micro-organisms were prepared in the following manner. To 250 ml conical flasks containing sporuiating cultures ofthe micro-organisms, growing on Oxoid Malt extract agar, a number of sterile 3mm glass beads and approximately 50 ml of a sterile solution of TWEEN 80 in water were added.
  • CA Candida albicans GR : Gliocladium roseum
  • PP Pencillium pinophylum (funiculosum)
  • BS Bacillus subtilis
  • EC Escherichia coli
  • PA Pseudomonas aeruginose
  • SA Staphylococcus aureus
  • French bean plants were selected with fully developed primaiy leaves. The growing points and leaf tips were removed, leaving 2 leaves per plant.
  • Adult-infested leaves from a Tetranychus urticae strain G90 culture were placed on the leaves of the selected french beans. The plants were left at 25°C, 60% relative humidity, for a 16 hour photoperiod overnight.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention porte sur un composé de la formule (I) dans laquelle A1 et A2 représentent, indépendamment, un phényle, un furyle ou un thiényle, chacun étant éventuellement substitués par un halogène, un alkyle C¿1?-C4, un alcoxy C1-C4, un alkylthio C1-C4, un haloalkyle C1-C4, un haloalcoxy C1-C4 ou un haloalkylthio C1-C4; R représente un alkyle C1-C4, un haloalkyle C1-C4, un alcényle C2-C4, un haloalcényle C2-C4, un cycloalkyle C3-C7, un cycloalkyle C3-C7 alkyle(C1-C4), un benzyle ou un phényle, ces deux derniers étant éventuellement substitués par un halogène, un alkyle C1-C4, un haloalkyle C1-C4, un alcoxy C1-C4, ou un haloalcoxy C1-C4. Dans cette formule, R?1 et R2¿ représentent indépendamment un hydrogène, un alkyle C¿1?-C8, un haloalkyle C1-C8, un alcoxy C1-C8, un haloalcoxy C1-C8, un halogène, un nitro, COR?7, NR5R6¿ ou un phényle (éventuellement à substitution halogène, alkyle C¿1?-C4, haloalkyle C1-C4, alcoxy C1-C4, haloalcoxy C1-C4 ou NR?5R6¿); ou bien R1 et R2 sont réunis pour constituer un cycle, pouvant éventuellement être substitué par un halogène, un alkyle C¿1?-C4, un haloalkyle C1-C4, un alcoxy C1-C4, un haloalcoxy C1-C4 ou un nitro, R?5, R6 et R7¿ représentent indépendamment un hydrogène ou un alkyle C¿1?-C4.
PCT/GB1996/002228 1995-09-25 1996-09-10 Fongicides WO1997011951A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU69354/96A AU6935496A (en) 1995-09-25 1996-09-10 Fungicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9519514.5 1995-09-25
GBGB9519514.5A GB9519514D0 (en) 1995-09-25 1995-09-25 Fungicides

Publications (1)

Publication Number Publication Date
WO1997011951A1 true WO1997011951A1 (fr) 1997-04-03

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1996/002228 WO1997011951A1 (fr) 1995-09-25 1996-09-10 Fongicides

Country Status (4)

Country Link
AU (1) AU6935496A (fr)
GB (1) GB9519514D0 (fr)
WO (1) WO1997011951A1 (fr)
ZA (1) ZA967770B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006087356A3 (fr) * 2005-02-18 2007-01-11 Janssen Pharmaceutica Nv Compositions antisalissures synergetiques comprenant du (4-isopropylpyridinio)methyldiphenylbore

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62277307A (ja) * 1986-05-12 1987-12-02 Sds Biotech Kk ホウ素化合物を含有する殺虫剤
EP0432987A2 (fr) * 1989-12-14 1991-06-19 Chevron Research And Technology Company Composés fongicides organoboranes-imidazoles et intermédiaires
EP0624315A1 (fr) * 1993-05-07 1994-11-17 American Cyanamid Company Agents fongicides de diaryle (pyridino et isoquinolino) de bore

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62277307A (ja) * 1986-05-12 1987-12-02 Sds Biotech Kk ホウ素化合物を含有する殺虫剤
EP0432987A2 (fr) * 1989-12-14 1991-06-19 Chevron Research And Technology Company Composés fongicides organoboranes-imidazoles et intermédiaires
EP0624315A1 (fr) * 1993-05-07 1994-11-17 American Cyanamid Company Agents fongicides de diaryle (pyridino et isoquinolino) de bore

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 109, no. 25, 19 December 1988, Columbus, Ohio, US; abstract no. 224723, MISU N ET AL: "Insecticidal, miticidal, and nematocidal compositions containing triarylboron amine complexes" XP002020364 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006087356A3 (fr) * 2005-02-18 2007-01-11 Janssen Pharmaceutica Nv Compositions antisalissures synergetiques comprenant du (4-isopropylpyridinio)methyldiphenylbore

Also Published As

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GB9519514D0 (en) 1995-11-29
ZA967770B (en) 1997-03-25
AU6935496A (en) 1997-04-17

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