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WO1997011952A1 - Fongicides - Google Patents

Fongicides Download PDF

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Publication number
WO1997011952A1
WO1997011952A1 PCT/GB1996/002230 GB9602230W WO9711952A1 WO 1997011952 A1 WO1997011952 A1 WO 1997011952A1 GB 9602230 W GB9602230 W GB 9602230W WO 9711952 A1 WO9711952 A1 WO 9711952A1
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WO
WIPO (PCT)
Prior art keywords
compound
alkyl
formula
phenyl
halogen
Prior art date
Application number
PCT/GB1996/002230
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 AU69356/96A priority Critical patent/AU6935696A/en
Publication of WO1997011952A1 publication Critical patent/WO1997011952A1/fr

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Classifications

    • 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
    • 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

Definitions

  • the present invention provides pyrazolylborane 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-organisms.
  • 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.
  • R is C 1-4 alkyl, C 1-4 haloalkyl, C 2-4 alkenyl, C 2-4 haloalkenyl, C 3 .7 cycloalkyl, C 3-7 cycloalkyl(C 1-4 )alkyl, benzyl or phenyl, wherein benzyl and phenyl are optionally substituted by halogen, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy or C 1-4 haloalkoxy; and R 1 , R 2 , R 3 and R 4 are, independently, hydrogen, C 1-8 alkyl, C 1-8
  • Alkyl, alkoxy and alkylthio groups are straight or branched chain and, for example, methyl, ethyl, n-propyl, iso-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, C 1-4 alkyl, or C 1-4 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 1-4 alkyl (especially methyl).
  • R 1 and R 2 or R 2 and R 3 join to form a ring
  • the ring formed is carbocyclic or heterocyclic (preferably comprising 1, 2 or 3 heteroatoms independently selected from nitrogen, oxygen and sulphur) and is, optionally, aromatic.
  • the ring is preferably a 5- or 6- membered ring.
  • R 1 and R 2 or R 2 and R 3 together with the ring to which they are attached, may join to form a benzene, cyclohexane, pyridine or imidazole ring.
  • the present invention provides a compound of formula (I) wherein R 1 , R 2 , R 3 and R 4 are, independently, hydrogen, C 1-8 alkyl, C 1-8 haloalkyl, halogen, COR 7 or phenyl; R 1 and R 2 or R 2 and R 3 may join together to form a ring, the ring being optionally substituted by halogen, C 1-4 alkyl, C 1-4 haloalkyl or nitro; provided that at least one of R 1 and R 4 is hydrogen.
  • the present invention provides a compound of formula (I) wherein R is C 1-4 alkyl (especially methyl or ethyl), C 2-4 alkenyl (especially vinyl), phenyl or C 3- 6 cycloalkyl (especially cyclopropyl); A 1 and A 2 are both phenyl (optionally substituted with halogen (especially fluorine) or C 1-4 alkyl (especially methyl)), 2-thienyl or 3-furanyl; R 1 , R 2 , R 3 and R 4 are, independently, hydrogen, halogen (especially chlorine or bromine), C 1-4 alkyl (especially methyl or ethyl), NO 2 , NH 2 , N(CH 3 ) 2 , C 1-4 haloalkyl (especially trifluoromethyl), benzyl or COR 7 (wherein R 7 is C 1-4 alkyl (especially methyl)); or R 1 and R 2 join to form a ring (R 1 and R 2 especially join to form the group C(
  • the present invention provides a compound of formula (I) wherein R is C 1-4 alkyl (especially methyl); A 1 and A 2 are both unsubstituted phenyl; R 1 is hydrogen, C 1-4 alkyl (especially methyl), phenyl or COR 7 ; R 2 , R 3 and R 4 are, independently, hydrogen, Cn alkyl (especially methyl), halogen (especially bromine), phenyl or COR 7 ; provided that at least one of R 1 or R 4 is hydrogen; and R 7 is C 1-4 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 RMgX, wherein R is as defined above and X is chlorine, bromine or iodine, and reacting the product formed with a compound of formula (III):
  • R 1 , R 2 , R 3 , and R 4 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).
  • a suitable solvent such as an ether (for example tetrahydrofuran or diethyl ether).
  • a compound of formula (I) can be prepared by reacting a compound of formula (IV): wherein R, A 1 and A 2 are as defined above, with a compound of formula (III) 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 1 and A 2 are as defined above, with a compound of formula (III) (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)
  • a compound of formula (I) can be prepared by reacting a compound of formula (VI):
  • a 1 and A 2 are as defined above and R* is C 1-4 alkoxy, with a Grignard reagent of formula RMgX (as hereinbefore described), and reacting the product formed with a compound of formula (III) (as hereinbefore described).
  • a Grignard reagent of formula RMgX (as hereinbefore described)
  • reacting the product formed with a compound of formula (III) (as hereinbefore described).
  • 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 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 1-4 alkyl)borate with a
  • Grignard reagent A 1 MgX or sequential addition of Grignard reagents A 1 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 about O°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, thiophe ⁇ e or furan compound using an alkyl lithium (such as n-butyl lithium), and reacting the product with a tri( C 1-4 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).
  • an alkyl lithium such as n-butyl lithium
  • a tri( C 1-4 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 of the 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.
  • 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 (e.g. 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 Leptosphaeria nodorum
  • Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals (e.g. wheat, barley, rye), turf and other hosts
  • Cercospora arachidicola and Cercospo ⁇ dium personatum on peanuts and other Cercospora species on other hosts for example, sugar beet, bananas, soya beans and rice
  • Botrytis cinerea grey mould
  • Alternaria 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.
  • Pseudoperonospora cubensis on cucurbits Pythium 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.
  • 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,
  • 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-bome disease of wheat), Ustilago spp. and Helminthosporium spp. on cereals, Rhizoctonia solani on cotton and Pyricularia oryzae on rice.
  • pathogens including Fusarium spp., Septoria spp., Tilletia spp., (e.g. bunt, a seed-bome 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. 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 but are more
  • 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 0.1g to 10kg, preferably lg to 8kg, more preferably lOg to 4kg, of active ingredient (invention compound) per hectare.
  • the compounds of the invention When used as seed dressings, the compounds of the invention are used at rates of 0.0001g (for example 0.001g 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.
  • 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.
  • 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.
  • compositions may be in the form of dustable powders or granules comprising the active ingredient (invention compound) and a solid 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 solid 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 application to the soil without further treatment.
  • These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler.
  • compositions for dressing seed 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
  • 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 form 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.
  • polar solvents such as ketones, alcohols and glycol ethers.
  • 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 of the 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 incorporating, for example coated with, a compound of formula (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 formula (I).
  • 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
  • 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
  • Suitable suspending agents are hydrophilic colloids (for example, polyvinylpyrrolidone and sodium
  • 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.
  • aqueous 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.
  • 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 formula (I) alone.
  • fungicidal compounds which may be included in the composition of the invention are (RS)-1-aminopropylphosphonic acid, (RS)- 4-(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4-triazoI-1-ylmethyl)butyronitrile, (Z)-N-but-2-enyloxymethyl-2-chloro-2',6'-diethylacetanilide, 1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea, 4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile, 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamide, 5-ethyl-5,8-dihydro
  • 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 solid 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 solid diluent or carrier for example kaolin, bentonite, kieselguhr, or talc
  • granules wherein the active ingredient is absorbed in a porous granular material for example pumice.
  • 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 of the 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.
  • 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.
  • 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
  • THFA tetrahydrofurfuryl alcohol
  • 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 of the 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 of the active ingredient or ingredients. When diluted to form aqueous preparations such preparations may contain varying amounts of the active ingredient depending upon the purpose for which they are to be used. For agricultural or horticultural purposes, an aqueous preparation containing between 0.0001% and 0.1% by weight of the active ingredient (approximately equivalent to from 5-2000g/ha) is particularly useful.
  • 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. Additionally 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
  • pirimicarb cloethocarb, carbofuran, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur or oxamyl
  • aryl carbamates such as pirimicarb, cloethocarb, carbofuran, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur or oxamyl
  • Organic tin compounds such as cyhexatin, fenbutatin oxide, or azocyclotin;
  • Macrolides such as avermectins or milbemycins, for example such as abamectin,
  • Hormones such as pheromones
  • Organochlorine compounds such as benzene hexachloride, DDT, chlordane or dieldrin; 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.
  • 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, hydroprcne, chlorfluazuron and diflubenzuron may also be included in the compositions.
  • ovo-larvicides such as clofentezine, flubenzimine, hexythiazox and tetradifon
  • acaricides such as dicofol, propargite, bromopropylate, chlorobenzilate
  • growth regulators such as hydramethylnon, cyromazine, methoprene, hydroprcne, chlorfluazuron and diflubenzuron
  • 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.
  • 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 of the pests in their adult and immature stages of growth, and may be applied to the infested host animal by topical, oral or parenteral administration.
  • organophosphate, pyrethroid or cyclodiene for example lindane or dieldrin
  • the compounds of formula (I) can be used to control one or more of the following micro-organisms: Aspergillus niger, Aureobasidium pullulans, Candida albicans,
  • Pseudomonas aeruginose or Staphylococcus aureus Pseudomonas aeruginose or Staphylococcus aureus.
  • Systems in which micro-organisms cause problems include liquid, 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 solid 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 of the 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) 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 medium to be protected is a solvent-based paint, lacquer or varnish
  • 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
  • the carrier is preferably water or a water-miscible organic solvent or mixture thereof.
  • suitable water-miscible organic solvents are acetic acid, N,N-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 1-4 alkyl carbitols (such as methyl carbitol).
  • 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 mixture typically contains from 1 to 99% by weight, and preferably from 40 to 60% by weight, of a compound of formula (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, N,N-dimethyl-N,N-didecylammonium chloride, N,N-dimethyl-N,N-didodecylammonium chloride, N,N,N-trimethyl-N-tetradecylammonium chloride, N-benzyl-N,N-dimethyl-N(C 12 -C 18 -alkyl)ammonium chloride, N-(dichlorobenzyl)-N,N-dimethyl-N-dodecylammonium chloride, N-hexadecylpyridinium chloride; N-hexadec
  • oxazolidine derivatives such as bis-oxazolidine; furan derivatives such as 2,5-dihydro-2,5-dialkoxy-2,5-dialkylfuran; carboxylic acids or salts or esters thereof such as sorbic acid and 4-hydroxybenzoic acid or their salts or esters; phenol derivatives such as 5-chloro-2-(2,4-dichlorophenoxy)phenol, thio-bis(4-chlorophenol) and 2-phenylphenol; sulphone derivatives such as diiodomethyl-p-tolyl sulphone, 2,3,5,6-tetrachloro-4-(methylsulphonyl)pyridine and hexachlorodimethyl sulphone; thioamides such as dimethyldithiocarbamate, ethylenebisdithiocarbamate and 2-mecaptopyridine-N-oxide or metal complexes thereof; and imides such as trict-loromethylmercaptophthalimide, fi
  • Methylmagnesium bromide (3.0 M solution in diethyl ether; 20 ml, 60 mmol) was added to a solution of diphenylborinic acid ethanolamine ester (4.5 g, 20 mmol) in
  • Methylmagnesium bromide 49.8ml of a 2.7M solution in diethyl ether was added to a stirred solution of diphenylborinic acid ethanolamine ester (10.0g) 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.
  • the compounds were tested against a variety of foliar fungal diseases of plants.
  • the technique employed was as follows.
  • 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
  • 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:
  • 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 sporulating cultures of the 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. Each flask was swirled so that the beads removed the spores and the resulting suspension was poured into a sterile 100gm medical flat bottle containing approximately 50 ml of the sterile 0.01 % v/v solution of TWEEN 80. The suspension was storable for up to four weeks at 4°C. The compounds of formula (I) were tested against the micro-organisms listed in the footnote to Table III. The data presented in Table III show the minimum concentration required for complete control of each micro-organism.
  • French bean plants were selected with fully developed primary 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)
  • Agricultural Chemicals And Associated Chemicals (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 C¿1?-C4 alkyle, un C1-C4 alkoxy, un C1-C4 alkylthio, un C1-C4 haloalkyle, un C1-C4 haloalkoxy ou un C1-C4 haloalkylthio; R représente un C1-C4 alkyle, un C1-C4 haloalkyl, un C2-C4 alcényle, un C2-C4 haloalcényle, un C3-C7 cycloalkyle, un C3-C7 cycloalkyle(C1-C4) alkyle, un benzyle ou un phényle, ces deux derniers étant, éventuellement, substitués par un halogène, un C1-C4 alkyle, un C1-C4 haloalkyle, un C1-C4 alkoxy, ou un C1-C4 haloalkoxy. Dans cette formule, R?1, R2, R3 et R4¿ représentent, indépendamment, un hydrogène, un C¿1?-C8 alkyle, un C1-C8 haloalkyle, un C1-C8 alkoxy, un C1-C8 haloalkoxy, un halogène, un nitro, COR?7, NR5R6¿, un benzyle ou un phényle (le benzyle et le phényle étant éventuellement substitués par un halogène, un C¿1?-C4 alkyle, un C1-C4 haloalkyle, un C1-C4 alkoxy, un C1-C4 haloalkoxy ou par NR?5R6), R1 et R2 ou R2 et R3¿ peuvent être réunis pour constituer un composé cyclique, pouvant éventuellement être substitué par un halogène, un C¿1?-C4 alkyle, un C1-C4 haloalkyle, un C1-C4 alkoxy, un C1-C4 haloalkoxy ou un nitro, R?5, R6 et R7¿ représentent, indépendamment, un hydrogène ou un C¿1?-C4 alkyle, à la condition que R?1 ou R4¿, ou bien les deux, représente un hydrogène.
PCT/GB1996/002230 1995-09-25 1996-09-10 Fongicides WO1997011952A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU69356/96A AU6935696A (en) 1995-09-25 1996-09-10 Fungicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB9519515.2A GB9519515D0 (en) 1995-09-25 1995-09-25 Fungicides
GB9519515.2 1995-09-25

Publications (1)

Publication Number Publication Date
WO1997011952A1 true WO1997011952A1 (fr) 1997-04-03

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PCT/GB1996/002230 WO1997011952A1 (fr) 1995-09-25 1996-09-10 Fongicides

Country Status (4)

Country Link
AU (1) AU6935696A (fr)
GB (1) GB9519515D0 (fr)
WO (1) WO1997011952A1 (fr)
ZA (1) ZA967771B (fr)

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 (2)

* 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 *
LAPKIN I I ET AL: "Study of the complexing of organoboron compounds. XXI. Complexing of triarylboranes with pyrazole series compounds", ZH. OBSHCH. KHIM. (ZOKHA4,0044460X);82; VOL.52 (12); PP.2772-8, PERM. GOS. UNIV.;PERM; USSR (SU), XP002020363 *

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AU6935696A (en) 1997-04-17
GB9519515D0 (en) 1995-11-29

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