WO1992011253A1 - Composes pesticides - Google Patents

Composes pesticides Download PDF

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Publication number
WO1992011253A1
WO1992011253A1 PCT/GB1991/002239 GB9102239W WO9211253A1 WO 1992011253 A1 WO1992011253 A1 WO 1992011253A1 GB 9102239 W GB9102239 W GB 9102239W WO 9211253 A1 WO9211253 A1 WO 9211253A1
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WO
WIPO (PCT)
Prior art keywords
compound
formula
methyl
hydrogen
compounds
Prior art date
Application number
PCT/GB1991/002239
Other languages
English (en)
Inventor
John Patrick Larkin
Alexander David Frenkel
Original Assignee
Roussel Uclaf
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 Roussel Uclaf filed Critical Roussel Uclaf
Priority to AU90545/91A priority Critical patent/AU663691B2/en
Priority to KR1019930701820A priority patent/KR930703328A/ko
Priority to JP4501738A priority patent/JPH06504046A/ja
Priority to BR919107168A priority patent/BR9107168A/pt
Priority to CS931142A priority patent/CZ114293A3/cs
Publication of WO1992011253A1 publication Critical patent/WO1992011253A1/fr
Priority to NO93932219A priority patent/NO932219L/no
Priority to FI932766A priority patent/FI932766A0/fi

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/08—Bridged systems
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/08—Six-membered rings

Definitions

  • the present invention relates to novel chemical compounds having pesticidal activity to methods for their preparation, to compositions containing them and to their use in the control of pests. More particularly, the invention relates to a class of sulphur containing heterocycles.
  • the present invention provides a compound of the formula (I):
  • n and n' are the same or different and are each 0, 1 or 2;
  • 1 2 3 is hydrogen or methyl, R is methyl, ethyl or cyclopropyl, R and R are the same or different and are each hydrogen or methyl; R is hydrogen or methyl, R is cyano or R and R are linked to form a group CHpenS(0)m where m is 0, 1 or 2.
  • R is hydrogen. a b When R and R are linked to form a group CHiffS(0)
  • R is ethyl
  • R and R are hydrogen.
  • n, n' are 0. a b
  • R is a hydrogen or methyl and R is cyano:
  • R , R and R are all methyl.
  • R, m, n and n' are as hereinbefore defined and R is as hereinbefore defined and preferably is ethyl.
  • a further preferred group of compounds of the formula (I) is that of the formula (III):
  • R, R , R , R , R , n and n' are as hereinbefore defined.
  • the compounds of the formula (III) may exist as a number of stereoisomers; the present invention relates to mixtures of isomers and the individual isomers themselves.
  • the present invention also encompasses radiolabelled compounds of the formula (I) , particularly
  • Preferred compounds of the formula (I) include: -
  • alkylating agent Suitable alkylating agents include 3,3-dimethylbutyl halides, for example the iodide.
  • the anion of the compound of the formula (IV) is suitably generated from the compound of the formula (IV) in-situ.
  • the reaction is suitably carried out in the presence of a strong base, for example butyllithium, in an inert solvent, for example an ether such as tetrahydrofuran, at a temperature between -100 and 20 C, suitably between -80 and -20 C.
  • the compounds of the formula (IV) wherein R is cyano may be prepared by conversion of the corresponding compound containing an aldehyde function instead of a nitrile group. This conversion may be carried out by the reaction of the aldehyde with a suitable reagent such as 0,N-bis(trifluoroacetyl)-hydroxylamine.
  • This aldehyde is prepared in turn from the 2-unsubstituted dithiane by reaction with a formylating agent, such as dimethylformamide in the presence of a strong base, for example butyllithium.
  • the reaction suitably takes place in an inert solvent, such as a halogenated hydrocarbon, for example dichloromethane, at a non-extreme temperature, e.g. between -100 and 50 C and conveniently at -60 C, in an inert atmos- phere, e.g. nitrogen.
  • a compound tBuCHingCH_CN in the presence of a suitable acid, e.g. hydrogen chloride gas.
  • reaction is suitably carried out in an inert solvent, for example an aromatic hydrocarbon, chlorinated hydrocarbon or an ether and conveniently toluene, dichloromethane or tetrahydrofuran, at a non-extreme temperature, i.e. -70 to 70 C and conveniently at 0°C.
  • an inert solvent for example an aromatic hydrocarbon, chlorinated hydrocarbon or an ether and conveniently toluene, dichloromethane or tetrahydrofuran
  • the compounds of the formula (V) may be prepared from the corresponding compound of the formula (VI):
  • R is a Q. , alkylsulphonyl or arylsulphonyl group, for example a me hanesulphonyl or paratoluenesulphonyl group.
  • reaction with sodium trithionocarbonate followed by sequential acid hydrolysis and reduction.
  • the reaction with sodium trithionocarbonate may be carried out in a solvent, for example a dipolar aprotic solvent such as dimethylformamide at a non-extreme temperature, for example between 10 and 150 C and conveniently between 20 and 130 C.
  • the acid hydrolysis is conveniently carried out using a dilute mineral acid, for example dilute sulphuric or hydrochloric acid at a non-extreme temperature, for example 0 to 100 C and conveniently 20 to 30 C.
  • the reduction is conveniently carried out using a reducing agent such as a metal hydride, for example lithium aluminium hydride, in a non-reactive solvent, for example an ether such as diethyl ether, at a non-extreme temperature, for example between 0 and 100 C and conveniently between 30 and 60 C.
  • a reducing agent such as a metal hydride, for example lithium aluminium hydride
  • a non-reactive solvent for example an ether such as diethyl ether
  • the alkaline hydrolysis is conveniently carried out with an alkali hydroxide such as sodium hydroxide in an aqueous solvent system suitably containing a miscible solvent such as ethanol at a non-extreme temperature, conveniently 0 to 70 C, for example 20 to 30 C.
  • the reduction is suitably carried out using a reducing agent, such as zinc, conveniently zinc powder and hydrochloric acid, conveniently concentrated hydrochloric acid, in a hydrocarbon solvent such as toluene at a non-extreme temperature, conveniently an elevated temperature, for example between 70 C and 120 C.
  • a bisdithiolanedisulphide which is then reduced to the compound of formula (VI) by reaction with a reducing agent such as zinc and hydrochloric acid.
  • the first reaction is conveniently carried out in a protic solvent, for example a C. , alkanol such as ethanol, at a non extreme temperature, for example between 0 C and 100 C and suitably between 60 C and 85 C.
  • the reduction is conveniently carried out with zinc dust and concentrated hydrochloric acid in a hydrocarbon solvent such as toluene at a non-extreme temperature, conveniently an elevated temperature, for example between 70 C and 120 C.
  • the compounds of the formula (I) wherein one or more of m, n and n' is other than 0 may be prepared by oxidation of the corresponding compound of a lower oxidation state.
  • This oxidation is usually carried out in an inert solvent such as acetonitrile or a halogenated hydrocarbon such as chloroform at a non-extreme temperature, for example between 0 and 100 C and preferably between 20 and 30 C.
  • Suitable oxidising agents include peracids such as metachloroperbenzoic acid.
  • the oxidation is conveniently carried out in the presence of a buffer such as anhydrous sodium acetate.
  • Compounds where m is 2 and n and n' are 0 may be prepared from compounds of the formula (I) where m is 0 or 1, using potassium permanganate in a ketone, for example, acetone, at a non extreme temperature for example -30 C to 100 C and conveniently between -10° and 30°C.
  • the compounds of formula (I) may be used to control pests such as arthropods e.g. insect and acarine pests, helminths, i.e. nematodes, and molluscs e.g. slugs.
  • arthropods e.g. insect and acarine pests
  • helminths i.e. nematodes
  • molluscs e.g. slugs.
  • the present invention provides a method for the control of arthropods, helminths and/or molluscs which comprises administering to the arthropod, helminth and/or mollusc or to their environment an effective amount of a compound of the formula (I) .
  • the present invention also provides a method for the control and/or eradication of arthropod, helminth and/or mollusc infestations of animals (including humans) and/or of plants, (including trees) and/or stored products which comprises administering to the animal or locus an effective amount of a compound of the formula (I).
  • the present invention further provides for the compounds of the formula (I) for use in human and veterinary medicine, in public health control and in agriculture for the control of arthropod, helminth and/or mollusc pests.
  • the compounds of formula (I) are of particular value in the protection of field, forage, plantation, glasshouse, orchard and vineyard crops, of ornamentals and of plantation and forest trees, for example, cereals (such as maize, wheat, rice, sorghum), cotton, tobacco, vegetables and salads (such as beans, cole crops, curcurbits, lettuce, onions, tomatoes and peppers), field crops (such as potato, sugar beet, ground nuts, soyabean, oil seed rape), sugar cane, grassland and forage (such as maize, sorghum, lucerne), plantations (such as of tea, coffee, cocoa, banana, oil palm, coconut, rubber, spices), orchards and groves (such as of stone and pip fruit, citrus, kiwifruit, avocado, mango, olives and walnuts), vineyards, ornamental plants, flowers and shrubs under glass and in gardens and parks, forest trees (both deciduous and evergreen) in forests, plantations and nurseries.
  • cereals such as maize
  • the compounds of general formula I are of particular value in the control of arthropods, helminths or molluscs which are injurious to, or spread or act as vectors of diseases in man and domestic animals, for example those hereinbefore mentioned, and more especially in the control of ticks, mites, lice, fleas, midges, biting, nuisance and myiasis flies and snails.
  • the compounds of Formula (I) may be used for such purposes by application of the compounds themselves or in diluted form in known fashion as a dip, spray, fog, lacquer, foam, dust, powder, aqueous suspension, paste, gel, cream, shampoo, grease, combustible solid, vapourising mat, combustible coil, bait, dietary supplement, wettable powder, granule, aerosol, emulsifiable concentrate, oil suspensions, oil solutions, pressure-pack, impregnated article, pour on formulation or other standard formulations well known to those skilled in the art.
  • Dip concentrates are not applied per se. but diluted with water and the animals immersed in a dipping bath containing the dip wash. Sprays may be applied by hand or by means of a spray race or arch.
  • the animal, soil, plant or surface being treated may be saturated with the spray by means of high volume application or superficially coated with the spray by means of light or ultra low volume application.
  • Aqueous suspensions may be applied in the same manner as sprays or dips. Dusts may be distributed by means of a powder applicator or, in the case of animals, incorporated in perforated bags attached to trees or rubbing bars.
  • Pastes, shampoos and greases may be applied manually or distributed over the surface of an inert material, such as that against which animals rub and transfer the material to their skins.
  • Pour-on formulations are dispensed as a unit of liquid of small volume on to the backs of animals such that all or most of the liquid is retained on the animals.
  • the compounds of Formula (I) may be prepared either as formulations ready for use on the animals, plants or surface or as formulations requiring dilution prior to application, but both types of formulation comprise a compound of Formula (I) in intimate admixture with one or more carriers or diluents.
  • the carriers may be liquid, solid or gaseous or comprise mixtures of such substances, and the compound of Formula (I) may be present in a concentration of from 0.025 to 99% w/v depending upon whether the formulation requires further dilution.
  • Dusts, powders and granules and other solid formulations comprise the compound of Formula (I) in intimate admixture with a powdered solid inert carrier for example suitable clays, kaolin, bentonite, attapulgite, adsorbent carbon black, talc, mica, chalk, gypsum, tricalcium phosphate, powdered cork, magnesium siliate, vegetable carriers, starch and diatomaceous earths.
  • a powdered solid inert carrier for example suitable clays, kaolin, bentonite, attapulgite, adsorbent carbon black, talc, mica, chalk, gypsum, tricalcium phosphate, powdered cork, magnesium siliate, vegetable carriers, starch and diatomaceous earths.
  • Such solid formulations are generally prepared by impregnating the solid diluents with solutions of the compound of formula (I) in volatile solvents, evaporating the solvents and, if desired grinding the products so
  • Sprays of a compound of Formula (I) may comprise a solution in an organic solvent (e.g. those listed below) or an emulsion in water (dip wash or spray wash) prepared in the field from an emulsifiable concentrate (otherwise known as a water miscible oil) which may also be used for dipping purposes.
  • the concentrate preferably comprises a mixture of the active ingredient, with or without an organic solvent and one or more emulsifiers.
  • Solvents may be present within wide limits but preferably in an amount of from 0 to 90% w/v of the composition and may be selected from kerosene, ketones, alcohols, xylene, aromatic naphtha, and other solvents known in the formulating art.
  • the concentration of emulsifiers may be varied within wide limits but is preferably in the range of 5 to 25% w/v and the emulsifiers are conveniently non-ionic surface active agents including polyoxyalkylene esters of alkyl phenols and polyoxyethylene derivatives of hexitol anhydrides and anionic surface active agents including Na lauryl sulphate, fatty alcohol ether sulphates, Na and Ca salts of alkyl aryl sulphonates and alkyl sulphosuccinates.
  • Cationic emulsifiers include benzalkoniu chloride and quaternary ammonium ethosuphates.
  • Amphoteric emulsifiers include carboxymethylated oleic imidazoline and alkyl dimethyl betain.
  • Vaporising mats normally comprise cotton and cellulose mix compressed into a board of approximately 35 x 22 x 3mm dimensions, treated with up to 0.3ml of concentrate comprising the active ingredient in an organic solvent and optionally an antioxidant, dye and perfume.
  • the insecticide is vaporised using a heat source such as an electrically operated mat heater.
  • Combustible solids normally comprise of wood powder and binder mixed with the active ingredient and formed into shaped (usually coiled) strips. Dye and fungicide may also be added.
  • Wettable powders comprise an inert solid carrier, one or more surface active agents, and optionally stabilisers and/or anti-oxidants. 253 ' "
  • Emulsifiable concentrates comprise emulsifying agents, and often an organic solvent, such as kerosene, ketones, alcohols, xylenes, aromatic naphtha, and other solvents known in the art.
  • organic solvent such as kerosene, ketones, alcohols, xylenes, aromatic naphtha, and other solvents known in the art.
  • Wettable powders and emulsifiable concentrates will normally contain from 5 to 95% by weight of the active ingredient, and are diluted, for example with water, before use.
  • Lacquers comprise a solution of the active ingredient in an organic solvent, together with a resin, and optionally a plasticiser.
  • Dip washes may be prepared not only from emulsifiable concentrates but also from wettable powders, soap based dips and aqueous suspensions comprising a compound of Formula (I) in intimate admixture with a dispersing agent and one or more surface active agents.
  • Aqueous suspensions of a compound of Formula (I) may comprise a suspension in water together with suspending, stabilizing or other agents.
  • the suspensions or solutions may be applied per se or in a diluted form in known fashion.
  • Greases may be prepared from vegetable oils, synthetic esters of fatty acids or wool fat together with an inert base such as soft paraffin. A compound of Formula (I) is preferably distributed uniformly through the mixture in solution or suspension. Greases may also be made from emulsifiable concentrates by diluting them with an ointment base.
  • Pastes and shampoos are also semi-solid preparations in which a compound of Formula (I) may be present as an uniform dispersion in a suitable base such as soft or liquid paraffin or made on a non-greasy basis with glycerin, mucilage or a suitable soap.
  • a suitable base such as soft or liquid paraffin or made on a non-greasy basis with glycerin, mucilage or a suitable soap.
  • As greases, shampoos and pastes are usually applied without further dilution they should contain the appropriate percentage of the compound of Formula (I) required for treatment.
  • Aerosol sprays may be prepared as a simple solution of the active ingredient in the aerosol propellant and co-solvent such as halogenated alkanes and the solvents referred to above, respectively.
  • Pour-on formulations may be made as a solution or suspension of a compound of Formula (I) in a liquid medium.
  • An avian or mammal host may also be protected against infestation of acarine ectoparasites by means of carrying a suitabl -moulded, shaped plastics article impregnated with a compound of Formula (I) .
  • Such articles include impregnated collars, tags, bands, sheets and strips suitably attached to appropriate parts of the body.
  • the plastics material is a polyvinyl chloride (PVC) .
  • the concentration of the compound of Formula (I) to be applied to an animal, premises or outdoor areas will vary according to the compound chosen, the interval between treatments, the nature of the formulation and the likely infestation, but in general 0.001 to 20.0% w/v and preferably 0.01 to 10% of the compound should be present in the applied formulation.
  • the amount of the compound deposited on an animal will vary according to the method of application, size of the animal, concentration of the compound in the applied formulation, factor by which the formulation is diluted and the nature of the formulation but in general will lie in the range of from 0.0001% to 0.5% w/w except for undiluted formulations such as pour-on formulations which in general will be deposited at a concentration in the range from 0.1 to 20.0% and preferably 0.1 to 10%.
  • the amount of compound to be applied to stored products in general will lie in the range of from 0.1 to 20ppm. Space sprays may be applied to give an average initial concentration of 0.001 to Img of compound of formula (I) per cubic metre of treated space.
  • the compounds of formula (I) are also of use in the protection and treatment of plant species, in which case an effective insecticidal, acaricidal, nematocidal or molluscicidal amount of the active ingredient is applied.
  • the application rate will vary according to the compound chosen, the nature of the formulation, the mode of application, the plant species, the planting density and likely infestation and other like factors but in general, a suitable use rate for agricultural crops is in the range 0.001 to 3kg/Ha and preferably between 0.01 and lkg/Ha.
  • Typical formulations for agricultural use contain between 0.0001% and 50% of a compound of formula (I) and conveniently between 0.1 and 15% by weight of a compound of the formula (I) .
  • Dusts, greases, pastes and aerosol formulations are usually applied in a random fashion as described above and concentrations of 0.001 to 20% w/v of a compound of Formula (I) in the applied formulation may be used.
  • the compounds of formula (I) have been found to have activity against the common housefly (Musca domestica) .
  • certain compounds of formula (I) have activity against other arthropod pests including Mvzus persicae. Tetranychus urticae. Plutella xylostella. Culex spp. Tribolium castaneum. Sitonhilus pranarius. Periplaneta americana and Blattella germanica.
  • the compounds of formula (I) are thus useful in the control of arthropods e.g. insects and acarines in any environment where these constitute pests, e.g. in agriculture, in animal husbandry, in public health control and in domestic situations.
  • Insect pests include members of the orders Coleoptera (e.g. Anobium. Ceutorhvnchus. Rhvnchophorus. Cosmopolites. Lissorhontrus. Meli ⁇ ethes. Hvpothenemus. Hylesinus. Acalvmma. Lema. Psylliodes. Leptinotarsa. Gonocephalum. Agriotes. Dermolepida. He eronvchus. Phaedon. Tribolium. Sitonhilus. Diabrotica. Anthonomus or Anthrenus spp.), Lepidoptera (e.g. Ephestia. Mamestra. Earias. Pectinonhora. Ostrinia.
  • Coleoptera e.g. Anobium. Ceutorhvnchus. Rhvnchophorus. Cosmopolites. Lissorhontrus. Meli ⁇ ethes. Hvpothenemus. Hylesinus. Acalvmm
  • Diptera e.g. Musca. Aedes. Anopheles. Culex. Glossina. Simulium. Stomoxys. Haematobia. Tabanus. Hydrotaea. Lucilia. Chrvs
  • Liriomyza and Meloohagus spp. Phthiraptera (Malophaga e.g. Damalina spp. and Anoplur e.g. Linognathus and Haematoninus spp.), Hemiptera (e.g. Aphis. Bemisia.Phorodon. Aeneolamia. Empoasca. Parkinsiella. Pyrilla. Aonidiella. Coccus. Pseudococus. Helopeltis. Lv us. Dvsdercus. Oxycarenus. Nezara. Aleurodes. Triatoma. Psylla. Mvzus. Me oura. Phylloxera.
  • Lepisma spp. Lepisma spp.
  • Dermaptera e.g. Forficula spp.
  • Pscoptera e.g. Peripsocus spp.
  • Thysanoptera e.g. Thrips tabaci
  • Acarine pests include ticks, e.g. members of the genera Boophilus. Ornithodorus. Rhipicephalus. Amblvomma. Hvalomma. Ixodes. Haemaphvsalis. Dermacentor and Anocentor. and mites and manges such as Acarus. Tetranychus. Psoroptes. Notoednes. Sarcoptes. Psorergates. Chorioptes. Eutrombicula. Demodex. Panonvchus. Brvobia. Eriophves. Blaniulus. Polyphagotarsonemus. Scutieerella. and Oniscus spp.
  • Nematodes which attack plants and trees of importance to agriculture, forestry, horticulture either directly or by spreading bacterial, viral, mycoplasma or, fungal diseases of the plants include root-knot nematodes such as Meloidogvne spp. (e.g. M. incognita); cyst nematodes such as Globodera spp. (e.g. G. rostochiensis) : Heterodera spp. (e.g. H. avenae) : Radopholus spp. (e.g. R. similis) : lesion nematodes such as Pratylenchus spp. (e.g. P.
  • root-knot nematodes such as Meloidogvne spp. (e.g. M. incognita); cyst nematodes such as Globodera spp. (e.g. G. rostochiensis) : Heterodera
  • Belonolaimus spp. e.g. B. gracilis
  • Tylenchulus spp. e.g. T. semipenetrans
  • Rotv1enchulus spp. e.g.R. reniformis
  • Rotylenchus spp. e.g. R. robustus
  • Helicotylenchus spp. e.g. H. multicinctus)iHemicycliophora spp.
  • Criconemoides spp. e.g. C . similis
  • Trichodorus spp. e.g.
  • T primitivus dagger nematodes such as Xiphinema spp. (e.g. X. diversicaudaturn) .
  • Lo ⁇ gidorus spp e.g. L. elongatus
  • Hoplolaimus spp. e.g. H. coronatus
  • Aphelenchoides spp. e.g. A. ritzema-bosi. A. bessevi
  • stem and bulb eelwor s such as Ditylenchus spp. (e.g. D. dipsaci) .
  • Mollusc pests which attack plants and trees of importance to agriculture, forestry and horticulture include slugs such as Deroceras spp. (eg. D. reticulatum - the grey field slug); the Arion group; Milax spp; land snails such as Helix spp. , and aquatic snails such as Planorbis spp.
  • Mollusc pests which act as vectors of diseases in man and domestic animals include Buiinus spp., Phvsopsis spp., Planorbis spp. , and Oricomelania spp.
  • Compounds of the invention may be combined with one or more other pesticidally active ingredients (for example pyrethroids, carbamates and organophosphates) and/or with attractants, repellents, bacteriocides, fungicides, nematocides, anthelmintics and the like. Furthermore, it has been found that the activity of the compounds of the invention may be enhanced by the addition of a synergist or potentiator, for example: one of the oxidase inhibitor class of synergists, such as piperonyl butoxide or propyl 2-propynylphenylphos- phonate; a second compound of the invention; or a pyrethroid pesticidal compound.
  • a synergist or potentiator for example: one of the oxidase inhibitor class of synergists, such as piperonyl butoxide or propyl 2-propynylphenylphos- phonate; a second compound of the invention
  • Stabilisers for preventing any chemical degradation which may occur with the compounds of the invention include, for example, antioxidants (such as tocopherols, butylhydroxyanisole and butylhydroxytoluene) and scavengers (such as epichlorhydrin) and organic or inorganic bases e.g. trialkylamines such as triethylamine which can act as basic stabilises and as scavengers.
  • antioxidants such as tocopherols, butylhydroxyanisole and butylhydroxytoluene
  • scavengers such as epichlorhydrin
  • organic or inorganic bases e.g. trialkylamines such as triethylamine which can act as basic stabilises and as scavengers.
  • Methanesulphonyl chloride (74.Og) was added dropwise over 30 minutes to a solution of 2-hydroxymethyl-2-n-propylpropan-l,3- diol (28.Og) (European Application No. 216624) in dry pyridine (200ml) under nitrogen at 0 C. The mixture was allowed to warm to room temperature. After stirring for 18 hours the mixture was poured into water (200ml) and extracted with chloroform (2x200ml) . The chloroform extracts were washed with water (2x100ml) , dried over anhydrous magnesium sulphate and evaporated .in vacuo to give a brown solid.
  • Steps (vii) , (viii) and (ix) below describe an improved synthesis of 2-mercaptomethyl-2-n-propylpropan-l,3-dithiol.
  • 1,3-diol trimethanesulphonate 300g in dry dimethylformamide (2000ml) was added potassium thiocyanate (900g) .
  • the stirred mixture was maintained at 140 C for 16 hours.
  • the mixture was cooled and the volume was reduced to about one third by distilling off some dimethylformamide (stillhead temperature 50 C, 15mm Hg) .
  • the residue was cooled and water (2000ml) and toluene (2000ml) were added.
  • the mixture was stirred vigorously.
  • the layers were separated.
  • the aqueous layer was extracted with further portions of toluene (3x1000ml) .
  • the combined toluene extracts were washed with water and brine and dried over anhydrous magnesium sulphate.
  • the solvent was removed in vacuo.
  • 2-n-Propyl-2-thiocyanatomethyl-l,3-dithio- cyanatopropane was obtained as a dark oil (14
  • Stages (x) and (xi) describe alternative routes to 1-(3,3-dime ⁇ thylbutyl)-4-n-propyl 2,6,7-trithiabicyclo[2.2.2] -octane.
  • Toluene was then removed from the organic layer by vacuum distillation (55-60 C, 150m bars, 120 litres). The residual solution of bis(4-propyl-l,2- dithiolane-4-ylmethyl)disulphide was used without further purification.
  • Tetrabutylphosphonium bromide (210g) , toluene (1.5 litres) and l-bromo-3,3-dimethylbutane (1023g) was added to a stirred solution of sodium cyanide (456g) in water (1 litres) under a blanket of nitrogen.
  • the stirred emulsion was heated to 50 C and then with caution (exotherm from 50 C to 63 C) to 85-88 C. After heating at this temperature for 6.5 hours the reaction mixture was cooled and stirred overnight.
  • the compounds of the invention were tested by dissolving the compounds in acetone (5%) and then diluting in water: 'Synperonic' (94.5%: 0.5%) to give an aqueous emulsion. The solution was then used to treat the following insects. Musca domestica:
  • Filter paper and food were sprayed and subsequently infested with 10 second instar larvae. Mortality was assessed after 48 hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention décrit un composé de formule (I), dans laquelle n et n' sont identiques ou différents et sont chacun égal à 0, 1 ou 2; R est de l'hydrogène ou du méthyle, R' est du méthyle, de l'éthyle ou du cyclopropyle, R2 et R3 sont identiques ou différents et sont chacun de l'hydrogène ou du méthyle, Ra est de l'hydrogène ou du méthyle, Rb est un cyano ou Ra et Rb sont liés de façon à former un groupe CH¿2?S(O)m où m est égal à 0, 1 ou 2. On décrit également un procédé destiné à la préparation des composés de formule (I), des formulations à base de pesticides contenant lesdits composés et leur utilisation pour lutter contre les parasites.
PCT/GB1991/002239 1990-12-17 1991-12-16 Composes pesticides WO1992011253A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AU90545/91A AU663691B2 (en) 1990-12-17 1991-12-16 Tri thiabicyclo {2.2.2.}octane derivatives as pesticides
KR1019930701820A KR930703328A (ko) 1990-12-17 1991-12-16 살충 화합물
JP4501738A JPH06504046A (ja) 1990-12-17 1991-12-16 有害生物駆除剤化合物
BR919107168A BR9107168A (pt) 1990-12-17 1991-12-16 Compostos pesticidas
CS931142A CZ114293A3 (en) 1990-12-17 1991-12-16 Pesticidal compounds
NO93932219A NO932219L (no) 1990-12-17 1993-06-16 Skadedyrdrepende forbindelser
FI932766A FI932766A0 (fi) 1990-12-17 1993-06-16 Pesticida foereningar

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9027246.9 1990-12-17
GB909027246A GB9027246D0 (en) 1990-12-17 1990-12-17 Pesticidal compounds

Publications (1)

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WO1992011253A1 true WO1992011253A1 (fr) 1992-07-09

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EP (1) EP0563104A1 (fr)
JP (1) JPH06504046A (fr)
KR (1) KR930703328A (fr)
AU (1) AU663691B2 (fr)
BR (1) BR9107168A (fr)
CA (1) CA2098390A1 (fr)
CZ (1) CZ114293A3 (fr)
FI (1) FI932766A0 (fr)
GB (1) GB9027246D0 (fr)
HU (1) HUT68462A (fr)
NO (1) NO932219L (fr)
WO (1) WO1992011253A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9427483B2 (en) 2014-04-04 2016-08-30 The Curators Of The University Of Missouri Radioisotope trithiol complexes

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023058673A1 (fr) * 2021-10-06 2023-04-13 参天製薬株式会社 Composé contenant du soufre utile pour le traitement ou la prévention de la presbytie ou analogue

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0073378A1 (fr) * 1981-08-27 1983-03-09 Bayer Ag 1,3-Dithiannes 2,5-disubstituées, leur procédé de préparation et leur utilisation
EP0294229A2 (fr) * 1987-06-05 1988-12-07 The Wellcome Foundation Limited Composés pesticides hétérocycliques
EP0372816A1 (fr) * 1988-11-30 1990-06-13 The Wellcome Foundation Limited Composés pesticides hétérocycliques
US5026874A (en) * 1989-01-24 1991-06-25 Wellcome Foundation Limited Pesticidal compounds

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PL159875B1 (pl) * 1987-07-22 1993-01-29 Wellcome Found Sposób wytwarzania nowych heterobicykloalkanów o dzialaniu szkodnikobójczym PL PL PL

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0073378A1 (fr) * 1981-08-27 1983-03-09 Bayer Ag 1,3-Dithiannes 2,5-disubstituées, leur procédé de préparation et leur utilisation
EP0294229A2 (fr) * 1987-06-05 1988-12-07 The Wellcome Foundation Limited Composés pesticides hétérocycliques
EP0294228A2 (fr) * 1987-06-05 1988-12-07 The Wellcome Foundation Limited Composés pesticides hétérocycliques
EP0372816A1 (fr) * 1988-11-30 1990-06-13 The Wellcome Foundation Limited Composés pesticides hétérocycliques
US5026874A (en) * 1989-01-24 1991-06-25 Wellcome Foundation Limited Pesticidal compounds

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, vol. 115, no. 19, 11 November 1991, (Columbus, Ohio, US), see page 1027, column 1, abstract no. 208024m, & US,A,5026874 (WELLCOME FOUNDATION LTD) 25 June 1991 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9427483B2 (en) 2014-04-04 2016-08-30 The Curators Of The University Of Missouri Radioisotope trithiol complexes

Also Published As

Publication number Publication date
CZ114293A3 (en) 1994-02-16
BR9107168A (pt) 1993-11-16
HU9301757D0 (en) 1993-09-28
EP0563104A1 (fr) 1993-10-06
AU663691B2 (en) 1995-10-19
FI932766A (fi) 1993-06-16
FI932766A0 (fi) 1993-06-16
CA2098390A1 (fr) 1992-06-18
NO932219D0 (no) 1993-06-16
JPH06504046A (ja) 1994-05-12
HUT68462A (en) 1995-06-28
AU9054591A (en) 1992-07-22
GB9027246D0 (en) 1991-02-06
KR930703328A (ko) 1993-11-29
NO932219L (no) 1993-06-16

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