EP0971918A1 - Derives d'amine bicyclique - Google Patents

Derives d'amine bicyclique

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Publication number
EP0971918A1
EP0971918A1 EP98910848A EP98910848A EP0971918A1 EP 0971918 A1 EP0971918 A1 EP 0971918A1 EP 98910848 A EP98910848 A EP 98910848A EP 98910848 A EP98910848 A EP 98910848A EP 0971918 A1 EP0971918 A1 EP 0971918A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
optionally substituted
formula
halogen
cyano
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP98910848A
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German (de)
English (en)
Inventor
Christopher Richard Ayles Godfrey
Roger Salmon
Charles Adam Russell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Ltd
Original Assignee
Zeneca Ltd
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Filing date
Publication date
Application filed by Zeneca Ltd filed Critical Zeneca Ltd
Publication of EP0971918A1 publication Critical patent/EP0971918A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D451/00—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof
    • C07D451/02—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof containing not further condensed 8-azabicyclo [3.2.1] octane or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane; Cyclic acetals thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D451/00—Heterocyclic compounds containing 8-azabicyclo [3.2.1] octane, 9-azabicyclo [3.3.1] nonane, or 3-oxa-9-azatricyclo [3.3.1.0<2,4>] nonane ring systems, e.g. tropane or granatane alkaloids, scopolamine; Cyclic acetals thereof

Definitions

  • This invention relates to a method of combating and controlling insect, acarine or nematode pests with bicyclic amine derivatives, to insecticidal, acaricidal or nematocidal compositions comprising said derivatives, to certain novel bicyclic amine derivatives and to processes for preparing said novel compounds.
  • R is hydrogen, formyl or cyano or a group selected from alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, arenesulfonyl, alkenyloxycarbonyl, aralkyloxycarbonyl, aryloxycarbonyl, heterocyclylalkyl, carbamyl, dithiocarboxyl or X'R 3 (where X' represents oxygen or a group NR 4 ), provided that when R is alkenyl, aralkenyl or alkynyl said group does not have an unsaturated carbon atom bonding directly to the ring nitrogen of formula (I);
  • Ar is optionally substituted phenyl or an optionally substituted 5-or 6-membered heterocyclic ring system containing from 1 to 3
  • bicyclic amine compounds of formula (I) are capable of existing in more than one isomeric form.
  • the present invention embraces within its scope all isomeric forms and mixtures thereof in all proportions.
  • Examples of 5- and 6-membered heterocyclic ring systems represented by Ar include those based on pyridine, pyrazine, pyridazine, pyrimidine, pyrrole, pyrazole, imidazole, 1,2,3- and 1,2,4-triazoles, furan, thiophene, oxazole, isoxazole, thiazole, isothiazole, 1,2,3- and 1,3,4-oxadiazoles, and 1,2,3- and 1,3,4-thiadiazoles, and partially reduced containing one double bond derived from these, as well as those based on oxathiole, dioxole, and dithiole rings containing one double bond.
  • Ar represents a halo-substituted phenyl, pyridyl or diazinyl group.
  • Ar is a 5- or 6- membered heterocyclic ring fused to a benzene ring it is preferably benzoxazole, indole, benzofuran, benzothiophen or benzimidazole.
  • Halogen includes fluorine, chlorine, bromine and iodine.
  • Alkyl moieties preferably contain from 1 to 6, more preferably from 1 to 4, carbon atoms. They can be in the form of straight or branched chains, for example methyl, ethyl, n- or iso-propyl, or n-, sec-, iso- or tert-butyl.
  • Haloalkyl is preferably C ⁇ -6 haloalkyl, especially fluoroalkyl (for example trifluoromethyl, 2,2,2-trifluoroethyl or 2,2-difluoroethyl) or chloroalkyl.
  • fluoroalkyl for example trifluoromethyl, 2,2,2-trifluoroethyl or 2,2-difluoroethyl
  • chloroalkyl is preferably C 2 _ 6 haloalkyl wherein there is no halogen on the ⁇ -carbon (for example it is 2,2,2- trifluoroethyl or 2,2-difluoroethyl).
  • Alkenyl and alkynyl moieties of R and substituents of Ar preferably contain from 2 to 6, more preferably from 2 to 4, carbon atoms.
  • alkenyl moieties can be of either (E)- or ⁇ -configuration.
  • Examples are vinyl, allyl and propargyl.
  • Aryl includes naphthyl but is preferably phenyl.
  • Heteroaryl includes 5- and 6-membered aromatic rings containing one, two, three or four heteroatoms selected from the list comprising oxygen, sulphur and nitrogen and can be fused to benzenoid ring systems.
  • heteroaryl are pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl (1,2,3-, 1,2,4- and 1,3,5-), furyl, thienyi, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (1,2,3- and 1,2,4-), tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, indohnyl, isoindolinyl
  • the heterocyclyl part of heterocyclylalkyl is a ring containing one or two heteroatoms selected from the list comprising oxygen, sulphur and nitrogen. Examples are piperidine, piperazine, pyrrolidine, tetrahydrofuran, morpholine, thietane, pyridine or thiazole.
  • the alkylenedioxy group is a substituent for a ring and is especially C ⁇ alkylenedioxy.
  • Alkylenedioxy groups are optionally substituted with halogen (especially fluorine) and are, for example, methylenedioxy (OCH 2 O) or difluoromethylenedioxy (OCF 2 O).
  • Suitable acid addition salts include those with an inorganic acid such as hydrochloric, hydrobro ic, sulfuric, nitric and phosphoric acids, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic and phthalic acids, or sulphonic acids such as methane, benzene and toluene sulphonic acids.
  • organic carboxylic acids include haloacids such as trifluoroacetic acid.
  • alkenyl alkynyl (especially C 3 _4 alkynyl), alkoxycarbonyl (especially C alkoxycarbonyl), alkanesulfonyl (especially CM alkylsulfonyl), arenesulfonyl (especially phenylsulfonyl), alkenyloxycarbonyl (especially C 3- alkenyl-oxycarbonyl), aralkyloxycarbonyl (especially phenyl(C 1-4 )alkoxycarbonyl), aryloxycarbonyl (especially phenoxycarbonyl), heterocyclylalkyl (especially heterocyclyl(C] -4 )alkyl, such as piperidinyl(C M )alkyl), carbamyl (H 2 NC(O)), dithiocarboxyl or X'R 3 (where X' represents oxygen or a group NR 4 ), provided that when R is alkenyl, aralkenyl or alkynyl said group
  • alkyl moieties of R, R 3 and R 4 comprise from 1 to 15 carbon atoms, and are optionally substituted with one or more substituents selected from halogen, cyano, carboxyl (HOC
  • the invention provides a method of combating and controlling insect, acarine or nematode pests which comprises treating said pests, or the locus of said pests, with an effective amount of a compound of formula (la) or (lb):
  • Ar represents an optionally substituted phenyl or 5-or 6-membered heterocyclic ring system containing from 1 to 3 heteroatoms individually selected from nitrogen, oxygen and sulfur atoms, and at least one unsaturation (double bond) between adjacent atoms in the ring, wherein the substutuents, if present, are selected from halogen atoms, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, alkylthio and alkyl amino groups, any of which groups contain up to six carbon, wherein R represents hydrogen or cyano or a group selected from alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl, alkanesulfonyl, arenesulfonyl, alkanyloxycarbonyl, aralkyl
  • W, X, Y and Z are selected from hydrogen, hydroxy, acyloxy, alkoxy, alkylsilyloxy and halogen; and acid addition salts and quaternary ammonium salts and N- oxides derived therefrom; or an effective amount of a composition comprising a compound of formula (I), as hereinbefore defined, and an insecticidally, acaricidally or nematocidally acceptable carrier or diluent therefor.
  • the present invention provides a method as hereinbefore described wherein A is CH 2 CH 2 .
  • Ar is phenyl, pyridinyl, pyridazinyl or pyrazinyl, all being optionally substituted with halogen (especially fluorine, chlorine or bromine), C M alkyl (especially methyl), C M alkoxy (especially methoxy), C 2- alkenyl, C - alkynyl or cyano.
  • C M alkyl such as CO 2 CH 3
  • C alkyl optionally substituted with cyano, CO 2 (CM alkyl) or phenyl (itself optionally substituted with halogen, C alkyl, CM alkoxy, C M haloalkyl or C M
  • the present invention provides a method as hereinbefore described wherein Ar is pyridyl (especially pyrin-3-yl) optionally substituted with halogen (especially chlorine or bromine).
  • Ar is, for example, 5-chloropyrid-3-yl, 6-chloropyrid-3-yl, 5,6- dichloropyrid-3-yl, 5-bromopyrid-3-yl, 6-bromopyrid-3-yl or 5,6-dibromopyrid-3-yl.
  • the present invention provides an insecticidal, acaricidal or nematicidal composition
  • an insecticidal, acaricidal or nematicidal composition comprising an effective amount of a compound of formula (I) as hereinbefore defined, and an insecticidally, acaricidally or nematicidally acceptable carrier or diluent therefor.
  • the present invention provides a compound of formula (I), wherein A is CH 2 CH 2 ; and Ar is pyridyl (especially pyrid-3-yl) optionally substituted with halogen (especially chlorine or bromine).
  • the preparation of the compounds of formula (I) may be accomplished by adaptation ods described in the literature, by use of one or more of the following synthetic techniques described below and further illustrated in the Examples, or by combining literature methods with those methods described below.
  • a compound of formula (I) can be prepared by dehydrating a compound of formula (II) under suitable conditions (for example diethylamino sulfurtrifluoride at a temperature in the range -30-40°C, or heating with an acid (such as p_-toluenesulfonic acid)).
  • suitable conditions for example diethylamino sulfurtrifluoride at a temperature in the range -30-40°C, or heating with an acid (such as p_-toluenesulfonic acid)).
  • a compound of formula (II) can be prepared by reacting a compound ArHal, wherein Hal is a halogen, with a suitable base (such as n-butyl lithium) and reacting the product so formed with a compound of formula (111).
  • a suitable base such as n-butyl lithium
  • Compounds of formula (I) wherein A is CH 2 CHZ (wherein Z is a suitable group, such as a thiono-4-tolyloxy group) can be prepared by treating compounds of formula (I) wherein A is CH 2 CH(OH) with a suitable chloroformate (such as 4-tolyl chlorothionoformate) in the presence of a suitable base (such as N,N-dimethylaminopyridine).
  • a suitable chloroformate such as 4-tolyl chlorothionoformate
  • a compound of formula (I) wherein A is CH 2 CHF can be prepared by fluorinating a compound of formula (I) wherein A is CH 2 CH(OH) with, for example, a mixture of hydrogen fluoride and sulfur trifluoride.
  • suitable conditions for example an acid chloride (such as oxalyl chloride) and dimethylsulfoxide at a suitable temperature (such as below -50°C) in the presence of a suitable base (such as triethylamine)].
  • a compound of formula (I) wherein A is CH 2 CH(OZ'), wherein Z' is a suitable group (such as SO 2 CH 3 ) can be prepared by reacting a compound of formula (I) wherein A is CH 2 CH(OH) with a suitable acid chloride (such as mesyl chloride).
  • the present invention provides processes for preparing compounds of formula (I), as hereinbefore described, and the intermediate compounds of formula (II).
  • the compounds of formula (I) [or an acid addition salt, quaternary ammonium salt or N-oxide of a compound of formula (I)] can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Homoptera and Coleoptera (including Diabrotica i.e. corn rootworms) and also other invertebrate pests, for example, acarine pests.
  • insect pests such as Lepidoptera, Diptera, Homoptera and Coleoptera (including Diabrotica i.e. corn rootworms) and also other invertebrate pests, for example, acarine pests.
  • insects and acarine pests which may be combated and controlled by the use of the compounds of formula (I) 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.
  • insect and acarine pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid), Aphis fabae (aphid), Aedes aegypti (mosquito), Anopheles spp. (mosquitos), Culex spp. (mosquitos), Dysdercus fasciatus
  • Diabrotica spp. rootworms
  • Agrotis spp. (cutworms), Chilo partellus (maize stem borer), Nilaparvata lugens (planthopper), Nephotettix cincticeps (leafhopper), Panonvchus ulmi (European red mite), Panonvchus citri (citrus red mite), Tetranychus urticae (two-spotted spider mite), Tetranychus cinnabarinus (carmine spider mite), Phyllcoptruta oleivora (citrus rust mite), Polyphagotarsonemus latus (broad mite) and Brevipalpus spp. (mites).
  • insects which adversely affect the health of the public or of animals.
  • the compound is usually formulated into a composition which includes in addition to a compound of formula (I) a suitable inert diluent or carrier material, and, optionally, a surface active agent.
  • the amount of composition generally applied for the control of nematode pests gives a rate of active ingredient from 0.01 to 10 kg per hectare, preferably from 0.1 to 6 kg per hectare.
  • compositions can be applied to the soil, plant or seed, to the locus of the pests, or to the habitat of the pests, in the form of dusting powders, wettable powders, granules (slow or fast release), emulsifiable concentrates, suspension concentrates, liquid solutions, emulsions, seed dressings, fogging/smoke formulations or controlled release compositions, such as microencapsulated granules or suspensions.
  • Dusting powders are formulated by mixing the active ingredient with one or more finely divided solid carriers and/or diluents, for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers.
  • solid carriers and/or diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers.
  • Granules are formed either by absorbing the active ingredient in a porous granular material for example pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths, ground com cobs, and the like, or by adsorbing the active ingredient on to hard core materials such as sands, silicates, mineral carbonates, sulphates, phosphates, or the like.
  • Agents which are commonly used to aid absorption or adsorption include aliphatic and aromatic petroleum solvents, alcohols, polyvinyl acetates, polyvinyl alcohols, ethers, ketones, esters, dextrins, sugars and vegetable oils.
  • Other additives may also be included in granules, such as emulsifying agents, wetting agents or dispersing agents.
  • Microencapsulated formulations may also be used, particularly for slow release over a period of time and for seed treatment.
  • compositions may be in the form of liquid preparations to be used as dips, irrigation additives 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).
  • the compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of an emulsifiable concentrate (EC) or a suspension concentrate (SC) containing a high proportion of the active ingredient or ingredients.
  • An EC is a homogeneous liquid composition, usually containing the active ingredient dissolved in a substantially non- volatile organic solvent.
  • SC is a fine particle size dispersion of solid active ingredient in water.
  • the concentrates are diluted in water and applied by means of a spray to the area to be treated.
  • Suitable liquid solvents for ECs include methyl ketones, methyl isobutyl ketone, cyclohexanone, xylenes, toluene, chlorobenzene, paraffins, kerosene, white oil, alcohols, (for example, butanol), methylnaphthalene, trimethylbenzene, trichloroethylene, N-methyl- 2-pyrrolidone and tefrahydrofurfuryl alcohol (THFA).
  • methyl ketones methyl isobutyl ketone, cyclohexanone, xylenes, toluene, chlorobenzene, paraffins, kerosene, white oil, alcohols, (for example, butanol), methylnaphthalene, trimethylbenzene, trichloroethylene, N-methyl- 2-pyrrolidone and tefrahydrofurfuryl alcohol (THFA).
  • Wetting agents, dispersing agents and emulsifying agents may be of the cationic, anionic or non-ionic type.
  • Suitable agents of the cationic type include, for example, quaternary ammonium compounds, for example cetyltrimethyl ammonium bromide.
  • Suitable agents of the anionic type include, for example, soaps, salts of aliphatic monoesters of sulphuric acid, for example sodium lauryl sulphate, salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, or butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl- and triisopropylnaphthalene sulphonates.
  • Suitable agents of the non-ionic type include, for example, the condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octyl phenol, nonyl phenol and octyl cresol.
  • Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins.
  • 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.
  • the compounds of formula (I) may also be formulated as powders (dry seed treatment DS or water dispersible powder WS) or liquids (flowable concentrate FS, liquid seed treatment LS, or microcapsule suspension CS) for use in seed treatments.
  • compositions are applied to the insect pests, to the locus of the pests, to the habitat of the pests, or to growing plants liable to infestation by the pests, by any of the known means of applying pesticidal compositions, for example, by dusting, spraying or incorporation of granules.
  • the compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as insecticides, synergists, herbicides, fungicides or plant growth regulators where appropriate.
  • additional active ingredients for inclusion in admixture with a compound of formula (I) may be compounds which will broaden the spectrum of activity of the compositions of the invention or increase their persistence in the location of the pest. They may synergise the activity of the compound of formula (I) or complement the activity for example by increasing the speed of effect or overcoming repellency. Additionally multi-component mixtures of this type may help to overcome or prevent the development of resistance to individual components.
  • suitable insecticides include the following: a) Pyrethroids such as permethrin, esfenvalerate, deltamethrin, cyhalothrin in particular lambda-cyhalothrin, biphenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids for example ethofenprox, natural pyrethrin, tetra ethrin, s-bioallethrin, fenfluthrin, pralletl ⁇ rin and 5-be ⁇ _zyl-3-furylmethyl- ⁇ -(lR,3S)-2,2-dimemyl-3-(2-oxothiolan- 3-ylidenemethyl) cyclopropane carboxylate; b) Organophosphates such as profenofos, sulprofos
  • 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 chlofentezine, flubenzimine, hexythiazox and tetradifon, motilicides such as dicofol or propargite, acaricides such as bromopropylate, chlorobenzilate, or growth regulators such as hydramethylron, cyromazine, methoprene, chlorofluazuron and diflubenzuron may also be included in the compositions.
  • suitable synergists for use in the compositions include piperonyl butoxide, sesamax, safroxan 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.
  • 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 formula (I) 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 at which it is usually employed, or at a slightly lower rate if synergism occurs.
  • Examples 1-9 illustrate the preparation of compounds of formula (I).
  • Examples 9-17 illustrate compositions suitable for the application of the compounds of formula (I).
  • the following ingredients are referred to by their Registered Trade Marks and have the composition as shown below.
  • EXAMPLE 1 This Example illustrates the preparation of 8-tert-butyloxycarbonyl-8- azabicyclo[3.2.1]octan-3-one.
  • Iodotrimethylsilane (0.87ml, 6.09mmol) was added dropwise to a stirred solution of N-carboethoxytropinone in dry chloroform at 0°C under nitrogen. A precipitate was formed. The mixture was heated to reflux for 5hours then allowed to cool to room temperature. Methanolic hydrochloric acid (2.0ml, 5M) was added at 0°C and effervescence was observed. The mixture was stirred for 1.5hours and then evaporated under reduced pressure. The crude brown solid was azeotroped with toluene and dried under reduced pressure (high vacuum).
  • EXAMPLE 2 This Example illustrates the preparation of exo-3-(6-chloropyrid-3-yl)-endo-3- hydroxy-8-tert-butyl-oxycarbonyl-8-azabicyclo[3.2.1]octane.
  • n-Butyl lithium (5.92ml, 2.5M solution in hexane) was added dropwise to a stirred solution of 2-chloro-5-iodopyridine (3.54g, 14.8mmol) in dry diethyl ether (60ml) and dry tetrahydrofuran (30ml) at -78°C under nitrogen. The solution became yellow turning to orange and an orange precipitate was formed.
  • EXAMPLE 3 This Example illustrates the preparation of e_xo-3-(6-chloropyrid-3-yl)-endo-3- hydroxy-8-methyl-8-azabicyclo[3.2. ljoctane. exo-3-(6-Chloropyrid-3-yl)-endo-3-hydroxy-8-tgrt-butyloxycarbonvl-8-azabicyclo [3.2.1]octane (0.30g, 0.89mmol) was dissolved in formic acid (4ml) and heated to reflux for lhour. Paraformaldehyde (0.30g) was added and refluxing continued for 3hours.
  • EXAMPLE 5 This Example illustrates the preparation of exo-3-(pyrid-3-yl -endo-3-hydroxy-8-tert- butyloxycarbonyl-8-azabicyclo[3.2.1 joctane.
  • EXAMPLE 6 This Example illustrates the preparation of exo-3-(pyrid-3-yl)-endo-3-hydroxv-8- methyl-8-azabicyclo[3.2. l]octane exo-3-(Pyrid-3-vl)-endo-3-hvdroxy-8-tert-butyloxycarbonyl-8-azabicyclo[3.2.n- octane (0.35g, 1.15mmol) was dissolved in formic acid (10ml) and heated to reflux for 1 hours. Paraformaldehyde (0.35g) was added and refluxing continued for 2hours.
  • This Example illustrates the preparation of exo-3-(5-bromopyrid-3-yl)-endo-3- hydroxy-8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]octane.
  • 3,5-Dibromopyridine (5.15g) was dissolved in dry diethyl ether (40ml) and cooled to -78°C with stirring under an atmosphere of nitrogen.
  • a solution of n-butyl lithium (8.35ml of a solution in hexane, 2.5M) was added dropwise maintaining the reaction below -65°C.
  • the mixture was stirred at -78°C for lhour then 8-(2,2,2-trifluoroethyl)-8-azabicyclo[3.2.1]- octan-3-one (see WO96/37494 for preparation, 2.0g) in dry tetrahydrofuran (15ml) was added dropwise.
  • the mixture was stored at ambient temperature for l ⁇ hours then further triethylamine (dry, 0.76ml) followed by methane sulfonylchloride (0.42ml) was added at room temperature. The mixture was stirred for 4hours at ambient temperature then stored for 2days. The mixture was poured into water and extracted with diethyl ether (three times). The extracts were combined, dried (magnesium sulfate) and evaporated under reduced pressure to give an orange gum. The gum was fractionated by chromatography (silica; 10-20% ethyl acetate in hexane) to give the required product, 0.48g, as a pale yellow oil.
  • EXAMPLE 10 This Example illustrates an emulsifiable concentrate composition which is readily convertible by dilution with water into a liquid preparation suitable for spraying purposes.
  • the concentrate has the following composition:
  • EXAMPLE 11 This Example illustrates a wettable powder composition which is readily convertible by dilution with water into a liquid preparation suitable ' for spraying purposes.
  • the wettable powder has the following composition: % Weight Compound No. 1 25.0
  • EXAMPLE 12 This Example illustrates a dusting powder which may be applied directly to plants or other surfaces and comprises 1 % by weight of Compound No. 1 and 99% by weight of talc.
  • This Example illustrates a concentrated liquid formulation suitable for apphcation by ultra low volume techniques after mixing with paraffinic diluents.
  • EXAMPLE 14 This Example illustrates a capsule suspension concentrate which is readily convertible by dilution with water to form a preparation suitable for apphcation as an aqueous spray.
  • Alkylbenzene solvent e.g. AROMASOL H
  • Polysaccharide e.g. KELTROL 0.1
  • EXAMPLE 15 A ready for use granular formulation: % Weight Compound No. 1 0.5
  • Nonylphenol ethoxylate eg Synperonic NP8
  • Calcium carbonate granules 0.3-0.7 mm
  • Nonylphenolethoxylate eg Synperonic NP8
  • Bactericide eg Proxel; Proxel is a registered Trade Mark
  • This Example illustrates a water dispersible granule formulation.
  • Montmorillonite powder 65 EXAMPLE 18 This Example illustrates the insecticidal properties of the compounds of formula (I).
  • the activity of the compounds of formula (I) was determined using a variety of pests. The pests were treated with a liquid composition containing 500 parts per million (ppm) by weight of the compound unless otherwise stated. The compositions were made by dissolving the compound in acetone and ethanol (50:50) mixture and diluting the solutions with water containing 0.05% by weight of a wetting agent sold under the trade name "SYNPERONIC” NP8 until the liquid composition contained the required concentration of the compound. "SYNPERONIC” is a Registered Trade Mark.
  • the test procedure adopted with regard to each pest was basically the same and comprised supporting a number of the pests on a medium which was usually a substrate, a host plant or a foodstuff on which the pests feed, and treating either or both the medium and the pests with the compositions.
  • the mortality of the pests was then assessed at periods usually varying from two to five days after the treatment.
  • the results of the tests against peach aphid (Myzus persicae) are presented below.
  • results indicate a grading of mortality (score) designated as A, B or C wherein C indicates less than 40% mortality, B indicates 40-79% mortality and A indicates 80-100% mortality; "-" indicates that either the compound was not tested or no meaningful result was obtained.
  • Score a grading of mortality
  • Chinese cabbage leaves were infested with aphids, the infested leaves were sprayed with the test composition, and the mortality assessed after 3 days.
  • Compound Nos. 1, 2 and 3 of Table I gave a mortality score of A.

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Abstract

L'invention concerne un procédé permettant de combattre et de supprimer les insectes, acariens ou nématodes nuisibles. Ce procédé consiste à traiter lesdites espèces nuisibles, ou le lieu où elles se trouvent, au moyen d'une dose suffisante d'un composé de la formule (I). Dans cette formule, A représente WXC-CYZ ou XC=CY; R représente hydrogène, formyle ou cyano ou un groupe sélectionné à partir d'alkyle, aryle, hétéroaryle, aralkyle, hétéroarylalkyle, alcényle, aralcényle, alcynyle, alcoxycarbonyle, alcanesulfonyle, arènesulfonyle, alcényloxycarbonyle, aralkyloxycarbonyle, aryloxycarbonyle, hétérocyclylalkyle, carbamyle, dithiocarboxyle ou X'R3 (où X' représente oxygène ou un groupe NR4), sous réserve que lorsque R représente alcényle, aralcényle ou alcynyle, ledit groupe ne possède pas un atome de carbone non saturé se liant directement à l'azote cyclique de la formule (I); Ar représente phényle éventuellement substitué ou un système à noyau hétérocyclique, éventuellement substitué, à 5 ou 6 chaînons et contenant de un à trois hétéroatomes individuellement sélectionnés à partir d'atomes d'azote, oxygène et soufre, et au moins une insaturation (double liaison) située entre des atomes adjacents du noyau, ledit noyau hétérocyclique étant éventuellement condensé à un noyau benzénique, les substituants, s'il y en a, sont sélectionnés à partir d'atomes d'halogène, de groupes cyano, alkyle, alcényle, alcynyle, alcoxy, haloalkyle, haloalcényle, alkylthio et alkyl-amino contenant tous jusqu'à six atomes de carbone; W, X, Y et Z représentent, indépendamment, hydrogène, hydroxy, acyloxy, alcoxy, alkylsilyloxy, cyano ou halogène; des fractions alkyles de R, R3 et R4 contiennent de 1 à 15 atomes de carbone et sont éventuellement substituées par un substituant, ou davantage, sélectionnés à partir de groupes halogène, cyano, carboxyle, acyle carboxylique, carbamyle, alcoxycarbonyle, alcoxy, alkylènedioxy, hydroxy, nitro, amino, acylamino, imidate et phosphonato; des fractions aryle, hétéroaryle, aralkyle, hétéroarylalkyle, alcényle, aralcényle, alcynyle, alcoxycarbonyle, alcanesulfonyle, arènesulfonyle, alcanyloxycarbonyle, aralkyloxycarbonyle, aryloxycarbonyle, hétérocyclylalkyle, carbamyle, dithiocarboxyle, de R, R3 et R4 contiennent de un à quinze atomes de carbone et sont éventuellement substituées par un substituant, ou davantage, sélectionnés à partir de groupes halogène, cyano, carboxyle, acyle carboxylique, carbamyle, alcoxycarbonyle, alcoxy, alkylènedioxy, hydroxy, nitro, haloalkyle, alkyle, amino, acylamino, imidate et phosphonato. L'invention concerne également un sel d'addition d'acide, un sel d'ammonium quaternaire ou un N-oxyde dérivés de ces groupes; ou bien une quantité suffisante d'une composition contenant un composé de la formule (I), telle qu'elle a été définie ci-dessus, et un excipient ou un diluant connexe acceptable du point de vue insecticide, acaricide ou nématicide. Par ailleurs, l'invention concerne des compositions contenant un composé de la formule (I), certains composés de la formule (I) et des procédés de fabrication desdits composés.
EP98910848A 1997-03-26 1998-03-04 Derives d'amine bicyclique Withdrawn EP0971918A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9706222 1997-03-26
GBGB9706222.8A GB9706222D0 (en) 1997-03-26 1997-03-26 Bicyclic amine derivatives
PCT/GB1998/000693 WO1998046600A1 (fr) 1997-03-26 1998-03-04 Derives d'amine bicyclique

Publications (1)

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EP0971918A1 true EP0971918A1 (fr) 2000-01-19

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ID=10809864

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98910848A Withdrawn EP0971918A1 (fr) 1997-03-26 1998-03-04 Derives d'amine bicyclique

Country Status (8)

Country Link
EP (1) EP0971918A1 (fr)
JP (1) JP2001521514A (fr)
KR (1) KR20010005634A (fr)
AR (1) AR012164A1 (fr)
AU (1) AU6507798A (fr)
GB (1) GB9706222D0 (fr)
WO (1) WO1998046600A1 (fr)
ZA (1) ZA982204B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HUP0002713A3 (en) 1997-05-30 2001-02-28 Neurosearch As 8-azabicyclo[3,2,1]oct-2-ene and octane derivatives, process for preparation thereof, pharmaceutical compositions comprising thereof and their use
ZA99681B (en) * 1998-01-28 1999-09-27 Neurosearch As 8-azabicyclo[3.2.1]oct-2-ene derivatives in labelled and unlabelled form and use of 8-azabicyclo[3.2.1]oct-2-ene derivatives in labelled or unlabelled form in diagnostic methods.
DE69914935T2 (de) * 1998-11-27 2009-10-01 Neurosearch A/S 8-azabicyclo[3.2.1]okt-2-en- und -oktanderivate
AU2278700A (en) 1999-01-28 2000-08-18 Neurosearch A/S Novel azabicyclo derivatives and their use

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9019973D0 (en) * 1990-09-12 1990-10-24 Wyeth John & Brother Ltd Azabicyclic derivatives
DK148392D0 (da) * 1992-12-09 1992-12-09 Lundbeck & Co As H Heterocykliske forbindelser
DE69637097T2 (de) * 1995-10-13 2007-09-20 Neurosearch A/S 8-Azabicyclo(3.2.1)Oct-2-en-Derivate, deren Herstellung und Anwendung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9846600A1 *

Also Published As

Publication number Publication date
ZA982204B (en) 1998-09-28
GB9706222D0 (en) 1997-05-14
AU6507798A (en) 1998-11-11
AR012164A1 (es) 2000-09-27
WO1998046600A1 (fr) 1998-10-22
KR20010005634A (ko) 2001-01-15
JP2001521514A (ja) 2001-11-06

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