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WO1991007380A1 - Arthropodicides - Google Patents

Arthropodicides Download PDF

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Publication number
WO1991007380A1
WO1991007380A1 PCT/AU1990/000534 AU9000534W WO9107380A1 WO 1991007380 A1 WO1991007380 A1 WO 1991007380A1 AU 9000534 W AU9000534 W AU 9000534W WO 9107380 A1 WO9107380 A1 WO 9107380A1
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Prior art keywords
compound
formula
compounds
fluorine
hydrogen
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PCT/AU1990/000534
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English (en)
Inventor
George Holan
David Francis O'keefe
Karen Elizabeth Jarvis
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Dunlena Pty Ltd
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Dunlena Pty Ltd
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Publication of WO1991007380A1 publication Critical patent/WO1991007380A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/22—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/04—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aldehyde or keto groups, or thio analogues thereof, directly attached to an aromatic ring system, e.g. acetophenone; Derivatives thereof, e.g. acetals
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing within the same carbon skeleton a carboxylic group or a thio analogue, or a derivative thereof, and a carbon atom having only two bonds to hetero atoms with at the most one bond to halogen, e.g. keto-carboxylic acids
    • 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
    • A01N43/26—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 five-membered rings
    • A01N43/28—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 five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—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 five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • 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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/40—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by doubly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/516—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of nitrogen-containing compounds to >C = O groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/04—Systems containing only non-condensed rings with a four-membered ring

Definitions

  • This invention relates to new compounds having arthropodicidal activity, to methods of preparing these compounds and to the use of the compounds as
  • arthropodicides especially as insecticides and
  • n 0 or 1
  • G is oxygen, sulphur, CH 2 or CX 3 X 4 wherein X 3 and X 4 are the same or different and each is fluorine, chlorine or bromine;
  • X 1 and X 2 are the s ame or different and each is hydrogen or fluorine, chlorine or bromine; and when n is 0, X 1 and X 2 may also be methyl groups;
  • R 1 is hydrogen, deuterium, CN, C ⁇ CH, fluorine, chlorine or bromine and R 6 is hydrogen or deuterium;
  • R 2 is oxygen, or both H and OH together, or N-OR 8 wherein R 3 is hydrogen or lower alkyl which is optionally substituted with one or more halo groups;
  • R 3 is a halo group, or a lower alkyl, lower alkoxy or lower alkylthio group, in each of which the alkyl group is optionally substituted with one or more halo groups;
  • R 4 is hydrogen or a halo or lower alkyl group
  • R 3 and R 4 may optionally form a methylenedioxy bridge which is optionally mono- or di- substituted with fluorine;
  • R 5 is hydrogen, OH, lower alkoxy, SH, lower
  • thioalkyl fluorine, chlorine, bromine or iodine
  • R 7 is H 2 , HD, D 2 or oxygen.
  • R 9 is H, lower alkoxy or lower alkylthio.
  • the lower alkyl groups have from 1 to 6 carbon atoms.
  • Alkyl groups having more than 2 carbon atoms may be straight chain or branched.
  • Halo groups may be fluoro, chloro or bromo.
  • Particularly preferred compounds are those having the following structures AA, BB and CC: Individual compounds which are presently preferred are those designated in the Examples as follows: Compound No. Example No.
  • the compounds of the invention are optically active and can be resolved into their optical isomers by conventional methods.
  • the invention thus includes the individual optical isomers of the compounds as well as the racemic forms.
  • the compounds of formula (I) may be prepared by the conventional methods of synthetic organic chemistry.
  • the compounds of formula (I) may be prepared by reacting an acid of the formula (A):
  • R 3 , R 4 , X 1 , X 2 , n and G are as defined above or a reactive derivative of such an acid with a compound of the formula (B):
  • R 1 , R 2 , R 6 and R 5 are as defined above and Z is a leaving group or a hydroxy group;
  • R 3 , R 4 , X 1 , X 2 , n and G are as defined above, R 7 is H 2 , HD or D 2 and Y is a leaving group, with the anion of 4-tosylmethyl isocyanide to produce an intermediate of the formula (D):
  • R 3 , R 4 , X 1 , X 2 and G are as defined above and R 7 is H 2 , HD or D 2 ; and reacting the anion of said intermediate with a compound of the formula (B):
  • R 1 , R 2 , R 5 , R 6 , B and Z are as defined above.
  • leaving group means a group which is easily displaced by a nucleophile, for example, tosylate, mesylate, bromo.
  • the compound of formula (E) may be synthesised by
  • the active compounds of the invention are well tolerated by plants, in contrast to many other
  • insecticides have a favourably low level of toxicity to warm-blooded animals and fish, and can be used for combating arthropod pests, especially insects or acarids, which are encountered in agriculture, in veterinary practice, in forestry, in the protection of stored products and of materials, and in the hygiene field.
  • the abovementioned pests include Lucilia cuprina (the Australian sheep blowfly), Blatella germanica (German cockroach), Helicoverpa punctigera (cotton budworm),
  • Musca domestica housefly Aedes Australis Australian mosquito, Periplaneta americana American cockroach, Pheidole megacephala coastal brown ant, Dermestes maculata hide beetle, Triboleum castaneum flour beetle, Stegobium paniceum, drug store beetle and Sitophilus oryzae rice weevil.
  • the present invention also provides arthropodicidal compositions containing as active ingredient(s) one or more compound(s) of the present invention.
  • the present invention also provides a method of combating arthropods (especially insects or acarids) which comprises applying to the arthropods, or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention.
  • the present invention also provides a method of freeing or protecting domesticated animals from
  • parasitical insects or acarids which comprises applying to said animals a compound according to the present invention, or a composition containing such a compound as the active ingredient.
  • the active compounds are converted into such customary formulations as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, and coating compositions for use on seed, as well as ULV cold mist and warm mist
  • formulations may be produced in known manner, for example by mixing the active compounds with
  • extenders i.e., liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface- active agents, i.e. emulsifying agents and/or dispersing agents and/or foam-forming agents.
  • surface- active agents i.e. emulsifying agents and/or dispersing agents and/or foam-forming agents.
  • auxiliary solvents such as for example, organic solvents, can also be used.
  • liquid diluents or carriers are aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride; aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions;
  • aromatic hydrocarbons such as xylene, toluene or alkyl naphthalenes
  • chlorinated aromatic or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride
  • aliphatic or alicyclic hydrocarbons such as cyclohexane or paraffins, for example mineral oil fractions
  • alcohols such as butanol or glycol, as well as their ethers; and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; and strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water.
  • liquefied gaseous diluents or carriers liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellents, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
  • solid carriers examples include ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth; and ground synthetic minerals, such a highly-dispersed silicic acid, alumina and silicates.
  • solid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite; as well as synthetic granules or inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
  • emulsifying and/or foam-forming agents are non-ionic and anionic emulsifiers, such as
  • polyoxyethylene-fatty acid esters polyoxy ethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates, as well as albumin hydrolysis products.
  • Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
  • Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, poiyvinyl alcohol and poiyvinyl acetate, can be used in the formulations. It is also possible to use colorants such as
  • inorganic pigments for example iron oxide, titanium oxide and Prussian Blue
  • organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs.
  • the formulations in general will contain from 0.01 to 99 per cent by weight of active compound, preferably from 0.5 to 95 per cent by weight.
  • the active compounds according to the invention may be used in the form of formulations of the types that are commercially available or in the use forms prepared from these formulations.
  • the active compound content of the use forms may be used in the form of formulations of the types that are commercially available or in the use forms prepared from these formulations.
  • the proportion of the active compound in such use forms can range from 0.0000001% (0.1 ppm) to 99.9% by weight, the preferred range being from 0.1 ppm to 10% by weight.
  • the compounds may be employed in a customary manner appropriate for the particular use forms.
  • the active compounds according to the invention are also suitable for combating ectoparasites and
  • the compounds may be used in a known manner, such as orally in the form of, for example, tablets, capsules, drenches and granules; dermally by means of, for example, dipping, spraying, pouring-on, spotting-on and powdering.
  • the compounds may be employed either as the sole toxic agent in compositions such as those described above, or in combination with other insecticides such as pyrethrum, rotenone, or with fungicidal or bactericidal agents, to provide compositions useful for household and agricultural dusts and sprays, textile coating and impregnation.
  • insecticides such as pyrethrum, rotenone, or with fungicidal or bactericidal agents
  • the compounds of the invention may be advantageously combined with other substances which have a synergistic or potentiating action.
  • such substances are of the class of microsomal oxidase
  • inhibitors i.e. they inhibit the detoxification of insecticides in insects produced by the action of
  • oxidative enzymes Typical substances of this type are the pyrethrin synergists of which the following are examples:-
  • Piperonyl butoxide is particularly useful as a potentiator.
  • the amount of piperonyl butoxide used may vary from 1/1000th to fifty times the weight of the compound (I) the preferred range being from about 1/100th to five parts by weight.
  • "Sesamex" also is a useful potentiator in similar amounts.
  • Triphenylphosphite methiodide (16 g, 35.4 mmole) was added over 3 minutes to a solution of 1-[4-ethoxyphenyl]- 2,2-difluorocyclopropylmethanol (6.8g, 29.5 mmole) in dry dimethylformamide (30 ml) maintained at 5-10°C. The mixture was stirred at 10-12°C for 30 minutes and then added to ice-cold 5% sodium hydroxide solution and extracted with diethyl ether. The extracts were washed with water and sodium thiosulphate solution, dried over anhydrous magnesium sulphate and evaporated, to yield an oil (18.2 g).
  • IR (film) ⁇ max 2980, 1720, 1660, 1610, 1597, 1578, 1515 cm -1 .
  • N-butyl lithium (1.78 ml, 4.44 mmole) (2.5 M in hexane) was added dropwise over five minutes to a stirred solution of 1-(1-[4-ethoxyophenyl]-2,2- difluorocyclopropyl)-2-isocyano-2-(4-toluenesulphonyl) ethane (1.50 g, 3.7 mmole) in anhydrous tetrahydrofuran (15 ml) at -70oC in an argon atmosphere. The reaction mixture was stirred for an additional eight minutes, then a solution of the acid chloride in tetrahydrofuran (10 ml) was added dropwise over seven minutes.
  • reaction mixture was stirred at -70°C for one hour and then allowed to warm slowly to room temperature and stirred for one hour.
  • Concentrated hydrochloric acid (8 ml) and dichloromethane (10 ml) was then added to the solution and the mixture stirred for one hour.
  • the reaction mixture was added to ice-water and extracted with
  • IR (film) ⁇ max 2970, 1715, 1675, 1660, 1605, 1590, 1572, 1508 cm -1 .
  • Diethylaminosulphurtrifluoride (0.555 g, 3.46 mmole) was added to a stirred solution of 1-[1-(4-ethoxyphenyl)- 2,2-difluorocyclopropyl]-3-(3-benzoylphenyl)-propan-2-one (0.50 g, 1.15 mmole) in dichloromethane (2ml) contained in a PTFE vessel at 20°C.
  • Triethylamine (0.225 g, 2.23 mmole), followed by 3- benzoylbenzyl bromide (0.612 g, 2.23 mmole) was added to a solution of 1-(4-ethoxyphenyl)-2,2,3,3-tetrafluoro- cyclobutane carboxylic acid (0.5 g, 1.7 mmole) in dry acetone (3 ml) in an argon atmosphere.
  • the reaction mixture was allowed to stir at room temperature for 16 hours, then diluted with petroleum spirit (40-60°C) and filtered through a pad of silica gel. The silica gel was washed with 10% ethyl acetate/petroleum spirit (40-60°C).
  • reaction mixture was stirred at room temperature for sixteen hours and then filtered through a pad of silica gel with 10% ethyl acetate/petroleum spirit (40-60°C) to yield a yellow oil (0.71 g).
  • the material was purified by HPLC on silica gel with 7.5% ethyl acetate/petroleum spirit (40-60°C) and filtered
  • IR (film) ⁇ max 2970, 2860, 1655, 1608, 1595, 1575, 1510, 1240 cm -1 .
  • Aluminium chloride (11.62g, 87.15mmole) was added over 5 minutes to a stirred mixture of 2-fluoro-5- methylbenzoyl chloride (10.0g, 57.94mmole) and benzene (20 ml). The mixture was heated to reflux for 2 hours then cooled, added to ice-water, and extracted with diethyl ether. The extract was washed with dilute
  • Insecticidal activity was investigated against blowfly, Lucilia cuprina.
  • the method used was as follows:- (a) The compounds were tested for activity against a susceptible strain.
  • test compound was applied in acetone solution, 0.5 ⁇ l dispensed with a Drummond micropipette to the dorsum of the thorax of 2-3 day old males.
  • Adult flies were fed on water and sugar-only and maintained at 25°C and 60-70% RH.
  • the mortalities were determined after 48 hours. Moribund flies were regarded as dead.
  • the LD 50 values, in terms of concentration, were interpolated from the probit/log dose relation using a computer program.
  • the LD 50 value was determined as described above.
  • Lake collected wild-type mosquito fish (Gambusia affinis) was laboratory adapted in conical flasks each containing 200 ml of filtered lake water (tap water is toxic due to chlorine content). The required

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Abstract

Composés selon la formule générale (I) et leurs formes isomériques et racémiques : caractérisés par le fait que n est 0 ou 1; A est oxygène, soufre, C=O, CH2, CF2, CD2, CDH, CHOH, CHX où X est fluor, chlore, brome ou iode; G est oxygène, soufre, CH2 ou CX3X4 où X3 et X4 sont similaires ou différents et chacun est fluor, chlore ou brome; X1 et X2 sont similaires ou différents et chacun est hydrogène ou fluor, chlore ou brome; et quand n est O, X1 et X2 peuvent également être des groupes méthyle; R1 est hydrogène, deutérium, CN, C=CH, fluor, chlore ou brome et R6 est hydrogène ou deutérium; ou R1 et R6 peuvent éventuellement former =O, ou (a) dans la formule (I) peut être (b) ou (c), R2 est oxygène, ou H et OH ensemble, ou N-OR8 où R8 est hydrogène ou alkyle inférieur éventuellement substitué par un ou plusieurs groupes halo; R3 est un groupe halo ou un groupe alkyle inférieur, alcoxy inférieur ou alkylthio inférieur, dans chacun desquels le groupe alkyle est éventuellement substitué par un ou plusieurs groupes halo; R4 est hydrogène ou un groupe halo ou alkyle inférieur; ou R3 et R4 peuvent éventuellement former un pont méthylènedioxy éventuellement mono- ou disubstitué par fluor; R5 est hydrogène, OH, alcoxy inférieur, SH, ou thioalkyle inférieur, fluor, chlore, brome ou iode; R7 est H2, HD, D2 ou oxygène. R9 est H, alcoxy inférieur ou alkylthio inférieur.
PCT/AU1990/000534 1989-11-08 1990-11-08 Arthropodicides Ceased WO1991007380A1 (fr)

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AUPJ728089 1989-11-08
AUPJ7280 1989-11-08

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WO1991007380A1 true WO1991007380A1 (fr) 1991-05-30

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1568718A1 (de) * 1965-10-19 1970-03-26 Gen Mills Inc Verfahren zur Herstellung von Benzophenoximen
GB1410542A (en) * 1972-02-03 1975-10-15 Basf Ag Process for the production of aromatic ketones
US4042613A (en) * 1974-04-23 1977-08-16 Dai Nippon Printing Co., Ltd. Benzophenone derivatives and their preparation and application
US4141995A (en) * 1975-04-17 1979-02-27 Lilly Industries Limited Ketone derivatives
GB2021559A (en) * 1978-02-27 1979-12-05 Synthelabo Benzylidene derivatives
US4305839A (en) * 1978-10-26 1981-12-15 Carstab Corporation Hydroxybenzophenones
JPS61282335A (ja) * 1985-06-06 1986-12-12 Honsyu Kagaku Kogyo Kk ヒドロキシベンゾフエノン類の製造方法
EP0209831A2 (fr) * 1985-07-23 1987-01-28 FRATELLI LAMBERTI S.p.A. Benzophénones substituées et leurs mélanges liquides utilisables comme initiateur de photopolymérisation
EP0273528A1 (fr) * 1986-12-19 1988-07-06 Shell Agrar GmbH & Co. KG Benzophénones et leur préparation
EP0279475A2 (fr) * 1987-02-17 1988-08-24 Ward Blenkinsop And Company Limited Dérivés de benzophénone

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1568718A1 (de) * 1965-10-19 1970-03-26 Gen Mills Inc Verfahren zur Herstellung von Benzophenoximen
GB1410542A (en) * 1972-02-03 1975-10-15 Basf Ag Process for the production of aromatic ketones
US4042613A (en) * 1974-04-23 1977-08-16 Dai Nippon Printing Co., Ltd. Benzophenone derivatives and their preparation and application
US4141995A (en) * 1975-04-17 1979-02-27 Lilly Industries Limited Ketone derivatives
GB2021559A (en) * 1978-02-27 1979-12-05 Synthelabo Benzylidene derivatives
US4305839A (en) * 1978-10-26 1981-12-15 Carstab Corporation Hydroxybenzophenones
JPS61282335A (ja) * 1985-06-06 1986-12-12 Honsyu Kagaku Kogyo Kk ヒドロキシベンゾフエノン類の製造方法
EP0209831A2 (fr) * 1985-07-23 1987-01-28 FRATELLI LAMBERTI S.p.A. Benzophénones substituées et leurs mélanges liquides utilisables comme initiateur de photopolymérisation
EP0273528A1 (fr) * 1986-12-19 1988-07-06 Shell Agrar GmbH & Co. KG Benzophénones et leur préparation
EP0279475A2 (fr) * 1987-02-17 1988-08-24 Ward Blenkinsop And Company Limited Dérivés de benzophénone

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DICTIONARY OF ORGANIC COMPOUNDS, Fifth Edition, (1982), CHAPMAN & HALL. See Compounds: C01502, Vol. 1, page 1138; D05723, Vol. 2, page 2086; H02334, Vol. 3, page 3117; M01030, Vol. 4, page 3757. *
PATENT ABSTRACTS OF JAPAN, C-421, page 166; & JP,A,61 282 335, (HONSYU KAGAKU KOGYO K.K.), 12 December 1986. *

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