GB2158826A - Pesticidal ketones - Google Patents

Pesticidal ketones Download PDF

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GB2158826A
GB2158826A GB08511838A GB8511838A GB2158826A GB 2158826 A GB2158826 A GB 2158826A GB 08511838 A GB08511838 A GB 08511838A GB 8511838 A GB8511838 A GB 8511838A GB 2158826 A GB2158826 A GB 2158826A
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Michael Elliott
Norman Frank Janes
Bhupinder Pall Singh Khambay
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National Research Development Corp UK
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • 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
    • A01N35/02—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 aliphatically bound aldehyde or keto groups, or thio analogues thereof; 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
    • A01N37/42—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/14—Unsaturated ethers
    • C07C43/17—Unsaturated ethers containing halogen
    • C07C43/174—Unsaturated ethers containing halogen containing six-membered aromatic rings
    • C07C43/1747—Unsaturated ethers containing halogen containing six-membered aromatic rings containing six membered aromatic rings and other rings
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    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
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    • C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
    • C07C43/295—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing hydroxy or O-metal 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C07C45/292—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with chromium derivatives
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/30—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation
    • C07C45/305—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with halogen containing compounds, e.g. hypohalogenation with halogenochromate reagents, e.g. pyridinium chlorochromate
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    • 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
    • C07C45/44—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reduction and hydrolysis of nitriles
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    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
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    • 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
    • C07C45/511—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 singly bound oxygen functional groups to >C = O groups
    • C07C45/513—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 singly bound oxygen functional groups to >C = O groups the singly bound functional group being an etherified hydroxyl group
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    • C07C47/00—Compounds having —CHO groups
    • C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
    • C07C47/24—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing halogen
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/38—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings
    • C07C47/457—Unsaturated compounds having —CHO groups bound to carbon atoms of rings other than six—membered aromatic rings containing halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups

Description

1 GB 2 158 826 A 1
SPECIFICATION
Improvements relating to pesticides This invention relates to presticides and in particular to pesticidal compounds, the preparation of such 5 compounds, intermediates for use in their preparation, compositions containing such compounds and the use of such compounds and compositions to control pests.
Accordingly the present invention comprises a compound of formula 1 1 RCH,COCHDR,, 10 in which formula;- RA represents a group ArCR^- in which Ar represents a phenyl or naphthyl group optionally substituted by one or more halogen, alkoxy, haloalkoxy, methylenedioxy or C,-C, alkyl or haloalkyl groups; R, and R, together with the carbon to which they are attached jointly represent a C,-C, cycloaklyl group 15 optionally substituted by one or more halogens atoms or C,-C, alkyl groups and R, represents the residue of an alcohol 11,,CHIDOH in which D is hydrogen or cyano and of which the PR, cis] 2,2-dimethyl3-(2,2-dibromovinyl)cyclopropane carboxylic ester is significantly insecticidal.
Ar is typically substituted phenyl and substitution is usually at the 3(meta) andlor 4-(para)-position by fluorine, bromine, chlorine, a CJ11-C, alkyl group e.g. methyl or tertbutyl, a C,-C, alkoxy group e.g. methoxy, ethoxy, a halomethoxy or haloethoxy group, which may comprise one or more halogens, e.g.
OCF,,0CF21-1 or halomethyl or haloethyl group e.g. CF,. Ar generally carries no more than two substi tuents, and typically only one.
The substituents R, and IR,, together with the carbon bearing them, typically represent a substituted or unsubstituted cyclopropyl group which, when substituted, preferably carries halogen and especially fluo25 rine as in 2,2-difluorocyclopropyl.
When the compound of formula 1 is chiral (as in the immediately foregoing case) it can of course exist in different stereoisomeric forms. Both mixtures of stereoisomers and single stereoisomers are included within the scope of the present invention.
R.CHD may represent the residue of any of the alcohols of formula R,, CHDOH claimed or described in 30 the specification for UK Patent No,1412491 which give rise to significant insecticidal activity when esteri fied with [IR, cis] -2,2-dimethyl-3-(3,2-dibromovinyi)carboxylic acid. Potency towards houseflies is usually at least 5 relative to bioresmethrin 100 and may be 10 or more.
Typically R,,CHID represents the residue of an alcohol R,Cl-11DOH which is 3-phenoxybenzyi, 4-phenoxy benzyi,u- cyano-3-phenoxybenzyI, 4-fluoro-3-phenoxybenzyl,ot- cyano-4- fluoro-3-phenoxybenzyl, 5-benzyi3-furyimethyl, 3-benzylbenzy], 4-benzyfbenzyi, 3-p henyl -2-m ethyl benzyi, 3-phenyl-2-chlorobenzyl or 3-ben zoylbenzyl alcohol.
Compounds of formula 1 may be produced in accordance with a further aspect of the present invention by reaction of an acid halide of formula R,CH,COX, in which X represents halogen e.g. chlorine with a reagent of formula IR,,Cl-lDMI, in which M represents a species comprising a metal, e.g. as in the Grignard 40 reagent R,,CHIDNIgY in which Y represents halogen, e.g, bromine.
In accordance with a further aspect of the present invention, a compound of formula 1 is produced by oxidation of an alcohol of formula R,Cl-1,i2CHOFICHDR,,, prepared, for example, by reaction of an alde hyde of formula RACH,CHO with a Grignard reagent of fornrula IR,,Cl- 11DIVIgY, in which Y represents halo gen, e.g. bromine. Oxidation of the alcohol is suitably effected by an appropriate oxidising agent such as 45 pyridinium chlorochromate or dichromate in a good solvent such as dichloromethane or chromium triox ide in acetone.
The present invention also includes within its scope intermediates of formula RA CH,COX and RA CH,CHOH CHDR,, In accordance with a further aspect of the present invention, one or more of the pesticidal compounds 50 of formula 1 is formulated with an inert carrier or diluent to give a pesticidal composition.
Compositions may be in the form of dusts, granular solids, wettable powders, mosquito coils or other solid preparations or as emulsions, emulsifiable concentrates, sprays or aerosols or other liquid prepara tions after the addition of the appropriate solvents, diluents and surfaceactive agents.
The pesticidal compositions of the invention will normally contain from 0. 001 to 25% by weight of the 55 compound of formula 1 but the compositions can contain higher concentrations of active ingredient of formula 1 e.g. up to 95% for compositions to be sold as concentrates for dilution before use by the ulti mate user.
The compositions of the invention can include diluents such as hydrocarbon oils, e.g. xylene or other petroleum fractions, water, anionic, cationic or non-ionic surface- active agents, anti-oxidants or other stabilisers as well as perfumes and colouring matters. These inert ingredients may be of the type and in proportions such as are conventionally used in pesticidal compositions containing pyrethroid-like corn pounds.
In addition to these inactive ingredients, the compositions of the present invention may contain one or more further active ingredients which may be other pesticidal compounds of the pyrethroid type or of 65 2 GB 2 158 826 A 2 other types and the composition may also include synergists of the type known to be capable of synergising the activity of natural pyrethrin and pyrethroid-like insecticides. Synergists of this type include piperonyl butoxide, tropital, sesamex and propyl prop-2-ynyl phenyl-phosphonate. Compounds of formula 1 can be used to control pest infestation in the domestic, horticultural or agri5 cultural or medical, including veterinary, areas. The compounds or compositions of the invention can be used to combat pest infestation by treating pests or surfaces of environments susceptible to pest infestation with effective amounts of the active compounds of formula 1 or of compositions containing them. For example, they may be used in a domestic environment for spraying rooms to combat infestation with houseflies or other insects, they can be used for treatment of stored crops or cereals to combat infestation by insects or other pests, they can 10 be used to spray growing crops, e.g. cotton or rice to combat infestation by common pests and they can be used in a medical or veterinary field, e. g. as a cattle spray to prevent or treat infestation by insects or other pests. The compounds may also find application in the control of virus acquisition by andlor transmission in plants particularly when mediated by aphids such as Nlyzus persicae, the peach-potato aphid. The compounds are additionally of interest for the control of pests such as the following:from the class of the lsopoda, for example Oniscus asellus, Armadillidium vulgare and Porcellio scaber; from the class of the Diplopoda, for example Blaniulus guttulatus; from the class of the Chilopoda, for example Geophilus carpophagus and Scutigera spec; from the class of the Symphyla, for example Scutigerella immaculata; from the order of the Thysanura, for example Lepisma saccharina; from the order of the Collembola, for example Onychiurus armatus; from the order of the Orthoptera, for example Blatta orientalis, Periplaneta americana, Leucophaea ma darae, Blattella germanica, Acheta domesticus, Cryllotalpa spp., Locusta migratoria migratorioides, Me- 25 lanoplus differentialis and Schistocerca gregaria; from the order of the Dermaptera, for example Forficula auricularia; from the order of the lsoptera, for example Reticulitermes spp; from the order of the Anoplura, for example Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp; from the order of the Mallophaga, for example Trichodectes spp. and Demalinea spp; from the order of the Thysanoptera, for example Hercinothrips fermoralis and Thrips tabaci; from the order of the Heteroptera, for example Eurygaster spp., Dysdercus intermedius, Piesma quad rata, Cimex lectularius, Rhodnius prolius and Triatoma spp.; from the order of the Homoptera, for example Aleurodes br brassicae, Bernisia tabaci, Trialeurodes 35 vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Er iosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalo siphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium comi, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, AondUella aurantii, Aspidiotus hederae, Pseudococcus spp.
and Psylla spp; from the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius, Cheimato bia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neus tria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Fieris spp., Chilo spp., 45 Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristo neura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana; from the order of the Coleoptera, for example Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica aini, Leptinotarsa decemlineata, Phae don cochle riae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestris, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimills, Hypera postica, Dermestes spp., Trogoderma spp. , Anthrenus spp., Attagenus spp., Lyetus spp., Meligethes aenus, Ptinus spp., Niptus hololeucus, Gibbium psylloids, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melointha, Amphimallon solstitialis and Costelytra zealandica; from the order of the Hymenoptera, for example Diprion spp., Hoplacampa spp., Lasius spp., Monomo rium pharaonis and Vespa spp., from the order of the Diptera, for example Aedes spp., A Anopheles spp., Culex spp., Drosophila me lanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., 60 Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa; from the order of the Siphonaptera, for example Xenopsylla cheopis and Ceratophyllus spp.; from the class of the Arachnida, for example Scorpio maurus and Latrodectus mactans; from the order of the Acarina, for exmaple Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus 65 3 GB 2 158 826 A 3 gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorloptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.
The invention is illustrated by the following Examples. Temperatures are in 'C and refractive indices 5 are measured at 2WC.
EXAMPLE 1 1-(4-ethoxyphenyl)-1-(3-(3-phenoxyphenyl)-2-oxopropyl)cyclopropane (Compound 1) jo A. 1-cyano-l-(4-ethoxyphenyl)cyclopropane (Compound a) 1.6M n-Butyllithium (680mi) is added over 5 min to a stirred solution of 4-ethoxyphenyl acetonitrile (56g) in anhydrous THF (600 mO at WC under an atmosphere of nitrogen. After l h, a solution of 1.2 dichloroethane (111g) in anhydrous THF (300 mO is added dropwise over 2h and the mixture stirred at 25'C for 16h. The mixture is then poured onto 3NIHICII (11), concentrated under reduced pressure, ex- tracted with diethyl ether (x3), washed with water, dried over anhydrous sodium sulphate, the solvent removed under reduced pressure and the residue distilled to give the product, b.p.1 16 - 1120'C, yield 40g. nj. 5320.
B. 1-(4-ethoxyphenyl)-1-cyclopropanemethanaI (Compound b) 1 M Diisobutylaluminium hydride (14mi) is added over 3 min. to a stirred solution of 1-cyano-l-(4ethoxyphenyl)- cyclopropane (1.4g) in dry benzene (35 m[) and dry n-heptane (14 mi) at 25'C under an atmosphere of nitrogen. After 3h the mixture is poured onto 2N H2S04 (100 mi), extracted with diethyl ether (x3), dried and the solvent removed under reduced pressure. Yield lg, n,, 1.5272 C. 1-(ethoxyphenyl)-1-(EIZ-2-methoxyethenyl)-cyclopropane (Compound c) 2.4M Phenyllithium (3.1 mi) is added to a stirred suspension of (methoxymethyl)tri phenyl phosphonium chloride (2.55g) in dry diethyl ether (50 mi) at room temperature under an atmosphere of nitrogen. After 30 min a solution of 1-(4-ethoxyphenyl)-1-cyclopropanemethanal (1g) in diethyl ether (5 mi) is added over 5 min. The mixture is stirred at room temperature overnight, poured onto saturated NIHI,Cl, extracted with diethyl ether (0, filtered, dried and the solvent evaporated under reduced pressure. The product is purified by column chromotography on florosif and petroleum ether (b.p.60-80'C) as eluant. Yield 1.6g, n,, 1. 5532.
D. 1-(4ethoxyphenyl)-1-(2-oxoethyl)cyclopropane (Compound cl) A solution of 1-(4-ethoxyphenyi)-1-(EIZ-2-methoxyethenyl)- cyclopropane (1.69) in THF (5 ml) is added 35 to a mixture of THF (50 m[) and concentrated HCl (6 m[), and stirred at room temperature for l h. The mixt re is poured onto water, concentrated under reduced pressure, extracted with diethyl ether (x3), washed with water, dried and the solvent evaporated under reduced pressure Yield 1.2g n,, 1.5375.
E. 1-(4-ethoxyphenyi)-1-(3-(3-phenoxyphenyi)-2-hydroxypropyl)cyclopropane (Compound e) A Grignard reagent prepared from 3-phenoxybenzyl bromide (0.98g), magnesium turnings (0.1g) in dry diethyl ether (15 mi) under an atmosphere of nitrogen, is cooled with vigorous stirring to 7WC. To this is added a solution of 1-(4-ethoxyphenyi)-1-(2-oxoethyi)cyclopropane (0. 5g) in diethyl ether (15 m]) over min. The resulting mixture is allowed to warm up to room temperature over 1h. Saturated N1H4C1 SolU_ tion is added and the mixture extracted with diethyl ether (x3), dried and the solvent evaporated under 45 reduced pressure. The product is purified by t.l.c. on silica eluted with 10% diethyl ether in petroleum ether (b.p. 60-80'C) Yield 0.25g, n,, 1.5444.
F. 1-(4-ethoxyphenyl)-1-(3-(3-pheno.xyphenyl)-2-oxopropyl)-cyclopropane (Compound 1) Jones reagent (2 mi, prepared by the method described in Fieser and Fieser Vol.1, p.142) is added 50 dropwise to a stirred solution of 1-(4-ethoxyphenyl)-1-(3-(3- phenoxyphenyi)-2-hydroxypropyi)-cyclopropane (0.25g) in acetone (5 mi) whilst maintaining the temperature below 5'C. After 15 min. the mixture is allowed to warn up to room temperature over 4h, diluted with water, extracted with diethyl ether (x3), washed with water, dried and the solvent evaporated under reduced pressure. The product is purified by thin layer chromatoghraphy on silica gel diluted with 15% diethyl ether in petroleum ether (b.p. 60-80'C). 55 Yield 0.03g, n, 1.5580.
EXAMPLE2 The following enol ether (f) is prepared as described in Example 1IC;60 f: 1-(4-ch 1 o rop he nyi)-1 -(E/Z-2-m eth oxyeth enyl)-cycl o pro pane n,) 1.5806 Compound f is made from 11-(4-chlo ro phenyl)cyclopropanemethanal, itself made by oxidation of l- (4chlorophenyi)cyclopropanemethanol with pyridium dichromate, under standard conditions (E.J. Corey and G. Schmidt, Tetrahedron Lett. 1979,399) Enol ether (f) is converted to the corresponding aldehyde (g) by following the method of Example 1 D:- 9:1-(4-chlorophenyi)-1-(2-oxethyi)-cyclopropane n, 1.5816.
4 GB 2 158 826 A 4 The above aldehyde (g) is reacted with a Grignard reagent by following the method of Example 1 E to give compound h:
h:. 1-(4-ch 1 o rophenyl)-1 -(3-(3-p hen oxyph enyl)-2- hydroxypropyi)cyclopropane. no 1.5325.
Compound h is oxidized to the corresponding ketone (compound 2) by means of pyridinium chloro5 chromate, the use of which is described in Corey & Suggs, Tetrahedron Lett.1975, 2647.
Compound 2: 1-(4-chlorophenyl)-1-(3-(3-phenoxyphenyl)-2-oxopropyl)cyclopropane, no 1.5782 Examples 3 & 4 The following alcohols (i & j.) are prepared from aldehydes d and g by reaction thereof with a Grignard 1 o reagent following procedure 1 E:
i. 1-(4-ch lo roph enyl)-l -(3-(4-f I u o ro-3-p hen oxyphenyl)- 2hydroxypropyl)-cyclopropane no 1.5500 j. 1-(4-ethoxyphenyl)-l-(3-(4fluoro-3-phenoxyphenyl)- 2-hydroxypropyl)-cyclopropane no 1.5630 Alcohols i & j are oxidised to the corresponding ketones (compounds 3 & 4) by following the procedure described in Examples 2 and 1 respectively:
Compound 3: 1-(4-chlorophenyi)-1-(3-(4-fluoro-3- phenoxyphenyi)-2oxopropyi)-cyclopropane, no 15 1.5764.
Compound 4: 1-(4-ethoxyphenyi)-1-(3-(4-fluoro-3- phenoxyphenyi)-2oxopropyi) cyclopropane n, 1.5580.
Pesticidal activity is assessed against houseflies and mustard beetles by using the following techniques- Houseflies (Musca domestica) Female flies are treated on the thorax with a one microlitre drop of insecticide dissolved in acetone.
Two replicates of 15 flies are used at each dose rate and 6 dose rates are used per compound under test.
After treatment, the flies are maintained at a temperature of 20' 1' and kill is assessed 24 and 48 hours after treatment. LD,, values are calculated in micrograms of insecticide per fly and relative toxicities are 25 calculated from the inverse ratios of the LD,,, values (see Sawicki et al, Bulletin of the World Health Or ganisation, 35, 893, (1966) Sawicki et al, Entomologia and Exp. Appli. 10 253, (1967)).
Mustard beetles (Phaedon cochleariae Fab) Acetone solutions of the test compound are applied ventrally to adult mustard beetles using a micro 30 drop applicator. The treated insects are maintained for 48 hours after which time kill is assessed. Two replicates of 40 to 50 mustard beetles are used at each dose level and 5 dose levels are used for each compound.
LID, values and thence relative potencies are calculated as for houseflies.
For both insect species relative potencies are calculated by comparison with 5-benzyl-3-fury[methyl (IR)-trans- chrysanthernate (Bioresmethrin) which is one of the more toxic chrysanthemate esters known to houseflies and mustard beetle, its toxicity being about 24 times that of allethrin to houseflies and 65 times that of allethrin to mustard beetles.
Results Relative potencies to Houseflies and Mustard Beetles (Bioresmethrin = 100) are given under HF and MB respectively in the Table.
TABLE
Compounds of formula R A CII 2 COCI1DR B 0P0B - 3 phenoxybenzyl Bioassay results 45 4F3P0B = 4-fluoro-3-phenoxybenzyl) Compound Ar CR 1 R 2 -CHDR B HF MB 50 1 4-ethoxyphenyl cyclopropyl 3P0B ca 6 3 2 4-chlorophenyl cyclopropyl 3P0B 2.1 8.7 55 3 4-chlorophenyl cyclopropyl 4F3P0B 33 4 4-ethoxyphenyl cyclopropyl 4F3P0B ca 6 5.1 GB 2 158 826 A 5

Claims (15)

1. A compound of formula 1 1 RACH,C0CHDRa 5 in which formula:- RA represents a group ArCR1R2 - in which Ar represents a phenyl or naphthyl group optionally substituted by one or more halogen, alkoxy, haloalkoxy, methylenedioxy or Cl-C, alkyl or haloalkyl groups; R, and R2 together with the carbon to which they are attached jointly represent a C,-C, cycloaklyl group 10 optionally substituted by one or more halogen atoms or C,-C, cycloakly] groups and Re represents the residue of an alcohol ReCHD01-1 in which D is hydrogen or cyano and of which the OR, cis] 2,2-dimethyi-3-(2,2-dibromovinyi)cyclopropane carboxylic ester is significantly insecticidal.
2. A compound according to Claim 1, in which Ar represents substituted or unsubstituted phenyl.
3. A compound according to Claim 1 or 2, in which Ar represents phenyl substituted at the 3 andlor 4 is position.
4. A compound according to any preceding claim in which Ar represents phenyl substituted by chlor ine or ethoxy.
5. A compound according to any preceding claim, in which CR,R2- represents cyclopropyl.
6. A compound according to any preceding claim, in which RaCHID represents the residue of a phen- 20 oxy, benzyi or benzoyl substituted benzyl alcohol.
7. A compound according to Claim 6, in which the residue is of 3phenoxybenzyl or 4-fluorophenoxy benzyl alcohol.
8. A compound of formula 1 substantially as described in any of the Examples.
9. A process for the production of a compound of formula 1 in which an acid halide of formula 25 R,Cl-12COX, X representing halogen, is reacted with a reagent of formula R,CHDM in which M represents a species comprising a metal, R,Re & D being as hereinbefore defined.
10. A process according to Claim 9, in which M represents MgBr
11. A process for the production of a compound of formula 1, in which an alcohol of formula R,Cl-1,Cl-101-ICHDRa is oxidised.
12. A process according to Claim 11, in which oxidation is effected by pyridinium chlorochromate, pyridinium dichromate or chromium dioxide in acetone.
13. An intermediate of formula R,Cl-12COX or R,Cl-1,Cl-ICHCHDRe, RA, D, Ru and X being as hereinbe fore defined.
14. A pesticidal composition which comprises a compound of formula 1 formulated with an inert car- 35 rier or diluent.
15. A method of combatting pest infestation in which a pest or a surface or environment susceptible to pest infestation is treated with an effective amount of a compound of formula 1.
Printed in the UK for HMSO, D8818935, 9i85, 7102.
Published by The Patent Office, 25 Southampton Buildings, London, WC2A lAY, from which copies may be obtained-
GB08511838A 1984-05-16 1985-05-10 Imrovements relating to pesticides Expired GB2158826B (en)

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US4829091A (en) * 1987-05-27 1989-05-09 The United States Of America As Represented By The Secretary Of Agriculture Process for the preparation of ketones and novel insecticides produced therefrom
US5157048A (en) * 1987-05-27 1992-10-20 The United States Of America, As Represented By The Secretary Of Agriculture Process for the preparation of ketones and novel insecticides produced therefrom
US5274136A (en) * 1987-05-27 1993-12-28 The United States Of America As Represented By The Secretary Of Agriculture Process for the preparation of ketones
FR2807434B1 (en) * 2000-04-05 2002-10-18 Hoechst Marion Roussel Inc NOVEL 1,2,3,4-TETRAHYDROISOQUINOLEIN DERIVATIVES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS FUNGICIDES

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US3997586A (en) * 1967-08-22 1976-12-14 Roussel-Uclaf Cyclopropanecarboxylic acids and esters
US3666789A (en) * 1969-05-21 1972-05-30 Sumitomo Chemical Co Cyclopropanecarboxylic acid esters
GB1413491A (en) * 1972-05-25 1975-11-12 Nat Res Dev 3-substituted-2,2-dimethyl-cyclopropane carboxylic acid esters their preparation and their use in pesticidal compositions
AU526817B2 (en) * 1978-06-21 1983-02-03 Ici Australia Limited Pesticides
US4218468A (en) * 1978-11-13 1980-08-19 Mobil Oil Corporation Ketone insecticides
US4206230A (en) * 1978-11-13 1980-06-03 Mobil Oil Corporation Phenyl cyclopropyl ketone insecticides
US4391820A (en) * 1980-06-13 1983-07-05 Commonwealth Scientific And Industrial Research Organization Insecticidal ester enantiomers
DE3025218A1 (en) * 1980-07-03 1982-02-11 Bayer Ag, 5090 Leverkusen 1-ARYL-CYCLOPROPAN-1-CARBONIC ACID ESTER, METHOD FOR THE PRODUCTION AND USE THEREOF IN PEST CONTROL
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US4418202A (en) * 1981-12-21 1983-11-29 Emery Industries, Inc. 2-Vinyl- and 2-ethylcyclopropane monocarboxylates
US4562213A (en) * 1982-05-12 1985-12-31 Sumitomo Chemical Company, Limited Certain phenoxy-benzyloxy ether derivatives and an insecticidal and/or acaricidal composition containing the same and methods of use

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GB8412480D0 (en) 1984-06-20
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US4713392A (en) 1987-12-15
EP0161921A3 (en) 1987-07-15
GB8511838D0 (en) 1985-06-19

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