Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

Definitions

• This invention relates to cyclopropyl carboxylate compounds pcs- sessing pesticidal activity, to a process for the manufacture and to their use as pesticides.
• the compounds are related to the so-called synthetic pyrethroids.
• United Kingdom Patent Specification 1,413,491 discloses, inter alia, 3-phenoxybenzyl esters and alpha-substituted 3-phenoxybenzyl esters of 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropanecarboxylic acids; it also discloses their use as insecticides. Whilst the high level of activity of this class of compounds against insects is disclosed, no mention is made to their activity against Acarines such as the Ixodidae family and the Tetranychidae family.
• the Applicant has now fourd a small group of 3-phenoxybenzyl esters and alpha-substituted-3-phenoxybenzyl esters of 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropanecarboxylie acids which not only exhibit high levels of insecticidal activity but also have a significant effect on acarines, for example Tetranychus urticae (glasshouse red spider mite) and Boophilus microplus (cattle tick).
• the present invention provides cyclopropyl carbcxy- late compounds in the form of single isomers or combinations thereof and having the general formula:- wherein X is a chlorine, bromine or iodine atom and Y is a hydrogen - atom or a cyano or ethynyl group.
• X is a chlorine atom.
• the compounds according to the invention can exist in a number of stereoisomeric forms.
• the hydrogen atoms carried by carbon atoms 1 and 3 in the cyclopropyl ring can be in a cis or trans relationship and because of asymmetrical substitution at these carbon atoms each cis isomer can exist in two stereoisomeric forms and each trans isomer can exist in two stereoisomeric forms.
• the absolute configuration of these four stereoisomeric forms can be satisfactorily defined using the Elliott nomenclature as defined by M. Elliott, A.W. Farnham, N.F. Janes, P.H. Needham and D.A. Pulman, Nature, 1974, 248, 710.
• the four stereoisomeric forms are designated (1R, cis), (1S, cis), (1R, trans) and (1S, trans).
• Y represents a cyano or ethynyl group
• a further site of asymmetry occurs at the alpha-carbon atom carrying the Y-substituent and the absolute configuration of this carbon atom may be designated R or S in accordance with the sequence rules of R.S. Cahn, C. Ingold, and V. Prelog, Angew. Chem. Int. Ed. 5, 385 (1966). It should be noted that the Elliot et al nomenclature and the Blackwood et al nomenclature are both based on these sequence rules.
• the compounds according to the invention can exist in 16 stereoisomeric forms and, whilst all isomers or combinations thereof come within the scope of the invention, it has been found that compounds derived from a cyclopropyl carboxylate having a configuration at carbon atoms 1 and 3 in one of the following forms:-(1R, 1S cis), or (1R, cis) give rise to better activity in terms of their acaiicidal and insecticidal effects.
• the cyclopropyl carboxylate of formula I may be prepared by known methods.
• a convenient process is the reaction of a compound of formula:- with a compound of formula:- wherein X and Y are as defined hereinbefore; one of the groups Q and Z represents a halogen, preferably a chlorine or bromine atom, and the other represents a hydroxy group.
• the reaction is preferably carried out in the presence of a suitable base, for example a tertiary amine suchastriethylamine.
• a suitable base for example a tertiary amine suchastriethylamine.
• the appropriate stereoisomeric starting materials should be selected.
• the compounds of the invention are of particular interest as acaricides and insecticides and therefore the invention includes pesticidal compositions comprising a compound according to the invention, a surface-active agent and/or carrier.
• the invention also includes a method for combating acarid and/or insect pests at a locus which comprises applying to the locus an acaricidally-active or in- seeticidally-active amount of a compound or composition according to the invention.
• carrier means a material, which may be inorganic or organic and of synthetic or natural origin, with which the active compound is mixed or formulated to facilitate its application to the plant, seed, soil or other object to be treated, or its storage, transport or handling.
• the carrier may be a solid or a fluid. Any of the material usually applied in formulating pesticides may be used as carrier.
• Suitable solid carriers are natural and synthetic clays and silicates, for example natural silicas such as diatomaceous earths; magnesium silicates, for example, tales; magnesium aluminium silicates, for example, kaolinites, montmorillinites and micas; calcium carbonates; calcium sulphate; synthetic hydrated silicon oxides and synthetic calcium or aluminium silicates; elements such as for exam- pie, carbon and sulphur; natural and synthetic resins such as for example, coumarone resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorophenols; bitumen; waxes such as for example, beeswax, paraffin wax, and chlorinated mineral waxes; and solid fertilisers, for example superphosphates.
• natural silicas such as diatomaceous earths
• magnesium silicates for example, tales
• magnesium aluminium silicates for example, kaolinites, montmorillinites and micas
• calcium carbonates calcium s
• suitable fluid carriers are water, alcohols, such as for example, isopropanol, glycols, ketones such as for example, acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic hydrocarbons, such as for example, benzene, toluene and xylene; petroleum fractions such as for example, kerosine, light mineral oils; chlorinated hydrocarbons, such as for example, carbon tetrachloride, perchloroethylene, trichloroethane, including liquefied normally vaporous gaseous compounds. Mixtures of different liquids are often suitable.
• the surface-active agent may be an emulsifying agent or a dispersing agent or a wetting agent; it may be nonionic or ionic. Any of the surface-active agents usually applied in formulating herbicides or insecticides may be used.
• suitable surface-active agents are the sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohols or alkyl phenols for example p-octyiphenol or p-octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkali or alka
• compositions of the invention may be formulated as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols, and will generally contain 0.5 to 95% w, preferably 0.5 to 75% w, of toxicant.
• Wettable powders are usually compounded to contain 25, 50 or 75% w, of toxicant and usually contain, in addition to solid carrier, 3-10% w of a dispersing agent and, where necessary, 0-10% w of stabiliser(s) and/or other additives such as penetrants or stickers.
• Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and are diluted in the field with further solid carrier to give a composition usually containing -10% w of toxicant.
• Granules are usually prepared to have a size between 10 and 100 BS mesh, and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain -25% w toxicant and 0-10% w of additives such as stabilisers, slow release modifiers and binding agents.
• Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w/v toxicant, 2-20% w/v and 0-20% W/V of appropriate additives such as stabilisers, penetrants and corrc- sion inhibitors.
• Suspension concentrates are compounded so as tc ot- tain a stable, non-sedimenting, flowable product and usually cortion 1-75% w toxicant, 0.5-15% w cf dispersing agents, 0.1-10% w of pending agents such as protective colloids and thixotropic agents.
• compositions of the invention may contain other ingredients, for example, protective colloids such as gelatin, glue, casein, gum, cellulose ethers, and polyvinyl alcohol; thixotropic agents e.g. bentonites, sodium polyphosphates; stabilisers such as ethylene diamine tetra-acetic acid, urea, triphenyl phosphate; other herbicides or pesticides; and stickers, for example non-volatile oils.
• protective colloids such as gelatin, glue, casein, gum, cellulose ethers, and polyvinyl alcohol
• thixotropic agents e.g. bentonites, sodium polyphosphates
• stabilisers such as ethylene diamine tetra-acetic acid, urea, triphenyl phosphate
• other herbicides or pesticides such as urea, triphenyl phosphate
• stickers for example non-volatile oils.
• Aqueou dispersions and emulsions for example, compositions obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, also lie within the scope of the present invention.
• the said emulsions may be of the water-in-oil or of the oil-in-water type, and may have a thick "mayonnaise"-like consistency.
• Example 1A Preparation of starting acid for Example 1 ((1S,1R,cis) (E/Z)-3-(2-chloro-2-chloro-2-fluorovingyl)-2,2-dimethyl-1-cyclo propanecarboxylic acid)
• Dichlorofluoromethane was dissolved in 100ml sodium-dried hexane at 0°C.
• the dichlorofluoromethane (7.2g; 0.07mol) solution was added with stirring over 20 minutes at 0°C under nitrogen to a flask containing 100ml dry hexane, potassium tertiary butoxide (7.85g; 0.07mol) and triphenylphosphine (18.3g; 0.07mol).
• the flask was allowed to warm to 15°C and then a hexane solucion of (1S,1R)-cis-earonaldehyde methyl ester (10.gl 0.064 mol) added over 15 minutes.
• the ester (3.3g) was hydrolysed to the free acid using ethanol and 2N-sodium hydroxide to yield 2.6g acid (84%).
• Example 8 Acaricidal activity of the cyclopropyl carboxylate competition
• the cyclopropyl carboxylates were formulated as solutions or suspensions in water containing 20% by weight of acetone and 0.05% by weight of Triton X100 as wetting agent: The formulations contained 0.4% by weight of the compound to be tested.
• Leaf discs cut from French bean plants were held on moist filter paper placed on a lid inside a waxed carton. Prior to testing, each leaf disc was infested with 10 adult mites. The mites and discs were then sprayed using a logarithmic spraying machine and held under standard glasshouse conditions. After 24 hours the percentage dead and moribund mites were assessed.

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• Life Sciences & Earth Sciences (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Cited By (6)

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Citations (2)

• 1978
  • 1978-05-29 CA CA304,269A patent/CA1123452A/fr not_active Expired
  • 1978-06-08 ZA ZA00783300A patent/ZA783300B/xx unknown
  • 1978-06-20 DE DE7878200056T patent/DE2861395D1/de not_active Expired
  • 1978-06-20 EP EP78200056A patent/EP0000229B1/fr not_active Expired
  • 1978-06-27 EG EG398/78A patent/EG13418A/xx active
  • 1978-06-28 NZ NZ187712A patent/NZ187712A/xx unknown
  • 1978-06-28 AU AU37513/78A patent/AU525337B2/en not_active Expired
  • 1978-06-28 BR BR7804122A patent/BR7804122A/pt unknown
  • 1978-06-28 IL IL55027A patent/IL55027A/xx unknown
  • 1978-06-28 GR GR56623A patent/GR64837B/el unknown
  • 1978-06-28 TR TR20942A patent/TR20942A/xx unknown
  • 1978-06-28 JP JP7755078A patent/JPS5412351A/ja active Pending
  • 1978-06-28 DK DK292478A patent/DK292478A/da not_active Application Discontinuation
  • 1978-06-28 IT IT7825089A patent/IT7825089A0/it unknown
  • 1978-06-28 MX MX787189U patent/MX5434E/es unknown

Patent Citations (2)

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