EP0000229B1 - Cyclopropancarbonsäure-ester, Verfahren zu deren Herstellung und ihre Verwendung als Pestizide - Google Patents

Cyclopropancarbonsäure-ester, Verfahren zu deren Herstellung und ihre Verwendung als Pestizide Download PDF

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Publication number
EP0000229B1
EP0000229B1 EP78200056A EP78200056A EP0000229B1 EP 0000229 B1 EP0000229 B1 EP 0000229B1 EP 78200056 A EP78200056 A EP 78200056A EP 78200056 A EP78200056 A EP 78200056A EP 0000229 B1 EP0000229 B1 EP 0000229B1
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Prior art keywords
compound
compounds
cis
manufacture
pesticides
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EP78200056A
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English (en)
French (fr)
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EP0000229A1 (de
Inventor
John Hugh Davies
John Stewart Badmin
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Shell Internationale Research Maatschappij BV
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Shell Internationale Research Maatschappij BV
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    • 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 possessing pesticidal activity, to a process for their manufacture and to their use as pesticides.
  • the compounds are related to the so-called synthetic pyrethroids.
  • United Kingdom Patent Specification 1,413,491 and French Patent Specification 2,240,914 disclose, inter alia, 3-phenoxybenzyl esters and alpha-substituted 3-phenoxybenzyl esters of 2,2-dimethyl-3-(2,2-dihalovinyl)cyclopropanecarboxylic acids; they also disclose the use of these compounds 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 present invention provides cyclopropyl carboxylate 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 (1 R, cis), (1 S, cis), (1R, trans) and (1 S, trans).
  • Y represents a cyano or ethynyl group
  • a further site of asymmetry occurs at the a/pha-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. lnt. 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 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 such as triethylamine.
  • a suitable base for example a tertiary amine such as triethylamine.
  • a particular isomeric form of the compounds according to the invention is required the appropriate stereoisomeric starting materials should be selected.
  • various isomers or isomer combinations can be isolated by physical separation techniques, e.g. fractional crystallization or chromatographic methods.
  • 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 insecticidally-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, talcs; 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 example, 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, talcs
  • magnesium aluminium silicates for example, kaolinites, montmorillinites and micas
  • calcium carbonates calcium
  • 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-octylphenol 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 (1.676-0.152 mm), and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 2-25% 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, cosolvent, 10-50 g/100 ml toxicant, 2-20 g/100 ml emulsifiers and 0-20 g/100 ml of appropriate additives such as stabilisers, penetrants and corrosion inhibitors.
  • Suspension concentrates are compounded so as to obtain a stable, non-sedimenting, flowable product and usually contain 1-75%w toxicant, 0.5-15%w of dispersing agents, 0.1-10% w of suspending agents such as protective colloids and thixotropic agents, 0-10%.w of appropriate additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and as carrier, water or an organic liquid in which the toxicant is substantially insoluble; certain organic solids or inorganic salts may be dissolved in the carrier to assist in preventing sedimentation or as anti-freeze agents for water.
  • 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.
  • Aqueous 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.
  • Dichlorofluoromethane was dissolved in 100 ml sodium-dried hexane at 0°C.
  • the dichlorofluoromethane (7.2 g; 0.07 mol) solution was added with stirring over 20 minutes at 0°C under nitrogen to a flask containing 100 ml dry hexane, potassium tertiary butoxide (7.85 g; 0.07 mol) and triphenylphosphine (18.3 g; 0.07 mol).
  • the flask was allowed to warm to 15°C and then a hexane solution of (1 S,2R)-cis-caronaldehyde methyl ester (10.0 g; 0.064 mol) added over 15 minutes.
  • the ester (3.3 g) was hydrolysed to the free acid using ethanol and 2N-sodium hydroxide to yield 2.6 g acid (84%).
  • 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 ("Triton" is a trade mark).
  • Triton is a trade mark.
  • 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.
  • the LC 50 used for the standard in this calculation was the mean value based on 20 determinations. The results are given in Table II.

Landscapes

  • 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)

Claims (6)

1. Cyclopropylcarbonsäureester in der Form einzelner Isomeren oder Kombinationen davon, dadurch gekennzeichnet, dass sie eine allgemeine Formel
Figure imgb0019
haben, in der X ein Chlor-, Brom- oder Jodatom ist und Y ein Wasserstoffatom oder eine Cyan- oder Äthinylgruppe ist.
2. Verbindungen nach Anspruch 1, dadurch gekennzeichnet, dass X ein Chloratom ist.
3. Verbindungen nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass sie eine Konfiguration an den Kohlenstoffatomen 1 und 3 von (1 R,1S,cis) oder (1R,cis) aufweisen.
4. Verfahren zur Herstellung von Verbindungen der allgemeinen Formel I, dadurch gekennzeichnet, dass eine Verbindung der Formel
Figure imgb0020
umgesetzt wird mit einer Verbindung der Formel
Figure imgb0021
in der X und Y wie in Anspruch 1 definiert sind, eine der Gruppen Q und Z ein Halogenatom bedeutet und die andere Gruppe für eine Hydroxygruppe steht.
5. Pestizides Mittel zur Bekämpfung von Milben und/oder Insektenschädlingen, dadurch gekennzeichnet, dass der Wirkstoff eine Verbindung nach einem der Ansprüche 1 bis 3 ist.
6. Verwendung einer Verbindung, die in einem der Ansprüche 1 bis 3 beansprucht ist als Schädlingsbekämpfungsmittel für Milben und/oder Schadinsekten.
EP78200056A 1977-06-30 1978-06-20 Cyclopropancarbonsäure-ester, Verfahren zu deren Herstellung und ihre Verwendung als Pestizide Expired EP0000229B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB2740977 1977-06-30
GB2740977 1977-06-30

Publications (2)

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EP0000229A1 EP0000229A1 (de) 1979-01-10
EP0000229B1 true EP0000229B1 (de) 1981-12-02

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EP78200056A Expired EP0000229B1 (de) 1977-06-30 1978-06-20 Cyclopropancarbonsäure-ester, Verfahren zu deren Herstellung und ihre Verwendung als Pestizide

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EP (1) EP0000229B1 (de)
JP (1) JPS5412351A (de)
AU (1) AU525337B2 (de)
BR (1) BR7804122A (de)
CA (1) CA1123452A (de)
DE (1) DE2861395D1 (de)
DK (1) DK292478A (de)
EG (1) EG13418A (de)
GR (1) GR64837B (de)
IL (1) IL55027A (de)
IT (1) IT7825089A0 (de)
MX (1) MX5434E (de)
NZ (1) NZ187712A (de)
TR (1) TR20942A (de)
ZA (1) ZA783300B (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4404640C1 (de) * 1994-02-14 1995-02-09 Siemens Ag Zahnärztliche Röntgendiagnostikeinrichtung zur Erstellung von Panorama-Röntgenaufnahmen vom Schädel eines Patienten

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1981002892A1 (fr) * 1980-04-10 1981-10-15 Dainippon Jochugiku Kk Esters de l'acide cyclopropane carboxylique, leur procede de preparation, et composition insecticide et acaricide les contenant a titre d'ingredients efficaces
FR2601360B2 (fr) * 1986-07-09 1988-11-10 Roussel Uclaf Nouveaux derives de l'acide cyclopropane carboxylique a substituant iode, leur preparation, leur application a la lutte contre les parasites des vegetaux et des animaux.
ES2014428B3 (es) * 1985-12-10 1990-07-16 Roussel-Uclaf Nuevos derivados del acido ciclopropano carboxilico con sustituyente iodado, su preparacion, su aplicacion a la lucha contra los parasitos de vegetales y de animales y las composiciones que encierran.
FR2591223B1 (fr) * 1985-12-10 1988-03-18 Roussel Uclaf Nouveaux derives de l'acide cyclopropane carboxylique a substituant iode, leur preparation, leur application a la lutte contre les parasites des vegetaux et des animaux
GB2187385A (en) * 1986-03-07 1987-09-09 Shell Int Research Method of combatting colorado beetles using chemical compounds and compositions containing the chemical compounds
JP2546339B2 (ja) * 1988-06-03 1996-10-23 住友化学工業株式会社 エステル化合物およびその殺虫、殺ダニ剤としての用途
FR2641275B1 (fr) * 1988-12-29 1991-10-11 Roussel Uclaf Nouveaux derives fluores de l'acide 3-ethenyl 2,2-dimethyl cyclopropane carboxylique, leur procede de preparation et leur application comme pesticides

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
IT1048189B (it) * 1973-08-15 1980-11-20 Nat Res Dev Perfezionamenti relativi a insetticidi

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4404640C1 (de) * 1994-02-14 1995-02-09 Siemens Ag Zahnärztliche Röntgendiagnostikeinrichtung zur Erstellung von Panorama-Röntgenaufnahmen vom Schädel eines Patienten

Also Published As

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TR20942A (tr) 1983-01-24
AU3751378A (en) 1980-01-03
CA1123452A (en) 1982-05-11
EP0000229A1 (de) 1979-01-10
IL55027A (en) 1981-07-31
GR64837B (en) 1980-06-04
MX5434E (es) 1983-08-05
IT7825089A0 (it) 1978-06-28
JPS5412351A (en) 1979-01-30
EG13418A (en) 1981-06-30
BR7804122A (pt) 1979-02-28
AU525337B2 (en) 1982-11-04
ZA783300B (en) 1979-09-26
IL55027A0 (en) 1978-08-31
NZ187712A (en) 1980-10-24
DE2861395D1 (en) 1982-01-28
DK292478A (da) 1978-12-31

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