EP0000508A1 - Phenyl acetates of 2-oxypyridyl, process for their preparation and their use as pesticides - Google Patents

Phenyl acetates of 2-oxypyridyl, process for their preparation and their use as pesticides Download PDF

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Publication number
EP0000508A1
EP0000508A1 EP78100376A EP78100376A EP0000508A1 EP 0000508 A1 EP0000508 A1 EP 0000508A1 EP 78100376 A EP78100376 A EP 78100376A EP 78100376 A EP78100376 A EP 78100376A EP 0000508 A1 EP0000508 A1 EP 0000508A1
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Prior art keywords
formula
compound
hydrogen
compound according
preparation
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German (de)
French (fr)
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EP0000508B1 (en
Inventor
Odd Dr. Kristiansen
Peter Dr. Ackermann
Jozef Dr. Drabek
Saleem Dr. Farooq
Laurenz Dr. Gsell
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/643—2-Phenoxypyridines; Derivatives thereof
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Definitions

  • the present invention relates to phenylacetates and their salts with inorganic and organic acids, processes for their preparation and their use in pest control.
  • the phenylacetates have the formula wherein R 1 is hydrogen, cyano, ethynyl or methyl and R 2 and R 3 are each hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
  • Inorganic salts such as HCl, H 2 SO 4 , HBr and H 3 PO 4 are used for salt formation, and saturated and unsaturated mono-, di- and tricarboxylic acids such as formic acid, acetic acid, oxalic acid, phthalic acid, succinic acid and citric acid are used as organic acids Consider.
  • Halogen at R 2 and R 3 is fluorine, chlorine, bromine and iodine, but especially chlorine.
  • the alkyl or alkoxy groups that can be used for R2 and R 3 can be straight-chain or branched. Examples of such groups include: methyl, methoxy, ethyl, ethoxy, propyl, propoxy, isopropyl, isopropoxy, n-butyl, n-butoxy-, i-, sec-, tert-butyl.
  • R 1 is Cvano and R 2 and R 3 each represent hydrogen or chlorine.
  • R 1 , R 2 and R 3 have the meaning given for the formula I.
  • Acid-binding agents for processes 1 and 2 include, in particular, tertiary amines such as trialkylamine and pyridine, furthermore hydroxides, oxides, carbonates and of alkali and alkaline earth metals as well as alkali metal carbonates such as, for example, potassium t-butoxide and sodium methylate.
  • Dicyclohexylcarbodiimide for example, can be used as the water-binding agent for process 3.
  • Processes 1 to 4 are carried out at a reaction temperature between -10 and 120 ° C, usually between 20 and 80 ° C at normal or elevated pressure and preferably in an inert solvent or diluent.
  • Suitable solvents or diluents are, for example, ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, dimethoxyethane and tetrahydrofuran; Amides such as N, N-dialkylated carboxamides, aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylene, chloroform and chlorobenzene; Nitriles such as acetonitrile; Dimethyl sulfoxide and ketones such as acetone and methyl ethyl ketone.
  • the compounds of formula 1 readies as demi from various optically active isomers before, if non-uniformly optically active starting materials were used in the preparation.
  • the various isomer mixtures can be separated into the individual isomers by known methods.
  • the compound of the formula is understood to mean both the individual isomers, Mixtures.
  • the compounds of formula I are suitable for controlling various types of animal and vegetable pests.
  • the compounds of the formula I are suitable for controlling insects, phytopathogenic mites and ticks, e.g. the orders Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonoptera, Mallophaga, Thysandre Isoptera, Psocoptera and Hymenoptera.
  • Active ingredients of the formula I also have a very favorable action against flies, e.g. Musca domestica and mosquito larvae.
  • acaricidal or insecticidal effect can be significantly broadened by adding other insecticides and / or acaricides and adapted to the given circumstances.
  • Suitable additives are e.g. org.phosphorus compounds; Nitrophenols and their derivatives; Formamidines: ureas; other pyrethrin-like compounds as well as carbamates and chlorinated hydrocarbons.
  • connections include Piperonyl butoxide, propynyl ether, propynyl oximes, propynyl carbamates and propynyl phosphonates, 2- (3,4-methylenedioxyphenoxy) -3,6,9-trioxaundecan (Sesamex or Sesoxane), S, S, S-tributylphosphorotrithioate, 1,2- Methylenedioxy-4- (2- (octylsulfonyl) propyl) benzene.
  • Suitable additives can be solid or liquid and correspond to the substances commonly used in formulation technology, e.g. natural or regenerated substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and / or fertilizers.
  • Agents according to the invention are produced in a manner known per se by intimate mixing and / or mixing len of the active ingredients of formula I. with the suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active ingredients.
  • the active substances can be present and used in the following processing forms:
  • Solid processing dusts, scattering agents, granules late (coating granules, impregnation granules and homogeneous granules);
  • the content of active ingredient in the agents described above is between 0.1 to 95%, it should be mentioned that concentrations of up to 99.5% or even pure active ingredient can be used in the application from the airplane or by means of other suitable application devices.
  • the active ingredients of Formula 1 can be formulated, for example, as follows (parts mean parts by weight):
  • Dusts The following substances are used to produce a) 5% and b) 2% dusts:
  • the active ingredient is mixed with the excipients and ground.
  • Granules The following substances are used to produce 5% granules:
  • the active ingredient is intimately mixed with the additive in suitable mixers and ground on appropriate mills and rollers.
  • Spray powder is obtained which can be thinned with water to form suspensions of any desired concentration.
  • Emulsifiable concentrates The following substances are used to prepare a) 10%, b) 25% and c) 50% emulsifiable concentrates.
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • Spray agent The following ingredients are used to produce a) 5% and b) 95% spray:
  • Cotton plants were sprayed with a 0.05% aqueous active ingredient emulsion (obtained from a 10% emulsifiable concentrate).
  • the cotton plants were each populated with Spodoptera littoralis and Heliothis virescens larvae L 3 .
  • the test was carried out at 24 ° C and 60% relative humidity.
  • Test for acaricidal activity with an infested leaf piece from a mass cultivation of Tetranychus urticae The overflowed moving stages were sprayed from a chromatography atomizer with the emulsified test preparations in such a way that the spray liquor did not run off. After two to seven days, larvae, adults and eggs under the binocular were evaluated for living and dead individuals and the result expressed as a percentage. During the "stopping time" the treated ones stood in greenhouse cabins at 25 ° C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (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)
  • Pyridine Compounds (AREA)

Abstract

Phenylacetate der Formel <IMAGE> worin R1 Wasserstoff, Cyano, Aethinyl oder Methyl und R2 und R3 je Wasserstoff, Halogen, C1-C4- Alkyl oder C1-C4-Alkoxy bedeuten, Verfahren zu ihrer Herstellung und ihre Verwendung in der Schädlingsbekämpfung.Phenylacetates of the formula <IMAGE> in which R1 is hydrogen, cyano, ethynyl or methyl and R2 and R3 are each hydrogen, halogen, C1-C4-alkyl or C1-C4-alkoxy, processes for their preparation and their use in pest control.

Description

Die vorliegende Erfindung betrifft Phenylacetate und ihre Salze mit anorganischen und organischen Säuren, Verfahren zu ihrer Herstellung und ihre Verwendung in der Schädlingsbekämpfung.The present invention relates to phenylacetates and their salts with inorganic and organic acids, processes for their preparation and their use in pest control.

Die Phenylacetate haben die Formel

Figure imgb0001
worin R1 Wasserstoff, Cyano, Aethinyl oder Methyl und R2 und R3 je Wasserstoff, Halogen, C1-C4-Alkyl oder C1-C4-Alkoxy bedeuten.The phenylacetates have the formula
Figure imgb0001
 wherein R 1 is hydrogen, cyano, ethynyl or methyl and R 2 and R 3 are each hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 alkoxy.

Für die Salzbildung kommen anorganische Säuren wie beispielsweise HCl, H2SO4, HBr und H3PO4 und als organische Säuren beispielsweise gesättigte und ungesättigte Mono-, Di- und Tricarbonsäuren wie z.B. Ameisensäure, Essigsäure, Oxalsäure, Phthalsäure, Bernsteinsäure und Zitronensäure in Betracht.Inorganic salts such as HCl, H 2 SO 4 , HBr and H 3 PO 4 are used for salt formation, and saturated and unsaturated mono-, di- and tricarboxylic acids such as formic acid, acetic acid, oxalic acid, phthalic acid, succinic acid and citric acid are used as organic acids Consider.

Unter Halogen bei R2 und'R3 sind Fluor, Chlor, Brom und Jod, insbesondere aber Chlor, zu verstehen.Halogen at R 2 and R 3 is fluorine, chlorine, bromine and iodine, but especially chlorine.

Die für R2 und R3 in Frage kommenden Alkyl- oder Alkoxygruppen können geradkettig oder verzweigt sein. Beispiele solcher Gruppen sind u.a.: Methyl, Methoxy, Aethyl, Aethoxy, Propyl, Propoxy, Isopropyl, Isopropoxy, n-Butyl, n-Butoxy-, i-, sek.-, tert.-Butyl.The alkyl or alkoxy groups that can be used for R2 and R 3 can be straight-chain or branched. Examples of such groups include: methyl, methoxy, ethyl, ethoxy, propyl, propoxy, isopropyl, isopropoxy, n-butyl, n-butoxy-, i-, sec-, tert-butyl.

Wegen ihrer Wirkung bevorzugt sind Verbindungen der Formel I, worin R1 Cvano und
R2 und R3 je Wasserstoff oder Chlor bedeuten.Because of their action, preference is given to compounds of the formula I in which R 1 is Cvano and
R 2 and R 3 each represent hydrogen or chlorine.

Die Verbindungen der Formel I werden nach an sich bekannten Methoden z.B. wie folgt hergestellt:

Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005
 The compounds of the formula I are prepared by methods known per se, for example as follows:
Figure imgb0002
Figure imgb0003
Figure imgb0004
Figure imgb0005

In den Formeln II bis VI haben R1, R2 und R3 die für die Formel I angegebene Bedeutung.In the formulas II to VI, R 1 , R 2 and R 3 have the meaning given for the formula I.

In den Formeln III und IV steht X für ein Halogenatom, insbesondere Chlor oder Brom und in der Formel VI steh. R für C1-C4-Alkyl, insbesondere für Methyl oder Aethyl. Als säurebindendes Mittel für die Verfahren 1 und 2 kommen insbesondere tertiäre Amine, wie Trialkylamin und Pyridin, ferner Hydroxide, Oxide, Carbonate und

Figure imgb0006
von Alkali- und Erdalkalimetallen sowie Alkalimetallakohlate wie z.B. Kalium-t.butylat und Natriummethylat in Be- tracht. Als wasserbindendes Mittel für das Verfahren 3 kann z.B. Dicyclohexylcarbodiimid verwendet werden. Die Verfahren 1 bis 4 werden bei einer Reaktionstemperatur zwischen -10 und 120°C, meist zwischen 20 und 80°C bei normalem oder erhöhtem Druck und vorzugsweise in einem inerten Lösungs- oder Verdünnungsmittel durchgeführt. Als Lösungs- oder Verdünnungsmittel eignen sich z.B. Aether und ätherartige Verbindungen wie Diäthyläther, Dipropyl- äther, Dioxan, Dimethoxyäthan und Tetrahydrofuran; Amide wie N,N-dialkylierte Carbonsäureamide, aliphatische, aromatische sowie halogenierte Kohlenwasserstoffe, insbesondere Benzol, Toluol, Xylol, Chloroform und Chlorbenzol; Nitrile wie Acetonitril; Dimethylsulfoxid und Ketone wie Aceton und Methyläthylketon.In the formulas III and IV, X represents a halogen atom, in particular chlorine or bromine, and in formula VI. R is C 1 -C 4 alkyl, especially methyl or ethyl. Acid-binding agents for processes 1 and 2 include, in particular, tertiary amines such as trialkylamine and pyridine, furthermore hydroxides, oxides, carbonates and
Figure imgb0006
of alkali and alkaline earth metals as well as alkali metal carbonates such as, for example, potassium t-butoxide and sodium methylate. Dicyclohexylcarbodiimide, for example, can be used as the water-binding agent for process 3. Processes 1 to 4 are carried out at a reaction temperature between -10 and 120 ° C, usually between 20 and 80 ° C at normal or elevated pressure and preferably in an inert solvent or diluent. Suitable solvents or diluents are, for example, ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, dimethoxyethane and tetrahydrofuran; Amides such as N, N-dialkylated carboxamides, aliphatic, aromatic and halogenated hydrocarbons, in particular benzene, toluene, xylene, chloroform and chlorobenzene; Nitriles such as acetonitrile; Dimethyl sulfoxide and ketones such as acetone and methyl ethyl ketone.

Die Ausgangsstoffe der Formeln II, IV und VI sind bekannt wohingegen die Ausgangsstoffe der Formeln III und V neu sind. Alle diese Ausgangsstoffe können analog bekannten Methoden hergestellt werden.The starting materials of formulas II, IV and VI are known, whereas the starting materials of formulas III and V are new. All of these starting materials can be prepared analogously to known methods.

Die Verbindungen der Formel 1 Liesan als demisch von verschien denen optisch aktiven Isomeren vor, wenn bei der Herstellung nicht einheitlich optisch aktive Ausgangsmateriallen verwendet wurden. Die verschiedenen Isomerengemische können nach bekannten Methoden in die einzelnen Isomeren aufgetrennt werden. Unter der Verbindung der Formel versteht man sowohl die einselnen Isomeren,

Figure imgb0007
Gemische.The compounds of formula 1 readies as demi from various optically active isomers before, if non-uniformly optically active starting materials were used in the preparation. The various isomer mixtures can be separated into the individual isomers by known methods. The compound of the formula is understood to mean both the individual isomers,
Figure imgb0007
Mixtures.

Die Verbindungen der Formel I eignen sich zur Bekämpfung von verschiedenartigen tierischen und pflanzlichen Schädlingen.The compounds of formula I are suitable for controlling various types of animal and vegetable pests.

Insbesondere eignen sich die Verbindungen der Formel I zur Bekämpfung von Insekten, phytopathogenen Milben und von Zecken z.B. der Ordnungen Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonoptera, Mallophaga, Thysandre Isoptera, Psocoptera und Hymenoptera.In particular, the compounds of the formula I are suitable for controlling insects, phytopathogenic mites and ticks, e.g. the orders Lepidoptera, Coleoptera, Homoptera, Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonoptera, Mallophaga, Thysandre Isoptera, Psocoptera and Hymenoptera.

Figure imgb0008
Myzus persicae).
Figure imgb0008
Myzus persicae).

Wirkstoffe der Formel I zeigenauch eine sehr günstige Wirkung gegen Fliegen wie z.B. Musca domestica und Mückenlarven.Active ingredients of the formula I also have a very favorable action against flies, e.g. Musca domestica and mosquito larvae.

Die akarizide bzw, insektizide Wirkung lässt sich durch Zusatz von anderen Insektiziden und/oder Akariziden wesentlich verbreitern und an,gegebene Umstände anpassen. Als Zusätze eignen sich z.B. org.Phosphorverbindungens; Nitrophenole und deren Derivate; Formamidine: Harnstoffe; andere pyrethrinartige Verbindungen sowie Karbamate und chlorierte Kohlenwasserstoff.The acaricidal or insecticidal effect can be significantly broadened by adding other insecticides and / or acaricides and adapted to the given circumstances. Suitable additives are e.g. org.phosphorus compounds; Nitrophenols and their derivatives; Formamidines: ureas; other pyrethrin-like compounds as well as carbamates and chlorinated hydrocarbons.

Mit'besonderem Vorteil werden Verbindungen der Formel I auch mit Substanzen kombiniert, welche einen synergistischen oder verstärkenden Effekt ausüben.With particular advantage, compounds of the formula I are also combined with substances which have a synergistic or reinforcing effect.

Beispiele solcher Verbindungen sind u.a. Piperonylbutoxid, Propinyläther, Propinyloxime, Propinylcarbamate und Propinylphosphonate, 2-(3,4-Methylendioxyphenoxy)-3,6,9-trioxaunde- can (Sesamex resp. Sesoxane), S,S,S-Tributylphosphorotri- thioate, 1,2-Methylendioxy-4-(2-(octylsulfonyl)-propyl)-benzol.Examples of such connections include Piperonyl butoxide, propynyl ether, propynyl oximes, propynyl carbamates and propynyl phosphonates, 2- (3,4-methylenedioxyphenoxy) -3,6,9-trioxaundecan (Sesamex or Sesoxane), S, S, S-tributylphosphorotrithioate, 1,2- Methylenedioxy-4- (2- (octylsulfonyl) propyl) benzene.

Verbindungen der Formel I können für sich allein oder zusammen mit geeigneten Träger-und/oder Zuschlagstoffen eingesetzt werden. Geeignete Zuschlagstoffe können fest oder flüssig sein und entsprechen den in der Formulierungstechnik üblichen Stoffen wie z.B. natürlichen oder regenerierten Stoffen, Lösungs-, Dispergier-, Netz-, Haft-, Verdickungs-, Bind- und/oder Düngemittel.Compounds of the formula I can be used alone or together with suitable carriers and / or additives. Suitable additives can be solid or liquid and correspond to the substances commonly used in formulation technology, e.g. natural or regenerated substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders and / or fertilizers.

Die Herstellung erfindungsgemässer Mittel erfolgt in an sich bekannter Weise durch inniges Vermischen und/oder Vermahlen der Wirkstoffe der Formel I.mit den geeigneten Trägerstoffen, gegebenenfalls unter Zusatz von gegenüber den Wirkstoffen inerten Dispergier- oder Lösungsmitteln. Die Wirkstoffe können können in den folgenden Aufarbeitungsformen vorliegen und angewendet werden:.Agents according to the invention are produced in a manner known per se by intimate mixing and / or mixing len of the active ingredients of formula I. with the suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active ingredients. The active substances can be present and used in the following processing forms:

Feste Aufarbeitungs- Stäubemittel, Streumittel, Granuformen: late (Umhüllungsgranulate, Imprägnierungsgranulate und Homogengranulate);Solid processing dusts, scattering agents, granules: late (coating granules, impregnation granules and homogeneous granules);

Flüssige Aufarbeitungsformen: ;

  • a) in Wasser dispergierbare Wirkstoffkonzentrate: Spritzpulver (wettable powders), Pasten, Emulsionen;
  • b) Lösungen
Liquid processing forms:;
  • a) active ingredient concentrates dispersible in water: wettable powders, pastes, emulsions;
  • b) solutions

Der Gehalt an Wirkstoff in den oben beschriebenen Mitteln liegt zwischen 0,1 bis 95%, dabei ist zu erwähnen, dass bei der Applikation aus dem Flugzeug oder mittels anderer geeigneter Applikationsgeräte Konzentrationen bis zu 99,5% oder sogar reiner Wirkstoff eingesetzt werden können. Die Wirkstoffe der Formel 1 können beispielsweise wie folgt formuliert werden (Teile bedeuten Gewichtsteile):The content of active ingredient in the agents described above is between 0.1 to 95%, it should be mentioned that concentrations of up to 99.5% or even pure active ingredient can be used in the application from the airplane or by means of other suitable application devices. The active ingredients of Formula 1 can be formulated, for example, as follows (parts mean parts by weight):

Stäubemittel: Zur Herstellung eines a) 5%igen und b) 2%igen Stäubemittels werden die folgenden Stoffe verwendet:

Figure imgb0009
Figure imgb0010
 Dusts: The following substances are used to produce a) 5% and b) 2% dusts:
Figure imgb0009
Figure imgb0010

Der Wirkstoff wird mit den Trägerstoffen vermischt und vermahlen.The active ingredient is mixed with the excipients and ground.

Granulat: Zur Herstellung eines 5%igen Granulates werden die folgenden Stoffe verwendet:

Figure imgb0011
Figure imgb0012
Figure imgb0013
 Granules: The following substances are used to produce 5% granules:
Figure imgb0011
Figure imgb0012
Figure imgb0013

Der Wirkstoff wird in geeigneten Mischern mit dem Zuschlagstoff innig vermischt und auf entsprechenden Mühlen und Walzen vermahlen. Man erhält Spritzpulver, die sich mit Wasser zu Suspensionen jeder gewünschten Konzentration werdünnen lassen.The active ingredient is intimately mixed with the additive in suitable mixers and ground on appropriate mills and rollers. Spray powder is obtained which can be thinned with water to form suspensions of any desired concentration.

Emulgierbare Konzentrate: Zur Herstellung eines a) 10%igen b) 25%igen und c) 50%igen emulgierbaren Konzentrates werden folgende Stoffe verwendet.

Figure imgb0014
Emulsifiable concentrates: The following substances are used to prepare a) 10%, b) 25% and c) 50% emulsifiable concentrates.
Figure imgb0014

Aus solchen Konzentraten können durch Verdünnen mit Wasser Emulsionen jeder gewünschten Konzentration hergestellt werden.Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.

Sprühmittel: Zur Herstellung eines a) 5%igen und b) 95% igen Sprühmittels werden die folgenden Bestandteile ver-wendet:

Figure imgb0015
Figure imgb0016
 Spray agent: The following ingredients are used to produce a) 5% and b) 95% spray:
Figure imgb0015
Figure imgb0016

Beispiel 1example 1

Herstellung von α,α-p-Chlorphenyl-iso-propyl-essignäure-α'-cyano-3'-pyridyl-2'-oxybenzylester.Production of α, α-p-chlorophenyl-iso-propyl-acetic acid-α'-cyano-3'-pyridyl-2'-oxybenzyl ester.

7,5 g α,α-p-Chlorphenyl-isopropyl-essigsäurechlorid in 10 ml abs.Toluol werden bei 5°C zu einer Lösung von α-Cyano-3-(pyridyl-2'-oxi)-benzylalkohol und 2,7 g Pyridin in 100 ml als Toluol zugetropft. Das Reaktionsgemisch wird 5 Stunden bei Raumtemperatur gerührt. Dann wird das Gemisch in Eiswasser gegossen. Die organische Schicht wird mit 3%iger Salzsäure, Wasser, 3%iger Natriumbikarbonat-Lösung und wieder mit Wasser gewaschen. Nach dem Trocknen über Natriumsulfat und dem Abdestillieren des Toluols erhält man die Verbindung der Formel

Figure imgb0017
als viskose Flüssigkeit mit einer Refraktion von nD 20°= 1,5556.7.5 g of α, α-p-chlorophenyl-isopropyl-acetic acid chloride in 10 ml of absolute toluene at 5 ° C to a solution of α-cyano-3- (pyridyl-2'-oxi) benzyl alcohol and 2.7 g of pyridine in 100 ml was added dropwise as toluene. The reaction mixture is stirred for 5 hours at room temperature. Then the mixture is poured into ice water. The organic layer is washed with 3% hydrochloric acid, water, 3% sodium bicarbonate solution and again with water. After drying over sodium sulfate and distilling off the toluene, the compound of the formula is obtained
Figure imgb0017
 as a viscous liquid with an R efraktion of n D 20 ° = 1.5556.

Auf analoge Weise werden auch folgende Verbindungen hergestellt:

Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
 The following connections are also made in an analogous manner:
Figure imgb0018
Figure imgb0019
Figure imgb0020
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028

Beispiel 2Example 2 A) Insektizide Frassgift-WirkungA) Insecticidal food poison effect

Baumwollpflanzen wurden mit einer 0,05%igen wässrigen Wirkstoffemulsion (erhalten aus einem 10%igen emulgierbaren Konzentrat) besprüht.Cotton plants were sprayed with a 0.05% aqueous active ingredient emulsion (obtained from a 10% emulsifiable concentrate).

Nach dem Antrocknen des Belages wurden die Baumwollpflanzen je mit Spodoptera littoralis- und Heliothis virescens-Larven L3 besetzt. Der Versuch wurde bei 24°C und 60% relativer Luftfeuchtigkeit durchgeführt.After the covering had dried on, the cotton plants were each populated with Spodoptera littoralis and Heliothis virescens larvae L 3 . The test was carried out at 24 ° C and 60% relative humidity.

Verbindungen gemäss Beispiel 1 zeigten im obigen Test eine gute insektizide Frassgift-Wirkung gegen Spodoptera- und Heliothis-Larven.Compounds according to Example 1 showed a good insecticidal feeding poison effect against Spodoptera and Heliothis larvae in the above test.

Beispiel 3Example 3 Wirkung gegen Chilo suppressalisEffect against Chilo suppressalis

Je 6 Reispflanzen der Sorts Caloro wurden

Figure imgb0029
die einen oberen Durchmesser von 17 cm aufweisen, verpflant6 rice plants of the Caloro variety were grown
Figure imgb0029
transplanted with an upper diameter of 17 cm

. und zu einer Höhe von ca. 60 cm aufgezogen. Die Infestation mit Chilo suppressalis Larven (L1: 3-4 mm lang) erfolgte 2 Tage nach der Wirkstoffzugabe in Grandlatform (Aufwandmenge 8 kg Aktivsustanz pro Hektare) in das Paduy-Wasser. Die Auswertung auf insektizide Wirkung erfolgte 10 nach der Zugabe des Granulates.. and raised to a height of approx. 60 cm. The infestation with Chilo suppressalis larvae (L 1 : 3-4 mm long) was carried out 2 days after the active ingredient had been added to the Paduy water in grandlat form (application rate 8 kg of active substance per hectare). The insecticidal activity was evaluated 10 after the addition of the granules.

Verbindungen gemäse Beispiel 1 wirkten im obigen Test vegen Chilo suppressalis.Compounds according to Example 1 acted against Chilo suppressalis in the above test.

Beispiel 4Example 4 Akarizide WirkungAcaricidal effects

Figure imgb0030
vulgaris Pflanzen wurden 12 Stunden ver dem
Figure imgb0030
vulgaris plants were ver 12 hours

Test auf akarizide Wirkung mit einem infestierten Blattstück aus einer Massenzucht von Tetranychus urticae belegt. Die überglelaufenen beweglichen Stadien wurden aus einem Chromatographiezerstäuber mit den emulgierten Testpräparaten derart besprüht, dass kein Ablaufen der Spritsbrühe eintrat. Nach zwei bis 7 Tagen wurden Larven, Adulte and Eier unter dem Binokular auf lebende und tote Individuen ausgewertet und das Ergebnis in Prozenten, ausgedrückt. Während der "Haltezeit" standen die behandelten

Figure imgb0031
in Gewächshuskabinen bei 25°C.Test for acaricidal activity with an infested leaf piece from a mass cultivation of Tetranychus urticae. The overflowed moving stages were sprayed from a chromatography atomizer with the emulsified test preparations in such a way that the spray liquor did not run off. After two to seven days, larvae, adults and eggs under the binocular were evaluated for living and dead individuals and the result expressed as a percentage. During the "stopping time" the treated ones stood
Figure imgb0031
in greenhouse cabins at 25 ° C.

Verbungen gemäss Beispiel wirkten im obigem Test

Figure imgb0032
Adulte, Larven
Figure imgb0033
von Tetranychus urticae.
Figure imgb0034
Verbs according to the example worked in the above test
Figure imgb0032
Adults, larvae
Figure imgb0033
from Tetranychus urticae.
Figure imgb0034

Claims (10)

l. Eine Verbindung der Formel
Figure imgb0035
worin R1 Wasserstoff, Cyano, Aethinyl oder Methyl und R2und R3 je Wasserstoff, Halogen, C1-C4-Alkyl oder C1-C4-hlkoxy bedeuten.l. A compound of the formula
Figure imgb0035
 wherein R 1 is hydrogen, cyano, ethynyl or methyl and R2 and R 3 are each hydrogen, halogen, C 1 -C 4 alkyl or C 1 -C 4 -alkoxy. 2. Eine Verbindung gemäss Anspruch 1, worin R1 Cyano und R2 und R3 ie Wasserstoff oder Chlor bedeuten.2. A compound according to claim 1, wherein R 1 is cyano and R 2 and R 3 are hydrogen or chlorine. 3. Die Verbindung gemäss Anspruch 2 der Formel
Figure imgb0036
 3. The compound according to claim 2 of the formula
Figure imgb0036
 4. Die Verbindung gemäss Anspruch 2 der Formel
Figure imgb0037
 4. The compound according to claim 2 of the formula
Figure imgb0037
 5. Die Verbindung gemäss Anspruch 2 der Formel
Figure imgb0038
 5. The compound according to claim 2 of the formula
Figure imgb0038
 6. Ein Verfahren zur Herstellung einer Verbindung gemäss Anspruch 1, dadurch gekennzeichnet, dass man eine Verbindung der Formel
Figure imgb0039
 in Gegenwart eines säurebindenden Mittels mit einer Ver- bindung der Formel
Figure imgb0040
 umsetzt, worin R1, R2 und R3 die im Anspruch 1
Figure imgb0041
Bedeutung haben und X für ein Halogenatom stoht 6. A process for the preparation of a compound according to claim 1, characterized in that a compound of the formula
Figure imgb0039
 in the presence of an acid-binding agent with a Ver - compound of the formula
Figure imgb0040
 implements, wherein R 1 , R 2 and R 3 that in claim 1
Figure imgb0041
Have meaning and X stands for a halogen atom 7- Ein Schädlingsbekämpfungsmittel, welches als aktive Komponente eine Verbindung gemäss Anspruch 1 und gesignete Träger und/oder andere Zuschlagstoffe enthalt.7- A pesticide which contains a compound as claimed in claim 1 and signed carriers and / or other additives as an active component. 8. Verwendung einer Verbindung gemäss Anspruch 1 zur Bekämpfung von verschiedenartigen tierischen und pflanzlichen Schädlingen.8. Use of a compound according to claim 1 for controlling various animal and vegetable pests. 9. Verwendung einer Verbindung gemäss Anspruch 9 zur Bekämpfung von Insekten und Vertretern der Ordnung Akarina.9. Use of a compound according to claim 9 for controlling insects and representatives of the order Akarina. 10
Figure imgb0042
Verbindung der Formel
Figure imgb0043
worin R1 Wasserstoff , Cyano Aethinyl-oder Methyl und X Wasserstoff oder Halogen bedeuten.10th
Figure imgb0042
Compound of formula
Figure imgb0043
 wherein R 1 is hydrogen, cyanoethynyl or methyl and X is hydrogen or halogen.
EP78100376A 1977-07-20 1978-07-12 Phenyl acetates of 2-oxypyridyl, process for their preparation and their use as pesticides Expired EP0000508B1 (en)

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CH899977 1977-07-20
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CH5777/78 1978-05-26

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2450254A1 (en) * 1979-03-02 1980-09-26 Zoecon Corp NOVEL PESTICIDE COMPOSITIONS BASED ON AMINO ACIDS AND THIOESTERS FOR THE CONTROL OF INSECTS AND THEIR METHOD OF APPLICATION
EP0026650A2 (en) * 1979-10-01 1981-04-08 The Dow Chemical Company Insecticidal synergistic mixtures of 0,0-diethyl 0-(3,5,6-trichloro-2-pyridinyl)phosphorothioate and 4-chloro-alpha-(1-methylethyl)benzene-acetic acid:cyano(6-phenoxy-2-pyridinyl)methyl ester and method of killing and controlling insects
EP0037851A2 (en) * 1980-04-15 1981-10-21 Sumitomo Chemical Company, Limited Carboxylates, a process for their production, an insecticidal and/or acaricidal composition and the use of the compounds as insecticides and/or acaricides
EP0206772A2 (en) * 1985-06-20 1986-12-30 E.I. Du Pont De Nemours And Company Herbicidal aryloxybenzeneacetic acid derivatives
WO2004087667A1 (en) * 2003-03-31 2004-10-14 Council Of Scientific And Industrial Research Ester derivatives of (pyridinyloxy-phenyl)-methanol and process of preparation thereof
KR101052620B1 (en) * 2008-08-28 2011-07-29 한국과학기술연구원 Novel phenylacetate derivative or pharmaceutically acceptable salt thereof, preparation method thereof and composition for the prevention or treatment of diseases caused by the activity of T-type calcium ion channel containing the same as an active ingredient

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4247701A (en) * 1979-09-24 1981-01-27 Zoecon Corporation Certain pesticidal substituted amino lower-alkanoates or lower-alkano-thioates containing pyridyl in the ester portion
US4248875A (en) * 1979-08-31 1981-02-03 Zoecon Corporation Pyridyl esters and thiolesters of α-substituted unsaturated acids
US4269981A (en) * 1979-09-24 1981-05-26 Zoecon Corporation Certain pyridylmethyl esters of formamido-lower-alkanoates and derivatives thereof
US4285954A (en) * 1980-11-19 1981-08-25 Zoecon Corporation Pesticidal S-pyridyl thioesters of phenylbutanoic acids and derivatives thereof
US4798839A (en) * 1982-03-31 1989-01-17 Rhone Poulenc Nederlands B.V. Synergistic insecticidal compositions
EP0150678B1 (en) * 1984-01-12 1989-03-01 Ciba-Geigy Ag Alpha-methyl-(6-phenoxy)-2-picolyl ester of cyclopropanecarboxylic acid
IL74868A0 (en) * 1984-04-13 1985-07-31 Fmc Corp Fluoropyridinylmethyl cyclopropanecarboxylate insecticides and intermediates

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FR2241533A1 (en) * 1972-07-11 1975-03-21 Sumitomo Chemical Co

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US4058622A (en) * 1972-07-11 1977-11-15 Sumitomo Chemical Company, Limited Substituted phenyl acetate, insecticidal composition and method of use
US4039680A (en) * 1972-07-11 1977-08-02 Sumitomo Chemical Company, Limited Insecticidal substituted acetate compounds
US4031233A (en) * 1976-02-09 1977-06-21 Sandoz, Inc. Phenoxyphenyl imidazolyl methanols and ketone derivatives thereof

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2450254A1 (en) * 1979-03-02 1980-09-26 Zoecon Corp NOVEL PESTICIDE COMPOSITIONS BASED ON AMINO ACIDS AND THIOESTERS FOR THE CONTROL OF INSECTS AND THEIR METHOD OF APPLICATION
EP0026650A2 (en) * 1979-10-01 1981-04-08 The Dow Chemical Company Insecticidal synergistic mixtures of 0,0-diethyl 0-(3,5,6-trichloro-2-pyridinyl)phosphorothioate and 4-chloro-alpha-(1-methylethyl)benzene-acetic acid:cyano(6-phenoxy-2-pyridinyl)methyl ester and method of killing and controlling insects
EP0026650A3 (en) * 1979-10-01 1981-04-22 The Dow Chemical Company Insecticidal synergistic mixtures of 0,0-diethyl 0-(3,5,6-trichloro-2-pyridinyl)phosphorothioate and 4-chloro-alpha-(1-methylethyl)benzene-acetic acid:cyano(6-phenoxy-2-pyridinyl)methyl ester and method of killing and controlling insects
EP0037851A2 (en) * 1980-04-15 1981-10-21 Sumitomo Chemical Company, Limited Carboxylates, a process for their production, an insecticidal and/or acaricidal composition and the use of the compounds as insecticides and/or acaricides
EP0037851A3 (en) * 1980-04-15 1982-08-04 Sumitomo Chemical Company, Limited Carboxylates, a process for their production, an insecticidal and/or acaricidal composition and the use of the compounds as insecticides and/or acaricides
EP0206772A2 (en) * 1985-06-20 1986-12-30 E.I. Du Pont De Nemours And Company Herbicidal aryloxybenzeneacetic acid derivatives
EP0206772A3 (en) * 1985-06-20 1988-05-11 E.I. Du Pont De Nemours And Company Herbicidal aryloxybenzeneacetic acid derivatives
WO2004087667A1 (en) * 2003-03-31 2004-10-14 Council Of Scientific And Industrial Research Ester derivatives of (pyridinyloxy-phenyl)-methanol and process of preparation thereof
KR101052620B1 (en) * 2008-08-28 2011-07-29 한국과학기술연구원 Novel phenylacetate derivative or pharmaceutically acceptable salt thereof, preparation method thereof and composition for the prevention or treatment of diseases caused by the activity of T-type calcium ion channel containing the same as an active ingredient

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GR72142B (en) 1983-09-20
CA1095052A (en) 1981-02-03
DE2861000D1 (en) 1981-11-26
IL55162A (en) 1981-07-31
EG13419A (en) 1981-06-30
NZ187885A (en) 1981-05-29
IL55162A0 (en) 1978-09-29
BR7804655A (en) 1979-03-20
JPS5422374A (en) 1979-02-20
IT7825893A0 (en) 1978-07-19
EP0000508B1 (en) 1981-09-02
US4172135A (en) 1979-10-23
ES471849A1 (en) 1979-02-01

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