EP0000508B1 - 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
EP0000508B1
EP0000508B1 EP78100376A EP78100376A EP0000508B1 EP 0000508 B1 EP0000508 B1 EP 0000508B1 EP 78100376 A EP78100376 A EP 78100376A EP 78100376 A EP78100376 A EP 78100376A EP 0000508 B1 EP0000508 B1 EP 0000508B1
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formula
compound
compound according
compounds
larvae
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German (de)
French (fr)
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EP0000508A1 (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 of 2-oxy-pyridyl and their salts with inorganic and organic acids, processes for their preparation and their use in pest control.
  • the phenylacetates of the formula I according to the invention differ from the known compounds in that the phenyl part of the phenoxy radical is replaced by a pyridyl radical and, on the other hand, are capable of salt formation because of the pyridyloxy radical.
  • 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 O 4 ' HBr and H 3 P0 4 are used for salt formation, and organic and organic acids include saturated and unsaturated mono-, di- and tricarboxylic acids such as formic acid, acetic acid, oxalic acid, phthalic acid, succinic acid and citric acid into consideration.
  • Halogen at R 2 and R 3 is fluorine, chlorine, bromine and iodine, but especially chlorine.
  • alkyl or alkoxy groups that are suitable for R 2 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 cyano and R 2 and R 3 are each hydrogen or chlorine.
  • R 1 , R 2 and R 3 have the meaning given for the formula I.
  • X represents a halogen atom, in particular chlorine or bromine
  • R represents C 1 -C 4 alkyl, in particular methyl or ethyl.
  • Suitable acid-binding agents for processes 1 and 2 are, in particular, tertiary amines, such as trialkylamine and pyridine, also hydroxides, oxides, carbonates and bicarbonates of alkali and alkaline earth metals and alkali metal alcoholates 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, especially 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 are present as a mixture of different optically active isomers if optically active starting materials were not used uniformly in the preparation.
  • the various isomer mixtures can be separated into the individual isomers by known methods.
  • the compound of the formula I is understood to mean both the individual isomers and their mixtures.
  • the compounds of the formula 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, Thysanura, Isoptera, Psocoptera and Hymenoptera.
  • Compounds of the formula I are particularly suitable for combating plant-damaging insects, in particular plant-damaging insects, in ornamental and useful plants, in particular in cotton crops (e.g. against Spodoptera littoralis and Heliothis virescens) and vegetable crops (e.g. against Leptinotarsa decemlineata and Myzus persicae).
  • Active ingredients of formula I also have a very beneficial effect against flies, such as 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-trioxaundecane (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.
  • Aqueous active ingredient emulsion were flanzen cotton p with a 0.05% (obtained from a 10% emulsifiable concentrate) sprayed.
  • 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.
  • Phaseolus vulgaris plants were covered with an infested leaf piece from a mass cultivation of Tetranychus urticae 12 hours before the test for acaricidal activity.
  • the overflowing movable stages were sprayed with the emulsified test preparations from a chromatography atomizer in such a way that the spray liquor did not run off.
  • larvae, adults and eggs under the binocular were evaluated for living and dead individuals and the result expressed as a percentage.
  • the treated plants were 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)

Description

Die vorliegende Erfindung betrifft Phenylacetate von 2-Oxy-Pyridyl und ihre Salze mit anorganischen und organischen Säuren, Verfahren zu ihrer Herstellung und ihre Verwendung in der Schädlingsbekämpfung.The present invention relates to phenylacetates of 2-oxy-pyridyl and their salts with inorganic and organic acids, processes for their preparation and their use in pest control.

In der französischen Patentschrift Nr. 2 241 533 sind insektizide Phenylacetate beschreiben.French Patent No. 2,241,533 describes insecticidal phenylacetates.

Die erfindungsgemässen Phenylacetate der Formel I unterscheiden sich von den bekannten Verbindungen durch den Ersatz des Phenylteiles des Phenoxyrestes durch einen Pyridylrest und sind demgegenüber, wegen dem Pyridyloxyrest, zur Salzbildung befähigt.The phenylacetates of the formula I according to the invention differ from the known compounds in that the phenyl part of the phenoxy radical is replaced by a pyridyl radical and, on the other hand, are capable of salt formation because of the pyridyloxy radical.

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 HCI, H2O4' HBr und H3P04 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 O 4 ' HBr and H 3 P0 4 are used for salt formation, and organic and organic acids include saturated and unsaturated mono-, di- and tricarboxylic acids such as formic acid, acetic acid, oxalic acid, phthalic acid, succinic acid and citric acid into consideration.

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 are suitable for R 2 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 1, worin R1 Cyano und R2 und R3 je Wasserstoff oder Chlor bedeuten.Because of their action, preference is given to compounds of the formula 1 in which R 1 is cyano and R 2 and R 3 are each 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 111 und IV steht X für ein Halogenatom, insbesondere Chlor oder Brom und in der Formel VI steht 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 Bicarbonate von Alkali- und Erdalkalimetallen sowie Alkalimetallalkoholate wie z.B. Kalium-t.butylat und Natriummethylat in Betracht. 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 normalen 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, Dipropyläther, 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 formulas 111 and IV, X represents a halogen atom, in particular chlorine or bromine, and in formula VI, R represents C 1 -C 4 alkyl, in particular methyl or ethyl. Suitable acid-binding agents for processes 1 and 2 are, in particular, tertiary amines, such as trialkylamine and pyridine, also hydroxides, oxides, carbonates and bicarbonates of alkali and alkaline earth metals and alkali metal alcoholates 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, especially 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 11, IV und VI sind bekannt wohingegen die Ausgangsstoffe der Formeln 111 und V neu sind. Alle diese Ausgangsstoffe können analog bekannten Methoden hergestellt werden.The starting materials of formulas 11, IV and VI are known, whereas the starting materials of formulas 111 and V are new. All of these starting materials can be prepared analogously to known methods.

Die Verbindungen der Formel 1 liegen als Gemisch von verschiedenen optisch aktiven Isomeren vor, wenn bei der Herstellung nicht einheitlich optisch aktive Ausgangsmaterialien verwendet wurden. Die verschiedenen Isomerengemische können nach bekannten Methoden in die einzelnen Isomeren aufgetrennt werden. Unter der Verbindung der Formel I versteht man sowohl die einzelnen Isomeren, als auch deren Gemische.The compounds of formula 1 are present as a mixture of different optically active isomers if optically active starting materials were not used uniformly in the preparation. The various isomer mixtures can be separated into the individual isomers by known methods. The compound of the formula I is understood to mean both the individual isomers and their mixtures.

Die Verbindungen der Formel eignen sich zur Bekämpfung von verschiedenartigen tierischen und pflanzlichen Schädlingen.The compounds of the formula 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, Thysanura, 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, Thysanura, Isoptera, Psocoptera and Hymenoptera.

Vor allem eignen sich Verbindungen der Formel I zur Bekämpfung von pflanzenschädigenden Insekten, insbesondere pflanzenschädigenden Frassinsekten, in Zier- und Nutzpfalnzen, Insbesondere in Baumwollkulturen (z.B. gegen Spodoptera littoralis und Heliothis virescens) und Gemüsekulturen (z.B. gegen Leptinotarsa decemlineata und Myzus persicae).Compounds of the formula I are particularly suitable for combating plant-damaging insects, in particular plant-damaging insects, in ornamental and useful plants, in particular in cotton crops (e.g. against Spodoptera littoralis and Heliothis virescens) and vegetable crops (e.g. against Leptinotarsa decemlineata and Myzus persicae).

Wirkstoffe der Formel I zeigen auch eine sehr günstige Wirkung gegen Fliegen wie z.B. Musca domestica und Mückenlarven.Active ingredients of formula I also have a very beneficial effect against flies, such as 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. Phosphorverbindungen; 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.Compounds of the formula I are particularly advantageously combined with substances which have a synergistic or reinforcing effect.

Beispiel solcher Verbindungen sind u.a. Piperonylbutoxid, Propinyläther, Propinyloxime, Propinylcarbamate und Propinylphosphonate, 2-(3,4-Methylendioxyphenoxy)-3,6,9-trioxaundecan (Sesamex resp. Sesoxane), S,S,S-Tributylphosphorotrithioate, 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-trioxaundecane (Sesamex or Sesoxane), S, S, S-tributylphosphorotrithioate, 1,2-methylenedioxy-4- (2- (octylsulfonyl) propyl) benzene.

Verbindungen der Formel 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 can be used on their own 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 1 mit den geeigneten Trägerstoffen, gegebenenfalls unter Zusatz von gegenüber den Wirkstoffen inerten Dispergier- oder Lösungsmitteln. Die Wirkstoffe können in den folgenden Aufarbeitungsformen vorliegen und angewendet werden:

  • Feste Aufarbeitungs formen:
  • Stäubemittel, Streumittel, Granulate (Umhüllungsgranulate, Impragnierungsgranulate und Homogengranulate);
  • Flüssige Aufarbeitungsformen:
    • a) in Wasser dispergierbare Wirkstoffkonzentrate: Spritzpulver (wettable powders), Pasten, Emulsionen; b)Lösungen
Agents according to the invention are prepared in a manner known per se by intimately mixing and / or grinding the active ingredients of the formula 1 with the suitable excipients, 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:
  • Forming fixed refurbishment:
  • Dusts, scattering agents, granules (coating granules, impregnation granules and homogeneous granules);
  • 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): 65

  • Stäubemittel: Zur Herstellung eines a) 5%igen und b) 2%igen Stäubemittels werden die folgenden Stoffe verwendet:
    Figure imgb0006
    Figure imgb0007
    Der Wirkstoff wird mit den Trägerstoffen vermischt und vermahlen.
  • Granulat: Zur Herstellung eines 5%igen Granulates werden die folgenden Stoffe verwendet:
    Figure imgb0008
    Die Aktivsubstanz wird mit Epichlorhydrin vermischt und mit 6 Teilen Aceton gelöst, hierauf wird Polyäthylenglykol und Cetylpolyglykoläther zugesetzt. Die so erhaltene Lösung wird auf Kaolin aufgesprüht und anschliessend das Aceton in Vakuum verdampft.
  • Spritzpulver: Zur Herstellung eines a) 40%igen, b) und c) 25%igen, d) 10%igen Spritzpulver werden folgende Bestandteile verwendet:
    Figure imgb0009
    Figure imgb0010
    Figure imgb0011
    Figure imgb0012
    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 verdünnen lassen.
  • Emulgierbare Konzentrate: Zur Herstellung eines a) 10%igen b) 25%igen und c) 50%igen emulgierbaren Konzentrates werden folgende Stoffe verwendet.
    Figure imgb0013
    Figure imgb0014
    Figure imgb0015
    Aus solchen Konzentraten können durch Verdünnen mit Wasser Emulsionen jeder gewünschten Konzentration hergestellt werden.
  • Sprühmittel: Zur Herstellung eines a) 5%igen und b) 95%-igen Sprühmittels werden die folgenden Bestandteile verwendet:
    Figure imgb0016
    Figure imgb0017
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. For example, the active ingredients of Formula 1 can be formulated as follows (parts mean parts by weight): 65
  • Dusts: The following substances are used to produce a) 5% and b) 2% dusts:
    Figure imgb0006
    Figure imgb0007
    The active ingredient is mixed with the excipients and ground.
  • Granules: The following substances are used to produce 5% granules:
    Figure imgb0008
    The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone, after which polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto kaolin and the acetone is then evaporated in vacuo.
  • Spray powder: The following ingredients are used to produce a) 40%, b) and c) 25%, d) 10% spray powder:
    Figure imgb0009
    Figure imgb0010
    Figure imgb0011
    Figure imgb0012
    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 diluted with water to form suspensions of any desired concentration.
  • Emulsifiable concentrates: The following substances are used to produce a) 10%, b) 25% and c) 50% emulsifiable concentrates.
    Figure imgb0013
    Figure imgb0014
    Figure imgb0015
    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:
    Figure imgb0016
    Figure imgb0017

Beispiel 1.Example 1. Herstellung von a,a-p-Chlorphenyl-iso-propyl-essigsäure-a'-cyano-3' pyridyl-2'-oxybenzylester.Production of a, a-p-chlorophenyl-iso-propyl-acetic acid-a'-cyano-3 'pyridyl-2'-oxybenzyl ester.

7,5 g α,α-Chlorphenyl-isopropyl-essigsäurechlorid in 10 ml abs.Toluol werden bei 5°C zu einer Lösung von 7,5 g 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 imgb0018
als viskose Flüssigkeit mit einer Refraktion von
Figure imgb0019
.7.5 g of α, α-chlorophenyl-isopropyl-acetic acid chloride in 10 ml of absolute toluene at 5 ° C. become a solution of 7.5 g 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 imgb0018
 as a viscous liquid with a refraction of
Figure imgb0019
 .

Auf analoge Weise werden auch folgende Verbindungen hergestellt:

Figure imgb0020
Smp. : 62-65°C
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
NMR-Daten 60 M Hz 2,3 ppm H' (m) 3,3 ppm H" (d) 6,4 ppm H"' (d) 14,5 ppm HIV (s)
Figure imgb0038
Figure imgb0039
 The following connections are also made in an analogous manner:
Figure imgb0020
 M.p .: 62-65 ° C
Figure imgb0021
Figure imgb0022
Figure imgb0023
Figure imgb0024
Figure imgb0025
Figure imgb0026
Figure imgb0027
Figure imgb0028
Figure imgb0029
Figure imgb0030
Figure imgb0031
Figure imgb0032
Figure imgb0033
Figure imgb0034
Figure imgb0035
Figure imgb0036
Figure imgb0037
 NMR data 60 M Hz 2.3 ppm H '(m) 3.3 ppm H "(d) 6.4 ppm H"' (d) 14.5 ppm H IV (s)
Figure imgb0038
Figure imgb0039

Beispiel 2.Example 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.Aqueous active ingredient emulsion were flanzen cotton p with a 0.05% (obtained from a 10% emulsifiable concentrate) sprayed.

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 3.Example 3. Wirkung gegen Chilo suppressalisEffect against Chilo suppressalis

Je 6 Reispflanzen der Sorte Caloro wurden in Plastiktöpfen, die einen oberen Durchmesser von 17 cm aufweisen, verpflanzt 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 Granulatform (Aufwandmenge 8 kg Aktivsubstanz pro Hektare) in das Paddy-Wasser. Die Auswertung auf insektizide Wirkung erfolgte 10 Tage nach der Zugabe des Granulates.6 rice plants of the Caloro variety were transplanted in plastic pots with an upper diameter of 17 cm and grown to a height of approx. 60 cm. The infestation with Chilo suppressalis larvae (L 1 : 3-4 mm long) took place in the paddy water 2 days after the addition of the active ingredient in granular form (application rate 8 kg of active ingredient per hectare). The insecticidal activity was evaluated 10 days after the addition of the granules.

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

Beispiel 4.Example 4. Akarizide WirkungAcaricidal effects

Phaseolus vulgaris Pflanzen wurden 12 Stunden vor dem 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 Test-präparaten derart besprüht, dass kein Ablaufen der Spritzbrühe eintrat. Nach zwei bis 7 Tagen wurden Larven, Adulte und Eier unter dem Binokular auf lebende und tote Individuen ausgewertet und das Ergebnis in Prozenten ausgedrückt. Während der "Haltezeit" standen die behandelten Pflanzen in Gewächshauskabinen bei 25°C.Phaseolus vulgaris plants were covered with an infested leaf piece from a mass cultivation of Tetranychus urticae 12 hours before the test for acaricidal activity. The overflowing movable stages were sprayed with the emulsified test preparations from a chromatography atomizer 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 "holding period", the treated plants were in greenhouse cabins at 25 ° C.

Verbindungen gemäss Beispiel 1 wirkten im obigen Test gegen Adulte, Larven und Eier von Tetranychus urticae.Compounds according to Example 1 were active in the above test against adults, larvae and eggs of Tetranychus urticae.

Beispiel 5.Example 5. Wirkung gegen ZeckenEffect against ticks A) Rhipicephalus bursaA) Rhipicephalus bursa

Je 5 adulte Zecken bzw. 50 Zeckenlarven wurden in ein Glasröhrchen gezählt und für 1 bis 2 Minuten in 2 ml einer wässrigen Emulsion aus einer Verdünnungsreihe mit je 100, 10, 1 oder 0,1 ppm Testsubstanz getaucht. Das Röhrchen wurde dann mit einem genormten Wattebausch verschlossen und auf den Kopf gestellt, damit die Wirkstoffemulsion von der Watte aufgenommen werden konnte.5 adult ticks and 50 tick larvae were counted in a glass tube and for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series with 100, 10, 1 or 0.1 ppm each Test substance immersed. The tube was then closed with a standardized cotton ball and turned upside down so that the active ingredient emulsion could be absorbed by the cotton wool.

Die Auswertung erfolgte bei den Adulten nach. 2 Wochen und bei den Larven nach 2 Tagen. Für jeden Versuch liefen 2 Wiederholungen.The evaluation was carried out for the adults. 2 weeks and for the larvae after 2 days. There were 2 repetitions for each attempt.

B) Boophilus microplus (Larven)B) Boophilus microplus (larvae)

Mit einer analogen Verdünnungsreihe wie beim Test A) wurden mit je 20 sensiblen resp. OPresistenten Larven Versuche durchgeführt. (Die Resistenz bezieht sich auf die Verträglichkeit von Diazinon). Verbindungen gemäss Beispiel 1 wirkten in diesen Tests gegen Adulte und Larven von Rhipicephalus bursa und sensible resp. OP-resistente Larven von Boophilus microplus.With an analog dilution series as in test A) with 20 sensitive resp. OP-resistant larval experiments were carried out. (The resistance relates to the tolerance of diazinon). Compounds according to Example 1 were active in these tests against adults and larvae of Rhipicephalus bursa and sensitive resp. OP-resistant larvae from Boophilus microplus.

Claims (9)

1. A compound of the formula
Figure imgb0052
wherein R1 represents hydrogen, cyano, ethynyl or methyl, and R2 and R3 each represent hydrogen, halogen, C1-C4-alkyl or C1-C4-alkoxy.
2. A compound according to Claim 1, wherein R1 represents cyano, and R2 and R3 each represent hydrogen or chlorine.
3. The compound according to Claim 2 of the formula
Figure imgb0053
4. The compound according to Claim 2 of the formula
Figure imgb0054
5. The compound according to Claim 2 of the formula
Figure imgb0055
6. A process for producing a compound according to Claim 1, which process comprises reacting a compound of the formula
Figure imgb0056
in the presence of an acid-binding agent, with a compound of the formula
Figure imgb0057
wherein R1, R2 and R3 have the meanings given in Claim 1, and X represents a halogen atom.
7. A pesticidal composition which comprises a compound according to Claim 1 as active ingredient, and suitable carriers and/or other additives.
8. A method of combating various animal and plant pests at a locus, which method comprises applying to the locus a compound as claimed in claim 1.
9. A method according to claim 8 for combating insects, and members of the order Acarina.
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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CH8999/77 1977-07-20
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CH15003/77 1977-12-07
CH5777/78 1978-05-26
CH577778 1978-05-26

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DE3005201A1 (en) * 1979-03-02 1980-09-11 Zoecon Corp NEW ESTERS AND THIOLESTERS OF N-PHENYL-SUBSTITUTED VALINE DERIVATIVES
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
US4301156A (en) * 1979-10-01 1981-11-17 The Dow Chemical Company Insecticidal synergistic mixtures of O,O-diethyl O-(3,5,6-trichloro-2-pyridinyl) phosphorothioate and 4-chloro-α-(1-methylethyl)benzeneacetic acid:cyano (6-phenoxy-2-pyridinyl)methyl ester
JPS56147770A (en) * 1980-04-15 1981-11-16 Sumitomo Chem Co Ltd Novel carboxylic ester, its preparation and insecticide and acaricide containing the same as active constituent
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
AU4232985A (en) * 1984-04-13 1985-11-01 Fmc Corporation Fluoropyridinylmethyl cyclopropanecarboxylate insecticides and intermediates
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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EG11383A (en) * 1972-07-11 1979-03-31 Sumitomo Chemical Co Novel composition for controlling nixious insects and process for preparing thereof
US4039680A (en) * 1972-07-11 1977-08-02 Sumitomo Chemical Company, Limited Insecticidal substituted acetate compounds
US4058622A (en) * 1972-07-11 1977-11-15 Sumitomo Chemical Company, Limited Substituted phenyl acetate, insecticidal composition and method of use
US4031233A (en) * 1976-02-09 1977-06-21 Sandoz, Inc. Phenoxyphenyl imidazolyl methanols and ketone derivatives thereof

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