CH622169A5 - Herbicidal composition containing, as active ingredient, pyridyloxyphenoxyalkanecarboxylic acid derivatives - Google Patents

Herbicidal composition containing, as active ingredient, pyridyloxyphenoxyalkanecarboxylic acid derivatives Download PDF

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Publication number
CH622169A5
CH622169A5 CH947076A CH947076A CH622169A5 CH 622169 A5 CH622169 A5 CH 622169A5 CH 947076 A CH947076 A CH 947076A CH 947076 A CH947076 A CH 947076A CH 622169 A5 CH622169 A5 CH 622169A5
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Switzerland
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sep
alkyl
hydrogen
halogen
formula
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CH947076A
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German (de)
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Rolf Dr Schurter
Hermann Dr Rempfler
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Ciba Geigy Ag
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Priority to CH947076A priority Critical patent/CH622169A5/en
Priority to US05/816,840 priority patent/US4133675A/en
Priority to DE19772732846 priority patent/DE2732846A1/en
Priority to FR7722230A priority patent/FR2359129A1/en
Priority to CA283,268A priority patent/CA1100973A/en
Priority to IL52572A priority patent/IL52572A/en
Priority to ES460957A priority patent/ES460957A1/en
Priority to AU27238/77A priority patent/AU513286B2/en
Priority to GB30918/77A priority patent/GB1561616A/en
Priority to ZA00774453A priority patent/ZA774453B/en
Priority to IT26027/77A priority patent/IT1080773B/en
Priority to SU772505504A priority patent/SU710499A3/en
Priority to BE179529A priority patent/BE857022A/en
Priority to NL7708185A priority patent/NL7708185A/en
Priority to JP8875577A priority patent/JPS5315382A/en
Priority to US05/962,518 priority patent/US4253866A/en
Publication of CH622169A5 publication Critical patent/CH622169A5/en
Priority to LV930558A priority patent/LV5151A3/en

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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
    • C07D213/69—Two or more oxygen atoms
    • 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
    • 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
    • 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
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/83—Thioacids; Thioesters; Thioamides; Thioimides
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • 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)

Abstract

A herbicidal composition which is suitable for selectively controlling weeds in crops and for inhibiting the formation of sucrose in tobacco contains, as active ingredient, novel pyridyloxyphenoxyalkanecarboxylic acid derivatives of the formula I <IMAGE> in which Z denotes a carboxylic acid radical COR3 or a 2-oxazoline radical which is optionally mono- or polysubstituted by lower alkyl, or the cyano group, R3 denotes the hydroxyl group or one of the radicals <IMAGE>, an ester radical -OR4, a thioester radical -SR5 or an amino radical <IMAGE> where the individual symbols have the meanings given in Patent Claim 1. The pyridyloxyphenoxyalkanecarboxylic acid derivatives are prepared by subjecting a halopyridinyl with a meta-hydroxyphenoxyalkanecarboxylic acid derivative or a 4-pyridyloxyphenol with an alpha -haloalkanecarboxylic acid derivative to a condensation reaction.

Description

       

  
 

**WARNUNG** Anfang DESC Feld konnte Ende CLMS uberlappen **.

 



   PATENTANSPRÜCHE
1. Herbizides Mittel, dadurch gekennzeichnet, dass es als aktive Komponente mindestens ein Pyridyloxy-phenoxy-alkancarbonsäurederivat der Formel I enthält,
EMI1.1     
 worin Z einen Carbonsäurerest COR3 oder einen gegebenenfalls durch Niederalkyl ein- oder mehrfach substituierten 2-Oxazolinrest oder die Cyanogruppe, A Wasserstoff, Halogen, Alkyl, Cyano oder Nitro, B Wasserstoff, Alkyl, C Wasserstoff, Halogen oder Cyano, D Halogen, Alkyl oder, falls C Cyano bedeutet, auch Wasserstoff, R1 Wasserstoff, Alkyl oder Phenyl, R2 Wasserstoff, Alkyl oder Carbonsäurerest COR3, R3 die Hydroxygruppe, oder einer der Reste
EMI1.2     

R4 eine Alkylgruppe, die unsubstituiert oder durch Halogen, Alkoxy, Alkylthio, Carboxy, Alkoxycarbonyl, Cycloalkyl, Aryl oder einen 5- bis 6gliedrigen heterocyclischen Ring substituiert sein kann;

  Cycloalkyl; einen Alkenylrest, der unsubstituiert oder durch Halogen substituiert sein kann; Alkinyl; einen Phenylring, der unsubstituiert oder ein- oder mehrfach durch Halogen, Alkyl, Alkoxy, Alkylthio, Cyano oder Nitro substituiert ist,    R5    einen Alkylrest, der unsubstituiert oder durch Cycloal   kyl,    Aryl oder einen 5- bis 6gliedrigen heterocyclischen Ring substituiert sein kann; Cycloalkyl- oder Alkenyl; den Phenylring, der unsubstituiert oder ein- oder mehrfach durch Halogen, Alkyl, Alkoxy, Alkylthio, Cyano oder Nitro substituiert sein kann,
R6 und R7 unabhängig voneinander je Wasserstoff oder einen Alkylrest, der gegebenenfalls durch Hydroxyl oder Alkoxy substituiert sein kann; Alkoxy; Alkenyl; Alkinyl;

  Phenyl oder Benzyl, wobei die Phenylringe ein- oder mehrfach durch Halogen, Alkyl, Alkoxy, Alkylthio, Cyano oder Nitro substituiert sein können oder
R6 und R7 können zusammen mit dem Stickstoffatom, an das sie gebunden sind auch einen 5- bis 6gliedrigen Heterocyclus bilden und    1 Mnf3 das Ion Äquivalent eines Alkali-, Erdalkalime-    tall-, Kupfer- oder Eisen-Ions oder einen quaternären Alkylammonium- oder Hydroxyalkylammonium-Rest bedeuten.



   2. Verfahren zur Herstellung der Pyridyloxy-phenoxy-alkancarbonsäurederivate der im Anspruch 1 genannten Formel I, dadurch gekennzeichnet, dass man a) ein substituiertes ortho-Halogenpyridin der Formel II
EMI1.3     
 mit einem para-Hydroxy-phenoxyalkancarbonsäurederivat der Formel III
EMI1.4     
 in Gegenwart einer Base umsetzt, oder b) einen Pyridyloxy-para-hydroxy-phenyläther der Formel IV
EMI1.5     
 mit einem   a -Halogencarbonsäurederivat    der Formel V
EMI1.6     
 in Gegenwart einer Base umsetzt, wobei in den Formeln II, III, IV und V A, B, C, D, R1, R2 und Z die in Formel I gegebenen Bedeutungen haben und Hal ein Halogenatom bedeutet.



   3. Verwendung der Pyridyloxy-phenoxy-alkancarbonsäure-Derivate der im Patentanspruch 1 genannten Formel I zur selektiven Bekämpfung von Unkräutern in   Kulturpflanzungen    im Nachauflaufverfahren.



   Die vorliegende Erfindung betrifft ein herbizides Mittel, welches neue Pyridyloxy-phenoxy-alkancarbonsäurederivate als aktive Komponente enthält, ein Verfahren zur Herstellung dieser Pyridyloxy-phenoxy-alkancarbonsäurederivate sowie deren Verwendung zur selektiven Bekämpfung von Unkräutern.



   Die neuen Pyridyloxy-phenoxy-alkan-carbonsäurederivate entsprechen der Formel 1
EMI1.7     
 worin
Z einen Carbonsäurerest COR3 oder einen gegebenenfalls durch Niederalkyl ein- oder mehrfach substituierten 2-Oxazolinrest oder die Cyanogruppe,
A Wasserstoff, Halogen, Alkyl, Cyano oder Nitro,
B Wasserstoff, Alkyl,
C Wasserstoff, Halogen oder Cyano,
D Halogen, Alkyl oder, falls C Cyano bedeutet, auch Wasserstoff,
R1 Wasserstoff, Alkyl oder Phenyl,
R2 Wasserstoff, Alkyl oder Carbonsäurerest COR3,
R3 die Hydroxygruppe oder einer der Reste  
EMI2.1     




   R4 eine Alkylgruppe, die unsubstituiert oder durch Halogen, Alkoxy, Alkylthio, Carboxy, Alkoxycarbonyl, Cycloalkyl, Aryl oder einen 5- bis 6gliedrigen heterocyclischen Ring substituiert sein kann; Cycloalkyl: einen Alkenylrest, der unsubstituiert oder durch Halogen substituiert sein kann; Alkinyl: einen Phenylring, der unsubstituiert oder ein- oder mehrfach durch Halogen, Alkyl, Alkoxy, Alkylthio, Cyano oder Nitro substituiert ist,    R5    einen Alkylrest, der unsubstituiert oder durch Cycloalkyl, Aryl oder einen 5- bis 6gliedrigen heterocyclischen Ring substituiert sein kann;

  Cycloalkyl- oder Alkenyl; den Phenylring, der unsubstituiert oder ein- oder mehrfach durch Halogen, Alkyl, Alkoxy, Alkylthio, Cyano oder Nitro substituiert sein kann,
R6 und R, unabhängig voneinander je Wasserstoff oder einen Alkylrest, der gegebenenfalls durch Hydroxyl oder Alkoxy substituiert sein kann; Alkoxy; Alkenyl; Alkinyl; Phenyl oder Benzyl, wobei die Phenylringe ein- oder mehrfach durch Halogen, Alkyl, Alkoxy, Alkylthio, Cyano oder Nitro substituiert sein können oder
R6 und R7 können zusammen mit dem Stickstoffatom, an das sie gebunden sind, auch einen 5- bis 6gliedrigen Heterocyclus bilden,   
1 Mn(3 das Ion Äquivalent eines Alkali-, Erdalkalime n    tall-, Kupfer- oder Eisen-lons oder einen quaternären Alkylammonium- oder Hydroxyalkylammonium-Rest bedeuten.



   In dieser Formel können Alkylreste bis zu 18 Kohlenstoffe enthalten, verzweigt oder unverzweigt sein. Wenn sie als Alkoxy-, Alkylthio-, Alkylaminoester auftreten, werden jedoch meistens niedere, 1 bis 4 Kohlenstoffatome enthaltende Reste bevorzugt. Cycloalkylgruppen können 3 bis 12 Kohlenstoffatome umfassen, Alkenyl- oder Alkinylgruppe 2 bis 8 Kohlenstoffatome. Unter Aryl können gegebenenfalls substituierte Naphthyl- oder Phenylringe verstanden werden, die Phenylringe sind bevorzugt.

  Zu den in Frage kommenden 5- bis 6gliedrigen Heterocyclen, welche die Reste R6 und   R,    mit dem Stickstoffatom, an das sie gebunden sind, bilden können, gehören die Pyrrol, Pyrrolidin, Oxazolin, Oxazolidin, Piperidin, Morpholin oder Thiomorpholinringe, die durch Alkyl, insbesondere Methyl substituiert sein können, wie auch die Piperazin, Alkylpiperazin, Phenyl- oder Benzylpiperazinringe. Quaternäre Ammonium- oder Hydroxyammoniumreste können bis zu 5 Kohlenstoffatome pro Alkylteil enthalten. Unter den Halogenatomen ist Chlor bevorzugt. Niederalkylreste können 1 bis 4 Kohlenstoffatome enthalten, es sind bevorzugt Methyl oder Äthyl.



   Aus der belgischen Patentschrift Nr. 834 495 sind 4-(Pyrid-2-yloxy)-alkancarbonsäuren und -ester mit herbizider Wirkung gegen Gräser, aber nicht gegen breitblättrige Pflanzen bekanntgeworden. Ferner sind aus der deutschen Offenlegungsschrift 2 223 894 4-Phenoxy-phenoxy-alkancarbonsäurederivate ähnlicher Struktur enthaltende herbizide Mittel mit spezieller Gräserwirkung zur selektiven Bekämpfung von Ungräsern in mono- und dikotylen Kulturpflanzen bekanntgeworden.



   Es wurde nun überraschenderweise gefunden, dass die neuen Wirkstoffe der Formel I gemäss vorliegender Erfindung eine mehr allgemeine, nicht spezifisch gegen Gräser gerichtete Herbizidwirkung besitzen, vor allem bei post-emergenter Anwendung und in mono- und dikotylen Kulturen als Unkrautmittel eingesetzt werden können.



   Die Pyridyloxy-phenoxy-alkancarbonsäurederivate besitzen auch günstige wachstumsregulierende Effekte (Wuchshemmung). Insbesondere hemmen sie das Wachstum von dicotylen Pflanzen. Beispiele für die nutzbringende Anwendung der erfindungsgemässen Verbindungen sind z. B.



  - die Reduktion des vegetativen Wachstums bei Soja und  ähnlichen Leguminosen, was zu einer Ertragssteigerung die ser Kulturen führt; - die Hemmung des unerwünschten Wachstums von Geiztrie ben bei Tabak, dessen Haupttrieb man geschnitten hat, was der Ausbildung grösserer und schönerer Blätter zugute kommt; - die Hemmung des Wachstums von Gras und dikotyledonen
Pflanzen, wie Obstbäume, Zierbäume, Gebüsche und Hek ken, zwecks Einsparung an Schnittarbeit.



   Die Pyridyloxy-phenoxy-alkancarbonsäurederivate der Formel I sind wenig giftig für Warmblüter und deren Applikation wirft keine Probleme auf. Die Aufwandmenge liegt zwischen 0,1 und 5 kg pro Hektar.



   Die Herstellung der neuen Verbindungen der Formel I erfolgt nach an sich bekannten Methoden.



   Nach einem ersten Verfahren setzt man ein substituiertes ortho-Halogen-pyridin der Formel II
EMI2.2     
 mit einem   para-Hydroxyphenoxy-alkan-carbonsäurederivat    der Formel III
EMI2.3     
 in Gegenwart einer Base um.

 

   Nach einem zweiten Verfahren setzt man einen Pyridyl oxy-para-hydroxy-phenyläther der Formel IV
EMI2.4     
 in Gegenwart einer Base mit einem a-Halogencarbonsäurederivat der Formel V um
EMI2.5     

Falls man bei diesen Verfahren als Ausgangsstoffe der Formeln III bzw. V eine Carbonsäure verwendet, so kann man nachträglich diese Gruppe in ein anderes definitionsgemässes Derivat der Formel I überführen. Umgekehrt kann man bei Verwendung z. B. eines Esters der Formel III bzw. V abschliessend durch Verseifung die Estergruppe in die freie Carbonsäure und weiter in ein Salz, Amid oder Hydrazid überführen.



   In den Formeln II bis V der Ausgangsstoffe haben die Reste   R1,    R2, A, B, C, D und Z die unter Formel I angegebenen  
Bedeutungen und Hal steht für ein Halogenatom, vorzugsweise Chlor oder Brom.



   Die genannten Umsetzungen können in An- oder Abwesenheit von gegenüber den Reaktionsteilnehmern inerten Lösungs- oder Verdünnungsmitteln durchgeführt werden. Bevorzugt sind polare organische Lösungsmittel wie Methyläthylketon, Acetonitril, Dimethylformamid, Dimethylsulfoxid usw.



  Die Reaktionstemperaturen liegen zwischen 0 und   200     und die Reaktionsdauer beträgt je nach gewählter Umsetzungs temperatur und Lösungsmittel zwischen 1/4 Stunde und mehre ren Tagen. Man arbeitet in der Regel bei Normaldruck oder einem leichten Überdruck. Als Basen (Kondensationsmittel) für die Umsetzung kommen z. B. NaOH, KOH, NaOCH3, NaH, K2CO3, Na2CO3, Kalium-tert. butylat usw. aber auch organische Basen in Betracht.



   Die Ausgangsstoffe der Formeln II bis V sind teilweise bekannt. Noch nicht beschriebene Ausgangsstoffe dieser Formeln lassen sich nach üblichen Verfahren und Techniken leicht herstellen.



   Substituierte 2-Halogen-pyridine gemäss Formel II können u. a. leicht aus den entsprechenden 2-Pyridinolen hergestellt werden, welche teilweise bekannt sind. Ausgangsprodukte der
Formel III können hergestellt werden, indem man z. B. Hydro chinonmonobenzyläther mit einem a -Halogencarbonsäure derivat, vorzugsweise einem Ester der Formel V, umsetzt und die Benzyl-phenyläther-Bindung durch katalysatische Hydrie rung spaltet, z. B. mit einem Palladium-auf-Kohle-Katalysator, wobei der Benzylrest als Toluol weggeht.



   Durch Umsetzung von Hydrochinon mit 2-Halogenpyridi nen in äquimolaren Mengen und in Gegenwart von Base kann man zu den Ausgangsprodukten der Formel IV gelangen.



   Carbonsäurederivate der Formel V sind ebenfalls bekannt.



  Als deren einfachste Vertreter seien z. B. die Chloressigsäure, deren Ester, Thioester, Amide und Hydrazide erwähnt.



   Die nachfolgenden Beispiele veranschaulichen das Verfahren für die Herstellung von Wirkstoffen der Formel I. Weitere in entsprechender Weise hergestellte Wirkstoffe sind in der anschliessenden Tabelle aufgeführt. Temperaturangaben bezie hen sich auf Celsius-Grade, Druckangaben sind in mm Hg  (Torr = 1,33 Millibar) gegeben.



   Diese Pyridyloxy-phenoxy-alkan-carbonsäurederivate der Formel I sind stabile Verbindungen, welche in üblichen organischen Lösungsmitteln, wie Alkoholen, Äthern, Ketonen, Dimethylformamid, Dimethylsulfoxyd usw, löslich sind.



   Beispiel 1    a-[4-(3',5'-Dichlor-6'-methyl-pyrid-2'-yl)-oxy- phenoxyl -propionsÅauremethylester   
In einen Kolben wurden 22,0 g (0,11 Mol) 5-Hydroxy    phenoxya-propionsäuremethylester    und 200 ml Dimethylsulf oxid gegeben. In dieser Mischung wurden 6,0 g Natriumme    thyIateingetragen    und   anschliessend    das entstandene Methanol bei vermindertem Druck, bei 11 Torr und einer Badtemperatur von   70-80     abdestilliert. Danach wurden 19,6 g (0,1 Mol)   6-Methyl-2,3,5-trichlor-pyridin    in 50 ml   lDimethylsulf-    oxid zugegeben und das Ganze 2 Stunden bei   60     gerührt. Anschliessend wurde das Dimethylsulfoxid abdestilliert, der Rückstand mit Eis und 2n NaOH versetzt und zweimal mit Essigester extrahiert.

  Die Extrakte wurden mit Salzsole gewa schen, mit Magnesiumsulfat getrocknet, am Rotavapor einge engt und der erhaltene Rückstand in Methanol umkristallisiert.



   Ausbeute: 16 g; Smp.   79-80     (Verbindung Nr. 21).



   Beispiel 2    a-[4-(3',5'-Dichlor-6'-methyl-pyrid-2'-yl)-oxy- phenoxy]-propionsäure   
10,5 g (0,03 Mol)   a-[4-(3',5'-Dichlor-6'-methyl-pyrid-2'-       yl)-oxy-phenoxy] -propionsäure-methylester,    50 ml 1N NaOH  (0,05 Mol) und 10   ml    Methylcellosolve wurden bei Raumtemperatur 12 Std. gerührt. Dann wurde mit   1n    HCl auf ein pH 2,5 gestellt, filtriert, mit Wasser gewaschen und getrocknet.



   Ausbeute: 10,15 g (99%), Smp.   117-120"    (Verbindung Nr. 22).



   Weitere gemäss diesem Beispiel hergestellte Pyridyloxyphenoxy-alkancarbonsäurederivate gemäss Formel I sind in der nachstehenden Tabelle aufgeführt:
EMI3.1     

EMI3.2     


<tb>  <SEP> Nr. <SEP> A <SEP> B <SEP> C <SEP> D <SEP> R1 <SEP> R2 <SEP> Z <SEP> Physikalische
<tb>  <SEP> Konstante
<tb>  <SEP> 1 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOCH3
<tb>  <SEP> 2 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOH
<tb>  <SEP> 3 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOCH2CCl3
<tb>  <SEP> 4 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3
<tb>  <SEP> 5 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F <SEP> 95-97 C
<tb>  <SEP> 6 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOH
<tb>  <SEP> 7 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> COOCH(CH3)2 <SEP> Eb <SEP> 1500C/0.0
<tb>  

   <SEP> 8 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COO-CsH1s
<tb>  <SEP> 9 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> WOOCH3 <SEP> F <SEP> 113-115"C
<tb> 10 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> H <SEP> -COOH <SEP> F <SEP> 170-179"C
<tb> 11 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> H <SEP> -COOCH(CH3)2 <SEP> F <SEP> 62-65"C
<tb> 12 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> H <SEP> -COOC2H4Br
<tb> 13 <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F <SEP> 93-96"C
<tb> 14 <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOH
<tb> 15 <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOC2H4OCH3
<tb>   
EMI4.1     


<tb> Nr.

  <SEP> A <SEP> B <SEP> C <SEP> D <SEP> R1 <SEP> R2 <SEP> Z <SEP> Physikalische
<tb>  <SEP> Konstante
<tb> 16 <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOC3H6
<tb> 17 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F1110C
<tb> 18 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOH
<tb> 19 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOC(C2M5)2
<tb> 2() <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COO < 
<tb> 21 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F <SEP> 79-80"C
<tb> 22 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOH <SEP> F <SEP> 117-120 C
<tb> 73 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> COOC2H4Br <SEP> F <SEP> 60-62"C
<tb> 2i <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> COOCH(CH3) <SEP> Eb <SEP> 

   150"C/0,01
<tb> 25 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> CH3 <SEP> -COOC2HsCOOC2Hs
<tb> 26 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> CH3 <SEP> -COOH <SEP> -COOH
<tb> 27 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOCH3
<tb> 28 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> -CM3 <SEP> -COOH
<tb> 29 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOCH2-C <SEP> 1
<tb> 30 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOC2Hs
<tb> 31 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> M3 <SEP> WOOCH3 <SEP> F <SEP> 54-56"C
<tb> 32 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> -CM3 <SEP> -COOH <SEP> F <SEP> 132-134"C
<tb> 33 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> M3 <SEP> -COOC6H12C
<tb> 34 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> H3 <SEP> -COO
<tb> 35 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOCH3 <SEP> F <SEP> 89-93 C
<tb> 

   36 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOH
<tb> 37 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> H3 <SEP> -COOs
<tb> 38 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOC112
<tb> 39 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> M3 <SEP> COOCH3 <SEP> F <SEP> 78-83"C
<tb> 40 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> H3 <SEP> -COOH
<tb> 41 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOC2H4OC4H9
<tb>  <SEP> cn,
<tb>  <SEP> 1
<tb> 42 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOCH
<tb> 43 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> -COOC2Hs-COOC2Hs
<tb> 44 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> -COOH <SEP> -COOH
<tb> 45 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> C2M5 <SEP> -COOH
<tb> 46 <SEP> Cl <SEP> H <SEP> Cl <SEP> C1 <SEP> H <SEP> 4 <SEP> -COOCH3
<tb> 47 <SEP> H <SEP> H <SEP> CN <SEP> 

   H <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F <SEP> 103-104 C
<tb> 48 <SEP> H <SEP> H <SEP> CN <SEP> H <SEP> H <SEP> CH3 <SEP> -COO <SEP> OH,N <SEP> O <SEP> (C,HOH),
<tb> 49 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COONa
<tb> 50 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOOH2NO(CH4oH),
<tb> 51 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> CON(CH3)2
<tb> 52 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CONHCH2-CH=CH2
<tb> 53 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CONHC2Hs
<tb> 54 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CON(CH3)2
<tb> 55 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CONHCH2-CH=CH2
<tb> 56 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CONHCH(CH3)2
<tb> 57 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CON(CH3)2
<tb> 58 <SEP> CN  

   <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> CONHCH2CH=CH2
<tb> 59 <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CON1IC1l2
<tb> 60 <SEP> CN <SEP> CH2 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CON(CH3)2
<tb> 61 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CONH-CH2-CH=CH2
<tb> 62 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CONg
<tb> 63 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> CON(CH3)2
<tb> 64 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> CONHCH2-CH=CH2
<tb>   
EMI5.1     


<tb> Nr.

  <SEP> A <SEP> B <SEP> C <SEP> D <SEP> R1 <SEP> R2 <SEP> Z <SEP> Physikalische
<tb>  <SEP> Konstante
<tb> 65 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CON3o
<tb> 66 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CON(CH3)2
<tb> 67 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> CH3 <SEP> CON(CH3)2 <SEP> WON(CH3)2
<tb> 68 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> CH3 <SEP> CONHCH2 <SEP> -CONH-CH2-CH=CH2
<tb>  <SEP> CH=CH2
<tb> 69 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CON(CH3)2
<tb> 70 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CONHCH2-CH=CH2
<tb> 71 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -COCH3
<tb> 72 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> CH3 <SEP> -CON(CH3)2
<tb> 73 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> CH3 <SEP> -CONHCH2-CH=CH2
<tb> 74 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> CH3 

   <SEP> -CONHnCöHl7
<tb> 75 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CON(CH3)2
<tb> 76 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CONHCH2-CH=CHa
<tb> 77 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CoNHCH(C2H532
<tb> 78 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CON(CH3)2
<tb> 79 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CONHCH2-CH=CH,
<tb> 80 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CONHC2H4OH
<tb> 81 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CONH-N(CH3)2
<tb> 82 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> ONWN(CH3)2
<tb> 83 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COSCH <SEP> 1
<tb>  <SEP> 2
<tb> 84 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COSCH2-CH=CH2
<tb> 85 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> 

   CH3 <SEP> -COSC2Hs
<tb> 86 <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COSC14(CH3)2
<tb> 87 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COSCH3
<tb> 88 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> COSnC3H7
<tb> 89 <SEP> H <SEP> H <SEP> CN <SEP> H <SEP> H <SEP> CH3 <SEP> -COS
<tb> 90 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> CH3 <SEP> -COSCH2COOC2Hs
<tb> 91 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -COSC8H17
<tb> 92 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> CH3 <SEP> -COr
<tb> 93 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> CH3 <SEP> -COONa
<tb> 94 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COONa <SEP> F <SEP> 115-120"C
<tb> 95 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOOH2No(C2H40H)2 <SEP> F <SEP> 133-135tC
<tb> 96 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> 

   CH3 <SEP> -COOC2Hs <SEP> F <SEP> 101-104 C
<tb> 97 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOC2Hs <SEP> Eb <SEP> 160 C/0,01
<tb> 98 <SEP> CN <SEP> CH3 <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F <SEP> 105-109 C
<tb> 99 <SEP> H <SEP> CH3 <SEP> CN <SEP> Cl <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F <SEP> 105-108"C
<tb> 100 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> COO8H2N(i)(C2Hs)2 <SEP> F <SEP> 145-146"C
<tb> 
Die Herstellung   erfindungsgemässer    Mittel erfolgt in an sich bekannter Weise durch inniges Vermischen und Vermahlen von Wirkstoffen der allgemeinen Formel I mit geeigneten Trägerstoffen und/oder Verteilungsmitteln, gegebenenfalls unter Zusatz von gegenüber den Wirkstoffen inerten Antischaum-, Netz-, Disperions- und/oder Lösungsmitteln.

  Die Wirkstoffe können in den folgenden Aufarbeitungsformen vorliegen und angewendet werden: Feste Aufarbeitungsformen
Stäubemittel, Streumittel, Granulate, Umhüllungsgranulate,
Imprägniergranulate und Homogengranulate: In Wasser dispergierbare Wirkstoffkonzentrate
Spritzpulver (wettable powder), Pasten, Emulsionen;
Emulsionskonzentrate Flüssige Aufarbeitungsformen
Lösungen
Die Wirkstoffkonzentrationen betragen in den erfindungsgemässen Mitteln 1 bis 80 Gewichtsprozent und können gegebenenfalls bei der Anwendung auch in geringen Konzentrationen wie etwa 0,05 bis   1%    vorliegen.



   Den beschriebenen erfindungsgemässen Mitteln lassen sich andere biozide Wirkstoffe oder Mittel beimischen. So können die neuen Mittel ausser den genannten Verbindungen der allgemeinen Formel I z. B. Insektizide, Fungizide, Bakterizide, Fungistatika, Bakteriostatika, Nematozide oder weitere Herbizide zur Verbreiterung des Wirkungsspektrums enthalten.



  Granulat
Zur Herstellung eines   5 %igen    Granulates werden die folgenden Stoffe verwendet:  
5 Teile eines der Wirkstoffe der Formel 1,
0,25 Teile Epichlorhydrin,
0,25 Teile Cetylpolyglykoläther,
3,50 Teile Polyäthylenglykol,
91 Teile Kaolin (Korngrösse: 0,3-0,8 mm).



   Die Aktivsubstanz wird mit Epichlorhydrin vermischt und in 6 Teilchen Aceton gelöst, hierauf wird Polyäthylenglykol und Cetylpolyglykoläther zugesetzt. Die so erhaltene Lösung wird auf Kaolin aufgesprüht und anschliessend im Vakuum verdampft.



  Spritzpulver
Zur Herstellung eines a) 70%igen und b)   10%igen    Spritzpulvers werden folgende Bestandteile verwendet: a) 70 Teile eines der Wirkstoffe der Formel I,
5 Teile Natriumdibutylnaphthylsulfonat,
3 Teile   Naphthalinsulfonsäuren-Phenolsulfonsäuren-   
Formaldehyd-Kondensat   3 :2:1,   
10 Teile Kaolin,
12 Teile Champagne-Kreide; b) 10 Teile   o-[4-(3',5'-Dichlor-6'-methyl-pyrid-2'-yl)-       phenoxyl-propionsäuremethylester   
3 Teile Gemisch der Natriumsalze von gesättigten    Fettalkoholsulfonaten,   
5 Teile Naphthalinsulfonsäuren-Formaldehyd-Kondensat,
82 Teile Kaolin.



   Der angegebene Wirkstoff wird auf die entsprechenden Trägerstoffe (Kaolin und Kreide) aufgezogen und anschliessend vermischt und vermahlen mit den übrigen Bestandteilen.



  Man erhält Spritzpulver von vorzüglicher Benetzbarkeit und Schwebefähigkeit. Aus solchen Spritzpulvern können durch Verdünnen mit Wasser Suspensionen von 0,1-8% Wirkstoff erhalten werden, die sich zur Unkrautbekämpfung in Pflanzenkulturen eignen.



  Paste
Zur Herstellung einer 45 %igen Paste werden folgende stoffe verwendet:
45 Teile   a-[4-(5'-Cyano-6'-methyl-pyrid-2'-yl)-oxy-       phenoxy]-propionsäuremethylester    oder eines anderen der genannten Wirkstoffe der Formel I,
5 Teile Natriumaluminiumsilikat,
14 Teile Cetylpolyglykoläther mit 8 Mol Äthylenoxid,
1 Teil Oleylpolyglykoläther mit 5 Mol Äthylenoxid,
2 Teile Spindelöl,
10 Teile Polyäthylenglykol,
23 Teile Wasser
Der Wirkstoff wird mit den Zuschlagstoffen in dazu geeigneten Geräten innig vermischt und vermahlen. Man erhält eine Paste, aus der sich durch Verdünnen mit Wasser   Suspen-.   



  sionen jeder gewünschten Konzentration herstellen lassen.



  Emulsionskonzentrat
Zur Herstellung eines   25 %igen    Emulsionskonzentrates werden
25 Teile   a-[4-(3',5',6'-Trichlorpyrid-2'-yl)-oxy-phenoxyl-    propionsäuremethylester oder eines anderen der ge nannten Wirkstoffe der Formel I,
5 Teile einer Mischung von Nonylphenolpolyoxy-äthylen oder Calciumdodecylbenzolsulfat,
35 Teile   3,5, 5-Trimethyl-2-cyclohexen-1 -on,   
35 Teile Dimethylformamid miteinander vermischt. Dieses Konzentrat kann mit Wasser zu Emulsionen auf geeignete Konzentrationen von z. B. 0,1-10% verdünnt werden. Solche Emulsionen eignen sich zur Bekämpfung von Unkräutern in   Kulturpflanzungen.   



   Die neuen   4-Pyridyloxyu -phenoxyalkancarbonsäuren    und ihre Derivate der Formel I sowie die sie enthaltenden Mittel besitzen eine ausgezeichnete selektiv-herbizide Wirkung gegen Unkräuter in den verschiedensten Kulturpflanzenbeständen. Sie haben ebenfalls eine das Pflanzenwachstum regulierende Wirkung.



   Obwohl die neuen Wirkstoffe der Formel I bei pre- und post-emergenter Anwendung wirksam sind, scheint die postemergente Applikation als Kontaktherbizide den Vorzug zu verdienen, obwohl auch der pre-emergente Einsatz von Interesse ist. Bevorzugt werden die neuen Wirkstoffe als z. B.



     25 %ige    Spritzpulver oder z. B. 20%ige emulgierbare Konzentrate formuliert und mit Wasser verdünnt, auf die Pflanzenbestände post-emergent appliziert.



   Herbizide Wirkung bei Applikation der Wirkstoffe nach dem Auflaufen der Pflanzen (post-emergent)
Verschiedene Kulturpflanzen und Unkräuter werden aus den Samen in Töpfen im Gewächshaus aufgezogen, bis sie das 4- bis 6-Blatt-Stadium erreicht haben. Dann werden die Pflanzen mit wässrigen Wirkstoffemulsionen (erhalten aus einem 20%igen emulgierbaren Konzentrat) in verschiedenen Dosierungen gespritzt. Die behandelten Pflanzen werden dann bei optimalen Bedingungen von Licht, Begiessung, Temperatur   (22-250    C) und Luftfeuchtigkeit (50-70% relativ) gehalten. 15 Tage nach Behandlung erfolgt die Auswertung der Versuche.



   Hemmung des Wachstums unerwünschter Geiztriebe bei Tabak
Im Gewächshaus wurde Tabak der Sorte  Xanti  aufgezogen und kurz vor dem Blühen gekappt. (Der Haupttrieb wurde abgeschnitten.) Einen Tag nach dem Kappen wurden jeweils 3 Pflanzen von oben her mit je 10 ml wässriger Zubereitungen einer Verbindung der Formel I bespritzt. Die gewählten Wirkstoffkonzentrationen entsprechen in einer normalen Pflanzenpopulation den Aufwandmengen von 12 kg Wirkstoff/ha resp. 6 kg WS/ha und 3 kg WS/ha. 14 Tage nach der Applikation ist die Hemmwirkung auf das unerwünschte Geiztriebwachstum evaluiert worden. Hierbei ist die durchschnittliche Länge der Geiztriebe aus den 6 obersten Blattachseln aller 3 Pflanzen ermittelt worden.

 

   Die mit den Verbindungen Nr. 21 und 97 behandelten Pflanzen zeigten kein oder nur ganz geringes Wachsen der Geiztriebe, welche bei unbehandelten Kontrollen eine durchschnittliche Länge von über 20 cm erreichen. 



  
 

** WARNING ** beginning of DESC field could overlap end of CLMS **.

 



   PATENT CLAIMS
1. Herbicidal agent, characterized in that it contains at least one pyridyloxy-phenoxy-alkane carboxylic acid derivative of the formula I as active component,
EMI1.1
 in which Z is a carboxylic acid residue COR3 or a 2-oxazoline residue which is mono- or polysubstituted or substituted by lower alkyl or the cyano group, A hydrogen, halogen, alkyl, cyano or nitro, B hydrogen, alkyl, C hydrogen, halogen or cyano, D halogen, alkyl or if C is cyano, also hydrogen, R1 is hydrogen, alkyl or phenyl, R2 is hydrogen, alkyl or carboxylic acid residue COR3, R3 is the hydroxyl group, or one of the residues
EMI1.2

R4 is an alkyl group which may be unsubstituted or substituted by halogen, alkoxy, alkylthio, carboxy, alkoxycarbonyl, cycloalkyl, aryl or a 5- to 6-membered heterocyclic ring;

  Cycloalkyl; an alkenyl radical which may be unsubstituted or substituted by halogen; Alkynyl; a phenyl ring which is unsubstituted or mono- or polysubstituted by halogen, alkyl, alkoxy, alkylthio, cyano or nitro, R5 an alkyl radical which may be unsubstituted or substituted by cycloalkyl, aryl or a 5- to 6-membered heterocyclic ring; Cycloalkyl or alkenyl; the phenyl ring which can be unsubstituted or substituted one or more times by halogen, alkyl, alkoxy, alkylthio, cyano or nitro,
R6 and R7 independently of one another are each hydrogen or an alkyl radical which can optionally be substituted by hydroxyl or alkoxy; Alkoxy; Alkenyl; Alkynyl;

  Phenyl or benzyl, where the phenyl rings can be substituted one or more times by halogen, alkyl, alkoxy, alkylthio, cyano or nitro or
R6 and R7 together with the nitrogen atom to which they are attached can also form a 5- to 6-membered heterocycle and 1 Mnf3 the ion equivalent of an alkali metal, alkaline earth metal, copper or iron ion or a quaternary alkylammonium or hydroxyalkylammonium -Rest mean.



   2. Process for the preparation of the pyridyloxy-phenoxy-alkanecarboxylic acid derivatives of the formula I mentioned in claim 1, characterized in that a) a substituted ortho-halopyridine of the formula II
EMI1.3
 with a para-hydroxy-phenoxyalkanecarboxylic acid derivative of the formula III
EMI1.4
 in the presence of a base, or b) a pyridyloxy-para-hydroxy-phenyl ether of the formula IV
EMI1.5
 with an α-halocarboxylic acid derivative of the formula V
EMI1.6
 in the presence of a base, wherein in the formulas II, III, IV and V A, B, C, D, R1, R2 and Z have the meanings given in formula I and Hal represents a halogen atom.



   3. Use of the pyridyloxy-phenoxy-alkanecarboxylic acid derivatives of the formula I mentioned in claim 1 for the selective control of weeds in crops by post-emergence.



   The present invention relates to a herbicidal composition which contains new pyridyloxy-phenoxy-alkanecarboxylic acid derivatives as active component, a process for the preparation of these pyridyloxy-phenoxy-alkanecarboxylic acid derivatives and their use for the selective control of weeds.



   The new pyridyloxy-phenoxy-alkane-carboxylic acid derivatives correspond to Formula 1
EMI1.7
 wherein
Z a carboxylic acid residue COR3 or a 2-oxazoline residue which is mono- or polysubstituted or substituted by lower alkyl, or the cyano group,
A is hydrogen, halogen, alkyl, cyano or nitro,
B hydrogen, alkyl,
C hydrogen, halogen or cyano,
D halogen, alkyl or, if C is cyano, also hydrogen,
R1 is hydrogen, alkyl or phenyl,
R2 is hydrogen, alkyl or carboxylic acid residue COR3,
R3 is the hydroxy group or one of the residues
EMI2.1




   R4 is an alkyl group which may be unsubstituted or substituted by halogen, alkoxy, alkylthio, carboxy, alkoxycarbonyl, cycloalkyl, aryl or a 5- to 6-membered heterocyclic ring; Cycloalkyl: an alkenyl radical which may be unsubstituted or substituted by halogen; Alkynyl: a phenyl ring which is unsubstituted or mono- or polysubstituted by halogen, alkyl, alkoxy, alkylthio, cyano or nitro, R5 an alkyl radical which may be unsubstituted or substituted by cycloalkyl, aryl or a 5- to 6-membered heterocyclic ring;

  Cycloalkyl or alkenyl; the phenyl ring which can be unsubstituted or substituted one or more times by halogen, alkyl, alkoxy, alkylthio, cyano or nitro,
R6 and R, independently of one another, are each hydrogen or an alkyl radical which can optionally be substituted by hydroxyl or alkoxy; Alkoxy; Alkenyl; Alkynyl; Phenyl or benzyl, where the phenyl rings can be substituted one or more times by halogen, alkyl, alkoxy, alkylthio, cyano or nitro or
R6 and R7 together with the nitrogen atom to which they are attached can also form a 5- to 6-membered heterocycle,
1 Mn (3 is the ion equivalent of an alkali, alkaline earth metal, copper or iron ion or a quaternary alkylammonium or hydroxyalkylammonium radical.



   In this formula, alkyl radicals can contain up to 18 carbons, be branched or unbranched. If they occur as alkoxy, alkylthio, alkylamino esters, however, lower radicals containing 1 to 4 carbon atoms are usually preferred. Cycloalkyl groups can have 3 to 12 carbon atoms, alkenyl or alkynyl groups can have 2 to 8 carbon atoms. Aryl can be understood as meaning optionally substituted naphthyl or phenyl rings; the phenyl rings are preferred.

  The 5- to 6-membered heterocycles which can form the radicals R6 and R, together with the nitrogen atom to which they are attached, include the pyrrole, pyrrolidine, oxazoline, oxazolidine, piperidine, morpholine or thiomorpholine rings which are substituted by alkyl , in particular methyl, can be substituted, as can the piperazine, alkylpiperazine, phenyl or benzylpiperazine rings. Quaternary ammonium or hydroxyammonium residues can contain up to 5 carbon atoms per alkyl part. Chlorine is preferred among the halogen atoms. Lower alkyl radicals can contain 1 to 4 carbon atoms, preferably methyl or ethyl.



   From Belgian patent specification No. 834 495 4- (pyrid-2-yloxy) -alkanecarboxylic acids and esters with herbicidal activity against grasses but not against broad-leaved plants have become known. Furthermore, herbicidal compositions containing a special grass effect for the selective control of grass weeds in monocotyledonous and dicotyledonous crop plants have become known from German Offenlegungsschrift 2,223,894, 4-phenoxyphenoxyalkanecarboxylic acid derivatives having a similar structure.



   It has now surprisingly been found that the new active compounds of the formula I according to the present invention have a more general herbicidal action which is not specifically directed against grasses, especially in post-emergent use and can be used as weed agents in monocotyledonous and dicotyledonous crops.



   The pyridyloxy-phenoxy-alkane carboxylic acid derivatives also have favorable growth-regulating effects (growth inhibition). In particular, they inhibit the growth of dicotyledonous plants. Examples of the beneficial use of the compounds according to the invention are e.g. B.



  - the reduction of vegetative growth in soybeans and similar legumes, which leads to an increase in the yield of these crops; - the inhibition of the undesirable growth of Geiztrie ben in tobacco, the main shoot has been cut, which benefits the formation of larger and more beautiful leaves; - inhibiting the growth of grass and dicotyledons
Plants, such as fruit trees, ornamental trees, bushes and hedges, to save on cutting work.



   The pyridyloxy-phenoxy-alkane carboxylic acid derivatives of the formula I are not very toxic to warm-blooded animals and their application does not pose any problems. The application rate is between 0.1 and 5 kg per hectare.



   The new compounds of the formula I are prepared by methods known per se.



   According to a first method, a substituted ortho-halopyridine of the formula II is used
EMI2.2
 with a para-hydroxyphenoxy-alkane-carboxylic acid derivative of the formula III
EMI2.3
 in the presence of a base.

 

   According to a second method, a pyridyl oxy-para-hydroxy-phenyl ether of the formula IV is used
EMI2.4
 in the presence of a base with an α-halocarboxylic acid derivative of the formula V.
EMI2.5

If a carboxylic acid is used as the starting material of the formulas III or V in these processes, this group can subsequently be converted into another derivative of the formula I by definition. Conversely, when using z. B. an ester of formula III or V finally by saponification convert the ester group into the free carboxylic acid and further into a salt, amide or hydrazide.



   In the formulas II to V of the starting materials, the radicals R1, R2, A, B, C, D and Z have those indicated under formula I.
Meanings and Hal stands for a halogen atom, preferably chlorine or bromine.



   The reactions mentioned can be carried out in the presence or absence of solvents or diluents which are inert to the reactants. Polar organic solvents such as methyl ethyl ketone, acetonitrile, dimethylformamide, dimethyl sulfoxide etc. are preferred.



  The reaction temperatures are between 0 and 200 and the reaction time is between 1/4 hour and several days, depending on the selected reaction temperature and solvent. You usually work at normal pressure or a slight overpressure. As bases (condensing agents) for the implementation come, for. B. NaOH, KOH, NaOCH3, NaH, K2CO3, Na2CO3, potassium tert. butylate etc. but also organic bases.



   Some of the starting materials of formulas II to V are known. Starting materials of these formulas that have not yet been described can be easily prepared by customary processes and techniques.



   Substituted 2-halopyridines according to formula II can u. a. can be easily prepared from the corresponding 2-pyridinols, some of which are known. Starting products of
Formula III can be prepared by e.g. B. hydroquinone monobenzyl ether with an a -halocarboxylic acid derivative, preferably an ester of formula V, and the benzyl phenyl ether bond cleavage tion by catalytic hydration, z. B. with a palladium-on-carbon catalyst, wherein the benzyl residue goes away as toluene.



   By reacting hydroquinone with 2-halopyridines in equimolar amounts and in the presence of base, the starting products of the formula IV can be obtained.



   Carboxylic acid derivatives of the formula V are also known.



  As their simplest representatives z. B. mentioned chloroacetic acid, its esters, thioesters, amides and hydrazides.



   The following examples illustrate the process for the preparation of active compounds of the formula I. Further active compounds prepared in a corresponding manner are listed in the table below. Temperatures refer to degrees Celsius, pressures are given in mm Hg (Torr = 1.33 millibars).



   These pyridyloxy-phenoxy-alkane-carboxylic acid derivatives of the formula I are stable compounds which are soluble in customary organic solvents, such as alcohols, ethers, ketones, dimethylformamide, dimethyl sulfoxide, etc.



   Example 1 a- [4- (3 ', 5'-Dichlor-6'-methyl-pyrid-2'-yl) -oxy-phenoxyl-propionic acid methyl ester
22.0 g (0.11 mol) of methyl 5-hydroxyphenoxypropionate and 200 ml of dimethyl sulfoxide were placed in a flask. 6.0 g of sodium methoxide were introduced into this mixture and the methanol formed was then distilled off under reduced pressure, at 11 torr and at a bath temperature of 70-80. Then 19.6 g (0.1 mol) of 6-methyl-2,3,5-trichloropyridine in 50 ml of dimethyl sulfoxide were added and the whole was stirred at 60 for 2 hours. The dimethyl sulfoxide was then distilled off, the residue was mixed with ice and 2N NaOH and extracted twice with ethyl acetate.

  The extracts were washed with brine, dried with magnesium sulfate, concentrated on a Rotavapor and the residue obtained was recrystallized from methanol.



   Yield: 16 g; M.p. 79-80 (compound no. 21).



   Example 2 a- [4- (3 ', 5'-Dichlor-6'-methyl-pyrid-2'-yl) -oxy-phenoxy] propionic acid
10.5 g (0.03 mol) of methyl a- [4- (3 ', 5'-dichloro-6'-methyl-pyrid-2'-yl) -oxyphenoxy] propionate, 50 ml of 1N NaOH (0.05 mol) and 10 ml of methyl cellosolve were stirred at room temperature for 12 hours. It was then adjusted to pH 2.5 with 1N HCl, filtered, washed with water and dried.



   Yield: 10.15 g (99%), mp 117-120 "(compound no. 22).



   Further pyridyloxyphenoxy-alkane carboxylic acid derivatives according to formula I prepared according to this example are listed in the table below:
EMI3.1

EMI3.2


<tb> <SEP> No. <SEP> A <SEP> B <SEP> C <SEP> D <SEP> R1 <SEP> R2 <SEP> Z <SEP> Physical
<tb> <SEP> constant
<tb> <SEP> 1 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOCH3
<tb> <SEP> 2 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOH
<tb> <SEP> 3 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOCH2CCl3
<tb> <SEP> 4 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3
<tb> <SEP> 5 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F <SEP> 95-97 C
<tb> <SEP> 6 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOH
<tb> <SEP> 7 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> COOCH (CH3) 2 <SEP> Eb <SEP> 1500C / 0.0
<tb>

   <SEP> 8 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COO-CsH1s
<tb> <SEP> 9 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> WOOCH3 <SEP> F <SEP> 113-115 "C
<tb> 10 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> H <SEP> -COOH <SEP> F <SEP> 170-179 "C
<tb> 11 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> H <SEP> -COOCH (CH3) 2 <SEP> F <SEP> 62-65 "C
<tb> 12 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> H <SEP> -COOC2H4Br
<tb> 13 <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F <SEP> 93-96 "C
<tb> 14 <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOH
<tb> 15 <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOC2H4OCH3
<tb>
EMI4.1


<tb> No.

  <SEP> A <SEP> B <SEP> C <SEP> D <SEP> R1 <SEP> R2 <SEP> Z <SEP> Physical
<tb> <SEP> constant
<tb> 16 <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOC3H6
<tb> 17 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F1110C
<tb> 18 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOH
<tb> 19 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOC (C2M5) 2
<tb> 2 () <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COO <
<tb> 21 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F <SEP> 79-80 "C
<tb> 22 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOH <SEP> F <SEP> 117-120 C
<tb> 73 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> COOC2H4Br <SEP> F <SEP> 60-62 "C
<tb> 2i <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> COOCH (CH3) <SEP> Eb <SEP>

   150 "C / 0.01
<tb> 25 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> CH3 <SEP> -COOC2HsCOOC2Hs
<tb> 26 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> CH3 <SEP> -COOH <SEP> -COOH
<tb> 27 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOCH3
<tb> 28 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> -CM3 <SEP> -COOH
<tb> 29 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOCH2-C <SEP> 1
<tb> 30 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOC2Hs
<tb> 31 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> M3 <SEP> WOOCH3 <SEP> F <SEP> 54-56 "C
<tb> 32 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> -CM3 <SEP> -COOH <SEP> F <SEP> 132-134 "C
<tb> 33 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> M3 <SEP> -COOC6H12C
<tb> 34 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> H3 <SEP> -COO
<tb> 35 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOCH3 <SEP> F <SEP> 89-93 C
<tb>

   36 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOH
<tb> 37 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> H3 <SEP> -COOs
<tb> 38 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOC112
<tb> 39 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> M3 <SEP> COOCH3 <SEP> F <SEP> 78-83 "C
<tb> 40 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> H3 <SEP> -COOH
<tb> 41 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOC2H4OC4H9
<tb> <SEP> cn,
<tb> <SEP> 1
<tb> 42 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> M3 <SEP> -COOCH
<tb> 43 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> -COOC2Hs-COOC2Hs
<tb> 44 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> -COOH <SEP> -COOH
<tb> 45 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> C2M5 <SEP> -COOH
<tb> 46 <SEP> Cl <SEP> H <SEP> Cl <SEP> C1 <SEP> H <SEP> 4 <SEP> -COOCH3
<tb> 47 <SEP> H <SEP> H <SEP> CN <SEP>

   H <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F <SEP> 103-104 C
<tb> 48 <SEP> H <SEP> H <SEP> CN <SEP> H <SEP> H <SEP> CH3 <SEP> -COO <SEP> OH, N <SEP> O <SEP> (C, HOH ),
<tb> 49 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COONa
<tb> 50 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOOH2NO (CH4oH),
<tb> 51 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> CON (CH3) 2
<tb> 52 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CONHCH2-CH = CH2
<tb> 53 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CONHC2Hs
<tb> 54 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CON (CH3) 2
<tb> 55 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CONHCH2-CH = CH2
<tb> 56 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CONHCH (CH3) 2
<tb> 57 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CON (CH3) 2
<tb> 58 <SEP> CN

   <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> CONHCH2CH = CH2
<tb> 59 <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CON1IC1l2
<tb> 60 <SEP> CN <SEP> CH2 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CON (CH3) 2
<tb> 61 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CONH-CH2-CH = CH2
<tb> 62 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CONg
<tb> 63 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> CON (CH3) 2
<tb> 64 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> CONHCH2-CH = CH2
<tb>
EMI5.1


<tb> No.

  <SEP> A <SEP> B <SEP> C <SEP> D <SEP> R1 <SEP> R2 <SEP> Z <SEP> Physical
<tb> <SEP> constant
<tb> 65 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CON3o
<tb> 66 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -CON (CH3) 2
<tb> 67 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> CH3 <SEP> CON (CH3) 2 <SEP> WON (CH3) 2
<tb> 68 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> CH3 <SEP> CONHCH2 <SEP> -CONH-CH2-CH = CH2
<tb> <SEP> CH = CH2
<tb> 69 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CON (CH3) 2
<tb> 70 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CONHCH2-CH = CH2
<tb> 71 <SEP> H <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -COCH3
<tb> 72 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> CH3 <SEP> -CON (CH3) 2
<tb> 73 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> CH3 <SEP> -CONHCH2-CH = CH2
<tb> 74 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> CH3

   <SEP> -CONHnCöHl7
<tb> 75 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CON (CH3) 2
<tb> 76 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CONHCH2-CH = CHa
<tb> 77 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CoNHCH (C2H532
<tb> 78 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CON (CH3) 2
<tb> 79 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CONHCH2-CH = CH,
<tb> 80 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CONHC2H4OH
<tb> 81 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> CH3 <SEP> -CONH-N (CH3) 2
<tb> 82 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> ONWN (CH3) 2
<tb> 83 <SEP> H <SEP> H <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COSCH <SEP> 1
<tb> <SEP> 2
<tb> 84 <SEP> H <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COSCH2-CH = CH2
<tb> 85 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP>

   CH3 <SEP> -COSC2Hs
<tb> 86 <SEP> CN <SEP> CH3 <SEP> H <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COSC14 (CH3) 2
<tb> 87 <SEP> CN <SEP> CH3 <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COSCH3
<tb> 88 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> COSnC3H7
<tb> 89 <SEP> H <SEP> H <SEP> CN <SEP> H <SEP> H <SEP> CH3 <SEP> -COS
<tb> 90 <SEP> H <SEP> H <SEP> H <SEP> Br <SEP> H <SEP> CH3 <SEP> -COSCH2COOC2Hs
<tb> 91 <SEP> NO2 <SEP> H <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -COSC8H17
<tb> 92 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> CH3 <SEP> -COr
<tb> 93 <SEP> Cl <SEP> H <SEP> Cl <SEP> Cl <SEP> H <SEP> CH3 <SEP> -COONa
<tb> 94 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COONa <SEP> F <SEP> 115-120 "C
<tb> 95 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOOH2No (C2H40H) 2 <SEP> F <SEP> 133-135tC
<tb> 96 <SEP> Cl <SEP> H <SEP> CN <SEP> CH3 <SEP> H <SEP>

   CH3 <SEP> -COOC2Hs <SEP> F <SEP> 101-104 C
<tb> 97 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> -COOC2Hs <SEP> Eb <SEP> 160 C / 0.01
<tb> 98 <SEP> CN <SEP> CH3 <SEP> H <SEP> Cl <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F <SEP> 105-109 C
<tb> 99 <SEP> H <SEP> CH3 <SEP> CN <SEP> Cl <SEP> H <SEP> CH3 <SEP> -COOCH3 <SEP> F <SEP> 105-108 "C
<tb> 100 <SEP> Cl <SEP> H <SEP> Cl <SEP> CH3 <SEP> H <SEP> CH3 <SEP> COO8H2N (i) (C2Hs) 2 <SEP> F <SEP> 145-146 " C.
<tb>
Agents according to the invention are prepared in a manner known per se by intimately mixing and grinding active ingredients of the general formula I with suitable carriers and / or distributing agents, if appropriate with the addition of antifoams, wetting agents, dispersants and / or solvents which are inert to the active ingredients.

  The active substances can be present and used in the following processing forms: Solid processing forms
Dusts, scattering agents, granules, coating granules,
Impregnation granules and homogeneous granules: water-dispersible active ingredient concentrates
Wettable powder, pastes, emulsions;
Emulsion concentrates Liquid processing forms
solutions
The active substance concentrations in the agents according to the invention are 1 to 80 percent by weight and, if appropriate, can also be present in low concentrations, such as 0.05 to 1%, when used.



   Other biocidal active substances or agents can be added to the agents according to the invention described. Thus, the new agents can, in addition to the compounds of general formula I mentioned for. B. insecticides, fungicides, bactericides, fungistatics, bacteriostatics, nematocides or other herbicides to broaden the spectrum of activity.



  granules
The following substances are used to produce 5% granules:
5 parts of one of the active ingredients of formula 1,
0.25 parts epichlorohydrin,
0.25 parts of cetyl polyglycol ether,
3.50 parts of polyethylene glycol,
91 parts of kaolin (grain size: 0.3-0.8 mm).



   The active substance is mixed with epichlorohydrin and dissolved in 6 particles of acetone, then polyethylene glycol and cetyl polyglycol ether are added. The solution thus obtained is sprayed onto kaolin and then evaporated in vacuo.



  Wettable powder
The following constituents are used to produce a) 70% and b) 10% wettable powder: a) 70 parts of one of the active compounds of the formula I,
5 parts of sodium dibutylnaphthyl sulfonate,
3 parts of naphthalenesulfonic acids-phenolsulfonic acids-
Formaldehyde condensate 3: 2: 1,
10 parts of kaolin,
12 parts of champagne chalk; b) 10 parts of methyl o- [4- (3 ', 5'-dichloro-6'-methyl-pyrid-2'-yl) phenoxyl-propionate
3 parts mixture of the sodium salts of saturated fatty alcohol sulfonates,
5 parts of naphthalenesulfonic acid-formaldehyde condensate,
82 parts of kaolin.



   The specified active ingredient is drawn onto the corresponding carrier substances (kaolin and chalk) and then mixed and ground with the other constituents.



  Spray powder of excellent wettability and suspension is obtained. From such wettable powders, suspensions of 0.1-8% active ingredient can be obtained by dilution with water, which are suitable for weed control in plant crops.



  paste
The following materials are used to make a 45% paste:
45 parts of methyl a- [4- (5'-cyano-6'-methyl-pyrid-2'-yl) -oxyphenoxy] propionate or another of the active compounds of the formula I mentioned,
5 parts of sodium aluminum silicate,
14 parts of cetyl polyglycol ether with 8 moles of ethylene oxide,
1 part of oleyl polyglycol ether with 5 moles of ethylene oxide,
2 parts spindle oil,
10 parts of polyethylene glycol,
23 parts of water
The active ingredient is intimately mixed and ground with the additives in suitable devices. A paste is obtained, from which Suspen- by dilution with water.



  have any desired concentration made.



  Emulsion concentrate
To prepare a 25% emulsion concentrate
25 parts of methyl a- [4- (3 ', 5', 6'-trichloropyrid-2'-yl) -oxy-phenoxyl-propionate or another of the active compounds of the formula I,
5 parts of a mixture of nonylphenol polyoxyethylene or calcium dodecylbenzenesulfate,
35 parts of 3,5, 5-trimethyl-2-cyclohexen-1-one,
35 parts of dimethylformamide mixed together. This concentrate can with water to emulsions to suitable concentrations of z. B. 0.1-10% can be diluted. Such emulsions are suitable for controlling weeds in crops.



   The new 4-pyridyloxyu -phenoxyalkanecarboxylic acids and their derivatives of the formula I and the compositions comprising them have an excellent selective herbicidal action against weeds in a wide variety of crop plants. They also have a regulating effect on plant growth.



   Although the new active ingredients of formula I are effective in pre- and post-emergent use, post-emergence application as contact herbicides seems to deserve preference, although pre-emergent use is also of interest. The new active ingredients are preferred as z. B.



     25% wettable powder or z. B. 20% emulsifiable concentrates formulated and diluted with water, applied post-emergent to the plant stands.



   Herbicidal effects when the active ingredients are applied after the plants have emerged (post-emergent)
Various crops and weeds are grown from the seeds in pots in the greenhouse until they reach the 4 to 6 leaf stage. Then the plants are sprayed with aqueous active ingredient emulsions (obtained from a 20% emulsifiable concentrate) in various doses. The treated plants are then kept under optimal conditions of light, watering, temperature (22-250 C) and humidity (50-70% relative). The tests are evaluated 15 days after treatment.



   Inhibiting the growth of unwanted greed drives in tobacco
Xanti tobacco was grown in the greenhouse and cut shortly before flowering. (The main shoot was cut off.) One day after trimming, 3 plants were in each case sprayed from above with 10 ml of aqueous preparations of a compound of the formula I. In a normal plant population, the selected active ingredient concentrations correspond to the application rates of 12 kg of active ingredient / ha or. 6 kg WS / ha and 3 kg WS / ha. 14 days after the application, the inhibitory effect on the undesirable growth of poultry has been evaluated. The average length of the stinging shoots from the 6 top leaf axils of all 3 plants was determined.

 

   The plants treated with the compounds No. 21 and 97 showed no or only very slight growth of the stinging shoots, which reach an average length of over 20 cm in the case of untreated controls.

Claims (3)

PATENTANSPRÜCHE 1. Herbizides Mittel, dadurch gekennzeichnet, dass es als aktive Komponente mindestens ein Pyridyloxy-phenoxy-alkancarbonsäurederivat der Formel I enthält, EMI1.1 worin Z einen Carbonsäurerest COR3 oder einen gegebenenfalls durch Niederalkyl ein- oder mehrfach substituierten 2-Oxazolinrest oder die Cyanogruppe, A Wasserstoff, Halogen, Alkyl, Cyano oder Nitro, B Wasserstoff, Alkyl, C Wasserstoff, Halogen oder Cyano, D Halogen, Alkyl oder, falls C Cyano bedeutet, auch Wasserstoff, R1 Wasserstoff, Alkyl oder Phenyl, R2 Wasserstoff, Alkyl oder Carbonsäurerest COR3, R3 die Hydroxygruppe, oder einer der Reste EMI1.2 R4 eine Alkylgruppe, die unsubstituiert oder durch Halogen, Alkoxy, Alkylthio, Carboxy, Alkoxycarbonyl, Cycloalkyl, Aryl oder einen 5- bis 6gliedrigen heterocyclischen Ring substituiert sein kann;  PATENT CLAIMS 1. Herbicidal agent, characterized in that it contains at least one pyridyloxy-phenoxy-alkane carboxylic acid derivative of the formula I as active component, EMI1.1  in which Z is a carboxylic acid residue COR3 or a 2-oxazoline residue which is mono- or polysubstituted or substituted by lower alkyl or the cyano group, A hydrogen, halogen, alkyl, cyano or nitro, B hydrogen, alkyl, C hydrogen, halogen or cyano, D halogen, alkyl or if C is cyano, also hydrogen, R1 is hydrogen, alkyl or phenyl, R2 is hydrogen, alkyl or carboxylic acid residue COR3, R3 is the hydroxyl group, or one of the residues EMI1.2 R4 is an alkyl group which may be unsubstituted or substituted by halogen, alkoxy, alkylthio, carboxy, alkoxycarbonyl, cycloalkyl, aryl or a 5- to 6-membered heterocyclic ring; Cycloalkyl; einen Alkenylrest, der unsubstituiert oder durch Halogen substituiert sein kann; Alkinyl; einen Phenylring, der unsubstituiert oder ein- oder mehrfach durch Halogen, Alkyl, Alkoxy, Alkylthio, Cyano oder Nitro substituiert ist, R5 einen Alkylrest, der unsubstituiert oder durch Cycloal kyl, Aryl oder einen 5- bis 6gliedrigen heterocyclischen Ring substituiert sein kann; Cycloalkyl- oder Alkenyl; den Phenylring, der unsubstituiert oder ein- oder mehrfach durch Halogen, Alkyl, Alkoxy, Alkylthio, Cyano oder Nitro substituiert sein kann, R6 und R7 unabhängig voneinander je Wasserstoff oder einen Alkylrest, der gegebenenfalls durch Hydroxyl oder Alkoxy substituiert sein kann; Alkoxy; Alkenyl; Alkinyl; Cycloalkyl; an alkenyl radical which may be unsubstituted or substituted by halogen; Alkynyl; a phenyl ring which is unsubstituted or mono- or polysubstituted by halogen, alkyl, alkoxy, alkylthio, cyano or nitro, R5 an alkyl radical which may be unsubstituted or substituted by cycloalkyl, aryl or a 5- to 6-membered heterocyclic ring; Cycloalkyl or alkenyl; the phenyl ring which can be unsubstituted or substituted one or more times by halogen, alkyl, alkoxy, alkylthio, cyano or nitro, R6 and R7 independently of one another are each hydrogen or an alkyl radical which can optionally be substituted by hydroxyl or alkoxy; Alkoxy; Alkenyl; Alkynyl; Phenyl oder Benzyl, wobei die Phenylringe ein- oder mehrfach durch Halogen, Alkyl, Alkoxy, Alkylthio, Cyano oder Nitro substituiert sein können oder R6 und R7 können zusammen mit dem Stickstoffatom, an das sie gebunden sind auch einen 5- bis 6gliedrigen Heterocyclus bilden und 1 Mnf3 das Ion Äquivalent eines Alkali-, Erdalkalime- tall-, Kupfer- oder Eisen-Ions oder einen quaternären Alkylammonium- oder Hydroxyalkylammonium-Rest bedeuten. Phenyl or benzyl, where the phenyl rings can be substituted one or more times by halogen, alkyl, alkoxy, alkylthio, cyano or nitro or R6 and R7 together with the nitrogen atom to which they are attached can also form a 5- to 6-membered heterocycle and 1 Mnf3 the ion equivalent of an alkali metal, alkaline earth metal, copper or iron ion or a quaternary alkylammonium or hydroxyalkylammonium -Rest mean. 2. Verfahren zur Herstellung der Pyridyloxy-phenoxy-alkancarbonsäurederivate der im Anspruch 1 genannten Formel I, dadurch gekennzeichnet, dass man a) ein substituiertes ortho-Halogenpyridin der Formel II EMI1.3 mit einem para-Hydroxy-phenoxyalkancarbonsäurederivat der Formel III EMI1.4 in Gegenwart einer Base umsetzt, oder b) einen Pyridyloxy-para-hydroxy-phenyläther der Formel IV EMI1.5 mit einem a -Halogencarbonsäurederivat der Formel V EMI1.6 in Gegenwart einer Base umsetzt, wobei in den Formeln II, III, IV und V A, B, C, D, R1, R2 und Z die in Formel I gegebenen Bedeutungen haben und Hal ein Halogenatom bedeutet.  2. Process for the preparation of the pyridyloxy-phenoxy-alkanecarboxylic acid derivatives of the formula I mentioned in claim 1, characterized in that a) a substituted ortho-halopyridine of the formula II EMI1.3  with a para-hydroxy-phenoxyalkanecarboxylic acid derivative of the formula III EMI1.4  in the presence of a base, or b) a pyridyloxy-para-hydroxy-phenyl ether of the formula IV EMI1.5  with an α-halocarboxylic acid derivative of the formula V EMI1.6  in the presence of a base, wherein in the formulas II, III, IV and V A, B, C, D, R1, R2 and Z have the meanings given in formula I and Hal represents a halogen atom. 3. Verwendung der Pyridyloxy-phenoxy-alkancarbonsäure-Derivate der im Patentanspruch 1 genannten Formel I zur selektiven Bekämpfung von Unkräutern in Kulturpflanzungen im Nachauflaufverfahren.  3. Use of the pyridyloxy-phenoxy-alkanecarboxylic acid derivatives of the formula I mentioned in claim 1 for the selective control of weeds in crops by post-emergence.   Die vorliegende Erfindung betrifft ein herbizides Mittel, welches neue Pyridyloxy-phenoxy-alkancarbonsäurederivate als aktive Komponente enthält, ein Verfahren zur Herstellung dieser Pyridyloxy-phenoxy-alkancarbonsäurederivate sowie deren Verwendung zur selektiven Bekämpfung von Unkräutern.  The present invention relates to a herbicidal composition which contains new pyridyloxy-phenoxy-alkanecarboxylic acid derivatives as active component, a process for the preparation of these pyridyloxy-phenoxy-alkanecarboxylic acid derivatives and their use for the selective control of weeds. Die neuen Pyridyloxy-phenoxy-alkan-carbonsäurederivate entsprechen der Formel 1 EMI1.7 worin Z einen Carbonsäurerest COR3 oder einen gegebenenfalls durch Niederalkyl ein- oder mehrfach substituierten 2-Oxazolinrest oder die Cyanogruppe, A Wasserstoff, Halogen, Alkyl, Cyano oder Nitro, B Wasserstoff, Alkyl, C Wasserstoff, Halogen oder Cyano, D Halogen, Alkyl oder, falls C Cyano bedeutet, auch Wasserstoff, R1 Wasserstoff, Alkyl oder Phenyl, R2 Wasserstoff, Alkyl oder Carbonsäurerest COR3, R3 die Hydroxygruppe oder einer der Reste **WARNUNG** Ende CLMS Feld konnte Anfang DESC uberlappen**.  The new pyridyloxy-phenoxy-alkane-carboxylic acid derivatives correspond to Formula 1 EMI1.7  wherein Z is a carboxylic acid residue COR3 or a 2-oxazoline residue which is mono- or polysubstituted or substituted by lower alkyl, or the cyano group, A is hydrogen, halogen, alkyl, cyano or nitro, B hydrogen, alkyl, C hydrogen, halogen or cyano, D halogen, alkyl or, if C is cyano, also hydrogen, R1 is hydrogen, alkyl or phenyl, R2 is hydrogen, alkyl or carboxylic acid residue COR3, R3 is the hydroxy group or one of the residues ** WARNING ** End of CLMS field could overlap beginning of DESC **.
CH947076A 1976-07-23 1976-07-23 Herbicidal composition containing, as active ingredient, pyridyloxyphenoxyalkanecarboxylic acid derivatives CH622169A5 (en)

Priority Applications (17)

Application Number Priority Date Filing Date Title
CH947076A CH622169A5 (en) 1976-07-23 1976-07-23 Herbicidal composition containing, as active ingredient, pyridyloxyphenoxyalkanecarboxylic acid derivatives
US05/816,840 US4133675A (en) 1976-07-23 1977-07-18 Pyridyloxy-phenoxy-alkanecarboxylic acid derivatives which are effective as herbicides and as agents regulating plant growth
DE19772732846 DE2732846A1 (en) 1976-07-23 1977-07-20 NEW HERBICIDE AND PLANT REGULATORY PYRIDYLOXY-PHENOXY-ALKANCARBONIC ACID DERIVATIVES
FR7722230A FR2359129A1 (en) 1976-07-23 1977-07-20 NEW DERIVATIVES OF PYRIDYLOXY-PHENOXY-ALKANECARBOXYLIC ACIDS WITH HERBICIDAL AND GROWTH REGULATING ACTIVITY
CA283,268A CA1100973A (en) 1976-07-23 1977-07-21 Pyridyloxy-phenoxy-alkanecarboxylic acid derivatives which are effective as herbicides and as agents regulating plant growth
IL52572A IL52572A (en) 1976-07-23 1977-07-21 Pyridyloxy-phenoxy-alkanecarboxylic acid derivatives,their production and their use as herbicides and as agents for regulating plant growth
AU27238/77A AU513286B2 (en) 1976-07-23 1977-07-22 Pridyloxy-phenoxy-alkane carboxylic acid derivatives
ES460957A ES460957A1 (en) 1976-07-23 1977-07-22 Pyridyloxy-phenoxy-alkanecarboxylic acid derivatives which are effective as herbicides and as agents regulating plant growth
GB30918/77A GB1561616A (en) 1976-07-23 1977-07-22 Pyridyloxyphenoxy-alkanecarboxylic acid derivatives which are effective as herbicides and as agents regulating plant growth
ZA00774453A ZA774453B (en) 1976-07-23 1977-07-22 Novel pyridyloxy-phenoxy-alkanecarboxylic acid derivatives which are effective as herbicides and as agents regulating plant growth
IT26027/77A IT1080773B (en) 1976-07-23 1977-07-22 PYRIDYLOXY-PHENOXY-ALCANCARBOXYLIC ACID DERIVATIVES AS HERBICIDES AND AS REGULATORS OF PLANTS, PROCEDURE FOR THEIR PREPARATION AND USE
SU772505504A SU710499A3 (en) 1976-07-23 1977-07-22 Herbicidic substance
BE179529A BE857022A (en) 1976-07-23 1977-07-22 NEW DERIVATIVES OF PYRIDYLOXY-PHENOXY-ALKANE-CARBOXYLIC ACIDS WITH HERBICIDAL AND GROWTH REGULATING ACTIVITY
NL7708185A NL7708185A (en) 1976-07-23 1977-07-22 PROCESS FOR THE PREPARATION OF HERBICIDE ACTIVE AND PLANT GROWTH REGULATING PYRIDYLOXY-PHENOXY-ALCANO CARBONIC ACIDS.
JP8875577A JPS5315382A (en) 1976-07-23 1977-07-23 Production of pyridyloxyy phenoxyyalkanecarboxylic acid derivatives and herbicidal or plant growth controlling containing same as effective component
US05/962,518 US4253866A (en) 1976-07-23 1978-11-20 Methyl α-[4-(6'-methyl-5'-carbothiamido-pyrid-2'-yl)-oxy-phenoxy]-proprionate
LV930558A LV5151A3 (en) 1976-07-23 1993-06-11 Herbicide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH947076A CH622169A5 (en) 1976-07-23 1976-07-23 Herbicidal composition containing, as active ingredient, pyridyloxyphenoxyalkanecarboxylic acid derivatives

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CH622169A5 true CH622169A5 (en) 1981-03-31

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CH (1) CH622169A5 (en)
ZA (1) ZA774453B (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0001473B1 (en) * 1977-08-12 1988-07-27 Imperial Chemical Industries Plc Herbicidal halogenomethyl--pyridyloxy-phenoxy-alkanecarboxylic acids and derivatives, and processes of controlling unwanted plants therewith
EP0003877B1 (en) * 1978-02-15 1988-02-03 Imperial Chemical Industries Plc Herbicidal derivatives of 2-(4(2-pyridyloxy)phenoxy)propane, processes for preparing them, and herbicidal compositions containing them

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BE857022A (en) 1978-01-23

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