EP0000176B1 - Pyridyloxy-phenoxy-alkanoic acid derivatives , processes for their preparation and their use as herbicides or plant growth regulators - Google Patents

Pyridyloxy-phenoxy-alkanoic acid derivatives , processes for their preparation and their use as herbicides or plant growth regulators Download PDF

Info

Publication number
EP0000176B1
EP0000176B1 EP78100209A EP78100209A EP0000176B1 EP 0000176 B1 EP0000176 B1 EP 0000176B1 EP 78100209 A EP78100209 A EP 78100209A EP 78100209 A EP78100209 A EP 78100209A EP 0000176 B1 EP0000176 B1 EP 0000176B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
formula
halogen
radical
substituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP78100209A
Other languages
German (de)
French (fr)
Other versions
EP0000176A1 (en
Inventor
Hermann Dr. Rempfler
Werner Dr. Föry
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0000176A1 publication Critical patent/EP0000176A1/en
Application granted granted Critical
Publication of EP0000176B1 publication Critical patent/EP0000176B1/en
Expired legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • C07D213/85—Nitriles in position 3

Definitions

  • the invention relates to pyridyloxy - phenoxy - alkane carboxylic acid derivatives which have a herbicidal and plant growth regulating action, processes for their preparation, furthermore compositions which contain these compounds as active compounds, and the use of the active compounds or the compositions containing them for the selective control of weeds and to regulate plant growth.
  • the alkyl radicals in this formula can be branched or unbranched and contain the stated number of carbon atoms.
  • the radicals R 5 and R 6 are preferably hydrogen and C 1 -C 4 alkyl radicals.
  • the active compounds of the formula I according to the invention have herbicidal activity, especially in the case of postemergent use and can be used as weed agents in mono- and dicotyledon crops.
  • the compounds according to the invention 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 compounds of the formula I are prepared by methods known per se.
  • an optionally substituted halopyridine of the formula II wherein C, D, E and n have the meaning given under formula I and Hal represents a halogen atom, preferably chlorine or bromine, with a hydroxyphenoxyalkane carboxylic acid derivative of the formula III wherein A, C, D, R 1 and R z have the meaning given under formula I in the presence of an acid-binding agent.
  • the pyridyloxy-phenoxy-alkanecarboxylic acid derivatives of the formula I are prepared by using a pyridyloxy-hydroxyphenyl ether of the formula IV wherein C, D, E and n have the meaning given under formula I, with an a-halocarboxylic acid derivative of the formula V.
  • A, R 1 and R 2 have the meaning given under formula I and Hal represents a halogen atom, preferably chlorine or bromine, in the presence of an acid-binding agent.
  • 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 ° C. and the reaction time is between 1/4 hour and several days, depending on the reaction temperature and solvent chosen. You usually work at normal pressure or a slight excess pressure.
  • Acid-binding agents for the reaction are inorganic, such as NaOH, KOH, NaOCH 3 , NaH, K z C0 3 , NaC0 3 or potassium tert. butylate but also organic bases.
  • Substituted 2-halopyridine according to formula II can i.a. can be easily prepared from the corresponding 2-pyridinols, some of which are known.
  • Starting materials of formula III can be prepared by e.g. reacting a monobenzyl ether of hydroquinone, resorcinol or catechol with an ⁇ -halogenocarboxylic acid derivative, preferably an ester of the formula V, and cleaving the benzylphenyl ether bond by catalytic hydrogenation, e.g. with a palladium-on-carbon catalyst, the benzyl residue leaving as toluene.
  • the starting products of the formula IV can be obtained by reacting hydroquinone, resorcinol or pyrocatechol with halopyridines in equimolar amounts and in the presence of a base.
  • Carboxylic acid derivatives of the formula V are also known.
  • the simplest representatives are, for example, chloroacetic acid, its esters, thioesters, amides and hydrazides.
  • other a-halocarboxylic acid derivatives substituted according to R 1 and R z can also be used.
  • 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 or dimethyl sulfoxide.
  • the content of active ingredient in the agents described above is between 0.1 to 95%, preferably between 1 to 80%.
  • Application forms can be diluted down to 0.001%.
  • the application rates are generally 0.1 to 10 kg ai / ha, preferably 0.25 to 5 kg ai / ha.
  • Other biocidal active substances or agents can also be added to the agents according to the invention described.
  • the active ingredients of Formula 1 can be formulated, for example, as follows (parts mean parts by weight):
  • the active ingredients are mixed and ground with the carriers.
  • the active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone, whereupon polyethylene glycol and cetylpolyethylene glycol ether are added.
  • the solution thus obtained is sprayed onto kaolin and then evaporated in vacuo.
  • the specified active ingredient is drawn onto the corresponding carrier substances (kaolin and chalk) and then mixed and ground. Spray powder of excellent wettability and suspension is obtained. Suspensions of any desired active ingredient concentration can be obtained from such wettable powders by dilution with water. Such suspensions are used to control weeds and weeds in crops in pre-emergence and for the treatment of lawns.
  • the active ingredient is intimately mixed and ground with the additives in suitable devices.
  • a paste is obtained, from which suspensions of any desired concentration can be prepared by dilution with water.
  • the suspensions are suitable for the treatment of lawns.
  • This concentrate can be diluted with water to emulsions to suitable concentrations.
  • the active substances contained in the agents according to the invention influence plant growth in various ways. In the first place, they inhibit, delay or prevent growth and germination. It is therefore both a pre- and post-emergent herbicide effect and an inhibition of growth.
  • Agents according to the invention which contain at least one compound of the formula I as the active component are particularly suitable for inhibiting the control of the plant growth of monocotyledon and dicotyledonous plants, such as grasses, shrubs, trees, crops of cereals and legumes, sugar cane, tobacco, soybeans, onions and Potato tubers, ornamental plants, fruit trees and vines.
  • monocotyledon and dicotyledonous plants such as grasses, shrubs, trees, crops of cereals and legumes, sugar cane, tobacco, soybeans, onions and Potato tubers, ornamental plants, fruit trees and vines.
  • the effect achieved primarily by the active compounds of the formula I consists in the desired reduction in the plant size, in particular the stature height. In general, this involves a certain change in the shape of the plant. In direct connection with the reduction in growth height, the plant is strengthened. Leaves and stems are stronger. The kink resistance is increased by shortening the internode spacing on monocotyledonous plants. In this way, crop failures due to thunderstorms, continuous rain, etc., which normally lead to the storage of crops of cereals and legumes, can be largely prevented and harvesting work can thus be made easier. As a side effect, the reduced height of crops leads to savings in fertilizers. This also applies to ornamental plants, ornamental turf, sports turf or other green plants.
  • active compounds of the formula 1 according to the invention can also advantageously influence the growth of shoots and / or the fertility of fruit trees and vines.
  • Ornamental plants with strong growth in length can be grown as compact potted plants by treatment with active substances according to the invention.
  • the active compounds of the formula I are also used to inhibit the growth of undesired poultry drives, e.g. in tobacco and ornamental plants, which avoids the labor-intensive breakout of these shoots by hand, also to prevent shoots in stored bulbs, for example in ornamental plant bulbs, in onions and potatoes, and finally to increase the yield in crops which grow strongly vegetatively, such as soybeans and sugar cane, by application active ingredients according to the invention the transition from the vegetative to the generative growth phase is accelerated.
  • the active compounds of the formula according to the invention are preferably used to inhibit the growth of grasses, cereal crops, tobacco, soybeans and ornamental plants.
  • the application rates are different and depend on the time of application. They are generally between 0.1 and 5 kg of active ingredient per hectare, preferably up to 4 kg per hectare when applied before emergence of the plants and for the treatment of existing crops.
  • This inhibition of growth occurs in some plant species at a dosage of 0.5 kg / ha and below.
  • the active compounds according to the invention are also interesting combination partners for a number of herbicides of the phenylurea and triazine series in cereal crops, maize, sugar cane and. in fruit and wine growing.
  • the active compounds according to the invention can be used as growth inhibitors in a wide variety of crops.
  • the weed cover is not removed, but only so strongly inhibited that the crop plants no longer compete.
  • the active ingredients of the formula are also characterized by a very strong pre-emergent herbicide effect, so they are also pronounced germination inhibitors.
  • the tested compounds according to the invention showed pronounced contact herbicidal activity on some plants and growth arrest on many plants as a symptom of the growth-inhibiting properties.
  • Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina and Dactylis glomerata were sown in plastic trays with a soil-peat-sand mixture (6: 3: 1) and watered normally.
  • the accumulated grasses were cut back to a height of 4 cm weekly and sprayed with aqueous spray liquors of an active ingredient of the formula 40 days after sowing and 1 day after the last cut.
  • the amount of active ingredient was the equivalent of 5 kg of active ingredient per hectare.
  • the growth of the grasses was assessed 10 and 21 days after application.
  • the active substances according to the invention cause a noticeable growth inhibition both in the grasses and in the cereals.

Landscapes

  • 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)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Die Erfindung betrifft Pyridyloxy - phenoxy - alkancarbonsäurederivate, welche eine herbizide und das Pflanzenwachstum regulierende Wirkung zeigen, Verfahren zu ihrer Herstellung, ferner Mittel, die diese Verbindungen als Wirkstoffe enthalten, sowie die Verwendung der Wirkstoffe oder der sie enthaltenden Mittel zur selektiven Bekämpfung von Unkräutern und zur Regulierung des Pflanzenwachstums.The invention relates to pyridyloxy - phenoxy - alkane carboxylic acid derivatives which have a herbicidal and plant growth regulating action, processes for their preparation, furthermore compositions which contain these compounds as active compounds, and the use of the active compounds or the compositions containing them for the selective control of weeds and to regulate plant growth.

Die erfindungsgemäßen Wirkstoffe entsprechen der Formel I

Figure imgb0001
worin

  • A die Cyanogruppe, einen Rest -COB oder einen gegebenenfalls durch Methyl ein- oder mehrfach substituierten 2-Oxazolinrest,
  • B einen Rest -OR3, -SR4 oder -NR5R6,
  • C je Halogen, C1-C4 Alkyl oder Nitro,
  • D je Wasserstoff, dasselbe wie C, C1-C4 Alkoxy, C1-C4-Alkylthio, Cyano, C1-C4-Alkylsulfinyl, C1-C4 Alkylsulfonyl, Thiocarbamid (-CSNH2), Mono- oder Di- C1-C4-alkylsulfamoyl,
  • E Wasserstoff, dasselbe wie C, Mono- oder Di-C1-C4- Alkylamin, C1-C5-Alkoxycarbonyl, C2 -C8-Alkoxyalkyl, Cyano, Trifluoromethyl,
  • n 0, 1 oder 2
  • R1 Wasserstoff, C1-C4-Alkyl, C2-C8-Alkoxyalkyl, C1-C4-Haloalkyl,
  • R2 Wasserstoff, C1-C4-Alkyl, Carbonyl, C1-C5-Alkoxycarbonyl,
  • R3 Wasserstoff oder 1
    das Kation einer Base - Mm⊕, m wobei
  • M ein Alkali-, Erdalkali-Kation oder ein Fe-, Cu-, Zn-,
    Figure imgb0002
  • m als ganze Zahl 1, 2 oder 3 die Wertigkeit des Kations berücksichtigt, während Ra, Rb, Re und Rd unabhängig voneinander Wasserstoff, Benzyl oder einen gegebenenfalls durch -OH, -NH2 oder C1-C4-Alkoxy substituierten C1-C4-Alkylrest bedeuten.
    Weiter bedeutet
  • R3 einen C1-C18-Alkyl-Rest, der unsubstituiert oder gegebenenfalls substituiert ist durch Halogen, Nitro, Cyano, C1-C8-Alkoxy, C2-C8-Alkoxyalkoxy, C3-C8-Alkenyloxy, C1-C8-Alkylthio, C2-C8-Alkanoyl, C2-C8-Acyloxy, C3-C8-Alkoxycarbonyl, Carbamoyl, Bis-(C1-C4-alkyl)-amino, Tris-(C1-C4-alkyl)-ammonio, C3-C8-Cycloalkyl, C3-C8-Cycloalkenyl, gegebenenfalls auch durch einen unsubstituierten oder seinerseits durch Halogen, C1-C4 -Alkyl, C1-C4 -Alkoxy, ein- oder mehrfach substituierten Phenyl-, Phenoxy-, Oxiranyl-, Piperidino-, Morpholino-, Pyrrolidino- oder Furylrest,
    • - einen unsubstituierten oder ein- bis vierfach durch Halogen oder einen durch Phenyl oder Methoxycarbonyl substituierten C3-C10-Alkenylrest,
    • - einen C3-C8-Alkinyl-Rest,
    • - einen gegebenenfalls durch Halogen oder Cl-C4-Alkyl substituierten C3-C12-Cycloalkyl-Rest,
    • - einen C3-C8-Cycloalkylen-Rest, einen Phenylrest, der unsubstituiert oder durch Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkylthio, -N02, -CF3, -COOH, -CN, -OH, -S03H, -NH2 oder -NH(C1-C4-Alkyl) oder -N(C1-C4-Alkyl)2 ein- oder mehrfach substituiert ist,
    • - einen Oxiran-, Piperidino-, Morpholino-, Pyrrolidino- oder Furan-Ring,
  • R4 einen C1-C12-Alkyl-Rest, der unsubstituiert oder gegebenenfalls substituiert ist durch C1-C8-Alkoxy, C2-C8-Alkoxycarbonyl, C3-C8-Cycloalkyl, gegebenenfalls auch durch einen unsubstituierten oder seinerseits durch Halogen, C1-C4-Alkyl, C1-C4- Alkoxy ein- oder mehrfach substituierten Phenyl-, Piperidino-, Morpholino-, Pyrrolidino- oder Furan-Ring,
    • - einen C3-C12-Alkenyl-Rest;
    • - einen gegebenenfalls durch C1-C4-Alkyl substituierten C3-C12-Cycloalkyl-Rest,
    • - einen Phenylrest, der unsubstituiert oder durch Halogen, C,-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkylthio, -NO2, -CF3 ein- oder mehrfach substituiert ist,
    • - einen Piperidino-, Morpholino-, Pyrrolidino- oder Furan-Ring,
  • R5 und R6 unabhängig voneinander je Wasserstoff,
    • - C1-C8-Alkyl, das durch Halogen, Hydroxyl oder Cyan substituiert und/oder dessen Kette durch Sauerstoff oder Carboxyoxy unterbrochen sein kann,
    • - C3-C6-Alkenyl, -Alkinyl oder -Cycloalkyl,
    • - Phenyl oder Benzyl, das durch Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, -NO2 oder -CF3 substituiert sein kann,
  • R5 und R6 zusammen mit dem Stickstoffatom, an das sie gebunden sind, auch einen Piperidino-, Morpholino- oder Pyrrolidino-Ring;
    wobei die Bestimmung gilt, dass der Alkancarbonsäurerest
    Figure imgb0003
    nicht in para-Stellung zu einem gegebenenfalls substituierten 2-Pyridyloxyrest
    Figure imgb0004
    stehen kann.
The active compounds according to the invention correspond to formula I.
Figure imgb0001
 wherein
  • A is the cyano group, a -COB radical or a 2-oxazoline radical which is mono- or polysubstituted or substituted by methyl,
  • B is a radical -OR 3 , -SR 4 or -NR 5 R 6 ,
  • C per halogen, C 1 -C 4 alkyl or nitro,
  • D each hydrogen, the same as C, C 1 -C4 alkoxy, C 1 -C 4 alkylthio, cyano, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, thiocarbamide (-CSNH 2 ), mono- or di C 1 -C 4 alkylsulfamoyl,
  • E hydrogen, the same as C, mono- or di-C 1 -C 4 alkylamine, C 1 -C 5 alkoxycarbonyl, C 2 -C 8 alkoxyalkyl, cyano, trifluoromethyl,
  • n 0, 1 or 2
  • R 1 is hydrogen, C 1 -C 4 alkyl, C 2 -C 8 alkoxyalkyl, C 1 -C 4 haloalkyl,
  • R 2 is hydrogen, C 1 -C 4 alkyl, carbonyl, C 1 -C 5 alkoxycarbonyl,
  • R 3 is hydrogen or 1
    the cation of a base - M m⊕ , m where
  • M an alkali, alkaline earth cation or an Fe, Cu, Zn,
    Figure imgb0002
  • m takes into account the valence of the cation as an integer 1, 2 or 3, while R a , R b , R e and R d independently of one another are hydrogen, benzyl or an optionally by -OH, -NH 2 or C 1 -C 4 alkoxy substituted C 1 -C 4 alkyl radical.
    Next means
  • R 3 is a C 1 -C 18 alkyl radical which is unsubstituted or optionally substituted by halogen, nitro, cyano, C 1 -C 8 alkoxy, C 2 -C 8 alkoxyalkoxy, C 3 -C 8 alkenyloxy, C 1 -C 8 alkylthio, C 2 -C 8 alkanoyl, C 2 -C 8 acyloxy, C 3 -C 8 alkoxycarbonyl, carbamoyl, bis (C 1 -C 4 alkyl) amino, tris (C 1 -C 4 -alkyl) -ammonio, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkenyl, optionally also by an unsubstituted or in turn by halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, mono- or polysubstituted phenyl, phenoxy, oxiranyl, piperidino, morpholino, pyrrolidino or furyl radical,
    • an unsubstituted or mono- to tetrasubstituted by halogen or a C 3 -C 10 alkenyl radical substituted by phenyl or methoxycarbonyl,
    • a C 3 -C 8 alkynyl radical,
    • a C 3 -C 12 cycloalkyl radical optionally substituted by halogen or C 1 -C 4 alkyl,
    • a C 3 -C 8 cycloalkylene radical, a phenyl radical which is unsubstituted or by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, -N0 2 , - CF3, -COOH, -CN, -OH, -S0 3 H, -NH 2 or -NH (C 1 -C 4 alkyl) or -N (C 1 -C 4 alkyl) 2 is substituted one or more times ,
    • an oxirane, piperidino, morpholino, pyrrolidino or furan ring,
  • R 4 is a C 1 -C 12 alkyl radical which is unsubstituted or optionally substituted by C 1 -C 8 alkoxy, C 2 -C 8 alkoxycarbonyl, C 3 -C 8 cycloalkyl, optionally also by an unsubstituted or in turn by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy mono- or polysubstituted phenyl, piperidino, morpholino, pyrrolidino or furan ring,
    • - a C 3 -C 12 alkenyl radical;
    • a C 3 -C 12 cycloalkyl radical which is optionally substituted by C 1 -C 4 alkyl,
    • - a phenyl radical which is unsubstituted or mono- substituted by halogen, C, -C 4- alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, -NO 2, -CF 3 or polysubstituted,
    • a piperidino, morpholino, pyrrolidino or furan ring,
  • R 5 and R 6 are each independently hydrogen,
    • C 1 -C 8 alkyl which can be substituted by halogen, hydroxyl or cyano and / or whose chain can be interrupted by oxygen or carboxyoxy,
    • - C 3 -C 6 alkenyl, alkynyl or cycloalkyl,
    • Phenyl or benzyl, which can be substituted by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, -NO 2 or -CF 3 ,
  • R 5 and R 6 together with the nitrogen atom to which they are attached also form a piperidino, morpholino or pyrrolidino ring;
    the provision being that the alkane carboxylic acid residue
    Figure imgb0003
     not in the para position to an optionally substituted 2-pyridyloxy radical
    Figure imgb0004
     can stand.

Die Alkylreste in dieser Formel können verzweigt oder unverzweigt sein und enthalten die angegebene Anzahl Kohlenstoffatome. Die Reste R5 und R6 sind Bevorzugt Wasserstoff und C1-C4-Alkylreste.The alkyl radicals in this formula can be branched or unbranched and contain the stated number of carbon atoms. The radicals R 5 and R 6 are preferably hydrogen and C 1 -C 4 alkyl radicals.

Die erfindungsgemäßen Wirkstoffe der Formel I besitzen Herbizidwirkung, vor allem bei postemergenter Anwendung und können in mono- und dikotylen Kulturen als Unkrautmittel eingesetzt werden.The active compounds of the formula I according to the invention have herbicidal activity, especially in the case of postemergent use and can be used as weed agents in mono- and dicotyledon crops.

Ferner besitzen sie 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 dieser Kulturen führt;
  • -die Hemmung des unerwünschten Wuchstums von Geiztrieben 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 Hecken, zwecks Einsparung an Schnittarbeit.
They 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, for example
  • - the reduction of vegetative growth in soybeans and similar legumes, which leads to an increase in the yield of these crops;
  • -inhibiting the undesirable growth of stinging shoots in tobacco, the main shoot of which has been cut, which benefits the formation of larger and more beautiful leaves;
  • - inhibiting the growth of grass and dicot plants, such as fruit trees, ornamental trees, bushes and hedges, in order to save on cutting work.

Die erfindungsgemäßen Verbindungen sind wenig giftig für Warmblüter und deren Applikation wirft keine Probleme auf. Die Aufwandmenge liegt zwischen 0.1 und 5 kg pro Hektar.The compounds according to the invention 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.

Die Herstellung der Verbindungen der Formel I erfolgt nach an sich bekannten Methoden.The compounds of the formula I are prepared by methods known per se.

Nach einem ersten dieser Verfahren setzt man ein gegebenenfalls substituiertes Halogen-pyridin der Formel II

Figure imgb0005
worin C, D, E und n die unter Formel I gegebene Bedeutung haben und Hal ein Halogenatom, vorzugsweise Chlor oder Brom bedeutet, mit einem Hydroxy - phenoxy - alkancarbonsäurederivat der Formel III
Figure imgb0006
worin A, C, D, R1 und Rz die unter Formel I gegebene Bedeutung haben, in Gegenwart eines säurebindenden Mittels um.According to a first of these processes, an optionally substituted halopyridine of the formula II is used
Figure imgb0005
 wherein C, D, E and n have the meaning given under formula I and Hal represents a halogen atom, preferably chlorine or bromine, with a hydroxyphenoxyalkane carboxylic acid derivative of the formula III
Figure imgb0006
 wherein A, C, D, R 1 and R z have the meaning given under formula I in the presence of an acid-binding agent.

Solche Umsetzungen sind an sich bekannt und ihre genaue Durchführung kann in Textbüchern wie z.B. in Houben-Weyl, Band 3, Seiten 85 ff nachgelesen werden.Such implementations are known per se and their exact implementation can be found in text books such as in Houben-Weyl, Volume 3, pages 85 ff.

Gemäss einem zweiten Verfahren stellt man die Pyridyloxy - phenoxy - alkancarbonsäurederivate der Formel I her, indem man einen Pyridyloxy-hydroxyphenyläther der Formel IV

Figure imgb0007
worin C, D, E und n die unter Formel I gegebene Bedeutung haben, mit einem a-Halogencarbonsäurederivat der Formel V
Figure imgb0008
worin A, R1 und R2 die unter Formel I gegebene Bedeutung haben und Hal ein Halogenatom, vorzugsweise Chlor oder Brom bedeutet, in Gegenwart eines säurebindenden Mittels umsetzt.According to a second process, the pyridyloxy-phenoxy-alkanecarboxylic acid derivatives of the formula I are prepared by using a pyridyloxy-hydroxyphenyl ether of the formula IV
Figure imgb0007
 wherein C, D, E and n have the meaning given under formula I, with an a-halocarboxylic acid derivative of the formula V.
Figure imgb0008
 wherein A, R 1 and R 2 have the meaning given under formula I and Hal represents a halogen atom, preferably chlorine or bromine, in the presence of an acid-binding agent.

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 etc. Die Reaktionstemperaturen liegen zwischen 0 und 200°C und die Reaktionsdauer beträgt je nach gewählter Umsetzungstemperatur und Lösungsmittel zwischen 1/4 Stunden und mehreren Tagen. Man arbeitet in der Regel bei Normaldruck oder einem leichten Ueberdruck. Als säurebindende Mittel für die Umsetzung kommen anorganische, wie z.B. NaOH, KOH, NaOCH3, NaH, KzC03, NaC03 oder Kaliumtert. butylat aber auch organische Basen in Betracht.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 ° C. and the reaction time is between 1/4 hour and several days, depending on the reaction temperature and solvent chosen. You usually work at normal pressure or a slight excess pressure. Acid-binding agents for the reaction are inorganic, such as NaOH, KOH, NaOCH 3 , NaH, K z C0 3 , NaC0 3 or potassium tert. butylate but also organic bases.

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

Substituierte 2-Halogen-pyridin 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. einen Monobenzyläther von Hydrochinon, Resorcin oder Brenzkatechin mit einem a-Halogen-carbonsäurederivat, vorzugsweise einem Ester der Formel V umsetzt und die Benzyl-phenyläther-Bindung durch katalytische Hydrierung spaltet z.B. mit einem Palladium-auf-Kohle-Katalysator, wobei der Benzylrest als Toluol weggeht.Substituted 2-halopyridine according to formula II can i.a. can be easily prepared from the corresponding 2-pyridinols, some of which are known. Starting materials of formula III can be prepared by e.g. reacting a monobenzyl ether of hydroquinone, resorcinol or catechol with an α-halogenocarboxylic acid derivative, preferably an ester of the formula V, and cleaving the benzylphenyl ether bond by catalytic hydrogenation, e.g. with a palladium-on-carbon catalyst, the benzyl residue leaving as toluene.

Durch Umsetzung von Hydrochinon, Resorcin oder Brenzkatechin mit Halogenpyridinen in äquimolaren Mengen und in Gegenwart einer Base kann man zu den Ausgangsproduktender Formel IV gelangen.The starting products of the formula IV can be obtained by reacting hydroquinone, resorcinol or pyrocatechol with halopyridines in equimolar amounts and in the presence of a base.

Carbonsäurederivate der Formel V sind ebenfalls bekannt. Als deren einfachste Vertreter seien z.B. die Chloressigsäure, deren Ester, Thioester, Amide und Hydrazide erwähnt. Es kommen aber auch andere gemäss R1 und Rz substituierte a - Halogencarbonsäure - derivate in Betracht.Carboxylic acid derivatives of the formula V are also known. The simplest representatives are, for example, chloroacetic acid, its esters, thioesters, amides and hydrazides. However, other a-halocarboxylic acid derivatives substituted according to R 1 and R z can also be used.

Die nachfolgenden Beispiele veranschaulichen das erfindungsgemässe Verfahren für willkürlich ausgewählte Wirkstoffe der Formel 1. Weitere in entsprechender Weise hergestellte Wirkstoffe sind in den anschliessenden Tabellen aufgeführt. Temperaturangaben beziehen sich jeweils auf Celsius-Grade.The following examples illustrate the process according to the invention for arbitrarily selected active substances of the formula 1. Further active substances produced in a corresponding manner are listed in the tables below. Temperatures refer to degrees Celsius.

Diese Pyridyloxy-phenoxy-alkancarbonsäurederivate der Formel I sind stabile Verbindungen, welche in üblichen organischen Lösungsmitteln, wie Alkoholen, Aethern, Ketonen, Dimethylformamid oder Dimethylsulfoxid löslich sind.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 or dimethyl sulfoxide.

Beispiel 1example 1 α[3-(3'-Chlor-5'-cyano-6'-methyl-pyrid-2'-yl)-oxyphenoxy]-propionsäure-methylesterα [3- (3'-Chloro-5'-cyano-6'-methyl-pyrid-2'-yl) -oxyphenoxy] propionic acid methyl ester

Figure imgb0009
Zu einer Dispersion von 2,6 g (0,1 Mol) Natriumhydroxid in 100 ml Dimethylsulfoxid werden 19,6 g (0,1 Mol) 3 - Hydroxy - phenoxy - a - propionsäuremethylester, gelöst in 50 ml Dimethylsulfoxid, unter Kühlen zugetropft. Wenn sich alles Natriumhydrid gelöst hat, werden 18,7 g (0,1 Mol) 2,3 - Dichlor - 5 - cyano - 6 - methyl - pyridin zugegeben. Nach 8-stündigem Rühren bei Raumtemperatur wird das Dimethylsulfoxid im Vakuum abgedampft, der Rückstand mit 500 ml Eiswasser versetzt und mit Aether ausgeschüttelt. Die Aetherextrakte werden über Magnesiumsulfat getrocknet und dann eingedampft. Der Rückstand wird aus Aether/Petroläther umkristallisiert. Man erhält 20,1 g (58% der Theorie) a - [3 - (3' - Chlor - 5' - cyano - 6' - methyl - pyrid - 2' - yl) - oxy - phenoxy] propionsäuremethylester vom Schmelzpunkt 106-109°.
Figure imgb0009
 19.6 g (0.1 mol) of methyl 3-hydroxyphenoxy-a-propionate, dissolved in 50 ml of dimethyl sulfoxide, are added dropwise with cooling to a dispersion of 2.6 g (0.1 mol) of sodium hydroxide in 100 ml of dimethyl sulfoxide. When all the sodium hydride has dissolved, 18.7 g (0.1 mol) of 2,3-dichloro-5-cyano-6-methyl-pyridine are added. After stirring for 8 hours at room temperature, the dimethyl sulfoxide is evaporated in vacuo, the residue is mixed with 500 ml of ice water and extracted with ether. The ether extracts are dried over magnesium sulfate and then evaporated. The residue is recrystallized from ether / petroleum ether. 20.1 g (58% of theory) of a - [3 - (3 '- chloro - 5' - cyano - 6 '- methyl - pyrid - 2' - yl) - oxy - phenoxy] propionic acid methyl ester of melting point 106- 109 °.

Beispiel 2Example 2 α-[3-(3',5'-Dichlorpyrid-2-yl)-oxy-phenoxy]-propionsäure-methylesterMethyl α- [3- (3 ', 5'-dichloropyrid-2-yl) oxyphenoxy] propionate

Figure imgb0010
30,8 g (0,1 Mol) 3-(3',5'-Dichlorpyrid-2'-yl)-oxy-phenol 18,2 g (0,13 Mol) Kaliumcarbonat und 22 g α-Brompropionsäuremethylester werden in 300 ml Aethylmethylketon während 3 Stunden unter Rückfluss erhitzt. Dann werden die anorganischen Salze abfiltriert und das Filtrat eingedampft. Durch Umkristallisieren aus Aether/Petroläther erhält man 29 g (70% der Theorie) Titelprodukt mit dem Schmelzpunkt 58-60°.
Figure imgb0010
 30.8 g (0.1 mol) of 3- (3 ', 5'-dichloropyrid-2'-yl) -oxyphenol 18.2 g (0.13 mol) of potassium carbonate and 22 g of methyl α-bromopropionate are dissolved in 300 ml of ethyl methyl ketone heated under reflux for 3 hours. Then the inorganic salts are filtered off and the filtrate is evaporated. Recrystallization from ether / petroleum ether gives 29 g (70% of theory) of the title product with a melting point of 58-60 °.

Beispiel 3Example 3 a-[3-(3',5'-Dichlorpyridyl-2'-oxy)-4-chlorphenoxypropionsäure-methylestera- [3- (3 ', 5'-Dichloropyridyl-2'-oxy) -4-chlorophenoxypropionic acid methyl ester

Figure imgb0011
17,3 g (0,05 Mol) a-[3-(3',5'-Dichlorpyrid-2-yl)-oxy-phenoxyJ-propionsäure-methylester (siehe Beispiel 2) werden in 260 ml Tetrachlorkohlenstoff und 17,3 ml Eisessig gelöst. Nach Zugabe einer katalytischen Menge Antimontrichlorid werden bei 50° 3,5 g Chlor eingeleitet. Nach einer Stunde wird die Lösung eingedampft und das zurückbleibende Oel aus Aether/Petroläther umkristallisiert. Man erhält so das Titelprodukt vom Schmelzpunkt 76-78°.
Figure imgb0011
 17.3 g (0.05 mol) of a- [3- (3 ', 5'-dichloropyrid-2-yl) -oxy-phenoxyJ-propionic acid methyl ester (see Example 2) are dissolved in 260 ml of carbon tetrachloride and 17.3 ml of glacial acetic acid dissolved. After adding a catalytic amount of antimony trichloride, 3.5 g of chlorine are introduced at 50 °. After an hour, the solution is evaporated and the remaining oil is recrystallized from ether / petroleum ether. This gives the title product of melting point 76-78 °.

Beispiel 4Example 4 3-(3',5'-Dichlorpyridyl-2'-oxy)-6-chlorphenylacetat (Zwischenprodukt)3- (3 ', 5'-dichloropyridyl-2'-oxy) -6-chlorophenylacetate (intermediate)

Eine Mischung von 256 g 3-(3',5'-Dichlorpyridyl-2'-oxy)-phenol, 1,9 Liter Eisessig und 280 ml Acetanhydrid wird während 12 Stunden bei Rückflusstemperatur gerührt. Die Lösung wird auf 40° gekühlt. Dann wird unter Rühren 81 g Natriumacetat zugegeben und während 7 Stunden bei 40° 106 g Chlorgas eingeleitet. Das überschüssige Chlorgas wird durch ein 2-stündiges Durchleiten von Stickstoff entfernt und die Lösung eingedampft.A mixture of 256 g of 3- (3 ', 5'-dichloropyridyl-2'-oxy) phenol, 1.9 liters of glacial acetic acid and 280 ml of acetic anhydride is stirred at reflux temperature for 12 hours. The solution is cooled to 40 °. Then 81 g of sodium acetate are added with stirring and 106 g of chlorine gas are passed in at 40 ° for 7 hours. The excess chlorine gas is removed by passing nitrogen through for 2 hours and the solution is evaporated.

Die Essigesterlösung (1000 ml) des öligen Rückstandes wird mit Wasser und gesättigter NaHCOg-Lösung gewaschen, getrocknet und eingedampft. Man erhält 343 g der Titelverbindung als braunes Oel, das mit 300 ml Petroläther verrieben, spontan kristallisiert. Smp.: 71-75°C.The ethyl acetate solution (1000 ml) of the oily residue is washed with water and saturated NaHCOg solution, dried and evaporated. 343 g of the title compound are obtained as a brown oil, which is triturated with 300 ml of petroleum ether and crystallizes spontaneously. M.p .: 71-75 ° C.

Beispiel 5Example 5 3-(3',5'-Dichlorpyridyl-2'-oxy)-6 resp. -4-Chlorphenol (Zwischenprodukt)3- (3 ', 5'-dichloropyridyl-2'-oxy) -6 resp. -4-chlorophenol (intermediate)

Eine Suspension von 2,26 g pulverisiertem KOH und 10 g 3 - (3',5' - Dichlorpyridyl - 2' - oxy) - 6 - phenylacetat in 30 ml absolutem Methanol wird unter Stickstoffatmosphäre während 20 Minuten bei 60° gerührt, auf Raumtemperatur gekühlt, mit 3,7 ml konzentrierter Salzsäure sauer gestellt und eingedampft.A suspension of 2.26 g of powdered KOH and 10 g of 3 - (3 ', 5' - dichloropyridyl - 2 '- oxy) - 6 - phenylacetate in 30 ml of absolute methanol is stirred under a nitrogen atmosphere at 60 ° for 20 minutes, to room temperature cooled, acidified with 3.7 ml of concentrated hydrochloric acid and evaporated.

Die Toluollösung (50 ml) des Rückstandes wird mit Wasser gewaschen, getrocknet, über Aktivkohle filtriert und eingedampft. Man erhält 8,4 g eines Oels, das aus einem Gemisch des -6-Chlor- und - 4-Chlorphenolisomeren im Verhältnis 7:3 besteht.The toluene solution (50 ml) of the residue is washed with water, dried, filtered through activated carbon and evaporated. 8.4 g of an oil are obtained, which consists of a mixture of the -6-chloro and - 4-chlorophenol isomers in a ratio of 7: 3.

Beispiel 6Example 6 a-[3-(3',5'-Dichlorpyridyl-2'-oxy)-6-chlorphenoxy]-propionsäure-methylestera- [3- (3 ', 5'-Dichloropyridyl-2'-oxy) -6-chlorophenoxy] propionic acid methyl ester

Figure imgb0012
25 g (0.085 Mol) eines Gemisches aus 3 - (3',5' - Dichlorpyridyl - 2' - oxy) - 6 - chlorphenol und 3 - (3',5' - Dichlorpyridyl - 2' - oxy) - 4 - chlorphenol (hergestellt nach Beispiel 5) 14,2 g (0.085 Mol) α - Brompropionsäure-methylester und 13,8 g (0.1 Mol) Kaliumcarbonat werden in 250 ml Methyläthylketon 6 Stunden unter Rückfluss erhitzt. Die anorganischen Salze werden abfiltriert und das Filtrat eingedampft. Das zurückbleibende gelbe Oel wird aus Aether/Petroläther umkristallisiert. Man erhält so 30,1 g (94% der Theorie) isomerenfreies Titelprodukt von Schmelzpunkt 82-83°.
Figure imgb0012
 25 g (0.085 mol) of a mixture of 3 - (3 ', 5' - dichloropyridyl - 2 '- oxy) - 6 - chlorophenol and 3 - (3', 5 '- dichloropyridyl - 2' - oxy) - 4 - chlorophenol (prepared according to Example 5) 14.2 g (0.085 mol) of methyl α-bromopropionate and 13.8 g (0.1 mol) of potassium carbonate are heated under reflux in 250 ml of methyl ethyl ketone for 6 hours. The inorganic salts are filtered off and the filtrate is evaporated. The remaining yellow oil is recrystallized from ether / petroleum ether. This gives 30.1 g (94% of theory) of isomer-free title product with a melting point of 82-83 °.

Beispiel 7Example 7 3-(3',5'-Dichlorpyridyl-2'-oxy)-6-brom-phenylacetat (Zwischenprodukt)3- (3 ', 5'-dichloropyridyl-2'-oxy) -6-bromophenylacetate (intermediate)

Eine Gemisch aus 205 g 3-(3',5'-Dichlorpyridyl-2'-oxy)-phenol, 1,1 Liter Eisessig und 224 ml Acetanhydrid wird während 12 Stunden bei Rückflusstemperatur gerührt. Die Lösung wird auf 60° gekühlt, dann wird unter Rühren 64,8 g Natriumacetat zugegeben und während 5t Stunden eine Lösung von 102 ml Brom in 400 ml Eisessig bei 60° zugetropft. Die Lösung wird eingedampft, der Rückstand in Essigester gelöst und die organische Phase nacheinander mit Wasser und gesättigtem NaHC03-Lösung gewaschen. Die vereinigten Essigesterextrakte werden getrocknet und eingedampft. Man erhält 302,5 g eines Oels, das mit 500 ml Petroläther (Sdp. 60-90°) überschichtet kristallisiert.A mixture of 205 g of 3- (3 ', 5'-dichloropyridyl-2'-oxy) phenol, 1.1 liters of glacial acetic acid and 224 ml of acetic anhydride is stirred at reflux temperature for 12 hours. The solution is cooled to 60 °, 64.8 g of sodium acetate are then added with stirring and a solution of 102 ml of bromine in 400 ml of glacial acetic acid is added dropwise at 60 ° for 5 hours. The solution is evaporated, the residue is dissolved in ethyl acetate and the organic phase is washed successively with water and saturated NaHC0 3 solution. The combined ethyl acetate extracts are dried and evaporated. 302.5 g of an oil are obtained, which are crystallized with a layer of 500 ml of petroleum ether (bp 60-90 °).

Das Titelprodukt schmilzt nach Umkristallisieren aus Cyclohexan bei 106-107°.After recrystallization from cyclohexane, the title product melts at 106-107 °.

Beispiel 8Example 8 3-(3',5`-Dichlorpyridyl-2'-oxy)-6-brom-phenol3- (3 ', 5`-dichloropyridyl-2'-oxy) -6-bromophenol

Eine Suspension von 28,0 g pulverisiertem KOH und 153,5 g 3 - (3',5' - Dichlorpyridyl - 2' - oxy) - 6 - brom - phenylacetat in einem Liter absolutem Methanol wird unter Stickstoffatmosphäre während 20 Minuten bei 60° gerührt, eingeengt und bei Raumtemperatur mit konzentrierter Salzsäure sauer gestellt und vollständig eingedampft. Die Toluollösung (400 ml) des Rückstandes wird mit Wasser gewaschen, getrocknet und eingedampft. Der ölige Rückstand wird mit Petroläther/Cyclohexan verrieben und filtriert. Man erhält 137 g des kristallinen Titelproduktes. Smp.: 93-95°.A suspension of 28.0 g of powdered KOH and 153.5 g of 3 - (3 ', 5' - dichloropyridyl - 2 '- oxy) - 6 - bromophenylacetate in one liter of absolute methanol is added under a nitrogen atmosphere for 20 minutes at 60 ° stirred, concentrated and acidified at room temperature with concentrated hydrochloric acid and evaporated completely. The toluene solution (400 ml) of the residue is washed with water, dried and evaporated. The oily residue is triturated with petroleum ether / cyclohexane and filtered. 137 g of the crystalline title product are obtained. M.p .: 93-95 °.

Beispiel 9Example 9 a-[3-(3',5'-Dichlorpyridyl-2'-oxy)-6-bromophenoxy]-proprionsäure-methylestera- [3- (3 ', 5'-Dichloropyridyl-2'-oxy) -6-bromophenoxy] propionic acid methyl ester

Figure imgb0013
50,2 g (0,15 Mol) 3 - (3',5' - Dichlorpyridyl - 2' - oxy) - 6 - bromphenol (hergestellt gemäss Beispiel 8) 27,5 g (0,165 Mol) αα - Brompropionsäure - methylester und 27,6 g (0,2 Mol) Kaliumcarbonat werden in 250 ml Methyläthylketon 5 Std. unter Rückfluss erhitzt. Die anorganischen Salze werden abfiltriert und das Filtrat eingedampft. Das rötliche Oel wird aus Aether/Petroläther umkristallisiert. Man erhält 58 g (91,8% der Theorie) der Titelverbindung mit einem Schmelzpunkt von 75°.
Figure imgb0013
 50.2 g (0.15 mol) of 3 - (3 ', 5' - dichloropyridyl - 2 '- oxy) - 6 - bromophenol (prepared according to Example 8), 27.5 g (0.165 mol) of methyl αα - bromopropionate and 27.6 g (0.2 mol) of potassium carbonate are heated under reflux in 250 ml of methyl ethyl ketone for 5 hours. The inorganic salts are filtered off and the filtrate is evaporated. The reddish oil is recrystallized from ether / petroleum ether. 58 g (91.8% of theory) of the title compound with a melting point of 75 ° are obtained.

Beispiel 10Example 10 a-[3-(3',5'-Dichlorpyridyl-4'-oxy)-6-chlorphenoxy]-propionsäure-methylestera- [3- (3 ', 5'-Dichloropyridyl-4'-oxy) -6-chlorophenoxy] propionic acid methyl ester

Figure imgb0014
Eine Gemisch aus 4,1 g 3-(3',5'-Dichlorpyridyl-4`-oxy)-6-chlorphenol, 2,15 g Kaliumcarbonat, 1,74 ml a-Brompropionsäuremethylester und 15 ml Aethylmethylketon wird 4 Stunden bei Rückflusstemperatur gerührt, filtriert und eingedampft.
Figure imgb0014
 A mixture of 4.1 g of 3- (3 ', 5'-dichloropyridyl-4`-oxy) -6-chlorophenol, 2.15 g of potassium carbonate, 1.74 ml of methyl a-bromopropionate and 15 ml of ethyl methyl ketone is kept at the reflux temperature for 4 hours stirred, filtered and evaporated.

Man erhält 5 g der Titelverbindung als Oel.5 g of the title compound are obtained as an oil.

n23 D: 1,5587n 23 D : 1.5587

Beispiel 11 1Example 11 1 α-[3-(3',5'-Dichlorpyridyl-2'-oxy)-6-nitrophenoxyl-propionsäure-methylesterMethyl α- [3- (3 ', 5'-dichloropyridyl-2'-oxy) -6-nitrophenoxyl propionate

Figure imgb0015
30,1 g (0,1 Mol) 3-(3',5'-Dichlorpyridyl-2'-oxy)-6-nitrophenol, 16,7 g (0,1Mol)α-Brompropionsäure- methylester und 20,7 g (0,15 Mol) Kaliumcarbonat werden in 400 ml Methyläthylketon während 14 Stunden unter Rückfluss erhitzt. Die anorganischen Salze werden abfiltriert, das Filtrat eingedampft und das verbleibende braune Oel in Chloroform aufgenommen und über eine kurze Kieselgelsäule filtriert. Man erhält so 22,4 g (58% der Theorie) Titelprodukt, das nach Umkristallisieren aus Hexan bei 102° schmilzt.
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
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
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0015
 30.1 g (0.1 mol) of 3- (3 ', 5'-dichloropyridyl-2'-oxy) -6-nitrophenol, 16.7 g (0.1 mol) of methyl α-bromopropionate and 20.7 g (0.15 mol) potassium carbonate in 400 ml of methyl ethyl ketone is heated under reflux for 14 hours. The inorganic salts are filtered off, the filtrate is evaporated and the remaining brown oil is taken up in chloroform and filtered through a short silica gel column. This gives 22.4 g (58% of theory) of the title product, which melts at 102 ° after recrystallization from hexane.
Figure imgb0016
Figure imgb0017
Figure imgb0018
Figure imgb0019
Figure imgb0020
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
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041

Die Herstellung erfindungsgemässer Mittel erfolgt in an sich bekannter Weise durch inniges Vermischen und Vermahlen von Wirkstoffen der Formel I mit geeigneten Trägerstoffen, gegebenenfalls unter Zusatz von gegenüber den Wirkstoffen inerten Dispersions- oder Lösungsmitteln. Die Wirkstoffe können in den folgenden Aufarbeitungsformen vorliegen und angewendet werden:

  • feste Aufarbeitungsformen:
    • Stäubemittel, Streumittel, Granulate, Umhüllungsgranulate,
    • Imprägnierungsgranulate und Homogengranulate;
  • in Wasser dispergierbare Wirkstoffkonzentrate:
    • Spritzpulver, (wettable powder)
    • Pasten, Emulsionen:
  • flüssige Aufarbeitungsformen:
    • Lösungen.
Agents according to the invention are prepared in a manner known per se by intimately mixing and grinding active ingredients of the formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active ingredients. The active ingredients can be present and used in the following processing forms:
  • fixed processing forms:
    • Dusts, scattering agents, granules, coating granules,
    • Impregnation granules and homogeneous granules;
  • Active ingredient concentrates dispersible in water:
    • Wettable powder, (wettable powder)
    • Pastes, emulsions:
  • liquid processing forms:
    • Solutions.

Der Gehalt an Wirkstoff in den oben beschriebenen Mitteln liegt zwischen 0,1 bis 95%, bevorzugt zwischen 1 bis 80%. Anwendungsformen können bis hinab zu 0,001% verdünnt werden. Die Aufwandmengen betragen in der Regel 0,1 bis 10 kg AS/ha, vorzugsweise 0,25 bis 5 kg AS/ha. Den beschriebenen erfindungsgemässen Mitteln lassen sich auch andere biozide Wirkstoffe oder Mittel beimischen. Die Wirkstoffe der Formel 1 können beispielsweise wie folgt formuliert werden (Teile bedeuten Gewichtsteile):The content of active ingredient in the agents described above is between 0.1 to 95%, preferably between 1 to 80%. Application forms can be diluted down to 0.001%. The application rates are generally 0.1 to 10 kg ai / ha, preferably 0.25 to 5 kg ai / ha. Other biocidal active substances or agents can also be added to the agents according to the invention described. The active ingredients of Formula 1 can be formulated, for example, as follows (parts mean parts by weight):

StäubemittelDusts

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

Figure imgb0042
Figure imgb0043
 The following substances are used to produce a) 5% and b) 2% dust:
Figure imgb0042
Figure imgb0043

Die Wirkstoffe werden mit den Trägerstoffen vermischt und vermahlen.The active ingredients are mixed and ground with the carriers.

GranulätGranules

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

Figure imgb0044
The following substances are used to produce 5% granules:
Figure imgb0044

Die Aktivsubstanz wird mit Epichlorhydrin vermischt und in 6 Teilen Aceton gelöst, hierauf werden Polyäthylenglykol und Cetylpolyäthylenglykoläther zugesetzt. Die so erhaltene Lösung wird auf Kaolin aufgesprüht und anschliessend im Vakuum eingedampft.The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone, whereupon polyethylene glycol and cetylpolyethylene glycol ether are added. The solution thus obtained is sprayed onto kaolin and then evaporated in vacuo.

SpritzpulverWettable powder

Zur Herstellung eines a) 50%igen, b) 25%igen und c) 10%igen Spritzpulvers werden folgende Bestandteile verwendet:

Figure imgb0045
Figure imgb0046
Figure imgb0047
 The following components are used to produce a) 50%, b) 25% and c) 10% wettable powder:
Figure imgb0045
Figure imgb0046
Figure imgb0047

Der angegebene Wirkstoff wird auf die entsprechenden Trägerstoffe (Kaolin und Kreide) aufgezogen und anschliessend vermischt und vermahlen. Man erhält Spritzpulver von vorzüglicher Benetzbarkeit und Schwebefähigkeit. Aus solchen Spritzpulvern können durch Verdünnen mit Wasser Suspensionen jeder gewünschten Wirkstoffkonzentration erhalten werden. Derartige Suspensionen werden zur Bekämpfung von Unkräutern und Ungräsern in Kulturpflanzungen in Vorauflaufverfahren und zur Behandlung von Rasenanlagen verwendet.The specified active ingredient is drawn onto the corresponding carrier substances (kaolin and chalk) and then mixed and ground. Spray powder of excellent wettability and suspension is obtained. Suspensions of any desired active ingredient concentration can be obtained from such wettable powders by dilution with water. Such suspensions are used to control weeds and weeds in crops in pre-emergence and for the treatment of lawns.

Pastepaste

Zur Herstellung einer 45%igen Paste werden folgende Stoffe verwendet:

Figure imgb0048
The following substances are used to produce a 45% paste:
Figure imgb0048

Der Wirkstoff wird mit den Zuschlagstoffen in dazu geigneten Geräten innig vermischt und vermahlen. Man erhält eine Paste, aus der sich durch Verdünnen mit Wasser Suspensionen jeder gewünschten Konzentration herstellen lassen. Die Suspensionen eignen sich zur Behandlung von Rasenanlagen.The active ingredient is intimately mixed and ground with the additives in suitable devices. A paste is obtained, from which suspensions of any desired concentration can be prepared by dilution with water. The suspensions are suitable for the treatment of lawns.

EmulsionskonzentratEmulsion concentrate

Zur Herstellung eines 25%igen Emulsionskonzentrates werden

Figure imgb0049
miteinander vermischt. Dieses Konzentrat kann mit Wasser zu Emulsionen auf geeignete Konzentrationen verdünnt werden.To prepare a 25% emulsion concentrate
Figure imgb0049
 mixed together. This concentrate can be diluted with water to emulsions to suitable concentrations.

Anstatt des jeweiligen in den vorhergehenden Formulierungsbeispielen angegebenen Wirkstoffs kann auch eine andere der von der Formel 1 umfassten Verbindungen verwendet werden.Instead of the particular active ingredient specified in the preceding formulation examples, another of the compounds encompassed by Formula 1 can also be used.

Die in den erfindungsgemässen Mitteln enthaltenen Wirkstoffe beeinflussen das Pflanzenwachstum in verschiedener Weise. So hemmen, verzögern oder unterbinden sie in erster Linie das Wachstum und die Keimung. Es handelt sich dabei also sowohl um pre- und post-emergente Herbizid- wirkung als auch um Wuchshemmung.The active substances contained in the agents according to the invention influence plant growth in various ways. In the first place, they inhibit, delay or prevent growth and germination. It is therefore both a pre- and post-emergent herbicide effect and an inhibition of growth.

Erfindungsgemässe Mittel, die als aktive Komponente mindestens eine Verbindung der Formel I enthalten, eignen sich besonders zur Hemmung Kontrolle des Pflanzenwachstums von monocotylen und dicotylen Pflanzen, wie Gräsern, Sträuchern, Bäumen, Getreide- und Leguminosenkulturen, Zuckerrohr, Tabak, Soja, Zwiebel- und Kartoffelknollen, Zierpflanzen, Obstbäumen und Reben.Agents according to the invention which contain at least one compound of the formula I as the active component are particularly suitable for inhibiting the control of the plant growth of monocotyledon and dicotyledonous plants, such as grasses, shrubs, trees, crops of cereals and legumes, sugar cane, tobacco, soybeans, onions and Potato tubers, ornamental plants, fruit trees and vines.

Die von den Wirkstoffen der Formel I in erster Linie erzielte Wirkung besteht in der gewünschten Reduktion der Pflanzengrösse, insbesondere der Wuchshöhe. Im allgemeinen ist damit eine gewisse Aenderung der Pflanzenform verbunden. In unmittelbarem Zusammenhang zur Verminderung der Wuchshöhe erfährt die Pflanze eine Festigung. Blätter und Stengel sind kräftiger ausgebildet. Durch Verkürzung der Internodienabstände an monocotylen Pflanzen wird die Knickfestigkeit erhöht. Auf diese Weise können Ernteausfälle durch Gewittersturm, Dauerregen, usw., die normalerweise zu einem Lagern von Getreide- und Leguminosenkulturen führen, weitgehend verhindert und damit die Erntearbeit erleichtert werden. Als Nebeneffekt führt verminderte Wuchshöhe bei Nutzpflanzen zu einer Einsparung an Düngemitteln. In gleichem Masse gilt dies auch für Zierpflanzen, Zierrasen, Sportrasen oder sonstige Grünanpflanzungen.The effect achieved primarily by the active compounds of the formula I consists in the desired reduction in the plant size, in particular the stature height. In general, this involves a certain change in the shape of the plant. In direct connection with the reduction in growth height, the plant is strengthened. Leaves and stems are stronger. The kink resistance is increased by shortening the internode spacing on monocotyledonous plants. In this way, crop failures due to thunderstorms, continuous rain, etc., which normally lead to the storage of crops of cereals and legumes, can be largely prevented and harvesting work can thus be made easier. As a side effect, the reduced height of crops leads to savings in fertilizers. This also applies to ornamental plants, ornamental turf, sports turf or other green plants.

Eines der wichtigsten Probleme an reinen Grasbepflanzungen ist jedoch der Grasschnitt selbst, sei es an Grünanlagen in Wohngegenden, auf Industriegeländen, auf Sportplätzen, an Autostrassen, Flugpisten, Eisenbahndämmen oder Uferböschungen von Gewässern. In all diesen Fällen ist ein periodisches Schneiden des Rasens bzw. des Graswuchses notwendig. Dies ist nicht nur im Hinblick auf Arbeitskräfte und Maschinen sehr aufwendig, sondern bringt im Verkehrsbereich auch erhebliche Gefahren für das betroffene Personal und die Verkehrsteilnehmer mit sich.However, one of the most important problems with pure grass planting is the cutting of grass itself, be it in green areas in residential areas, on industrial sites, on sports grounds, on car roads, airstrips, railway embankments or bank embankments of water. In all of these cases, periodic cutting of the lawn or grass growth is necessary. This is not only very complex in terms of labor and machinery, but also entails considerable dangers for the personnel and road users involved in the transport sector.

Es besteht daher gerade in Gebieten mit grossen Verkehrsnetzen ein dringendes Bedürfnis, die im Hinblick auf die Verfestigung von Seitenstreifen und Böschungen an Verkehrswegen notwendige Grasnarbe einerseits zu erhalten und zu pflegen, andererseits aber mit einfachen Massnahmen während der gesamten Vegetationsperiode auf einer mittleren Wuchshöhe zu halten. Dies wird durch Applikation erfindungsgemässer Wirkstoffe der Formel I auf sehr günstige Weise erreicht.There is therefore an urgent need, especially in areas with large traffic networks, to maintain and maintain the turf necessary for the consolidation of verges and embankments on traffic routes, but also to keep them at an average height during the entire growing season with simple measures. This is achieved in a very favorable manner by applying active compounds of the formula I according to the invention.

In analoger Weise kann durch Behandlung von Bäumen, Sträuchern und Hecken, vort allem in Wohn- und Industriegebieten, mit erfindungsgemässen Verbindungen der Formel 1 die arbeitsaufwendige Schnitterarbeit rerduziert werden.In an analogous manner, by treating trees, shrubs and hedges, especially in Residential and industrial areas, with the compounds of formula 1 according to the invention, the labor-intensive cutting work can be reduced.

Durch den Einsatz erfindungsgemässer Wirkstoffe der Formel 1 können auch das Triebwachstum und/oder die Fruchtbarkeit von Obstbäumen und Reben vorteilhaft beeinflusst werden.The use of active compounds of the formula 1 according to the invention can also advantageously influence the growth of shoots and / or the fertility of fruit trees and vines.

Zierpflanzen mit starkem Längenwachstum können durch Behandlung mit erfindungsgemässen Wirkstoffen als kompakte Topfpflanzen gezogen werden.Ornamental plants with strong growth in length can be grown as compact potted plants by treatment with active substances according to the invention.

Die Wirkstoffe der Formel I finden auch Anwendung zur Hemmung des Wachstums unerwünschter Geiztriebe, z.B. bei Tabak und Zierpflanzen, wodurch das arbeitsintensive Ausbrechen dieser Triebe von Hand vermieden wird, ferner zur Austriebhemmung bei lagernden Knollen, beispielsweise bei Zierpflanzenknollen, bei Zwiebeln und Kartoffeln, und schliesslich zur Ertragssteigerung bei stark vegetativ wachsenden Kulturpflanzen, wie Soja und Zuckerrohr, indem durch Applikation erfindungsgemässer Wirkstoffe der Uebgergang von der vegetativen zur generativen Wachstumsphase beschleunigt wird.The active compounds of the formula I are also used to inhibit the growth of undesired poultry drives, e.g. in tobacco and ornamental plants, which avoids the labor-intensive breakout of these shoots by hand, also to prevent shoots in stored bulbs, for example in ornamental plant bulbs, in onions and potatoes, and finally to increase the yield in crops which grow strongly vegetatively, such as soybeans and sugar cane, by application active ingredients according to the invention the transition from the vegetative to the generative growth phase is accelerated.

Bevorzugt setzt man die erfindungsgemässen Wirkstoffe der Formel zur Wachstumshemmung an Gräsern, Getreidekulturen, Tabak, Soja und Zierpflanzen ein.The active compounds of the formula according to the invention are preferably used to inhibit the growth of grasses, cereal crops, tobacco, soybeans and ornamental plants.

Die Aufwandmengen sind verschieden und von Applikationszeitpunkt abhängig. Sie liegen im allgemeinen zwischen 0,1 und 5 kg Wirkstoff pro Hektar, bei Applikation vor dem Auflaufen der Pflanzen und für die Behandlung von bestehenden Kulturen vorzugsweise bis zu 4 kg pro Hektar.The application rates are different and depend on the time of application. They are generally between 0.1 and 5 kg of active ingredient per hectare, preferably up to 4 kg per hectare when applied before emergence of the plants and for the treatment of existing crops.

Grosse wirtschaftliche Bedeutung hat die Erleichterung der Fruchtabszission bei der mechanischen und manuellen Ernte von Oliven und Citrusfrüchten gewonnen. Blattabszissionswirkung und Defoliation ist bei der Baumwollernte von Bedeutung.The facilitation of fruit removal in the mechanical and manual harvesting of olives and citrus fruits has gained great economic importance. Leaf absorbency and defoliation is important in the cotton harvest.

Die Entfaltung der Wirkung der erfindungsgemässen Wirkstoffe erfolgt sowohl über die oberirdischen Pflanzenteilte (Kontaktwirkung), insbesondere die Blätter, als auch über den Boden, als preemergentes Herbizid (Keimhemmung).The development of the action of the active compounds according to the invention takes place both via the parts of the plants above ground (contact action), in particular the leaves, and also via the soil, as a pre-allergenic herbicide (inhibition of germs).

Die Wirkung als starke Wachstumshemmer zeigt sich darin, dass die meisten post-emergent behandelten Pflanzenarten nach dreiwöchiger Versuchsdauer einen Wachstumsstillstand zeigen, wobei die behandelten Pflanzenteile eine dunkelgrüne Färbung annehmen. Die Blätter fallen aber nicht ab.The effect as a strong growth inhibitor can be seen in the fact that most post-emergent treated plant species show a growth standstill after three weeks of experiment, whereby the treated plant parts take on a dark green color. The leaves do not fall off.

Diese Wuchshemmung tritt bei einigen Pflanzenarten schon bei einer Dosierung von 0,5 kg/ha und darunter auf.This inhibition of growth occurs in some plant species at a dosage of 0.5 kg / ha and below.

Da nicht alle Pflanzenarten gleich stark gehemmt werden, ist bei Wahl einer bestimmten niederen Dosierung ein selektiver Einsatz möglich.Since not all plant species are inhibited to the same extent, selective use is possible if a certain low dosage is selected.

Die erfindungsgemässen Wirkstoffe sind auch interessant Kombinationspartner für eine Reihe von Herbiziden der Phenylharnstoff- und Triazinreihe in Getreidekulturen, Mais, Zuckerrohr bezw. im Obst-und Weinbau.The active compounds according to the invention are also interesting combination partners for a number of herbicides of the phenylurea and triazine series in cereal crops, maize, sugar cane and. in fruit and wine growing.

In Gebiet mit erhöhter Erosionsgefahr können die erfindungsgemässen Wirkstoffe als Wuchshemmer in den verschiedensten Kulturen eingesetzt werden.In areas with an increased risk of erosion, the active compounds according to the invention can be used as growth inhibitors in a wide variety of crops.

Dabei wird die Unkrautdecke nicht beseitigt, sondern nur so stark gehemmt, dass keine Konkurrenzierung der Kulturpflanzen mehr auftritt.The weed cover is not removed, but only so strongly inhibited that the crop plants no longer compete.

Die Wirkstoffe der Formel zeichnen sich überdies durch eine sehr starke pre-emergente Herbizid- wirkung aus, sind also auch ausgeprägte Keimungshemmer.The active ingredients of the formula are also characterized by a very strong pre-emergent herbicide effect, so they are also pronounced germination inhibitors.

Zum Nachweis der Brauchbarkeit als Herbizide (pre- und post-emergent) und als Wuchshemmer dienten folgende Testmethoden:The following test methods were used to demonstrate the usability as herbicides (pre- and post-emergent) and as growth inhibitors:

Pre-emergence Herbizid-Wirkung (Keimungshemmung)Pre-emergence herbicide effect (inhibition of germination)

Im Gewächshaus wird unmittelbar nach der Einsaat der Versuchspflanzen in Saatschalen die Erdoberfläche mit einer wässerigen Suspension der Wirkstoffe, erhalten aus einem 25%-igen Spritzpulver, behandelt. Es wurden vier verschiedene Konzentrationsreihen angewendet, entsprechend 4, 2, 1 und 0,5 kg Wirksubstanz pro Hektar. Die Saatschalen werden im Gewächshaus bei 22-25°C und 50-70% rel. Luftfeuchtigkeit gehalten und der Versuch nach 3 Wochen ausgewertet und die Resultate nach folgender Notenskala bonitiert:

  • 1 = Pflanzen nicht gekeimt oder total abgestorben
  • 2-8 = Zwischenstufen der Schädigung
  • 9 = Pflanzen ungeschädigt (wie unbehandelte Kontrolle).
Immediately after sowing the test plants in seed trays, the earth's surface is treated in the greenhouse with an aqueous suspension of the active ingredients, obtained from a 25% wettable powder. Four different concentration series were used, corresponding to 4, 2, 1 and 0.5 kg of active substance per hectare. The seed pans are in the greenhouse at 22-25 ° C and 50-70% rel. Humidity and the test evaluated after 3 weeks and the results were rated according to the following grading scale:
  • 1 = plants not germinated or totally dead
  • 2-8 = intermediate stages of damage
  • 9 = plants undamaged (like untreated control).

Post-emergente Herbizid-Wirkung (Kontakherbizid)Post-emergent herbicide effect (contact herbicide)

Eine grössere Anzahl (mindestens 7) Unkräuter und Kulturpflanzen, sowohl monocotyle wie dicotyle, wurden nach den Auflaufen (im 4 - bis - 6 - Blattstadium) mit einer wässerigen Wirkstoffemulsion in Dosierungen von 0,5; 1; 2 und 4 kg Wirksubstanz pro Hektar auf die Pflanzen gespritzt und diese bei 24-26°C und 45-60% rel. Luftfeuchtigkeit gehalten. 5 Tage und 15 Tage nach Behandlung wird der Versuch ausgewertet und das Ergebnis wie im pre-emergent-Versuch nach derselben Notenskala bonitiert.A larger number (at least 7) of weeds and crop plants, both monocotyledon and dicotyledon, were treated with an aqueous active ingredient emulsion in doses of 0.5; 1; 2 and 4 kg of active ingredient per hectare sprayed onto the plants and these at 24-26 ° C and 45-60% rel. Humidity kept. 5 days and 15 days after treatment, the test is evaluated and the result is rated according to the same grading scale as in the pre-emergent test.

Die geprüften Verbindungen gemäss der Erfindung zeigten auf einigen Pflanzen ausgeprägte kontaktherbizide Wirkung und auf vielen Pflanzen Wachstumsstillstand als Symptom der wachstumshemmenden Eigenschaften.The tested compounds according to the invention showed pronounced contact herbicidal activity on some plants and growth arrest on many plants as a symptom of the growth-inhibiting properties.

Wuchshemmung bei GräsernInhibition of growth in grasses

In Kunststoffschalen mit Erde-Torf-Sand-Gemisch (6:3:1) wurden Samen der Gräser Lolium perenne, Poa pratensis, Festuca ovina und Dactylis glomerata ausgesät und normal bewässert. Die aufgelaufenen Gräser wurden wöchentlich bis auf 4 cm Höhe zurückgeschnitten und 40 Tage nach der Aussaat und 1 Tag nach dem letzten Schnitt mit wässerigen Spritzbrühen eines Wirkstoffs der Formel bespritzt. Die Wirkstoffmenge betrug umgerechnet 5 kg Aktivsubstanz pro Hektar. 10 und 21 Tage nach Applikation wurde das Wachstum der Gräser beurteilt.Seeds of the grasses Lolium perenne, Poa pratensis, Festuca ovina and Dactylis glomerata were sown in plastic trays with a soil-peat-sand mixture (6: 3: 1) and watered normally. The accumulated grasses were cut back to a height of 4 cm weekly and sprayed with aqueous spray liquors of an active ingredient of the formula 40 days after sowing and 1 day after the last cut. The amount of active ingredient was the equivalent of 5 kg of active ingredient per hectare. The growth of the grasses was assessed 10 and 21 days after application.

Wuchshemmung bei GetreideInhibition of growth in cereals

In Kunststoffbechern wurde Sommerweizen (Triticum aestivum), Sommergerste (Hordeum vulgare) und Roggen (Secale) in sterilisierter Erde angesät und im Gewächshaus gezogen. Die Getreidesprösslinge werden 5 Tage nach Aussaat mit einer Spritzbrühe des Wirkstoffs behandelt. Die Blattapplikation entsprach 6 kg Wirkstoff pro Hektar. Die Auswertung erfolgt nach 21 Tage.In plastic Echern b spring wheat (Triticum aestivum), spring barley (Hordeum vulgare) and rye (Secale) were sown in sterilized soil and grown in the greenhouse. The grain sprouts are treated with a spray mixture of the active ingredient 5 days after sowing. The leaf application corresponded to 6 kg of active ingredient per hectare. The evaluation takes place after 21 days.

Die erfindungsgemässen Wirkstoffe bewirken eine merkliche Wuchshemmung sowohl bei den Gräsern wie beim Getreide.The active substances according to the invention cause a noticeable growth inhibition both in the grasses and in the cereals.

Claims (19)

1. A pyridyloxy-phenoxyalkanecarboxylic acid derivative of the formula I
Figure imgb0062
wherein
A is the cyano group, a radical -COB or a 2-oxazoline radical which is unsubstituted or substituted by one or more methyl groups,
B is a radical -OR3, -SR4 or -NR5R6,
C is halogen, C,-C4alkyl or nitro,
D is hydrogen, has the same meaning as C, or is C1-C4alkoxy, C1-C4alkylthio, cyano, C1-C4alkyl- sulfynyl, C1-C4alkylsulfonyl, thiocarbamide (-CSNH2), mono or di-C,-C4alkylsulfamoyl,
E has the same meaning as C, or is C1-C4mono- or dialkylamine, C1-C5alkoxycarbonyl, C2-C8alkoxyalkyl, cyano, or trifluoromethyl,
n is 0, 1 or 2,
R1 is hydrogen, Cl-C4alkyl, C2-C8alkoxyalkyl, C1-C4haloalkyl,
R2 is hydrogen, C1-C4alkyl, carbonyl, C1-C5alkoxycarbonyl,
1 R3 is hydrogen or the cation of a base -Mm⊕, m

wherein M is an alkali metal cation or an alkaline earth metal cation or a Fe, Cu, Zn or
Figure imgb0063
and m as integer 1, 2 or 3 corresponds to the valency of the cation, whilst Ra, Rb, Re und Rd, each independently of the other, are hydrogen, benzyl or a C1-C4alkyl radical which is unsubstituted or substituted by -OH, ―NH2 or C1-C4alkoxy; and
R3 is further
C1-C8alkoxy, C2-C8alkoxyalkoxy; C3-C8alkenyloxy, C1-C8alkylthio, C2-C8alkanoyl, C2-C8acyloxy, C2-C8alkoxycarbonyl, carbamoyl; bis(C1-C4alkyl)amino, tris(C1-C4alkyl)-ammonio, C3-C8cycloalkyl, C3-Cscycloalkenyl, and also by a phenyl, phenoxy or pyridyl, piperidyl, morpholyl, pyrolidinyl or furyl radical which is unsubstituted or is itself substituted by one or more halogen atoms, C1-C4alkyl or C1-C4alkoxy groups;
- a C3-C10alkenyl radical which is unsubstituted or substituted by 1 to 4 halogen atoms or monosubstituted by phenyl or methoxycarbonyl;
- a C3-C8alkynyl radical;
- a C3-C12cycloalkyl radical which is unsubstituted or substituted by halogen or C1-C4alkyl;
- a C3-C8cycloalkylene radical;
- a phenyl radical which is unsubstituted or substituted by one or more halogen atoms, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, NO2, CF3, COOH, CN, OH, S03H, NH2 or -NH(Cl-C4alkyl) or -N(C1-C4alkyl)2 groups;
- an oxirane, piperidino, morpholino, pyrrolidino or furane ring;
R4 is a C1-C12alkyl radical which is unsubstituted or substituted by C1-C8alkoxy, C2- C8alkoxycarbonyl, C3-C8cycloalkyl, also by a phenyl, piperidino, morpholino, pyrrolidino or furane ring, which is unsubstituted or is itself substituted by one or more halogen atoms, C1-C4alkyl or C1-C4alkoxy groups;
- a C3-C12alkenyl radical;
- a C3-C12 cycloalkyl radical which is unsubstituted or substituted by Cl-C4alkyl;
- a phenyl radical which is unsubstituted or substituted by one or more halogen atoms, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, NO2 or CF3 groups;
- a piperidino, morpholino, pyrrolidino or furane ring;
R5 and R6, each independently of the other, are C1-C8alkyl which can be substituted by halogen, hydroxyl or cyano and/or interrupted in the chain by oxygen or carboxyloxy,
- C3-C6alkenyl, alkynyl or cycloalkyl, phenyl or benzyl which can be substituted by halogen, C1-C4alkyl; C1-C4alkoxy, NO2 or CF3;
- or together with the nitrogen atom to which they are attached are also a piperidino, morpholino or pyrrolidino ring,

with the proviso that the alkanecarboxylic acid radical
Figure imgb0064
may not be in the para-position to an unsubstituted or substituted 2-pyridyloxy radical.
2. A compound according to claim 1 of the formula
Figure imgb0065
wherein each of C and D is halogen or D is nitro, cyano, C1-C4alkyl or thiocarbamide, and E is hydrogen or trifluoromethyl, whilst A, n, R1 and R2 are as defined for formula I in claim 1.
3. A compound according to claim 1 of the formula
Figure imgb0066
wherein each of C and D is halogen or D is nitro, cyano, C1-C4alkyl or thiocarbamide and E is hydrogen or trifluoromethyl, whilst A, n, R1 and R2 are as defined for formula I in claim 1.
4. A compound according to claim 1 of the formula
Figure imgb0067
wherein each of C and D is halogen or D is nitro, cyano, C1-C4alkyl or thiocarbamide, and E is hydrogen or trifluoromethyl, whilst A, n, R1 and R2 are as defined for formula I in claim 1.
5. A compound according to claim 1 of the formula
Figure imgb0068
wherein "Hal" is halogen, D is halogen or nitro, whilst R3 is as defined for formula I in claim 1.
6. A compound of the formula I according to claim 1, wherein
A is a cyano, -COB or
Figure imgb0069
B is a radical -OR3, SR3 or NR5R6,
C is halogen,
D is halogen, C1-C4alkyl, cyano, nitro or thiocarbamide,
E is hydrogen, halogen, trifluoromethyl, C1-C4alkyl, C1-C4alkoxycarbonyl or nitro,
n is 0, 1 or 2,
R1 is hydrogen or C1-C4alkyl,
R2 is hydrogen or C1-C4alkyl,
R3 is hydrogen, the cation of an alkali metal or alkaline earth metal or of a quaternary ammonium salt, C1-C6alkyl, phenyl which is unsubstituted or substituted by halogen, cyano, nitro or C,-C4alkoxy,
R4 is C1-C4alkyl, alkenyl or alkynyl,
R5 and R6, each independently of the other, is hydrogen or Cl-C4alkyl which is unsubstituted or substituted by halogen, cyano, hydroxy or C1-C4alkyl,
R5 and R6 together are a piperidino, morpholino or pyrrolidino ring.
7. a-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-chlorophenoxyJ propionic acid methyl ester.
8. a-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenoxy] propionic acid methyl ester.
9. α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-nitrophenoxy] propionic acid methyl ester.
10. α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-chlorophenoxy] propionic acid isopropyl ester.
11. α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-nitrophenoxy] propionamide.
12. a-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-nitrophenoxy] propionic acid ethylamide.
13. A process for the manufacture of a novel pyridyloxyphenoxyalkanecarboxylic acid derivative of the formula I according to claim 1, characterised in that a compound of the formula II
Figure imgb0070
wherein C, D, E and n are as defined for formula I and Hal is a halogen atom, preferably chlorine or bromine, is reacted in a manner known per se with a hydroxyphenoxyalkanecarboxylic acid derivative of the formula III
Figure imgb0071
wherein A, C, D and R2 are as defined for formula I, in the presence of an acid acceptor.
14. A process for the production of a pyridyloxyphenoxyalkanecarboxylic acid derivative of the formula I according to claim 1, characterised in that a pyridyloxyhydroxyphenyl ether of the formula IV
Figure imgb0072
wherein C, D, E and n are as defined for formula I, is reacted in a manner known per se with an α-halocarboxylic acid derivative of the formula V
Figure imgb0073
wherein A, R1 and R2 are as defined for formula I and Hal is a halogen atom, preferably chlorine or bromine, in the presence of an acid acceptor.
15. A herbicidal and plant growth-regulating composition, characterised in that it contains, as active ingredient, at least one pyridyloxyphenoxyalkanecarboxylic acid derivative of the formula I according to claim 1.
16. Use of a pyridyloxyphenoxyalkanecarboxylic acid derivative of the formula I according to claim 1 or of a composition containing such a compound as herbicide.
17. Use of a pyridyloxyphenoxyalkanecarboxylic acid derivative of the formula I according to claim 1 or of a composition containing such a compound for influencing plant growth.
EP78100209A 1977-06-29 1978-06-21 Pyridyloxy-phenoxy-alkanoic acid derivatives , processes for their preparation and their use as herbicides or plant growth regulators Expired EP0000176B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH802377 1977-06-29
CH8023/77 1977-06-29

Publications (2)

Publication Number Publication Date
EP0000176A1 EP0000176A1 (en) 1979-01-10
EP0000176B1 true EP0000176B1 (en) 1981-09-16

Family

ID=4333965

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100209A Expired EP0000176B1 (en) 1977-06-29 1978-06-21 Pyridyloxy-phenoxy-alkanoic acid derivatives , processes for their preparation and their use as herbicides or plant growth regulators

Country Status (17)

Country Link
US (5) US4329167A (en)
EP (1) EP0000176B1 (en)
JP (1) JPS5412379A (en)
AT (1) AT362956B (en)
AU (1) AU526393B2 (en)
BR (1) BR7804115A (en)
CA (1) CA1100964A (en)
CS (1) CS222264B2 (en)
DD (1) DD137879A5 (en)
DE (1) DE2861073D1 (en)
ES (1) ES471216A1 (en)
HU (1) HU180704B (en)
IL (1) IL55016A (en)
IT (1) IT1097282B (en)
PH (1) PH18510A (en)
TR (1) TR20086A (en)
ZA (1) ZA783719B (en)

Families Citing this family (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1110460B (en) * 1977-03-02 1985-12-23 Ciba Geigy Ag PRODUCTS THAT PROMOTE THE GROWTH OF PLANTS AND PRODUCTS THAT PROTECT PLANTS BASED ON BODY ETHERS AND BODY ESTERS THEIR PREPARATION AND USE
UA6300A1 (en) * 1977-07-21 1994-12-29 Ісіхара Сангіо Кайся Лтд HERBICIDAL COMPOSITION
TR19824A (en) * 1977-07-21 1980-01-24 Ishihara Sangyo Kaisha TRILOROMETHYLPIRIDOXIFENOXYPROPIONIC AS TUEREVLER AND HERBISIDES THAT CONTAIN THEM
US4491468A (en) * 1977-07-22 1985-01-01 The Dow Chemical Company Herbicidal trifluoromethyl pyridinyloxyphenoxy and pyridinylthiophenoxy propanenitriles and derivatives thereof
EP0028870B1 (en) * 1977-08-12 1988-03-16 Imperial Chemical Industries Plc Phenoxypyridine compound
CH632731A5 (en) * 1978-01-11 1982-10-29 Ciba Geigy Ag METHOD FOR PRODUCING ALKOXY-SUBSTITUTED POLYCYCLIC AROMATIC COMPOUNDS.
US4309210A (en) * 1978-12-01 1982-01-05 Ciba-Geigy Corporation Preemergence method of selectively controlling weeds in crops of cereals and composition therefor
JPS6033389B2 (en) * 1979-02-22 1985-08-02 日産化学工業株式会社 Heterocyclic ether phenoxy fatty acid derivative, its production method, and herbicide containing the derivative
JPS55151503A (en) * 1979-05-15 1980-11-26 Kumiai Chem Ind Co Ltd Sucrose content improver for sugar cane
EP0021613B1 (en) * 1979-06-20 1983-04-06 Imperial Chemical Industries Plc Pyridine derivatives, processes for preparing them, herbicidal compositions containing them and methods of killing plants therewith
US4326880A (en) * 1979-08-14 1982-04-27 Ciba-Geigy Corporation Derivatives of 5-(pyridyl-2-oxy)-2-nitrobenzoic acid, and herbicidal compositions containing them, and herbicidal methods for using same
US4311514A (en) * 1979-09-13 1982-01-19 Ciba-Geigy Corporation Sulfur-containing alkanecarboxylic acid derivatives with herbicidal and plant growth-regulating action, production thereof and method of use
US4738710A (en) * 1979-11-19 1988-04-19 Ici Australia Limited Herbicidal alkane carboxylic acid derivatives
AU541697B2 (en) * 1979-11-19 1985-01-17 Ici Australia Limited Quinoline derivatives
NZ197420A (en) * 1980-07-01 1984-04-27 Ici Australia Ltd -(quinazolin-(2-or 4-)(oxy,ylthio or amino)phen(oxy or ylthio)alkanoic acid derivatives
US4451284A (en) * 1981-07-28 1984-05-29 Ciba-Geigy Corporation Derivatives of 2-nitro-4- or -5-pyridyloxyphenylphosphonic acid, the preparation thereof, the use thereof as herbicides and/or plant growth regulators
US4371537A (en) * 1981-08-13 1983-02-01 The Dow Chemical Company Sulfur-substituted phenoxypyridines having antiviral activity
US4505743A (en) * 1981-12-31 1985-03-19 Ciba-Geigy Corporation α-[4-(3-Fluoro-5'-halopyridyl-2'-oxy)-phenoxy]-propionic acid derivatives having herbicidal activity
US4529438A (en) * 1982-03-23 1985-07-16 Zoecon Corp. Pyridyloxy-phenoxy-alkanoic acid esters and derivatives
US4518416A (en) * 1982-06-04 1985-05-21 Bayer Aktiengesellschaft Certain trimethyl silyl-lower-alkyl esters of pyridyloxy-phenoxy-lower alkanoic acids, compositions containing same and herbicidal method of use
CA1215067A (en) * 1982-10-18 1986-12-09 Sudarshan K. Malhotra 2-(6-phenoxy-3-nitro-2-pyridinoxy)-propionate compounds
US4558134A (en) * 1983-01-03 1985-12-10 The Dow Chemical Company Certain phenoxy-pyridine-carbonitriles having antiviral activity
US4486593A (en) * 1983-01-19 1984-12-04 The Upjohn Company 2-,3-, or 4-Pyridinylmethylamino arylic acids as thromboxane A2 synthetase and 5-lipoxygenase inhibitors
US4599105A (en) * 1983-06-20 1986-07-08 The Dow Chemical Company 2-[16-(3-fluoro-5-trifluoromethyl-pyridinyl-2-oxy)-3-nitro-phenoxy]-propionic acid derivatives, herbicidal compositions containing same and herbicidal method of use
US4539039A (en) * 1984-04-26 1985-09-03 The Dow Chemical Company Herbicidal (-3-fluoro-5-trifluoromethyl-pyridyl)oxy phenyloxime derivatives
US4775410A (en) * 1985-08-19 1988-10-04 Sandoz Ltd. 2-[4-(2-pyridinyloxy)phenoxy]propionyl-2-oxazolidinones
BR8801855A (en) * 1987-04-20 1988-11-22 Agro Kanesho Co Ltd HERBICIDE COMPOSITION UNDERSTANDING AS A ACTIVE INGREDIENT A PHENOXYPROPIONIC ACID DERIVATIVE DERIVATIVE AND PROCESS FOR THE PRODUCTION OF PHENOXYPROPIONIC ACER DERIVATIVES
US5205855A (en) * 1987-08-11 1993-04-27 Suntory Limited Herbicidally active phenoxyalkanecarboxylic acid derivatives
CA1257598A (en) * 1987-08-11 1989-07-18 Harukazu Fukami Herbicidally active phenoxyalkanecarboxylic acid derivatives
GB9005965D0 (en) * 1990-03-16 1990-05-09 Shell Int Research Herbicidal carboxamide derivatives
NZ238624A (en) * 1990-06-19 1994-08-26 Meiji Seika Co Pyridine derivatives, compositions, preparations and use thereof
GB9025828D0 (en) * 1990-11-28 1991-01-09 Shell Int Research Herbicidal carboxamide derivatives
TR25135A (en) * 1991-03-13 1992-11-01 Shell Int Research CARBODAMIDE DERIVATIVES WITH HERBISID PROPERTIES
CN109553574B (en) * 2018-12-27 2020-07-24 北京颖泰嘉和生物科技股份有限公司 Pyridine acid compound, preparation method thereof, herbicide composition and application thereof

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4003734A (en) 1974-01-22 1977-01-18 The Dow Chemical Company Substituted pyridinyloxy(thio)phenyl-acetamides, -ureas and urea derivatives and herbicidal compositions and methods containing said compounds
US3931201A (en) * 1974-01-22 1976-01-06 The Dow Chemical Company Substituted pyridinyloxy(thio)phenyl -acetamides, -ureas and urea derivatives
US4028092A (en) * 1974-01-22 1977-06-07 The Dow Chemical Company Substituted pyridinylalkoxy-, pyridinylalkylsulfonyl- and pyridinylalkylthiophenylurea herbicides
DK154074C (en) * 1974-10-17 1989-02-27 Ishihara Sangyo Kaisha ALFA- (4- (5 OR 3.5 SUBSTITUTED PYRIDYL-2-OXY) -PHENOXY) -ALKANE CARBOXYLIC ACIDS OR DERIVATIVES THEREOF USED AS HERBICIDES, HERBICIDES AND PROCEDURES
JPS51106735A (en) * 1975-03-13 1976-09-21 Ishihara Sangyo Kaisha JOSOZAI
JPS5327768B2 (en) * 1974-10-17 1978-08-10
JPS51139627A (en) * 1975-05-28 1976-12-02 Ishihara Sangyo Kaisha Ltd A herbicide
JPS51142537A (en) * 1975-05-30 1976-12-08 Ishihara Sangyo Kaisha Ltd A herbicide
GB1512189A (en) * 1975-10-29 1978-05-24 Ishihara Mining & Chemical Co Herbicidal composition and method of use thereof
JPS52131542A (en) * 1976-04-28 1977-11-04 Ishihara Sangyo Kaisha Ltd Phenoxypropionic acid derivatives and herbicides containing them
US4133675A (en) * 1976-07-23 1979-01-09 Ciba-Geigy Corporation Pyridyloxy-phenoxy-alkanecarboxylic acid derivatives which are effective as herbicides and as agents regulating plant growth
JPS54163582A (en) * 1978-06-09 1979-12-26 Ishihara Mining & Chemical Co 22phenoxyy55 trifluoromethypiridine compound

Also Published As

Publication number Publication date
EP0000176A1 (en) 1979-01-10
AU526393B2 (en) 1983-01-06
US4384882A (en) 1983-05-24
DE2861073D1 (en) 1981-12-03
US4443247A (en) 1984-04-17
IL55016A (en) 1982-02-28
ATA470878A (en) 1980-11-15
ES471216A1 (en) 1979-09-01
TR20086A (en) 1980-07-07
DD137879A5 (en) 1979-10-03
CA1100964A (en) 1981-05-12
IT7825083A0 (en) 1978-06-28
AU3751778A (en) 1980-01-03
US4329167A (en) 1982-05-11
US4433998A (en) 1984-02-28
AT362956B (en) 1981-06-25
HU180704B (en) 1983-04-29
CS222264B2 (en) 1983-06-24
IT1097282B (en) 1985-08-31
IL55016A0 (en) 1978-08-31
JPS5412379A (en) 1979-01-30
BR7804115A (en) 1979-02-20
US4425157A (en) 1984-01-10
ZA783719B (en) 1979-06-27
PH18510A (en) 1985-08-02

Similar Documents

Publication Publication Date Title
EP0000176B1 (en) Pyridyloxy-phenoxy-alkanoic acid derivatives , processes for their preparation and their use as herbicides or plant growth regulators
DE2732846C2 (en)
EP0004317B1 (en) Derivatives of phenoxy-alkanecarboxylic acids, their preparation, weed-killing products containing them and their use
DE2650604A1 (en) MEANS AND METHODS OF INFLUENCING PLANT GROWTH AND NEW 1-PHENYL-2-OXO-PYRROLIDINE-4-CARBONIC ACID DERIVATIVES
DE2657728C2 (en)
EP0017946B1 (en) Salts of alpha-aminoacetanilides, process for their preparation and their use as plant growth regulators
DE2548231A1 (en) 1- (BIS-TRIFLUOROMETHYLPHENYL) -2-OXOPYRROLIDINE-4-CARBONIC ACID DERIVATIVES, THEIR PRODUCTION AND USE AS PLANT GROWTH REGULATORS AND HERBICIDES
EP0003295B1 (en) Phenoxy-phenoxy-alkylcarboxylic acid derivatives with herbicidal activity, their preparation, compositions containing them and their use
EP0008624B1 (en) O-(pyridyloxy-phenyl)-lactic acid esters, process for their preparation and their use as herbicides and plant growth regulants
DE3133917A1 (en) 1-AMINO-CYCLOPROPANCARBONIC ACID METAL COMPLEX COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THE USE THEREOF AS PLANT GROWTH REGULATORS
EP0058347B1 (en) Benzyl-pyrimidinylalkyl ethers, process for their preparation, their use as plant growth regulation agents and fungicides, as well as intermediates and their preparation
DE2637886A1 (en) 3-PYRIDYL-OXY-ALCANCARBONIC ACID AMIDE
EP0050097B1 (en) Alpha-(pyridyl-2-oxy-phenoxy)-propionic-acid derivatives, process for their preparation and their use as herbicides and/or plant growth regulators
DE1567131A1 (en) Herbicidal composition and method for its application
EP0000474B1 (en) Substituted 3-(2'-nitro phenoxy)-alpha-phenoxy alcanoic acids and their derivatives, their preparation and their use as herbicides
EP0071572B1 (en) Derivatives of 2-nitro-4- or-5-pyridyloxy-phenylphosphonic acid, process for their preparation, their use as herbicides and/or regulators of plant growth and/or microbicides, as well as the intermediates used for their preparation, the process for their preparation and their use as herbicides
EP0030922A2 (en) Ethinyl-phenyl ureas, process for their preparation and their use as herbicides
EP0002757B1 (en) Phenoxy-phenylthio-lactic acid derivatives, their preparation, herbicides and plant-growth regulators containing them, as well as their use
EP0001641A1 (en) 2-(2'-Nitro-5-(2"-chloro-4"-trifluoromethylphenoxy)-phenoxy)-propionic acid-methoxyethyester, a composition containing this ester as active ingredient and its use as a herbicide.
DD262992A5 (en) NEMATICIDES AND INSECTICIDES COMPOSITION
EP0119457A1 (en) Agent for regulating the growth of plants
DE2709854A1 (en) HYDROXAMIC ACID DERIVATIVES FOR INFLUENCING PLANT GROWTH
DE3300056C2 (en) 3-Nitrobenzenesulfonanilide derivatives and fungicidal agents containing them
DE2601376A1 (en) PHENOXYCARBONIC ACID-ARYLOXY (THIO) CARBONYLAMINOMETHYLESTER, THE METHOD FOR THEIR PRODUCTION AND THEIR USE FOR REGULATING PLANT GROWTH
CH677664A5 (en)

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE CH DE FR GB NL

17P Request for examination filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE CH DE FR GB NL

Designated state(s): BE CH DE FR GB NL

REF Corresponds to:

Ref document number: 2861073

Country of ref document: DE

Date of ref document: 19811203

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19840521

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19840601

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19840630

Year of fee payment: 7

Ref country code: BE

Payment date: 19840630

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19840727

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19860101

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Effective date: 19870630

BERE Be: lapsed

Owner name: CIBA-GEIGY A.G.

Effective date: 19870630

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19880226

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19880301

GBPC Gb: european patent ceased through non-payment of renewal fee
REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19881117

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Effective date: 19890630

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT