EP0000474A1 - Substituted 3-(2'-nitro phenoxy)-alpha-phenoxy alcanoic acids and their derivatives, their preparation and their use as herbicides - Google Patents

Substituted 3-(2'-nitro phenoxy)-alpha-phenoxy alcanoic acids and their derivatives, their preparation and their use as herbicides Download PDF

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Publication number
EP0000474A1
EP0000474A1 EP78100218A EP78100218A EP0000474A1 EP 0000474 A1 EP0000474 A1 EP 0000474A1 EP 78100218 A EP78100218 A EP 78100218A EP 78100218 A EP78100218 A EP 78100218A EP 0000474 A1 EP0000474 A1 EP 0000474A1
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Prior art keywords
radical
substituted
halogen
formula
alkyl
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EP78100218A
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German (de)
French (fr)
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EP0000474B1 (en
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Otto Dr. Rohr
Georg Dr. Pissiotas
Dieter Dr. Dürr
Beat Dr. Böhner
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Novartis AG
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Ciba Geigy AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/39—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups
    • C07C205/42—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/43—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by esterified hydroxy groups having nitro groups or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • 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
    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C07C205/38—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to a carbon atom of a six-membered aromatic ring, e.g. nitrodiphenyl ethers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids

Definitions

  • the present invention relates to novel, herbicidal and regulating plant growth-acting phenoxy-phenoxy-alkanecarboxylic acid derivatives, processes for their preparation, compositions which contain these derivatives as an active ingredient and the use of these derivatives or compositions containing them to combat unwanted plant growth or for regulation the same.
  • alkyl radicals are both branched and unbranched and contain the given number of carbon atoms.
  • the radicals R 7 and R 8 are preferably hydrogen or lower alkyl groups. However, some of them can also be unsaturated or aromatic (phenyl) or araliphatic (benzyl) and both together with the nitrogen atom to which they are attached can form a 5-6-membered heterocycle.
  • Herbicidal active ingredients based on substituted diphenyl ethers have become known, e.g. from the Swiss patent specification No. 424 326. Recently, herbicidally active phenoxy-phenoxyalkane carboxylic acids, see e.g. DOS 2 433 067.
  • This invention opens up a new group of phenoxy-phenoxy-alkane carboxylic acid derivatives which are able to influence the growth of the plants in a manner which is advantageous for agriculture in small amounts.
  • the new active compounds of the formula I according to the present invention have a general herbicidal action which is not specifically directed against grasses, especially in the case of post-emergent use and can be used as weed agents in monocotyledonous and dicotyledonous crops.
  • the compounds of the present invention are not very toxic to warm-blooded animals, and their application should not cause any problems.
  • the suggested application rates are between 0.1 and 5 kg per hectare.
  • Hal is a halogen atom, preferably chlorine or bromine, while A, R 1 , R 2 and R 4 have the meaning given in formula I.
  • a nitro group By nitrating in glacial acetic acid, ethylene chloride or sulfuric acid, a nitro group can be introduced into the still free para position of the diphenyl ether. A chlorine atom can be introduced into this position by treatment with chlorine in glacial acetic acid. If R 3 has the meaning of cyan or bromine, the chlorine atom at this stage is converted, for example. replaced with KCN (see Adv.Chem.Ser. 132 (1974) 252 or J.Organomet.Chem. 54 (1973) C 57) or KBr or NaBr or the aniline obtained by reduction of the NO 2 group is subjected to a Sandmeyer -Reaction.
  • the inventive method for the preparation of phenoxy - phenoxy-alkanecarboxylic acid derivatives of formula I is characterized in that, in per se known manner, a diphenyl ether of the formula II wherein X is hydrogen or the cation of an alkali or alkaline earth metal and R 3 and R 4 have the meaning given in formula I, with a-halogeno-carboxylic acid derivative of the formula III wherein A, R 1 and R 2 have the meaning given in formula I, while Hal represents a halogen atom, preferably chlorine or bromine.
  • the reactants of formulas II and III are used in approximately stoichiometric amounts.
  • the reaction is advantageously carried out in the presence of an organic solvent which is inert to the reactants, at a temperature between room temperature and the boiling point of the reaction mixture, if appropriate i.e. when X is hydrogen, in the presence of an acid binding agent.
  • reaction product is isolated, e.g. by distilling off the solvent. and pouring the residue into ice water.
  • Organic aprotic solvents which can dissolve the reaction partners but do not react with them are particularly suitable as solvents for this reaction.
  • the condensing agents are inorganic bases such as NaOH, KOH, NaOCH 3 etc. but also organic bases such as tertiary amines.
  • phenoxy-phenoxy-alkane-carboxylic acid derivatives of the formula I are stable compounds which are soluble in customary organic solvents, such as alcohols, ethers, ketones, dimethylformamide, dimethyl sulfoxide, etc.
  • the invention also relates to herbicidal and plant growth regulating agents which receive a new active ingredient of the formula I, and to processes for pre- and post-emergent weed control and for inhibiting the growth of monocotyledonous and dicotyledonous plants, in particular grasses, cereals, soybeans and tobacco stingers.
  • the agents according to the invention can be present in the usual formulations.
  • 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.
  • the active compounds of the formula I can be formulated, for example, as follows (parts mean parts by weight):
  • the following substances are used to produce a) 5% and b) 2% dust:
  • 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 carriers and then mixed and ground. This gives wettable powders of excellent wettability and suspension which, when diluted with water, give suspensions of any desired concentration of active compound.
  • 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-emergence herbicide effect as well as growth inhibition.
  • Agents according to the invention which contain at least one compound of the formula I as active component are particularly suitable for inhibiting and controlling the plant growth of monocotyledonous 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.
  • monocotyledonous 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 new 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 plum. 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.
  • the labor-intensive cutting work can be reduced by treating trees, shrubs and hedges, especially in residential and industrial areas, with compounds of the formula I according to the invention.
  • active compounds of the formula I according to the invention can also advantageously influence the growth of shoots and / or the fertility of fruit trees and vines.
  • 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 substances according to the invention the transition from the vegetative to the generative growth phase is accelerated.
  • the active compounds of the formula I 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, when applied before emergence of the plants and for the treatment of existing crops, preferably up to 4 kg per hectare.
  • active ingredients of formula 1 and compositions containing them are also suitable for other influences on plant growth, such as, in particular, to facilitate fruit and leaf abscess by forming separating tissues on the fruit and leaf stems, which results in a considerable reduction in the tear-off force and thus brings great harvest relief.
  • 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 or. in fruit and wine growing.
  • the weed cover is not removed, but only so strongly inhibited that the crop plants no longer compete.
  • the new active ingredients of Formula I are also characterized by a very strong pre-emergent herbicide effect, so they are also pronounced germination inhibitors,
  • the tested compounds according to the present 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 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 I 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.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

1. A 3-(2'-nitrophenoxy)-alpha-phenoxyalkanecarboxylic acid derivative of the general formula I see diagramm : EP0000474,P15,F3 wherein R1 represents hydrogen, C1 -C4 alkyl or C2 -C8 alkoxyalkyl, R2 represents hydrogen or C1 -C4 alkyl, R3 represents halogen, cyano or nitro, R4 represents halogen, cyano or trifluoromethyl, A represents cyano or the group -COB, B represents a radical OR5 , SR6 or NR7 R8 , R5 represents hydrogen or the cation of a base 1/n M**n (anion), wherein M represents an alkali metal or alkaline earth metal cation or an ammonium radical see diagramm : EP0000474,P15,F4 n as integer 1, 2 or 3 corresponds to the valency of the cation, whilst Ra , Rb , Rc and Rd , each independently of the other, represent hydrogen, benzyl or an alkyl radical which is unsubstituted or substituted by -OH, -NH2 or C1 -C4 alkoxy ; and R5 further represents, a C1 -C8 alkyl radical which can be unsubstituted or substituted by halogen, cyano, nitro, hydroxyl or a 5- to 6-membered nitrogen-containing heterocyclic ring system, and a C2 -C8 alkyl radical which can be interrupted by oxygen, sulphur, nitrogen, carbonyl or carbonyloxy, a C3 -C6 cycloalkyl radical, a C3 -C6 alkenyl or alkynyl radical which can be substituted by halogen, a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, C1 -C4 alkyl, C1 -C4 alkoxy or trifluoromethyl, R6 represents a C1 -C8 alkyl radical which can be substituted by halogen, cyano, nitro or hydroxyl or interrupted by oxygen, sulphur, nitrogen, carbonyl or carbonyloxy, a C3 -C6 cycloalkyl radical, a C3 -C6 alkenyl or alkynyl radical which can be substituted by halogen, a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, C1 -C4 alkyl, C1 -C4 alkoxy or trifluoromethyl, R7 represents hydrogen, a C1 -C8 alkyl radical which can be substituted by halogen, cyano or hydroxyl, and a C2 -C8 alkyl radical which can be interrupted by oxygen, R8 represents a C1 -C4 alkyl radical or a C3 -C4 alkyl radical, and R7 and R8 , together with the nitrogen atom to which they are attached, also represent a 5- to 6-membered heterocyclic radical which can be interrupted by oxygen, sulphur, an imino, C1 -C4 alkylimino or phenylimino group.

Description

Die vorliegende Erfindung betrifft neue, herbizid und regulierend auf das Pflanzenwachstum einwirkende Phenoxy-phenoxy-alkancarbonsäure-Derivate, Verfahren zu ihrer Herstellung, Mittel die diese Derivate als Wirkstoff enthalten sowie die Verwendung dieser Derivate oder sie enthaltender Mittel zur Bekämpfung von unerwünschtem Pflanzenwachstum oder zur Regulierung desselben.The present invention relates to novel, herbicidal and regulating plant growth-acting phenoxy-phenoxy-alkanecarboxylic acid derivatives, processes for their preparation, compositions which contain these derivatives as an active ingredient and the use of these derivatives or compositions containing them to combat unwanted plant growth or for regulation the same.

Die neuen Phenoxy-phenoxy-alkancarbonsäure-Derivate entsprechen der Formel I

Figure imgb0001
worin R1 Wasserstoff, C1-C4 Alkyl oder C2-C8 Alkoxyalkyl,

  • R2 Wasserstoff oder C1-C4 Alkyl,
  • R3 Halogen, Cyano oder Nitro,
  • R4 Halogen, Cyano oder Trifluormethyl;
  • . A Cyan oder die Gruppe -COB,
  • B einen Rest OR5, SR6 oder NR7R8,
  • R5 Wasserstoff oder das Kation einer Base 1 Mn ⊕,
wobei M ein Alkali-, Erdalkalimetall-Kation oder einen Ammoniorest
Figure imgb0002
  • n als ganze Zahl 1, 2 oder 3 die Wertigkeit des Kations berücksichtigt, während Ra, Rb, Rc und Rd unabhängig voneinander Wasserstoff, Benzyl oder einen gegebenenfalls durch -OH, -NH2 oder C1-C4 Alkoxy substituierten C1-C4 Alkylrest bedeuten,
  • R5 bedeutet weiter einen C1-C8 Alkylrest, der unsubstituiert oder durch Halogen, Cyan, Ntro, Hydroxyl oder einen 5-6 gliedrigen Stickstoff enthaltenden Heterocyclus substituiert sowie einen C2-C8 Alkylrest der durch Sauerstoff, Schwefel, Stickstoff, Carbonyl oder Carbonyloxy unterbrochen sein kann,
  • einen C3-C6 Cycloalkylrest,
  • einen C3-C6 Alkenyl- oder Alkinylrest der durch Halogen substituiert sein kann,
  • einen Phenyl oder Benzylrest der durch Halogen, Cyan, Nitro, C1-C4 Alkyl, C1-C4 Alkoxy oder Trifluormethyl substituiert sein kann,
  • R6 bedeutet einen C1-C8 Alkylrest der durch Halogen, Cyano, Nitro oder Hydroxyl sub- stituiert, oder durch Sauerstoff, Schwefel, Stickstoff, Carbonyl oder Carbonyloxy unterbrochen sein kann,
  • einen C3-C6 Cycloalkylrest,
  • einen C3-C6 Alkenyl- oder Alkinylrest, der durch Halogen substituiert sein kann,
  • einen Phenyl- oder Benzylrest, der durch Halogen, Cyan, Nitro, Cl-C4 Alkyl, C1-C4 Alkoxy oder Trifluormethyl substituiert sein kann,
  • R7 Wasserstoff, einen C1-C8 Alkylrest, der durch Halogen, Cyan oder Hydroxyl substituiert sein kann, sowie einen C2-C8 Alkylrest, der durch Sauerstoff unterbrochen sein kann,
  • R8 Wasserstoff, einen C1-C4 Alkylrest oder einen C3-C4 Alkylrest,
  • R7 und R8 zusammen mit dem Stickstoffatom an das sie gebunden sind, auch einen 5-6 gliedrigen heterocyclischen Rest, der durch Sauerstoff, Schwefel, eine Imino-, C1-C4 Alkylimino- oder Phenyliminogruppe unterbrochen sein kann.
The new phenoxy-phenoxy-alkane carboxylic acid derivatives correspond to the formula I.
Figure imgb0001
 wherein R 1 is hydrogen, C 1 -C 4 alkyl or C 2 -C 8 alkoxyalkyl,
  • R2 is hydrogen or C 1 -C 4 alkyl,
  • R 3 halogen, cyano or nitro,
  • R 4 is halogen, cyano or trifluoromethyl;
  • . A cyan or the group -COB,
  • B a residue OR 5 , SR 6 or NR 7 R 8 ,
  • R 5 is hydrogen or the cation of a base 1 M n ⊕,
where M is an alkali, alkaline earth metal cation or an ammonium radical
Figure imgb0002
  • n takes into account the valence of the cation as an integer 1, 2 or 3, while R a , R b , R c and R d independently of one another are hydrogen, benzyl or an optionally substituted by -OH, -NH 2 or C 1 -C 4 alkoxy Are C 1 -C 4 alkyl,
  • R 5 also means a C 1 -C 8 alkyl radical which is unsubstituted or substituted by halogen, cyano, nitro, hydroxyl or a 5-6 membered nitrogen-containing heterocycle and a C 2 -C 8 alkyl radical which is substituted by Oxygen, sulfur, nitrogen, carbonyl or carbonyloxy can be interrupted,
  • a C 3 -C 6 cycloalkyl radical,
  • a C 3 -C 6 alkenyl or alkynyl radical which can be substituted by halogen,
  • a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or trifluoromethyl,
  • R 6 represents a C 1 -C 8 alkyl radical which can be substituted by halogen, cyano, nitro or hydroxyl, or can be interrupted by oxygen, sulfur, nitrogen, carbonyl or carbonyloxy,
  • a C 3 -C 6 cycloalkyl radical,
  • a C 3 -C 6 alkenyl or alkynyl radical which can be substituted by halogen,
  • a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or trifluoromethyl,
  • R 7 is hydrogen, a C 1 -C 8 alkyl radical which can be substituted by halogen, cyano or hydroxyl, and a C 2 -C 8 alkyl radical which can be interrupted by oxygen,
  • R 8 is hydrogen, a C 1 -C 4 alkyl radical or a C 3 -C 4 alkyl radical,
  • R 7 and R 8 together with the nitrogen atom to which they are attached also form a 5-6-membered heterocyclic radical which can be interrupted by oxygen, sulfur, an imino, C 1 -C 4 alkylimino or phenylimino group.

In dieser Formel sind die Alkylreste sowohl verzweigt wie unverzweigt und enthalten die gegebene Anzahl Kohlenstoffatome. Die Reste R7 und R8 sind bevorzugt Wasserstoff oder niedere Alkylgruppen. Einzelne unter ihnen können jedoch auch ungesättigt oder aromatisch (Phenyl) oder araliphatisch (Benzyl) sein und beide können zusammen mit dem Stickstoffatom an das sie gebunden sind, einen 5-6 gliedrigen Heterocyclus bilden.In this formula the alkyl radicals are both branched and unbranched and contain the given number of carbon atoms. The radicals R 7 and R 8 are preferably hydrogen or lower alkyl groups. However, some of them can also be unsaturated or aromatic (phenyl) or araliphatic (benzyl) and both together with the nitrogen atom to which they are attached can form a 5-6-membered heterocycle.

Es sind herbizide Wirkstoffe auf der Basis von substituierten Diphenyläthern bekannt geworden, z.B. aus der schweizerischen Patentschrift No. 424 326. Neuerdings wurden herbizid wirksame Phenoxy-phenoxyalkancarbonsäuren, siehe z.B. die DOS 2 433 067, beschrieben.Herbicidal active ingredients based on substituted diphenyl ethers have become known, e.g. from the Swiss patent specification No. 424 326. Recently, herbicidally active phenoxy-phenoxyalkane carboxylic acids, see e.g. DOS 2 433 067.

Diese Erfindung erschliesst eine neue Gruppe von Phenoxy-phenoxy-alkancarbonsäure-Derivaten, die in geringen Aufwandmengen das Wachstum der Pflanzen in einer für die Landwirtschaft vorteilhafter Weise zu beeinflussen vermögen.This invention opens up a new group of phenoxy-phenoxy-alkane carboxylic acid derivatives which are able to influence the growth of the plants in a manner which is advantageous for agriculture in small amounts.

Die neuen Wirkstoffe der Formel I gemäss vorliegender Erfindung besitzen eine allgemeine, nicht spezifisch gegen Gräser gerichtete Herbizidwirkung, vor allem bei post-emergenter Anwendung und können in mono- und dikotylen Kulturen als Unkrautmittel eingesetzt werden.The new active compounds of the formula I according to the present invention have a general herbicidal action which is not specifically directed against grasses, especially in the case of post-emergent use and can be used as weed agents in monocotyledonous and dicotyledonous crops.

Die erfindungsgemässen Wirkstoffe besitzen auch günstige wachstumsregulierende Effekte (Wuchshemmung). Sie hemmen vor allem 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 Kultur führt;
  • - die Hemmung des unerwünschten Wachstums 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.
The active compounds according to the invention also have favorable growth-regulating effects (growth inhibition). Above all, 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 this culture;
  • - the inhibition of 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 dicotyledonous plants, such as fruit trees, ornamental trees, bushes - and hedges, in order to save on cutting work.

Die Verbindungen vorliegender Erfindung sind wenig giftig für Warmblüter deren Applikation dürfte keine Probleme verursachen. Die vorgeschlagenen Aufwandmengen liegen zwischen 0.1 und 5 kg pro Hektar.The compounds of the present invention are not very toxic to warm-blooded animals, and their application should not cause any problems. The suggested application rates are between 0.1 and 5 kg per hectare.

Die Herstellung der neuen Verbindungen der Formel I erfolgt nach an sich bekannten Reaktionen der chemischen Synthese, z.B. gemäss dem untenstehenden Schema:

Figure imgb0003
In diesen Formeln ist Hal ein Halogenatom, vorzugsweise Chlor oder Brom während A, R1, R2 und R4 die in Formel I gegebene Bedeutung haben.The new compounds of the formula I are prepared by reactions known per se in chemical synthesis, for example according to the scheme below:
Figure imgb0003
 In these formulas, Hal is a halogen atom, preferably chlorine or bromine, while A, R 1 , R 2 and R 4 have the meaning given in formula I.

In para-Stellung durch den Rest R4 substituiertes ortho Nitro-chlorbenzol wird in Gegenwart eines säurebindenden Mittels bei erhöhter Temperatur mit Resorcin reagiert. Das Resorcin sollte gegenüber dem Chlorbenzol in leichtem Ueberschuss vorhanden sein. Nach vollzogener Reaktion wird die Reaktionsmasse in Wasser gegeben und der entstandene Diphenyläther mit einem mit Wasser nicht mischbaren Lösungsmittel aus der wässrigen Suspension extrahiert zur Beschleunigung der Kondensation kann eine Spur Kupferpulver zugegeben werden. Die Kondensation wird vorteilhafterweise im Oelbad bei ca. 200°C durchgeführt. Siehe dazu folgende Literaturangaben: Weygand Hilgetag "Organisch Chemische Experimentierkunst 3. Auflage 1964 435; US Patent No. 3 080 225, DOS 2 433 066 und DAS 1 187 852.Ortho nitro-chlorobenzene substituted in the para position by the radical R 4 is reacted with resorcinol in the presence of an acid-binding agent at elevated temperature. The resorcinol should be present in a slight excess over the chlorobenzene. After the reaction is complete, the reaction mass is poured into water and the diphenyl ether formed is extracted from the aqueous suspension with a water-immiscible solvent. A trace of copper powder can be added to accelerate the condensation. The condensation is advantageously carried out in an oil bath at approximately 200.degree. See the following references: Weygand Hilgetag "Organic Chemical Experimental Art 3rd Edition 1964 435; US Patent No. 3 080 225, DOS 2 433 066 and DAS 1 187 852.

Durch Nitrieren in Eisessig, Aethylenchlorid oder Schwefelsäure kann in die noch freie para-Stellung des Diphenyläthers eine Nitrogruppe eingeführt werden. Durch Behandeln mit Chlor in Eisessig kann in diese Stellung ein Chloratom eingeführt werden. Hat R3 die Bedeutung von Cyan oder Brom, so wird in diesem Stadium das Chloratom z.B. durch Umsetzung. mit KCN (s. Adv.Chem.Ser. 132 (1974) 252 oder J.Organomet.Chem. 54 (1973)C 57) oder KBr oder NaBr ersetzt oder man unterwirft das durch Reduktion der NO2-Gruppe erhaltene Anilin einer Sandmeyer-Reaktion.By nitrating in glacial acetic acid, ethylene chloride or sulfuric acid, a nitro group can be introduced into the still free para position of the diphenyl ether. A chlorine atom can be introduced into this position by treatment with chlorine in glacial acetic acid. If R 3 has the meaning of cyan or bromine, the chlorine atom at this stage is converted, for example. replaced with KCN (see Adv.Chem.Ser. 132 (1974) 252 or J.Organomet.Chem. 54 (1973) C 57) or KBr or NaBr or the aniline obtained by reduction of the NO 2 group is subjected to a Sandmeyer -Reaction.

Das erfindungsgemässe Verfahren zur Herstellung von Phenoxy-phenoxy-alkancarbonsäure Derivatender Formel I ist dadurch gekennzeichnet, dass man in an sich bekannter Weise einen Diphenyläther der Formel II

Figure imgb0004
worin X Wasserstoff oder das Kation eines Alkali- oder Erdalkalimetalls bedeutet und R3 und R4 die in Formel I gegebene Bedeutung haben, mit a-Halogen-carbonsäurederivat der Formel III
Figure imgb0005
worin A, R1 und R2 die in Formel I gegebene Bedeutung haben während Hal ein Halogenatom, vorzugsweise Chlor oder Brom bedeutet, umsetzt.The inventive method for the preparation of phenoxy - phenoxy-alkanecarboxylic acid derivatives of formula I is characterized in that, in per se known manner, a diphenyl ether of the formula II
Figure imgb0004
 wherein X is hydrogen or the cation of an alkali or alkaline earth metal and R 3 and R 4 have the meaning given in formula I, with a-halogeno-carboxylic acid derivative of the formula III
Figure imgb0005
 wherein A, R 1 and R 2 have the meaning given in formula I, while Hal represents a halogen atom, preferably chlorine or bromine.

Die Reaktionspartner der Formeln II und III werden in etwa stöchiometrischen Mengen eingesetzt. Die Reaktion erfolgt vorteilhafterweise in Anwesenheit eines organischen den Reaktionspartnern gegenüber inerten Lösungsmittels, bei einer Temperatur zwischen Raumtemperatur und der Siedetemperatur des Reaktionsgemisches, gegebenenfalls d.h. wenn X Wasserstoff ist, in Gegenwart eines säurebindenden Mittels.The reactants of formulas II and III are used in approximately stoichiometric amounts. The reaction is advantageously carried out in the presence of an organic solvent which is inert to the reactants, at a temperature between room temperature and the boiling point of the reaction mixture, if appropriate i.e. when X is hydrogen, in the presence of an acid binding agent.

Nach Beendigung der Reaktion, welche zwischen 1 und 8 Stunden dauern kann, wird das Reaktionsprodukt isoliert, z.B. durch Abdestillieren des Lösungsmittels. und Eingiessens des Rückstandes in Eiswasser.Upon completion of the reaction, which may take between 1 and 8 hours, the reaction product is isolated, e.g. by distilling off the solvent. and pouring the residue into ice water.

Als Lösungsmittel kommen für diese Reaktion vor allem organische aprotische Lösungsmittel in Frage welche die Reaktionspartner zwar lösen aber nicht mit ihnen reagieren. Die Kondensationsmittel sind anorganische Basen, wie NaOH, KOH, NaOCH3 etc. aber auch organische Basen wie tertiäre Amine.Organic aprotic solvents which can dissolve the reaction partners but do not react with them are particularly suitable as solvents for this reaction. The condensing agents are inorganic bases such as NaOH, KOH, NaOCH 3 etc. but also organic bases such as tertiary amines.

Die nachfolgenden Beispiele veranschaulichen erfindungsgemässe Herstellungsverfharen für einige Wirkstoffe der Formel I. Weitere in entsprechender Weise hergestellte Wirkstoffe sind in der anschliessenden Tabelle aufgeführt. Temperaturangaben beziehen sich jeweils auf Celsius-Grade.The following examples illustrate production processes according to the invention for some active substances of the formula I. Further active substances produced in a corresponding manner are listed in the table below. Temperatures refer to degrees Celsius.

Diese Phenoxy-phenoxy-alkan-carbonsäure-Derivate der Formel I sind stabile Verbindungen, welche in üblichen organischen Lösungsmitteln, wie Alkoholen, Aethern, Ketonen, Dimethylformamid, Dimethylsulfoxyd etc. löslich sind.These phenoxy-phenoxy-alkane-carboxylic acid derivatives of the formula I are stable compounds which are soluble in customary organic solvents, such as alcohols, ethers, ketones, dimethylformamide, dimethyl sulfoxide, etc.

Beispiel 1example 1

34,1 g (0,1 Mol) 2-Nitro-4-.trifluormethyl-3'-acet oxy-diphenyläther werden in 200 ml Essigsäure gelöst und unter gutem Rühren bei 40°C äquimolare Mengen Chlor eingeleitet. Die Reaktion wird gaschromatographisch verfolgt. Nach beendeter Reaktion giesst man die erhaltene Lösung in Eiswasser und extrahiert mit Toluol/Essigester 1:1. Nach Abdestillieren des organischen Lösungsmittels erhält man ein Oel, das mittels 30%iger methanolischer Natronlauge zum freien Phenol verseift wird. Das so erhaltene Oel hat einen Kp: von 159°-165° bei 0,03 mm Hg. Ausbeute 23,5 g.34.1 g (0.1 mol) of 2-nitro-4-.trifluoromethyl-3'-acet oxy-diphenyl ether are dissolved in 200 ml of acetic acid and equimolar amounts of chlorine are introduced at 40 ° C. with good stirring. The reaction is followed by gas chromatography. When the reaction is complete, the solution obtained is poured into ice water and extracted with toluene / ethyl acetate 1: 1. After the organic solvent has been distilled off, an oil is obtained which is saponified to free phenol using 30% strength methanolic sodium hydroxide solution. The oil thus obtained has a bp: of 159 ° -165 ° with 0.03 mm Hg. Yield 23.5 g.

23,5 g 2-Nitro-4-trifluormethyl-3'-hydroxy-4'-chlor-diphenyläther werden in 30 ml Aethylmethylketon gelöst. Dazu setzt man 18 ml 2-Brompropionsäuremethylester, 18 g Kaliumcarbonat und eine Spatelspitze Kaliumjodid. Das Reaktionsgemisch wird über Nacht bei 80°C Badtemperatur gerührt, von unlöslichen Anteilen abfitlriert und das Lösungsmittel abdestilliert. Das so erhaltene Oel wird im Hochvakuum destilliert. Kp: 172°/0,015 mm Hg Ausbeute 20,8 g.

Figure imgb0006
23.5 g of 2-nitro-4-trifluoromethyl-3'-hydroxy-4'-chloro-diphenyl ether are dissolved in 30 ml of ethyl methyl ketone. 18 ml of 2-bromopropionate, 18 g of potassium carbonate and a spatula tip of potassium iodide are added. The reaction mixture is stirred overnight at a bath temperature of 80 ° C., insoluble constituents are removed and the solvent is distilled off. The oil thus obtained is distilled in a high vacuum. Bp: 172 ° / 0.015 mm Hg yield 20.8 g.
Figure imgb0006

Beispiel 2Example 2

  • a) 68,2 g 2-Nitro-4-trimethyl-3'-acetoxy-diphenyläther werden in 80 ml Aethylenchlorid gelöst und bei 0°-5° 40 ml Nitriersäure (1:1) zugetropft. Nach beendetem Zutropfen wird noch 1/2 Stunde ausgerührt, das Reaktionsprodukt in Wasser gegossen und das ausgefallene Produkt mit Essigester-Toluol 1:1 extrahiert. Nach Abdestillieren des organischen Lösungsmittel erhalt man ein festes Produkt, das aus Alkohol/Wasser unkristallisiert wird. Smp.: 129°-130°, Ausbeute: 47,4g = 61,4% d.Th.a) 68.2 g of 2-nitro-4-trimethyl-3'-acetoxy-diphenyl ether are dissolved in 80 ml of ethylene chloride and 40 ml of nitrating acid (1: 1) are added dropwise at 0 ° -5 °. After the dropwise addition has ended, the mixture is stirred for a further 1/2 hour, the reaction product is poured into water and the precipitated product is extracted with ethyl acetate-toluene 1: 1. After the organic solvent has been distilled off, a solid product is obtained which is uncrystallized from alcohol / water. M.p .: 129 ° -130 °, yield: 47.4g = 61.4% of theory
  • b) 47,4 g 2,4'-Dinitro-4-trifluormethyl-3'-acetoxy- diphenyläther werden mit 200 ml Methanol versetzt und nach Zugabe der äquimolaren Menge methanolischer KOH eine halbe Stunde stehengelassen. Nach Abdestillieren des Lösungsmittels wird der Rückstand in Wasser gelöst und nach Ansäuern mit 2n HCl das ausgeschiedene Phenol mit Essigester/Toluol 1:1 extrahiert. Nach Abdestillieren des Lösungsmittel erhält man 44,5 g Oel, das beim stehen kristallisiert. Schmelzpunkt: 78°-79°.b) 47.4 g of 2,4'-dinitro-4-trifluoromethyl-3'-acetoxydiphenyl ether are mixed with 200 ml of methanol and, after addition of the equimolar amount of methanolic KOH, left to stand for half an hour. After the solvent has been distilled off, the residue is dissolved in water and, after acidification with 2N HCl, the phenol which has separated out is extracted with ethyl acetate / toluene 1: 1. After the solvent has been distilled off, 44.5 g of oil are obtained, which crystallizes on standing. Melting point: 78 ° -79 °.
  • c) 17,2 g 2,4'-Dinitro-4-trifluormethyl-3'-hydroxy- diphenyläther werden in 50 ml 2-Butanon gelöst und nach Zugabe von 13,4 g 2-Brom-propionsäuremethylester, 13,8 g Kaliumcarbonat und einer Spatelspitze Kaliumjodid über Nacht bei 80° Badtemperatur gerührt. Anschliessend wird filtriert, das Filtrat eingedampft und das erhaltene Oel im Hochvakuum destilliert. Kp: 217°/0,05 Torr Ausbeute: 6,2 g
    Figure imgb0007
    Figure imgb0008
    Figure imgb0009
    Figure imgb0010
    Figure imgb0011
    c) 17.2 g of 2,4'-dinitro-4-trifluoromethyl-3'-hydroxydiphenyl ether are dissolved in 50 ml of 2-butanone and, after adding 13.4 g of 2-bromo-propionic acid methyl ester, 13.8 g of potassium carbonate and a spatula tip of potassium iodide stirred overnight at 80 ° bath temperature. Then it is filtered the filtrate was evaporated and the oil obtained was distilled under high vacuum. K p : 217 ° / 0.05 Torr yield: 6.2 g
    Figure imgb0007
    Figure imgb0008
    Figure imgb0009
    Figure imgb0010
    Figure imgb0011

Die Erfindung betrifft auch herbizide und pflanzenwachstumsregulierende Mittel, welche einen neuen Wirkstoff der Formel I erhalten, sowie Verfahren zur pre- und post-emergenten Umkrautbekämpfung und zur Hemmung des Pflanzenwuchses von monocotylen und dicotylen Pflanzen, insbesondere Gräsern, Getreide, Soja und Tabakgeiztrieben.The invention also relates to herbicidal and plant growth regulating agents which receive a new active ingredient of the formula I, and to processes for pre- and post-emergent weed control and for inhibiting the growth of monocotyledonous and dicotyledonous plants, in particular grasses, cereals, soybeans and tobacco stingers.

Die erfindungsgemässen Mittel können in den üblichen Formulierungen vorliegen.The agents according to the invention can be present in the usual formulations.

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:
  • flussige 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:
  • solid processing forms: dusts, scattering agents, granules, coating granules, impregnation granules and homogeneous granules;
  • water dispersible
  • Active ingredient concentrates: wettable powder, (wettable powder), pastes, emulsions:
  • liquid forms of processing: 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. Die Wirkstoffe der Formel I 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. The active compounds of the formula I can be formulated, for example, as follows (parts mean parts by weight):

Als Beispiele für die Herstellung der erfindungsgemässen Mittel sind nachstehend einige feste und flüssige Aufarbeitungsformen beschrieben.Some solid and liquid work-up forms are described below as examples of the preparation of the agents according to the invention.

Stäubemittel:Dusts:

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

Figure imgb0012
Die Wirkstoffe werden mit den Trägerstoffen vermischt und vermahlen.The following substances are used to produce a) 5% and b) 2% dust:
Figure imgb0012
 The active ingredients are mixed and ground with the carriers.

GranulateGranules

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

Figure imgb0013
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 verdampft.The following substances are used to produce 5% granules:
Figure imgb0013
 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 imgb0014
The following components are used to produce a) 50%, b) 25% and c) 10% wettable powder:
Figure imgb0014

Der angegebene Wirkstoff wird auf die entspr echenden Trägerstoffe aufgezogen und anschliessend vermischt und vermahlen. Man erhält so Spritzpulver von vorzüglicher Benetzbarkeit und Schwebefähigkeit, die durch Verdünnen mit Wasser Suspensionen jeder gewünschten Wirkstoffkonzentration ergeben.The specified active ingredient is drawn onto the corresponding carriers and then mixed and ground. This gives wettable powders of excellent wettability and suspension which, when diluted with water, give suspensions of any desired concentration of active compound.

Pastepaste

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

Figure imgb0015
Der Wirkstoff wird mit den Zuschlagstoffen in dazu geeigneten Geräten innig vermischt und vermahlen. Man erhält eine Paste, aus der sich durch Verdünnen mit Wasser Suspensionen jeder gewünschten Konzentration herstellen lassen. Die Suspensionen eignen sich zur Behandlung von Rasenanlagen.The following substances are used to produce a 45% paste:
Figure imgb0015
 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 imgb0016
miteinander vermischt. Dieses Konzentrat kann mit Wasser zu Emulsionen auf geeignete Konzentrationen verdünnt werden.To prepare a 25% emulsion concentrate
Figure imgb0016
 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 I umfassten Verbindungen verwendet werden.Instead of the respective active ingredient specified in the preceding formulation examples, another of the compounds encompassed by the formula I 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 postemergente Herbizidwirkung 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-emergence herbicide effect as well as growth inhibition.

Erfindungsgemässe Mittel, die als aktive Komponente mindestens eine Verbindung der Formel I enthalten, eignen sich besonders zur Hemmung und Kontrolle des Pflanzenwachstums von monocotylen und dicotylen Pflanzen, wie Gräsern, Sträuchern, Bäumen, Getreide- und Leguminosenkulturen, Zuckerrohr, Tabak, Soja, Zwiebeln- und Kartoffelknollen, Zierpflanzen, Obstbäumen und Reben.Agents according to the invention which contain at least one compound of the formula I as active component are particularly suitable for inhibiting and controlling the plant growth of monocotyledonous 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 neuen 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 Pflauzenform 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.The effect achieved primarily by the new 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 plum. 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.

Eines der wichtigsten Probleme an reinen Gras- bepflanzungen 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 main problems of pure grass be p flanzungen is the grass cut itself, whether to green spaces in residential areas, on industrial sites, sports grounds, on highways, runways, railway embankments or embankments of water supplies. 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, vor allem in Wohn-und Industriegebieten, mit erfindungsgemässen Verbindungen der Formel I die arbeitsaufwendige Schnittarbeit reduziert werden.In an analogous manner, the labor-intensive cutting work can be reduced by treating trees, shrubs and hedges, especially in residential and industrial areas, with compounds of the formula I according to the invention.

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

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 Uebergang 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 substances according to the invention the transition from the vegetative to the generative growth phase is accelerated.

Bevorzugt setzt man die erfindungsgemässen Wirkstoffe der Formel I zur Wachstumshemmung an Gräsern, Getreidekulturen, Tabak, Soja und Zierpflanzen ein.The active compounds of the formula I 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 vom Applikationszeitpunkt abhängig. Sie liegen im allgemeineu 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, when applied before emergence of the plants and for the treatment of existing crops, preferably up to 4 kg per hectare.

Ferner'eignen sich viele der Wirkstoffe der Formel 1 und diese enthaltende Mittel auch für andere Beeinflussungen des Pflanzenwachstums, wie insbesondere zur Erleichterung der Frucht- und Blattabszission durch Ausbildung von Trenngeweben an den Frucht- und Blattstielen, was eine beträchtliche Reduktion der Abreisskraft und somit ein grosse Ernteerleichterung mit sich bringt.Furthermore, many of the active ingredients of formula 1 and compositions containing them are also suitable for other influences on plant growth, such as, in particular, to facilitate fruit and leaf abscess by forming separating tissues on the fruit and leaf stems, which results in a considerable reduction in the tear-off force and thus brings great harvest relief.

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 Pflan zenteile (Kontakwirkung), insbesondere die Blätter, als auch über den Boden, als pre-emergentes Herbizid (Keimhemmung).The development of the action of the active compounds according to the invention takes place both via the aerial plant parts (contact action), in particular the leaves, and also via the soil as a pre-emergent 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 growth arrest 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 interessante Kombinationspartner für eine Reihe von Herbiziden der Phenylharnstoff- und Triazinreihe in Getreid kulturen, 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 or. in fruit and wine growing.

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 neuen Wirkstoffe.der Formel I zeichnen sich Überdies durch eine sehr starke pre-emergente Herbizid- wirkung aus, sind also auch ausgeprägte Keimungshemmer,The new active ingredients of Formula I 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-emergente Herbizid-Wi.rkung (Keimhemmung)Pre-emergent herbicide action (germ inhibition)

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 bönitiert:

  • 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 was maintained and the test was evaluated after 3 weeks and the results were based on 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-emergence herbicide effect (contact herbicide)

Eine grössere Anzahl (mindestens 7) Unkräuter und Kulturpflanzen, sowohl monocotyle wie dicotyle, wurden nach dem Auflaufen (im-4-vis-6-Blattstadium) mit einer wässrigen 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-emorgent-Versuch nach derselben Notenskala bonitiert.A larger number (at least 7) of weeds and crop plants, both monocotyledon and dicotyledon, were sprayed with an aqueous active ingredient emulsion in doses of 0.5; 1 ; 2 and 4 kg of active substance 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-emorgent test.

Die geprüften Verbindungen gemäss vorliegender Erfindung zeigten auf einigen Pflanzen ausgeprägte kontaktherbizide Wirkung und auf vielen Pflanzen Wachstumsstillstand als Symptom der wachstumshemmenden Eigenschaften.The tested compounds according to the present 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 I 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 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 I 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.Summer wheat (Triticum aestivum), spring barley (Hordeum vulgare) and rye (Secale) were sown in sterilized soil in plastic cups 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.

Claims (10)

1. Phenoxy-phenoxy-alkancarbonsäure der Formel I
Figure imgb0017
worin R1 Wasserstoff, Cl-C4 Alkyl oder C2-C8 Alkoxyalkyl, R2 Wasserstoff oder C1-C4 Alkyl, R3 Halogen, Cyano.oder Nitro, R4 Halogen, Cyano oder Trifluormethyl, A Cyan oder die Gruppe -COB, B einen Rest OR5, SR6 oder NR7R8, R5 Wasserstoff oder das Kation einer Base
Figure imgb0018
 Mn ⊕, wobei M ein Alkali-, Erdalkalimetall-Kation oder einen Ammoniorest
Figure imgb0019
 n als ganze Zahl 1, 2 oder 3 die Wertigkeit des Kations berücksichtigt, während Ra, Rb, Rc und Rd unabhängig voneinander Wasserstoff; Benzyl oder einen gegebenenfalls durch -OH, -NH2 oder C1-C4 Alkoxy substituierten Cl-C4 Alkylrest bedeuten, R5 bedeutet weiter einen C1-C8 Alkylrest, der unsubstituiert oder durch Halogen, Cyan, Nitro, Hydroxyl oder einen 5-6 gliedrigen Stickstoff enthaltenden Heterocyclus substituiert sowie einen C2-C8 Alkylrest der durch Sauerstoff, Schwefel, Stickstoff, Carbonyl oder Carbonyloxy unterbrochen sein kann, einen C3-C6 Cycloalkylrest, einen C3-C6 Alkenyl- oder Alkinylrest der durch Halogen substituiert sein kann, einen Phenyl oder Benzylrest der durch Halogen, Cyan, Nitro, C1-C4 Alkyl, C1-C4 Alkoxy oder Trifluormethyl substituiert sein kann, R6 bedeutet einen C1-C8 Alkylrest der durch Halogen, Cyano, Nitro oder Hydroxyl substituiert, oder durch Sauerstoff, Schwefel, . Stickstoff, Carbonyl oder Carbonyloxy unterbrochen sein kann, einen C3-C6 Cycloalkylrest, einen C3-C6 Alkenyl- oder Alkinylrest, der durch Halogen substituiert sein kann, einen Phenyl- oder Benzylrest, der durch Halogen, Cyan, Nitro, Cl-C4 Alkyl, C1-C4 Alkoxy oder Trifluormethyl substituiert sein kann, R7 Wasserstoff einen C1-C8 Alkylrest, der durch Halogen, Cyan oder Hydroxyl substituiert sein kann, sowie einen C2-C8 Alkylrest, der durch Sauerstoff unterbrochen sein kann, R8 Wasserstoff, einen C1-C4 Alkylrest oder einen C3-C4 Alkylrest, R7 und R8 zusammen mit dem Stickstoffatom an das sie gebunden sind, auch einen 5-6 gliedrigen heterocyclischen Rest, der durch Sauerstoff, Schwefel, eine Imino-, C1-C4 Alkylimino- oder Phenyliminogruppe unterbrochen sein kann. 1. Phenoxy-phenoxy-alkane carboxylic acid of the formula I.
Figure imgb0017
 where R 1 is hydrogen, C 1 -C 4 alkyl or C 2 -C 8 alkoxyalkyl, R 2 is hydrogen or C 1 -C 4 alkyl, R 3 halogen, cyano or nitro, R 4 halogen, cyano or trifluoromethyl, A cyan or the group -COB, B a residue OR 5 , SR 6 or NR 7 R 8 , R 5 is hydrogen or the cation of a base
Figure imgb0018
 M n ⊕, where M is an alkali, alkaline earth metal cation or an ammonium radical
Figure imgb0019
 n takes into account the valence of the cation as an integer 1, 2 or 3, while R a , R b , R c and R d are independently hydrogen; Benzyl or optionally substituted by -OH, -NH 2 or C 1 -C 4 alkoxy substituted C l -C 4 alkyl radical, R 5 also denotes a C 1 -C 8 alkyl radical which is unsubstituted or substituted by halogen, cyano, nitro, hydroxyl or a 5-6 membered nitrogen-containing heterocycle and a C 2 -C 8 alkyl radical which is substituted by oxygen, sulfur, nitrogen, carbonyl or carbonyloxy can be interrupted, a C 3 -C 6 cycloalkyl radical, a C 3 -C 6 alkenyl or alkynyl radical which can be substituted by halogen, a phenyl or benzyl radical which is substituted by halogen, cyano, nitro, C 1 -C 4 alkyl, C 1 -C 4 alkoxy or trifluoromethyl can be substituted, R 6 represents a C 1 -C 8 alkyl radical which is substituted by halogen, cyano, nitro or hydroxyl, or by oxygen, sulfur,. Nitrogen, carbonyl or carbonyloxy can be interrupted, a C 3 -C 6 cycloalkyl radical, a C 3 -C 6 alkenyl or alkynyl radical which may be substituted by halogen, a phenyl or benzyl radical which is substituted by halogen, cyano, nitro, C. l -C 4 alkyl, C 1 -C 4 alkoxy or trifluoromethyl, R 7 hydrogen is a C 1 -C 8 alkyl radical which can be substituted by halogen, cyano or hydroxyl, and a C 2 -C 8 alkyl radical which can be interrupted by oxygen, R 8 is hydrogen, a C 1 -C 4 alkyl radical or a C 3 -C 4 alkyl radical, R 7 and R 8 together with the nitrogen atom to which they are attached also form a 5-6-membered heterocyclic radical which can be interrupted by oxygen, sulfur, an imino, C 1 -C 4 alkylimino or phenylimino group. 2. Die Verbindungen der Formel I, Anspruch 1, in denen R1 Wasserstoff ist während R2, R3, R4 und A die unter Formel I, Anspruch 1 gegebene Bedeutung haben.2. The compounds of formula I, claim 1, in which R 1 is hydrogen while R 2 , R 3 , R 4 and A have the meaning given under formula I, claim 1. 3. Die Verbindungen der Formel I, Anspruch l in denen R1 Wasserstoff A, -COB und B -COR5 sind während R2, R3 R die unter Formel I, Anspruch 1 gegebene Bedeutung haben.3. The compounds of formula I, claim 1 in which R 1 is hydrogen A, -COB and B -COR 5 while R 2 , R 3 R have the meaning given in formula I, claim 1. 4. Die Verbindungen der Formel I, Anspruch 1 in denen R1 Wasserstoff, A, -CDB und B -NR7R8 bedeuten während R2, R3 und R4 die gegebene Bedeutung haben.4. The compounds of formula I, claim 1 in which R 1 is hydrogen, A, -CDB and B -NR 7 R 8 mean while R 2 , R 3 and R 4 have the meaning given. 5. Die Verbindungen der Formel I, Anspruch 1 in denen R1 Wasserstoff, A-COB und B -SR6 bedeuten während R2, R3 und R4 die unter Formel I, Anspruch 1 gegebene Bedeutung haben.5. The compounds of formula I, claim 1 in which R 1 is hydrogen, A-COB and B -SR 6 while R 2 , R 3 and R 4 have the meaning given in formula I, claim 1. 6. Als Verbindung gemäss Anspruch 1, Formel I 2-Chlor-5-(2'-Nitro-4'-trifluormethylphenoxy)-a-phenoxy-propionsäure-methylester.6. As a compound according to claim 1, formula I 2-chloro-5- (2'-nitro-4'-trifluoromethylphenoxy) -a-phenoxy-propionic acid methyl ester. 7. Verfahren zur Herstellung der Phenoxy-phenoxyalkancarbonsäur-Derivate der Formel I, Anspruch 1, dadurch gekennzeichnet, dass in an sich bekannter Weise ein Diphenyläther der Formel II
Figure imgb0020
worin R3 und R4 die in Formel I gegebene Bedeutung haben und X Wasserstoff oder das Kation eines Alkali-oder Erdalkalimetalles bedeutet, in an sich bekannter Weise mit einem a-Halogencarbonsäurederivat der Formel III
Figure imgb0021
worin A R1 und R2 die unter Formel I gegebene Bedeutung naben und Hal ein Halogenatom bedeutet, umsetzt.7. A process for the preparation of the phenoxy-phenoxyalkanecarboxylic acid derivatives of the formula I, claim 1, characterized in that a diphenyl ether of the formula II
Figure imgb0020
 wherein R 3 and R 4 have the meaning given in formula I and X is hydrogen or the cation of an alkali or alkaline earth metal, in a manner known per se with an a-halocarboxylic acid derivative of the formula III
Figure imgb0021
 wherein AR 1 and R 2 have the meaning given under formula I and Hal represents a halogen atom. 8. Herbizides und auf das Pflanzenwachstum einwirkendes Mittel, dadurch gekennzeichnet, dass es als Wirkstoff mindestens eine Verbindung der Formel I, Anspruch 1 enthält.8. Herbicidal and agent acting on plant growth, characterized in that it contains at least one compound of the formula I, claim 1, as active ingredient. 9. Die Verwendung der Phenoxy-phenoxy-alkancarbonsäure-Derivate der Formel I, Anspruch 1 oder sie enthaltenden Mittel zur Unkrautbekämpfung.9. The use of the phenoxy-phenoxy-alkanecarboxylic acid derivatives of the formula I, claim 1 or compositions containing them for weed control. 10. Die Verwendung der Phendxy-phenoxy-alkancarbonsäure-Derivate der Formel I, Anspruch 1 oder sie enthaltenden Mittel zur Regulierung des Pflanzenwachstums.10. The use of the Phendxy-phenoxy-alkanecarboxylic acid derivatives of the formula I, claim 1 or compositions containing them for regulating plant growth.
EP78100218A 1977-06-30 1978-06-22 Substituted 3-(2'-nitro phenoxy)-alpha-phenoxy alcanoic acids and their derivatives, their preparation and their use as herbicides Expired EP0000474B1 (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011802A1 (en) * 1978-11-24 1980-06-11 Hoechst Aktiengesellschaft Phenoxy-phenoxy-propionic acid amides, processes for their preparation, herbicidal compositions containing them and their use in controlling the growth of weeds
EP0012717A1 (en) * 1978-12-01 1980-06-25 Ciba-Geigy Ag Method and composition for the selective pre-emergent control of weeds in cereal cultures
EP0078536A2 (en) * 1981-11-02 1983-05-11 Sandoz Ag Phosphinates and phosphonates and their use in the control of weeds

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2639796A1 (en) * 1975-09-03 1977-03-31 Rohm & Haas NEW DIPHENYL ETHERS
FR2325638A1 (en) * 1975-09-27 1977-04-22 Ishihara Mining & Chemical Co PHENOXY PHENOXY ALKANE CARBOXYLIC ACID HERBICIDES
FR2348182A1 (en) * 1976-04-15 1977-11-10 Sori Soc Rech Ind NEW DERIVATIVES OF M-PHENYL-PHENOXY-PROPIONIC ACIDS
NL7708091A (en) * 1976-07-21 1978-01-24 Ciba Geigy Process for the preparation of phenoxy-phenoxy-alkanecarboxylic acid derivatives.
NL7707921A (en) * 1976-07-20 1978-01-24 Hoechst Ag METHOD FOR PREPARING COMPOUNDS WITH HERBICIDE ACTION

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2639796A1 (en) * 1975-09-03 1977-03-31 Rohm & Haas NEW DIPHENYL ETHERS
FR2325638A1 (en) * 1975-09-27 1977-04-22 Ishihara Mining & Chemical Co PHENOXY PHENOXY ALKANE CARBOXYLIC ACID HERBICIDES
FR2348182A1 (en) * 1976-04-15 1977-11-10 Sori Soc Rech Ind NEW DERIVATIVES OF M-PHENYL-PHENOXY-PROPIONIC ACIDS
NL7707921A (en) * 1976-07-20 1978-01-24 Hoechst Ag METHOD FOR PREPARING COMPOUNDS WITH HERBICIDE ACTION
NL7708091A (en) * 1976-07-21 1978-01-24 Ciba Geigy Process for the preparation of phenoxy-phenoxy-alkanecarboxylic acid derivatives.

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0011802A1 (en) * 1978-11-24 1980-06-11 Hoechst Aktiengesellschaft Phenoxy-phenoxy-propionic acid amides, processes for their preparation, herbicidal compositions containing them and their use in controlling the growth of weeds
EP0012717A1 (en) * 1978-12-01 1980-06-25 Ciba-Geigy Ag Method and composition for the selective pre-emergent control of weeds in cereal cultures
EP0078536A2 (en) * 1981-11-02 1983-05-11 Sandoz Ag Phosphinates and phosphonates and their use in the control of weeds
EP0078536A3 (en) * 1981-11-02 1983-07-27 Sandoz Ag Phosphinates and phosphonates and their use in the control of weeds

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DE2860339D1 (en) 1981-02-12
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IT7825138A0 (en) 1978-06-29
CA1090367A (en) 1980-11-25
ES471398A1 (en) 1979-02-01
IL55029A0 (en) 1978-08-31
IL55029A (en) 1982-09-30

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