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EP0000474B1 - 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
EP0000474B1
EP0000474B1 EP78100218A EP78100218A EP0000474B1 EP 0000474 B1 EP0000474 B1 EP 0000474B1 EP 78100218 A EP78100218 A EP 78100218A EP 78100218 A EP78100218 A EP 78100218A EP 0000474 B1 EP0000474 B1 EP 0000474B1
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Prior art keywords
radical
halogen
substituted
nitro
cyano
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EP78100218A
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German (de)
French (fr)
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EP0000474A1 (en
Inventor
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 invention relates to new, substituted herbicidal and regulating plant growth, substituted 3- (2'-nitro-phenoxy) -alpha-phenoxy-alkane carboxylic acids and their derivatives, processes for their preparation, agents which contain these derivatives as active ingredients and the use thereof or agents containing them for controlling or regulating undesirable plant growth.
  • the alkyl radicals are both branched and unbranched and contain the given number of carbon atoms.
  • the radicals R 7 and R a are preferably hydrogen or lower alkyl groups. However, some of them can also be unsaturated or aromatic (phenyl) or aralipha be table (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-phenoxy-alkane carboxylic acids, see e.g. DE-OS 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 plants in a small amount in an advantageous manner for agriculture.
  • the new active compounds of the general formula I according to the invention have a general herbicidal action which is not specifically directed against grasses, especially in the case of post-emergence use and can be used as weed compositions in mono- and dicotyledon crops.
  • the compounds of the invention are not very toxic to warm-blooded animals; their application should not cause any problems.
  • the suggested application rates are between 0.1 and 5 kg per hectare.
  • the new compounds of general formula 1 are prepared by reactions known per se, for example according to the scheme:
  • Hal represents a halogen atom, preferably chlorine or bromine, while A, R 1 , R 2 and R 4 have the meaning given in general 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.
  • R 3 has the meaning of cyan or bromine, so at this stage the chlorine atom is converted, for example, by reaction with KCN [s. 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 process according to the invention for the preparation of phenoxy-phenoxy-alkane carboxylic acid derivatives of the general formula 1 is characterized in that a diphenyl ether of the general formula II in which X denotes hydrogen or the cation of an alkali or alkaline earth metal and R 3 and R 4 have the meaning given in general formula I, with an ⁇ -halogeno-carboxylic acid derivative of the general formula III wherein A, R, and R 2 have the meaning given in general formula I, while Hal represents a halogen atom, preferably chlorine or bromine.
  • the reactants of the general 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 dissolve the reactants 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 general formula 1 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 compositions which comprise a new active ingredient of the general 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 above formulations.
  • the preparation he f indungsgemtreur means takes place in known manner by intimately mixing and grinding of active substances of general formula I with suitable carriers, optionally with the addition of inert to the active substances dispersing or solvents.
  • suitable carriers optionally with the addition of inert to the active substances dispersing or solvents.
  • the active ingredients can be present and used in the following processing forms:
  • 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 ingredients of the general formula I 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 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 general 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 substances of the general formula consists in the desired reduction in the plant size, in particular the stature height.
  • the plant In direct connection to Ver the plant is reduced in stature. 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, downpours, etc., which normally lead to the storage of crops of cereals and legumes, can be largely prevented, thus making harvesting easier.
  • 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 general formula I according to the invention.
  • active compounds of the general 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 general formula 1 are also used to inhibit the growth of undesirable 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 general 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, preferably up to 4 kg per hectare when applied before emergence of the plants and for the treatment of existing crops.
  • active ingredients of the general formula I and compositions containing them are also suitable for other influences on plant growth, such as in particular to facilitate the 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 a brings great harvest relief.
  • the development of the action of the active compounds according to the invention takes place both via the aerial parts of the plant (contact action), in particular the leaves, and also via the soil as a pre-allergenic herbicide (inhibition of germs).
  • 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 and sugar cane. 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 the general formula 1 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 general 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.

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

Description

Die Erfindung betrifft neue, herbizid und regulierend auf das Pflanzenwachstum einwirkende, substituierte 3-(2'-Nitro-phenoxy)-alpha-phenoxy-alkancarbonsäuren und ihre Derivate, Verfahren zu ihrer Herstellung, Mittel die diese Derivate als Wirkstoff enthalten sowie die Verwendung derselben oder sie enthaltender Mittel zur Bekämpfung von unerwünschtem Pflanzenwachstum oder zur Regulierung desselben.The invention relates to new, substituted herbicidal and regulating plant growth, substituted 3- (2'-nitro-phenoxy) -alpha-phenoxy-alkane carboxylic acids and their derivatives, processes for their preparation, agents which contain these derivatives as active ingredients and the use thereof or agents containing them for controlling or regulating undesirable plant growth.

Die substituierten 3-(2'-Nitro-phenoxy)-alpha-phenoxy-alkancarbonsäuren und ihre Derivate entsprechen der allgemeincy 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
    Figure imgb0002
    wobei
    • M ein Alkali-, Erdalkalimetall-Kation oder einen Ammoniumrest
      Figure imgb0003
  • 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, Nitro, Hydroxyl oder einen 5-6 gliedrigen Stickstoff enthaltenden Heterocyclus substituiert sein kann 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 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,
  • 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,
  • Ra 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, bedeuten.
The substituted 3- (2'-nitro-phenoxy) -alpha-phenoxy-alkane carboxylic acids and their derivatives correspond to the general formula I
Figure imgb0001
  • wherein 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 imgb0002
     in which
    • M is an alkali, alkaline earth metal cation or an ammonium residue
      Figure imgb0003
  • n as an integer 1, 2 or 3 takes into account the valence of the cation, while R a , R b , R c 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,
  • R 5 furthermore denotes a C 1 ―C 8 -alkyl radical which can be 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 can be 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 denotes 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 a 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 mean 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 allgemeinen Formel sind die Alkylreste sowohl verzweigt wie unverzweigt und enthalten die un gegebene Anzahl Kohlenstoffatome. Die Reste R7 und Ra 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 general formula, the alkyl radicals are both branched and unbranched and contain the given number of carbon atoms. The radicals R 7 and R a are preferably hydrogen or lower alkyl groups. However, some of them can also be unsaturated or aromatic (phenyl) or aralipha be table (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-phenoxy-alkancarbonsäuren, siehe z.B. die DE - OS 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-phenoxy-alkane carboxylic acids, see e.g. DE-OS 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 plants in a small amount in an advantageous manner for agriculture.

Die neuen Wirkstoffe der allgemeinen Formel I gemäss Erfindung besitzen eine allgemeine, nicht spezifisch gegen Gräser gerichtete Herbizidwirkung, vor allem bei post-emergenter Anwendung und können in mono- und dicotylen, Kulturen als Unkrautmittel eingesetzt werden.The new active compounds of the general formula I according to the invention have a general herbicidal action which is not specifically directed against grasses, especially in the case of post-emergence use and can be used as weed compositions in mono- and dicotyledon 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 dicotyledonen 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 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 invention are not very toxic to warm-blooded animals; 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 allgemeinen Formel 1 erfolgt nach an sich bekannten Reaktionen z.B. gemäss dem Schema:

Figure imgb0004
The new compounds of general formula 1 are prepared by reactions known per se, for example according to the scheme:
Figure imgb0004

In diesen Formeln bedeutet Hal ein Halogenatom, vorzugsweise Chlor oder Brom, während A, R1, R2 und R4 die in der allgemeinen Formel I an gegebene Bedeutung haben.In these formulas, Hal represents a halogen atom, preferably chlorine or bromine, while A, R 1 , R 2 and R 4 have the meaning given in general formula I.

In para-Stellung durch den Rest R4 substituiertes ortho Nitro-chlorbenzol wird in Gegenwart eines säurebindenden Mittels bei erhöhter Temperatur mit Resorcin umgesetet. 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, vgl: Weygand Hilgetag "Organisch Chemische Experimentierkunst, 3. Auflage 1964, 435; U.S. Patent No. 3 080 225, DE-OS 2 433 066 und DE-AS 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 about 200 ° C., see: Weygand Hilgetag "Organic Chemical Experimental Art, 3rd Edition 1964, 435; US Patent No. 3 080 225, DE-OS 2 433 066 and DE-AS 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. R 3 has the meaning of cyan or bromine, so at this stage the chlorine atom is converted, for example, by reaction with KCN [s. 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 allgemeinen Formel 1 ist dadurch gekennzeichnet, dass man in an sich bekannter Weise einen Diphenyläther der allgemeinen Formel II

Figure imgb0005
worin X Wasserstoff oder das Kation eines Alkali- oder Erdalkalimetalls bedeutet und R3 und R4 die in der allgemeinen Formel I an gegebene Bedeutung haben,
mit einem α-Halogen-carbonsäurederivat der allgemeinen Formel III
Figure imgb0006
worin A, R, und R2 die in der allgemeinen Formel I an gegebene Bedeutung haben, während Hal ein Halogenatom, vorzugsweise Chlor oder Brom bedeutet, umsetzt.The process according to the invention for the preparation of phenoxy-phenoxy-alkane carboxylic acid derivatives of the general formula 1 is characterized in that a diphenyl ether of the general formula II
Figure imgb0005
 in which X denotes hydrogen or the cation of an alkali or alkaline earth metal and R 3 and R 4 have the meaning given in general formula I,
with an α-halogeno-carboxylic acid derivative of the general formula III
Figure imgb0006
 wherein A, R, and R 2 have the meaning given in general formula I, while Hal represents a halogen atom, preferably chlorine or bromine.

Die Reaktionspartner der allgemeinen 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 bedeutet, in Gegenwart eines säurebindenden Mittels.The reactants of the general 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 dissolve the reactants 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 Herstellungsverfahren für einige Wirkstoffe der allgemeinen Formel I. Weitere in entsprechender Weise hergestellte Wirkstoffe sind in der anschliessenden Tabelle aufgeführt. Temperaturangaben bezeihen sich jeweils auf Celsius-Grade.The following examples illustrate production processes according to the invention for some active ingredients of the general formula I. Further active ingredients prepared in a corresponding manner are listed in the table below. Temperatures are in degrees Celsius.

Die Phenoxy-phenoxy-alkan-carbonsäure-Derivate der allgemeinen Formel 1 sind stabile Verbindungen, welche in üblichen organischen Lösungsmitteln, wie Alkoholen, Aethern, Ketonen, Dimethylformamid, Dimethylsulfoxyd etc. löslich sind.The phenoxy-phenoxy-alkane-carboxylic acid derivatives of the general formula 1 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'-acetoxy-diphenyläther werden in 200 ml Essigsäure gelöst und unter gutem Rühren bei 40 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'-acetoxy-diphenyl ether are dissolved in 200 ml of acetic acid and introduced with good stirring at 40 equimolar amounts of chlorine. 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-Brom-propionsäuremethylester, 18 g Kaliumcarbonat und eine Spatelspitze Kaliumjodid. Das Reaktionsgemisch wird über Nacht bei 80° 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 imgb0007
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-bromo-propionic acid methyl ester, 18 g of potassium carbonate and a spatula tip of potassium iodide are added. The reaction mixture is stirred at 80 ° bath temperature overnight, insoluble portions 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 imgb0007

Beispiel 2Example 2

  • a) 68,2 g 2-Nitro-4-trifluormethyl-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 Lösungsmittels erhält man ein festes Produkt, das aus Alkohol/Wasser unkristallisiert wird. Smp.: 129-130°, Ausbeute: 47,4 g = 61,4% d.Th.a) 68.2 g of 2-nitro-4-trifluoromethyl-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 ° C. After the dropwise addition has ended, 1/2 Stirred for an hour, the reaction product poured into water and the precipitated product 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: 47.4 g = 61.4% of theory
  • b) 47,4 g 2,4'-Dinitro-4-trifluormethyl-3'-acetoxydiphenyläther 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 HCI 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 excreted phenol 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'-hydroxydiphanyläther werden in 50 ml 2-Butanon gelöst und nach Zugabe von 13,4 g 2-Brom-propionsäuremethylester, 13,8 Kaliumcarbonat und einer Spatelspitze Kaliumjodid über Nacht bei 80°. Badtemperatur gerührt. Anschliessend wird filtriert, das Filtrat eingedampft und das erhaltene Oel im Rochvakuum destilliert. Kp: 217°/0,05 Torr Ausbeute: 6,2 g
    Figure imgb0008
         c) 17.2 g of 2,4'-dinitro-4-trifluoromethyl-3'-hydroxydiphanyl ether are dissolved in 50 ml of 2-butanone and after the addition of 13.4 g of 2-bromo-propionic acid methyl ester, 13.8 potassium carbonate and a spatula tip Potassium iodide overnight at 80 °. Bath temperature stirred. It is then filtered, the filtrate is evaporated and the oil obtained is distilled in a vacuum. Bp: 217 ° / 0.05 torr yield: 6.2 g
    Figure imgb0008

Auf analoge Weise zu diesen Beispielen sind folgende Verbindungen hergestellt worden:

Figure imgb0009
Figure imgb0010
Figure imgb0011
 The following compounds were prepared in an analogous manner to these examples:
Figure imgb0009
Figure imgb0010
Figure imgb0011

Die Erfindung betrifft auch herbizide und pflanzenwachstumsregulierende Mittel, welche einen neuen Wirkstoff der allgemeinen Formel I enthalten, 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 compositions which comprise a new active ingredient of the general 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 überlichen Formulierungen vorliegen.The agents according to the invention can be present in the above formulations.

Die Herstellung erfindungsgemässer Mittel erfolgt in an sich bekannter Weise durch inniges Vermischen und Vermahlen von Wirkstoffen der allgemeinen 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:

Figure imgb0012
The preparation he f indungsgemässer means takes place in known manner by intimately mixing and grinding of active substances of general formula I with suitable carriers, optionally with the addition of inert to the active substances dispersing or solvents. The active ingredients can be present and used in the following processing forms:
Figure imgb0012

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 allgomeinen 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 ingredients of the general formula I can be formulated, for example, as follows (parts mean parts by weight):

Stäubemittel:Dusts:

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

Figure imgb0013
Figure imgb0014
 The following substances are used to produce a) 5% and b) 2% dust:
Figure imgb0013
Figure imgb0014

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

GranulateGranules

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

Figure imgb0015
The following substances are used to produce 5% granules:
Figure imgb0015

Die Aktivsubstanz wird mit Epichlorhydrin vermischt und in 6 Teilen Aceton gelöst, hierauf werden Polyäthylenglycol und Cetylpolyäthylenglycoläther zugesetzt. Die so erhaltene Lösung wird auf Kaolin aufgesprüht und anschliessend im Vakuum verdampft.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

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

Figure imgb0016
Figure imgb0017
Figure imgb0018
 7 The following ingredients are used to produce a) 50%, b) 25% and c) 10% wettable powder:
Figure imgb0016
Figure imgb0017
Figure imgb0018

Der angegebene Wirkstoff wird auf die entsprechenden 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 imgb0019
The following substances are used to produce a 45% paste:
Figure imgb0019

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 Suspension 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 imgb0020
miteinander vermischt. Dieses Konzentrat kann mit Wasser zu Emulsionen auf geeignete Konzentrationen verdünnt werden.To prepare a 25% emulsion concentrate
Figure imgb0020
 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 allgermeinen Formel 1 umfassten Verbindungen verwendet werden.Instead of the particular active ingredient specified in the preceding formulation examples, another of the compounds encompassed by the general 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 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 allgemeinen 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 general 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 allgemeinen Formel 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, Daurregen, 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 substances of the general formula 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 to Ver the plant is reduced in stature. 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, downpours, etc., which normally lead to the storage of crops of cereals and legumes, can be largely prevented, thus making harvesting easier. As a side effect, the reduced height of crops leads to savings in fertilizers.

Eines der wichtigsten Probleme an reinen Grasbepflanzungen ist jedoch der Grasschnitt selbst, sie 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.One of the most important problems with pure grass planting, however, is the cutting of grass itself, in green areas in residential areas, on industrial sites, on sports fields, 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 and Verkehreswegen notwendige Grasnarbe einersiets 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 allgemeinen 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 shoulder strips and embankments and traffic routes, but on the other hand to keep them at a medium height during the entire growing season with simple measures. This is achieved by applying active ingredients of the general formula I according to the invention in a very favorable manner.

In analoger Weise kann durch Behandlung von Bäumen, Sträuchern und Hecken, vor allem in Wohnund Industriegebeiten, mit erfindungsgemässen Verbindungen der allgemeinen 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 general formula I according to the invention.

Durch den Einsatz erfindungsgemässer Wirkstoffe der allgemeinen Formel I können auch das Triebwachstum und/oder die Fruchtbarkeit von Obstbäumen und Reben vorteilhaft beeinflusst werden.The use of active compounds of the general 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 allgemeinen Formel 1 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 general formula 1 are also used to inhibit the growth of undesirable 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 allgemeinen Formel I zur Wachstumshemmung an Gräsern, Getreidekulturen, Tabak, Soja und Zierpflanzen ein.The active compounds of the general 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 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.

Ferner eignen sich viele der Wirkstoffe der allgemeinen Formel I 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 eine grosse Ernteerleichterung mit sich bringt.Furthermore, many of the active ingredients of the general formula I and compositions containing them are also suitable for other influences on plant growth, such as in particular to facilitate the 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 a 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 Pflanzenteile (Kontakwirkung), 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 aerial parts of the plant (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 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 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 and sugar cane. 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 allgemeinen Formel 1 zeichnen sich überdies durch eine sehr starke pre-emergente Herbizidwirkung aus, sind also auch ausgeprägte Keimungshemmer.The new active ingredients of the general formula 1 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:

  • Pre-emergente Herbizid-Wirkung (Keimhemmung)
The following test methods were used to demonstrate the usability as herbicides (pre- and post-emergent) and as growth inhibitors:
  • Pre-emergent herbicide effect (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 22­25°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 series of concentrations were used accordingly 4, 2, 1 and 0.5 kg of active ingredient per hectare. The seed pans are in the greenhouse at 2225 ° 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 (Kontaktherbizid)Post-emergent herbicide effect (contact herbicide)

Eine grössere Anzahl (mindestens 7) Unkräuter und Kulturpflanzen, sowohl monocotyle wie dicotyle, wurden nach dem Auflaufen (im 4-bis-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-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; after emergence (in the 4 to 6 leaf stage); 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 allgemeinen 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 general 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. D:e 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. D: e 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. A 3-(2'-nitrophenoxy)-a-phenoxyalkanecarboxylic acid derivative of the general formula I
Figure imgb0031
wherein
R, represents hydrogen, C1―C4alkyl or C2―C8alkoxyalkyl,
R2 represents hydrogen or C1―C4alkyl,
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 NR7R8,
R5 represents hydrogen or the cation of a base
Figure imgb0032
wherein
M represents an alkali metal or alkaline earth metal cation or an ammonium radical
Figure imgb0033
n as integer 1, 2 or 3 corresponds to the valency of the cation, whilst Ra, Rb, Re and Rd, each independently of the other, represent hydrogen, benzyl or an alkyl radical which is unsubstituted or substituted by ―OH, ―NH2 or C1―C4alkoxy; and R5 further represents,
a C1―C8alkyl 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―C8alkyl radical which can be interrupted by oxygen, sulphur, nitrogen, carbonyl or carbonyloxy,
a C3―C6cycloalkyl radical,
a C3―C6alkenyl or alkynyl radical which can be substituted by halogen,
a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, C1―C4alkyl, C1―C4alkoxy or trifluoromethyl,
R6 represents a C1―C8alkyl radical which can be substituted by halogen, cyano, nitro or hydroxyl or interrupted by oxygen, sulphur, nitrogen, carbonyl or carbonyloxy,
a C3―C6cycloalkyl radical,
a C3―C6alkenyl or alkynyl radical which can be substituted by halogen,
a phenyl or benzyl radical which can be substituted by halogen, cyano, nitro, C1―C4alkyl, C1―C4alkoxy or trifluoromethyl,
R7 represents hydrogen, a C1―C8alkyl radical which can be substituted by halogen, cyano or hydroxyl, and a C2―C8alkyl radical which can be interrupted by oxygen,
Ra represents a C1―C4alkyl radical or a C3―C4alkyl 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―C4alkylimino or phenylimino group.
2. A compound according to claim 1, wherein R1 represents hydrogen and A, R2, R3 and R4 have the given meanings.
3. A compound according to claim 1, wherein A represents ―COB, B represents ―OR5, and R1 represents hydrogen, and R2, R3, R4 and R5 have the given meanings.
4. A compound according to claim 1, wherein A represents ―COB, B represents ―NR7R8 and R1 represents hydrogen, and R2, R3, R4, R7 and Ra have the given meanings..
5. A compound according to claim 1, wherein A represents ―COB, B represents ―SR6 and R1 represents hydrogen, and R2, R3 and R4 have the given meanings.
6. a-[2-Chloro-5-(2'-nitro-4'-trifluoromethyl(phenoxy)phenoxy]propionic acid methyl ester.
7. A process for the manufacture of a 3-(2'-nitrophenoxy)-α-phenoxyalkanecarboxylic acid derivative according to claim 1, characterised in that a diphenyl ether of the general formula II
Figure imgb0034
wherein R3 and R4 have the given meanings and X represents hydrogen or the cation of an alkali metal or alkaline earth metal, is reacted, in a manner known per se, with an α-halocarboxylic acid derivative of the general formula III
Figure imgb0035
wherein A, R, and R2 have the given meanings and Hal represents a halogen atom.
8. A herbicidal and plant growth-regulating composition, characterised in that it contains, as active ingredient, at least one compound of the general formula I in claim 1.
9. The use of a 3-(2'-nitrophenoxy)-α-phenoxyalkanecarboxylic acid derivative of the general formula I in claim 1, or of a composition containing such a compound, for controlling weeds.
10. The use of a 3-(2'-nitrophenoxy)-α-phenoxyalkanecarboxylic acid derivative of the formula I in claim 1, or of a composition containing such a compound, 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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CH8068/77 1977-06-30

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DE2850902A1 (en) * 1978-11-24 1980-06-12 Hoechst Ag NEW PHENOXY-PHENOXI-PROPIONIC ACID AMIDES AND THEIR USE AS HERBICIDES
US4309210A (en) * 1978-12-01 1982-01-05 Ciba-Geigy Corporation Preemergence method of selectively controlling weeds in crops of cereals and composition therefor
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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GB1565972A (en) * 1976-04-15 1980-04-23 Sori Soc Rech Ind M-substituted phenoxypropionic acid dervatives
DE2632581C2 (en) * 1976-07-20 1982-07-15 Hoechst Ag, 6000 Frankfurt Substituted nitrodiphenyl ethers, processes for their preparation and herbicidal compositions containing them
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