EP0000176A1 - Pyridyloxy-phenoxy-alkanoic acid derivatives , processes for their preparation and their use as herbicides or plant growth regulators - Google Patents
Pyridyloxy-phenoxy-alkanoic acid derivatives , processes for their preparation and their use as herbicides or plant growth regulators Download PDFInfo
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- EP0000176A1 EP0000176A1 EP78100209A EP78100209A EP0000176A1 EP 0000176 A1 EP0000176 A1 EP 0000176A1 EP 78100209 A EP78100209 A EP 78100209A EP 78100209 A EP78100209 A EP 78100209A EP 0000176 A1 EP0000176 A1 EP 0000176A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/83—Thioacids; Thioesters; Thioamides; Thioimides
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
- C07D213/85—Nitriles in position 3
Definitions
- the present invention relates to new pyridyloxy-phenoxy-alkane carboxylic acid derivatives which have a herbicidal and plant growth-regulating action, processes for their preparation, compositions which comprise these new compounds as active compounds, and the use of the new active compounds or the compositions containing them for selective purposes Control weeds and regulate plant growth.
- the alkyl radicals in this formula can be branched or unbranched and contain the stated number of carbon atoms.
- the radicals R 5 and R 6 can be hydrogen or aliphatic, cycloaliphatic, aromatic radicals or, together with the nitrogen atom to which they are attached, they can form a heterocyclic, preferably 5-6-membered, heterocycle which can also contain a second heteroatom.
- hydrogen and lower, C 1 -C 4 alkyl radicals are preferred.
- the new active compounds of the formula I according to the present invention have herbicidal activity, especially in the case of post-emergence use, and can be used as weed agents in mono- and dicotyledon crops.
- the compounds of the present invention are not very toxic to warm-blooded animals and their application poses no problems.
- the application rate is between 0.1 and 5 kg per hectare.
- the new compounds of formula I are prepared according to. known methods.
- an optionally substituted halopyridine of the formula II is used.
- C, D , E and n have the meaning given under formula I and
- Hal represents a halogen atom, preferably chlorine or bromine, with a hydroxyphenoxyalkanecarboxylic acid derivative of the formula III wherein A, C, D, R 1 and R 2 have the meaning given under formula I in the presence of an acid-binding agent.
- the pyridyloxy-phenoxy-alkane carboxylic acid derivatives of the formula I are prepared by using a pyridyloxy-hydroxyphenyl ether of the formula IV wherein C, D, E and n have the meaning given under formula I, with an a-halocarboxylic acid derivative of the formula V.
- A, R 1 and R 2 have the meaning given under formula I and Hal represents a halogen atom, preferably chlorine or bromine, in the presence of an acid-binding agent.
- the reactions mentioned can be carried out in the presence or absence of solvents or diluents which are inert to the reactants.
- Polar organic solvents such as methyl ethyl ketone, acetonitrile, dimethylformamide, dimethyl sulfoxide etc. are preferred.
- the reaction temperatures are between 0 and 200 ° and the reaction time is between 1/4 hour and several days, depending on the reaction temperature and solvent chosen. You usually work at normal pressure or a slight overpressure.
- acid-binding agents for the reaction come inorganic such as NaOH, KOH, NaOCH 3 , NaH, K 2 CO 3 , NaC0 3 , potassium tert. butylate etc. but also organic bases.
- Substituted 2-halopyridine according to formula II can i.a. can be easily prepared from the corresponding 2-pyridinols, some of which are known.
- Starting materials of formula III can be prepared by e.g. reacting a monobenzyl ether of hydroquinone, resorcinol or catechol with an ⁇ -halocarboxylic acid derivative, preferably an ester of the formula V, and cleaving the benzylphenyl ether bond by catalytic hydrogenation, e.g. with a palladium on carbon catalyst, the benzyl residue leaving as toluene.
- the starting products of the formula IV can be obtained by reacting hydroquinone, resorcinol or pyrocatechol with halopyridines in equimolar amounts and in the presence of a base.
- Carboxylic acid derivatives of the formula V are also known. The simplest representatives are, for example, chloroacetic acid and its esters; Thioesters, amides and hydrazides mentioned. But there are also other ⁇ -halocarboxylic acid derivatives substituted according to R 1 and R 2 .
- pyridyloxy-phenoxy-alkane carboxylic acid derivatives of the formula I are stable compounds which are soluble in customary organic solvents, such as alcohols, ethers, ketones, dimethylformamide, dimethyl sulfoxide etc.
- 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.
- 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:
- the active ingredients are mixed and ground with the carriers.
- the active substance is mixed with epichlorhidrin and dissolved in 6 parts of acetone, whereupon polyethylene glycol and cetylpolyethylene glycol ether are added.
- the solution thus obtained is sprayed onto kaolin and then evaporated in vacuo.
- the specified active ingredient is drawn onto the corresponding carrier substances (kaolin and chalk) and then mixed and ground. Spray powder of excellent wettability and suspension is obtained. Suspensions of any desired active ingredient concentration can be obtained from such wettable powders by dilution with water. Such suspensions Ions are used to control weeds and grass weeds in pre-emergence crops and to treat lawns.
- the active ingredient is intimately mixed and ground with the additives in suitable equipment.
- a paste is obtained, from which suspensions of any desired concentration can be prepared by dilution with water.
- the suspensions are suitable for the treatment of lawns.
- This concentrate can be diluted with water to emulsions to suitable concentrations.
- the active substances contained in the agents according to the invention influence plant growth in various ways. In the first place, they inhibit, delay or prevent growth and germination. It is therefore both a pre- and post-emergent herbicide effect 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 monocotyledon and dicotyledonous plants, such as grasses, shrubs, trees, crops of cereals and legumes, sugar cane, tobacco, soybeans, onions and potato tubers, ornamental plants, fruit trees and vines.
- monocotyledon and dicotyledonous plants such as grasses, shrubs, trees, crops of cereals and legumes, sugar cane, tobacco, soybeans, onions and potato tubers, ornamental plants, fruit trees and vines.
- the effect achieved primarily by the 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 plant. In direct connection with the reduction in growth height, the plant is strengthened; leaves and stems are more strongly developed. 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, reduced height of crops in crops leads to EL savings in fertilizers. This also applies to ornamental plants, ornamental turf, sports turf or other green plants.
- the labor-intensive cutting work can be reduced by treating trees, bushes 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.
- Ornamental plants with strong growth in length can be grown as compact potted plants by treatment with active substances according to the invention.
- the active compounds of the formula I are also used to inhibit the growth of undesired poultry drives, e.g. in tobacco and ornamental plants, which avoids the labor-intensive breakout of these shoots by hand, further to inhibit expulsion of stored tubers, for example ornamental plant tubers, onions and potatoes, and finally to increase the yield of strongly growing vegetative crops, such as soybeans and sugar cane, by Application of active ingredients 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, preferably up to 4 kg per hectare when applied before emergence of the plants and for the treatment of existing crops.
- This inhibition of growth occurs in some plant species at a dosage of 0.5 kg / ha and below.
- the active compounds according to the invention are also interesting combination partners for a number of herbicides of the phenylurea and triazine series in cereal crops, maize and sugar cane. in fruit and wine growing.
- the active compounds according to the invention can be used as growth inhibitors in a wide variety of crops.
- the weed cover is not removed, but only so strongly inhibited that there is no longer any competition between the crop plants.
- 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 compounds tested 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.
- the active substances according to the invention cause a noticeable growth inhibition both in the grasses and in the cereals.
Abstract
Die vorliegende Erfindung betrifft neue Pyridyloxyphenoxy-alkancarbonsäurederivate mit herbizider und das Pflanzenwaschstum beeinflussender Wirkung, ein Verfahren zur Herstellung dieser Derivate, Mittel welche diese Verbindungen enthalten sowie die Verwendung derselben. Die neuen Pyridyloxy-phenoxy-alkancarbonsäurederivate entsprechen der Formel <IMAGE> worin A eine Cyanogruppe, eine Carboxylgruppe ein Ester-, Thioester-, Amidrest, ein Carboxyl-Kation oder quat. Ammoniumsalz, C bis E individuell Reste, ausgelesen aus Wasserstoff, Halogen, Alkyul, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Thiocarbamid, Monooder Di-alkyl-sulfamoyl, Alkoxy-alkyl-sulfamoyl, Alkoxyalkyl, Cyano und Nitro, n 0, 1 oder 2, R1 Wasserstoff, Alkyl, Haloalkyl oder Alkoxyalkyl, R2 Wasserstoff, Alkyl, Carboxyl oder Alkoxycarbonyl Bedeuten.The present invention relates to new pyridyloxyphenoxy-alkanecarboxylic acid derivatives having a herbicidal action which influences plant laundering, a process for the preparation of these derivatives, compositions which comprise these compounds and the use thereof. The new pyridyloxy-phenoxy-alkane carboxylic acid derivatives correspond to the formula <IMAGE> in which A is a cyano group, a carboxyl group, an ester, thioester or amide radical, a carboxyl cation or quat. Ammonium salt, C to E individual residues, selected from hydrogen, halogen, alkylul, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, thiocarbamide, mono or di-alkylsulfamoyl, alkoxy-alkylsulfamoyl, alkoxyalkyl, cyano and nitro, n 0, 1 or 2, R1 is hydrogen, alkyl, haloalkyl or alkoxyalkyl, R2 is hydrogen, alkyl, carboxyl or alkoxycarbonyl.
Description
Die vorliegende Erfindung betrifft neue Pyridyloxy-phenoxy-alkancarbonsäurederivate, welche eine herbizide und das Pflanzenwachstum regulierende Wirkung zeigen, Verfahren zu ihrer Herstellung, ferner Mittel, die diese neuen Verbindungen als Wirkstoffe enthalten, sowie die Verwendung der neuen Wirkstoffe oder der sie enthaltenden Mittel zur selektiven Bekämpfung von Unkräutern und zur Regulierung des Pflanzenwachstums.The present invention relates to new pyridyloxy-phenoxy-alkane carboxylic acid derivatives which have a herbicidal and plant growth-regulating action, processes for their preparation, compositions which comprise these new compounds as active compounds, and the use of the new active compounds or the compositions containing them for selective purposes Control weeds and regulate plant growth.
Die neuen Wirkstoffe entsprechen der Formel I
- A die Cyanogruppe, einen Rest -COB oder ein gegebenenfalls durch Methyl ein- oder mehrfach substituierter 2-Oxazolinrest,
- B einen Rest -OR3, -SR4 oder -NR5 R 6,
- C je Halogen, C1-C4 Alkyl oder Nitro,
- D je Wasserstoff, dasselbe wie C, C1-C4 Alkaxy, C1-C4 Alkylthio, Cyano, C1-C4 Alkylsulfinyl, C1-C4 Alkylsulfonyl, Thiocarbamid (-CSNH2), Mono- oder Di- C1-C4 alkylsulfamoyl,
- E Wasserstoff, dasselbe wie C, C1-C4 Alkoxy Mono- oder Di-C1-C4 Alkylamin, C1-C5 Alkoxycarbonyl, C2-C8 Alkoxyalkyl, Cyano, Trifluormethyl,
- n 0, 1 oder 2
- R1 Wasserstoff, C1-C4 Alkyl, C2-C8 Alkoxyalkyl, C1-C4 Haloalkyl,
- R2 Wasserstoff C1-C4 Alkyl, Carbonyl, C1-C5 Alkoxycarbonyl
- R3 Wasserstoff oder das Kation einer Base
- M ein Alkali-, Erdalkali-Kation oder ein Fe, Cu-, Zn-,
- m als ganze Zahl 1, 2 oder 3 die Wertigkeit des Kations berücksichtigt, während Ra, Rb, Rc und Rd unabhängig voneinander Wasserstoff, Benzyl cder einen gegebenenfalls durch -OH, -NH2 oder C1-C4 Alkoxy substituierten C1-C4 Alkylrest bedeuten. Weiter bedeutet
- R3 einen C1-C18 Alkyl-Rest, der unsubstituiert oder gegebenenfalls substituiert ist durch Halogen, Nitro, Cyano, C1-C8 Alkoxy, C2-C8-Alkoxyalkoxy; C3-C6 Alkenyloxy, C1-C8 Alkylthio, C2-C8 Alkanoyl, C2-C8 Acyloxy, C2-C8 Alkoxycarbonyl, Carbamoyl; Bis (C1-C4 alkyl)amino, Tris (C1-C4 alkyl)ammonio, C3-C8 Cycloalkyl, C3-C8 Cycloalkenyl, gegebenenfalls auch durch einen unsubstituierten oder seinerseits durch Halogen, C1-C4-Alkyl, C1-C4-Alkoxy ein- oder mehrfach substituierten Phenyl-, Phenoxy- oder 5-6-gliedrigen heterocyclischen Rest mit 1 bis 3 Heteroatomen;
- - einen unsubstituierten oder ein- bis vierfach durch Halogen oder einem durch Phenyl oder Methoxycarbonyl substituierten C3-C10 Alkenylrest;
- - einen C3-C8 Alkinyl-Rest;
- - einen gegebenenfalls durch Halogen oder C1-C4 Alkyl substituierten C3-C12 Cycloalkyl-Rest;
- - einen C3-C8 Cycloalkylen-Rest;
- - einen Phenylrest, der unsubstituiert oder durch Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkylthio, NO2, CF3, COOH, CN, OH, SO3H, NH2 oder -NH(C1-C4 Alkyl) oder -N(C1-C4 Alkyl)2 ein- oder mehrfach substituiert ist; weiter bedeutet R3
- - einen 5- bis 6-gliedrigen heterocyclischen Ring mit 1 bis 3 Heteroatomen;
- R 4 einen C1-C12 Alkyl-Rest, der unsubstituiert oder gegebenenfalls substituiert ist durch C1-C8 Alkoxy, C2-C8 Alkoxycarbonyl, C3-C8-Cycloalkyl, gegebenenfalls auch durch einen unsubstituierten oder seinerseits durch Halogen, C1-C4-Alkyl, C1-C4-Alkoxy ein- oder mehrfach substituierten Phenyl-, oder 5-6-gliedrigen heterocyclischen Rest mit 1 bis 3 Heteroatomen;
- - einen unsubst. C3-C12 Alkenyl-Rest;
- - einen gegebenenfalls durch C1-C4-Alkyl substituierten C3-C12 Cycloalkyl-Rest; 12
- - einen Phenylrest, der unsubstituiert oder durch Halogen, C1-C4-Alkyl, C1-C4-Alkoxy, C1-C4-Alkylthio, NO2, CF3, ein- oder mehrfach substituiert ist;
- - einen 5- bis 6-gliedrigen heterocyclischen-Ring mit 1 bis 3 Heteroatomen;
- R- und R6 Wasserstoff oder gegebenenfalls substituierte aliphatische oder cycloaliphatische,aromatische . oder heterocyclische Reste,
wobei die Bestimmung gilt, dass der Alkancarbonsäurerest
- A is the cyano group, a -COB radical or a 2-oxazoline radical which is optionally mono- or polysubstituted by methyl,
- B is a radical -OR 3 , -SR 4 or -NR 5 R 6 ,
- C per halogen, C 1 -C 4 alkyl or nitro,
- D each hydrogen, the same as C, C 1 -C 4 alkaxy, C 1 -C 4 alkylthio, cyano, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, thiocarbamide (-CSNH 2 ), mono- or di- C 1 -C 4 alkylsulfamoyl,
- E hydrogen, the same as C, C 1 -C 4 alkoxy mono- or di-C 1 -C 4 alkylamine, C 1 -C 5 alkoxycarbonyl, C 2 -C 8 alkoxyalkyl, cyano, trifluoromethyl,
- n 0, 1 or 2
- R 1 is hydrogen, C 1 -C 4 alkyl, C 2 -C 8 alkoxyalkyl, C 1 -C 4 haloalkyl,
- R2 hydrogen C 1 -C 4 alkyl, carbonyl, C 1 -C 5 alkoxycarbonyl
- R3 is hydrogen or the cation of a base
- M an alkali, alkaline earth cation or an Fe, Cu, Zn,
- m 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 C 1 -C 4 alkyl radical. Next means
- R 3 is a C 1 -C 18 alkyl radical which is unsubstituted or optionally substituted by halogen, nitro, cyano, C 1 -C 8 alkoxy, C 2 -C 8 alkoxyalkoxy; C 3 -C 6 alkene y loxy, C 1 -C 8 alkylthio, C 2 -C 8 alkanoyl, C 2 -C 8 acyloxy, C 2 -C 8 alkoxycarbonyl, carbamoyl; Bis (C 1 -C 4 alkyl) amino, tris (C 1 -C 4 alkyl) ammonio, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkenyl, optionally also by an unsubstituted or in turn by halogen, C 1 -C 4- alkyl, C 1 -C 4 -alkoxy mono- or polysubstituted phenyl, phenoxy or 5-6-membered heterocyclic radical with 1 to 3 heteroatoms;
- - An unsubstituted or mono- to tetrasubstituted by halogen or a C 3 -C 10 alkenyl radical substituted by phenyl or methoxycarbonyl;
- - a C 3 -C 8 alkynyl radical;
- - A C 3 -C 12 cycloalkyl radical optionally substituted by halogen or C 1 -C 4 alkyl;
- - a C 3 -C 8 cycloalkylene radical;
- a phenyl radical which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, NO 2 , CF 3 , COOH, CN, OH, SO 3 H, NH 2 or -NH (C 1 -C 4 alkyl) or -N (C 1 -C 4 alkyl) 2 is mono- or polysubstituted; furthermore R 3 means
- - A 5- to 6-membered heterocyclic ring with 1 to 3 heteroatoms;
- R 4 is a C 1 -C 12 alkyl radical which is unsubstituted or optionally substituted by C 1 -C 8 alkoxy, C 2 -C 8 alkoxycarbonyl, C 3 -C 8 cycloalkyl, optionally also by an unsubstituted or in turn by halogen , C 1 -C 4 alkyl, C 1 -C 4 alkoxy mono- or polysubstituted phenyl, or 5-6-membered heterocyclic radical having 1 to 3 heteroatoms;
- - an unsubst. C 3 -C 12 alkenyl residue;
- - A C 3 -C 12 cycloalkyl radical optionally substituted by C 1 -C 4 alkyl; 12
- - A phenyl radical which is unsubstituted or substituted by halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, NO 2 , CF 3 , one or more times;
- - A 5- to 6-membered heterocyclic ring with 1 to 3 heteroatoms;
- R - and R 6 are hydrogen or optionally substituted aliphatic or cycloaliphatic, aromatic. or heterocyclic radicals,
the provision being that the alkane carboxylic acid residue
Die Alkylreste in dieser Formel können verzweigt oder unverzweigt sein und enthalten die angegebene Anzahl Kohlenstoffatome. Die Reste R5 und R6 können Wasserstoff oder aliphatische, cycloaliphatische, aromatische Reste sein oder sie können, zusammen mit dem Stickstoffatom an das sie gebunden sind einen heterocyclischen vorzugsweise 5-6 gliedrigen Heterocyclus bilden, der auch noch ein zweites Heteroatom enthalten kann. Bevorzugt jedoch sind Wasserstoff und niedrige, C1-C4 Alkylreste.The alkyl radicals in this formula can be branched or unbranched and contain the stated number of carbon atoms. The radicals R 5 and R 6 can be hydrogen or aliphatic, cycloaliphatic, aromatic radicals or, together with the nitrogen atom to which they are attached, they can form a heterocyclic, preferably 5-6-membered, heterocycle which can also contain a second heteroatom. However, hydrogen and lower, C 1 -C 4 alkyl radicals are preferred.
Die neuen Wirkstoffe der Formel I gemäss vorliegender Erfindung besitzen 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 herbicidal activity, especially in the case of post-emergence use, and can be used as weed agents in mono- and dicotyledon crops.
Ferner besitzen sie günstige wachstumsregulierende Effekte (Wuchshemrnung). Insbesondere hemmen sie das Wachstum von dicotylen Pflanzen. Beispiele für die nutzbringende Anwendung der erfindungsgemässen Verbindungen sind z.B.
- - die Reduktion des vegetativen Wachstums bei Soja und ähnlichen Leguminosen, was zu einer Ertragssteigerung dieser Kulturen führt;
- - die Hemmung des unerwünschten Wuchstums von Geiztrieben bei Tabak, dessen Haupttrieb man geschnitten hat, was der Ausbildung grösserer und schönerer Blätter zugute kommt;
- - die Hemmung des Wachstums von Gras und dikotyledonen Pflanzen, wie Obstbäume, Zierbäume, Gebüsche und Hecken, zwecks Einsparung an Schnittarbeit.
- - the reduction of vegetative growth in soybeans and similar legumes, which leads to an increase in the yield of these crops;
- - the inhibition of the undesirable growth of stinging shoots in tobacco, the main shoot of which has been cut, which benefits the formation of larger and more beautiful leaves;
- - inhibiting the growth of grass and dicot plants, such as fruit trees, ornamental trees, bushes and hedges, in order to save on cutting work.
Die Verbindungen vorliegender Erfindung sind wenig giftig für Warmblüter und deren Applikation wirft keine Probleme auf. Die Aufwandmenge liegt zwischen 0.1 und 5 kg pro Hektar.The compounds of the present invention are not very toxic to warm-blooded animals and their application poses no problems. The application rate is between 0.1 and 5 kg per hectare.
Die Herstellung der neuen Verbindungen der Formel I erfolgt nach an. sich bekannten Methoden.The new compounds of formula I are prepared according to. known methods.
Nach einem ersten dieser Verfahren setzt man ein gegebenenfalls substituiertes Halogen-pyridin der Formel II .
Solche Umsetzungen sind an sich bekannt und ihre genaue Durchführung kann in Textbüchern wie z.B. in Houben-Weyl, Band,3, Seiten 85 ff nachgelesen werden.Such implementations are known per se and their exact implementation can be found in text books such as in Houben-Weyl, volume, 3, pages 85 ff.
Gemäss einem zweiten Verfahren stellt man die Pyridyloxy-phenoxy-alkancarbonsäurederivate der Formel I her, indem man einen Pyridyloxy-hydroxyphenyläther der Formel IV
Die genannten Umsetzungen können in An- oder Abwesenheit von gegenüber den Reaktionsteilnehmern inerten Lösungs- oder Verdünnungsmitteln durchgeführt werden. Bevorzugt sind polare organische Lösungsmittel wie Methyläthylketon, Acetonitril, Dimethylformamid, Dimethylsulfoxid etc. Die Reaktionstemperaturen liegen zwischen 0 und 200° und die Reaktionsdauer beträgt je nach gewählter Umsetzungstemperatur und Lösungsmittel , zwischen 1/4 Stunden und mehreren Tagen. Man arbeitet .in der Regel bei Normaldruck oder einem leichten Ueberdruck. Als säurebindende Mittel für die Umsetzung kommen anorganische wie z.B. NaOH, KOH, NaOCH3, NaH, K2CO3, NaC03, Kalium-tert. butylat etc. aber auch organische Basen in Betracht.The reactions mentioned can be carried out in the presence or absence of solvents or diluents which are inert to the reactants. Polar organic solvents such as methyl ethyl ketone, acetonitrile, dimethylformamide, dimethyl sulfoxide etc. are preferred. The reaction temperatures are between 0 and 200 ° and the reaction time is between 1/4 hour and several days, depending on the reaction temperature and solvent chosen. You usually work at normal pressure or a slight overpressure. As acid-binding agents for the reaction come inorganic such as NaOH, KOH, NaOCH 3 , NaH, K 2 CO 3 , NaC0 3 , potassium tert. butylate etc. but also organic bases.
Die Ausgangsstoffe der Formel II bis V sind teilweise bekannt. Noch nicht beschriebene Ausgangsstoffe dieser Formeln lassen sich nach üblichen Verfahren und Techniken leicht herstellen.Some of the starting materials of the formulas II to V are known. Starting materials of these formulas that have not yet been described can be easily prepared by customary processes and techniques.
Substituierte 2-Halogen-pyridin gemäss Formel II können u.a. leicht aus den entsprechenden 2-Pyridinolen hergestellt werden, welche teilweise bekannt sind. Ausgangsprodukte der Formel III können hergestellt werden, indem man z.B. einen Monobenzyläther von Hydrochinon, Resorcin oder Brenzkatechin mit einem a-Halogencarbonsäurederivat, vorzugsweise einem Ester der Formel V umsetzt und die Benzyl-phenyläther Bindung durch katalytische Hydrierung spaltet z.B. mit einem Palladium auf Kohle Katalysator, wobei der Benzylrest als Toluol weggeht.Substituted 2-halopyridine according to formula II can i.a. can be easily prepared from the corresponding 2-pyridinols, some of which are known. Starting materials of formula III can be prepared by e.g. reacting a monobenzyl ether of hydroquinone, resorcinol or catechol with an α-halocarboxylic acid derivative, preferably an ester of the formula V, and cleaving the benzylphenyl ether bond by catalytic hydrogenation, e.g. with a palladium on carbon catalyst, the benzyl residue leaving as toluene.
Durch Umsetzung von Hydrochinon, Resorcin oder Brenzkatechin mit Halogenpyridinen in äquimolaren Mengen und in Gegenwart einer Base kann man zu den Ausgangsproduktender Formel IV gelangen.The starting products of the formula IV can be obtained by reacting hydroquinone, resorcinol or pyrocatechol with halopyridines in equimolar amounts and in the presence of a base.
Carbonsäurederivate der Formel V sind ebenfalls bekannt. Als deren einfachste Vertreter seien z.B. die Chloressigsäure, deren Ester; Thioester, Amide und Hydrazide erwähnt. Es kommen aber auch,andere gemäss R1 und R2 substituierte a-Halogencarbonsäure-derivate in Betracht.Carboxylic acid derivatives of the formula V are also known. The simplest representatives are, for example, chloroacetic acid and its esters; Thioesters, amides and hydrazides mentioned. But there are also other α-halocarboxylic acid derivatives substituted according to R 1 and R 2 .
Die nachfolgenden Beispiele veranschaulichen das erfindungsgemässe Verfahren für willkürlich ausgewählte Wirkstoffe der Formel I. Weitere in entsprechender Weise hergestellte Wirkstoffe sind in den anschliessenden Tabellen aufgeführt. Temperaturangaben beziehen sich jeweils auf Celsius-Grade.The following examples illustrate the process according to the invention for arbitrarily selected active substances of the formula I. Further active substances produced in a corresponding manner are listed in the tables below. Temperatures refer to degrees Celsius.
Diese Pyridyloxy-phenoxy-alkancarbonsäurederivate der Formel I sind stabile Verbindungen, welche in üblichen organischen Lösungsmitteln, wie Alkoholen, Aethern, Ketonen, Dimethylformamid, Dimethylsufoxid etc. löslich sind.These pyridyloxy-phenoxy-alkane carboxylic acid derivatives of the formula I are stable compounds which are soluble in customary organic solvents, such as alcohols, ethers, ketones, dimethylformamide, dimethyl sulfoxide etc.
Zu einer Dispersion von 2,6 g (0,11 Mol) Natriumhydrid in 100 ml Dimethylsulfoxid werden 19,6 g (0,1 Mol) 3-Hydroxy-phenoxy-α-propionsäuremethylester, gelöst in 50 ml Dimethylsulfoxid, unter Kühlen zugetropft. Wenn sich alles Natriumhydrid gelöst hat, werden 18,7g (0,1 Mol) 2,3-Dichlor-5-cyano-6-methyl-pyridin zugegeben. Nach 8-stündigem Rühren bei Raumtemperatur wird das Dimethylsulfoxid am Vakuum abgedampft, der Rückstand mit 500 ml Eiswasser versetzt und mit Aether ausgeschüttelt. Die Ae-therextrakte werden über Magnesiumsulfat getrocknet und eingedampft. Der Rückstand wird aus Aether/Petroläther umkristallisiert..Man erhält 20,1 g (58% der Theorie) a-[3-(3'-Chlor-5'-cyano-6'-methyl-pyrid-2'-yl)oxy-phenoxyj-propionsäure-methylester vom Schemlzpunkt 106-109° .19.6 g (0.1 mol) of methyl 3-hydroxyphenoxy-α-propionate, dissolved in 50 ml of dimethyl sulfoxide, are added dropwise with cooling to a dispersion of 2.6 g (0.11 mol) of sodium hydride in 100 ml of dimethyl sulfoxide. When all sodium hydride has dissolved, 18.7 g (0.1 mol) of 2,3-dichloro-5-cyano-6-methyl-pyridine are added. After stirring for 8 hours at room temperature, the dimethyl sulfoxide is evaporated off in vacuo, the residue is mixed with 500 ml of ice water and extracted with ether. The AE extracts are dried over magnesium sulfate and evaporated. The residue is recrystallized from ether / petroleum ether. 20.1 g (58% of theory) of a- [3- (3'-chloro-5'-cyano-6'-methyl-pyrid-2'-yl) are obtained. oxy-phenoxyj-propionic acid methyl ester with a melting point of 106-109 °.
30,8 g (0,1 Mol) 3-(3',5'-Dichlorpyrid-2'-yl)-oxy-phenol 18,2 g (0,13Mol) Kaliumcarbonat und 22 g α-Brompropion- , säuremethylester werden in 300 ml Aethylmethylketon während 3 Stunden unter Rückfluss erhitzt. Dann werden die anorganischen Salze abfiltriert und das Filtrat eingedampft. Durch Umkristallisieren aus Aether/Petroläther erhält man 29 g (70% der Theorie) Titelprodukt mit dem Schmelzpunkt 58-60°.30.8 g (0.1 mol) of 3- (3 ', 5'-dichloropyrid-2'-yl) oxyphenol, 18.2 g (0.13 mol) of potassium carbonate and 22 g of methyl α-bromopropionate heated in 300 ml of ethyl methyl ketone under reflux for 3 hours. Then the inorganic salts are filtered off and the filtrate is evaporated. Recrystallization from ether / petroleum ether gives 29 g (70% of theory) of the title product with a melting point of 58-60 °.
17,3 g (0,05 Mol) a-[3-(3',5'-Dichlorpyrid-2-yl)-oxy- phenoxyl-propionsäure-methylester (siehe Beispiel 2) werden in 260 ml Tetrachlorkohlenstoff und 17,3 ml Eisessig gelöst. Nach Zugabe einer katalytischen Menge Antimontrichlorid werden bei 50° 3,5 g Chlor eingeleitet. Nach einer Stunde wird die Lösung eingedampft und das zurückbleibende Oel aus Aether/Petroläther umkristallisiert. Man erhält so das Titelprodukt vom Schmelzpunkt 76-78°.17.3 g (0.05 mol) of a- [3- (3 ', 5'-dichloropyrid-2-yl) -oxy-phenoxyl-propionic acid methyl ester (see Example 2) are dissolved in 260 ml of carbon tetrachloride and 17.3 ml of glacial acetic acid dissolved. After adding a catalytic amount of antimony trichloride, 3.5 g of chlorine are introduced at 50 °. After one hour, the solution is evaporated and the remaining oil is recrystallized from ether / petroleum ether. The title product of melting point 76-78 ° is thus obtained.
Eine Mischung von 256 g 3-(3',5'-Dichlorpyridyl-2'-oxy)-phenol, 1,9 Liter Eisessig und 280 ml Acetanhydrid wird während 12 Stunden bei Rückflusstemperatur gerührt. Die Lösung wird auf 40° gekühlt. Dann wird unter Rühren 81 g Natriumacetat zugegeben und während 7 Stunden bei 40° 106 g Chlorgas eingeleitet. Das überschüssige Chlorgas wird durch ein 2-stündiges Durchleiten von Stickstoff entfernt und die Lösung eingedampft.A mixture of 256 g of 3- (3 ', 5'-dichloropyridyl-2'-oxy) phenol, 1.9 liters of glacial acetic acid and 280 ml of acetic anhydride is stirred at reflux temperature for 12 hours. The solution is cooled to 40 °. Then 81 g of sodium acetate are added with stirring and 106 g of chlorine gas are passed in at 40 ° for 7 hours. The excess chlorine gas is removed by passing nitrogen through for 2 hours and the solution is evaporated.
Die Essigesterlösung (1000 ml) des öligen Rückstande wird mit Wasser und gesättigter NaHCO3-Lösung gewaschen, getrocknet und eingedampft. Man erhält 343 g der Tittlverbindung als braunes Oel, das mit 300 ml Petroläther verrieben, spontan kristallisiert. Smp: 71-75°C.The ethyl acetate solution (1000 ml) of the oily residue is washed with water and saturated NaHCO 3 solution, dried and evaporated. 343 g of the Tittl compound are obtained as a brown oil, which is triturated with 300 ml of petroleum ether and crystallizes spontaneously. M.p .: 71-75 ° C.
Eine Suspension von 2,26 g pulverisiertem KOH und 10 g 3-(3',5'-Dichlorpyridyl-2'-oxy)-6-phenylacetat in 30 ml absolutem Methanol wird unter Stickstoffatmosphäre während 20 Minuten bei 60° gerührt, auf Raumtemperatur gekühlt, mit,3,7 ml konzentrierter Salzsäure sauer gestellt und eingedampft.A suspension of 2.26 g of powdered KOH and 10 g of 3- (3 ', 5'-dichloropyridyl-2'-oxy) -6-phenylacetate in 30 ml of absolute methanol is stirred under a nitrogen atmosphere at 60 ° for 20 minutes to room temperature cooled, acidified with 3.7 ml of concentrated hydrochloric acid and evaporated.
Die Toluollösung (50 ml) des Rückstandes wird mit Wasser gewaschen, getrocknet, über Aktivkohle filtriert und eingedampft. Man erhält 8,4 g eines Oels, das' aus einem Gemisch des
-6-Chlor- und -4-Chlorphenolisomeren im Verhältnis 7:3 besteht.The toluene solution (50 ml) of the residue is washed with water, dried, filtered through activated carbon and evaporated. 8.4 g of an oil are obtained which 'from a mixture of
-6-chloro and -4-chlorophenol isomers in a ratio of 7: 3.
25 g (0.085 Mol) eines Gemisches von 3-(3',5'-Dichlor- pyridyl-2'-oxy)-6-chlorphenol und 3-(3',5'-Dichlorpyridyl--2'-oxy)-4-chlorphenol (hergestellt nach Beispiel 5) 14,2 g (0.085 Mol) a-Brompropionsäure-methylester und 13,8 g (0.1 Mol) Kaliumcarbonat werden in 250 ml Methyläthylketon 6 Stunden unter Rückfluss erhitzt. Die anorganischen Salze werden abfiltriert und das Filtrat eingedampft. Das zurückbleibende gelbe Oel wird aus Aether/Petroläther umkristallisiert. Man erhält so 30,1 g (94 % der Theorie) isomerenfreies Titelprodukt vom Schmelzpunkt 82-83°.25 g (0.085 mol) of a mixture of 3- (3 ', 5'-dichloropyridyl-2'-oxy) -6-chlorophenol and 3- (3', 5'-dichloropyridyl - 2'-oxy) - 4-chlorophenol (prepared according to Example 5) 14.2 g (0.085 mol) of methyl a-bromopropionate and 13.8 g (0.1 mol) of potassium carbonate are heated under reflux in 250 ml of methyl ethyl ketone for 6 hours. The inorganic salts are filtered off and the filtrate is evaporated. The remaining yellow oil is recrystallized from ether / petroleum ether. This gives 30.1 g (94% of theory) of isomer-free title product with a melting point of 82-83 °.
Eine Mischung vbn 205 g 3-(3',5'-Dichlorpyridyl-2'-oxy)-phenol, 1,1 Liter Eisessig und 224 ml Acetanhydrid wird während 12 Stunden bei Rückflusstemperatur gerührt. Die Lösung wird auf 60° gekühlt, dann wird unter Rühren 64,8 g Natriumacetat zugegeben und während 53/4 Stunden eine Lösung von 102 ml Brom in 400 ml Eisessig bei - 60° zugetropft. Die Lösung wird eingedampft, der Rückstand in Essigester gelöst und die organische Phase ' nacheinander mit Wasser und gesättigtem NaHCO3-Lösung gewaschen. Die vereinigten Essigesterextrakte werden getrocknet und eingedampft. Man erhält 302,5 g eines Oels, das mit 500 ml Petroläther (Sdp. 60-90°C) überschichtet kristallisiert.A mixture of 205 g of 3- (3 ', 5'-dichloropyridyl-2'-oxy) phenol, 1.1 liters of glacial acetic acid and 224 ml of acetic anhydride is stirred at reflux temperature for 12 hours. The solution is cooled to 60 °, then 64.8 g of sodium acetate are added with stirring and a solution of 102 ml of bromine in 400 ml of glacial acetic acid is added dropwise at -60 ° for 5 3/4 hours. The solution is evaporated, the residue is dissolved in ethyl acetate and the organic phase is washed successively with water and saturated NaHCO 3 solution. The combined ethyl acetate extracts are dried and evaporated. 302.5 g of an oil are obtained, which are crystallized with 500 ml of petroleum ether (bp 60-90 ° C.).
Das Titelprodukt schmilzt nach Umkristallisieren aus Cyclohexan bei 106-107°.After recrystallization from cyclohexane, the title product melts at 106-107 °.
Eine Suspension von 28,0 g pulverisiertem KOH und 153,5 g 3-(3',5'-Dichlorpyridyl-2'-oxy-)-6-brom-phenylacetat in einem Liter absolutem Methanol wird unter Stickstoffatmosphäre während 20 Minuten bei 60° gerührt, eingeengt und bei Raumtemperatur mit konzentrierter Salzsäure sauer gestellt und vollständig eingedampft.A suspension of 28.0 g of powdered KOH and 153.5 g of 3- (3 ', 5'-dichloropyridyl-2'-oxy -) - 6-bromophenylacetate in one liter of absolute methanol is stirred at 60 for 20 minutes under a nitrogen atmosphere ° stirred, concentrated and acidified at room temperature with concentrated hydrochloric acid and evaporated completely.
Die Toluollösung (400 ml) des Rückstandes wird mit Wasser gewaschen, getrocknet und eingedampft. Der ölige Rückstand wird mit Petroläther/Cyclohexan verrieben und filtriert. Man erhält 137 g des kristallinen Titelproduktes. Smp: 93-95°.The toluene solution (400 ml) of the residue is washed with water, dried and evaporated. The oily residue is triturated with petroleum ether / cyclohexane and filtered. 137 g of the crystalline title product are obtained. M.p .: 93-95 °.
Man erhält 5 g der Titelverbindung als Oel. 
Die Herstellung erfiridungsgemässer 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:
Der Gehalt an Wirkstoff in den oben beschriebenen . Mitteln liegt zwischen 0,1 bis 95%, bevorzugt zwischen 1 bis 80%. Anwendungsformen können bis hiab 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):
- Den beschriebenen erfindungsgemässen Mitteln lassen sich auch andere biozide Wirkstoffe oder Mittel beimischen
- Other biocidal active substances or agents can also be added to the agents according to the invention described
Zur Herstellung eines a) 5%igen und b) 2%igen Stäubemittels werden die folgenden Stoffe verwendet:
Die Wirkstoffe werden mit den Trägerstoffen vermischt und vermahlen.The active ingredients are mixed and ground with the carriers.
Zur Herstellung eines 5%igen Granulates werden die folgenden Stoffe verwendet:
Die Aktivsubstanz wird mit Epichlorhidrin 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 active substance is mixed with epichlorhidrin 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.
Zur Herstellung eines a) 50%igen, b) 25%igen und c) 10%igen Spritzpulvers werden folgende Bestandteile verwendet:
Der angegebene Wirkstoff wird auf die entsprechenden Trägerstoffe (Kaolin und Kreide) aufgezogen und anschliessend vermischt und vermahlen. Man erhält Spritzpulver von vorzüglicher Benetzbarkeit und Schwebefähigkeit. Aus solchen Spritzpulvern können durch Verdünnen mit Wasser Suspensionen jeder gewünschten Wirkstoffkonzentration erhalten werden. Derartige Suspensionen werden zur Bekämpfung von Unkräutern und Ungräsern in Kulturpflanzungen im Vorauflaufverfahren und zur Behandlung von Rasenanlagen verwendet.The specified active ingredient is drawn onto the corresponding carrier substances (kaolin and chalk) and then mixed and ground. Spray powder of excellent wettability and suspension is obtained. Suspensions of any desired active ingredient concentration can be obtained from such wettable powders by dilution with water. Such suspensions Ions are used to control weeds and grass weeds in pre-emergence crops and to treat lawns.
Zur Herstellung einer 45%igen Paste werden folgende Stoffe verwendet:
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 active ingredient is intimately mixed and ground with the additives in suitable equipment. 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.
Zur Herstellung eines 25%igen Emulsionskonzentrates werden
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 erfindungsgamässen Mitteln enthaltenen Wirkstoffe beeinflussen das Pflanzenwachstum in verschiedener Weise. So hemmen, verzögern oder untrbinde sie in erster Linie das Wachstum und die Keimung. Es handelt sich dabei also sowohl um pre- und post-emergente 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-emergent 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, Zwiebel- 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 monocotyledon and dicotyledonous plants, such as grasses, shrubs, trees, crops of cereals and legumes, sugar cane, tobacco, soybeans, onions and potato tubers, ornamental plants, fruit trees and vines.
Die von den 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 Pflanzenform verbunden. In unmittelbarem Zusammenhang zur Verminderung der Wuchshöhe erfährt die Pflanze eine Festigung.Blätter und Stengel sind kräftiger ausgebildet. Durch Verkürzung der Internodienabstände an monocotylen Pflanzen wird die Knickfestigkeit erhöht. Auf diese Weise können Ernteausfälle durch Gewittersturm, Dauerregen, usw., die normalerweise zu einem Lagern von Getreide- und Leguminosenkulturen führen, weitgehend verhindert und damit die Erntearbeit erleichtert werden. Als Nebeneffekt führt verminderte Wuchshöhe bei Nutzpflanzen zu einer ELnsparung an Düngemitteln. In gleichem Masse gilt dies auch für Zierpflanzen, Zierrasen, Sportrasen oder sonstige Grünanpflanzungen.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 plant. In direct connection with the reduction in growth height, the plant is strengthened; leaves and stems are more strongly developed. 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, reduced height of crops in crops leads to EL savings in fertilizers. This also applies to ornamental plants, ornamental turf, sports turf or other green plants.
Eines der wichtigsten Probleme an reinen Grasbepflanzungen ist jedoch der Grasschnitt selbst, sei es an Grünanlagen in Wohngegenden, auf Industriegeländen, auf Sportplätzen, an Autostrassen, Flugpisten, Eisenbahndämmen oder Uferböschungen von Gewässern. In all diesen Fällen ist ein periodisches Schneiden des Rasens bzw. des Graswuchses notwendig. Dies ist.nicht nur im Hinblick auf Arbeitskräfte und Maschinen sehr aufwendig, sondern bringt im Verkehrsbereich auch erhebliche Gefahren für das betroffen Personal und die Verkehrsteilnehmer mit sich.However, one of the most important problems with pure grass planting is the cutting of grass itself, be it in green areas in residential areas, on industrial sites, on sports grounds, on car roads, airstrips, railway embankments or bank embankments of water. In all of these cases, periodic cutting of the lawn or grass growth is necessary. This is not only very expensive in terms of workers and machines, but also brings considerable dangers for the staff involved and the road users 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 mittlere Wuchshöhe zu halten. Dies wird durch Applikation erfindungsgemässer Wirkstoffe der Forml 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 application of 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, bushes 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.
Zierpflanzen mit starkem Längenwachstum können .durch Behandlung mit erfindungsgemässen Wirkstoffen als kompakte Topfpflanzen gezogen werden.Ornamental plants with strong growth in length can be grown as compact potted plants by treatment with active substances according to the invention.
Die Wirkstoffe der Formel I finden auch Anwendung zur Hemmung des Wachstums unerwünschter Geiztriebe, z.B. bei Tabak und Zierpflanzen, wodurch das arbeitsintensive Ausbrechen dieser Triebe von Hand vermieden wird, ferner zur Austriebhemmung bei lagernden Knollen, beispielsweise bei Zierpflanzenknollen, bei Zweibeln und Kartoffeln, und schliesslich zur Ertra gssteigerung bei stark vegetativ wachsenden Kulturpflanzen, wie Soja und Zuckerrohr, indem durch Applikation erfindungsgemässer Wirkstoffe der Uebgergang von der vegetativen zur generativen Wachstumsphase beschleunigt wird.The active compounds of the formula I are also used to inhibit the growth of undesired poultry drives, e.g. in tobacco and ornamental plants, which avoids the labor-intensive breakout of these shoots by hand, further to inhibit expulsion of stored tubers, for example ornamental plant tubers, onions and potatoes, and finally to increase the yield of strongly growing vegetative crops, such as soybeans and sugar cane, by Application of active ingredients according to the invention the transition from the vegetative to the generative growth phase is accelerated.
Bevorzugt setzt man die erfindungsgemässen Wirkstoffe der Formel 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 allgemeinen zwischen 0,1 und 5 kg Wirkstoff pro Hektar, bei Applikation vor dem Auflaufen der Pflanzen und für die Behandlung von bestehenden Kulturen vorzugsweise bis zu 4 kg pro Hektar.The application rates are different and depend on the time of application. They are generally between 0.1 and 5 kg of active ingredient per hectare, preferably up to 4 kg per hectare when applied before emergence of the plants and for the treatment of existing crops.
Grosse wirtschaftliche Bedeutung hat die Erleichterung der Fruchtabszission bei der mechanischen und manuellen Ernte von Oliven und Citrusfrüchten gewonnen. Blattabszissionswirkung und Defoliation ist bei der Baumwollernte von Bedeutung.The facilitation of fruit removal in the mechanical and manual harvesting of olives and citrus fruits has gained great economic importance. Leaf absorbency and defoliation is important in the cotton harvest.
Die Entfaltung der Wirkung der erfindungsgemässen Wirkstoffe erfolgt sowohl über die oberirdischen Pflanzenteilte (Kontaktwirkung), insbesondere die Blätter, als auch über den Boden, als pre-emergentes Herbizid (Keimhemmung).The development of the action of the active compounds according to the invention takes place both via the parts of the plants above ground (contact action), in particular the leaves, and also via the soil as a pre-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 shows. show that most post-emergent treated plant species show a growth standstill after three weeks of experiment, whereby the treated plant parts take on a dark green color. The leaves do not fall off.
Diese Wuchshemmung tritt bei einigen Pflanzenarten schon bei einer Dosierung von 0,5 kg/ha und darunter auf.This inhibition of growth occurs in some plant species at a dosage of 0.5 kg / ha and below.
Da nicht alle Pflanzenarten gleich stark gehemmt werden, ist bei Wahl einer bestimmten niederen Dosierung ein selektiver Einsatz möglich.Since not all plant species are inhibited to the same extent, selective use is possible if a certain low dosage is selected.
Die erfindungsgemässen Wirkstoffe sind auch 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.
In Gebiet mit erhöhter Erosionsgefahr können die erfindungsgemässen Wirkstoffe als Wuchshemmer in den verschiedensten Kulturen eingesetzt werden.In areas with an increased risk of erosion, the active compounds according to the invention can be used as growth inhibitors in a wide variety of crops.
Dabei wird die Unkrautdecke nicht beseitigt, sondern nur so stark gehemmt, dass .keine Konkurrenzierung der Kulturpflanzen mehr auftritt.The weed cover is not removed, but only so strongly inhibited that there is no longer any competition between the crop plants.
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:
- Pre-emergente Herbizid-Wirkung (Keimungshemmung)
- Pre-emergent herbicide effect (inhibition of germination)
Im Gewächshaus wird unmittelbar nach der Einsaat der Versuchspflanzen in Saatschälen die Erdoberfläche mit einer wässerigen Suspension der Wirkstoffe, erhalten aus einem 25%-igen Spritzpulver, behandelt. Es wurden vier verschiedene Konzentrationsreihen angewendet,.entsprechend 4, 2, 1 und 0,5 kg Wirksubstanz pro Hektar. Die Saatschalen werden im Gewächshaus bei 22-25°C und 50-70% rel. Luftfeuchtigkeit gehalten und der Versuch nach 3 Wochen ausgewertet und die Resultate nach folgender Notenskala bonitiert:
- 1 =, Pflanzen nicht gekeimt oder total abgestorben
- 2-8 = Zwischenstufen der Schädigung
- 9 = Pflanzen-ungeschädigt (wie unbehandelte Kontrolle).
- 1 =, plants not germinated or totally dead
- 2-8 = intermediate stages of damage
- 9 = plant-undamaged (like untreated control).
Eine grössere,Anzahl (mindestens 7) Unkräuter und Kulturpflanzen, sowohl monocotyle wie dicotyle, wurden nach dem Auflaufen (im 4-bis-6-Blattstadium) mit einer wässerigen Wirkstoffemulsion in Dosierungen von 0,5; 1 ; 2 und 4 kg Wirksubstanz pro Hektar auf die Pflanzen gespritzt und diese bei 24°-26°C und 45-60% rel. Luftfeuchtigkeit gehalten. 5 Tage und 15 Tage nach Behandlung wird der Versuch ausgewertet und das Ergebnis wie im pre-emergent-Versuch nach derselben Notenskala bonitiert.A larger number (at least 7) of weeds and crop plants, both monocotyledon and dicotyledon, were 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-emergent test.
Die geprtiften Verbindungen gemäss vorliegender Erfindung zeigten auf einigen Pflanzen ausgeprägte kontaktherbizide Wirkung und auf vielen Pflanzen Wachstumsstillstand als Symptom der wachs tumshemmenden Eigenschaften.The compounds tested 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.
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 Spritzbruhen 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.
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.
Die erfindungsgemässen Wirkstoffe bewirken eine merkliche Wuchshemmung sowohl bei den Gräsern wie beim Getreide.The active substances according to the invention cause a noticeable growth inhibition both in the grasses and in the cereals.
Claims (17)
weiter bedeutet R3
wobei die Bestimmung gilt, dass der Alkancarbonsäurerest
furthermore R 3 means
the provision being that the alkane carboxylic acid residue
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH802377 | 1977-06-29 | ||
| CH8023/77 | 1977-06-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000176A1 true EP0000176A1 (en) | 1979-01-10 |
| EP0000176B1 EP0000176B1 (en) | 1981-09-16 |
Family
ID=4333965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100209A Expired EP0000176B1 (en) | 1977-06-29 | 1978-06-21 | Pyridyloxy-phenoxy-alkanoic acid derivatives , processes for their preparation and their use as herbicides or plant growth regulators |
Country Status (17)
| Country | Link |
|---|---|
| US (5) | US4329167A (en) |
| EP (1) | EP0000176B1 (en) |
| JP (1) | JPS5412379A (en) |
| AT (1) | AT362956B (en) |
| AU (1) | AU526393B2 (en) |
| BR (1) | BR7804115A (en) |
| CA (1) | CA1100964A (en) |
| CS (1) | CS222264B2 (en) |
| DD (1) | DD137879A5 (en) |
| DE (1) | DE2861073D1 (en) |
| ES (1) | ES471216A1 (en) |
| HU (1) | HU180704B (en) |
| IL (1) | IL55016A (en) |
| IT (1) | IT1097282B (en) |
| PH (1) | PH18510A (en) |
| TR (1) | TR20086A (en) |
| ZA (1) | ZA783719B (en) |
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| EP0109751A1 (en) * | 1982-10-18 | 1984-05-30 | The Dow Chemical Company | Compounds and method for selectively controlling weeds in the presence of valuable crops |
| US4486593A (en) * | 1983-01-19 | 1984-12-04 | The Upjohn Company | 2-,3-, or 4-Pyridinylmethylamino arylic acids as thromboxane A2 synthetase and 5-lipoxygenase inhibitors |
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| TR25135A (en) * | 1991-03-13 | 1992-11-01 | Shell Int Research | CARBODAMIDE DERIVATIVES WITH HERBISID PROPERTIES |
| CN109553574A (en) * | 2018-12-27 | 2019-04-02 | 北京颖泰嘉和生物科技股份有限公司 | Pyridine acid compounds and preparation method thereof, herbicidal composition and its application |
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| CH632731A5 (en) * | 1978-01-11 | 1982-10-29 | Ciba Geigy Ag | METHOD FOR PRODUCING ALKOXY-SUBSTITUTED POLYCYCLIC AROMATIC COMPOUNDS. |
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| US4326880A (en) * | 1979-08-14 | 1982-04-27 | Ciba-Geigy Corporation | Derivatives of 5-(pyridyl-2-oxy)-2-nitrobenzoic acid, and herbicidal compositions containing them, and herbicidal methods for using same |
| US4738710A (en) * | 1979-11-19 | 1988-04-19 | Ici Australia Limited | Herbicidal alkane carboxylic acid derivatives |
| AU541697B2 (en) * | 1979-11-19 | 1985-01-17 | Ici Australia Limited | Quinoline derivatives |
| NZ197420A (en) * | 1980-07-01 | 1984-04-27 | Ici Australia Ltd | -(quinazolin-(2-or 4-)(oxy,ylthio or amino)phen(oxy or ylthio)alkanoic acid derivatives |
| US4505743A (en) * | 1981-12-31 | 1985-03-19 | Ciba-Geigy Corporation | α-[4-(3-Fluoro-5'-halopyridyl-2'-oxy)-phenoxy]-propionic acid derivatives having herbicidal activity |
| US4529438A (en) * | 1982-03-23 | 1985-07-16 | Zoecon Corp. | Pyridyloxy-phenoxy-alkanoic acid esters and derivatives |
| US4518416A (en) * | 1982-06-04 | 1985-05-21 | Bayer Aktiengesellschaft | Certain trimethyl silyl-lower-alkyl esters of pyridyloxy-phenoxy-lower alkanoic acids, compositions containing same and herbicidal method of use |
| US4558134A (en) * | 1983-01-03 | 1985-12-10 | The Dow Chemical Company | Certain phenoxy-pyridine-carbonitriles having antiviral activity |
| US4599105A (en) * | 1983-06-20 | 1986-07-08 | The Dow Chemical Company | 2-[16-(3-fluoro-5-trifluoromethyl-pyridinyl-2-oxy)-3-nitro-phenoxy]-propionic acid derivatives, herbicidal compositions containing same and herbicidal method of use |
| US4539039A (en) * | 1984-04-26 | 1985-09-03 | The Dow Chemical Company | Herbicidal (-3-fluoro-5-trifluoromethyl-pyridyl)oxy phenyloxime derivatives |
| US4775410A (en) * | 1985-08-19 | 1988-10-04 | Sandoz Ltd. | 2-[4-(2-pyridinyloxy)phenoxy]propionyl-2-oxazolidinones |
| US5205855A (en) * | 1987-08-11 | 1993-04-27 | Suntory Limited | Herbicidally active phenoxyalkanecarboxylic acid derivatives |
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| FR2398059A1 (en) * | 1977-07-21 | 1979-02-16 | Ishihara Mining & Chemical Co | 4- (5-FLUOROMETHYL-2-PYRIDYLOXY) -PHENOXY-ALCANECARBOXYLIC ACIDS AND THEIR DERIVATIVES, AND HERBICIDE COMPOSITIONS CONTAINING THEM |
| FR2501470A1 (en) * | 1977-07-21 | 1982-09-17 | Ishihara Mining & Chemical Co | Pyridyl:oxy-phenoxy-alkanoic acid derivs. - useful as selective herbicides against grassy 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 |
| DE3004770A1 (en) * | 1979-02-22 | 1980-08-28 | Nissan Chemical Ind Ltd | PHENOXY FATTY ACID DERIVATIVES OF THE TYPE HETEROCYCLIC AETHER AND HERBICIDAL AGENTS WITH A CONTENT THEREOF |
| DE3051172C2 (en) * | 1979-02-22 | 1993-01-28 | Nissan Chemical Industries, Ltd., Tokio/Tokyo, Jp | |
| EP0021613A1 (en) * | 1979-06-20 | 1981-01-07 | Imperial Chemical Industries Plc | Pyridine derivatives, processes for preparing them, herbicidal compositions containing them and methods of killing plants therewith |
| US4308053A (en) * | 1979-06-20 | 1981-12-29 | Imperial Chemical Industries Limited | Certain 2-pyridinyloxy-N-lower-alkane-sulfonyl benzamides and their use as herbicides |
| US4401460A (en) * | 1979-06-20 | 1983-08-30 | Imperial Chemical Industries Plc | Herbicidal phenoxypyridines |
| EP0025773A1 (en) * | 1979-09-13 | 1981-03-25 | Ciba-Geigy Ag | Alkylcarboxylic acid derivatives that contain sulphur and that show a herbicidal and plant growth controlling activity, their preparation and use |
| US4451284A (en) * | 1981-07-28 | 1984-05-29 | Ciba-Geigy Corporation | Derivatives of 2-nitro-4- or -5-pyridyloxyphenylphosphonic acid, the preparation thereof, the use thereof as herbicides and/or plant growth regulators |
| EP0072529A1 (en) * | 1981-08-13 | 1983-02-23 | The Dow Chemical Company | Sulfur-substituted phenoxypyridines having antiviral activity |
| EP0109751A1 (en) * | 1982-10-18 | 1984-05-30 | The Dow Chemical Company | Compounds and method for selectively controlling weeds in the presence of valuable crops |
| US4486593A (en) * | 1983-01-19 | 1984-12-04 | The Upjohn Company | 2-,3-, or 4-Pyridinylmethylamino arylic acids as thromboxane A2 synthetase and 5-lipoxygenase inhibitors |
| EP0288275A3 (en) * | 1987-04-20 | 1989-01-11 | Tosoh Corporation | Novel phenoxypropionic acid derivatives for use as herbicides |
| US4948421A (en) * | 1987-04-20 | 1990-08-14 | Tosoh Corporation | Phenoxypropionic acid ester derivatives as herbicides |
| EP0288275A2 (en) * | 1987-04-20 | 1988-10-26 | Tosoh Corporation | Phenoxypropionic acid derivatives for use as herbicides |
| EP0447004A2 (en) * | 1990-03-16 | 1991-09-18 | Shell Internationale Researchmaatschappij B.V. | Herbicidal carboxamide derivatives |
| EP0447004A3 (en) * | 1990-03-16 | 1992-04-29 | Shell Internationale Research Maatschappij B.V. | Herbicidal carboxamide derivatives |
| EP0488474A1 (en) * | 1990-11-28 | 1992-06-03 | Shell Internationale Researchmaatschappij B.V. | Herbicidal carboxamide derivatives |
| TR25360A (en) * | 1990-11-28 | 1993-03-01 | Shell Int Research | CARBODAMIDE DERIVATIVES OF HERBISID. |
| US5384305A (en) * | 1990-11-28 | 1995-01-24 | Shell Research Limited | Herbicidal carboxamide compounds |
| TR25135A (en) * | 1991-03-13 | 1992-11-01 | Shell Int Research | CARBODAMIDE DERIVATIVES WITH HERBISID PROPERTIES |
| CN109553574A (en) * | 2018-12-27 | 2019-04-02 | 北京颖泰嘉和生物科技股份有限公司 | Pyridine acid compounds and preparation method thereof, herbicidal composition and its application |
Also Published As
| Publication number | Publication date |
|---|---|
| DD137879A5 (en) | 1979-10-03 |
| TR20086A (en) | 1980-07-07 |
| IT1097282B (en) | 1985-08-31 |
| IL55016A (en) | 1982-02-28 |
| US4433998A (en) | 1984-02-28 |
| ES471216A1 (en) | 1979-09-01 |
| AU3751778A (en) | 1980-01-03 |
| CA1100964A (en) | 1981-05-12 |
| PH18510A (en) | 1985-08-02 |
| IT7825083A0 (en) | 1978-06-28 |
| ATA470878A (en) | 1980-11-15 |
| US4329167A (en) | 1982-05-11 |
| US4425157A (en) | 1984-01-10 |
| ZA783719B (en) | 1979-06-27 |
| AT362956B (en) | 1981-06-25 |
| JPS5412379A (en) | 1979-01-30 |
| US4384882A (en) | 1983-05-24 |
| CS222264B2 (en) | 1983-06-24 |
| DE2861073D1 (en) | 1981-12-03 |
| AU526393B2 (en) | 1983-01-06 |
| HU180704B (en) | 1983-04-29 |
| EP0000176B1 (en) | 1981-09-16 |
| BR7804115A (en) | 1979-02-20 |
| US4443247A (en) | 1984-04-17 |
| IL55016A0 (en) | 1978-08-31 |
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