WO1997009883A1 - Using n-phosphonomethyl glycine esters in aqueous solution as a herbicide - Google Patents

Using n-phosphonomethyl glycine esters in aqueous solution as a herbicide Download PDF

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Publication number
WO1997009883A1
WO1997009883A1 PCT/EP1996/003789 EP9603789W WO9709883A1 WO 1997009883 A1 WO1997009883 A1 WO 1997009883A1 EP 9603789 W EP9603789 W EP 9603789W WO 9709883 A1 WO9709883 A1 WO 9709883A1
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WO
WIPO (PCT)
Prior art keywords
formula
phosphonomethyl
glycine
aqueous solution
active ingredient
Prior art date
Application number
PCT/EP1996/003789
Other languages
German (de)
French (fr)
Inventor
Hans-Jochem Riebel
Uwe Priesnitz
Raphael Wieschollek
Markus Dollinger
Ingo Wetcholowsky
Original Assignee
Bayer Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU69850/96A priority Critical patent/AU6985096A/en
Publication of WO1997009883A1 publication Critical patent/WO1997009883A1/en

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Classifications

    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals

Definitions

  • the invention relates to the novel use of N-phosphonomethylglycine esters, some of which are already known as herbicidally active compounds, in aqueous solution with the addition of additives (adjuvants, emulsifiers, wetting agents, surfactants) as herbicides.
  • additives adjuvants, emulsifiers, wetting agents, surfactants
  • N-phosphonomethyl-glycine alkyl esters have herbicidal properties and - generally in formulated use forms, i.e. combined with certain additives - can be used to kill unwanted plants (cf. DE 2 152 826, DE 2 166 573, US 3 977 860).
  • N-phosphonomethylglycine esters of the general formula (I) N-phosphonomethylglycine esters of the general formula (I)
  • R represents alkyl
  • additives adjuvants, emulsifiers, wetting agents, surfactants
  • the invention thus relates to a new process for controlling or killing undesired plants by the action of N-phosphonomethylglycine alkyl esters on such plants, which is characterized in that at least one N-phosphonomethylglycine ester of the above formula (I) , or one of its acid adducts, in the form of an aqueous solution with the addition of additives (adjuvants, emulsifiers, wetting agents, surfactants).
  • additives adjuvants, emulsifiers, wetting agents, surfactants
  • the aqueous solutions of the active compounds of the formula (I) - and of acid adducts of these compounds - with the addition of additives (adjuvants, emulsifiers, wetting agents, surfactants) - without combination with the formulations customary in agrochemicals - can be used directly to kill unwanted plants become.
  • additives adjuvants, emulsifiers, wetting agents, surfactants
  • the invention preferably relates to the use of compounds of the formula (I) in which
  • R represents straight-chain or branched alkyl having 1 to 10 carbon atoms
  • the invention relates in particular to the use of compounds of the formula (I) in which
  • R represents straight-chain or branched alkyl having 2 to 6 carbon atoms
  • N-phosphonomethylglycine ethyl ester The use of N-phosphonomethylglycine ethyl ester according to the invention should be particularly emphasized
  • acid adducts are generally to be understood as addition products of compounds of the formula (I) and acids.
  • Suitable acids are in this case preferably strong protic acids, such as for example hydrogen fluoride, hydrogen chloride (hydrochloric acid), hydrogen bromide, Hydrogen ⁇ iodide, sulfuric acid, phosphoric acid, trifluoroacetic acid, methanesulfonic acid, Ethansulfonsaure, Propansulfonsaure, Butansulfonsaure, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid
  • the compounds of formula (I) to be used according to the invention are already known and / or can be prepared by processes known per se (cf. DE 2 152 826, DE 2 166 573, US 3 977 860).
  • N-phosphonomethyl-glycine esters of the general formula (I) are obtained if N-phosphonomethyl-glycine of the formula (II)
  • the compounds of the formula (I) can be used in defoliants, herbicides and in particular in weed killers - especially in the semi-selective and in the non-selective area of weed control.
  • Weeds in the broadest sense are all plants that grow in places where they are undesirable, i.e. e.g. also unwanted trees in the forest.
  • the active ingredients to be used according to the invention can be used both in conventional cultivation methods (row crops with a suitable row width), in plantation crops (e.g. wine, fruit, citrus) and in industrial and track systems, on paths and squares, but also for stubble treatment and the so-called
  • Minimum Tillage method can be used. They are also suitable as burners (killing herbs, for example in potatoes) or as defoliants (for example in tree wool). They are also suitable for use on fallow land. Other areas of application are tree nurseries, forestry, grassland and ornamental plant cultivation.
  • active compounds of the formula (I) according to the invention can also be used as selective herbicides in crop plants which are resistant to glyphosate and other EPSP synthase inhibitors.
  • weeds which can be combated well by the active compounds to be used according to the invention are:
  • Sorghum Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
  • the compounds of the formula (I) are particularly suitable for controlling monocotyledon and dicotyledon weeds in the post-emergence process. They show strong herbicidal activity and a broad spectrum of activity when applied to aerial parts of plants. They also show significantly better activity compared to the known compound N-phosphonomethyl-glycine (glyphosate).
  • the compounds of the formula (I) according to the invention are used in aqueous solution with the addition of additives (adjuvants, emulsifiers, wetting agents, surfactants).
  • additives preferably include highly refined mineral oils, emulsifiable ones Vegetable oils, ethoxylated taigamines, ethoxylated alkyl amines, ethoxylated alkyl phenols, ethoxylated alkyl alcohols, phosphate esters, alkyl and aryl ether phosphates, soy phospholipids and synthetic latex.
  • Suitable additives are the following commercially available products [which are, at least in part, registered trademarks]:
  • Sprayprover Spreader Sticker, Stefes Spread and Seal, Stik-It, Surfor, Swirl, Team, Tenac AS, Tonic, Top Farm Non-ionic 90, TopUp, Tradename A, Trend, Tri Mix, Tripart Acer, Tripart Cropspray 1 1E, Tripart Lentus, Tripart Minax, Vassgro Spreader, Vegelux, Wayfarer.
  • Additives are used, for example alkynediols which have become known under the name Surfynole (cf. EP 531269, US 5258359), alkyltris (hydroxypolyalkoxyalkyl) ammonium salts or dialkyl-bis which have become known as Ethoquad - (hydroxypolyalkoxyalkyl) ammonium salts (cf. WO 9402021, US 5317003), furthermore trialkyl
  • aqueous solutions for using the compounds of the formula (I) generally contain between 1 and 50 percent by weight, preferably between 5 and 30 percent by weight, of active ingredient.
  • the compounds of the formula (I) can be used as such - in aqueous solution - or else in a mixture with other known herbicides for weed control, these mixtures in the given case as "tank mixes", i.e. as spray or pouring broth prepared by the user.
  • tank mixes i.e. as spray or pouring broth prepared by the user.
  • Known herbicidal substances from practically all relevant classes of substances come into consideration for these mixtures.
  • the amount of active ingredient used can be varied within a substantial range. It essentially depends on the type of effect desired. In general, the application rates are between 10 g and 10 kg of active ingredient per hectare, preferably between 50 g and 5 kg of active ingredient per hectare, in particular between 200 g and 2 kg of active ingredient of the formula (I) per hectare of soil area.
  • Formula (I) very good properties for use in the semi-selective and in the non-selective area of weed control.
  • Active ingredient diluted with water to the desired concentration and adds 1 part by weight of emulsifier
  • Test plants which have a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area.
  • the concentration of the spray broth is chosen so that the respectively desired amounts in 500 to 1000 1 water / ha Active ingredient quantities are brought out
  • the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
  • N-phosphonomethyl-gtycin-ethyl ester 250 30 70 100 90 (according to the invention)
  • the plants are treated with 1 mg per plant as standard.
  • the active substances are dissolved in acetone / water (1: 1).
  • Preparation solution treated the preparation is dropped onto the leaf using an Eppendorf pipette and then distributed over approximately 10 cm 2 on the leaf. Three repetitions are created for each treatment. After 18 days, the ratings are given visually in percent effectiveness compared to the untreated control. An average is formed from the three individual results.
  • Hydrogen chloride gas is introduced into a suspension of 200 g (1.2 mol) of N-phosphonomethylglycine in 3000 ml of ethanol until saturation. Then the
  • reaction mixture was heated under reflux for 3 hours and then - after cooling to room temperature - concentrated in a water jet vacuum.
  • the residue is dissolved in 1500 ml of ethanol and triethylamine (approx. 140 g) is added dropwise to this solution until the color changes from reddish brown to light yellow.
  • the crystalline product is isolated by suction.
  • Vortex layer drying, paddle drying or forced-air drying in each case combined, if appropriate, with technically customary comminution processes, such as, for example, air jet grinding, crushers, rollers, grinding).

Abstract

The invention concerns a process to combat undesired plant growth characterized by applying to the undesired plants N-phosphonomethyl glycine esters of the formula (I): (HO)2P(O)-CH2-NH-CH2-CO-O-R, where R is alkyl, or one of their acid addition products, in the form of an aqueous solution with the addition of additives (adjuvants, emulsifying agents, wetting agents or surface-active agents).

Description

Verwendung von N-Phosphonomethyl-glvcinestern in wässriger Lösung als HerbizideUse of N-phosphonomethyl-glvcinestern in aqueous solution as herbicides
Die Erfindung betrifft die neuartige Verwendung von N-Phosphonomethyl-glycin- estern, welche teilweise bereits als herbizid wirksame Verbindungen bekannt sind, in wässriger Lösung unter Zusatz von Additiven (Adjuvantien, Emulgatoren, Netz¬ mitteln, Tensiden) als Herbizide.The invention relates to the novel use of N-phosphonomethylglycine esters, some of which are already known as herbicidally active compounds, in aqueous solution with the addition of additives (adjuvants, emulsifiers, wetting agents, surfactants) as herbicides.
Es ist bekannt, daß einige N-Phosphonomethyl-glycin-alkylester herbizide Eigen- schaften aufweisen und - im allgemeinen in formulierten Anwendungsformen, d.h. mit bestimmten Zuschlagsstoffen kombiniert - zur Abtötung von unerwünschten Pflanzen verwendet werden können (vgl. DE 2 152 826, DE 2 166 573, US 3 977 860).It is known that some N-phosphonomethyl-glycine alkyl esters have herbicidal properties and - generally in formulated use forms, i.e. combined with certain additives - can be used to kill unwanted plants (cf. DE 2 152 826, DE 2 166 573, US 3 977 860).
Es wurde nun gefunden, daß N-Phosphonomethyl-glycinester der allgemeinen For- mel (I)It has now been found that N-phosphonomethylglycine esters of the general formula (I)
(HO)2P(O)-CH2-NH-CH2-CO-O-R (I),(HO) 2 P (O) -CH 2 -NH-CH 2 -CO-OR (I),
in welcherin which
R für Alkyl steht,R represents alkyl,
- sowie Säureaddukte von Verbindungen der Formel (I) -- and acid adducts of compounds of the formula (I) -
in wässriger Lösung unter Zusatz von Additiven (Adjuvantien, Emulgatoren, Netz¬ mitteln, Tensiden) mit sehr gutem Erfolg zur Abtötung unerwünschter Pflanzen verwendet werden können.in aqueous solution with the addition of additives (adjuvants, emulsifiers, wetting agents, surfactants) can be used with very good success to kill unwanted plants.
Gegenstand der Erfindung ist somit ein neues Verfahren zur Bekämpfung bzw. Abtötung von unerwünschten Pflanzen durch Einwirkung von N-Phosphono- methylglycin-alkylestern auf solche Pflanzen, welches dadurch gekennzeichnet ist, daß man zumindest einen N-Phosphonomethyl-glycinester der obigen Formel (I), oder eines seiner Säureaddukte, in Form einer wäßrigen Lösung unter Zusatz von Additiven (Adjuvantien, Emulgatoren, Netzmitteln, Tensiden) zur Anwendung bringt. Überraschenderweise können also die wässrigen Losungen der Wirkstoffe der Formel (I) - sowie von Saureaddukten dieser Verbindungen - unter Zusatz von Additiven (Adjuvantien, Emulgatoren, Netzmitteln, Tensiden) - ohne Kombination mit den sonst bei Agrochemikalien üblichen Formulierungsmitteln - unmittelbar zur Abtötung unerwünschter Pflanzen eingesetzt werden. Angesichts der sonst üblichen Praxis bei der Anwendung von Pflanzenbehandlungsmitteln, d h. der Ver¬ wendung von formulierten Wirkstoffen, stellt die nun gefundene neue An- wendungsmoglichkeit für die erfindungsgemäß einzusetzenden Wirkstoffe der Formel (I) eine völlig überraschende, sehr einfache und damit wirtschaftlich sehr gunstige Problemlosungsmoglichkeit in Land- und Forstwirtschaft darThe invention thus relates to a new process for controlling or killing undesired plants by the action of N-phosphonomethylglycine alkyl esters on such plants, which is characterized in that at least one N-phosphonomethylglycine ester of the above formula (I) , or one of its acid adducts, in the form of an aqueous solution with the addition of additives (adjuvants, emulsifiers, wetting agents, surfactants). Surprisingly, the aqueous solutions of the active compounds of the formula (I) - and of acid adducts of these compounds - with the addition of additives (adjuvants, emulsifiers, wetting agents, surfactants) - without combination with the formulations customary in agrochemicals - can be used directly to kill unwanted plants become. In view of the otherwise customary practice when using plant treatment agents, i.e. the use of formulated active ingredients, the new application now found for the active ingredients of the formula (I) to be used according to the invention represents a completely surprising, very simple and therefore economically very inexpensive solution to problems in agriculture and forestry
Die erfindungsgemäße Verwendungsmöglichkeit für die Verbindungen der Formel (I) stellt somit eine sehr wertvolle Bereicherung des Standes der Technik darThe possible use of the compounds of the formula (I) according to the invention thus represents a very valuable enrichment of the prior art
Die Erfindung betrifft vorzugsweise die Verwendung von Verbindungen der Formel (I), in welcherThe invention preferably relates to the use of compounds of the formula (I) in which
R für geradkettiges oder verzweigtes Alkyl mit 1 bis 10 Kohlenstoffatomen stehtR represents straight-chain or branched alkyl having 1 to 10 carbon atoms
Die Erfindung betrifft insbesondere die Verwendung von Verbindungen der Formel (I), in welcherThe invention relates in particular to the use of compounds of the formula (I) in which
R für geradkettiges oder verzweigtes Alkyl mit 2 bis 6 Kohlenstoffatomen stehtR represents straight-chain or branched alkyl having 2 to 6 carbon atoms
Ganz besonders sei die erfindungsgemäße Verwendung von N-Phosphonomethyl- glycin-ethylester hervorgehobenThe use of N-phosphonomethylglycine ethyl ester according to the invention should be particularly emphasized
Als Säureaddukte sind im Zusammenhang mit der vorliegenden Erfindung all¬ gemein Additionsprodukte aus Verbindungen der Formel (I) und Sauren zu ver- stehen. Geeignete Sauren sind hierbei vorzugsweise starke Protonensauren, wie z B Hydrogenfluorid, Hydrogenchlorid (Salzsaure), Hydrogenbromid, Hydrogen¬ iodid, Schwefelsaure, Phosphorsaure, Trifluoressigsaure, Methansulfonsäure, Ethansulfonsaure, Propansulfonsaure, Butansulfonsaure, Trifluormethansulfonsaure, Benzolsulfonsaure und p-Toluolsulfonsaure Die erfindungsgemäß zu verwendenden Verbindungen der Formel (I) sind bereits bekannt und/oder können nach an sich bekannten Verfahren hergestellt werden (vgl. DE 2 152 826, DE 2 166 573, US 3 977 860).In the context of the present invention, acid adducts are generally to be understood as addition products of compounds of the formula (I) and acids. Suitable acids are in this case preferably strong protic acids, such as for example hydrogen fluoride, hydrogen chloride (hydrochloric acid), hydrogen bromide, Hydrogen¬ iodide, sulfuric acid, phosphoric acid, trifluoroacetic acid, methanesulfonic acid, Ethansulfonsaure, Propansulfonsaure, Butansulfonsaure, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid The compounds of formula (I) to be used according to the invention are already known and / or can be prepared by processes known per se (cf. DE 2 152 826, DE 2 166 573, US 3 977 860).
Man erhält die N-Phosphonomethyl-glycinester der allgemeinen Formel (I), wenn man N-Phosphonomethyl-glycin der Formel (II)The N-phosphonomethyl-glycine esters of the general formula (I) are obtained if N-phosphonomethyl-glycine of the formula (II)
(HO)2P(O)-CH2-NH-CH2-COOH (II)(HO) 2 P (O) -CH 2 -NH-CH 2 -COOH (II)
mit einem Alkohol der Formel (III)with an alcohol of formula (III)
HO-R (III),HO-R (III),
in welcherin which
R die oben angegebene Bedeutung hat,R has the meaning given above,
in Gegenwart einer Säure, wie z.B. Hydrogenchlorid (Chlorwasserstoff), bei Temperaturen zwischen 40°C und 150°C umsetzt und das hierbei gebildete Säure- addukt der Verbindung der Formel (I) - gegebenenfalls nach Zwischenisolierung - mit einem Säurebindemittel, wie z.B. Triethylamin oder Propylenoxid, bei Temperaturen zwischen 0°C und 60°C umsetzt (vgl. die Herstellungsbeispiele).in the presence of an acid, e.g. Hydrogen chloride (hydrogen chloride), reacted at temperatures between 40 ° C and 150 ° C and the acid adduct thus formed of the compound of formula (I) - optionally after intermediate isolation - with an acid binder, such as Triethylamine or propylene oxide, at temperatures between 0 ° C and 60 ° C (see. The preparation examples).
Die Verbindungen der Formel (I) können erfindungsgemäß in Defoliants, Krautab- tötungsmitteln und insbesondere in Unkrautvernichtungsmitteln - vor allem im semi-selektiven und im nicht-selektiven Bereich der Unkrautbekämpfung - ver¬ wendet werden. Unter Unkraut im weitesten Sinn sind dabei alle Pflanzen zu ver- stehen, die an Orten wachsen, wo sie unerwünscht sind, d.h. z.B. auch uner¬ wünschte Bäume im Wald.According to the invention, the compounds of the formula (I) can be used in defoliants, herbicides and in particular in weed killers - especially in the semi-selective and in the non-selective area of weed control. Weeds in the broadest sense are all plants that grow in places where they are undesirable, i.e. e.g. also unwanted trees in the forest.
Die erfindungsgemäß zu verwendenden Wirkstoffe können sowohl in kon¬ ventionellen Anbauverfahren (Reihenkulturen mit geeigneter Reihenweite), in Plantagenkulturen (z.B. Wein, Obst, Zitrus) sowie in Industrie- und Gleisanlagen, auf Wegen und Plätzen, aber auch zur Stoppelbehandlung und beim sogenanntenThe active ingredients to be used according to the invention can be used both in conventional cultivation methods (row crops with a suitable row width), in plantation crops (e.g. wine, fruit, citrus) and in industrial and track systems, on paths and squares, but also for stubble treatment and the so-called
"Minimum-Tillage"-Verfahren eingesetzt werden. Sie eignen sich weiterhin als Ab- brenner (Krautabtötung z.B. in Kartoffeln) oder als Defoliantien (z.B. in Baum- wolle). Ferner sind sie für den Einsatz auf Bracheflächen geeignet. Weitere Ein¬ satzgebiete sind Baumschulen, Forst, Grünland und Zierpflanzenbau."Minimum Tillage" method can be used. They are also suitable as burners (killing herbs, for example in potatoes) or as defoliants (for example in tree wool). They are also suitable for use on fallow land. Other areas of application are tree nurseries, forestry, grassland and ornamental plant cultivation.
Darüberhinaus können die Wirkstoffe der Formel (I) gemäß der Erfindung auch als selektive Herbizide in solchen Kulturpflanzen, welche gegenüber Glyphosate und anderen EPSP-Synthase-Inhibitoren resistent sind, eingesetzt werden.In addition, the active compounds of the formula (I) according to the invention can also be used as selective herbicides in crop plants which are resistant to glyphosate and other EPSP synthase inhibitors.
Als Unkräuter, die durch die erfindungsgemäß zu verwendenden Wirkstoffe gut bekämpft werden können, seien beispielsweise genannt:Examples of weeds which can be combated well by the active compounds to be used according to the invention are:
Dikotyle Unkräuter der Gattungen Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia,Dicotyledon weeds of the genera Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia,
Solanum, Cirsium, Carduus, Sonchus, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Sida, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxum, Mentha.Solanum, Cirsium, Carduus, Sonchus, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Sida, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxum, Mentha.
Monokotyle Unkräuter der Gattungen Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,Monocotyledonous weeds of the genera Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus,
Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Die erfindungsgemäße Verwendung der Wirkstoffe der Formel (I) ist jedoch keineswegs auf diese Gattungen beschränkt, sondern erstreckt sich in gleicherHowever, the use according to the invention of the active compounds of the formula (I) is by no means restricted to these genera, but extends in the same way
Weise auch auf andere Pflanzen.Also in other plants.
Die Verbindungen der Formel (I) eignen sich bei erfindungsgemäßer Anwendung insbesondere zur Bekämpfung von monokotylen und dikotylen Unkräutern im Nachauflauf-Verfahren. Sie zeigen starke herbizide Aktivität und ein breites Wirkungsspektrum bei Anwendung auf oberirdische Pflanzenteile. Sie zeigen auch deutlich bessere Wirksamkeit im Vergleich mit der bekannten Verbindung N- Phosphonomethyl-glycin (Glyphosate).When used according to the invention, the compounds of the formula (I) are particularly suitable for controlling monocotyledon and dicotyledon weeds in the post-emergence process. They show strong herbicidal activity and a broad spectrum of activity when applied to aerial parts of plants. They also show significantly better activity compared to the known compound N-phosphonomethyl-glycine (glyphosate).
Die erfindungsgemäßen Verbindungen der Formel (I) werden in wässriger Lösung unter Zusatz von Additiven (Adjuvantien, Emulgatoren, Netzmitteln, Tensiden) an- gewendet. Hierzu gehören vorzugsweise hochraffinierte Mineralöle, emulgierbare Pflanzenöle, ethoxylierte Taigamine, ethoxylierte Alkylamine, ethoxylierte Alkyl¬ phenole, ethoxylierte Alkylalkohole, Phosphatester, Alkyl- und Aryl-ether- phosphate, Sojaphospholipide und synthetischer Latex.The compounds of the formula (I) according to the invention are used in aqueous solution with the addition of additives (adjuvants, emulsifiers, wetting agents, surfactants). These preferably include highly refined mineral oils, emulsifiable ones Vegetable oils, ethoxylated taigamines, ethoxylated alkyl amines, ethoxylated alkyl phenols, ethoxylated alkyl alcohols, phosphate esters, alkyl and aryl ether phosphates, soy phospholipids and synthetic latex.
Als Beispiele für geeignete Additive (Adjuvantien, Emulgatoren, Netzmittel, Tenside) seien folgende handelsübliche Produkte [wobei es sich, zumindest teilweise, um eingetragene Warenzeichen handelt] genannt:Examples of suitable additives (adjuvants, emulsifiers, wetting agents, surfactants) are the following commercially available products [which are, at least in part, registered trademarks]:
Actiplus, Actipron (AM), Actirob B, Adder, Addwet, Adhesol, Adjuvant DHAI, Agral (90), Agrirob, Agrisorb, Agriwet, Agropen, Arnos Non-ionic Wetter, Anphix, APSA 80, Ashlade Adjuvant Oil, Atlas Adherbe, Atlas Adjuvant Oil, Atlas Libsorb, Banole (HV), Barclay Dryfast XL, Carbol, Chiltern Cropspray 1 1E,Actiplus, Actipron (AM), Actirob B, Adder, Addwet, Adhesol, Adjuvant DHAI, Agral (90), Agrirob, Agrisorb, Agriwet, Agropen, Arnos Non-ionic Wetter, Anphix, APSA 80, Ashlade Adjuvant Oil, Atlas Adherbe, Atlas Adjuvant Oil, Atlas Libsorb, Banole (HV), Barclay Dryfast XL, Carbol, Chiltern Cropspray 1 1E,
Citowett, Clifton Alkyl 90, Clifton Glyphosate Additive, Clifton Wetter, Codaeide Oil, Compatibility Agent 2, Cutonol, Du Pont Adjuvant, Emerald, Emulsol, Enhance, Enhance Low Foam, Ethokem, Ethokem C/12, Ethywet, Event, Exell, Farmon Blue, Farmon Wetter, Forestry Bee, Frigate, Fyzol 11E, Galion, Genamin T 200 BM, Glifor, Headland Guard, Headland Intake, Heliosol, High TreesCitowett, Clifton Alkyl 90, Clifton Glyphosate Additive, Clifton Wetter, Codaeide Oil, Compatibility Agent 2, Cutonol, Du Pont Adjuvant, Emerald, Emulsol, Enhance, Enhance Low Foam, Ethokem, Ethokem C / 12, Ethywet, Event, Exell, Farmon Blue, Farmon Wetter, Forestry Bee, Frigate, Fyzol 11E, Galion, Genamin T 200 BM, Glifor, Headland Guard, Headland Intake, Heliosol, High Trees
Mixture B, HT Non-ionic Wetter, Huile 970, Huile Schering L, Hyspray, Jogral, LI 700, Lo-Dose, Mangard, Minder, Nu Film P, Orchan 263, Oura S, PBI spreader, Pest Oil 7, Planet, Quad-Fast, Quadrangle Cropspray 11E, Quadrangle Q 900, Rapide, Rosemox, Sandovit 63, Seppic 1 IE, Seppic Ete, Silwet L 77, Solar, Sopratom, Sprayfast, Spraymate Activator 90, Spraymate Bond, Spraymate LI-700,Mixture B, HT Non-ionic Wetter, Huile 970, Huile Schering L, Hyspray, Jogral, LI 700, Lo-Dose, Mangard, Minder, Nu Film P, Orchan 263, Oura S, PBI spreader, Pest Oil 7, Planet, Quad-Fast, Quadrangle Cropspray 11E, Quadrangle Q 900, Rapide, Rosemox, Sandovit 63, Seppic 1 IE, Seppic Ete, Silwet L 77, Solar, Sopratom, Sprayfast, Spraymate Activator 90, Spraymate Bond, Spraymate LI-700,
Sprayprover, Spreader Sticker, Stefes Spread and Seal, Stik-It, Surfor, Swirl, Team, Tenac AS, Tonic, Top Farm Non-ionic 90, TopUp, Tradename A, Trend, Tri Mix, Tripart Acer, Tripart Cropspray 1 1E, Tripart Lentus, Tripart Minax, Vassgro Spreader, Vegelux, Wayfarer.Sprayprover, Spreader Sticker, Stefes Spread and Seal, Stik-It, Surfor, Swirl, Team, Tenac AS, Tonic, Top Farm Non-ionic 90, TopUp, Tradename A, Trend, Tri Mix, Tripart Acer, Tripart Cropspray 1 1E, Tripart Lentus, Tripart Minax, Vassgro Spreader, Vegelux, Wayfarer.
Weiter können auch neuere, aus der (Patent-)Literatur bekannte Arten vonFurthermore, newer types known from the (patent) literature
Additiven (Adjuvantien, Emulgatoren, Netzmitteln, Tensiden) eingesetzt werden, beispielsweise unter dem Namen Surfynole bekannt gewordene Alkindiole (vgl. EP 531269, US 5258359), unter dem Namen Ethoquad bekannt gewordene Alkyl- tris-(hydroxypolyalkoxyalkyl)-ammoniumsalze oder Dialkyl-bis-(hydroxypoly- alkoxyalkyl)-ammoniumsalze (vgl. WO 9402021, US 5317003), femer Trialkyl-Additives (adjuvants, emulsifiers, wetting agents, surfactants) are used, for example alkynediols which have become known under the name Surfynole (cf. EP 531269, US 5258359), alkyltris (hydroxypolyalkoxyalkyl) ammonium salts or dialkyl-bis which have become known as Ethoquad - (hydroxypolyalkoxyalkyl) ammonium salts (cf. WO 9402021, US 5317003), furthermore trialkyl
(alkoxypolyalkoxyalkyl)-ammoniumsalze und Polypropylenglycol (vgl. EP 526444) sowie sekundäre oder tertiäre Alkohol -Alkoxylate (vgl. WO 9516351). Die wässrigen Lösungen zur Anwendung der Verbindungen der Formel (I) enthalten im allgemeinen zwischen 1 und 50 Gewichtsprozent, vorzugsweise zwischen 5 und 30 Gewichtsprozent Wirkstoff.(alkoxypolyalkoxyalkyl) ammonium salts and polypropylene glycol (cf. EP 526444) and secondary or tertiary alcohol alkoxylates (cf. WO 9516351). The aqueous solutions for using the compounds of the formula (I) generally contain between 1 and 50 percent by weight, preferably between 5 and 30 percent by weight, of active ingredient.
Die Verbindungen der Formel (I) können als solche - in wässriger Lösung - oder auch in Mischung mit anderen bekannten Herbiziden zur Unkrautbekämpfung ver¬ wendet werden, wobei diese Mischungen im gegebenen Fall als "Tankmischun¬ gen", d.h. als vom Anwender zubereitete Spritz- oder Gießbrühen zur Anwendung kommen. Für diese Mischungen kommen bekannte herbizide Stoffe aus praktisch allen relevanten Stoffklassen in Betracht.The compounds of the formula (I) can be used as such - in aqueous solution - or else in a mixture with other known herbicides for weed control, these mixtures in the given case as "tank mixes", i.e. as spray or pouring broth prepared by the user. Known herbicidal substances from practically all relevant classes of substances come into consideration for these mixtures.
Die angewandte Wirkstoffmenge kann in einem größeren Bereich variiert werden. Sie hängt im wesentlichen von der Art des gewünschten Effektes ab. Im all¬ gemeinen liegen die Aufwandmengen zwischen 10 g und 10 kg Wirkstoff pro Hektar, vorzugsweise zwischen 50 g und 5 kg Wirkstoff pro Hektar, insbesondere zwischen 200 g und 2 kg Wirkstoff der Formel (I) pro Hektar Bodenfläche.The amount of active ingredient used can be varied within a substantial range. It essentially depends on the type of effect desired. In general, the application rates are between 10 g and 10 kg of active ingredient per hectare, preferably between 50 g and 5 kg of active ingredient per hectare, in particular between 200 g and 2 kg of active ingredient of the formula (I) per hectare of soil area.
In den durchgeführten Anwendungsversuchen zeigten die Verbindungen derIn the application tests carried out, the compounds of the
Formel (I) sehr gute Eigenschaften für die Anwendung im semi-selektiven und im nicht-selektiven Bereich der Unkrautbekämpfung.Formula (I) very good properties for use in the semi-selective and in the non-selective area of weed control.
Die Herstellung und die Verwendung der Verbindungen der Formel (I) geht aus den nachfolgenden Beispielen hervor. The preparation and use of the compounds of the formula (I) can be seen from the examples below.
AnwendungsbeispieleExamples of use
Beispiel AExample A
Post-emergence-TestPost emergence test
Emulgator 1 Gewichtsteil AlkylarylpolyglycoletherEmulsifier 1 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung legt man 1 GewichtsteilTo produce a suitable preparation of active compound, 1 part by weight is placed
Wirkstoff vor, verdünnt mit Wasser auf die gewünschte Konzentration und gibt 1 Gewichtsteil Emulgator dazuActive ingredient, diluted with water to the desired concentration and adds 1 part by weight of emulsifier
Mit der Wirkstoffzubereitung spritzt man Testpflanzen, welche eine Hohe von 5 - 15 cm haben, so, daß die jeweils gewünschten Wirkstoffmengen pro Flachen- einheit ausgebracht werden Die Konzentration der Spritzbruhe wird so gewählt, daß in 500 bis 1000 1 Wasser/ha die jeweils gewünschten Wirkstoffmengen aus¬ gebracht werdenTest plants which have a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. The concentration of the spray broth is chosen so that the respectively desired amounts in 500 to 1000 1 water / ha Active ingredient quantities are brought out
Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in % Schädigung im Vergleich zur Entwicklung der unbehandelten Kontrolle.After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
Es bedeutenMean it
0 % = keine Wirkung (wie unbehandelte Kontrolle)0% = no effect (like untreated control)
100 % = totale Vernichtung100% = total annihilation
In diesem Test zeigt beispielsweise die Verbindung gemäß Herstellungsbeispiel 1 stärkere Wirkung gegen Unkräuter als die Verbindung N-Phosphonomethyl-glycin (Glyphosate) Tabelle AI : Post-emergence-Test / GewächshausIn this test, the compound according to Preparation Example 1, for example, shows stronger activity against weeds than the compound N-phosphonomethyl-glycine (glyphosate) Table AI: Post emergence test / greenhouse
Wirkstoff Aufwandmenge Abutilon XanthiumActive ingredient application rate Abutilon Xanthium
(g/ha) N-Phosphonomethyl-glycin (Vergleichsverbindung) 2000 60 70(g / ha) N-phosphonomethyl-glycine (comparative compound) 2000 60 70
N-Phosphonom ethyl - glycin-ethylester 2000 100 100N-phosphonom ethyl-glycine ethyl ester 2000 100 100
(erfindungsgemäß)(according to the invention)
Tabelle A2: Post-emergence-Test / GewächshausTable A2: Post emergence test / greenhouse
Wirkstoff Aufwandmenge Raps Cyperus Digitaria CassiaActive ingredient application rate Rape Cyperus Digitaria Cassia
(g/ha) N-Phosphonomethyl- glycin 250 60 30 80 70(g / ha) N-phosphonomethylglycine 250 60 30 80 70
(Vergleichsverbindung)(Comparison connection)
N-Phosphonomethyl- gtycin-ethylester 250 30 70 100 90 (erfindungsgemäß)N-phosphonomethyl-gtycin-ethyl ester 250 30 70 100 90 (according to the invention)
Tabelle A3: Post-emergence-Test / GewächshausTable A3: Post emergence test / greenhouse
Wirkstoff Aufwandmenge Cyperus Digitaria Sorghum GaliumActive ingredient application rate Cyperus Digitaria Sorghum Galium
(g/ha)(g / ha)
N-Phosphonomethyl- glycin 500 50 90 60 70 (Vergleichsverbindung)N-phosphonomethylglycine 500 50 90 60 70 (comparative compound)
N-Phosphonomethyl- glycin-ethylester 500 70 100 80 90N-phosphonomethylglycine ethyl ester 500 70 100 80 90
(erfindungsgemäß) Beispiel B(according to the invention) Example B
Systemizitätsversuch an Abutilon theophrastiSystemicity attempt at Abutilon theophrasti
Material:Material:
Abutilon theophrasti wird im Gewächshaus bei 22°C (Tag) und 19°C (Nacht) an- gezogen. Die Töpfe haben einen Durchmesser von ca. 10 cm. Die Pflanzen werden im 6-8-Blatt-Stadium behandelt; sie sind dann ca. 3 Wochen alt.Abutilon theophrasti is grown in a greenhouse at 22 ° C (day) and 19 ° C (night). The pots have a diameter of approx. 10 cm. The plants are treated in the 6-8 leaf stage; then they are about 3 weeks old.
Ansatz der Präparatelösung:Approach of the preparation solution:
Die Pflanzen werden standardmäßig mit 1 mg pro Pflanze behandelt. Die Wirk¬ stoffe werden in Aceton/Wasser (1 :1) gelöst. Um zu gewährleisten, daß die Lösung nicht vom Blatt tropft, wird der Lösung als Netzmittel 0,1% Renex 36 (=The plants are treated with 1 mg per plant as standard. The active substances are dissolved in acetone / water (1: 1). In order to ensure that the solution does not drip off the leaf, the solution is mixed with 0.1% Renex 36 (=
Polyoxyethylen-(6)-tridecylether) zugesetzt.Polyoxyethylene (6) tridecyl ether) added.
Applikation der Präparatelösung:Application of the preparation solution:
Zuerst werden die Stiele der zu behandelnden Pflanzen - z.B. mit Lanolin - abge¬ dichtet, um zu verhindern, daß die Präparatelösung am Stiel herunterläuft und da- durch falsche Ergebnisse verursacht werden. Das dritte Laubblatt wird mit 0,04 mlFirst the stems of the plants to be treated - e.g. with lanolin - sealed to prevent the preparation solution from running down the stem and thereby causing incorrect results. The third leaf is made with 0.04 ml
Präparatelösung behandelt; das Präparat wird mit Hilfe einer Eppendorf-Pipette auf das Blatt getropft und anschließend auf ca. 10 cm2 auf dem Blatt verteilt. Pro Be¬ handlung werden drei Wiederholungen angelegt. Die Bonitierung erfolgt nach 18 Tagen visuell in Prozent Wirkung im Vergleich zur unbehandelten Kontrolle. Aus den drei Einzelergebnissen wird ein Mittelwert gebildet.Preparation solution treated; the preparation is dropped onto the leaf using an Eppendorf pipette and then distributed over approximately 10 cm 2 on the leaf. Three repetitions are created for each treatment. After 18 days, the ratings are given visually in percent effectiveness compared to the untreated control. An average is formed from the three individual results.
In diesem Test zeigt die Verbindung gemäß Herstellungsbeispiel 1 erheblich stärkere systemische Wirkungseigenschaften als die Vergleichsverbindung N- Phosphonomethyl-glycin. Tabelle B Systemizitatsversuch an Abutilon theophrastiIn this test, the compound according to Preparation Example 1 shows considerably stronger systemic properties than the comparative compound N-phosphonomethyl-glycine. Table B attempted systemicity on Abutilon theophrasti
Wirkstoff Aufwandmenge BonitierungActive ingredient application rate rating
(mg/Pflanze) (an Abutilon)(mg / plant) (on Abutilon)
N-Phosphonomethyl-glycinN-phosphonomethyl-glycine
(Vergleichsverbindung) 1 16,7(Comparative compound) 1 16.7
N-Phosphonomethyl-glycin- ethylester 1 78,3N-phosphonomethyl-glycine ethyl ester 1 78.3
(erfindungsgemaß) (according to the invention)
HerstellungsbeispieleManufacturing examples
Beispiel 1example 1
(HO)2P(O)-CH2-NH-CH2-CO-O-C2H5 (HO) 2 P (O) -CH 2 -NH-CH 2 -CO-OC 2 H 5
In eine Suspension von 200 g (1,2 Mol) N-Phosphonomethyl-glycin in 3000 ml Ethanol wird Chlorwasserstoff-Gas bis zur Sättigung eingeleitet. Dann wird dieHydrogen chloride gas is introduced into a suspension of 200 g (1.2 mol) of N-phosphonomethylglycine in 3000 ml of ethanol until saturation. Then the
Reaktionsmischung 3 Stunden unter Rückfluß erhitzt und anschließend - nach Ab¬ kühlen auf Raumtemperatur - im Wasserstrahlvakuum eingeengt. Der Rückstand wird in 1500 ml Ethanol gelöst und zu dieser Lösung wird Triethylamin (ca. 140 g) tropfenweise gegeben, bis ein Farbumschlag von rötlich-braun nach hell- gelb erfolgt. Das hierbei kristallin anfallende Produkt wird durch Absaugen isoliert.The reaction mixture was heated under reflux for 3 hours and then - after cooling to room temperature - concentrated in a water jet vacuum. The residue is dissolved in 1500 ml of ethanol and triethylamine (approx. 140 g) is added dropwise to this solution until the color changes from reddish brown to light yellow. The crystalline product is isolated by suction.
Man erhält 201 g (85% der Theorie) N-Phosphonomethyl-glycin-ethyl ester vom Schmelzpunkt >220°C.201 g (85% of theory) of N-phosphonomethylglycine-ethyl ester with a melting point> 220 ° C. are obtained.
Die "Trocknung" des gemäß Beispiel 1 erhaltenen Produktes - d.h. die Entfernung des Alkohols - kann - gegebenenfalls mit technisch üblichen Zerkleinerungsver¬ fahren kombiniert - beispielsweise nach folgenden, technisch üblichen Methoden erfolgen:The "drying" of the product obtained according to Example 1 - i.e. the alcohol can be removed, if appropriate combined with technically customary comminution processes, for example by the following technically customary methods:
Wirbel Schichttrocknung, Schaufeltrocknung oder Umlufttrocknung (jeweils gege¬ benenfalls mit technisch üblichen Zerkleinerungsverfahren, wie z.B. Luftstrahl- mahlung, Brechern, Walzen, Mahlen kombiniert).Vortex layer drying, paddle drying or forced-air drying (in each case combined, if appropriate, with technically customary comminution processes, such as, for example, air jet grinding, crushers, rollers, grinding).
Beispiel 2Example 2
(HO)2P(O)-CH2-NH-CH2-CO-O-C2H5 x HCI(HO) 2 P (O) -CH 2 -NH-CH 2 -CO-OC 2 H 5 x HCl
In eine Suspension von 5,1 g (30 mMol) N-Phosphonomethyl-glycin in 80 ml Ethanol wird Chlorwasserstoff-Gas bis zur Sättigung eingeleitet. Dann wird die Reaktionsmischung 2 Stunden unter Rückfluß erhitzt und anschließend im Wasser¬ strahlvakuum eingeengt. Der Rückstand wird mit Aceton verrührt und das kristalline Produkt durch Absaugen isoliert. Man erhält 3,0 g (43% der Theorie) N-Phosphonomethyl-glycin-ethylester-Hydro- chlorid als hygroskopische Kristalle, welche beim Erhitzen zerfließen. Hydrogen chloride gas is introduced into a suspension of 5.1 g (30 mmol) of N-phosphonomethyl-glycine in 80 ml of ethanol until it is saturated. The reaction mixture is then heated under reflux for 2 hours and then concentrated in a water jet vacuum. The residue is stirred with acetone and the crystalline product isolated by suction. 3.0 g (43% of theory) of N-phosphonomethyl-glycine-ethyl ester hydrochloride are obtained as hygroscopic crystals which melt when heated.

Claims

Patentansprüche claims
1. Verfahren zur Bekämpfung bzw. Abtötung von unerwünschten Pflanzen durch Einwirkung von N-Phosphonomethyl-glycin-alkylestern auf solche Pflanzen, dadurch gekennzeichnet, daß man zumindest einen N-Phosphono- methyl-glycinester der Formel (I)1. A method for controlling or killing undesired plants by the action of N-phosphonomethylglycine alkyl esters on such plants, characterized in that at least one N-phosphonomethylglycine ester of the formula (I)
(HO)2P(O)-CH2-NH-CH2-CO-O-R (I),(HO) 2 P (O) -CH 2 -NH-CH 2 -CO-OR (I),
in welcherin which
R für Alkyl steht,R represents alkyl,
oder eines seiner Säureaddukte, in Form einer wäßrigen Lösung unter Zusatz von Additiven (Adjuvantien, Emulgatoren, Netzmitteln, Tensiden) zur Anwendung bringt.or one of its acid adducts, in the form of an aqueous solution with the addition of additives (adjuvants, emulsifiers, wetting agents, surfactants).
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man einen N- Phosphonomethyl-glycinester der Formel (I) einsetzt, in welcher2. The method according to claim 1, characterized in that one uses an N-phosphonomethyl-glycine ester of the formula (I) in which
R für geradkettiges oder verzweigtes Alkyl mit 1 bis 10 Kohlenstoff- atomen steht.R represents straight-chain or branched alkyl having 1 to 10 carbon atoms.
3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man einen N- Phosphonomethyl-glycinester der Formel (I) einsetzt, in welcher3. The method according to claim 1, characterized in that one uses an N-phosphonomethyl-glycine ester of the formula (I) in which
R für geradkettiges oder verzweigtes Alkyl mit 2 bis 6 Kohlenstoff¬ atomen steht.R represents straight-chain or branched alkyl having 2 to 6 carbon atoms.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als N-4. The method according to claim 1, characterized in that as N-
Phosphonomethyl-glycinester der Formel (I) N-Phosphonomethyl-glycin- ethylester einsetzt.Phosphonomethyl-glycine ester of formula (I) uses N-phosphonomethyl-glycine ethyl ester.
5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die verwendete wäßrige Lösung zwischen 1 und 50, vorzugsweise zwischen 5 und 30 Gewichtsprozent Wirkstoff der Formel (I) enthält. 5. The method according to claim 1, characterized in that the aqueous solution used contains between 1 and 50, preferably between 5 and 30 percent by weight of active ingredient of formula (I).
6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Aufwand¬ mengen an Wirkstoff der Formel (I) zwischen 10 g und 10 kg, vorzugs¬ weise zwischen 50 g und 5 kg, insbesondere zwischen 200 g und 2 kg Wirkstoff pro Hektar Bodenfläche liegen.6. The method according to claim 1, characterized in that the expenditure amounts of active ingredient of formula (I) between 10 g and 10 kg, preferably between 50 g and 5 kg, in particular between 200 g and 2 kg of active ingredient per hectare of soil lie.
i 7. Verwendung von N-Phosphonomethyl-glycinestern der Formel (I) gemäßi 7. Use of N-phosphonomethyl-glycine esters of the formula (I) according to
Anspruch 1, oder von deren Säureaddukten, in Form wäßriger Lösungen, welchen als Hilfsstoffe Additive (Adjuvantien, Emulgatoren, Netzmittel, Tenside) zugesetzt sind, zur Bekämpfung bzw. Abtötung unerwünschter Pflanzen. Claim 1, or of their acid adducts, in the form of aqueous solutions, to which additives (adjuvants, emulsifiers, wetting agents, surfactants) have been added as auxiliaries for combating or killing undesired plants.
PCT/EP1996/003789 1995-09-11 1996-08-29 Using n-phosphonomethyl glycine esters in aqueous solution as a herbicide WO1997009883A1 (en)

Priority Applications (1)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977860A (en) * 1971-08-09 1976-08-31 Monsanto Company Herbicidal compositions and methods employing esters of N-phosphonomethylglycine

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977860A (en) * 1971-08-09 1976-08-31 Monsanto Company Herbicidal compositions and methods employing esters of N-phosphonomethylglycine

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
AGROKHIMIYA (1987), (7), 100-4 CODEN: AGKYAU;ISSN: 0002-1881, 1987 *
CHEMICAL ABSTRACTS, vol. 107, no. 19, 9 November 1987, Columbus, Ohio, US; abstract no. 170484, UGRYUMOV, E. P. ET AL: "Herbicidal activity of some N-phosphonomethylglycine esters" XP002022564 *

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