WO1997031534A1 - Use of n-phosphonomethylglycine esters in aqueous solution as herbicides, and new n-phosphonomethylglycine esters - Google Patents

Use of n-phosphonomethylglycine esters in aqueous solution as herbicides, and new n-phosphonomethylglycine esters Download PDF

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Publication number
WO1997031534A1
WO1997031534A1 PCT/EP1997/000731 EP9700731W WO9731534A1 WO 1997031534 A1 WO1997031534 A1 WO 1997031534A1 EP 9700731 W EP9700731 W EP 9700731W WO 9731534 A1 WO9731534 A1 WO 9731534A1
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Prior art keywords
alkyl
alkoxy
hydroxy
mono
carboxy
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PCT/EP1997/000731
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German (de)
French (fr)
Inventor
Hans-Jochem Riebel
Markus Dollinger
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Bayer Aktiengesellschaft
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Priority claimed from DE19638301A external-priority patent/DE19638301A1/en
Application filed by Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU17906/97A priority Critical patent/AU1790697A/en
Publication of WO1997031534A1 publication Critical patent/WO1997031534A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl

Definitions

  • N-phosphonomethyl-glvcinester in aqueous solution as herbicides and new N-FhosphonomethvI-glvcinester
  • the invention relates to the novel use of partially known N-phosphonomethylglycine esters and their acid adducts in aqueous solution as herbicides, and to a subset of new N-phosphonomethylglycine esters and their acid adducts, a process for their preparation and their use as herbicides.
  • N-phosphonomethyl-glycine glyphosate
  • glyphosate shows strong herbicidal activity
  • said compound is a component of some commercially available products, such as "Roundup” and “Touchdown”.
  • the action of this compound against weeds and its tolerance to crop plants are not satisfactory in all cases.
  • N-phosphonomethylglycine alkyl esters have herbicidal properties and - generally in formulated application forms, i.e. combined with certain additives - can be used to kill undesired plants (cf. DE 2152826, DE 2166573, US 3977860).
  • N-phosphonomethylglycine esters of the general formula (I) N-phosphonomethylglycine esters of the general formula (I)
  • R for alkyl which is mono- or polysubstituted by hydroxy, carboxy, halogen, alkoxy, hydroxyalkoxy, alkoxyalkoxy, hydroxyalkoxyalkoxy, alkoxyalkoxyalkoxy, alkylcarbonyl, hydroxyalkylcarbonyl or alkoxycarbonyl. for each optionally by hydroxy, carboxy.
  • C j -C 6 - alkoxy carbonyl mono- to pentasubstituted C j -C jQ alkyl for by C 2 -C 6 alkoxy mono- to tri-substituted C j -C jQ -alkyl or by C, -C 6 -alkoxy mono- to tri-substituted alkyl C 3 -C 10, for in each case by hydroxy, carboxy, halogen or C, -C 6 alkoxy-carbonyl mono- to tri-substituted C 2 -C] 0 - alkenyl or C 2 -C 10 alkynyl, for C 3 mono- to trisubstituted by hydroxyl, carboxy, halogen, C j -Cg alkyl, hydroxy-C j -C 6 alkyl or C j -C 6 alkoxycarbonyl -C 6 -cycloalkyl or C 3 -C 6 -cyclo
  • the invention thus relates to a new process for controlling or killing undesired plants by the action of N-phosphonomethylglycine 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, ie without the addition of other auxiliaries.
  • the aqueous solutions of the pure active compounds of the formula (I) - and of acid adducts of these compounds - can be used directly without destroying the formulation auxiliaries which are otherwise customary in agrochemicals to kill off undesired plants.
  • the new application now found for the active ingredients of the formula (I) to be used according to the invention is a completely surprising, very simple and therefore economically very economical problem-solving option in agriculture and forestry.
  • the invention preferably relates to the use of compounds of the formula (I) in which
  • C 2 -C 6 alkynyl for each optionally by hydroxy, carboxy, fluorine, chlorine, C ] -C 4 alkyl, hydroxy-C j -C 4 alkyl or C r C 4 alkoxy-carbonyl one or two times substituted C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl- C 1 -C 4 alkyl, or for each C 2 -C 5 oxacycloalkyl optionally substituted by C j -C 4 alkyl, C j -C 4 -dioxacycloalkyl, C 2 -C 5 -oxacycloalkyl-C 1 -C 4 -alkyl or C 2 -C 5 -dioxacycloalkyl-C 1 -C 4 -alkyl.
  • the invention also relates preferably to new compounds of the formula (IA) in which
  • A represents hydroxy by one to four times substituted C j -C 8 alkyl, C, -C 6 - alkoxy-C j -C 8 -alkoxy, hydroxy-C, -C 6 alkoxy-C j-C6 alkoxy , C, -C 6 -alkoxy-
  • Alkyl means in all defined areas, also in connection with heteroatoms, e.g. in alkoxy or hydroxyalkyl, in each case straight-chain or branched alkyl.
  • the invention relates in particular to the use of compounds of the formula (I) in which R represents ethyl mono- or di-substituted by hydroxyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-Pentyl, 2,2-dimethyl-propyl, 1,3-dimethyl-propyl, 1,1-dimethyl-butyl or 2,2-dimethyl-butyl, for each by carboxy, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl mono- or disubstituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, each with methoxy - ethoxy, ethoxyeth
  • the invention relates in particular to new compounds of the formula (IA) in which
  • a for ethyl which is mono- or disubstituted by hydroxy, n- or i-propyl, for n-, i-, s- or t-butyl, n-, i-, s- or n-, i-, s- or t-substituted by hydroxy t-pentyl, 2,2-dimethyl-propyl, 1,3-dimethyl-propyl, 1,1-dimethyl-butyl or 2,2-dimethyl-butyl, for each by carboxy, methoxycarbonyl or ethoxycarbonyl, one or two times sub- substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, for each by ethoxy, n- or i-propoxy, n-, i-, s
  • the new compounds of the formula (IA) and the acid adducts thereof are notable for strong and selective herbicidal activity. They also have very favorable biological transport properties, i.e. they are very well absorbed by the target organisms and quickly distributed within the treated plants.
  • acid adducts are generally understood to mean addition products of compounds of the formula (I) or (IA) and acids.
  • Suitable acids are preferably protonic acids, such as e.g. Hydrogen fluoride, hydrogen chloride (hydrochloric acid), hydrogen bromide, hydrogen iodide, sulfuric acid, phosphoric acid, acetic acid, trifluoroacetic acid, mandelic acid, citric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.
  • Hydrogen fluoride hydrogen chloride (hydrochloric acid)
  • hydrogen bromide hydrogen iodide
  • sulfuric acid phosphoric acid
  • acetic acid trifluoroacetic acid
  • mandelic acid citric acid
  • methanesulfonic acid ethanesulf
  • the acid adducts of the compounds of the formula (IA) obtained in the process according to the invention for the preparation of the compounds of the formula (IA) are treated with acid binders.
  • di-C 3 -C 6 come - alkyl-amine with branched alkyl groups, di-C 5 -C 6 -cycloalkyl-amines, tri-C j -C 6 - alkyl-amines having straight-chain and / or branched alkyl groups, N, N-Di- C j -C 6 -alkyl-NC 5 -C 6 -cycloalkylamines with straight-chain and / or branched AI- alkyl groups and N, N-di-C 5 -C 6 -cycloaljtyl-NC r C 6 -alkylamines with straight-chain or branched alkyl groups.
  • Oxiranes which are unsubstituted or mono- or disubstituted by alkyl or aryl groups are also preferred as acid binders.
  • examples include oxirane (ethylene oxide),
  • Methyloxirane (propylene oxide, 1,2-epoxy-propane), ethyloxirane (1,2-butylene oxide, 1,2-epoxy-butane), propyloxirane (1,2-epoxy-pentane) and phenyloxirane (styrene oxide, epoxystyrene) .
  • reaction temperatures can be increased
  • Range can be varied. In general, temperatures between 30 ° C and 150 ° C, preferably between 60 ° C and 120 ° C.
  • the process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
  • one mole of phosphonomethylglycine of the formula (II) is generally between 1 and 100 moles, preferably between 10 and 50 moles of an alcohol of the formula (III) and between 1 and 5 moles, preferably between 1, 5 and 3 mol of an acid and optionally between 1 and 5 mol, preferably between 1.5 and 3 mol of an acid binder.
  • the phosphonomethylglycine of the formula (II) is suspended in an alcohol of the formula (III) and an acid is slowly metered in. The reaction mixture is then kept at the required temperature until the reaction is practically complete.
  • the mixture is concentrated under reduced pressure, optionally digested with a suitable organic solvent, such as acetone, and the acid adduct is isolated by suction.
  • a suitable organic solvent such as acetone
  • the residue which essentially contains the acid adduct, or the acid adduct isolated in crystalline form as described above, is again taken up in an alcohol of formula (III) and mixed with added to an acid binder.
  • the product of the formula (IA) is obtained in crystalline form and can be isolated by suction
  • the active compounds of the formulas (I) or (IA) can be used in defoliants, desiccants, herbicides and in particular in weed killers - above all in the semi-selective and in the non-selective area of weed control. Weeds in the broadest sense are all
  • 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 (for example wine, fruit, citrus) and in industrial and track systems, on paths and squares, but also for stubble treatment and in the so-called " "Minimum Tillage” process can also be used as a burner (killing herbs, for example in potatoes) or as defoamers (for example, in cotton). They are also suitable for use on fallow land. Forest, grassland and ornamental plant growing
  • active compounds of the formulas (I) or (IA) according to the invention can also be used as herbicides in crop plants which are resistant to glyphosates and other EPSP synthase inhibitors
  • the active compounds according to the invention can be used, for example, in the following plants
  • T ⁇ fohum Ranunculus, Taraxacum Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
  • the compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover.
  • the compounds for weed control in permanent crops e.g. Forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture land and for selective purposes Weed control can be used in annual crops.
  • the compounds of the formulas (I) and (IA) according to the invention are particularly suitable for controlling monocotyledon and dicotyledon weeds in the post-emergence process.
  • the compounds of the formulas (I) and (IA) can - as stated above - be used in aqueous solution without further additives; however, they can also be used, if appropriate, with the addition of additives (adjuvants, emulsifiers, wetting agents, surfactants).
  • additives preferably include highly refined mineral oils, emulsifiable vegetable oils, ethoxylated taigamines, ethoxylated alkylamines, ethoxylated alkylphenols, ethoxylated alkyl alcohols, phosphate esters, alkyl and aryl ether phosphates, soy phospholipids and synthetic latex.
  • suitable additives are the following commercially available products, at least some of which are registered trademarks:
  • alkynediols which have become known under the name Surfynole (cf. EP 531269, US 5258359), under the name Ethoquad known alkyl tris (hydroxypolyalkoxyalkyl) ammonium salts or dialkyl bis (hydroxypolyalkoxyalkyO ammonium salts (cf. WO 9402021, US 5317003), trialkyl (alkoxypolyalkoxyalkyl) ammonium salts and polypropylene glycol (cf. EP 526444) and secondary or tertiary alcohol alkoxylates (cf. WO 9516351).
  • Surfynole cf. EP 531269, US 5258359
  • Ethoquad known alkyl tris hydroxypolyalkoxyalkyl
  • dialkyl bis hydroxypolyalkoxyalkyO ammonium salts
  • 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. - n -
  • the compounds of the formulas (I) or (IA) 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 mixtures", i.e. as spray or pouring broth prepared by the user.
  • herbicidal substances from practically all relevant classes of substances are suitable for these mixtures, for example acetochlor, acifluorfen (sodium), aclonifene, alachlor, alloxydim (sodium), ametryne, amidochlor, amidosulfuron, amiprophos (methyl), amitrole, anilofos, Asulam, Atrazin, Azim-sulfuron, Benazolin, Benfuresate, Bensulfuron (-methyl), Bensulide, Bentazon,
  • EPTC Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethofumesate, Ethoxyfen, Etobenzanid, Fenoxaprop (-ethyl), Flamprop (-isopropyl), Flamprop (-methyl), Flazasulfuron, Fluazifop (-butyl), Flumetsulam (Flumiclorac -pentyl), flumi- oxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil, flurenol (n-butyl ester), fluridone, fluroxypyr, flurpri ⁇ midol, flurtamone, fomesafen, glufosiumate, -ammos , Haloxyfop (-ethoxyethyl), Hexazinone, Imazamethabenz (-methyl), Imazamet
  • a mixture with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
  • the amount of active ingredient used can vary over a wide 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 of soil, preferably between 50 g and 5 kg per ha.
  • Ethoxyethanol is introduced to hydrogen chloride gas until saturation.
  • the reaction mixture is then heated under reflux for 2 hours, about 50 ml of 2-ethoxyethanol being removed by distillation.
  • the mixture is then concentrated in a water jet vacuum.
  • the residue is mixed with propylene oxide until the color changes from reddish brown to light yellow.
  • the crystalline product obtained is isolated by suction.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is added, diluted with water to the desired concentration and 1 part by weight of emulsifier is added.
  • 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 liquor is chosen so that the desired amounts of active compound are applied in 500 to 1000 l of water / ha.
  • the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

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Abstract

The invention concerns the new use of N-phosphonomethylglycine esters, some of them prior art, of formula (I): (HO)2P(O)-CH2-NH-CH2-CO-O-R, in which R is alkyl substituted with one or more hydroxy, carboxylic, halogen, alkoxy, hydroxyalkoxy, alkoxyalkoxy, hydroxyalkoxyalkoxy, alkoxyalkoxyalkoxy, alkylcarbonyl, hydroxyalkylcarbonyl or alkoxycarbonyl groups; alkenyl or alkinyl optionally substituted with one or more hydroxy, carboxylic, halogen or alkoxycarbonyl groups; cycloalkyl or cycloalkylalkyl optionally substituted with one or more hydroxy, carboxylic, halogen, alkyl, hydroxyalkyl, alkoxyalkyl, alkoxy or alkoxycarbonyl groups; or oxacycloalkyl, dioxacycloalkyl, oxacycloalkylalkyl or dioxacycloalkylalkyl optionally substituted with alkyl; or acid adducts thereof, alone in aqueous solution, i.e. without additives, as herbicides, as well as a sub-group of new N-phosphonomethylglycine esters, of the formula (IA): (HO)2P(O)-CH2-NH-CH2-CO-O-A, in which A is as defined in the description. The invention also concerns a method of producing such compounds and their use as herbicides.

Description

Verwendung von N-Phosphonomethyl-glvcinestern in wässriger Lösung als Herbizide und neue N-FhosphonomethvI-glvcinesterUse of N-phosphonomethyl-glvcinester in aqueous solution as herbicides and new N-FhosphonomethvI-glvcinester
Die Erfindung betrifft die neuartige Verwendung von teilweise bekannten N- Phosphonomethyl-glycinestern und deren Säureaddukten in wässriger Lösung als Herbizide, sowie eine Untergruppe von neuen N-Phosphonomethyl-glycinestern und deren Säureaddukte, ein Verfahren zu deren Herstellung sowie deren Ver¬ wendung als Herbizide.The invention relates to the novel use of partially known N-phosphonomethylglycine esters and their acid adducts in aqueous solution as herbicides, and to a subset of new N-phosphonomethylglycine esters and their acid adducts, a process for their preparation and their use as herbicides.
Es ist bekannt, daß N-Phosphonomethyl-glycin (Glyphosate) starke herbizide Wirksamkeit zeigt (vgl. DE 2152826). Die genannte Verbindung ist als herbizid aktive Komponente Bestandteil einiger im Handel befindlicher Produkte, wie z.B. "Roundup" und "Touchdown". Die Wirkung dieser Verbindung gegen Unkräuter und ihre Verträglichkeit gegenüber Kulturpflanzen sind jedoch nicht in allen Fällen zufriedenstellend.It is known that N-phosphonomethyl-glycine (glyphosate) shows strong herbicidal activity (cf. DE 2152826). As a herbicidally active component, said compound is a component of some commercially available products, such as "Roundup" and "Touchdown". However, the action of this compound against weeds and its tolerance to crop plants are not satisfactory in all cases.
Weiter ist bekannt, daß einige N-Phosphonomethyl-glycin-alkylester herbizide Eigenschaften aufweisen und - im allgemeinen in formulierten Anwendungsfor¬ men, d.h. mit bestimmten Zuschlagsstoffen kombiniert - zur Abtotung von uner¬ wünschten Pflanzen verwendet werden können (vgl. DE 2152826, DE 2166573, US 3977860).It is also known that some N-phosphonomethylglycine alkyl esters have herbicidal properties and - generally in formulated application forms, i.e. combined with certain additives - can be used to kill undesired plants (cf. DE 2152826, DE 2166573, US 3977860).
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 durch Hydroxy, Carboxy, Halogen, Alkoxy, Hydroxyalkoxy, Alkoxy¬ alkoxy, Hydroxyalkoxyalkoxy, Alkoxyalkoxyalkoxy, Alkylcarbonyl, Hy¬ droxyalkylcarbonyl oder Alkoxycarbonyl ein- oder mehrfach substituiertes Alkyl. für jeweils gegebenenfalls durch Hydroxy, Carboxy. Halogen oder Alkoxycarbonyl ein- oder mehrfach substituiertes Alkenyl oder Alkinyl, für jeweils gegebenenfalls durch Hydroxy, Carboxy, Halogen, Alkyl, Hydroxv- alkyl, Alkoxyalkyl, Alkoxy oder Alkoxycarbonyl ein- oder mehrfach sub¬ stituiertes Cycloalkyl oder Cycloalkylalkyl, oder für jeweils aeεebenenfalls durch Alkyl substituiertes Oxacycloalkyl, Dioxacycloalkyl, Oxacycloalkyl¬ alkyl oder Dioxacycloalkylalkyl steht,R for alkyl which is mono- or polysubstituted by hydroxy, carboxy, halogen, alkoxy, hydroxyalkoxy, alkoxyalkoxy, hydroxyalkoxyalkoxy, alkoxyalkoxyalkoxy, alkylcarbonyl, hydroxyalkylcarbonyl or alkoxycarbonyl. for each optionally by hydroxy, carboxy. Halogen or alkoxycarbonyl monosubstituted or polysubstituted alkenyl or alkynyl, for cycloalkyl or cycloalkylalkyl which is mono- or polysubstituted or substituted by hydroxyl, carboxy, halogen, alkyl, hydroxylalkyl, alkoxyalkyl, alkoxy or alkoxycarbonyl, or for each case likewise in each case optionally oxacycloalkyl, dioxacycloalkyl, oxacycloalkylalkyl or dioxacycloalkylalkyl substituted by alkyl,
sowie Säureaddukte der Verbindungen der Formel (I)and acid adducts of the compounds of the formula (I)
allein in wässriger Lösung, d.h. ohne Verwendung weiterer Hilfsstoffe, mit sehr gutem Erfolg zur Abtotung unerwünschter Pflanzen verwendet werden können.alone in aqueous solution, i.e. can be used with very good success to kill unwanted plants without the use of other auxiliaries.
Es wurden weiter die neuen Verbindungen der Formel (IA)The new compounds of the formula (IA)
(HO)2P(O)-CH2-NH-CH2-CO-O-A (IA)(HO) 2 P (O) -CH 2 -NH-CH 2 -CO-OA (IA)
in welcherin which
A für durch Hydroxy, Carboxy, Hydroxy-CrC6-alkoxy, C.-C8-AIkoxy-Cj-C8- alkoxy,
Figure imgf000004_0001
A for by hydroxy, carboxy, hydroxy-C r C 6 -alkoxy, C.-C 8 -alkoxy-C j -C 8 -alkoxy,
Figure imgf000004_0001
Cj-Cß-alkoxy, C,-C6-Alkyl-carbonyl, Hydroxy-C,-C6-alkyl-carbonyl oderC j -C ß alkoxy, C, -C 6 alkyl carbonyl, hydroxy-C, -C 6 alkyl carbonyl or
Cj-C6- Alkoxy -carbonyl ein- bis fünffach substituiertes Cj-CjQ-Alkyl, für durch C2-C6-Alkoxy ein- bis dreifach substituiertes Cj-CjQ-Alkyl oder für durch C,-C6-Alkoxy ein- bis dreifach substituiertes C3-C10-Alkyl, für je- weils durch Hydroxy, Carboxy, Halogen oder C,-C6-Alkoxy-carbonyl ein- bis dreifach substituiertes C2-C]0- Alkenyl oder C2-C10- Alkinyl, für jeweils durch Hydroxy, Carboxy, Halogen, Cj-Cg-Alkyl, Hydroxy-Cj-C6- Alkyl oder Cj-C6-Alkoxy-carbonyl ein- bis dreifach substituiertes C3-C6-Cyclo- alkyl oder C3-C6-Cycloalkyl-C1-C6-alkyl, oder für jeweils gegebenenfalls durch C1-C6- Alkyl substituiertes C2-C5-Oxacycloalkyl, C2-C4-Dioxacyclo- alkyl, C2-C5-Oxacycloalkyl-CrC6-alkyl oder C2-C4-Dioxacycloalkyl-C]-C4- alkyl steht,C j -C 6 - alkoxy carbonyl mono- to pentasubstituted C j -C jQ alkyl, for by C 2 -C 6 alkoxy mono- to tri-substituted C j -C jQ -alkyl or by C, -C 6 -alkoxy mono- to tri-substituted alkyl C 3 -C 10, for in each case by hydroxy, carboxy, halogen or C, -C 6 alkoxy-carbonyl mono- to tri-substituted C 2 -C] 0 - alkenyl or C 2 -C 10 alkynyl, for C 3 mono- to trisubstituted by hydroxyl, carboxy, halogen, C j -Cg alkyl, hydroxy-C j -C 6 alkyl or C j -C 6 alkoxycarbonyl -C 6 -cycloalkyl or C 3 -C 6 -cycloalkyl-C 1 -C 6 -alkyl, or for C 2 -C 5 -oxacycloalkyl optionally substituted by C 1 -C 6 -alkyl, C 2 -C 4 -Dioxacycloalkyl, C 2 -C 5 -oxacycloalkyl-C r C 6 -alkyl or C 2 -C 4 -dioxacycloalkyl-C ] -C 4 - alkyl,
sowie Säureaddukte der Verbindungen der Formel (IA) gefunden.and acid adducts of the compounds of formula (IA) found.
Man erhält die neuen Verbindungen der allgemeinen Formel (IA), wenn man N-Phosphonomethyl-glycin der Formel (II)The new compounds of the general formula (IA) are obtained if N-phosphonomethylglycine 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) HO-A (III)with an alcohol of formula (III) HO-A (III)
in welcherin which
A die oben angegebene Bedeutung hat,A has the meaning given above,
in Gegenwart von Chlor-trimethylsilan oder einer Protonensäure umsetzt, das ge- gebenenfalls hierbei gebildete Säureaddukt der Verbindung der Formel (IA) gege¬ benenfalls isoliert und gegebenenfalls mit einem Säurebindemittel umsetzt.in the presence of chloro-trimethylsilane or a protonic acid, optionally isolating the acid adduct of the compound of the formula (IA) formed in this case and optionally reacting it with an acid binder.
Gegenstand der Erfindung ist also ein neues Verfahren zur Bekämpfung bzw. Ab¬ totung von unerwünschten Pflanzen durch Einwirkung von N-Phosphonomethyl- glycinestern auf solche Pflanzen, welches dadurch gekennzeichnet ist, daß man zu- mindest einen N-Phosphonomethyl-glycinester der obigen Formel (I), oder eines seiner Säureaddukte, in Form einer wäßrigen Lösung, d.h. ohne Zusatz weiterer Hilfsstoffe, zur Anwendung bringt.The invention thus relates to a new process for controlling or killing undesired plants by the action of N-phosphonomethylglycine 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, ie without the addition of other auxiliaries.
Überraschenderweise können also die wässrigen Lösungen der reinen Wirkstoffe der Formel (I) - sowie von Säureaddukten dieser Verbindungen - ohne Kombi- nation mit den sonst bei Agrochemikalien üblichen Formulierungshilfsstoffen - un¬ mittelbar zur Abtotung unerwünschter Pflanzen eingesetzt werden. Angesichts der sonst üblichen Praxis bei der Anwendung von Pflanzenbehandlungsmitteln, d.h. der Verwendung von mit Hilfsstoffen kombinierten, formulierten Wirkstoffen, stellt die nun gefundene neue Anwendungsmöglichkeit für die erfindungsgemäß einzusetzenden Wirkstoffe der Formel (I) eine völlig überraschende, sehr einfache und damit wirtschaftlich sehr günstige Problemlösungsmöglichkeit in Land- und Forstwirtschaft dar.Surprisingly, the aqueous solutions of the pure active compounds of the formula (I) - and of acid adducts of these compounds - can be used directly without destroying the formulation auxiliaries which are otherwise customary in agrochemicals to kill off undesired plants. In view of the otherwise usual practice when using plant treatment agents, i.e. the use of formulated active ingredients combined with auxiliaries, the new application now found for the active ingredients of the formula (I) to be used according to the invention is a completely surprising, very simple and therefore economically very economical problem-solving option in agriculture and forestry.
Die erfindungsgemäße Verwendungsmöglichkeit für die Verbindungen der Formel (I) stellt somit eine sehr wertvolle Bereicherung des Standes der Technik dar.The 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 For¬ mel (I), in welcherThe invention preferably relates to the use of compounds of the formula (I) in which
R für durch Hydroxy ein- bis vierfach substituiertes C,-C6-Alkyl, für durchR for C to C 6 alkyl which is mono- to tetrasubstituted by hydroxyl, for by
Carboxy, Fluor, Chlor, CrC6-Alkoxy oder CrC6-Alkoxy-carbonyl ein- oder zweifach substituiertes CrC6-Alkyl, für durch Hydroxy-CrC4-alkoxy, C1-C4-Alkoxy-C1-C4-alkoxy, Hydroxy-C]-C4-alkoxy-C1-C4-alkoxy, C,-C4- Alkoxy-C1-C4-alkoxy-C1-C4-alkoxy, Cj-C4-Alkyl-carbonyl oder Hydroxy- C1-C4-alkyl-carbonyl einfach substituiertes C,-C4-Alkyl, für jeweils ge¬ gebenenfalls durch Hydroxy, Carboxy, Fluor, Chlor oder CrC4-Alkoxy- carbonyl ein- oder zweifach substituiertes C2-C6-Alkenyl oderCarboxy, fluorine, chlorine, C r C 6 alkoxy or C r C 6 alkoxy-carbonyl mono- or disubstituted C r C 6 alkyl, for hydroxy-C r C 4 alkoxy, C 1 -C 4 alkoxy-C 1 -C 4 alkoxy, hydroxy-C ] -C 4 alkoxy-C 1 -C 4 alkoxy, C, -C 4 - alkoxy-C 1 -C 4 alkoxy- C 1 -C 4 -alkoxy, C j -C 4 alkyl-carbonyl or hydroxy C 1 -C 4 alkyl-carbonyl monosubstituted C, -C 4 alkyl, ge for each optionally substituted by hydroxy, carboxy, fluoro , Chlorine or C r C 4 alkoxy carbonyl mono- or disubstituted C 2 -C 6 alkenyl or
C2-C6-Alkinyl, für jeweils gegebenenfalls durch Hydroxy, Carboxy, Fluor, Chlor, C]-C4-Alkyl, Hydroxy-Cj-C4-alkyl oder CrC4-Alkoxy-carbonyl ein- oder zweifach substituiertes C3-C6-Cycloalkyl oder C3-C6-Cycloalkyl- C1-C4-alkyl, oder für jeweils gegebenenfalls durch Cj-C4-Alkyl sub- stituiertes C2-C5-Oxacycloalkyl, Cj-C4-Dioxacycloalkyl, C2-C5-Oxacyclo- alkyl-C1-C4-alkyl oder C2-C5-Dioxacycloalkyl-C1-C4-alkyl steht.C 2 -C 6 alkynyl, for each optionally by hydroxy, carboxy, fluorine, chlorine, C ] -C 4 alkyl, hydroxy-C j -C 4 alkyl or C r C 4 alkoxy-carbonyl one or two times substituted C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl- C 1 -C 4 alkyl, or for each C 2 -C 5 oxacycloalkyl optionally substituted by C j -C 4 alkyl, C j -C 4 -dioxacycloalkyl, C 2 -C 5 -oxacycloalkyl-C 1 -C 4 -alkyl or C 2 -C 5 -dioxacycloalkyl-C 1 -C 4 -alkyl.
Die Erfindung betrifft außerdem vorzugsweise neue Verbindungen der Formel (IA), in welcherThe invention also relates preferably to new compounds of the formula (IA) in which
A für durch Hydroxy ein- bis vierfach substituiertes Cj-C8-Alkyl, C,-C6- Alkoxy-Cj-C8-alkoxy, Hydroxy-C,-C6-alkoxy-Cj-C6-alkoxy, C,-C6-Alkoxy-A represents hydroxy by one to four times substituted C j -C 8 alkyl, C, -C 6 - alkoxy-C j -C 8 -alkoxy, hydroxy-C, -C 6 alkoxy-C j-C6 alkoxy , C, -C 6 -alkoxy-
C1-C6-alkoxy-C1-C6-alkoxy, C,-C6-Alkyl-carbonyl, Hydroxy-CrC6-alkyl- carbonyl oder C1-C6-Alkoxy-carbonyl ein- bis fünffach substituiertes C,- C10-Alkyl, für durch C2-C6-Alkoxy ein- bis dreifach substituiertes C,-C10- Alkyl oder für durch C,-C6-Alkoxy ein- bis dreifach substituiertes C3-C] 0- Alkyl, für jeweils durch Hydroxy, Carboxy, Halogen oder C1-C6-Alkoxy- carbonyl ein- bis dreifach substituiertes C2-C10- Alkenyl oder C2-C10- Alkinyl, für jeweils durch Hydroxy, Carboxy, Halogen, C^Q-Alkyl, Hydroxy-C,-C6- Alkyl oder Cj-C6-Alkoxy-carbonyl ein- bis dreifach sub¬ stituiertes C3-C6-Cycloalkyl oder C3-C6-Cycloalkyl-CrC6-alkyl, oder für jeweils gegebenenfalls durch Cj-C6-Alkyl substituiertes C2-C5-Oxacyclo- alkyl, C2-C4-Dioxacycloalkyl, C2-C5-Oxacycloalkyl-C1-C6-alkyl oder C2- C4-Dioxacycloalkyl-C1 -C4-alkyl steht,C 1 -C 6 alkoxy-C 1 -C 6 alkoxy, C, -C 6 alkyl carbonyl, hydroxy-C r C 6 alkyl carbonyl or C 1 -C 6 alkoxy carbonyl one to five times substituted C, - C 10 alkyl, for by C 2 -C 6 -alkoxy mono- to tri-substituted C, -C 10 - alkyl or by C, -C 6 alkoxy mono- to tri-substituted C 3 -C] 0 - alkyl, for C 2 -C 10 -alkenyl or C 2 -C 10 -alkynyl mono- to trisubstituted by hydroxyl, carboxy, halogen or C 1 -C 6 -alkoxy-carbonyl, each in each case by hydroxyl, carboxy, halogen, C ^ Q-alkyl, hydroxy-C, -C 6 - alkyl or C j -C 6 alkoxy-carbonyl mono- to trisubstituted sub¬ stituiertes C 3 -C 6 -cycloalkyl or C 3 -C 6 cycloalkyl C r C 6 alkyl, or for C 2 -C 5 oxacycloalkyl optionally substituted by C j -C 6 alkyl, C 2 -C 4 dioxacycloalkyl, C 2 -C 5 oxacycloalkyl-C 1 -C 6 alkyl or C 2 - C 4 -Dioxacycloalkyl-C 1 -C 4 -alkyl,
Alkyl bedeutet in allen definierten Bereichen, auch in Verknüpfung mit Heteroatomen, wie z.B. in Alkoxy oder Hydroxyalkyl, jeweils geradkettiges oder verzweigtes Alkyl.Alkyl means in all defined areas, also in connection with heteroatoms, e.g. in alkoxy or hydroxyalkyl, in each case straight-chain or branched alkyl.
Die Erfindung betrifft insbesondere die Verwendung von Verbindungen der Formel (I), in welcher R für jeweils durch Hydroxy ein- oder zweifach substituiertes Ethyl, n- oder i-Propyl, für jeweils durch Hydroxy ein- bis dreifach substituiertes n-, i-, s- oder t-Butyl, n-, i-, s- oder t-Pentyl, 2,2-Dimethyl-propyl, 1,3-DimethyI- propyl, 1,1-Dimethyl-butyl oder 2,2-Dimethyl-butyl, für jeweils durch Carboxy, Fluor, Chlor, Methoxy, Ethoxy, Methoxycarbonyl oder Ethoxy- carbonyl ein- oder zweifach substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, n-, i-, s- oder t-Pentyl, für jeweils durch Methoxy- ethoxy, Ethoxyethoxy, n-Propoxyethoxy, i-Propoxyethoxy, n-Butoxyethoxy, i-Butoxyethoxy, s-Butoxyethoxy, t-Butoxyethoxy, Methoxyethoxyethoxy oder Ethoxyethoxyethoxy einfach substituiertes Ethyl, n- oder i-Propyl, für jeweils gegebenenfalls durch Hydroxy, Carboxy, Fluor, Chlor, Methoxy¬ carbonyl oder Ethoxycarbonyl ein- oder zweifach substituiertes Propenyl, Butenyl, Pentenyl, Propinyl, Butinyl oder Pentinyl, für jeweils gegebenen¬ falls durch Hydroxy, Carboxy, Fluor, Chlor, Methyl, Ethyl, Hydroxy- methyl, Hydroxyethyl, Methoxycarbonyl oder Ethoxycarbonyl ein- oder zweifach substituiertes Cyclopentyl oder Cyclohexyl, oder für Tetrahydro- furyl oder Tetrahydrofurylmethyl steht.The invention relates in particular to the use of compounds of the formula (I) in which R represents ethyl mono- or di-substituted by hydroxyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-Pentyl, 2,2-dimethyl-propyl, 1,3-dimethyl-propyl, 1,1-dimethyl-butyl or 2,2-dimethyl-butyl, for each by carboxy, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl mono- or disubstituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, each with methoxy - ethoxy, ethoxyethoxy, n-propoxyethoxy, i-propoxyethoxy, n-butoxyethoxy, i-butoxyethoxy, s-butoxyethoxy, t-butoxyethoxy, methoxyethoxyethoxy or ethoxyethoxyethoxy monosubstituted ethyl, n- or i-propyl, each optionally substituted by hydroxy, carboxy , Fluorine, chlorine, methoxycarbonyl or ethoxycarbonyl monosubstituted or disubstituted propenyl, butenyl, pentenyl, propynyl, butynyl or pentynyl, if appropriate by hydroxyl, carboxy, flu or, chlorine, methyl, ethyl, hydroxymethyl, hydroxyethyl, methoxycarbonyl or ethoxycarbonyl mono- or disubstituted cyclopentyl or cyclohexyl, or for tetrahydrofuryl or tetrahydrofurylmethyl.
Die Erfindung betrifft insbesondere neue Verbindungen der Formel (IA), in welcherThe invention relates in particular to new compounds of the formula (IA) in which
A für jeweils durch Hydroxy ein- oder zweifach substituiertes Ethyl, n- oder i-Propyl, für jeweils durch Hydroxy ein- bis dreifach substituiertes n-, i-, s- oder t-Butyl, n-, i-, s- oder t-Pentyl, 2,2-Dimethyl-propyl, 1,3-Dimethyl- propyl, 1,1-Dimethyl-butyl oder 2,2-Dimethyl-butyl, für jeweils durch Carboxy, Methoxycarbonyl oder Ethoxycarbonyl ein- oder zweifach sub- stituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, n-, i-, s- oder t-Pentyl, für jeweils durch Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t- Butoxy ein- oder zweifach substituiertes Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, für jeweils durch Methoxy ein- oder zweifach substituiertes n- oder i-Propyl, n-, i-, s- oder t-Butyl, für jeweils durch Methoxy ethoxy, Ethoxyethoxy, n-Propoxyethoxy, i-Propoxyethoxy, n-Butoxyethoxy, i -Butoxy ethoxy, s-Butoxyethoxy, t-Butoxy ethoxy, Methoxyethoxyethoxy oder Ethoxyethoxyethoxy einfach substituiertes Ethyl, n- oder i-Propyl, für jeweils gegebenenfalls durch Hydroxy, Carboxy, Fluor, Chlor, Methoxy¬ carbonyl oder Ethoxycarbonyl ein- oder zweifach substituiertes Propenyl. Butenyl, Pentenyl, Propinyl, Butinyl oder Pentinyl, für jeweils gegebenen- falls durch Fluor, Chlor, Carboxy, Methyl, Ethyl, Hydroxymethyl, Hydroxyethyl, Methoxycarbonyl oder Ethoxycarbonyl ein- oder zweifach substituiertes Cyclopentyl oder Cyclohexyl, oder für Tetrahydrofuryl oder Tetrahydrofurylmethyl steht.A for ethyl which is mono- or disubstituted by hydroxy, n- or i-propyl, for n-, i-, s- or t-butyl, n-, i-, s- or n-, i-, s- or t-substituted by hydroxy t-pentyl, 2,2-dimethyl-propyl, 1,3-dimethyl-propyl, 1,1-dimethyl-butyl or 2,2-dimethyl-butyl, for each by carboxy, methoxycarbonyl or ethoxycarbonyl, one or two times sub- substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, for each by ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy mono- or disubstituted ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each for n- or i-disubstituted by methoxy or i-propyl, n-, i-, s- or t-butyl, each for methoxy ethoxy, ethoxyethoxy, n-propoxyethoxy, i-propoxyethoxy, n-butoxyethoxy, i-butoxyethoxy, s-butoxyethoxy, t-butoxy ethoxy, methoxyethoxyethoxy or ethoxyethoxyethoxy monosubstituted ethyl, n- or i-propyl, for each optionally propenyl mono- or disubstituted by hydroxy, carboxy, fluorine, chlorine, methoxycarbonyl or ethoxycarbonyl. Butenyl, pentenyl, propynyl, butynyl or pentynyl, for each given if cyclopentyl or cyclohexyl which is mono- or disubstituted by fluorine, chlorine, carboxy, methyl, ethyl, hydroxymethyl, hydroxyethyl, methoxycarbonyl or ethoxycarbonyl, or is tetrahydrofuryl or tetrahydrofurylmethyl.
Die neuen Verbindungen der Formel (IA) sowie die Säureaddukte hiervon zeichnen sich durch starke und selektive herbizide Wirksamkeit aus. Sie besitzen auch sehr günstige biologische Transporteigenschaften, d.h. sie werden sehr gut von den Zielorganismen aufgenommen und rasch innerhalb der behandelten Pflanzen verteilt.The new compounds of the formula (IA) and the acid adducts thereof are notable for strong and selective herbicidal activity. They also have very favorable biological transport properties, i.e. they are very well absorbed by the target organisms and quickly distributed within the treated plants.
Als Säureaddukte sind im Zusammenhang mit der vorliegenden Erfindung all¬ gemein Additionsprodukte aus Verbindungen der Formel (I) bzw. (IA) und Säuren zu verstehen. Geeignete Säuren sind hierbei vorzugsweise Protonensäuren, wie z.B. Hydrogenfluorid, Hydrogenchlorid (Salzsäure), Hydrogenbromid, Hydrogen- iodid, Schwefelsäure, Phosphorsäure, Essigsäure, Trifluoressigsäure, Mandelsäure, Citronensäure, Methansulfonsäure, Ethansulfonsäure, Propansulfonsäure, Butan- sulfonsäure, Trifluormethansulfonsäure, Benzolsulfonsäure und p-Toluolsulfon¬ säure.In the context of the present invention, acid adducts are generally understood to mean addition products of compounds of the formula (I) or (IA) and acids. Suitable acids are preferably protonic acids, such as e.g. Hydrogen fluoride, hydrogen chloride (hydrochloric acid), hydrogen bromide, hydrogen iodide, sulfuric acid, phosphoric acid, acetic acid, trifluoroacetic acid, mandelic acid, citric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid.
Verwendet man beispielsweise N-Phosphonomethyl-glycin und 2-Hydroxy-ethanol (Glykol) als Ausgangsstoffe sowie Hydrogenbromid als Säure, so kann der Re- aktionsablauf beim erfindungsgemäßen Verfahren durch das folgende Formel¬ schema skizziert werden:If, for example, N-phosphonomethyl-glycine and 2-hydroxyethanol (glycol) are used as starting materials and hydrogen bromide as acid, the course of the reaction in the process according to the invention can be outlined using the following formula:
+ HOCH2CH2OH + HBr+ HIGH 2 CH 2 OH + HBr
(HO)2P(0)-CH2-NH-CH2-CO-OH ►(HO) 2 P (0) -CH 2 -NH-CH 2 -CO-OH ►
(HO)2P(0)-CH2-NH-CH2-CO-0-CH2CH2-OH x HBr(HO) 2 P (0) -CH 2 -NH-CH 2 -CO-0-CH 2 CH 2 -OH x HBr
Die beim erfindungsgemaßen Verfahren zur Herstellung der Verbindungen der Formel (IA) anfallenden Säureaddukte der Verbindungen der Formel (IA) werden mit Säurebindemitteln behandelt. Als solche kommen vorzugsweise Di-C3-C6- alkyl-amine mit verzweigten Alkylgruppen, Di-C5-C6-cycloalkyl-amine, Tri-Cj-C6- alkyl-amine mit geradkettigen und/oder verzweigten Alkylgruppen, N,N-Di- Cj-C6-alkyl-N-C5-C6-cycloalkylamine mit geradkettigten und/oder verzweigten AI- kylgruppen und N,N-Di-C5-C6-cycloaljtyl-N-CrC6-alkylamine mit geradkettigen oder verzweigten Alkylgruppen in Betracht.The acid adducts of the compounds of the formula (IA) obtained in the process according to the invention for the preparation of the compounds of the formula (IA) are treated with acid binders. As such, preferably di-C 3 -C 6 come - alkyl-amine with branched alkyl groups, di-C 5 -C 6 -cycloalkyl-amines, tri-C j -C 6 - alkyl-amines having straight-chain and / or branched alkyl groups, N, N-Di- C j -C 6 -alkyl-NC 5 -C 6 -cycloalkylamines with straight-chain and / or branched AI- alkyl groups and N, N-di-C 5 -C 6 -cycloaljtyl-NC r C 6 -alkylamines with straight-chain or branched alkyl groups.
Weiter kommen vorzugsweise auch Oxirane (Epoxide) als Säurebindemittel in Betracht, welche unsubstituiert oder ein- oder zweifach durch Alkyl- oder Aryl- gruppen substituiert sind. Als Beispiele hierfür seien Oxiran (Ethylenoxid),Oxiranes (epoxides) which are unsubstituted or mono- or disubstituted by alkyl or aryl groups are also preferred as acid binders. Examples include oxirane (ethylene oxide),
Methyloxiran (Propylenoxid, 1,2-Epoxy-propan), Ethyloxiran (1,2-Butylen-oxid, 1,2-Epoxy-butan), Propyloxiran (1,2-Epoxy-pentan) und Phenyloxiran (Styroloxid, Epoxystyrol) genannt.Methyloxirane (propylene oxide, 1,2-epoxy-propane), ethyloxirane (1,2-butylene oxide, 1,2-epoxy-butane), propyloxirane (1,2-epoxy-pentane) and phenyloxirane (styrene oxide, epoxystyrene) .
Die Reaktionstemperaturen können bei der Durchführung des erfindungsgemäßen Verfahrens zur Herstellung der Verbindungen der Formel (IA) in einem größerenWhen carrying out the process according to the invention for the preparation of the compounds of the formula (IA), the reaction temperatures can be increased
Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen 30°C und 150°C, vorzugsweise zwischen 60°C und 120°C.Range can be varied. In general, temperatures between 30 ° C and 150 ° C, preferably between 60 ° C and 120 ° C.
Das erfindungsgemäße Verfahren wird im allgemeinen unter Normaldruck durch¬ geführt. Es ist jedoch auch möglich, das erfindungsgemäße Verfahren unter er- höhtem oder vermindertem Druck - im allgemeinen zwischen 0,1 bar und 10 bar - durchzuführen.The process according to the invention is generally carried out under normal pressure. However, it is also possible to carry out the process according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
Zur Durchführung des erfindungsgemäßen Verfahrens setzt man auf ein Mol Phosphonomethyl-glycin der Formel (II) im allgemeinen zwischen 1 und 100 Mol, vorzugsweise zwischen 10 und 50 Mol eines Alkohols der Formel (III) und zwischen 1 und 5 Mol, vorzugsweise zwischen 1,5 und 3 Mol einer Säure sowie gegebenenfalls zwischen 1 und 5 Mol, vorzugsweise zwischen 1,5 und 3 Mol eines Säurebindemittels ein.To carry out the process according to the invention, one mole of phosphonomethylglycine of the formula (II) is generally between 1 and 100 moles, preferably between 10 and 50 moles of an alcohol of the formula (III) and between 1 and 5 moles, preferably between 1, 5 and 3 mol of an acid and optionally between 1 and 5 mol, preferably between 1.5 and 3 mol of an acid binder.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird das Phosphonomethyl-glycin der Formel (II) in einem Alkohol der Formel (III) suspendiert und eine Säure wird langsam eindosiert. Die Reaktionsmischung wird dann bei der erforderlichen Temperatur gehalten, bis die Umsetzung praktisch ab¬ geschlossen ist.In a preferred embodiment of the process according to the invention, the phosphonomethylglycine of the formula (II) is suspended in an alcohol of the formula (III) and an acid is slowly metered in. The reaction mixture is then kept at the required temperature until the reaction is practically complete.
Zur Isolierung des Säureadduktes der Verbindung der Formel (IA) wird unter ver¬ mindertem Druck eingeengt, gegebenenfalls mit einem geeigneten organischen Lösungsmittel, wie z.B. Aceton digeriert und das Säureaddukt durch Absaugen isoliert. Zur Isolierung der "freien" Verbindung der Formel (IA) wird nach Einengen der Rückstand, der im wesentlichen das Säureaddukt enthält, oder das wie oben be¬ schrieben in kristalliner Form isolierte Säureaddukt wieder in einem .Alkohol der Formel (III) aufgenommen und mit einem Saurebindemittel versetzt Das Produkt der Formel (IA) fallt dabei in kristalliner Form an und kann durch Absaugen isoliert werdenTo isolate the acid adduct of the compound of formula (IA), the mixture is concentrated under reduced pressure, optionally digested with a suitable organic solvent, such as acetone, and the acid adduct is isolated by suction. To isolate the "free" compound of formula (IA), after concentration, the residue, which essentially contains the acid adduct, or the acid adduct isolated in crystalline form as described above, is again taken up in an alcohol of formula (III) and mixed with added to an acid binder. The product of the formula (IA) is obtained in crystalline form and can be isolated by suction
Die Wirkstoffe der Formeln (I) bzw (IA) können erfindungsgemäß in Defoliants, Desiccants, Krautabtotungsmitteln und insbesondere in Unkrautvernichtungsmitteln - vor allem im semi-selektiven und im nicht-selektiven Bereich der Unkrautbe- kampfung - verwendet werden Unter Unkraut im weitesten Sinne sind alleAccording to the invention, the active compounds of the formulas (I) or (IA) can be used in defoliants, desiccants, herbicides and in particular in weed killers - above all in the semi-selective and in the non-selective area of weed control. Weeds in the broadest sense are all
Pflanzen zu verstehen, die an Orten aufwachsen, wo sie unerwünscht sind, d h z B auch unerwünschte Baume im WaldTo understand plants that grow up in places where they are undesirable, i.e. also undesirable trees in the forest
Die erfindungsgemaß 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 sogenannten "Mιnimum-Tillage"-Verfahren eingesetzt werden Sie eignen sich weiterhin als Ab- brenner (Krautabtotung z B in Kartoffeln) oder als Defohantien (z B m Baum¬ wolle) Ferner sind sie für den Einsatz auf Bracheflachen geeignet Weitere Ein- satzgebiete sind Baumschulen, Forst, Grünland und ZierpflanzenbauThe 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 (for example wine, fruit, citrus) and in industrial and track systems, on paths and squares, but also for stubble treatment and in the so-called " "Minimum Tillage" process can also be used as a burner (killing herbs, for example in potatoes) or as defoamers (for example, in cotton). They are also suitable for use on fallow land. Forest, grassland and ornamental plant growing
Darüber hinaus können die Wirkstoffe der Formeln (I) bzw (IA) gemäß der Erfindung auch als Herbizide in solchen Kulturpflanzen, welche gegenüber Gly- phosate und anderen EPSP-Synthase-Inhibitoren resi stent sind, eingesetzt werdenIn addition, the active compounds of the formulas (I) or (IA) according to the invention can also be used as herbicides in crop plants which are resistant to glyphosates and other EPSP synthase inhibitors
Die erfindungsgemaßen Wirkstoffe können z B bei den folgenden Pflanzen verwendet werdenThe active compounds according to the invention can be used, for example, in the following plants
Dikotyle Unkräuter der Gattungen Sinapis, Lepidium, Galium, Stellaria, Matπcaπa, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Roπppa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea,Dicotyledonous weeds of the genera Sinapis, Lepidium, Galium, Stellaria, Matπcaπa, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Sonppa, Carduus, Sol Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea,
Tπfohum, Ranunculus, Taraxacum Dikotyle Kulturen der Gattungen: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.Tπfohum, Ranunculus, Taraxacum Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monokotyle Unkräuter der Gattungen: 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.Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Iochasumirumum, Scalumumum, Scalumumum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monokotyle Kulturen der Gattungen. Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.Monocot cultures of the genera. Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.
Die Verwendung der erfindungsgemäßen Wirkstoffe ist jedoch keineswegs auf diese Gattungen beschränkt, sondern erstreckt sich in gleicher Weise auch auf andere Pflanzen.However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.
Die Verbindungen eignen sich in Abhängigkeit von der Konzentration zur Total- Unkrautbekämpfung z.B. auf Industrie- und Gleisanlagen und auf Wegen und Plätzen mit und ohne Baumbewuchs. Ebenso können die Verbindungen zur Unkrautbekämpfung in Dauerkulturen, z.B. Forst, Ziergehölz-, Obst-, Wein-, Citrus-, Nuß-, Bananen-, Kaffee-, Tee-, Gummi-, Ölpalm-, Kakao-, Beerenfrucht- und Hopfenanlagen, auf Zier- und Sportrasen und Weideflächen und zur selektiven Unkrautbekämpfung in einjährigen Kulturen eingesetzt werden.Depending on the concentration, the compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, e.g. Forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants, on ornamental and sports turf and pasture land and for selective purposes Weed control can be used in annual crops.
Die erfindungsgemäßen Verbindungen der Formeln (I) bzw. (IA) eignen sich ins¬ besondere zur Bekämpfung von monokotylen und dikotylen Unkräutern im Nach¬ auflauf- Verfahren.The compounds of the formulas (I) and (IA) according to the invention are particularly suitable for controlling monocotyledon and dicotyledon weeds in the post-emergence process.
Die Verbindungen der Formeln (I) bzw. (IA) können - wie oben dargelegt - in wässriger Lösung ohne weitere Zusätze eingesetzt werden; sie können aber auch gegebenenfalls unter Zusatz von Additiven (Adjuvantien, Emulgatoren, Netz¬ mitteln, Tensiden) angewendet werden. Hierzu gehören vorzugsweise hochraffi¬ nierte Mineralöle, emulgierbare Pflanzenöle, ethoxylierte Taigamine, ethoxylierte Alkylamine, ethoxylierte Alkylphenole, ethoxylierte Alkylalkohole, Phosphatester, Alkyl- und Aryl-etherphosphate, Sojaphospholipide und synthetischer Latex. Als Beispiele für geeignete Additive (Adjuvantien, Emulgatoren, Netzmittel, Ten¬ side) seien folgende handelsübliche Produkte, wobei es sich, zumindest teilweise, um eingetragene Warenzeichen handelt, genannt:The compounds of the formulas (I) and (IA) can - as stated above - be used in aqueous solution without further additives; however, they can also be used, if appropriate, with the addition of additives (adjuvants, emulsifiers, wetting agents, surfactants). These preferably include highly refined mineral oils, emulsifiable vegetable oils, ethoxylated taigamines, ethoxylated alkylamines, ethoxylated alkylphenols, ethoxylated alkyl alcohols, phosphate esters, alkyl and aryl ether phosphates, soy phospholipids and synthetic latex. Examples of suitable additives (adjuvants, emulsifiers, wetting agents, surfactants) are the following commercially available products, at least some of which are registered trademarks:
Actiplus, Actipron (AM), Actirob B, Adder, Addwet, Adhesol, Adjuvant DHAI, Agral (90), Agrirob, Agrisorb, Agriwet, Agropen, Arnos Non-Ionic Wetter,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 11E, 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,Anphix, APSA 80, Ashlade Adjuvant Oil, Atlas Adherbe, Atlas Adjuvant Oil, Atlas Libsorb, Banole (HV), Barclay Dryfast XL, Carbol, Chiltern Cropspray 11E, 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 HE, 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 QFarmon Blue, Farmon Wetter, Forestry Bee, Frigate, Fyzol HE, 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 HE, 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 HE, Tripart Lentus, Tripart Minax,900, Rapide, Rosemox, Sandovit 63, Seppic HE, 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 HE, Tripart Lentus, Tripart Minax,
Vassgro Spreader, Vegelux, Wayfarer.Vassgro Spreader, Vegelux, Wayfarer.
Weiter können auch neuere, aus der (Patent-)Literatur bekannte Arten von 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-(hydroxypolyal- koxyalkyO-ammoniumsalze (vgl. WO 9402021, US 5317003), ferner Trialkyl- (alkoxypolyalkoxyalkyl)-ammoniumsalze und Polypropylenglycol (vgl. EP 526444) sowie sekundäre oder tertiäre Alkohol-Alkoxylate (vgl. WO 9516351).Furthermore, newer types of additives (adjuvants, emulsifiers, wetting agents, surfactants) known from the (patent) literature can also be used, for example alkynediols which have become known under the name Surfynole (cf. EP 531269, US 5258359), under the name Ethoquad known alkyl tris (hydroxypolyalkoxyalkyl) ammonium salts or dialkyl bis (hydroxypolyalkoxyalkyO ammonium salts (cf. WO 9402021, US 5317003), trialkyl (alkoxypolyalkoxyalkyl) ammonium salts and polypropylene glycol (cf. EP 526444) and secondary or tertiary alcohol alkoxylates (cf. WO 9516351).
Die wässrigen Lösungen zur Anwendung der Verbindungen der Formel (I) ent¬ halten im allgemeinen zwischen 1 und 50 Gewichtsprozent, vorzugsweise zwi¬ schen 5 und 30 Gewichtsprozent Wirkstoff. - n -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. - n -
Die Verbindungen der Formeln (I) bzw. (IA) können als solche - in wässriger Lö¬ sung - oder auch in Mischung mit anderen bekannten Herbiziden zur Unkrautbe¬ kämpfung verwendet werden, wobei diese Mischungen im gegebenen Fall als "Tankmischungen", d.h. als vom Anwender zubereitete Spritz- oder Gießbrühen zur Anwendung kommen.The compounds of the formulas (I) or (IA) 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 mixtures", i.e. as spray or pouring broth prepared by the user.
Für diese Mischungen kommen bekannte herbizide Stoffe aus praktisch allen relevanten Stoffklassen in Betracht, beispielsweise Acetochlor, Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amidochlor, Amidosulfuron, Amiprophos (-methyl), Amitrol, Anilofos, Asulam, Atrazin, Azim- sulfuron, Benazolin, Benfuresate, Bensulfuron (-methyl), Bensulide, Bentazon,Known herbicidal substances from practically all relevant classes of substances are suitable for these mixtures, for example acetochlor, acifluorfen (sodium), aclonifene, alachlor, alloxydim (sodium), ametryne, amidochlor, amidosulfuron, amiprophos (methyl), amitrole, anilofos, Asulam, Atrazin, Azim-sulfuron, Benazolin, Benfuresate, Bensulfuron (-methyl), Bensulide, Bentazon,
Benthiocarb, Benzofenap, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bromacil, Bromobutide, Bromofenoxim, Bromoxynil, Butachlor, Butamifos, Butenachlor, Butylate, Cafenstrole, Carbetamide, Chlomethoxyfen, Chloramben, Chloridazon, Chlorimuron (-ethyl), Chlormethoxynil, Chlornitrofen, Chlorsulfuron, Chlortoluron, Cinmethylin, Cinosulfuron, Clethodim, Clodinafop (-propargyl), Clomazone, Clo- meprop, Clopyralid, Clopyrasulfuron, Cloransulam (-methyl), Cumyluron, Cyan- azine, Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, Des- medipham, Dicamba, Dichlorprop, Diclofop (-methyl), Difenzoquat, Diflufenican, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Demethenamid, Di- nitramine, Diphenamid, Diquat, Dithiopyr, Diuron, Dymron (Daimuron, Dimuron),Benthiocarb, Benzofenap, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bromacil, Bromobutide, Bromofenoxim, Bromoxynil, Butachlor, Butamifos, Butenachlor, Butylate, Cafenstrole, Carbetamide, Chlomethoxyfen, Chloramben, Chloridazon, Chlorimurilormllmethyllilonuryl (Methyl) Chlorsulfuron, Chlortoluron, Cinmethylin, Cinosulfuron, Clethodim, Clodinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyrasulfuron, Cloransulam (-methyl), Cumyluron, Cyanazine, Cycloate, Cyclofulfamuron, Cyclosulfamuron 2,4-D, desmedipham, dicamba, dichloroprop, diclofop (-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, demethenamid, di-nitramine, diphenamide, diquat, dithiopyr, diuron, dymron (daimur Dimuron),
EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethofumesate, Ethoxy- fen, Etobenzanid, Fenoxaprop (-ethyl), Flamprop (-isopropyl), Flamprop (-methyl), Flazasulfuron, Fluazifop (-butyl), Flumetsulam, Flumiclorac (-pentyl), Flumi- oxazin, Flumipropyn, Fluometuron, Fluorochloridone, Fluoroglycofen (-ethyl), Flupoxam, Flupropacil, Flurenol (n-butylester), Fluridone, Fluroxypyr, Flurpri¬ midol, Flurtamone, Fomesafen, Glufosinate (-ammonium), Glyphosate, Haloxyfop (-ethoxyethyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imaza- mox, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Ioxynil, Isopropalin, Iso- proturon, Isoxaben, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, Mecoprop, Mefenacet, Metamitron, Metazachlor, Methabenzthiazuron, Metobenz- uron, Metobromuron, Metolachlor, Metosulam, Metoxuron, Metribuzin, Met- sulfuron (-methyl), Molinate, Monolinuron, Naproanilide, Napropamide, Neburon, Nicosulfuron, Nitrofen, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxyfluorfen, Paraquat, Pendimethalin, Phenmedipham, Piperophos, Pretilachlor, Primisulfuron (-methyl), Prometryn, Propachlor, Propanil, Propaquizafop, Pro- pyzamide, Prosulfocarb, Prosulfuron, Pyrazolate, Pyrazosulfuron (-ethyl), Pyr- azoxyfen, Pyributicarb, Pyridate, Pyrithiobac (-sodium), Quinchlorac, Quinmerac, Quizalofop (-ethyl), Quizalofop (-p-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Tebutam, Tebuthiuron, Terbuthylazine, Terbutryn, Thenylchlor, Thiazopyr, Thidiazimin, Thi- fensulfuron (-methyl), Thiobencarb, Tiocarbazil, Tralkoxydim, Triallate, Tria- sulfuron, Tribenuron (-methyl), Tricyclopyr, Tridiphane, Trifluralin, Triflusulfuron.EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethofumesate, Ethoxyfen, Etobenzanid, Fenoxaprop (-ethyl), Flamprop (-isopropyl), Flamprop (-methyl), Flazasulfuron, Fluazifop (-butyl), Flumetsulam (Flumiclorac -pentyl), flumi- oxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen (-ethyl), flupoxam, flupropacil, flurenol (n-butyl ester), fluridone, fluroxypyr, flurpri¬ midol, flurtamone, fomesafen, glufosiumate, -ammos , Haloxyfop (-ethoxyethyl), Hexazinone, Imazamethabenz (-methyl), Imazamethapyr, Imazamox, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, Ioxynil, Isopropalin, Isoproturon, Isoxaben, Isoxaflutole, Isactapyrifopil, Lactoxyrofenop, Lactoxapyrifac, MCP , Mecoprop, Mefenacet, Metamitron, Metazachlor, Methabenzthiazuron, Metobenzuron, Metobromuron, Metolachlor, Metosulam, Metoxuron, Metribuzin, Metulfuron (-methyl), Molinate, Monolinuron, Naproanilide, Napropamide, Nururonazon, Nicuronazonitron Oryzalin Oxadiargyl, Oxadiazon, Oxyfluorfen, Paraquat, Pendimethalin, Phenmedipham, Piperophos, Pretilachlor, Primisulfuron (-methyl), Prometryn, Propachlor, Propanil, Propaquizafop, Pro pyzamide, Prosulfocarb, Prosulfuron, Pyrazoluron- Pyrazolon (Pyrazolate) azoxyfen, pyributicarb, pyridate, pyrithiobac (-sodium), quinchlorac, quinmerac, quizalofop (-ethyl), quizalofop (-p-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron (-methyl) Tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thidiazimin, thifensulfuron (-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, tri-sulfuron, tribenuron (-methyl), tricyclopyriflurifliphonurifliphonurifliphonurifliphoniphonluriflurifliphonlurifluriflurifluronlifurinlfuriflurifluronlurifluronlifurinlurifluronlifurinlurifluronlifurinlurifluriflurifluriflurifluriflurifurlphuriflurifluronlifurinlurifuriflurifuriphylurylphyluryltrylphyryltrylphyryltrylphyryltrylphyryltrylphyluryltrylphyryltrylphylyltrylphyrylfl
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Fungiziden, Insektiziden, Akariziden, Nematiziden, Schutzstoffen gegen Vogelfraß, Pflanzen¬ nährstoffen und Bodenstrukturverbesserungsmitteln ist möglich.A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
Die angewandte Wirkstoffmenge kann in einem größeren Bereich schwanken. Sie hängt im wesentlichen von der Art des gewünschten Effektes ab. Im allgemeinen liegen die Aufwandmengen zwischen 10 g und 10 kg Wirkstoff pro Hektar Boden¬ fläche, vorzugsweise zwischen 50 g und 5 kg pro ha.The amount of active ingredient used can vary over a wide 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 of soil, preferably between 50 g and 5 kg per ha.
Die Herstellung und die Verwendung der erfindungsgemäßen Wirkstoffe geht aus den nachfolgenden Beispielen hervor. The preparation and use of the active compounds according to the invention can be seen from the examples below.
Herstellungsbeispiele;Manufacturing examples;
Beispiel 1example 1
(HO)2P(O)-CH2-CO-O-CH2-CH2-OH(HO) 2 P (O) -CH 2 -CO-O-CH 2 -CH 2 -OH
Zu einer Suspension von 8,5 g (50 mMol) N-Phosphonom ethyl -glycin in 100 ml Ethan-l,2-dioI werden 30 ml Chlor-trimethylsilan bei Raumtemperatur (ca. 20°C) tropfenweise gegeben. Dann wird die Reaktionsmischung ca. 15 Stunden bei Raumtemperatur gerührt, filtriert und das Filtrat im Wasserstrahlvakuum eingeengt. Zum Rückstand wird Propylenoxid tropfenweise gegeben, bis ein Farbumschlag von rötlich-braun nach hellgelb erfolgt. Das hierbei kristallin anfallende Produkt wird durch Absaugen isoliert.30 ml of chloro-trimethylsilane are added dropwise to a suspension of 8.5 g (50 mmol) of N-phosphonom ethylglycine in 100 ml of ethane-1,2-dioI at room temperature (approx. 20 ° C.). Then the reaction mixture is stirred for about 15 hours at room temperature, filtered and the filtrate is concentrated in a water jet vacuum. Propylene oxide is added dropwise to the residue until the color changes from reddish brown to light yellow. The crystalline product is isolated by suction.
Man erhält 6,0 g (56% der Theorie) N-Phosphonomethyl-glycin-(2-hydroxy-ethyl- ester) vom Schmelzpunkt 230°C (Zersetzung).6.0 g (56% of theory) of N-phosphonomethyl-glycine (2-hydroxy-ethyl ester) with a melting point of 230 ° C. (decomposition) are obtained.
Beispiel 2Example 2
(HO)2P(O)-CH2-NH-CH2-CO-O-CH2CH2-OC2H5-(HO) 2 P (O) -CH 2 -NH-CH 2 -CO-O-CH 2 CH 2 -OC 2 H 5 -
In eine Suspension von 16 g (0,10 Mol) N-Phosphonomethyl-glycin in 250 ml 2-In a suspension of 16 g (0.10 mol) of N-phosphonomethyl-glycine in 250 ml of 2-
Ethoxy-ethanol wird Chlorwasserstoff-Gas bis zur Sättigung eingeleitet. Dann wird die Reaktionsmischung 2 Stunden unter Rückfluß erhitzt, wobei ca. 50 ml 2- Ethoxy-ethanol destillativ entfernt werden. Die Mischung wird anschließend im Wasserstrahl Vakuum eingeengt. Der Rückstand wird mit Propylenoxid versetzt, bis ein Farbumschlag von rötlich-braun nach hellgelb erfolgt. Das hierbei kristallin an¬ fallende Produkt wird durch Absaugen isoliert.Ethoxyethanol is introduced to hydrogen chloride gas until saturation. The reaction mixture is then heated under reflux for 2 hours, about 50 ml of 2-ethoxyethanol being removed by distillation. The mixture is then concentrated in a water jet vacuum. The residue is mixed with propylene oxide until the color changes from reddish brown to light yellow. The crystalline product obtained is isolated by suction.
Man erhält 15,8 g (66% der Theorie) N-Phosphonomethyl-glycin-(2-ethoxy-ethyl- ester) vom Schmelzpunkt 220°C (Zersetzung).15.8 g (66% of theory) of N-phosphonomethyl-glycine (2-ethoxy-ethyl ester) with a melting point of 220 ° C. (decomposition) are obtained.
Analog zu den Beispielen 1 und 2 können beispielsweise auch die in der nach- stehenden Tabelle 1 aufgeführten Verbindungen der Formel (I) bzw. der FormelAnalogously to Examples 1 and 2, for example the compounds of the formula (I) or of the formula listed in Table 1 below can also be used
(IA) hergestellt werden. Tabelle 1: Beispiele für die Verbindungen der Formel (I) bzw. (IA)(IA) can be produced. Table 1: Examples of the compounds of the formula (I) or (IA)
ύύ
Figure imgf000016_0001
Tabelle 1: (Fortsetzung)
Figure imgf000016_0001
Table 1: (continued)
Figure imgf000017_0001
Tabelle 1: (Fortsetzung)
Figure imgf000017_0001
Table 1: (continued)
Figure imgf000018_0001
Figure imgf000018_0001
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 Gewichtsteil Wirkstoff vor, verdünnt mit Wasser auf die gewünschte Konzentration und gibt 1 Gewichtsteil Emulgator dazu.To produce a suitable preparation of active compound, 1 part by weight of active compound is added, diluted with water to the desired concentration and 1 part by weight of emulsifier is added.
Mit der Wirkstoffzubereitung spritzt man Testpflanzen, welche eine Höhe von 5 - 15 cm haben, so, daß die jeweils gewünschten Wirkstoffmengen pro Flächen- einheit ausgebracht werden. Die Konzentration der Spritzbrühe wird so gewählt, daß in 500 bis 1000 1 Wasser/ha die jeweils gewünschten Wirkstoffmengen aus¬ gebracht werden.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 liquor is chosen so that the desired amounts of active compound are applied in 500 to 1000 l of water / ha.
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 bedeuten.Mean it.
0 % = keine Wirkung (wie unbehandelte Kontrolle)0% = no effect (like untreated control)
100 % = totale Vernichtung100% = total annihilation
In diesem Test zeigen beispielsweise die Verbindungen gemäß Herstellungs¬ beispiel 1, 2, 5, 6, 14, 15, 18, 19, 33, 34 und 35 starke Wirkung gegen Unkräuter (vgl. Tabellen AI und A2). Tabelle AI: Post-emergence-Test / GewächshausIn this test, for example, the compounds according to example 1, 2, 5, 6, 14, 15, 18, 19, 33, 34 and 35 show strong activity against weeds (cf. Tables AI and A2). Table AI: Post emergence test / greenhouse
Figure imgf000020_0001
Figure imgf000020_0001
oO
Tjbj≥l]e_A2 Post-emergence-Test / Gewächshaus -4 VITjbj≥l] e_A2 Post emergence test / greenhouse -4 VI
XO IXO I
Figure imgf000021_0001
Figure imgf000021_0001
nn
M vc o o -J M vc o o -J

Claims

PatentansprücheClaims
1. Verfahren zur Bekämpfung bzw. Abtotung von unerwünschten Pflanzen durch Einwirkung von N-Phosphonomethyl-glycinestern auf solche Pflan¬ zen, dadurch gekennzeichnet, daß man zumindest einen N-Phosphonome- thyl-glycinester der Formel (I),1. A method for controlling or killing undesired plants by the action of N-phosphonomethylglycine esters on such plants, characterized in that at least one N-phosphonomethyl-glycine 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 durch Hydroxy, Carboxy, Halogen, Alkoxy, Hydroxyalkoxy,R for by hydroxy, carboxy, halogen, alkoxy, hydroxyalkoxy,
Alkoxyalkoxy, Hydroxyalkoxyalkoxy, Alkoxyalkoxyalkoxy, Alkyl- carbonyl, Hydroxyalkylcarbonyl oder Alkoxycarbonyl ein- oder mehrfach substituiertes Alkyl, für jeweils gegebenenfalls durch Hydroxy, Carboxy, Halogen oder Alkoxycarbonyl ein- oder mehr¬ fach substituiertes Alkenyl oder Alkinyl, für jeweils gegebenenfalls durch Hydroxy, Carboxy, Halogen, Alkyl, Hydroxyalkyl, Alkoxy- alkyl, Alkoxy oder Alkoxycarbonyl ein- oder mehrfach substitu¬ iertes Cycloalkyl oder Cycloalkylalkyl, oder für jeweils gegebenen¬ falls durch Alkyl substituiertes Oxacycloalkyl, Dioxacycloalkyl, Oxacycloalkylalkyl oder Dioxacycloalkylalkyl steht,Alkoxyalkoxy, hydroxyalkoxyalkoxy, alkoxyalkoxyalkoxy, alkylcarbonyl, hydroxyalkylcarbonyl or alkoxycarbonyl alkyl which is mono- or polysubstituted, for alkenyl or alkynyl which is monosubstituted or polysubstituted or substituted by hydroxyl, carboxy, halogen or alkoxycarbonyl, or in each case optionally by hydroxyl, carboxy, Halogen, alkyl, hydroxyalkyl, alkoxyalkyl, alkoxy or alkoxycarbonyl mono- or polysubstituted cycloalkyl or cycloalkylalkyl, or represents in each case optionally substituted alkyl with oxacycloalkyl, dioxacycloalkyl, oxacycloalkylalkyl or dioxacycloalkylalkyl,
oder eines seiner Säureaddukte, in Form einer wäßrigen Lösung, d.h. ohne Zusatz weiterer Hilfsstoffe, zur Anwendung bringt.or one of its acid adducts, in the form of an aqueous solution, i.e. without the addition of other auxiliaries.
2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man Verbin¬ dungen der Formel (I) zur Anwendung bringt, in welcher2. The method according to claim 1, characterized in that one uses compounds of the formula (I) in which
R für durch Hydroxy ein- bis vierfach substituiertes CrC6-Alkyl, für durch Carboxy, Fluor, Chlor, Cj-C6-Alkoxy oder CrC6-Alkoxy- carbonyl ein- oder zweifach substituiertes Cj-C6-Alkyl, für durchR is hydroxy by one to four times substituted C r C 6 alkyl, for by carboxyl, fluorine, chlorine, C j -C 6 alkoxy or C r C 6 alkoxy carbonyl mono- or di-substituted C 6 -C j -Alkyl, for by
Hydroxy-C,-C4-alkoxy, C]-C4-Alkoxy-C]-C4-alkoxy, Hydroxy- C1-C4-alkoxy-C1-C4-alkoxy, C]-C4-Alkoxy-C1-C4-alkoxy-C,-C4-al- koxy, C1-C4-Alkyl-carbonyl oder Hydroxy-C]-C4-alkyl-carbonyl ein¬ fach substituiertes C]-C4-Alkyl, für jeweils gegebenenfalls durch Hydroxy, Carboxy, Fluor, Chlor oder Cj-C4-Alkoxy carbonyl ein- oder zweifach substituiertes C2-C6-Alkenyl oder C2-C6 -Alkinyl, für jeweils gegebenenfalls durch Hydroxy, Carboxy, Fluor, Chlor, C1-C4-Alkyl, Hydroxy-CrC4-alkyl oder CrC4-Alkoxy-carbonyl ein- oder zweifach substituiertes C3-C6-CycloalkyI oder C3-C6-Cyclo- alkyl-C ]-C4-alkyl, oder für jeweils gegebenenfalls durch C,-C4- Alkyl substituiertes C2-C5-Oxacycloalkyl, Cj -^-Dioxacyclo¬ alkyl, C2-C5-Oxacycloalkyl-C,-C4-alkyl oder C2-C5-Dioxacyclo- alkyl-C,-C4-alkyl steht.Hydroxy-C, -C 4 -alkoxy, C ] -C 4 -alkoxy-C ] -C 4 -alkoxy, hydroxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkoxy, C ] -C 4 - Alkoxy-C 1 -C 4 -alkoxy-C, -C 4 -alkoxy, C 1 -C 4 -alkylcarbonyl or hydroxy-C ] -C 4 -alkylcarbonyl, monosubstituted C ] -C 4 Alkyl, for each optionally by Hydroxy, carboxy, fluorine, chlorine or C j -C 4 alkoxy carbonyl mono- or disubstituted C 2 -C 6 alkenyl or C 2 -C 6 alkynyl, each optionally with hydroxy, carboxy, fluorine, chlorine, C 1 -C 4 alkyl, hydroxy-C r C 4 -alkyl or C r C 4 -alkoxy-carbonyl mono- or disubstituted C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl-C ] - C 4 -alkyl, or for C 2 -C 5 -oxacycloalkyl optionally substituted by C, -C 4 -alkyl, C j - ^ - dioxacyclo-alkyl, C 2 -C 5 -oxacycloalkyl-C, -C 4 -alkyl or C 2 -C 5 dioxacycloalkyl-C, -C 4 -alkyl.
Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, daß man Verbin¬ dungen der Formel (I) zur Anwendung bringt, in welcherProcess according to Claim 1, characterized in that compounds of the formula (I) are used in which
R für jeweils durch Hydroxy ein- oder zweifach substituiertes Ethyl, n- oder i-Propyl, für jeweils durch Hydroxy ein- bis dreifach sub¬ stituiertes n-, i-, s- oder t-Butyl, n-, i-, s- oder t-Pentyl, 2,2-Di- methyl-propyl, 1,3-Dimethyl-propyl, 1,1-Dimethyl-butyl oder 2,2-R for ethyl which is mono- or disubstituted by hydroxy, n- or i-propyl, for n-, i-, s- or t-butyl, n-, i-, s, which is mono- to trisubstituted by hydroxy - or t-pentyl, 2,2-dimethyl-propyl, 1,3-dimethyl-propyl, 1,1-dimethyl-butyl or 2,2-
Dimethyl-butyl, für jeweils durch Carboxy, Fluor, Chlor, Methoxy, Ethoxy, Methoxycarbonyl oder Ethoxycarbonyl ein- oder zweifach substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, n-, i-, s- oder t-Pentyl, für jeweils durch Methoxyethoxy, Ethoxy- ethoxy, n-Propoxyethoxy, i-Propoxyethoxy, n-Butoxyethoxy, i-Dimethyl-butyl, for each substituted by carboxy, fluorine, chlorine, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n -, i-, s- or t-pentyl, for each by methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, i-propoxyethoxy, n-butoxyethoxy, i-
Butoxyethoxy, s-Butoxyethoxy, t-Butoxy ethoxy, Methoxyethoxy¬ ethoxy oder Ethoxyethoxyethoxy einfach substituiertes Ethyl, n- oder i-Propyl, für jeweils gegebenenfalls durch Hydroxy, Carboxy, Fluor, Chlor, Methoxycarbonyl oder Ethoxycarbonyl ein- oder zwei- fach substituiertes Propenyl, Butenyl, Pentenyl, Propinyl, Butinyl oder Pentinyl, für jeweils gegebenenfalls durch Hydroxy, Carboxy, Fluor, Chlor, Methyl, Ethyl, Hydroxymethyl, Hydroxyethyl, Methoxycarbonyl oder Ethoxycarbonyl ein- oder zweifach substitu¬ iertes Cyclopentyl oder Cyclohexyl, oder für Tetrahydrofuryl oder Tetrahydrofurylmethyl steht. N-Phosphonomethyl-glycinester der Formel (IA),Butoxyethoxy, s-butoxyethoxy, t-butoxy ethoxy, methoxyethoxyethoxy or ethoxyethoxyethoxy monosubstituted ethyl, n- or i-propyl, for propenyl which is mono- or di-substituted by hydroxyl, carboxy, fluorine, chlorine, methoxycarbonyl or ethoxycarbonyl , Butenyl, pentenyl, propynyl, butynyl or pentynyl, for cyclopentyl or cyclohexyl which is mono- or disubstituted by hydroxy, carboxy, fluorine, chlorine, methyl, ethyl, hydroxymethyl, hydroxyethyl, methoxycarbonyl or ethoxycarbonyl, or for tetrahydrofuryl or tetrahydrofurylmethyl stands. N-phosphonomethylglycine ester of the formula (IA),
(HO)2P(O)-CH2-NH-CH2-CO-O-A (IA)(HO) 2 P (O) -CH 2 -NH-CH 2 -CO-OA (IA)
in welcherin which
A für durch Hydroxy, Carboxy, Hydroxy-CrC6-alkoxy, C,-C6-Al- koxy-C,-C6-alkoxy, Hydroxy-CrC6-alkoxy-CrC6-alkoxy, CrC6-A for by hydroxy, carboxy, hydroxy-C r C 6 -alkoxy, C, -C 6 -alkoxy-C, -C 6 -alkoxy, hydroxy-C r C 6 -alkoxy-C r C 6 -alkoxy, C r C 6 -
Alkoxy-CrC6-alkoxy-C,-C6-alkoxy, CrC6-Alkyl-carbonyl, Hy- droxy-C1-C6-alkyl-carbonyl oder CpCg-Alkoxy-carbonyl ein- bis fünffach substituiertes C,-C,0-Alky\, für durch C2-C6-Alkoxy ein- bis dreifach substituiertes CJ-CJQ- Alkyl oder für durch C,-C6- Alkoxy ein- bis dreifach substituiertes C -Cι0-Alkyl, für jeweils durch Hydroxy, Carboxy, Halogen oder C]-C6-Alkoxy-carbonyl ein- bis dreifach substituiertes C2-C10-Alkenyl oder C2-C10-Alkιnyl, für jeweils durch Hydroxy, Carboxy, Halogen, Cj-C6-Alkyl, Hydroxy- CrC6-Alkyl oder Cj-C6-Alkoxy-carbonyl ein- bis dreifach substitu- iertes C3-C6-Cycloalkyl oder C3-C6-Cycloalkyl-C1-C6-alkyl, oder für jeweils gegebenenfalls durch Cj-C6-Alkyl substituiertes C2-C5-Oxa- cycloalkyl, C2-C4-Dioxacycloalkyl, C2-C5-Oxacycloalkyl-C1-C6- alkyl oder C2-C4-Dιoxacycloalkyl-C,-C4-alkyl steht,Alkoxy-C r C 6 -alkoxy-C, -C 6 -alkoxy, C r C 6 -alkyl-carbonyl, hydroxy-C 1 -C 6 -alkyl-carbonyl or CpCg-alkoxy-carbonyl mono- to pentasubstituted C, -C, 0 -Alky \ for by C 2 -C 6 alkoxy mono- to tri-substituted CJ-CJ Q - alkyl or by C, -C 6 - alkoxy mono- to tri-substituted C -Cι 0 - Alkyl, for each by hydroxy, carboxy, halogen or C ] -C 6 alkoxycarbonyl mono- to trisubstituted C 2 -C 10 alkenyl or C 2 -C 10 alkynyl, each by hydroxy, carboxy, halogen, C j -C 6 alkyl, hydroxy-C r C 6 alkyl or C j -C 6 alkoxy-carbonyl mono- to trisubstituted C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl-C 1 -C 6 alkyl, or for each optionally substituted by C j -C 6 alkyl substituted C 2 -C 5 oxacycloalkyl, C 2 -C 4 dioxacycloalkyl, C 2 -C 5 oxacycloalkyl-C 1 -C 6 - alkyl or C 2 -C 4 -dioacycloalkyl-C, -C 4 -alkyl,
sowie Säureaddukte der Verbindungen der Formel (IA)and acid adducts of the compounds of the formula (IA)
Verbindungen der Formel (IA) gemäß Anspruch 4, dadurch gekenn¬ zeichnet, daß darinCompounds of formula (IA) according to claim 4, characterized gekenn¬ characterized in that
A für durch Hydroxy ein- bis vierfach substituiertes Cj-Cg- Alkyl, für durch Carboxy oder Cj-C4-Alkoxycarbonyl ein- oder zweifach substituiertes Cj-C6-Alkyl, für durch C2-C4-Alkoxy ein- oder zweifach substituiertes C2-C6- Alkyl oder für durch Cj-C4- Alkoxy ein- oder zweifach substituiertes C3-C6-Alkyl, für durch Hydroxy- Cj-C4-alkoxy, Cj-C^-Alkoxy-Cj-Qj-alkoxy, Hydroxy-C]-C4-alkoxy- CrC4-alkoxy, CrC4-Alkoxy-CrC4-alkoxy-CrC4-alkoxy, CrC4- Alkyl-carbonyl oder Hydroxy-C1-C4-alkyl-carbonyl einfach substitu- iertes CrC4-Alkyl, für jeweils durch Hydroxy, Carboxy, Fluor,A represents hydroxy by one to four times substituted C j -Cg- alkyl, mono- for 4 alkoxycarbonyl by carboxy or C j -C or disubstituted C j-C6 alkyl, for by C 2 -C 4 alkoxy, a - or doubly substituted C 2 -C 6 -alkyl or for C 3 -C 6 -alkyl mono- or disubstituted by C j -C 4 -alkoxy, for hydroxy-C j -C 4 -alkoxy, C j -C ^ -Alkoxy-C j -Q j -alkoxy, hydroxy-C ] -C 4 -alkoxy- C r C 4 -alkoxy, C r C 4 -alkoxy-C r C 4 -alkoxy-C r C 4 -alkoxy, C r C 4 - alkyl-carbonyl or hydroxy-C 1 -C 4 -alkyl-carbonyl monosubstituted C r C 4 -alkyl, for each by hydroxy, carboxy, fluorine,
Chlor oder Cj-Cj-Alkoxycarbonyl ein- bis zweifach substituiertes C2-C6-Alkenyl oder C2-C6- Alkinyl, für jeweils durch Hydroxy, Carboxy, Fluor, Chlor, CrC4-Alkyl, Hydroxy-CrC4 -alkyl oder Cr C-Alkoxy-carbonyl ein- oder zweifach substituiertes C3-C6-Cyclo- alkyl oder C3-C6-Cycloalkyl-CrC3-alkyl, oder für jeweils gegebe- nenfalls durch C,-C4-Alkyl substituiertes C2-C5-Oxacycloalkyl, C2-Chlorine or C j -C j alkoxycarbonyl mono- or disubstituted C 2 -C 6 alkenyl or C 2 -C 6 alkynyl, for each by hydroxy, carboxy, fluorine, chlorine, C r C 4 alkyl, hydroxy-C r C 4 -alkyl or C r C-alkoxy-carbonyl mono- or disubstituted C 3 -C 6 cycloalkyl or C 3 -C 6 cycloalkyl-C r C 3 alkyl, or for C 2 -C 5 substituted in each case by C, -C 4 alkyl -Oxacycloalkyl, C 2 -
C4-Dioxacycloalkyl, C2-C5-Oxacycloalkyl-Cj-C4-alkyl oder C2-C4- Dioxacyloalkyl-C,-C4-alkyl steht.C 4 -dioxacycloalkyl, C 2 -C 5 -oxacycloalkyl-C j -C 4 -alkyl or C 2 -C 4 - dioxacyloalkyl-C, -C 4 -alkyl.
6. Verbindungen der Formel (IA) gemäß Anspruch 4, dadurch gekennzeich¬ net, daß darin6. Compounds of formula (IA) according to claim 4, characterized gekennzeich¬ net that therein
A für jeweils durch Hydroxy ein- oder zweifach substituiertes Ethyl, n- oder i-Propyl, für jeweils durch Hydroxy ein- bis dreifach sub¬ stituiertes n-, i-, s- oder t-Butyl, n-, i-, s- oder t-Pentyl, 2,2-Di- methyl-propyl, 1,3-Dimethyl-propyl, 1,1-Dimethyl-butyl oder 2,2- Dimethyl-butyl, für jeweils durch Carboxy, Methoxycarbonyl oder Ethoxycarbonyl ein- oder zweifach substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, n-, i-, s- oder t-Pentyl, für jeweils durch Ethoxy, n- oder i-Propoxy, n-, i-, s- oder t-Butoxy ein- oder zweifach substituiertes Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, für jeweils durch Methoxy ein- oder zweifach substitu- iertes n- oder i-Propyl, n-, i-, s- oder t-Butyl, für jeweils durchA for ethyl which is mono- or disubstituted by hydroxyl, n- or i-propyl, for n-, i-, s- or t-butyl, n-, i-, s- substituted by hydroxy or trisubstituted in each case - or t-pentyl, 2,2-dimethyl-propyl, 1,3-dimethyl-propyl, 1,1-dimethyl-butyl or 2,2-dimethyl-butyl, for each of which by carboxy, methoxycarbonyl or ethoxycarbonyl or disubstituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- or t-pentyl, each with ethoxy, n- or i- Propoxy, n-, i-, s- or t-butoxy mono- or disubstituted ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each mono- or disubstituted by methoxy - ized n- or i-propyl, n-, i-, s- or t-butyl, for each by
Methoxy ethoxy, Ethoxyethoxy, n-Propoxyethoxy, i-Propoxyethoxy, n-Butoxy ethoxy, i-Butoxyethoxy, s-Butoxyethoxy, t-Butoxyethoxy, Methoxyethoxyethoxy oder Ethoxyethoxyethoxy einfach sub¬ stituiertes Ethyl, n- oder i-Propyl, für jeweils gegebenenfalls durch Hydroxy, Carboxy, Fluor, Chlor, Methoxycarbonyl oder Ethoxy¬ carbonyl ein- oder zweifach substituiertes Propenyl, Butenyl, Pentenyl, Propinyl, Butinyl oder Pentinyl, für jeweils gegebenenfalls durch Fluor, Chlor, Carboxy, Methyl, Ethyl, Hydroxymethyl, Hydroxyethyl, Methoxycarbonyl oder Ethoxycarbonyl ein- oder zweifach substituiertes Cyclopentyl oder Cyclohexyl, oder für Tetra¬ hydrofuryl oder Tetrahydrofurylmethyl steht.Methoxy ethoxy, ethoxyethoxy, n-propoxyethoxy, i-propoxyethoxy, n-butoxy ethoxy, i-butoxyethoxy, s-butoxyethoxy, t-butoxyethoxy, methoxyethoxyethoxy or ethoxyethoxyethoxy are simply substituted ethyl, n- or i-propyl, each optionally by Hydroxy, carboxy, fluorine, chlorine, methoxycarbonyl or ethoxycarbonyl mono- or disubstituted propenyl, butenyl, pentenyl, propynyl, butynyl or pentynyl, each optionally by fluorine, chlorine, carboxy, methyl, ethyl, hydroxymethyl, hydroxyethyl, methoxycarbonyl or Ethoxycarbonyl mono- or disubstituted cyclopentyl or cyclohexyl, or for tetrahydrofuryl or tetrahydrofurylmethyl.
7. Verfahren zur Herstellung von Verbindungen der Formel (IA) gemäß An¬ spruch 4, dadurch gekennzeichnet, daß man N-Phosphonomethyl-glycin der Formel (II), (HO)2P(O)-CH2-NH-CH2-COOH (II)7. A process for the preparation of compounds of the formula (IA) according to claim 4, characterized in that N-phosphonomethylglycine of the formula (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-A (III)HO-A (III)
in welcherin which
A die in Anspruch 4 angegebene Bedeutung hat,A has the meaning given in claim 4,
in Gegenwart von Chlor-trimethylsilan oder einer Protonensäure umsetzt, das gegebenenfalls hierbei gebildete Säureaddukt der Verbindung der For¬ mel (IA) gegebenenfalls isoliert und gegebenenfalls mit einem Säurebinde¬ mittel umsetzt.in the presence of chloro-trimethylsilane or a protonic acid, optionally isolating the acid adduct of the compound of the formula (IA) formed in this case and optionally reacting it with an acid binder.
Verwendung von N-Phosphonomethyl-glycinestern der Formel (IA) gemäßUse of N-phosphonomethyl-glycine esters of the formula (IA) according to
Anspruch 4 als Herbizide. Claim 4 as herbicides.
PCT/EP1997/000731 1996-02-28 1997-02-17 Use of n-phosphonomethylglycine esters in aqueous solution as herbicides, and new n-phosphonomethylglycine esters WO1997031534A1 (en)

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