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

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

Use of 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.

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.

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).

It has now been found that N-phosphonomethylglycine esters of the general formula (I)

(HO) ₂ P (O) -CH ₂ -NH-CH ₂ -CO-OR (I)

in which

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,

and acid adducts of the compounds of the formula (I)

alone in aqueous solution, i.e. can be used with very good success to kill unwanted plants without the use of other auxiliaries.

The new compounds of the formula (IA)

(HO) ₂ P (O) -CH ₂ -NH-CH ₂ -CO-OA (IA)

in which

A for by hydroxy, carboxy, hydroxy-C _r C ₆ -alkoxy, C.-C ₈ -alkoxy-C _j -C ₈ -alkoxy,

C _j -C _ß alkoxy, C, -C ₆ alkyl carbonyl, hydroxy-C, -C ₆ alkyl carbonyl or

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,

and acid adducts of the compounds of formula (IA) found.

The new compounds of the general formula (IA) are obtained if N-phosphonomethylglycine of the formula (II)

(HO) ₂ P (O) -CH ₂ -NH-CH ₂ -COOH (II)

with an alcohol of formula (III) HO-A (III)

in which

A has the meaning given above,

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.

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.

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.

The possible use of the compounds of the formula (I) according to the invention thus represents a very valuable enrichment of the prior art.

The invention preferably relates to the use of compounds of the formula (I) in which

R for C to C ₆ alkyl which is mono- to tetrasubstituted by hydroxyl, for by

Carboxy, 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

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-

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 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, 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.

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- 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.

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.

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.

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:

+ HIGH ₂ CH ₂ OH + HBr

(HO) ₂ P (0) -CH ₂ -NH-CH ₂ -CO-OH ►

(HO) ₂ P (0) -CH ₂ -NH-CH ₂ -CO-0-CH ₂ CH ₂ -OH x HBr

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.

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),

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) .

When carrying out the process according to the invention for the preparation of the compounds of the formula (IA), the 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.

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 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.

To 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

According 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

To understand plants that grow up in places where they are undesirable, i.e. also undesirable 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 (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

In 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

The active compounds according to the invention can be used, for example, in the following plants

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 Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

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.

Monocot cultures of the genera. Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

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.

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.

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). 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,

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 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,

Vassgro Spreader, Vegelux, Wayfarer.

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).

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 -

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.

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, 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, 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

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.

The preparation and use of the active compounds according to the invention can be seen from the examples below.

Manufacturing examples;

example 1

(HO) ₂ P (O) -CH ₂ -CO-O-CH ₂ -CH ₂ -OH

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.

6.0 g (56% of theory) of N-phosphonomethyl-glycine (2-hydroxy-ethyl ester) with a melting point of 230 ° C. (decomposition) are obtained.

Example 2

(HO) ₂ P (O) -CH ₂ -NH-CH ₂ -CO-O-CH ₂ CH ₂ -OC ₂ H ₅ -

In a suspension of 16 g (0.10 mol) of N-phosphonomethyl-glycine in 250 ml of 2-

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.

15.8 g (66% of theory) of N-phosphonomethyl-glycine (2-ethoxy-ethyl ester) with a melting point of 220 ° C. (decomposition) are obtained.

Analogously 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) can be produced. Table 1: Examples of the compounds of the formula (I) or (IA)

ύ

Tabelle 1: (Fortsetzung)

Table 1: (continued)

Tabelle 1: (Fortsetzung)

Table 1: (continued)

Examples of use

Example A

Post emergence test

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

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.

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.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

Mean it.

0% = no effect (like untreated control)

100% = total annihilation

In 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

O

Tjbj≥l] e_A2 Post emergence test / greenhouse -4 VI

XO I

n

M vc o o -J

Claims

Claims 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) ₂ P (O) -CH ₂ -NH-CH ₂ -CO-OR (I) in which R for by hydroxy, carboxy, halogen, alkoxy, hydroxyalkoxy, 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, or one of its acid adducts, in the form of an aqueous solution, i.e. without the addition of other auxiliaries. 2. The method according to claim 1, characterized in that one uses compounds of the formula (I) in which R 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, -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. Process according to Claim 1, characterized in that compounds of the formula (I) are used in which 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, 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, 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) ₂ P (O) -CH ₂ -NH-CH ₂ -CO-OA (IA) in which 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-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, and acid adducts of the compounds of the formula (IA) Compounds of formula (IA) according to claim 4, characterized gekenn¬ characterized in that 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, 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 - C ₄ -dioxacycloalkyl, C ₂ -C ₅ -oxacycloalkyl-C _j -C ₄ -alkyl or C ₂ -C ₄ - dioxacyloalkyl-C, -C ₄ -alkyl. 6. Compounds of formula (IA) according to claim 4, characterized gekennzeich¬ net that therein A 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 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. 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) with an alcohol of formula (III) HO-A (III) in which A has the meaning given in claim 4, 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. Use of N-phosphonomethyl-glycine esters of the formula (IA) according to Claim 4 as herbicides.