DE19638301A1 - Use of N-phosphonomethyl-glycine esters in aqueous solution as herbicides and new N-phosphonomethyl-glycine 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

The invention relates to the novel use of partially known N-phosphonomethyl-glycine esters and their acid adducts in aqueous solution as Herbicides, as well as a subset of new N-phosphonomethyl-glycine esters and their acid adducts, a process for their preparation and their Ver use as herbicides.

It is known that N-phosphonomethyl-glycine (glyphosate) is potent herbicidal Shows effectiveness (cf. DE 21 52 826). The compound mentioned is herbicidal active component part of some commercial products, such as B. "Roundup" and "Touchdown". The effect of this compound against weeds and their tolerance to crops is not in all Cases satisfactory.

It is also known that some N-phosphonomethyl-glycine alkyl esters are herbicidal Have properties and - generally in formulated application form men, d. H. combined with certain additives - to kill off un desired plants can be used (cf. DE 21 52 826, DE 21 66 573, US 3977860).

It has now been found that N-phosphonomethyl-glycine esters of the general For mel (I),

(HO) ₂P (O) -CH₂-NH-CH₂-CO-O-R (I)

in which
R for alkyl which is mono- or polysubstituted by hydroxy, carboxy, halogen, alkoxy, hydroxyalkoxy, alkoxyalkoxy, hydroxyalkoxyalkoxy, alkoxyalkoxyalkoxy, alkylcarbonyl, hy droxyalkylcarbonyl or alkoxycarbonyl, for alkenyl which is mono- or polysubstituted or substituted by hydroxy, carboxy, halogen or alkoxycarbonyl or alkynyl, in each case optionally substituted by hydroxy, carboxy, halogen, alkyl, hydroxyalkyl, alkoxyalkyl, alkoxy or alkoxycarbonyl, cycloalkyl or cycloalkylalkyl which is substituted one or more times, or for oxacycloalkyl, dioxacycloalkyl, oxacycloalkyl alkyl or dioxacycloalkylalkyl optionally substituted by alkyl,
and acid adducts of the compounds of the formula (I)
alone in aqueous solution, ie without the use of other auxiliaries, can be used with very good success to kill unwanted plants.

The new compounds of the formula (IA)

(HO) ₂P (O) -CH₂-NH-CH₂-CO-O-A (IA)

in which
A for by hydroxy, carboxy, hydroxy-C₁-C₆-alkoxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy, hydroxy-C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₁-C₆-alkoxy-C₁-C₆- alkoxy- C₁-C₆-alkoxy, C₁-C₆-alkyl-carbonyl, hydroxy-C₁-C₆-alkyl-carbonyl or C₁-C₆-alkoxy-carbonyl mono- to pentasubstituted C₁-C₁₀-alkyl, for by C₂-C₆- Alkoxy mono- to trisubstituted C₁-C₁₀-alkyl or for C₃-C₁-alkoxy monosubstituted to trisubstituted C₃-C₁₀-alkyl, for each by hydroxy, carboxy, halogen or C₁-C₆-alkoxy-carbonyl one to triply substituted C₂-C₁₀ alkenyl or C₂-C₁₀ alkynyl, for each by hydroxy, carboxy, halogen, C₁-C₆-alkyl, hydroxy-C₁-C₆-alkyl or C₁-C₆-alkoxy-carbonyl mono- to trisubstituted C₃ -C₆-cyclo alkyl or C₃-C₆-cycloalkyl-C₁-C₆-alkyl, or for C₂-C₅-oxacycloalkyl optionally substituted by C₁-C₆-alkyl, C₂-C₄-dioxacyclo alkyl, C₂- C₅-oxacycloalkyl-C₁-C₆-alkyl or C₂-C₄-dioxacyclo alkyl-C₁-C₄-alkyl,
and acid adducts of the compounds of formula (IA) found.

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

(HO) ₂P (O) -CH₂-NH-CH₂-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 resulting acid adduct of the compound of the formula (IA) and optionally reacting it with an acid binder.

The invention thus relates to a new method for controlling or ab killing unwanted plants by exposure to N-phosphonomethyl glycine esters on such plants, which is characterized in that at least one N-phosphonomethyl-glycine ester of formula (I) above, or one its acid adducts, in the form of an aqueous solution, d. H. without adding any more Auxiliaries.

Surprisingly, the aqueous solutions of the pure active ingredients can of the formula (I) - and of acid adducts of these compounds - without a combination nation with the formulation auxiliaries normally used in agrochemicals - un indirectly used to kill unwanted plants. Given the otherwise usual practice in the use of plant treatment agents, d. H. the use of formulated active ingredients combined with auxiliary substances, represents the new application now found for the invention Active ingredients of formula (I) to be used are a completely surprising, very simple one and thus economically very cheap problem solving in rural and Forestry.

The possible use according to the invention for the compounds of the formula (I) is therefore a very valuable addition to the state of the art.

The invention preferably relates to the use of compounds of formula (I) in which
R for C₁-C₆-alkyl mono- to tetrasubstituted by carboxy, fluorine, chlorine, C₁-C₆-alkoxy or C₁-C₆-alkoxy-carbonyl mono- or di-substituted C₁-C₆-alkyl, for by hydroxy -C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkoxy, hydroxy-C₁-C₄-alkoxy-C₁-C₄-alkoxy, C₁-C₄- alkoxy-C₁-C₄-alkoxy-C₁-C₄-alkoxy , C₁-C₄-alkyl-carbonyl or hydroxy-C₁-Cyl-alkyl-carbonyl monosubstituted C₁-C₄-alkyl, for each ge optionally substituted by hydroxy, carboxy, fluorine, chlorine or C₁-C₄-alkoxy carbonyl mono- or disubstituted C₂-C₆-alkenyl or C₂-C₆-alkynyl, for each optionally mono- or disubstituted by hydroxy, carboxy, fluorine, chlorine, C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl or C₁-C₄-alkoxy-carbonyl C₃-C₆-cycloalkyl or C₃-C₆-cycloalkyl-C₁-C₄-alkyl, or for each optionally substituted by C₁-C₄-alkyl substituted C₂-C₅-oxacycloalkyl, C₁-C₄-dioxacyc loalkyl, C₂-C₅-oxacyclo alkyl-C₁-C₄-alkyl or C₂-C₅-dioxacycloalkyl-C₁-C₄-alkyl.

The invention also relates preferably to new compounds of the formula (IA) in which
A for C₁-C₆-alkyl which is mono- to tetrasubstituted by hydroxy, C₁-C₆-alkoxy-C₁-C₆-alkoxy, hydroxy-C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₁-C₆-alkoxy- C₁- C₆-alkoxy-C₁-C₆-alkoxy, C₁-C₆-alkyl-carbonyl, hydroxy-C₁-C₆-alkyl carbonyl or C₁-C₆-alkoxy-carbonyl mono- to pentasubstituted C₁- C₁₀-alkyl, for by C₂-C₆ -Alkoxy monosubstituted to trisubstituted C₁-C₁-Al or for C₃-C₆-alkoxy monosubstituted to trisubstituted C₃-C₁₀-alkyl, for each by hydroxyl, carboxy, halogen or C₁-C₆-alkoxy carbonyl one to triply substituted C₂-C₁₀ alkenyl or C₂-C₁₀-Al kinyl, for each by hydroxy, carboxy, halogen, C₁-C₆-alkyl, hydroxy-C₁-C₆-alkyl or C₁-C₆-alkoxy-carbonyl mono- to triple sub substituted C₃-C₆-cycloalkyl or C₃-C₆-cycloalkyl-C₁-C₆-alkyl, or for each optionally substituted by C₁-C₆-alkyl substituted C₂-C₅-oxacyclo alkyl, C₂-C₄-dioxa cycloalkyl, C₂-C₅-oxacycloalkyl-C₁-C₆-alkyl or C₂-C₄-dioxacycloalkyl-C₁-C₄-alkyl,
Alkyl means in all defined areas, also in connection with heteroatoms, such as. B. in alkoxy or hydroxyalkyl, each 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 Ethoxy carbonyl 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, methoxy carbonyl or ethoxycarbonyl monosubstituted or disubstituted propenyl, butenyl, pentenyl, propynyl, butynyl or pentynyl, if appropriate by hydroxyl, carboxy, fluorine, chlorine or, methyl, ethyl, hydroxy methyl, hydroxyethyl, methoxycarbonyl or ethoxycarbonyl mono- or disubstituted cyclopentyl or cyclohexyl, or for tetrahydro furyl 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 methyl substituted by carboxy, methoxycarbonyl or ethoxycarbonyl , 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-substituted by methoxy -Propyl, n-, i-, s- or t-butyl, for each by methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, i-propoxyethoxy, n-butoxyethoxy, i-butoxyethoxy, s-butoxyethoxy, t-butoxyethoxy, methoxyethoxyethoxy or ethoxyethoxyethoxy monosubstituted ethyl, n- or i-propyl, each optionally by H ydroxy, carboxy, fluorine, chlorine, methoxy carbonyl or ethoxycarbonyl monosubstituted or disubstituted propenyl, butenyl, pentenyl, propynyl, butynyl or pentynyl, if appropriate by fluorine, chlorine, carboxy, methyl, ethyl, hydroxymethyl, hydroxyethyl, methoxycarbonyl or Ethoxycarbonyl mono- or disubstituted cyclopentyl or cyclohexyl, or stands for tetrahydrofuryl or tetrahydrofurylmethyl.

The new compounds of formula (IA) and the acid adducts thereof are characterized by strong and selective herbicidal activity. You own also very favorable biological transport properties, d. H. they will be very good absorbed by the target organism and quickly within the treated Plants distributed.

As acid adducts in connection with the present invention, all common addition products from compounds of formula (I) or (IA) and acids to understand. Suitable acids are preferably protonic acids, such as e.g. B. 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, butane sulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid and p-toluenesulfone acid.

For example, N-phosphonomethyl-glycine and 2-hydroxyethanol are used (Glycol) as starting materials and hydrogen bromide as acid, so the Re Action sequence in the method according to the invention by the following formula scheme are outlined:

The process according to the invention for the preparation of the compounds of Formula (IA) resulting acid adducts of the compounds of formula (IA) treated with acid binders. As such, preferably come Di-C₃-C₆-al kyl-amines with branched alkyl groups, di-C₅-C₆-cycloalkyl-amines, tri-C₁-C₆-al alkyl amines with straight-chain and / or branched alkyl groups, N, N-di C₁-C₆-alkyl-N-C₅-C₆-cycloalkylamines with straight-chain and / or branched Al  alkyl groups and N, N-di-C₅-C₆-cycloalkyl-N-C₁-C₆-alkylamines with straight-chain or branched alkyl groups.

Oxiranes (epoxides) are also preferred as acid binders Consider which is unsubstituted or mono- or disubstituted by alkyl or aryl groups are substituted. Examples include oxirane (ethylene oxide), Methyloxirane (propylene oxide, 1,2-epoxypropane), ethyloxirane (1,2-butylene oxide, 1,2-epoxy-butane), propyloxirane (1,2-epoxy-pentane) and phenyloxirane (styrene oxide, Called epoxystyrene).

The reaction temperatures can be carried out when carrying out the process according to the invention Process for the preparation of the compounds of formula (IA) in a larger one Range can be varied. Generally one works at 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 guided. However, it is also possible to use the method according to the invention high or reduced pressure - generally between 0.1 bar and 10 bar - perform.

One mol is used to carry out the process according to the invention Phosphonomethylglycine of the formula (II) in general between 1 and 100 mol, preferably between 10 and 50 moles of an alcohol of formula (III) and between 1 and 5 moles, preferably between 1.5 and 3 moles of an acid and optionally between 1 and 5 moles, preferably between 1.5 and 3 moles an acid binder.

In a preferred embodiment of the method according to the invention the phosphonomethylglycine of the formula (II) in an alcohol of the formula (III) suspended and an acid is slowly metered in. The reaction mixture is then kept at the required temperature until the reaction is virtually off closed is.

To isolate the acid adduct of the compound of formula (IA) under ver reduced pressure, optionally with a suitable organic Solvents such as B. digested acetone and the acid adduct by suction isolated.  

To isolate the "free" compound of formula (IA) after concentration of the Residue essentially containing the acid adduct, or as above wrote in a crystalline form isolated acid adduct again in an alcohol of Formula (III) added and mixed with an acid binder. The product The formula (IA) is obtained in crystalline form and can be suctioned off be isolated.

According to the invention, the active compounds of the formulas (I) and (IA) can be found in defoliants, Desiccants, herbicides and especially in weed killers - especially in the semi-selective and in the non-selective area of the weed weed fighting - be used. Everyone is under weeds in the broadest sense Understand plants that grow in places where they are undesirable, d. H. e.g. B. also unwanted trees in the forest.

The active compounds to be used according to the invention can be used both in con conventional cultivation methods (row crops with a suitable row size), in Plantation crops (e.g. wine, fruit, citrus) as well as in industrial and track systems, on paths and squares, but also for stubble treatment and the so-called "Minimum Tillage" method can be used. They are still suitable as Ab burner (herb killing e.g. in potatoes) or as defoliantia (e.g. in tree wool). They are also suitable for use on fallow land. Another one Areas of application are tree nurseries, forestry, grassland and ornamental plant cultivation.

In addition, the active ingredients of the formulas (I) and (IA) according to the Invention also as herbicides in crops which, compared to Gly phosate and other EPSP synthase inhibitors are resistant.

The active compounds according to the invention can, for. B. in the following plants be used:

Dicotyledon weeds of the genera

Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.  

Dicotyledon cultures of the genera

Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, lactuca, cucumis, cucurbita.

Monocotyledonous weeds of the genera

Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, apera.

Monocot cultures of the genera

Oryza, Zea, Triticum, Hordeum, Avena, Secale, sorghum, panicum, saccharum, pineapple, asparagus, allium.

However, the use of the active compounds according to the invention is by no means limited to limited to these genera, but also extends in the same way other plants.

Depending on the concentration, the compounds are suitable for the total weed control z. B. on industrial and track systems and on paths and Places with and without tree cover. Likewise, the connections to Weed control in permanent crops, e.g. B. forest, ornamental trees, fruit, wine, Citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and Hop plants, on ornamental and sports turf and pastures and for selective Weed control can be used in annual crops.

The compounds of the formulas (I) or (IA) according to the invention are particularly suitable especially for the control of monocotyledon and dicotyledon weeds afterwards casserole procedure.

The compounds of the formulas (I) and (IA) can - as explained above - in aqueous solution can be used without further additives; but you can too optionally with the addition of additives (adjuvants, emulsifiers, network agents, surfactants) can be used. These include hochraffi nated mineral oils, emulsifiable vegetable oils, ethoxylated tallow amines, 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, ten-side) 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, Amos 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, Codacide Oil, Compatibility Agent 2, Cutonol, Du Pont Adjuvant, Emerald, Emulsol, Enhance, Enhance Low Foam, Ethokem, Ethokem C / 12, Ethywet, Event, Exell, Farmon Blue, Farmon Wetter, Forestry Bee, Frigate, Fyzol 11E, Galion, Genamin T 200 BM, Glifor, Headland Guard, Headland Intake, Heliosol, High Trees Mixture B, HT Non-ionic Wetter, Huile 970, Huile Schering L, Hyspray, Jogral, LI 700, Lo-Dose, Mangard, Minder, Nu Film P, Orchan 263, Oura S, PBI spreader, Pest Oil 7, Planet, Quad-Fast, Quadrangle Cropspray 11E, Quadrangle Q 900, Rapide, Rosemox, Sandovit 63, Seppic 11E, Seppic Ete, Silwet L 77, Solar, Sopratom, Spray fast, 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 11E, Tripart Lentus, Tripart Minax, Vassgro Spreader, Vegelux, Wayfarer.

Furthermore, newer types known from the (patent) literature Additives (adjuvants, emulsifiers, wetting agents, surfactants) are used, for example alkynediols known under the name Surfynole (cf. EP 531269, US 5258359), alkyl known under the name Ethoquad tris (hydroxypolyalkoxyalkyl) ammonium salts or dialkyl bis (hydroxypolyal koxyalkyl) ammonium salts (cf. WO 9402021, US 5317003), and also trialkyl (alkoxypolyalkoxyalkyl) ammonium salts and polypropylene glycol (cf. EP 526444) as well as secondary or tertiary alcohol alkoxylates (cf. WO 9516351).

The aqueous solutions for using the compounds of formula (I) ent generally hold between 1 and 50 percent by weight, preferably between 5 and 30 percent by weight of active ingredient.  

As such, the compounds of the formulas (I) and (IA) can - in aqueous solution solution - or as a mixture with other known herbicides for weed plants Combat are used, these mixtures in the given case as "Tank mixes", i.e. H. as spray or pouring broth prepared by the user come into use.

Known herbicidal substances come from practically all of these mixtures relevant classes of substances into consideration, for example acetochlor, acifluorfen (-sodium), aclonifene, alachlor, alloxydim (-sodium), ametryne, amidochlor, Amidosulfuron, Amiprophos (-methyl), Amitrol, Anilofos, Asulam, Atrazin, Azim sulfuron, benazolin, benfuresate, bensulfuron (-methyl), bensulide, bentazone, Benthiocarb, Benzofenap, Benzoylprop (-ethyl), Bialaphos, Bifenox, Bromacil, Bromobutide, bromofenoxim, bromoxynil, butachlor, butamifos, butenachlor, Butylates, cafenstroles, carbetamides, chloromethoxyfen, chloramben, chloridazon, Chlorimuron (-ethyl), chloromethoxynil, chloronitrofen, chlorosulfuron, chlorotoluron, 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, diphenamide, diquat, dithiopyr, diuron, dymron (daimuron, dimuron), EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethofumesate, Ethoxy fen, etobenzanide, 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, glufosinate (ammonium), glyphosate, haloxyfop (-ethoxyethyl), hexazinones, 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, nofflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, Oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachlor, Primisulfuron (-methyl), Prometryn, Propachlor, Propanil, Propaquizafop, Pro pyzamide, prosulfocarb, prosulfuron, pyrazolates, pyrazosuifuron (-ethyl), pyr  azoxyten, pributicarb, 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.

A mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, plants nutrients and soil structure improvers are possible.

The amount of active ingredient used can vary over a wide range. she depends essentially 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 area, preferably between 50 g and 5 kg per ha.

The manufacture and use of the active compounds according to the invention start out the following examples.

Manufacturing examples example 1

(HO) ₂P (O) -CH₂-CO-O-CH₂-CH₂-OH

To a suspension of 8.5 g (50 mmol) of N-phosphonomethyl-glycine in 100 ml Ethane-1,2-diol 30 ml chloro-trimethylsilane at room temperature (approx. 20 ° C) given dropwise. Then the reaction mixture is at about 15 hours Stirred at room temperature, filtered and the filtrate concentrated in a water jet vacuum. Propylene oxide is added dropwise to the residue until a color change from reddish brown to light yellow. The product obtained in crystalline form is isolated by suction.

6.0 g (56% of theory) of N-phosphonomethylglycine (2-hydroxyethyl) are obtained ester) with a melting point of 230 ° C (decomposition).

Example 2

(HO) ₂P (O) -CH₂-NH-CH₂-CO-O-CH₂CH₂-OC₂H₅

In a suspension of 16 g (0.10 mol) of N-phosphonomethyl-glycine in 250 ml 2-ethoxyethanol is introduced to hydrogen chloride gas until saturation. Then it will be the reaction mixture was heated under reflux for 2 hours, about 50 ml 2-ethoxyethanol are removed by distillation. The mixture is then in Water jet vacuum concentrated. The residue is mixed with propylene oxide until the color changes from reddish brown to light yellow. This crystallized falling product is isolated by suction.

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

Analogously to Examples 1 and 2, for example, those in the following Compounds of formula (I) or the formula listed in Table 1 above (IA) can be produced.  

table

Examples of the compounds of the formula (I) or (IA)

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 is placed Active ingredient, diluted with water to the desired concentration and gives 1 Add part by weight of emulsifier.

Test plants with a height of 5-15 cm are sprayed with the active substance preparation have so that the desired amounts of active ingredient per area unit can be deployed. The concentration of the spray liquor is chosen so that in 500 to 1000 l of water / ha the desired amounts of active ingredient to be brought.

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

It means:

0% = no effect (like untreated control)
100% = total annihilation

In this test, for example, show the connections according to the manufacturing process example 1, 2, 5 and 6 strong action against weeds.  

Table A1

Post emergence test / greenhouse

Claims (8)

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-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 alkenyl which is mono- or polysubstituted by hydroxyl, carboxy, halogen or alkoxycarbonyl or alkynyl, for cycloalkyl or cycloalkylalkyl which is mono- or polysubstituted or substituted by hydroxy, carboxy, halogen, alkyl, hydroxyalkyl, alkoxyalkyl, alkoxy or alkoxycarbonyl, or for oxacycloalkyl, dioxa cycloalkyl, oxacycloalkylalkyl or dioxacycloalkylalkyl which is optionally substituted by alkyl,
or one of its acid adducts, in the form of an aqueous solution, ie without the addition of other auxiliaries. 2. The method according to claim 1, characterized in that compounds of formula (I) are used, in which
R for C₁-C₆-alkyl which is monosubstituted to tetrasubstituted by hydroxy, for carboxy, fluorine, chlorine, C₁-C₆-alkoxy or C₁-C₆-Al koxy-carbonyl mono- or di-substituted C₁-C₆-alkyl, for by Hydroxy-C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkoxy, Hy droxy-C₁-C₄-alkoxy-C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkoxy- C₁-C₄ -alkoxy, C₁-C₄-alkyl-carbonyl or hydroxy-C₁-C₄-alkyl carbonyl monosubstituted C₁-C₄-alkyl, for each optionally mono- or disubstituted by hydroxy, carboxy, fluorine, chlorine or C₁-C₄-alkoxycarbonyl C₂-C₆-Al kenyl or C₂-C₆-alkynyl, for each optionally by Hy, hydroxy, carboxy, fluorine, chlorine, C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl or C₁-C₄-alkoxy-carbonyl one or doubly substituted C₃-C₆-cycloalkyl or C₃-C₆-cycloalkyl-C₁-C₄-alkyl, or for each optionally substituted by C₁-C₄-alkyl C₂-C₅-oxacycloalkyl, C₁-C₄-dioxacy cloalkyl, C₂-C₅-oxacycloalkyl-C₁-C₄-alkyl or C₂-C₅-dioxacycloalkyl-C₁-C₄-alkyl. 3. The method according to claim 1, characterized in that one uses connec tions of formula (I) in which
R for ethyl which is mono- or disubstituted by hydroxyl, n- or i-propyl, for 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, for each by Methoxy ethoxy, ethoxyethoxy, n-propoxyethoxy, i-propoxyethoxy, n-but oxyethoxy, i-butoxyethoxy, s-butoxyethoxy, t-butoxyethoxy, methoxyethoxyethoxy or ethoxyethoxyethoxy simply substituted ethyl, n- or i-propyl, each optionally by hydroxy , Carboxy, fluorine, chlorine, methoxycarbonyl or ethoxycarbonyl monosubstituted or disubstituted propenyl, butenyl, pentenyl, propynyl, butynyl or pentynyl, each optionally by hydroxyl, carboxy, fluorine, Chlorine, methyl, ethyl, hydroxymethyl, hydroxyethyl, methoxycarbonyl or ethoxy carbonyl mono- or disubstituted cyclopentyl or cyclo hexyl, or for tetrahydrofuryl or tetrahydrofurylmethyl. 4. N-phosphonomethyl-glycine ester of the formula (IA), (HO) ₂P (O) -CH₂-NH-CH₂-CO-OA (IA) in which
A for by hydroxy, carboxy, hydroxy-C₁-C₆-alkoxy, C₁-C₆-Al koxy-C₁-C₆-alkoxy, hydroxy-C₁-C₆-alkoxy-C₁-C₆-alkoxy, C₁-C₆-Al koxy-C₁ -C₆-alkoxy-C₁-C₆-alkoxy, C₁-C₆-alkyl-carbonyl, Hy droxy-C₁-C₆-alkyl-carbonyl or C₁-C₆-alkoxy-carbonyl mono- to pentasubstituted C₁-C₁₀-alkyl, for by C₂-C₆-alkoxy monosubstituted to trisubstituted C₁-C₁₀-alkyl or for C₃-C₆-alkoxy monosubstituted to trisubstituted C₃-C₁₀-alkyl, each by hydroxy, carboxy, halogen or C₁-C₆-alkoxy-carbonyl mono- to trisubstituted C₂-C₁₀ alkenyl or C₂-C₁₀ alkynyl, for each by hydroxy, carboxy, halogen, C₁-C₆-alkyl, hydroxy-C₁-C₆-alkyl or C₁-C₆-alkoxy-carbonyl one to triply substituted C₃-C₆-cycloalkyl or C₃-C₆-cycloalkyl-C₁-C₆-alkyl, or for C₂-C₅-oxa cycloalkyl, C₂-C₄-dioxacycloalkyl, C₂-C₄-dioxacycloalkyl, C optionally substituted in each case by C₁-C₆-alkyl -C₅-oxacycloalkyl-C₁-C₆-alkyl or C₂-C₄-Dioxacycloalkyl-C₁-C₄-alkyl,
and acid adducts of the compounds of the formula (IA). 5. Compounds of formula (IA) according to claim 4, characterized in that therein
A for C₁-C₆-alkyl which is mono- to tetrasubstituted by hydroxy, for C₁-C₆-alkyl which is mono- or disubstituted by carboxy or C₁-C₁-alkoxycarbonyl, for C₂-C₄-alkoxy which is mono- or di-substituted by C₂-C₄-alkoxy -Alkyl or for C₃-C₄-alkoxy mono- or disubstituted C₃-C₆-alkyl, for by hydroxy-C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkoxy, hydroxy-C₁-C₄-alkoxy - C₁-C₄-alkoxy, C₁-C₄-alkoxy-C₁-C₄-alkoxy-C₁-C₄-alkoxy, C₁-C₄-alkyl carbonyl or hydroxy-C₁-C₄-alkyl-carbonyl monosubstituted C₁-C₄-alkyl, for C₂-C₆-alkenyl or C₂-C₆-alkynyl which are monosubstituted or disubstituted by hydroxyl, carboxy, fluorine, chlorine or C₁-C ,alkoxycarbonyl, each of which is substituted by hydroxy, carboxy, fluorine, chlorine, C₁-C₄alkyl, Hydroxy-C₁-C₄-alkyl or C₁-C-alkoxy-carbonyl mono- or disubstituted C₃-C₆-cyclo alkyl or C₃-C₆-cycloalkyl-C₁-C₃-alkyl, or for each ge if necessary by C₁-Cac-alkyl substituted C₂-C₅-oxacycloalkyl, C₂-C₄-dioxacycloalkyl, C₂-C₅-oxacycloalkyl-C₁-C₄-alkyl or C₂-C₄-dioxacyloalkyl-C₁-C₄-alkyl. 6. Compounds of formula (IA) according to claim 4, characterized in 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- or t-pentyl, 2,2-dimethyl-propyl, 1,3-dimethyl-propyl, 1,1-dimethyl-butyl or 2,2-dimethyl-butyl, each one or two times by carboxy, methoxycarbonyl or ethoxycarbonyl substituted 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, for n each substituted by methoxy or n-substituted - or i-propyl, n-, i-, s- or t-butyl, for each by methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, i-propoxyethoxy, n-butoxyethoxy, i-butoxyethoxy, s-butoxyethoxy, t-butoxyethoxy, Methoxyethoxyethoxy or ethoxyethoxyethoxy simply substituted ethyl, n- or i-propyl, for each optionally by durc h 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 formula (IA) according to claim 4, characterized in that N-phosphonomethyl-glycine of formula (II), (HO) ₂P (O) -CH₂-NH-CH₂-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 formed here of the compound of the formula (IA) and optionally reacting it with an acid binding agent. 8. Use of N-phosphonomethyl-glycine esters of the formula (IA) according to Claim 4 as herbicides.