MXPA01005961A - Cyclohexenone oxime ether / (glyphosates / gluphosinates) suspension concentrates - Google Patents

Abstract

The invention relates to a largely anhydrous formulation of plant-protectant active ingredients essentially consisting of:a) a cyclohexenone oxime ether of formula (I) in which R1 is ethyl, propyl;R2 is hydrogen or an equivalent of an agriculturally useful cation;R3 is 2-(thioethyl)propyl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 1-(methylthio)cyclopropyl, 5-(isopropyl)-isoxazole-3-yl, 2,5-dimethylpyrazole-3-yl, 2,4,6-trimethylphenyl or 2,4,6-trimethyl-3-butyrylphenyl;R4, R5 are H, CH3, CO-OCH3;Alk is CH2CH2, CH2CH(CH3) CH2CH=CH, CH2CH=C(C1), CH2CH2CH=CH;R6 is H, phenyl, halogen phenyl, dihalogen phenyl, phenoxy, halogen phenoxy, dihalogen phenoxy;b) N-phosphonomethyl glycine, an ester or salt thereof, DL-homoalanine-4-yl (methyl)phospinic acid or the ammonium salt thereof;c) between 20 and 80%by weight of an aprotic or weakly protic solvent in which the components a) and b) are suspended;d) possibly emulsifiers, tensides and surface-active and/or reinforcing additives.

Description

CONCENTRATES IN SUSPENSION OF CYCLOHEXENONE OXYME ETHER / (GLYPHOSATES / GLUCOSINATES) FIELD OF THE INVENTION The present invention relates to a new, substantially anhydrous formulation of phytosanitary products which is composed, substantially of a) a cyclohexenone oxime of the formula I where the variables have the following meanings: R1 ethyl or propyl; R2 hydrogen or an equivalent of a cation useful in agriculture; R 3 2- (thiothyl) propyl, tetrahydrothiopyran-3-yl, tetra-hydrothiopyran-4-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 1- (methylthio) cyclopropyl, 5- (isopropyl) -isoxazole 3-yl, 2, 5-dimethylpyrazol-3-yl, 2,4,6-trimethyl-phenyl or 2,, 6, -trimethyl-3-butyrylphenyl; R4 and R5 each independently of the other, hydrogen, methyl or methoxycarbonyl; Alk CH2CH2, CH2CH (CH3), CH2CH = CH, CH2CH = C (C1) or CH2CH2CH = CH; R6 is hydrogen, phenyl halogen phenyl, phanoxy phenyl, phenoxy, nalofenophenoxy or dihalogenophenoxy; b) N-phosphonomethylglycine (glyphosate), an ester or a salt thereof, DL-homoalamin-4-yl) ethyl) phosphinic acid (glufosinate) or its ammonium salt; c) 20 to 80% by weight of an aprotic or slightly protic solvent, in which components a) and b) are suspended; d) if desired, emulsifiers, surfactants, surfactant auxiliaries and / or enhancers of the effect.

BACKGROUND OF THE INVENTION Furthermore, the invention relates to a process for obtaining a spray mixture for combating unwanted plants. As is known, herbicides of the class of cyclohexenone oxides tend to decompose hydrolytically or to chemically degrade in aqueous or protic solvents. For this reason, cyclohexenone oxides are usually prepared and applied to date only as anhydrous emulsion concentrates. One possible alternative is solid formulations, as described in WO 96/29869.

However, emulsion concentrates and solid formulations have the disadvantage that no additions can be incorporated to enhance the effect, for example, lipophilic esters, such as methyl oleate, esters of lauric and adipic acid, if appropriate. , in combination with selected emulsifiers. On the other hand, with mixtures of ethers cyclonesenone oxime and N-phosphonomethylglycine or a derivative thereof, it is better to destroy unwanted grasses than with the glyphosates alone. Combating "Round up Ready" volunteer maize in "Round up Ready" soya is only profitable in this way.

DESCRIPTION OF THE INVENTION It is therefore an object of the present invention to provide a liquid ready formulation, which contains a cyclohexenone oxime ether herbicide, N-phosphonomethylglycine or a derivative thereof and, if desired, an enhancer of the effect, and which is both Storage is sufficiently stable. Therefore, the suspension concentrates defined above were found. In addition, a process for obtaining a spray broth of herbicidal action was found.

The characteristic of the present suspension concentrates is that the proportion of free water (water not fixed in crystalline form) amounts to 0 to 5% by weight, preferably 0 to 2% by weight, especially only 0 to 0.5% by weight. weight. Preferred herbicidal component a) are, preferably, the cyclohexenone oxides of the group: Sethoxydim, Cyclodexid, Cletodim, Traxoxidime, Butroxydim, 2- (1- (3-chloroalyloxy) iminopropyl) -5- (tetrahi-dropyran-4-yl) - 3-hydroxy-cyclohex-2-enone, 2- [1- (2-p-chloro-phenoxypropyloxy) -iminobutyl] -5- (tetrahydrothiopyran-3-ill) -3-hydroxy-cyclohex-2-enone or mixtures thereof , especially cletodirr or 2- (1- (3-chloroalkyloxy) iminopropyl) -5- (tetrahi-dropyran-4-yl) -3-hydroxy-cyclohex-2-enone. Most preferably an alkaline or alkaline earth metal salt of the aforementioned cyclohexenone oxides is used as preferred or especially preferred. The salts of the active substances are advantageous, which in combination with selected auxiliaries are substantially insoluble in the continuous oleic phase. Thus, those salts of cyclohexenanoxime ether, which are present in dissolved form in < 1%, most preferably in < 0.1 - 0.5% in the oleic phase, whereby the degradation of the active substances 1 is substantially avoided.

The salts of the cyclohexenone oxime ethers I can be obtained, generally, by reaction of the free compounds I (R2 = hydrogen) with basic metal solutions. Suitable basic metal sources are typically hydroxides, carbonates or phosphates of alkali metals, alkaline earth metals or transient metals. Cations of higher valencies, such as calcium and magnesium, which were used in approximate ratio. Equimolar with respect to the compounds I, may additionally be associated with anions of mineral or organic acids for the saturation of the charge. Next, the granulates can be prepared by spray drying the aqueous solution of a potassium or calcium salt, containing approximately 100% by weight of the metal salt of cyclohexenone oxime. Component b) represents known commercial products. Their common names are glyphosate, sulfosate and glufosinate, as well as the corresponding trade names, RoundUp®, Touchdown® or Basta®. Within the framework of the present invention, it is especially preferred to use the mixtures, which contain as N-phosphonomethylglycine derivative the isopropylammonium salt of N-phosphonomethylglycine known as glyphosate. Other known derivatives of phosphonomethylglycine is the trimethylsulfonium salt known under the name sulfosate. But the above-mentioned product which is known as glyphosate is especially preferred. The tri-deprotonated salt of N-phosphonomethylglycine, especially an alkali metal, alkaline earth metal salt, has been proved as a herbicidal component b). As a rule, component b) is used in excess of up to 12 times the molar amount, especially about 5 to 8 times the molar amount, with respect to the amount of component a). Among the aprotic or weakly protic solvents suitable as components c) the non-polar, polar or zwitterionic aliphatic or aromatic solvents are provided, which have no or only a reduced solvent effect against components a) and b). In order to obtain stable formulations for storage, the solubility of the substances of the active substances in the oleic phase should be below 1%. Hydrocarbons, such as benzene, alkylbenzene and naphthalene, as well as their mono- and polysubstituted alkyl and / or partially hydrogenated derivatives, the n- or iso-paraffins with 8 to 30 carbon atoms, the aliphatic or aromatic esters of acids are preferred. - mono or dicarboxylic, such as, for example, methyl oleate, laurate and octyl adipate and the acid esters benzoic, or modified native or natural fats and oils, such as soybean oil, sunflower oil and rapeseed oil methyl ester. Solvents of the benzene or naphthalene series, such as for example Solvesso 150 and Solvesso 200 (alkyromatics of the Exxon Company) are most preferred. Together with component c), the formulations of the invention generally contain emulsifiers, surfactants and surfactant auxiliaries, such as humectants and dispersants, as other components. Useful surfactants, humectants and dispersants are, for example: 1. Anionic surfactants and dispersants, especially soaps (alkali metal, alkaline earth or ammonium salts of fatty acids), for example potassium stearate; alkyl sulfates; sulfates of alkyl ethers, for example hexa, hepta and sulfated octadecanols and fatty alcohol glycol ether; alkyl or isoalkyl sulfonates; alkali metal, alkaline earth metal or ammonium salts of arylsulphonic or alkylbenzenesulphonic acids, for example lignin sulphonic, naphthalenesulphonic and dibutylnaphthalenesulphonic acids, or docylbenzenesulphonate Na; alkylnaphthalene sulfonates; alkylmethyl ester sulfonates; acyl glutamates; sulphonates of alkylsuccinic acid esters; alkyl mono / diphosphonates; sarcosinates, for example Na-lauryl sarcosinate; tauratos; condensates of sulfonated naphthalene and its derivatives with formaldehyde; condensates of naphthalisulfonic, phenolic and / or phenolsulfonic acids, formaldehyde and urea; albumin hydrolysates; lignin-sulphite waste liquors and methylcellulose, these substances acting, in particular, as dispersants; 2. Cationic surfactants: alkyltrimethylammonium halides / alkyl sulphates; alkylpyridinium halides; dialkyldimethylammonium halides / alkyl sulfates; 3. Nonionic surfactants: polyoxyethylene fatty acid esters, such as, for example, polyoxyethylene ether lauryl alcohol acetate; alkyl polyoxyethylene or polyoxypropylene ethers, for example iso-tridecyl alcohol and polyoxyethylene fatty alcohol ethers; polyoxyethylene ethers of alkylaryl alcohol, such as, for example, octylphenol-polyoxyethylene ether; alkoxylated animal / vegetable fats or oils, for example, corn oil ethoxylates, castor oil ethoxylates and sebaceous fat ethoxylates; glycerin esters, such as glycerin monostearate; fatty alcohol alkoxylates or oxoalcohol alkoxylates; fatty acid alkoxylates, for example oleic acid ethoxylates; alkylphenol alkoxylates, by example, iso-octyl-, octyl- or nonylphenol ethoxylates and tri-butylphenol-polyoxyethylene ether; fatty amine alkoxylates; fatty amide alkoxylates; sugar surfactants, sorbitan esters, for example sorbitan fatty acid ester (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid ester, alkyl polyglycosides and N-alkylgluonamides; alkylmethyl sulfoxides; alkyldimethylphosphine oxides, for example tetradecyldimethylphosphine oxide; 4. Bipolar ionic surfactants: sulfobetaines; carboxybetaines; alkyldimethylamine oxides, for example tetradecyldimethylammonium oxide; 5. Polymeric surfactants: di- and multi-block polymers of the type (AB) X, ABA and BAB, for example, polyethylene oxide-polypropylene oxide block or polystyrene-polyethylene oxide block; AB-polymers in a comb, for example, polymethyl-acrylate-polyethylene oxide-comb; 6. Other surfactants, for example: perfluorinated surfactants; silicone surfactants; phospholipids, for example lecithin or chemically modified lecithins; amino acid surfactants, for example N-lauroyl glutamate; homo and copolymerized surfactants, such as polyvinylpyrrolidone, polyacrylic acid, polyvinyl alcohol, polyethylene oxide, anhydride copolymers maleic-isobutene and copolymers of vinylpyrrolidone-vinyl acetate. Mixtures of the surfactants mentioned above are also suitable. Particularly suitable are the nonionic surfactants of the polyoxyethylene-sugar alcohol alkyl-carboxylate group, for example the polyoxyethylene (40) -sorbitol Atlas G 1086 hexaheratolates (No. GAS 057171-56-9) of the ICI Company. Surfactants, as well as the ionic surfactants of the alkali and alkaline earth alkyl-, dialkyl- or alkylaryl sulphonates series. Also advantageous are emulsifiers and surfactants, which are obtained by reacting a natural oil, especially castor oil, with ethylene oxide or propylene oxide (see the explanations in DE-A 19701123). The alkyl chains of the surfactants, humectants and dispersants mentioned above can be linear or branched, the length of the alkyl chains generally increasing to 8 to 20 carbon atoms. The formulations of the invention may also contain, in order to improve the physical properties in the sense of reduced serum formation or reduced sedimentation, called thickeners, a term by which, in general, mineral components are understood, such as Bentonites, talcites and hextorites or derivatives of castor oil. As a result of the resulting increase in viscosity, chemical processes in the formulations are suppressed during storage, which may lead to a better stability of the active substances. With respect to auxiliaries that intensify the effect, such as for example adipate, methyl oleate and other technical esters based on carboxylic acids, dicarboxylic acids or naturally occurring fatty acids, reference has been made to WO 96/22020, DE- A 44 45 546, as well as the literature quoted therein. All the mentioned auxiliaries can be added before or after grinding to the preparation of the formulation. Their total proportion amounts, as a rule, to 0 to 80% by weight, especially 5 to 40% by weight. The formulations may contain, if desired, also 0 to 60% by weight, especially 1 to 30% by weight, of a third herbicidal active substance from the group of aryloxyphenoxypropionic acids and their esters, preferably clodinafop, cyhalofop, fenoxaprop, fluazifop , haloxifop, propaquizafop, quizalofop or an ester of these compounds, especially clodinafop, quizalofop, quizalofop-etil or quizalofop-tefurilo.

Enantiomers of these compounds are also suitable, for example quizalofop-P. Quizalofop-P-ethyl and quizalofop-P-tefur Lio are suitable. The new formulations of the invention are diluted, advantageously, with water, for example in the tank mixing process, before applying them, before or after emergence on the plants or their habitat. The amount of water required here is, for example, 100 to 400 1 / ha. To reduce the pH of the tank mixture and to further increase the effect, it may be advantageous to add the usual adjuvants for tank mixtures in an amount of 0.1 to 5.0 kg / ha or 0.1 to 5, 0 1 / ha, for example, ammonium salts, such as ammonium sulfate and ammonium nitrate, urea, oil emulsifier additives and, especially, Dash HC (ex BASF). The suspension concentrates of the invention are prepared by intensively grinding the active substances a) and b) in crystalline form and the compound c), as well as, if desired, the auxiliaries and / or other active substances by means of ball mills, of pearls or agitator. Grinding bodies are used, for example, metal grinding bodies in a size of 0.1 to 30 mm, preferably 0.6 to 2 mm, and the suspension is comminuted, as a rule, for a sufficient time so that the average particle size is markedly below 10 μm. Here, it is particularly advantageous when the finely particulate active substances are dissolved quantitatively in the form of their salts by diluting them with water in the tank mixture. In this way the active substance is available to the plant in a homogeneous and practically monomolecular form, which is why, in particular, particularly advantageous herbicidal properties are achieved. High proportions of lipophilic auxiliaries and bipolar surfactants increase the penetration or transduction / transmission of the active substances in the leaves. Such auxiliaries are the native fats and oils and, especially, their fatty acid methyl esters, for example, methyl oleate. Using solvents, in which the cyclohexenone oxime ethers I are substantially insoluble in their free form (R2 = hydrogen), especially paraffin, it is also possible to grind these herbicides directly with N-phosphonomethylglycine. The present substantially anhydrous formulations also allow an application in the ULV process (ultra low volume), being able to For example, for aircraft application, mix or dilute the formulation directly with an anhydrous oil concentrate (eg Spraytex oil, a product of the Exxon Company) of approximately 10-50 1 per hectare, generally achieving a good compatibility The formulations of the invention stand out for being excellently effective against a broad spectrum of unwanted harmful plants. Furthermore, they are especially suitable for use in the control of the growth of unwanted plants in crops, in which the crop plant by means of an appropriate modification has been endowed with a high resistance against N-phosphonomethylglycine which itself acts as a herbicide total. The formulations of the invention are used as herbicides. The corresponding herbicidal products control very well the growth of unwanted plants on surfaces not intended for cultivation, especially in high amounts of application. In crops of dicotyledonous plants, genetically modified, highly resistant against N-phosphonomethylglycine, such as soybean, rapeseed, sugar beet, flaxseed, potatoes, lentils and cotton are active against weeds and unwanted grasses, without damaging them. to a degree worth mentioning to the crop plants. This effect already occurs with low amounts of application.

The formulations of the invention are especially suitable for controlling the growth of unwanted plants in soybean crops, the soy plants themselves being resistant against N-phosphonomethylglycine and its esters or salts. It has proved especially advantageous here that unwanted corn plants can be selectively combated, which can appear in soybean crops due to the annual alternation between soybeans and corn (the so-called "volunteer corn"). Depending on the respective application method, the formulations of the invention or the spray liquors prepared therefrom can be used in a number of other modified crop plants, to eliminate unwanted plants in them. The following crops are considered: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. , very high, Beta vulgaria spec. , rapa, Brassica napus var. Napus, Brassica napus var. Napobrassica, Brassica rapa var. Silvestris, Camellia sinensis, Carthamus tintoriius, Carya illinoinensis, Citrus limon, Ci trus sinensis, Cof fea arabica (Cof fea canephora, Cof fea liberica), Cucumis sativus, Cynodon dactilon, Daucus carota, Elaesis gineensis, Basque fragaria, glicinae max, gossypi jm hirsutum, (Gossypium arboreum, Gossypiium herbaceum, Gossapiuum vitifoliium), Helianthus annus, Hevea Brasiliensis, Hordeum vulgare, Humulus Lupulus Ipomoea batatas, Junglans regia, Lens cultinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manibot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), European Olea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, pirus communis, Ribes wild, Ricinus communis, Saccharum officinarum, Sécale cereale, Selanum tuberosum, Sorghum bicolor (S. vulgare), Theobroma cacao , trifolium pratense, triticum aestivum, triticum durum, Vicia faba, Vitis vinifera and Zea mays. The mixtures or the herbicidal products can be applied before or after the emergency. When the active substances are less tolerated by the crop plants, then application methods can be used, in which the herbicidal products are sprayed with the aid of spray apparatus in such a way that they do not fall on the leaves of the crop plants. sensitive, but only on the leaves of unwanted plants that grow below the first or on the ground covered with unwanted plants (post-directed, lay-by).

The application quantities of the ready spray mixture amount, depending on the end of application, the time of year, the target plants and their growth state, at 0.001 to 3.0, preferably 0.01 to 2.0 kg / ha active substances (sa). In addition, it may be useful to apply the spray liquor by itself only in combination with other herbicides, also in conjunction with other plant protection products, for example, with products for controlling parasites or phytopathogenic fungi, for example, bacteria. Additionally, miscibility is interesting with solutions of mineral salts, which are used to alleviate nutrient deficiencies and micro-elements. You can also add oil and non-phytotoxic oil concentrates. The growth of undesired plants is controlled in such a way that an active herbicidal amount of a phytosanitary active substance formulation based on the formulation according to the invention is activated on the crop plant, its habitat and / or the seeds.

EXAMPLES OF OBTAINING Example 1 Using 0.9-1.2 mm glass beads as grinding aids, generally at about 0-30 ° C, the active substances of components a) and b) are ground with component c) and, if desired , other formulation aids and / or herbicidal active substances. The active substance concentration amounts to approximately 10-60%, generally, to 30-60%. It is milled in a dynamic mill of the Bachofen Company, which has a preparation size of 0.5 to one liter, using the step method. After, generally, 5 steps (transportation of the suspension by means of a hose pump), mean particle sizes of 1-10 μm are obtained after microscopic evaluation. It is then incorporated and diluted with the other auxiliaries for 10 minutes. It is homogenized by means of KPG or -magnetic stirrers.

Example 2 Inputs (basic general recipe): 240-480 g / 1 of glyphosates (calculated on the basis of the proportion of pure active substance) -80 g / 1 of cyclohexenone-oxime ether 100-350 g / 1 of emulsifier (s) 1 1 with diluent / aprotic solvent Per 1 of oil suspension concentrate is used according to the basic recipe above, glyphosate, as a compound free or as salt, together with the emulsifiers, calculated on the basis of 0.9 1 volume. The components are prehomogenized, grinding for 1-2 minutes and transported by means of a hose pump in a glass or dynamic bead mill. According to the crystalline form and size of the active substance, glyphosate, the dry active substance must be pre-comminuted, for example with a pin mill.

Grinding parameters: Grinding vessel volume: 0.5 1, glass bead filling: approximately 80%, 1.0-1.4 mm diameter glass beads; 5 discontinuous steps; Cooling the mill with water (10 ° C inlet temperature and approximately 20 ° C outlet temperature). Typical particle sizes: 0.1 to 10 μm after grinding, especially 30-50% < 2 μm or smaller.

Homogeneous oil suspension concentrates are obtained in part slightly viscous or preconcentrated suspension of glyphosate-oil. Subsequently, the expected amounts of cyclohexenone-oxime I ether are introduced under stirring, if appropriate, as pre-concentrates diluted at about 20 ° C to the glyphosate-oil suspension concentrate (approximately 30 minutes by dissolving at 800 rpm), finally, complete the mixture with diluent or solvent at 1.0 1 a.

Example 3 Storage stability.

The glyphosate salts are prepared in a manner known per se, by mixing or homogenizing the corresponding metal hydroxides or carbonates and glyphosate, concentrating them in vacuum and drying them in the drying cabinet at 10-50 mbar during the night, generally. residual moisture of less than 0.5% water. The quantitative syndications for glyphosate salts are calculated based on the active substance, pure glyphosate.

The stability indications apply only to the cyclohexenone-oxime ether, since the glyphosates and their salts in the mixtures according to the invention are generally not subject to any degradation. As the cyclohexenone oxime I, 2- [1- (3-chloroalyloxy) -iminopropyl] -5- (tetrahydropyran-4-yl) -3-hydroxy-cyclohex-2-enone is used. rO n ro n n tn Table 1: *) according to serum analysis the lithium salt is transformed into the formulation by the glyphosate calcium salt, due to the residual acidity of the tribasic acid glyphosate in the mixed Ca-Li salt of glyphosate; **) alor obtained from two tests.

Explanations regarding the auxiliaries: Atlas G 1086 is a polyoxyethylene- (40) -sorbitolhexaoleate (CAS No. 057171-56-9); product of Uniqema Company, formerly ICI Surfactants; Solvesso 200 is an aromatic of CÍO substituted by alkyl; product of the Solvesso series of the Exxon Company; Aerosol OT-A is a sodium dioctylsulfosuccinate, CAS No. 000577-11-7, product of Cytec Company; Lutensol ON 110 is isodecanol ethoxylate; product of the BASF AG Company; Sokalan HP 50 is a polyvinylpyrrolidone; product of the BASF AG Company Example 4 Comparative examples In the comparative tests, 2- [1- (3-chloroalyloxy) -iminopropyl] -5- (tetrahydropyran-4-yl) -3-hydroxy-cyclohex-2-enone * is incorporated with the auxiliaries indicated in Tab.La 2 for agitation in Roundup® Ultra (product and label of Monsanto Company, 25% glyphosate). After storage for two weeks, the still present proportion of the cyclohexenone oxime is examined. r roo in n n Table 2; **) with respect to the active substance glyphosate ***) biphasic system after long rest, but easy to re-homogenize by agitation; ****) degradation of active substance > 99%; homogenous monobasic formulation The tests of examples 3 and 4 show that the cyclohexane oxime I ethers in the form of the oil suspension concentrate formulations, surprisingly, can be formulated n glyphosates, giving stable products.

Claims (10)

RE IVI ND I CAC I ONE S

1. A virtually waterless formulation of crop protection agents consists mainly of: a) at least one cyclohexenone oxime ether of the formula I where the variables are defined as follows: R1 is ethyl or propyl, R2 is hydrogen or an equivalent of a cation for agricultural use, R3 is 2- (thioethyl) propyl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, tetrahydropyran 3-yl, tetrahydropyran-4-yl, 1- (methylthio) cyclopropyl, 5- (isopropyl) -isoxazol-3-yl, 2,5-dimethylpyrazol-3-yl, 2,4,6-trimethylphenyl or 2,4,6-trimethyl-3-butyrylphenyl, R 4 and R 5, independent of each other, they are each hydrogen, methyl or methoxycarbonyl;

Alk CH2CH2, CH2CH (CH3), CH2CH = CH, CH2CH = C (C1) or

CH2CH2CH = CH, R6 is hydrogen, phenyl, halophenyl, dihalophenyl, phenoxy, halofenoxy or dihalophenoxy; b) N-phosphonomethyl glycine, an ester or salt thereof, BL-homoalanin-4-yl (methyl) phosphonic acid or its ammonium salt; c) from 20 to 80% by weight of a weak protic or aprotic solvent in which components a) and b) are dissolved or suspended; d) if desired, emulsifiers, surfactants, surface active auxiliaries and / or enhancers of the activity. 2 . The practically waterless formulation according to claim 1 comprises as component a) a cyclohexenone oxime ether selected from the group consisting of sethoxydim, cyclodexid, clethodima, tralkoxydima, butroxydima, 2- [l- (3-chloroalloxy) iminopro- pil] -5- (tetrahydropyran-4-yl) -3-hi-droxycyclohex-2-enone, 2- [1- (2-chlorophenoxypropyloxy) imino-butyl] -5- (tetrahydrothiopyran-3-yl) -3- hydroxycyclohex-2-ene-na, its alkali metal or alkaline earth metal salts or mixtures of these active ingredients. 3 . The virtually waterless formulation according to claim 1 comprises as component b) a mono-, di- or tri-protonated glyphosate salt.

4. The formulation practically without water according to claim 1 or 2, further comprises from 0 to. 80% by weight of at least one auxiliary of the formulation selected from the classes of ionic or non-ionic surfactants, surface active agents, dispersants, other solvents and thickeners.

5. The formulation practically without water according to claim 1, further comprises from 0 to 60% by weight of a third active compound as a herbicide selected from the group consisting of the aryloxy-Eenoxy propionic acids and their esters.

6. A process for preparing a spray liquid for the control of undesirable plants, which consists of mixing a formulation as claimed in claim 1 with ammonium salts, water and, if desired, other adjuvants for mixing in tank.

7. A lithium salt of 2- [1- (3-chloroalyloxy) iminopropyl] -5- (tetrahydropyran-4-yl) -3-hydroxycyclohex-2-enone.

8. An oil suspension concentrate, which contains mainly: a) at least one cyclohexenone oxime ether salt of the formula I where the variables are defined as follows: R1 is ethyl or propyl, R1 is an equivalent of a cation for agricultural use, is 2- (thioethyl) propyl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, tetrahydropyran 3-yl, tetrahydropyran-4-yl, 1- (methylthio) cyclopropyl, 5- (isopropyl) -isoxazol-3-yl, 2,5-dimethylpyrazol-3-yl, 2,4,6-trimethylphenyl or 2, 4 , 6-trimethyl-3-butyrylphenyl, Rq R5, independent of each other, are each hydrogen, methyl or methoxycarbonyl; Alk CH2CH2, CH2CH (CH3), CH2CH = CH, CH2CH = C (C1) or CH2CH2CH = CH, Rfe is hydrogen, phenyl, halophenyl, dihalophenyl, phenoxy, halofenoxy or dihalophenoxy; Or from 20 to 80% by weight of a weak protic or aprotic solvent in which component a) is suspended; d) if desired, emulsifiers, surfactants, surface active auxiliaries and / or activity improvers.

9. The oil suspension concentrate according to claim 8 contains as component a) at least one cyclohexenone oxime ether salt of the formula I, wherein R2 is an equivalent of an alkali metal or alkaline earth metal cation.

10. The oil suspension concentrate according to claim 9, wherein the cyclohexenone oxime ether salt is present in solution in the oil phase in an amount of less than 1%. SUMMARY OF THE INVENTION The invention relates to a practically anhydrous formulation of protective active ingredients r of plants consisting mainly of: a) an ether cyclohexenone oxime of the formula I wherein R1 is ethyl or propyl; R2 is hydrogen or an equivalent of a cation for agricultural use; R3 is 2- (thioethyl) propyl, tetrahydrothiopyran-3-yl; tetrahydrothio-pyran-4-yl, tetrahydro-iran-3-yl, tetrahydropyran-4-yl, 1- (methylthio) cyclopropyl, 5- (isopropyl) -isoxazol-3-yl, 2,5-dimethylpyrazol-3-yl, 2,4,6-trimethylphenyl or 2,4,6-trimethyl-3-butyrylphenyl, R 4 and Rs, are H, CH3, CO-OCH3; CH2CH2, CH2CH (CH3), CH2CH = CH, CH2CH = C (C1), CH2CH2CH = CH, R6 is H, phenyl, halogen phenyl, dihalogen phenyl, phenoxy, halogen phenoxy, dihalogen phenoxy; b) N-phosphonomethyl glycine, an ester or salt thereof, BL-homoalanin-4-yl (methyl) phosphonic acid or the ammonium salt thereof; c) between 20 and 80% by weight of a weak protic or aprotic solvent in which components a) and b) are suspended; d) possibly emulsifiers, surfactants, and additives for activated surface and / or reinforcers.