MXPA97007103A - Solid stable formulations of ciclohexenonoxim eteres herbici - Google Patents

Abstract

Formulations of phytosanitary active substances containing cyclohexenoxyether of the general formula I, in which the radicals R 1 -R 6 have the following meanings: R 1 signifies ethyl or propyl, R 2 signifies hydrogen or an equivalent of a cation useful in agriculture; R 3 means 2- (thioethyl) propyl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 1- (methylthio) cyclopropyl, 5- (iso-propyl) isoxazol-3-yl, , 5-dimethylpyrazol-3-yl, 2,4,6-trimethylphenyloxy-2,4,6-trimethyl-3-butyrylphenyl, R 4 and R 5 each independently of each other, hydrogen, methyl, methoxycarbonyl: alk means CH 2 CH 2, CH 2 CH ( CH 3), CH 2 CH = CH, CH 2 CH = C (Cl) or CH 2 CH 2 CH = CH, R 6 denotes hydrogen, phenyl, halogen phenyl, phenyl halogen, phenoxy, halogen-phenoxy or di-halogen-phenoxy, and a water-soluble basic salt of an acid with a pK value above 5, The hydroxides and alkaline carbonates are excluded, as well as their obtaining and use as erbicid

Description

Stable solid formulations of cyclohexenonoxim ethers herbicides Description The present invention relates to formulations of phytosanitary active substances containing a cyclohexenoxim ether of the general formula I, OR2 N- O-alqu- R6 Rl wherein the Ri-R6 radicals have the following meanings: R1 means ethyl or propyl; R2 means hydrogen or an equivalent of a cation useful in agriculture; R3 means 2- (thioethyl) propyl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 1- (methylthio) cyclopropyl, 5- (iso-propyl) ) isoxazol-3-yl, 2,5-dimethylpyrazol-3-yl, 2,4,6-trimethylphenyl or 2,4,6-trimethyl-3-butyrylphenyl; R4 and R5 mean, each independently of the other, hydrogen, methyl, methoxycarbonyl; Alk means CH2CH2, CH2CH (CH3), CH2CH = CH, CH2CH = C (Cl) or CH2CH2CH = CH; R6 signifies hydrogen, phenyl, halogen phenyl, dihalogen phenyl, phenoxy, halogen-phenoxy or di-halogen-phenoxy; and a water-soluble basic salt of an acid with a pK value above 5, as well as obtaining and using it as herbicides.

The cyclohexenonemimethers of the general formula I have long been known as herbicides. Furthermore, they are active in small amounts as growth regulators.

The cyclohexenonemimethers of the general formula I active as herbicides are known from DE-A 24 39 104, DE-A 28 22 304, DE-A 38 08 072, DE-A 38 38 309, EP-A 046 860, EP-A 066 195, EP-A 071 707, EP-A 088 299, EP-A 088 301, EP-A 115 808, EP-A 125 094, EP-A 137 174, EP-A 142 741, EP-A 177 913, EP-A 228 598, EP-A 230 235, EP-A 230 260, EP-A 238 021, EP-A 243 313, EP-A 254 514, EP-A 319 835, EP-A 456 068, EP-A 456 069, EP-A 456 112, EP-A 456 118, U.S. 4,440,566, JP-A 54/191 945 and Proceedings Brit. Crop Protection Conference -Weeds 1985, Vol. 1, p. 93 - 98.

The metal salts of the cyclohexenonemimethers are known, for example, from the earlier German patent application with file number 195 45 212.7.

These compounds are generally used in the form of water-dispersible powders (WP) or as water-dispersible granules (WG), as well as in the form of emulsifiable concentrates (EC). Some compounds of this class of substances are sold as water-soluble formulations, in which the active substance is present in the form of an alkaline salt. The disadvantage of these emulsifiable concentrates is that large amounts of organic solvents must also be added together with the active substance itself. Furthermore, it has been found that the active substances in the organic solvents are unstable in the presence of emulsifiers or traces of water and decompose (see, for example, EP-A 394 847 and EP-A 266 068).

The solid, water-dispersible formulations (WP or WG) do not contain organic solvents, but are often much more difficult and expensive to manufacture the formulation. For liquid active substances or low melting point frequently have to be applied on a support material to be subjected to the necessary fine grinding. The addition of auxiliary and carrier substances results, moreover, in that the contents of active substance in the formulations have to be low, which increases the costs of packaging and transport. Examples of formulations of this type are found, for example, in EP-A 488 645.

Water-soluble formulations have also been previously described. But here, too, it has been found that the chemical instability of cyclohexenonemyl ethers is counterproductive to a practicable solution. For example, a lithium salt is described in patent JP 62089 635.

In several patent applications, the production of different salts, inter alia, the salts of transient metals, is described by recrystallization of the salt. However, this procedure does not seem appropriate for the practice, since in the end a satisfactory stability is not reached (JP 59 1633 63, JP 8144 384, US 47 41 768, DE 3941160)..

The alkali salts are preferably obtained by extracting the active substances from an organic solution by means of an aqueous solution of the alkali hydroxides (for example DE 3941160).

The object of the present invention was therefore to develop stable stable formulations for the storage of cyclohexe-nonoxymethters of the general formula I, as well as a process for their preparation.

This object is achieved, surprisingly, by means of the formulation of active substance at the beginning described.

Cyclohexenonemimethers in the sense of the present invention are weak organic acids with pKs values between 4 and 5. Their low solubility in water in the neutral region markedly increases at basic pH values. So it is possible by suitable combination of cyclohexenones with water-soluble basic substances (acid acceptors) to obtain water-soluble mixtures.

In addition to the hydroxides and alkali metal carbonates mentioned in the literature, it is also suitable for those basic water-soluble substances which are to be considered as alkaline salts of those acids whose pKs value is much greater than 5. Preferably, the pKs value of the corresponding cyclohexenone and then a basic substance is selected whose fundamental pKs value is greater than that of the respective cyclohexenone.

It can be assumed that in the presence of water the following reaction takes place: A condition for the subsequent formation of a clear solution is, in addition, that the conjugated HX acid to be formed is also soluble in water.

In addition to the solubility in water, the formulations of the invention from cyclohexenone and basic salt (acid acceptor) have a much higher storage stability at high temperatures, than, for example, the free active substances or their alkali salts , obtained from the cyclohexenones with hydroxides or alkaline carbonates.

Satisfactory storage stability is an essential characteristic of commercially available and registrable phytosanitary products. Above this, a reduced decomposition of the active substance is in itself advantageous from the economic point of view.

In order to achieve water solubility and storage stability, the following active substances are suitable as basic, water-soluble salts: metaborates, phosphates, hydrogen phosphates, pyrophosphates, metasilicates, orthosilicates, tetraborates, sulphites, tripolyphosphates, polyphosphates, meta-phosphates, citrates , Tetrasodium EDTA, trisódiconitrilotriacetic acid, guanidine acetate, guanidine carbonate, as well as mixtures of the mentioned salts.

Preferred basic salts, soluble in water, are: metaborates, tetraborates, metasilicates, ortho-silicates, phosphates, hydro-genphosphates, pyrophosphates, tripolyphosphates, polyphosphates, sulphites, ammonium and alkali citrates, tetrasodium EDTA, trisódiconitrilotriacetic acid, guanidine carbonate, acetate of gunidina. The salts can be used in anhydrous form, as well as in the form of their hydrates.

Particular preference is given to alkali metaborates, alkali tetraborates, alkali and ammonium metasilicates, trialkaline and triamonic phosphates, alkali and ammonium hydrogen phosphates, alkali pyrophosphates, alkali tripolyphosphates, alkali sulphites, alkali citrates, tetrasodium EDTA, trisódiconitrilotriacetic acid, guanidine acetate, guanidine carbonate, the salts being able to be present in anhydrous form or in the form of their hydrates.

Sodium and potassium salts are preferred.

A tetrasodium pyrophosphate, dipotassium hydrogen phosphate, guanidine carbonate, tetrasodium EDTA, trisódiconitrilotriacetic acid, and above all, sodium metaborate, sodium metasilicate, trisodium phosphate, of which sodium metasilicate stands out above all have been especially accredited.

Preferred cyclohexenone herbicides are: 2- (N-ethoxybutyrimidoyl) -5- (2-ethylthiopropyl) -3-hydroxy-2-cyclohexenon-l-one (Setoxydim), 2- (1-allyloxyiminobutyl) -4-methoxycarbonyl-5,5-dimethyl-3-oxoxy-clohexenol (Alloxydim), 2- (N-ethoxybutyrimidoyl) -5- (2-phenylthiopropyl) 3-hydroxy-2-cycle -hexen-1-one, 5- (2, 4, 6-trimethylphenyl) -3-hydroxy-2- [l- (ethoxyimethyl) -propyl] -cyclohex-2-en-l-on (Tralkoxydi), 2- (N-ethoxybutyrimidoyl) -3-hydroxy-5- (tetrahydropyran-3-yl) -cyclohexen-1-one, 1- [1-ethoxyimino) -butyl] -3-hydroxy-5- (tetrahydrothiopyran 3-yl) -2-cyclohexen-l-one (Cycloxydim), 2- [1- [(E) -3-chloroalyloxy] -iminopropyl] -5- (2-ethylthiopro-pyl) -3-hydroxycyclohex-2- enone (Clethodim), 2- (1- (3-chloroalyloxy-iminobutyl) -5- (2-yl io) -propyl) -3-hydroxy-cyclohex-2-enone (Cloproxydim), 2- (1 - (3-Chloroxyloxy) -iminipropyl) -5- (1,3-dimethylpyraz-zol-5-yl) -3-hydroxy-cyclohex-2-enone, 2- (1- (3-chloroalyloxy) -iminopropyl) - 5- (1-thiomethyl-cyclopro-pyl) -3-hydroxy-cyclohex-2-enone, 2- (1-ethoxyiminopropyl) -5- (2,4,6-trimethyl-3-butyrylphenyl) -3-hi- droxi-cyclohex-2-enone (Butroxydim), 2- (1- (3-chloro lyloxy) -iminopropyl) -5- (tetrahydropyran-4-yl) -3-hydroxy-cyclohex-2-enone, 2- (1- (2-p-chlorophenoxypropyloxy) -iminobutyl-5- (tetrahydrothiopyran- 3-yl) -3-hydroxy-cyclohex-2-enone or mixtures thereof.

Especially preferred cyclohexenone herbicides are: Se-toxidim, Cycloxydim, Clethodim, Tralkoxydim, Butroxydim, 2- (1- (3-chloroalyloxy) -iminopropyl) -5- (tetrahydropyran-4-yl) -3-hydroxy-cyclohex -2-enone, 2- (1- (2-p-chlorophenoxy-propyloxy) -iminobutyl-5- (tetrahydrothiopyran-3-yl) -3-hydroxy-cyclohex-2-enone or mixtures thereof.

The cyclohexenonemimethers of the general formula I can be obtained in their preparation in the form of isomeric mixtures, with the E- / Z isomeric mixtures as well as the enantiomeric or diastereomeric mixtures being possible. The isomeric mixtures can be separated, using conventional methods, for example by chromatography or crystallization.

Cyclohexenone oximethers of the general formula I can be present in various tautomeric forms, all of which are encompassed by the present invention.

The invention comprises solid water-soluble formulations, preferably pulverulent or granular, which contain as a hardened component a cyclohexenonemimether and a basic salt soluble in water. The proportion of the cyclohexe-nonoxim ether varies between 5 and 95%, preferably between 10 and 85%; the proportion of the basic salt ranges from 5 to 95%, preferably from 15 to 90%, with respect to the sum of cyclohexenonoxim ether and basic salt.

To ensure proper application for practice, it may be necessary to add other formulation aids. These include, for example, compounds of herbicidal activity, antidotes, water-soluble salts, humectants, binders, lubricants, absorbent supports, defoamers, preservatives, dyes, pigments and other auxiliaries or surfactants customary in agricultural practice.

Additional water-soluble salts can be: sodium chloride, potassium chloride, ammonium sulfate, sodium sulfate, potassium sulfate, as well as urea, potassium carbonate and sodium carbonate.

As other compounds of herbicidal action can be used: 2,4-D, 2,4-DB, Acetochlor, Acifluorfen, Aclonifen, Alachlor, Alidochlor, Ametryn, Amidosulfuron, Amitrol, Anilofos, Asulam, Atrazin, Azimsulfuron, Aziprotryn, Barban, Benazolin, Benefin, Benfuresates, Bensulfuron, Bensulides, Bentazone, Benzofenap, Benzofluor, Benzoylprop, Benzthiazuron, Bifenox, Bisalafos, Bromacil, Bromobutidas, Bromophenoxime, Bromoxynil, Buminafos, Butachlor, Butamifos, Buten-acloro, Buthidazole, Butralin, Bu-turon, Butylate, Cafenstrole, Carbetamid, Chloramben, Chlor- bromuron, Chlorbufam, Chlorfenac, Chloridazon, Chlorimuron, Chlornitrofen, Chlorophenprop, Chloroxuron, Chlorpropham, Chlorsul furon, Chlorthal-dimethyl, Chlorthiamid, Chlortoluron, Cinmethylin, Cinosulfuron, Clodinafop, Clomazone, Clomeprop, Clopyralid, Cumyluron, Cyanazine Cycloates, Cyclosulfamuron, Cyuron , Cyhalofop, Cyperquat, Cyprazines, Cyprazoles, Dala-pon, Desmedipham, Desmetryn, Diallatos, Dicamba, Dichlobenil, Dichlorprop, Dichlorprop-P, Diclofop, Diethatyl, Difenoxuron, Difenzoquat, Dif Lufenican, Dimefuron, Dimethachlor, Dimetha-methryn, Di ethenamid, Dinitramin, Dinoseb, Dinoseb, Dinoterb, Diphenamid, Dipropetryn, Diquat, Dithiopyr, Diuron, DNOC, Dymron, Eglinazin, Endothall, EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron, Ethidimuron, Ethiozin , Ethofumesate, Ethoxyfen, Etobenzanid, Fenoprop, Fenoxaprop, Fenoxaprop-p, Fenthia-prop, Fenuron, Flamprop, Flazasulfuron, Fluazifop, Fluazifop-p, Fluchloralin, Flumetsulam, Flumiclorac, Flumioxazin, Flumi-propyn, Fluometuron, Fluorbentranil, Fluorochloridones , Fluo-rodifen, Fluoroglycofen, Flupoxam, Flupropacil, Fluridones, Fluroxypyr, Flurtamonas, Fomesafen, Fosamin, Furyloxyfen, Glu-fosinate-ammonium, Glyphosate, Halosulfuron, Haloxyfop, Haloxyfop, Haloxyfop-p, Hexazinon, Imazamethapyr, Imazapyr, Imaza-quin , Imazethabenz, Imazethapyr, Imazosulfuron, Ioxynil, Isocarbamide, Isopropalin, Isoproturon, Isourona, Isoxaben, Iso-xapyrifop, Karbutylate, Lactofen, Lenacil, Linuron, Maleic, Hydrazide, MCPA, MCPB, Mecoprop, Meco prop-P, Mefenacet, Me-fluidide, Metamitron, Metazachlor, Methabenzthiazuron, Metha-zoles, Metobenzuron, Metolachlor, Metosulam, Metoxuron, Metri-buzin, Metsulfuron, Minoterb, Molinates, Monalide, Monolinu-ron, Monuron, Napropamides, Napropanilides, Naptalamos, NCC 330, Neburon, Nicosulfuron, Nipyraclofen, Nitralin, Nitrofen, Nitrofluorfen, Norflurazon, Orbencarb, Oryzalin, Oxadiargyl, Oxadiazon, Oxyfluorfen, Paraquat, Pebulate, Pendimethalin, Perfluidones, Phenisopham, Phenmedipham, Picloram, Piperophos, PPG-1013, Pretilachlor, Primisulfuron, Procyazine, Prodiamines, Profluralin, Prometon, Prometryn, Propyzamid, Propachlor, Propanil, Propaquizafop, Propazin, Propha, Prosulfocarb, Pro-sulfuron, Prynachlor, gPyrazolates, gPyrazosulfuron, gPyrazoxy-fen, gPyributicarb, Pyridates, Pyrithiobac, Quinclorac, Quinme- rac, Quizalofop, Quizalofop-p, Quizalofop, Rimsulfuron, Secbu-meton, Siduron, Simazin, Simetryn, Sulcotrione, Sulfallate, Sulfentrazone, Sulfometuron-methyl, Sulfosate, Tebuthiuron, Terbacil, Terbucarb, Terbucher, Terbumeton, Terbuthylazin, Terbutryn, Thiazopyr, Thidiazimin, Thifensulfuron-methyl, Thi-obencarb, Thiocarbazil, Triaulfuron, Triazofena-id, Tribenuron, Triclopyr, Tridiphane, Trietazin, Triflura-lin, Triflusulfuron, Tri eturon , Vernolatos, Xylacloro or mixtures of these substances. The co-herbicides can be soluble or not soluble in water.

In the case of compounds that are not soluble in water, they are present as finely ground powders. In addition, it is also possible to incorporate these into the formulation as water-dispersible granules. In the case of water-soluble co-herbicides, these may be present in the form of the free acid or in the form of their salt.

As dispersants or wetting agents, for example, alkylaryl sulfonates; phenyl sulfonates; alkyl sufferers; alkyl sulfonates; alkyl ether sulfates; alkylaryl ether sulfates; alkylaryl glycol ether phosphates; polyarylphenyl ether phosphates; alkyl sulfosuccinates; olefin sulfonates; paraffin sulfonates; petroleum sulfonates; taurids; sarcocides; fatty acids; alky1-naphthalenesulfonic acids; Naphthalenesulfonic acids; lignin-nuosulfonic acids; condensed from sulfonated naphthalenes with formaldehyde; or with formaldehyde and phenol; sulphite residual liquors; including its alkaline, alkaline-ferric, ammonium and amine salts; alkylphenol alkoxylates; alcohol alkoxylates; fatty amine alkoxylates; polyoxyethylene glycerol fatty acid ester; castor oil alkoxylates; fatty acid alkoxylates; fatty amide alkoxylates; polydiethanolamides of fatty acids; lanolin ethoxylates; copolymers of EO / PO blocks; polyglycol fatty acid ester; isotridecylic alcohol; fatty amides; methylcellulose; esters of fatty acids; silicone oils; alkyl polyglycosides; fatty ester glycerol; alkyl phosphates; quaternary ammonium compounds; amine oxides; Betaine and mixtures of these compounds. Dispersants and humectants are known and described in greater detail, for example in: McCutchesons: Emulsifiers & Detergents, MC Divisiona, Glen Rock NJ; Stache, Tensid Taschenbuch, Hanser Verlag.

As binders there may be used: polyvinylpyrrolidone, polyvinyl alcohol, carboxymethylcellulose, starch, vinylpyrrolidine-vinyl acetate copolymers and mixtures thereof.

As lubricants, the following can be used: Mg stearate, Na stearate, talc, polyethylene glycol and mixtures thereof.

Suitable absorbent support materials are: mineral earths, such as silicas, silica gels, silicates, talc, kaolin, attaclay, limestone, chalk, talc, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate and sulfate magnesium, magnesium oxide, milled plastics, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, vegetable products, such as cereal flours, bark, wood and nutshells, powders of cellulose attapulgitas montmorrilloritas, mica, vermiculites, synthetic silicic acids, synthetic calcium silicates and their mixtures.

Suitable defoamers are silicone emulsions, long-chain alcohols, fatty acids, organic fluorine compounds and mixtures thereof.

The formulation auxiliaries can be used in a concentration of 0 to 95% by weight in the phytosanitary active substance formulation. They form an integral part of the formulation and have been accredited in a concentration of 5 to 95% by weight.

Other phytosanitary active substances can be added in a concentration of 0 to 90% by weight. They form an integral part of the formulation and have been accredited in a concentration of 10 to 90% by weight. The percents by weight refer to the total weight of the phytosanitary active substance formulation.

The solid formulations of the invention can be prepared by different methods known in principle to the expert.

Suitable formulations are powders, granules, agglomerates, tablets and similar formulations. The granules are especially preferred together with the powders. The powders can be soluble or dispersible in water. The granulates can be water soluble or dispersible granules, suitable for spray application, or they can be spray granules for direct application. The average particle size of the granulates varies between 200 μm and 2 m.

Since these formulations are frequently hygroscopic bodies, and for the preventive protection of the user, the formulations can be packed in water-soluble foil bags. Preferably, an outer water vapor tight coating, such as a sheet of polyethylene, a paper laminated with polyethylene or an aluminum foil, will be incorporated into the packaging.

Suitable water-soluble films consist of the following materials: polyvinyl alcohol, cellulose derivatives, such as methylcellulose or carboxymethylcellulose.

The fight against the growth of unwanted plants is carried out in such a way that an active herbicidal amount of the phytosanitary active substance formulation is made to act on the crop plant, its living space and / or the seeds.

The following obtaining procedures are suitable for the formulations of the invention: a) Active substance is solid 1) Mixture of active substance, basic salt and other auxiliary substances, optional comminution and subsequent agglomeration.

For agglomeration, for example, granulation processes in extruders, plate granulation, fluidized layer granulation or granulation in mixers are suitable. If necessary, the granules obtained are then dried. 2) Mixture of the active substance, the basic salt and the other auxiliary substances, optional crushing and subsequent compaction. b) Active substance is an oil or a solid 1) Extraction of the cyclohexenonoxim ether dissolved in an organic solvent by an aqueous solution of the basic salt in the aqueous phase and subsequent removal of water.

Suitable organic solvents are non-miscible or partially miscible solvents with water, such as, for example, hydrocarbons, aromatic hydrocarbons, aliphatic or halogenated aromatic hydrocarbons, ethers, carboxylic esters, carboxylic amides, ketones, alcohols.

For the evaporation of water, for example, spray drying, vacuum drying, fluidized bed drying, lyophilization are appropriate.

The solids obtained here can be further processed in the manner described in a).

In addition, the obtained aqueous solution can be applied on an absorbent support, for example by spraying or mixing. In this way, it is possible to obtain, for example, spray granules.

Formulation examples: a) Test methods The active substance content of the formulations is determined in each case by means of quantitative HPLC and is indicated in percent.

Storage stability tests To examine the storage stability, samples of the corresponding formulation are stored for a determined period in sealed glass containers at the indicated storage temperature in each case. Next, the samples are examined and compared with the comparative value determined at the beginning of storage (zero value). Content The active substance is indicated as a relative proportion with respect to the zero value (in percent).

Examples relating to dissolution behavior 2 g of the formulation are poured into 100 ml of standard CIPAC D water, which is stirred by means of a magnetic stirrer with ca. 100 rpm. The time that has elapsed until the solid product is measured is measured with a stopwatch has decomposed or is dissolved. b) Formulation tests For the formulation tests the following were used compounds: Compound A Setoxydim Compound B Cycloxy im Compound C 2- (1- (3-Chloroxyloxy) -imino-30 propyl) -5- (tetrahydropyran-4-yl) -3-hydroxy-cyclohex-2-enone Compound D: 2- (1- {2-p-chlorophenoxypropyloxy) -imino-butyl-5- (tetrahydrothiopran-3-yl) -3-hydroxy-cyclohexenone Comparative example 1 51.4 g of compound C (content 97%) are mixed for 60 seconds with a mixture of 1 part of sodium carbonate and 1 part of sodium hydrogen carbonate (48.6 g) in an IKA laboratory mill (type M 20). ). The mixture dissolves in water within less than 5 min. The content of active substance is 49.3%.

Example 1: 51.4 g of compound C (content 97%) are milled for 60 seconds with sodium metasilicate (48.6 g) in an IKA laboratory mill (type M 20). The mixture is soluble in water in clear form within less than 5 min. The content of active substance is 42%.

Example 2: 51.4 g of compound C and 48.6 g of trisodium phosphate dodecahi-drato are mixed in the manner described in example 1. Active substance content: 46%.

Storage stability at room temperature is observed for 3 months and compared.

Comparative example 2: 500 g of active substance C are dissolved in 1000 g of toluene. This solution is mixed for 1 hour with a solution of 58.5 g of sodium hydroxide in 650 g of water. After separation of the phases, the homogeneous aqueous phase is separated and then dried in a laboratory fluidized bed granulator at 120 ° C inlet temperature of the drying air, giving a granulate. The content of active substance amounts to 86.8%. The granulate dissolves quickly and completely when introduced into water.

Comparative example 3: 92.3 g of active substance D are dissolved in 90 g of toluene. This solution is mixed for one hour with a solution of 7.66 g of sodium hydroxide solution in 100 g of water. After phase separation the homogeneous aqueous phase is separated, washed with MTB-ether and then dried in the drying cabinet at 40 ° C drying temperature, giving a solid product. The solid product has an active substance content of 87.1% and dissolves quickly and completely when introduced into water.

Comparative example 4: A 30% solution of active substance D in toluene is extracted with 2.5% NaOH. The aqueous phases are collected and dried at 70 ° C in the vacuum drying cabinet. The solid obtained has an active substance content of 84.6% and dissolves in water within 2 min in clear form.

Example 3: 50 ml of a 50% solution of compound A in tere. -butylmethyl ether is stirred with a solution of 10.2 g of sodium metasilicate in 50 ml of water. Having separated the aqueous phase, the ether phase is washed with 30 ml of water. The combined aqueous phases are concentrated at 70 ° C in a vacuum. The solid residue obtained is soluble in water within 2 min in clear form. Content of active substance: 70%.

Example 4: 50 ml of a solution of Cycloxydim (compound B) in Solvesso 150 (430 g / 1) are extracted with a solution of 17.7 g of sodium metasilicate in 85 ml extrahiert water. Having separated the aqueous phase, the organic phase is washed with 30 ml of water and the combined aqueous phases are concentrated at 70 ° C in a vacuum. The obtained residue is soluble in water within 2 min in clear form. Active substance content: 57%.

Example 5: A mixture of sodium hydrate metaborate (48.6 g) and compound C (51.4 g) are mixed, first, in a universal mill I-KA, type M 20, and then successively mixed with 7.2 ml of Water. The mass thus obtained is dried in an extruder with cage, table apparatus, (Fitzpatrick Company Europe, type ICAR 75) given a sieve size of 0.8 mm. The obtained granules are dried at 60 ° C. Content of active substance: 55%. The granulate dissolves completely in water in less than 4 min.

Example 6: A mixture of sodium phosphate dodecahydrate (58.9 g) and compound C (41.1 g) is extruded with the addition of 3.8 ml of water in the manner described in example 5. Content of active substance: 52%. The granulate dissolves in water within 3 min in clear form.

Example 7: A mixture of sodium metasilicate (48.6 g) and compound C (51.4 g) is extruded with the addition of 25 ml of water in the manner described in example 5. Active substance content: 45%. The granulate dissolves in water within 2 min in clear form.

Example 8: A mixture of compound C (72%) and sodium metasilicate (28%) is mixed in a universal IKA mill, type M 20, and mixed by the addition of, in total, 22.5 g of water. The obtained mass is extruded in the manner described in example 5 and the obtained granulate is dried at 60 ° C. Content of active substance: 64%. The granules dissolve within 2 minutes in water in clear form.

Example 9: 217.5 g of active substance C are dissolved in 200 g of to-luene. This solution is mixed for one hour with a solution of 82.5 g of sodium metasilicate in 300 g of water. After the phase separation in the separating funnel, the homogeneous aqueous phase is separated and then dried in a laboratory fluidized bed granulator (Co bi Coatosr, Cia. Niro Aeromatic) at 120 ° C inlet temperature of the drying air , giving a granulate. The content of active substance amounts to 64.2%. The granulate dissolves quickly and completely in water.

Example 10: In 100 g of water are mixed and reacted with 16.0 g of sodium metasilicate and 84.82 g of the active substance C. An aqueous solution is formed. This is dried at 70 ° C in the drying cabinet, giving a solid product. The content of active substance amounts to 73.7%. The solid product dissolves quickly and completely in water.

Example 11: 79.8 g of active substance D are dissolved in 100 g of toluene. This solution is mixed and reacted for one hour with a solution of 20.8 g of sodium metasilicate in 100 g of water. When it is left at rest, 3 phases are formed. The two lower aqueous phases are separated in the separating funnel and then dried at 70 ° C drying temperature in the drying cabinet, giving a solid product with an active substance content of 78.7%. The solid product dissolves quickly and completely in water ..

Example 12: 88.75 g of the active substance D are dissolved in 100 g of toluene. This solution is mixed and transformed for one hour with a solution of 11.6 g of sodium metasilicate in 100 g of water. When it is left at rest, 3 phases are formed. The two lower aqueous phases are separated in the separating funnel and then dried at 70 ° C drying temperature in the drying cabinet, giving a solid product with an active substance content of 88.4%. The solid product dissolves quickly and completely in water.

Example 13: Compound C (7.6 g) and bentazone sodium salt (84.7 g, contained approximately 85%) are mixed intimately in a universal laboratory mill with sodium metasilicate (7.7 g) and then moistened with 8 g. , 5 ml of water. Having extruded the mixture, you get a granulate that soluble in water within 1 min in clear form. Content of active substance (compound C): 6.8% Example 14: As described in example 13, 84.7 g of bentazone Na, 7.6 g of compound C, 7.7 g of sodium metaborate and 6 ml of water are mixed and extruded. The obtained granulate dissolves in water within 1 min in clear form.

Content of active substance (compound C): 6.5% Table: Results of storage stability tests of active substances in formulations at certain temperatures and during a storage period of 30 days. The relative content of the active substance (%) is indicated with respect to the initial content.

° C 30 ° C 40 ° C 50 ° C Ex. comp. No. 2 100 99 88 42 3 100 98 88 40 4 100 96 80 19 Example No. 4 100 100 96 96 5 100 100 98 83 6 100 99 99 87 7 100 100 100 99 8 100 100 100 100 9 100 100 100 78 10 100 100 99 77 11 99 99 99 85 12 99 99 99 90

Claims (6)

CLAIMS 1. The use of1 a. sa basic 1 soluble in auua of a? > . That it has a higher value than the alkaline; and c a rbon .. t -. of metale.- .lcalinir., par3 the prep raci n un., ot ol a > In addition to the active compounds for the protection of crops, soluble in ^ and m, it is for the first year, which includes the ether and the formula. general I where the *. radicals P1-P6 i nen os identifies meanings: R 1 is ethyl or p rop 11 o; P2 is hydrogen or an equivalent of a cation that can be used in agriculture 5 P3 is 2- ioet i Ipropi, tet rahidrot iop i ran - 3 i1, tel rahidrot iopí ran-4-? Lo, tetrahidropi ran- 3-? What is tetrahydrapyriran-4-i lo, 1-me 11 t 10c icloprapilo,? i i sop rop i 1 i so: < at nal -3-. what, 2,5 - di m t i lp i weird! -3- i lo, 2,4,6-pmet 11 fem lo or 2, 4,6-tr i met i 1-3-but i ri 1 pheny 105 P4 P5, independently of each other are hydrogen, methyl or well I put;, icarboni 1 o; At i > - > < • ...? HP? .G;, p-THI? H3. ,? HG? H-CH, CH2CH-C < CI. O bien CH2CH2CH-CH; Pó, s hydrogen, fem », lulofeTu So, d i has 1 o1 eni lo, feno. i, has 11 > phenoxy i or d .11 -t 1 • > O- ».) :, i; for »on?" ru3 a. r -Í t »- '. j.-d <? i ón not -nt-a a _ 2. Fl so do vm - ,, 41 .. |? 4. lnble on * ym •.}. .. • nr¡ for my dad with the ¡viviiiijn ".i? ó * > 1 t -.- iitj.ii den Go »" »of the rupo ue?" On ..? a e ile tnií t jbi > ? - < lo, fo.f'ttij, f os f a »- '".? to hydrogen, P 3 l'Q f i .1.1 f -. ti Ifll-l ¡i i > ? s 11 i c t l í h.ii a! • o. f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f f ff ff FDT A trindi?., 11 flr ¿1 oiriu? - > 111 ot »i -od 11, a. j t.t tu e guaní di na, c 3 rbona ¡n rio g < n.¡.d ¡mn I > »- n OIÍ-.T] J 3 of loa os for the [H WC III. 'H mu fo? Ul-solid ion of the" OlH | IU to- af I i ": ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,. -? - 1! 1 g --11> -, o.¡? | - > 3o? - > n ¡ju-? Lipn o de grupo qn? I COÍG.J 5J? "? -1 di --- m. Bi 4 '1 i-' mi-d 1 l .a-, -111., 1 Ii'abora lo t- ifn- ': &l os. ]? ~ al ??> fi?,? n > jl -.- ij 1 j?. li. i.le ammonium and etalen. 3 lo 3 nos, fo .fa o > J »11.1.M..Ü x. tiiiH read lri. -i3 l. no., f? '? f-i l atitOfU -.i f > I said eno and do a--! a 3 > -. > • - > ! ! 1"to 1 jn» .-->, pi rofosfato di-- 'o I - < 1 e * -. A 3? - ~ - <! 1,,, -:, 1 > > 1 f., -, f, l>, 13, -3 »•« (= »l, ^ t 1 > -»;, a li. A 3 J () • ") -; ,. »13 f 'l > 1 i '«n- 3 o- a 3 • .3 1 ¡ti,, j pol 1 fo-i -H • 1 do me lal» - - al ».1 n«? .- rr. ? ! ), < , »? 'I? - m lrt l» d? 1 -o.-ol - t > "» Iri -iócIjCO, f a r! »? ?? -i 1 »») »•» i '-í i? 11 n-? , < 4C > J * t > > > l? yii lllld l! W 1. luen mor »- < -. ilf- »3 > 1-. t > m? »., f > 1 ia la fuvfi n'di fn do ¡pn f rmu 3 a '"i? Nd" - 1 1 1 .1i1.1sti - -1 »!, (.0-. -ól t" "i -i pa 3 • < &3; > - >? 1 io of the harvests in accordance with 3rd re gard - A > - > - on reivi dication 1 to well in la rei vin »d? ca» :: ión 2, 4. The use of a basic salt soluble in ag a> g. with fond d with cua 1 is uí raí 'of the reivin ications ta 3 pta the preparation of lin f > tm? lac io n sol? »:! a> g y cm o" • * * - 3 t vos for the ei ct ón of the harvest-n, »" jue c » imprani e < orno; ompnosto ac ivo e? ro3'e. "ci p of the" oner. -i a.'- let do o. f »ta» ie cyclulu .. eiwna within the group that your isti- »..ooo; itma- i. Nil i jdiitta, let ima, * ra3» o, j on, bu h'fn idi ma, 2- < 1- í3- 1 o roa 3 i 1 o: -, i ) a? no í i 1 '< - "" »-tetrah i drop i rap-4- i 1' '-3 -hidt o; iciclohe. * - -enone,"' - M- '2 -? - -1.1 ro phenol 'J roft i 1 ».»: I "' --i i nnbut i l-'i-fte r h rot l p i GJH- "* .- i 3) - 3-h idroi; ? > : i lo-ho: 2-enona or m ar ían of lo. i nino ».. _ > . The use of a soluble salt in a and na »ie cor» f > -. np »1a» 1 »~. (i -t 1 ski i »e la- = ry ivini». a ss for a solid formulation »-ie i > - > can, o'i ai i »vo> μai'3 the protection of the first, that? -omp ren e -i.-tem.-i-an, i 3 ia res of formul ión., or,. use of a sl-ho ^^^ soluble in a »jn do c» -m fin 'f d-> d • n cu <: f 1 siqu er i do 1? ari inclii ipn nb 1 a ^ ¡> ..? - 1 a pr o? Ü 'i ón »1 > - > a f ui-i i ón -aól ida > de c»: n? ¡Pf fe =, =. »I? V» -.? - > ri 3-f pt '?) »» Ju < ót? e l -., cosei has, that l omprende 3 liorna .-. ? n i 3 i A i o-, of f 11 i-mu 1 '4 »J ó? i, ", F3 n -? _? of mine .3 I) - • water soluble solution of > For example, it is necessary to prepare a single formulation of compounds for the protection of crops, which includes f g ^ '. : > of an ether of o. * ima di c? clo e?> nopa of the general formula I, from 5 to ^ by weight of a basic sl soluble in a »3¡-fa t from 0 to ( ^ "5" by weight of a formulation agent, of 90% by weight of additional active compounds for the protection of seams 8. A solid formula of compounds for each protection. of the crops, soluble in water, stable, comprising an ether of UMKI. »ie ci lahe. anona de la ft muí-general I • where radicals R.-P6 have 1 > DS next igrp f icado; P 1 is ethyl or propyl or P 2 is hydrogen or an equivalent of a cation that can be used in agriculture; 3 is 2-t loet 1 lpropí lo, you rah id rof íop 1 ran-3-? what, tet rahidrot lopí i n-4-? what, tetrahydropyr -3- 1 lo, tet rah id rop i ran-4-? lo, 1-met 111 ioc iclaprap 13 > : > , 5-1 sa op i 1 iso. azo] -3- J 1 o, 2, 5-d imet 1 lpi rano1-3- 11 »n, 2,4,6-tpmet 1 Ifeni lo or else 2,4,6-tr imet 11-3-but ip 1 fe i lo; * R P and R,? N »je or (i» erd órnen e between the are hydrogen, me il »» or bi n nwl, "ic. Rhoni 3 o; All e ~ CHSCH ?, rn? L? H < CH3>, CH2CHßCH, CH2CR = C (C1. Or CH? G, H2? H-CH; R? E-5 hydrogen, fem l>., Halophenyl, diha lofeni 1, ferian i, hali If you have a K above 5 - o- 3 u \ hydride oxides of alkaline metals, • to i hona I or > do im- '- > 3 e-, to 1 -. to the mua, a-í co or ammonium salts. Q. Uu3 for mula »i ón -.?l wave > ie »> .mpnes. QS ac 1 ivon for the Iro ei-i i on »lf * l -t > ? »»: -o? .hj -. , -lolnble n water, e t bl, de • ou ff > r does not give »! i on 1 ¡I H,, I H¡IIH ai. i n 8, thu understands how • i impii e-.l or ai i, i uu n u. 1 i protection of the harvest, an ether of o 'oita de i o 3 ... in-' -oii iii eulro de3 grupo consißle de se »1 oil i.i-t, i. ? ? I -, i i 1 i.; .1 eto i ma 3 ra 1 »: s?» I ima u 'ni i d i ni -',? - 3 - (- c 1 »:? R or 111».: I) uni i? Op rop il) - - (lf »1 r bil i rop» i -o i- 4 i 1. - " ", - huiro» »3>: 1 ot le; -. -2-enona,? - p - í 2 ~ -p-». lo iof? i ?? "?» tp i 1, < -> > > oi uotint i 1 -5- f tet rah i rot ipi ra u - 3 -i 3 > -3 - h id ro; o o o »» • • -7 i -'fürn or niís'cla ».ie l» n my smos 3. A f? rm >? n? a? &? g? n? n .umpues tos 13 vos pa a la ro ttr * o 1 ói te 3 i > i »! •• it .i" -, "-» > ") 3 >» blo f- i Í I. J »..a , of i »..U f Ol'ilM i 'i' on ii. .._- - ,. if i- 1 - (i | f 3 a .. IO f V i fld if MI p) l |;, f)? _ > 9, that i Ouip fi ti fi l, l, i, i u u u e in a ua M ol now to, f?) - fp li), fo-- f = t »» di- '!. ili? I- II) j μ 11 of sfa to, m »- *? t -x, 1 ¡i -fio, i¡lo - 1 3 fi -i I 11 , '' I, I, I, I, I, I, I, I, I, I, p ai o, FDT A I, p só ic, ni i, r »3 n 'j a» o. trisódica, rel ato e «jn -ip id > na, carbonate of gn - M • d m-. or else I ... "" those of the same ... 11"A clear formulation -i ^" «imputo- a. í» r v-, ¡-ii the 5 p eelec tion of the.- cfCn-'i Ipa, s ». > 3 ubi o in '" - «u, de uní f orm» Ja «on cu. le -. ».. ¡u i > »» E the re i v md i », n. i u »? > - _ R o 9, gue ». omp rende co o -.a I b? 11 > - -i, ..liuble in ai? a niel.? ural, u (je alkalino metals., tol abi ira tu de metale-a to 1 -41 KÍH?, m '. s 31 i ca • oem «-» tril? r. 1 ». J.1 i no .., phosphat« .le -tu- *, 3 o-. 10 I. r i a 3 > ra 1 i no, phosphate > .le h 3 di Ó »J > -.MI > . > or put it on »- < 3? No-., Pirofoafato fie metale- • 3 c to I ino-n, t r i μ ".l i f o.a f ato e im-., J 1 o -, a 1 c a 1 i nos, its 1 f i to > : ie me - 11 ... alc l i no-,, pol f. - =. f a t, or of alkaline metals, F.DTA l r i -sod i ro, nor t 1 1 a ». eta to t, r i. só »J i co, i rbona to o ijo a i na, ac t to de ijiia- ünki o 15 b 11-'1 !! tiierl's of loa m i _ > a ... 32. A formulation can be given (1) to 1, 2, 3, 2, 1, 2, 1, 2, 1, 2, 1 , set up.> | or with «3a« .i with the-, re vi n n n ac - - R R R R R R 4 4 4 4 4 11 11 11 11 11 11 or or or or or or or or or or or i n.? ("; 33. A formul to»: on sol t »L? of omp > > as active, par -i the pcotecc ion of the-, i ii.iO has. -lob him in -jgua, e '-'.! g, or »onformidatl with 1 a - :, í ..? ud? c. (C lone-. R a 3 ?, that onipreude J l ??? ti? compues o.- .oli vu. for] ^ pro'l "io" .i »• l as i o.» o h -i. ".i? f > -g? 1 l da .- inpno-,! í, ai ti vos. p. iai -. proloc t ón -le la.- «o -.e..h i -, soluble rí a« jua, esiahl, of a form with cu-t le-, qn n »r. or the rejections R a 13, qu. -1 comf > ren »: ie from 5 to 95 *. in t.-m? .le he «-i e o,, i? b de > : i »: 1 ohe- < - > n > > n-? of the 5 general formula 1, of 5? in id «-j fui-" '-a.3 I?' r; ni .oluble e gu4., do 0 3 95 *. in e fio mi -, < to 0 * eu commuesto peso 1 - »ut 1 v is a» iu: «.« > na 1 o'- ¡m 4] d pr'otec: c 1 of the * > ~ n »»? ha .. tO 15. I tu ¡imcH.'i? - < r, (l? p «'' jp« to »f on a fcmnl i?? n .ól? >!? de» _ mpuestoa --t¡ I ¿j? ¡¡¡¡¡- »3 4? ro» a- > >? ói? de la--, 1 .1 .I- h -.-, de L »> nfr 1> .laci with 1-t.? »e 1., - 1, say 1 in - f), 4 14,» «or« - • > up > i- ' f »e the one of an ei of .Jo 11, >? (1-? ¡? - > n f., oi?" H do 1 ffi iiml-i > - «enei al I, of 1-,,. | ii nn.-i solubl »-'U - <? j ?? < .do? - 15 a¡ui! (res do fi mnlai on, -,? ^, le : -, * • »3 _ and» »>? 11. 11. - - -, I» »-. Assets to» J 1 rÍOÍI-41 or-- - -i I ulei i 1 of 1 -, 1 0 »» i 1., or S »- ', the li'l lo * - > ffo, .. f -ed .ie, and de -.μnn'-'. a agglomeration or ti 3 eu 1 HUIF "tai t n. le ',, a proc.e.io o a l -i ¡it'i-' .i 4? U 'I of Hita ffir l .i 1 ío, 3 («i t 7"jf]? -. 1 ompnost" .siii vo-i pa 1 -4 3 - ro!, »- 1! • 1 ón de l -. 1 1» -.g- .- 11 <,; , -, - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - -

1-1, that i'fimpt »-» f »» "1e 1 - < > \, -11! ._ *.?, - ', p? ¡? -_ in the oi'?!? I .) &? f? i.lo f "3». I olio; .4 n > i'-f »i 1.1 fói mul -i ijorior-. l I oU ntt -,? p .'.- ii '^ pi'ijíinn,! < -_ e; I i .1 1 1 1?, N a --ulm j ón. »U»? -? . d »1 1.-1 i? ri ll - '* -. 1» a Si.lnbl e 1- ^ 1 -f »f.i f \? li' - pne-? 1 -1 1 '?'? Ll? Ir 1 i'-li d »3 n.11, 17» A process in conformance with the rei indicates », ion 16, where the formula soli» ja of active compounds for the pt'ole'c. 1-to-1-coars are crushed, if desired, after the water is re-ionized and then agglomerated or compacted, 3 18. A process in accordance with any »ie 3:, claims 1 * 3 or 17, where a granulation ion is used by or t t í a, rt gra,, i i i en en en en en. ! j cc »s, granular i n eu» _? ¡? f3? f > d? or 3 ??? - u gi cancellation in mixer for 1 -4 > • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • - »fine quantity herbr» "?«] Ament «- 41. l, ii nri formul -ttn .-, 01 wave of active compounds p ri l -? teo i ón de l < «• • > : > e? -l, n-s, of oonf or i »jad con io i o i v i nd t > .. gone in 1 to -i laughed i saw fifi or i i s 8 to 14 and > : Ffe pei mi te * "» ai 1,11.1 'inb. E la p larda. »E i o-.ee ha, your habi at / o -ms -, em i 31-4 - .. SUMMARY OF THE INVENTION. Formulations of phytosanitary active substances containing a cyclohexenoxim ether of the general formula I, wherein the Ri-R6 radicals have the following meanings: R1 means ethyl or propyl; R2 means hydrogen or an equivalent of a cation useful in agriculture; R3 dignifies

2- (thioethyl) propyl, tetrahydrothiopyran-

3-yl, tetrahydrothiopyran-

4-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, 1- (methylthio) cyclopropyl,

5- (iso-propyl) ) isoxazol-3-yl, 2,5-dimethylpyrazol-3-yl, 2,4,

6-trimethylphenyl or 2,4,6-trimethyl-3-butyrylphenyl; R4 and R5 mean, each independently of the other, hydrogen, methyl, methoxycarbonyl; alkyl means CH2CH2. CH2CH. { CH3), CH2CH = CH, CH2CH = C (C1) or CH2CH2CH = CH; R6 signifies hydrogen, phenyl, halogen phenyl, dihalogen phenyl, phenoxy, halogen-phenoxy or di-halogen-phenoxy; and a water-soluble basic salt of an acid with a pKs value above 5, hydroxides and alkaline carbonates being excluded, as well as their preparation and use as herbicides. . -.