Patent EA-000880-B1 (EA)
Title: STABLE SOLID FORMULATIONS OF CYCLOHEXENONE OXIME EtHER HERBICIDES
Inventor: BRATZ MATTHIAS
IPC: A01N43/18
Filed: 1996-03-12
Abstract: 1. The use of a water-soluble basic salt of an acid having a pKa of greater than 5, alkali metal hydroxides and alkali metal carbonates being excluded, for preparing a storage-stable, water-soluble crop protection solid active compound formulation, comprising a cyclohexenone oxime ether of the general formula I   where the radicals R<1>-R<6> have the following meanings: R<1> is ethyl or propyl; R<2> is hydrogen or an equivalent of an agriculturally utilizable cation; R<3> is 2-thioethylpropyl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, tetrahydropyran-3-yl, tetrahydropyran 4-yl, 1-methylthiocyclopropyl, 5-isopropylisoxazol -3-yl, 2,5-dimethylpyrazol-3-yl, 2,4,6-trimethylphenyl or 2,4,6-trimethyl-3-butyrylphenyl; R<4> and R<5> independently of one another are hydrogen, methyl or methoxycarbonyl; Alk is CH2CH2, CH2CH(CH3), CH2CH=CH, CH2CH=C(C1) or CH2CH2CH=CH; R<6> is hydrogen, phenyl, halophenyl, dihalophenyl, phenoxy, halophenoxy or dihalophenoxy. 2. The use as claimed in claim 1, wherein the salt is selected from the group consisting of metaborate, phosphate, hydrogen phosphate, pyrophosphate, metasilicate, orthosilicate, tetraborate, sulfite, tripolyphosphate, polyphosphate, metaphosphate, tetrasodium EDTA, trisodium nitrilotriacetate, guanidine acetate, guanidine carbonate or mixtures thereof. 3. The use as claimed in claim 1 to2, wherein the salt is seledted from the group consisting of alkali metal metaborate, alkali metal tetraborate, alkali metal and ammonium metasilicate, trialkali metal and triammonium phosphate, alkali metal and ammonium hydrogen phosphate, alkali metal pyrophosphate, alkali metal tripolyphosphate, alkali metal sulfite, alkali metal polyphosphate, tetrasodium EDTA, trisodium nitrilotriacetate, guanidine carbonate, guanidine acetate or mixtures thereof.n claim 1 or 2.  4. The use as claimed in claims 1 to 3 for preparing a crop protection solid active compound formulation, comprising, as crop protection active compound, a cyclohexenone oxime ether from the group consisting of sethoxydim, cycloxydim, clethodim, tralkoxydim, butroxydim, 2-(1-(3-chloroallyloxy)iminopropyl)-5-(tetrahydropyran-4-yl)-3-hydroxycyclohex-2-enone, 2-(1-(2-p-chlorophenoxypropyloxy)-iminobutyl-5-(tetrahydrothiopyran-3-yl)-3-hydroxycyclo-hex-2-enone or mixtures thereof. 5. The use as claimed in claims 1 to 4 for preparing a crop protection solid active compound formulation, furthermore comprising formulation auxiliaries. 6. The use of a water-soluble basic salt as claimed in claims 1 to 5 for preparing a crop protection solid active compound formulation, furthermore comprising formulation auxiliaries. 7. The use of a water-soluble basic salt as claimed in claims 1 to 6 for preparing a crop protection solid active compound formulation, comprising  from 5 to 95% by weight of a cyclohexenone oxime ether of the general formula I, from 5 to 95% by weight of a water-soluble basic salt, from 0 to 95% by weight of a formulation auxiliary, from 0 to 90% by weight of further crop protection active compounds. 8. A stable, water-soluble crop protection solid active compound formulation, comprising a cyclohexenone oxime ether of the general formula I   where the radicals R<1>-R<6> have the following meanings: R<1> is ethyl or propyl; R2 is hydrogen or an equivalent of an agriculturally utilizable cation; R<3> is 2-thioethylpropyl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, tetrahydropyran-3-yl, tetrahydropyran -4-yl, 1-methylthiocyclopropyl, 5-isopropylisoxazol -3-yl, 2,5-dimethylpyrazol-3-yl, 2,4,6-trimethylphenyl or 2,4,6-trimethyl-3-butyrylphenyl; R<4> and R<5> independently of one another are hydrogen, methyl or methoxycarbonyl; Alk is CH2CH2, CH2CH(CH3), CH2CH=CH, CH2CH=C(C1) or CH2CH2CH=CH; or CH2CH2CH=CH; R<6> is hydrogen, phenyl, halophenyl, dihalophenyl, phenoxy, halophenoxy or dihalophenoxy; and a water-soluble basic salt of an acid having a pKa of greater than 5, alkali metal hydroxides, alkali metal carbonates and ammonium salts being excluded. 9. A stable, water-soluble crop protection solid active compound formulation as claimed in claim 8, comprising, as crop protection active compound, a cyclohexenone oxime ether from the group consisting of sethoxydim, cycloxydim, clethodim, tralkoxydim, butroxydim, 2-(1-(3-chloroallyloxy)iminopropyl)-5-(tetrahydropyran-4-yl)-3-hydroxycyclohex-2-enone, 2-(1-(2-p-chlorophenoxypropyloxy)-iminobutyl-5-(tetrahydro-4-thiopyran-3-yl)-3-hydroxycyclohex-2-enone or mixtures thereof. 10. A stable, water-soluble crop protection solid active compound formulation as claimed in claim 8 or 9, comprising as water-soluble salt a metaborate, phosphate, hydrogen phosphate, pyrophosphate, metasilicate, orthosilicate, tetraborate, sulfite, tripolyphosphate, polyphosphate, metaphosphate, tetrasodium EDTA, trisodium nitrilotriacetate, guanidine acetate, guanidine carbonate or mixtures thereof. 11. A stable, water-soluble crop protection solid active compound formulation as claimed in claim 8 or 9, comprising as water-soluble basic salt an alkali metal metaborate, alkali metal tetraborate, alkali metal metasilicate, trialkali metal phosphate, alkali metal hydrogen phosphate, alkali metal pyrophosphate, alkali metal tripolyphosphate, alkali metal sulfite, alkali metal polyphosphate, tetrasodium EDTA, trisodium nitrilotriacetate, guanidine carbonate, guanidine acetate or mixtures thereof. 12. A stable, water-soluble crop protection solid active compound formulation as claimed in claims 8 to 11, furthermore comprising formulation auxiliaries. 13. A stable, water-soluble crop protection solid active compound formulation as claimed in claims 8 to 12, comprising further crop protection active compounds. 14. A stable, water-soluble crop protection solid active compound formulation as claimed in claims 8 to 13, comprising from 5 to 95% by weight of a cyclohexenone oxime ether of the general formula I, from 5 to 95% by weight of a water-soluble basic salt, from 0 to 95% by weight of a formulation auxiliary, from 0 to 90% by weight of further crop protection active compounds. 15. A stable, water-soluble crop protection solid active compound formulation as claimed in claims 8, comprising a cyclohexenone oxime ether of the general formula I where R<2> is sodium; R<3> is tetrahydrothiopyran-3-yl; R<4> and R<5> are hydrogen; Alk is CH2CH(CH3)- and R<6> is para-fluorophenoxy and para-chlorophenoxy. 16. A stable, water-soluble crop protection solid active compound formulation as claimed in claims 8 to 14, further comprising, as crop protection active compound, glyphosate andthe salt therof 17.  17. A sodium salt 2-[1-(2para-chlorophenoxypropyloxy)iminobutyl]-5-(tetrahydrothiopyran-3-yl)-3-hydroxycyclohexenone. 18. A process for preparing a crop protection solid active compound formulation as claimed in claims 8 to 14, which comprises mixing a cyclohexenone oxime ether of the general formula I, the water-soluble basic salt, formulation auxiliaries if desired and further crop protection active compounds if desired, comminuting if desired and then agglomerating or compacting. 19. A process for preparing a crop protection solid active compound formulation as claimed in claims 8 to 14, which comprises dissolving a cyclohexenone oxime ether of the general formula I in an organic solvent, extracting with an aqueous solution of the water-soluble basic salt and then removing the water. 20. A process as claimed in claim 19, wherein the crop protection solid active compound formulation is comminuted if desired after removing the water and then agglomerated or compacted. 21. A process as claimed in claim 18 or 20, wherein extruder granulation, disk granulation, fluidized bed granulation or mixer granulation is used for agglomeration.