Title of Invention

HERBICIDAL COMPOSITIONS COMPRISING SUBSTITUTED PHENOXYSULFONYLUREAS

Abstract The present invention relates to herbicidal compositions comprising A) one or more herbicidal ingredients from the group of the substituted phenoxysulfonylureas of the formula I and their salts and one or more herbicidally active compounds from the group consisting of Ba) herbicides effective selectively in rice, predominantly against grasses, said herbicides being selected from the group consisting of fentrazamid (NBA 061), haloxyfop, sethoxydim, dithiopyr, etobenzanid, clefoxidim, KIH 6127 and clethodim, Bb) herbicides effective selectively in rice, predominantly against harmful dicotyledonous and cyperaceous plants, said herbicides being selected from the group consisting of 2,4-0, MCPA, mecoprop, mecoprop-P, tritosulfuron, halosulfuron. methyl, dicamba, acif/uorfen, carfentrazone, bentazon and triclopyr, Bc) herbicides effective selectively in rice, predominantly against grasses and harmful dicotyledonous and cyperaceous plants, said herbicides being selected from the group consisting of pendimethalin. clomazone, KIH 2023, oxadiargyl, cyclosulfamuron (AC 322, 140), azimsulfuron (DPX-A-a947), nicosulfuron, cinmethylin, indanofan, pentoxazone, pyribenzoxim, oxaziclomefone (MY -100), fluthiamid and mesotrione, preferably in a weight ratio of compounds of the formula I or their salts (type A compounds) to compounds from group B in the range from 1:20,000 to 200:1, preferably from 1:8000 to 100:1 and, with particular preference, from 1:4000 to 50:1, for controlling unwanted harmful plants, preferably in rice cultures.
Full Text Description
Herbicidal compositions comprising substituted phenoxysulfonylureas
Tine invention relates to the technical field of crop protection compositions and in particular to herbicidal compositions comprising certain phenoxysulfonylureas and/or salts thereof which are outstandingly suitable for controlling rice weeds that to date have been difficult to control using individual herbicides, especially gramineous, dicotyledonous and/or hyperaceous weeds in rice or transgenic rice cultures.
T 1270985 discloses herbicidal compositions comprising an effective amount of substituted phenoxysulfonylureas in combination with herbicidal active ingredients.
n rice In particular there exists a range of economically significant nonocotyledonous weeds, e.g., primarily Echinochloa crus-galli, schaemum ssp. or Heptachlor, which cannot be controlled satisfactorily vith rice herbicides known to date, or mixtures thereof, alone. Also known rom global rice cultivation systems are harmful plants, such as Sagittaria ipp., Eleocharis spp., e.g., Eleocharls kuroguwai, Cyperus serotinus, Scirpus juncoides, and other harmful plants as wed, which germinate pedominantly from perennial organs in the soil and so are more difficult to control than weeds which germinate from seeds, and also broadleaf pecies whose optimum control across the whole breadth of the spectrum if weeds Is not easy, Furthermore, there is an increasing incidence of esistant species (including Cyperus ssp or Echinochloa ssp) which it Is often no longer possible to control using individual active ingredients or even conventional combinations.
the light of the prior art Indicated and discussed herein it was the object the invention to provide mixtures having herbicidal activity so as to place be practitioner in a position to control the spectrum of weeds, or individual reed species whose control is difficult, in rice using one application or a applications of herbicides.

It has surprisingly been found that this object, inter alia, is achieved by herbicidal compositions having the features of claim 1. The present invention therefore provides herbicidal compositions comprising A) one or more herbicidal ingredients from the group of the substituted phenoxysulfonylureas of the formula I and their salts

and
B) one or more herbicidaliy active compounds from the
group consisting of
Ba) herbicides effective selectively in rice, predominantly
against grasses, said herbicides being selected from the group consisting of fentrazamid (NBA 061), haloxyfop, sethoxydim, dithiopyr, etobenzanid, clefoxidim, KIH 6127, and clethodim,
Bb) herbicides effective selectively in rice, predominantly
against harmful dicotyledonous and cyperaceous plants,
said herbicides being selected from the group consisting
of 2,4-D, MCPA, mecoprop, mecoprop-P, tritosulfuron,
haiosulfuron-methyl, dicamba, acifluorfen,
carfentrazone, bentazon and triclopyr,
Be) herbicides effective selectively in rice, predominantly
against grasses and harmful dicotyledonous and cyperaceous plants, said herbicides being selected from the group consisting of pendimethalin, clomazone, KIH 2023, oxadiargyl, cyclosulfamuron (AC 322,140), azimsuifuron (DPX-A-8947), nicosulfuron, cinmethyiin, indanofan, pentoxazone, pyribenzoxim, oxaziclomefone (MY-100), fluthiamid and mesotrione.
By means of the novel combinations of herbicidal active ingredients of types A and B it is made possible in a particularly advantageous manner to achieve the \eve\ of weed-spectrum control required by the practltfoner, embracing even individual species which are difficult to control.

Furthermore, with the combinations of the Invention It is possible-to reduce considerably the application rates of jhg individual co-components present_ in the combination, thereby perrnitting more economic solutions on the part of users.
Finally, It has surprisingly proved possible to obtain increases in activity which go beyond the expected degree, so that the herbicidal compositions of the invention to a wide extent exhibit synergistic activities. In addition, many resistant species can be controlled to outstanding effect.
The compounds of the formula I can form salts in which the hydrogen of the -SO2-NH- group is replaced by an agriculturally appropriate cation. Examples of these salts are metal salts, especially alkali metal salts (e.g., Na or K salts), or alkaline earth metal salts, or else ammonium salts or salts of organic amines. Salts can also be formed by adding a strong acid onto the heterocyclic moiety of the compounds of the formula I. Examples of suitable such acids are HCI, HNO3, trichloroacetic acid, acetic acid and palmitic acid. In particularly advantageous compounds the salt of the herbicide of the formula (I) is formed by replacing the hydrogen of the -SO2-NH- group by a cation from the group consisting of the alkali metals, alkaline earth metals and ammonium, preferably sodium.
Where the compounds of the formula I include one or more asymmetric carbon atoms or double bonds, which are not indicated separately in the general formula, these compounds still belong to the type A compounds. The possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereo isomers and Z and E isomers are all embraced by the formula I and can be obtained by conventional methods from mixtures of these stereoisomers or else can be prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials. Said stereoisomers in pure form, and their mixtures, can therefore be employed in accordance with the invention.
Phenoxysulfonylureas of the .formulaJ are indeed embraced in principle, for example, by the general formula I from IT 127 09 85, which also describes their suitability as synergistic partners for herbicides for use in crop plants. The outstanding suitability of the specific phenoxysulfonylureas of group A as co-components in synergistic mixtures with other herbicides that can be employed in rice, however, cannot be derived from the prior art. In

particular, the disclosed literature contains no indications that combinations of compounds of group A with the rice herbicides of group B occupy such an exceptional position in the control of the major harmful plants in rice cultures. In this context it should be also be borne in mind in particular that it is not possible to extrapolate from the use of a combination in other cultures to its activity in rice cultures. Even if the compounds of group A are suitable per se for controlling harmful plants in rice, it is impossible to predict with a good, or even any, chance of success whether combinations of other rice herbicides will permit increases in weed control activity which go beyond the additive activity.
A preferred co-component from group A is the compound A1
(ethoxysulfuron): 1-(2-ethoxyphenoxysulfonyl)-3-(4,6-dimethoxy-
2-pyrimldinyl)urea

which is known, inter alia, from Pesticide Manual (pub). British Crop Protection Council), 11th edition, 1997, pp. 488-489. This compound is preferably used as sole active ingredient of group A and can be combined with one or more herbicidally active compounds of group B.
The specific sulfonylureas of group A, especially the compound A1, are outstandingly suitable, in combination with other herbicides of type B, for the effective control of rice culture weed species that are difficult to control. In this context, in particular, unexpected special effects occur in terms of activity against resistant grass weeds.
The co-components of type B are generally standard herbicides which, however, are selected in accordance with specific criteria. For instance, they comprise without exception herbicides which are effective selectively in rice against unwanted plants. The harmful plants to be controlled in this context include in particular grasses and dicotyledonous/cyperaceous plants. The written format dicotyledonous/cyperaceous" here is intended

to express the fact that although activity against dicotyledonous and cyperaceous plants exists, the activity against dicotyledonous plants is to the fore.
With regard to the activity of the standard herbicides of type B it Is possible in turn to carry out a gradation in respect of the focus of the plants controlled. Thus one subsection of the type B herbicides is predominantly, or almost exclusively, active against grasses (subgroup Ba)), another subsection is active predominantly against dicotyledonous and cyperaceous plants (subgroup Bb)), while a further group develops its activity against both grasses and dicotyledon ous/cyperaceous plants (subgroup Bc)).
An optimized spectrum of activity for the combinations of the invention results from addition to and intensification of the herbicidal properties of the compounds of type A. so that increases in activity against harmful olants in other target groups can be achieved as well.
n a further, especially judicious embodiment, the herbicidally active mixture of the invention comprises as its type B herbicides one or more herbicides which are active selectively in rice against grasses and are selected from the group Ba) consisting of
31) NBA 061 - fentrazamid or BAY YRC 2388
4-{2-chlorophenyl)-5-oxo-4,5-dihydrotetrazole-1-carboxyiic add
cyclohexylethyl amide
Conference volume: The 1997 Brighton Crop Protection Conference, Weeds (publ. British Crop Protection Council), pp. 67-68
J2) haloxyfop
(±)-2-[4-[[3-ch(oro-5-itrifIuoromethyl)-2-pyridinyl]oxo]phenoxy]-propionic acid, embracing inter alia the use forms haloxyfop-ethyl, haloxyfop-methyl, ha[oxyfop-methyl[(R) isomer], the abovementioned compounds B2) being known from Pesticide Manual, 10th ed. 1994. pp. 551-554;
13) sethoxydim

(±)-{EZ)-2-{1-ethoxyiminobutyl)-5-[2-{ethylthio)propyl]-3-hydroxy-
cyclohex-2-enone,
Pesticide Manual, 11th edition, 1997, pp. 1101-1103,
B4) dithiopyr
S,S"-dimethyl 2-difluoromethyl-4-isobutyl-6-trifluoromethylpyrldine-
3,5-dicarbothloate
Pesticide Manual, 11th edition, 1997, pp. 442-443
B5) etobenzanid = IVIY-52
2", 3"-dichloro-4-ethoxymethoxybenzanilide Pesticide Manual, 11th edition, 1997, pp. 492-493
B6) clefoxidem = BAS 625 H
2-[1-{2-(4-chlorophenoxy)propoxyimino)butyl]-3-oxo-5-thion-3-yl-cyclohex-1 -enol
AG Chem, New Compound Review (publ. Agranova), vol. 17, 1999, p. 26
B7) KIH 6127 = pyriminobac-methyl
methyl 2-(4,6-dimethoxy-2-pyrimidinyloxy)-6-{1-methoxyiminoethyi)-benzoate, also as the acid or sodium salt Pesticide Manual, 11th edition 1997, pp. 1071-1072,
B7a) clethodim
(±)-2-[(E)-1-[(E)-3-chloroallyloxyimino]propyl]-5-[2-(ethylthio)propyl]-
3-hydroxycyclohex-2-enone
Pesticide Manual, 11th edition, 1997, pp.250-251
Although the representatives of group Ba) have chemical structures which are in some cases relatively different, they nevertheless form a coherent subgroup on the basis of their activity spectrum and the fact that they constitute synergists for the compounds of type A.
Also of particular interest are herbicidal compositions comprising as their type B compound one or more compounds active selectively in rice against dicotyledonous and in some cases cyperaceous plants as well (subgroup Bb)), said compounds being selected from the group consisting of the
herbicides

B8) 2,4-D
(2,4-dichlorophenoxy)acetic acid
frequently employed forms: 2,4-D-butotyl, 2,4-D-butyl, 2,4-D-
dimethylammonium, 2,4-D-diolamin, 2,4-D-isooctyl, 2,4-D-isopropyl,
2,4-D-trolamln,
Pesticide Manual, 10th edition, 1994, pp. 271-273,
B9} MCPA
{4-chloro-2-methylphenoxy)aceticacid
predominantly employed forms include MCPA-butotyl, MCPA-
dimethylammonium, MCPA-isoctyl, MCPA-potassium, MCPA-
sodium,
Pesticide Manual, 10th edition, 1994, pp. 638-640,
BIO) mecoprop, mecoprop-P
(RS)-2-(4-chloro-o-tolyloxy)propionic acid
(R)-2-{4-chioro-o-tolyloxy)proplonic acid
Pesticide Manual, 10th edition, 1994, pp. 646-647 and 647-648,
811) tritosulfuron
N-[[[4-methoxy-6-{trifluoromethyl)-1,3,5-triazin-2-yl]amino]carbonyl]-
2-(trifluoromethylbenzenesulfonamide)
AG Chem, New Compound Review (publ. Agranova), vol. 17, 1999,
p. 24
B12) halosulfuron-methyl
methyl 3-chloro-5-{4,6-dimethoxypyrimidin-2-ylcarbamoylsulfamoyl)-
1 -methylpyrazole-4-carboxylate
Pesticide Manual, 11th edition, 1997, pp. 657-659;
B13) dicamba
3,6-dichloro-o-anisic acid
used inter alia as dicamba-dimethylammonium, dicamba-potassium,
dicamba-sodium, dicamba-trolamine.
Pesticide Manual, 10th edition 1994, pp. 298-300,
814) acifluorfen
5-(2-chloro-α,α,α:(-trifluoro-D-tolvloxvl-2-nitrobenzoic acid.

also used as acifluorfen-sodium,
Pesticide Manual, 10th edition, 1994, pp. 12-13,
B15) carfentrazone
ethyl (RS)-2-chloro-3-[2-chloro-5-{4-difluoromethyl-4,5-dihydro-
3-methyl-5-oxo-1 H-1,2,4-triazol-1 -yl)-4-fluorophenyl]propionate used inter alia as carfentrazone-ethyl (as indicated) or else as the acid. Pesticide Manual, 11th edition, 1997, pp. 191-193,
B16) bentazone
3-isopropyl-1H-2,1,3-benzothiadiaztn-4(3H)-one 2,2-dioxide Pesticide Manual, 10th edition, 1994, pp. 90-91,
817) triclopyr
[(3,5,6-trichloro-2-pyridyl)oxy]acetic acid,
preferably In the form of triciopyr, triclopyr-butotyl, triclopyr-
triethylammonium,
Pesticide Manual, 10th edition, 1994, pp, 1015-1017,
In a further preferred embodiment of the present invention the herbicidally active combinations comprise as type B herbicides one or more herbicides active selectively in rice predominantly against grasses and dicotyledonous/cyperaceous plants (subgroup Be)) from the group consisting of
B18) pendimethalin
N-(1-ethylpropyl)-2,6-dinitro-3,4-xylidine Pesticide Manual, 10th edition, 1994, pp. 779-780
B19) clomazone
2-[(2-chlorophenyl)-4,4-dimethyl-3-isoxazolidinone; Pesticide Manual, 10th edition, 1994, pp.220-221
820) KIH 2023
sodium 2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoate, the preferred form being the sodium salt Pesticide Manual, 10th edition, 1994, p. 620,
B21) oxadiargyl

5-tert-butyf-3-[2,4-dichloro-5-(prop-2-yny(oxy)pheny(J-1,3,4-oxa-
diazol-2{3H)-one,
Pesticide Manual, 11th edition, 1997, pp. 904-905.
822) AC 322,140 = cyclosulfamuron
N-[[[2-{cyclopropylcarbonyl)phenyl]amino]sulfonyl]-N1-
(4,6-dimethoxypyrimidin-2-yl)urea
Pesticide Manual, 10th edition, 1994. pp. 8-9
B23) azimsulfuron (DPX-A8947),
1-(4,6-dimethoxypyrimldin-2-yl)-3-[1-methyl-4-(2-methyl-2H-tetrazol-
5-yl)pyrazol-5-ylsulfonylurea
Pesticide Manual, 11th edition, 1997, pp. 63-65
B24) nicosulfuron
1-(4,6-dimethoxypyrimidin-2-yl)-3-{3-dimethylcarbamoyl-2-
pyridy[sulfonyl)urea
Pesticide Manual, 10th edition, 1994, pp. 734-735,
826) cinmethylin
(1RS, 25R, 4SR)-1,4-epoxy-p-menth-2-yl 2-methylbenzyl ether Pesticide Manual, 11th edition, 1997, pp. 246-248
827) indanofan (RS)-2-[2-(3-chlorophenyl)-2,3-epoxypropyl]ethyiindane-1,3-dione Pesticide Manual, 11th edition, p. 715
828) pentoxazone 3-(4-chloro-5-cyclopentyloxy-2-fluorophenyl)-5-isopropylidene-
1,3-oxazolidine-2,4-dione. Pesticide Manual, 11th edition, 1997, pp. 942-943
829) LGC-40863 = pyribenzoxim
benzophenone 0-[2,6-bis[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzoyl]
oxime
Conference volume: The 1997 Brighton Crop Protection
Conference, Weeds (publ. British Crop Protection Council)
pp. 39-40

B30) oxaziclomefone = MY100
3-[1-(3,5-dichlorophenyl)-1-methylethyl]-2,3-dihydro-6-methyl-5-phenyl-4H-1,3-oxa2im-4-one
Conference volume: The 1997 Brighton Crop Protection Conference, Weeds (publ. British Crop Protection Council) pp. 73-74
B31) fluthiamid = BAY FOE 5043
4"-fluoro-N-isopropyl-2-{5-trifluoromethyl-1,3,4-thiadiazol-2-yloxy)-
acetanllide
Pesticide Manual, 11th edition, 1997, pp. 82-83
832) mesotrione
2-[4-{methylsulfonyl)-2-nitrobenzoyl]-1,3-cyclohexanedione
AG Chem, New Compound Review (publ. Agranova), vol. 16, 1998,
p. 51
The compounds B1) to B32) comprise herbicides which are known, for example, from the source indicated for the respective compound, which are employed specifically in combination with the compounds of group A) of the invention, and which are selective in rice, including transgenic rice. In addition to the basic substance, whose regular formula is also indicated for illustration, reference is also made in some cases lo commonly employed modifications of the basic substances, these modifications likewise being employable in the context of the present invention. Where optically active forms of the type B compounds are customary, these are likewise part of the invention, and in some cases reference has been made to these forms too (e.g. mecoprop and mecoprop-P, etc.).
Combinations of the active ingredients A + B exhibit superadditive effects; in other words, for a given level of control of the harmful plants, the herbicidal compositions of the invention make it possible to reduce the application rate and/or to increase the safety margin in rice cultures. Both of these are sensible both economically and environmentally. The choice of the amounts of components A + B to be employed, the ratio of the components A:B, and the chronological sequence of their application are dependent, as is, for example, the chosen formulation, on a wide range of factors.

Not insignificant amongst such factors are, inter alia, the nature of the co-components, the development stage of the broadleaf or grass weeds, the spectrum of weeds to be controlled, environmental factors, climatic conditions, soil conditions, etc.
In a particularly preferred embodiment in accordance with the invention, herbicidal compositions of the invention comprise a synergistically effective amount of a combination of the compounds of the formula I or their salts [type A compounds) with compounds from group B. In this context it should be emphasized above all that, even in combinations with application rates or weight ratios A:B for which synergy cannot be readily demonstrated in every case - for instance, because the individual compounds are usually employed in the combination at very different application rates or else because the harmful plants are already very well controlled by the ndividual compounds - a synergistic activity is generally inherent in the lerbicidal compositions of the invention.
"he application rates of the type A herbicide are generally between 1 and 20 g ai/ha (ai = active ingredient, i.e., application rate based on the active ingredient), preferably between 5 and 90 g ai/ha.
like their application rates, the weight ratios A:B of the combined erbicides can, as mentioned, vary within wide limits. An application rate atios range (wt/wt) in accordance with the invention for A:B is from :20,000 to about 200:1. In the context of the invention, preference is given / compositions comprising compounds of the formula I or their salts (type , compounds) and compounds from group B in a weight ratio of from :8000 to 100:1. Especially judicious are compositions having application ate ratios A;B of between 1:4000 and 50:1. The specific picture for the arious herbicides of group B is as follows, i.e., the following application ates and weight ratios (A:B) are employed with preference:




The active-ingredient combinations of the invention can be present either as mixed formulations of the two components, which are then conventionally applied in aqueous dilution, or as tank mixes prepared by jointly diluting the separately formulated components with water. The active ingredients of types A and B can be formulated in various ways depending on the prevailing biological and/or chemicophysical parameters.
The following are examples of suitable formulation possibilities:
Wettable powders (WP), emulsifiable concentrates (EC), water-soluble powders (SP), water-soluble concentrates (SL), concentrated emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions or emulsions, capsule suspensions (CS), oil- or water-based dispersions (SC), suspoemulsions, suspension concentrates, dusts (DP), oil-miscible solutions (OL), dressing agents, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, granules of soil application or broadcasting, water-soluble granules (SG), water-dispersible granules (WG), ULV formulations, microcapsules, and waxes.
Of these, preference is given to water-soluble wettable powders (WP), water-dispersib/e granules (WG), water-emulslfiable granules (EC), suspoemulsions (SE) and oil suspension concentrates (SC).

The individual types of formulation are known in principle and are described for example in: Winnacker-KDchler, "Chemlsche Technologie" volume 7, C. Hauser Verlag, Munich, 4th ed. 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker N.Y,, 1973; K. Martens, "Spray Drying Handbook" 3rd ed, 1979. G. Goodwin Ltd., London.
The required formulation auxiliaries, such as inert materials, surfactants,
solvents and further additives, are likewise known and are described for
example in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers",
2nd ed.. Darland Books, Caldwell N.J.; H. v. Olphen "Introduction to Clay
Colloid Chemistry", 2nd ed.. J. Wiley & Sons, N.Y. Marsden "Solvents
Guide, 2nd ed., Interscience. N.Y. 1963; McCutcheon"s "Detergents and
Emuisifiers Annual", MC Publ. Corp.. Ridgewood N.J.; Sisley and Wood,
"Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964;
Schonfeldt, "Grenzflachenaktive Athylenoxidaddukte", Wiss.
Veriagsgesellschaft, Stuttgart 1976; Winnacker-Kuchler "Chemlsche Technologie", volume 7, C. Hauser Verlag, Munich. 4th ed., 1986.
On the basis of these formulations it is also possible to prepare combinations with other pesiticides, herbicides, insecticides, fungicides and antidotes, safeners, ferliiizers and/or growth regulators, in the form, for example, of a ready-to-apply formulation or as tank mix. With particular advantage, the herbicide combinations of the invention are prepared by formulating the compounds of the formula I or their salts (type A compounds) with one or more compounds of type B in the manner of a conventional crop protection formulation from the group consisting of water-soluble wettable powders (WP), water-dispersible granules (WDG), water-emulsifiable granules (WEG), suspoemulsions (SE) and oil suspension concentrates (SC),
Wettable powders are preparations which can be dispersed uniformly in water and which in addition to the active ingredients and a diluent or inert substance comprise surfactants of ionic and/or nonionic type (wetting agents, dispersants), e.g., polyethoxylated alkylphenols, polyethoxylated fatty alcohols and fatty amines, fatty alcohol polyglycol ether sulfates, aikanesulfonates or alkylar^"lsulfonates, sodium ligninsulfonate, sodium 2.2"-dinaphthylmethane-6.6"-disulfonate. sodium dibutylnaphthalene-sulfonate and sodium oleylmethyltaurinate.

Emulsifiable concentrates are prepared by dissolving the active ingredient or ingredients in an organic solvent, e.g., butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons, with the addition of one or more ionic and/or nonionic surfactants (emulsifiers). Examples of emulsifiers which can be used are: calcium alkylarylsulfonates, such as Ca dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol poiyglycol ethers, propylene oxide-ethylene oxide condensation products (e.g. block copolymers), alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene-sorbitan fatty acid esters or other polyoxyethylenesorbitan esters.
Dusts are obtained by grinding the active ingredient or ingredients with finely divided substances, e.g.. talc, natural clays, such as kaolin, bentonite and pyrophylllte, or diatomaceous earth.
Granules can be prepared either by finely spraying the active ingredient or ingredients onto adsorptive, granulated inert material or by applying active-ingredient concentrates to the surface of carriers such as sand, kaolinites or granulated inert material with the aid of binders, e.g., polyvinyl alcohol, sodium poiyacrylate or mineral oils. Water-dlspersible granules are prepared generally by the customary techniques such as spray drying, fluidized-bed granulation, disk granulation, mixing using high-speed mixers, and extrusion without solid inert material. Suitable active ingredients can also be granulated in the manner which is customary in the preparation of fertilizer granules, if desired in the form of a mixture with fertilizers.
The agrochemical formulations of the invention generally contain from 0.1 to 99% by weight, in particular from 2 to 95% by weight and, of very particular preference, from 3 to 92% by weight of active ingredients of types A and B, in addition to customary formulating auxiliaries.
The concentrations of the active ingredients A + B in the formulations can be different. In wettable powders, the active-ingredient concentration is for example from about 10 to 95"= by weight, the remainder to 100% by weight consisting of customary formulation constituents. In the case of emulsifiable concentrates the active-ingredient concentration can be from about 1 to 85% by weight, preferably from 5 to 80% by weight. Dust formulations contain from about 1 to 25% by weight, usually from 5 to 20% by weight, of active ingredients, sprayable solutions from about 0.2 to 25%

by weight, preferably from 2 to 20% by weight, of active ingredients. In the case of granules such as dispersible granules the level of active ingredient depends in part on whether the active compound is a solid or a liquid and on the granulating aids and fillers used. The amount in the case of water-dispersible granules is generally between 10 and 90% by weight.
In addition, the specified active-ingredient formulations may comprise the adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents, solvents, fillers, colorants, carriers, antifoams, evaporation inhibitors and pH and viscosity regulators which are customary in each case.
Because of the relatively low application rate of the combinations A + B of the invention, their compatibility is already very good as a general rule. In particular, the combinations of the invention achieve a reduction in the absolute application rate as compared with individual application of a herbicidai active ingredient. In order to increase the tolerance and/or selectivity of the herbicide combinations of the invention even further, if desired, however, it is advantageous to apply them together with safeners or antidotes, either jointly in a mixture of at different points in time. Compounds suitable as safeners or antidotes for the combinations of the invention are known, for example, from EP-A-333 131 (ZA-89/1960), EP-A-269 806 (US-A-4,891.057), EP-A-346 620 (AU-A-89/34951) and the international patent applications PCT/EP 90/01966 {WO-9iy08202) and PCT/EP 90/02020 (WO-91/07874) and from literature cited therein or can be prepared by the methods described therein. Other suitable safeners are known from EP-A-94 349 (US-A-4,902,304), EP-A-191 736 (US-A-4,881,966) and EP-A-0 492 366 and the literature cited therein.
Advantageously, the herbicidai mixtures or combinations of the invention additionally comprise C) one or more compounds which act as safeners.
Particularly preferred antidotes or safeners, or groups of compounds which have been suitable as safeners or antidotes for the above-described product combinations of the invention, include:
a) compounds of the dichlorophenylpyrazoline-3-carboxylic acid type, preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (compound

i--1-1^ dnu rmaibu uurripuuiiua, ct^j ucsunutiu tii um iiutjiiieiuuiicii
application WO 91/07874 (PCT/EP 90/02020);
b) derivatives of dichlorophenylpyrazolecarboxylic acid, preferably compounds such as ethyl 1-(2,4-dichlorophenyl}-5-methylpyrazo[e-3-carboxylate (compound CI-2), ethyl 1-(2,4-dichlorophenyl)-5-lsopropylpyrazo(e-3-carboxylate (compound C1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1.1-dimethylethyl}pyrazole-3-carboxylate (compound C1 -4), ethyl 1 -(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (compound CI-5) and related compounds, as described in EP-A-0 333 131 and EP-A-0 269 SOS;
c) compounds of the triazolecarboxylic acid type, preferably compounds such as ethyl 1-(2,4-dichlorophenyi)-5-trichloromethyl-(1H)-1,2.4-triazole-3-carboxy(ate (compound C1-6, fenchlorazole) and related compounds (see EP-A-0 174 562 and EP-A-0 346 620);
d) compounds of the dichlorobenzyl-2-isoxazo[ine-3-carboxylic acid type, compounds of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxyIic acid type, preferably compounds such as ethyl 5-(2,4-dichloroben2yf)-2-isoxazoiine-3-carboxylate (compound CI-7) or ethyl 5-ph6nyl-2-isoxa2oline-3-carboxylate (compound CI-8) and related compounds as described in the international patent application WO 91/08202 (PCT/EP 90/01966);
e) compounds of the 8-quinolinoxyacetic acid type, preferably compounds such as
1-methylhex-1-yl (5-chloro-8-quinolinoxy)acetate (C2-1),
1,3-dimethylbut-1-y! (5-chloro-8-quinolinoxy)acetate (C2-2),
4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate (C2-3),
1-allyloxyprop-2-yl (5-chloro-8-quinolinoxy)acetate (C2-4),
ethyl (5-chloro-8-quinolinoxy)acetate (C2-5),
methyl (5-chloro-8-quinolinoxy)acetate (C2-6),
allyl (5-chloro-8-quinolinoxy)acetate (C2-7),
2-(2-propylideniminooxy)-1-ethyl (5-chloro-8-quinolinoxy)acetate
(C2-8),
2-oxoprop-1-yl (5-chloro-8-quinolinoxy)acetate (C2-9)
and related compounds as described in EP-A-0 086 750,
EP-A-0 094 349 and EP-A-0 191 736 or EP-A-0 492 366;

f) compounds of the (5-chloro-8-quinolinoxy)malonic acid type, preferably compounds such as diethyl (5-chloro-8-quinoiinoxy)malonate, diailyl (5-chloro-8-quinolinoxy)maionate, methyl ethyl (5-chloro-8-quinolinoxy)malonate and related compounds as described and proposed in the patent application EP-A-0 582 198;
g) active ingredients of the type of the phenoxyacetic and phenoxypropionic acid derivatives and of the aromatic carboxylic acids, such as 2.4-dichlorophenoxyacetic acid (esters), (2,4-D), 4-chloro-2-methylphenoxypropionic esters (mecoprop), fvlCPA, or 3,6-dichloro-2-methoxybenzoic acid (esters) (dicamba);
h) compounds of the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid type, preferably ethyl 5,5-diphenyl-2-isoxazoline-3-carboxylate (C3-1);
i) compounds known as safeners for rice, such as fenclorim (=4,6-dichloro-2-phenylpyrimidine, Pesticide Manual, 11th edition, 1997, pp. 511-512), dimepiperate (= S-1-methyl-1-phenylethyl piperidin-1-thiocarboxylate, Pesticide Manual, 11th edition, 1997, pp. 404-405), daimuron (= 1-(1-methyl-1-phenylethyl)-3-p-tolylurea, Pesticide Manual, 11 th edition, 1997, p. 330), cumyluron (= 3-{2-chlorophenylmethyl)-1 -(1 -methyl-1 -phenylethyl)urea, JP-A-60/087254), methoxyphenone (= 3,3"-dimethyl-4-methoxy-benzophenone), and CSB (= 1-bromo-4-(chloromethyl-sulfonyl)benzene, CAS Reg. No. 54091-06-4).
At least some of the compounds specified are also described in EP-A-0 640 587, the disclosure content of which is hereby incorporated by reference.
j) A further important group of compounds suitable as safeners and antidotes is known from WO 95/07897.
The safeners (antidotes) of the above groups a) to j) reduce or prevent phytotoxic effects which may occur when the product combinations of the invention are used in crops of useful plants, without affecting the activity of the herbicides against harmful plants. By this means it is possible to extend

very considerably the sphere of use of the herbicide mixtures of the invention, and in particular the use of safeners enables combinations to be used which hitherto could be employed only to a limited extent or without satisfactory success; that is, combinations which without safeners lead to inadequate control of the harmful plants in low doses with little breadth of action.
The herbicidal mixtures of the invention and the abovementioned safeners can be applied together (as a ready-to-use formulation or as a tank mix) or in arbitrary sequence. The weight ratio of safener to herbicide (group A, i.e., compound of the formula I and its salts) can vary within wide limits and is preferably in the range from 1:100 to 100:1, in particular from 1:100 to 50:1. The optimum amounts of herbicides (type A and type B compounds) and safeners in each case are usually dependent on the type of herbicide mixture used and/or on the safener used, and also on the nature of the plant stock to be treated.
Depending on their properties, the safeners of type C) can be used to pretreat the seed of the crop plant (seed dressing) or can be introduced into the seed drills prior to sowing, or can be applied together with ths herbicide mixture before or after the emergence of the plants. Preemergence treatment includes both the treatment of the cultivation ares, prior to sowing and the treatment of the areas under cultivation which have been sown but are not yet showing growth. Preference is given to conjoint application with the herbicide mixture. Tank mixes or ready-to-use formulations can be employed for this purpose.
The required application rates of the safeners can vary within wide limits depending on the indication and the herbicide used and are generally in .the range from 0.001 to 1 kg, preferably from 0.005 to 0.2 kg, of active ingredient per hectare. Particularly advantageous herbicidal compositions, outstandingly suitable for use in rice, are produced, within the context of the invention, when herbicides from group A are employed in combination with type B compounds and with the safener C2-1 and/or C3-1.
For application, the formulations in commercially customary form are conventionally diluted, if desired, using water, for example, in the case of wettable powders, emuisifiable concentrates, dispersions and water-dispersible granules. Preparations in the form of dusts, soil granules.

granules for broadcasting, and sprayable solutions, are conventionally not diluted further with other inert substances prior to application.
The invention also provides a method of controlling unwanted plants, which comprises applying a herbicidally active amount of a novel combination of active ingredients A + B to said plants or to the area under cultivation. The active ingredients can be applied to the plants, to parts of the plants, to seeds of the plants, or to the area under cultivation.
In a preferred variant of the method, the compounds of the formula (I) or their salts (type A compounds) are applied at rates of from 1 to 20 g ai/ha, preferably from 5 to 90 g ai/ha and, with very particular preference, between 6 and 60 g ai/ha. while the application rates for the type B compounds are generally from 1 to 5000 g ai/ha. Application of the active ingredients of types A and B simultaneously or at separate points in time In a weight ratio of from 1:20,000 to 200:1 is preferred. Particular preference, furthermore, is given to the conjoint application of the active ingredients in the form of tank mixes, where the optimally formulated concentrated formulations of the individual active ingredients are mixed together in the tank with water, and the resulting spray mixture is applied.
Since the crop tolerance of the novel combinations is extremely good and at the same time allows the harmful plants to be controlled to a very high degree, they can be regarded as selective. In a preferred modification of the method, herbicidal compositions comprising the active-ingredient combinations of the invention are therefore employed for selectively controlling unwanted plants.
The method for selectively controlling harmful plants takes on a particularly advantageous embodiment when the herbicidal compositions of the invention are employed in rice.
When used alone in rice the co-components of type A control a limited spectrum of annual and perennial broadleaf weeds and cyperaceous plants. The spectrum of action of the type A compounds is further improved, however, by combining them with their type B partners as specified in the invention, allowing individual groups of species to be controlled in addition. Depending on the nature of the co-component B, the

herbicidal combinations of the invention can be employed with advantage for controlling unwanted plants in transgenic rice cultures as well.
Transgenic cultures are those in which the plants have been made resistant to herbicides or pesticides by means of genetic manipulation. Rice plants modified in this way then permit a selective use.
All in all, the invention therefore additionally provides for the use of herbicidal compositions comprising
A) one or more herbicidal ingredients from the group of the
substituted phenoxysulfonyiureas of the formula I and their salts

and
B) one or more herbicidally active compounds from the
group consisting of
Ba) herbicides effective selectively in rice, predominantly
against grasses, said herbicides being selected from the group consisting of fentrazamid (NBA 061), haloxyfop, sethoxydim, dithiopyr, etobenzanid (MY-52), clefoxidim, KIH6127, and ciethodim,
Bb) herbicides effective selectively in rice, predominantly
against harmful dicotyledoneous and cyperaceous plants, said herbicides being selected from a group consisting of 2.4-D, MCPA, mecoprop, mecoprop-P, tritosulfuron, haiosulfuron-methyl, dicamba, acifluorfen, carfentrazone. bentazon and triclopyr.
Be) herbicides effective selectively in rice, predominantly
against grasses and harmful dicotyledonous and cyperaceous plants, said herbicides being selected from the group consisting of pendimetha)in, clomazone, KiH 2023, oxadiargyl, cyclosulfamuron (AC 322,140), azimsulfuron (DPX-A-8947), nicosulfuron, cinmethylin,

indanofan, pentoxazone, pyribenzoxim, oxaziciomefone (MY-IOO), fluthiamid and mesotrione
for controlling unwanted harmful plants, preferably in plant cultures such as rice cultures. The weight ratio of compounds of the formula I or their salts (type A compounds) and compounds from group B is generally in the range from 1:20,000 to 200:1, preferably from 1:8000 to 100:1 and, with particular preference, from 1:4000 to 50:1.
A preferred use is that of combinations comprising a synergisticaily effective amount of A and B compounds.
Preference is also given to the use of mixtures comprising combinations of A) and Ba) for selectively controlling grasses in rice. Also preferred is the use of mixtures comprising combinations of A) and Bb) for selectively controlling dicotyledonous and cyperaceous plants in rice. Preference is given, furthermore, to the use of mixtures comprising combinations of A) and Be) for selectively controlling grasses and dicotyledonous and cyperaceous plants in rice.
The invention also embraces mixtures of one or more co-components A), preferably only A1 (ethoxysulfuron), and one or more co-components B), alone or in combination with one or more safeners C).
Preferred examples which may be mentioned of the active-ingredient mixtures of the invention are the following combinations of A1 (ethoxysulfuron) with co-components B1-B32, although this is not intended to imply any restriction only to the combinations explicitly mentioned:
A1+B1: fentrazamid, A1+B2: haloxyfop, A1+B3: sethoxydim, A1+B4: dithiopyr, A1+B5: etobenzanid, A1+B6: clefoxidim, A1+B7: KIH 6127. A1+B7a: clethodim, A1+B8: 2,4-D, A1+B9: MCPA, A1+B10: mecoprop mecoprop-P, A1+B11: tritosulfuron, A1+B12: halosulfuron-methyl, A1+B13: dicamba, A1+B14; acifJuorfen, A1+B15: carfentrazone, A1-fBl6: bentazon, A1+B17: triclopyr, A1+B18: pendimethalin, A1-(-Bl9: clomacone, A1-(-B20 KIH 2023, A1+B21; oxadiargyl, A1+B22: cyclosulfamuron, A1+B23 azimsulfuron, A1+B24: nicosulfuron, A1+B25: thenylchjor, A1+B26 sinmethylin, A1+B27: indanofan, A1+B28: pentoxazone, A1+B29

pyribenzoxim, A1+B30: oxaziclomefone A1+B31: fluthiamid, A1+B32: mesotrione.
The mixtures described above can judiciously be employed together with one or more safeners. Examples of preferred safeners are 1-methylhex-1-yl (5-chloro-8-quinolinoxy)acetate (C2-1) and methyl 5,5-diphenyl-2-isoxazol(ne-3-carboxyJate (C3-1).
In the combinations listed, the use of a safener offers considerable advantages since it reduces possible damage to the crop plant, such as rice, as may be caused by sulfonylurea derivatives or other herbicidally active ingredients.
Furthermore, the safeners C2-1 and C3-1 can advantageously be replaced by one or more compounds of the following group of safeners or employed together with one or more of the following compounds:
• ethyl 1-(2,4-dichlorophenyl)-5-{ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (Cl-l),
• ethyl 1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (CI-2),
• ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (C1-3),
• ethyl 1 -(2,4-dichlorophenyl)-5-(1,1 -dimethyleJhyl)pyrazole-3-carboxylate (Cl-4),
• ethyl 1-(2,4-dichlorophenyi)-5-phenylpyrazole-3-carboxylate (C1-5),
• ethyl 1-(2,4-dichiorophenyl)-5-trichloromethyl-1H-1,2,4-triazole-3-carboxylate (CI-6. fenchlorazole),
• ethyJ 5-(2,4-dich)orobenzyl)-2-isoxazoline-3-carbDxylate (Cl -7),
• ethyl 5-phenyl-2-isoxazoline-3-carboxylate (C1-8),
• 1,3-dimethylbut-1-yl (5-ch[oro-8-quino[;noxy)acetate (C2-2),
• 4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate (02-3),
• 1-allyloxyprop-2-yl (5-chloro-8-quinolinoxy}acetate (C2-4),
• ethyl {5-chloro-8-quinolinoxy)acetate (C2-5),
• methyl (5-chloro-8-quinolinoxy)acetate (C2-6),
• allyl (5-chloro-8-quinolinoxy)acetate (02-7),
• 2-(2-propylideneiminooxy)-1 -ethyl (5-chloro-8-quinolinoxy)acetate (C2-8),
• 2-oxoprop-1-yl (5-chloro-8-quinoiinoxy)acetate (C2-9),
• diethyl (5-chloro-8-quinolinoxy)malonate,
• diallyl (5-ch(oro-8-quinolinoxy)maionate,

cypermethrin, zeta-cypermethrin, cyphenotrin, cyproconazole, cyromazine,
daminozide, dazomel, 2,4-DB, DCIP, debacarb, decan-1-oI, deltamethrin,
demeton-S-methyl, desmedipham, desmetryn, diafenthiuron, diazinon,
dichlobenil, dichlofluanid, dichlone, dichlormid, dichiorophen, 1,3-
dichloropropene, dichlorprop, dichlorprop-P, dichlorvos, diclofop,
diclomezine, dicloran, diclofol, dicrotophos, dienochlor, diethofencarb,
diethyitoiuamide, difenacoum, diefenoconazoiB, difenzoquat, difethialone,
diflubenzuron. diflufenican, dikegulac, dimefuron, dimethachlor,
dimethametryn, dimethenamid, dimethipin, dimethirimol, dimethoate,
dimethomorph, dimethyl phthalate, dimethylvlnphos, diniconazole,
dinitramine, dinocap, dinoterb, diofenolan, dioxabenzofos, diphacinone,
diphenamid, diphenylamine, dipropyl pyridine-2,5-dicafboxylate, diquat,
disulfuton, dithianon, diuron, DKA-24, DNOC, dodemorph, dodine,
edifenphos, empenthrin, endosulfan, endothal, ENT8184, EPN, EPTC,
ergocalciferol, esfen vale rate, esprocarb, ET751, ethalfluraiin,
ethametsulfuron-methyl, ethephon, ethiofencarb, ethion, ethirimol,
ethofumesate, ethoprophos, ethoxyquin, ethychlozate, ethylene dibromide,
ethylene dlchJoride, etofenprox, etrldlazole, F8426, famphur, fenamlphos,
fenarimol, fenazaquin, fenbuconazole, fenbutatin oxide, fenchlorazole,
fenclorim, fenfuram, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb,
fenpiclonil. fenpropathrin, tenpropidin, fenpropimorph, fenpyroximate,
fenthion, fentin, fenuron, fenvalerate, ferbam, ferimzone, fipronil, flamprop,
flamprop-M, flazasulfuron, flocoumafen, fluazifop, fluazlfop-P, fluazinam,
fluazuron, fluchloralin, flucycloxuron, flucythrinate, fludioxonil, flufenoxuron,
flumetralin, flumetsulam, flumiclorac, flumioxazin, fluometuron,
fluoroacetamide, fluoroglycofen, fluoromide, flupoxam, flupropanate,
fluquinconazole, flurazole, flurenol, fluridone, flurochloridone, fluroxypyr,
flurprimidol, flurtamone, tiusilazole, flusulfamide, flutolanil, flutriafol, tau-
fluvalinate, fluxofenlm, folpet, fomesafen, fonofos, forchlorfenuron,
formetanate, formothion, fosamine, fosetyl, fosthiazate, fuberidazole,
furalaxyl, furathiocarb, furilazole, gibberellic acid, gibberellin A4, gibberellin
A7, guazatlne, GY-81, halfenprox, halosulfuron, HC-252, gamma-HCH,
heptachlor, heptenophos, hexachlorobenzene, hexaconazole,
hexaflumuron, hexazinone, hexythiazox, hydramethylnon,
2-hydrazinoethanol, hydroprene, 8-hydroxyquinotine sulfate, hymexazol. "CIA0858, ICIA5504, imazalil, imazamethabenz, imazapyr, imazaquin, mazethapyr, imibenconazole, imidacloprid, iminoctadien, inabenfide, Indol-3-ylacetic acid, 4-indol-3-ylbutyric acid, ipconazole, iprobenfos, iprodione, sazofos, Isofenphos, isopamphos, isoprocarb, isoprothiolane, isoproturon.

isouron, isoxaben, isoxapyrifop, isoxathion, kasugamycin, KIH9201, lactogen, lambda-cyhalothrin, lenacil, linuron, lufenuron, malathion, maleic hydrazide, mancopper, mancozeb, maneb, MCPA-thioethyl, MCPB, mecarbam, mefluidide, mepanlpyrim, mephosfolan, mepiquat, mepronii, metalaxyl, metaldehyde, metam, metamitron, metazachlor, metconazole, methabenzthiazuron, methacrifos, methamidophos, methasulfocarb, methidathion, methiocarb, methomyl, methoprene, methoxychlor, methylarsonic acid, methyl bromide, methyjdymron, methyl isothiocyanate. metiram, metobenzuron, metobromuron, metolcarb, metoxuron, metribuzin, mevlnphos, milbemectin, MK-243, monocrotophos, monolinuron, muscalure, myclobutanil, nabam, naled, naphthenic acid, 2-{1-naphthyl)acetamide, (l-naphthyl)acetic acid, (2-naphthoyloxy)acetic acid, napropamide, naptalam, natamycin, NC-330, neburon, NI-25, nickel bis(dimethyldithiocarbamate), niclosamide, nicotine, nitenpyram, nithlazine, nitrapyrin, nitrothal-isopropyl, norflurazon, nuarimol, octhilinone, 2-{octyithio)ethanol, ofurace, omethoate, orbencarb, oryzaiin, oxabetrinil, oxadixyl, oxamyl, oxine-copper, oxolinic acid, oxycarboxin, oxydemeton-methyl, paclobutrazol, paraquat, parathion, parathion-methyl, pebulate, perfurazoate, penconazole, pencycuron, pentachlorophenol, pentanochlor, permethrin, phenmedipham, phenothrin, phenthoate, 2-phenylphenol, N-phenylphttialamic acid, phorate, phosalone, phosdiphen, phosmet, phosphamidon, phoxim, phthalide, pindone, piperalin, piperonyl butoxide, pirimicarb, pirimiphos-ethyl, pirimiphos-methyi, polyoxins, pratlethrin, pretilachlor, primisulfuron, probenazole, prochloraz, procymidone, prodiamine, profenofos, prohexadlone, prometon, propachlor, propamocarb, propaphos, propaquizafop, propargite, propazine, propetamphos, propham, propiconazole, propineb, propisochlor, propoxur, propyzamide, prosulfocarb, prosulfuron, prothiofos, pymetrozine, pyraclofos, pyrethrins, pyridaben, pyridaphenthion, pyridate, pyrifenox, pyrimethanil, pyrimidifen, pyriproxyfen, pyrithiobac-sodium, pyroquilon, quinalophos, quinmerac, quinoclamine, quintozene, quizalofop, quizalofop-P, resmethrin, rimsulfuron, rotenone, RU15525, S421, siduron, silafluofen, smazine. sodium fluoroacetate, SSF-109, SSI-121, streptomycin, strychnine, sulcofuron, sulfentrazone, sulfluramid, sulfometuron. sulfotep, sulfur, sulprofos. tar oils, 2,3,6-TBA, TCA-sodium, tebuconazole, tebufenozide, tebufenpyrad, tebutam, tebulhiuron, tecloftalam, tecnazene, tetlubenzuron, tetluthrin. temephos. terbacil, terbufos, terbumeton, terbuthylazine, terbutryn, tetrachlorvinphos, tetraconazole, tetradifon, tetramethrin, tetramethrin[(lR)-isomers], thiabendazole, thidiazuron,

thifensulfuron, thifluzamlde, thiocyclam, thiodicarb, thiofanox, thiometon, thiophanate-methyl, thiram, tiocarbazil, tolclofos-methyl, tolylfluanid, tralkoxydim, tralomethrin, transfluthrln, triadimefon, triadimenol, tri-allate, triazamate, triazophos, triazoxide, tribenuron, S,S,S-tributyl phosphorotrithioate, trichlorfen, tricyclazole, tridemorph, tnetazine, triflumizole, triflumuron, trifluralin, triflusulfuron, triforine, trimethacarb, trinexapac, triticonazole, uniconazole, validamycin, vamidothion, vernolate, vinclozolin, warfarin, XDE537, XMC, xylylcarb, zineb and ziram.
There are therefore numerous possibilities which result for combining two or more active ingredients with one another and employing them conjointly for weed control in rice cultures, without departing from the concept of the
invention.
The herbicidal compositions (combinations) of the invention exhibit an excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. In addition, perennial broadleaf weeds which are difficult to control and which propagate from seeds or rhizomes, rootstocks or other perennial organs are effectively controlled by the active-ingredient combinations. In this context it is irrelevant whether the substances are applied before sowing, preemergence or postemergence.
On the side of the monocotyledonous broadleaf weed species, for example, Echlnochloa and Cyperus species, from the annual group, and perennial Cyperus species, are effectively controlled.
The broadleaf weeds which occur under specific cultivation conditions in rice, such as Sagittaria, Alisma, Rotala, Monochoria, Eleocharis, Scirpus, Cyperus etc., for example, are controlled to outstanding effect by the active-ingredient combinations of the invention.
Where the herbicidal compositions of the invention are applied before germination, then either the emergence of the weed seedlings is completely prevented or the weeds grow until the cotyledon stage, then stop growing and finally die away completely after three to four weeks have elapsed.

When the active-ingredient combination of the invention is applied postemergence to the green parts of plants, there is likewise a drastic halt to growth very soon after treatment. The weed plants remain in the growth stage prevailing at the time of application, or die off more or less quickly after a certain time, so that in this way, using the compositions of the invention, the weed competition, which is harmful for crop plants, can be prevented very early and sustainedly, along with its attendant quantitative and qualitative harvest losses.
Although the compositions of the invention display an excellent herbicidal activity against mono- and dicotyledonous broadleaf weeds, the crop plant is damaged only insignificantly if at all. For this reason, the compositions are exceptionally suitable In rice in particular for selectively controlling unwanted plant growth.
The harmful plants to be controlled include especially, as already specified, grasses, dicotyledonous plants and/or cyperaceous plants which are otherwise difficult to control, in particular. Harmful plants which can be controlled with preference using the novel combinations of type A and type B compounds include, inter alia, Echinochloa colonum, Echinochloa chinesis, Echinochloa crus-galli, Leptochloa chin./fil., Paspalum dis., Brachiaria platyphylla, Digitaria spp., Ischaemum, Leersia hexandra, Oryza sativa (red rice), Cenchrus echinatus, Rottboellia exaltata, Leersia and the like on the side of the grasses, Monochona vag., Potamogeton dis., Rotala indica, Marsilea crenata. Ludwigia ad., Salvina mol., Ipomoea, Sesbania ex., Heteranthera, Commelinia, Butomus, Aeschynomene, Alisma plantago, Eclypta, Murdania, Xanthium, Alteranthera spp., Spenodea zey., Sagittaria, luncus spp., Polygonum, Ammania ind. on the side of the broadleaf weeds, and Cyperus diff., Cyperus iria, Fimbristylis litt., Cyperus ferax, Cyperus esculentes on the side of the annual cyperaceous plants and also Eleocharis spp., Scirpus spp., Scirpus mucronatus and Cyperus rotundus on the side of the perennial cyperaceous plants.
To summarize, it can be said that superadditive (= synergistic) effects occur when sulfonylureas of the formula I and/or their salts are applied conjointly with one or more active ingredients from group B. The activity in the combinations here exceeds that of the individual products when applied alone.

These effects permit, inter aiia, a reduction In the rate of application, the control of a broader spectrum of broadleaf and gramineous weeds, the closing of loopholes in activity, including those with respect to resistant species, a more rapid and more reliable activity, a longer duration of action, complete control of the harmful plants with just one or a few applications, and an extension of the application period of the active ingredients in combination.
The abovementioned properties are required in practical weed control in order to keep agricultural cultures free from unwanted plant competitors and so to safeguard, and/or increase, the quality and quantity of the yields. The combinations of the invention markedly exceed the state of the art in respect of the properties describe above.
In addition, the combinations of the invention permit excellent control of otherwise resistant harmful plants.
The examples which follow serve to illustrate the invention and have no limiting character:
1. Formulation examples
a) A dust is obtained by mixing 10 parts by weight of an active-ingredient combination according to the invention and 90 parts by weight of talc as inert substance and comminuting the mixture in a hammer mill.
b) A readily water-dispersible wettable powder is obtained by mixing 25 parts by weight of active ingredients A + B, 64 parts by weight of kaolin-containing quartz as inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltaurinate as wetting agent and dispersant and grinding the mixture in a pinned-disk mill.
c) A readily water-dispersible dispersion concentrate is obtained by mixing 20 parts by weight of active ingredients A + B with 6 parts by weight of alkylphenol polygiycol ether (®Triton X 207), 3 parts by weight of isotridecanol polygiycol ether {8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range for example about 255 to 277°C) and grinding the mixture in a bowl mill to a fineness of less than 5 microns.

d) An emulsifiable concentrate is obtained from 15 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenoi as emulsiffer.
e) Water-disperslble granules are obtained by mixing 75 parts by weight of active ingredients A + B,
10 parts by weight of calcium ligninsulfonate,
5 parts by weight of sodium (auryl sulfate,
3 parts by weight of polyvinyl alcohol, and
7 parts by weight of kaolin,
grinding the mixture on a pinned-disk mill and granulating the
powder in a fluidized bed by spraying on water as granulating liquid.
f) Water-dispersible granules are also obtained by homogenizing and
precomminuting, in a colloid mill,
25 parts by weight of active ingredients A + B,
5 parts by weight of sodium 2,2"-dinaphthylmethane-6,6"-disulfonate,
2 parts by weight of sodium oleoylmethyltaurinate,
1 part by weight of polyvinyl alcohol,
17 parts by weight of calcium carbonate, and
50 parts by weight of water,
then grinding the mixture in a bead mill and atomizing and drying the
resulting suspenion in a spray tower by means of a single-substance
nozzle.
g) Extruded granules are obtained by mixing 20 parts by weight of the
active ingredients A + B. 3 parts by weight of sodium ligninsulfonate,
1 part by weight of carboxymethylcellulose and 76 parts by weight of
kaolin, grinding the mixture and wetting it with water. This mixture is
extruded and subsequently dried in a stream of air.
2. Biologlcal examples
The examples given below were carried out in the greenhouse and in some cases in field trials.
i) Preemergence weed control
Seeds or pieces of rhizome of monocotyledonous and dicotyledonous broadleaf weed plants are placed in sandy loam soil in plastic pots with a diameter of 9 cm and are covered with earth. Broadleaf weeds which occur in rice-growing are cultivated in soil saturated with water, the amount of

water placed in the pots being such as to extend to the soil surface or several millimeters above it. The active-ingredient combinations of the invention, formulated in the form of wettable powders or emulsifiable concentrates, and in parallel tests the individual active ingredients formulated accordingly, are then applied as aqueous suspensions or emulsions in different dosages to the surface of the covering earth or, in the case of rice, are poured into the irrigation water, the water-based application rate corresponding to from 300 to 600 I/ha.
Following the treatment, the pots are placed in a greenhouse and maintained under good growth conditions (temperature, atmospheric humidity, water supply) for the broadleaf weeds. The visual rating of the plants and the emergence damage was made following the emergence of the test plants after a test period of 3 to 4 weeks, in comparison to untreated controls. The tests are set up statistically with multiple - up to five-fold - repetition. The herbicidal compositions of the invention exhibit a good herbicidal activity when applied preemergence to a broad spectrum of gramineous and broadleaf weeds.
ii) Postemergence weed control
Seeds or pieces of rhizome of monocotyledonous and dicotyledonous broadleaf weed plants are placed in sandy loam soil in plastic pots, covered with earth and cultivated in a greenhouse under good growth conditions (temperature, atmospheric humidity, water supply). Broadleaf weeds occurring in rice-growing are cultivated in pots in which water is standing up to 2 cm above the soil surface. Three weeks after sowing, the test plants are treated at the three-leaf stage. The active-ingredient combinations of the invention formulated as wettable powders or emulsifiable concentrates, and in parallel tests the correspondingly formulated individual active ingredients, are applied in various dosages to the green parts of the plants by spraying, at a water-based application rate which corresponds to 300 to 600 I/ha, and after about 3 to 4 weeks in a greenhouse under optimum growth conditions (temperature, atmospheric humidity, water supply) the test plants are rated visually for the activity of the preparations in comparison to untreated controls. In the case of rice or of broadleaf weeds which occur in rice-growing, the active ingredients are also added directly to the irrigation water (application in analogy to so-called granule application) or sprayed onto plants and into the irrigation

water. The tests are set up with multiple - up to fivefold - repetition. The herbicidal compositions of the invention also display good herbicidal activity when applied postemergence to a broad spectrum of economically important gramineous and broadleaf weeds.
iii) Field trials
Field trials are set up on conventionally farmed areas with natural sanding. Following the sowing and emergence of the crop/broad leaf/gramineous plants, application was made to plots of about 20 to 10 m2 In 2 to 4 repetitions, using plot sprayers. The effects of the herbicides/combinations are rated visually in a period of 1 to 8 weeks following application and the effects are determined as percentages (0-100%) in comparison to untreated control plots. The results represent means of the 2 to 4 repetitions for the respective broadleaf/grass weed species.
iv) Evaluation of the combination effects in the examples
In evaluating the combination effects, the activity of the individual components is added and compared with the activity of the mixtures in equal doses. It was frequently observed that the combinations show higher efficacies than the sum of the individual activities.
In cases with less clear effects, the expected value was calculated using the COLBY formula and was compared with the empirically determined result. The calculated efficacy of a combination, that to be expected in theory, is determined in accordance with the formula of S.R. Colby: "Calculation of synergistic and antagonistic responses of herbicide combinations", Weeds 15 (1957), pages 20 to 22.
For two-way combinations, this formula reads;

Synergistic effects can be assumed when the empirical value exceeds the expected value. In the case of combinations with individual components with the same active ingredients, it is also possible to make comparisons by way of the total formula.

In the majority of cases, however, the synergistic increase in activity is so pronounced that the criterion of Colby can be dispensed with; in this case, the activity of the combination clearly exceeds the formal {numerical) sum of the activities of the individual substances.
Particular mention may be made of the fact that an assessment of the synergism in the case of the active ingredients employed here must take into account the great differences in the application rates of the individual active ingredients. Thus it does not make sense to compare the activities of the active ingredient combinations and the Individual active ingredients in each case at identical application rates. The application rates that can be saved on in accordance with the invention only become apparent from the superaddltive Increase in activity when the combined application rates are employed or from the reduction In the application rates of two individual active Ingredients In the combinations in comparison to the individual active ingredients with identical activity in each case.
Special experimenta} examples
In the following tables:
g al/ha = grams of active ingredient per hectare
expected values for the herbicide combinations are indicated in brackets.












The examples show that the individual active ingredients provide enective control of individual harmful plants only at high doses. When applied In low doses, the co-components generally display only a low level of activity which fails by far to conform to the activity required in practice. Only through the conjoint application of the active ingredients is it possible to obtain good effects against all harmful plants tested. These effects markedly exceeded the additive activity of the individual components; In other words, the required level of control is obtained by means of much lower application rates. These effects significantly broaden the activity spectrum.
Evaluated in the form of damage, there is no adverse effect on crop tolerance; in other words, the combinations can be said to be fully selective.


WE CLAIM:
1. A herbicidal composition comprising
A) one or more herbicidal ingredients from the group of the substituted phenoxysulfonylureas of the formula I and their salts

and
B) one or more herbicidally active compounds from the group consisting of
i) herbicides effective selectively in rice, predominantly against
grasses, said herbicides being selected from the group
consisting of fentrazamid {NBA 061), haloxyfop, sethoxydim,
dithiopyr, clefoxidim. KIH 6127 and clethodim,
ii) herbicides effective selectively in rice, predominantly against
harmful dicotyledonous and cyperaceous plants, said
herbicides being selected from the group consisting of 2,4-D,
MCPA, mecoprop, mecoprop-P, tritosulfuron, halosulfuron-
methyl, decamp, acifluorfen, carfentrazone, bentazon and triclopyr,
iii) herbicides effective selectively in rice, predominantly against
grasses and harmful dicotyledonous and cyperaceous plants,
said herbicides being selected from the group consisting of
pendimethalin. coumarone, KIH 2023, oxadiargyl,

cyclosulfamuron (AC 322, 140), azimsulfuron (DPX-A-8947),
nicosulfuron, cinmethylin, indanofan, pentoxazone,
pyribenzoxim, oxaziclomefone (MY-100), fluthiamid and
mesotrione.
2. The herbicidal composition as claimed in claim 1, which comprises a synergistic amount of a combination of the compounds of the formula I or their salts (type A compound) with compounds from group B.
3. The herbicidal composition as claimed in one or both of the preceding claims, which comprises compounds of the formula I or their salts {type A compounds) and the compounds from group B in a weight ratio of from 1:20,000 to 200:1, preferably from 1:8000 to 100:1 and, with particular preference, from 1:4000 to 50:1.
4. The herbicidal composition as claimed in one or more of the preceding claims, which comprises one or more further components from the group consisting of active plant protection ingredients of other types, active softener ingredients, formulation aids and additives customary in plant protection.
5. A process for producing a herbicidal composition as claimed in one or more of claims 1 to 4, wherein the compound(s) of the formula I or salts thereof (type A compounds) is or are formulated with one or more compounds of type B in analogy to a customary plant protection formulation from the group consisting of wet table powders, emulsifiable concentrates, aqueous solutions, emulsions, sprayable solutions (tank mixes), oil- or water-based dispersions, suspoemulsions, dusts, granules for soil application or broadcasting, water-dispersible granules, ULV formulations, microcapsules and waxes.

6. The method of controlling harmful plants, which comprises applying the herbicides of a herbicidal composition as claimed in one or more of claims 1 to 4 together or separately, reemergence, postemergence or both pre- and postemergence, to the plants, parts of plants, plant seeds, or cultivation area.
7. A herbacidal composition, substainlly as hereinabove described and exemplified.

Documents:

in-pct-2000-60-che.jpg

in-pct-2001-0060-che abstract-duplicate.pdf

in-pct-2001-0060-che abstract.pdf

in-pct-2001-0060-che claims-duplicate.pdf

in-pct-2001-0060-che claims.pdf

in-pct-2001-0060-che correspondence-others.pdf

in-pct-2001-0060-che correspondence-po.pdf

in-pct-2001-0060-che description(complete)-duplicate.pdf

in-pct-2001-0060-che description(complete).pdf

in-pct-2001-0060-che form-1.pdf

in-pct-2001-0060-che form-19.pdf

in-pct-2001-0060-che form-26.pdf

in-pct-2001-0060-che form-3.pdf

in-pct-2001-0060-che form-5.pdf

in-pct-2001-0060-che other.pdf

in-pct-2001-0060-che pct.pdf

in-pct-2001-0060-che petition.pdf


Patent Number 213046
Indian Patent Application Number IN/PCT/2001/60/CHE
PG Journal Number 13/2008
Publication Date 28-Mar-2008
Grant Date 19-Dec-2007
Date of Filing 12-Jan-2001
Name of Patentee AVENTIS CROPSCIENCE GMBH
Applicant Address 65929 Frankfurt,
Inventors:
# Inventor's Name Inventor's Address
1 Erwin HACKER Margarethenstrasse 16, D-65239 Hochheim,
2 Hermann BIERINGER Eichenweg 26, D-65817 Eppstein,
3 Thomas AULER Kastanienweg 7, D-65451 Kels,
4 Alvaro MELENDEZ Sulzbacher Strasse 16, D-65824 Schwalbach,
PCT International Classification Number A01N 47/36
PCT International Application Number PCT/EP1999/004957
PCT International Filing date 1999-07-14
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 199 28 453.9 1999-06-24 Germany
2 198 32 017.5 1998-07-16 Germany