阅读说明：本技术 控制als耐受性植物生长的方法 (Methods of controlling ALS-tolerant plant growth ) 是由 詹姆斯·蒂莫西·布里斯托 于 2016-09-13 设计创作，主要内容包括：提供了一种控制ALS耐受性植物生长的方法,该方法包括向这些植物和/或它们的所在地施用除草有效量的(A)嗪草酮和(B)一种或更多种磺酰脲类的组合。还提供了一种组合物,该组合物包含(A)嗪草酮和(B)一种或更多种磺酰脲类的组合。(A method is provided for controlling the growth of ALS-tolerant plants, which comprises applying to the plants and/or to the locus thereof a herbicidally effective amount of a combination of (a) metribuzin and (B) one or more sulfonylureas. Also provided is a composition comprising a combination of (a) metribuzin and (B) one or more sulfonylureas.)

1. A method for controlling ALS-resistant plant growth, which comprises applying to the plants and/or their locus a herbicidally effective amount of (a) metribuzin and (B) iodosulfuron, wherein the weight ratio of (a) metribuzin and (B) iodosulfuron is at most 400: 1.

2. The method of claim 1, wherein components (a) metribuzin and (B) iodosulfuron are applied at an application rate of 0.03 kilograms per hectare (kg/ha) to 2kg/ha of the total amount of active ingredient applied.

3. The method of claim 1, wherein components (a) metribuzin and (B) iodosulfuron are applied at an application rate of 0.05kg/ha to 1.5kg/ha of the total amount of active ingredients.

4. The method of any one of claims 1 to 3, wherein component (A) metribuzin is applied in an amount of at least 5 g/ha.

5. The method of any one of claims 1 to 3, wherein component (A) metribuzin is applied in an amount of at least 20 g/ha.

6. The method of any one of claims 1 to 3, wherein iodosulfuron is applied in a total amount of at least 1 g/ha.

7. The method of any one of claims 1 to 3, wherein iodosulfuron is applied in a total amount of at least 2 g/ba.

8. The process of any one of claims 1 to 3, wherein the weight ratio of (A) metribuzin and (B) iodosulfuron is at most 70: 1.

9. The process of any one of claims 1 to 3, wherein the weight ratio of (A) metribuzin and (B) iodosulfuron is at most 10: 1.

10. The method of any one of claims 1 to 3, wherein the weight ratio of (A) metribuzin and (B) iodosulfuron is greater than 1: 20.

11. The method of any one of claims 1 to 3, wherein the weight ratio of (A) metribuzin and (B) iodosulfuron is greater than 1: 5.

12. The method of any one of claims 1 to 3, wherein the weight ratio of (A) metribuzin and (B) iodosulfuron is greater than 1: 1.

13. The process of any one of claims 1 to 3, wherein the weight ratio of (A) metribuzin and (B) iodosulfuron is from 250: 1 to 1: 4.

14. The process of any one of claims 1 to 3, wherein the weight ratio of (A) metribuzin and (B) iodosulfuron is from 100: 1 to 1: 1.

15. The process of any one of claims 1 to 3, wherein the weight ratio of (A) metribuzin and (B) iodosulfuron is from 70: 1 to 1: 1.

16. The method of any one of claims 1 to 3, wherein the components (A) metribuzin and (B) iodosulfuron are applied to the plants and/or their locus after germination.

17. The method of any one of claims 1 to 3, wherein the ALS resistant plant is present in a crop of: wheat, barley, rye, oat, corn, rice, sorghum, triticale, legumes, peanuts, cotton, flax, hemp, jute, spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato or pepper.

18. The method of any one of claims 1 to 3, wherein the ALS resistant plant is present in a crop of: wheat, barley, rye, oats, triticale, corn, rice, soybean, cotton, tomato, and potatoes.

19. The method of any one of claims 1 to 3, wherein the ALS resistant plant is present in a crop of: wheat, barley, rye, oats and triticale.

20. The method of any one of claims 1 to 3, wherein the ALS resistant plant is present in a crop of: lentils, peas, soybeans, soft wheat, and hard wheat.

21. The method of any one of claims 1-3, wherein the ALS-tolerant plant comprises Stellaria spp, Papavera spp or Matricaria spp.

22. The method of any one of claims 1 to 3, wherein the ALS-tolerant plant comprises chickweed (Stellaria media), corn poppy (Papaver rhoeas), chamomile (Matricaria chamomilla), or chamomile (Matricaria inodora).

23. The method of any one of claims 1 to 3, wherein components (A) and (B) are administered in the form of one or more formulations selected from: water Dispersible Granules (WDG), water Soluble Granules (SG) and oil based suspension concentrates (OD).

24. Use of a herbicidally effective amount of a combination of (a) metribuzin and (B) iodosulfuron in a weight ratio of (a) metribuzin to (B) iodosulfuron of at most 400: 1 for controlling ALS-resistant plant growth.

25. A composition for controlling ALS-tolerant plants comprising a herbicidally effective amount of a combination of (a) metribuzin and (B) iodosulfuron, wherein the weight ratio of (a) metribuzin and (B) iodosulfuron is at most 400: 1.

Technical Field

The present invention relates to methods of controlling the growth of ALS-tolerant plants.

Background

Undesirable vegetation inhibits crop growth, and protecting crops from undesirable vegetation is a long-standing problem in agriculture. To address this problem, researchers are struggling to develop a wide range of chemicals and chemical formulations that can effectively control this undesirable growth. Many types of chemical herbicides have been disclosed in the literature, and a large number are in commercial use.

However, the development of plants which exhibit resistance or tolerance to one or more herbicidal active ingredients is a problem which is present due to the continued use of chemical herbicides. One particular class of herbicides that is subject to increased tolerance by target plants is the sulfonylureas. Sulfonylureas are branched chain amino acid synthesis (ALS) inhibitors. These compounds act by inhibiting the biosynthesis of the essential amino acids valine and isoleucine, thereby terminating plant cell division and plant growth. More and more plants develop ALS inhibitor tolerance, which in turn reduces or eliminates the effectiveness of sulfonylureas in controlling the growth of such plants. In some cases, certain undesirable plants have developed such degrees of tolerance to ALS inhibitors that sulfonylureas exhibit little or no activity in their control.

Thus, there is a need for improved methods for controlling the growth of plants exhibiting ALS inhibitor tolerance (referred to herein as 'ALS-tolerant plants').

Metribuzin (IUPAC name: 4-amino-6-tert-butyl-4, 5-dihydro-3-methylsulfanyl-1, 2, 4-triazin-5-one; 4-amino-6-tert-butyl-3-methylsulfanyl-1, 2, 4-triazin-5 (4H) -one) is a triazinone herbicide and has the following chemical structure:

metribuzin is an inhibitor of plant photosynthesis. The compound can be absorbed by the roots and leaves of the plant and then transferred into the xylem. Metribuzin is effective in controlling grasses and broadleaf weeds. Metribuzin is commercially available as a herbicidal composition and methods for its preparation are known in the art.

It has been surprisingly found that the combination of metribuzin and one or more sulfonylureas provides effective treatment of ALS-tolerant plants and allows control of plant growth. In particular, it has been found that the combination of metribuzin and one or more sulfonylureas shows a synergistic effect in the control of ALS-tolerant plants and shows an activity that is significantly greater than the activity of metribuzin alone or the level of activity expected from the combination of the individual active ingredients.

Combinations of sulfonylurea and triazinone herbicides are proposed in WO 95/08265, US 6,872,689, US 6,221,809 and US 5,990,047. However, there is no specific example of a combination of metribuzin and sulfonylurea. More specifically, there is no teaching or suggestion therein that the combination of metribuzin and one or more sulfonylureas shows a synergistic effect in controlling ALS intolerant plants, as has now been found.

Disclosure of Invention

Accordingly, in a first aspect, the present invention provides a method for controlling the growth of ALS-resistant plants, which method comprises applying to the plants and/or to the locus thereof a herbicidally effective amount of a combination of (a) metribuzin and (B) one or more sulfonylureas.

In another aspect, the invention provides the use of a herbicidally effective amount of a combination of (a) metribuzin and (B) one or more sulfonylureas in controlling ALS-resistant plant growth.

The invention also provides a composition for controlling ALS-tolerant plants comprising a herbicidally effective amount of a combination of (a) metribuzin and (B) one or more sulfonylureas.

Detailed Description

The term "herbicide" as used herein refers to a compound that exhibits activity in controlling plant growth. The term "herbicidally effective amount" as used herein refers to an amount of such a compound or combination of such compounds that is capable of exerting a controlling effect on plant growth. Control includes all differences from the natural development and growth of a plant, including, for example, killing the plant, retarding one or more aspects of plant development and growth, leaf scald, albinism, dwarfing, and the like.

The term "plant" as used herein refers to all material parts of a plant, including shoots, leaves, needles, stalks, stems, fruit bodies, fruits, seeds, roots, tubers and rhizomes.

If the abbreviation "common name" of the herbicide is used in the present specification, it is to be understood as including all conventional derivatives, such as esters (in particular lower alkyl esters, in particular methyl esters) and salts and isomers (in particular optical isomers), as well as all commercially available forms of the compound. If the "common name" refers to an ester or a salt, it also includes all other common derivatives, such as other esters and salts, free acids, neutral compounds and isomers, in particular optical isomers, and all commercially available forms. The name of a chemical compound stated refers to at least one of the compounds covered by the "common name", usually referring to the preferred compound. In the case of sulfonylureas, salts thereof also include salts formed by cation exchange of the hydrogen atom on the sulfonamide group.

The present invention uses a combination of (a) metribuzin and (B) one or more sulfonylureas. The invention makes it possible to use as component (B) a mixture of a plurality of different sulfonylureas, for example 2, 3 or more sulfonylureas. In many preferred embodiments, component (B) is a single sulfonylurea.

As noted above, metribuzin is a known herbicidal compound and is commercially available.

Similarly, suitable herbicidal sulfonylureas for use in the present invention are known in the art and are commercially available. Suitable sulfonylureas used as component (B) are, for example, amidosulfuron (amidosulfuron), azimsulfuron (azimsulfuron), bensulfuron (bensulfuron), chlorimuron (chlorimuron), chlorsulfuron (chlorsulfuron), sulfosulfuron (chlorimuron), cinosulfuron (cinosulfuron), cyclosulfamuron (cyclosulfuron), ethametsulfuron (ethametsulfuron), sulfosulfuron (ethosulfuron), flazasulfuron (flusulfuron), foramsulfuron (formasulfuron), halosulfuron (halosulfuron), halosulfuron (pyrazosulfuron), sulfosulfuron (imazosulfuron), sulfosulfuron (iodosulfuron), sulfosulfuron (sulfosulfuron), sulfosulfuron (thiosulfuron), sulfosulfuron (pyrisulfuron), sulfosulfuron (oxasulfuron), sulfosulfuron (pyrisulfuron), sulfosulfuron (thiosulfuron), sulfosulfuron (pyrisulfuron (sulfamuron (pyrisulfuron), sulfosulfuron (pyrisulfuron), sulfosulfuron (sulfamuron (pyrisulfuron), sulfosulfuron (pyrisulfuron) (pyrosulfuron), sulfosulfuron (pyrisulfuron), sulfosulfuron) (pyrosulfuron), sulfosulfuron (pyrisulfuron), sulfosulfuron) (pyrosulfuron), sulfosulfuron) (pyrosulfuron (sulfosulfuron), sulfosulfuron (sulfosulfuron) (pyrosulfuron), sulfosulfuron) (pyrosulfuron), sulfosulfuron (pyrosulfuron), sulfosulfuron (pyrosulfuron), sulfosulfuron, Sulfometuron (sulfometuron), sulfosulfuron (sulfosulfuron), thifensulfuron (thifensulfuron), triasulfuron (triasulfuron), tribenuron (tribenuron), trifloxysulfuron (trifloxysulfuron), triflusulfuron (triflusulfuron), and triflusulfuron (tritosulfuron). A preferred sulfonylurea is thifensulfuron-methyl. Preferred sulfonylureas are thifensulfuron-methyl, tribenuron-methyl, metsulfuron-methyl, sulfosulfuron, amidosulfuron, mesosulfuron-methyl, iodosulfuron-methyl, rimsulfuron, nicosulfuron, and halosulfuron-methyl.

In one embodiment, the invention uses one or more sulfonylureas as component (B) with the proviso that component (B) is not metsulfuron-methyl or thifensulfuron-methyl or tribenuron-methyl, in particular with the proviso that the invention does not use a combination of metribuzin and metsulfuron-methyl or thifensulfuron-methyl or tribenuron-methyl, or with the proviso that the invention does not use a combination of metribuzin, florasulam and metsulfuron-methyl or thifensulfuron-methyl or metsulfuron-methyl.

In general, the application rate of the active ingredients (a) metribuzin and (B) one or more sulfonylureas depends on factors such as the type of weeds, the type of crop plants, the type of soil, the season, the climate, the soil ecology and various other factors. The application rates of the components for a given set of conditions can be readily determined by routine experimentation.

Typically, the components (a) metribuzin and (B) one or more sulfonylureas can be applied at an application rate of from about 0.03 kilograms per hectare (kg/ha) to about 2kg/ha of the total amount of active ingredient applied. Preferably, the application rate is from about 0.05kg/ha to about 1.5kg/ha of the total amount of active ingredients.

Metribuzin can be applied in an amount of at least 5g/ha, preferably at least 10g/ha, more preferably at least 15g/ha, still more preferably at least 20 g/ha. Metribuzin can be applied at an application rate of at most 700g/ha, preferably at most 600g/ha, more preferably at most 500g/ha, still more preferably at most 400 g/ha. For many embodiments, application rates of up to 100g/ha are well suited. In some preferred embodiments, metribuzin is applied in an amount of 70 g/ha.

One or more sulfonylureas may be applied in a total amount of at least 1g/ha, preferably at least 1.5g/ha, more preferably at least 2 g/ha. In many embodiments, an application rate of at least 5g/ha, preferably at least 10g/ha, is highly suitable. One or more sulfonylureas may be applied in a total amount of up to 200g/ha, preferably up to 150g/ha, more preferably up to 125g/ha, still more preferably up to 100 g/ha. For many embodiments, application rates of 30g/ha to 80g/ha are well suited.

When the two components are combined or used together in a wide range of weight ratios, (a) metribuzin and (B) one or more sulfonylureas exhibit a synergistic effect. Components (a) and (B) may be applied in similar or equal amounts. Component (B) one or more sulfonylureas may be applied in greater amounts by weight than component (a) metribuzin. More preferably, for many embodiments, component (a) metribuzin is applied in a higher amount by weight than component (B) one or more sulfonylureas.

In the process of the present invention, the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is preferably at most 400: 1, more preferably at most 300: 1, still more preferably at most 200: 1, still more preferably at most 150: 1, and in many embodiments a ratio of at most 70: 1 is preferred. For many embodiments, a weight ratio of (a) metribuzin to (B) one or more sulfonylureas of at most 20: 1 is very suitable, preferably at most 15: 1, more preferably at most 10: 1, for example at most 5: 1.

(A) The weight ratio of metribuzin and (B) one or more sulfonylureas is preferably greater than 1: 20, more preferably greater than 1: 10, still more preferably greater than 1: 5, still more preferably greater than 1: 2, and a ratio of greater than 1: 1 is suitable for many embodiments. The weight ratio of metribuzin to sulfonylureas is preferably in the range of 300: 1 to 1: 5. Preferably, the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is from about 250: 1 to about 1: 4, more preferably from about 200: 1 to about 1: 1, still more preferably from about 100: 1 to about 1: 1, still more preferably from about 70: 1 to about 1: 1. In many embodiments, the weight ratio of (A) metribuzin to (B) one or more sulfonylureas is from 1: 1 to 15: 1, preferably from 1: 1 to 10: 1, still more preferably from 1: 1 to 5: 1.

The components (a) metribuzin and (B) one or more sulfonylureas may be applied to the plants and/or their locus simultaneously and/or sequentially. The components may be used in the form of separate formulations. Alternatively, the components may be used as a mixture in a single formulation.

The components (a) metribuzin and (B) one or more sulfonylureas may be applied at any stage in the growth of the plants to be controlled. For example, these components may be applied to the locus prior to germination, for example as a soil treatment. Alternatively or additionally, the components may be applied after germination of the plant to be controlled, for example as foliar application or soil treatment. The present invention has been found to be particularly effective in controlling a range of ALS resistant plants when applied post-emergence.

The components (a) metribuzin and (B) one or more sulfonylureas can be applied to the plant or the locus thereof in a single application. Alternatively, the components may be applied multiple times. Effective control of undesirable vegetation is achieved using a single application of these components or two time-spaced applications.

(A) The combination of metribuzin and (B) one or more sulfonylureas can be used to treat a range of crops, including cereals, such as wheat (including both soft and hard), barley, rye, oats, maize, rice, sorghum, triticale and related crops; fruits such as pomes, stone fruits and soft fruits (e.g., apples, grapes, pears, plums, peaches, almonds, cherries and berries (e.g., strawberries, raspberries and blackberries)); leguminous plants, such as beans, lentils, peas, soybeans and peanuts; oil plants such as rape, mustard and sunflower; cucurbitaceae, such as zucchini, cucumber and melon; fiber plants, such as cotton, flax, hemp and jute; citrus fruits such as oranges, lemons, grapefruits and mandarins (mandarin); vegetables such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato and capsicum; ornamental plants, such as flowers, shrubs, broad-leaved trees and evergreens (e.g., conifers) and sugar cane.

In a preferred embodiment, the invention is used for controlling the growth of undesired plants in cereals, leguminous plants, fibrous plants and vegetables, preferably wheat (including both soft and hard wheat), barley, rye, oats, maize, rice, sorghum, triticale, beans, lentils, peas, soybeans and peanuts, cotton, flax, hemp, jute, spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes and peppers, more preferably wheat (including both soft and hard wheat), barley, rye, oats, triticale, maize, rice, soybean, cotton, tomatoes and potatoes.

The present invention has been found to be particularly effective in controlling undesirable ALS-resistant plants in wheat (including both soft and hard), barley, rye, oats and triticale.

Suitable crops that may be treated include those that are resistant to metribuzin and sulfonylureas. Tolerance may be natural tolerance produced by selective breeding, or may be introduced artificially by genetic modification of the crop plant. In this respect, 'tolerance' means low sensitivity to damage caused by one or more specific herbicides (in this case metribuzin and sulfonylureas).

The invention can be used to control a wide range of plants that have developed tolerance or resistance to ALS inhibitors, particularly sulfonylureas. ALS-tolerant plants that can be controlled include broadleaf weeds, grasses and sedges, such as Abutilon (Abutilon spp.); acalypha (Acalypha spp.); spinifera (Acanthospermum spp.); genus nostoc (Agrostemma spp.); myrtle (Alopecurus spp.); amaranthus (Amaranthus spp.); ragweed (Ambrosia spp.); juglans (Amsinckia spp.); malva spp (Anoda spp.); camomile (Anthemis spp.); genus pellagra (aspeugo spp.); genus Atriplex (Atriplex spp.); avena (Avena spp.); genus Boraginaceae (Boraginaceae spp.); pygeum (Brachiaria spp.); brassica (Brassica spp.); brome (Bromus spp.); camelina (Camelina spp.); genus camelina (Capsella spp.); cardamine spp; cassia (Cassia spp.); tribulus (Cenchrus spp.); genus Pleurotus (Cerastium spp.); chenopodium (Chenopodium spp.); ionic mustard (choispora spp.); genus chunnella (Claytonia spp.); genus Erigerontis (Conyza spp.); cyperus spp; cogongrass (dactylotenium spp.); datura (Datura spp.); descurainia (Descurainia spp.); desmodium spp; digitaria spp (Digitaria spp.); lepidium (Draba spp.); barnyard grass (Echinochloa spp.); 26926genus (Eleusines spp.); elymus spp (Elymus spp.); texas (Eragrostis spp.); genus wild millet (Eriochloa spp.); geranium spp (eriodium spp.); eupatorium spp; euphorbia (Euphorbia spp.); polygonum (Fallopia spp.); corydalus strobilacea (Fumaria spp.); the genus hemiptelea (Galeopsis spp.); achyranthes spp (Galinsoga spp.); galium spp.; geranium spp (Geranium spp.); crowndaisy chrysanthemum (Glebainis spp.); sunflower (Helianthus spp.); hibiscus (Hibiscus spp.); barley (Hordeum spp.); ipomoea spp; petunia (dacquem ontia spp.); kochia spp (Kochia spp.); lactuca spp; genus picrasma (Lamium spp.); lepidium spp; leptospira (Leptochloa spp.); lithospermum (Lithospermum spp.); lolium spp (Lolium spp.); matricaria spp; genus pinus (Melochia spp.); lonicera (Mercurialis spp.); castanopsis (molugo spp.); forgetfula (Myosotis spp.); evening primrose (Oenoth era spp.); oryza spp; panicum (Panicum spp.); poppy (Papaver spp.); polygonum (Persicaria spp.); poa sp.); polemonium spp (Polemonium spp.); polygonum (Polygonum spp.); portulaca spp (Portulaca spp.); ranunculus spp (Ranunculus spp.); raphanus (Raphanus spp.); luteolin (Reseda spp.); alfalfa genus (Richardia spp.); rumex spp (Rumex spp.); senecio spp (Senecio spp.); sesbania (Sesbania spp.); setaria spp; sida spp; sinapis alba (Sinapis spp.); allium spp (Sisymbrium spp.); genus Slda (Slda spp.); solanum (Solanum spp.); sonchus (Sonchus spp.); sorghum (Sorghum spp.); genus macrorrhiza (specula spp.); stellaria spp; thalassia (Thlaspi spp.); trifolium spp; triticum spp; nettle (Urtica spp.); malpighia spp; grandma (Veronica spp.); vicia spp (Vicia spp.); viola (Viola spp.); and Xanthium spp.

(A) The combination of metribuzin and (B) one or more sulfonylureas is effective in controlling the following plants of ALS-tolerant varieties: chorionic villous leaf (Abutilon theoprasta); acalypha australis (Acalypha australis); sphaeranthus fruticosus (Bristly Starbur, Acanthospermum hispidum); radix cercis mairei (cornockle, Agrostemma gitnago); blackgrass (Alopecurus myosuroides); wild amaranth (amaranth); common grass (Common Ragweed, Ambrosia artemisiifolia); camomile flowers (Tarweed Fiddleneck, Amsinckia lycopsides); a dotted sunflower (normal Anoda, Anoda cristata); chamomile (Mayweeds) (chamomile costula); cleavers (Catchweed) (cardamine (madworth)) (brown grass (aspeugo procumbens)); atriplex canescens (Common orache) (Atriplex canescens (Atriplex patula)); wild oat (Wild-Oat, Avena fatua); wild Oat (Wild Oat) (Avena spp.); herba Hedyotidis Diffusae (Bugloss) (Boraginaceae)); broadleaf Signalprass (Brachiaria grasses) (Brachiaria platyphylla); volunteer rape (volester oil rape) (elsholtzia type rape (Brassica napus)); wild mustard (Wild Mustards) (Brassica spp.); bromus palustris (Rescuegras, Bromus cataticus); brome (Japanese bromine, Bromus japonica); canary (riput broome, Bromus rigidus); sparrow wheat (cheetgrass, Bromus harvester); camelina sativa (Smallseed falseflax) (Camelina sativa (Camelina microcarpa)); shepherd's purse (Capsella bursa-pastoris); cardamine hirsuta (Bittercress, Cardamine hirsuta); cassia tora (Cassia obtipod, Cassia obtusifolia); tribulus terrestris (Sandbur) (tribulus terrestris (Cenchrus spp.))); chickweed (mouse chickweed) (white fungus (Cerastium vulgatum)); chenopodium album (Fat-hen, Chenopodium album); chenopodium album (chenopodium); ion mustard (Blue mustard, Chorispora tenella); primrose (Miners lette, Claytonia perfoliata); canna canadensis (horseweeed Marestail, Conyza canadensis); cyperus esculentus (Yellow nutswedge, Cyperus esculentus); cogongrass (crowfoot grass, dactylotenium aegyptium); stramonium (Jimsonweed, Datura stramnonium); artemisia anethoides (Tansy mustard) (Descurainia pinnata); desmodium flareum (Desmodium fortuneum) manillen (Florida beqarawed); large Crabgrass (Crabgrass) (genus large Crabgrass spp.); herba Botrychii (Spring whitlowgrass) (Frnals) (Draba verna)) in Spring; junglerice (Echinochloa colonum); barnyardgrass (Barnyardgrass, Echinochloa crus-galli); goosegrass (goose grass, Eleusine indica); common creeping grass (Common corn) (Elymus repens)); tequila (Stinkgrass) (agrostis spp.); cupola (cupras) (southwestern broomcorn millet (Eriochloa gracilis)); red-stem ferulace (filiree, Redstem) (geranium celery (eriodium cicutarium)); eupatorium adenophorum (Dogfennel, Eupatorium capllifolium); sun spurge (European heliosporia); euphorbia maculata (Spotted Spurge, Eurorbia maculata); polygonum convolvulus (Black-bindweed, Fallopia convolulus); corydalis plant (fumiory) (corydalis impatiens (Fumaria officinalis)); petal (hemap-nettle) (magapillaria (Galeopsis)); achyranthis bidentata (Galinsoga) (achyranthis spp.); cleavers (Galium aparine); plants of the genus Geranium (Crane's-bill) (Geranium (Geranium)); geranium (Geranium) (Geranium spp.); pearl chrysanthemum (Corn Marigold) (Chrysanthemum indicum (Glebais segetum)); sunflower (genus sunflower spp.); watermelon seedlings (Venice Mallow, Hibiscus trionum); small barley (Little barley, Hordeum pusillum); morning glory (Ivyleaf morningqlorv) (Ipomoea hederacea)); petunia (Morningglory, Pitted) (Ipomoea lactiana); morning glory (Tall morningqloray) (round leaf morning glory); petunia (Smallflower morningqlorv) (jacquengoia (Jacquemontia tamnifolia)); kochia (Kochia scoparia); lactuca sativa (Prickly lette) (Lactuca seriola); gelidium amansicaue (Lamium amplexicaule); sesamom indicum (Lamium purpureum); striga asiatica (Lepidium virginicum); leptospira (Leptochloa spp.); lithospermum (Lithospermum spp.); perennial ryegrass (Lolium perenne); chamomile (pineapple) (Matricaria discoidea); red weeds (red weed) (masson pine (Melochia corifolia)); root of common Yam (Mercury, Annula) (indigo (Mercury annua) and Linesma nivea (Meluguiaria verticillata), forget-me-not (Polysyis arvensis), Potentilla (Pollugguata), Potentilla (Ocothera lacniata), Oryza sativa (Oryza sativa), Imperata (Panicum calvatica/Hare), Panicum miliaceum (Fapanicum paniculatum) (Polygonum dichotomiforum), Potentilla fusca (Browntop et) (Polygonum graminearum millaria) (Polygonum ramosum), Panicum paniculata (Papanicum texanum), Potentilla (Pohua), Potentilla (Polygonum pratensis) and Potentilla (Potentilla pratensis), Potentilla pratensis (Potentilla pratensis (Potentilla pratensis) and Potentilla (Potentilla pratensis) are), Potentilla (Potentilla pratensis (Potentilla) and Potentilla pratensis (Potentilla) are pratensis (Potentilla) to poeda Genus (Portulaca oleracea)); purslane (portulaa carocera); buttercup (Buttercup) (Buttercup (ranuculus spp.)); wild radish (Raphanus raphnistum); wild luteolin (Wild mignonette) (yellow clover (Reseda lutea)); purslane Florida Pusley (lucerne (Richardia scabra)); rumex acetosella; senecio scandens (Senecio); sesbania (Sesbania spp.); setaria spp; green bristlegrass (Setaria viridis); russian Thistle (Russian Thistle) (Sida spinosa); white mustard (Sinapis arvensis); carmustine (gamble mustard) (Jim Hill) (garlic (Sisymbrium altissimum)); sida acuta/Teaweed (Slda spinosa); black nightshade (Solanum nigrum); solanum rostratum (Buffalobur) (Solanum rostratum)); herba Sonchi Oleracei (Smooth sow-thistle) (Sonchus oleraceus)); shattercane (Sorghum saccharatum (Sorghum bicolor)); sorghum halepense (Sorghum halepense); sorghum autogenous (volumeter Sorghum) (Sorghum spp.); ottelia macrogola (Spergula arvensis); chickweed (Stellaria media); herba Patriniae (Field pennyress) (Thlaspi arvense); clover (Trifolium); volunteer wheat (Triticum wheat) (Triticum spp.); small nettle (Urtica urens); cabbage (Vaccaria hispanica); veronica officinalis (Veronica hederifolia); veronica (Veronica spp) Winter vetch (Winter vetch) (Vicia villosa)); pansy (Field pansy) (Viola arvensis); and Xanthium (Xanthium Pensylvanicum).

Specific examples of ALS-tolerant plants that can be very well controlled by the present invention include Stellaria spp, Papavera spp and Matricaria spp. Specific species of plants that have developed ALS tolerance and can be controlled include chickweed (Stellaria media), corn poppy (Papaver rhoeas), chamomile (Matricaria chamomilla), and chamomile (Matricaria inodora).

As indicated above, the components (a) metribuzin and (B) one or more sulfonylureas can be used in the form of one or more compositions containing the active ingredient.

The composition of active ingredients for use in the present invention may be formulated in conventional manner, for example by mixing metribuzin and/or one or more sulfonylureas with suitable adjuvants. Suitable adjuvants will depend on factors such as the type of formulation and end use. Suitable auxiliaries are commercially available and known to the person skilled in the art.

In particular, the composition may comprise one or more adjuvants selected from: fillers, carriers, solvents, surfactants, stabilizers, defoamers, antifreeze agents, preservatives, antioxidants, colorants, thickeners, solid adhesion agents, fillers, wetting agents, dispersants, lubricants, antiblocking agents, and diluents. Such adjuvants are known in the art and are commercially available. Their use in the formulation of compositions for use in the present invention will be apparent to those skilled in the art.

Suitable formulations for applying a combination of metribuzin and one or more sulfonylureas (either together or separately) include soluble Solution (SL), Emulsifiable Concentrate (EC), aqueous Emulsion (EW), Microemulsion (ME), Suspension (SC), oil-based suspension (OD), suspended seed coating (FS), Water Dispersible Granule (WDG), Soluble Granule (SG), Wettable Powder (WP), Soluble Powder (SP), Granule (GR), micro-Capsule Granule (CG), Fine Granule (FG), macro-granule (GG), Suspoemulsion (SE), micro-Capsule Suspension (CS) and micro-granule (MG).

Preferred formulation types to be used in the composition of the present invention are Water Dispersible Granules (WDG), Soluble Granules (SG) and oil based suspension concentrates (OD).

The composition may comprise one or more inert fillers. Such inert fillers are known in the art and are commercially available. Suitable fillers include, for example, naturally ground minerals such as kaolin, alumina, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth; or synthetic ground minerals such as highly dispersed silicic acid, alumina, silicates, and calcium hydrogenphosphates. Suitable inert fillers for the granules include, for example, crushed and fractionated natural minerals (such as calcite, marble, pumice, sepiolite and dolomite), or synthetic granules of inorganic and organic abrasive materials, and granules of organic materials (such as sawdust, coconut shells, corn cobs and tobacco stalks).

The composition may comprise one or more surfactants, which are preferably nonionic, cationic and/or anionic in character, and which are mixtures of surfactants with good emulsifying, dispersing and wetting properties, depending on the active compound being formulated. Suitable surfactants are known in the art and are commercially available.

Suitable anionsThe surfactant may be both a so-called water-soluble soap (water-soluble soap) and a water-soluble synthetic surface-active compound (water-soluble synthetic surface-active compound). Soaps that may be used include higher fatty acids (C)₁₀-C₂₂) For example, sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures.

The surfactant system may comprise an ionic or non-ionic emulsifier, dispersant or wetting agent. Examples of such surfactants include salts of polyacrylic acids, salts of lignosulfonic acids, salts of benzenesulfonic or naphthalenesulfonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (especially alkylphenols), sulfosuccinate ester salts, taurine derivatives (especially alkyl taurates), and phosphoric esters of polyethoxylated phenols or alcohols.

The presence of at least one surfactant is generally required when the active compound and/or inert carrier and/or adjuvant/adjuvant is not soluble in water and the medium for the final application of the composition is water.

The composition optionally further comprises one or more polymeric stabilizers. Suitable polymeric stabilizers that may be used in the present invention include, but are not limited to, polypropylene, polyisobutylene, polyisoprene, copolymers of mono-and diolefins, polyacrylates, polystyrene, polyvinyl acetate, polyurethanes, or polyamides. Suitable stabilizers are known in the art and are commercially available.

It is generally believed that the surfactants and polymeric stabilizers described above impart stability to the composition, thereby allowing the composition to be formulated, stored, transported, and applied.

Suitable antifoaming agents include all substances which can be used for this purpose in agrochemical compositions in general. Suitable defoamers are known in the art and are commercially available. Particularly preferred defoamers are mixtures of polydimethylsiloxanes and perfluoroalkylphosphonic acids, for example silicone defoamers commercially available from GE or Compton (Compton).

Suitable solvents for inclusion in the composition may be selected from all common organic solvents which completely dissolve the active compounds metribuzin and flazasulfuron. Suitable organic solvents for metribuzin and flazasulfuron are also known in the art. The following solvents may be considered preferred: n-methylpyrrolidone, N-octylpyrrolidone, cyclohexyl-1-pyrrolidone; or mixtures of paraffinic, isoparaffinic, naphthenic and aromatic hydrocarbons, e.g. SOLVESSO^TM200. Suitable solvents are commercially available.

Suitable preservatives for use in the compositions include all materials which may be conventionally used for this purpose in agrochemical compositions of this type and are also well known in the art. Suitable examples which may be mentioned include commercially available preservatives(from Bayer (Bayer AG)) and(from bayer).

Suitable antioxidants for use in the composition are all substances which can be used for this purpose in agrochemical compositions in general, as known in the art. Butylated hydroxytoluene is preferred.

Suitable thickeners for use in the composition include all materials which are commonly used for this purpose in agrochemical compositions, for example xanthan gum, PVOH, cellulose and its derivatives, clay hydrated silicates, magnesium aluminium silicate or mixtures thereof. Again, such thickeners are known in the art and are commercially available.

The composition may further comprise one or more solid attachment agents. Such adhesives are known in the art and are commercially available. They include organic binders including tackifiers, such as cellulose or substituted cellulose, natural and synthetic polymers in the form of powders, granules, or latices, and inorganic binders, such as gypsum, silica, or cement.

In the methods and uses of the invention, the combination of active ingredients (a) metribuzin and (B) one or more sulfonylureas may be applied to the plants by any convenient method, for example to the foliage of the plants, and/or the locus where they are desired to be controlled, such as the surrounding soil. By "locus" is meant the location where the plant is growing, the location where the plant propagation material of the plant is sown or the location where the plant propagation material of the plant is to be sown. Suitable methods for applying the components are known in the art and include coating, spraying, showering, dipping, soaking, injecting, irrigating, and the like.

In addition to the combination of (a) metribuzin and (B) one or more sulfonylureas, the method of the invention can also use other pesticides. For example, the compositions used in the present invention may contain or be mixed with other pesticides (e.g., fungicides, insecticides, and nematicides), growth factor enhancers, and fertilizers to enhance the treatment activity of the present invention or to broaden its activity range. Similarly, the methods of the present invention may be used in conjunction with one or more of the aforementioned active ingredients, again to achieve enhanced efficacy or a broader range of activity.

Embodiments of the present invention will now be described by way of the following examples.

Unless otherwise indicated, percentages are by weight.

Examples

Formulation examples

a)Water dispersible granule (WG) formulation

Water dispersible granule (WG) formulations were prepared from the components outlined in table 1 below.

TABLE 1

b)Oil-based suspension (OD) formulations

Oil-based suspension concentrate (OD) formulations were prepared from the components summarized in table 2 below.

TABLE 2

c)Soluble Granule (SG) formulation

A Soluble Granule (SG) formulation was prepared from the components summarized in table 3 below.

TABLE 3

A series of different formulations were prepared according to the above method. The formulation types and active ingredients present in the formulations are summarized in table 4 below. For comparison purposes, examples C1 to C11 were prepared. Examples 1 to 16 are examples of the present invention.

In the formulations prepared, component (a) is metribuzin and components (B1) to (B10) are the sulfonylureas:

b1: thifensulfuron methyl

B2: tribenuron-methyl

B3: metsulfuron methyl

B4: sulfonyl sulfuron methyl

B5: amidosulfuron-methyl

B6: mesosulfuron-methyl

B7: iodine sulforon

B8: rimsulfuron

B9: nicosulfuron

B10: halosulfuron-methyl

TABLE 4

Biological examples

A synergistic effect of the combination of two active compounds occurs when the activity of the combination of two active compounds is greater than the sum of the activities of the two active compounds administered alone.

The expected activity of a given combination of two active compounds can be calculated by the so-called "coll ratio (Colby) formula" (see s.r. coll ratio (Colby), "Calculating the Synergistic and Antagonistic Responses of Herbicide Combinations" (Weeds)1967, 15, 20-22):

whereby:

E＝A+B-(A×B/100)

wherein:

a-percent activity of compound a when active compound a was used at an application rate of m g/ha;

b-percent activity of compound B when active compound B was used at an application rate of n g/ha;

e-percentage activity estimated when compounds a and B were used together at application rates of m g/ha and n g/ha.

If the actual activity observed for the combination of compounds a and B is greater than the activity calculated using the above formula, the activity of the combination is superadditive, i.e. there is a synergistic effect.

The biological activity of plants exhibiting resistance to sulfonylureas was tested against the formulations of examples C1 to C11 and 1 to 16 as follows:

seeds of normal wild species and ALS-resistant varieties of each of chickweed, corn poppy, chamomile and light chamomile were sown in trays of peat-based compost placed in a greenhouse to allow germination. At the cotyledon stage, four uniform-sized seedlings were transplanted into each 9 cm-diameter plastic pot containing loam mixed with 25% by volume of horticultural silver sand and further mixed with coarse sand in a ratio of 3: 1. The resulting potting medium was supplemented with Osmacote slow release fertilizer (16: 8: 9+ Mg) to provide 1.4g per 0.35L pot.

The formulations of each of examples C1 to C11 and 1 to 16 were applied to seedlings by spraying. Three replicate pots were used for each treatment. The plants were watered at the top prior to spraying. To ensure the leaves were dry, no water was applied on the day of spraying, and a final top watering was performed the day before spraying. The herbicide formulation was prepared from tap water. The laboratory track sprayer was equipped with a Lurmark OIE80 Even spray nozzle to deliver 200 liters per ha using a pressure of gears 4 and 210Pa (30 psi). The application rates of the active ingredients are listed in table 5 below.

After spraying, the plants were moved back to the greenhouse and the sprayed pots were arranged in three random blocks. The temperature range of the greenhouse is 12.2 ℃ to 16.1 ℃ in the daytime and 10.9 ℃ to 13.3 ℃ at night. The relative humidity ranges from 75% to 101%.

Throughout the experiment, plants were irrigated to maintain soil close to field capacity. After herbicide treatment, the plants were watered by sub-irrigation using separate plastic trays for each pot to avoid any risk of cross-contamination.

The visual percentage of the control based on the 0-100 linear scale was evaluated 21 Days After Treatment (DAT). The linear scale ranged from 0 (no effect) to 100 (plant death).

The results of the visual inspection are summarized in table 6 below. In table 6, 'Obs' indicates the observed results, and 'Exp' indicates the results expected by applying the Colby equation discussed above.

By reading the data presented in tables 5 and 6 above, metribuzin caused damage to both ALS-resistant plants and wild plants as expected (composition C1).

Furthermore, as expected, sulfonylureas, i.e. thifensulfuron-methyl, tribenuron-methyl, metsulfuron-methyl, sulfosulfuron, amidosulfuron, mesosulfuron-methyl, iodosulfuron, rimsulfuron, nicosulfuron, halosulfuron-methyl had little effect on all ALS-tolerant plants (composition C2-C11), while significantly damaging wild (non-tolerant) plants.

Surprisingly, the damage caused by metribuzin in combination with each sulfonylurea significantly exceeded the damage caused by metribuzin alone on ALS-tolerant plants. The data indicate that the combination of metribuzin and sulfonylureas shows a synergistic effect in controlling ALS-tolerant plants.

Features and aspects of the invention are summarized in the following numbered items:

1. a method for controlling the growth of ALS-resistant plants, which method comprises applying to the plants and/or to the locus thereof a herbicidally effective amount of a combination of (a) metribuzin and (B) one or more sulfonylureas.

2. The method of item 1, wherein component (B) is a single sulfonylurea.

3. The method of any one of items 1 or 2, wherein the one or more sulfonylureas are selected from the group consisting of amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, flazasulfuron, fluazimsulfuron, foramsulfuron, halosulfuron, iodosulfuron-methyl, thiophenesulfone, metrisulfuron-methyl, methisulfuron-methyl, mesosulfuron, monosulfuron, nicosulfuron, pyrisulfuron, epoxysulfuron, primisulfuron, prosulfuron, halosulfuron, rimsulfuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron-methyl, trifloxysulfuron, prosulfuron, and triflusulfuron.

4. The method of item 3, wherein the one or more sulfonylureas are selected from the group consisting of thifensulfuron-methyl, tribenuron-methyl, metsulfuron-methyl, sulfosulfuron, amidosulfuron, mesosulfuron, iodosulfuron, rimsulfuron, nicosulfuron, and halosulfuron-methyl.

5. The method according to any preceding claim, wherein components (a) metribuzin and (B) one or more sulfonylureas are applied at an application rate of from 0.03 kilograms per hectare (kg/ha) to 2kg/ha of the total amount of active ingredient applied.

6. The method of item 5, wherein components (A) metribuzin and (B) one or more sulfonylureas are applied at an application rate of from 0.05kg/ha to 1.5kg/ha of the total amount of active ingredients.

7. The method of any preceding claim, wherein component (a) metribuzin is applied in an amount of at least 5 g/ha.

8. The method of item 7, wherein component (A) metribuzin is applied in an amount of at least 20 g/ha.

9. The method of any preceding claim, wherein component (a) metribuzin is applied in an amount of up to 700 g/ha.

10. The method of item 9, wherein component (a) metribuzin is applied in an amount of 70 g/ha.

11. A method according to any preceding claim, wherein the one or more sulfonylureas are applied in a total amount of at least 1 g/ha.

12. The method of item 11, wherein the one or more sulfonylureas are applied in a total amount of at least 2 g/ha.

13. A method according to any preceding claim, wherein the one or more sulfonylureas are applied in a total amount of up to 200 g/ha.

14. The method of item 13, wherein the one or more sulfonylureas are applied in a total amount of up to 100 g/ha.

15. The method of any preceding claim, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is at most 400: 1.

16. The method of item 15, wherein the weight ratio of (a) metribuzin and (B) one or more sulfonylureas is at most 70: 1.

17. The method of any preceding claim, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is at most 10: 1.

18. The method of any preceding claim, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is greater than 1: 20.

19. The method of item 18, wherein the weight ratio of (a) metribuzin and (B) one or more sulfonylureas is greater than 1: 5.

20. The method of item 19, wherein the weight ratio of (a) metribuzin and (B) one or more sulfonylureas is greater than 1: 1.

21. The method of any preceding claim, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is from 250: 1 to 1: 4.

22. The method of item 21, wherein the weight ratio of (a) metribuzin and (B) one or more sulfonylureas is from 100: 1 to 1: 1.

23. The method of item 22, wherein the weight ratio of (a) metribuzin and (B) one or more sulfonylureas is from 70: 1 to 1: 1.

24. A method according to any preceding claim, wherein components (A) metribuzin and (B) one or more sulfonylureas are applied to the plants and/or their locus simultaneously and/or sequentially.

25. A method according to any preceding claim, wherein components (A) metribuzin and (B) one or more sulfonylureas are applied to the plants and/or their locus after germination.

26. The method according to any preceding claim, wherein the ALS-resistant plant is present in a crop of: wheat (including both soft and hard wheat), barley, rye, oats, corn, rice, sorghum, triticale, beans, lentils, peas, soybeans and peanuts, cotton, flax, hemp, jute, spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or peppers.

27. The method of item 26, wherein the ALS resistant plants are present in: wheat (including both soft and hard), barley, rye, oats, triticale, corn, rice, soybean, cotton, tomato, and potato.

28. The method of item 27, wherein the ALS resistant plant is present in a crop of: wheat (including both soft and hard), barley, rye, oats and triticale.

29. The method of any preceding claim, wherein the ALS-tolerant plant comprises Stellaria, Papaver or Matricaria.

30. The method of item 29, wherein the ALS-tolerant plant comprises chickweed, corn poppy, chamomile, or tanacetum parthenium.

31. The method according to any one of the preceding claims, wherein components (a) and (B) are applied in the form of one or more formulations selected from soluble agents (SL), Emulsifiable Concentrates (EC), aqueous Emulsions (EW), Microemulsions (ME), suspending agents (SC), oil-based suspending agents (OD), suspended seed coatings (FS), Water Dispersible Granules (WDG), Soluble Granules (SG), Wettable Powders (WP), Soluble Powders (SP), Granules (GR), micro-encapsulated granules (CG), Fine Granules (FG), macro-granules (GG), Suspoemulsions (SE), micro-encapsulated suspensions (CS) and micro-granules (MG).

32. The method of item 31, wherein components (a) and (B) are administered in the form of one or more formulations selected from Water Dispersible Granules (WDG), Soluble Granules (SG) and oil based suspension concentrates (OD).

33. Use of a herbicidally effective amount of a combination of (a) metribuzin and (B) one or more sulfonylureas in controlling ALS-resistant plant growth.

34. The use according to item 33, wherein component (B) is a single sulfonylurea.

35. The use according to any one of items 33 or 34, wherein the one or more sulfonylureas are selected from amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, mazosulfuron, flazasulfuron, fluazimsulfuron, foramsulfuron, halosulfuron-methyl, iodosulfuron, thiophenesulfone, metrisulfuron-methyl, methisulfuron-methyl, mesosulfuron, monosulfuron, nicosulfuron, pyrisulfuron, epoxysulfuron, primisulfuron, prosulfuron, halosulfuron, rimsulfuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron-methyl, trifloxysulfuron-methyl, triflusulfuron-methyl, and triflusulfuron-methyl.

36. The use of item 35, wherein the one or more sulfonylureas are selected from the group consisting of thifensulfuron-methyl, tribenuron-methyl, metsulfuron-methyl, sulfosulfuron, amidosulfuron, mesosulfuron, iodosulfuron, rimsulfuron, nicosulfuron, and halosulfuron-methyl.

37. The use according to any one of items 33 to 36, wherein components (a) metribuzin and (B) one or more sulfonylureas are applied at an application rate of from 0.03 kilograms per hectare (kg/ha) to 2kg/ha of the total amount of active ingredient applied.

38. The use according to item 37, wherein components (a) metribuzin and (B) one or more sulfonylureas are applied at an application rate of from 0.05kg/ha to 1.5kg/ha of the total amount of active ingredients.

39. The use according to any one of claims 33 to 38, wherein component (a) metribuzin is applied in an amount of at least 5 g/ha.

40. The use according to item 39, wherein component (A) metribuzin is applied in an amount of at least 20 g/ha.

41. The use according to any one of claims 33 to 40, wherein component (A) metribuzin is applied in an amount of up to 700 g/ha.

42. The use according to item 41, wherein component (A) metribuzin is applied in an amount of 70 g/ha.

43. The use according to any one of claims 33 to 42, wherein the one or more sulfonylureas are applied in a total amount of at least 1 g/ha.

44. The use of item 43, wherein the one or more sulfonylureas are applied in a total amount of at least 2 g/ha.

45. The use according to any one of claims 33 to 44, wherein the one or more sulfonylureas are applied in a total amount of up to 200 g/ha.

46. The use of item 45, wherein the one or more sulfonylureas are applied in a total amount of up to 100 g/ha.

47. The use of any one of claims 33 to 46, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is at most 400: 1.

48. The use of item 47, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is at most 70: 1.

49. The use of any one of claims 33 to 48, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is at most 10: 1.

50. The use of any one of claims 33 to 49, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is greater than 1: 20.

51. The use of item 50, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is greater than 1: 5.

52. The use of item 51, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is greater than 1: 1.

53. The use of any one of claims 33 to 52, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is from 250: 1 to 1: 4.

54. The use of item 53, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is from 100: 1 to 1: 1.

55. The use of item 54, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is from 70: 1 to 1: 1.

56. Use according to any one of claims 33 to 55, wherein components (A) metribuzin and (B) one or more sulfonylureas are applied to the plants and/or their locus simultaneously and/or sequentially.

57. Use according to any one of claims 33 to 56, wherein the components (A) metribuzin and (B) one or more sulfonylureas are applied to the plants and/or their locus after germination.

58. The use according to any one of claims 33 to 57, wherein the ALS resistant plants are present in: wheat (including both soft and hard wheat), barley, rye, oats, corn, rice, sorghum, triticale, beans, lentils, peas, soybeans and peanuts, cotton, flax, hemp, jute, spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or peppers.

59. The use according to item 58, wherein the ALS resistant plants are present in: wheat (including both soft and hard), barley, rye, oats, triticale, corn, rice, soybean, cotton, tomato, and potato.

60. The use according to item 59, wherein the ALS resistant plants are present in: wheat (including both soft and hard), barley, rye, oats and triticale.

61. The use of any one of items 33 to 60, wherein the ALS-tolerant plant comprises Stellaria, Papaveris, or Matricaria.

62. The use of item 61, wherein the ALS-tolerant plant comprises chickweed, corn poppy, chamomile, or tanacetum parthenium.

63. The use according to any one of claims 33 to 62, wherein components (A) and (B) are applied in the form of one or more formulations selected from soluble agents (SL), Emulsifiable Concentrates (EC), aqueous Emulsions (EW), Microemulsions (ME), Suspensions (SC), oil-based suspensions (OD), suspended seed coatings (FS), Water Dispersible Granules (WDG), Soluble Granules (SG), Wettable Powders (WP), Soluble Powders (SP), Granules (GR), micro-encapsulated granules (CG), Fine Granules (FG), macro granules (GG), Suspoemulsions (SE), micro-encapsulated suspensions (CS) and Micro Granules (MG).

64. The use according to item 63, wherein components (A) and (B) are administered in the form of one or more formulations selected from Water Dispersible Granules (WDG), Soluble Granules (SG) and oil based suspension concentrates (OD).

65. A composition for controlling ALS-tolerant plants comprising a herbicidally effective amount of a combination of (a) metribuzin and (B) one or more sulfonylureas.

66. The composition of item 65, wherein component (B) is a single sulfonylurea.

67. The composition of any one of items 65 or 66, wherein the one or more sulfonylureas are selected from amidosulfuron, azimsulfuron, bensulfuron, chlorimuron, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, mazosulfuron, flazasulfuron, fluazimsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, thienylsulfone, azimsulfuron, methisulfuron-methyl, metsulfuron-methyl, mesosulfuron, monosulfuron, nicosulfuron, pyrisulfuron, epoxysulfuron, primisulfuron, prosulfuron, halosulfuron, rimsulfuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, and triflusulfuron.

68. The composition of item 67, wherein the one or more sulfonylureas are selected from the group consisting of thifensulfuron-methyl, tribenuron-methyl, metsulfuron-methyl, sulfosulfuron, amidosulfuron, mesosulfuron, iodosulfuron, rimsulfuron, nicosulfuron, and halosulfuron-methyl.

69. The composition of any one of items 65 to 68, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is at most 400: 1.

70. The composition of item 69, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is at most 70: 1.

71. The composition of any one of claims 65 to 70, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is at most 10: 1.

72. The composition of any one of items 65 to 71, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is greater than 1: 20.

73. The composition of item 72, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is greater than 1: 5.

74. The composition of item 73, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is greater than 1: 1.

75. The composition of any one of items 65 to 74, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is from 250: 1 to 1: 4.

76. The composition of item 75, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is from 100: 1 to 1: 1.

77. The composition of item 76, wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is from 70: 1 to 1: 1.

78. The composition of any one of items 65 to 77, wherein the composition is a formulation selected from: soluble agent (SL), Emulsifiable Concentrate (EC), aqueous Emulsion (EW), Microemulsion (ME), suspending agent (SC), oil-based suspending agent (OD), suspended seed coating agent (FS), Water Dispersible Granule (WDG), Soluble Granule (SG), Wettable Powder (WP), Soluble Powder (SP), Granule (GR), micro-Capsule Granule (CG), Fine Granule (FG), large granule (GG), Suspoemulsion (SE), micro-capsule suspending agent (CS) and micro-granule (MG).

79. The composition of item 78, wherein the composition is a formulation selected from: water Dispersible Granules (WDG), water Soluble Granules (SG) and oil based suspension concentrates (OD).

The following corresponds to the original claims in the parent application, which are now incorporated as part of the specification:

1. a method for controlling the growth of ALS-resistant plants, which comprises applying to the plants and/or to the locus thereof a herbicidally effective amount of a combination of (a) metribuzin and (B) one or more sulfonylureas.

2. The method of item 1, wherein the one or more sulfonylureas are selected from the group consisting of amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, mazosulfuron, flazasulfuron, foramsulfuron, halosulfuron-methyl, iodosulfuron, thienylsulfone, oxazinosulfuron-methyl, methisulfuron-methyl, metsulfuron-methyl, mesosulfuron, monosulfuron, nicosulfuron, orthosulfamuron, epoxysulfuron, primisulfuron, prosulfuron, halosulfuron, rimsulfuron, sulsulfuron, sulfosulfuron, thifensulfuron, triasulfuron, trifloxysulfuron, and triflusulfuron; preferably wherein the one or more sulfonylureas are selected from thifensulfuron-methyl, tribenuron-methyl, metsulfuron-methyl, sulfosulfuron, amidosulfuron, mesosulfuron-methyl, iodosulfuron, rimsulfuron, nicosulfuron, and halosulfuron-methyl.

3. The method of any one of the preceding claims, wherein components (a) metribuzin and (B) one or more sulfonylureas are applied at an application rate of 0.03 kilograms per hectare (kg/ha) to 2kg/ha of the total amount of active ingredient applied; preferably, wherein the components (A) metribuzin and (B) one or more sulfonylureas are applied at an application rate of from 0.05kg/ha to 1.5kg/ha of the total amount of active ingredients.

4. The method of any one of the preceding claims, wherein component (a) metribuzin is applied in an amount of at least 5 g/ha; preferably, wherein component (A) metribuzin is applied in an amount of at least 20 g/ha.

5. The method of any one of the preceding claims, wherein the one or more sulfonylureas are applied in a total amount of at least 1 g/ha; preferably, wherein the one or more sulfonylureas are applied in a total amount of at least 2 g/ha.

6. The method of any one of the preceding claims, wherein the weight ratio of (a) metribuzin and (B) one or more sulfonylureas is at most 400: 1; preferably wherein the weight ratio of (a) metribuzin and (B) one or more sulfonylureas is at most 70: 1; more preferably wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is at most 10: 1.

7. The method of any one of the preceding claims, wherein the weight ratio of (a) metribuzin and (B) one or more sulfonylureas is greater than 1: 20; preferably wherein the weight ratio of (a) metribuzin and (B) one or more sulfonylureas is greater than 1: 5; more preferably wherein the weight ratio of (a) metribuzin and (B) one or more sulfonylureas is greater than 1: 1; in particular wherein the weight ratio of (a) metribuzin and (B) one or more sulfonylureas is from 250: 1 to 1: 4; more particularly wherein the weight ratio of (a) metribuzin and (B) one or more sulfonylureas is from 100: 1 to 1: 1; still more particularly wherein the weight ratio of (A) metribuzin and (B) one or more sulfonylureas is from 70: 1 to 1: 1.

8. The method of any one of the preceding claims, wherein components (a) metribuzin and (B) one or more sulfonylureas are applied to the plants and/or their locus after germination.

9. The method of any one of the preceding claims, wherein the ALS resistant plant is present in a crop of: wheat (including both soft and hard wheat), barley, rye, oats, corn, rice, sorghum, triticale, beans, lentils, peas, soybeans and peanuts, cotton, flax, hemp, jute, spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or peppers; preferably, wherein said ALS resistant plants are present in: wheat (including both soft and hard), barley, rye, oats, triticale, corn, rice, soybean, cotton, tomato, and potato; more preferably, wherein said ALS resistant plants are present in the following crops: wheat (including both soft and hard), barley, rye, oats and triticale.

10. The method of any one of the preceding claims, wherein the ALS-tolerant plant comprises Stellaria spp, Papavera spp or Matricaria spp; preferably, wherein the ALS-tolerant plant comprises chickweed (Stellaria media), Papaver rhoeas (Papaver rhoeas), chamomile (Matricaria chamomilla), or chamomile (Matricaria inodora).

11. The method of any one of the preceding claims, wherein components (a) and (B) are administered in the form of one or more formulations selected from: water Dispersible Granules (WDG), water Soluble Granules (SG) and oil based suspension concentrates (OD).

12. Use of a herbicidally effective amount of a combination of (a) metribuzin and (B) one or more sulfonylureas in controlling ALS-resistant plant growth.

13. The use of item 12, wherein the one or more sulfonylureas are selected from the group consisting of thifensulfuron-methyl, tribenuron-methyl, metsulfuron-methyl, sulfosulfuron, amidosulfuron, mesosulfuron, iodosulfuron, rimsulfuron, nicosulfuron, and halosulfuron-methyl.

14. A composition for controlling ALS-tolerant plants comprising a herbicidally effective amount of a combination of (a) metribuzin and (B) one or more sulfonylureas.

15. The composition of item 14, wherein the one or more sulfonylureas are selected from the group consisting of thifensulfuron-methyl, tribenuron-methyl, metsulfuron-methyl, sulfosulfuron, amidosulfuron, mesosulfuron, iodosulfuron, rimsulfuron, nicosulfuron, and halosulfuron-methyl.