CN108777959B

CN108777959B - Safeners and use of PPO inhibitor herbicides

Info

Publication number: CN108777959B
Application number: CN201780017166.6A
Authority: CN
Inventors: S·L·希恩; G·S·查郝尔; F·J·小达米克
Original assignee: FMC Corp
Current assignee: FMC Corp
Priority date: 2016-03-15
Filing date: 2017-03-06
Publication date: 2022-04-15
Anticipated expiration: 2037-03-06
Also published as: AR107843A1; AU2023214309A1; BR112018068518A2; JP2019511499A; CN108777959A; TW201735791A; WO2017160524A1; MX2018011137A; AU2021204658A1; KR20230012657A; AU2017234507A1; KR20180119603A; EP3429353A4; CA3016885A1; EP3429353A1; JP2022058528A; TWI755382B

Abstract

Methods, compositions, and methods of making such compositions for reducing crop injury by applying to a crop a composition containing one or more safeners and a herbicide composition containing a protoporphyrinogen oxidase (PPO) inhibitor are disclosed. In a particular aspect, the safener composition comprises cloquintocet-mexyl and/or mefenpyr-diethyl.

Description

Safeners and use of PPO inhibitor herbicides

Technical Field

The presently disclosed subject matter relates to the field of agricultural compositions and formulations, particularly safener compositions and formulations for use with herbicides.

Background

One of the more preferred methods of controlling weeds in crops relates to the post-emergence control of weeds, wherein the herbicide is applied after the emergence of the problem crop from the soil. Post-emergence control is desirable because it requires application of the herbicide only in areas where weed infestation occurs. In contrast, pre-emergence control requires the application of the herbicide early in the growing season before most weeds germinate, with the result that these chemicals must be applied throughout the field, even if this is not ultimately required.

Protoporphyrinogen Oxidase (PPO) is an enzyme found in both plants and animals that is responsible for the seventh step in the biosynthesis of protoporphyrin IX. This porphyrin is a biosynthetic precursor of hemoglobin in animals and chlorophyll in plants. The enzyme catalyzes the dehydrogenation of protoporphyrinogen IX to protoporphyrin IX.

Fast-acting herbicides such as PPO herbicides are not safe for many crops when applied post-emergence. Protoporphyrinogen Oxidase (PPO) inhibitors are herbicides that act by blocking the production of chlorophyll and heme in plants, which ultimately leads to the accumulation of protoporphyrinogen IX, which is toxic to plants.

For example, herbicides such as carfentrazone-ethyl and fluthiacet-methyl may damage cereal crops.

Safeners are compounds used in combination with herbicides to make the herbicide "safer" when used in crops. This may include reducing the effect of the herbicide on the crop plants, and/or improving the selectivity between the weed species and the crop plants against which the herbicide is directed.

Disclosure of Invention

One aspect of the present invention relates to a method of selectively controlling weeds in crops of plants comprising applying to the weeds in the crop an herbicidally effective amount of an herbicide composition comprising a fast acting herbicide and an effective amount of a safener composition.

In some aspects, the safener composition comprises one or more safeners selected from the group consisting of: cloquintocet-mexyl, mefenacet, Benoxacor (Benoxacor), dichlormid (dichlormid), isoxadifen-ethyl, cyprosulfamide (cyprosulfamide), fenclorim (fenclorim), fenchlorazole-ethyl (fenchlorazole-ethyl), fluxofenamate (fluxofenim), naphthalic anhydride (naphthalic anhydride), cyanamide (cyclometril), oxabetrinil (oxabetrinil), fenchloraz (fluazuole), fenchlorazole (furilazole), vanilliron (daimuron), cumyluron (cumyluron), dimeglute (dimepierate) and phorate (dimeholate).

In some aspects, fast acting herbicides include protoporphyrinogen oxidase (PPO) inhibitor class herbicides, diquat, paraquat, glufosinate-ammonium and bialaphos.

Another aspect of the present invention relates to a method of selectively controlling weeds in crops of plants comprising applying to the weeds in the crop a herbicidally effective amount of a herbicide composition comprising a protoporphyrinogen oxidase (PPO) inhibitor and an effective amount of a safener composition. In some aspects, the safener comprises cloquintocet-mexyl, mefenpyr-diethyl, or a mixture thereof.

In some aspects, a formulation is disclosed comprising a protoporphyrinogen oxidase (PPO) inhibitor herbicide and a safener composition. In some aspects, the safener comprises cloquintocet-mexyl, mefenpyr-diethyl, or a mixture thereof.

In some aspects, methods of making formulations for selectively controlling weeds in crops comprising mixing a herbicide composition comprising a protoporphyrinogen oxidase (PPO) inhibitor with a composition comprising a safener are disclosed. In some aspects, the safener composition comprises cloquintocet-mexyl, mefenpyr-diethyl, or a mixture thereof.

Detailed Description

As used herein and unless otherwise specified, the term "herbicide" refers to a combination mixture that is produced, sold, or used in the field to kill or inhibit unwanted plants (such as, but not limited to, harmful or annoying weeds, broadleaf plants, grasses, and sedges); and can be used for crop protection, building protection or turf protection. The term "herbicide" includes herbicidal products for end use. The composition may be a pure compound, a solution of a chemical compound, a mixture of chemical compounds, an emulsion, a suspension, a solid-liquid mixture, or a liquid-liquid mixture. The term "herbicide" also refers to a product that is commercially available from a manufacturer to an end user who can apply the purchased herbicide to the affected field or mix it with other excipients.

The term "weeds" means and includes any plant that grows in an undesirable place, including volunteer crop plants or pesticide-resistant plants.

When used with respect to herbicides, the term "effective" or "herbicidally effective amount" refers to an amount necessary to produce an observable herbicidal effect on unwanted plant growth, including one or more of the following: necrosis, death, growth inhibition, replication inhibition, proliferation inhibition and removal, destruction or reduction of the appearance and activity of unwanted plants.

The term "herbicidally active ingredient" means an active ingredient in a herbicide that enables the herbicide to prevent, destroy, combat or reduce any weeds. Other ingredients of the herbicide that are not herbicidally active ingredients are excipients that help to allow the herbicidally active ingredients to be formed, stored or delivered to a target.

The term "herbicidal composition" is defined to mean a herbicide, as well as any composition comprising a herbicidally active ingredient. The composition may be a solution or a mixture. In addition, the definition of the term "herbicidal composition" also refers to any product intended for manufacture or intended for formulation or repackaging into other pesticidal products.

As used herein, the term "nominal use rate", or "registered use rate", or "nominal application rate" or "registered application rate" for a herbicidal composition refers to the rate of application to a field containing crops and/or weeds established by the agrochemical industry as indicated by the provisions of the Environmental Protection Agency (EPA) as being suitable for controlling a specified weed species. The registered usage rates are displayed on the commercial formulation package with an appropriate label.

Fast acting herbicides such as PPO herbicides are not safe for many crops when applied post-emergence. For example, carfentrazone-ethyl is known to cause damage to cereals. The herbicide metrizazin is not indicated for use in cereals because it is not safe for cereals. Herein, the inventors demonstrate that co-application of safener/safener mixtures provides grain safety against these herbicides. In addition, it is believed that the use of safe compositions with these herbicides can extend their usefulness on cereal crops.

In some embodiments, the herbicide and safener are applied separately. In other embodiments, a mixture comprising a herbicide and a safener may be applied.

One aspect of the present invention relates to a method of selectively controlling weeds in crops of plants comprising applying to the weeds of the crop an herbicidally effective amount of an herbicide composition comprising a fast acting herbicide and an effective amount of a safener composition.

In some embodiments, the safener composition comprises one or more safeners selected from the group consisting of: cloquintocet-mexyl, mefenacet, Benoxacor (Benoxacor), dichlormid (dichlormid), isoxadifen-ethyl, cyprosulfamide (cyprosulfamide), fenclorim (fenclorim), fenchlorazole-ethyl (fenchlorazole-ethyl), fluxofenamate (fluxofenim), naphthalic anhydride (naphthalic anhydride), cyanamide (cyclometril), oxabetrinil (oxabetrinil), fenchloraz (fluazuole), fenchlorazole (furilazole), vanilliron (daimuron), cumyluron (cumyluron), dimeglute (dimepierate) and phorate (dimeholate).

In some aspects, fast acting herbicides include protoporphyrinogen oxidase (PPO) inhibitors, diquat (diquat), paraquat (paraquat), glufosinate-ammonium, and bialaphos (bialaphos).

Examples of such PPO inhibitors include, but are not limited to: acifluorfen (acifluorfen), acifluorfen sodium (acifluorfen-sodium), carfentrazone-ethyl (azafenidin), bifenox (bifenox), butafenacil (butafenacil), metoxyfen (chlorin), fluroxypyr ether (ethofen-ethyl), fluroxypyr ether (fluorofenacet), fluorofen-ethyl (fluorofenacet), fluorofen (fluoroodifen), fluorofen-ethyl (fluoroglycofen-ethyl), fluorofen (fluorofenofen), fluorofen (fluoroxyfen), fluorofen (fluorofen-ethyl), fluorofen (fluorofenofen), fluorofen (fluoroxyfen), fluoroniflumen (fluorofenoxan), fluoronifron (fluoroxyfen), fluoroniflumfonamide (halosan), lactofen (fluorofen), fluorofen (fluroxypfen), fluroxypfen (fluroxypfen), fluroxypyr (fluroxypyr), fluroxypfen (fluroxypyr), fluroxypyr (fluroxypfen (fluroxypyr), fluroxypyr (fluroxypfen), fluroxypfen (fluroxypyr), fluroxypfen (fluroxypfen), fluroxypyr (fluroxypfen), fluroxypyr (fluroxypfen), fluroxypyr (fluroxypfen-ethyl (fluroxypfen), fluroxypfen (fluroxypfen), fluroxypyr (fluroxypyr), fluroxypfen-ethyl), fluroxypfen (fluroxypyr), fluroxypfen-ethyl (fluroxypfen), fluroxypyr (fluroxypfen-ethyl (fluroxypfen), fluroxypyr (fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr, fluroxypen (fluroxypyr, fluroxypyr (fluroxypyr), fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr, indoxyl (cinidon-ethyl), propyribac-sodium (flumipropyn), primisulfuron-methyl (flupropacil), fluthiacet-methyl (fluthiacet-methyl), thidiazuron (thiazimin), azafenidin (azafenidin), carfentrazone-acid (carfentrazone), carfentrazone-ethyl (carfentrazone-ethyl), sulfentrazone (sulffentrazone), pyribenzoxim (saflufenacil), flufenpyr-ethyl (flunpyr-ethyl), ET-751, JV 485, diclofen (nipyraclofen), or a mixture of two or more thereof.

Another aspect of the present invention relates to a method of selectively controlling weeds in crops comprising applying to the crop weeds a herbicidally effective amount of a herbicidal composition comprising a protoporphyrinogen oxidase (PPO) inhibitor and applying an effective amount of a composition comprising a safener ingredient.

Another aspect of the present invention relates to a method of selectively controlling weeds in crops comprising applying to crop weeds a formulation comprising a protoporphyrinogen oxidase (PPO) inhibitor and a safener composition.

In some embodiments, the safener comprises one or more safeners selected from the group consisting of: cloquintocet-mexyl, mefenpyr-diethyl, cumyluron (daimuron), curyluron (cumyluron), piprazole (dimepierate), fenclorim (fenclorim), fenclozole-ethyl (fenclozole-ethyl), isoxadifen-ethyl (isoxadifen-ethyl), cyprosulfamide (cyprosulfamide), clomazone (Benoxacor), dichlormid (dichlormid), furazol (furilazole), fluquine (fluxazole), oxabetrinil (oxabetrinil), chloracetonil (cyometrinil), naphthalic anhydride (naphthalic anhydride), phos-phos (dietholate), flufenxim (flufenxom) and mixtures thereof. In some embodiments, the safener is preferably cloquintocet-mexyl, mefenpyr-diethyl, or a mixture thereof.

In some embodiments, the PPO inhibitor may be selected from: pyraclononic acid, carfentrazone-ethyl, sulfentrazone, oxadiazine, pyribenzoxim and mixtures of two or more thereof. In some embodiments, the PPO inhibitor is preferably carfentrazone-ethyl or metribuzin.

In another embodiment, the protoporphyrinogen oxidase (PPO) inhibitor is selected from the group consisting of: diphenyl ether, oxadiazole, cyclic imide or pyrazole. Examples of these PPO classes include, but are not limited to: acifluorfen (acifluorfen), acifluorfen sodium (acifluorfen-sodium), carfentrazone-ethyl (azafenidin), bifenox (bifenox), butafenacil (butafenacil), metoxyfen (chlorin), fluroxypyr ether (ethofen-ethyl), fluroxypyr ether (fluorofenacet), fluorofen-ethyl (fluorofenacet), fluorofen (fluoroodifen), fluorofen-ethyl (fluoroglycofen-ethyl), fluorofen (fluorofenofen), fluorofen (fluoroxyfen), fluorofen (fluorofen-ethyl), fluorofen (fluorofenofen), fluorofen (fluoroxyfen), fluoroniflumen (fluorofenoxan), fluoronifron (fluoroxyfen), fluoroniflumfonamide (halosan), lactofen (fluorofen), fluorofen (fluroxypfen), fluroxypfen (fluroxypfen), fluroxypyr (fluroxypyr), fluroxypfen (fluroxypyr), fluroxypyr (fluroxypfen (fluroxypyr), fluroxypyr (fluroxypfen), fluroxypfen (fluroxypyr), fluroxypfen (fluroxypfen), fluroxypyr (fluroxypfen), fluroxypyr (fluroxypfen), fluroxypyr (fluroxypfen-ethyl (fluroxypfen), fluroxypfen (fluroxypfen), fluroxypyr (fluroxypyr), fluroxypfen-ethyl), fluroxypfen (fluroxypyr), fluroxypfen-ethyl (fluroxypfen), fluroxypyr (fluroxypfen-ethyl (fluroxypfen), fluroxypyr (fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr, fluroxypen (fluroxypyr, fluroxypyr (fluroxypyr), fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr (fluroxypyr), fluroxypyr, indoxyl (cinidon-ethyl), propyribac-sodium (flumipropyn), primisulfuron-methyl (flupropacil), fluthiacet-methyl (fluthiacet-methyl), thidiazuron (thiazimin), azafenidin (azafenidin), carfentrazone-acid (carfentrazone), carfentrazone-ethyl (carfentrazone-ethyl), sulfentrazone (sulffentrazone), pyribenzoxim (saflufenacil), flufenpyr-ethyl (flunpyr-ethyl), ET-751, JV 485, diclofen (nipyraclofen), or a mixture of two or more thereof.

The herbicidal compositions herein may be in any conventional agriculturally acceptable form, for example, in a two-pack form or in the form of a ready-to-use formulation or a tank-mix formulation. Furthermore, the active ingredients may be supplied in any suitable formulation type (either alone or pre-mixed), for example, Emulsion Concentrates (EC), Suspension Concentrates (SC), suspension-emulsions (SE), Capsule Suspensions (CS), water dispersible particles (WG), emulsifiable particles (EG), water-in-oil Emulsions (EO), water-in-water Emulsions (EW), micro-emulsions (ME), Oil Dispersions (OD), oil miscible flowable formulations (OF), oil miscible liquids (OL), soluble concentrates (SL), ultra low volume Suspensions (SU), ultra low volume liquids (UL), Dispersible Concentrates (DC), Wettable Powders (WP), mixed multi-phase formulations OF CS and EW (zw), or any other technically feasible formulation, in combination with agriculturally acceptable adjuvants. For tank-mixing, commercially available formulations of PPO inhibitor and safener are mixed in appropriate proportions in the tank prior to application to provide the target weight ratio of the active ingredients. In some embodiments, the herbicidal compositions of the present disclosure are tank mix formulations. In other embodiments, the herbicidal compositions of the present disclosure are provided as premixed Emulsifiable Concentrates (ECs).

The rate of application of the tank-mixed individual formulation active ingredients or compositions will vary depending on the prevailing conditions, such as the targeted weeds, extent of infestation, climatic conditions, soil conditions, crop species, mode of application and time of application. The composition comprising the PPO inhibitor and/or the safener may be applied as a spray, for example a water-dispersible concentrate, a wettable powder, or a water-dispersible granule.

In some embodiments, the application rate of each active ingredient ("ai"), e.g., herbicide or safener, may vary depending on the crop. In some embodiments, different application rate ranges may be employed for different PPO inhibitor herbicides. In some embodiments, the herbicide is applied at a rate of from about 5g active ingredient per hectare (g ai/ha) to about 420g active ingredient per hectare. In some embodiments, the application rate of the safener is from about 5g active ingredient/hectare to about 350g active ingredient/hectare, or from about 10g to about 300g active ingredient/hectare. In some embodiments, the weight ratio between safener and herbicide is from about 10:1 (safener/herbicide) to about 1:30 (safener/herbicide).

In one embodiment, the present disclosure describes an agricultural formulation or tank mix comprising a fast acting herbicide and a safener composition. The fast acting herbicide may comprise PPO. In some embodiments, the PPO inhibitor is selected from: pyraclononic acid, carfentrazone-ethyl, sulfentrazone, oxadiazine, pyribenzoxim or a mixture of two or more thereof. In some embodiments, the PPO inhibitor is preferably carfentrazone-ethyl or metribuzin. In some embodiments, the safener comprises cloquintocet-mexyl, mefenpyr-diethyl, or a mixture thereof. In some embodiments, the safener composition and the fast-acting herbicide are present in a weight ratio of about 10:1 (safener/herbicide) to about 1:30 (safener/herbicide). In some embodiments, these may be in the form of a tank-mixed, commercially available formulation at the time of application, or a suitable pre-mixed formulation. Suitable pre-mix formulations include, but are not limited to: suspension Concentrates (SC) and Emulsifiable Concentrates (EC).

In some embodiments, the crop plant may be selected from genetically modified and unmodified turf, wheat, barley, corn, rice, sorghum, oats, and triticale.

In some embodiments, susceptible weed species may include, but are not limited to: amaranthus retroflexus (redroot pigweed), Amaranthus praecox (Palmer amaranth), Cannabis sativa (common water hemp), Abutilon abutilon (velvetleaf), morning glory (morningglory species), Solanum nigrum (brightshade species), Chenopodium album (common lambsquarers), Brassica juncea (wild mustard), Geranium celery (red stem leaf), Potentilla chinensis (field pennyres), Malva sylvestris (common meow), Amaranthus viridis (smooth pigweed), Amaranthus album (promoter pigweed), Amaranthus spinosus (spine amaranth), Euphorbia hirta (spurred litchi innoda), Galium aparine (garden), Amaranthus hypochondriacutus (garden clover), Morus rotundifolia (common sowthistle), Morus sativa (common sowthistle), Morus chinensis (common sowthistle), Morus sativa (garden weed), Morus chinensis (garden weed), Morus sativa), Morus chinensis (wild celery seed), Morus sativa (wild grass), Morus chinensis (wild grass), Morus sativa (wild grass), Morus (wild rice grass), Morus sativa), Morus (wild rice grass), Morus chinensis (wild rice grass), Morus (wild rice grass), Morus sativus (wild rice grass), Morus sativus (wild rice grass), Morus (wild rice grass), wild rice grass (wild rice grass) and wild rice grass (wild rice grass) of the root (wild rice grass), wild rice grass (wild rice grass), wild rice grass (rice grass) of rice grass), wild rice grass) of the root (wild rice grass), wild rice grass (rice grass), wild rice grass) of the rice grass (rice grass), wild rice grass (rice grass) of the root of the rice grass (rice grass), wild rice grass (rice grass), wild rice grass (rice grass), wild rice grass) of the root of the stem, wild rice grass (rice grass, wild rice grass), wild rice grass (rice grass) of the stem, wild rice grass) of the rice grass of the root of the rice grass of the root of the rice grass of the, chickweed (common chickweed), white fungus (ear chickweed), achyranthes aspera (hair galinsoga), Bellis americana (American daisy), Polygonum (smartweeds), Chamomile (chamomile mayweed), Rubus coreanum (wild pointsetia), Portulaca oleracea (common purulane), Sida rosea (privly sida), large crabgrass (large crabgrass), large crabgrass (small crabgrass), small crabgrass (small crabgrass), goosegrass (googlegrass), orchard grass (orchardgrass), switchgrass (autumn panicum), hair line millet (witch grass), large brow (stinkgrass), Bidens pilosula (hair beggarticks), field revolved (bindweed), buckwheat (wild grass), wild grass (wild grass), dandelion (wild grass), common artichoke (common artichoke), common artichoke (common nightshade grass), common artichoke (common grass).

The compositions and tank mixes of the present disclosure may additionally comprise other crop protection agents, including but not limited to: fungicides, insecticides, nematocides, plant growth regulators, herbicides other than PPO herbicides, fertilizers, and mixtures thereof.

In some embodiments, weed control is effective for at least about 14 days after treatment, preferably at least about 60 days after treatment.

The compositions of the present disclosure may also include a preservative. Suitable preservatives include, but are not limited toLimited to: c₁₂-C₁₅Alkyl benzoate, alkyl p-hydroxybenzoate, aloe extract, ascorbic acid, benzalkonium chloride, benzoic acid, C₉-C₁₅Benzoic acid esters of alcohols, butylated hydroxytoluene, butylated hydroxyanisole, tert-butylhydroquinone, castor oil, cetyl alcohol, chlorocresol, citric acid, cocoa butter, coconut oil, diazolidinyl urea, diisopropyl adipate, dimethylpolysiloxane, DMDM hydantoin, ethanol, ethylene diamine tetraacetic acid, fatty acids, fatty alcohols, cetyl alcohol, hydroxybenzoates, iodopropynyl butylcarbamate, isononyl isononanoate, jojoba oil, lanolin oil, mineral oil, oleic acid, olive oil, parabens, polyethers, polyoxypropylene butyl ether, polyoxypropylene cetyl ether, potassium sorbate, propyl gallate, silicone oil, sodium propionate, sodium benzoate, sodium bisulfite, sorbic acid, stearyl fatty acid, sulfur dioxide, vitamin E acetate and derivatives, esters, salts and mixtures thereof. Preferred preservatives include sodium o-phenylphenol, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 1, 2-benzisothiazolin-3-one (1, 2-benzisothiazolin-3-one).

Disclosed herein are compositions and methods for providing control of crop weeds in a crop. It has now been shown that the addition of safeners (e.g. cloquintocet-mexyl or mefenpyr-diethyl) or safener mixtures (e.g. cloquintocet-mexyl plus mefenpyr-diethyl) reduces the damage of herbicides (e.g. carfentrazone-ethyl and mefenpyr-diethyl) to crops without affecting the efficacy of these herbicides. It is believed that co-application of the safener/safener mixture and the PPO herbicide allows for higher herbicide application rates to the indicated crops and extends the application of the herbicide to crops to unidentified crops.

The following examples are merely illustrative of the invention and should not be construed as limiting the scope of the invention in any way, as further modifications encompassed by the disclosed invention will be apparent to those skilled in the art. All such modifications are considered to be within the scope of the invention as disclosed in the specification and claims.

Examples

Example 1

Materials and methods

To investigate the safening efficacy of one or both safeners on crops, 25 or 50g ai/ha carfentrazone-ethyl or 5.6 or 11.2g ai/ha methyl oxazinate was applied in combination with cloquintocet plus mefenpyr, cloquintocet plus naphthalic anhydride, mefenpyr, cloquintocet, or naphthalic anhydride. Safeners cloquintocet-mexyl, mefenpyr-diethyl and naphthalic anhydride were applied at 6.6, 27.2 and 74.1g ai/ha, respectively. Other treatments include the administration of carfentrazone-ethyl or metribuzin methyl ester alone. 0.25% (v/v) nonionic surfactant was added to all carfentrazone-ethyl and metribuzin methyl ester treatments. The crops were treated with carfentrazone-ethyl and metribuzin 10 days after planting. Wheat and weeds were planted with a merrilide mix (metro-mix) in 3 "plastic pots. The chamber was orbital with compressed air and treated at 30GPA using a 40PSI TeeJet 8001E showerhead. Data were analyzed using Minitab statistical software with 95% confidence intervals. There was no significant difference in the mean of the rating intervals for the same letter percent wheat damage within the 95% confidence interval.

Naphthalic anhydride was not included in the oxazine methyl oxalate study.

Crop damage was assessed by visual rating. The method is based on a score of 0-100%, where 0% indicates no injury and 100% indicates complete crop death. Table 1 shows a linear rating scale that can be used to evaluate weed control or crop injury. (based on Frans et al, revised 1986). Crop damage of less than or equal to 10% is considered commercially acceptable. A damage score of less than or equal to 20% indicates that the crop is not significantly adversely affected and recovers quickly and completely. Commercially acceptable levels of crop injury vary from crop to crop. Any damage level above 20% is generally not commercially acceptable.

In this study, a commercially unacceptable reduction in crop injury to commercially acceptable levels was observed with safener/herbicide treatment.

TABLE 1

Example 2

In greenhouse studies, wheat was investigated for safeners, cloquintocet-mexyl or a mixture of cloquintocet-mexyl and safeners, and the safening effect of cloquintocet-mexyl plus clomexyl was investigated. The efficacy of PPO inhibitor herbicides in the presence of safeners or safener mixtures was also investigated. To investigate the safening efficacy of the safener or safener mixture, 7.5% w/w cloquintocet-mexyl and 3.39% w/w mefenpyr-diethyl were applied together with the herbicide. Carfentrazone-ethyl was applied at 25 or 50g ai/ha and mefenzine oxalate was applied at 5.6 or 11.2g ai/ha. The safener was applied at the following ratio: 6.61g ai/ha cloquintocet-mexyl and 27g ai/ha mefenpyr-diethyl. All treatments (single, tank mix, premix) were applied at the seedling stage of the crop (10 days post planting). Carfentrazone-ethyl or metribuzin oxalate was administered alone or in combination with a safener/safener mixture.

TABLE 2

Percentage of wheat damage when carfentrazone-ethyl is applied in combination with different combinations of safeners, the wheat species "yellow stone (yellowstone)" is used "

The mean number per rating interval for the same letter percent wheat damage did not differ significantly within the 95% confidence interval.

Wheat damage was assessed using the visual rating method described above. The percentage of wheat damage is rated according to the PPO inhibitor causing browning (bronzing), chlorosis and necrosis of wheat leaves. These are typical symptoms (browning, chlorosis and necrosis) caused by PPO inhibitors on sensitive plants.

In all studies, treatment was compared to carfentrazone-ethyl alone. The data in this and other tables indicate that the extent of damage to wheat is reduced by the addition of one or more safeners. For example, at 3DAT (days post-treatment), 25g ai/ha of carfentrazone-ethyl caused 34% damage to wheat compared to less than or equal to 10% of carfentrazone-ethyl when applied with safeners, such as cloquintocet-mexyl + mefenpyr-diethyl.

Regardless of the carfentrazone-ethyl ratio, the wheat injury was less than or equal to 12% with the safener present, with the exception of naphthalic anhydride alone, which injury was greater than 35% at 3 DAT. Carfentrazone-ethyl alone caused damage of 34% and 43% at 25 and 50g, respectively (tables 2 and 3).

TABLE 3

Percentage of wheat injury when carfentrazone-ethyl was applied in combination with different combinations of safeners, using the wheat seed topaz (yerllowstone) "

Example 3

TABLE 4

Percentage damage to wheat varieties "Jagger" and "yellow stone" 10 days after emergence with carfentrazone-ethyl and one or two safeners

The results shown demonstrate that wheat damage was 13% or less for both varieties (Jagger and topaz) in the presence of cloquintocet-mexyl plus mefenpyr-diethyl or cloquintocet-mexyl alone, regardless of the ratio of carfentrazone-ethyl and the rating interval (3 and 7 DAT).

Similar results were seen in pre-mixed carfentrazone-ethyl and cloquintocet-mexyl. The application of mefenpyr-diethyl and 50g of carfentrazone-ethyl in a tank mix or premix resulted in more than 20% damage to both varieties (table 4). The damage to both varieties with either 25g or 50g of carfentrazone-ethyl without the addition of safener was greater than 35% or greater than 40%, respectively (table 4).

Percent weed control was determined using a method similar to the 0-100% rating system described above, and is repeated below for ease of reference. The same Weed control rating system can also be found in Research Methods in Weed Science ("Research Methods in Weed Science"), second edition, ed.b. truelove; southern Weed Science Society (Southern Weed Science Society); university of Auburn University, Auburn, Alabama, 1977.

TABLE 5

At 7DAT, all treatments had 100% control over abutilon and morning glory (table 6).

TABLE 6

Percentage weed control 10 days after emergence when carfentrazone-ethyl and one or two safeners are applied together

Example 4

TABLE 7

Percentage of wheat injury when mefenpyr (F-M) is applied in combination with safeners cloquintocet (C-M) or mefenpyr (M-D) or alone as a tank mix

In both tests (1 and 2) shown in Table 7, methyl oxazinolate alone caused damage (. gtoreq.10%) to the wheat yellow stone variety at both rates, and was safe (. ltoreq.10%) to Jagger wheat when applied alone at 5.6g ai/ha. In test 1, the oxazine oxalic acid methyl ester is safe for the xanthite (1) and Jagger at 14DAT when administered with a safener, alone or in combination. At test 1, abutilon and morning glory were controlled in all cases (data not shown). In test 2, when 5.6 or 11.2g of metribuzin oxalate and cloquintocet plus mefenpyr-diethyl were administered together as a tank mix, it was safe for the xanthite (2) at 14 DAT. 5.6g of methyl oxazinecarboxylate together with any safener were safe for the xanthate at 14 DAT.

While features or aspects of the present invention are described in terms of Markush groups (Markush groups) or other alternative groups, those skilled in the art will recognize that the present invention also may be described in terms of any individual component or subgroup of the Markush groups or other groups described herein.

Unless indicated to the contrary, all numerical ranges herein include all combinations and sub-groups of all ranges and specific integers included therein. Such a range is also within the scope of the present invention.

Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims

1. A method of selectively controlling weeds in a crop, comprising applying to the weeds of the crop a herbicidally effective amount of a herbicidal composition, the active ingredient of which is a combination of a fast acting herbicide selected from the group consisting of carfentrazone acid (carfentrazone) and carfentrazone-ethyl and an effective amount of a safener composition; the safener composition is a combination of two safeners selected from cloquintocet-mexyl, mefenpyr-diethyl and naphthalic anhydride.

2. The method of claim 1, wherein the safener composition comprises cloquintocet-mexyl and mefenpyr-diethyl.

3. The method of claim 2, wherein the fast acting herbicide is carfentrazone-ethyl.

4. The method of claim 1, wherein the weed is selected from the group consisting of: amaranthus retroflexus (redroot pigweed), Amaranthus praecox (Palmer amaranth), Cannabis sativa (common water hemp), Abutilon abutilon (velvetleaf), morning glory (morningglory species), Solanum nigrum (brightshade species), Chenopodium album (common lambsquarers), Brassica juncea (wild mustard), Geranium celery (red stem leaf), Potentilla chinensis (field pennyres), mallow brassica chinensis (common meow), Amaranthus viridis (smooth pigweed), Amaranthus glauca (promoter pigweed), Amaranthus spinosus (spine amaranth), Euphorbia joram (spurge), Balanophora diffusa (wild grass), Amaranthus mangium chinense (wild grass), Amaranthus hypochondriacutus (garden), Agrimonia gigantea (common sown), Acacia mangium chinense (common grass), Amaranthus praecola indica (garden grass), Brassica sativa (wild grass), Amaranthus chinensis (wild grass), Morus sativa (wild grass), Sauropus chinensis (wild grass), Sambucus chinensis (wild grass), Linnakai (wild grass), Sambucus chinensis (wild grass), Linnakai (wild grass) and wild grass (wild grass) can (wild grass), wild grass (wild grass) can (wild grass, wild grass (wild grass) can (wild grass, wild grass (wild grass, wild, chickweed (common chickweed), white fungus (ear chickweed), achyranthes aspera (hair galinsoga), Bellis americana (American daisy), Polygonum (smartweeds), Chamomile (chamomile mayweed), Rubus coreanum (wild pointsetia), Portulaca oleracea (common purulane), Sida rosea (privly sida), large crabgrass (large crabgrass), large crabgrass (small crabgrass), small crabgrass (small crabgrass), goosegrass (googlegrass), orchard grass (orchardgrass), switchgrass (autumn panicum), hair line millet (witch grass), large brow (stinkgrass), Bidens pilosula (hair beggarticks), field revolved (bindweed), buckwheat (wild grass), wild grass (wild grass), dandelion (wild grass), common artichoke (common artichoke), common artichoke (common nightshade grass), common artichoke (common grass).

5. The method of claim 1, wherein the crop is selected from the group consisting of: genetically modified and unmodified turf, wheat, barley, corn, rice, sorghum, oat, and triticale.

6. The method of claim 1, wherein the weed control is effective for at least 14 days after treatment.

7. The method of claim 1, wherein the herbicide is applied simultaneously, separately, or sequentially with a safener.

8. The method of claim 1, wherein the safener and herbicide are applied in a weight ratio range of 10:1 (safener/herbicide) to 1:30 (safener/herbicide).

9. The method of claim 1, wherein the herbicide is applied at a rate of from 5g active ingredient per hectare (g ai/ha) to 420g ai/ha.

10. The method of claim 1, wherein the safener is applied at a rate of from 5g active ingredient per hectare (g ai/ha) to 350g ai/ha.

11. A formulation, the active ingredient of which is a combination of a herbicide selected from carfentrazone-acid (carfentrazone) and carfentrazone-ethyl (carfentrazone-ethyl) and an effective amount of a safener composition which is a combination of two safeners selected from cloquintocet-mexyl, mefenpyr-diethyl and naphthalic anhydride.

12. The formulation of claim 11, wherein the herbicide is carfentrazone-ethyl.

13. A method of preparing a formulation for selectively controlling weeds in crops comprising mixing a herbicide composition with an effective amount of a safener composition, wherein the active ingredient of the herbicide composition is selected from carfentrazone-acid (carfentrazone) and carfentrazone-ethyl (carfentrazone-ethyl), the safener composition being a combination of two safeners selected from cloquintocet-mexyl, mefenpyr-diethyl and naphthalic anhydride.