RU2788123C2 - Control of weeds with herbicidal combinations of fluroxypyr and als inhibitors - Google Patents

Abstract

FIELD: agriculture.

SUBSTANCE: herbicidal composition contains a) fluroxypyr or its agriculturally acceptable composite ester or salt and b) an herbicide inhibiting ALS, where the herbicide inhibiting ALS is diclosulam, cloransulam, chlorimuron, or thifensulfuron or their agriculturally acceptable composite ester or salt. The mass ratio of fluroxypyr to thifensulfuron is in the range from 110:1 to 167:1. The mass ratio of fluroxypyr to diclosulam is in the range from 1:2 to 560:1. The mass ratio of fluroxypyr to cloransulam is in the range from 1:2 to 560:1. The mass ratio of fluroxypyr to chlorimuron is in the range from 1:3.6 to 560:1.

EFFECT: proposed herbicidal composition provides synergetic activity in control of undesired vegetation in soybean, cotton, corn, sorghum, sunflower, sugar cane, sugar beet, alfalfa, grain crops, in a fallow field, perennial crop, fruit crop, or fields with plantation crops.

39 cl, 4 tbl, 2 ex

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to US Provisional Application Serial No. 62/009717, filed June 9, 2014, which is expressly incorporated herein by reference.

BACKGROUND OF THE INVENTION

Protecting crops from weeds and other vegetation that inhibits crop growth is a constant challenge in agriculture. Thus, there remains a need for compositions and methods that are effective in controlling unwanted vegetation.

BRIEF DESCRIPTION OF THE INVENTION

This document describes herbicidal compositions containing synergistically effective amounts of (a) fluroxypyr, or an agriculturally acceptable ester or salt thereof, and (b) an acetolactate synthase (ALS) inhibitory herbicide, including, but not limited to, diclosulam, cloransulam, chlorimuron, and thifensulfuron, or an agriculturally acceptable ester or salt thereof.

Also disclosed herein are methods for controlling unwanted vegetation which include contacting the unwanted vegetation or locus thereof with herbicide effective amounts of: (a) fluroxypyr, or an agriculturally acceptable ester or salt thereof, and (b) an ALS inhibiting herbicide, including , but not limited to, diclosulam, cloransulam, chlorimuron and triphensulfuron, or an agriculturally acceptable ester or salt thereof.

Unwanted vegetation may include herbicide-resistant or tolerant weeds, including weeds that grow in soybean, sunflower, sugar beet, rapeseed, oilseed rape, cotton, corn, sorghum, cereals (including, but not limited to, wheat , barley, rice and oats), non-crop crops, fallow field, permanent crops, horticultural crops or fields with plantation crops.

DETAILED DESCRIPTION OF THE INVENTION

I. Definitions

The term "herbicide" as used herein means an active ingredient that kills, controls or otherwise adversely modifies plant growth. As used herein, the term "herbicidally effective amount or vegetative control amount" is an amount of an active ingredient that causes a "herbicidal effect", that is, a negatively altering effect, and includes deviations from natural development, destruction, regulation, drying, developmental delay.

As used herein, controlling unwanted vegetation means preventing, reducing, eradicating, or otherwise adversely modifying plant development and vegetation.

As used herein, the terms "plants" and "vegetation" include, but are not limited to, germinated seeds, germinated seeds, plants emerging from shoots, and established vegetation.

As used herein, immature vegetative refers to small vegetative plants up to the reproductive stage, and mature vegetative refers to vegetative plants during and after the reproductive stage.

As used herein, agriculturally acceptable salts or esters refer to salts and esters that have herbicidal activity or that are or can be converted in plants, water or soil to the indicated herbicidal or active groups. Typical agriculturally acceptable esters are esters which are or can be hydrolyzed, oxidized, metabolized or otherwise converted, for example in plants, water or soil, to the corresponding carboxylic acid, which, depending on pH, can be in dissociated or undissociated form.

Typical salts include salts derived from alkali or alkaline earth metals and salts derived from ammonia and amines. Representative cations include the sodium, potassium, magnesium, and aluminum cations of the formula:

R ¹ R ² R ³ R ⁴ N ⁺

where each R ¹ , R ² , R ³ and R ⁴ independently represents hydrogen or C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkenyl, C ₃ -C ₁₂ alkynyl or aryl, each of which is optionally substituted with one or more groups hydroxy, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio or phenyl group, provided that R ¹ , R ² , R ³ and R ⁴ are sterically compatible. In addition, any two of R ¹ , R ² , R ³ and R ⁴ together may represent an aliphatic difunctional group containing from one to twelve carbon atoms and up to two oxygen or sulfur atoms. Salts can be prepared by treatment with a metal hydroxide such as sodium hydroxide, an amine such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine, or a tetraalkylammonium hydroxide such as tetramethylammonium hydroxide or hydroxide choline.

Typical esters include those derived from C ₁ -C ₁₂ alkyl, C ₃ -C ₁₂ alkenyl, C ₃ -C ₁₂ alkynyl, or C ₇ -C ₁₀ aryl-substituted alkyl alcohols such as methanol, isopropyl alcohol, 1 -butanol, 2-ethylhexanol, butoxyethanol, methoxypropanol, allyl alcohol, propargyl alcohol, cyclohexanol or unsubstituted or substituted benzyl alcohols. Benzyl alcohols may be substituted with 1-3 substituents independently selected from halogen, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy. Esters can be prepared by condensation of acids with alcohol using any number of suitable activating agents, such as those used for peptide condensation such as dicyclohexylcarbodiimide (DCC) or carbonyldiimidazole (CDI); by reacting acids with alkylating agents such as alkyl halides or alkyl sulfonates in the presence of a base such as triethylamine or lithium carbonate; by reacting the corresponding carboxylic acid chloride with the corresponding alcohol; by reacting an appropriate acid with an appropriate alcohol in the presence of an acid catalyst, or by transesterification.

II. Synergistic Blends

Herbicidal compositions comprising synergistically effective amounts of (a) fluroxypyr, or an agriculturally acceptable ester or salt thereof, and (b) an ALS-inhibiting herbicide. In some embodiments, the ALS-inhibiting herbicide is diclosulam, cloransulam, chlorimuron, or triphensulfuron, or an agriculturally acceptable ester or salt thereof.

A. Fluroxypyr

The compositions described herein contain fluroxypyr, or an agriculturally acceptable salt or ester thereof. Fluroxypyr (2-[(4-amino-3,5-dichloro-6-fluoro-2-pyridinyl)oxy]acetic acid) is a herbicide in the class of synthetic auxins. Fluroxypyr can be used, for example, as a post-emergence foliar application to control broadleaf weeds, for example in small crops, to control Rumex and Urtica dioica species in pastures, and to control Trifolium repens in a meadow. Other examples include its use to control grass and woody broadleaf weeds, for example in orchards and crop plantations, and broadleaf shrubs, for example in coniferous forests. Its herbicidal activity is described in Tomlin, CDS, Ed. The Pesticide Manual: A World Compendium ^, 15th edition; BCPC: Alton, 2009 (hereinafter ʺ The Pesticide Manual , Fifteenth Edition, 2009).

Fluroxypyr can be used as an acid (as shown above) or as an agriculturally acceptable salt or ester thereof. Examples of agricultural salts of fluroxypyr include, but are not limited to, sodium salts, potassium salts, ammonium salts or substituted ammonium salts, in particular mono-, di- and tri-C ₁ -C ₈ -alkylammonium salts such as methylammonium, dimethylammonium and isopropylammonium, mono-, di- and tri-hydroxy-C ₂ -C ₈ -alkylammonium salts, such as hydroxyethylammonium, di(hydroxyethyl)ammonium, tri(hydroxyethyl)ammonium, hydroxypropylammonium, di(hydroxypropyl)ammonium and tri(hydroxypropyl)ammonium salts, olamine salts and diglycolamine salts. In some embodiments, fluroxypyr is provided as an agriculturally acceptable ester. Suitable esters include, but are not limited to, C ₁ -C ₈ alkyl esters and C ₁ -C ₄ alkoxy-C ₂ -C ₄ alkyl esters such as methyl esters, ethyl esters, isopropyl esters, butyl, hexyl, heptyl, isoheptyl, isooctyl, 2-ethylhexyl and butoxyethyl esters; and aryl esters such as benzyl. Examples of agriculturally acceptable fluoxypyr esters are butomethyl and fluroxypyr MHE (fluroxypyr-methylheptyl ester, aka fluroxypyr-meptyl).

B. Herbicides Inhibiting ALS

In addition to fluroxypyr, the compositions include one or more acetolactate synthase (ALS) inhibitory herbicides. ALS inhibitors interfere with the production of amino acids in the plant, which ultimately leads to inhibition of DNA synthesis. ALS inhibitors include, but are not limited to, sulfonylureas and triazolopyrimidine sulfonamides. In some embodiments, the composition may include an ALS inhibitor selected from the class of sulfonylurea and triazolopyrimidine sulfonamides.

In some embodiments, the herbicidal composition comprises a herbicidally effective amount of: (a) fluroxypyr, or an agriculturally acceptable ester or salt thereof, and (b) an ALS-inhibiting herbicide of the sulfonamide class. In some embodiments, the ALS-inhibiting sulfonamide herbicide is diclosulam or cloransulam, or an agriculturally acceptable ester or salt thereof.

In some embodiments, the herbicidal composition comprises a herbicidally effective amount of (a) fluroxypyr, or an agriculturally acceptable ester or salt thereof, and (b) an ALS-inhibiting herbicide of the sulfonylurea class. In some embodiments, the ALS-inhibiting sulfonylurea herbicide is chlorimuron or thifensulfuron, or an agriculturally acceptable ester or salt thereof.

1. Diclosulam

Diclosulam ( N- (2,6-dichlorophenyl)-5-ethoxy-7-fluoro[1,2,4]triazolo[1,5 -c ]pyrimidine-2-sulfonamide) is a herbicide that inhibits ALS. Diclosulam can be used, for example, to control broadleaf weeds in peanut and soybean crops. Its herbicidal activity is described in The Pesticide Manual , Fifteenth Edition, 2009.

In some embodiments of the compositions and methods described herein, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is used in combination with diclosulam. With regard to compositions, in some embodiments, the weight ratio of fluroxypyr, or an agriculturally acceptable ester or salt thereof (acid equivalent) to diclosulam (active ingredient) ranges from about 1:2 to about 560:1. In some embodiments, the weight ratio is from about 25-200 fluroxypyr, or an agriculturally acceptable ester or salt thereof, to about 1.1-25.2 diclosulam. In some embodiments, the weight ratio is in the range from about 1:1 to about 182:1. In some embodiments, the weight ratio ranges from about 1:1 to about 2:1, from about 2:1 to about 2.8:1, from about 2.8:1 to about 4:1, from about 4: 1 to about 5.7:1, about 5.7:1 to about 7.9:1, about 7.9:1 to about 11.4:1, about 11.4:1 to about 22, 7:1, about 22.7:1 to about 45.5:1, about 45.5:1 to about 91:1, or about 91:1 to about 182:1. In some embodiments of the present invention, the weight ratio is in the range from about 2:1 to about 92:1. In some embodiments, the weight ratio is in the range from about 3:1 to about 46:1. In some embodiments, the weight ratio is in the range from about 5:1 to about 23:1. In some embodiments of the present invention, the weight ratio is in the range from about 8:1 to about 23:1. In one embodiment, the weight ratio is in the range of about 5.7:1 to about 7.9:1. In another embodiment, the weight ratio is in the range of about 7.9:1 to about 11.4:1. In another embodiment, the weight ratio is in the range from about 11.4:1 to about 22.7:1. In one embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is fluroxypyr-meptyl.

As for the methods, in some embodiments, the methods include contacting the unwanted vegetation with the composition described herein, or with the components of the composition described herein, for example , sequentially or simultaneously. In some embodiments, the composition is applied at a rate of from about 26 grams of acid equivalent per hectare (g ae/ha) to about 610 g ae/ha, based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at a rate of about 26 g ae/ha to about 226 g ae/ha, based on the total amount of active ingredients in the composition. In some embodiments, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 25 g ae/ha to about 560 g ae/ha and diclosulam is applied at a rate of about 1 gram of active ingredient per hectare (g a.i./ha) to approximately 50 g a.i./ha. In some embodiments, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 25 g ae/ha to about 200 g ae/ha and diclosulam is applied at a rate of about 1.1 g a.i./ha to about 25.2 g a.i./ha. In one embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 25 g ae/ha to about 50 g ae/ha and diclosulam is applied at a rate of about 1.1 g ai/ha to about 8.8 g ai/ha. In yet another embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 50 g ae/ha to about 100 g ae/ha and diclosulam is applied at a rate of about 2.2 g ai/ha to about 8.8 g ai/ha. In some embodiments, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 100 g ae/ha to about 200 g ae/ha and diclosulam is applied at a rate of about 4.4 g a.i./ha to about 25.2 g a.i./ha. In one embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is fluroxypyr-meptyl.

In some embodiments of the compositions and methods described herein, the only herbicidally active ingredients are fluroxypyr, or an agriculturally acceptable ester or salt thereof, ( eg , fluroxypyr-meptyl) and diclosulam. In other embodiments, the compositions and methods described herein optionally use additional herbicidally active ingredients.

2. Cloransulam

Cloransulam (3-chloro-2-[[(5-ethoxy-7-fluoro[1,2,4]-triazolo[1,5 -c ]pyrimidin-2-yl)sulfonyl]amino]-benzoic acid) is herbicide that inhibits ALS. Cloransulam can be used to control post-emergence broadleaf weeds in soybeans and other broadleaf crops. Its herbicidal activity is described in The Pesticide Manual , Fifteenth Edition, 2009.

Cloransulam can be presented as an acid (as shown above) or as an agriculturally acceptable salt or ester thereof. Examples of agricultural salts of cloransulam include, but are not limited to, sodium salts, potassium salts, ammonium salts or substituted ammonium salts, in particular mono-, di- and tri-C ₁ -C ₈ -alkylammonium salts such as methylammonium, dimethylammonium and isopropylammonium, mono-, di- and tri-hydroxy-C ₂ -C ₈ -alkylammonium salts, such as hydroxyethylammonium, di(hydroxyethyl)ammonium, tri(hydroxyethyl)ammonium, hydroxypropylammonium, di(hydroxypropyl)ammonium and tri(hydroxypropyl)ammonium salts, olamine salts and diglycolamine salts. In some embodiments, cloransulam is in the form of an agriculturally acceptable ester. Suitable esters include, but are not limited to, C ₁ -C ₈ alkyl esters and C ₁ -C ₄ alkoxy-C ₂ -C ₄ alkyl esters such as methyl esters, ethyl esters, isopropyl esters, butyl, hexyl, heptyl, isoheptyl, isooctyl, 2-ethylhexyl and butoxyethyl esters; and aryl esters such as benzyl. Examples of agriculturally acceptable cloransulam esters include, for example, cloransulam-methyl (methyl 3-chloro-2-[[(5-ethoxy-7-fluoro[1,2,4]triazolo[1,5 -c ]pyrimidine-2- yl)sulfonyl]amino]benzoate).

In some embodiments of the compositions and methods described herein, fluoxypyr, or an agriculturally acceptable ester or salt thereof, is used in combination with cloransulam, or an agriculturally acceptable ester or salt thereof. With respect to compositions, in some embodiments, the weight ratio of fluroxypyr, or an agriculturally acceptable ester or salt thereof (acid equivalent) to cloransulam, or an agriculturally acceptable ester or salt thereof, (active ingredient) is in the range of about 1:2 up to about 560:1. In some embodiments, the weight ratio is in the range from about 1:1 to about 182:1. In some embodiments, the weight ratio ranges from about 1:1 to about 2:1, from about 2:1 to about 2.8:1, from about 2.8:1 to about 4:1, from about 4: 1 to about 5.7:1, about 5.7:1 to about 7.9:1, about 7.9:1 to about 11.4:1, about 11.4:1 to about 22, 7:1, about 22.7:1 to about 45.5:1, about 45.5:1 to about 91:1, or about 91:1 to about 182:1. In some embodiments, the weight ratio is from about 25-100 fluroxypyr, or an agriculturally acceptable ester or salt thereof, to about 1.1-8.8 cloransulam, or an agriculturally acceptable ester or salt thereof. In some embodiments, the implementation of the present invention, the mass ratio is in the range from about 2.8:1 to about 91:1. In some embodiments, the weight ratio is in the range of about 5.7:1 to about 91:1. In one embodiment, the weight ratio is in the range of about 5.7:1 to about 11.4:1. In another embodiment, the weight ratio is in the range from about 11.4:1 to about 23:1. In another embodiment, the weight ratio is in the range from about 23:1 to about 91:1. In one embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is fluroxypyr-meptyl. In one embodiment, cloransulam, or an agriculturally acceptable ester or salt thereof, is cloransulam-methyl.

As for the methods, in some embodiments, the methods include contacting the unwanted vegetation with the composition described herein, or with the components of the composition described herein, for example , sequentially or simultaneously. In some embodiments, the composition is applied at a rate of about 26 g ae/ha to about 610 g ae/ha, based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at a rate of about 26 g ae/ha to about 300 g ae/ha, based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at a rate of from about 26 g ae/ha to about 109 g ae/ha, based on the total amount of active ingredients in the composition. In some embodiments, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 25 g ae/ha to about 560 g ae/ha, and cloransulam, or an agriculturally acceptable ester or salt thereof are applied at a rate of about 1 g a.i./ha to about 50 g a.i./ha. In some embodiments, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 25 g ae/ha to about 100 g ae/ha, and cloransulam, or an agriculturally acceptable ester or salt thereof, applied at a rate of about 1.1 g a.i./ha to about 8.8 g a.i./ha. In one embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 25 g ae/ha to about 50 ae/ha, and cloransulam, or an agriculturally acceptable ester or salt thereof are applied at a rate of about 1.1 g a.i./ha to about 8.8 g a.i./ha. In yet another embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 50 g ae/ha to about 100 ae/ha, and cloransulam, or an agriculturally acceptable ester or salt thereof are applied at a rate of about 1.1 g a.i./ha to about 8.8 g a.i./ha. In one embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is fluroxypyr-meptyl. In one embodiment, cloransulam, or an agriculturally acceptable ester or salt thereof, is cloransulam-methyl.

In some embodiments of the compositions and methods described herein, the only herbicidally active ingredients are fluroxypyr, or an agriculturally acceptable ester or salt thereof ( e.g. , fluroxypyr-meptyl) and cloransulam, or an agriculturally acceptable ester or salt thereof, ( e.g. , cloransulam-methyl). In other embodiments, the compositions and methods described herein optionally use additional herbicidally active ingredients.

3. Chlorimuron

Chlorimuron ([[[[(4-chloro-6-methoxy-2-pyrimidinyl)amino]-carbonyl]amino]sulfonyl]benzoic acid) is a herbicide that inhibits ALS. Chlorimuron can be used, for example, for post-emergence control of important broadleaf weeds such as cocklebur, gauze, sunflower, annual bindweed, and other broadleaf weeds in soybean and peanut crops. Its herbicidal activity is described in The Pesticide Manual , Fifteenth Edition, 2009.

Chlorimuron can be presented as an acid (as shown above) or as an agriculturally acceptable salt or ester. Examples of agricultural salts of chlorimuron include, but are not limited to, sodium salts, potassium salts, ammonium salts or substituted ammonium salts, in particular mono-, di- and tri-C ₁ -C ₈ -alkylammonium salts such as methylammonium, dimethylammonium and isopropylammonium, mono-, di- and tri-hydroxy-C ₂ -C ₈ -alkylammonium salts, such as hydroxyethylammonium, di(hydroxyethyl)ammonium, tri(hydroxyethyl)ammonium, hydroxypropylammonium, di(hydroxypropyl)ammonium and tri(hydroxypropyl)ammonium salts, olamine salts and diglycolamine salts. In some embodiments, chlorimuron is provided as an agriculturally acceptable ester. Suitable esters include, but are not limited to, C ₁ -C ₈ alkyl esters and C ₁ -C ₄ alkoxy-C ₂ -C ₄ alkyl esters such as methyl esters, ethyl esters, isopropyl esters, butyl, hexyl, heptyl, isoheptyl, isooctyl, 2-ethylhexyl and butoxyethyl esters; and aryl esters such as benzyl. Examples of agriculturally acceptable chlorimuron esters include, for example, chlorimuron-ethyl (ethyl 2-[[[[(4-chloro-6-methoxy-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate).

In some embodiments of the compositions and methods described herein, fluoxypyr, or an agriculturally acceptable ester or salt thereof, is used in combination with chlorimuron, and an agriculturally acceptable ester or salt thereof. With respect to compositions, in some embodiments, the weight ratio of fluroxypyr, or an agriculturally acceptable ester or salt thereof (acid equivalent) to chlorimuron, or an agriculturally acceptable ester or salt thereof, (active ingredient) is in the range of about 1:3 .6 to about 560:1. In some embodiments, the weight ratio is in the range from about 1:2 to about 560:1. In some embodiments, the weight ratio is in the range from about 1:1 to about 182:1. In some embodiments, the weight ratio ranges from about 1:1 to about 2:1, from about 2:1 to about 2.8:1, from about 2.8:1 to about 4:1, from about 4: 1 to about 5.7:1, about 5.7:1 to about 7.9:1, about 7.9:1 to about 11.4:1, about 11.4:1 to about 22, 7:1, about 22.7:1 to about 45.5:1, about 45.5:1 to about 91:1, or about 91:1 to about 182:1. In some embodiments, the weight ratio is from about 25-100 fluroxypyr, or an agriculturally acceptable ester or salt thereof, to about 1.1-8.8 chlorimuron, and an agriculturally acceptable ester or salt thereof. In some embodiments, the implementation of the present invention, the mass ratio is in the range from about 2.8:1 to about 91:1. In some embodiments of the present invention, the weight ratio is in the range from about 2.8:1 to about 46:1. In one embodiment, the weight ratio is in the range of about 2.8:1 to about 45.5:1. In another embodiment, the weight ratio is in the range from about 11.4:1 to about 23:1. In one embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is fluroxypyr-meptyl. In one embodiment, chlorimuron, or an agriculturally acceptable ester or salt thereof, is chlorimuron-ethyl.

As for the methods, in some embodiments, the methods include contacting the unwanted vegetation with the composition described herein, or with the components of the composition described herein, for example , sequentially or simultaneously. In some embodiments, the composition is applied at a rate of from about 26 g ae/ha to about 650 g ae/ha, based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at a rate of from about 26 g ae/ha to about 109 g ae/ha, based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at a rate of about 33 g ae/ha to about 103 g ae/ha, based on the total amount of active ingredients in the composition. In some embodiments, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 25 g ae/ha to about 560 g ae/ha, and chlorimuron, or an agriculturally acceptable ester or salt thereof are applied at a rate of about 1 g a.i./ha to about 90 g a.i./ha. In some embodiments, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 25 g ae/ha to about 100 g ae/ha, and chlorimuron, or an agriculturally acceptable ester or salt thereof, applied normally from about 1.1 g ai/ha to about 8.8 g ai/ha. In one embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 25 g ae/ha to about 50 ae/ha, and chlorimuron, or an agriculturally acceptable ester or salt thereof are applied at a rate of about 1.1 g a.i./ha to about 8.8 g a.i./ha. In another embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 50 g ae/ha to about 100 ae/ha, and chlorimuron, or an agriculturally acceptable ester or salt thereof are applied at a rate of about 1.1 g a.i./ha to about 2.2 g a.i./ha. In one embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is fluroxypyr-meptyl. In one embodiment, chlorimuron, or an agriculturally acceptable ester or salt thereof, is chlorimuron-ethyl.

In some embodiments of the compositions and methods described herein, the only herbicidally active ingredients are fluroxypyr, or an agriculturally acceptable ester or salt thereof ( e.g. , fluroxypyr-meptyl) and chlorimuron, or an agriculturally acceptable ester or salt thereof, ( e.g. , chlorimuron-ethyl). In other embodiments, the compositions and methods described herein optionally use additional herbicidally active ingredients.

4. Tifensulfuron

Tripensulfuron ( [[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl]-2-thiophenecarboxylic acid) is a herbicide that inhibits ALS. Tryphensulfuron can be used, for example, to control annual weeds in cereals, corn, soybeans and pastures. Its herbicidal activity is described in The Pesticide Manual , Fifteenth Edition, 2009.

.

.

Tifensulfuron can be presented as an acid (as shown above) or as an agriculturally acceptable salt or ester. Examples of agricultural salts of thifensulfuron include, but are not limited to, sodium salts, potassium salts, ammonium salts or substituted ammonium salts, in particular mono-, di- and tri-C ₁ -C ₈ -alkylammonium salts, such as methylammonium, dimethylammonium and isopropylammonium, mono-, di- and tri-hydroxy-C ₂ -C ₈ -alkylammonium salts, such as hydroxyethylammonium, di(hydroxyethyl)ammonium, tri(hydroxyethyl)ammonium, hydroxypropylammonium, di(hydroxypropyl)ammonium and tri(hydroxypropyl)ammonium salts, olamine salts and diglycolamine salts. In some embodiments, thifensulfuron is in the form of an agriculturally acceptable ester. Suitable esters include, but are not limited to, C ₁ -C ₈ alkyl esters and C ₁ -C ₄ alkoxy-C ₂ -C ₄ alkyl esters such as methyl esters, ethyl esters, isopropyl esters, butyl, hexyl, heptyl, isoheptyl, isooctyl, 2-ethylhexyl and butoxyethyl esters; and aryl esters such as benzyl. In some embodiments, the corresponding carboxylic acid (tifensulfuron), thifensulfuron carboxylate salt, other thifensulfuron esters, such as an alkyl or arylalkyl ester, or thifensulfuron-methyl salt is used. Typical agriculturally acceptable esters of thifensulfuron include, for example, thifensulfuron-methyl (methyl 3-[[[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)amino]carbonyl]amino]sulfonyl] -2-thiophenecarboxylate).

In some embodiments of the compositions and methods described herein, fluoxypyr, or an agriculturally acceptable ester or salt thereof, is used in combination with thifensulfuron, and an agriculturally acceptable ester or salt thereof. With respect to compositions, in some embodiments, the weight ratio of fluroxypyr, or an agriculturally acceptable ester or salt thereof (acid equivalent) to thifensulfuron, or an agriculturally acceptable ester or salt thereof, (active ingredient) is in the range of about 1:1 up to approximately 1120:1. In some embodiments, the weight ratio is in the range from about 1.1:1 to about 500:1. In some embodiments of the present invention, the weight ratio is in the range from about 1.2:1 to about 334:1. In some embodiments, the weight ratio is from about 17.5-100 fluroxypyr, or an agriculturally acceptable ester or salt thereof, to about 0.6-13 thifensulfuron, or an agriculturally acceptable ester or salt thereof. In some embodiments, the weight ratio is in the range of about 1.3:1 to about 167:1. In some embodiments, the weight ratio ranges from about 1.3:1 to about 3.8:1, from about 3.8:1 to about 7.7:1, from about 7.7:1 to about 8: 1, from about 8:1 to about 16:1, from about 16:1 to about 23:1, from about 23:1 to about 29:1, from about 29:1 to about 45.5:1, from about 45.5:1 to about 83:1, from about 83:1 to about 91:1, or from about 91:1 to about 167:1. In one embodiment, the weight ratio is in the range of about 1.3:1 to about 5:1. In another embodiment, the weight ratio is in the range of about 1.3:1 to about 10:1. In another embodiment, the weight ratio is in the range from about 1.3:1 to about 14:1. In yet another embodiment, the weight ratio is in the range from about 1.3:1 to about 18:1. In yet another embodiment, the weight ratio is in the range from about 1.3:1 to about 23:1. In another embodiment, the weight ratio is in the range from about 23:1 to about 91:1. In another embodiment, the weight ratio is in the range from about 35:1 to about 91:1. In another embodiment, the weight ratio is in the range from about 50:1 to about 91:1. In another embodiment, the weight ratio is in the range of about 60:1 to about 91:1. In another embodiment, the weight ratio is in the range from about 70:1 to about 91:1. In another embodiment, the weight ratio is in the range from about 91:1 to about 167:1. In another embodiment, the weight ratio is in the range from about 110:1 to about 167:1. In another embodiment, the weight ratio is in the range from about 130:1 to about 167:1. In another embodiment, the weight ratio is in the range from about 7.7:1 to about 29.2:1. In one embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is fluroxypyr-meptyl. In one embodiment, thifensulfuron, or an agriculturally acceptable ester or salt thereof, is thifensulfuron-methyl.

As for the methods, in some embodiments, the methods include contacting the unwanted vegetation with the composition described herein, or with the components of the composition described herein, for example , sequentially or simultaneously. In some embodiments, the composition is applied at a rate of from about 25.5 g ae/ha to about 585 g ae/ha, based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at a rate of about 18 g ae/ha to about 113 g ae/ha, based on the total amount of active ingredients in the composition. In certain embodiments, the composition is applied at a rate of from about 30.5 g ae/ha to about 102 g ae/ha, based on the total amount of active ingredients in the composition. In some embodiments, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 25 g ae/ha to about 560 g ae/ha, and thifensulfuron, or an agriculturally acceptable ester or salt thereof are applied at a rate of about 0.5 g a.i./ha to about 25 g a.i./ha. In some embodiments, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 17.5 g ae/ha to about 100 g ae/ha, and thifensulfuron, or an agriculturally acceptable ester thereof or salt, applied at a rate of about 0.6 g a.i./ha to about 13 g a.i./ha. In some embodiments, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 17.5 g ae/ha to about 50 g ae/ha, and thifensulfuron, or an agriculturally acceptable ester thereof or salt, applied at a rate of about 2.2 g a.i./ha to about 13 g a.i./ha. In yet another embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is applied at a rate of about 50 g ae/ha to about 100 ae/ha, and thifensulfuron, or an agriculturally acceptable ester or salt thereof are applied at a rate of about 0.6 g a.i./ha to about 2.2 g a.i./ha. In one embodiment, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is fluroxypyr-meptyl. In one embodiment, thifensulfuron, or an agriculturally acceptable ester or salt thereof, is thifensulfuron-methyl.

In some embodiments of the compositions and methods described herein, the only herbicidally active ingredients are fluroxypyr, or an agriculturally acceptable ester or salt thereof, ( e.g. , fluroxypyr-meptyl) and thifensulfuron , or an agriculturally acceptable ester or salt, , thifensulfuron-methyl). In other embodiments, the compositions and methods described herein optionally use additional herbicidally active ingredients. In one embodiment, the compositions do not contain, and the methods do not use, metsulfuron, or an agriculturally acceptable ester or salt thereof. In one embodiment, the compositions do not contain and the methods do not use metsulfuron. In yet another embodiment, the compositions do not contain and the methods do not use metsulfuron-methyl. In yet another embodiment, the compositions comprise, and the methods use, metsulfuron, or an agriculturally acceptable ester or salt thereof, wherein the weight ratio of thifensulfuron, or an agriculturally acceptable ester or salt thereof, to metsulfuron, or an agriculturally acceptable ester or salt thereof, is more or less 1:1.

In one embodiment, the composition containing fluroxypyr, or an agriculturally acceptable ester or salt thereof ( e.g. , fluroxypyr-meptyl) and thifensulfuron, or an agriculturally acceptable ester or salt thereof, ( e.g. , thifensulfuron-methyl) is not an oil suspension . In another embodiment, a composition containing fluroxypyr or an agriculturally acceptable ester or salt thereof ( eg , fluroxypyr-meptyl) and thifensulfuron, or an agriculturally acceptable ester or salt thereof ( eg , thifensulfuron-methyl) is not in the form of microcapsules.

In one embodiment, the herbicidal composition comprises a herbicidally effective amount of: (A) fluroxypyr, or an agriculturally acceptable ester or salt thereof, and (b) an ALS-inhibiting herbicide, wherein the ALS-inhibiting herbicide is diclosulam, cloransulam-methyl, chlorimuron -ethyl or thifensulfuron-methyl.

In one embodiment of the compositions or methods described herein, fluroxypyr, or an agriculturally acceptable ester or salt thereof, is fluroxypyr-meptyl.

In one embodiment of the compositions or methods described herein, cloransulam, or an agriculturally acceptable ester or salt thereof, is cloransulam-methyl.

In one embodiment of the compositions or methods described herein, chlorimuron, or an agriculturally acceptable ester or salt thereof, is chlorimuron-ethyl.

In one embodiment of the compositions or methods described herein, thifensulfuron, or an agriculturally acceptable ester or salt thereof, is thifensulfuron-methyl.

In some embodiments, the only herbicidally active ingredients used in the compositions and methods described herein are (a) fluroxypyr, or an agriculturally acceptable ester or salt thereof, and (b) an ALS-inhibiting herbicide. Such compositions do not contain any herbicidally active or essential herbicidally active ingredients other than fluroxypyr, or an agriculturally acceptable ester or salt thereof, and an ALS-inhibiting herbicide, but may optionally contain additional components that are herbicidally inert. In some embodiments, the only active ingredients are fluoxypyr, or an agriculturally acceptable ester or salt thereof, and diclozulam, cloransulam, chlorimuron, or fluoxypyr, or an agriculturally acceptable ester or salt thereof. In other embodiments, the compositions and methods described herein optionally use additional herbicidally active ingredients.

In addition, in some embodiments of the present invention, the combination of fluoxypyr and ALS inhibitors is synergistic, i. the herbicidally active ingredients are more effective in combination than when used alone. Synergy has been defined as "the interaction of two or more factors such that the effect of their combination is greater than the effect expected from the response to each factor applied alone". Shaner, D.L., Ed. Herbicide Handbook, ^10th edition, Lawrence: Weed Science Society of America, 2014. In some embodiments, the compositions have synergism as defined by the Colby equation (Colby, SR Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 1967 , 15 , 20 -22).

III. Herbicidal formulations

In some embodiments, fluroxypyr and ALS inhibitors are used in combination with other herbicides that complement the spectrum of weeds controlled by these compounds when used normally. In some embodiments, the compositions described herein and other additional herbicides are used simultaneously, either as a combined formulation or as a tank mix, with simultaneous or sequential application.

The mixtures described herein can be used in combination with one or more other herbicides to control a wider range of unwanted vegetation. When used in combination with other herbicides, the composition may be combined with the other herbicide or herbicides, tank mixed with the other herbicide or herbicides, or used sequentially with the other herbicide or herbicides. Some herbicides that may be used in combination with the compositions and methods described herein include, but are not limited to, optically active isomers, acid forms, salt, choline salt, and ester forms of the following herbicides: 4-CPA, 4-CPB , 4-CPP, 3.4-DA, 2.4-DB, 3.4-DB, 3.4-DP, 2.3.6-TBA, 2.4.5-T, 2.4.5 -TB, acetochlor, acifluorfen, aclonifen, acrolein, alachlor, allidochlor, alloxydim, allyl alcohol, alorak, ametridione, ametrin, amibusin, amicarbazone, amidosulfuron, aminocyclopyrachlor, aminopyralid, amiprofos-methyl, amitrolone, ammonium sulfamate, anilofos, anisoulam , atratone, atrazine, azaphenidin, azimsulfuron, aciprotrin, barban, BCRS, beflubutamide, benazoline, bencarbazone, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, benthiocarb, benzadox, benzfendison, benzipram, benzobicyclone, benzofluphenorone, benzipram, benzobicyclone, benzofluraphenap, benzofluphenorap, , bicyclopyrone, bifenox, bilanafos, bispyribac sodium, borax, bromacil, bromobonyl, bromo butide, bromophenoxime, bromoxynil, brompyrazone, butachlor, butafenacil, butamiphos, butenachlor, butidazole, buthiuron, butralin, butroxydim, buturon, butylate, cacodylic acid, cafenstrol, calcium chlorate, calcium cyanamide, cambendichlor, carbasulam, carbetamide, carboxazole, chlorprocarb, carfentrazone ( e.g. carfentrazone-ethyl), CDEA, CEPC, chlomethoxifene, chloramben, chloranocryl, chlorazifop, chlorazine, chlorbromuron, chlorbufam, chlorethuron, chlorfenac, chlorfenprop, chlorflurazol, chlorflurenol, chloridazone, chlorimuron, chlornitrofen, chloropon, chlorotoluron, chloroxyluron, chlorpropham, chlorsulfuron, chlorthal, chlorthiamide, cynidone ( e.g. cynidone-ethyl), cinmethylin, cinosulfuron, cisanilide, cletodym, cliodinate, clodinafop-propargyl, clofop, clomazone, clomeprop, cloprop, cloproxidim, clopyralid, CMA, copper sulfate, CPMF, CPPC, credazine, cresol, cumilurone, cyanathrine, cyanazine, cycloate, cyclosulfamuron, cyclooxydim, cycluron, cyhalofop ( e.g. cyhalofop-butyl), cyperquat, cyprus zine, cyprazole, cypromide, daimuron, dalapon, dazomet, delachlor, desmedifam, desmetrin, diallat, dicamba, dichlobenil, dichloralurea, dichlormate, dichlorprop, dichlorprop-P, diclofop-methyl, dietamquat, diethatyl, diphenopentene, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethamethrin, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamide, dipropetrin, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronase, EPTC, erbon, esprocarb, ethbenzamide, ethalfluralin, ethametsulfuron, etidimuron, ethiolate, ethbenzamide, etobenzamide, etofumesate, ethoxyfen, ethoxysulfuron, ethinophene, ethnipromide, etobenzanide, EXD, fenasulam, fenoprop, fenoxaprop, P ( e.g. , fenoxaprop-P-ethyl), fenoxaprop-P-ethyl+isoxadifen-ethyl, fenoxasulfone, fenquinotrion, fenteracol, fentiaprop, fentrazamide, fenuron, iron(II) sulfate, flamprop, flamprop-M, flazasulfuron, flo rasulam, fluazifop, fluazifop-P, ( e.g. fluazifop-p-butyl), fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenican, flufenpyr ( e.g. flufenpyr-ethyl), flumetsulam, flumezin, flumiclorac ( e.g. flumiclorac-pentyl ), flumioxazine, flumipropine, fluometuron, fluorodifen, fluoroglycofen, fluoromidin, fluoronitrofen, fluothiuron, flupoxam, flupropacil, flupropanate, flupyrsulfuron, fluridone, flurochloridone, flurtamone, fluthiacet, fomesafen, foramsulfuron, fosamine, fumiclofenate, gluammonate, glucinammonium, furamsulfuron haloxifen, halosafen, halosulfuron ( e.g. halosulfuron-methyl), haloxydin, haloxifop-methyl, haloxifop-P ( e.g. haloxifop-p-methyl), hexachloroacetone, hexaflurate, hexazinon, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosesulfuron, indanophane, indaziflam, iodobonil, iodomethane, iodosulfuron, iodosulfuron-ethyl-sodium, iofensulfuron, ioxynil, ipazine, ipfencarbazone, iprimidam, isocarbamide, isocyl, isomethiosin, isonoruron, isopolynate, isopropaline, isoproturon, isouron, isoxaben, isoxachlorothol, isoxaflutol, isoxapyrifop, carbutylate, ketospiradox, lactofen, lenacil, linuron, MAA, MAMA, MCPA esters and amines, MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, medinoterb, mefenacet, mefluidide, mesoprazine, mesosulfuron, mesotrione, metam, methamifop, metamitron, metazachlor, metazosulfuron, metflurazone, metabenzthiazuron, metalpropaline, metazol, methiobencarb, methiozoline, methiuron, methomethone, metoprotrin, methyl bromide, methoben, methylisothiocyanate, methylisothiocyanate metolachlor, methosulam, methoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monalide, monisouron, monochloroacetic acid, monolinuron, monouron, morphamquat, MSMA, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, nipyraclofen, nitraline , nitrofluorfen, norflurazon, noruron, OCH, orbencarb, ortho -dichlorobenzene, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxapirazon, oxasul furon, oxaziclomefon, oxyfluorfen, parafluron, paraquat, pebulate, pelargonic acid, pendimethalin, pentachlorophenol, pentanochlor, pentoxazone, perfluidone, petoxamide, fenizofam, phenmedifam ( e.g. , phenmedipham-ethyl), fenobenzuron, phenylmercury acetate, picloram, picolinafen, pinoxaden, piperofos , potassium arsenite, potassium azide, potassium cyanate, pretilachlor, primisulfuron ( e.g. primisulfuron-methyl), procyazine, prodiamine, profluazole, profluralin, profoxidim, proglinazine, prohexadione-calcium, promethone, promethrin, propachlor, propanil, propaquizafop, propazine, profam , propisochlor, propoxycarbazone, propyrisulfuron, propizamide, prosulfaline, prosulfocarb, prosulfuron , proxan, prinachlor, pidanon, pyraclonil, pyraflufen pyridafol, pyridate, pyrifthalide, pyriminobac, pyrimisulfan, pyrithiobac sodium, pyroxasulfone, pyroxsulam, quinclorac, qui nmerac, quinoclamin, quinonamide, quizalofop, quizalofop-P ( e.g. quizalofop-P-ethyl), rodetanil, rimsulfuron, saflufenacil, S-metolachlor, sebutylazine, secbumeton, sethoxydim, siduron, simazine, simeton, symetrin, SMA, sodium arsenite, sodium azide, sodium chlorate, sulcotrione, sulfallate, sulfentrazone, sulfometuron, sulfosate, sulfosulfuron, sulfuric acid, sulglycapine, swep, TCA, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumetone, terbutylazine, terbutrin, tetraflurone , tenylchlor, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone-methyl, thiobencarb, thiafenacil, thiocarbazil, thioclorim, tolpyralate, topramesone, tralkoxydim, triallate, triasulfuron, triaziflam, tribenuron ( e.g. tribenuron-methyl), tricambu, triclopyr ( e.g. triclopyr choline salt), triclopyr, tridiphan, trietazine, trifloxysulfuron, trifludimoxazine, trifluralin, triflusulfuron, tripfop, tripfopsim, trihydroxytriazine, trimeturon, tripropind an, tritac, tritosulfuron, vernolate, xylachlor, benzyl 4-amino-3-chloro-5-fluoro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylate and mixtures thereof.

In some embodiments of the present invention, the compositions of the present invention further comprise at least one agriculturally acceptable excipient or carrier. Suitable adjuvants or carriers should not be phytotoxic to valuable crops, especially at the concentrations used when applying the selective weed control compositions in the presence of crop plants, and should not chemically react with the herbicidal components or other ingredients of the composition. Such mixtures may be designed to be applied directly to weeds or weeds, or may be concentrates or formulations that are usually diluted with additional carriers and excipients prior to use. They may be solids, such as, for example, fine powders, granules, water-dispersible granules, microcapsules or wettable powders, or liquids, such as, for example, emulsifiable concentrates, solutions, emulsions or suspensions. They can also be provided as a ready mix or tank mix.

Suitable agricultural adjuvants and carriers include, but are not limited to, vegetable oil concentrate; nonylphenol ethoxylate; quaternary ammonium salt of benzylcocoalkyldimethyl; a mixture of petroleum hydrocarbons, alkyl esters, organic acids and anionic surfactants; C ₉ -C ₁₁ alkyl polyglycosides; phosphated alcohol ethoxylate; ethoxylate of natural primary (C ₁₂ -C ₁₆ ) alcohols; di- sec -butylphenol EO/PO block copolymers; polysiloxane-methyl cap; noniphenol ethoxylate + urea ammonium nitrate; emulsified methylated vegetable oil; tridecyl alcohol ethoxylate (synthetic) (8EO); thalamine ethoxylate (15 EO); PEG(400) dioleate-99.

In some embodiments, the compositions described herein are used in combination with one or more herbicide safeners such as AD-67 (MON 4660), benoxacor, bentiocarb, brassinolide, cloquintocet (mexyl), cyometrinil, daimuron, dichlormide, dicyclonone, dimepiperate, disulfotone, fenchlorazole-ethyl, fenchlorim, flurazol, fluxofenim, furiazole, harpin proteins, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, naphthalic anhydride (NA), oxabethrinyl, R29148 and N -phenylsulfonylbenzoic acid amides, to enhance their selectivity. In some embodiments, safeners are used on rice, cereal, corn, or mayse crops. In some embodiments, the antidote is Cloquintocet, or an ester or salt thereof. In some embodiments, the implementation of clochintocet is used to counteract the negative effects of the compositions on crops of rice and cereals. In some embodiments, the antidote is cloquintocet (mexil).

Liquid carriers that may be used include water and organic solvents. Organic solvents include, but are not limited to, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffin oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; esters of monohydric or dihydric, trihydric or other lower polyalcohols (4-6 hydroxy containing) such as 2-ethylhexyl stearate, n -butyl oleate, isopropyl myristate, propylene glycol dioleate, di-octyl succinate, di-butyl adipate, di-octyl phthalate and the like; esters of mono-, di- and polycarboxylic acids; and the like. Specific organic solvents include, but are not limited to, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, trichlorethylene, perchlorethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methyl alcohol, ethyl alcohol, isopropyl alcohol, amyl alcohol, ethylene glycol, propylene glycol, glycerin, N -methyl-2-pyrrolidone, N,N -dimethylalkylamides, dimethyl sulfoxide, liquid mineral fertilizers and the like. In some embodiments, water is the carrier for diluting the concentrates.

Suitable solid carriers include, but are not limited to, talc, pyrophyllite clay, silica, attapulgated clay, kaolin clay, diatomaceous earth, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, fuller's earth, cottonseed husk, wheat flour, soy flour , pumice, wood flour, walnut flour, lignin, cellulose and the like.

In some embodiments, the compositions described herein further comprise one or more surfactants. In some embodiments, such surfactants are used in solid and liquid formulations, and in some embodiments, they are intended to be diluted with a carrier prior to use. Surfactants may be anionic, cationic, or non-ionic in nature and may be used as emulsifiers, wetting agents, suspending agents, or for other purposes. Surfactants that can also be used in the present compositions are described, inter alia , in McCutcheon's Detergents and Emulsifiers Annualʺ, MC Publishing Corp. , Ridgewood, New Jersey, 1998, and in Encyclopedia of Surfactants, Vol. I-III , Chemical Publishing Company: New York, 1980-81. Surfactants include, but are not limited to, alkyl sulfate salts such as diethanol ammonium lauryl sulfate; alkylarylsulfonate salts such as calcium dodecylbenzenesulfonate; alkylphenol-alkylene oxide addition products such as nonylphenol-C ₁₈ ethoxylate; alcohol-alylene oxide addition products such as tridecyl alcohol-C ₁₆ ethoxylate; soaps such as sodium stearate; alkylnaphthalenesulfonate salts such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl)sulfosuccinate; esters of sorbitol such as sorbitol oleate; quaternary amines such as lauryltrimethylammonium chloride; polyethylene glycol fatty acid esters such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; salts of complex mono- and dialkyl phosphate esters; vegetable oils such as soybean oil, rapeseed/canola oil, olive oil, castor oil, sunflower oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil, etc. similar; and esters of the vegetable oils listed above, and in some embodiments, methyl esters.

In some embodiments, these substances, such as vegetable oils and their esters, can be used interchangeably as an agricultural aid, as a liquid carrier, or as a surfactant.

Other examples of additives for use in the formulations provided herein include, but are not limited to, compatibilizers, antifoams, coupling agents, neutralizing agents and buffers, corrosion inhibitors, colorants, odorants, spreaders, penetrants, adhesives, dispersing agents. , thickeners, antifreezes, bactericidal additives and the like. The compositions may also contain other compatible components, for example, other herbicides, plant growth regulators, fungicides, insecticides, and the like, and may be mixed with liquid or solid fertilizers, separate fertilizer carriers, such as ammonium nitrate, urea, and the like.

In some embodiments, the concentration of active ingredients in the compositions described herein is from about 0.0005 to 98% by weight. In some embodiments, the concentration is from about 0.0006 to about 90% by weight. In compositions formulated for use as concentrates, the active ingredients are typically present in concentrations of from 0.1 to 98% by weight, and in some embodiments, from about 5 to 90% by weight. Such compositions, in some embodiments, are diluted with an inert carrier such as water prior to application. Diluted compositions, typically applied to weeds or weed patches, contain in some embodiments from about 0.003 to 99% by weight of the active ingredient, and in some embodiments from about 0.08 to 25% by weight.

IV. Application methods

Also disclosed herein are methods of controlling unwanted vegetation, comprising contacting the vegetation, or a locus thereof, e.g., an area adjacent to the vegetation, with a herbicidally effective amount of (a) fluroxypyr, or an agriculturally acceptable ester or salt thereof, and (b) an ALS-inhibiting herbicide, including but not limited to diclosulam, cloransulam, chlorimuron and triphensulfuron, or an agriculturally acceptable ester or salt thereof.

In one embodiment, methods for controlling unwanted vegetation are described herein, comprising contacting the vegetation, or a locus thereof, e.g., an area adjacent to the vegetation, with a herbicidally effective amount of (a) fluroxypyr, or an agriculturally acceptable ester or salt thereof, and (b) an ALS-inhibiting herbicide. In some embodiments, the ALS-inhibiting herbicide is diclosulam, cloransulam-methyl, chlorimuron-ethyl, or thifensulfuron-methyl.

The herbicidal activity is exhibited by the compounds when they are applied after emergence directly to the plant or to the plant foci at any stage of growth. The observed effect depends on the plant species to be eradicated, the growth stage of the plant, the parameters of the dilution used and the size of the sprayed droplets, the particle size of the solid components, the environmental conditions at the time of application, the specific compound used, the specific excipients and carriers, the type of soil, and the like, and the amount of chemical applied. These and other factors can be adjusted to provide non-selective or selective herbicidal action. In some embodiments, the compositions described herein are used post-emergence, applied to relatively immature and mature unwanted vegetation to achieve maximum weed control.

The compositions and methods provided herein can be used to control unwanted vegetation. Unwanted vegetation includes, but is not limited to, undesired vegetation found in soybean, cotton, corn, canola/rapeseed, sugar beet, sunflower, alfalfa, sorghum, rice, wheat, barley, oats and other cereals, non-agricultural fields, including but not limited to pastures, meadows, pastures, fallow land, fence land, car parks, oil storage, storage areas, right-of-way, industrial areas, turf, forestry, pond, industrial vegetation control (IVM) and garden beds fallow before sowing crops; in perennial crops, where, when applied, the composition comes into contact with unwanted vegetation, but does not come into contact with the foliage of cultivated plants, such as fruit trees and vineyards, including, but not limited to, citrus, grape, almond, apple, apricot, avocado, beech tree, Brazil nut, California gray walnut, cashew, cherry, noble chestnut, dwarf chestnut, forest apple, date, feijoa, fig, hazelnut, hickory walnut, kiwi, Japanese medlar, macadamia nut, summer hawthorn, nectarine, olive trees, peach, pear , pecan, persimmon, pistachio, plum, pomegranate, house plum, quince and walnut; horticultural crops ( eg blueberries, guava, papaya, strawberries, taro, blackberries and raspberries); and plantation crops (including but not limited to coffee, cocoa, rubber and palm oil).

In some embodiments, the methods described herein are used to control unwanted vegetation found in row crops. In specific embodiments of the present invention, the unwanted vegetation is Abutilon theophrasti Medik. (Theophrastus' cable car, ABUTH), Amaranthus palmeri S. Wats. (Amaranth Palmer, AMAPA), Amaranthus species (amaranth and amaranth, AMASS), Amaranthus retroflexus (upturned amaranth, AMARE), Amaranthus rudis Sauer (dirty amaranth, AMATA), Ambrosia artemisiifolia L. (ragweed ragweed, AMBEL), Ambrosia psilostachya DC . (ragweed, AMBPS), Ambrosia trifida L. (giant ragweed, AMBTR), Asclepias syriaca L. (Syriac ragweed, ASCSY), Chenopodium album L. (common ragweed, CHEAL), Cirsium arvense (L.) Scop. (field sow thistle, CIRAR), Commelina benghalensis L. (commelina bengal, COMBE), Cyperus esculentus L. (yellow sucrose, CYPES), Cyperus rotundus L. (round succulent, CYPRO), Datura stramonium L. (common datura, DATST) , Daucus carota L. ( wild carrot , DAUCA), Euphorbia heterophylla L. (wild poinsettia, EPHHL), Erigeron bonariensis L. (fleece, ERIBO), Erigeron canadensis L. (Canadian fleabane, ERICA), Helianthus annuus L. ( annual sunflower, HELAN), Jacquemontia tamnifolia (L.) Griseb. (Ipomoea hairy, IAQTA), Ipomoea hederacea (L.) Jacq. (ivy morning glory, IPOHE), Ipomoea lacunosa L. (pitted morning glory, IPOLA), Lactuca serriola L./Torn. (wild lettuce, LACSE), Portulaca oleracea L. ( garden purslane, POROL), Sida cordifolia L. (cordial leaf sida, SIDCO), Sida spinosa L. (spiny brisket, SIDSP), Sinapis arvensis L. (field mustard, SINAR) , Solanum ptychanthum Dunal (eastern black nightshade, SOLPT) or Xanthium strumarium L. (common cocklebur, XANST).

In some embodiments, the methods provided herein are used to control unwanted vegetation found in plantings and vines, perennials, and uncultivated areas. In specific embodiments of the present invention, the unwanted vegetation is Amaranthus palmeri S. Wats. (Amaranth Palmer, AMAPA), Amaranthus species (amaranth and amaranth, AMASS), Amaranthus retroflexus (upturned amaranth, AMARE), Amaranthus rudis Sauer (dirty amaranth, AMATA), Sesbania exaltata (Raf.) Cory/Rydb. Ex Hill (sesbania tall, SEBEX), Abutilon theophrasti Medik . (Theophrastus' ropeworm, ABUTH), Ambrosia artemisiifolia L. (Artemisiifolia ragweed, AMBEL), Ambrosia psilostachya DC. (ragweed ragweed, AMBPS), Ambrosia trifida L. (giant ragweed, AMBTR), Anoda cristata (L.) Schlecht. (comb anode, ANVCR), Asclepias syriaca L. (Syriac milkwort, ASCSY), Bidens pilosa L. (hairy string, BIDPI), Borreria species (BOISS), Borreria alata (Aubl.) DC. or Spermacoce alata Aubl. or Spermacoce latifolia (winged spermacoca, BOILF), Chenopodium album L. (common marshmallow, CHEAL), Cirsium arvense (L.) Scop. (field sow thistle, CIRAR), Commelina benghalensis L. (commelina Bengal, COMBE), Datura stramonium L. (common datura, DATST), Cyperus esculentus L. (yellow sucrose, CYPES), Cyperus rotundus L. (round succulent, CYPRO) , Daucus carota L. ( wild carrot , DAUCA), Euphorbia heterophylla L. (wild poinsettia, EPHHL), Euphorbia hirta L. or Chamaesyce hirta (L.) Millsp. (garden spurge, EPHHI), Euphorbia dentata Michx. (Spurge serrated, EPHDE), Erigeron bonariensis L. or Conyza bonariensis (L.) Cronq. ( Erigeron canadensis L. or Conyza canadensis (L.) Cronq.) (Canadian sunflower, ERICA), Conyza sumatrensis (Retz.) EH Walker (Sumatran smallweed, ERIFL), Helianthus annuus L. (common sunflower, HELAN), Jacquemontia tamnifolia (L.) Griseb. (Ipomoea hairy, IAQTA), Ipomoea hederacea (L.) Jacq. (ivy morning glory, IPOHE), Ipomoea lacunosa L. (pitted morning glory, IPOLA), Lactuca serriola L./Torn. (compass lettuce, LACSE), Portulaca oleracea L. ( garden purslane, POROL), Richardia species (large-flowered purslane, RCHSS), Salsola tragus L. (Russian thistle, SASKR), specimens of Sida (breast, SIDSS), Sida spinosa L. (spiny thorn, SIDSP), Sinapis arvensis L. (field mustard, SINAR), Solanum ptychanthum Dunal (eastern black nightshade, SOLPT), Tridax procumbens L. (procumbent tridax, TRQPR) or Xanthium strumarium L. (common cocklebur, XANST) .

In some embodiments, implementation of the present invention, the methods proposed herein can be used to control unwanted vegetation in pasture and pasture. In particular embodiments of the present invention, the unwanted vegetation isAmaranthus palmeri S. Wats. (Amaranth Palmer, AMAPA), speciesAmaranthus (amaranth and amaranth, AMASS),Ambrosia artemisiifolia L. (ragweed, AMBEL),Ambrosia trifida L. (giant ragweed, AMBTR),Cassia obtusifolia (Canadian rezuha, CASOB),Centaurea maculosa auct. non Lam. (spotted cornflower, CENMA),Cirsium arvense (L.) Scop. (field thistle, CIRAR),Convolvulus arvensis L. (field bindweed, CONAR),Conyza canadensis(L.) Cronq. (Canadian small-scale, ERICA),Euphorbia esula L. (spurge spurge, EPHES),Lactuca serriola L./Torn. (compass lettuce, LACSE),Plantago lanceolata L. (lanceolate plantain, PLALA), Rumex obtusifolius L. (dull sorrel, RUMOB),Salsola tragus L. (Russian thistle, SASKR),Sesbania exaltata (Raf.) Cory/Rydb. Ex Hill (sesbania tall, SEBEX),Sida spinosa L. (spiny thorax, SIDSP), Sinapisarvensis L. (field mustard, SINAR),Sonchus arvensisL. (yellow field thistle, SONAR),Solidago species (goldenrod, SOOSS),Taraxacum officinale G.H. Weber ex Wiggers (dandelion, TAPOF),Trifolium repens L. (white clover, TRFRE) orUrtica dioica L. (stinging nettle, URTDI).

In some embodiments, the methods provided herein can be used to control unwanted vegetation in rice crops. In specific embodiments of the present invention, the unwanted vegetation is Cyperus difformis L. (Red-nosed shrimp, CYPDI), Cyperus esculentus L. (Yellow rhizome, CYPES), Cyperus iria L. (Iria rhizome, CYPIR), Cyperus rotundus L. , CYPRO), Eleocharis species (ELOSS), Fimbristylis miliacea (L.) Vahl (forked bulrush, FIMMI), Schoenoplectus juncoides Roxb. (Japanese bulrush, SCPJU), Schoenoplectus maritimus L. (giant bulrush, SCPMA), Schoenoplectus mucronatus L. (spiky bulrush, SCPMU), Aeschynomene spp., (ambach, AESSS), Alternanthera philoxeroides (Mart.) Griseb. (anther phylloxera, ALRPH), Alisma plantago-aquatica L. (common plantain, ALSPA), Amaranthus species, (amaranth and amaranth, AMASS), Ammannia coccinea Rottb. (bright red ammania, AMMCO), Eclipta alba (L.) Hassk. (American false daisy, ECLAL), Heteranthera limosa (SW.) Willd./Vahl (duck grass, HETLI) , Heteranthera reniformis R.&P. (round-leaved heteranther, HETRE), Ipomoea hederacea (L.) Jacq. (ivy morning glory, IPOHE), Lindernia dubia (L.) Pennell (lindernia doubtful, LIDDU), Monochoria korsakowii Regel & Maack (monochory, MOOKA), Monochoria vaginalis (Burm. F.) C. Presl ex Kuhth, (monochory, MOOVA ), Murdannia nudiflora (L.) Brenan (pigeongrass, MUDNU), Polygonum pensylvanicum L., (Pennsylvania water pepper, POLPY), Polygonum persicaria L. (Polygonum persicaria, POLPE), Polygonum hydropiperoides Michx. (POLHP, weak water pepper), Rotala indica (Willd.) Koehne (Indian Rotala, ROTIN), Sagittaria spp., (Speared, SAGSS), Sesbania exaltata (Raf.) Cory/Rydb. Ex Hill (sesbania tall, SEBEX) or Sphenoclea zeylanica Gaertn . (Sphenoclea Ceylon, SPDZE).

In some embodiments of the present invention, the methods provided herein can be used to control unwanted vegetation in crops of breadmarks. In specific embodiments of the present invention, the unwanted vegetation is Cirsium arvense (L.) Scop. (field thistle, CIRAR ), Galium aparine L. (tenacious bedstraw, GALAP), Kochia scoparia (L.) Schrad. (Kochia, KCHSC), Lamium purpureum L. (Purple Lamb, LAMPU), Matricaria recutita L. (wild chamomile, MATCH), Matricaria matricarioides (Less.) Porter (odorous chamomile, MATMT), Papaver rhoeas L. ( self-seed poppy, PAPRH), Polygonum convolvulus L. (bindweed buckwheat, POLCO), Salsola tragus L. (Russian thistle, SASKR), Stellaria media (L.) Vill. (stellate medium, STEME), Veronica persica Poir. (Veronica Persian, VERPE), Viola arvensis Murr. (field violet, VIOAR) or Viola tricolor L. (wild violet, VIOTR).

In some embodiments of the present invention, the combination of fluroxypyr and ALS inhibitors can be used to synergistically inhibit Abutilon theophrasti (Theophrastus' ropeworm, ABUTH), Amaranthus retroflexus L. (upturned amaranth, AMARE), Amaranthus rudis Sauer (dirty amaranth, AMATA), Amaranthus palmeri S .Wats. (Palmer's amaranth, AMAPA), Chenopodium album (common white gauze, CHEAL), Commelina benghalensis (commelina Bengal, COMBE), Polygonum convolvulus L. (bindweed buckwheat, POLCO) and Sida cordifolia L. (cordifolia sida, SIDCO).

In specific embodiments of the present invention, methods and compositions using fluroxypyr, or an agriculturally acceptable ester or salt thereof, ( e.g. , fluroxypyr-meptyl) and diclosulam, can be used to control ABUTH, AMATA, CHEAL, COMBE, or SIDCO.

In specific embodiments of the present invention, methods and compositions using fluroxypyr, or an agriculturally acceptable ester or salt thereof, ( e.g. , fluroxypyr-meptyl) and cloransulam, or an agriculturally acceptable ester or salt, ( e.g. , cloransulam-methyl) , can be used to deal with ABUTH, AMATA, or CHEAL.

In specific embodiments of the present invention, methods and compositions using fluroxypyr, or an agriculturally acceptable ester or salt thereof, ( e.g. , fluroxypyr-meptyl) and chlorimuron, or an agriculturally acceptable ester or salt, ( e.g. , chlorimuron-ethyl) , can be used to deal with ABUTH or AMATA.

In particular embodiments of the present invention, methods and compositions using fluroxypyr, or an agriculturally acceptable ester or salt thereof ( e.g. , fluroxypyr-meptyl) and thifensulfuron, or an agriculturally acceptable ester or salt thereof, ( e.g. , thifensulfuron-methyl) , can be used against AMARE, ABUTH, AMAPA, CHEAL or POLCO.

Fluroxypyr and ALS inhibitors can be used to control weeds resistant or tolerant to herbicides. The methods using the combination of fluroxypyr and ALS inhibitors and the compositions described herein can also be used to control herbicide resistant or tolerant weeds. Examples of weeds resistant or tolerant to herbicides include, but are not limited to, biotypes resistant or tolerant to acetolactate synthase (ALS) or acetohydroxy acid synthase (AHAS) inhibitors ( e.g. -carbonyltrizolinones), photosystem II inhibitors ( e.g. phenylcarbamates, pyridazinones, triazines, triazinones, uracils, amides, ureas, benzothiadiazinones, nitriles, phenylpyridazines), acetyl CoA carboxylase (ACCase) inhibitors ( e.g. aryloxyphenoxypropionates, cyclohexadiones, phenylpyrazolines), synthetic auxins ( eg benzoic acid, phenoxycarboxylic acids, pyridinecarboxylic acids, quinolinecarboxylic acids), auxin transport inhibitors ( eg phthalamates, semicarbazones), photosystem I inhibitors ( eg bipyridylium), inhibitors of 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase ( e.g. glyphosate), inhibitor glutamine synthetase inhibitors ( eg glufosinate, bialaphos), microtubule assembly inhibitors ( eg benzamides, benzoic acids, dinitroanilines, phosphoroamidates, pyridines), mitosis inhibitors ( eg carbamates), VLCFA inhibitors ( eg acetamides , chloroacetamides, hydroxyacetamides, tetrazolinones), fatty acid and lipid synthesis inhibitors ( e.g. phosphorodithioates, thiocarbamates, benzofurans, chlorocarbonic acids), protoporphyrinogen oxidase (PPO) inhibitors ( e.g. , thiadiazoles, triazolinones), carotenoid biosynthesis inhibitors ( e.g. clomazone, amitrol, aclonifen), phytoene desaturase (PDS) inhibitors ( e.g. amides, anilidex, furanones, phenoxybutanamides, pyridiazinones, pyridines), 4-hydroxyphenyl pyruvate dioxygenase (HPPD) inhibitors ) ( e.g. callistemones, isoxazoles, pyrazoles, triketones), inhibitors of cellulose biosynthesis ( e.g. , nitriles, benzamides, quinclorac, triazolocarboxamides), herbicides with multiple mechanisms of action such as quinclorac, and unclassified herbicides such as arylaminopropionic acids, diphenzoquat, endothall and organic arsenic preparations. Examples of weeds resistant or tolerant to herbicides include, but are not limited to, biotypes with resistance or tolerance to one or more herbicides, biotypes with resistance or tolerance to one or more chemical classes, biotypes with resistance or tolerance to one or more herbicides with multiple mechanisms of action, as well as biotypes with one or more mechanisms of resistance or tolerance ( for example , resistance to the target site or metabolic resistance).

The compositions and methods described herein can also be used to control unwanted vegetation in glyphosate, 2,4-D, and glufosinate tolerant soybean, corn, and cotton crops, which can also have dicamba tolerant characteristics ( e.g. DMO ), pyridyloxy auxin tolerance ( e.g. aad-12, aad-13 ), auxin tolerance, auxin transport inhibitor tolerance, acetyl CoA carboxylase (ACCase) inhibitory herbicide tolerance [ e.g. chemical mixtures of aryloxyphenoxy propionate, cyclohexanedione and phenylpyrazoline ( e.g. various ACCase genes and the aad-1 gene)], tolerance to a tolacetolacatate synthase ( ALS ) inhibitory herbicide ( e.g. 4-hydroxyphenylpyruvate dioxygenase inhibitor (HPPD), phytoendesaturase inhibitor tolerance (PDS) ( e.g. pds , CYP1A1 , CYP2B6 , CYP2C19 ), carotenoid biosynthesis inhibitor tolerance, protoporphyrinogen oxidase (PPO) inhibitor tolerance, cellulose biosynthesis inhibitor tolerance ( e.g. , ixr2-1, CYP1A1 ), mitosis inhibitor tolerance, inhibitor tolerance microtubules, very long chain fatty acid (VLCFA) inhibitor tolerance ( e.g. CYP1A1 , CYP2B6 , CYP2C19 ), fatty acid and lipid biosynthesis inhibitor tolerance ( e.g. CYP1A1 ), photosystem I inhibitor tolerance ( e.g. SOD), tolerance to a photosystem II inhibitor (triazine, nitrile and phenylurea chemistries) ( e.g. psbA , CYP1A1 , CYP2B6 , CYP2C19 , and Bxn ), in crops (such as but not limited to soybean, corn, cotton, canola/rapeseed, rice , cereals, sargo, sunflower, sugar beet, sugar cane, alfalfa and turf), e.g. in combination with glyphosate, 5-enolpyruvylshikimate-3-phosphate inhibitors (EPSP) синтазы, ингибиторами глютаминсинтазы, дикамба, фенокси ауксины, пиридилокси ауксины, синтетические ауксины, ингибиторы транспорта ауксина, арилоксифеноксипропионаты, циклогександионы, фенилпиразолины, ингибиторы АССазы, имидазолиноны, сульфонилмочевины, пиримидинилтиобензоаты, диметокси-пиримидинов, триазолопиримидин сульфаниламиды, сульфониламинокарбонилтриазолиноны, ALS или ингибиторы Acetohydroxy acid synthases (AHAS), HPPD inhibitors, PDS inhibitors, carotenoid biosynthesis inhibitors, PPO inhibitors, cellulose biosynthesis inhibitors, mitosis inhibitors, microtubule inhibitors, very long chain fatty acid inhibitors, fatty acid and lipid biosynthesis inhibitors, photosystem I inhibitors, photosystem inhibitors II, triazines and bromoxynins. The compositions and methods can be used to control unwanted vegetation in soybean, corn or cotton crops having one or more or a combination of characteristics that confer tolerance to one or more chemicals and/or inhibitors with multiple mechanisms of action. In some embodiments, glyphosate-dimethylammonium (glyphosate-DMA), 2,4-D-choline, and ammonium glufosinate are used in combination with herbicides that are selective for the soybean, corn, or cotton being treated and that complement the spectrum of weeds that these compounds control under normal use. In some embodiments, the compositions described herein and other additional herbicides are used simultaneously, either as a combined formulation or as a tank mix, with simultaneous or sequential application.

As used herein, 2,4-D tolerance refers to crops of soybean, corn, cotton, wheat, barley, oats, sorghum, sunflower, sugarcane, sugar beet, canola/oilseed rape, and rice that are genetically modified to to have tolerance to 2,4-D. Examples of tolerance to 2,4-D include soybeans containing the gene aad-12 that provides tolerance to 2,4-D (patent US 8283522 B2). As used herein, 2,4-D tolerant corn refers to corn that is 2,4-D tolerant as a result of genetic modification. Examples of 2,4-D tolerant corn include corn containing the aad-1 gene which confers 2,4-D tolerance (US Patent 7,838,733 B2). As used herein, 2,4-D-tolerant cotton refers to cotton that has 2,4-D tolerance as a result of genetic modification. Examples of 2,4-D tolerant cotton include cotton containing the aad-12 gene which confers 2,4-D tolerance. However, it should be taken into account that tolerance in each such culture is due to the aad-1 or aad-12 genes or alternative genes, providing additional or alternative tolerance to transgenic crops [ for example , aad-13 (patent US 8278505 B2), tfdA (patent US 6153401 A) or 24dt02 (CN 103060279)] is provided in soy, corn or cotton with 2,4-D and glufosinate tolerance as described herein.

As used herein, glyphosate tolerance refers to crops of soybean, corn, cotton, wheat, barley, oats, sorghum, sugar beet, sunflower, canola/oilseed rape, and rice that have glyphosate tolerance as a result of genetic modification. Tolerance to glyphosate can be due, for example, to the CP4 gene (US Pat. No. 5,627,061 A) or 2mEPSPS (US Pat. No. 6,566,587 B1), as shown herein; however, glyphosate tolerance in terms of glyphosate, 2,4-D and glufosinate tolerance in soybean, corn, cotton, wheat, barley, oats, sorghum, sunflower, sugar cane, sugar beet, canola/oilseed rape and rice, described herein may be due to other genes conferring tolerance to glyphosate in the transgenic culture [ eg , AroA and other class II EPSPS (patent US 7893234 B2); GLG23 and other class III EPSPS (patent US 7700842 B2); GAT (patent US 7405074 B2), Gox (patent US 5463175 A) or other glyphosate metabolism gene; or DGT-28 or other class IV EPSPS (U.S. Patent Application 20130217577A1)] and should be noted that they are covered by the tolerance for 2,4-D, glyphosate and glufosinate in soybean, corn, cotton, wheat, barley, oats , sorghum and rice as described in this document.

As used herein, glufosinate tolerance refers to crops of soybean, cotton, wheat, barley, oats, sunflower, alfalfa, canola/oilseed rape, sugar beet, and rice that have glufosinate tolerance as a result of genetic modification. Tolerance to glufosinate can be due, for example, to the " pat " gene (US 5,587,903 A) as shown herein; however, tolerance to glufosinate in terms of tolerance to 2,4-D- and glufosinate of soybean, corn or cotton crops can also be due to other genes conferring tolerance to glufosinate in a transgenic crop [ for example , bar (patent US 5561236 A) and dsm2 ( PCT international application WO2008070845)].

The components of the mixtures described herein may be used individually, sequentially, as a tank mix, or as part of a mixture or multiple herbicide system.

The compositions of the present invention can be applied to weeds or weeds using conventional soil or air sprayers, sprayers and granular fertilizer machines, and other conventional means known to those skilled in the art.

The described embodiments and the following examples are for illustration only and are not intended to limit the scope of the claims. Other modifications, uses or combinations in the context of the compositions described herein will be apparent to the average person skilled in the art without departing from the essence and without going beyond the claimed subject matter of the invention.

EXAMPLES

Example 1 Evaluation of the herbicidal activity of mixtures in a greenhouse

Methodology

Seeds of the target test plant species were planted in Metro- ^{Mix 360®} peat-based potting mix in plastic pots with a surface area ^of 128 square centimeters (cm2). culture medium (with gypsum), slow release nitrogen and dolomitic limestone. Plants were grown for 7-19 days in a greenhouse with an approximately 14-hour (h) photoperiod, which was kept at 29°C during the day and 26°C at night. Nutrients and water were added regularly, and additional light was provided by overhead 1000 W halogen lamps as needed. Plants were treated with a post-emergence foliar application when they reached the third-fourth leaf stage. All treatments were performed using an experimental design of randomized complete blocks, with 4 repetitions per treatment.

The treatment consisted of the compounds listed in Tables 1-4, each compound applied alone and in combination. Fluroxypyr-meptyl commercially blended products (STARANE^™, 333 g acid equivalent per liter (g ae/l) EC), diclosulam (SPIDER^® 84WG), cloransulam-methyl (FIRSTRATE^™ 84WG), chlorimuron-ethyl (CLASSIC^® 25WG) and thifensulfuron-methyl (HARMONY^® 50SG). Mixed amounts of fluroxypyr-meptyl, diclosulam, cloransulam-methyl, chlorimuron-ethyl and thifensulfuron-methyl were placed in 60 milliliter (ml) glass vials and dissolved in a volume of 30 or 60 ml of an aqueous solution containing Agri-Dex vegetable oil concentrate at a ratio of 1% v/v (v/v). Conditions for compounds are based on using either 30 or 60 ml volume at a rate of 200 liters per hectare (l/ha). Spray solutions for mixtures were prepared by adding stock solutions to the appropriate amount of dilution solution to form either 30 or 60 ml of spray solution with the active ingredients in one-part and two-part combinations. Spray solutions of the mixtures were prepared by adding stock solutions to the appropriate dilution amount of the solution to form either 30 ml or 60 ml spray solution with the active ingredients in single and double combinations. The formulated compounds were applied to the plant material with a top-fed Generation III Research Sprayer, manufactured by DeVries Manufacturing in Hollandal, MN, USA. The weed machine was equipped with an 8002E spray tip calibrated to produce 200 l/ha, at a spray height of 18 inches (43 centimeters (cm)) above average plant height.

The treated plants and untreated plants were housed in the greenhouse as described above and irrigated with subsoil water to prevent washout of the test compounds.

Grade

The treatment was evaluated from 7 to 21 days after application (DAA) in comparison with untreated control plants. Visual control of weeds was scored on a scale from 0 to 100 percent, where 0 corresponds to no damage and 100 corresponds to complete destruction.

Example 2. Evaluation of the herbicidal activity of mixtures in the field

Methodology

Field trials were carried out using standard herbicide testing methods on small plots. The size of the plots varied from 3×3.3 meters (m) to 4.5×10 m (width×length) with 4 repetitions per treatment. The crops used in the field were grown using conventional soil preparation, fertilization, seeding and maintenance practices to ensure satisfactory crop and weed growth.

All field treatments were carried out using a backpack sprayer with compressed air or carbon dioxide (CO ₂ ) or bicyclic sprayers calibrated to apply a spray volume of 100-187 l/ha. All experiments used Flat Fan spray tips with water as diluent applied at 275-300 kilo Pascal (kPa). Weed heights at use ranged from 10 to 40 cm. Commercially available products are fluroxypyr-meptyl (STARANE ^™ , 180 and 333 g a.i./L EC), diclosulam ( ^SPIDER® 84WG), and thifensulfuron-methyl (Harmony® ^75WG ) was mixed in water at the appropriate level of mixed product to achieve the desired levels, based on unit area of application (hectare) to achieve the desired levels as shown. The excipients were tank mixed for any field treatment used. The treatment was evaluated from 14 to 26 days after application in comparison with untreated control plants. Visual control of weeds was scored on a scale from 0 to 100 percent, where 0 corresponds to no damage and 100 corresponds to complete destruction.

Grade

The treated areas and control areas were blinded at various time intervals after application. Data were presented on the basis of percentage (%) of visual control, where 0 corresponds to no visual effect/weed control, and 100 corresponds to the complete destruction of the target weeds.

Tables 1-4 show the herbicidal synergistic weed control efficacy of fluroxypyr-meptyl tank mixes. All treatment results, both for single product and blends, averaged 4 replicates, and tank blend interactions were significant at P > 0.05.

The spectrum of weeds includes, but is not limited to, Abutilon theophrasti (Theophrastus ropeweed, ABUTH), Amaranthus retroflexus L. (upturned amaranth, AMARE), Amaranthus rudis Sauer (dirty amaranth, AMATA), Amaranthus palmeri S. Wats. (Palmer's amaranth, AMAPA), Chenopodium album (common white gauze, CHEAL), Commelina benghalensis (commelina Bengal, COMBE), Polygonum convolvulus L. (bindweed buckwheat, POLCO) and Sida cordifolia L. (cordifolia sida, SIDCO).

The Colby equation was used to determine the herbicidal effect expected from the mixtures (Colby, SR Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 1967 15 , 20-22). A t-test (alpha=0.05) between Colby's predictive data and observed combinations was used to test for significant differences indicative of synergism or antagonism. The results presented in the Tables were significant according to the described criteria.

The following equation was used to calculate the expected activity of mixtures containing two active ingredients, A and B:

Expected=A+B-(A×B/100)

A=observed efficacy of active ingredient A at the same concentration used in the mixture;

B=observed efficacy of active ingredient B at the same concentration used in the mixture.

The results are presented in Tables 1-4.

Table 1. Synergistic activity of post-emergence herbicidal weed control (percentage (%) of visual control) of fluroxypyr-meptyl and diclosulam combinations in greenhouse trials 8-26 days after application 1 (DAA1). Fluroxypyr-meptyl Diclosulam Combination Bayer weed Evaluation interval g ae/ha Average % weed control g ae/ha Average % weed control Average % weed control Forecast. average % weed control according to Colby ABUTH 14DAA1 25 70.0 1.1 28.8 98.5 78.3 ABUTH 21DAA1 25 72.5 1.1 30.0 100.0 80.6 AMATA 21DAA1 50 37.5 8.8 28.8 96.3 55.5 AMATA 8DAA1 50 60.0 8.8 51.3 95.5 80.4 CHEAL 8DAA1 50 43.3 8.8 38.3 75.0 66.2 CHEAL 14DAA1 50 20.0 2.2 3.3 43.3 22.3 CHEAL 14DAA1 50 20.0 8.8 21.7 73.3 37.3 AMATA 14DAA1 50 43.8 8.8 27.5 95.0 59.9 CHEAL 21DAA1 50 18.3 2.2 5.0 43.3 22.3 CHEAL 21DAA1 50 18.3 4.4 16.7 41.7 32.8 CHEAL 21DAA1 50 18.3 8.8 31.7 70.0 43.6 AMATA 14DAA1 one hundred 37.5 4.4 28.8 63.8 54.8 AMATA 14DAA1 one hundred 37.5 8.8 27.5 65.0 55.8 CHEAL 21DAA1 one hundred 21.0 4.4 16.7 48.3 34.0 AMATA 21DAA1 one hundred 38.8 4.4 25.0 65.0 52.9 AMATA 21DAA1 one hundred 38.8 8.8 28.8 66.3 56.7 COMBE 14DAA1 200 27.5 25.2 41.3 72.5 57.5 COMBE 26DAA1 200 25.0 25.2 17.5 61.3 37.8 SIDCO 14DAA1 200 30.0 25.2 23.3 61.7 49.0

Table 2. Synergistic activity of post-emergence herbicidal weed control (% visual control) of fluroxypyr-meptyl and cloransulam-methyl combinations in field trials 8-21 days after application 1 (DAA1). Fluroxypyr-meptyl Cloransulam-methyl Combination Weed
Bayer Evaluation interval g ae/ha Average % weed control g ae/ha Average % weed control Average % weed control Forecast.
average % weed control according to Colby AMATA 8DAA1 25 42.5 4.4 58.8 98.8 76.3 CHEAL 8DAA1 25 33.3 4.4 35.0 68.3 56.7 ABUTH 14DAA1 25 68.3 1.1 38.3 92.0 80.5 ABUTH 14DAA1 25 70.0 4.4 70.0 99.0 91.2 CHEAL 14DAA1 25 10.0 4.4 11.7 71.7 20.5 AMATA 14DAA1 25 21.3 4.4 38.8 97.5 51.9 ABUTH 21DAA1 25 71.7 1.1 40.0 94.0 82.8 ABUTH 21DAA1 25 72.5 4.4 70.0 100.0 91.8 CHEAL 21DAA1 25 18.3 4.4 11.0 73.3 27.3 AMATA 21DAA1 25 22.5 4.4 37.5 95.0 52.0 CHEAL 21DAA1 50 18.3 8.8 10.0 36.7 27.2 CHEAL 14DAA1 one hundred 33.3 1.1 16.7 55.0 44.7 CHEAL 21DAA1 one hundred 21.0 1.1 8.3 43.3 28.8 CHEAL 21DAA1 one hundred 21.0 4.4 11.0 43.3 30.0 CHEAL 21DAA1 one hundred 21.0 8.8 10.0 53.3 28.7

Table 3. Synergistic activity of post-emergence herbicidal weed control (% visual control) of fluroxypyr-meptyl and chlorimuron-ethyl combinations in field trials 7-14 days after application 1 (DAA1). Fluroxypyr-meptyl Chlorimuron-ethyl Combination Weed
Bayer Evaluation interval g ae/ha Average % weed control g ae/ha Average % weed control Average % weed control Forecast. Average % Colby Weed Control AMATA 7DAA1 25 25.0 8.8 41.3 68.8 55.8 AMATA 14DAA1 25 7.5 8.8 28.8 46.3 34.1 ABUTH 14DAA1 50 67.0 1.1 56.3 89.3 85.1 ABUTH 14DAA1 one hundred 80.8 2.2 62.5 95.0 92.5

Table 4. Synergistic activity of post-emergence herbicidal weed control (% visual control) of fluroxypyr-meptyl and thifensulfuron-methyl combinations in field trials 7-21 days after application 1 (DAA1).

Fluroxypyr-meptyl Tifensulfuron-methyl Combination bayer weed Evaluation interval g ae/ha Average % weed control g ae/ha Average % weed control Average % weed control Forecast.
average % weed control according to Colby AMARE 21DAA1 17.5 3.8 13.0 90.0 97.5 90.4 CHEAL 21DAA1 17.5 3.8 13.0 90.0 97.5 90.4 POLCO 21DAA1 17.5 2.5 13.0 90.0 97.5 90.5 AMAPA 7DAA1 50 48.8 2.2 22.5 75.0 60.4 ABUTH 14DAA1 one hundred 80.8 0.6 56.3 100.0 91.3 ABUTH 14DAA1 one hundred 80.8 1.1 73.8 99.0 94.8

AMARE= Amaranthus retroflexus L. (upturned amaranth)

ABUTH= Abutilon theophrasti (Theophrastus' cable car)

AMATA= Amaranthus rudis Sauer (dirty amaranth)

AMAPA = Amaranthus palmeri S. Wats . (Amaranth Palmer)

CHEAL= Chenopodium album

COMBE= Commelina benghalensis

SIDCO= Sida cordifolia L.

POLCO= Polygonum convolvulus L. (bindweed buckwheat)

g ae/ha=gram acid equivalent per hectare

g a.i./ha = grams of active ingredient per hectare

DAA1=days after use 1

The compositions and methods claimed in the appended claims are not limited in scope to the specific compositions and methods described herein, which are intended to illustrate several aspects of the invention, and any compositions and methods that are functionally equivalent are considered to be within the scope of the claims. Various modifications of the compositions and methods, in addition to those shown and described herein, are considered to be within the scope of the appended claims. In addition, while only some of the characteristic composition components and method steps described herein are specifically described, other combinations of composition components and method steps are also considered to be within the scope of the appended claims, even if not specifically indicated. Thus, a combination of steps, elements, components, or constituents may be specifically referred to herein; however, other combinations of steps, elements, components, and constituents are included, even if not specifically stated. The term "comprising" and its variations, as used herein, is used synonymously with the term "including" and its variations and are open, non-limiting terms. While the terms "comprising" and "comprising" are used herein to describe various embodiments, the terms "substantially consisting of" and "consisting of" may be used in place of "comprising" and "comprising" to describe more specific embodiments of the invention, as well as described.

Claims (44)

1. A herbicidal composition comprising a synergistically effective amount of (a) fluroxypyr, or an agriculturally acceptable ester or salt thereof, and (b) an ALS-inhibiting herbicide, wherein the ALS-inhibiting herbicide is diclosulam, cloransulam, chlorimuron, or thifensulfuron, or agriculturally acceptable ester or salt, wherein: when the ALS-inhibiting herbicide is thifensulfuron or an agriculturally acceptable ester or salt thereof, the weight ratio of fluroxypyr or an agriculturally acceptable ester or salt thereof (acid equivalent) to thifensulfuron or an agriculturally acceptable ester or salt thereof (active ingredient) is in the range of 110:1 to 167:1; when the ALS-inhibiting herbicide is diclosulam or its agriculturally acceptable ester or salt, the weight ratio of fluroxypyr or its agriculturally acceptable ester or salt (acid equivalent) to diclosulam, its agriculturally acceptable ester or salt (active ingredient) is in the range of 1:2 to 560:1; when the ALS-inhibiting herbicide is cloransulam or an agriculturally acceptable ester or salt thereof, the weight ratio of fluroxypyr or an agriculturally acceptable ester or salt thereof (acid equivalent) to cloransulam or an agriculturally acceptable ester or salt thereof (active ingredient) is in the range of 1:2 to 560:1; when the ALS-inhibiting herbicide is chlorimuron or an agriculturally acceptable ester or salt thereof, the weight ratio of fluroxypyr or an agriculturally acceptable ester or salt thereof (acid equivalent) to chlorimuron or an agriculturally acceptable ester or salt thereof (active ingredient) is in the range of 1:3.6 to 560:1. 2. The composition of claim 1 wherein the fluroxypyr, or an agriculturally acceptable ester or salt thereof, is fluroxypyr-meptyl. 3. A composition according to claim 1 or 2, wherein the ALS-inhibiting herbicide is diclosulam. 4. Composition according to claim 3, wherein the weight ratio of fluroxypyr or its agriculturally acceptable ester or salt (acid equivalent) to diclosulam (active ingredient) is in the range from 1:1 to 182:1 or from 5:1 to 23:1 . 5. A composition according to claim 1 or 2, wherein the ALS-inhibiting herbicide is cloransulam or an agriculturally acceptable ester or salt thereof. 6. Composition according to claim 5, wherein the weight ratio of fluroxypyr or its agriculturally acceptable ester or salt (acid equivalent) to cloransulam or its agriculturally acceptable ester or salt (active ingredient) is in the range of 2.8:1 to 91: 1 or from 5.7:1 to 91:1. 7. Composition according to claim 5 or 6, wherein cloransulam or an agriculturally acceptable ester or salt thereof is cloransulam-methyl. 8. A composition according to claim 1 or 2, wherein the ALS-inhibiting herbicide is chlorimuron or an agriculturally acceptable ester or salt thereof. 9. The composition according to claim 8, wherein the weight ratio of fluroxypyr or its agriculturally acceptable ester or salt (acid equivalent) to chlorimuron or its agriculturally acceptable ester or salt (active ingredient) is in the range from 2.8:1 to 91: 1 or from 2.8:1 to 45.5:1. 10. The composition according to claim 8 or 9, wherein the chlorimuron, or an agriculturally acceptable ester or salt thereof, is chlorimuron-ethyl. 11. A composition according to claim 1 or 2, wherein the ALS-inhibiting herbicide is thifensulfuron or an agriculturally acceptable ester or salt thereof. 12. The composition of claim 11, wherein the weight ratio of fluroxypyr or its agriculturally acceptable ester or salt (acid equivalent) to thifensulfuron or its agriculturally acceptable ester or salt (active ingredient) is in the range of 130:1 to 167:1. 13. Composition according to claim 11 or 12, wherein thifensulfuron or an agriculturally acceptable ester or salt thereof is thifensulfuron-methyl. 14. The composition according to any one of paragraphs. 1-13, additionally containing a herbicidally effective amount of additional herbicide. 15. The composition according to any one of paragraphs. 1-14, additionally containing an agriculturally acceptable excipient. 16. A method of dealing with unwanted vegetation, including bringing into contact unwanted vegetation or its focus with a composition according to any one of paragraphs. 1-15. 17. The method of claim 16 wherein fluroxypyr or an agriculturally acceptable ester or salt thereof is applied at a rate of 25 g ae/ha to 560 g ae/ha or 25 g ae/ha to 200 g ae/ha, while diclosulam is applied at a rate of 1 g a.i./ha to 50 g a.i./ha or 1.1 g a.i./ha to 25.2 g a .i./ha. 18. The method of claim 16 wherein the ALS-inhibiting herbicide is cloransulam or an agriculturally acceptable ester or salt thereof. 19. The method of claim 18 wherein fluroxypyr or an agriculturally acceptable ester or salt thereof is applied at a rate of 25 g ae/ha to 560 g ae/ha or 25 g ae/ha to 100 g ae/ha, and cloransulam or an agriculturally acceptable ester or salt thereof is applied at a rate of 1 g a.i./ha to 50 g a.i./ha or 1.1 g a.i. /ha to 8.8 g a.i./ha. 20. The method of claim 16, wherein cloransulam, or an agriculturally acceptable ester or salt thereof, is cloransulam-methyl. 21. The method of claim 16, wherein the ALS-inhibiting herbicide is chlorimuron or an agriculturally acceptable ester or salt thereof. 22. The method of claim 21 wherein fluroxypyr or an agriculturally acceptable ester or salt thereof is applied at a rate of 25 g ae/ha to 560 g ae/ha or 25 g ae/ha to 100 g ae/ha, and chlorimuron or an agriculturally acceptable ester or salt thereof is applied at a rate of 1 g a.i./ha to 90 g a.i./ha or from 1.1 g a.i. /ha to 8.8 g a.i./ha. 23. The method of claim 21 or 22, wherein the chlorimuron or agriculturally acceptable ester or salt thereof is chlorimuron-ethyl. 24. The method of claim 16 wherein the ALS-inhibiting herbicide is thifensulfuron or an agriculturally acceptable ester or salt thereof. 25. The method of claim 24 wherein fluroxypyr or an agriculturally acceptable ester or salt thereof is applied at a rate of 50 g ae/ha to 560 g ae/ha or 50 g ae/ha to 100 g ae/ha, and thifensulfuron or an agriculturally acceptable ester or salt thereof is applied at a rate of 0.5 g a.i./ha to 25 g a.i./ha or 0.6 g a.i. i./ha up to 13 g a.i./ha. 26. The method of claim 16, wherein the thifensulfuron or agriculturally acceptable ester or salt thereof is thifensulfuron-methyl. 27. The method according to any one of paragraphs. 16-26 wherein a composition comprising fluroxypyr or an agriculturally acceptable ester or salt thereof and an ALS inhibiting herbicide is applied to the unwanted vegetation or crop after emergence. 28. The method according to any one of paragraphs. 16-27, where the unwanted vegetation contains weeds with herbicide resistance or tolerance, where the weeds with resistance or tolerance are a biotype with resistance or tolerance to acetohydroxy acid synthase (AHAS) inhibitors, to photosystem II inhibitors, to acetyl-CoA-carboxylase inhibitors ( ACCase), photosystem I inhibitors, 5-enolpyruvyl-shikimate-3-phosphate (EPSP) synthase inhibitors, microtubule assembly inhibitors, lipid synthesis inhibitors, protoporphyrinogen oxidase (PPO) inhibitors, carotenoid biosynthesis inhibitors, fatty acid inhibitors very long chain (VLCFA), phytoene desaturase (PDS) inhibitors, glutamine synthetase inhibitors, 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, mitosis inhibitors, cellulose biosynthesis inhibitors, herbicides with multiple mechanisms of action, quinclorac, arylaminopropionic acids, diphenzoquat , endothal or organic arsenic preparations. 29. The method of claim 28, wherein the herbicide resistant or tolerant weeds are biotypes with resistance or tolerance to one or more herbicides, or one or more chemical classes, or inhibitors with one or more herbicide mechanisms of action. 30. The method according to any one of paragraphs. 16-29 where unwanted vegetation is controlled in soybean, canola, sunflower, sugar beet, alfalfa, corn, cotton, wheat, barley, oats, sorghum, or rice, in an uncultivated area, perennial crop, orchard, or field with perennial crop, which includes bringing into contact undesirable vegetation or its locus in a row crop, seeded crop, fallow bed, fallow field, non-crop crop, perennial crop, fruit crop, or plantation crop field. 31. The method according to claim 30, where the control of unwanted vegetation takes place on an area not sown with agricultural crops, and the area not sown with agricultural crops is a pasture, meadow, pasture, fallow land, strips of land around the fence, parking lot, oil storage, storage area, strip exclusion, industrial area, lawn, forestry, pond, vegetation on the industrial site (IVM) and fallow beds. 32. The method of claim 31, wherein contact with unwanted vegetation occurs prior to planting the crop. 33. The method of claim 30, wherein the control of the unwanted vegetation takes place in a perennial crop field and leaves of the perennial crop do not come into contact upon contact with the unwanted vegetation. 34. The method of claim 33 wherein the perennial crop is trees or vineyards. 35. The method of claim 34, wherein the trees or vineyards are selected from citrus, grape, almond, apple, apricot, avocado, beech, Brazil nut, California gray walnut, cashew, cherry, noble chestnut, dwarf chestnut, forest apple, date, feijoa, fig, hazelnut, hickory, kiwi, Japanese medlar, macadamia nut, summer hawthorn, nectarine, olive trees, peach, pear, pecan, persimmon, pistachio, plum, pomegranate, house plum, quince and walnut walnut. 36. The method of claim. 30, where the control of unwanted vegetation takes place in the field with the fruit crop, and the leaves of the fruit crop are not in contact when in contact with the unwanted vegetation. 37. The method of claim 36 wherein the fruit crop is selected from blueberry, guava, papaya, strawberry, taro, blackberry and raspberry. 38. The method of claim. 30, where the control of unwanted vegetation takes place in fields with plantation crops, and the leaves of the plantation crops are not in contact when in contact with unwanted vegetation. 39. The method of claim 38 wherein the plantation crop is selected from coffee, cocoa, rubber and palm oil.