NOVEL ADDITIVES FOR AGROCHEMICAL FORMULATIONS

Abstract

The invention relates to an agrochemical composition comprising a compound of formula (I) [R-(A)x-OSO3−]-M+ (I); wherein M+ is a monoethanolammonium cation, and wherein the further variables have a meaning as defined herein. It also relates to an adjuvant solution comprising said compound of formula (I) and an organic solvent. Other objects are a compound of formula (I), wherein R is a linear alkyl and M+ is ethanolammonium and wherein the other variables have a meaning as defined herein; and a method of controlling undesired vegetation, and/or for regulating the growth of plants, wherein the agrochemical composition is allowed to act on the respective pests, their environment, or the crop plants to be protected from the respective pest, on the soil and/or on the crop plants and/or on their environment.

Description

The invention relates to compounds of formula (I)

[R-(A)_x-OSO₃⁻]-M⁺  (I);

wherein the variables have a meaning as defined herein below. The invention further relates to an adjuvant solution comprising 40 to 95 wt % of the compound of formula (I), an organic solvent, and up to 5 wt % of water. Another object is an agrochemical composition comprising the surfactant of formula (I) and an agrochemical active ingredient. Further objects are a method for controlling undesirable vegetation, which method comprises applying the agrochemical composition to a locus where undesirable vegetation is present or is expected to be present; the use of the compound of formula (I) for increasing the solubility of an agrochemical active ingredient in liquid agrochemical compositions; a method for increasing the biological effect of agrochemical active ingredients comprising the step of contacting the agrochemical active ingredient with a compound of formula (I); a method of producing the agrochemical composition comprising the step of contacting the compound of formula (I) with the agrochemical active ingredient; plant propagation material comprising the agrochemical composition; to a method for controlling phytopathogenic fungi and/or unwanted plant growth and/or unwanted insect or mite infestation and/or for regulating the growth of plants, wherein the agrochemical composition is caused to act on the respective pests, their habitat or the plants to be protected from the respective pest, to the soil and/or to unwanted plants and/or the crop plants and/or their habitat.and to a method for treating plant propagation material comprising the step of treating plant propagation material with the agrochemical composition.

There is an ongoing need to find additives for agrochemical compositions that enhance the biological effectivity of the composition, increase its physical and/or chemical stability, or increase the loading of the agrochemical composition with active ingredients and/or adjuvants.

Increased biological effectivity allows for lower application rates of the active ingredient, which reduces costs and health risks for the applicant. Higher loading of agrochemical compositions reduces the weight of a given packaging unit, thereby facilitating transportation and handling of the canisters containing the agrochemical compositions. However, agrochemical compositions with higher loading of agrochemical active ingredients and/or adjuvants suffer from stability problems, such as gelling, flocculation, and creaming. Also agrochemical compositions with higher loading often have a high viscosity, which negatively affects their handling by the applicant.

U.S. Pat. No. 10,091,994B2 discloses additives for agrochemical compositions. The additives are alkoxylated and sulfonated alcohols, which are present in the form of salts and wherein the cation may be sodium. A disadvantage of these additives is that compositions containing higher concentrations of these substituents form inhomogeneous and difficult to homogenize and solubilize compositions.

It was the objective of the present invention to provide additives for agrochemical compositions that increase the biological effectivity of the agrochemical composition, improve the physical and/or chemical stability, in particular improve the flowability and storage stability. Further objectives are an increased loading of the agrochemical composition with agrochemical active ingredients and/or adjuvants, as well as an improved handling by the applicant.

The inventive compounds of formula (I) have an increased solubility both in aqueous and oily compositions as compared to those described in prior art. It is thus possible to create highly-concentrated adjuvant solutions of compounds of formula (I). These adjuvant solutions have a comparatively low viscosity and are easy to handle for the applicant. Such adjuvant solutions can be used, for example as tank-mix additives by the farmer. Alternatively, compounds of formula (I) can be built into ready-to-use formulations at a very high concentration, thereby also increasing the maximum loading with agrochemical active ingredient.

Accordingly, the objective was achieved with compounds of formula (I)

[R-(A)_x-OSO₃⁻]-M⁺  (I);

whereinR is C₁₀-C₁₆-alkyl, C₁₀-C₁₆-alkenyl, or C₁₀-C₁₆-alkynyl;each A is independently a group

wherein

• • R^A, R^B, R^C, and R^D are independently H, CH₃, or CH₂CH₃ with the proviso that the sum of C-atoms of R^A, R^B, R^C, and R^D is up to 2;
• M⁺ is an ammonium cation of a primary, secondary, or tertiary amine having a molecular weight of from 32 to 200 g/mol; andthe index x is a number from 1 to 10.

It was surprisingly found that liquid compositions can be loaded with high compounds of formula (I) and at the same time stay stable and flowable, that agrochemical compositions with high concentrations of agrochemical active ingredients and/or compounds of formula (I) can be produced that are stable and flowable and that compounds of formula (I) increase the biological effectiveness of the agrochemical composition.

The present invention refers to and comprises the compound(s) as defined herein and/or stereoisomer(s), tautomer(s) or N-oxide(s) thereof. The term “compound(s) of the present invention” is to be understood as equivalent to the term “compound(s) according to the invention”, therefore also comprising stereoisomer(s), tautomer(s) or N-oxide(s) of compounds of formula (I). The terms compounds of formula (I) and compound of formula (I) as used herein have the same meaning and refer to a situation in which at least one compound of formula (I) is present. In general, terms mentioned in their plural form refer to a situation wherein only the singular term applies as well unless specifically expressed otherwise. The term “composition(s) according to the invention” or “composition(s) of the present invention” encompasses composition(s) comprising at least one compound of formula (I) according to the invention as defined above, therefore also including a stereoisomer, tautomer or an N-oxide of the compounds of formula (I). The term “N-oxide” includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.

The organic moieties groups mentioned in the above definitions of the variables are—like the term halogen—collective terms for individual listings of the individual group members. The prefix C_n-C_m indicates in each case the possible number of carbon atoms in the group.

The term “substituted with”, e.g. as used in “partially, or fully substituted with” means that one or more, e.g. 1, 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by one or more, same or different substituents. Accordingly, for substituted cyclic moieties, e.g. 1-cyanocyclopropyl, one or more of the hydrogen atoms of the cyclic moiety may be replaced by one or more, same or different substituents.

The term “C_n-C_m-alkyl” as used herein (and also in C_n-C_m-alkylamino, di-C_n-C_m-alkylamino, C_n-C_m-alkylaminocarbonyl, di-(C_n-C_m-alkylamino)carbonyl) refers to a branched or unbranched saturated hydrocarbon group having n to m, e.g. 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl and their isomers. C₁-C₄-alkyl means for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

The term “C₂-C_m-alkenyl” as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl.

The term “C₂-C_m-alkynyl” as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, and the like.

Similarly, “C_n-C_m-alkoxy” refers to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen at any bond in the alkyl group. Examples include C₁-C₄-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy.

The term “hetaryl” or “aromatic heterocycle” or “aromatic heterocyclic ring” includes monocyclic 5- or 6-membered heteroaromatic radicals comprising as ring members 1, 2, 3 or 4 heteroatoms selected from N, O and S. Examples of 5- or 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, or 4-pyridyl, pyrimidinyl, i.e. 2-, 4- or 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2- or 3-thienyl, furyl, i.e. 2- or 3-furyl, pyrrolyl, i.e. 2- or 3-pyrrolyl, oxazolyl, i.e. 2-, 3- or 5-oxazolyl, isoxazolyl, i.e. 3-, 4- or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiazolyl, i.e. 3-, 4- or 5-isothiazolyl, pyrazolyl, i.e. 1-, 3-, 4- or 5-pyrazolyl, i.e. 1-, 2-, 4- or 5-imidazolyl, oxadiazolyl, e.g. 2- or 5-[1,3,4]oxadiazolyl, 4- or 5-(1,2,3-oxadiazol)yl, 3- or 5-(1,2,4-oxadiazol)yl, 2- or 5-(1,3,4-thiadiazol)yl, thiadiazolyl, e.g. 2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1,2,3-thiadiazol)yl, 3- or 5-(1,2,4-thiadiazol)yl, triazolyl, e.g. 1H-, 2H- or 3H-1,2,3-triazol-4-yl, 2H-triazol-3-yl, 1H-, 2H-, or 4H-1,2,4-triazolyl and tetrazolyl, i.e. 1H- or 2H-tetrazolyl.

The terms “heterocycle”, “heterocyclyl” or “heterocyclic ring” includes, unless otherwise indicated, in general 5- or 6-membered, in particular 6-membered monocyclic heterocyclic radicals. The heterocyclic radicals may be saturated, partially unsaturated, or fully unsaturated. As used in this context, the term “fully unsaturated” also includes “aromatic”. In a preferred embodiment, a fully unsaturated heterocycle is thus an aromatic heterocycle, preferably a 5- or 6-membered aromatic heterocycle comprising one or more, e.g. 1, 2, 3, or 4, preferably 1, 2, or 3 heteroatoms selected from N, O and S as ring members. Examples of aromatic heterocycles are provided above in connection with the definition of “hetaryl”. Unless otherwise indicated, “hetaryls” are thus covered by the term “heterocycles”. The heterocyclic non-aromatic radicals usually comprise 1, 2, 3, 4 or 5, preferably 1, 2 or 3 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO₂. Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S-oxothietanyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1,3- and 1,4-dioxanyl, thiopyranyl, S. oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxodihydrothiopyranyl, S-dioxodihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetrahydrothiopyranyl, S-dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl, S-dioxothiomorpholinyl, thiazinyl and the like. Examples for heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin-2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl and the like.

Compounds of formula (I) can be prepared by standard methods of organic chemistry. The anionic moiety (I-a)

R-(A)_x-OSO₃⁻  (I-a)

is commercially available in the form of sodium or potassium salts, e.g. under the tradename Genapol LRO from Clariant, and can be prepared as described in U.S. Ser. No. 10/091,994B2, columns 1-2, which is incorporated herein by reference.

Compounds of formula (I) are ionic compounds that comprise the anionic moiety (I-a) and the cationic ammonium moiety M⁺, which is positively and singly charged.

The compounds of formula (I) contain an ammonium cation M⁺ of a primary, secondary, or tertiary amine, i.e. a protonated primary, secondary or tertiary amine. Compounds of formula (I) are available from the commercially available sodium or potassium salts by ion exchange chromatography. Alternatively, compounds of formula (I) are available by reaction of compounds of formula (I) with SO₃ or ClSO₃H and subsequent addition of the respective amine base M as depicted in Scheme 1

wherein all variables have a meaning as defined for formula (I). Reactions of this type are typically carried out at temperatures of 50 to 100° C. under addition of an excess of SO₃ or ClSO₃H compared to the amount of compound of formula (I). Compounds of formula (I) are commercially available under various tradenames, e.g. the Lutensol TO series from BASF, and may be produced from the respective alcohols R—OH by alkoxylation with ethylene oxide, propylene oxide, or butylene oxide as described in U.S. Ser. No. 10/091,994B2. Amine bases M are equally commercially available and form the respective ammonium cations M⁺ in compounds of formula (I).

Compounds of formula (I) may also form in situ in a given composition from a salt of the anionic moiety (I-a) with any given cation N⁺ as displayed by formula (I-b) in the presence of the salt of an ammonium cation M⁺ with any given anion B⁻ as displayed in Scheme 2

wherein N⁺ represents any cation different from M⁺ (such as Na⁺ or K⁺), wherein B⁻ represents any anion different from anion (I-a), and wherein all other variables have a meaning as defined for formula (I). Ion exchange reactions of this type usually occur in liquid compositions and reach an equilibrium in which both the reaction yielding compounds of formula (I) and the backward reaction to compounds of formula (I-b) are in equilibrium.

Compounds of formula (I) may also form in situ in a given composition from the free acid compounds of formula (I-c) and the respective amine M as displayed in Scheme 3

wherein M is a primary, secondary, or tertiary amine as described herein and wherein all variables have a meaning as defined for formula (I). This acid-base reaction may be carried out before the addition of compound of formula (I) to the agrochemical composition, or it may occur in situ by adding compounds of formula (I-c) and the amine component M separately.

The invention thus also pertains to a situation wherein the compound of formula (I) and the compounds of formula (I-b) and/or the compounds of formula (I-c) are present at the same time in various molar ratios. For example, the agrochemical composition may contain compounds of formula (I) in a molar ratio of 1:50 to 1:1 compared with the total molarity of the sum of compounds of formula (I), compounds of formula (I-b) and compounds of formula (I-c) in the agrochemical composition, preferably in a molar ratio of 1:20 to 1:1, more preferably from 1:10 to 1:1. Compounds of formula (I) as produced by the above methods can be obtained from the crude reaction product by standard purification methods such as extraction or column chromatography. If any of the compounds falling within the scope of formula (I) is not directly obtainable by the methods as described above, they are obtainable by derivatization of those compounds of formula (I) that are directly accessible by the methods described above.

The variables of formula (I) have the following preferred meanings and embodiments. Combinations of such preferred meanings and embodiments of all levels of preference are within the scope of the invention.

R is a C₁₀-C₁₆-alkyl, C₁₀-C₁₆-alkenyl, or C₁₀C₁₆-alkenyl. Typically, R is a C₁₀-C₁₆-alkyl, preferably C₁₀-C₁₄-alkyl, more preferably C₁₁-C₁₃-alkyl, and in particular C₁₂-alkyl (e.g. a linear C12-alkyl). In another embodiment, R is C₁₀-C₁₆-alkenyl, preferably C₁₀-C₁₄-alkenyl, more preferably C₁₁-C₁₃-alkenyl, and in particular C₁₂-alkenyl. In another embodiment, R is C₁₀-C₁₆-alkynyl, preferably C₁₀-C₁₄-alkynyl, more preferably C₁₁-C₁₃-alkynyl, and in particular C₁₂-alkynyl.

Each A is independently a group

whereinR^A, R^B, R^C, and R^D are independently H, CH₃, or CH₂CH₃ with the proviso that the sum of C-atoms of R^A, R^B, R^C, and R^D is up to 2.

Typically, the sum of C-atoms of R^A, R^B, R^C, and R^D is up to 1. Preferably, R^A, R^B, R^C and R^D are H. Typically, each group A is the same, preferably wherein R^A, R^B, R^C and R^D are H.

In one embodiment, a mixture of different groups A is present, such as a mixture of groups A, wherein all substituents R^A, R^B, R^C and R^D are H, with groups A, wherein one substituent R^A, R^B, R^C or R^D is CH₃.

In another embodiment, a mixture of different groups A is present, such as a mixture of groups A, wherein all substituents R^A, R^B, R^C and R^D are H, with groups A, wherein one substituent R^A, R^B, R^C or R^D is CH₂CH₃.

In case a mixture of different groups A is present, the molar ratio of groups A, wherein all substituents R^A, R^B, R^C and R^D are H, is typically at least 10 mol %, preferably at least 25 mol %, more preferably at least 50 mol %, and in particular at least 80 mol %.

The index x is from 1 to 10. The index x represents a molar mean of all molecules of compounds of formula (I) in a given ensemble and is any number from 1 to 10, including real numbers between 1 and 10. The skilled person is aware that the common synthesis of compounds of formula (I) includes an alkoxylation step of alcohol R—OH, as outlined above, which alkoxylation step results in a statistical distribution of species R-(A)_x-OH, and in turn results in a statistical distribution of compounds of formula (I) regarding the index x.

Typically, the index x is up to 8, preferably up to 6, more preferably up to 4, most preferably up to 3. The index x may be at least 1.5, preferably at least 2. The index x is typically from 1 to 5, preferably from 1 to 4, more preferably from 1 to 3, most preferably from 1.5 to 3, and in particular from 1.5 to 2.5.

M⁺ is an ammonium cation of a primary, secondary, or tertiary amine having a molecular weight of from 32 to 200 g/mol. In other words, M⁺ is a protonated primary, secondary, or tertiary amine M having a molecular weight of from 32 to 200 g/mol. Typically, the ammonium cation M⁺ contains only one nitrogen atom per molecule.

The ammonium cation M⁺ and the amine M form a conjugated acid/base pair and are in equilibrium in aqueous conditions as displayed in Scheme 4

The invention thus also pertains to a situation wherein the amine is present both in its protonated state M⁺ and in its non-protonated state M. The molar ratio of protonated amine M⁺ to non-protonated amine M is typically at least 1:1, preferably at least 3:1, more preferably at least 5:1 most preferably at least 10:1. The molar ratio of protonated amine M⁺ to non-protonated amine M is typically up to 50:1, preferably up to 20:1, more preferably up to 15:1 most preferably up to 8:1. The molar ratio of protonated amine M⁺ to non-protonated amine M depends on the pH value of the agrochemical composition.

The pH is typically from 5 to 12, preferably from 6 to 10, more preferably from 6.5 to 9. The pH may be adjusted by the addition of an acid, such as HCl, H₂SO₄, H₂SO₃, or methylsulfonic acid.

Accordingly, the compound of formula (I) may contain a mixture of cations, wherein not all of said cations are ammonium cations of primary, secondary, or tertiary amines M⁺. Other cations that may be present are lithium, sodium, potassium, magnesium, calcium, NH₄⁺, or quaternary ammonium cations. The invention thus also pertains to a situation in which the molar concentration of the ammonium cation M⁺ compared to the total amount of the moiety (I-a), e.g. as present in compounds of formula (I), compounds of formula (I-b) and compounds of formula (I-c) is less than 100 mol-%. The molar concentration of the ammonium cation M⁺ compared to the total amount of the moiety (I-a) is typically at least 10 mol %, preferably at least 20 mol-%, more preferably at least 30 mol-%, most preferably at least 50 mol %, and in particular at least 80 mol-%, such as at least 90 mol-%.

The ammonium cation M⁺ has a molecular weight of from 32 to 200 g/mol. In one embodiment, the molecular weight of the ammonium cation M⁺ is at least 35 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is at least 40 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is at least 45 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is at least 50 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is at least 55 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is at least 60 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is at least 61 g/mol. In one embodiment, the molecular weight of the ammonium cation M⁺ is up to 195 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is up to 190 g/mol g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is up to 185 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is up to 180 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is up to 175 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is up to 170 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is up to 160 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is up to 150 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is up to 140 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is up to 130 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is up to 120 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is up to 110 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is up to 105 g/mol. In one embodiment, the molecular weight of the ammonium cation M⁺ is from 35 g/mol to 190 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is from 55 g/mol to 180 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is from 40 g/mol to 140 g/mol. In another embodiment, the molecular weight of the ammonium cation M⁺ is from 50 g/mol to 120 g/mol. In one embodiment, the molecular weight of the ammonium cation M⁺ is from 55 g/mol to 110 g/mol. In one embodiment, the molecular weight of the ammonium cation M⁺ is from 60 g/mol to 110 g/mol.

Preferable, the ammonium cation M⁺ may be represented by formula (II)

whereinR¹, R² and R³ are independently H or C₁-C₁₀-alkyl, which is unsubstituted or substituted with OH, C₁-C₁₀-alkoxy, or hydroxy-C₁-C₁₀-alkoxy; ortwo of the substituents R¹, R², or R³ form, together with the N-atom to which they are bound, a 5-, or 6-membered, saturated, partially- or fully unsaturated heterocycle containing additionally none, one or two atoms O, or S, and wherein said S-atom(s) are independently oxidized or non-oxidized,with the proviso that at least one substituent R¹, R², or R³ is not H.

The substituents R¹, R² and R³ typically contain up to 20 carbon atoms (“C-atoms”), preferably up to 18 C-atoms, more preferably up to 16 C-atoms, most preferably up to 14 C-atoms, especially preferably up to 12 C-atoms, utmost preferably up to 10 C-Atom, in particular up to 8 C-atoms, such as up to 6 C-atoms.

In one embodiment, the substituents R¹, R² and R³ contain up to 9 C-atoms. In another embodiment, the substituents R¹, R² and R³ contain up to 7 C-atoms. In another embodiment, the substituents R¹, R² and R³ contain up to 5 C-atoms. In another embodiment, the substituents R¹, R² and R³ contain up to 4 C-atoms. In another embodiment, the substituents R¹, R² and R³ contain up to 3 C-atoms.

The substituents R¹, R² and R³ contain at least one C-atom, preferably at least 2 C-atoms, more preferably at least 3 C-atoms.

In one embodiment, the substituents R¹, R² and R³ contain from 1 to 15 C-atoms. In another embodiment, the substituents R¹, R² and R³ contain from 1 to 12 C-atoms. In another embodiment, the substituents R¹, R² and R³ contain from 1 to 10 C-atoms. In another embodiment, the substituents R¹, R² and R³ contain from 2 to 12 C-atoms. In another embodiment, the substituents R¹, R² and R³ contain from 2 to 10 C-atoms. In another embodiment, the substituents R¹, R² and R³ contain from 1 to 6 C-atoms. In another embodiment, the substituents R¹, R² and R³ contain from 1 to 4 C-atoms. In another embodiment, the substituents R¹, R² and R³ contain from 1 to 3 C-atoms.

In one embodiment R¹, R² and R³ are independently H or C₁-C₁₀-alkyl, which is unsubstituted or substituted with OH, C₁-C₁₀-alkoxy, or hydroxy-C₁-C₁₀-alkoxy, wherein at least one substituent R¹, R² or R³ is not H. In another embodiment, R¹, R² and R³ are independently H or C₁-C₃-alkyl, which is unsubstituted or substituted with OH, C₁-C₃-alkoxy, or hydroxy-C₁-C₃-alkoxy, wherein at least one substituent R¹, R² or R³ is not H. In another embodiment, R¹, R² and R³ are independently H or C₁-C₇-alkyl, which is unsubstituted or substituted with OH, C₁-C₄-alkoxy, or hydroxy-C₁-C₄-alkoxy, wherein at least one substituent R¹, R² or R³ is not H. In another embodiment, R¹, R² and R³ are independently H or C₁-C₃-alkyl, which is unsubstituted or substituted with OH, C₁-C₄-alkoxy, or hydroxy-C₁-C₄-alkoxy, wherein at least one substituent R¹, R² or R³ is not H. In another embodiment, R¹, R² and R³ are independently H or C₁-C₃-alkyl, which is unsubstituted or substituted with OH, C₁-C₂-alkoxy, or hydroxy-C₁-C₂-alkoxy, wherein at least one substituent R¹, R² or R³ is not H.

In another embodiment, two of the substituents R¹, R², or R³ form, together with the N-atom to which they are bound, a 5-, or 6-membered, saturated, partially- or fully unsaturated heterocycle containing additionally none, one or two atoms O, or S, and wherein said S-atom(s) are independently oxidized or non-oxidized, and the remaining substituent R¹, R², or R³ is either H, or C₁-C₁₀-alkyl, which is unsubstituted or substituted with OH, C₁-C₁₀-alkoxy, or hydroxy-C₁-C₁₀-alkoxy.

In another embodiment, two of the substituents R¹, R², or R³ form, together with the N-atom to which they are bound, a 5-, or 6-membered, saturated, partially- or fully unsaturated heterocycle containing additionally none, one or two atoms O, or S, and wherein said S-atom(s) are non-oxidized, and the remaining substituent R¹, R², or R³ is either H, or C₁-C₄-alkyl, which is unsubstituted or substituted with OH, C₁-C₄-alkoxy, or hydroxy-C₁-C₄-alkoxy.

In another embodiment, two of the substituents R¹, R², or R³ form, together with the N-atom to which they are bound, a 5-, or 6-membered, saturated, partially- or fully unsaturated heterocycle containing additionally none, one or two atoms O, or S, and wherein said S-atom(s) are non-oxidized, and the remaining substituent R¹, R², or R³ is either H, or C₁-C₃-alkyl, which is unsubstituted or substituted with OH.

In another embodiment, two of the substituents R¹, R², or R³ form, together with the N-atom to which they are bound, a 6-membered, saturated, partially- or fully unsaturated heterocycle containing additionally none, one or two atoms O, or S, and wherein said S-atom(s) are non-oxidized, and the remaining substituent R¹, R², or R³ is either H, or C₁-C₂-alkyl, which is unsubstituted or substituted with OH.

The ammonium cation M⁺ is typically a protonated amine selected from ethanolamine, diethanolamine, diglycolamine, 1-aminopropan-2-ol, 2-dimethylaminoethanol, 2-(butylamino)ethanol, 2-diethylaminoethanol, 2-(tert-butylamino)ethanol, N-(tertbutyl)diethanolamine, triethanolamine, 2-ethylaminoethanol, 2-aminoheptan, triisopropylamine, N-(2-hydroxyethyl)morpholin, N-methylmorpholine, N-butyldiethanolamin, 2-(dibutylamino)ethanol, and mixtures thereof.

In one embodiment, the ammonium cation M⁺ is protonated ethanolamine (ethanolammonium; or also called monoethanolammonium; CAS number 141-43-5). In another embodiment, the ammonium cation M⁺ is protonated diethanolamine (diethanolammonium). In another embodiment, the ammonium cation M⁺ is protonated diglycolamine (diglycolammonium). In another embodiment, the ammonium cation M⁺ is protonated 1-aminopropan-2-ol. In another embodiment, the ammonium cation M⁺ is protonated 2-dimethylaminoethanol. In another embodiment, the ammonium cation M⁺ is protonated 2-(butylamino)ethanol. In another embodiment, the ammonium cation M⁺ is protonated 2-diethylaminoethanol. In another embodiment, the ammonium cation M⁺ is protonated 2-(tert-butylamino)ethanol. In another embodiment, the ammonium cation M⁺ is protonated N-(tert-butyl)diethanolamine (N-(tertbutyl)diethanolammonium). In another embodiment, the ammonium cation M⁺ is protonated triethanolamine (triethanolammonium). In another embodiment, the ammonium cation M⁺ is protonated 2-ethylaminoethanol. In another embodiment, the ammonium cation M⁺ is protonated 2-aminoheptan. In another embodiment, the ammonium cation M⁺ is triisopropylamine (triisopropylammonium). In another embodiment, the ammonium cation M⁺ is N-(2-hydroxyethyl)morpholin, In another embodiment, the ammonium cation M⁺ is protonated N-methylmorpholine. In another embodiment, the ammonium cation M⁺ is protonated N-butyldiethanolamine (N-butyldiethanolammonium). In another embodiment, the ammonium cation M⁺ is protonated 2-(dibutylamino)ethanol.

In another embodiment, the ammonium cation M⁺ is a protonated amine selected from triethanolamine, 2-ethylaminoethanol, 2-aminoheptane, triisopropylamine, N-(2-hydroxyethyl)-morpholin, N-methylmorpholine, N-butyldiethanolamin, 2-(dibutylamino)ethanol, or a mixture thereof.

In one embodiment, the invention relates to compounds of formula (I), wherein R is C₁₀-C₁₄-alkyl;

each A is independently a group

wherein

• R^A, R^B, R^C, and R^D are independently H, CH₃, or CH₂CH₃ with the proviso that the sum of C-atoms of R^A, R^B, R^C, and R^D is up to 2;
• M⁺ is an ammonium cation of a primary, secondary, or tertiary amine having a molecular weight of from 32 to 200 g/mol; andthe index x is a number from 1 to 5.

In another embodiment, the invention relates to compounds of formula (I), wherein R is C₁₀-C₁₄-alkyl;

each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;

• M⁺ is an ammonium cation of a primary, secondary, or tertiary amine having a molecular weight of from 32 to 190 g/mol; andthe index x is a number from 1 to 5.

In another embodiment, the invention relates to compounds of formula (I), wherein R is C₁₀-C₁₄-alkyl;

each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;

• M⁺ is an ammonium cation of a primary, secondary, or tertiary amine having a molecular weight of from 32 to 190 g/mol; andthe index x is a number from 1 to 5.

In another embodiment, the invention relates to compounds of formula (I), wherein R is C₁₀-C₁₄-alkyl;

each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;

• M⁺ is an ammonium cation of a primary, secondary, or tertiary amine having a molecular weight of from 60 to 110 g/mol; andthe index x is a number from 1 to 5.

In another embodiment, the invention relates to compounds of formula (I), wherein R is C₁₂-alkyl;

each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;

• M⁺ is an ammonium cation of a primary, secondary, or tertiary amine having a molecular weight of from 60 to 110 g/mol; andthe index x is a number from 1 to 3.

In another embodiment, the invention relates to compounds of formula (I), wherein R is C₁₂-alkyl;

each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;the index x is a number from 1 to 3; andM⁺ is an ammonium cation of formula (II)

• • wherein
  • R¹, R² and R³ are independently H, or C₁-C₁₀-alkyl, which is unsubstituted or substituted with OH, C₁-C₁₀-alkoxy, or hydroxy-C₁-C₁₀-alkoxy; or
  • two of the substituents R¹, R², or R³ form, together with the N-atom to which they are bound, a 5-, or 6-membered, saturated, partially- or fully unsaturated heterocycle containing additionally none, one or two atoms O, or S, and wherein said S-atom(s) are independently oxidized or non-oxidized,
  • with the proviso that at least one substituent R¹, R², or R³ is not H.

In another embodiment, the invention relates to compounds of formula (I), wherein R is C₁₂-alkyl;

each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;the index x is a number from 1 to 3; and

• M⁺ is protonated amine selected from ethanolamine, diethanolamine, diglycolamine, 1-aminopropan-2-ol, 2-dimethylaminoethanol, 2-(butylamino)ethanol, 2-diethylaminoethanol, 2-(tert-butylamino)ethanol, N-(tert-butyl)diethanolamine, triethanolamine, 2-ethylaminoethanol, 2-aminoheptane, triisopropylamine, N-(2-hydroxyethyl)morpholin, N-methylmorpholine, N-butyldiethanolamin, 2-(dibutylamino)ethanol, and mixtures thereof.

In another embodiment, the invention relates to compounds of formula (I), wherein R is C₁₂-alkyl;

each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;the index x is a number from 1 to 3; and

• M⁺ is protonated amine selected from ethanolamine, diethanolamine, diglycolamine, 1-aminopropan-2-ol, 2-dimethylaminoethanol, and mixtures thereof, preferably selected from diethanolamine and 1-aminopropan-2-ol.

In another embodiment, the invention relates to compounds of formula (I), wherein R is linear C₁₂-alkyl (lauryl);

each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;the index x is a number from 1 to 3, preferably 1.5 to 2.5; andM⁺ is ethanolammonium.

In one embodiment, the invention does not relate to liquid herbicidal compositions comprising

a) a protoporphyrinogen-IX oxidase inhibitor, or an agrochemically acceptable salt, stereoisomer, tautomer, or N-oxide thereof;b) a compound of formula (I)

[R-(A)_x-OSO₃⁻]-M⁺  (I);

whereinR is C₁₀-C₁₆-alkyl, C₁₀-C₁₆-alkenyl, or C₁₀-C₁₆-alkynyl, preferably linear C12-alkyl;each A is independently a group

wherein

• R^A, R^B, R^C, and R^D are independently H, CH₃, or CH₂CH₃ with the proviso that the sum of C-atoms of R^A, R^B, R^C, and R^D is up to 2, preferably wherein R^A, R^B, R^C, and R^D are H;
• M⁺ is a monovalent cation, preferably selected from ammonium cations of a primary, secondary, and tertiary amines; and quaternary ammonium cations;
  • wherein the molecular weight of the ammonium cations or of quaternary ammonium cation is from 32 to 200 g/mol, preferably ethanolammonium or sodium;and mixtures thereof; andthe index x is a number from 1 to 10.

In one embodiment, the invention does not relate to a liquid herbicidal composition comprising

a) glufosinate, or a salt thereof;b) an amine component selected from primary, secondary, tertiary amines, and ammonium salts thereof, and quaternary ammonium salts:wherein the molecular weight of the primary, secondary or tertiary amines, of the ammonium cation in the ammonium salts, or of the quaternary ammonium cation in the quaternary ammonium salts is from 32 to 200 g/mol, preferably ethanolamine;c) a compound of formula (I)

[R-(A)_x-OSO₃⁻]-M⁺  (I);

whereinR is C₁₀-C₁₆-alkyl, C₁₀-C₁₆-alkenyl, or C₁₀-C₁₆-alkynyl, preferably linear C₁₂-alkyl; each A is independently a group

wherein

• R^A, R^B, R^C, and R^D are independently H, CH₃, or CH₂CH₃ with the proviso that the sum of C-atoms of R^A, R^B, R^C, and R^D is up to 2 (preferably R^A, R^B, R^C, and R^D are H);
• M⁺ is a monovalent cation, which is preferably different from the ammonium cations in the ammonium salts of the primary, secondary or tertiary amines, or the quaternary ammonium cations in the quaternary ammonium salts; andthe index x is a number from 1 to 10.

The invention also relates to an agrochemical composition comprising the compound of formula (I) as defined above and an agrochemical active ingredient.

The agrochemical composition may comprise the compound of formula (I) in a concentration of at least 1 wt %, preferably at least 5 wt % more preferably at least 10 wt %, most preferably at least 20 wt % (e.g. more than 25 wt %, such as at least 26 wt %, preferably at least 27 wt %, more preferably at least 28 wt %, especially at least 29 wt %), in particular at least 30 wt %, and especially at least 40 wt %, such as at least 45 wt % based on the total weight of the agrochemical composition. The agrochemical composition may comprise the compound of formula (I) in a concentration of up to 90 wt %, preferably up to 70 wt %, more preferably up to 50 wt % based on the total weight of the agrochemical composition. The agrochemical composition may comprise the compound of formula (I) in a concentration of from 15 to 70 wt %, preferably 25 to 60 wt %, more preferably 35 to 50 wt % based on the total weight of the composition. The agrochemical composition is typically a liquid agrochemical composition that contains the compound of formula (I) in dissolved state.

The agrochemical active ingredient is typically either present in dissolved or in suspended form in the agrochemical composition. If the agrochemical composition is an aqueous composition, the agrochemical active ingredient is typically dissolved, such as in soluble concentrates. If the agrochemical composition is an oily composition, the agrochemical active ingredient is typically present in particulate form as suspended particles, in particular in oil dispersions.

The agrochemical compositions containing compounds of formula (I) have a comparatively low dynamic viscosity and stay homogeneous even at high concentrations of compound of formula (I). The dynamic viscosity as referred to herein can be measured by means of a Brookfield viscosimeter, i.e. a rotational viscosimeter with a cone-plate geometry. The dynamic viscosity may be determined according to industry standard EN ISO 2555:2018. Usually, the dynamic viscosity is measured at 25° C. In this method, the shear rate of the rotation viscosimeter is constantly increased and the shear stress is measured. For Newtonian Fluids, the measurement results in a linear dataset according to a direct proportionality between the shear stress and the shear rate. For non-Newtonian fluids, the measurement results in a non-linear dependency between shear stress and shear rate. The dynamic viscosity, also called apparent viscosity, is typically determined by measuring the slope of a line through the origin of the coordinate system and the shear stress as determined at a shear rate of 100/second. The true viscosity, which may be different from the apparent viscosity for non-Newtonian fluids, is determined by calculating the slope of the tangent of the experimental curve as measured at a shear rate of 100/second.

The agrochemical composition usually has a true viscosity at 20° C. less than to 2000 mPas, preferably less than 1000 mPas, more preferably less than 500 mPas. The agrochemical composition usually has an apparent viscosity at 20° C. less than to 3000 mPas, preferably less than 1500 mPas, more preferably less than 1000 mPas.

An agrochemical composition typically comprises an agrochemically effective amount of an agrochemical active ingredient. The term “effective amount” denotes an amount of the composition or of the agrochemical active ingredient contained therein, which is sufficient to achieve a biological effect, such as controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the pest species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific agrochemical active ingredient used.

The agrochemical composition contains an agrochemical active ingredient. The term “agrochemical active ingredient” refers to a substance that confers a desirable biological activity to the agrochemical composition. Typically, the agrochemical active is a pesticide. Agrochemical actives may be selected from fungicides, insecticides, nematicides, herbicides, safeners, micronutrients, biopesticides, nitrification inhibitors, and/or growth regulators. In one embodiment, the agrochemical active is an insecticide. In another embodiment, the agrochemical active is a fungicide, such as mefentrifluconazol. In yet another embodiment the agrochemical active is a herbicide, preferably glufosinate or a salt thereof, or a protoporphyrinogen-IX oxidase inhibitor (PPO inhibitor) (e.g. saflufenacil). In another embodiment, the agrochemical active is not a PPO inhibitor. In another embodiment, the agrochemical active is not glufosinate or a salt thereof. The skilled worker is familiar with such pesticides, which can be found, for example, in the Pesticide Manual, 16th Ed. (2013), The British Crop Protection Council, London. Suitable insecticides are insecticides from the class of the carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds nereistoxin analogs, benzoylureas, diacylhydrazines, and METI acarizides. Suitable fungicides are fungicides from the classes of dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzyl carbamates, carbamates, carboxamides, carboxylic acid diamides, chloronitriles cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy-(2-amino)pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic substances, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oximinoacetates, oximinoacetamides, peptidylpyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, pyrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulfamides, sulfamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiophanates, thiophenecarboxamides, toluamides, triphenyltin compounds, triazines, triazoles.

Suitable herbicides are herbicides from the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanlines, dinitrophenol, diphenyl ether, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl(thio)benzoates, quinolinecarboxylic acids, semicarbazones, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas. Preferred herbicides are salts of glufosinate, such as the ammonium salt of L-glufosinate, and protoporphyrinogen-IX oxidase inhibitors. Examples of PPO-inhibitors are acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chlorphthalim, cinidon-ethyl, cyclopyranil, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil, trifludimoxazin, ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate (CAS 353292-31-6; S-3100), N-ethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452098-92-9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452100-03-7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione (CAS 451484-50-7), 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1,3-dione (CAS 1300118-96-0), 1-methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidine-2,4-dione (CAS 1304113-05-0), methyl (E)-4-[2-chloro-5-[4-chloro-5-(difluoromethoxy)-1H-methyl-pyrazol-3-yl]-4-fluoro-phenoxy]-3-methoxy-but-2-enoate (CAS 948893-00-3), and 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)-1H-pyrimidine-2,4-dione (CAS 212754-02-4), 2-[2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]-4-fluorophenoxy]-2-methoxy-acetic acid methyl ester (CAS 1970221-16-9), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]-acetic acid methyl ester (CAS 2158274-96-3), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy] acetic acid ethyl ester (CAS 2158274-50-9), methyl 2-[[3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluoro-phenoxy]-2-pyridyl]oxy]acetate (CAS 2271389-22-9), ethyl 2-[[3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluoro-phenoxy]-2-pyridyl]oxy]acetate (CAS 2230679-62-4), 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]-acetic acid methyl ester (CAS 2158275-73-9), 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy] acetic acid ethyl ester (CAS 2158274-56-5), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]-N-(methylsulfonyl)-acetamide (CAS 2158274-53-2), and 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]-N-(methylsulfonyl)-acetamide (CAS 2158276-22-1). Suitable plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releasers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators, and further unclassified plant growth regulators. Suitable micronutrients are compounds comprising boron, zinc, iron, copper, manganese, chlorine, and molybdenum.

The agrochemical composition may comprise the agrochemical active ingredient in a concentration of at least 1 wt %, preferably at least 5 wt % more preferably at least 10 wt %, most preferably at least 25 wt %, and in particular at least 30 wt % based on the total weight of the agrochemical composition. The agrochemical composition may comprise the agrochemical active in a concentration of up to 90 wt %, preferably up to 70 wt %, more preferably up to 50 wt % based on the total weight of the agrochemical composition. The agrochemical composition may comprise the agrochemical active in a concentration of from 1 to 70 wt %, preferably 1 to 60 wt %, more preferably 5 to 50 wt % based on the total weight of the composition.

The agrochemical composition relates to any customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6^th Ed. May 2008, CropLife International. The agrochemical composition is typically a liquid composition, i.e. it contains a liquid continuous phase. Typically, the agrochemical composition is an aqueous agrochemical composition or an agrochemical composition with a continuous oily phase containing a non-aqueous organic solvent. Preferred formulation types of the agrochemical composition are solutions, emulsifiable concentrates, and dispersions, more preferably solutions, suspension concentrates and oil dispersions.

Accordingly, the agrochemical composition may comprise water. Typically, the agrochemical composition comprises water in a concentration of at least 1 wt %, preferably at least 5 wt, more preferably at least 10 wt %. The agrochemical composition may comprise water in a concentration of up to 50 wt %, preferably up to 40 wt %, more preferably up to 30 wt %, and in particular up to 25 wt %. The agrochemical composition typically comprises water in a concentration of from 5 to 35 wt %, preferably from 10 to 30 wt %. If the concentration of water in the agrochemical composition is at least 5 wt %, such compositions may be referred to as aqueous compositions.

The agrochemical composition may also comprise at least one organic solvent. Typically, the agrochemical composition comprises the organic solvent in a concentration of at least 1 wt %, preferably at least 5 wt, more preferably at least 15 wt %. The agrochemical composition may comprise the organic solvent in a concentration of up to 60 wt %, preferably up to 50 wt %, more preferably up to 45 wt %, and in particular up to 35 wt %. The agrochemical composition typically comprises the organic solvent in a concentration of from 5 to 50 wt %, preferably from 10 to 40 wt %. If the concentration of water in the agrochemical composition is at least 20 wt %, such compositions may be referred to as “oily” compositions. Suitable organic solvents are defined herein below. Preferred are such organic solvents that have a water-solubility of at least 1 wt % at 20° C., preferably at least 10 wt % at 20° C.

Suitable organic solvents are aliphatic hydrocarbons, preferably an aliphatic C₅-C₁-hydrocarbon, more preferably a C₅-C₁₆-alkane, or C₅-C₁₆-cycloalkane, such as pentane, hexane, cyclohexane, or petrol ether; aromatic hydrocarbons, preferably an aromatic C₆-C₁₀-hydrocarbons, such as benzene, toluene, o-, m-, and p-xylene; halogenated hydrocarbons, preferably halogenated aliphatic C₁-C₆-alkanes, or halogenated aromatic C₆-C₁₀-hydrocarbons, such as CH₂Cl₂, CHCl₃, CCl₄, CH₂ClCH₂Cl, CCl₃CH₃, CHCl₂CH₂Cl, CCl₂CCl₂, or chlorobenzene; ethers, preferably C₁-C₆-cycloalkyl ethers, C₁-C₆-alkyl-C₁-C₆-alkyl ethers and C₁-C₆-alkyl-C₆-C₁₀-aryl ethers, such as CH₃CH₂OCH₂CH₃, (CH₃)₂CHOCH(CH₃)₂, CH₃OC(CH₃)₃ (MTBE), CH₃OCH₃ (DME), CH₃OCH₂CH₂OCH₃, dioxane, anisole, and tetrahydrofurane (THF); esters, preferably esters of aliphatic C₁-C₆-alcohols with aliphatic C₁-C₆-carboxylic acids, esters of aromatic C₆-C₁₀-alcohols with aromatic C₆-C₁₀-carboxylic acids, cyclic esters of ω-hydroxy-C₁-C₆-carboxylic acids, such as CH₃C(O)OCH₂CH₃, CH₃C(O)OCH₃, CH₃C(O)OCH₂CH₂CH₂CH₃, CH₃C(O)OCH(CH₃)CH₂CH₃, CH₃C(O)OC(CH₃), CH₃CH₂CH₂C(O)OCH₂CH₃, CH₃CH(OH)C(O)OCH₂CH₃, CH₃CH(OH)C(O)OCH₃, CH₃C(O)OCH₂CH(CH₃)₂, CH₃C(O)OCH(CH₃)₂, CH₃CH₂C(O)OCH₃, benzyl benzoate, and γ-butyrolactone; carbonates, such as ethylene carbonate, propylene carbonate, CH₃CH₂OC(O)OCH₂CH₃, and CH₃OC(O)OCH₃; nitriles, preferably C₁-C₆-nitriles, such as CH₃CN, and CH₃CH₂CN; ketones, preferably C₁-C₆-alkyl-C₁-C₆-alkyl ketones, such as CH₃C(O)CH₃, CH₃C(O)CH₂CH₃, CH₃CH₂C(O)CH₂CH₃, and CH₃C(O)C(CH₃)₃ (MTBK); alcohols, preferably C₁-C₄-alcohols, such as CH₃OH, CH₃CH₂OH, CH₃CH₂CH₂OH, CH₃CH(OH)CH₃, CH₃(CH₂)₃OH, C(CH₃)₃OH, propylene glycol, dipropylene glycol, propylene glycol monomethylether (1-methoxy-2-propanol); amides and urea derivatives, preferably dimethyl formamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethyl acetamide (DMA), 1,3-dimethyl-2-imidazolidinone (DMI), 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU), hexamethylphosphamide (HMPA); moreover dimethyl sulfoxide (DMSO), and sulfolane. Preferred solvents are propylene glycol, dipropylene glycol and propyleneglycol monomethyl ether, more preferred propylene glycol and dipropylene glycol.

The agrochemical compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005. Typically, the agrochemical compositions are prepared by contacting the compound of formula (I) with the agrochemical active ingredient. In one embodiment, the method comprises the step of contacting water with the compound of formula (I), the agrochemical active ingredient, wherein the order of the contacting is of no particular importance. In another embodiment, the method comprises contacting an organic solvent with the agrochemical active ingredient, wherein the order of the contacting is of no particular importance, whereupon the resulting mixture is typically grinded to generate a suspension with a particle size D50 of from 1.5 to 15 μm.

The invention also relates to a method of stabilizing an agrochemical composition comprising an agrochemical active ingredient as defined herein at low temperatures, such as at temperatures from −40 to 10° C., such as from −35 to 5° C., e.g. from −10 to 5° C.), comprising the step of contacting the compound of formula (I) with the agrochemical active ingredient. In one embodiment, the method comprises the step of contacting water with the compound of formula (I), the agrochemical active ingredient, wherein the order of the contacting is of no particular importance. In another embodiment, the method comprises contacting an organic solvent with the agrochemical active ingredient, wherein the order of the contacting is of no particular importance, whereupon the resulting mixture is typically grinded to generate a suspension with a particle size D50 of from 1.5 to 15 μm.

The agrochemical composition typically comprises at least one auxiliary. Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents.

Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.

Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.

Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.

Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.

Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.

Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones. Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.

Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids. Particularly preferred for agrochemical compositions containing glufosinate are silicone-based anti-foaming agents such as polydimethylsiloxanes (e.g. SAG 1572 as available from Momentive, Silcolapse-481 or Silcolapse-482 from Elkem). Suitable silicone-based anti-foaming agents in the context of glufosinate have also been described in WO2005/117590A2, Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

Examples for composition types and their preparation are:

i) Water-Soluble Concentrates (SL, LS)

10-60 wt % of an agrochemical active ingredient and 5-60 wt % of compound of formula (I) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) ad 100 wt %. The active substance dissolves upon dilution with water.

ii) Dispersible Concentrates (DC)

5-25 wt % of an agrochemical active ingredient, 5 to 60 wt % of compound of formula (I) and 1-10 wt % dispersant (e. g. polyvinylpyrrolidone) are dissolved in organic solvent (e.g. cyclohexanone) ad 100 wt %. Dilution with water gives a dispersion.

iii) Emulsifiable Concentrates (EC)

15-70 wt % of an agrochemical active ingredient according to the invention and 5-10 wt % emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) and 5-60 wt % of compound of formula (I) are dissolved in water-insoluble organic solvent (e.g. aromatic hydrocarbon) ad 100 wt %. Dilution with water gives an emulsion.

iv) Emulsions (EW, EO, ES)

5-40 wt % of an agrochemical active ingredient according to the invention and 1-10 wt % emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) and 5-60 wt % of compound of formula (I) are dissolved in 20-40 wt % water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt % by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.

v) Suspensions (SC, OD, FS)

In an agitated ball mill, 20-60 wt % of an agrochemical active ingredient according to the invention are comminuted with addition of 2-10 wt % dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0, 1-2 wt % thickener (e.g. xanthan gum), 5-60 wt % of compound of formula (I), and water ad 100 wt % to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt % binder (e.g. polyvinylalcohol) is added.

vi) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50-80 wt % of an agrochemical active ingredient are ground finely with addition of dispersants, 5-40 wt % of compound of formula (I) and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt % and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.

vii) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, WS)

50-80 wt % of an agrochemical active ingredient are ground in a rotor-stator mill with addition of 1-5 wt % dispersants (e.g. sodium lignosulfonate), 1-3 wt % wetting agents (e.g. alcohol ethoxylate), and 5-40 wt % of compound of formula (I) and solid carrier (e.g. silica gel) ad 100 wt %. Dilution with water gives a stable dispersion or solution of the active substance.

viii) Gel (GW, GF)

In an agitated ball mill, 5-25 wt % of an agrochemical active ingredient are comminuted with addition of 3-10 wt % dispersants (e.g. sodium lignosulfonate), 1-5 wt % thickener (e.g. carboxymethylcellulose), 5-60 wt % of compound of formula (I) and water ad 100 wt % to give a fine suspension of the active substance. Dilution with water gives a stable gel of the active substance.

iv) Microemulsion (ME)

5-20 wt % of an agrochemical active ingredient according to the invention are added to 5-30 wt % organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt % surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water ad 100%. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.

iv) Microcapsules (CS)

An oil phase comprising 5-50 wt % of an agrochemical active ingredient, 0-40 wt % water insoluble organic solvent (e.g. aromatic hydrocarbon), 5-60 wt % of compound of formula (I), 2-15 wt % acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt % of a agrochemical active ingredient according to the invention, 0-40 wt % water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4′-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of a polyurea microcapsules. The monomers amount to 1-10 wt %. The wt % relate to the total CS composition.

ix) Dustable Powders (DP, DS)

1-10 wt % of an agrochemical active ingredient according to the invention are ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) and 1-30 wt % of compound of formula (I) ad 100 wt %.

x) Granules (GR, FG)

0.5-30 wt % of an agrochemical active ingredient is ground finely and associated with solid carrier (e.g. silicate) and 1-30 wt % of compound of formula (I) ad 100 wt %. Granulation is achieved by extrusion, spray-drying or the fluidized bed.

xi) Ultra-Low Volume Liquids (UL)

1-50 wt % of an agrochemical active ingredient and compound of formula (I) are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt %.

The compositions types i) to xi) may optionally comprise further auxiliaries, such as 0, 1-1 wt % bactericides, 5-15 wt % anti-freezing agents, 0, 1-1 wt % anti-foaming agents, and 0, 1-1 wt % colorants.

Exemplary formulation types that are suitable in the context of the present invention regarding glufosinate compositions have been described in WO2007/092351A1 and WO2005/117583A2.

Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, concentrations of the agrochemical active ingredient of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying the agrochemical composition, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, the agrochemical composition is applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.

When employed in plant protection, the amounts of agrochemical active ingredients are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.

When used in the protection of materials or stored products, the amount of agrochemical active ingredient applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.

Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the agrochemical composition comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.

The user applies the agrochemical composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

According to one embodiment, individual components of the agrochemical composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.

In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds of formula (I) and/or the agrochemical active substance may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.

In a further embodiment, either individual components of the agrochemical composition according to the invention or partially premixed components, e. g. components comprising compounds of formula (I) and/or the agrochemical active ingredient can be applied jointly (e.g. after tank mix) or consecutively.

A particularly preferred agrochemical active ingredient is glufosinate. Glufosinate (CAS Reg. No. 51276-47-2), with IUPAC-Name (2RS)-2-amino-4-[hydroxy(methyl)phosphinoyl]butyric acid, or 4-[hydroxy(methyl)phosphinoyl]-DL-homoalanine) or DL-4-[hydroxyl(methyl)phosphinoyl]-DL-homoalaninate, is known, as well as agronomically acceptable salts thereof, in particular glufosinate-ammonium (IUPAC-Name: ammonium (2RS)-2-amino-4-(methylphosphinato)butyric acid, CAS Reg. No. 77182-82-2).

U.S. Pat. No. 4,168,963 describes phosphorus-containing compounds with herbicidal activity, of which, in particular, phosphinothricin (2-amino-4-[hydroxy(methyl)phosphinoyl]butanoic acid; common name: glufosinate) and its salts have acquired commercial importance in the agrochemistry (agricultural chemistry) sector.

For example, glufosinate and its salts—such as glufosinate ammonium—and its herbicidal activity have been described e.g. by F. Schwerdtle et al. Z. Pflanzenkr. Pflanzenschutz, 1981, Sonderheft IX, pp. 431-440.

Glufosinate as racemate and its salts are commercially available under the trade-names Basta™ and Liberty™.

Glufosinate is represented by the following structure (IV):

The compound of formula (IV) is a racemate.

Glufosinate is a racemate of two enantiomers, out of which only one shows sufficient herbicidal activity (see e.g. U.S. Pat. No. 4,265,654 and JP92448/83). Even though various methods to prepare L-glufosinate (and respective salts) are known, the mixtures known in the art do not point at the stereochemistry, meaning that the racemate is present (e.g. WO 2003024221, WO2011104213, WO 2016113334, WO 2009141367).

In one embodiment, the agrochemical composition comprises racemic glufosinate mixtures as described above, wherein the glufosinate comprises about 50% by weight of the L-enantiomer and about 50% by weight of the D-enantiomer. In another embodiment, the agrochemical composition comprises glufosinate, wherein at least 70% by weight of the glufosinate is L-glufosinate or a salt thereof. Agrochemical compositions comprising glufosinate or a salt thereof, preferably (L)-glufosinate or a salt thereof, more preferably the ammonium salt of (L)-glufosinate, are herein referred to as “glufosinate compositions”.

L-glufosinate, with IUPAC-Name (2S)-2-amino-4-[hydroxy(methyl)phosphinoyl]butyric acid (CAS Reg. No. 35597-44-5) and also called glufosinate-P, can be obtained commercially or may be pre-pared for example as described in WO2006/104120, U.S. Pat. No. 5,530,142, EP0248357A2, EP0249188A2, EP0344683A2, EP0367145A2, EP0477902A2, EP0127429 and J. Chem. Soc. Perkin Trans. 1, 1992, 1525-1529.

Preferably, the agronomically acceptable salts of glufosinate or (L)-glufosinate are the sodium, potassium or ammonium (NH₄⁺) salts of glufosinate or L-glufosinate, in particular glufosinate-P-ammonium (IUPAC-Name: ammonium (2S)-2-amino-4-(methylphosphinato)butyric acid, CAS Reg. No. 73777-50-1), glufosinate-P-sodium (IUPAC-Name: sodium (2S)-2-amino-4-(methylphosphinato)butyric acid; CAS Reg. No. 70033-13-5) and glufosinate-P-potassium (IUPAC-Name: potassium (2S)-2-amino-4-(methylphosphinato)butyric acid) for L-glufosinate.

Hence, mixtures according to the agrochemical composition may contain (L)-glufosinate-ammonium or (L)-glufosinate-sodium or (L)-glufosinate-potassium as (L)-glufosinate salts and (L)-glufosinate as free acid, preferably (L)-glufosinate. Especially preferred are agrochemical compositions, which contain (L)-glufosinate-ammonium.

The term “glufosinate” as used in the present invention typically comprises, in one embodiment of the invention, about 50% by weight of the L-enantiomer and about 50% by weight of the D-enantiomer; and in another embodiment of the invention, more than 70% by weight of the L-enantiomer; preferably more than 80% by weight of the L-enantiomer; more preferably more than 90% of the L-enantiomer, most preferably more than 95% of the L-enantiomer and can be prepared as referred to above.

Accordingly, in one embodiment, the invention relates to a glufosinate composition comprising

a) glufosinate or a salt thereof, preferably the ammonium salt of glufosinate; andb) a compound of formula (I).

In another embodiment, the invention relates to an agrochemical composition comprising

a) glufosinate or a salt thereof, preferably L-glufosinate or a salt thereof; andb) a compound of formula (I), whereinR is C₁₀-C₁₄-alkyl;each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;

• M⁺ is an ammonium cation of a primary, secondary, or tertiary amine having a molecular weight of from 32 to 190 g/mol; andthe index x is a number from 1 to 5.

In another embodiment, the invention relates to a glufosinate composition comprising

a) glufosinate or a salt thereof, preferably the ammonium salt of glufosinate; andb) a compound of formula (I), whereinR is C₁₂-alkyl, preferably linear C₁₂-alkyl;each A is independently a group

whereinR^A, R^B, R¹, and R^D are H;the index x is a number from 1 to 3; andM⁺ is an ammonium cation of formula (II)

• • wherein
  • R¹, R² and R³ are independently H, or C₁-C₁₀-alkyl, which is unsubstituted or substituted with OH, C₁-C₁₀-alkoxy, or hydroxy-C₁-C₁₀-alkoxy; or
  • two of the substituents R¹, R², or R³ form, together with the N-atom to which they are bound, a 5-, or 6-membered, saturated, partially- or fully unsaturated heterocycle containing additionally none, one or two atoms O, or S, and wherein said S-atom(s) are independently oxidized or non-oxidized,
  • with the proviso that at least one substituent R¹, R², or R³ is not H; preferably ethanolammonium.

In another embodiment, the invention relates to a glufosinate composition comprising

a) glufosinate or a salt thereof, preferably the ammonium salt of glufosinate; andb) a compound of formula (I), whereinR is C₁₂-alkyl, preferably linear C₁₂-alkyl;each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;the index x is a number from 1 to 3; and

• M⁺ is protonated amine selected from ethanolamine, diethanolamine, diglycolamine, 1-aminopropan-2-ol, 2-dimethylaminoethanol, 2-(butylamino)ethanol, 2-diethylaminoethanol, 2-(tert-butylamino)ethanol, N-(tert-butyl)diethanolamine, triethanolamine, 2-ethylaminoethanol, 2-aminoheptane, triisopropylamine, N-(2-hydroxyethyl)morpholin, N-methylmorpholine, N-butyldiethanolamin, 2-(dibutylamino)ethanol, and mixtures thereof, preferably ethanolammonium.

Another particularly preferred group of agrochemical active ingredients are PPO-inhibitors as described above. Agrochemical composition(s) comprising an agrochemical active ingredient selected from PPO-inhibitors is referred to as “PPO composition(s)”.

Accordingly, in one embodiment, the invention relates to a PPO-composition comprising

a) a PPO-inhibitor or an agrochemically acceptable salt, stereoisomer, tautomer, or N-oxide thereof; andb) a compound of formula (I).

In another embodiment, the invention relates to a PPO-composition comprising

a) a PPO-inhibitor or a salt thereof; andb) a compound of formula (I), whereinR is C₁₀-C₁₄-alkyl;each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;

• M⁺ is an ammonium cation of a primary, secondary, or tertiary amine having a molecular weight of from 32 to 190 g/mol; andthe index x is a number from 1 to 5.

In another embodiment, the invention relates to a PPO-composition comprising

• a) a PPO-inhibitor or an agrochemically acceptable salt, stereoisomer, tautomer, or N-oxide thereof; and
• b) a compound of formula (I), whereinR is C₁₂-alkyl, preferably linear C₁₂-alkyl;each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;the index x is a number from 1 to 3; andM⁺ is an ammonium cation of formula (II)

• • wherein
  • R¹, R² and R³ are independently H, or C₁-C₁₀-alkyl, which is unsubstituted or substituted with OH, C₁-C₁₀-alkoxy, or hydroxy-C₁-C₁₀-alkoxy; or
  • two of the substituents R¹, R², or R³ form, together with the N-atom to which they are bound, a 5-, or 6-membered, saturated, partially- or fully unsaturated heterocycle containing additionally none, one or two atoms O, or S, and wherein said S-atom(s) are independently oxidized or non-oxidized,
  • with the proviso that at least one substituent R¹, R², or R³ is not H; preferably ethanolammonium.

In another embodiment, the invention relates to a PPO-composition comprising

a) a PPO-inhibitor or an agrochemically acceptable salt, stereoisomer, tautomer, or N-oxide thereof; andb) a compound of formula (I), whereinR is C₁₂-alkyl, preferably linear C₁₂-alkyl;each A is independently a group

whereinR^A, R^B, R^C, and R^D are H;the index x is a number from 1 to 3; and

• M⁺ is protonated amine selected from ethanolamine, diethanolamine, diglycolamine, 1-aminopropan-2-ol, 2-dimethylaminoethanol, 2-(butylamino)ethanol, 2-diethylaminoethanol, 2-(tert-butylamino)ethanol, N-(tert-butyl)diethanolamine, triethanolamine, 2-ethylaminoethanol, 2-aminoheptane, triisopropylamine, N-(2-hydroxyethyl)morpholin, N-methylmorpholine, N-butyldiethanolamin, 2-(dibutylamino)ethanol, and mixtures thereof, preferably ethanolammonium.

In one embodiment, the PPO-inhibitor is acifluorfen. In another embodiment, the PPO-inhibitor is acifluorfen-sodium. In another embodiment, the PPO-inhibitor is azafenidin. In another embodiment, the PPO-inhibitor is bencarbazone. In another embodiment, the PPO-inhibitor is benzfendizone. In another embodiment, the PPO-inhibitor is bifenox. In another embodiment, the PPO-inhibitor is butafenacil. In another embodiment, the PPO-inhibitor is carfentrazone. In another embodiment, the PPO-inhibitor is carfentrazone-ethyl. In another embodiment, the PPO-inhibitor is chlomethoxyfen. In another embodiment, the PPO-inhibitor is chlorphthalim. In another embodiment, the PPO-inhibitor is cinidon-ethyl. In another embodiment, the PPO-inhibitor is cyclopyranil. In another embodiment, the PPO-inhibitor is fluazolate. In another embodiment, the PPO-inhibitor is flufenpyr. In another embodiment, the PPO-inhibitor is flufenpyr-ethyl. In another embodiment, the PPO-inhibitor is flumiclorac. In another embodiment, the PPO-inhibitor is flumiclorac-pentyl. In another embodiment, the PPO-inhibitor is flumioxazin. In another embodiment, the PPO-inhibitor is fluoroglycofen. In another embodiment, the PPO-inhibitor is fluoroglycofen-ethyl. In another embodiment, the PPO-inhibitor is fluthiacet. In another embodiment, the PPO-inhibitor is fluthiacet-methyl. In another embodiment, the PPO-inhibitor is fomesafen. In another embodiment, the PPO-inhibitor is halosafen. In another embodiment, the PPO-inhibitor is lactofen. In another embodiment, the PPO-inhibitor is oxadiargyl. In another embodiment, the PPO-inhibitor is oxadiazon. In another embodiment, the PPO-inhibitor is oxyfluorfen. In another embodiment, the PPO-inhibitor is pentoxazone. In another embodiment, the PPO-inhibitor is profluazol. In another embodiment, the PPO-inhibitor is pyraclonil. In another embodiment, the PPO-inhibitor is pyraflufen. In another embodiment, the PPO-inhibitor is pyraflufen-ethyl. In another embodiment, the PPO-inhibitor is saflufenacil. In another embodiment, the PPO-inhibitor is sulfentrazone. In another embodiment, the PPO-inhibitor is thidiazimin. In another embodiment, the PPO-inhibitor is tiafenacil. In another embodiment, the PPO-inhibitor is trifludimoxazin. In another embodiment, the PPO-inhibitor is ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate. In another embodiment, the PPO-inhibitor is N-ethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide. In another embodiment, the PPO-inhibitor is N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide. In another embodiment, the PPO-inhibitor is N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide. In another embodiment, the PPO-inhibitor is N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide. In another embodiment, the PPO-inhibitor is 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione. In another embodiment, the PPO-inhibitor is 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1,3-dione. In another embodiment, the PPO-inhibitor is 1-methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidine-2,4-dione. In another embodiment, the PPO-inhibitor is methyl (E)-4-[2-chloro-5-[4-chloro-5-(difluoromethoxy)-1H-methyl-pyrazol-3-yl]-4-fluoro-phenoxy]-3-methoxy-but-2-enoate. In another embodiment, the PPO-inhibitor is and 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)-1H-pyrimidine-2,4-dione. In another embodiment, the PPO-inhibitor is 2-[2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]-4-fluorophenoxy]-2-methoxy-acetic acid methyl ester. In another embodiment, the PPO-inhibitor is 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]-acetic acid methyl ester. In another embodiment, the PPO-inhibitor is 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy] acetic acid ethyl ester. In another embodiment, the PPO-inhibitor is methyl 2-[[3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluoro-phenoxy]-2-pyridyl]oxy]acetate. In another embodiment, the PPO-inhibitor is ethyl 2-[[3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluoro-phenoxy]-2-pyridyl]oxy]acetate. In another embodiment, the PPO-inhibitor is 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]-acetic acid methyl ester. In another embodiment, the PPO-inhibitor is 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy] acetic acid ethyl ester. In another embodiment, the PPO-inhibitor is 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]-N-(methylsulfonyl)-acetamide. In another embodiment, the PPO-inhibitor is 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]-N-(methylsulfonyl)-acetamide.

Especially preferred embodiments are summarized in the following clauses C1 to C15:

• C1) A compound of formula (I)

[R-(A)_x-OSO₃⁻]-M⁺  (I);

• • wherein
  • R is C₁₀-C₁₆-alkyl, C₁₀-C₁₆-alkenyl, or C₁₀-C₁₆-alkynyl;
  • each A is independently a group

• • wherein
    • R^A, R^B, R^C, and R^D are independently H, CH₃, or CH₂CH₃ with the proviso that the sum of C-atoms of R^A, R^B, R^C, and R^D is up to 2;
  • M⁺ is an ammonium cation of a primary, secondary, or tertiary amine having a molecular weight of from 32 to 200 g/mol; and
  • the index x is a number from 1 to 10.
• C2) The compound according to C1, wherein the index x is from 1 to 3.
• C3) The compound according to any of C1 or C2, wherein R^A, R^B, R^C, and R^D are H.
• C4) The compound according to any of C1 to C3, wherein the molecular weight of the ammonium cation M⁺ is from 55 to 180 g/mol.
• C5) The compound according to any of C1 to C4, wherein the ammonium cation M⁺ contains exactly one nitrogen atom per molecule.
• C6) The compound of formula (I) according to any of C1 to C5, wherein the ammonium cation M⁺ is of formula (II)

• • wherein
  • R¹, R² and R³ are independently H, or C₁-C₁₀-alkyl, which is unsubstituted or substituted with OH, C₁-C₁₀-alkoxy, or hydroxy-C₁-C₁₀-alkoxy; or
  • two of the substituents R¹, R², or R³ form, together with the N-atom to which they are bound, a 5-, or 6-membered, saturated, partially- or fully unsaturated heterocycle containing additionally none, one or two atoms O, or S, and wherein said S-atom(s) are independently oxidized or non-oxidized,
  • with the proviso that at least one substituent R¹, R², or R³ is not H.
• C7) The compound of formula (I) of C6, wherein the sum of R¹, R², and R³ comprise from 1 to 12 carbon atoms.
• C8) The compound of formula (I) according to C1 to C7, wherein the ammonium cation M⁺ is a protonated amine selected from ethanolamine, diethanolamine, diglycolamine, 1-aminopropan-2-ol, 2-dimethylaminoethanol, 2-(butylamino)ethanol, 2-diethylaminoethanol, 2-(tert-butylamino)ethanol, N-(tert-butyl)diethanolamine, triethanolamine, 2-ethylaminoethanol, 2-aminoheptan, triisopropylamine, N-(2-hydroxyethyl)morpholin, N-methylmorpholine, N-butyldiethanolamin, 2-(dibutylamino)ethanol, and mixtures thereof.
• C9) The compound of formula (I) according to any of C1 to C8, wherein the ammonium cation M⁺ is a protonated amine selected from ethanolamine, diethanolamine, triethanolamine, diglycolamine, 1-aminopropan-2-ol, 2-dimethylaminoethanol, and mixtures thereof.
• C10) An adjuvant solution comprising from 40 to 95 wt % of a compound of formula (I) as defined in any of C1 to C9, an organic solvent, and up to 5 wt % of water.
• C11) The solution of C10, wherein the organic solvent has a water-solubility of at least 10 wt % at 20° C.
• C12) An agrochemical composition comprising
  • a) the compound of formula (I) as defined in any of C1 to C9;
  • b) an agrochemical active ingredient.
• C13) The agrochemical composition of C12, wherein the agrochemical active ingredient is glufosinate or (L)-glufosinate, or a salt thereof, preferably the ammonium salt of glufosinate or L-glufosinate
• C14) The agrochemical composition of C12, wherein the agrochemical active ingredient is a protoporphyrinogen-IX oxidase inhibitor or a salt thereof.
• C15) A method for controlling undesirable vegetation, which method comprises applying the agrochemical composition as defined in any of C12 to C14 to a locus where undesirable vegetation is present or is expected to be present.

The agrochemical compositions comprising a herbicide (hereinafter referred to as “herbicidal compositions”), preferably the glufosinate composition or the PPO-composition, are suitable as herbicides. Accordingly, these compositions control vegetation on non-crop areas very efficiently, especially at high rates of application. They act against broad-leafed weeds and grass weeds in crops such as wheat, rice, corn, soybeans and cotton without causing any significant damage to the crop plants. This effect is mainly observed at low rates of application.

The herbicidal compositions according to the invention are applied to the plants mainly by spraying the leaves. Here, the application can be carried out using, for example, water as carrier by customary spraying techniques using spray liquor amounts of from about 100 to 1000 I/ha (for example from 300 to 400 I/ha). The herbicidal compositions may also be applied by the low-volume or the ultra-low-volume method, or in the form of microgranules.

Application of the herbicidal compositions according to the present invention can be done before, during and/or after, preferably during and/or after, the emergence of the undesirable plants.

The herbicidal compositions according to the present invention can be applied pre- or post-emergence or together with the seed of a crop plant. It is also possible to apply the herbicidal agrochemical composition by applying seed, pretreated with the herbicidal composition of the invention, of a crop plant. If the active compounds are less well tolerated by certain crop plants, application techniques may be used in which the herbicidal compositions are sprayed, with the aid of the spraying equipment, in such a way that as far as possible they do not come into contact with the leaves of the sensitive crop plants, while the active compounds reach the leaves of undesirable plants growing underneath, or the bare soil surface (post-directed, lay-by).

In a further embodiment, the herbicidal composition according to the invention can be applied by treating plant propagation material, such as seed. The treatment of seed comprises essentially all procedures familiar to the person skilled in the art (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting) based on the herbicidal compositions. Here, the herbicidal compositions can be applied diluted or undiluted. The term “seed” comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, seedlings and similar forms. Here, preferably, the term seed describes corns and seeds. The seed used can be seed of the useful plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods.

Moreover, it may be advantageous to apply the herbicidal compositions of the present invention on their own or jointly in combination with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria or with groups of active compounds which regulate growth. Also of interest is the miscibility with mineral salt solutions which are employed for treating nutritional and trace element deficiencies. Nonphytotoxic oils and oil concentrates can also be added.

When employed in plant protection, the amounts of agrochemical active ingredients without formulation auxiliaries, are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha and in particular from 0.1 to 0.75 kg per ha.

In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of agrochemical active ingredients of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.

When used in the protection of materials or stored products, the amount of agrochemical active ingredient applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of agrochemical active ingredient per cubic meter of treated material.

In the methods of the present invention it is immaterial whether the compound of formula (I) and the agrochemical active ingredient are formulated and applied jointly or separately.

In the case of separate application, it is of minor importance, in which order the application takes place. It is only necessary, that the compound of formula (I) and the agrochemical active ingredient are applied in a time frame that allows simultaneous action of the active ingredients on the plants, preferably within a time-frame of at most 14 days, in particular at most 7 days.

Depending on the application method in question, the agrochemical compositions according to the invention can additionally be employed in a further number of crop plants for eliminating undesirable pests, such as invertebrate pests, fungi, or weeds, preferably weeds. Examples of suitable crops are the following:

Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Brassica oleracea, Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot escu-lenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.

The agrochemical compositions according to the invention can also be used in crops which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.

The term “crops” as used herein includes also (crop) plants which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait.

Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome. Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect.

Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the genome of a plant in order to add a trait or improve a trait. These integrated genes are also referred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, which differ in the genomic locus in which a transgene has been integrated. Plants comprising a specific transgene on a specific genomic locus are usually described as comprising a specific “event”, which is referred to by a specific event name. Traits which have been introduced in plants or have been modified include in particular herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.

Herbicide tolerance has been created by using mutagenesis as well as using genetic engineering. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbicides by conventional methods of mutagenesis and breeding comprise plant varieties commercially available under the name Clearfield®. However, most of the herbicide tolerance traits have been created via the use of transgenes.

Herbicide tolerance has been created to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbicides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides and 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione.

Transgenes which have been used to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 and aad-12, for tolerance to dicamba: dmo, for tolerance to oxynil herbicies: bxn, for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA, for tolerance to ALS inhibitor herbicides: csr1-2, for tolerance to HPPD inhibitor herbicides: hppdPF, W336 and avhppd-03.

Transgenic corn events comprising herbicide tolerance genes are for example, but not excluding others, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHG0JG, HCEM485, VCO-Ø1981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.

Transgenic soybean events comprising herbicide tolerance genes are for example, but not excluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS-81419-2, GU262, SYHTOH2, W62, W98, FG72 and CV127.

Transgenic cotton events comprising herbicide tolerance genes are for example, but not excluding others, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB1119, GHB614, LLCotton25, T303-3 and T304-40.

Transgenic canola events comprising herbicide tolerance genes are for example, but not excluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.

Insect resistance has mainly been created by transferring bacterial genes for insecticidal proteins to plants. Transgenes which have most frequently been used are toxin genes of Bacillus spec. and synthetic variants thereof, like cry1A, cry1Ab, cry1Ab-Ac, cry1Ac, cry1A.105, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A(a), vip3Aa20. However, also genes of plant origin have been transferred to other plants. In particular genes coding for protease inhibitors, like CpTI and pinII. A further approach uses transgenes in order to produce double stranded RNA in plants to target and downregulate insect genes. An example for such a transgene is dvsnf7.

Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA are for example, but not excluding others, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418 and MZIR098.

Transgenic soybean events comprising genes for insecticidal proteins are for example, but not excluding others, MON87701, MON87751 and DAS-81419.

Transgenic cotton events comprising genes for insecticidal proteins are for example, but not excluding others, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.

Increased yield has been created by increasing ear biomass using the transgene athb17, being present in corn event MON87403, or by enhancing photosynthesis using the transgene bbx32, being present in the soybean event MON87712.

Crops comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON87769.

Tolerance to abiotic conditions, in particular to tolerance to drought, has been created by using the transgene cspB, comprised by the corn event MON87460 and by using the transgene Hahb-4, comprised by soybean event IND-00410-5.

Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process. Preferred combination of traits are herbicide tolerance to different groups of herbicides, insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, herbicide tolerance with one or several types of insect resistance, herbicide tolerance with increased yield as well as a combination of herbicide tolerance and tolerance to abiotic conditions.

Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art. For example, detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations “International Service for the Acquisition of Agri-biotech Applications (ISAAA)” (http://www.isaaa.org/gmapprovaldatabase) and the “Center for Environmental Risk Assessment (CERA)” (http://cera-qmc.org/GMCropDatabase), as well as in patent applications, like EP3028573 and WO2017/011288.

The use of agrochemical compositions according to the invention on crops may result in effects which are specific to a crop comprising a certain gene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors. Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigor, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.

Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of ingredients or new ingredients, specifically to improve raw material production, e.g., potatoes that produce increased amounts of amylopectin (e.g. Amflora® potato, BASF SE, Germany).

Furthermore, it has been found that the herbicidal compositions according to the invention are also suitable for the defoliation and/or desiccation of plant parts, for which crop plants such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton, are suitable. In this regard herbicidal agrochemical compositions have been found for the desiccation and/or defoliation of plants, processes for preparing these compositions, and methods for desiccating and/or defoliating plants using the herbicidal agrochemical compositions according to the invention.

As desiccants, herbicidal compositions according to the invention are suitable in particular for desiccating the above-ground parts of crop plants such as potato, oilseed rape, sunflower and soybean, but also cereals. This makes possible the fully mechanical harvesting of these important crop plants.

Also of economic interest is the facilitation of harvesting, which is made possible by concentrating within a certain period of time the dehiscence, or reduction of adhesion to the tree, in citrus fruit, olives and other species and varieties of pomaceous fruit, stone fruit and nuts. The same mechanism, i.e. the promotion of the development of abscission tissue between fruit part or leaf part and shoot part of the plants is also essential for the controlled defoliation of useful plants, in particular cotton.

Moreover, a shortening of the time interval in which the individual cotton plants mature leads to an increased fiber quality after harvesting.

If the agrochemical composition is a glufosinate composition, the herbicidal composition preferably contains a second agrochemical active ingredient selected from

B) herbicides of class b1) to b15):

• • b1) lipid biosynthesis inhibitors;
  • b2) acetolactate synthase inhibitors (ALS inhibitors);
  • b3) photosynthesis inhibitors;
  • b4) protoporphyrinogen-IX oxidase inhibitors (PPO inhibitor),
  • b5) bleacher herbicides;
  • b6) enolpyruvyl shikimate 3-phosphate synthase inhibitors (EPSP inhibitors);
  • b7) glutamine synthetase inhibitors;
  • b8) 7,8-dihydropteroate synthase inhibitors (DHP inhibitors);
  • b9) mitosis inhibitors;
  • b10) inhibitors of the synthesis of very long chain fatty acids (VLCFA inhibitors);
  • b11) cellulose biosynthesis inhibitors;
  • b12) decoupler herbicides;
  • b13) auxinic herbicides;
  • b14) auxin transport inhibitors; and
  • b15) other herbicides selected from the group consisting of bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, indaziflam, maleic hydrazide, mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine, triaziflam, tridiphane and 6-chloro-3-(2-cyclopropyl-6-methylphenoxy)-4-pyridazinol (CAS 499223-49-3) and its salts and esters;including their agriculturally acceptable salts or derivatives; andC) safeners.

In one embodiment, the agrochemical composition contains glufosinate or a salt thereof, preferably the ammonium salt of glufosinate, more preferably the ammonium salt of L-glufosinate, and a second agrochemical active ingredient selected from groups b1) to b15) and C) as defined herein.

If the herbicidal compounds B and/or the safeners C as described herein are capable of forming geometrical isomers, for example E/Z isomers, it is possible to use both, the pure isomers and mixtures thereof, in the agrochemical composition according to the invention.

If the herbicidal compounds B and/or the safeners C as described herein have one or more centres of chirality and, as a consequence, are present as enantiomers or diastereomers, it is possible to use both, the pure enantiomers and diastereomers and their mixtures, in the compositions according to the invention.

If the herbicidal compounds B and/or the safeners C as described herein have ionizable functional groups, they can also be employed in the form of their agriculturally acceptable salts. Suitable are, in general, the salts of those cations and the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the activity of the active compounds.

Preferred cations are the ions of the alkali metals, preferably of lithium, sodium and potassium, of the alkaline earth metals, preferably of calcium and magnesium, and of the transition metals, preferably of manganese, copper, zinc and iron, further ammonium and substituted ammonium in which one to four hydrogen atoms are replaced by C₁-C₄-alkyl, hydroxy-C₁-C₄-alkyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, hydroxy-C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diethylammonium, diisopropylammonium, trimethylammonium, triethylammonium, tris(isopropyl)ammonium, heptylammonium, dodecylammonium, tetradecylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium (olamine salt), 2-(2-hydroxyeth-1-oxy)eth-1-ylammonium (diglycolamine salt), di(2-hydroxyeth-1-yl)ammonium (diolamine salt), tris(2-hydroxyethyl)ammonium (trolamine salt), tris(2-hydroxypropyl)ammonium, benzyltrimethylammonium, benzyltriethylammonium, N,N,N-trimethylethanolammonium (choline salt), furthermore phosphonium ions, sulfonium ions, preferably tri(C₁-C₄-alkyl)sulfonium, such as trimethylsulfonium, and sulfoxonium ions, preferably tri(C₁-C₄-alkyl)sulfoxonium, and finally the salts of polybasic amines such as N,N-bis-(3-aminopropyl)methylamine and diethylenetriamine.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, iodide, hydrogensulfate, methylsulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and also the anions of C₁-C₄-alkanoic acids, preferably formate, acetate, propionate and butyrate.

Herbicidal compounds B and/or safeners C as described herein having a carboxyl group can be employed in the form of the acid, in the form of an agriculturally suitable salt as mentioned above or else in the form of an agriculturally acceptable derivative, for example as amides, such as mono- and di-C₁-C₆-alkylamides or arylamides, as esters, for example as allyl esters, propargyl esters, C₁-C₁₀-alkyl esters, alkoxyalkyl esters, tefuryl ((tetrahydrofuran-2-yl)methyl) esters and also as thioesters, for example as C₁-C₁₀-alkylthio esters. Preferred mono- and di-C₁-C₆-alkylamides are the methyl and the dimethylamides. Preferred arylamides are, for example, the anilides and the 2-chloroanilides. Preferred alkyl esters are, for example, the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, mexyl (1-methylhexyl), meptyl (1-methylheptyl), heptyl, octyl or isooctyl (2-ethylhexyl) esters. Preferred C₁-C₄-alkoxy-C₁-C₄-alkyl esters are the straight-chain or branched C₁-C₄-alkoxy ethyl esters, for example the 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl (butotyl), 2-butoxypropyl or 3-butoxypropyl ester. An example of a straight-chain or branched C₁-C₁₀-alkylthio ester is the ethylthio ester.

According to a first embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient an inhibitor of the lipid biosynthesis (herbicide b1). These are compounds that inhibit lipid biosynthesis. Inhibition of the lipid biosynthesis can be affected either through inhibition of acetylCoA carboxylase (hereinafter termed ACC herbicides) or through a different mode of action (hereinafter termed non-ACC herbicides). The ACC herbicides belong to the group A of the HRAC classification system whereas the non-ACC herbicides belong to the group N of the HRAC classification.

According to a second embodiment of the invention the glufosinate composition contains as second agrochemical active ingredient an ALS inhibitor (herbicide b2). The herbicidal activity of these compounds is based on the inhibition of acetolactate synthase and thus on the inhibition of the branched chain amino acid biosynthesis. These inhibitors belong to the group B of the HRAC classification system.

According to a third embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient an inhibitor of photosynthesis (herbicide b3). The herbicidal activity of these compounds is based either on the inhibition of the photosystem II in plants (so-called PSII inhibitors, groups C1, C2 and C3 of HRAC classification) or on diverting the electron transfer in photosystem I in plants (so-called PSI inhibitors, group D of HRAC classification) and thus on an inhibition of photosynthesis. Amongst these, PSII inhibitors are preferred.

According to a fourth embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient an inhibitor of protoporphyrinogen-IX-oxidase (herbicide b4). The herbicidal activity of these compounds is based on the inhibition of the protoporphyrinogen-IX-oxidase. These inhibitors belong to the group E of the HRAC classification system.

According to a fifth embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient a bleacher-herbicide (herbicide b5), preferably a HPPD inhibitor. The herbicidal activity of these compounds is based on the inhibition of the carotenoid biosynthesis. These include compounds which inhibit carotenoid biosynthesis by inhibition of phytoene desaturase (so-called PDS inhibitors, group F1 of HRAC classification), compounds that inhibit the 4-hydroxyphenylpyruvate-dioxygenase (HPPD inhibitors, group F2 of HRAC classification), compounds that inhibit DOXsynthase (group F4 of HRAC class) and compounds which inhibit carotenoid biosynthesis by an unknown mode of action (bleacher—unknown target, group F3 of HRAC classification).

According to a sixth embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient an EPSP synthase inhibitor (herbicide b6). The herbicidal activity of these compounds is based on the inhibition of enolpyruvyl shikimate 3-phosphate synthase, and thus on the inhibition of the amino acid biosynthesis in plants. These inhibitors belong to the group G of the HRAC classification system.

According to a seventh embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient a glutamine synthetase inhibitor (herbicide b7). The herbicidal activity of these compounds is based on the inhibition of glutamine synthetase, and thus on the inhibition of the amino acid biosynthesis in plants. These inhibitors belong to the group H of the HRAC classification system.

According to an eighth embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient a DHP synthase inhibitor (herbicide b8). The herbicidal activity of these compounds is based on the inhibition of 7,8-dihydropteroate synthase. These inhibitors belong to the group I of the HRAC classification system.

According to a ninth embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient a mitosis inhibitor (herbicide b9). The herbicidal activity of these compounds is based on the disturbance or inhibition of microtubule formation or organization, and thus on the inhibition of mitosis. These inhibitors belong to the groups K1 and K2 of the HRAC classification system. Among these, compounds of the group K1, in particular dinitroanilines, are preferred.

According to a tenth embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient a VLCFA inhibitor (herbicide b10). The herbicidal activity of these compounds is based on the inhibition of the synthesis of very long chain fatty acids and thus on the disturbance or inhibition of cell division in plants. These inhibitors belong to the group K3 of the HRAC classification system.

According to an eleventh embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient a cellulose biosynthesis inhibitor (herbicide b11). The herbicidal activity of these compounds is based on the inhibition of the biosynthesis of cellulose and thus on the inhibition of the synthesis of cell walls in plants. These inhibitors belong to the group L of the HRAC classification system.

According to a twelfth embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient a decoupler herbicide (herbicide b12). The herbicidal activity of these compounds is based on the disruption of the cell membrane. These inhibitors belong to the group M of the HRAC classification system.

According to a thirteenth embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient an auxinic herbicide (herbicide b13). These include compounds that mimic auxins, i.e. plant hormones, and affect the growth of the plants. These compounds belong to the group O of the HRAC classification system.

According to a fourteenth embodiment of the invention, the glufosinate composition contains as second agrochemical active ingredient an auxin transport inhibitor (herbicide b14). The herbicidal activity of these compounds is based on the inhibition of the auxin transport in plants. These compounds belong to the group P of the HRAC classification system.

As to the given mechanisms of action and classification of the active substances, see e.g. “HRAC, Classification of Herbicides According to Mode of Action”, http://www.plantprotection.org/hrac/MOA.html).

Examples of herbicides B which can be used as second agrochemical active ingredient in the glufosinate composition, according to the present invention are:

b1) from the group of the lipid biosynthesis inhibitors:ACC-herbicides such as alloxydim, alloxydim-sodium, butroxydim, clethodim, clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P-methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofoptefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepraloxydim, tralkoxydim,4-(4′-Chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1312337-72-6); 4-(2′,4′-Dichloro-4-cyclopropyl[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1312337-45-3); 4-(4′-Chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1033757-93-5); 4-(2′,4′-Dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (CAS 1312340-84-3); 5-(Acetyloxy)-4-(4′-chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1312337-48-6); 5-(Acetyloxy)-4-(2′,4′-dichloro-4-cyclopropyl-[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one; 5-(Acetyloxy)-4-(4′-chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1312340-82-1); 5-(Acetyloxy)-4-(2′,4′-dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1033760-55-2); 4-(4′-Chloro-4-cyclopropyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1312337-51-1); 4-(2′,4′-Dichloro-4-cyclopropyl-[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester; 4-(4′-Chloro-4-ethyl-2′-fluoro[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1312340-83-2); 4-(2′,4′-Dichloro-4-ethyl[1,1′-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1033760-58-5); and non ACC herbicides such as benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;b2) from the group of the ALS inhibitors:sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron,imidazolinones such as imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr, triazolopyrimidine herbicides and sulfonanilides such as cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam,pyrimidinylbenzoates such as bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid-1-methylethyl ester (CAS 420138-41-6), 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid propyl ester (CAS 420138-40-5), N-(4-bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzenemethanamine (CAS 420138-01-8),sulfonylaminocarbonyl-triazolinone herbicides such as flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone and thiencarbazone-methyl; and triafamone;b3) from the group of the photosynthesis inhibitors:amicarbazone, inhibitors of the photosystem II, e.g 1-(6-tert-butylpyrimidin-4-yl)-2-hydroxy-4-methoxy-3-methyl-2H-pyrrol-5-one (CAS 1654744-66-7), 1-(5-tert-butylisoxazol-3-yl)-2-hydroxy-4-methoxy-3-methyl-2H-pyrrol-5-one (CAS 1637455-12-9), 1-(5-tert-butylisoxazol-3-yl)-4-chloro-2-hydroxy-3-methyl-2H-pyrrol-5-one (CAS 1637453-94-1), 1-(5-tert-butyl-1-methyl-pyrazol-3-yl)-4-chloro-2-hydroxy-3-methyl-2H-pyrrol-5-one (CAS 1654057-29-0), 1-(5-tert-butyl-1-methyl-pyrazol-3-yl)-3-chloro-2-hydroxy-4-methyl-2H-pyrrol-5-one (CAS 1654747-80-4), 4-hydroxy-1-methoxy-5-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one; (CAS 2023785-78-4), 4-hydroxy-1,5-dimethyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (CAS 2023785-79-5), 5-ethoxy-4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (CAS 1701416-69-4), 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (CAS 1708087-22-2), 4-hydroxy-1,5-dimethyl-3-[1-methyl-5-(trifluoromethyl)pyrazol-3-yl]imidazolidin-2-one (CAS 2023785-80-8), 1-(5-tert-butylisoxazol-3-yl)-4-ethoxy-5-hydroxy-3-methyl-imidazolidin-2-one (CAS 1844836-64-1), triazine herbicides, including of chlorotriazine, triazinones, triazindiones, methylthiotriazines and pyridazinones such as ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn, hexazinone, metribuzin, prometon, prometryn, propazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn and trietazin, aryl urea such as chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron and thiadiazuron, phenyl carbamates such as desmedipham, karbutilat, phenmedipham, phenmedipham-ethyl, nitrile herbicides such as bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters, uraciles such as bromacil, lenacil and terbacil, and bentazon and bentazon-sodium, pyridate, pyridafol, pentanochlor and propanil and inhibitors of the photosystem I such as diquat, diquat-dibromide, paraquat, paraquatdichloride and paraquat-dimetilsulfate.b4) from the group of the protoporphyrinogen-IX oxidase inhibitors:acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chlorphthalim, cinidon-ethyl, cyclopyranil, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil, trifludimoxazin, ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate (CAS 353292-31-6; S-3100), N-ethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452098-92-9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5-methyl-1H-pyrazole-1-carboxamide (CAS 452100-03-7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl]-1,5-dimethyl-6-thioxo-[1,3,5]triazinan-2,4-dione (CAS 451484-50-7), 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1,3-dione (CAS 1300118-96-0), 1-methyl-6-trifluoromethyl-3-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-benzo[1,4]oxazin-6-yl)-1H-pyrimidine-2,4-dione (CAS 1304113-05-0), methyl (E)-4-[2-chloro-5-[4-chloro-5-(difluoromethoxy)-1H-methyl-pyrazol-3-yl]-4-fluoro-phenoxy]-3-methoxy-but-2-enoate (CAS 948893-00-3), and 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)-1H-pyrimidine-2,4-dione (CAS 212754-02-4), 2-[2-chloro-5-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]-4-fluorophenoxy]-2-methoxy-acetic acid methyl ester (CAS 1970221-16-9), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]-acetic acid methyl ester (CAS 2158274-96-3), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy] acetic acid ethyl ester (CAS 2158274-50-9), methyl 2-[[3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluoro-phenoxy]-2-pyridyl]oxy]acetate (CAS 2271389-22-9), ethyl 2-[[3-[2-chloro-5-[4-(difluoromethyl)-3-methyl-5-oxo-1,2,4-triazol-1-yl]-4-fluoro-phenoxy]-2-pyridyl]oxy]acetate (CAS 2230679-62-4), 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]-acetic acid methyl ester (CAS 2158275-73-9), 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy] acetic acid ethyl ester (CAS 2158274-56-5), 2-[2-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]phenoxy]-N-(methylsulfonyl)-acetamide (CAS 2158274-53-2), 2-[[3-[[3-chloro-6-[3,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-1(2H)-pyrimidinyl]-5-fluoro-2-pyridinyl]oxy]-2-pyridinyl]oxy]-N-(methylsulfonyl)-acetamide (CAS 2158276-22-1);b5) from the group of the bleacher herbicides:PDS inhibitors: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyrimidine (CAS 180608-33-7), HPPD inhibitors: benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquinotrione, isoxaflutole, mesotrione, oxotrione (CAS 1486617-21-3), pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone, bleacher, unknown target: aclonifen, amitrole flumeturon, 2-chloro-3-methylsulfanyl-N-(1-methyltetrazol-5-yl)-4-(trifluoromethyl)benzamide (CAS 1361139-71-0), bixlozone and 2-(2,5-dichlorophenyl)methyl-4,4-dimethyl-3-isoxazolidinone (CAS 81778-66-7);b6) from the group of the EPSP synthase inhibitors:glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosate-trimesium (sulfosate);b7) from the group of the glutamine synthase inhibitors:bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate-ammonium;b8) from the group of the DHP synthase inhibitors: asulam;b9) from the group of the mitosis inhibitors:compounds of group K1: dinitroanilines such as benfluralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin, pendimethalin, prodiamine and trifluralin, phosphoramidates such as amiprophos, amiprophos-methyl, and butamiphos, benzoic acid herbicides such as chlorthal, chlorthal-dimethyl, pyridines such as dithiopyr and thiazopyr, benzamides such as propyzamide and tebutam; compounds of group K2: carbetamide, chlorpropham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl and propham; among these, compounds of group K1, in particular dinitroanilines are preferred;b10) from the group of the VLCFA inhibitors:chloroacetamides such as acetochlor, alachlor, amidochlor, butachlor, dimethachlor, dimethenamid, dimethenamid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, propisochlor and thenylchlor, oxyacetanilides such as flufenacet and mefenacet, acetanilides such as diphenamid, naproanilide, napropamide and napropamideM, tetrazolinones such fentrazamide, and other herbicides such as anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone and isoxazoline compounds of the formulae II.1, II.2, II.3, II.4, II.5, II.6, II.7, II.8 and 11.9

the isoxazoline compounds of the formula (II) are known in the art, e.g. from WO2006/024820, WO2006/037945, WO2007/071900 and WO2007/096576;among the VLCFA inhibitors, preference is given to chloroacetamides and oxyacetamides; b11) from the group of the cellulose biosynthesis inhibitors:chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam and 1-cyclohexyl-5-pentafluorphenyloxy-14-[1,2,4,6]thiatriazin-3-ylamine (CAS 175899-01-1);b12) from the group of the decoupler herbicides:dinoseb, dinoterb and DNOC and its salts;b13) from the group of the auxinic herbicides:2,4-D and its salts and esters such as clacyfos, 2,4-DB and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as aminopyraliddimethylammonium, aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, dichlorprop-P and its salts and esters, flopyrauxifen, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, halauxifen and its salts and esters (CAS 943832-60-8); MCPA and its salts and esters, MCPA-thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, florpyrauxifen, florpyrauxifen-benzyl (CAS 1390661-72-9) and 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)picolinic acid (CAS 1629965-65-6);b14) from the group of the auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam-sodium;b15) from the group of the other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, cyclopyrimorate (CAS 499223-49-3) and its salts and esters, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hydrazide, mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, quinoclamine and tridiphane.

In another embodiment of the present invention the second agrochemical active ingredient in the glufosinate composition is a safener C.

Safeners are chemical compounds which prevent or reduce damage on useful plants without having a major impact on the herbicidal action of the herbicidal active components of the present compositions towards unwanted plants. They can be applied either before sowings (e.g. on seed treatments, shoots or seedlings) or in the pre-emergence application or post-emergence application of the useful plant. The safeners and the agrochemical composition and/or the herbicides B can be applied simultaneously or in succession.

Suitable safeners are e.g. (quinolin-8-oxy)acetic acids, 1-phenyl-5-haloalkyl-1H-1,2,4-triazol-3-carboxylic acids, 1-phenyl-4,5-dihydro-5-alkyl-1H-pyrazol-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3-isoxazol carboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenonoximes, 4,6-dihalo-2-phenylpyrimidines, N-[[4-(aminocarbonyl)phenyl]sulfonyl]-2-benzoic amides, 1,8-naphthalic anhydride, 2-halo-4-(haloalkyl)-5-thiazol carboxylic acids, phosphorthiolates and N-alkyl-O-phenylcarbamates and their agriculturally acceptable salts and their agriculturally acceptable derivatives such amides, esters, and thioesters, provided they have an acid group.

Examples of preferred safeners C are benoxacor, cloquintocet, cyometrinil, cyprosulfamide, dichlormid, dicyclonon, dietholate, fenchlorazole, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen, mefenpyr, mephenate, naphthalic anhydride, oxabetrinil, 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (MON4660, CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (R-29148, CAS 52836-31-4), metcamifen and BPCMS (CAS 54091-06-4).

The active compounds B of groups b1) to b15) and the active compounds C are known herbicides and safeners, see, for example, The Compendium of Pesticide Common Names (http://www.alanwood.net/pesticides/); Farm Chemicals Handbook 2000 volume 86, Meister Publishing Company, 2000; B. Hock, C. Fedtke, R. R. Schmidt, Herbizide [Herbicides], Georg Thieme Verlag, Stuttgart 1995; W. H. Ahrens, Herbicide Handbook, 7th edition, Weed Science Society of America, 1994; and K. K. Hatzios, Herbicide Handbook, Supplement for the 7th edition, Weed Science Society of America, 1998. 2,2,5-Trimethyl-3-(dichloroacetyl)-1,3-oxazolidine [CAS No. 52836-31-4] is also referred to as R-29148. 4-(Dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane [CAS No. 71526-07-3] is also referred to as AD-67 and MON 4660.

The assignment of the active compounds to the respective mechanisms of action is based on current knowledge. If several mechanisms of action apply to one active compound, this substance was only assigned to one mechanism of action.

Active compounds B and C having a carboxyl group can be employed in the form of the acid, in the form of an agriculturally suitable salt as mentioned above or else in the form of an agriculturally acceptable derivative in the compositions according to the invention.

In the case of dicamba, suitable salts include those, where the counterion is an agriculturally acceptable cation. For example, suitable salts of dicamba are dicamba-sodium, dicamba-potassium, dicamba-methylammonium, dicamba-dimethylammonium, dicamba-isopropylammonium, dicamba-diglycolamine, dicamba-olamine, dicamba-diolamine, dicamba-trolamine, dicamba-N,N-bis-(3-aminopropyl)methylamine and dicamba-diethylenetriamine. Examples of a suitable ester are dicamba-methyl and dicamba-butotyl.

Suitable salts of 2,4-D are 2,4-D-ammonium, 2,4-D-dimethylammonium, 2,4-D-diethylammonium, 2,4-D-diethanolammonium (2,4-D-diolamine), 2,4-D-triethanolammonium, 2,4-D-isopropylammonium, 2,4-D-triisopropanolammonium, 2,4-D-heptylammonium, 2,4-D-dodecylammonium, 2,4-D-tetradecylammonium, 2,4-D-triethylammonium, 2,4-D-tris(2-hydroxypropyl)ammonium, 2,4-D-tris(isopropyl)ammonium, 2,4-D-trolamine, 2,4-D-lithium, 2,4-D-sodium and 2,4-D-N,N,N-trimethylethanolammonium (2,4-D choline). Examples of suitable esters of 2,4-D are 2,4-D-butotyl, 2,4-D-2-butoxypropyl, 2,4-D-3-butoxypropyl, 2,4-D-butyl, 2,4-D-ethyl, 2,4-D-ethylhexyl, 2,4-D-isobutyl, 2,4-D-isooctyl, 2,4-D-isopropyl, 2,4-D-meptyl, 2,4-D-methyl, 2,4-D-octyl, 2,4-D-pentyl, 2,4-D-propyl, 2,4-D-tefuryl and clacyfos.

Suitable salts of 2,4-DB are for example 2,4-DB-sodium, 2,4-DB-potassium and 2,4-DB-dimethylammonium. Suitable esters of 2,4-DB are for example 2,4-DB-butyl and 2,4-DB-isoctyl.

Suitable salts of dichlorprop are for example dichlorprop-sodium, dichlorprop-potassium and dichlorprop-dimethylammonium. Examples of suitable esters of dichlorprop are dichlorpropbutotyl and dichlorprop-isoctyl.

Suitable salts and esters of MCPA include MCPA-butotyl, MCPA-butyl, MCPA-dimethylammonium, MCPA-diolamine, MCPA-ethyl, MCPA-thioethyl, MCPA-2-ethylhexyl, MCPA-isobutyl, MCPA-isoctyl, MCPA-isopropyl, MCPA-isopropylammonium, MCPA-methyl, MCPA-olamine, MCPA-potassium, MCPA-sodium and MCPA-trolamine.

A suitable salt of MCPB is MCPB sodium. A suitable ester of MCPB is MCPB-ethyl.Suitable salts of clopyralid are clopyralid-potassium, clopyralid-olamine and clopyralid-tris-(2-hydroxypropyl)ammonium. Example of suitable esters of clopyralid is clopyralid-methyl. Examples of a suitable ester of fluroxypyr are fluroxypyr-meptyl and fluroxypyr-2-butoxy-1-methylethyl, wherein fluroxypyr-meptyl is preferred.

Suitable salts of picloram are picloram-dimethylammonium, picloram-potassium, picloramtriisopropanolammonium, picloram-triisopropylammonium and picloram-trolamine. A suitable ester of picloram is picloram-isoctyl.

A suitable salt of triclopyr is triclopyr-triethylammonium. Suitable esters of triclopyr are for example triclopyr-ethyl and triclopyr-butotyl.

Suitable salts and esters of chloramben include chloramben-ammonium, chlorambendiolamine, chloramben-methyl, chloramben-methylammonium and chloramben-sodium. Suitable salts and esters of 2,3,6-TBA include 2,3,6-TBA-dimethylammonium, 2,3,6-TBA-lithium, 2,3,6-TBA-potassium and 2,3,6-TBA-sodium.

Suitable salts and esters of aminopyralid include aminopyralid-potassium, aminopyraliddimethylammonium, and aminopyralid-tris(2-hydroxypropyl)ammonium.

Suitable salts of glyphosate are for example glyphosate-ammonium, glyphosate-diammonium, glyphoste-dimethylammonium, glyphosate-isopropylammonium, glyphosate-potassium, glyphosate-sodium, glyphosate-trimesium as well as the ethanolamine and diethanolamine salts, preferably glyphosate-diammonium, glyphosate-isopropylammonium and glyphosate-trimesium (sulfosate).

A suitable salt of glufosinate is for example glufosinate-ammonium.

A suitable salt of glufosinate-P is for example glufosinate-P-ammonium.

Suitable salts and esters of bromoxynil are for example bromoxynil-butyrate, bromoxynilheptanoate, bromoxynil-octanoate, bromoxynil-potassium and bromoxynil-sodium.

Suitable salts and esters of ioxonil are for example ioxonil-octanoate, ioxonil-potassium and ioxonil-sodium.

Suitable salts and esters of mecoprop include mecoprop-butotyl, mecopropdimethylammonium, mecoprop-diolamine, mecoprop-ethadyl, mecoprop-2-ethylhexyl, mecoprop-isoctyl, mecoprop-methyl, mecoprop-potassium, mecoprop-sodium and mecoprop-trolamine.

Suitable salts of mecoprop-P are for example mecoprop-P-butotyl, mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl, mecoprop-P-isobutyl, mecoprop-P-potassium and mecoprop-P-sodium.

A suitable salt of diflufenzopyr is for example diflufenzopyr-sodium.

A suitable salt of naptalam is for example naptalam-sodium.

Suitable salts and esters of aminocyclopyrachlor are for example aminocyclopyrachlordimethylammonium, aminocyclopyrachlor-methyl, aminocyclopyrachlortriisopropanolammonium, aminocyclopyrachlor-sodium and aminocyclopyrachlor-potassium.

A suitable salt of quinclorac is for example quinclorac-dimethylammonium.

A suitable salt of quinmerac is for example quinmerac-dimethylammonium.

A suitable salt of imazamox is for example imazamox-ammonium.

Suitable salts of imazapic are for example imazapic-ammonium and imazapic-isopropylammonium.

Suitable salts of imazapyr are for example imazapyr-ammonium and imazapyr-isopropylammonium.

A suitable salt of imazaquin is for example imazaquin-ammonium.

Suitable salts of imazethapyr are for example imazethapyr-ammonium and imazethapyr-isopropylammonium.

A suitable salt of topramezone is for example topramezone-sodium.

Here and below, the term “binary glufosinate composition” refers to a glufosinate composition comprising as second agrochemical active ingredient a compound B selected from groups b1) to b15), or a safener C), as defined above.

In binary glufosinate compositions comprising a compound B, the weight ratio of glufosinate or its salt to the active compound B is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1.

In binary glufosinate compositions comprising a safener C, the weight ratio of glufosinate or its salt to the active compound C is generally in the range of from 1:1000 to 1000:1, preferably in the range of from 1:500 to 500:1, in particular in the range of from 1:250 to 250:1 and particularly preferably in the range of from 1:75 to 75:1.

The glufosinate composition may be applied in or on permanent cropland, or on permanent crops.

A permanent crop is one produced from plants which last for many seasons, rather than being re-planted after each harvest. Permanent crops are grown on permanent crop land in the form of agricultural land that includes grasslands and shrublands, e.g. used to grow grape vines or coffee; orchards used to grow fruit or olives; and forested plantations, e.g. used to grow nuts or rubber. It does not include, however, tree farms intended to be used for wood or timber.

Preferred permanent croplands in the context of the present invention are plantations, grasslands and shrublands. Preferably, the permanent crops in the context of the present invention are plantation crops, and preferably are selected from the group consisting fruit crops and orchard crops (preferably fruit trees, citrus trees, mango trees, olive trees, grape vines, coffee, cocoa, tea, and berries (such as strawberries, raspberries, blueberries and currants)), Musaceae sp. crops (for example banana or plantain crops), nut trees (preferably almond trees, walnut trees, pistachio trees, pecan trees, hazelnut trees), oil palm trees, rubber trees, sugarcane and cotton.

More preferably, the permanent crops are fruit trees (preferably pome fruit trees and stone fruit trees; preferred fruit trees are apple trees, pear trees, apricot trees, plum trees, cherry trees, peach trees), olive trees, grape vines, coffee, tea), Musaceae sp. crops (preferably banana crops or plantain crops), nut trees (preferably almond trees, walnut trees, pistachio trees, pecan trees, hazelnut trees), oil palm trees, rubber trees, and citrus crops (preferably lemon, orange or grapefruit crops). Even more preferably, the permanent crops are selected from the group consisting of apple trees, pear trees, apricot trees, plum trees, cherry trees, peach trees, olive trees, grape vines, coffee, tea, banana crops, nut trees (preferably almond trees, walnut trees, pistachio trees), oil palm trees, rubber trees, and citrus crops (preferably lemon, orange or grapefruit crops). Particularly preferably, the permanent crops are selected from the group consisting of apple trees, pear trees, apricot trees, plum trees, cherry trees, peach trees, olive trees, grape vines, coffee, tea, banana crops, almond trees, walnut trees, oil palm trees, rubber trees, lemon crops, orange crops and grapefruit crops

The glufosinate composition may also be applied on row crops and as well on specialty crops.

Row crops can be planted in rows wide enough to allow it to be tilled or otherwise cultivated by agricultural machinery, machinery tailored for the seasonal activities of row crops. The particularity of row crops is that they are planted and cultivated on a seasonal or yearly basis. Therefore, such crops yield products and profit relatively quickly and predictably. A row crop is one produced from plants which last for many seasons, rather than being re-planted after each harvest. Examples of row crops include soybeans, corn, canola, cotton, cereals or rice, but as well sunflower, potato, dry bean, field pea, flax, safflower, buckwheat and sugar beets.

Specialty crops are to be understood as fruits, vegetables or other specialty or plantation permanent crops such as trees, nuts, vines, (dried) fruits, ornamentals, oil palm, banana, rubber and the like, Horticulture and nursery crops, including floriculture, may also fall under the definition of specialty crops. Vegetable crops includes for example aubergine, beans, bell pepper, cabbage, chili, cucum-ber, eggplant, lettuce, melon, onion, potato, sweet potato, spinach and tomato. Plants being considered specialty crops are in general intensively cultivated. For weed control in vegetable crops, it may be desirable to shield the crops from contact with the spray solution that contains the herbicidal mixture according to the present invention.

In general, the crops which may be treated with the glufosinate composition, may be of conventional origin or may be herbicide tolerant crops, preferably glufosinate tolerant crops.

In a preferred embodiment, the glufosinate composition is applied once, twice or three times per Gregorian calendar year, i.e. in one application, in two applications or in three applications per year according to the Gregorian calendar. In a preferred embodiment, the glufosinate composition is applied twice per Gregorian calendar year, i.e. in two applications per year according to the Gregorian calendar. In an alternatively preferred embodiment, the glufosinate composition is applied one time per Gregorian calendar year, i.e. in one application per year according to the Gregorian calendar. In a preferred embodiment, the glufosinate composition is applied one time in about 12 months, i.e. in one application in about 12 months. In an alternative preferred embodiment, the glufosinate composition is applied between one and ten times per Gregorian calendar year, i.e. in up to ten applications per year according to the Gregorian calendar. This alternative preferred method is of particular usefulness in permanent crops, in particular those grown under tropical conditions; in which case weeds grow vigorously at any time of the year, and herbicide applications are to be re-peated as soon as the previous treatment loses its effectiveness and weeds start to regrow.

The glufosinate compositions are preferably used in post-emergence applications.

The invention includes the use and methods of application of the glufosinate composition for controlling undesirable vegetation in crops in a burndown program, wherein the crop is produced by genetic engineering or by breeding, are resistant to one or more herbicides and/or pathogens such as plant-pathogenous fungi, and/or to attack by insects; preferably resistant to glufosinate.

Preferred are crops, which are tolerant to glufosinate, wherein the glufosinate tolerant crop plant is preferably selected from the group consisting of rice, canola, soybean, corn and cotton plants.

Transgenic corn events comprising glufosinate tolerance genes are for example, but not excluding others, 5307×MIR6Ø4×Bt11×TC1507×GA21×MIR162 (event code: SYN-Ø53Ø7-1×SYN-IR6Ø4-5×SYN-BTØ11-1×DAS-Ø15Ø7-1×MON-ØØØ21-9×SYN-IR162-4, gene: pat, e.g. commercially available as Agrisure® Duracade™ 5222), 59122 (event code: DAS-59122-7, gene: pat, e.g. commercially available as Herculex™ RW), 5307×MIR6Ø4×Bt11×TC1507×GA21 (event code: SYN-Ø53Ø7-1×SYN-IR6Ø4-5×SYN-BTØ11-1×DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure® Duracade™ 5122), 59122×NK603 (event code: DAS-59122-7×MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as Herculex™ RW Roundup Ready™ 2), Bt10 (gene: pat, e.g. commercially available as Bt10), Bt11 (X4334CBR, X4734CBR) (event code: SYN-BTØ11-1, gene: pat, e.g. commercially available as Agrisure™ CB/LL), BT11×59122×MIR6Ø4×TC1507×GA21 (event code: SYN-BTØ11-1×DAS-59122-7×SYN-IR6Ø4-5×DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure® 3122), Bt11×GA21 (event code: SYN-BTØ11-1×MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure™ GT/CB/LL), Bt11×MIR162 (event code: SYN-BTØ11-1×SYN-IR162-4, gene: pat, e.g. commercially available as Agrisure® Viptera™ 2100), Bt11×MIR162×GA21 (event code: SYN-BTØ11-1×SYN-IR162-4×MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure® Viptera™ 3110), BT11×MIR162×MIR6Ø4 (event code: SYN-BTØ11-1×SYN-IR162-4×SYN-IR6Ø4-5, gene: pat, e.g. commercially available as Agrisure® Viptera™ 3100), Bt11×MIR162×MIR6Ø4×GA21 (event code: SYN-BTØ11-1×SYN-IR162-4×SYN-IR6Ø4-5×MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure® Viptera™ 3111, Agrisure® Viptera™ 4), Bt11×MIR162×TC1507×GA21 (event code: SYN-BTØ11-1×SYN-IR162-4×DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure™ Viptera 3220), Bt11×MIR6Ø4 (event code: SYN-BTØ11-1×SYN-IR6Ø4-5, gene: pat, e.g. commercially available as Agrisure™ CB/LL/RW), BT11×MIR6Ø4×GA21 (event code: SYN-BTØ11-1×SYN-IR6Ø4-5×MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure™ 3000GT), Bt176 (176) (event code: SYN-EV176-9, gene: bar, e.g. commercially available as NaturGard KnockOut™, Maximizer™), CBH-351 (event code: ACS-ZMØØ4-3, gene: bar, e.g. commercially available as Starlink™ Maize), DBT418 (event code: DKB-89614-9, gene: bar, e.g. commercially available as Bt Xtra™ Maize), MON89034×TC1507×MON88017×59122 (event code: MON-89Ø34-3×DAS-Ø15Ø7-1×MON-88017-3×DAS-59122-7, gene: pat, e.g. commercially available as Genuity® SmartStax™), MON89034×TC1507×NK603 (event code: MON-89Ø34-3×DAS-Ø15Ø7-1×MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as Power Core™) NK603×T25 (event code: MON-ØØ6Ø3-6×ACS-ZMØØ3-2, gene: pat, e.g. commercially available as Roundup Ready™ Liberty Link™ Maize), T14 (event code: ACS-ZMØØ2-1, gene: pat, e.g. commercially available as Liberty Link™ Maize), T25 (event code: ACS-ZMØØ3-2, gene: pat, e.g. commercially available as Liberty Link™ Maize), T25×MON810 (event code: ACS-ZMØØ3-2×MON-ØØ81Ø-6, gene: pat, e.g. commercially available as Liberty Link™ Yieldgard™ Maize), TC1507 (event code: DAS-Ø15Ø7-1, gene: pat, e.g. commercially available as Herculex™ I, Herculex™ CB), TC1507×59122×MON810×MIR6Ø4×NK603 (event code: DAS-Ø15Ø7-1×DAS-59122-7×MON-ØØ81Ø-6×SYN-IR6Ø4-5×MON-ØØ6Ø3, gene: pat, e.g. commercially available as Optimum™ Intrasect Xtreme), TC1507×59122 (event code: DAS-Ø15Ø7-1×DAS-59122-7, gene: pat, e.g. commercially available as Herculex XTRA™), TC1507×59122×MON810×NK603 (event code: DAS-Ø15Ø7-1×DAS-59122-7×MON-ØØ81Ø-6×MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as Optimum™ Intrasect XTRA), TC1507×59122×NK603 (event code: DAS-Ø15Ø7-1×DAS-59122-7×MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as HercuIex XTRA™ RR), TC1507×MIR6Ø4×NK603 (event code: DAS-Ø15Ø7-1×SYN-IR6Ø4-5×MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as Optimum™ TRisect), TC1507×MON810×NK603 (event code: DAS-Ø15Ø7-1×MON-ØØ81Ø-6×MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as Optimum™ Intrasect), TC1507×NK603 (event code: DAS-Ø15Ø7-1×MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as Herculex™ I RR), 3272×Bt11 (event code: SYN-E3272-5×SYN-BTØ11-1 gene: pat), 3272×Bt11×GA21 (event code: SYN-E3272-5×SYN-BTØ11-1×MON-ØØØ21-9, gene: pat), 3272×Bt11×MIR6Ø4 (event code: SYN-E3272-5×SYN-BTØ11-1×SYN-IR6Ø4-5, gene: pat), 3272×BT11×MIR6Ø4×GA21 (event code: SYN-E3272-5×SYN-BTØ11-1×SYN-IR6Ø4-5×MON-ØØØ21-9, gene: pat), 33121 (event code: DP-Ø33121-3, gene: pat), 4114 (event code: DP-ØØ4114-3, gene: pat), 59122×GA21 (event code: DAS-59122-7×MON-ØØØ21-9, gene: pat), 59122×MIR6Ø4 (event code: DAS-59122-7×SYN-IR6Ø4-5, gene: pat), 5307×MIR6Ø4×Bt11×TC1507×GA21×MIR162 (event code: gene: pat), 59122×MIR6Ø4×GA21 (event code: DAS-59122-7×SYN-IR6Ø4-5×MON-ØØØ21-9, gene: pat), 59122×MIR6Ø4×TC1507 (event code: DAS-59122-7×SYN-IR6Ø4-5×DAS-Ø15Ø7-1, gene: pat), 59122×MIR6Ø4×TC1507×GA21 (event code: gene: pat), (event code: DAS-59122-7×SYN-IR6Ø4-5×DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat), 59122×MON810 (event code: DAS-59122-7×MON-ØØ81Ø-6, gene: pat), 59122×MON810×NK603 (event code: DAS-59122-7×MON-ØØ81Ø-6×MON-ØØ6Ø3-6, gene: pat), 59122×TC1507×GA21 (event code: DAS-59122-7×DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat), 676 (event code: PH-000676-7, gene: pat), 678 (event code: PH-ØØØ678-9, gene: pat), 680 (event code: PH-000680-2, gene: pat), 98140×59122 (event code: DP-Ø9814Ø-6×DAS-59122-7, gene: pat), 98140×TC1507 (event code: DP-Ø9814Ø-6×DAS-Ø15Ø7-1, gene: pat), 98140×TC1507×59122 (event code: DP-Ø9814Ø-6×DAS-Ø15Ø7-1×DAS-59122-7, gene: pat), 59122×MON88017 (event code: DAS-59122-7×MON-88017-3, gene: pat), Bt11×59122 (event code: SYN-BTØ11-1×DAS-59122-7, gene: pat), Bt11×59122×GA21 (event code: SYN-BTØ11-1×DAS-59122-7×MON-ØØØ21-9, gene: pat), Bt11×59122×MIR6Ø4 (event code: SYN-BTØ11-1×DAS-59122-7×SYN-IR6Ø4-5, gene: pat), Bt11×59122×MIR6Ø4×GA21 (event code: SYN-BTØ11-1×DAS-59122-7×SYN-IR6Ø4-5×MON-ØØØ21-9, gene: pat), Bt11×59122×MIR6Ø4×TC1507 (event code: Bt11×59122×MIR6Ø4×TC1507, gene: pat), Bt11×59122×TC1507 (event code: SYN-BTØ11-1×DAS-59122-7×DAS-Ø15Ø7-1, gene: pat), Bt11×59122×TC1507×GA21 (event code: SYN-BTØ11-1×DAS-59122-7×DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat), Bt11×MIR162×TC1507 (event code: SYN-BTØ11-1×SYN-IR162-4×DAS-Ø15Ø7-1, gene: pat), Bt11×MIR6Ø4×TC1507 (event code: SYN-BTØ11-1×SYN-IR6Ø4-5×DAS-Ø15Ø7-1, gene: pat), Bt11×TC1507 (event code: SYN-BTØ11-1×DAS-Ø15Ø7-1, gene: pat), Bt11×TC1507×GA21 (event code: SYN-BTØ11-1×DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat), GA21×T25 (event code: MON-ØØØ21-9×ACS-ZMØØ3-2, gene: pat), MIR162×TC1507 (event code: SYN-IR162-4×DAS-Ø15Ø7-1, gene: pat), MIR162×TC1507×GA21 (event code: SYN-IR162-4×DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat), MIR6Ø4×TC1507 (event code: SYN-IR6Ø4-5×DAS-Ø15Ø7-1, gene: pat), MON87427×MON89034×TC1507×MON88017×59122 (event code: MON-87427-7×MON-89Ø34-3×DAS-Ø15Ø7-1×MON-88017-3×DAS-59122-7, gene: pat), MON89034×59122 (event code: MON-89Ø34-3×DAS-59122-7, gene: pat), MON89034×59122×MON88017 (event code: gene: pat), MON89034×TC1507 (event code: MON-89Ø34-3×DAS-59122-7×MON-88017-3, gene: pat), (event code: MON-89034-3×DAS-Ø15Ø7-1, gene: pat), MIR6Ø4×TC1507 (event code: SYN-IR6Ø4-5×DAS-Ø15Ø7-1, gene: pat), MON87427×MON89034×TC1507×MON88017×59122 (event code: MON-87427-7×MON-89Ø34-3×DAS-Ø15Ø7-1×MON-88017-3×DAS-59122-7, gene: pat), MON89034×59122 (event code: MON-89Ø34-3×DAS-59122-7, gene: pat), MON89034×59122×MON88017 (event code: gene: pat), MON89034×TC1507 (event code: MON-89Ø34-3×DAS-59122-7×MON-88017-3, gene: pat), (event code: MON-89034-3×DAS-Ø15Ø7-1, gene: pat), DLL25 (B16) (event code: DKB-8979Ø-5, gene: bar), MIR6Ø4×TC1507 (event code: SYN-IR6Ø4-5×DAS-Ø15Ø7-1, gene: pat), MON87427×MON89034×TC1507×MON88017×59122 (event code: MON-87427-7×MON-89Ø34-3×DAS-Ø15Ø7-1×MON-88017-3×DAS-59122-7, gene: pat), MON89034×59122 (event code: MON-89Ø34-3×DAS-59122-7, gene: pat), MON89034×59122×MON88017 (event code: MON-89Ø34-3×DAS-59122-7×MON-88017-3, gene: pat), MON89034×TC1507 (event code: MON-89Ø34-3×DAS-Ø15Ø7-1, gene: pat), MON89034×TC1507×59122 (event code: MON-89Ø34-3×DAS-Ø15Ø7-1×DAS-59122-7, gene: pat), MON89034×TC1507×MON88017 (event code: MON-89Ø34-3×DAS-Ø15Ø7-1×MON-88017-3, gene: pat), MON89034×TC1507×MON88017×59122×DAS40278 (event code: MON-89Ø34-3×DAS-Ø15Ø7-1×MON-88017-3×DAS-59122-7×DAS-40278-9, gene: pat), MON89034×TC1507×MON88017×DAS40278 (event code: MON-89Ø34-3×DAS-Ø15Ø7-1×MON-88017-3×DAS-59122-7×DAS-40278-9, gene: pat), MON89034×TC1507×NK603×DAS40278 (event code: MON-89Ø34-3×DAS-Ø15Ø7-1×MON-ØØ6Ø3-6×DAS-40278-9, gene: pat), NK603×MON810×4114×MIR 604 (event code: MON-ØØ6Ø3-6×MON-ØØ81Ø-6×DP004114-3×SYN-IR6Ø4-4, gene: pat), TC1507×MON810×MIR6Ø4×NK603 (event code: DAS-Ø15Ø7-1×MON-ØØ81Ø-6×SYN-IR6Ø4-5×MON-ØØ6Ø3-6, gene: pat), TC1507×59122×MON810 (event code: DAS-Ø15Ø7-1×DAS-59122-7×MON-ØØ81Ø-6, gene: pat), TC1507×59122×MON88017 (event code: DAS-Ø15Ø7-1×DAS-59122-7×MON-88017-3, gene: pat), TC1507×GA21 (event code: DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat), TC1507×MON810 (event code: DAS-Ø15Ø7-1×MON-ØØ81Ø-6, gene: pat), TC1507×MON810×MIR162×NK603 (event code: DAS-Ø15Ø7-1×MON-ØØ81Ø-6×SYN-IR162-4×MON-ØØ6Ø3-6, gene: pat), 3272×Bt11×MIR6Ø4×TC1507×5307×GA21 (event code: SYN-E3272-5×SYN-BTØ11-1×SYN-IR6Ø4-5×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), TC1507×MIR162×NK603 (event code: DAS-Ø15Ø7-1×SYN-IR162-4×MON-ØØ6Ø3-6, gene: pat), TC1507×MON810×MIR162 (event code: DAS-Ø15Ø7-1×MON-ØØ81Ø-6×SYN-IR162-4, gene: pat), MON87419 (event code: MON87419-8, gene: pat), TC1507×MON88017 (event code: DAS-Ø15Ø7-1×MON-88017-3, gene: pat), TC6275 (event code: DAS-06275-8, gene: bar), MZHG0JG (event code: SYN-ØØØJG-2, gene: pat), MZIR098 (event code: SYN-ØØØ98-3, gene: pat), Bt11×MIR162×MON89034 (event code: SYN-BTØ11-1×SYN-IR162-4×MON-89Ø34-3, gene: pat) and Bt11×MIR162×MON89Ø34×GA21 (event code: SYN-BTØ11-1×SYN-IR162-4×MON-89Ø34-3×MON-ØØØ21-9, gene: pat), 59122×DAS40278 (event code: DAS-59122-7×DAS-40278-9, gene: pat), 59122×MON810×MIR6Ø4 (event code: DAS-59122-7×MON-ØØ81Ø-6×SYN-IR6Ø4-5, gene: pat), 59122×MON810×NK603×MIR6Ø4 (event code: DAS-59122-7×MON-ØØ81Ø-6×MON-ØØ6Ø3-6×SYN-IR6Ø4-5, gene: pat), 59122×MON88017×DAS40278 (event code: DAS-59122-7×MON-88017-3×DAS-40278-9, gene: pat), 59122×NK603×MIR6Ø4 (event code: DAS-59122-7×MON-ØØ6Ø3-6×SYN-IR6Ø4-5, gene: pat), Bt11×5307 (event code: SYN-BTØ11-1×SYN-Ø53Ø7-1, gene: pat), Bt11×5307×GA21 (event code: SYN-BTØ11-1×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), Bt11×MIR162×5307 (event code: SYN-BTØ11-1×SYN-IR162-4×SYN-Ø53Ø7-1, gene: pat), Bt11×MIR162×5307×GA21 (event code: SYN-BTØ11-1×SYN-IR162-4×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), BT11×MIR162×MIR604×5307 (event code: SYN-BTØ11-1×SYN-IR162-4×SYN-IR6Ø4-5×SYN-Ø53Ø7-1, gene: pat), Bt11×MIR162×MIR604×5307×GA21 (event code: SYN-BTØ11-1×SYN-IR162-4×SYN-IR6Ø4-5×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), Bt11×MIR162×MIR6Ø4×MON89034×5307×GA21 (event code: SYN-BTØ11-1×SYN-IR162-4×SYN-IR6Ø4-5×MON-89Ø34-3×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), BT11×MIR162×MIR6Ø4×TC1507 (event code: SYN-BTØ11-1×SYN-IR162-4×SYN-IR6Ø4-5×DAS-Ø15Ø7-1, gene: pat), BT11×MIR162×MIR604×TC1507×5307 (event code: SYN-BTØ11-1×SYN-IR162-4×SYN-IR6Ø4-5×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1, gene: pat), Bt11×MIR162×MIR6Ø4×TC1507×GA21 (event code: SYN-BTØ11-1×SYN-IR162-4×SYN-IR6Ø4-5×DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat), Bt11×MIR162×TC1507×5307 (event code: SYN-BTØ11-1×SYN-IR162-4×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1, gene: pat), BT11×MIR162×MIR6Ø4×TC1507×5307 (event code: SYN-BTØ11-1×SYN-IR162-4×SYN-IR6Ø4-5×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1, gene: pat), Bt11×MIR162×MIR6Ø4×TC1507×GA21 (event code: SYN-BTØ11-1×SYN-IR162-4×SYN-IR6Ø4-5×DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat), Bt11×MIR162×TC1507×5307 (event code: SYN-BTØ11-1×SYN-IR162-4×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1, gene: pat), Bt11×MIR162×TC1507×5307×GA21 (event code: SYN-BTØ11-1×SYN-IR162-4×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), Bt11×MIR604×5307 (event code: SYN-BTØ11-1×SYN-IR6Ø4-5×SYN-Ø53Ø7-1, gene: pat), Bt11×MIR604×5307×GA21 (event code: SYN-BTØ11-1×SYN-IR6Ø4-5×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), Bt11×MIR6Ø4×TC1507×5307 (event code: SYN-BTØ11-1×SYN-IR6Ø4-5×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1, gene: pat), Bt11×MIR6Ø4×TC1507×GA21 (event code: SYN-BTØ11-1×SYN-IR6Ø4-5×DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat), Bt11×MON89034 (or Bt11×MON89Ø34) (event code: SYN-BTØ11-1×MON-89Ø34-3, gene: pat), Bt11×MON89034×GA21 (event code: SYN-BTØ11-1×MON-89Ø34-3×MON-ØØØ21-9, gene: pat), Bt11×MON89034×GA21 (event code: SYN-BTØ11-1×MON-89Ø34-3×MON-ØØØ21-9, gene: pat), Bt11×TC1507×5307 (event code: SYN-BTØ11-1×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1, gene: pat), Bt11×TC1507×5307×GA21 (event code: SYN-BTØ11-1×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), MIR162×MIR6Ø4×TC1507×5307 (event code: SYN-IR162-4×SYN-IR6Ø4-5×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1, gene: pat), MIR162×MIR6Ø4×TC1507×5307×GA21 (event code: SYN-IR162-4×SYN-IR6Ø4-5×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), MIR162×MIR6Ø4×TC1507×GA21 (event code: SYN-IR162-4×SYN-IR6Ø4-5×DAS-Ø15Ø7-1×MON-ØØØ21-9, gene: pat), MIR162×TC1507×5307 (event code: SYN-IR162-4×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1, gene: pat), MIR162×TC1507×5307×GA21 (event code: SYN-IR162-4×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), MIR6Ø4×TC1507×5307 (event code: SYN-IR6Ø4-5×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1, gene: pat), MIR162×TC1507×5307 (event code: SYN-IR162-4×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1, gene: pat), MIR162×TC1507×5307×GA21 (event code: SYN-IR162-4×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), MIR6Ø4×TC1507×5307 (event code: SYN-IR6Ø4-5×DAS-Ø15Ø7-1×SYN-Ø53Ø7-1, gene: pat), MIR6Ø4×TC1507×5307×GA21 (event code: SYN-IR6Ø4-5×TC1507×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), MIR6Ø4×TC1507×GA21 (event code: SYN-IR6Ø4-5×TC1507×MON-ØØØ21-9, gene: pat), MON87427×59122 (event code MON-87427-7×DAS-59122-7, gene: pat), MON87427×MON89034×59122 (event code: MON-87427-7×MON-89Ø34-3×DAS-59122-7, gene: pat), MON87427×MON89034×MON88017×59122 (event code: MON-87427-7×MON-89Ø34-3×MON-88Ø17-3×59122, gene: pat), MON87427×MON89034×TC1507 (event code: MON-87427-7×MON-89Ø34-3×DAS-Ø15Ø7-1, gene: pat), MON87427×MON89034×TC1507×59122 (event code: MON-87427-7×MON-89Ø34-3×DAS-Ø15Ø7-1×DAS-59122-7, gene: pat), MON87427×MON89034×TC1507×MON87411×59122 (event code: MON-87427-7×MON-89Ø34-3×DAS-Ø15Ø7-1×MON-87411-9×DAS-59122-7, gene: pat), MON87427×MON89034×TC1507×MON87411×59122×DAS40278 (event code: MON-87427-7×MON-89Ø34-3×DAS-Ø15Ø7-1×MON-87411-9×DAS-59122-7×DAS-40278-9, gene: pat), MON87427×MON89034×TC1507×MON88017 (event code: MON-87427-7×MON-89Ø34-3×DAS-Ø15Ø7-1×MON-88017-3, gene: pat), MON87427×TC1507 (event code: MON-87427-7×DAS-Ø15Ø7-1, gene: pat), MON87427×TC1507×59122 (event code: MON-87427-7×DAS-Ø15Ø7-1×DAS-59122-7, gene: pat), MON87427×TC1507×MON88017 (event code: MON-87427-7×DAS-Ø15Ø7-1xMON-88017-3, gene: pat), MON87427×TC1507×MON88017×59122 (event code: MON-87427-7×DAS-Ø15Ø7-1×MON-88017-3×DAS-59122-7, gene: pat), MON89034×59122×DAS40278 (event code: MON-89Ø34-3×DAS-59122-7×DAS-40278-9, gene: pat), MON89034×59122×MON88017×DAS40278 (event code: MON-89Ø34-3×DAS-59122-7×MON-88017-3×DAS-40278-9, gene: pat), MON89034×TC1507×59122×DAS40278 (event code: MON-89Ø34-3×DAS-Ø15Ø7-1×DAS-59122-7×DAS-40278-9, gene: pat), MON89034×TC1507×DAS40278 (event code: MON-89Ø34-3×DAS-Ø15Ø7-1×DAS-40278-9, gene: pat), MON89034×TC1507×NK603×MIR162 (event code: MON-89Ø34-3×DAS-Ø15Ø7-1×MON-ØØ6Ø3-6×SYN-IR162-4, gene: pat), TC1507×5307 (event code: DAS-Ø15Ø7-1×SYN-Ø53Ø7-1, gene: pat), TC1507×5307×GA21 (event code: DAS-Ø15Ø7-1×SYN-Ø53Ø7-1×MON-ØØØ21-9, gene: pat), TC1507×59122×DAS40278 (event code: DAS-Ø15Ø7-1×DAS-59122-7×DAS-40278-9, gene: pat), TC1507×59122×MON810×MIR6Ø4 (event code: DAS-Ø15Ø7-1×DAS-59122-7×MON-ØØ81Ø-6×SYN-IR6Ø4-5, gene: pat), TC1507×59122×MON88017×DAS40278 (event code: DAS-Ø15Ø7-1×DAS-59122-7×MON-88017-3×DAS-40278-9, gene: pat), TC1507×59122×NK603×MIR6Ø4 (event code: gene: pat) DAS-Ø15Ø7-1×DAS-59122-7×MON-ØØ6Ø3-6×SYN-IR6Ø4-5, TC1507×DAS40278 (event code: DAS-Ø15Ø7-1×DAS-40278-9, gene: pat), TC1507×MON810×MIR6Ø4 (event code: DAS-Ø15Ø7-1×MON-ØØ81Ø-6×SYN-IR6Ø4-5, gene: pat), TC1507×MON810×NK603×MIR6Ø4 (event code: DAS-Ø15Ø7-1×MON-Ø81Ø-6×MON-ØØ6Ø3-6×SYN-IR6Ø4-5, gene: pat), TC1507×MON88017×DAS40278 (event code: DAS-Ø15Ø7-1×MON-88017-3×DAS-40278-9, gene: pat) and TC1507×NK603×DAS40278 (event code: DAS-Ø15Ø7-1×MON-ØØ6Ø3-6×DAS-40278-9, gene: pat).

Transgenic soybean events comprising glufosinate tolerance genes are for example, but not excluding others, A2704-12 (event code: ACS-GMØØ5-3, gene: pat, e.g. commercially available as Liberty Link™ soybean), A2704-21 (event code: ACS-GMØØ4-2, gene: pat, e.g. commercially available as Liberty Link™ soybean), A5547-127 (event code: ACS-GMØØ6-4, gene: pat, e.g. commercially available as Liberty Link™ soybean), A5547-35 (event code: ACS-GMØØ8-6, gene: pat, e.g. commercially available as Liberty Link™ soybean), GU262 (event code: ACS-GMØØ3-1, gene: pat, e.g. commercially available as Liberty Link™ soybean), W62 (event code: ACS-GMØØ2-9, gene: pat, e.g. commercially available as Liberty Link™ soybean), W98 (event code: ACS-GMØØ1-8, gene: pat, e.g. commercially available as Liberty Link™ soybean), DAS68416-4 (event code: DAS-68416-4, gene: pat, e.g. commercially available as Enlist™ Soybean), DAS44406-6 (event code: DAS-44406-6, gene: pat), DAS68416-4×MON89788 (event code: DAS-68416-4×MON-89788-1, gene: pat), SYHTØH2 (event code: SYN-ØØØH2-5, gene: pat), DAS81419×DAS44406-6 (event code: DAS-81419-2×DAS-44406-6, gene: pat) and FG72×A5547-127 (event code: MST-FG072-3×ACS-GMØØ6-4, gene: pat).

Transgenic cotton events comprising glufosinate tolerance genes are for example, but not excluding others, 3006-210-23×281-24-236×MON1445 (event code: DAS-21Ø23-5×DAS-24236-5×MON-01445-2, gene: bar, e.g. commercially available as WideStrike™ Roundup Ready™ Cotton), 3006-210-23×281-24-236×MON88913 (event code: DAS-21Ø23-5×DAS-24236-5×MON-88913-8, gene: bar, e.g. commercially available as Widestrike™ Roundup Ready Flex™ Cotton), 3006-210-23×281-24-236×MON88913×COT102 (event code: DAS-21Ø23-5×DAS-24236-5×MON-88913-8×SYN-IR1Ø2-7, gene: pat, e.g. commercially available as Widestrike™×Roundup Ready Flex™×VIPCOT™ Cotton), GHB614×LLCotton25 (event code: BCS-GHØØ2-5×ACS-GHØØ1-3, gene: bar, e.g. commercially available as GlyTol™ Liberty Link™), GHB614×T304-40×GHB119 (event code: BCS-GHØØ2-5×BCS-GHØØ4-7×BCS-GHØØ5-8, gene: bar, e.g. commercially available as Glytol™×Twinlink™), LLCotton25 (event code: ACS-GHØØ1-3, gene: bar, e.g. commercially available as ACS-GHØØ1-3), GHB614×T304-40×GHB119×COT102 (event code: BCS-GHØØ2-5×BCS-GHØØ4-7×BCS-GHØØ5-8×SYN-IR1Ø2-7, gene: bar, e.g. commercially available as Glytol™×Twinlink™×VIPCOT™ Cotton), LLCotton25×MON15985 (event code: ACS-GHØØ1-3×MON-15985-7, gene: bar, e.g. commercially available as Fibermax™ Liberty Link™ Bollgard II™), T304-40×GHB119 (event code: BCS-GHØØ4-7×BCS-GHØØ5-8, gene: bar, e.g. commercially available as TwinLink™ Cotton), GHB614×T304-40×GHB119×COT102 (event code: BCS-GHØØ2-5×BCS-GHØØ4-7×BCS-GHØØ5-8×SYN-IR1Ø2-7, gene: bar, e.g. commercially available as Glytol™×Twinlink™×VIPCOT™ Cotton), GHB119 (event code: BCS-GHØØ5-8, gene: bar), GHB614×LLCotton25×MON15985 (event code: CS-GHØØ2-5×ACS-GHØØ1-3×MON-15985-7, gene: bar), MON 88701-3 (event code: MON88701, gene: bar), T303-3 (event code: BCS-GHØØ3-6, gene: bar), T304-40 (event code: BCS-GHØØ3-6, gene: bar), (event code: BCS-GHØØ4-7, gene: bar), 81910 (event code: DAS-81910-7, gene: pat), MON8870 (event code: MON 88701-3, gene: bar), MON88701×MON88913 (event code: MON 88701-3×MON-88913-8, gene: bar), MON88701×MON88913×MON15985 (event code: MON 88701-3×MON-88913-8×MON-15985-7, gene: bar), 281-24-236×3006-210-23×COT102×81910 (event code: DAS-24236-5×DAS-21Ø23-5×SYN-IR1Ø2-7×DAS-81910-7, gene: pat), COT102×MON15985×MON88913×MON88701 (event code: SYN-IR1Ø2-7×MON-15985-7×MON-88913-8×MON 887Ø1-3, gene: bar) and 3006-210-23×281-24-236×MON88913×COT102×81910 (event code: DAS-21Ø23-5×DAS-24236-5×MON-88913-8×SYN-IR1Ø2-7×DAS-81910-7, gene: pat).

Transgenic canola events comprising glufosinate tolerance genes are for example, but not excluding others, HCN10 (Topas 19/2) (event code: gene: bar, e.g. commercially available as Liberty Link™ Independence™), HCN28 (T45) (event code: ACS-BNØØ8-2, gene: pat, e.g. commercially available as InVigor™ Canola), HCN92 (Topas 19/2 (event code: ACS-BNØØ7-1, gene: bar, e.g. commercially available as Liberty Link™ Innovator™), MS1 (B91-4) (event code: ACS-BNØØ4-7, gene: bar, e.g. commercially available as InVigor™ Canola), MS1×RF1 (PGS1) (event code: ACS-BNØØ4-7×ACS-BNØØ1-4, gene: bar, e.g. commercially available as InVigor™ Canola), MS1×RF2 (PGS2) (event code: ACS-BNØØ4-7×ACS-BNØØ2-5, gene: bar, e.g. commercially available as InVigor™ Canola), MS1×RF3 (event code: ACS-BNØØ4-7×ACS-BNØØ3-6, gene: bar, e.g. commercially available as InVigor™ Canola), MS8 (event code: ACS-BNØØ5-8, gene: bar, e.g. commercially available as InVigor™ Canola), MS8×RF3 (event code: ACS-BNØØ5-8×ACS-BNØØ3-6, gene: bar, e.g. commercially available as InVigor™ Canola), RF1 (B93-101) (event code: ACS-BNØØ1-4, gene: bar, e.g. commercially available as InVigor™ Canola), RF2 (B94-2) (event code: ACS-BNØØ2-5, gene: bar, e.g. commercially available as InVigor™ Canola), RF3 (event code: ACS-BNØØ3-6, gene: bar, e.g. commercially available as InVigor™ Canola), MS1×MON88302 (event code: ACS-BNØØ4-7×MON-88302-9, gene: bar, e.g. commercially available as InVigor™×TruFlex™ Roundup Ready™ Canola), MS8×MON88302 (event code: ACS-BNØØ5-8×MON-88302-9, gene: bar, e.g. commercially available as InVigor™ X TruFlex™ Roundup Ready™ Canola), RF1×MON88302 (event code: ACS-BNØØ1-4×MON-88302-9, gene: bar, e.g. commercially available as InVigor™×TruFlex™ Roundup Ready™ Canola), RF2×MON88302 (event code: ACS-BNØØ2-5×MON-88302-9, gene: bar, e.g. commercially available as InVigor™×TruFlex™ Roundup Ready™ Canola), HCN28×MON88302 (event code: ACS-BNØØ8-2×MON-88302-9, gene: pat, e.g. commercially available as InVigor™×TruFlex™ Roundup Ready™ Canola), HCN92×MON88302 (event code: ACS-BNØØ7-1×MON-88302-9, gene: bar, e.g. commercially available as Liberty Link™ Innovator™×TruFlex™ Roundup Ready™ Canola), HCR-1 (gene: pat), MON88302×MS8×RF3 (event code: MON-88302-9×ACS-BNØØ5-8×ACS-BNØØ3-6, gene: bar), MON88302×RF3 (event code: MON-88302-9×ACS-BNØØ3-6, gene: bar), MS8×RF3×GT73 (RT73) (event code: gene: bar), PHY14 (event code: ACS-BNØØ5-8×ACS-BNØØ3-6×MON-00073-7, gene: bar), PHY23 (gene: bar), PHY35 (gene: bar) and PHY36 (gene: bar) and 73496×RF3 (event code: DP-073496-4×ACS-BNØØ3-6, gene: bar).

Transgenic rice events comprising glufosinate tolerance genes are for example, but not excluding others, LLRICE06 (event code: ACS-OSØØ1-4, e.g. commercially available as Liberty Link™ rice), LLRICE601 (event code: BCS-OSØØ3-7, e.g. commercially available as Liberty Link™ rice) and LLRICE62 (event code: ACS-OSØØ2-5, e.g. commercially available as Liberty Link™ rice).

The glufosinate compositions have an outstanding herbicidal activity against a broad spectrum of economically important harmful monocotyledonous and dicotyledonous harmful plants. Also here, post-emergence application is preferred.

Specifically, examples may be mentioned of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the combinations according to the invention, without the enumeration being a restriction to certain species.

In the context of the present text, reference may be made to growth stages according to the BBCH monograph “Growth stages of mono- and dicotyledonous plants”, 2nd edition, 2001, ed. Uwe Meier, Federal Biological Research Centre for Agriculture and Forestry (Biologische Bundesanstalt fQr Land und Forstwirtschaft).

Examples of monocotyledonous harmful plants on which the glufosinate combinations act efficiently are from amongst the genera Hordeum spp., Echinochloa spp., Poa spp., Bromus spp., Digitaria spp., Eriochloa spp., Setaria spp., Pennisetum spp., Eleusine spp., Eragrostis spp., Panicum spp., Lolium spp., Brachiaria spp., Leptochloa spp., Avena spp., Cyperus spp., Axonopris spp., Sorghum spp., and Melinus spp.

Particular examples of monocotyledonous harmful plants species on which the glufosinate compositions act efficiently are selected from amongst the species Hordeum murinum, Echinochloa crusgalli, Poa annua, Bromus rubens L., Bromus rigidus, Bromus secalinus L., Digitaria sanguinalis, Digitaria insularis, Eriochloa gracilis, Setaria faberi, Setaria viridis, Pennisetum glaucum, Eleusine indica, Eragrostis pectinacea, Panicum miliaceum, Lolium multiflorum, Brachiaria platyphylla, Leptochloa fusca, Avena fatua, Cyperus compressus, Cyperus esculentes, Axonopris offinis, Sorghum halapense, and Melinus repens.

In a preferred embodiment, the glufosinate compositions are used to control monocotyledonous harmful plant species, more preferably monocoty-ledonous plants of the species Echinochloa spp., Digitaria spp., Setaria spp., Eleusine spp. and Bra-chiarium spp.

Examples of dicotyledonous harmful plants on which the glufosinate compositions act efficiently are from amongst the genera Amaranthus spp., Erigeron spp., Conyza spp., Polygonum spp., Medicago spp., Mollugo spp., Cyclospermum spp., Stellaria spp., Gnaphalium spp., Taraxacum spp., Oenothera spp., Amsinckia spp., Erodium spp., Erigeron spp., Senecio spp., Lamium spp., Kochia spp., Chenopodium spp., Lactuca spp., Malva spp., Ipomoea spp., Brassica spp., Sinapis spp., Urtica spp., Sida spp, Portulaca spp., Richardia spp., Ambrosia spp., Calandrinia spp., Sisymbrium spp., Sesbania spp., Capsella spp., Sonchus spp., Euphorbia spp., Helianthus spp., Coronopus spp., Salsola spp., Abutilon spp., Vicia spp., Epilobium spp., Cardamine spp., Picris spp., Trifolium spp., Galinsoga spp., Epimedium spp., Marchantia spp., Solanum spp., Oxalis spp., Metricaria spp., Plantago spp., Tribulus spp., Cenchrus spp. Bidens spp., Veronica spp., and Hypochaeris spp.

Particular examples of dicotyledonous harmful plants species on which the glufosinate compositions act efficiently are selected from amongst the species Amaranthus spinosus, Polygonum convolvulus, Medicago polymorpha, Mollugo verticillata, Cyclospermum leptophyllum, Stellaria media, Gnaphalium purpureum, Taraxacum officinale, Oenothera laciniata, Amsinckia intermedia, Erodium cicutarium, Erodium moschatum, Erigeron bonariensis (Conyza bonariensis), Senecio vulgaris, Lamium amplexicaule, Erigeron canadensis, Polygonum aviculare, Kochia scoparia, Chenopodium album, Lactuca serriola, Malva parviflora, Malva neglecta, Ipomoea hederacea, Ipomoea lacunose, Brassica nigra, Sinapis arvensis, Urtica dioica, Amaranthus blitoides, Amaranthus retroflexus, Amaranthus hybridus, Amaranthus lividus, Sida spinosa, Portulaca oleracea, Richardia scabra, Ambrosia artemisiifolia, Calandrinia caulescens, Sisymbrium irio, Sesbania exaltata, Capsella bursapastoris, Sonchus oleraceus, Euphorbia maculate, Helianthus annuus, Coronopus didymus, Salsola tragus, Abutilon theophrasti, Vicia benghalensis L., Epilobium paniculatum, Cardamine spp, Picris echioides, Trifolium spp., Galinsoga spp., Epimedium spp., Marchantia spp., Solanum spp., Oxalis spp., Metricaria matriccarioides, Plantago spp., Tribulus terrestris, Salsola kali, Cenchrus spp., Bidens bipinnata, Veronica spp., and Hypochaeris radicata.

In a preferred embodiment, the glufosinate compositions are used to control dicotyledonous harmful plant species, more preferably dicotyledonous plants of the species Amaranthus spp., Erigeron spp., Conyza spp., Kochia spp. and Abutilon spp.

Glufosinate compositions are also suitable for controlling a large number of annual and perennial sedge weeds including Cyperus species such as purple nutsedge (Cyperus rotundus L.), yellow nutsedge (Cyperus esculentus L.), hime-kugu (Cyperus brevifolius H.), sedge weed (Cyperus microiria Steud), rice flatsedge (Cyperus iria L.), Cyperus difformis, Cyperus difformis L., Cyperus esculentus, Cyperus ferax, Cyperus flavus, Cyperus iria, Cyperus lanceolatus, Cyperus odoratus, Cyperus rotundus, Cyperus serotinus Rottb., Eleocharis acicularis, Eleocharis kuroguwai, Fimbristylis dichotoma, Fimbristylis miliacea, Scirpus grossus, Scirpus juncoides, Scirpus juncoides Roxb, Scirpus or Bolboschoenus maritimus, Scirpus or Schoenoplectus mucronatus, Scirpus planiculmis Fr. Schmidt and the like.

If the glufosinate combinations are applied post-emergence to the green parts of the plants, growth likewise stops drastically a very short time after the treatment and the weed plants remain at the growth stage of the point of time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the crops, is eliminated at a very early point in time and in a sustained manner.

The glufosinate compositions are characterized by a rapidly commencing and long-lasting herbicidal action. As a rule, the rainfastness of the active compounds in the herbicide combinations according to the present invention is advantageous. In particular when the glufosinate compositions are employed application rates may be reduced, a broader spectrum of broad-leaved weeds and grass weeds maybe controlled, the herbicidal action may take place more rapidly, the duration of action may be longer, the harmful plants may be controlled better while using only one, or few, applications, and the application period which is possible to be extended.

The abovementioned properties and advantages are of benefit for weed control practice to keep agricultural crops free from undesired competing plants and thus to safeguard and/or increase the yields from the qualitative and/or quantitative point of view. These glufosinate compositions markedly exceed the technical state of the art with a view to the properties described.

Owing to their herbicidal and plant-growth-regulatory properties, the glufosinate compositions can be employed for controlling harmful plants in genetically modified crops or crops obtained by mutation/selection. These crops are distinguished as a rule by particular, advantageous properties, such as resistances to herbicidal compositions or resistances to plant diseases or causative agents of plant diseases such as particular insects or microorganisms such as fungi, bacteria or viruses. Other particular properties relate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. Thus, for example, transgenic plants are known whose starch content is increased or whose starch quality is altered, or those where the harvested material has a different fatty acid composition.

The present invention also relates to a method of controlling undesired vegetation (e.g. harmful plants), which comprises applying the glufosinate compositions, preferably by the post-emergence method, to harmful or undesired plants, parts of said harmful or undesired plants, or the area where the harmful or undesired plants grow, for example the area under cultivation.

In the context of the present invention “controlling” denotes a significant reduction of the growth of the harmful plant(s) in comparison to the untreated harmful plants. Preferably, the growth of the harmful plant(s) is essentially diminished (60-79%), more preferably the growth of the harmful plant(s) is largely or fully suppressed (80-100%), and in particular the growth of the harmful plant(s) is almost fully or fully suppressed (90-100%).

Thus, in a further aspect, the present invention relates to a method for controlling undesired plant growth, and/or controlling harmful plants, comprising the step of applying the glufosinate composition (preferably in one of the preferred embodiments defined herein) onto the undesired plants or the harmful plants, on parts of the undesired plants or the harmful plants, or on the area where the undesired plants or the harmful plants grow.

The glufosinate composition(s) may be used for controlling undesirable vegetation in burndown programs, in industrial vegetation management and forestry, in vegetable and perennial crops and in turf and lawn, wherein the glufosinate composition(s) can be applied pre- or post-emergence, i.e. before, during and/or after emergence of the undesirable plants. Preferred is the application as post-emergence treatment, i.e. during and/or after emergence of the undesirable plants. Herein, the glufosinate composition(s) are applied to a locus where crops will be planted before planting or emergence of the crop.

In industrial weed management and forestry, it is desirable to control a broad range of weeds for an extended period of time. The control of large weeds, or taller species such as bushes or trees may also be desirable. Industrial weed management includes for example railway and right-of-way management, fence lines and non-crop land such as industrial and building sites, gravel areas, roads or sidewalks. Forestry includes for example the clearing of existing forest or bushland, the removal of regrowth after mechanical forest cutting, or the management of weeds under forestry plantations. In the latter case, it may be desirable to shield desirable trees from contact with the spray solution that contains the herbicidal mixture according to the present invention.

The glufosinate composition can also be used for weed control in turf and lawn provided the desirable grass species are tolerant to glufosinate composition. In particular, such glufosinate compositions can be used in desirable grass that has been rendered tolerant to the respective agrochemical active ingredient, e.g. glufosinate or its salts, by mutagenesis or genetic engineering.

Glufosinate and its salts are non-selective systemic herbicides having a good post-emergence activity against numerous weeds and thus can be used in burndown programs, in industrial vegetation management and forestry, in vegetable and perennial crops and in turf and lawn.

Therefore, the present invention also relates to a method for burndown treatment of undesirable vegetation in crops, comprising applying the glufosinate composition, to a locus where crops will be planted before planting (or seeding) or emergence of the crop. Herein, the glufosinate composition is applied undesirable vegetation or the locus thereof.

The present invention also relates to a method for controlling undesirable vegetation, which method comprises applying the glufosinate composition, to a locus where undesirable vegetation is present or is expected to be present. The application may be done before, during and/or after, preferably during and/or after, the emergence of the undesirable vegetation. In one embodiment, the application is carried out before emergence of the crop, which is cultivated at the locus where the undesirable vegetation is present or is expected to be present. In another embodiment, the application is carried out before planting the crop.

As used herein, the terms “controlling” and “combating” are synonyms.

As used herein, the terms “undesirable vegetation”, “undesirable species”, “undesirable plants”, “harmful plants”, “undesirable weeds”, or “harmful weeds” are synonyms.

The term “locus”, as used herein, means the area in which the vegetation or plants are growing or will grow, typically a field.

In burndown programs, the glufosinate composition(s) can be applied prior to seeding (planting) or after seeding (or planting) of the crop plants but before the emergence of the crop plants, in particular prior to seeding. The herbicidal compositions are preferably applied prior to seeding of the crop plants. For burndown, the herbicidal composition(s) will generally be applied a date up to 9 months, frequently up to 6 months, preferably up to 4 months prior to planting the crop. The burndown application can be done at a date up to 1 day prior to emergence of the crop plant and is preferably done at a date prior to seeding/planting of the crop plant, preferably at a date of at least one day, preferably at least 2 days and in particular at least one 4 days prior to planting or from 6 months to 1 day prior emergence, in particular from 4 months to 2 days prior emergence and more preferably from 4 months to 4 days prior emergence. It is, of course, possible to repeat the burndown application once or more, e.g. once, twice, three times, four times or five times within that time frame.

It is a particular benefit of the glufosinate compositions that they have a very good post-emergence herbicide activity, i.e. they show a good herbicidal activity against emerged undesirable plants. Thus, in a preferred embodiment of invention, the glufosinate compositions are applied post-emergence, i.e. during and/or after, the emergence of the undesirable plants. It is particularly advantageous to apply the glufosinate composition post emergent when the undesirable plant starts with leaf development up to flowering. The herbicidal compositions are particularly useful for controlling undesirable vegetation which has already developed to a state, which is difficult to control with conventional burndown mixtures, i.e. when the individual weed is taller than 10 cm (4 inches) or even taller than 15 cm (6 inches) and/or for heavy weed populations. In the case of a post-emergence treatment of the plants, the glufosinate compositions are preferably applied by foliar application.

The glufosinate compositions can be applied in conventional manner by using techniques as skilled person is familiar with. Suitable techniques include spraying, atomizing, dusting, spreading or watering. The type of application depends on the intended purpose in a well known manner; in any case, they should ensure the finest possible distribution of the active ingredients according to the invention.

In one embodiment, the glufosinate compositions are applied to locus mainly by spraying, in particular foliar spraying of an aqueous dilution of the active ingredients of the mixture. Application can be carried out by customary spraying techniques using, for example, water as carrier and spray liquor rates of from about 10 to 2000 I/ha or 50 to 1000 I/ha (for example from 100 to 500 I/ha). Application of the inventive mixtures by the low-volume and the ultra-low-volume method is possible, as is their application in the form of microgranules.

The required application rate of the glufosinate composition depends on the density of the undesired vegetation, on the development stage of the plants, on the climatic conditions of the location where the mixture is used and on the application method.

In general, the rate of application of L-glufosinate or its salt is usually from 50 g/ha to 3000 g/ha and preferably in the range from 100 g/ha to 2000 g/ha or from 200 g/ha to 1500 g/ha of active substance (a.i.).

When using the glufosinate composition in the methods of the present invention, the glufosinate or a salt thereof and the compound of formula (I) can be applied simultaneously or in succession, where undesirable vegetation may occur. Herein, it is immaterial whether the individual compounds present in the inventive mixtures are formulated jointly or separately and applied jointly or separately, and, in the case of separate application, in which order the application takes place. It is only necessary, that the individual compounds present in the inventive mixtures are applied in a time frame, which allows simultaneous action of the active ingredients and/or the compound of formula (I) on the undesirable plants.

The glufosinate compositions show a persistent herbicidal activity, even under difficult weathering conditions, which allows a more flexible application in burndown applications and minimizes the risk of weeds escaping. Apart from that, the glufosinate compositions show superior crop compatibility with certain conventional crop plants and with herbicide tolerant crop plants, i.e. their use in these crops leads to a reduced damage of the crop plants and/or does not result in increased damage of the crop plants. Thus, the glufosinate compositions can also be applied after the emergence of the crop plants. The glufosinate compositions may also show an accelerated action on harmful plants, i.e. they may affect damage of the harmful plants more quickly.

Glufosinate compositions are also suitable for controlling weeds that are resistant to commonly used herbicides such as, for example, weeds that are resistant to glyphosate, weeds that are resistant to auxin inhibitor herbicides such as e. g. 2,4-D or dicamba, weeds that are resistant to photosynthesis inhibitors such as e. g. atrazine, weeds that are resistant to ALS inhibitors such as e. g. sulfonylureas, imidazolinones or triazolopyrimidines, weeds that are resistant to ACCase inhibitors such as e. g. clodinafop, clethodim or pinoxaden or weeds that are resistant to protoporphyrinogen-IX-oxidase inhibitors such as e. g. sulfentrazone, flumioxazine, fomesafen or acifluorfen, for example the weeds that are listed in the International Survey of Resistant Weeds (http://www.weedscience.org/Summary/SpeciesbySOATable.aspx). In particular, they are suitable for controlling the resistant weeds that are listed in the International Survey of Resistant Weeds, for example ACCase resistant Echinochloa crusgalli, Avena fatua, Alopecurus myosuroides, Echinochloa colona, Alopecurus japonicus, Bromus tectorum, Hordeum murinum, Ischaemum rugosum, Setaria viridis, Sorghum halepense, Alopecurus aequalis, Apera spicaventi, Avena sterilis, Beckmannia szygachne, Bromus diandrus, Digitaria sanguinalis, Echinocloa oryzoides, Echinochloa phyllopogon, Phalaris minor, Phalaris paradoxa, Setaria faberi, Setaria viridis, Brachypodium distachyon, Bromus diandrus, Bromus sterilis, Cynosurus echinatus, Digitaria insularis, Digitaria ischaemum, Leptochloa chinensis, Phalaris brachystachis, Rotboellia cochinchinensis, Digitaria ciliaris, Ehrharta longiflora, Eriochloa punctata, Leptochloa panicoides, Lolium persicum, Polypogon fugax, Sclerochloa kengiana, Snowdenia polystacha, Sorghum sudanese and Brachiaria plantaginea, ALS inhibitor resistant Echinochloa crusgalli, Poa annua, Avena fatua, Alopecurus myosuroides, Echinochloa colona, Amaranthus hybridus, Amaranthus palmeri, Amaranthus rudis, Conyza sumatrensis, Amaranthus retroflexus, Ambrosia artemisifolia, Conyza canadensis, Kochia scoparia, Raphanus raphanistrum, Senecio vernalis, Alopecurus japonicus, Bidens pilosa, Bromus tectorum, Chenopodium album, Conyza bonariensis, Hordeum murinum, Ischaemum rugosum, Senecio vulgaris, Setaria viridis, Sisymbrium orientale, Sorghum halepense, Alopecurus aequalis, Amaranthus blitum, Amaranthus powellii, Apera spicaventi, Avena sterilis, Brassica rapa, Bromus diandrus, Descurainia sophia, Digitaria sanguinalis, Echinochloa oryzoides, Echinochloa phyllopogon, Euphorbia heterophylla, Lactuca serriola, Phalaris minor, Phalaris paradoxa, Setaria faberi, Setaria viridis, Sinapis arvensis, Solanum ptycanthum, Sonchus oleraceus, Stellaria media, Amaranthus blitoides, Amaranthus spinosus, Amaranthus viridis, Ambrosia trifida, Bidens subalternans, Bromus diandrus, Bromus sterilis, Capsella bursapastoris, Centaurea cyanus, Cynosurus echinatus, Cyperus difformis, Fimbristilis miliacea, Galeopsis tetrahit, Galium aparine, Galium spurium, Helianthus annuus, Hirschfeldia incana, Limnocharis flava, Limnophila erecta, Papaver rhoeas, Parthenium hysterophorus, Phalaris brachystachis, Polygonum convolvulus, Polygonum lapathifolium, Polygonum persicaria, Ranunculus acris, Rottboellia cochinchinensis, Sagittaria montevidensis, Salsola tragus, Schoenoplectus mucronatus, Setaria pumila, Sonchus asper, Xanthium strumarium, Ageratum conyzoides, Alisma canaliculatum, Alisma plantago-aquatica, Ammannia auriculata, Ammannia coccinea, Ammannia arvensis, Anthemis cotula, Bacopa rotundifolia, Bifora radians, Blyxa aubertii, Brassica tournefortii, Bromus japonicus, Bromus secalinus, Lithospermum arvense, Camelina microcarpa, Chamaesyce maculata, Chrysanthemum coronarium, Clidemia hirta, Crepis tectorum, Cuscuta pentagona, Cyperus brevifolis, Cyperus compressus, Cyperus esculentus, Cyperus iria, Cyperus odoratus, Damasonium minus, Diplotaxis erucoides, Diplotaxis tenuifolia, Dopatrum junceum, Echium plantagineum, Elatine triandra, Eleocharis acicularis, Erucaria hispanica, Erysimum repandum, Galium tricornutum, Iva xanthifolia, Ixophorus unisetus, Lamium amplexicaule, Limnophilia sessiliflora, Lindernia dubia, Lindernia micrantha, Lindernia procumbens, Ludwigia prostrata, Matricaria recutita, Mesembryanthemum crystallinum, Monochoria korsakowii, Monochoria vaginalis, Myosoton aquaticum, Neslia paniculata, Oryza sativa var. sylvatica, Pentzia suffruticosa, Picris hieracioides, Raphanus sativus, Rapistrum rugosum, Rorippa indica, Rotala indica, Rotala pusilla, Rumex dentatus, Sagittaria guayensis, Sagittaria pygmaea, Sagittaria trifolia, Schoenoplectus fluviatilis, Schoenoplectus juncoides, Schoenoplectus wallichii, Sida spinosa, Silene gallica, Sinapis alba, Sisymbrium thellungii, Sorghum bicolor, Spergula arvensis, Thlaspi arvense, Tripleurospermum perforatum, Vaccaria hispanica and Vicia sativa, photosynthesis inhibitor resistant Echinochloa crusgalli, Poa annua, Alopecurus myosuroides, Echinochloa colona, Amaranthus hybridus, Amaranthus palmeri, Amaranthus rudis, Conyza sumatrensis, Amaranthus retroflexus, Ambrosia artemisifolia, Conyza canadensis, Kochia scoparia, Raphanus raphanistrum, Senecio vernalis, Alopecurus japonicus, Bidens pilosa, Bromus tectorum, Chenopodium album, Conyza bonariensis, Ischaemum rugosum, Senecio vulgaris, Setaria viridis, Sisymbrium orientale, Amaranthus blitum, Amaranthus powellii, Apera spicaventi, Beckmannia syzigachne, Brassica rapa, Digitaria sanguinalis, Euphorbia heterophylla, Phalaris minor, Phalaris paradoxa, Setaria faberi, Setaria viridis, Sinapis arvensis, Solanum ptycanthum, Stellaria media, Amaranthus blitoides, Amaranthus viridis, Bidens subalternans, Brachypodium distachyon, Capsella bursapastoris, Chloris barbata, Cyperus difformis, Echinochloa erecta, Epilobium ciliatum, Polygonum aviculare, Polygonum convolvulus, Polygonum lapathifolium, Polygonum persicaria, Portulaca oleracea, Schoenoplectus mucronatus, Setaria pumila, Solanum nigrum, Sonchus asper, Urochloa panicoides, Vulpia bromoides, Abutilon theophrasti, Amaranthus albus, Amaranthus cruentus, Arabidopsis thaliana, Arenaria serpyllifolia, Bidens tripartita, Chenopodium album, Chenopodium ficifolium, Chenopodium polyspermum, Crypsis schoenoides, Datura stramonium, Epilobium tetragonum, Galinsoga ciliata, Matricaria discoidea, Panicum capillare, Panicum dichotomiflorum, Plantago lagopus, Polygonum hydopiper, Polygonum pensylvanicum, Polygonum monspeliensis, Rostraria, smyrnacea, Rumex acetosella, Setaria verticillata and Urtica urens, PS-I-electron diversion inhibitor resistant Poa annua, Conyza sumatrensis, Conyza canadensis, Alopecurus japonicus, Bidens pilosa, Conyza bonariensis, Hordeum murinum, Ischaemum rugosum, Amaranthus blitum, Solanum ptycanthum, Arctotheca calendula, Epilobium ciliatum, Hedyotis verticillata, Solanum nigrum, Vulpia bromoides, Convolvulus arvensis, Crassocephalum crepidioides, Cuphea carthagensis, Erigeron philadelphicus, Gamochaeta pensylvanica, Landoltia punctata, Lepidium virginicum, Mazus fauriei, Mazus pumilus, Mitracarpus hirtus, Sclerochloa dura, Solanum americanum and Youngia japonica, glyphosate resistant Poa annua, Echinochloa colona, Amaranthus hybridus, Amaranthus palmeri, Amaranthus rudis, Conyza sumatrensis, Ambrosia artemisifolia, Conyza canadensis, Kochia scoparia, Raphanus raphanistrum, Bidens pilosa, Conyza bonariensis, Hordeum murinum, Sorghum halepense, Brassica rapa, Bromus diandrus, Lactuca serriola, Sonchus oleraceus, Amaranthus spinosus, Ambrosia trifida, Digitaria insularis, Hedyotis verticillata, Helianthus annuus, Parthenium hysterophorus, Plantago lanceolata, Salsola tragus, Urochloa panicoides, Brachiaria eruciformis, Bromus rubens, Chloris elata, Chloris truncata, Chloris virgata, Cynodon hirsutus, Lactuca saligna, Leptochloa virgata, Paspalum paniculatum and Tridax procumbens, microtubule assembly inhibitor resistant Echinochloa crusgalli, Poa annua, Avena fatua, Alopecurus myosuroides, Amaranthus palmeri, Setaria viridis, Sorghum halepense, Alopecurus aequalis, Beckmannia syzigachne and Fumaria densifloria, auxin herbicide resistant Echinochloa crusgalli, Echinochloa colona, Amaranthus hybridus, Amaranthus rudis, Conyza sumatrensis, Kochia scoparia, Raphanus raphanistrum, Chenopodim album, Sisymbrium orientale, Descurainia sophia, Lactuca serriola, Sinapis arvensis, Sonchus oleraceus, Stellaria media, Arctotheca calendula, Centaurea cyanus, Digitaria ischaemum, Fimbristylis miliacea, Galeopsis tetrahit, Galium aparine, Galium spurium, Hirschfeldia incana, Limnocharis flava, Limnocharis erecta, Papaver rhoeas, Plantago lanceolata, Ranunculus acris, Carduus nutans, Carduus pycnocephalus, Centaurea soltitialis, Centaurea stoebe ssp. Micranthos, Cirsium arvense, Commelina diffusa, Echinochloa cruspavonis, Soliva sessilis and Sphenoclea zeylanica, HPPD inhibitor resistant Amaranthus palmeri and Amaranthus rudis, PPO inhibitor resistant Acalypha australis, Amaranthus hybridus, Amaranthus palmeri, Amaranthus retroflexus, Amaranthus rudis, Ambrosia artemisifolia, Avena fatua, Conyza sumatrensis, Descurainia sophia, Euphorbia heterophylla and Senecio vernalis, carotenoid biosynthesis inhibitor resistant Hydrilla verticillata, Raphanus raphanistrum, Senecio vernalis and Sisymbrium orientale, VLCFA inhibitor resistant Alopecurus myosuroides, Avena fatua and Echinochloa crusgalli.

The glufosinate compositions are suitable for combating/controlling common harmful plants in fields, where useful plants shall be planted (i.e. in crops). The inventive mixtures are generally suitable, such as for burndown of undesired vegetation, in fields of the following crops:

Grain crops, including e.g. cereals (small grain crops) such as wheat (Triticum aestivum) and wheat like crops such as durum (T. durum), einkorn (T. monococcum), emmer (T. dicoccon) and spelt (T. spelta), rye (Secale cereale), triticale (Tritiosecale), barley (Hordeum vulgare); maize (corn; Zea mays); sorghum (e.g. Sorghum bicolour); rice (Oryza spp. such as Oryza sativa and Oryza glaberrima); and sugar cane;

Legumes (Fabaceae), including e.g. soybeans (Glycine max.), peanuts (Arachis hypogaea and pulse crops such as peas including Pisum sativum, pigeon pea and cowpea, beans including broad beans (Vicia faba), Vigna spp., and Phaseolus spp. and lentils (lens culinaris var.);

brassicaceae, including e.g. canola (Brassica napus), oilseed rape (OSR, Brassica napus), cabbage (B. oleracea var.), mustard such as B. juncea, B. campestris, B. narinosa, B. nigra and B. tournefortii; and turnip (Brassica rapa var.);other broadleaf crops including e.g. sunflower, cotton, flax, linseed, sugarbeet, potato and tomato;

TNV-crops (TNV: trees, nuts and vine) including e.g. grapes, citrus, pomefruit, e.g. apple and pear, coffee, pistachio and oilpalm, stonefruit, e.g. peach, almond, walnut, olive, cherry, plum and apricot;

turf, pasture and rangeland;

onion and garlic;

bulb ornamentals such as tulips and narcissus;

conifers and deciduous trees such as pinus, fir, oak, maple, dogwood, hawthorne, crabapple, and rhamnus (buckthorn); andgarden ornamentals such as roses, petunia, marigold and snapdragon.

In one embodiment, the method for controlling undesired vegetation is applied in cultivated rice, maize, pulse crops, cotton, canola, small grain cereals, soybeans, peanut, sugarcane, sunflower, plantation crops, tree crops, nuts or grapes. In another embodiment, the method is applied in cultivated crops selected from glufosinate-tolerant crops.

The glufosinate agrochemical compositions are in particular suitable for burndown of undesired vegetation in fields of the following crop plants: small grain crops such as wheat, barley, rye, triticale and durum, rice, maize (corn), sugarcane, sorghum, soybean, pulse crops such as pea, bean and lentils, peanut, sunflower, sugarbeet, potato, cotton, brassica crops, such as oilseed rape, canola, mustard, cabbage and turnip, turf, pasture, rangeland, grapes, pomefruit, such as apple and pear, stonefruit, such as peach, almond, walnut, pecans, olive, cherry, plum and apricot, citrus, coffee, pistachio, garden ornamentals, such as roses, petunia, marigold, snap dragon, bulb ornamentals such as tulips and narcissus, conifers and deciduous trees such as pinus, fir, oak, maple, dogwood, hawthorne, crabapple and rhamnus.

The glufosinate compositions are most suitable for burndown of undesired vegetation in fields of the following crop plants: small grain crops such as wheat, barley, rye, triticale and durum, rice, maize, sugarcane, soybean, pulse crops such as pea, bean and lentils, peanut, sunflower, cotton, brassica crops, such as oilseed rape, canola, turf, pasture, rangeland, grapes, stonefruit, such as peach, almond, walnut, pecans, olive, cherry, plum and apricot, citrus and pistachio.

The PPO-compositions are generally applied to row crops and specialty crops. Examples of row crops include soybeans, corn, canola, cotton, cereals or rice, but as well sunflower, potato, dry bean, field pea, flax, safflower, buckwheat and sugar beets. Preferred crops for the application methods with PPO-compositions are corn, soy, sunflower, rice, cereals and sugarcane.

Specialty crops are to be understood as fruits, vegetables or other specialty or plantation permanent crops such as trees, nuts, vines, (dried) fruits, ornamentals, oil palm, banana, rubber and the like, Horticulture and nursery crops, including floriculture, may also fall under the definition of specialty crops. Vegetable crops includes for example aubergine, beans, bell pepper, cabbage, chili, cucum-ber, eggplant, lettuce, melon, onion, potato, sweet potato, spinach and tomato. Plants being considered specialty crops are in general intensively cultivated. For weed control in vegetable crops, it may be desirable to shield the crops from contact with the spray solution that contains the herbicidal mixture according to the present invention.

In general, the crops which may be treated, may be of conventional origin or may be herbicide tolerant crops, preferably PPO-inhibitor tolerant crops. Typically, the PPO-tolerant crop has a tolerance against the PPO-inhibitor that is present in the PPO-composition.

Preferred crops, which are tolerant to PPO-inhibitors, are selected from the group consisting of rice, sugarcane, sunflower, cereals (e.g. wheat, barley, sorghum, mullet, oats, rye, triticae), rapeseed corn, soybean, canola and cotton, more preferably from soybean, corn, cotton, rice, sunflower, most preferably soybean, cotton, rapeseed and corn.

In general, the crops which may be treated with the PPO-composition, may be of conventional origin or may be herbicide tolerant crops, preferably PPO-inhibitor tolerant crops.

In a preferred embodiment, the PPO-composition is applied once, twice or three times per Gregorian calendar year, i.e. in one application, in two applications or in three applications per year according to the Gregorian calendar. In a preferred embodiment, the PPO-composition is applied twice per Gregorian calendar year, i.e. in two applications per year according to the Gregorian calendar. In an alternatively preferred embodiment, the glufosinate composition is applied one time per Gregorian calendar year, i.e. in one application per year according to the Gregorian calendar. In a preferred embodiment, the PPO-composition is applied one time in about 12 months, i.e. in one application in about 12 months. In an alternative preferred embodiment, the PPO-composition is applied between one and ten times per Gregorian calendar year, i.e. in up to ten applications per year according to the Gregorian calendar. This alternative preferred method is of particular usefulness in permanent crops, in particular those grown under tropical conditions; in which case weeds grow vigorously at any time of the year, and herbicide applications are to be re-peated as soon as the previous treatment loses its effectiveness and weeds start to regrow.

The PPO-compositions are preferably used in post-emergence applications.

The invention includes the use and methods of application of the herbicidal composition for controlling undesirable vegetation in crops, preferably in a burndown program. In one embodiment, the herbicidal composition is applied to a locus before the seeding of a desired crop plant but after the emergence of the undesired vegetation.

Therefore, the present invention also relates to a method for burndown treatment of undesirable vegetation in crops, comprising applying the herbicidal composition, to a locus where crops will be planted before planting (or seeding) or emergence of the crop. Herein, the herbicidal composition is applied undesirable vegetation or the locus thereof.

In burndown programs, the herbicidal composition(s) can be applied prior to seeding (planting) or after seeding (or planting) of the crop plants but before the emergence of the crop plants, in particular prior to seeding. The herbicidal compositions are preferably applied prior to seeding of the crop plants. For burndown, the herbicidal composition(s) will generally be applied a date up to 9 months, frequently up to 6 months, preferably up to 4 months prior to planting the crop. The burndown application can be done at a date up to 1 day prior to emergence of the crop plant and is preferably done at a date prior to seeding/planting of the crop plant, preferably at a date of at least one day, preferably at least 2 days and in particular at least one 4 days prior to planting or from 6 months to 1 day prior emergence, in particular from 4 months to 2 days prior emergence and more preferably from 4 months to 4 days prior emergence. It is, of course, possible to repeat the burndown application once or more, e.g. once, twice, three times, four times or five times within that time frame.

It is a particular benefit of the herbicidal compositions that they have a very good post-emergence herbicide activity, i.e. they show a good herbicidal activity against emerged undesirable plants. Thus, in a preferred embodiment of invention, the herbicidal compositions are applied post-emergence, i.e. during and/or after, the emergence of the undesirable plants. It is particularly advantageous to apply the herbicidal composition post emergent when the undesirable plant starts with leaf development up to flowering. The herbicidal compositions are particularly useful for controlling undesirable vegetation which has already developed to a state, which is difficult to control with conventional burndown mixtures, i.e. when the individual weed is taller than 10 cm (4 inches) or even taller than 15 cm (6 inches) and/or for heavy weed populations. In the case of a post-emergence treatment of the plants, the herbicidal compositions are preferably applied by foliar application.

The herbicidal compositions show a persistent herbicidal activity, even under difficult weathering conditions, which allows a more flexible application in burndown applications and minimizes the risk of weeds escaping. Apart from that, the herbicidal compositions show superior crop compatibility with certain conventional crop plants and with herbicide tolerant crop plants, i.e. their use in these crops leads to a reduced damage of the crop plants and/or does not result in increased damage of the crop plants. Thus, the herbicidal compositions can also be applied after the emergence of the crop plants. The herbicidal compositions may also show an accelerated action on harmful plants, i.e. they may affect damage of the harmful plants more quickly.

The herbicidal compositions are suitable for combating/controlling common harmful plants in fields, where useful plants shall be planted (i.e. in crops). The herbicidal compositions are generally suitable, such as for burndown of undesired vegetation, in fields of the following crops: soybean, cotton, cereals (corn, rice, barley, wheat, maize, millet, etc.) canola, and sunflower, in particular soybean and cereals.

In another embodiment, the herbicidal composition is applied to a locus after the seeding of a desired crop plant, wherein the desired crop plant is tolerant to the PPO-inhibitor contained in the herbicidal composition, preferably wherein the undesired vegetation has already emerged.

Accordingly, the invention includes the use and methods of application of the herbicidal composition for controlling undesirable vegetation in crops in a burndown program, wherein the crop is produced by genetic engineering or by breeding, are resistant to one or more herbicides and/or pathogens such as plant-pathogenous fungi, and/or to attack by insects; preferably tolerant to PPO-inhibitors, and in particular to the PPO-inhibitor contained in the herbicidal composition.

Preferred are methods of application wherein the crop is produced by genetic engineering or by breeding, are tolerant to one or more herbicides and/or resistant to pathogens such as plant-pathogenous fungi, and/or to attack by insects; preferably tolerant to PPO-inhibitors as mentioned herein.

Preferred are crops, which are tolerant to PPO-inhibitors, wherein the PPO-tolerant crop plant is preferably selected from the group consisting of rice, sugarcane, sunflower, cereals (e.g. wheat, barley, sorghum, mullet, oats, rye, triticae), corn, cotton, rapeseed, and soy.

In crops such as soybean, cotton, oilseed rape, flax, lentils, rice, sugar beet, sunflower, tobacco and cereals, such as, for example maize or wheat, the PPO-compositions are typically used against broad-leaved weeds and grass weeds and provide for less damage to the crop plants in comparison with conventional formulations of PPO-inhibitors. This effect is particularly observed at low application rates.

Depending on the application method in question, the PPO-compositions can additionally be employed in a further number of crop plants to remove undesired plants.

Crops which are suitable are, for example, the following: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus, var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N. rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus armeniaca, Prunus avium, Prunus cerasus, Prunus dulcis, Prunus domesticua, Prunus persica, Pyrus communis, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.

Moreover, it has been found that the PPO-compositions are also suitable for the defoliation and desiccation of plant parts, for which crops plants such as cotton, potato, oilseed rape, sunflower, soybean or field beans, in particular cotton, are suitable.

As desiccants, the PPO-compositions are particularly suitable for desiccating the aerial parts of crop plants such as potato, oilseed rape, sunflower and soybean. This makes possible the fully mechanical harvesting of these important crop plants. Also of economic interest is to facilitate harvesting, which is made possible by concentrating within a certain period of time the dehiscence, or reduction of adhesion to the tree, in citrus fruit, olives or other species and varieties of pome fruit, stone fruit and nuts. The same mechanism, i.e. the promotion of the development of abscission tissue between fruit part or leaf part and shoot part of the plants is also essential for the controlled defoliation of useful plants, in particular cotton.

Moreover, a shortening of thetime interval within which the individual cotton plants mature leads to an increased fiber quality after harvesting.

Moreover, it has been found that the PPO-compositions of the invention are also suitable for

the control of conifers, in particular of conifer seedlings which grow naturally, and specifically for the control of pine seedlings which grow naturally.

The PPO-compositions have an outstanding herbicidal activity against a broad spectrum of economically important harmful monocotyledonous and dicotyledonous harmful plants. Also here, post-emergence application is preferred.

Specifically, examples may be mentioned of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the combinations according to the invention, without the enumeration being a restriction to certain species.

Examples of monocotyledonous harmful plants on which the herbicidal compositions act efficiently are selected from Cenchrus pauciflorus, Chloris spp. (e.g. Chloris virgata), Commelina erecta, Cynodon dactylon, Cyperus spp, Sorghum halepense, Trichloris crinita, Zea mays (Volunteer), Cenchrus echinatus, Commelina benghalensis, Pennisetum americanum, Digitaria spp (e.g. Digitaria insularis, Digitaria sanguinalis, Digitaria horizontalis, Digitaria nuda), Panicum spp (e.g. Panicum maximum, Panicum dichotomiflorum, Panicum fasciculatum), Eleusine indica, Lolium spp (e.g. Lolium multiflorum), Urochloa or Brachiaria spp. (e.g. Urochloa or Brachiaria platyphylla, Urochloa or Brachiaria plantaginea, Urochloa or Brachiaria plantaginea (Link) R. D. Webster, Urochloa or Brachiaria decumbens), Dactyloctenium aegyptium, Commelina communis, Rottboellia cochinchinensis, Setaria spp. (e.g. Setaria viridis, Setaria faberi, Setaria verticillata, Setaria glauca or pumila) Elymus repens, Leptochloa spp (e.g. Leptochloa filiformis, Leptochloa fascicularis, Leptochloa chinensis, Leptochloa panicoides), Echinochloa spp. (e.g. Echinochloa colona, Echinochloa oryzicola, Echinochloa cruspavonis, Echinochloa crusgalli, Echinochloa cruspavonis (Kunth) J. A. Schultes, Echinochloa walteri (Pursh) Heller, Echinochloa colonum), Leersia japonica, Ischaemum rogusum, Oryza sativa, Leerisa hexandra, Oryza latifolia, Hordeum spontaneum, Rottboellia exaltata, Luziola subintegra, Paspalum spp. (e.g. Paspalum distichum), Oryza rufipogon, Alopecurus japonicus Steud, Alopecurus aequalis Sobol, Alopecurus myosuroides, Apera spicaventi, Avena spp, (e.g. Avena fatua L., Avena sterillis, Avena strigose), Aegilops tauschii Coss, Aegilops cylindrica, Sclerochloa kengiana (Ohwi) Tzvel., Beckmannia syzigachne (Steud.) Fernald, Lolium multiflorum Lam, Poa trivialis L., Ploypogon fugax. N., Phleum paniculatum, Puccinellia distans, Lolium rigidum, Urochloa panicoides, Bromus spp. (e.g. Bromus sterilis, Bromus japonicus Thunb, Bromus tectorum) Hordeum leporinum, Phalaris spp. (e.g. Phalaris minor, Phalaris brachystachys, Phalaris persicaria), Poa annua, Agrostis alba, Agropyron repens, Lolium perenne, Phragmites australia, Imperata cylindrica, Poa spp, Lolium persicum, Hordeum jubatum, Secale cereale, Rotboellia conchrinchinensis (Lour.) W. D. Clayton, Urochloa ramosa (L.) Nguyen, Murdannia nudiflora (L.) Brenan, Sorghum almum, Pennisetum purpureum, Echnichloa colonum, Ixophorus unisetus, Commelina diffusa.

In a preferred embodiment, the herbicidal compositions are used to control monocotyledonous harmful plant species, more preferably Zea mays (Volunteer), Cenchrus echinatus, Avena strigose, Pennisetum americanum, Panicum maximum, Digitaria spp (e.g. Digitaria insularis, Digitaria horizontalis, Digitaria nuda), Eleusine indica, Lolium spp. (e.g. Lolium multiflorum), Urochloa or Brachiaria spp. (e.g.Urochloa or Brachiaria plantaginea, Urochloa or Brachiaria plantaginea (Link) R. D. Webster, Urochloa or Brachiaria decumbens), Ischaemum rogusum, Oryza sativa, Echinochloa colona, Leerisa hexandra, Leptochloa spp. (e.g. Leptochloa panicoides), Rottboellia cochichinensis or exaltata, Avena spp. (e.g. Avena fatua L), Lolium spp. (e.g. Lolium multiflorum Lam), Cynodon dactylon (L.) Pers., and Chloris spp.

Examples of dicotyledonous harmful plants on which the herbicidal compositions act efficiently are selected Amaranthus spp. (e.g. Amaranthus palmeri, Amaranthus hybridus, Amaranthus spinosus, Amaranthus lividus, Amaranthus tuberculatus/rudis, Amaranthus quitensis, Amaranthus retroflexus), Chenopodium spp. (e.g. Chenopodium album, Chenopodium quinoa, Chenopodium serotinum, Ambrosia artemisiifolia, Ambrosia trifida, Kochia scoparia, Conyza canadensis, Helianthus annuus, Helianthus theophrasti, Borreria spp. (e.g. Borreria verticillata), Brassica rapa, Carduus acanthoides, Malva neglecta, Parietaria debilis, Portulaca oleracea, Raphanus spp. (e.g. Raphanus raphanistrum, Raphanus sativus L. var sativus), Conyza bonariensis, Ipomoea spp. (e.g. Ipomoea grandifolia, Ipomoea indivisa, Ipomoea hederacea, Ipomoea lacunosa, Ipomoea wrightii, Ipomoea lonchophylla), Bidens pilosa, Senna obtusifolia, Sida spp. (e.g. Sida rhombifolia, Sida spinosa L.), Spermacoce latifolia, Tridax procumbens, Parthenium hysterophorus, Acalypha australis, Sinapsis arvensis, Ammi majus, Atriplex spp. (e.g. Atriplex patula), Matricaria spp. (e.g. Matricaria inodora, Matricaria chamomilla), Galinsoga spp, Orobanche spp, Papaver rhoeas, Mercurialis annua, Convolvulus arvensis, Cirsium arvense, Calystegia sepium, Stellaria media, Galium aparine, Lamium spp. (e.g. Lamium amplexicaule), Viola spp. (e.g. Viola arvensis), Datura stramonium, Xanthium spp., Celosia argentea, Melampodium divaricatum, Cleome viscosa, Molugo verticilatus, Borhevia erecta, Gomphrena spp., Nicandra physalodes, Ricinus communis, Monochoria vaginalis, Eichhornia crassipes, Linderina pyxidaria L., Lindernia dubia, Rotala indica, Eclipta prostrata, Bidens frondosa, Aneilema keisak, Sagittaria pygmaea Miq., Sagittaria trifolia L., Potamogeton distinc, Alisma canaliculatum, Sphenoclea zeylanica, Jussiaea spp., Monochoria hastata, Heteranthera limosa, Ammannia spp. (e.g. Ammannia coccinea), Alisma plantago-aquatica, Sagittaria montevidensis, Echinodorus grandiflorus, Aeschynomene spp. (e.g. Aeschynomene rudis, Aeschynomene denticulata, Aeschynomene indica), Eclipta alba, Ludwigia spp. (e.g. Ludwigia octovallis), Caperonia palustris, Murdannia nudiflora, Limnocharis flava, Pistia stratiotes, Rotala ramosior, Sesbania herbacea, Macroptilium lathyroides, Macropthilium lathyroides, Cyperus odoratus, Alternanthera philoxeroides, Alternanthera tenella, Bacopa rotundifolia, Caperonia castaneifolia, Eleocharis spp., Lindernia pyxidaria, Physalis spp., Sagittaria sagittifolia, Sesbania exaltata, Galium aparine L, Descuminia sophia (L.), Capsella bursapastoris(L.) Medic, Stellaria media (Linn.), Malachium aquaticum (L.), Sonchus spp. (e.g. Sonchus oleraceus, Sonchus arvensis, Sonchus asper), Polygonum spp. (e.g. Polygonum persicaria, Polygonum convolvulus, Polygonum aviculare, Polygonum pensylvanicum), Fallopia convulvulus, Eigerone bonariensis, Rumex dentatus, Corynopus didymus, Melilotus sp, Midicago sativus, Malwa parviflora, Anagallis arvensis, Capsella media, Rorippa islandica, Rumex obtusifolius, Glycine max, Sisymbrium spp. (e.g. Sisymbrium officinale), Silene gallica, Spergula arvensis, Anthemis cotula, Anthemis arvensis, Crepis capillarisLitospermum arvense, Cephalanoplos segetum, Geranium spp. (e.g. Geranium donianum Sweet., Geranium pusillum, Geranium dissectum), Leucas chinensis, Arenaria serpyllifolia, Anacamtodon fortunei Mitt., Solanum spp. (e.g. Solanum nigrum), Trianthema spp. (e.g. Trianthema portulacastrum), Euphorbia spp. (e.g. Euphorbia hirta, Euphorbia helioscopia Linn, Euphorbia dentata, Euphorbia heterophylla), Vicia sativa, Lathyrus aphaca, Asphodelus tenuifolius, Brassica kaber, Argemone mexicana, Launea mudicaulis, Centaurea cyanus, Sinapis arvensis, Tripleurospermum inodorum, Senecio vulgaris, Salsola tragus, Lactuca serriola, Brassica napus, Thlaspi arvense, Crepis tectorum, Myosotis arvensis, Equisetum arvense, Descurainia pinnata, Veronica spp. (e.g., Veronica persica, Veronica polita Fries), Mucuna spp., Momordica charantia, Merremia aegyptia, Commelina benghalensis Kallstroemia maxima, Croton lobatus, Melampodium divaricatum, Oxalis neaei, Richardia scabra, Phylanthus sp, Sicyos polyacanthus.

Preferred examples of dicotyledonous harmful plants on which the herbicidal compositions act efficiently are Ipomoea spp. (e.g. Ipomoea grandifolia), Mucuna spp, Ricunus communis, Mormordica charantia, Merremia aegyptia, Senna obtusifolia, Commelina benghalensis, Amaranthus spp. (e.g. Amaranthus quitensis), Conyza bonariensis, Bidens pilosa, Euphorbia heterophylla, Sida spp, Spermacoce latifolia, Tridax procumbens, Borreria verticillata, Sagittaria motevidensis, Lidwigia octovallis, Aeschynomene rudis, Echinodorus grandiflorus, Alternanthera philoxeroides, Raphanus raphanistrum, Glycine max, Raphanus sativus L. var sativus.

Herbicidal compositions are also suitable for controlling a large number of annual and perennial sedge weeds including Cyperus esculentus, Cyperus rotundus, Cyperus odoratus, Cyperus flavus, Cyperus iria, Cyperus ferax, Eleocharis acicularis, Cyperus spp., Scirpus or Bolboschoenus maritimus, Scirpus or Schoenoplectus mucronatus, Cyperus difformis L., Scirpus juncoides Roxb, Cyperus serotinus Rottb., Eleocharis kuroguwai, Scirpus juncoides, Cyperus iria, Fimbristylis miliacea, Scirpus grossus, Cyperus ferax, Cyperus lanceolatus, Fimbristylis dichotoma, Scirpus planiculmis Fr. Schmidt, Cyperus odoratus, and Cyperus difformis

Preferred examples of sedge weeds on which the herbicidal compositions act efficiently are Cyperus spp, Cyperus difformus L., Cyperus iria, Cyperus ferax, Cyperus esulentus, and Cyperus lanceolatus.

If the PPO-combinations are applied post-emergence to the green parts of the plants, growth likewise stops drastically a very short time after the treatment and the weed plants remain at the growth stage of the point of time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the crops, is eliminated at a very early point in time and in a sustained manner.

The PPO-compositions are characterized by a rapidly commencing and long-lasting herbicidal action. As a rule, the rainfastness of the active compounds in the herbicide combinations according to the present invention is advantageous. In particular when the glufosinate compositions are employed application rates may be reduced, a broader spectrum of broad-leaved weeds and grass weeds maybe controlled, the herbicidal action may take place more rapidly, the duration of action may be longer, the harmful plants may be controlled better while using only one, or few, applications, and the application period which is possible to be extended.

The abovementioned properties and advantages are of benefit for weed control practice to keep agricultural crops free from undesired competing plants and thus to safeguard and/or increase the yields from the qualitative and/or quantitative point of view. These PPO-compositions markedly exceed the technical state of the art with a view to the properties described.

Owing to their herbicidal and plant-growth-regulatory properties, the PPO-compositions can be employed for controlling harmful plants in genetically modified crops or crops obtained by mutation/selection. These crops are distinguished as a rule by particular, advantageous properties, such as resistances to herbicidal compositions or resistances to plant diseases or causative agents of plant diseases such as particular insects or microorganisms such as fungi, bacteria or viruses. Other particular properties relate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. Thus, for example, transgenic plants are known whose starch content is increased or whose starch quality is altered, or those where the harvested material has a different fatty acid composition.

The present invention also relates to a method of controlling undesired vegetation (e.g. harmful plants), which comprises applying the PPO-compositions, preferably by the post-emergence method, to harmful or undesired plants, parts of said harmful or undesired plants, or the area where the harmful or undesired plants grow, for example the area under cultivation.

In the context of the present invention “controlling” denotes a significant reduction of the growth of the harmful plant(s) in comparison to the untreated harmful plants. Preferably, the growth of the harmful plant(s) is essentially diminished (60-79%), more preferably the growth of the harmful plant(s) is largely or fully suppressed (80-100%), and in particular the growth of the harmful plant(s) is almost fully or fully suppressed (90-100%).

Thus, in a further aspect, the present invention relates to a method for controlling undesired plant growth, and/or controlling harmful plants, comprising the step of applying the PPO-composition (preferably in one of the preferred embodiments defined herein) onto the undesired plants or the harmful plants, on parts of the undesired plants or the harmful plants, or on the area where the undesired plants or the harmful plants grow.

The PPO-compositions are also suitable for controlling weeds that are resistant to commonly used herbicides such as, for example, weeds that are resistant to glyphosate, weeds that are resistant to auxin inhibitor herbicides such as e. g. 2,4-D or dicamba, weeds that are resistant to photosynthesis inhibitors such as e. g. atrazine, weeds that are resistant to ALS inhibitors such as e. g. sulfonylureas, imidazolinones or triazolopyrimidines, weeds that are resistant to ACCase inhibitors such as e. g. clodinafop, clethodim or pinoxaden or weeds that are resistant to protoporphyrinogen-IX-oxidase inhibitors such as e. g. sulfentrazone, flumioxazine, fomesafen or acifluorfen, for example the weeds that are listed in the International Survey of Resistant Weeds (http://www.weedscience.org/Summary/SpeciesbySOATable.aspx), preferably weeds that are resistant to PPO-inhibitors.

Accordingly, the present invention also provides a method for controlling the growth of PPO resistant weeds, which comprises contacting such weeds, parts of it, its propagation material or its habitat with the PPO-composition wherein the PPO resistant weeds are weeds, that are resistant to PPO-inhibiting herbicides and compositions containing them, except for PPO-composition.

The invention particularly relates to a method for controlling PPO resistant weeds in crops which comprises applying the PPO-composition to crops, where said PPO herbicide resistant weeds occur or might occur.

The term “PPO resistant weed” refer to a plant that, in relation to a treatment with an appropriate or over-appropriate rate of PPO-inhibiting herbicide application, has inherited, developed or acquired an ability 1) to survive that treatment, if it is one that is lethal to (i.e. eradicates) the wild type weed; or 2) to exhibit significant vegetative growth or thrive after that treatment, if it is one that suppresses growth of the wild-type weed.

Effective weed control is defined as at least 70% weed suppression or eradication from the crop, or as at least 70% weed plant phototoxicity, as determined 2 weeks after treatment.

Thus, PPO resistant weeds are weeds, which are not controlled by the application of PPO inhibitors or compositions containing them except for the herbicidal composition, whereas the respective sensitive biotype is controlled at that use rate.

Here, “not controlled” means that in a visual rating the weed control (herbicidal effect) is <70% of weed suppression or eradication as determined 2 weeks after treatment; and “controlled” means that in a visual rating the weed control is >90% of weed suppression or eradication as determined 2 weeks after treatment.

Preferably, PPO resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is <70% of weed suppression or eradication as determined 2 weeks after treatment) by the application of PPO-inhibiting herbicides or compositions containing them except for the herbicidal composition.

Also preferably, PPO resistant weeds are weeds, which are not controlled (i.e. in a visual rating the weed control is <70% of weed suppression or eradication as determined 2 weeks after treatment) by the application rate of 200 g/ha or lower, particularly preferred 100 g/ha or lower, especially preferred 50 to 200 g/ha, more preferred 50 to 100 g/ha, of PPO-inhibiting herbicides or compositions containing them except the herbicidal composition, whereas the respective sensitive biotype is controlled (i.e. in a visual rating the weed control is >90% of weed suppression or eradication as determined 2 weeks after treatment) at that use rate.

Also preferably PPO-resistant weeds are those classified as being “PPO resistant” and thus listed according to Anonymous: List of herbicide resistant weeds by herbicide mode of action—weeds resistant to PPO-inhibitors (URL: http://www.weedscience.org/summary/MOA.aspx).

Particularly preferred the PPO resistant weeds are selected from the group consisting of Acalypha ssp., Amaranthus ssp., Ambrosia ssp., Avena ssp., Conyza ssp., Descurainia ssp., Eleusine spp., Euphorbia ssp., Lolium spp., and Senecio ssp.; especially preferred Amaranthus ssp., Ambrosia ssp. and Euphorbia ssp.; more preferred Amaranthus ssp. and Ambrosia ssp.

The PPO-compositions are particularly useful to combat PPO-resistant weeds that are resistant to PPO-inhibitors in general, such as Acalypha austrails, Amaranthus hybridus, Amaranthus palmeri, Amaranthus retroflexus, Amaranthus tuberculatus, Ambrosia artemisifolia, Avena fatua, Conyza sumatrensis, Descurainia sophia, Eleusine indica, Euphorbia heterophylia, Lolium rigidum, and Senecio vernalis.

Also particularly preferred the PPO resistant weeds are selected from the group consisting of

Asian copperleaf Amaranthus rudis, Conyza ambigua, Conyza Canadensis, Descurainia Sophia.

Most PPO resistant weeds, in particular the biotypes of Amaranthus tuberculatus, are resistant due to a codon deletion on the nuclear-encoded gene PPX2L that codes for the PPO enzyme which is dual-targeted to the mitochondria and the chloroplasts. This results in a loss of the glycine amino acid in position 210 (see e.g. B. G. Young et al, Characterization of PPO-Inhibitor-Resistant Waterhemp (Amaranthus tuberculatus) Response to Soil-Applied PPO-Inhibiting Herbicides, Weed Science 2015, 63, 511-521).

A second type of mutation, in particular in a resistant biotype of Ambrosia artemisiifolia, was identified as a mutation that expressed a R98L change of the PPX2 enzyme (S. L. Rousonelos, R. M. Lee, M. S. Moreira, M. J. VanGessel, P. J. Tranel, Characterization of a Common Ragweed (Ambrosia artemisiifolia) Population Resistant to ALS- and PPO-Inhibiting Herbicides, Weed Science 60, 2012, 335-344).

Accordingly, preferably PPO-resistant weeds are weeds whose Protox enzyme is resistant to the application of PPO inhibitors due to a mutation that is expressed as a ΔG210 or R98L change of said Protox enzyme or equivalents to the PPX2L or PPX2 respectively, in particular that is expressed as a ΔG210 or R98L change of said Protox enzyme.

The PPO-compositions are useful for combating undesired vegetation. For this purpose, the PPO-compositions may be applied as such or are preferably applied after dilution with water. Preferably, for various purposes of end user application, a so-called aqueous spray-liquor is prepared by diluting the compositions of the present invention with water, e.g. tap water. The spray-liquors may also comprise further constituents in dissolved, emulsified or suspended form, for example fertilizers, active substances of other groups of herbicidal or growth-regulatoryactive substances, further active substances, for example active substances for controlling animal pests or phytopathogenic fungi or bacteria, furthermore mineral salts which are employed for alleviating nutritional and trace element deficiencies, and nonphytotoxic oils or oil concentrates. As a rule, these constituents are added to the spray mixture before, during or after dilution of the PPO-compositions according to the invention. The compositions of the invention can be applied by the pre-emergence or the post-emergence method. If the PPO-inhibitor is less well tolerated by certain crop plants, application techniques may be employed where the herbicidal compositions are sprayed, with the aid of the spraying apparatus, in such a way that the leaves of the sensitive crop plants ideally do not come into contact with them, while the activesubstances reach the leaves of undesired plants which grow underneath, or the bare soil surface (post-directed, lay-by).

Depending on the aim of the control measures, the season, the target plants and the growth stage, the compositions of the invention are applied to such a degree that the application rates of the PPO-inhibitor are from 0.001 to 3.0, preferably from 0.01 to 1.0 kg/ha.

The invention also relates to an adjuvant solution comprising a compound of formula (I) (preferably from 40 to 95 wt % of the compound of formula (I), an organic solvent, and preferably up to 5 wt % of water. In one embodiment, the adjuvant solution comprises a compound of formula (I), wherein M⁺ is a monoethanolammonium cation, and more than 10 wt % of an organic solvent.

The adjuvant solution may contain up to 5 wt % of water, preferably up to 2 wt %, more preferably up to 1 wt %, most preferably up to 0.5 wt %. In one embodiment, the adjuvant solution does not contain water.

The adjuvant composition may comprise from 40 to 95 wt % of the compound of formula (I). The adjuvant composition may comprise the compound of formula (I) at a concentration of at least 50 wt %, preferably at least 60 wt %, more preferably at least 70 wt %, most preferably at least 75 wt %, especially preferably at least 80 wt %, and in particular at least 83 wt %, such as at least 85 wt %. The adjuvant composition may comprise the compound of formula (I) at a concentration of up to 90 wt %, preferably up to 88 wt %, more preferably up to 85 wt %. Typically, the adjuvant composition comprises the compound of formula (I) at a concentration of from 40 to 95 wt %, preferably from 55 to 90 wt %, more preferably from 65 to 90 wt %, most preferably from 75 to 90 wt %.

The adjuvant solution comprises an organic solvent. The organic solvent typically has a water-solubility of at least 1 wt % at 20° C., preferably at least 5 wt % at 20° C., more preferably at least 10 wt % at 20° C., most preferably at least 20 wt % at 20° C. The adjuvant solution typically comprises the organic solvent in a concentration of at least 5 wt %, preferably more than 10 wt %, most preferably at least 15 wt %, such as at least 20 wt %. The adjuvant solution may comprise the organic solvent in a concentration of up to 50 wt %, preferably up to 40 wt %, more preferably up to 35 wt %, most preferably up to 30 wt %, such as up to 25 wt %, especially up to 20 wt %.

Suitable organic solvents are aliphatic hydrocarbons, preferably an aliphatic C₅-C₁-hydrocarbon, more preferably a C₅-C₁₆-alkane, or C₅-C₁₆-cycloalkane, such as pentane, hexane, cyclohexane, or petrol ether; aromatic hydrocarbons, preferably an aromatic C₆-C₁₀-hydrocarbons, such as benzene, toluene, o-, m-, and p-xylene; halogenated hydrocarbons, preferably halogenated aliphatic C₁-C₆-alkanes, or halogenated aromatic C₆-C₁₀-hydrocarbons, such as CH₂Cl₂, CHCl₃, CCl₄, CH₂ClCH₂Cl, CCl₃CH₃, CHCl₂CH₂Cl, CCl₂CCl₂, or chlorobenzene; ethers, preferably C₁-C₆-cycloalkyl ethers, C₁-C₆-alkyl-C₁-C₆-alkyl ethers and C₁-C₆-alkyl-C₆-C₁₀-aryl ethers, such as CH₃CH₂OCH₂CH₃, (CH₃)₂CHOCH(CH₃)₂, CH₃OC(CH₃)₃ (MTBE), CH₃OCH₃ (DME), CH₃OCH₂CH₂OCH₃, dioxane, anisole, and tetrahydrofurane (THF); esters, preferably esters of aliphatic C₁-C₆-alcohols with aliphatic C1-C₆-carboxylic acids, esters of aromatic C₆-C₁₀-alcohols with aromatic C₆-C₁₀-carboxylic acids, cyclic esters of ω-hydroxy-C₁-C₆-carboxylic acids, such as CH₃C(O)OCH₂CH₃, CH₃C(O)OCH₃, CH₃C(O)OCH₂CH₂CH₂CH₃, CH₃C(O)OCH(CH₃)CH₂CH₃, CH₃C(O)OC(CH₃), CH₃CH₂CH₂C(O)OCH₂CH₃, CH₃CH(OH)C(O)OCH₂CH₃, CH₃CH(OH)C(O)OCH₃, CH₃C(O)OCH₂CH(CH₃)₂, CH₃C(O)OCH(CH₃)₂, CH₃CH₂C(O)OCH₃, benzyl benzoate, and γ-butyrolactone; carbonates, such as ethylene carbonate, propylene carbonate, CH₃CH₂OC(O)OCH₂CH₃, and CH₃OC(O)OCH₃; nitriles, preferably C1-C₆-nitriles, such as CH₃CN, and CH₃CH₂CN; ketones, preferably C₁-C₆-alkyl-C₁-C₆-alkyl ketones, such as CH₃C(O)CH₃, CH₃C(O)CH₂CH₃, CH₃CH₂C(O)CH₂CH₃, and CH₃C(O)C(CH₃)₃ (MTBK); alcohols, preferably C₁-C₄-alcohols, such as CH₃OH, CH₃CH₂OH, CH₃CH₂CH₂OH, CH₃CH(OH)CH₃, CH₃(CH₂)₃OH, C(CH₃)₃OH, propylene glycol, dipropylene glycol, propylene glycol monomethylether (1-methoxy-2-propanol); amides and urea derivatives, preferably dimethyl formamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethyl acetamide (DMA), 1,3-dimethyl-2-imidazolidinone (DMI), 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU), hexamethylphosphamide (HMPA); moreover dimethyl sulfoxide (DMSO), and sulfolane. Preferred solvents are propylene glycol, dipropylene glycol and propyleneglycol monomethyl ether, more preferred propylene glycol and dipropylene glycol.

The adjuvant solution may comprise at least one auxiliary. Suitable auxiliaries are listed above for the agrochemical composition.

The adjuvant solution is typically free of any agrochemical active ingredient. The adjuvant solution may comprise an agrochemical active ingredient in a concentration of up to 5 wt %, preferably up to 1 wt %.

The adjuvant solution may be used to prepare the agrochemical composition. To this end, the adjuvant solution is contacted with the agrochemical active ingredient, usually by mixing. Water or other solvents may be added optionally. Preferably, no solvent is added and a highly concentrated composition is obtained.

The adjuvant solution may also be used as a tank-mix additive by the applicant. Accordingly, the adjuvant solution may be used by the farmer to prepare the ready-to-use spray mix by mixing the adjuvant solution with various other agrochemical products comprising agrochemical active ingredients, adjuvants, auxiliaries, and water.

The invention also relates to plant propagation material comprising the agrochemical composition; and to a method for treating plant propagation material comprising the step of treating plant propagation material with the agrochemical composition.

In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of agrochemical active ingredient of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.

The treatment of plant propagation material comprises the step of contacting the plant propagation material with the agrochemical composition. The contacting may be carried out by all procedures familiar to the person skilled in the art (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting) based on the agrochemical compositions. Here, the agrochemical compositions can be applied diluted or undiluted. The term “seed” comprises seed of all types, such as, for example, corns, seeds, fruits, tubers, seedlings and similar forms. Here, preferably, the term seed describes corns and seeds. The seed used can be seed of the useful plants mentioned above, but also the seed of transgenic plants or plants obtained by customary breeding methods. Preferably, the term seed refers to a seed of a modified plant that is resistant against glufosinate.

The invention also relates to the use of the compound of formula (I) for increasing the solubility an agrochemical active ingredient in liquid agrochemical compositions. It was surprisingly found that the compounds of formula (I) can increase the maximum loading with agrochemical active ingredients in liquid agrochemical compositions. Formulations of prior art that have a high viscosity under high loading conditions and suffer from physical instabilities like gelling, flocculation, caking, and reduced flowability. By contrast, the present agrochemical compositions keep the agrochemical active ingredient in solution even under high loading conditions. Accordingly, compounds of formula (I) can be used to increase the solubility of an agrochemical active ingredient. As used herein, the terms “increase the solubility” and “solubilize” have the same meaning. The term “increase the solubility” generally refers to a situation, wherein two liquid composition of the same loading with agrochemical active ingredient are compared at 20° C., wherein one of the compositions contains a compound of formula (I), and wherein the other composition does not contain the compound of formula (I). The increase of solubility can be measured by experimental determination of the maximum concentration of agrochemical active ingredient in the respective compositions that does not lead to physical instabilities.

The invention also relates to a method for controlling phytopathogenic fungi and/or unwanted plant growth and/or unwanted insect or mite infestation and/or for regulating the growth of plants, wherein the agrochemical composition is caused to act on the respective pests, their habitat or the plants to be protected from the respective pest, to the soil and/or to unwanted plants and/or the crop plants and/or their habitat.

Further objects of the invention are the use of the amine component for increasing the herbicidal activity of liquid herbicidal compositions comprising glufosinate, or a salt thereof, and a compound of formula (I); and a method for increasing the herbicidal activity of liquid herbicidal compositions comprising glufosinate or a salt thereof, and a compound of formula (I) comprising the step of contacting the liquid herbicidal composition with the amine component. The term “increasing the herbicidal activity” refers to an enhanced controlling of undesired vegetation as compared to a composition lacking the amine component. The increased controlling rate may typically be an enhancement of at least 10%, preferably at least 25% as compared to a composition lacking the amine component. The contacting in the method of application usually refers to admixing the amine component to the composition.

Advantages: the inventive compounds of formula (I) have a high solubility in organic solvents and aqueous compositions. It is therefore possible to create compositions with a very high loading with compounds of formula (I) without generating handling problems due to high viscosity or heterogeneous compositions. It is also possible to produce compositions with a very high concentration of active ingredient. The agrochemical compositions have a very high storage stability, especially at low temperatures. Compounds of formula (I) are finally powerful additives that enhance the biological activity of agrochemical active ingredients.

The following examples illustrate the invention.

Ingredients:

Pesticide A: ammonium salt of glufosinatePesticide B: mefentrifluconazolPesticide C: saflufenacilAdjuvant A: aqueous solution of alkylpolyglycosides, based on C8-C19-alcoholAdjuvant B: aluminum magnesium silicate, hydratedAdjuvant C: organic derivative of smectite clayAdditive A: sodium laurylethersulfate containing approximately two molecules of polymerized ethylene oxide, 70 wt % in waterAdditive B: laurylethersulfate containing approximately two molecules of polymerized ethylene oxide, diethanolammonium salt, 77 wt % in dipropylene glycol.Additive C: laurylethersulfate containing approximately two molecules of polymerized ethylene oxide, monoisopropanol ammonium salt, 85 wt % in propylene glycolAdditive D: laurylethersulfate containing approximately two molecules of polymerized ethylene oxide, monoethanolammonium salt, 82 wt % in dipropylene glycol.Antifoam: emulsion of polydimethylsiloxane

EXAMPLE-1

Two compositions A1 and A2 as well as comparative composition AC were prepared by mixing Pesticide A, water, and either Additive A or Additive B in the concentrations as provided in Table A.

TABLE A
Ingredients of compositions AC, A1, and A2 in [wt %].
	Ingredient	AC	A1	A2
	Pesticide A	13.5	13.5	13.5
	Additive A	73.0	—	—
	Additive B	—	73.0	66.5
	Water	13.5	13.5	20
	1)Dynamic viscosity	2)	1139	543
	(apparent) [mPas]
	1)The viscosities were measured according to CIPAC MT 192 by using a rotational viscometer. The given values are the apparent viscosity which were determined at shear sate of 100 s-1 at 20° C..
	2): the mixture was in homogenous and therefore the viscosity could not be measured accurately.

Visual inspection of the compositions showed that compositions A1 and A2 had formed clear solutions, whereas composition AC had formed a heterogenous and insoluble gel.

EXAMPLE-2

Two compositions B1 and B2 as well as comparative composition BC were prepared by mixing Pesticide A, water, optionally ethanol, and either Additive A or Additive B in the concentrations as provided in Table B.

TABLE B
Ingredients of compositions BC, B1, and B2 in [wt %].
	Ingredient	BC	B1	B2
	Pesticide A	16.2	16.2	16.2
	Additive A	63.1	—	—
	Additive B	—	63.1	57.4
	Ethanol	4.5	—	—
	Water	16.2	20.7	26.4
	1)Dynamic viscosity	2)	457	424
	(apparent) [mPas]
	1)The viscosities were measured according to CIPAC MT 192 by using a rotational viscometer. The given values are the apparent viscosity which were determined at shear sate of 100 s-1 at 20° C..
	2): the mixture was inhomogenous and therefore the viscosity could not be measured accurately.

Visual inspection of the compositions showed that compositions B1 and B2 had formed clear solutions, whereas composition BC had formed a heterogenous an insoluble gel.

EXAMPLE-3

Two compositions C1 and C2 as well as comparative composition CC were prepared by mixing Pesticide A, water, ethanol and either Additive A or Additive B in the concentrations as provided in Table C.

TABLE C
Ingredients of compositions CC, C1, and C2 in [wt %].
	Ingredient	CC	C1	C2
	Pesticide A	16.65	16.65	16.65
	Additive A	61.4	—	—
	Additive B	—	61.4	55.9
	Ethanol	4.4	4.4	4.4
	Water	17.55	17.55	23.05
	1)Dynamic viscosity	2)	403	216
	(apparent) [mPas]
	1)The viscosities were measured according to CIPAC MT 192 by using a rotational viscometer. The given values are the apparent viscosity which were determined at shear sate of 100 s-1 at 20° C..
	2): the mixture was in homogenous and therefore the viscosity could not be measured accurately.

Visual inspection of the compositions showed that compositions C1 and C2 had formed clear solutions, whereas composition CC had formed a heterogenous an insoluble gel.

EXAMPLE-4

Two compositions D1 and D2 as well as comparative composition DC were prepared by mixing Pesticide A, water, ethanol and either Additive A or Additive B in the concentrations as provided in Table D.

TABLE D
Ingredients of compositions DC, D1, and D2 in [wt %].
	Ingredient	DC	D1	D2
	Pesticide A	17.4	17.4	17.4
	Additive A	60.9	—	—
	Additive B	—	60.9	55.4
	Ethanol	3.5	3.5	3.5
	Water	18.2	18.2	23.7
	1)Dynamic viscosity	2)	452	246
	(apparent) [mPas]
	1)The viscosities were measured according to CIPAC MT 192 by using a rotational viscometer. The given values are the apparent viscosity which were determined at shear sate of 100 s-1 at 20° C..
	2): the mixture was in homogenous and therefore the viscosity could not be measured accurately.

Visual inspection of the compositions showed that compositions D1 and D2 had formed clear solutions, whereas composition DC had formed a heterogenous an insoluble gel.

EXAMPLE-5

Two compositions E1 and E2 as well as comparative composition EC were prepared by mixing Pesticide A, water, Adjuvant A and either Additive A or Additive B in the concentrations as provided in Table E.

TABLE E
Ingredients of compositions EC, E1, and E2 in [wt %].
	Ingredient	EC	E1	E2
	Pesticide A	30.6	30.6	30.6
	Additive A	40.0	—	—
	Additive B	—	40.0	36.0
	Adjuvant A	9.0	9.0	9.0
	Water	20.4	20.4	24.4
	1)Dynamic viscosity	3243	1289	726
	(apparent) [mPas]

Visual inspection of the compositions showed that compositions E1 and E2 had formed clear solutions, whereas composition EC had formed a heterogenous an insoluble gel.

EXAMPLE-7

Four compositions F1 and F2 as well as comparative composition FC1, were prepared with the ingredients as listed in Table F. To prepare oil dispersions, ingredients except for the Adjuvant B were mixed and the composition was grinded with Maxine A to a mean particle size of 2 μm, upon which Adjuvant B was added and the compositions were mixed until homogenous.

TABLE F
Ingredients of compositions C1 ,F1, F2, in [wt %].
	Ingredient	FC1	F1	F2
	Pesticide B	10.0	10.0	10.0
	Additive A	60.0	—	—
	Additive D	—	60.0	—
	Additive B	—	—	60.0
	Adjuvant B	1.0	1.0	1.0
	Propylene	—	—	—
	glycol
	Dipropylene	29.0	29.0	29.0
	glycol
	1)Dynamic	2)	480	512
	viscosity
	(apparent) [mPas]
	1)The viscosities were measured according to CIPAC MT 192 by using a rotational viscometer, The given values are the apparent viscosity which were determined at shear sate of 100 s -1 at 20° C..
	2): the mixture was in homogenous and therefore the viscosity could not be measured accurately.

Visual inspection of the compositions showed that compositions F1, F2, F3 and F4 had formed free flowing white oil dispersions, whereas FC1 and FC2 had formed inhomogeneous gel like mixtures that could not be milled.

EXAMPLE-8

Three compositions G1 to G3 as well as comparative composition GC1, GC2 and GC3 were prepared with the ingredients as listed in Table F. To prepare oil dispersions, ingredients except for the Adjuvant C were mixed and the composition was grinded with Maxine A to a mean particle size of 2 μm, upon which Adjuvant C was added and the compositions were mixed until homogenous.

TABLE G
Ingredients of compositions GC1, GC2,
GC3, G1, G2, and G3 [wt %].
Ingredient	GC1	GC2	GC3	G1	G2	G3
Pesticide A	33.0	33.0	33.0	33.0	33.0	33.0
Additive A	40.0	40.0	40.0	—	—	—
Additive C	—	—	—	40.0	40.0	—
Additive B	—	—	—	—	—	40.0
Adjuvant C	0.5	0.5	0.5	0.5	0.5	0.5
Propylene glycol	26.5	4.0	—	26.5	4.0	—
Propyleneglycol-	—	22.5	26.5	—	22.5	26.5
monomethylether
1)Dynamic vis-	2)	2)	2)	1802	907	Not
cosity (apparent)						measured
[mPas]
1)The viscosities were measured according to CIPAC MT 192 by using a rotational viscometer. The given values are the apparent viscosity which were determined at shear sate of 100 s−1 at 20° C.
2)the mixture was in homogenous and therefore the viscosity could not be measured accurately.

Visual inspection of the compositions showed that compositions G1, G2, and G3 had formed free flowing white oil dispersions, whereas GC1 and GC2 had formed inhomogeneous gel like mixtures that could not be milled.

EXAMPLE-9

Four compositions H1 to H4 as well as comparative composition HC1, HC2 and HC3 were prepared with the ingredients as listed in Table H. To prepare oil dispersions, ingredients except for the Adjuvant B were mixed and the composition was grinded with Maxine A to a mean particle size of 2 μm, upon which Adjuvant B was added and the compositions were mixed until homogenous.

TABLE H
Ingredients of compositions HC1, HC2, HC3, H1, H2,
H3 and H4 [wt %].
Ingredient	HC1	HC2	HC3	H1	H2	H3	H4	H5
Pesticide C	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0
Additive A	66.7	60.4	62.6	—	—	—	—	—
Additive B	—	—	—	66.7	60.4	—	—	—
Additive C	—	—	—	—	—	62.6	60.4	—
Additive D	—	—	—	—	—	—	—	60.4
Adjuvant B	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0
Propylene	—	—	26.4	—	—	26.4	—	—
glycol
Dipropylene	22.3	28.6	—	22.3	28.6	—	28.6	28.6
glycol
1)Dynamic vis-	2)	2)	2)	602	540	403	465	518
cosity
(apparent) [mPas]
1)The viscosities were measured according to CIPAC MT 192 by using a rotational viscometer. The given values are the apparent viscosity which were determined at shear sate of 100 s−1 at 20° C.
2)the mixture was in homogenous and therefore the viscosity could not be measured accurately.

Visual inspection of the compositions showed that compositions H1, H2, H3 and H4 had formed free flowing white oil dispersions, whereas HC1, HC2 and HC3 had formed inhomogeneous gel like mixtures that could not be milled.

EXAMPLE-10

Two compositions K1 and K2 were prepared by mixing Pesticide A, water, ethanol, Adjuvant A and Additive B in the concentrations as provided in Table K.

TABLE K
Ingredients of compositions K1 and K2 [wt %].
Ingredient	K1	K2
Pesticide A	29.6	24.56
Additive B	34.1	30.25
Ethanol	4.5	—
Propyleneglycol	—	5.7
monomethyl ether
Adjuvant A	10.6	13.10
Water	21.2	26.39
Dynamic viscosity	n.m.	n.m.
(apparent) [mPas]
n.m = not measured

Visual inspection of the compositions showed that compositions K1 and K2 had formed clear solutions

EXAMPLE-11

Two compositions L1 and L2 were prepared by mixing the ingredients as provided in the concentrations as provided in Table K.

TABLE L
Ingredients of compositions L1 and L2 [wt %].
Ingredient	L1	L2
Pesticide A	13.5	16.5
Additive A	58.91	—
Additive D	—	57.9
Propylene glycol	—	3.21
Ethanol	—	5.5
Propyleneglycol	10.0	—
monomethyl ether
Antifoam	0.1	0.09
Water	to 100	to 100

The compositions L1 and L2 were cooled to 0° C. Composition L1 froze, whereas composition L2 remained liquid at 0° C.The compositions L1 and L2 were cooled to −30° C., whereupon both compositions froze. After thawing at room temperature, composition L2 was still homogeneous whereas composition L1 showed phase separation.

Claims

1. An agrochemical composition comprising a compound of formula (I) [R-(A)x-OSO3−]-M+  (I);whereinR is C10-C16-alkyl, C10-C16-alkenyl, or C10-C16-alkynyl;each A is independently a group

2. The agrochemical composition according to claim 1, wherein the index x is from 1 to 3.

3. The agrochemical composition according to claim 1, wherein RA, RB, RC, and RD are H.

4. The agrochemical composition according to claim 1, wherein the agrochemical active ingredient is glufosinate or (L)-glufosinate, or a salt thereof.

5. The agrochemical composition according to claim 1, wherein the agrochemical active ingredient is a protoporphyrinogen-IX oxidase inhibitor or a salt thereof.

6. The agrochemical composition according to claim 1, wherein the concentration of the compound of formula (I) in the agrochemical composition is more than 25 wt %.

7. The agrochemical composition according to claim 1, wherein the concentration of the agrochemical active ingredient in the agrochemical composition is from 5 to 50 wt %.

8. A compound of formula (I) as defined in claim 1, wherein R is a linear C12-alkyl; andRA, RB, RC, and RD are H; andM+ is a monoethanolammonium cation.

9. An adjuvant solution comprising a compound of formula (I) as defined in claim 1, and more than 10 wt % of an organic solvent.

10. The solution of claim 9, wherein the organic solvent has a water-solubility of at least 10 wt % at 20° C.

11. A method for controlling undesirable vegetation, which method comprises applying the agrochemical composition as defined in claim 1 to a locus where undesirable vegetation is present or is expected to be present.

12. The agrochemical composition according to claim 4 wherein the agrochemical active ingredient is an ammonium salt of glufosinate or L-glufosinate.