US20230082754A1

US20230082754A1 - Glufosinate formulations containing amines or ammonium salts

Info

Publication number: US20230082754A1
Application number: US17/793,475
Authority: US
Inventors: Murat Mertoglu; Steffen Kuhn; Wolfgang Meier; Ingo Meiers; Roland Wihelm; Martin Hartmueller; Gina Nash
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2020-01-23
Filing date: 2021-01-14
Publication date: 2023-03-16
Also published as: WO2021148302A1; BR112022014435A2; CR20220358A; CO2022010230A2; KR20220130702A; BR112022014559A2; MX2022009010A; CN115023139A; WO2021148303A1; AU2021210110A1; KR20220130701A; CL2022001963A1; JP2023511937A; CN115460923A; EP4093196A1; AU2021211090A1; KR20220130709A; US20230096769A1; CA3165272A1; JP2023511431A

Abstract

The invention relates to a liquid herbicidal composition comprising a) glufosinate, or a salt thereof, an amine component; and a compound of formula (I) [R-(A)x-OSO3−]-M+ (I); wherein al variables have a meaning as defined herein. It also relates to 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; and to a method for treating plant propagation material comprising the step of treating plant propagation material with the herbicidal composition.

Description

The invention relates 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; and c) a compound of formula (I)
[R-(A)_x-OSO₃ ⁻]-M⁺ (I);
wherein the variables have a meaning as defined herein below.
Further objects are a method for controlling undesirable vegetation, which method comprises applying the herbicidal composition to a locus where undesirable vegetation is present or is expected to be present; 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); 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; a method of producing the herbicidal composition comprising the step of contacting the amine component with the compound of formula (I) and glufosinate or a salt thereof in any given order; plant propagation material comprising the herbicidal composition; and to a method for treating plant propagation material comprising the step of treating plant propagation material with the herbicidal 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.
It was the objective of the present invention to provide herbicidal compositions of glufosinate or its salts that have an increased biological effect, in particular an increased herbicidal effect against undesired vegetation, have an enhanced physical and/or chemical stability, high loading with agrochemical active ingredients and/or adjuvants and at the same can be easily handled by the applicant.
It was surprisingly found that the amine component increases the biological activity of liquid herbicidal compositions comprising glufosinate. The improved biological activity relates both the increased herbicidal effect against unwanted vegetation, to a reduced damage of certain crop plants, and an enhanced defoliation effect. Further advantages are that the herbicidal compositions have a high loading with glufosinate, that they are physically stable upon storage.
Accordingly, the invention relates 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;
- c) 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^Dare independently H, CH₃, or CH₂CH₃with the proviso that the sum of C-atoms of R^A, R^B, R^C, and R^Dis up to 2;
- M⁺ is a monovalent cation; and
- the index x is a number from 1 to 10.

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 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_mindicates 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.
The term “ammonium” per se refers to the cation NH₄ ⁺. The expression “ammonium cations of primary, secondary or tertiary amines”, as used similarly in the expression “primary, secondary, tertiary amines, and ammonium salts thereof” refers to protonated primary, secondary or tertiary amines. The protonation of such ammonium cations is dependent on the pH and the positive charge varies accordingly. The term “quaternary ammonium (cat)ion(s)” refers to permanently positively charged cations containing a nitrogen atom with four organic binding partners, e.g. alkyl groups. Accordingly, the term “quaternary ammonium salt(s)” refers to a salt containing a quaternary ammonium cation. Examples of quaternary ammonium ions are tetramethylammonium, tetraethylammonium, tetraethanolammonium, cholin, 2-hydroxyethyltrimethyl ammonium, and trishydroxyethylmethyl ammonium.
The liquid herbicidal composition contains 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

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 monovalent cation M⁺, which is positively and singly charged.
The compounds of formula (I) may contain an ammonium cation M⁺ of a primary, secondary, or tertiary amine, i.e. a protonated primary, secondary or tertiary amine, or a quaternary ammonium cation. Such compounds are available from the commercially available sodium or potassium salts by ion exchange chromatography or other methods suitable for ion exchange. Alternatively, compounds of formula (I), wherein M⁺ is NH₄ ⁺ or an ammonium cation of a primary, secondary, or tertiary amine, are available by reaction of compounds of formula (I) with SO₃or CISO₃H and subsequent addition of the respective amine base or ammonia 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 SO₃or CISO₃H 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⁺ of primary, secondary, or tertiary amines in compounds of formula (I).
The monovalent cation M⁺ is thus typically selected from
α) alkali metal cations, e.g. Li⁺, Na⁺, and K⁺;
β) NH₄ ⁺;
γ) ammonium cations of a primary, secondary, and tertiary amines; and
δ) quaternary ammonium cations.
In one embodiment, the monovalent cation M⁺ is an alkali metal cation or NH₄ ⁺. In another embodiment, the monovalent cation M⁺ is an alkali metal cation, preferably Na⁺ or K⁺, more preferably Na⁺.
If the amine component contains an ammonium salt or a quaternary ammonium salt, the monovalent cation M⁺ is typically different from the ammonium cation or quaternary ammonium cation in said ammonium salt or quaternary ammonium salt. Accordingly, M⁺ is typically different from the protonated amine component if the amine component is a primary, secondary or tertiary amine.
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 C₁₀-C₁₆-alkenyl. Typically, R is a C₁₀-C₁₆-alkyl, preferably C₁₀-C₁₄-alkyl, more preferably C₁₁-C₁₃-alkyl, and in particular C₁₂-alkyl, such as 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
wherein
R^A, R^B, R^C, and R^Dare independently H, CH₃, or CH₂CH₃with the proviso that the sum of C-atoms of R^A, R^B, R^C, and R^Dis up to 2.
Typically, the sum of C-atoms of R^A, R^B, R^C, and R^Dis up to 1. Preferably, R^A, R^B, R^Cand R^Dare H. Typically, each group A is the same, preferably wherein R^A, R^B, R^Cand R^Dare 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^Cand R^Dare H, with groups A, wherein one substituent R^A, R^B, R^Cor R^Dis 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^Cand R^Dare H, with groups A, wherein one substituent R^AR^B, R^Cor R^Dis 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^Cand R^Dare 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.
In one embodiment, the substituents of formula (I) have the following meaning: R is C₁₀-C₁₄-alkyl;
each A is independently a group
wherein

R^A, R^B, R^C, and R^Dare independently H, CH₃, or CH₂CH₃with the proviso that the sum of C-atoms of R^A, R^B, R^C, and R^Dis up to 2;
M⁺ is a monovalent cation; and
the index x is a number from 1 to 5.

In another embodiment, the substituents of formula (I) have the following meaning: R is C₁₀-C₁₄-alkyl;
each A is independently a group
wherein
R^A, R^B, R¹, and R^Dare H;
M⁺ is a monovalent cation; and
the index x is a number from 1 to 5.
In another embodiment, the substituents of formula (I) have the following meaning: R is C₁₀-C₁₄-alkyl;
each A is independently a group
wherein
R^A, R^B, R^C, and R^Dare H;
M⁺ is a monovalent cation; and
the index x is a number from 1 to 5.
In another embodiment, the substituents of formula (I) have the following meaning: R is C₁₀-C₁₄-alkyl;
each A is independently a group
wherein
R^A, R^B, R^C, and R^Dare H;
M⁺ is a monovalent cation; and
the index x is a number from 1 to 5.
In another embodiment, the substituents of formula (I) have the following meaning: R is C₁₂-alkyl, preferably linear C₁₂-alkyl;
each A is independently a group
wherein
R^A, R^B, R^C, and R^Dare H:
M⁺ is a monovalent cation; and
the index x is a number from 1 to 3.
In another embodiment, the substituents of formula (I) have the following meaning: R is C₁₂-alkyl, preferably linear C₁₂-alkyl;
each A is independently a group
wherein
R^A, R^B, R^C, and R^Dare H;
the index x is a number from 1 to 3; and
M⁺ is a monovalent cation selected from Na⁺, and K⁺.
In another embodiment, the substituents of formula (I) have the following meaning: R is C₁₂-alkyl, preferably linear C₁₂-alkyl;
each A is independently a group
wherein
R^A, R^B, R^C, and R^Dare H;
the index x is a number from 1 to 3; and
M⁺ is Na⁺.
The herbicidal 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 15 wt %, in particular at least 20 wt %, and especially at least 30 wt %, such as at least 40 wt % based on the total weight of the herbicidal composition. The herbicidal 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 herbicidal composition. The herbicidal composition may comprise the compound of formula (I) in a concentration of from 5 to 70 wt %, preferably 5 to 60 wt %, more preferably 10 to 50 wt %, most preferably 15 to 40 wt % based on the total weight of the herbicidal composition. In one embodiment, the agrochemical composition comprises the compound of formula (I) in a concentration of more than 25 wt %, preferably at least 26 wt %, more preferably at least 27 wt %, especially at least 28 wt %, such as at least 29 wt %.
The composition also contains 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. Such amine components are commercially available. The amine component is commercially available or obtainable by standard methods of organic chemistry.
In one embodiment, the amine component comprises a primary, secondary, tertiary amine or an ammonium salt thereof (i.e. the salt of a protonated primary, secondary or tertiary amine). In another embodiment, the amine component is a quaternary ammonium salt. Typically, the amine component contains only one nitrogen atom per molecule.
The molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is from 32 to 200 g/mol. In one embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is from is at least 35 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is at least 40 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is at least 45 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is at least 50 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt is at least 55 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is at least 60 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt in the ammonium salt, is at least 61 g/mol. In one embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is up to 195 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is up to 190 g/mol g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is up to 185 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is up to 180 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is up to 175 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is up to 170 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is up to 160 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is up to 150 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is up to 140 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is up to 130 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt, is up to 120 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt is up to 110 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt is up to 105 g/mol. In one embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt is from 35 g/mol to 150 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt is from 40 g/mol to 140 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt is from 55 g/mol to 180 g/mol. In another embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt is from 50 g/mol to 120 g/mol. In one embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt is from 55 g/mol to 110 g/mol. In one embodiment, the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt or the quaternary ammonium cation in the quaternary ammonium salt is from 60 g/mol to 110 g/mol.
The primary, secondary or tertiary amine N and the protonated ammonium form N⁺ form a conjugated acid/base pair and are in equilibrium in aqueous conditions as displayed in Scheme 1
N+H₂O
N+H₃O⁺ Scheme 1:
The invention thus also pertains to a situation wherein the amine is present both in its protonated state N⁺ and in its non-protonated state N.
The molar ratio of protonated amine N⁺ to non-protonated amine N 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 N⁺ to non-protonated amine N is typically up to 50:1, preferably up to 20:1, more preferably up to 15:1 most preferably up to 8:1.
The ratio is dependent of the pH of the liquid herbicidal 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. By addition of an acid, the amine N is protonated and present in the form of its ammonium salt, such as the chloride salt, the sulfate salt, the sulfonate salt, or the methyl sulfonate salt. Thus, the ammonium salt of the primary, secondary or tertiary amine is formed in situ by reaction of the acid with the amine N. Alternatively, the respective ammonium salt of the primary, secondary or tertiary amine may be added to the composition.
Since compounds of formula (I) are ionic compounds, and since the amine component may contain, or form an ammonium salt, or contain a quaternary ammonium salt, the compounds of formula (I) and the amine component may exchange their respective counterions in solution as displayed in Scheme 2
[R-(A)_x-OSO₃ ₋]-M⁺(I)+[B⁻]-[Q⁺]
[R-(A)_x-OSO₃ ₋]-Q⁺(I-b)+[B⁻][M⁺] Scheme 2:
wherein B⁻ is a monovalent anion, such as Cl⁻, SO₄ ⁻, SO₃ ⁻, or CH₃SO₃ ⁻, wherein Q⁺ is an ammonium cation of the primary, secondary, or tertiary amine, or a quaternary ammonium cation of the quaternary ammonium salt, 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-b) and the backward reaction to compounds of formula (I) are in equilibrium. Thus, the invention also pertains to a situation in which the herbicidal composition contains compounds of formula (I) and compounds of formula (I-b) in any given ratio. For example, the molar ratio of compounds of formula (I) to compounds of formula (I-b) may be from 100:1 to 1:100, preferably from 10:1 to 1:10.
Accordingly, the herbicidal composition may contain a mixture of cations, including monovalent cations M⁺ and the cations of the ammonium salt(s) of primary, secondary, and tertiary amine(s) and of the quaternary ammonium salts Q⁺. The invention thus also pertains to a situation in which the molar ratio of the monovalent cations M⁺ compared to the cations Q⁺ as defined above is at least 1:100, preferably at least 1:10, more preferably at least 1:1, most preferably at least 2:1, and in particular at least 10:1, such as at least 50:1. The molar ratio of cations M⁺ to cations Q⁺ may be from 100:1 to 1:100, preferably from 20:1 to 1:20.
The invention also pertains to a situation in which the molar concentration of the monovalent cations M⁺ compared to the total amount of the moiety (I-a) in the composition, either in the form of compound of formula (I), as compound of formula (I-b) or as a different salt, is less than 100 mol-%. The molar concentration of the monovalent 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-%. Preferably the molar concentration of the monovalent cations M⁺ compared to the total amount of the moiety (I-a) is at least 99 mol-%, in particular 100 mol-%.
Preferable, the amine component the amine component contains a salt of the cation of formula (II) or a primary, secondary, or tertiary ammine of formula (III)
wherein

R¹, R², R⁴, R⁵, R⁶, and R⁷are 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, R³, and R⁴, or of the substituents R⁵, R⁶, and R⁷form, 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, R³, or R⁴is not H; and
- with the proviso that at least one substituent R⁵, R⁶, or R⁷is not H.

The sum of substituents R¹, R², R³, and R⁴typically contain up to 18 carbon atoms (“C-atoms”), preferably up to 16 C-atoms, more preferably up to 14 C-atoms, most 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 sum of substituents R¹, R², R³and R⁴contain up to 9 C-atoms. In another embodiment, the sum of substituents R¹, R², R³and R⁴contain up to 7 C-atoms. In another embodiment, the sum of substituents R¹, R², R³and R⁴contain up to 5 C-atoms. In another embodiment, the sum of substituents R¹, R², R³and R⁴contain up to 4 C-atoms. In another embodiment, the sum of substituents R¹, R²and R³contain up to 3 C-atoms.
The sum of substituents R¹, R²and R³contain at least one C-atom, preferably at least 2 C-atoms, more preferably at least 3 C-atoms.
In one embodiment, the sum of substituents R¹, R², R³and R⁴contain from 1 to 15 C-atoms. In another embodiment, the sum of substituents R¹, R², R³and R⁴contain from 1 to 12 C-atoms. In another embodiment, the sum of substituents R¹, R², R³and R⁴contain from 1 to 10 C-atoms. In another embodiment, the substituents R¹, R², R³, and R⁴contain from 2 to 12 C-atoms. In another embodiment, the sum of substituents R¹, R², R³and R⁴contain from 2 to 10 C-atoms. In another embodiment, the sum of substituents R¹, R², R³and R⁴contain from 1 to 6 C-atoms. In another embodiment, the substituents R¹, R², R³and R⁴contain from 1 to 4 C-atoms. In another embodiment, the substituents R¹, R², R³and R⁴contain from 1 to 3 C-atoms.
The sum of substituents R⁵, R⁶, and R⁷typically contain up to 18 carbon atoms (“C-atoms”), preferably up to 16 C-atoms, more preferably up to 14 C-atoms, most 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 sum of substituents R⁵, R⁶, and R⁷contain up to 9 C-atoms. In another embodiment, the sum of substituents R⁵, R⁶, and R⁷contain up to 7 C-atoms. In another embodiment, the sum of substituents R⁵, R⁶, and R⁷contain up to 5 C-atoms. In another embodiment, the sum of substituents R⁵, R⁶, and R⁷contain up to 4 C-atoms. In another embodiment, the sum of substituents R⁵, R⁶and R⁷contain up to 3 C-atoms.
The sum of substituents R⁵, R⁶and R⁷contain at least one C-atom, preferably at least 2 C-atoms, more preferably at least 3 C-atoms.
In one embodiment, the sum of substituents R⁵, R⁶, and R⁷contain from 1 to 15 C-atoms. In another embodiment, the sum of substituents R⁵, R⁶, and R⁷contain from 1 to 12 C-atoms. In another embodiment, the sum of substituents R⁵, R⁶, and R⁷contain from 1 to 10 C-atoms. In another embodiment, the substituents R⁵, R⁶, and R⁷contain from 2 to 12 C-atoms. In another embodiment, the sum of substituents R⁵, R⁶, and R⁷contain from 2 to 10 C-atoms. In another embodiment, the sum of substituents R⁵, R⁶, and R⁷contain from 1 to 6 C-atoms. In another embodiment, the substituents R⁵, R⁶, and R⁷contain from 1 to 4 C-atoms. In another embodiment, the substituents R⁵, R⁶, and R⁷contain from 1 to 3 C-atoms.
In one embodiment R¹, R², R⁴, R⁵, R⁶, and R⁷are 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, R³, or R⁴is not H, and wherein at least one substituent R⁵, R⁶, or R⁷is not H.
In another embodiment R¹, R², R⁴, R⁵, R⁶, and R⁷are 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, R³, or R⁴is not H, and wherein at least one substituent R⁵, R⁶, or R⁷is not H.
In another embodiment R¹, R², R⁴, R⁵, R⁶, and R⁷are 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, R³, or R⁴is not H, and wherein at least one substituent R⁵, R⁶, or R⁷is not H.
In another embodiment R¹, R², R⁴, R⁵, R⁶, and R⁷are 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, R³, or R⁴is not H, and wherein at least one substituent R⁵, R⁶, or R⁷is not H.
In another embodiment R¹, R², R⁴, R⁵, R⁶, and R⁷are independently H, or C₁-C₂-alkyl, which is unsubstituted or substituted with OH, C₁-C₂-alkoxy, or hydroxy-C₁-C₂-alkoxy, wherein at least one substituent R¹, R², R³, or R⁴is not H, and wherein at least one substituent R⁵, R⁶, or R⁷is not H.
In another embodiment, two of the substituents R¹, R², R³and R⁴, or of the substituents R⁵, R⁶, and R⁷form, 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 substituents are 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, R³and R⁴, or of the substituents R⁵, R⁶, and R⁷form, 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 substituents are 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, R³and R⁴, or of the substituents R⁵, R⁶, and R⁷form, 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 substituents are either H, or C₁-C₃-alkyl, which is unsubstituted or substituted with OH, C₁-C₃-alkoxy, or hydroxy-C₁-C₃-alkoxy.
In another embodiment, two of the substituents R¹, R², R³and R⁴, or of the substituents R⁵, R⁶, and R⁷form, 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 substituents are either H, or C₁-C₂-alkyl, which is unsubstituted or substituted with OH, C₁-C₂-alkoxy, or hydroxy-C₁-C₂-alkoxy.
The amine component is typically an amine selected from ethanolamine (also called monoethanolamine, CAS number 141-43-5), 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, or an ammonium salt thereof, i.e. the salt of a protonated amine selected from those above. In another embodiment, the amine component is a salt of a quaternary ammonium cation selected from 2-hydroxyethyltrimethyl ammonium, trishydroxyethylmethyl ammonium.
Salts of quaternary ammonium cations may contain any suitable mono, or divalent anion, preferably monovalent anion. Examples of anions are nitrate, sulfate, chloride, bromide, iodide, carbonate, bicarbonate, acetate, formate, phosphate and phosphonate. In one embodiment, the quaternary ammonium cation contains chloride as anion.
In one embodiment, the amine component is ethanolamine or an ammonium salt thereof. In another embodiment, the amine component is diethanolamine or an ammonium salt thereof. In another embodiment, the amine component is diglycolamine or an ammonium salt thereof. In another embodiment, the amine component is 1-aminopropan-2-ol or an ammonium salt thereof. In another embodiment, the amine component is 2-dimethylaminoethanol or an ammonium salt thereof. In another embodiment, the amine component is 2-(butylamino)ethanol or an ammonium salt thereof. In another embodiment, the amine component is protonated 2-diethylaminoethanol or an ammonium salt thereof. In another embodiment, the amine component is 2-(tert-butylamino)ethanol or an ammonium salt thereof. In another embodiment, the amine component is N-(tert-butyl)diethanolamine or an ammonium salt thereof. In another embodiment, the amine component is triethanolamine or an ammonium salt thereof. In another embodiment, the amine component is 2-ethylaminoethanol or an ammonium salt thereof. In another embodiment, the amine component is 2-aminoheptan or an ammonium salt thereof. In another embodiment, the amine component is triisopropylamine or an ammonium salt thereof.
In another embodiment, the amine component is N-(2-hydroxyethyl)morpholin or an ammonium salt thereof, In another embodiment, the amine component is N-methylmorpholine or an ammonium salt thereof. In another embodiment, the amine component is protonated N-butyl-diethanolamine or an ammonium salt thereof. In another embodiment, the amine component is 2-(dibutylamino)ethanol or an ammonium salt thereof. In another embodiment, the amine component is a salt of 2-hydroxyethyltrimethyl ammonium. In another embodiment, the amine component is a salt of trishydroxyethylmethyl ammonium.
In another embodiment, the amine component is selected from ethanolamine, diethanolamine, diglycolamine, 1-aminopropan-2-ol, 2-dimethylaminoethanol, or an ammonium salt thereof, or a salt of trishydroxyethylmethyl ammonium. In another embodiment, the amine component is selected from ethanolamine, diglycolamine, triethanolamine, and ammonium salts thereof, and a salt of 2-hydroxyethyltrimethyl ammonium.
The herbicidal composition may comprise the amine component in a concentration of at least 1 wt %, preferably at least 5 wt % more preferably at least 10 wt %, most preferably at least 15 wt %, in particular at least 20 wt %, and especially at least 30 wt %, such as at least 40 wt % based on the total weight of the herbicidal composition. The herbicidal composition may comprise the amine component 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 herbicidal composition. The herbicidal composition may comprise the amine component in a concentration of from 5 to 70 wt %, preferably 5 to 50 wt %, more preferably 10 to 50 wt %, most preferably 15 to 40 wt % based on the total weight of the herbicidal composition.
The liquid herbicidal composition comprises glufosinate or a salt thereof. 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 tradenames 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 herbicidal 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 herbicidal composition comprises glufosinate, wherein at least 70% by weight of the glufosinate is L-glufosinate or a salt thereof.
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 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 herbicidal 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 herbicidal compositions, which contain (L)-glufosinate-ammonium, i.e. the ammonium (NH₄ ⁺) salt of glufosinate.
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.
Preferably, the herbicidal composition comprises an agrochemically effective amount of the glufosinate or salt thereof. The term “effective amount” denotes an amount of an agrochemically active ingredient or composition, 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 herbicidal composition may comprise the glufosinate, or a salt thereof, in a concentration of at least 1 wt %, preferably at least 5 wt % more preferably at least 10 wt %, most preferably at least 15 wt %, in particular at least 20 wt %, and especially at least 25 wt %, such as at least 30 wt % based on the total weight of the herbicidal composition. The herbicidal composition may comprise the glufosinate, or a salt thereof, 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 herbicidal composition.
The herbicidal composition may comprise the glufosinate, or a salt thereof, in a concentration of from 5 to 70 wt %, preferably 5 to 50 wt %, more preferably 10 to 50 wt %, most preferably 15 to 40 wt % based on the total weight of the herbicidal composition.
Accordingly, in one embodiment, the invention relates to a herbicidal composition comprising
a) L-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 the quaternary ammonium cation in the quaternary ammonium salts, is from 32 to 200 g/mol;
c) 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

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

a) L-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 the quaternary ammonium cation in the quaternary ammonium salts, is from 32 to 200 g/mol;
c) a compound of formula (I), wherein
R is C₁₀-C₁₄-alkyl;
each A is independently a group

wherein
R^A, R^B, R^C, and R^Dare H;
M⁺ is monovalent cation; and
the index x is a number from 1 to 5.
In another embodiment, the invention relates to a herbicidal composition comprising

a) L-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 the quaternary ammonium cation in the quaternary ammonium salts, is from 32 to 200 g/mol;
c) a compound of formula (I), wherein
R is C₁₂-alkyl, preferably linear C₁₂-alkyl;
each A is independently a group

wherein
R^A, R^B, R^C, and R^Dare H;
M⁺ is monovalent cation; and
the index x is a number from 1 to 3.
In another embodiment, the invention relates to a herbicidal composition comprising
a) L-glufosinate or a salt thereof;
b) an amine component selected from salts of the cation of formula (II) and from primary, secondary, and tertiary ammines of formula (III)
wherein

R¹, R², R⁴, R⁵, R⁶, and R⁷are 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, R³, and R⁴, or of the substituents R⁵, R⁶, and R⁷form, 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, R³, or R⁴is not H; and
- with the proviso that at least one substituent R⁵, R⁶, or R⁷is not H;
  wherein the molecular weight of the primary, secondary or tertiary amine, or of the ammonium cation in the ammonium salt, is from 32 to 200 g/mol;
  c) a compound of formula (I), wherein
  R is C₁₂-alkyl;
  each A is independently a group

wherein
R^A, R^B, R^C, and R^Dare H;
M⁺ is Na⁺; and
the index x is a number from 1 to 3.
In another embodiment, the invention relates to a herbicidal composition comprising

a) the ammonium salt of L-glufosinate;
b) an amine component 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 ammonium salts thereof;
- and salts of a quaternary ammonium cation selected from 2-hydroxyethyltrimethyl ammonium, trishydroxyethylmethyl ammonium;
- and mixtures thereof.
  wherein the molecular weight of the primary, secondary or tertiary amine, of the ammonium cation in the ammonium salt, or of the quaternary ammonium cation in the quaternary ammonium salt is from 32 to 200 g/mol;
c) a compound of formula (I), wherein
R is C₁₂-alkyl, preferably linear C₁₂-alkyl;
each A is independently a group

wherein
R^A, R^B, R^C, and R^Dare H;
M⁺ is a monovalent cation; and
the index x is a number from 1 to 3.
The following clauses C1 to C15 relate to preferred embodiments and combinations of embodiments

C1) 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;
- c) 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^Dare independently H, CH₃, or CH₂CH₃with the proviso that the sum of C-atoms of R^A, R^B, R^C, and R^Dis up to 2;
- M⁺ is a monovalent cation; and
- the index x is a number from 1 to 10.
C2) The composition according to C1, wherein the index x is from 1 to 3.
C3) The composition according to any of C1 or C2, wherein R^A, R^B, R^C, and R^Dare H.
C4) The composition according to any of C1 to C3, wherein the molecular weight of the primary, secondary, tertiary amine, or the ammonium cation of the ammonium salt thereof or of the quaternary ammonium salt is from 55 to 180 g/mol.
C5) The composition according to any of C1 to C4, wherein the primary, secondary, or tertiary amine, or the ammonium salt thereof, or the quaternary ammonium salt, contains exactly one nitrogen atom per molecule.
C6) The composition according to any of C1 to C5, wherein M⁺ is Na⁺.
C7) The composition according to any of C1 to C6, wherein the amine component contains a salt of the cation of formula (II) or a primary, secondary, or tertiary ammine of formula (III)

- wherein
- R¹, R², R³, R⁴, R⁵, R⁶, and R⁷are 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, R³, and R⁴, or of the substituents R⁵, R⁶, and R⁷form, 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, R³, or R⁴is not H; and
- with the proviso that at least one substituent R⁵, R⁶, or R⁷is not H.
C8) The composition of C7, wherein the sum of R¹, R², R³and R⁴, or the sum of R⁵, R⁶, and R⁷comprises from 1 to 12 carbon atoms.
C9) The composition according to any of C1 to C8, wherein the amine component is an 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 ammonium salts thereof;
- or a salt of a quaternary ammonium cation selected from 2-hydroxyethyltrimethyl ammonium, trishydroxyethylmethyl ammonium;
- or a mixture thereof.
C10) The composition according to any of C1 to C9, wherein the amine component is an amine selected from ethanolamine, diethanolamine, diglycolamine, 1-aminopropan-2-ol, 2-dimethylaminoethanol, or an ammonium salt thereof, or a salt of trishydroxyethylmethyl ammonium.
C11) The composition according to any of C1 to C10, wherein the pH is from 6 to 10.
C12) The composition according to any of C1 to C11, wherein the amine component is a chloride, sulfate, sulfonate, or methylsulfonate salt of a primary, secondary, or tertiary ammonium cation.
C13) The composition according to any of C1 to C12, wherein the component a) is the ammonium salt of glufosinate.
C14) The composition according to any of C1 to C13, comprising
- a) 5 to 50 wt % of glufosinate, (L)-glufosinate, or a salt thereof;
- b) 5 to 50 wt % of the amine component;
- c) 5 to 60 wt % of the compound of formula (I).
C15) The composition according to any of C1 to C14 containing a second agrochemical active ingredient selected from herbicides of classes b1) to b15) and safeners C).

The molar ratio of the glufosinate to the amine component is typically from 100:1 to 1:100, preferably from 50:1 to 1:50, more preferably from 10:1 to 1:10, most preferably from 5:1 to 1:5.
The molar ratio of the amine component to the compound of formula (I) may be from 100:1 to 1:100, preferably 50:1 to 1:50, more preferably 5:1 to 1:20.
The herbicidal composition relates to any liquid customary types of agrochemical compositions, e. g. solutions, emulsions, or suspensions. Typically, the amine component and the compound of formula (I) are present in dissolved form in the composition. In one embodiment, the glufosinate or salt thereof is present in dissolved form. In another embodiment, the glufosinate or salt thereof is present in particulate form as suspended solid particles, e.g. with a particles size (d50) of from 0.1 to 15 μm.
Examples for composition types are solutions, suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), and emulsions (e.g. EW, EO, ES, ME), and capsule formulations (e.g. CS, ZC). These and further compositions types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6^thEd. May 2008, CropLife International. The herbicidal composition is a liquid composition, i.e. it contains a liquid continuous phase. Typically, the herbicidal composition is an aqueous herbicidal composition or a herbicidal composition with a continuous oily phase containing a non-aqueous organic solvent. Preferred formulation types of the herbicidal composition are solutions, emulsifiable concentrates, and dispersions, more preferably aqueous solutions. Typically, the components of the herbicidal composition, i.e. the glufosinate or a salt thereof, the amine component, and the compound of formula (I) are present in dissolved state in the herbicidal composition. The agrochemical active ingredient is typically either present in dissolved or in suspended form in the herbicidal composition. If the herbicidal composition is an aqueous composition, the agrochemical active ingredient is typically dissolved. If the herbicidal composition is an oily composition, the agrochemical active ingredient is typically present in particulate form as suspended particles, in particular in oil dispersions.
Accordingly, the herbicidal composition may comprise water. Typically, the herbicidal composition comprises water 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 %. The herbicidal 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 herbicidal composition typically comprises water in a concentration of from 1 to 50 wt %, preferably from 5 to 30 wt %. If the concentration of water in the herbicidal composition is at least 5 wt %, such compositions may be referred to as aqueous compositions.
The herbicidal composition may also comprise at least one organic solvent. Typically, the herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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-C₁₆-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 herbicidal 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. The invention also relates to a method of producing the herbicidal composition comprising the step of contacting the amine component with the compound of formula (I) and glufosinate or a salt thereof in any given order. In one embodiment, the method of producing the herbicidal composition comprises the steps of a) contacting the amine component with the compound of formula (I); and b) contacting the glufosinate, or a salt thereof with the compound of formula (I), wherein steps a) and b) may be carried out in any given order. Typically, the method for producing the herbicidal composition also includes a step of adding water at either stage of the method.
The herbicidal 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 as defined herein below. 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 emulsifier, 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-substituted 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 auxiliaries. 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 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 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 glufosinate or a salt thereof, 5-60 wt % of compound of formula (I) and 1-50 wt % of the amine component are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) ad 100 wt %.
ii) Dispersible Concentrates (DC)
5-25 wt % of glufosinate or a salt thereof, 5 to 60 wt % of compound of formula (I), 1-50 wt % of the amine component, 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 glufosinate or a salt thereof, 5-10 wt % emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate), 5-60 wt % of compound of formula (I) and 1 to 50 wt % of the amine component 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 glufosinate or a salt thereof and 1-10 wt % emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) 5-60 wt % of compound of formula (I) and 1-50 wt % of the amine component 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 glufosinate or a salt thereof 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), 1-50 wt % of the amine component, 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) Microemulsion (ME)
5-20 wt % of glufosinate or a salt thereof 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), 1-50 wt % of the amine component, and 5-60 wt % of the compound of formula (I) and water ad 100%. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
vii) Microcapsules (CS)
An oil phase comprising 5-50 wt % of glufosinate or a salt thereof, 0-40 wt % water insoluble organic solvent (e.g. aromatic hydrocarbon), 5-60 wt % of compound of formula (I), 5-50 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 glufosinate or a salt thereof, 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 microcapsules are added to an aqueous composition containing 1-50 wt % of the amine component. The monomers amount to 1-10 wt %. The wt % relate to the total CS composition.
The compositions types i) to vii) 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.
Solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), emulsions (ES), emulsifiable concentrates (EC) 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 glufosinate or a salt thereof 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 herbicidal 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 herbicidal 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.
Exemplary formulation types of the herbicidal composition have been described in WO2007/092351A1 and WO2005/117583A2.
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 herbicidal composition comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the herbicidal 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 herbicidal composition according to the invention usually from a pre-dosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the herbicidal 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 herbicidal 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 herbicidal 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 herbicidal composition according to the invention or partially premixed components, e. g. components comprising compounds of formula (I) and/or glufosinate or a salt thereof and/or the amine component 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 herbicidal composition according to the invention or partially premixed components, e. g. components comprising compounds of formula (I) and/or glufosinate or a salt thereof and/or the amine component can be applied jointly (e.g. after tank mix) or consecutively.
The herbicidal compositions 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.
The herbicidal composition may contain a second agrochemical active ingredient. Typically, the second agrochemical active ingredient is a pesticide, preferably selected from fungicides, insecticides, nematicides, herbicides, safeners, micronutrients, biopesticides, nitrification inhibitors, and/or growth regulators. In one embodiment, the second agrochemical active ingredient is an insecticide. In another embodiment, the second agrochemical active ingredient is a fungicide. In yet another embodiment the second agrochemical active ingredient is a herbicide. 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, dinitroanilines, 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. 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 herbicidal composition may comprise the second 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 herbicidal composition. The herbicidal composition may comprise the second agrochemical active ingredient 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 herbicidal composition. The herbicidal composition may comprise the second agrochemical active ingredient 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.
Usually, the herbicidal composition contains glufosinate or a salt thereof, preferably the ammonium salt of glufosinate, and 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;
  and
  C) safeners.

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 herbicidal 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-C₅-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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal, 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, quizalofop-tefuryl, 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, thio-bencarb, 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, met-azosulfuron, 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, paraquat-dichloride 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-trifluoro-methylphenoxy)-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-trifluoro-methylphenoxy)-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, glyphosate-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 napropamide-M, 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 II.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 aminopyralid-dimethylammonium, 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 herbicidal 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 herbicidal 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 dichlorprop-butotyl 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, picloram-triisopropanolammonium, 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, chloramben-diolamine, 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, aminopyralid-dimethylammonium, and aminopyralid-tris(2-hydroxypropyl)ammonium.
Suitable salts of glyphosate are for example glyphosate-ammonium, glyphosate-diammonium, glyphosate-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, bromoxynil-heptanoate, 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, mecoprop-dimethylammonium, 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 aminocyclopyrachlor-dimethylammonium, aminocyclopyrachlor-methyl, aminocyclopyrachlor-triisopropanolammonium, 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 herbicidal composition” refers to herbicidal compositions comprising glufosinate or a salt thereof, preferably L-glufosinate or a salt thereof, such as the ammonium salt of glufosinate, and a herbicide B or a safener C.
In binary herbicidal compositions, the weight ratio of glufosinate or a salt thereof to 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 compositions comprising glufosinate or a salt thereof and a safener C, the weight ratio of glufosinate or a salt thereof 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 herbicidal compositions are suitable as herbicides. Accordingly, these herbicidal 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 composition by applying seed, pretreated with a 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 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. Non-phytotoxic oils and oil concentrates can also be added.
When employed in plant protection, the amounts of glufosinate or salt thereof 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 glufosinate or salt thereof is 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 glufosinate or salt thereof 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 glufosinate or salt thereof, the compound of formula (I), the amine component, and optionally the second 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 glufosinate or salt thereof, the compound of formula (I), the amine component, and optionally the second 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 herbicidal 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 esculenta, 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 herbicidal 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, preferably a resistance against glufosinate or its salts.
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, SYHTØH2, 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, GHB119, 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-gmc.org/GMCropDatabase), as well as in patent applications, like EP3028573 and WO2017/011288.
The use of herbicidal 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 vigour, 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 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 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.
The herbicidal 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 herbicidal 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, cucumber, 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 glufosinate tolerant crops. The herbicidal composition shows high herbicidal effects also against select crop plants, such as barley and soybean. This effect can be used to control crop plants in crop rotation methods of previously grown crop cultures. Typically, residual crop plants from previous rotation cycles remain after harvest and continue to grow within the subsequently grown crop variety. This reduces the yield since the crop plants of two different crop rotation cycles compete on the same locus of growth. The herbicidal composition may thus be applied to control residual crop plants from previous crop rotation cycles to allow for a homogeneous coverage with the subsequent crop plant.
In a preferred embodiment, the herbicidal 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 herbicidal 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 herbicidal 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 herbicidal composition is applied one time in about 12 months, i.e. in one application in about 12 months. In an alternative preferred embodiment, the herbicidal 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 herbicidal 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 in a burndown program, 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 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 x MIR604 x Bt11 x TC1507 x GA21 x MIR162 (event code: SYN-Ø53Ø7-1 x SYN-IR6Ø4-5 x SYN-BTØ11-1 x DAS-Ø15Ø7-1 x MON-ØØØ21-9 x 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 x MIR604 x Bt11 x TC1507 x GA21 (event code: SYN-Ø53Ø7-1 x SYN-IR6Ø4-5 x SYN-BTØ11-1 x DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure® Duracade™ 5122), 59122 x NK603 (event code: DAS-59122-7 x 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 x 59122 x MIR604 x TC1507 x GA21 (event code: SYN-BTØ11-1 x DAS-59122-7 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure® 3122), Bt11 x GA21 (event code: SYN-BTØ11-1 x MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure™ GT/CB/LL), Bt11 x MIR162 (event code: SYN-BTØ11-1 x SYN-IR162-4, gene: pat, e.g. commercially available as Agrisure® Viptera™ 2100), Bt11 x MIR162 x GA21 (event code: SYN-BTØ11-1 x SYN-IR162-4 x MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure® Viptera™ 3110), BT11 x MIR162 x MIR604 (event code: SYN-BTØ11-1 x SYN-IR162-4 x SYN-IR6Ø4-5, gene: pat, e.g. commercially available as Agrisure® Viptera™ 3100), Bt11 x MIR162 x MIR604 x GA21 (event code: SYN-BTØ11-1 x SYN-IR162-4 x SYN-IR6Ø4-5 x MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure® Viptera™ 3111, Agrisure® Viptera™ 4), Bt11 x MIR162 x TC1507 x GA21 (event code: SYN-BTØ11-1 x SYN-IR162-4 x DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat, e.g. commercially available as Agrisure™ Viptera 3220), Bt11 x MIR604 (event code: SYN-BTØ11-1 x SYN-IR6Ø4-5, gene: pat, e.g. commercially available as Agrisure™ CB/LL/RW), BT11 x MIR604 x GA21 (event code: SYN-BTØ11-1 x SYN-IR6Ø4-5 x 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 Star-link™ Maize), DBT418 (event code: DKB-89614-9, gene: bar, e.g. commercially available as Bt Xtra™ Maize), MON89034 x TC1507 x MON88017 x 59122 (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-88Ø17-3 x DAS-59122-7, gene: pat, e.g. commercially available as Genuity® SmartStax™), MON89034 x TC1507 x NK603 (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as Power Core™), NK603 x T25 (event code: MON-ØØ6Ø3-6 x 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 x MON810 (event code: ACS-ZMØØ3-2 x 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 x 59122 x MON810 x MIR604 x NK603 (event code: DAS-Ø15Ø7-1 x DAS-59122-7 x MON-ØØ81Ø-6 x SYN-IR6Ø4-5 x MON-ØØ6Ø3, gene: pat, e.g. commercially available as Optimum™ Intrasect Xtreme), TC1507 x 59122 (event code: DAS-Ø15Ø7-1 x DAS-59122-7, gene: pat, e.g. commercially available as Herculex XTRA™), TC1507 x 59122 x MON810 x NK603 (event code: DAS-Ø15Ø7-1 x DAS-59122-7 x MON-ØØ81Ø-6 x MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as Optimum™ Intrasect XTRA), TC1507 x 59122 x NK603 (event code: DAS-Ø15Ø7-1 x DAS-59122-7 x MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as Herculex XTRA™ RR), TC1507 x MIR604 x NK603 (event code: DAS-Ø15Ø7-1 x SYN-IR6Ø4-5 x MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as Optimum™ TRIsect), TC1507 x MON810 x NK603 (event code: DAS-Ø15Ø7-1 x MON-ØØ81Ø-6 x MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as Optimum™ Intrasect), TC1507 x NK603 (event code: DAS-Ø15Ø7-1 x MON-ØØ6Ø3-6, gene: pat, e.g. commercially available as Herculex™ I RR), 3272 x Bt11 (event code: SYN-E3272-5 x SYN-BTØ11-1 gene: pat), 3272 x Bt11 x GA21 (event code: SYN-E3272-5 x SYN-BTØ11-1 x MON-ØØØ21-9, gene: pat), 3272 x Bt11 x MIR604 (event code: SYN-E3272-5 x SYN-BTØ11-1 x SYN-IR6Ø4-5, gene: pat), 3272 x BT11 x MIR604 x GA21 (event code: SYN-E3272-5 x SYN-BTØ11-1 x SYN-IR6Ø4-5 x MON-ØØØ21-9, gene: pat), 33121 (event code: DP-Ø33121-3, gene: pat), 4114 (event code: DP-ØØ4114-3, gene: pat), 59122 x GA21 (event code: DAS-59122-7 x MON-ØØØ21-9, gene: pat), 59122 x MIR604 (event code: DAS-59122-7 x SYN-IR6Ø4-5, gene: pat), 5307 x MIR604 x Bt11 x TC1507 x GA21 x MIR162 (event code: gene: pat), 59122 x MIR604 x GA21 (event code: DAS-59122-7 x SYN-IR6Ø4-5 x MON-ØØØ21-9, gene: pat), 59122 x MIR604 x TC1507 (event code: DAS-59122-7 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1, gene: pat), 59122 x MIR604 x TC1507 x GA21 (event code: gene: pat), (event code: DAS-59122-7 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat), 59122 x MON810 (event code: DAS-59122-7 x MON-ØØ81Ø-6, gene: pat), 59122 x MON810 x NK603 (event code: DAS-59122-7 x MON-ØØ81Ø-6 x MON-ØØ6Ø3-6, gene: pat), 59122 x TC1507 x GA21 (event code: DAS-59122-7 x DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat), 676 (event code: PH-ØØØ676-7, gene: pat), 678 (event code: PH-ØØØ678-9, gene: pat), 680 (event code: PH-ØØØ68Ø-2, gene: pat), 98140 x 59122 (event code: DP-Ø9814Ø-6 x DAS-59122-7, gene: pat), 98140 x TC1507 (event code: DP-Ø9814Ø-6 x DAS-Ø15Ø7-1, gene: pat), 98140 x TC1507 x 59122 (event code: DP-Ø9814Ø-6 x DAS-Ø15Ø7-1 x DAS-59122-7, gene: pat), 59122 x MON88017 (event code: DAS-59122-7 x MON-88Ø17-3, gene: pat), Bt11 x 59122 (event code: SYN-BTØ11-1 x DAS-59122-7, gene: pat), Bt11 x 59122 x GA21 (event code: SYN-BTØ11-1 x DAS-59122-7 x MON-ØØØ21-9, gene: pat), Bt11 x 59122 x MIR604 (event code: SYN-BTØ11-1 x DAS-59122-7 x SYN-IR6Ø4-5, gene: pat), Bt11 x 59122 x MIR604 x GA21 (event code: SYN-BTØ11-1 x DAS-59122-7 x SYN-IR6Ø4-5 x MON-ØØØ21-9, gene: pat), Bt11 x 59122 x MIR604 x TC1507 (event code: Bt11 x 59122 x MIR604 x TC1507, gene: pat), Bt11 x 59122 x TC1507 (event code: SYN-BTØ11-1 x DAS-59122-7 x DAS-Ø15Ø7-1, gene: pat), Bt11 x 59122 x TC1507 x GA21 (event code: SYN-BTØ11-1 x DAS-59122-7 x DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat), Bt11 x MIR162 x TC1507 (event code: SYN-BTØ11-1 x SYN-IR162-4 x DAS-Ø15Ø7-1, gene: pat), Bt11 x MIR604 x TC1507 (event code: SYN-BTØ11-1 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1, gene: pat), Bt11 x TC1507 (event code: SYN-BTØ11-1 x DAS-Ø15Ø7-1, gene: pat), Bt11 x TC1507 x GA21 (event code: SYN-BTØ11-1 x DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat), GA21 x T25 (event code: MON-ØØØ21-9 x ACS-ZMØØ3-2, gene: pat), MIR162 x TC1507 (event code: SYN-IR162-4 x DAS-Ø15Ø7-1, gene: pat), MIR162 x TC1507 x GA21 (event code: SYN-IR162-4 x DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat), MIR604 x TC1507 (event code: SYN-IR6Ø4-5 x DAS-Ø15Ø7-1, gene: pat), MON87427 x MON89034 x TC1507 x MON88017 x 59122 (event code: MON-87427-7 x MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-88Ø17-3 x DAS-59122-7, gene: pat), MON89034 x 59122 (event code: MON-89Ø34-3 x DAS-59122-7, gene: pat), MON89034 x 59122 x MON88017 (event code: gene: pat), MON89034 x TC1507 (event code: MON-89Ø34-3 x DAS-59122-7 x MON-88Ø17-3, gene: pat), (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1, gene: pat), MIR604 x TC1507 (event code: SYN-IR6Ø4-5 x DAS-Ø15Ø7-1, gene: pat), MON87427 x MON89034 x TC1507 x MON88Ø17 x 59122 (event code: MON-87427-7 x MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-88Ø17-3 x DAS-59122-7, gene: pat), MON89034 x 59122 (event code: MON-89Ø34-3 x DAS-59122-7, gene: pat), MON89Ø34 x 59122 x MON88017 (event code: gene: pat), MON89034 x TC1507 (event code: MON-89Ø34-3 x DAS-59122-7 x MON-88Ø17-3, gene: pat), (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1, gene: pat), DLL25 (B16) (event code: DKB-8979Ø-5, gene: bar), MIR604 x TC1507 (event code: SYN-IR6Ø4-5 x DAS-Ø15Ø7-1, gene: pat), MON87427 x MON89Ø34 x TC15Ø7 x MON88Ø17 x 59122 (event code: MON-87427-7 x MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-88Ø17-3 x DAS-59122-7, gene: pat), MON89034 x 59122 (event code: MON-89Ø34-3 x DAS-59122-7, gene: pat), MON89034 x 59122 x MON88017 (event code: MON-89Ø34-3 x DAS-59122-7 x MON-88Ø17-3, gene: pat), MON89034 x TC1507 (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1, gene: pat), MON89034 x TC1507 x 59122 (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1 x DAS-59122-7, gene: pat), MON89034 x TC1507 x MON88017 (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-88Ø17-3, gene: pat), MON89034 x TC1507 x MON88017 x 59122 x DAS40278 (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-88Ø17-3 x DAS-59122-7 x DAS-4Ø278-9, gene: pat), MON89034 x TC1507 x MON88017 x DAS40278 (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-88Ø17-3 x DAS-59122-7 x DAS-4Ø278-9, gene: pat), MON89034 x TC1507 x NK603 x DAS40278 (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-ØØ6Ø3-6 x DAS-4Ø278-9, gene: pat), NK603 x MON810 x 4114 x MIR 604 (event code: MON-00603-6 x MON-00810-6 x DP004114-3 x SYN-IR604-4, gene: pat), TC1507 x MON810 x MIR604 x NK603 (event code: DAS-Ø15Ø7-1 x MON-ØØ81Ø-6 x SYN-IR6Ø4-5 x MON-ØØ6Ø3-6, gene: pat), TC1507 x 59122 x MON810 (event code: DAS-Ø15Ø7-1 x DAS-59122-7 x MON-ØØ81Ø-6, gene: pat), TC1507 x 59122 x MON88017 (event code: DAS-Ø15Ø7-1 x DAS-59122-7 x MON-88Ø17-3, gene: pat), TC1507 x GA21 (event code: DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat), TC1507 x MON810 (event code: DAS-Ø15Ø7-1 x MON-ØØ81Ø-6, gene: pat), TC1507 x MON810 x MIR162 x NK603 (event code: DAS-Ø15Ø7-1 x MON-ØØ81Ø-6 x SYN-IR162-4 x MON-ØØ6Ø3-6, gene: pat), 3272 x Bt11 x MIR604 x TC1507 x 5307 x GA21 (event code: SYN-E3272-5 x SYN-BTØ11-1 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), TC1507 x MIR162 x NK603 (event code: DAS-Ø15Ø7-1 x SYN-IR162-4 x MON-ØØ6Ø3-6, gene: pat), TC1507 x MON810 x MIR162 (event code: DAS-Ø15Ø7-1 x MON-ØØ81Ø-6 x SYN-IR162-4, gene: pat), MON87419 (event code: MON87419-8, gene: pat), TC1507 x MON88017 (event code: DAS-Ø15Ø7-1 x MON-88Ø17-3, gene: pat), TC6275 (event code: DAS-Ø6275-8, gene: bar), MZHG0JG (event code: SYN-ØØØJG-2, gene: pat), MZIR098 (event code: SYN-ØØØ98-3, gene: pat), Bt11 x MIR162 x MON89034 (event code: SYN-BTØ11-1 x SYN-IR162-4 x MON-89Ø34-3, gene: pat) and Bt11 x MIR162 x MON89Ø34 x GA21 (event code: SYN-BTØ11-1 x SYN-IR162-4 x MON-89Ø34-3 x MON-ØØØ21-9, gene: pat), 59122 x DAS40278 (event code: DAS-59122-7 x DAS-4Ø278-9, gene: pat), 59122 x MON810 x MIR604 (event code: DAS-59122-7 x MON-ØØ81Ø-6 x SYN-IR6Ø4-5, gene: pat), 59122 x MON810 x NK603 x MIR604 (event code: DAS-59122-7 x MON-ØØ81Ø-6 x MON-ØØ6Ø3-6 x SYN-IR6Ø4-5, gene: pat), 59122 x MON88017 x DAS40278 (event code: DAS-59122-7 x MON-88Ø17-3 x DAS-4Ø278-9, gene: pat), 59122 x NK603 x MIR604 (event code: DAS-59122-7 x MON-ØØ6Ø3-6 x SYN-IR6Ø4-5, gene: pat), Bt11 x 5307 (event code: SYN-BTØ11-1 x SYN-Ø53Ø7-1, gene: pat), Bt11 x 5307 x GA21 (event code: SYN-BTØ11-1 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), Bt11 x MIR162 x 5307 (event code: SYN-BTØ11-1 x SYN-IR162-4 x SYN-Ø53Ø7-1, gene: pat), Bt11 x MIR162 x 5307 x GA21 (event code: SYN-BTØ11-1 x SYN-IR162-4 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), BT11 x MIR162 x MIR604 x 5307 (event code: SYN-BTØ11-1 x SYN-IR162-4 x SYN-IR6Ø4-5 x SYN-Ø53Ø7-1, gene: pat), Bt11 x MIR162 x MIR604 x 5307 x GA21 (event code: SYN-BTØ11-1 x SYN-IR162-4 x SYN-IR6Ø4-5 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), Bt11 x MIR162 x MIR604 x MON89034 x 5307 x GA21 (event code: SYN-BTØ11-1 x SYN-IR162-4 x SYN-IR6Ø4-5 x MON-89Ø34-3 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), BT11 x MIR162 x MIR604 x TC1507 (event code: SYN-BTØ11-1 x SYN-IR162-4 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1, gene: pat), BT11 x MIR162 x MIR604 x TC1507 x 5307 (event code: SYN-BTØ11-1 x SYN-IR162-4 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1, gene: pat), Bt11 x MIR162 x MIR604 x TC1507 x GA21 (event code: SYN-BTØ11-1 x SYN-IR162-4 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat), Bt11 x MIR162 x TC1507 x 5307 (event code: SYN-BTØ11-1 x SYN-IR162-4 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1, gene: pat), BT11 x MIR162 x MIR604 x TC1507 x 5307 (event code: SYN-BTØ11-1 x SYN-IR162-4 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1, gene: pat), Bt11 x MIR162 x MIR604 x TC1507 x GA21 (event code: SYN-BTØ11-1 x SYN-IR162-4 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat), Bt11 x MIR162 x TC1507 x 5307 (event code: SYN-BTØ11-1 x SYN-IR162-4 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1, gene: pat), Bt11 x MIR162 x TC1507 x 5307 x GA21 (event code: SYN-BTØ11-1 x SYN-IR162-4 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), Bt11 x MIR604 x 5307 (event code: SYN-BTØ11-1 x SYN-IR6Ø4-5 x SYN-Ø53Ø7-1, gene: pat), Bt11 x MIR604 x 5307 x GA21 (event code: SYN-BTØ11-1 x SYN-IR6Ø4-5 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), Bt11 x MIR604 x TC1507 x 5307 (event code: SYN-BTØ11-1 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1, gene: pat), Bt11 x MIR604 x TC1507 x GA21 (event code: SYN-BTØ11-1 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat), Bt11 x MON89034 (or Bt11 x MON89Ø34) (event code: SYN-BTØ11-1 x MON-89Ø34-3, gene: pat), Bt11 x MON89034 x GA21 (event code: SYN-BTØ11-1 x MON-89Ø34-3 x MON-ØØØ21-9, gene: pat), Bt11 x MON89Ø34 x GA21 (event code: SYN-BTØ11-1 x MON-89Ø34-3 x MON-ØØØ21-9, gene: pat), Bt11 x TC1507 x 5307 (event code: SYN-BTØ11-1 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1, gene: pat), Bt11 x TC1507 x 5307 x GA21 (event code: SYN-BTØ11-1 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), MIR162 x MIR604 x TC1507 x 5307 (event code: SYN-IR162-4 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1, gene: pat), MIR162 x MIR604 x TC1507 x 5307 x GA21 (event code: SYN-IR162-4 x SYN-IR6Ø4-5 x DAS-01507-1 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), MIR162 x MIR604 x TC1507 x GA21 (event code: SYN-IR162-4 x SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x MON-ØØØ21-9, gene: pat), MIR162 x TC1507 x 5307 (event code: SYN-IR162-4 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1, gene: pat), MIR162 x TC1507 x 5307 x GA21 (event code: SYN-IR162-4 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), MIR604 x TC1507 x 5307 (event code: SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1, gene: pat), MIR162 x TC1507 x 5307 (event code: SYN-IR162-4 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1, gene: pat), MIR162 x TC1507 x 5307 x GA21 (event code: SYN-IR162-4 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), MIR604 x TC1507 x 5307 (event code: SYN-IR6Ø4-5 x DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1, gene: pat), MIR604 x TC1507 x 5307 x GA21 (event code: SYN-IR6Ø4-5 x TC1507 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), MIR604 x TC1507 x GA21 (event code: SYN-IR6Ø4-5 x TC1507 x MON-ØØØ21-9, gene: pat), MON87427 x 59122 (event code MON-87427-7 x DAS-59122-7: gene: pat), MON87427 x MON89034 x 59122 (event code: MON-87427-7 x MON-89Ø34-3 x DAS-59122-7, gene: pat), MON87427 x MON89034 x MON88017 x 59122 (event code: MON-87427-7 x MON-89Ø34-3 x MON-88Ø17-3 x 59122, gene: pat), MON87427 x MON89034 x TC1507 (event code: MON-87427-7 x MON-89Ø34-3 x DAS-Ø15Ø7-1, gene: pat), MON87427 x MON89034 x TC1507 x 59122 (event code: MON-87427-7 x MON-89Ø34-3 x DAS-Ø15Ø7-1 x DAS-59122-7, gene: pat), MON87427 x MON89034 x TC1507 x MON87411 x 59122 (event code: MON-87427-7 x MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-87411-9 x DAS-59122-7, gene: pat), MON87427 x MON89034 x TC1507 x MON87411 x 59122 x DAS40278 (event code: MON-87427-7 x MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-87411-9 x DAS-59122-7 x DAS-4Ø278-9, gene: pat), MON87427 x MON89034 x TC1507 x MON88017 (event code: MON-87427-7 x MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-88Ø17-3, gene: pat), MON87427 x TC1507 (event code: MON-87427-7 x DAS-Ø15Ø7-1, gene: pat), MON87427 x TC1507 x 59122 (event code: MON-87427-7 x DAS-Ø15Ø7-1 x DAS-59122-7, gene: pat), MON87427 x TC1507 x MON88017 (event code: MON-87427-7 x DAS-Ø15Ø7-1 x MON-88Ø17-3, gene: pat), MON87427 x TC1507 x MON88017 x 59122 (event code: MON-87427-7 x DAS-Ø15Ø7-1 x MON-88Ø17-3 x DAS-59122-7, gene: pat), MON89034 x 59122 x DAS40278 (event code: MON-89Ø34-3 x DAS-59122-7 x DAS-40278-9, gene: pat), MON89034 x 59122 x MON88017 x DAS40278 (event code: MON-89Ø34-3 x DAS-59122-7 x MON-88Ø17-3 x DAS-4Ø278-9, gene: pat), MON89034 x TC1507 x 59122 x DAS40278 (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1 x DAS-59122-7 x DAS-4Ø278-9, gene: pat), MON89Ø34 x TC1507 x DAS40278 (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1 x DAS-4Ø278-9, gene: pat), MON89034 x TC1507 x NK603 x MIR162 (event code: MON-89Ø34-3 x DAS-Ø15Ø7-1 x MON-ØØ6Ø3-6 x SYN-IR162-4, gene: pat), TC1507 x 5307 (event code: DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1, gene: pat), TC1507 x 5307 x GA21 (event code: DAS-Ø15Ø7-1 x SYN-Ø53Ø7-1 x MON-ØØØ21-9, gene: pat), TC1507 x 59122 x DAS40278 (event code: DAS-Ø15Ø7-1 x DAS-59122-7 x DAS-4Ø278-9, gene: pat), TC1507 x 59122 x MON810 x MIR604 (event code: DAS-Ø15Ø7-1 x DAS-59122-7 x MON-ØØ81Ø-6 x SYN-IR6Ø4-5, gene: pat), TC1507 x 59122 x MON88017 x DAS40278 (event code: DAS-Ø15Ø7-1 x DAS-59122-7 x MON-88Ø17-3 x DAS-4Ø278-9, gene: pat), TC1507 x 59122 x NK603 x MIR604 (event code: gene: pat) DAS-Ø15Ø7-1 x DAS-59122-7 x MON-ØØ6Ø3-6 x SYN-IR6Ø4-5, TC1507 x DAS40278 (event code: DAS-Ø15Ø7-1 x DAS-4Ø278-9, gene: pat), TC1507 x MON810 x MIR604 (event code: DAS-Ø15Ø7-1 x MON-ØØ81Ø-6 x SYN-IR6Ø4-5, gene: pat), TC1507 x MON810 x NK603 x MIR604 (event code: DAS-Ø15Ø7-1 x MON-ØØ81Ø-6 x MON-ØØ6Ø3-6 x SYN-IR6Ø4-5, gene: pat), TC1507 x MON88017 x DAS40278 (event code: DAS-Ø15Ø7-1 x MON-88Ø17-3 x DAS-4Ø278-9, gene: pat) and TC1507 x NK603 x DAS40278 (event code: DAS-Ø15Ø7-1 x MON-ØØ6Ø3-6 x DAS-4Ø278-9, 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 x MON89788 (event code: DAS-68416-4 x MON-89788-1, gene: pat), SYHTOH2 (event code: SYN-ØØØH2-5, gene: pat), DAS81419 x DAS444Ø6-6 (event code: DAS-81419-2 x DAS-444Ø6-6, gene: pat) and FG72 x A5547-127 (event code: MST-FGØ72-3 x ACS-GMØØ6-4, gene: pat).
Transgenic cotton events comprising glufosinate tolerance genes are for example, but not excluding others, 3006-210-23 x 281-24-236 x MON1445 (event code: DAS-21Ø23-5 x DAS-24236-5 x MON-Ø1445-2, gene: bar, e.g. commercially available as WideStrike™ Roundup Ready™ Cotton), 3006-210-23 x 281-24-236 x MON88913 (event code: DAS-21Ø23-5 x DAS-24236-5 x MON-88913-8, gene: bar, e.g. commercially available as Widestrike™ Roundup Ready Flex™ Cotton), 3006-210-23 x 281-24-236 x MON88913 x COT102 (event code: DAS-21Ø23-5 x DAS-24236-5 x MON-88913-8 x SYN-IR102-7, gene: pat, e.g. commercially available as Widestrike™ x Roundup Ready Flex™ x VIPCOT™ Cotton), GHB614 x LLCotton25 (event code: BCS-GHØØ2-5 x ACS-GHØØ1-3, gene: bar, e.g. commercially available as GlyTol™ Liberty Link™), GHB614 x T304-40 x GHB119 (event code: BCS-GHØØ2-5 x BCS-GHØØ4-7 x BCS-GHØØ5-8, gene: bar, e.g. commercially available as Glytol™ x Twinlink™) LLCotton25 (event code: ACS-GHØØ1-3, gene: bar, e.g. commercially available as ACS-GHØØ1-3), GHB614 x T304-40 x GHB119 x COT102 (event code: BCS-GHØØ2-5 x BCS-GHØØ4-7 x BCS-GHØØ5-8 x SYN-IR102-7, gene: bar, e.g. commercially available as Glytol™ x Twinlink™ x VIPCOT™ Cotton), LLCotton25 x MON15985 (event code: ACS-GHØØ1-3 x MON-15985-7, gene: bar, e.g. commercially available as Fibermax™ Liberty Link™ Bollgard II™), T304-40 x GHB119 (event code: BCS-GHØØ4-7 x BCS-GHØØ5-8, gene: bar, e.g. commercially available as TwinLink™ Cotton), GHB614 x T304-40 x GHB119 x COT102 (event code: BCS-GHØØ2-5 x BCS-GHØØ4-7 x BCS-GHØØ5-8 x SYN-IR1Ø2-7, gene: bar, e.g. commercially available as Glytol™ x Twinlink™ x VIPCOT™ Cotton), GHB119 (event code: BCS-GHØØ5-8, gene: bar), GHB614 x LLCotton25 x MON15985 (event code: CS-GHØØ2-5 x ACS-GHØØ1-3 x MON-15985-7, gene: bar), MON 887Ø1-3 (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 887Ø1-3, gene: bar), MON88701 x MON88913 (event code: MON 887Ø1-3 x MON-88913-8, gene: bar), MON88701 x MON88913 x MON15985 (event code: MON 887Ø1-3 x MON-88913-8 x MON-15985-7, gene: bar), 281-24-236 x 33 3006-210-23 x COT102 x 81910 (event code: DAS-24236-5 x DAS-21Ø23-5 x SYN-IR1Ø2-7 x DAS-81910-7, gene: pat), COT102 x MON15985 x MON88913 x MON88701 (event code: SYN-IR1Ø2-7 x MON-15985-7 x MON-88913-8 x MON 887Ø1-3, gene: bar) and 3006-210-23 x 281-24-236 x MON88913 x COT102 x 81910 (event code: DAS-21Ø23-5 x DAS-24236-5 x MON-88913-8 x SYN-IR1Ø2-7 x 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 x RF1 (PGS1) (event code: ACS-BNØØ4-7 x ACS-BNØØ1-4, gene: bar, e.g. commercially available as InVigor™ Canola), MS1 x RF2 (PGS2) (event code: ACS-BNØØ4-7 x ACS-BNØØ2-5, gene: bar, e.g. commercially available as InVigor™ Canola), MS1 x RF3 (event code: ACS-BNØØ4-7 x 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 x RF3 (event code: ACS-BNØØ5-8 x 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 x MON88302 (event code: ACS-BNØØ4-7 x MON-883Ø2-9, gene: bar, e.g. commercially available as InVigor™ x TruFlex™ Roundup Ready™ Canola), MS8 x MON88302 (event code: ACS-BNØØ5-8 x MON-883Ø2-9, gene: bar, e.g. commercially available as InVigor™ x TruFlex™ Roundup Ready™ Canola), RF1 x MON88302 (event code: ACS-BNØØ1-4 x MON-883Ø2-9, gene: bar, e.g. commercially available as InVigor™ x TruFlex™ Roundup Ready™ Canola), RF2 x MON88302 (event code: ACS-BNØØ2-5 x MON-883Ø2-9, gene: bar, e.g. commercially available as InVigor™ x TruFlex™ Roundup Ready™ Canola), HCN28 x MON88302 (event code: ACS-BNØØ8-2 x MON-883Ø2-9, gene: pat, e.g. commercially available as InVigor™ x TruFlex™ Roundup Ready™ Canola), HCN92 x MON88302 (event code: ACS-BNØØ7-1 x MON-883Ø2-9, gene: bar, e.g. commercially available as Liberty Link™ Innovator™ x TruFlex™ Roundup Ready™ Canola), HCR-1 (gene: pat), MON88302 x MS8 x RF3 (event code: MON-883Ø2-9 x ACS-BNØØ5-8 x ACS-BNØØ3-6, gene: bar), MON88302 x RF3 (event code: MON-883Ø2-9 x ACS-BNØØ3-6, gene: bar), MS8 x RF3 x GT73 (RT73) (event code: gene: bar), PHY14 (event code: ACS-BNØØ5-8 x ACS-BNØØ3-6 x MON-ØØØ73-7, gene: bar), PHY23 (gene: bar), PHY35 (gene: bar) and PHY36 (gene: bar) and 73496 x RF3 (event code: DP-Ø73496-4 x 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 herbicidal 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 für 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 herbicidal compositions act efficiently are selected from amongst the species Hordeum murinum, Echinochloa crus-galli, 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 herbicidal 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 herbicidal 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 herbicidal compositions act efficiently are selected from amongst the species Amaranthus spinosus, Polygonum convolvulus, Medicago polymorpha, Mollugo verticillata, Cyclospermum leptophyllum, Stellaria media, Gnaphalium purpureum, Taraxacum offi cinale, 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 cau-lescens, Sisymbrium irio, Sesbania exaltata, Capsella bursa-pastoris, Sonchus oleraceus, Euphorbia maculate, Helianthus annuus, Coronopus didymus, Salsola tragus, Abutilon theophrasti, Vicia ben-ghalensis 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 herbicidal 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.
Herbicidal 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 herbicidal compositions 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal 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 herbicidal composition can also be used for weed control in turf and lawn provided the desirable grass species are tolerant to herbicidal composition. In particular, such herbicidal 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 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.
The present invention also relates to a method for controlling undesirable vegetation, which method comprises applying the herbicidal 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 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 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 herbicidal 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 herbicidal 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 herbicidal 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 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 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 resistant go glufosinate or its salts, such as listed in the International Survey of Resistant Weeds, for example ACCase resistant Echinochloa crus-galli, Avena fatua, Alopecurus myosuroides, Echinochloa colona, Alopecurus japonicus, Bromus tectorum, Hordeum murinum, Ischaemum rugosum, Setaria viridis, Sorghum halepense, Alopecurus aequalis, Apera spica-venti, 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 crus-galli, 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 spica-venti, 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 crus-galli, 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 spica-venti, 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 bursa-pastoris, 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 crus-galli, 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 crus-pavonis, 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 crus-galli.
The herbicidal 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); and garden 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 herbicidal 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 herbicidal 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 invention also relates to plant propagation material comprising the herbicidal composition; and to a method for treating plant propagation material comprising the step of treating plant propagation material with the herbicidal composition.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of glufosinate or salt thereof 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 herbicidal 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 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. Preferably, the term seed refers to a seed of a modified plant that is resistant against glufosinate.
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 herbicidal compositions have an enhanced biological effect on undesired vegetation as compared to liquid glufosinate formulations that contain a compound of formula (I) but not containing the amine component. Another advantage is the reduced damage of certain crop plants by the herbicidal composition, and a defoliation effect on other crop plants. Further advantages are a higher loading with glufosinate, lower application rates, and higher maximum concentrations with compounds of formula (I).
The following examples illustrate the invention.

Ingredients:

Pesticide A: ammonium salt of glufosinate
Adjuvant A: aqueous solution of alkylpolyglycosides, based on C₈-C₁₉-alcohol
Additive A: sodium laurylethersulfate containing two molecules of polymerized ethylene oxide, 70 wt % in water

EXAMPLE-1: PREPARATION OF HERBICIDAL COMPOSITIONS AND COMPARATIVE COMPOSITIONS

Four compositions according to the invention A1 to A4, as well as four comparative compositions AC1 to AC4 were prepared by mixing the ingredients at the concentrations as provided in Tables A and B.

TABLE A

Ingredients of compositions
A1, A2, A3 and A4 in [g/l].

Ingredient [g/l]	A1	A2	A3	A4

Pesticide A	280	280	280	280
Additive A	222	222	222	222
Adjuvant A	—	—	—	—
Propylene glycol	46	46	46	46
monomethyl ether
Dipropylene glycol	116	116	116	116
Triethanolamine	176	—	—	—
Ethanolamine	—	176	—	—
Diglycolamine	—	—	176	—
Cholin chloride	—	—	—	176
Water	to 1	to 1	to 1	to 1
	liter	liter	liter	liter

TABLE B

Ingredients of compositions AC1, AC2, AC3, and AC4 in [g/l].

Ingredient [g/l]	AC1	AC2	AC3	AC4

Pesticide A	280	280	280	280
Additive A	222	222	296.4	222
Adjuvant A	—	123	123	—
Propylene glycol	46	46	46	46
monomethyl ether
Dipropylene glycol	116	116	116	116
Hexadecyltrimethyl	176	—	—	—
ammonium chloride
Ethanolamine	—	—	—	—
Diglycolamine	—	—	—	—
Cholin chloride	—	—	—	—
Water	to 1 liter	to 1 liter	to 1 liter	to 1 liter

EXAMPLE-2: BIOLOGICAL TESTING ON CROP PLANTS

The compositions A1 to A4, and AC1 to AC4 as prepared in Example-1 were tested for their biological effect on the crops spring barley, Hordeum vulgare var. Adonis, and soybean, Glycine max var. Sultana. To this end, spring barley was grown to growth stage of 12/13 according to the BBCH scale. Soybean plants were grown to growth stages 14/15 according to the BBCH scale. Directly before application the plants were watered as needed. Application of the herbicidal compositions was carried out in a spraying chamber. The herbicidal compositions were diluted with water and applied in a rate of 200 liters/hectare. The amount of Pesticide A applied is listed in Tables C, C, E and F. After application the plant remained for 30 minutes minimum in a drying tunnel (air flow volume 3000 m³/h) to get the surface of the plants complete dry before putting them in the greenhouse. The herbicidal activity was evaluated 7 and 20 days after treatment by awarding scores to the treated plants in comparison to the untreated control plants (Tables C, D, E and F). The evaluation scale ranges from 0% go 100% activity. 100% activity means the complete death of at least those parts of the plant that are above ground. Conversely, 0% activity means that there were no differences between treated and untreated plants. Experiments that were carried out on the same days at the same time have the same letter in brackets in Tables C, D, E and F.

TABLE C

control of spring barley with inventive compositions A1,
A2, A3, and A4. The letter in brackets behind the
composition name indicates a testing series from which
the respective data were obtained. DAT is days after
treatment; GS is growth stage according to BBCH scale.

	Application	Control of	Control of
	rate	Barley [%],	Barley [%],
	[grams a.i./	GS 12/13,	GS 12/13,
Composition	hectare]	7 DAT	20 DAT

A1(b)	300	58	63
A2(b)	300	40	45
A3(b)	300	53	60
A4(c)	300	38	45

TABLE D

control of spring barley with comparative compositions AC1,
AC2, AC3, and AC4. The letter in brackets behind the
composition name indicates a testing series from
which the respective data were obtained. DAT is days
after treatment; GS is growth stage according to BBCH scale.

AC1(a)	300	35	25
AC2(b)	300	28	40
AC3(d)	300	50	38
AC4(b)	300	33	40

TABLE E

control of soybean plants with inventive
compositions A1, A2, A3, and A4. The letter in
brackets behind the composition name indicates
the testing series from which the respective
data were obtained. DAT is days after treatment;
GS is growth stage according to BBCH scale.

	Application	Control of	Control of
	rate	Soybean [%],	Soybean [%],
	[grams a.i./	GS 14/15,	GS 14/15,
Composition	hectare]	7 DAT	20 DAT

A1(b)	150	80	75
A2(b)	150	80	78
A3(b)	150	85	83
A4(c)	150	88	73

TABLE F

control of soybean plants with comparative compositions
AC1, AC2, AC3, and AC4. The letter in brackets behind the
composition name indicates the testing series from which the
respective data were obtained. DAT is days after treatment;
GS is growth stage according to BBCH scale.

AC1(a)	150	58	15
AC2(b)	150	60	74
AC3(d)	150	70	50
AC4(b)	150	33	45

EXAMPLE-3: BIOLOGICAL TESTING ON ECHINACEA CRUS-GALLI

The compositions A1 to A4, and AC1 to AC4 as prepared in Example-1 were tested for their biological effect on the Echinacea crus-galli. To this end, weeds were grown to growth stage of 16/18 according to the BBCH scale. Directly before application the plants were watered as needed. Application of the herbicidal compositions was carried out in a spraying chamber. The herbicidal compositions were diluted with water and applied in a rate of 200 liters/hectare. The amount of Pesticide A applied is listed in Tables G, and H. After application the plant remained for 30 minutes minimum in a drying tunnel (air flow volume 3000 m³/h) to get the surface of the plants complete dry before putting them in the greenhouse. The herbicidal activity was evaluated 7 and 20 days after treatment by awarding scores to the treated plants in comparison to the untreated control plants (Tables G, and H). The evaluation scale ranges from 0% go 100% activity. 100% activity means the complete death of at least those parts of the plant that are above ground. Conversely, 0% activity means that there were no differences between treated and untreated plants. Experiments that were carried out on the same days at the same time have the same letter in brackets in Tables G, and H

TABLE G

control of Echinacea crus-galli with inventive compositions A1, A2,
A3, and A4. The letter in brackets behind the composition name
indicates a testing series from which the respective data were obtained.
DAT is days after treatment; GS is growth stage according to BBCH scale.

	Application	Control of	Control of
	rate	E.crus-galli [%],	E.crus-galli [%],
	[grams a.i./	GS 16/18,	GS 16/18,
Composition	hectare]	7 DAT	20 DAT

A1(b)	150	93	93
A2(b)	150	90	83
A3(b)	150	93	95
A4(c)	150	85	78

TABLE H

control of Echinacea crus-galli with comparative compositions
AC1, AC2, AC3, and AC4. The letter in brackets behind the
composition name indicates a testing series from which the
respective data were obtained. DAT is days after treatment;
GS is growth stage according to BBCH scale.

AC1(a)	150	45	18
AC2(b)	150	88	78
AC3(d)	150	40	28
AC4(b)	150	78	75

EXAMPLE-4: BIOLOGICAL TESTING ON GALIUM APARINE

The compositions A1 to A4, and AC1 to AC4 as prepared in Example-1 were tested for their biological effect on Galium aparine. To this end, weeds were grown to growth stage of 12/13 according to the BBCH scale. Directly before application the plants were watered as needed. Application of the herbicidal compositions was carried out in a spraying chamber. The herbicidal compositions were diluted with water and applied in a rate of 200 liters/hectare. The amount of Pesticide A applied is listed in Tables L, and M. After application the plant remained for 30 minutes minimum in a drying tunnel (air flow volume 3000 m³/h) to get the surface of the plants complete dry before putting them in the greenhouse. The herbicidal activity was evaluated 7 and 20 days after treatment by awarding scores to the treated plants in comparison to the untreated control plants (Tables L, and M). The evaluation scale ranges from 0% go 100% activity. 100% activity means the complete death of at least those parts of the plant that are above ground. Conversely, 0% activity means that there were no differences between treated and untreated plants. Experiments that were carried out on the same days at the same time have the same letter in brackets in Tables L, and M.

TABLE L

control of Galium aparine with inventive compositions A1, A2, A3,
and A4. The letter in brackets behind the composition name indicates
a testing series from which the respective data were obtained. DAT
is days after treatment; GS is growth stage according to BBCH scale.

	Application	Control of	Control of
	rate	G.aparine [%],	G.aparine [%],
	[grams a.i./	GS 12/13,	GS 12/13,
Composition	hectare]	7 DAT	20 DAT

A1(b)	150	83	63
A2(b)	150	75	53
A3(b)	150	90	80
A4(c)	150	65	55

TABLE H

control of Galium aparine with comparative compositions
AC1, AC2, AC3, and AC4. The letter in brackets behind
the composition name indicates a testing series from
which the respective data were obtained. DAT is days
after treatment; GS is growth stage according to BBCH scale.

AC1(a)	150	68	43
AC2(b)	150	80	53
AC3(d)	150	85	68
AC4(b)	150	48	18

EXAMPLE-5: BIOLOGICAL TESTING ON ABUTILON THEOPHRASTI

The compositions A1 to A4, and AC1 to AC4 as prepared in Example-1 were tested for their biological effect on Abutilon theophrasti. To this end, weeds were grown to growth stage of 14/15 according to the BBCH scale. Directly before application the plants were watered as needed. Application of the herbicidal compositions was carried out in a spraying chamber. The herbicidal compositions were diluted with water and applied in a rate of 200 liters/hectare. The amount of Pesticide A applied is listed in Tables N, and O. After application the plant remained for 30 minutes minimum in a drying tunnel (air flow volume 3000 m³/h) to get the surface of the plants complete dry before putting them in the greenhouse. The herbicidal activity was evaluated 7 and 20 days after treatment by awarding scores to the treated plants in comparison to the untreated control plants (Tables N, and O). The evaluation scale ranges from 0% go 100% activity. 100% activity means the complete death of at least those parts of the plant that are above ground. Conversely, 0% activity means that there were no differences between treated and untreated plants. Experiments that were carried out on the same days at the same time have the same letter in brackets in Tables N, and O.

TABLE N

control of Abutilon theophrasti with inventive compositions
A1, A2, A3, and A4. The letter in brackets behind the composition
name indicates a testing series from which the respective data
were obtained. DAT is days after treatment; GS is growth stage
according to BBCH scale.

	Application	Control of A.theo-	Control of A.theo-
	rate	phrasti [%],	phrasti [%],
	[grams a.i./	GS 14/15,	GS 14/15,
Composition	hectare]	7 DAT	20 DAT

A1(b)	300	97	98
A2(b)	300	97	98
A3(b)	300	98	98
A4(c)	300	95	98

TABLE O

control of Abutilon theophrasti with comparative compositions
AC1, AC2, AC3, and AC4. The letter in brackets behind the
composition name indicates a testing series from which the
respective data were obtained. DAT is days after treatment;
GS is growth stage according to BBCH scale.

AC1(a)	300	88	85
AC2(b)	300	98	98
AC3(d)	300	65	63
AC4(b)	300	97	97

EXAMPLE-6: BIOLOGICAL TESTING ON SETARIA MACROSTACHYA

The compositions A1 to A4, and AC1 to AC4 as prepared in Example-1 were tested for their biological effect on Setaria macrostachya. To this end, weeds were grown to growth stage of 12/13 according to the BBCH scale. Directly before application the plants were watered as needed. Application of the herbicidal compositions was carried out in a spraying chamber. The herbicidal compositions were diluted with water and applied in a rate of 200 liters/hectare. The amount of Pesticide A applied is listed in Tables P, and Q. After application the plant remained for 30 minutes minimum in a drying tunnel (air flow volume 3000 m³/h) to get the surface of the plants complete dry before putting them in the greenhouse. The herbicidal activity was evaluated 7 and 20 days after treatment by awarding scores to the treated plants in comparison to the untreated control plants (Tables P, and Q). The evaluation scale ranges from 0% go 100% activity. 100% activity means the complete death of at least those parts of the plant that are above ground. Conversely, 0% activity means that there were no differences between treated and untreated plants. Experiments that were carried out on the same days at the same time have the same letter in brackets in Tables P, and Q.

TABLE P

control of Setaria macrostachya with inventive compositions
A1, A2, A3, and A4. The letter in brackets behind the composition
name indicates a testing series from which the respective data were
obtained. DAT is days after treatment; GS is growth stage
according to BBCH scale.

	Application	Control of Setaria	Control of Setaria
	rate	macrostachya [%],	macrostachya [%],
	[grams a.i./	GS 12/13,	GS 12/13,
Composition	hectare]	7 DAT	20 DAT

A1(b)	75	95	98
A2(b)	75	93	98
A3(b)	75	95	98
A4(c)	75	93	90

TABLE Q

control of Setaria macrostachya with comparative
compositions AC1, AC2, AC3, and AC4. The letter in brackets
behind the composition name indicates a testing series from
which the respective data were obtained. DAT is days after
treatment; GS is growth stage according to BBCH scale.

AC1(a)	75	85	78
AC2(b)	75	95	98
AC3(d)	75	90	93
AC4(b)	75	—	—

EXAMPLE-7: BIOLOGICAL TESTING ON BASSIA SCOPARIA

The compositions A1 to A4, and AC1 to AC4 as prepared in Example-1 were tested for their biological effect on Bassia scoparia. To this end, weeds were grown to growth stage of 14/15 according to the BBCH scale. Directly before application the plants were watered as needed. Application of the herbicidal compositions was carried out in a spraying chamber. The herbicidal compositions were diluted with water and applied in a rate of 200 liters/hectare. The amount of Pesticide A applied is listed in Tables R, and S. After application the plant remained for 30 minutes minimum in a drying tunnel (air flow volume 3000 m³/h) to get the surface of the plants complete dry before putting them in the greenhouse. The herbicidal activity was evaluated 7 and 20 days after treatment by awarding scores to the treated plants in comparison to the untreated control plants (Tables R, and S). The evaluation scale ranges from 0% go 100% activity. 100% activity means the complete death of at least those parts of the plant that are above ground. Conversely, 0% activity means that there were no differences between treated and untreated plants. Experiments that were carried out on the same days at the same time have the same letter in brackets in Tables R, and S.

TABLE P

control of Bassia scoparia with inventive compositions
A1, A2, A3, and A4. The letter in brackets behind
the composition name indicates a testing series from
which the respective data were obtained DAT is days after
treatment; GS is growth stage according to BBCH scale.

	Application	Control of Bassia	Control of Bassia
	rate	scoparia [%],	scoparia [%],
	[grams a.i./	GS 14/15,	GS 14/15,
Composition	hectare]	7 DAT	20 DAT

A1(b)	150	75	87
A2(b)	150	75	87
A3(b)	150	78	79
A4(c)	150	90	94

TABLE Q

control of Bassia scoparia with comparative compositions
AC1, AC2, AC3, and AC4. The letter in brackets behind
the composition name indicates a testing series from which the
respective data were obtained. DAT is days after treatment;
GS is growth stage according to BBCH scale.

AC1(a)	150	25	30
AC2(b)	150	83	98
AC3(d)	150	70	79
AC4(b)	150	75	20

Claims

1. 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;

c) 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^Dare independently H, CH₃, or CH₂CH₃with the proviso that the sum of C-atoms of R^A, R^B, R^C, and R^Dis up to 2;

M⁺ is a monovalent cation; and

the index x is a number from 1 to 10;

wherein the amine component is an amine selected from ethanolamine, diglycolamine, 1-aminopropan-2-ol, 2-dimethylaminoethanol, or an ammonium salt thereof, or a salt of trishydroxyethylmethyl ammonium.

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

3. The composition according to claim 1, wherein R^A, R^B, R^C, and R^Dare H.

4. The composition according to claim 1, wherein M⁺ is Na⁺.

5. The composition according to claim 1, wherein the pH is from 6 to 10.

6. The composition according to claim 1, wherein the amine component is a chloride, sulfate, sulfonate, or methylsulfonate salt of a primary, secondary, or tertiary ammonium cation.

7. The composition according to claim 1, wherein the component a) is the ammonium salt of glufosinate.

8. The composition according to claim 1, comprising

a) 5 to 50 wt % of glufosinate, (L)-glufosinate, or a salt thereof;

b) 5 to 50 wt % of the amine component;

c) 5 to 60 wt % of the compound of formula (I).

9. The composition according to claim 1, wherein the amine component is ethanolamine.

10. The composition according to claim 1 containing a second agrochemical active ingredient selected from herbicides of classes b1) to b15) and safeners C).

11. A method for increasing an herbicidal activity of a liquid herbicidal composition comprising a) glufosinate or a salt thereof and b) a compound of formula (I) comprising contacting the liquid herbicidal composition with c) an amine component as defined in claim 1.

12. A method for treating plant propagation material comprising the treating plant propagation material with the herbicidal composition as defined in claim 1.