Herbicidal compositions comprising cornexistin and/or hydroxycornexistin

The present invention relates to compositions and agrochemical compositions comprising cornexistin and/or hydroxycornexistin. The invention also relates to a process for preparation thereof and to the use of these compositions for controlling undesired vegetation as well as to corresponding methods.

In crop protection it is desirable to effectively control unwanted plants vegetating along with useful plants (crop plants) and depriving them of natural resources. At the same time it is important that pesticides, in particular herbicides, are tolerated by useful plants in question. With many highly effective herbicides there is a problem that their compatibility with useful plants is not always satisfactory, i.e. in addition to unwanted plants, the crop plants, too, are damaged on a scale which cannot be tolerated. By reducing the application rates, useful plants are spared; however, naturally, the extent of control of unwanted plants decreases, too.

Hence, an herbicide shall have a good compatibility with crops, high efficacy and reliability of action. Also desirable is a broad spectrum of activity of such an herbicide allowing the simultaneous control of multiple unwanted plants. Therefore, it is always desirable to improve at least one or even more of the above characteristics of herbicides.

Cornexistin (I.a1 ) and its corresponding dibasic acid (I.a2) are known from EP-A 0 290 193.

The herbicidal activity and particular formulations of these compounds are also known from the cited references.

Nevertheless, there is still room for improvement, e.g. regarding activity, scope of activity, application rates and compatibility with useful plants of the known herbicidal compositions.

It is an object of the present invention to provide herbicidal compositions that show enhanced herbicidal activity against unwanted plants. At the same time, the compositions should have good compatibility with useful plants. In addition, the compositions should have a broad spectrum of activity. A further object of the present invention is reducing the application rates of active ingredients.

This and further objects are achieved by the herbicidal compositions below. Accordingly, the present invention provides for a herbicidal composition comprising: A) a compound of formula I (herbicide A)

wherein

R ¹ is CH ₃ or CH ₂ OH; and

R ² and R ³ together with the neighboring carbon atoms form a dihydro-2,5-dioxofuran ring or

including agriculturally acceptable salts and derivatives thereof; and B) a surfactant selected from anionic and/or non-ionic surfactants having an unsubstituted OH group of an acid and/or alcohol function (surfactant B) wherein at least 50% by weight of the surfactant B is present in non-ionized form. Surprisingly, the compositions according to the present invention demonstrate a better herbicidal activity against unwanted plants than would have been expected by the herbicidal activity of the active compounds alone. In other words, the herbicidal activity of the herbicides A) is increased when they are used together with the surfactants according to the present invention. Hence, the compositions of the invention show very good herbicidal activity, in particular at low application rates of active compounds, against a broad spectrum of weeds that have high economic impact. Further, compositions of the present invention demonstrate very good compatibility with useful plants, i.e. their use in crops does not result in increased damage when compared to the application of the individual components or mixtures thereof.

The compositions according to the present invention are suitable as herbicides as such or as appropriately formulated compositions (agrochemical compositions). As used herein, the term "agrochemical composition" refers to a composition according to the present invention additionally comprising at least one inert liquid and/or solid carrier and, if appropriate, at least one auxiliary customary for agrochemical formulations.

Hence, the present invention also provides for agrochemical compositions comprising a herbicidally active amount of a composition according to the present invention and at least one inert liquid and/or solid carrier and, if appropriate, at least one auxiliary customary for herbicidal formulations.

The present invention further provides for ready to use herbicidal formulations obtainable by diluting compositions according to the present invention or agrochemical compositions according to the present invention with water.

The use of both compositions and agrochemical compositions according to the present invention for controlling undesired vegetation falls within this invention.

Further, the invention provides for a process for preparation of the composition or the agrochemical composition according to the present invention, which comprises the steps of mixing the individual components of the composition, if appropriate, with agitation and/or heating.

Further, the invention provides for a method for controlling undesirable vegetation, which method comprises allowing a herbicidally active amount of the composition or an agrochemical composition according to the present invention to act on plants, their environment or on seed.

Further embodiments of the present invention are evident from the claims, the description and the examples. It is to be understood that the features mentioned above and still to be illustrated below of the subject matter of the invention can be applied not only in the combination given in each particular case but also in other combinations, without leaving the scope of the invention. As used herein, the terms "undesirable vegetation" and "unwanted plants" are synonyms.

The term "cornexistin" means the compound of formula (I.a1 ) as well as agriculturally acceptable salts thereof.

The term "dibasic acid of cornexistin" means the compound of formula (I.a2) as well as agriculturally acceptable salts thereof.

The term "hydroxycornexistin" means the compound of formula (I.a3) as well as agriculturally acceptable salts thereof.

The term "dibasic acid of hydroxycornexistin" means the compound of formula (I.a4) as well as agriculturally acceptable salts thereof. The compounds of formulae (I.a1 ) to (I.a4) as described herein are capable of forming geometrical isomers, for example E/Z isomers. Accordingly, the terms "cornexistin", "dibasic acid of cornexistin", "hydroxycornexistin" and "dibasic acid of hydroxycornexistin" also encompass the pure E or Z isomers and mixtures thereof. As used herein, the term "safeners" means organic active compounds, some of which may also have herbicidal activity, which reduce or even prevent damage to the crop plants by herbicides.

As used herein, the term "agriculturally acceptable salts" means the salts of those cations and the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the herbicidal activity of an active compound.

Preferred cations are the ions of the alkali metals, preferably of lithium, sodium and potassium, of the alkali 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 Ci-C4-alkyl, hydroxy-Ci-C4-alkyl, C1-C4- alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl, preferably ammonium, methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, heptylammonium, dodecylammonium, tetradecylammonium,

tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2 hydroxyethyl-ammonium (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-hydroxy- propyl)ammonium, benzyltrimethylammonium, benzyltriethylammonium, Ν,Ν,Ν-trimethylethanol- ammonium (choline salt), furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4- alkyl)sulfonium, such as trimethylsulfonium, and sulfoxonium ions, preferably tri(Ci-C4- alkyl)sulfoxonium, and finally the salts of polybasic amines such as N,N-bis-(3-amino- propyl)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 Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate.

As used herein, the term "agriculturally acceptable esters" means, for example, allyl esters, propargyl esters, Ci-Cio-alkyl esters, alkoxyalkyl esters, tefuryl ((tetrahydrofuran-2-yl)methyl) esters. Preferred alkyl esters are, for example, the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, mexyl (1 -methylhexyl), methyl (1 -methylheptyl), heptyl, octyl or isooctyl (2- ethylhexyl) esters. Preferred Ci-C4-alkoxy-Ci-C4-alkyl esters are the straight-chain or branched Ci-C4-alkoxy ethyl esters, for example the 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl (butotyl), 2-butoxypropyl or 3-butoxypropyl ester.

As used herein, all hydrocarbon chains can be straight-chain or branched, the prefix C _n -C _m is denoting in each case the possible number of carbon atoms in the group.

The term poly(C2-Ce)alkoxylates refers to polyether moieties derived from ethyleneoxide (EO), propyleneoxide (PO), butyleneoxide (BO), pentylene oxide (PO), hexylene oxide (HO) or any mixtures thereof. The term poly(C2-C4)alkoxylates refers to polyether moieties derived from ethyleneoxide, propyleneoxide, butyleneoxide or any mixtures thereof. The term polyethoxylate refers to a polyether radical derived from ethyleneoxide. The term polyalkoxylates also includes mixed polyether derived from at least two different alkylene oxides, e.g. polyethoxylates-co- propoxylates derived from a mixture of EO and PO. The number of repeating units in the polyether moieties will preferably vary from 2 to 50, more preferably from 2 to 30, most preferably from 2 to 20.

The composition of the present invention comprises a compound of formula I (herbicide A) as defined herein above. Herbicide A is preferably selected from: a1 ) cornexistin (I.a1 ),

a2) the dibasic acid of cornexistin (I.a2),

a3) hydroxycornexistin (I.a3),

a4) the dibasic acid of hydroxycornexistin (I.a4),

a5) mixtures of cornexistin (I .a 1 ) and the dibasic acid of cornexistin (I.a2),

a6) mixtures of hydroxycornexistin (I.a3) and the dibasic acid of hydroxycornexistin (I.a4) a7) mixtures of cornexistin (I.a1 ) and hydroxycornexistin (I.a3),

a8) mixtures of cornexistin (I.a1 ) and the dibasic acid of hydroxycornexistin (I.a4),

a9) mixtures of the dibasic acid of cornexistin (I.a2) and hydroxycornexistin (I.a3),

a10) mixtures of the dibasic acid of cornexistin (I.a2) and the dibasic acid of hydroxycornexistin (I.a4) and

a1 1 ) mixtures cornexistin (I .a 1 ), the dibasic acid of cornexistin (I.a2), hydroxycornexistin (I.a3) and the dibasic acid of hydroxycornexistin (I.a4) including agriculturally acceptable salts and derivatives thereof.

The composition of the present invention further comprises a surfactant B selected from anionic and/or non-ionic surfactants having an unsubstituted OH group of an acid and/or alcohol function, preferably an unsubstituted anionizable OH group of an acid and/or alcohol function, more preferably an unsubstituted anionizable OH group of an acid and/or alcohol function that upon dilution (1 -10%) in water do not ionize completely, i.e. less than 99.9%, preferably less than 99%, more preferably less than 90%. From the aforementioned surfactants anionic surfactants are most preferred, anionic surfactants having an unsubstituted OH group of an acid function are particularly preferred.

As used herein, the term "anionizable OH group" refers to an OH group of an acid and/or alcohol function that in aqueous solutions is able to donate a proton to water setting up equilibrium:— OH + H ₂ 0 ¾— O ^" + H ₃ 0 ⁺ .

Examples of acid functions having an anionizable OH groups include— COOH,— S(=0)20H,— P(=0)(OH) ₂ , and >P(=0)(OH). Examples of acid functions having anionizable OH groups that upon dilution (1 -10%) in water do not ionize completely include—COOH,— P(=0)(OH) ₂ , and >P(=0)(OH).

Preferably at least 30% by weight, more preferably at least 50% by weight, most preferably at least 75% by weight and particularly preferred at least 85% by weight of the surfactant B according to the present invention are present in non-ionized (protonated) form in the formulation.

The surfactant B according to the present invention preferably has pKa in water at 25°C in the range from 0 to 12, more preferably in the range from 0 to 8, most preferably in the range from 0 to 5, and particularly preferably in the range from 0.5 to 4. pKa can be determined, for example, by titration at 25±1 °C with 0.1 M sodium hydroxide using a METROHM 726 Titroprocessor (see Langmuir, 2003, 19, 2034-2038). According to one embodiment the surfactant B according to the present invention is selected from anionic surfactants having an unsubstituted OH group of an acid function, preferably an unsubstituted anionizable OH group of an acid function, more preferably an unsubstituted anionizable OH group of an acid function that upon dilution (1 -10%) in water do not ionize completely, i.e. less than 99.9%, preferably less than 99%, more preferably less than 90%.

Anionic surfactants B according to the present invention preferably have pKa in water at 25°C in the range from 0 to 5, more preferably in the range from 0.25 to 4.5, most preferably in the range from 0.5 to 4.

Preferred anionic surfactants B according to the present invention are phosphate esters, in particular mono-phosphate esters, di-phosphate esters, any mixtures of mono-phosphate esters and di-phosphate esters, carboxylated surfactants, as well as any mixtures thereof. More preferred anionic surfactants B according to the present invention are phosphate esters, in particular mono-phosphate esters, di-phosphate esters, and any mixtures thereof.

Examples of preferred anionic surfactants B according to the present invention are:

- phosphate esters of C3-C22-alkanols;

- phosphate esters of C3-C22-alkenols;

- phosphate esters of Ci-Ci6-alkylphenols;

- phosphate esters of poly(C2-C6)alkoxylated C3-C22-alkanols;

- phosphate esters of poly(C2-C6)alkoxylated C3-C22-alkenols;

- phosphate esters of poly(C2-C6)alkoxylated Ci-Ci6-alkylphenols;

- poly(C2-C6)alkoxylates of mono- di- or tristyryl phenyl etherphosphate esters;

- polyphosphate esters such as hexametaphosphates and triphosphate esters (=

tripolyphosphate esters);

- carboxylated C3-C22-alkanols;

- carboxylated C3-C22-alkenols;

- carboxylated Ci-Ci6-alkylphenols;

- carboxylated poly(C2-C6)alkoxylated C3-C22-alkanols;

- carboxylated poly(C2-C6)alkoxylated C3-C22-alkenols;

- carboxylated poly(C2-C6)alkoxylated Ci-Ci6-alkylphenols;

- polycarboxylated polyoxyethylenes, in particular homo- and copolymers of monoethylenically unsaturated mono- or dicarboxylic acids having from 3 to 8 carbon atoms, and the copolmyers also having polyethylene oxide side chains.

Examples of more preferred anionic surfactants B according to the present invention are the aforementioned anionic surfactants comprising at least one poly(C2-C6)alkoxylate moiety.

Examples of most preferred anionic surfactants B according to the present invention are:

- phosphate esters of poly(C2-C4)alkoxylated C6-C22-alkanols;

- phosphate esters of poly(C2-C4)alkoxylated C6-C22-alkenols;

- phosphate esters of poly(C2-C4)alkoxylated Ci-Ci6-alkylphenols;

- poly(C2-C4)alkoxylates of mono- di- or tristyryl phenyl etherphosphate esters;

- carboxylated poly(C2-C4)alkoxylated C6-C22-alkanols;

- carboxylated poly(C2-C4)alkoxylated C6-C22-alkenols; and

- carboxylated poly(C2-C4)alkoxylated C4-Ci6-alkylphenols;

Examples of particularly preferred anionic surfactants B according to the present invention are:

- phosphate esters of poly(C2-C4)alkoxylated C6-C22-alkanols; - phosphate esters of poly(C2-C4)alkoxylated C6-C22-alkenols;

- phosphate esters of poly(C2-C4)alkoxylated C6-Ci6-alkylphenols; and

- poly(C2-C4)alkoxylates of mono- di- or tristyryl phenyl etherphosphate esters. Suitable salts of anionic surfactants B according to the present invention are alkaline metal salts, earth alkaline metal salts, zinc salts and/or ammonium salts, preferably alkaline metal salts, most preferably sodium and potassium salts.

According to another embodiment the surfactant B according to the present invention is selected from non-ionic surfactants having an unsubstituted OH group of an alcohol function, preferably an unsubstituted anionizable OH group of an alcohol function, more preferably an unsubstituted anionizable OH group of an alcohol function that upon dilution (1 -10%) in water do not ionize completely, i.e. less than 99.9%, preferably less than 99%, more preferably less than 90%.

Preferable non-ionic surfactants B according to the present invention are alkoxylated fats or oils of animal or vegetable origin such as maize oil ethoxylates, castor oil ethoxylates, tallow fat ethoxylates, glycerol esters such as glycerol monostearate, fatty alcohol alkoxylates and oxoalcohol alkoxylates, fatty acid alkoxylates such as oleic acid ethoxylate, alkylphenyl alkoxylates such as isononyl-, isooctyl-, tributyl- and tristearylphenyl ethoxylates, fatty amine alkoxylates, fatty acid amide alkoxylates, sugar emulsifiers such as sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), polyoxyethylene sorbitan fatty acid esters, alkylpolyglycosides, N-alkylgluconamides, alkylmethyl sulfoxides, alkyldimethylphosphine oxides such as tetradecyldimethylphosphine oxide, ethylene oxide/propylene oxide copolymers and mixtures of such non-ionic surfactants.

Examples of preferred non-ionic surfactants B according to the present invention are:

- poly(C2-C6)alkoxylates of C3-C22-alkanols, and esters thereof, such as acetates;

- poly(C2-C6)alkoxylates of C3-C22-alkenols and esters thereof, such as acetates;

- poly(C2-C6)alkoxylates of arylalcohols;

- poly(C2-C6)alkoxylates of Ci-Ci6-alkylaryl alkohols, in particular polyethoxylates of C1-C16- alkylphenols, such as polyethoxylates of nonylphenol, decylphenol, isodecylphenol, dodecylphenol or isotridecylphenol,

- poly(C2-C6)alkoxylates of mono-, di- or tristyryl phenols, in particular polyethoxylates of mono-, di- und tristyrylphenols; and the formaldehyde condensates thereof and the agriculturally acceptable esters thereof, e.g. the acetates;

- C3-C22-alkylglucosides and C3-C22-alkyl polyglucosides;

- polyethoxylates of C3-C22-alkylglucosides and polyethoxylates of C3-C22-alkyl polyglucosides;

- polyethoxylates of fatty amines, fatty amides or of fatty acid diethanolamides;

- polyethoxylates of fatty acids and polyethoxylates of hydroxyl fatty acids; - partial esters of polyols with C3-C22-alkanoic acids, in particular mono- and diesters of glycerine and mono-, di- and triesters of sorbitan, such as glycerine monostearate, sorbitanmonooleat, sorbitantristearat; and triglyceride polyalkoxylates;

- polyethoxylates of partial esters of polyols with C3-C22-alkanoic acids, in particular

polyethoxylates of mono- and diesters of glycerine and polyethoxylates of mono-, di- and triesters of sorbitan, such as polyethoxylates of glycerine monostearate, polyethoxylates of sorbitanmonooleat, polyethoxylates of sorbitanmonostearat and polyethoxylates of sorbitantristearat;

- polyethoxylates of vegetable oils, such as soya oil, rapeseed oil, corn oil, sunflower oil, cotton seed oil, linseed oil, coconut oil, palm oil, safflower oil, walnut oil, peanut oil, olive oil or castor oil or animal fats, such as lard, tallow, milkfat, cod liver oil and whale oil; preferred are polyethoxylated vegetable oils; and

- acetylene glycols such as 2,4,7,9-tetramethyl-4,7-bis(hydroxy)-5-decyne. Examples of more preferred non-ionic surfactants B according to the present invention are the aforementioned non-ionic surfactants comprising at least one poly(C2-C6)alkoxylate moiety.

Examples of most preferred non-ionic surfactants B according to the present invention are:

- poly(C2-C4)alkoxylates of C8-C22-alkanols and esters thereof, such as acetates;

- poly(C2-C4)alkoxylates of C8-C22-alkenols and esters thereof, such as acetates;

- poly(C2-C4)alkoxylates of C4-Ci6-alkylphenols, such as polyethoxylates of nonylphenol, decylphenol, isodecylphenol, dodecylphenol or isotridecylphenol,

- polyethoxylates of fatty acids and polyethoxylates of hydroxyl fatty acids;

- polyethoxylates of vegetable oils, such as soya oil, rapeseed oil, corn oil, sunflower oil, cotton seed oil, linseed oil, coconut oil, palm oil, safflower oil, walnut oil, peanut oil, olive oil or castor oil or animal fats, such as lard, tallow, milkfat, cod liver oil and whale oil; preferred are polyethoxylated vegetable oils.

Examples of particularly preferred non-ionic surfactants B according to the present invention are:

- poly(C2-C4)alkoxylates of C8-C22-alkanols and esters thereof, such as acetates;

- poly(C2-C4)alkoxylates of C8-C22-alkenols and esters thereof, such as acetates; and

- poly(C2-C4)alkoxylates of C6-Ci6-alkyl phenols, such as polyethoxylates of nonylphenol, decylphenol, isodecylphenol, dodecylphenol or isotridecylphenol.

In another embodiment the compositions according to the present invention comprising a non- ionic surfactants B as defined above additionally comprise an acid. The acid is preferably selected from sulfuric, phosphoric, nitric, and/or carboxylic acids like e.g. formic, acetic, citric, propionic, glycolic, oxalic, tartaric, malic, maleic, fumaric acid. More preferred is phosphoric acid. The surfactant B according to the present invention preferably has at least one mole of (C3- Ce)alkoxylate units per molecule, more preferably at least one mole of (C3-C4)alkoxylate units per molecule. Further, the surfactant B according to the present invention preferably has 2 to 15 ethoxylate units per molecule, more preferably 2 to 12 ethoxylate units per molecule, most preferably 2 to 10 ethoxylate units per molecule, particularly preferable 2 to 7 ethoxylate units per molecule.

In a preferred embodiment the surfactant B according to the present invention has at least one mole of (C3-Ce)alkoxylate units per molecule, preferably at least one mole of (C3-C4)alkoxylate units per molecule and 2 to 15 ethoxylate units per molecule, more preferably 2 to 12 ethoxylate units per molecule, most preferably 2 to 10 ethoxylate units per molecule, particularly preferable 2 to 7 ethoxylate units per molecule. According to one embodiment the composition according to the present invention comprises at least one, preferably exactly one surfactant B.

According to another embodiment the composition according to the present invention comprises at least two, preferably two surfactants B different form each other.

The abovementioned anionic and non-ionic surfactants are known compounds or can be prepared by customary methods with which a skilled person is familiar and in apparatuses conventionally used for this purpose. Particular examples of the aforementioned surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).

The alcohol moieties of the surfactants B according to the present invention are obtainable both from natural sources, for example by obtaining and, if required or desired, by hydrolyzing, transesterifying, and/or hydrogenating glycerides and fatty acids, and by synthetic routes, for example by building up from starting materials having a smaller number of carbon atoms. Thus, for example, the SHOP process (Shell Higher Olefin Process) gives, starting from ethene, olefin fractions having a number of carbon atoms suitable for further processing to produce

surfactants. The functionalization of the olefins to form the corresponding alcohols is carried out, for example, by hydroformylation and hydrogenation.

Olefins having a number of carbon atoms suitable for further processing to give suitable alcohols can also be obtained by oligomerization of C3-C6-alkenes, in particular propene, butene or mixtures of these. Moreover, lower olefins can be oligomerized by means of heterogeneous, acidic catalysts, e.g. supported phosphoric acid, and subsequently functionalized to give alcohols. A general possibility of synthesizing to produce branched alcohols is, for example, the reaction of aldehydes or ketones with Grignard reagents (Grignard synthesis). Instead of Grignard reagents, it is also possible to employ aryllithium or alkyllithium compounds, which are distinguished by higher reactivity.

Moreover, the branched alcohols can be obtained by the Guerbet reaction, the skilled worker being familiar with the reaction conditions.

The alkoxylation is the result of the reaction with suitable alkylene oxides which, as a rule, have 2 to 6, preferably 2 to 4, carbon atoms. The following may be mentioned in particular in this context: ethylene oxide (EO), propylene oxide (PO), butylene oxide (EO), pentylene oxide (PeO) and hexylene oxide (HO).

The respective degree of alkoxylation is a function of the amounts of alkylene oxide(s) chosen for the reaction. It is, as a rule, a statistic mean since the number of alkylene oxide units of the alcohol alkoxylates resulting from the reaction varies.

The alcohols are reacted with the alkylene oxide(s) by customary methods with which the skilled worker is familiar and in apparatuses conventionally used for this purpose. The alkoxylation may be catalyzed by strong bases such as alkali metal hydroxides and alkaline earth metal hydroxides, Bronsted acids or Lewis acids, such as AlC , BF3 and the like. Catalysts such as hydrotalcite or DMC (double metal cyanides) may be used for alcohol alkoxylates with a narrow distribution. The alkoxylation is preferably carried out at temperatures in the range of from approximately 80 to 200°C, preferably approximately 100 to 180°C. The pressure range is preferably between atmospheric pressure and 10 bar. If desired, the alkylene oxide may comprise an admixture of inert gas, for example of from approximately 5 to 60%. Alkyl phosphates and alkyl ether phosphates are made by treating alcohols or alcohol alkoxylate with a phosphorylating agent, e.g. di-, meta- or poly-phosphoric acids, PC or P4O4, preferred are phosphorus pentoxide P ₄ Oio or polyphosphoric acid. The reaction yields a mixture of mono- and di-esters of phosphoric acid which can be separated, if necessary. The ratio between the two esters is determined by the ratio of the reactants.

In one preferred embodiment, the composition of the present invention contains

A) 1 to 60%, preferably 5 to 55%, more preferably 10 to 50%, and most preferably 15 to 45% by weight, based on the total weight of the composition of the herbicide A, and

B) 0.5 to 40%, preferably 1 to 35%, more preferably 5 to 30%, and most preferably 20 to 30% by weight, based on the total weight of the composition of the surfactant B. The weight ratio between components A) and B) in the composition of the present invention is, as a rule, in the range from 20:1 to 1 :20, preferably in the range from 15:1 to 1 :15, more preferably in the range of from 10:1 to 1 :10 and most preferably in the range from 5:1 to 1 :5. The composition of the present invention can also comprise an acid. The acid is preferably selected from sulfuric, phosphoric, nitric, and/or carboxylic acids like e.g. formic, acetic, citric, propionic, glycolic, oxalic, tartaric, malic, maleic, fumaric acid. More preferred is phosphoric acid. The composition of the present invention can also comprise an agriculturally acceptable oil. Preferred oils are paraffin oil, mineral oil, plant oil, aromatic oil, methyl oleate or fatty acid dialkylamides, more preferred oils are methyl oleate or fatty acid dialkylamides. The oil preferably has a weight average number of carbon atoms between 12 and 25, preferably 14 to 20.

To widen the spectrum of action and to obtain synergistic effects, the compositions of the invention can be mixed with a large number of further herbicidal or growth-regulatory active substances or applied together with these. Examples of such herbicides and plant growth regulators suitable for the compositions according to the present invention are 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(6 H)-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-o ne (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 '-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-p yran-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-pyr an-3-yl carbonic acid methyl ester (CAS 1033760-58-5); and non ACC herbicides such as benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate; from the group of the ALS inhibitors:

sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron-methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, metazosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron,

pyrazosulfuron-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron,

thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron,

imidazolinones such as imazamethabenz, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin and imazethapyr, triazolopyrimidine herbicides and sulfonanilides such as cloransulam, cloransulam-methyl, diclosulam, flumetsulam, florasulam, metosulam,

penoxsulam, pyrimisulfan and pyroxsulam,

pyrimidinylbenzoates such as bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, 4-[[[2-[(4,6-dimethoxy-2- pyrimidinyl)oxy]phenyl]methyl]amino]-benzoic acid-1 -methylethyl ester (CAS 420138-41 -6), 4- [[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]- benzoic acid propyl ester (CAS 420138-40-5), N-(4-bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzen emethanamine (CAS 420138-01 -8),

sulfonylaminocarbonyl-triazolinone herbicides such as flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone and thiencarbazone-methyl; and triafamone; from the group of the photosynthesis inhibitors:

amicarbazone, inhibitors of the photosystem II, e.g. 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; from the group of the protoporphyrinogen-IX oxidase inhibitors:

acifluorfen, acifluorfen-sodium, azafenidin, bencarbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, cinidon-ethyl, 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, ethyl [3-[2-chloro-4-fluoro-5-(1 -methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4- tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate (CAS 353292-31 -6; S-3100), N-ethyl-3- (2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1 /-/-pyrazole-1 -carboxamide (CAS 452098-92- 9), N-tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenox y)-5-methyl-1 H-pyrazole-1 - carboxamide (CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-5- methyl-1 H-pyrazole-1 -carboxamide (CAS 452099-05-7), N-tetrahydrofurfuryl-3-(2-chloro-6- fluoro-4-trifluoromethylphenoxy)-5-methyl-1 H-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, 1 ,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl )-3,4- dihydro-2H-benzo[b][1 ,4]oxazin-6-yl)-1 ,3,5-triazinane-2,4-dione (CAS 1258836-72-4), 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, 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)-1 H-pyrimidine-2,4-dione, methyl (E)-4-[2-chloro-5-[4-chloro-5- (difluoromethoxy)-l H-methyl-pyrazol-3-yl]-4-fluoro-phenoxy]-3-methoxy-but-2-eno ate [CAS 948893-00-37, and 3-[7-Chloro-5-fluoro-2-(trifluoromethyl)-1 H-benzimidazol-4-yl]-1 -methyl-6- (trifluoromethyl)-1 H-pyrimidine-2,4-dione (CAS 212754-02-4); from the group of the bleacher herbicides:

PDS inhibitors: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone, norflurazon, picolinafen, and 4-(3-trifluoromethylphenoxy)-2-(4-trifluoromethylphenyl)pyri midine (CAS 180608-33-7), HPPD inhibitors: benzobicyclon, benzofenap, clomazone, fenquintrione, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, topramezone and bicyclopyrone, bleacher, unknown target: aclonifen, amitrole and flumeturon; from the group of the EPSP synthase inhibitors:

glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosate-trimesium (sulfosate); from the group of the glutamine synthase inhibitors:

bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate- ammonium; from the group of the DHP synthase inhibitors:

asulam; 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: chlorpropham, propham and carbetamide; from the group of the VLCFA inhibitors:

chloroacetamides such as acetochlor, alachlor, 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 11.1 , II.2, 11.3 , II.4, II.5, II.6, II.7, II.8 and II.9

II.6 II.7

II.8 ii.g the isoxazoline compounds of the formula (l)l are known in the art, e.g. from WO

2006/024820, WO 2006/037945, WO 2007/071900 and WO 2007/096576; from the group of the cellulose biosynthesis inhibitors:

chlorthiamid, dichlobenil, flupoxam, isoxaben and 1 -Cyclohexyl-5-pentafluorphenyloxy-1 ⁴ - [1 ,2,4,6]thiatriazin-3-ylamine; from the group of the decoupler herbicides:

dinoseb, dinoterb and DNOC and its salts; 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, 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 and triclopyr and its salts and esters; - from the group of the auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam-sodium; 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, 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 and tridiphane.

Preferred herbicides and plant growth regulators suitable for compositions according to the present invention, are from the group of the lipid biosynthesis inhibitors:

ACC-herbicides such as clethodim, clodinafop, clodinafop-propargyl, cycloxydim, pinoxaden, and sethoxydim; and non ACC herbicides such as butylate, ethofumesate, flupropanate, molinate, thiobencarb, and vernolate; from the group of the ALS inhibitors:

sulfonylureas such as metsulfuron, metsulfuron-methyl, nicosulfuron, and tritosulfuron;

imidazolinones such as imazamox, imazapic, imazapyr, imazaquin and imazethapyr;

triazolopyrimidine herbicides and sulfonamides such as florasulam, metosulam, penoxsulam, and pyroxsulam; pyrimidinylbenzoates such as bispyribac, bispyribac-sodium, pyribenzoxim, and pyriftalid; sulfonylaminocarbonyl-triazolinone herbicides such as thiencarbazone and thiencarbazone-methyl; - from the group of the photosynthesis inhibitors:

amicarbazone, inhibitors of the photosystem II, pyridazinones such as atrazine, cyanazine, metribuzin, prometryn, simazine, and terbuthylazin; aryl urea such as diuron, and linuron;

phenyl carbamates such as desmedipham; nitrile herbicides such as bromoxynil and its salts and esters; uraciles such as bromacil; and bentazon, bentazon-sodium, pyridate, and propanil and inhibitors of the photosystem I such as paraquat, paraquat-dichloride and paraquat- dimetilsulfate; from the group of the protoporphyrinogen-IX oxidase inhibitors:

carfentrazone, carfentrazone-ethyl, flumioxazin, lactofen, oxadiargyl, oxyfluorfen, saflufenacil, sulfentrazone, and 1 ,5-dimethyl-6-thioxo-3-(2,2,7-trifluoro-3-oxo-4-(prop-2-ynyl )-3,4-dihydro-2H- benzo[b][1 ,4]oxazin-6-yl)-1 ,3,5-triazinane-2,4-dione (CAS 1258836-72-4); from the group of the bleacher herbicides:

PDS inhibitors: diflufenican, norflurazon and picolinafen; HPPD inhibitors: benzobicyclon, clomazone, isoxaflutole, mesotrione, sulcotrione, tembotrione, topramezone and bicyclopyrone; from the group of the EPSP synthase inhibitors:

glyphosate, glyphosate-isopropylammonium, glyposate-potassium and glyphosate-trimesium (sulfosate); from the group of the glutamine synthase inhibitors:

bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P and glufosinate- ammonium; - from the group of the mitosis inhibitors:

compounds of group K1 : dinitroanilines such as pendimethalin, and trifluralin; phosphor- amidates such as butamiphos; pyridines such as dithiopyr; benzamides such as tebutam; compounds of group K2: carbetamide; from the group of the VLCFA inhibitors:

chloroacetamides such as acetochlor, alachlor, dimethenamid, dimethenamid-P, metolachlor, metolachlor-S, pretilachlor and propachlor; oxyacetanilides such as flufenacet and mefenacet; acetanilides such as diphenamid; tetrazolinones such as fentrazamide, and other herbicides such as cafenstrole, and pyroxasulfone; from the group of the cellulose biosynthesis inhibitors: isoxaben; from the group of the decoupler herbicides: dinoseb; from the group of the auxinic herbicides:

2,4-D and its salts and esters such as clacyfos, dicamba and its salts and esters, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, MCPA and its salts and esters, MCPA-thioethyl, quinclorac and quinmerac; from the group of the auxin transport inhibitors: diflufenzopyr; - from the group of the other herbicides: indaziflam and pelargonic acid.

The aforementioned herbicides and plant growth regulators are known compounds, see, for example, The Compendium of Pesticide Common Names

(http://www.alanwood.net/pesticides/). As to the mechanisms of action and classification of the active compounds, see e.g. "HRAC, Classification of Herbicides According to Mode of Action", (http://www.plantprotection.org/hrac/MOA.html).

The compositions according to the present invention can also comprise at least one safener. Examples of preferred safeners 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) and N-(2-Methoxybenzoyl)-4- [(methylaminocarbonyl)amino]benzenesulfonamide (CAS 129531 -12-0).

More preferred safeners are benoxacor, cloquintocet, cyprosulfamide, dichlormid,

fenchlorazole, fenclorim, furilazole, isoxadifen, mefenpyr, 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).

The safeners are known compounds, 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 herbicides, plant growing regulators and/or safeners as described herein having a carboxyl, hydroxy and/or an amino group can be employed as such or in form of an agriculturally suitable salt as mentioned above or in the form of an agriculturally acceptable derivative, for example as amides, such as mono- and di-Ci-C6-alkylamides or arylamides, as esters, for example as allyl esters, propargyl esters, Ci-Cio-alkyl esters, alkoxyalkyl esters, tefuryl ((tetrahydrofuran-2- yl)methyl) esters and also as thioesters, for example as Ci-Cio-alkylthio esters. Preferred mono- and di-Ci-C6-alkylamides are the methyl and the dimethylamides. Preferred arylamides are, for example, the anilides and the 2-chloroanilides. Preferred alkyl esters are, for example, the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, mexyl (1 -methylhexyl), meptyl (1 - methylheptyl), heptyl, octyl or isooctyl (2-ethylhexyl) esters. Preferred Ci-C4-alkoxy-Ci-C4-alkyl esters are the straight-chain or branched Ci-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 Ci-Cio-alkylthio ester is the ethylthio ester.

The invention also relates to agrochemical compositions comprising the composition according to the present invention, at least one inert liquid and/or solid carrier and, if appropriate, at least one auxiliary customary for herbicidal formulations.

Examples for agrochemical composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further agrochemical compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6 ^th Ed. May 2008, CropLife International.

The agrochemical 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. Customary agitating (e.g. mixing) devices which, if appropriate, can be heated may be used for preparing the mixtures.

Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin,

tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

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 auxiliaries are solvents, surfactants differing from the surfactant B according to the present invention, dispersants, emulsifiers, wetters, adjuvants, solubilizers, uptake enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders. 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, 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. Suitable non-ionic 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 homo- 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 compounds of formula (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), inorganic 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.

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 polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.

Suitable preservatives, colorants and perfumes are known to the skilled worker, for example from the literature mentioned above in connection with surfactants, and from Watkins,

"Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.; H. v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y.; and C. Marsden, "Solvents Guide"; 2nd Ed., Interscience, N.Y. 1963.

The herbicidal compositions of the invention affect a very good control of vegetation in non-crop areas, especially at high application rates. In crops such as soybean, cotton, oilseed rape, flax, lentils, rice, sugar beet, sunflower, tobacco and cereals, such as, for example maize or wheat, they are active against broad-leaved weeds and grass weeds without inflicting substantial damage to the crop plants. This effect is particularly observed at low application rates.

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

Suitable crops are, for example, 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 and Zea mays. In addition, the compositions of the invention can also be used in crops which tolerate the effect of herbicides as the result of breeding, including genetic engineering methods.

Furthermore, the compositions of the invention can also be used in crops which tolerate attack by insects or fungi as the result of breeding, including genetic engineering methods.

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

Depending on the aim of the control measures, the season, the target plants and the growth stage, the compositions of the invention are applied to such a degree that the application rates of component A) are from 0.001 to 3.0 kg/ha, preferably from 0.01 to 1.0 kg/ha, more preferably from 0.01 to 0.5 kg/ha active ingredient (a.i.).

It is of also possible to use the compositions of the present invention as a tank-mix partner with other formulations.

Moreover, it may be useful to apply the compositions of the invention, separately or in combination with other herbicides, jointly as a mixture with yet further plant protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria.

The following examples are intended to further illustrate the present invention without limiting its scope in any way.

1. Preparation of surfactants

1.1. Preparation of alcohol alkoxylates

The fatty alcohol was fed to a reactor, then 0.2 w% of a solution of KOH in water (50 w% KOH and 50 w% water) was added and the mixture stirred. Then the mixture was dried in dynamic vacuum for 1 hour at 80°C and < 30 mbar. The valve to the vacuum was closed, the mixture heated to 165°C and the respective amount of alkylene oxide added. During dosing the pressure was always kept below 5 bar. After the desired amount of alkylene oxide had been added, the mixture was post-reacted for 30 minutes at 165°C, then cooled to 60°C and neutralized with a solution of lactic acid (80% lactic acid and 20% water). Finally the stirring was stopped and the alkyl alkoxide discharged.

1.2. Preparation of mono-phosphates Tetraphosphoric acid (1 equivalent, calculated as H6P4O13) was fed to a reactor, the latter flushed with nitrogen and heated to 40°C. Upon stirring 2.5 equivalents of alcohol alkoxylate were added, at a speed that allowed the temperature of the mixture in the reactor to stay at max. 60°C. After complete addition of the alkoxylate, the temperature was raised to 90°C, and the reaction mixture was post-reacted upon stirring for 6 hours at 90°C. The reactor was discharged to yield the crude monophosphate of the alkoxylate, which was used in the subsequent trials without further purification.

1.3. Preparation of mono-/di-phosphates

Alcohol alkoxylate (6 equivalents) was fed to a reactor, the latter flushed with nitrogen and heated to 40°C. Upon stirring 1 equivalent of P4O10 was added, at a speed that allowed the temperature of the mixture in the reactor to stay at max. 60°C. After complete addition of the phosphorous oxide, the temperature was raised to 90°C, and the reaction mixture was post- reacted upon stirring for 2 hours at 90°C. The reactor was discharged to yield the crude mixture of mono- and diphosphate of the alkoxylate, which was used in the subsequent trials without further purification. 1.4. Preparation of sulfates

The fatty alcohol alkoxylate (1 equivalent) was mixed with the same amount of methylene chloride to yield a 50 w% solution, then charged into a reactor, flushed with nitrogen, stirred and cooled to +5°C. Then 1 equivalent chlorosulfonic acid was added at a speed that allowed the temperature of the mixture in the reactor to stay at max. 20°C. After complete addition of the HSO3CI the reaction mixture was post-reacted for 3 hours at room temperature.

In the next step, the crude alkoxilate sulfate was added upon stirring to a solution of 1.6 equivalents of NaOH in 30 equivalents of water. Depending on the alkoxilate starting material, further water had to be added to prevent solidification of the system. Then the resulting mixture was adjusted to pH 7 by addition of 10 w% H2SO4 or 10 w% NaOH.

In the last step the mixture was slowly heated upon stirring under dynamic vacuum (ca. 20 mbar) to 85°C to remove the methylene chloride and to concentrate the mixture to 17-19% dry matter. Table 1 : Surfactants

n of n of

Surfactant Fatty alcohol Polymerization type End group

EO PO

1.1. alcohol alkoxylates

1.1.1 Cio-oxoalcohol 6 - - -OH

1.1.2 Cio-oxoalcohol 7 7 random -OH

1.1.3 Cio-Guerbet alcohol 6 5 multi-block -OH

1.1.4 Cio-Guerbet alcohol 8 5 multi-block -OH

1.1.5 iso-Ci3-alcohol 6 3 block -OH

1.1.6 iso-Ci3-alcohol 7 - - -OH

1.1.7 Ci3/i5-oxoalcohol 6 3 block -OH

1.1.8 Ci3/i5-oxoalcohol 2 2 random -OH

1.1.9 Ci3/i5-oxoalcohol 2 5 block, first PO, then EO -OH 1.1.10 Ci3/i5-oxoalcohol 12 6 random -OH

1.1.11 cetylstearyl alcohol 12 - - -OH

1.1.12 oleyl alcohol 2 - - -OH

1.1.13 nonylphenol 8 - - -OH

1.2 mono-phosphates

1.2.1 Cio-oxoalcohol 6 - - -OP(0)(OH) ₂

1.2.2 Cio-oxoalcohol 7 7 random -OP(0)(OH) ₂

1.2.3 Cio-Guerbet alcohol 6 5 multi-block -OP(0)(OH) ₂

1.2.4 Cio-Guerbet alcohol 8 5 multi-block -OP(0)(OH) ₂

1.2.5 iso-Ci3-alcohol 6 3 block -OP(0)(OH) ₂

1.2.6 iso-Ci3-alcohol 7 - - -OP(0)(OH) ₂

1.2.7 Ci3/i5-oxoalcohol 6 3 block -OP(0)(OH) ₂

1.2.8 Ci3/i5-oxoalcohol 2 2 random -OP(0)(OH) ₂

1.2.9 Ci3/i5-oxoalcohol 2 5 block, first PO, then EO -OP(0)(OH) ₂

1.2.11 cetylstearyl alcohol 12 - - -OP(0)(OH) ₂

1.2.12 oleyl alcohol 2 - - -OP(0)(OH) ₂

1.2.13 nonylphenol 8 - - -OP(0)(OH) ₂

1.3 mono-/di-phosphates

-OP(0)(OH) ₂ /

1.3.7 Ci3/i5-oxoalcohol 6 3 block

(-0) ₂ P(0)OH

-OP(0)(OH) ₂ /

1.3.10 Ci3/i5-oxoalcohol 12 6 random

(-0) ₂ P(0)OH

1.4 sulfates

1.4.8 Ci3/i5-oxoalcohol 2 2 random -OSOsNa

1.4.9 Ci3/i5-oxoalcohol 2 5 block, first PO, then EO -OSOsNa

Cio-oxoalcohol - prepared by hydrogenation of hydroformylated trimeric propene

iso-Ci3-alcohol prepared by hydrogenation of hydroformylated trimeric buten

Ci3/i5-oxoalcohol (prepared by hydrogenation of hydroformylated Ci ₂ -Ci4-a-olefin 2. Preparation examples

2.1 Formulation of alcohol alkoxylates (non-ionic surfactants):

An alcohol alkoxylate of table 1 , section 1 .1 (71 .4 % by weight) was mixed with alcohol alkoxylate 1.1.5 (28.6 % by weight) acting as retention enhancer and hydrotrope to get a clear viscous solution. Optionally orthophosphoric acid was admixed in a molar ratio orthophosphoric acid : surfactant = 1 : 1 (see table 3).

2.2 Formulation of mono-phosphates (anionic surfactants):

in acid from:

A phosphate of table 1 , section 1 .2 (71.4 % by weight) was mixed with alcohol alkoxylate 1 .1 .5 (28.6 % by weight) acting as retention enhancer and hydrotrope to get a clear viscous solution. in salt form:

A phosphate of table 1 , section 1.2 (25 % by weight) and alcohol alkoxylate 1 .1 .5 (10 % by weight) were mixed with 50% by weight of a 20% by weight aqueous solution of ethanol and agitated. The pH of the mixture was adjusted to 6.5 - 7.5 using potassium hydroxide in form of 50% aqueous solution. The resulted mixture was filled up to 100% by weight with the aforesaid 20% by weight aqueous solution of ethanol to get a clear low viscous solution.

2.3. Formulation of mono-/di-phosphates

According to section 2.2 using mono-/di-phosphates of table 1 , section 1 .3.

2.4. Formulation of sulfates

A sulfate of table 1 , section 1.4 was mixed with alcohol alkoxylate 1 .1 .5 in a surfactant weight ratio of 2.5 parts sulfate to 1 part isotridecanol alkoxilate. The resulted mixture was 2-fold diluted with ethanol to yield a clear low viscous solution.

2.5. Formulation of oil-containing adjuvant

a) methyl oleate or b) paraffin oil: 90% by weight of methyl oleate or paraffin oil, respectively, was mixed with 10% by weight of emulsifier (consisting of castor oil ethoxylate and calcium arylalkylsulfonate) to yield a clear emulsifiable oil.

c) fatty acid dimethyl amide: 20 w% tristyryl phenol alkoxilate (Soprophor® 796 P) was mixed with 5 w% water and 75 w% decanoic acid Ν,Ν-dimethyl amide (Genagen® 4296) to yield a clear emulsifiable oil.

2.6. Formulation of cornexistin

Cornexistin or hydroxycornexistin was added to a mixture of cyclohexanone (80% by weight of the mixture) and castor oil ethoxylate (20% by weight of the mixture) to get a soluble liquid comprising 200 g/l of an active ingredient.

3. Preparation of spray liquors

Type I (comparative)

A spray liquor comprising 133 mg/l of cornexistin or 100 mg/l hydroxycornexistin was prepared by tank mixing a formulation according to section 2.6 with water.

Type II (inventive)

A spray liquor comprising 133 mg/l of cornexistin or 100 mg/l hydroxycornexistin and 0.36% by weight of a surfactant according to Table 1 was prepared by tank mixing a formulation according to section 2.6 with a formulation according to the sections 2.1 -2.4 and water.

Type III (inventive) The formulations according to the sections 2.1 - 2.6 were tank mixed with water to get a spray liquor comprising:

• 133 mg/l cornexistin or 100 mg/l hydroxycornexistin,

• 0.25 % by weight of a surfactant according to Table 1 ,

· 0.1 % alcohol alkoxilate 1 .1.5

• 0.50 % by weight of an adjuvant containing methyl oleate, and

• optionally orthophosphoric acid.

Type IV (inventive) - different oil-containing adjuvants

The formulations according to the sections 2.1 -2.6, were tank mixed with water to get a spray liquor comprising:

• 133 mg/l cornexistin or 100 mg/l hydroxycornexistin,

• 0.36 % by weight of a surfactant according to Table 1 ,

• 0.14 % alcohol alkoxilate 1.1.5, and

· 1 .00% by weight of an oil-containing adjuvans.

4. Biological examples

Grass weeds (ALOMY, SETVI, SETFA, LOLRI, ECHCG, PANMI, DIGSA) and broadleaf weeds (ABUTH, AMBEL, ERICA, CHEAL, SOLNI) where treated with a spray liquor prepared according to section 3 (375 l/ha, corresponds to 50 g/ha of cornexistin and 38g/ha of hydroxycornexistin).

The plants used in the greenhouse experiments were of the following species:

Bayer Code Latin name of the weed

Grass weeds

ALOMY Alopecurus myosuroides

DIGSA Digitaria sanguinalis (L.)

ECHCG Echinochloa crus-galli (L.)

LOLRI Lolium rigidum Gaudin

PANMI Panicum miliaceum L.

SETFA Setaria faberi

SETVI Setaria viridis (L.)

Broadleaf weeds

ABUTH Abutilon theophrasti

AMBEL Ambrosia artemisiifolia L.

CHEAL Chenopodium album

ERICA Erigeron canadensis L.

SOLNI Solanum nigrum L. The culture containers were plastic flower pots containing loamy sand with approximately 3.0% of humus as the substrate.

The test plants were first grown to a height of 3 to 15 cm depending on the plant habit and only then treated with the active compounds suspended in water. They were either grown directly in the test containers or transplanted as seedlings into the test containers a few days prior to treatments.

Depending on the species the plants were kept at 10 to 25°C or 20 to 35°C. The test period extended over three weeks. During this time the plants were tended and their response to the individual treatment was evaluated.

Damage by the herbicidal compositions was evaluated with reference to a scale of 0% to 100% in comparison with untreated control plots. 0 means no damage and 100 means complete destruction of the plants. The mean value was calculated for grass weeds and broadleaf weeds.

Table 2 Post-emergence treatment by spray liquors of Type I (comparative) and by spray liquors of Type II (inventive). Application rate of cornexistin is 50g/ha and of hydroxycornexistin is 38g/ha.

Table 3 Post-emergence treatment by spray liquors of Type I (comparative) and by spray liquors of Type III (inventive) comprising cornexistin as an active ingredient. Application rate of

mono-phosphates

1.2.2 acid 74 90

1.2.2 salt 59 88

1.2.3 acid 91 100

1.2.3 salt 68 85

1.2.6 acid 82 89

1.2.6 salt 76 81

1.2.7 acid 84 88

1.2.7 salt 68 79

Table 4 Post-emergence treatment by spray liquors of Type I (comparative) and by spray liquors of Type IV (inventive). Application rate of cornexistin is 50g/ha.

Treatment,

Damage [%]

Active Gramineous Broad leaf

Surfactant Oil

ingredient weeds weeds

Cornexistin - - 39 75

Cornexistin 1.2.12 acid Methyl oleate 87 100

Cornexistin 1.2.12 acid Paraffin oil 81 86

Cornexistin 1.2.12 acid Ν,Ν-dimethyldecane amide 82 92