WO2011003776A2 - Substituted cyanobutyrates having a herbicidal effect - Google Patents

Abstract

The invention relates to substituted cyanobutyrates of the formula (I), wherein the variables are defined according to the description, to a method and intermediate products for producing the compounds of the formula (I) and the N-oxides thereof, to the agriculturally useful salts thereof, to agents comprising the same, and to the use thereof as herbicides, and to a method for treating undesirable plant growth.

Description

 Substituted cyanobutyrates with herbicidal activity

description

The present invention relates to substituted cyanobutyrates of the formula I.

wherein the variables have the following meaning:

R is halogen, cyano, nitro, C -C alkyl ₄ -alkyl, Ci-C ₄ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ -alkyl kinyl,

Z- (tri-C 1 -C ₄ -alkyl) silyl,

R ¹ is hydrogen, Z-CN, d-Cβ-alkyl, ZC ₃ -C ₆ cycloalkyl, d-Cβ-haloalkyl, C ₃ -C ₈ -alkenyl -Al-, ZC ₃ -C ₆ cycloalkenyl, C ₃ -C ₈ -alkynyl, Z- (tri-C 1 -C ₄ -alkyl) silyl, ZC (= O) -R ^a , ZP (= O) (R ^a ) 2, Z-phenyl, C or N bonded 3- to 7-membered monocyclic or 9- or 10-membered bicyclic saturated, unsaturated or aromatic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S, partially or completely by groups R ^a and / or R ^b may be substituted,

R ^a is hydrogen, OH, Ci-C ₈ -alkyl, C ₄ haloalkyl, ZC ₃ -C ₆ cycloalkyl, C ₂ -C ₈ - alkenyl, ZC ₅ -C ₆ cycloalkenyl, C ₂ -C ₈ Alkynyl, Z-Ci-C ₆ alkoxy, Z-CrC ₄ - haloalkoxy, ZC ₃ -C ₈ alkenyloxy, ZC ₃ -C ₈ alkynyloxy, NR ¹ R ", Ci-C ₆ alkyl sulfonyl, Z- (tri-C 1 -C ₄ -alkyl) silyl, Z-phenyl, Z-phenoxy, Z-phenylamino and

5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S, wherein the cyclic groups unsubstituted or by 1, 2, 3 or 4 groups R ^{b are} substituted, means;

R ¹ , R "independently of one another are hydrogen, C 1 -C ₈ -alkyl, C 1 -C ₄ -haloalkyl,

C ₃ -C ₈ alkenyl, C ₃ -C ₈ -alkyl kinyl, ZC ₃ -C ₆ -cycloalkyl, Z-C ₈ alkoxy, Z-C ₈ haloalkoxy, ZC (= O) -R ^A , wherein R ^{A is} OH or Ci-C ₄ alkoxy;

R ¹ and R "can also together with the N-atom to which they are bonded form a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S;

R ^b independently of one another Z-CN, Z-OH, Z-NO ₂ , Z-halogen, Ci-C ₈ -

Alkyl, Ci-C ₄ haloalkyl, C ₂ -C ₈ -alkenyl -alkyl, C ₂ -C ₈ -alkyl kinyl, Z-C ₈ alkoxy, Z-C ₈ haloalkoxy, ZC ₃ -Cio- Cycloalkyl, 0-ZC ₃ -Cio-cycloalkyl, ZC (= O) -R ^a , NR ¹ R ", Z- (tri-C 1 -C ₄ -alkyl) silyl, Z-phenyl and S (O) _m R ^bb , wherein

R ^{bb is} C 1 -C ₈ -alkyl and C ₁ -C ₆ -haloalkyl;

 m is 0, 1 or 2;

R ^b can also form, together with the group R ^b attached to the adjacent carbon atom, a five- or six-membered saturated, partially or completely unsaturated ring which, in addition to carbon atoms, can contain 1, 2 or 3 heteroatoms selected from O, N and S. ;

 Z is a covalent bond or Ci-Cs-alkylene;

 n is 0, 1, 2, 3, 4 or 5;

R ² , R ³ independently of one another are halogen, cyano, nitro, C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy,

S (O) _m R ^bb , NR ¹ R ", C ¹ -C ₄ -haloalkyl, C ¹ -C ₄ -haloalkoxy;

R ² and R ³ may also together form a five- or six-membered saturated, partially or completely unsaturated mono- or bicyclic ring which may contain, in addition to carbon, 1, 2 or 3 heteroatoms selected from O, N and S and groups R ^b may be substituted;

where in groups R and R ¹ and their sub-substituents the carbon chains and / or the cyclic groups may be partially or completely substituted by groups R ^a and / or R ^b ,

with the proviso that not both R ² and R ^{3 are} chlorine when R is hydrogen and R ^{1 is} ethyl or allyl;

and their N-oxides and agriculturally suitable salts.

Moreover, the invention relates to processes and intermediates for the preparation of the compounds of formula I and their N-oxides, their agriculturally useful salts, agents containing them and their use as herbicides, i. for controlling harmful plants, and a method for controlling undesired plant growth, comprising allowing a herbicidally effective amount of at least one compound of formula I or an agriculturally useful salt thereof to act on plants, their seeds and / or their habitat.

 Further embodiments of the present invention can be taken from the claims, the description and the examples. It is understood that the features mentioned above and those yet to be explained of the subject matter according to the invention can be used not only in the particular combination specified, but also in other combinations, without departing from the scope of the invention.

EP-A 5 341, EP-A 266 725, EP-A 270 830, JP 04/297 454, JP 04/297 455 and JP 05/058 979 disclose herbicidal cyanobutyrates, their herbicidal action, in particular at low levels However, application rates or their compatibility with crops remains in need of improvement. An object of the present invention is to provide compounds having herbicidal activity. In particular, active ingredients should be made available which have a high herbicidal action, in particular even at low application rates, and their compatibility with crop plants for commercial exploitation is sufficient.

 These and other objects are achieved by the compounds of the formula I defined above and by their N-oxides, as well as their agriculturally suitable salts.

The compounds according to the invention can be prepared analogously to the synthetic routes described in the cited documents by standard methods of organic chemistry, for example according to the following synthesis route:

Phenylacetonitrile derivatives of the formula II can be reacted with cinnamate derivatives of the formula III in the sense of a Michael addition to give compounds of the formula I. In formulas II and III, the variables have the meaning given for formula I.

This reaction is usually carried out at temperatures of -100 ⁰ C to 150 ⁰ C, preferably -78 ° C to 50 ⁰ C, in a solvent in the presence of a base and / or a catalyst [see. J. Chem. Soc. (1945), p. 438].

 Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane , Anisole and tetrahydrofuran (THF), nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert. Butanol, and dimethyl sulfoxide, dimethylformamide and dimethylacetamide and Wassser, more preferably THF and methanol. It is also possible to use mixtures of the solvents mentioned.

Bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydrogen carbonates such as sodium hydrogencarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and also alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxy magnesium, furthermore organic bases, eg tertiary amines such as trimethylamine, triethylamine, tributylamine, Di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Particularly preferred are potassium tert-butoxide, lithium bis (trimethylsilyl) amide and 7-methyl-1, 5,7-triazabicyclo [4.4.0] dec-5-ene.

 The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.

 Acid catalysts include inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, ferric chloride, tin IV chloride, titanium IV chloride, scandium III triflate and zinc -ll-chloride, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid,

Camphorsulfonic acid, citric acid and trifluoroacetic acid use.

 The acids are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.

Alternatively, the compounds of formula I can also be obtained by U-esterification of other Cyanobutyrate be obtained. This can be done by various methods, for example according to the following:

The transesterification can be carried out in the presence of molecular sieve in an alcohol R ¹ -OH, optionally in an aprotic solvent. This reaction is usually carried out at temperatures of 0 ⁰ C to 180 ° C, preferably 20 ⁰ C to 80 ⁰ C in the presence of a Lewis or Branstedtsäure or an enzyme [cf.. J. Org. Chem. 2002, 67, 431].

Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and THF, nitriles such as acetonitrile and propionitrile, ketones, as well as dimethyl sulfoxide, dimethylformamide and dimethylacetamide, more preferably alcohol R ¹ -OH. It is also possible to use mixtures of the solvents mentioned. Alternatively, transesterification may be by acid or base saponification of other cyanobutyrates (a), followed by reaction with an alcohol R ¹ -OH. These reactions are usually carried out at temperatures of from ⁰ C to 12O ⁰ C, preference example, 2O ⁰ C to 5O ⁰ C in the presence of a base, or an acid and / or a catalyst [see. J. Am. Chem. Soc. 2007, 129 (43), 13321; J. Org. Chem. 1984, 49 (22), 4287.]. Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane , Anisole and THF, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethyl sulfoxide, dimethylformamide and Dimethylacetamide and water, more preferably (a) water, THF; (b) R ¹ -OH. It is also possible to use mixtures of the solvents mentioned.

 Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and Calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate and alkali metal hydrogen carbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, Alkylmeas- siumhalogenide such as methylmagnesium chloride and alkali metal and Alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxy magnesium, in addition to organic bases, eg tertiary amines such as trimethylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Lithium hydroxide is particularly preferred. The bases are generally used in catalytic amounts, but they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.

 As acids and acidic catalysts are inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, ferric chloride, stannic chloride, titanium IV chloride and zinc II chloride , and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid use.

The acids are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent. The starting materials required for the preparation of the compounds I are known in the literature or can be prepared according to the cited literature.

 The reaction mixtures are worked up in the usual way, e.g. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products. The intermediate and end products are z.T. in the form of colorless or pale brownish, viscous oils, which are freed or purified under reduced pressure and at moderately elevated temperature from volatile constituents. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.

 If individual compounds I are not accessible in the above-described ways, they can be prepared by derivatization of other compounds I.

 However, if mixtures of isomers are involved in the synthesis, separation is generally not required because some of the isomers may partially interconvert during processing for application or application (e.g., under light, acid, or base action). Corresponding conversions may also take place after use, for example in the treatment of plants in the treated plant or in the harmful plant to be controlled. The organic molecular moieties mentioned for the substituents of the compounds according to the invention are collective terms for individual listings of the individual group members. All hydrocarbon chains, such as alkyl, halo (gen) alkyl, alkenyl, alkynyl, and the alkyl moieties and alkenyl moieties in alkoxy, halo (gen) alkoxy, Alkylamino, dialkylamino, N-alkylsulfonylamino, alkenyloxy, alkynyloxy, alkoxyamino, alkylaminosulfonylamino, dialkylaminosulfonylamino, alkenylamino, alkynylamino, N- (alkenyl) -N- (alkyl) -amino, N- (alkynyl) -N- (alkyl) -amino, N- (alkoxy) -N- (alkyl) -amino, N- (alkenyl) -N- (alkoxy) -amino or N- (alkynyl) -N- (alkoxy) -amino straight-chain or branched.

The prefix C _n -Cm- indicates the respective carbon number of the hydrocarbon moiety. Unless otherwise stated, halogenated substituents preferably carry one to five identical or different halogen atoms, in particular fluorine atoms or chlorine atoms.

 The meaning halogen in each case represents fluorine, chlorine, bromine or iodine.

 Furthermore, for example:

Alkyl and the alkyl moieties, for example, in alkoxy, alkylamino, dialkylamino, N-alkylsulfonylamino, alkylaminosulfonylamino, dialkylaminosulfonylamino, N- (alkenyl) -N- (alkyl) -amino, N- (alkynyl) -N- (alkyl) -amino, N- (Alkoxy) -N- (alkyl) -amino: saturated, straight-chain or branched hydrocarbon radicals having one or more C atoms, for example 1 to 2, 1 to 4, or 1 to 6 carbon atoms, for example C ₁ -C ₆ -alkyl such as 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-methylpene tyl, 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. In one embodiment of the invention, alkyl is a small alkyl group such as C 1 -C ₄ -alkyl. In another embodiment of the invention, alkyl is greater alkyl groups such as Cs-Cβ-alkyl.

 Haloalkyl (also referred to as haloalkyl): an alkyl radical as mentioned above, the hydrogen atoms of which are partially or completely substituted by halogen atoms such as fluorine, chlorine, bromine and / or iodine, e.g. Chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-di-fluoroethyl, 2,2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-di-fluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3, 3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl.

Cycloalkyl and the cycloalkyl moieties, for example, in cycloalkoxy or cycloalkylcarbonyl: monocyclic, saturated hydrocarbon groups having three or more C atoms, e.g. 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

 Alkenyl and alkenyl moieties, for example, in alkenylamino, alkenyloxy, N- (alkenyl) -N- (alkyl) -amino, N- (alkenyl) -N- (alkoxy) -amino: monounsaturated, straight-chain or branched hydrocarbon radicals having two or more carbon atoms. Atoms, z. 2 to 4, 2 to 6 or 3 to 6 carbon atoms and a double bond in any position, e.g. C2-C6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 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-buteny 1, 2, 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-butoxy enyl, 2-ethyl-3-butenyl, 1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 1-ethyl 2-methyl-2-propenyl.

 Cycloalkenyl: monocyclic, monounsaturated hydrocarbon groups having 3 to 6, preferably 5 to 6 carbon ring members, such as cyclopenten-1-yl, cyclopentene-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl ,

 Alkynyl and alkynyl moieties, for example in alkynyloxy, alkynylamino, N- (alkynyl) -N- (alkyl) -amino or N- (alkynyl) -N- (alkoxy) -amino: straight-chain or branched hydrocarbon groups having two or more carbon atoms , z. B. 2 to 4, 2 to 6, or 3 to 6 carbon atoms and a triple bond in any position, for. C 2 -C 6 -alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl 2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2- Methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1, 1-Dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1, 2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1 - butinyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl.

 Alkoxy: alkyl, as defined above, which is bonded via an oxygen atom: z. Methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1, 1- Dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethylbutoxy, 1, 2 Dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2-trimethylpropoxy, 1, 2, 2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy.

 5- or 6-membered heterocycle: a cyclic group having 5 or 6 ring atoms wherein 1, 2, 3 or 4 ring atoms are heteroatoms selected from O, S and N, the cyclic group being saturated, partially unsaturated or aromatic is.

The compounds of formula I contain two chiral centers and, depending on the substitution pattern, may contain one or more others. The compounds according to the invention can therefore be present as pure enantiomers or diastereomers or as enantiomer or diastereomer mixtures. The invention relates to both the pure enantiomers or diastereomers and mixtures thereof.

Die Verbindungen der Formel I können auch in Form der N-Oxide und/oder ihrer landwirtschaftlich brauchbaren Salze vorliegen, wobei es auf die Art des Salzes in der Regel nicht ankommt. Im Allgemeinen kommen die Salze derjenigen Kationen oder die Säureadditionssalze derjenigen Säuren in Betracht, deren Kationen, beziehungsweise Anionen, die herbizide Wirkung der Verbindungen I nicht negativ beeinträchtigen.

The compounds of the formula I can also be present in the form of the N-oxides and / or their agriculturally useful salts, the type of salt generally not being important. In general, the salts of those cations or the acid addition salts of those acids come into consideration whose cations, or anions, do not adversely affect the herbicidal activity of the compounds I.

The cations used are, in particular, ions of the alkali metals, preferably lithium, sodium or potassium, the alkaline earth metals, preferably calcium or magnesium, and the transition metals, preferably manganese, copper, zinc or iron. It is likewise possible to use ammonium as cation, in which case, if desired, one to four hydrogen atoms are represented by C 1 -C ₄ -alkyl, hydroxy-C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy-C 1 -C ₄ -alkyl, hydroxyC 1 -C ₄ alkoxy-C 1 -C 4 -alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-1-oxy) eth-1-ylammonium, di (2-hydroxyethyl) 1-yl) ammonium, trimethylbenzylammonium. Also suitable as the ammonium cation is the pyridine nitrogen atom of the formula I quaternized by alkylation or arylation. Further suitable are phosphonium ions, sulfonium ions, preferably tri (C 1 -C 4 -alkyl) sulfonium or sulfoxonium ions, preferably tri (C 1 -C 4 -alkyl) sulfoxonium.

 Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate, Butyrate or trifluoroacetate.

The particularly preferred embodiments of the intermediates with respect to the variables correspond to those of the groups of the formula I.

 In a particular embodiment, the variables of the compounds of the formula I have the following meanings, these being considered both individually and in combination with one another in particular embodiments of the compounds of the formula I:

In one embodiment of the compounds of the formula I, the subscript n stands for a value of 0 to 3, preferably for 0 or 1, in particular for 1. In another embodiment, it stands for 0. If at least one group R is present, it stands preferably in the positions 3, 4 and / or 5, in particular 3 or 4. If the index n is 2, the groups R are preferably in positions 2.5 or 3.4.

Embodiments of the group (s) R concern halogen, in particular chlorine or fluorine. Further embodiments of the group (s) R concern cyano or nitro, in particular cyano. Particularly preferred embodiments of the group R _n include the following:

3-F; 3,4-F ₂ ; 3,5-F ₂ ; 3,4,5-F ₃ ; 3-F.4-Cl; 4-CI; 4-F; 3-CN.

Preferred embodiments of the group R ¹ relate to hydrogen, C ₁ -C ₆ -alkyl, cyano-C ₁ -C ₄ -alkyl, C ₃ -C ₆ -alkynyl, C ₃ -C ₆ -alkynyl, C ₁ -C ₈ -haloalkyl, if appropriate subst. Z-phenyl or NR'R "-C-ι-C4-alkyl, wherein R ^{1 is} hydrogen or Ci-C ₄ alkyl and R" is hydrogen, Ci-C4-alkyl or C (= O) -R ^A , Particularly preferred embodiments of the group R ¹ relate to hydrogen, C 1 -C 4 -alkyl, cyanomethyl, allyl, propargyl, C 1 -C 4 -haloalkyl containing preferably 1 to 3 halogen atoms, phenyl or benzyl, which aromatic groups may be partially or completely substituted. Particularly preferred embodiments for R ¹ include the following: H, CH ₃ , C ₂ H ₅ , CH ₂ CN, CH ₂ C≡CH, CH ₂ CH ₂ F, CH ₂ CHF ₂ , CH ₂ CF ₃ , CH ₂ OCH ₃ ,

Preferred embodiments of the group R ² relate to halogen, cyano, nitro, C _T C ₄ - AI alkyl, Ci-C ₄ alkoxy, S (O) _m R ^bb, NR ¹ R "Ci-C ₄ haloalkyl, Ci- C ₄ haloalkoxy Particularly preferred embodiments of the group R ² include halogen, CN, NO ₂ , CH ₃ , CHF ₂ , CF ₃ , OCHF ₂ , OCF _3. Particularly preferred embodiments of the group R ² are selected from fluorine, chlorine, bromine and more preferably, R ^{2 is} not chlorine.

More preferably, R ^{2 is} fluorine.

More preferably, R ^{2 is} bromine.

More preferably, R ^{2 is} iodine.

Preferred embodiments of the group R ³ relate to halogen, cyano, nitro, Ci-C ₄ - AI alkyl, Ci-C ₄ alkoxy, S (O) _m R ^bb, NR ¹ R "Ci-C ₄ haloalkyl, Ci- C ₄ haloalkoxy Particularly preferred embodiments of the group R ³ relate to halogen, CN, NO ₂ , CH ₃ , CHF ₂ , CF ₃ , OCHF ₂ , OCF _3. Particularly preferred embodiments of the group R ³ are selected from fluorine, chlorine, bromine and iodine, more preferably R ^{3 is} not chlorine.

More preferably, R ^{3 is} fluorine.

More preferably, R ^{3 is} bromine.

More preferably, R ^{3 is} iodine.

Particularly preferred are the following combinations of R ² and R ³ :

2,3-F ₂ ; 2-F.3-CI; 2-F, 3-Br; 2-F, 3-CN; 2-F, 3-NO ₂ ; 2-F, 3-CF ₃ ; 2-F, 3-OCH ₃ ; 2-CI.3-F.

In particular, with regard to their use, the compounds of the formula I compiled in the following tables are preferred. The groups mentioned in the tables for a substituent, taken separately, independently of the combination in which they are mentioned, also represent a particularly preferred embodiment of the substituent in question. Table 1

Compounds of the formula I in which R _{n is} 3-CN and the combination of R ¹ , R ² and R ³ for a compound corresponds in each case to one row of Table A.

 Table 2

Compounds of the formula I in which R _{n is} 4-CI and the combination of R ¹ , R ² and R ³ for a compound corresponds in each case to one row of Table A.

 Table 3

Compounds of the formula I in which R _{n is} 3-F and the combination of R ¹ , R ² and R ³ for a compound corresponds in each case to one row of Table A.

 Table 4

Compounds of the formula I in which R _{n is} 4-F and the combination of R ¹ , R ² and R ³ for a compound corresponds in each case to one row of Table A.

 Table 5

Compounds of the formula I in which R _{n is} 3,4-F ² and the combination of R ¹ , R ² and R ³ for a compound corresponds in each case to one row of Table A.

 Table 6

Compounds of the formula I in which R _{n is} 3,5-F ² and the combination of R ¹ , R ² and R ³ for a compound corresponds in each case to one row of Table A.

 Table 7

Compounds of the formula I in which R _{n is} 3-F, 4-CI and the combination of R ¹ , R ² and R ³ for a compound corresponds in each case to one row of Table A.

 Table 8

Compounds of the formula I in which R _{n is} 3,4,5-F ³ and the combination of R ¹ , R ² and R ³ for a compound corresponds in each case to one row of Table A.

Table A - Compounds of the formula I

The compounds I and their agriculturally useful salts are suitable - both as mixtures of isomers and in the form of pure isomers - as herbicides. They are suitable as such or as appropriately formulated agent. The herbicidal compositions containing the compound I, in particular the preferred embodiments thereof, control plant growth on non-crop surfaces very well, especially at high application rates. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and grass weeds without significantly damaging the crops. This effect occurs especially at low application rates. Depending on the particular application method, the compounds I, in particular the preferred embodiments thereof, or agents containing them can be used in a further number of crop plants for the removal of undesirable plants. For example, the following cultures may be considered:

 Allium cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beta vulgaris spec. altissima, Beta vulgaris spec. rapeseed, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Brassica oleracea, Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus monon, 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 Priscus vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and Prunus domestica, Ribes sylvestre, Ricinus communis, p accharum officinarum, Seeale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (s. vulgaris), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.

The term crops also includes those that have been modified by breeding, mutagenesis or genetic engineering methods. Genetically engineered plants are plants whose genetic material has been altered in a manner that does not occur under natural conditions by crossing, mutations or natural recombination (i.e., rearrangement of genetic information). As a rule, one or more genes are integrated into the genome of the plant in order to improve the properties of the plant.

 The term crops thus also encompasses plants which by breeding and genetic engineering measures tolerance to certain herbicide classes, such as hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors, acetolactate synthase (ALS) inhibitors, such as. Sulfonylureas (EP-A 257 993, US Pat. No. 5,013,659) or imidazolinones (see, for example, US Pat. Nos. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, US Pat.

WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357,

WO 03/13225, WO 03/14356, WO 04/16073), enolpyruvylshikimate-3-phosphate synthase (EPSPS) -inhibitors such. Glyphosate (see, for example, WO 92/00377), glutamine synthetase (GS) inhibitors such as. Glufosinate (see eg EP-A 242 236, EP-A 242 246) or oxynil herbicides (see eg US 5,559,024).

With the help of classical breeding methods (mutagenesis) numerous crops, eg. As Clearfield® rapeseed, which produces a tolerance to imidazolinones, z. As imazamox, have. With the aid of genetic engineering methods, crops such as soybean generated yes, cotton, corn, beets and rape, which are resistant to glyphosate or glufosinate, which under the trade names RoudupReady ^® (glyphosate) and Liberty Link ^® (glufosinate) can be obtained.

The term crops thus also includes plants that use genetic engineering measures one or more toxins, eg. As those from the bacterial strain Bacillus ssp., Produce. Toxins produced by such genetically engineered plants include e.g. Insecticidal proteins of Bacillus spp., In particular B. thuringiensis such as the endotoxins CrylAb, CrylAc, CrylF, Cry1Fe2, Cry2Ab, Cry3A, Cry3Bb1, Cry9c, Cry34Ab1 or Cry35Ab1; or vegetative insecticidal proteins (VIPs) ₁ eg VIP1, VIP2, VIP3, or VIP3A; insecticidal proteins of nematode-colonizing bacteria, e.g. B. Photorhabdus spp. or Xenorhabdus spp .; Toxins from animal organisms, eg. B. Wepsen, spider or scorpion toxins; fungal toxins, e.g. B. from streptomycetes; herbal lectins, e.g. From pea or barley; agglutinins; Proteinase inhibitors, e.g. Trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; Ribosome Inactivating Proteins (RIPs), e.g. Ricin, corn RIP, abrin, luffin, saporin or bryodin; Steroid metabolizing enzymes, e.g. 3-hydroxysteroid oxidase, ecdysteroid IDP glycosyltransferase, cholesterol oxidase, ecdysone inhibitors or HMG-CoA reductase; ion channel blocker, e.g. B. inhibitors of sodium or calcium channels; Juvenile hormone esterase; Receptors for the diuretic hormone (helicokinin receptors); Stilbene synthase, bibenzyl synthase, chitinases and glucanases. These toxins can also be produced in the plants as proteoxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a novel combination of different protein domains (see, for example, WO 2002/015701). Further examples of such toxins or genetically modified plants which produce these toxins are described in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878,

WO 03/018810 and WO 03/052073. The methods for producing these genetically modified plants are known in the art and z. As set forth in the publications mentioned above. Many of the aforementioned toxins confer on the plants that produce them a tolerance to pests of all taxonomic arthropod classes, in particular to beetles (Coeleropta), diptera (Diptera) and butterflies (Lepidoptera) and nematodes (Nematoda).

Genetically engineered plants that produce one or more genes encoding insecticidal toxins, e.g. As described in the publications mentioned above and partly commercially available, such. B. YieldGard ^® (corn cultivars producing the toxin CrylAb), YieldGard ^® Plus (corn cultivars producing the toxins CrylAb and Cry3Bb1), StarLink ^® (corn cultivars producing the toxin Cry9c), Herculex ^® RW (corn cultivars toxins which Cry34Ab1, Cry35Ab1 and the enzyme phosphinothricin N-acetyltransferase [PAT] produce); NuCOTN ^® 33B (cotton varieties which produce the toxin CrylAc), Bollgard ^® I (cotton cultivars producing the toxin CrylAc), Bollgard ^® Il (cotton varieties which the toxins and CrylAc

Produce Cry2Ab2); VIPCOT ^® (cotton varieties that produce a VIP toxin); NewLeaf ^® (potato cultivars producing the Cry3A toxin); Bt Xtra ^®, NatureGard® ^®, KnockOut ^®, BiteGard ^®, Protecta ^®, Bt11 (z. B. Agrisure ^® CB) and Bt176 from Syngenta Seeds SAS, France (corn varieties which produce the toxin CrylAb and the PAT enzyme) , MIR604 from Syngenta Seeds SAS, France (maize strains producing a modified version of the toxin Cry3A, see WO 03/018810), MON 863 from Monsanto Europe SA, Belgium (maize strains producing the toxin Cry3Bb1), IPC 531 from Monsanto Europe SA, Belgium (cottons producing a modified version of the toxin CrylAc) and 1507 from Pioneer Overseas Corporation, Belgium (maize varieties producing the toxin Cryl F and the PAT enzyme).

 The term crops thus also includes plants that produce by genetic engineering measures one or more proteins that cause increased resistance or resistance to bacterial, viral or fungal pathogens, such as. B. so-called pathogenesis-related proteins (PR proteins, see EP-A 392 225), resistance proteins (eg, potato varieties that produce two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum) or T4 lysozyme (z. Potato varieties resistant to bacteria such as Erwinia amylvora by the production of this protein).

 The term crops thus also includes plants whose productivity has been improved by means of genetic engineering methods by z. For example, yield (eg biomass, grain yield, starch, oil or protein content), tolerance to drought, salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral pathogens may be increased.

The term crops also includes plants whose ingredients have been modified in particular to improve the human or animal diet using genetic engineering methods by z. For example, oil plants can produce health-promoting long-chain omega-3 fatty acids or monounsaturated omega-9 fatty acids (eg Nexera ^® oilseed rape).

The term crops also includes plants that have been modified for the improved production of raw materials by means of genetic engineering methods by z. B. the amylopectin content of potatoes (Amflora ^® potato) was increased.

 Furthermore, it has been found that the compounds of the formula I 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, come into consideration. In this regard, compositions for the desiccation and / or defoliation of plants, processes for the preparation of these agents and methods for the desiccation and / or defoliation of plants with the compounds of formula I have been found.

Desiccants are the compounds of formula I in particular for drying the aerial parts of crop plants such as potato, rape, sunflower and soybean but also cereals. This enables a completely mechanical harvesting of these important crops. Of economic interest is also the relief of the crop, which is made possible by the time-concentrated drop or decrease in the adhesion to the tree in citrus fruits, olives or other types and varieties of pome, stone and peel fruit. The same mechanism, that is, the promotion of the formation of release tissue between fruit or leaf and shoot part of the plants is also essential for a well controllable defoliation of crops, especially cotton. In addition, shortening the time interval in which the individual cotton plants ripen results in increased fiber quality after harvest.

The compounds I or the herbicidal compositions containing them can, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, even high-percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules by spraying, atomizing , Dusting, scattering, pouring or treatment of the seed or mixing with the seed. The forms of application depend on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.

 The herbicidal compositions contain a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries customary for the formulation of crop protection agents.

 Examples of the Formulation of Pesticides Commonly used auxiliaries are preferred auxiliaries, solid carriers, surface-active substances (such as dispersants, protective colloids, emulsifiers, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if necessary, dyes and for seed formulations adhesives.

 Examples of thickeners (ie, compounds which impart modified flowability to the formulation, ie, high-level at low viscosity and low viscosity in the agitated state) are polysaccharides such as xanthan gum (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum ® (RT Vanderbilt) and organic and inorganic layer minerals such as Attaclay® (Engelhardt).

 Examples of antifoams are silicone emulsions (such as, for example, Silikon® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.

 Bactericides may be added to stabilize the aqueous herbicidal formulation. Examples of bactericides are bactericides based on diclorophene and benzyl alcohol hemiformal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) as well as isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide MBS der Fa. Thor Chemie)

Examples of antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol. Examples of colorants are both water-insoluble pigments and water-soluble dyes. Examples which may be mentioned under the names rhodamine B, Cl. Pigment Red 112 and Cl. Solvent Red 1 known dyes, and pigment blue 15: 4, pigment blue 15: 3, pigment blue 15: 2, pigment blue 15: 1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 1 12, pigment red 48: 1, pigment red 48: 1, pigment red 57: 1, pigment red 53: 1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

 Examples of adhesives are polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.

Suitable inert additives are, for example:

 Mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, eg. As amines such as N-methylpyrrolidone or water.

 Solid carriers are mineral soils such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

As surface-active substances (adjuvants, wetting agents, adhesives, dispersants and emulsifiers), the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, eg lignosulfonic acids (eg Borrespers types, Borregaard), phenolsulfonic acids, naphthalenesulfonic acids (Morwet types , Akzo Nobel) and dibutylnaphthalenesulfonic acid (Nekal types, BASF SE), as well as fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenol and formaldehyde, polyoxyethylene octyl phenol ethers, ethoxylated isooctyl, octyl or nonyl phenol, alkylphenyl, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide Condensates, ethoxylated castor oil, polyoxyethyleneal ethers, denatured proteins, polysaccharides (eg methylcellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol types Clariant), polycarboxylates (BASF SE, Sokalan types), polyalkoxylates, polyalkoxylates, polyalkoxylates, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulfite deposits, Polyvinylamine (BASF SE, Lupamine Types), polyethylenimine (BASF SE, Lupasol types), polyvinylpyrrolidone and copolymers thereof.

 Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

 Granules, e.g. Coating, impregnation and homogeneous granules can be prepared by binding the active compounds to solid carriers.

 Aqueous application forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the compounds of the formula I or Ia, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of active substance, wetting, adhesion, dispersing or emulsifying agent and possibly solvent or oil, which are suitable for dilution with water.

 The concentrations of the compounds of the formula I in the ready-to-use formulations can be varied within wide limits. The formulations generally contain from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight, of at least one active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

The compounds I according to the invention can be formulated, for example, as follows:

 1. Products for dilution in water

 A Water-soluble concentrates

10 parts by weight of active compound are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with 10 wt .-% active ingredient content.

 B Dispersible concentrates

20 parts by weight of active compound are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion. The active ingredient content is 20% by weight

 C Emulsifiable concentrates

 15 parts by weight of active compound are dissolved in 75 parts by weight of an organic solvent (for example alkylaromatics) with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has 15% by weight active ingredient content.

 D emulsions

25 parts by weight of active compound are dissolved in 35 parts by weight of an organic solvent (for example alkylaromatics) with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added by means of an emulsifying machine (eg Ultraturax) in 30 parts by weight of water and a homogeneous emulsion brought. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.

 E suspensions

 20 parts by weight of active compound are comminuted with the addition of 10 parts by weight dispersing and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight.

 F Water-dispersible and water-soluble granules

50 parts by weight of active compound are finely ground with the addition of 50 parts by weight of dispersants and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient. The formulation has an active ingredient content of 50% by weight.

 G Water-dispersible and water-soluble powders

 75 parts by weight of active compound are ground with the addition of 25 parts by weight of dispersing and wetting agents and silica gel in a rotor-Strator mill. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

 H gel formulations

 In a ball mill, 20 parts by weight of the active ingredient, 10 parts by weight of the dispersant, 1 part by weight of the gelling agent and 70 parts by weight of water or an organic solvent are ground to a fine suspension. Dilution with water results in a stable suspension with 20% by weight active ingredient content.

2. Products for direct application

 I dusts

 5 parts by weight of active compound are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with 5 wt .-% active ingredient content. J Granules (GR, FG, GG, MG)

 0.5 parts by weight of active compound are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.

 K ULV solutions (UL)

10 parts by weight of active compound are dissolved in 90 parts by weight of an organic solvent such as xylene. This gives a product for direct application with 10% by weight of active ingredient content. The application of the compounds I or the herbicidal compositions containing them can be carried out in the pre-emergence, postemergence or together with the seed of a crop. It is also possible, the herbicidal agents or agents in that seed of a crop plant pretreated with the herbicidal agents or active substances is applied. If the active ingredients are less compatible with certain crops, then application techniques may be employed whereby the herbicidal agents are sprayed by the sprayers so as not to hit the leaves of the sensitive crop if possible, while the active ingredients affect the leaves underneath growing undesirable plants or the uncovered floor surface (post-directed, lay-by).

In a further embodiment, the application of the compounds of the formula I or of the herbicidal compositions can be carried out by treating seed.

 The treatment of seed comprises essentially all techniques familiar to the skilled worker (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting) based on the compounds of the formula according to the invention I or funds produced therefrom. Here, the herbicidal agents can be diluted or applied undiluted.

 The term seed includes seeds of all kinds, e.g. Grains, seeds, fruits, tubers, cuttings and similar forms. The term seed preferably describes grains and seeds here.

 Seeds of the abovementioned crops but also the seeds of transgenic or obtained by conventional breeding methods plants can be used as seeds.

Depending on the control target, season, target plants and growth stage, the application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance (a. S.). For seed treatment, the compounds I are usually used in amounts of 0.001 to 10 kg per 100 kg of seed.

It may also be advantageous to use the compounds of the formula I in combination with safeners. Safeners are chemical compounds that prevent or reduce damage to crops without significantly affecting the herbicidal activity of the compounds of formula I on undesirable plants. They can be used both before sowing (for example in seed treatments, cuttings or seedlings) as well as in the pre- or post-emergence of the crop. The safeners and the compounds of formula I can be used simultaneously or sequentially. Suitable safeners are, for example, (quinoline-δ-oxy) acetic acids, 1-phenyl-5-haloalkyl-1H-1, 2,4-triazole-3-carboxylic acids, 1-phenyl-4,5-dihydro-5 alkyl-1H-pyrazole-3,5-dicarboxylic acids, 4,5-dihydro-5,5-diaryl-3-isoxazolecarboxylic acids, dichloroacetamides, alpha-oximinophenylacetonitriles, acetophenone oximes, 4,6-dihalo-2-phenylpyrimidines, N- [ [4- (aminocarbonyl) phenyl] sulfonyl] -2-benzoic acid amides, 1,8-naphthalic anhydride, 2-halo-4- (haloalkyl) -5-thiazolecarboxylic acids, phosphorothiolates and N-alkyl-O-phenylcarbamates and their agriculturally useful salts, and provided they have an acid function, their agriculturally useful derivatives, such as amides, esters and thioesters.

 To widen the spectrum of action and to achieve synergistic effects, the compounds of formula I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups or with safeners and applied together. For example, 1, 2,4-thiadiazoles, 1, 3,4-thiadiazoles, amides, aminophosphoric acid and derivatives thereof, aminotriazoles, anilides, aryloxy / heteroaryloxyalkanoic acids and their derivatives, benzoic acid and derivatives thereof, benzothiadiazinones, (Hetaroyl / aroyl) -1, 3-cyclohexanediones, heteroaryl-aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and derivatives thereof, chloroacetanilides, cyclohexenone oxime ether derivatives, diazines, dichloropropionic acid and its derivatives, dihydrobenzofurans, dihydroxy furan-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy and heteroaryloxyphenoxypropionic acid esters, phenylacetic acid and its derivatives, 2-phenylpropionic acid and derivatives thereof, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and their derivatives, pyrimidyl ethers, sulfonamides, sulfonylureas, triazines, triazinones, triazolinones, triazolecarboxamides, uracils and also phenylpyrazolines and isoxazolines and derivatives thereof.

 In addition, it may be useful to use the compounds I alone or in combination with other herbicides or even mixed with other crop protection agents, together, for example, with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used for the elimination of nutritional and trace element deficiencies. Other additives such as non-phytotoxic oils and oil concentrates may also be added.

 Examples of herbicides which can be used in combination with the pyridine compounds of the formula I according to the present invention are:

 b1) from the group of lipid biosynthesis inhibitors:

 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, FIuac-p-P, Fluazifop-P-butyl, Haloxyfop, Haloxyfop-methyl, Haloxyfop-P, Haloxyfop-P-methyl, Metamifop, Pinoxaden, Profoxydim, Propaquizafop, Quizalofop, Quizalofopethyl, Quizalofop-tefuryl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop-P-tefuryl, Sethoxydim, Tepraloxydim, Tralkoxydim, Benfuresat, Butylate, Cycloat, Dalapon, Dimepiperate, EPTC, Esprocarb, Ethofumesate, Flupropanate, Molinate, Orbencarb, Pebulate, Prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;

 b2) from the group of ALS inhibitors:

Amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, bispyribac, bispyribac-sodium, chlorimuron, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, cloransulam, Cloransulam-methyl, Cyclosulfamuron, Diclosulam, Ethametsulfuron, Ethametsulfuron-methyl, Ethoxysulfuron, Flazasulfuron, Florasulam, Flucarbazone, Flucarbazone-Sodium, Flucetosulfuron, Flumetsulam, Flupyrsulfuron, Flupyrsulfuron-methyl-Sodium, Foram-Sulfurone, Halosulfuron, Halosulfuron-methyl, Imazamethabenz, Imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron, iodosulfuron-methyl-sodium, mesosulfuron, metosulam, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, penoxsulam, primisulfuron, primisulfuron methyl, propoxycarbazone, propoxycarbazone sodium, prosulfuron, pyrazosulfuron, pyrazosulfuron-ethyl, pyribenzoxime, pyrimisulfan, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, pyroxsulam, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, Thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-meth yl, trifloxysulfuron, triflusulfuron, triflusulfuron-methyl and tritosulfuron;

 b3) from the group of photosynthesis inhibitors:

Ametryn, amicarbazone, atrazine, bentazone, bentazone sodium, bromacil, bromofenoxime, bromoxynil and its salts and esters, chlorobromuron, chloridazon, chlorotoluron, chloroxuron, cyanazine, desmedipham, desmetryn, dimefuron, dimethametryn, diquat, diquat-dibromide , Diuron, fluometuron, hexazinone, loxynil and its salts and esters, isoproturon, isourone, carbutilate, lenacil, linuron, metamitron, methabenzthiazirone, metobenzuron, methoxuron, metribuzin, monolinuron, neburon, paraquat, paraquat dichloride, paraquat dimethylsulfate, pentanochlor, phenmedipham, phenmediphamethyl, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, terbumetone, terbuthylazine, terbutryn, thidiazuron and trietazine;

 b4) from the group of protoporphyrinogen IX oxidase inhibitors:

 Acifluorfen, acifluorfen sodium, azafenidine, bencarbazone, benzfendizone, bifenox, buafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, cinidone-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac-pentyl, flumioxazine, fluoroglycofene, Fluoroglycofen-ethyl, Fluthiacet, Fluthiacet-methyl, Fomesafen, Halosafen, Lactofen, Oxadiargyl, Oxadiazon, Oxyfluorfen, Pentoxazone, Profluazole, Pyraclonil, Pyrafluene, Pyraflufen-ethyl, Saflufenacil, Sulfentrazone, Thidiazimin, 2-Chloro-5- [3,6-dihydro-3-methyl-2,6-dioxo-4- (trifluoromethyl) -1 (2H) -pyrimidinyl] -4-fluoro-N - [(isopropyl) methylsulfamoyl] benzamide (B-1 CAS 372137-35-4), [3- [2-chloro-4-fluoro-5- (1-methyl-6-trifluoromethyl-2,4-dioxo-1,2,3,4-tetrahydropyrimidine 3-yl) phenoxy] -2-pyridyloxy] acetic acid ethyl ester (B-2; CAS 353292-31-6), N-ethyl-3- (2,6-dichloro-4-trifluoromethylphenoxy) -5-methyl- 1 H -pyrazole-1-carboxamide (B-3; CAS 452098-92-9), N-tetrahydrofurfuryl-3- (2,6-dichloro-4-trifluoromethylphenoxy) -5-methyl-1 H-pyrazole-1-carboxamide (B-4; CAS 915396-43-9), N-ethyl-3- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -5-methyl-1H-pyrazole-1-carboxamide (B-5; CAS 452099- 05-7) and N-tetrahydrofurfuryl-3- (2-chloro-6-fluoro-4-trifluoromethylphenoxy) -5-methyl-1H-pyrazole-1-carboxamide (B-6; CAS 452100-03-7 );

b5) from the group of bleacher herbicides: Aclonifen, Amitrole, Beflubutamide, Benzobicyclone, Benzofenap, Clomazone, Diflufenicanone, Fluridone, Flurochloridone, Flurtamone, Isoxaflutole, Mesotrione, Norflurazon, Picolinefine, Pyrasulfutole, Pyrazolynate, Pyrazoxyfen, Sulcotrione, Tefuryltrione, Tembotrione, Topramezone, 4- Hydroxy-3 - [[2 - [(2-methoxyethoxy) methyl] -6- (trifluoromethyl) -3-pyridyl] carbonyl] bicyclo [3.2.1] oct-3-en-2-one (B-7 CAS 352010-68-5) and 4- (3-trifluoromethylphenoxy) -2- (4-trifluoromethylphenyl) pyrimidine (B-8; CAS 180608-33-7);

 b6) from the group of EPSP synthase inhibitors:

Glyphosate, glyphosate isopropylammonium and glyphosate trimesium (sulfosate);

 b7) from the group of glutamine synthase inhibitors:

Bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and glufosinate-ammonium; b8) from the group of DHP synthase inhibitors: asulam;

 b9) from the group of mitosis inhibitors:

 Amiprophos, Amiprophos-methyl, Benfluralin, Butamiphos, Butraline, Carbetamide, Chlorpropham, Chlorthal, Chlorthal-dimethyl, Dinitramine, Dithiopyr, Ethalfluralin, Flu chlorin, Oryzalin, Pendimethalin, Prodiamine, Propham, Propyzamide, Tebutam, Thiazopyr and Trifluralin;

 b10) from the group of VLCFA inhibitors:

 Acetochlor, Alachlor, Anilofos, Butachlor, Cafenstrol, Dimethachlor, Dimethanamide, Dimethenamid-P, Diphenamid, Fentrazamide, Flufenacet, Mefenacet, Metazachlor, Metolachlor, Metolachlor-S, Naproanilide, Napropamide, Pethoxamide, Piperophos, Pretilochlor, Propachlor, Propisochlor, Pyroxasulfone (KIH-485) and Thenylchlor;

Compounds of the formula 2:

wherein the variables have the following meanings:

Y is phenyl or 5- or 6-membered heteroaryl as defined above, which may be substituted by one to three groups R ^aa ; R ²¹ , R ²² , R ²³ , R ^{24 are} H, halogen, or C 1 -C ₄ -alkyl; X is O or NH; n 0 or 1.

In particular, compounds of the formula 2 have the following meanings:

 where # is the bond to the molecular skeleton; and

R ²¹ , R ²² , R ²³ , R ^{24 are} H, Cl, F or CH ₃ ; R ^{25 is} halogen, C 1 -C ₄ -alkyl or C 1 -C ₄ -haloalkyl; R ^{26 is} C 1 -C ₄ -alkyl; R ^{27 is} halogen, C 1 -C ₄ -alkoxy or C 1 -C ₄ -haloalkoxy; R ²⁸ is H, halogen, Ci-C ₄ - alkyl, Ci-C ₄ haloalkyl or _{Ci-C4-haloalkoxy;} m is 0, 1, 2 or 3; X oxygen;

n 0 or 1.

Preferred compounds of the formula 2 have the following meanings:

R ²¹ H; R ^22, R ²³ F; R ²⁴ H or F; X oxygen; n 0 or 1.

 Particularly preferred compounds of the formula 2 are:

 3- [5- (2,2-Difluoroethoxy) -1-methyl-3-trifluoromethyl-1H-pyrazol-4-ylmethanesulfonyl] -4-fluoro-5,5-dimethyl-4,5-dihydro-isoxazole (2-1); 3 - {[5- (2,2-Difluoroethoxy) -1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl] -fluoro-methanesulfonyl} -5,5-dimethyl-4,5 dihydro-isoxazole (2- 2); 4- (4-Fluoro-5,5-dimethyl-4,5-dihydroisoxazol-3-sulfonylmethyl) -2-methyl-5-trifluoromethyl-2H- [1,2,3] triazole (2-3 ); 4 - [(5,5-dimethyl-4,5-dihydroisoxazol-3-sulfonyl) fluoromethyl] -2-methyl-5-trifluoromethyl-2H- [1,2,3] triazole (2-4 ); 4- (5,5-dimethyl-4,5-dihydroisoxazol-3-sulfonylmethyl) -2-methyl-5-trifluoromethyl-2H- [1,2,3] triazole (2-5); 3 - {[5- (2,2-Difluoroethoxy) -1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl] -difluoro-methanesulfonyl} -5,5-dimethyl-4,5-dihydro -isoxazole (2-6); 4 - [(5,5-Dimethyl-4,5-dihydro-isoxazol-3-sulfonyl) -difluoro-methyl] -2-methyl-5-trifluoromethyl-2H- [1,2,3] triazole (2-7 ); 3 - {[5- (2,2-difluoroethoxy) -1-methyl-3-trifluoromethyl-1H-pyrazol-4-yl] difluoro-methanesulfonyl} -4-fluoro-5,5-dimethyl-4 , 5-dihydroisoxazole (2-8); 4- [Difluoro (4-fluoro-5,5-dimethyl-4,5-dihydroisoxazol-3-sulfonyl) methyl] -2-methyl-5-trifluoromethyl-2H- [1,2,3] triazole (2-9);

 b1 1) from the group of cellulose biosynthesis inhibitors:

Chlorthiamide, Dichlobenil, Flupoxam and Isoxaben;

 b12) from the group of decoupling herbicides:

Dinoseb, Dinoterb and DNOC and its salts;

 b13) from the group of auxin herbicides:

 2,4-D and its salts and esters, 2,4-DB and its salts and esters, aminopyralid and its salts, such as aminopyralid tris (2-hydroxypropyl) ammonium and its esters, benazoline, benazolin-ethyl, chloroamben 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, 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, quineme-rac, TBA (2, 3,6) and its salts and esters, triclopyr and its salts and esters, and 5,6-dichloro-2-cyclopropyl-4-pyrimidinecarboxylic acid (B-9; CAS 858956-08-8) and its salts and esters;

 b14) from the group of auxin transport inhibitors: diflufenzopyr, diflufenzopyrsodium, naptalam and naptalam sodium;

b15) from the group of the other herbicides: bromobutide, chlorofluorol, chlorofluorolmethyl, cinmethylin, cumyluron, dalapon, dazomet, difenzoquat, difenzoquat-metylsulfate, dimethipine, DSMA, dymron, endothal and its salts, etobenzanide, flamprop, Flamprop-isopropyl, Flamprop-methyl Flamprop-M-isopropyl, Flamprop-M-methyl, Flurenol, Flurenol-butyl, Flurprimidol, Fosamine, Fosamine-ammonium, Indano fan, maleic acid hydrazide, Mefluidide, Metam, methyl azide, methyl bromide, methyl -dym- ron, methyl iodine id. MSMA, oleic acid, oxaziclomefon, pelargonic acid, pyributicarb, quinoclamin, triaziflam, tridiphan and 6-chloro-3- (2-cyclopropyl-6-methylphenoxy) -4-pyridazinol (B-10; CAS 499223-49-3 ) and its salts and esters.

 Examples of preferred safeners C are Benoxacor, Cloquintocet, Cyometrinil, Cyprusulfamide, Dichlormid, Dicyclonon, Dietholate, Fenchlorazole, Fenclorim, Flurazole, Fluxofenim, Furilazole, Isoxadifen, Mefenpyr, Mephenate, Naphthalic Anhydride, Oxabetrinile, 4- (Dichloroacetyl ) -1-oxa-4-azaspiro [4.5] decane (B-1 1, MON4660, CAS 71526-07-3) and 2,2,5-trimethyl-3- (dichloroacetyl) -1,3-oxazolidine (B -12; R-29148, CAS 52836-31-4). The active compounds of groups b1) to b15) and the safeners C are known herbicides and safeners, see, for example, US Pat. B. The Compendium of Pesticide Common Names

 (Http://www.alanwood.net/pesticides/); B. Hock, C. Fedtke, RR Schmidt, herbicides, Georg Thieme Verlag, Stuttgart 1995. Further herbicidal active compounds are known from WO 96/26202, WO 97/411 16, WO 97/41 117, WO 97/411 18, WO 01 / 83459 and WO

2008/074991 as well as from W. Krämer et al. (ed.) "Modern Crop Protection Compounds", Vol. 1, Wiley VCH, 2007 and the literature cited therein.

The compounds I and the compositions according to the invention may also have a plant-strengthening effect. They are therefore suitable for mobilizing plant-own defenses against infestation by undesirable microorganisms, such as harmful fungi, but also viruses and bacteria. In this context, plant-strengthening (resistance-inducing) substances are to be understood as meaning substances which are capable of stimulating the defense system of treated plants in such a way that they develop extensive resistance to these microorganisms during subsequent inoculation with undesired microorganisms.

 The compounds I can be used to protect plants against attack by undesired microorganisms within a certain period of time after the treatment. The period within which protection is provided generally extends from 1 to 28 days, preferably 1 to 14 days after treatment of the plants with the compounds I or after treatment of the seed, up to 9 months after sowing.

 The compounds I and the compositions according to the invention are also suitable for increasing crop yield.

 They are also low toxicity and have good plant tolerance. In the following, the preparation of pyridine compounds of the formula I is explained by way of examples without limiting the subject matter of the present invention to the examples shown.

synthesis Examples

The instructions given in the Synthesis Examples below, with appropriate modification of the starting compounds for obtaining further I used connections. The compounds thus obtained are listed in the following table with physical data.

The characterization of the products shown below was carried out by determining the melting point, by NMR spectroscopy or by means of

 HPLC-MS spectrometry determined masses ([m / z]) or retention time (RT, [min.]).

[HPLC-MS = High Performance Liquid Chromatography combined with mass spectrometry; HPLC column:

RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany), 50 ^* 4.6 mm; Eluent: acetonitrile + 0.1% trifluoroacetic acid (TFA) / water + 0.1% TFA, with a gradient of 5:95 to 100: 0 in 5 minutes at 40 ^° C., flow rate 1, 8 ml / min.

 MS: Quadrupole electrospray ionization, 80V (positive mode).] I. Preparations

 Example 1: Preparation of 3- (3-chloro-2-fluoro-phenyl) -4-cyano-4- (4-fluoro-phenyl) -butyric Acid Methyl Ester [I-46]

 To a solution of 52.5 mg of 3- (3-chloro-2-fluoro-phenyl) -acrylic acid methyl ester in THF was added 0.33 g of 4-fluorophenylacetonitrile under inert gas (Ar). After 5 minutes, 0.42 ml of 7-methyl-1, 5,7-triazabicyclo [4.4.0] dec-5-ene was added. The

Reaction solution was stirred for 2 d at 50 ⁰ C. Then ethyl acetate was added and the reaction mixture washed with sat. Washed NH ₄ Cl solution. The organic phase was dried and the solvent removed in vacuo. From the residue, after chromatography on silica gel (cyclohexane: ethyl acetate 10: 1-4: 1), 60 mg of the title compound (threo / erythro ratio 3: 1) were obtained.

Table I: Compounds of the formula I:

applications

The herbicidal activity of the compounds of the formula I was demonstrated by greenhouse experiments:

The culture vessels used were plastic pots with loamy sand with about 3.0% humus as substrate. The seeds of the test plants were sown separately by species. In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles. The jars were lightly rained to promote germination and growth and then covered with clear plastic hoods until the plants had grown. This cover causes a uniform germination of the test plants, if it was not affected by the active ingredients.

For the postemergence treatment, the test plants were grown depending on the growth form only to a height of from 3 to 15 cm and then treated with the suspended or emulsified in water agents. For this purpose, the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.

The plants were kept species-specific at temperatures of 10 - 25 ° C and 20 - 35 ° C, respectively. The trial period lasted for 2 to 4 weeks. During this time, the plants were cared for, and their response to each treatment was evaluated.

The plants used in the greenhouse experiments are composed of the following species:

The scale was rated from 0 to 100. 100 means no plants rising or completely destroying at least the above-ground parts and 0 means no damage or normal growth. A good herbicidal activity is at values of at least 70 and a very good herbicidal activity is given at values of at least 85.

1) The active ingredient 1-105 showed at a rate of 0.125 kg / ha in the wake of ALOMY a good and the active ingredients I-94, I-99, 1-1 14, 1-1 19, 1-120, resp I-

121 a very good herbicidal action.

 2) The active ingredient 1-100 showed at a rate of 0.25 kg / ha postemergence against ALOMY a good and the active ingredients I-87, I-88, I-89, 1-101, 1-102, 1-174 , I-224, I-226, I-227, and I-228 a very good herbicidal activity.

 3) The active compounds I-32, I-94, I-96, 1-106, 1-107, 1-108, 1-109, 1-1 10, 1-1 12, 1-1 13, 1-122 , 1-124, and 1-192 showed at a rate of 0.125 kg / ha postemergence against AMARE a very good herbicidal activity.

 4) The active compounds 1-176, and I-223 showed at a rate of 0.13 kg / ha postemergence against AMARE a very good herbicidal activity.

 5) The active compounds I-79, I-87, I-88, I-89, 1-125, 1-126, 1-173, 1-175, 1-178, 1-182, 1-183, I-

184, 1-197, I-205, I-206, I-207, I-208, I-209, 1-210, 1-211, 1-212, 1-213, 1-214, 1-215, I-216, 1-217, 1-218, 1-219, I-220, 1-221, I-222, and I-244, respectively, showed a great postemergence against AMARE at a rate of 0.25 kg / ha good herbicidal action.

 6) The active compounds I-76, I-99, 1-100, 1-114, 1-144, 1-150, 1-151, 1-152, 1-153, 1-154, 1-155, 1- 156, 1-159, and 1-171 showed at a rate of 0.125 kg / ha postemergence against AVEFA a very good herbicidal activity.

 7) The active ingredients 1-160, and 1-161 showed at a rate of 0.13 kg / ha postemergence against AVEFA a very good herbicidal activity.

 8) The active compounds I-95, 1-101, 1-125, 1-130, 1-143, 1-164, 1-165, 1-166, 1-167, 1-168, I-169, 1- 170, 1-172, 1-179, 1-180, 1-181, 1-182, 1-183, 1-184, 1-196, 1-197, I-222, I-224, I-

226, I-227, I-228, and I-244 showed at a rate of 0.25 kg / ha postemergence against AVEFA a very good herbicidal activity.

 9) The active compounds 1-110, and 1-121 showed at a rate of 0.125 kg / ha postemergence against SETVI a very good herbicidal activity.

10) The active compounds 1-1 18, or 1-154 showed at a rate of 0, 125 kg / ha post-emergence against POLCO a good and the active ingredients I-32, I-76, I-94, I-96, 1-105, 1-106, 1-107, 1-108, 1-109, 1-112, 1-113, 1-119, 1-120, 1-122, 1-124, 1-144, 1- 150, I-151, 1-152, 1-153, 1-155, 1-156, 1-159, 1-171, and 1-192, respectively, has a very good herbicidal activity.

 1 1) The active ingredients 1-160, 1-161, 1-176, and I-223 showed at a rate of 0.13 kg / ha in postemergence against POLCO a very good herbicidal activity.

 12) The active ingredients I-87, I-95, 1-130, 1-215, and 1-216 showed at a rate of 0.25 kg / ha post-emergence against POLCO a good and the active ingredients I-79, I -88, 1-102, 1-126, 1-143, 1-164, 1-165, 1-166, 1-167, 1-168, 1-169, 1-170, 1-172, 1-173 , I-174, 1-175, 1-178, 1-179, 1-180, 1-181, 1-196, I-205, I-206, I-207, I-208, I-209, 1 -210, I-211, 1-212, 1-213, 1-214, 1-217, 1-218, 1-219, 1-220, and 1-221 a very good herbicidal activity.

Claims

claims: 1. Cyanobutyrates of the formula I.

 wherein the variables have the following meaning R is halogen, cyano, nitro, _Ci-C4-alkyl, Ci-C ₄ haloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ - Alkynyl, Z- (tri-C 1 -C ₄ -alkyl) silyl, R ¹ is hydrogen, Z-CN, Ci-C ₈ alkyl, ZC ₃ -C ₆ -cycloalkyl, C ₈ haloalkyl, C ₃ -C ₈ - Alkenyl, ZC ₃ -C ₆ -cycloalkenyl, C ₃ -C ₈ -alkynyl, Z- (tri-C ₁ -C ₄ -alkyl) silyl, ZC (= O) -R ^a , ZP (= O) (R ^a ) ₂ , Z-phenyl, C or N bonded 3- to 7-membered monocyclic or 9- or 10-membered bicyclic saturated, unsaturated or aromatic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S. which may be partially or completely substituted by groups R ^a and / or R ^b , R ^{a is} hydrogen, OH, C ₁ -C ₈ -alkyl, C ₁ -C ₄ -haloalkyl, ZC ₃ -C ₆ -cycloalkyl, C ₂ -C ₈ -alkynyl, ZC ₅ -C ₆ -cycloalkenyl, C ₂ -C ₈ -alkynyl, Z-C ₁ -C ₆ -alkoxy, Z-C ₁ -C ₄ -haloalkoxy, ZC ₃ -C ₈ - Alkenyloxy, ZC ₃ -C ₈ -alkynyloxy, NR ¹ R ", C ¹ -C ₆ -alkylsulfonyl, Z- (tri-C 1 -C ₄ -alkyl) silyl, Z-phenyl, Z-phenoxy, Z-phenylamino and or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S, wherein the cyclic groups unsubstituted or substituted by 1, 2, 3 or 4 groups R ^b are, means; R ^1, R "are independently hydrogen, Ci-C ₈ alkyl, Ci-C ₄ -HaIo- alkyl, C ₃ -C ₈ -alkenyl, C ₃ -C ₈ -alkyl kinyl, ZC ₃ -C ₆ cycloalkyl , Z-Ci-C ₈ - Alkoxy, Z-Ci-C ₈ haloalkoxy, ZC (= O) -R ^A , wherein R ^{A is} OH or C 1 -C ₄ alkoxy; R ¹ and R "may also together with the N-atom to which they are attached form a 5- or θ-membered monocyclic or 9- or 10-membered bicyclic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S; R ^b is independently Z-CN, Z-OH, Z-NO _2, Z is halogen, C ₈ alkyl, Ci-C ₄ haloalkyl, C ₂ -C ₈ alkenyl d-, C ₂ -C ₈ -Al kinyl, Z-C 1 -C ₈ -alkoxy, Z-C 1 -C ₈ -haloalkoxy, ZC ₃ -cyclo-cycloalkyl, O-ZC ₃ -Ci ₀ - Cycloalkyl, ZC (= O) -R ^a , NR ¹ R ", Z- (tri-C 1 -C ₄ -alkyl) silyl, Z-phenyl and S (O) _m R ^bb , wherein R ^{bb is} Ci-C ₈ -alkyl and d-Ce-haloalkyl;  m is 0, 1 or 2; R ^b can also form, together with the group R ^b attached to the adjacent carbon atom, a five- or six-membered saturated, partially or completely unsaturated ring which, in addition to carbon atoms, can contain 1, 2 or 3 heteroatoms selected from O, N and S. ;  Z is a covalent bond or Ci-Cs-alkylene;  n is 0, 1, 2, 3, 4 or 5; R ² , R ³ independently of one another are halogen, cyano, nitro, C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy, S (O) _m R ^bb , NR ¹ R ", C ¹ -C ₄ -haloalkyl, C ¹ -C ₄ -haloalkoxy; R ² and R ³ may also together form a five- or six-membered saturated, partially or fully unsaturated mono- or bicyclic ring which may contain, in addition to carbon, 1, 2 or 3 heteroatoms selected from O, N and S and groups R ^b may be substituted; where in groups R and R ¹ and their sub-substituents the carbon chains and / or the cyclic groups may be partially or completely substituted by groups R ^a and / or R ^b , with the proviso that not both R ² and R ^{3 are} chlorine when R is hydrogen and R ^{1 is} ethyl or allyl;  and their N-oxides and agriculturally suitable salts. 2. Compounds of formula I according to claim 1, wherein R ² and R ³ do not form a ring together. 3. Compounds of formula I according to claim 1 or 2, wherein R ² and R ^{3 are} not both chlorine when R is hydrogen. 4. Compounds of formula I according to claim 1 or 2, wherein R ² and R ^{3 are} not both chlorine when R is methyl. 5. Compounds of formula I according to any one of claims 1 to 4, wherein R ² and R ^{3 are} not both chlorine. 6. Compounds of formula I according to any one of claims 1 to 5, wherein R ² and R ^{3 is} 2,3-F ₂ ; 2-F.3-CI; 2-F, 3-Br; 2-F, 3-CN; 2-F, 3-NO ₂ ; 2-F, 3-CF ₃ ; 2-F, 3-OCH ₃ or 2-CI.3-F. 7. Compounds of formula I according to any one of claims 1 to 6, wherein R ^{2 is} fluorine. 8. Compounds of formula I according to any one of claims 1 to 7, wherein R ² and R ^{3 are} fluorine. 9. Compounds of formula I according to any one of claims 1 to 8, wherein R is chlorine, fluorine, cyano or nitro and the index n is 1 or 2. 10. Compounds of formula I according to any one of claims 1 to 9, wherein R _{n is} 3-F; 3,4-F ₂ ; 3,5-F ₂ ; 3,4,5-F ₃ ; 3-F.4-Cl; 4-CI; 4-F or 3-CN stands. 1 1. A compound of formula I according to any one of claims 1 to 10, wherein R is fluorine and the index n is 1. 12. Compounds of formula I according to any one of claims 1 to 11, wherein R ^{1 is} H, CH ₃ , C ₂ H ₅ , CH ₂ CN, CH ₂ CH ₂ F, CH ₂ CHF ₂ , CH ₂ CF ₃ , CH ₂ OCH ₃ or CH ₂ C≡ CH. 13. Compounds of formula I according to any one of claims 1 to 12, wherein R ^{1 is} CH ₃ . 14. A composition containing a herbicidally effective amount of at least one Cyanobutyrat- compound of the formula I or an agriculturally suitable salt thereof according to any one of claims 1 to 13 and for the formulation of pesticides customary auxiliaries. 15. A method for controlling undesired plant growth, which comprises acting on plants, their seeds and / or their habitat, a herbicidally effective amount of at least one cyanobidinutyrate compound of formula I or an agriculturally useful salt thereof according to any one of claims 1 to 13 leaves.