EP2438071A1 - Substituted pyrazine (thio)pyrans with a herbicidal action - Google Patents

Abstract

The invention relates to substituted pyrazines of formula I, in which the variables are defined according to the description, the agriculturally suitable salts of said pyrazines, methods and intermediate products for producing the pyrazines of formula I, means containing said pyrazines and the use of said pyrazines as herbicides, i.e., to control weeds, and a method for controlling unwanted plant growth, in which a quantity of at least one pyrazine compound of formula I with a herbicidal action is allowed to act on plants, the seeds thereof, and/or the habitats thereof.

Description

 SUBSTITUTED PYRAZINE (THIO) PYRANEES WITH HERBICIDAL EFFECT

description

The present invention Formula I

wherein the variables have the following meaning R ¹ 0-R ^A , S (O) _n -R ^A or OS (O) _n -R ^A ;

R ^{A is} hydrogen, C 1 -C ₄ -alkyl, ZC ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -haloalkyl, C ₂ -C ₆ -alkenyl, ZC ₃ -C ₆ -cycloalkenyl, C ₂ -C ₆ Alkynyl, Z- (tri-C 1 -C ₄ -alkyl) silyl,

ZC (= O) -R ^a , ZP (= O) (R ^a ) ₂ , C 3- or N-linked 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, Ci-C ₈ -alkyl, C ₄ haloalkyl, ZC ₃ -C ₆ cycloalkyl, C ₂ -C ₈ -alkenyl-Al, 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 5- or 6-membered monocyclic or 9- or

A 10-membered bicyclic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S, wherein the cyclic groups are unsubstituted or substituted by 1, 2, 3 or 4 groups R ^b ; 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-C 1 -C ₈ -alkoxy, Z-C 1 -C ₈ -haloalkoxy;

R ¹ and R "may also together with the N-atom to which they are attached 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; Z is a covalent bond or C 1 -C ₄ -alkylene; n is O, 1 or 2;

R ^{2 is} phenyl, naphthyl or and 5- or 6-membered monocyclic or 9- or 10-membered bicyclic aromatic 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 ^b is independently Z-CN, Z-OH, Z-NO _2, Z is halogen, Ci-C ₈ -alkyl, C d- ₄ haloalkyl, C ₂ -C ₈ -alkenyl, C ₂ -C ₈ Alkynyl, Z-Ci-C ₈ -alkoxy, Z-Ci-C ₈ -HiIo- alkoxy, ZC ₃ -Cio-cycloalkyl, O-ZC ₃ -Cio-cycloalkyl, ZC (= O) -R ^a , NR ¹ R ", Z- (tri-C 1 -C ₄ -alkyl) silyl, Z-phenyl and S (O) _n R ^bb , where R ^bb is C ₁ -C 8 -alkyl and C ₁ -C ₆ -haloalkyl, and n is 0, 1 or 2, R ^b1 , R ^{b2 is} one of the groups mentioned for R ^b , R ^b , R ^b1 , R ^b2 can independently of one another also form, together with the group R ^b , R ^b1 or R ^b2 bound to the adjacent carbon atom, a five- or six-membered saturated, partially or completely unsaturated ring which, besides carbon-1, 2 or 3 may contain heteroatoms selected from O, N and S; YO or S;

X is O, S or NR ^3;

R ³ is hydrogen, Ci-C ₆ alkyl, Ci-C ₄ haloalkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ kinyl Al,

ZC ₃ -Cio-cycloalkyl, C ₁ -C ₆ -alkoxy-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -cyanoalkyl, Z-phenyl, ZC (OO) -R a ² and tri-C 1 -C ₄ -alkylsilyl; R ^{a2 is} C ₁ -C ₆ -alkyl, C ₁ -C ₄ -haloalkyl, Z-C ₁ -C ₆ -alkoxy, Z-C ₁ -C ₄ -haloalkoxy and

NR ¹ R "; in groups R ^A , R ² , R ³ and their sub-substituents, the carbon chains and / or the cyclic groups may be partially or completely substituted by groups R ^a , and their N-oxides and agriculturally suitable salts.

Moreover, the invention relates to processes and intermediates for the preparation of the pyrazines of the formula I and their N-oxides, their agriculturally useful salts, as well as active ingredient combinations containing them, 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 pyrazine compound of formula I or an agriculturally useful salt of I to act on plants, their seeds and / or their habitat. Further embodiments of the present invention are 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.

In WO 2008/009908 and WO 2008/071918 herbicidal pyrazines are described, their herbicidal activity at low application rates, or compatibility with crops remains in need of improvement.

An object of the present invention is to provide compounds having herbicidal activity. In particular, agents should be made available, the have a high herbicidal activity, in particular even at low application rates, and their compatibility with crop plants for commercial use 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 by standard methods of organic chemistry, for example according to the following synthesis route:

Pyridinecarboxylic acids of the formula II can be reacted with compounds of the formula III to give compounds of the formula IV. In formulas II and III, the variables have the meaning given for formula I. The group R 'is d-C4 alkoxy, Hal is a halogen atom or other suitable nucleophilic leaving group, such as alkoxy or phenoxy, and SG is a protecting group which reduces the reactivity of Y, for example optionally subst. Benzyl.

This reaction is usually carried out at temperatures of -78 ⁰ C to 12O ⁰ C, preferably -2O ⁰ C to 5O ⁰ C, in an inert organic solvent in the presence of a base (see Greene's Protective Groups in Organic Synthesis, Wiley).

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, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, dimethylformamide (DMF) and dimethylacetamide, more preferably halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene. 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 alkali metal hydrogencarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyl lithium and phenyllithium, alkyl magnesium halides such as methyl magnesium chloride and alkali metal and alkaline earth metal such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxy magnesium, as well as organic bases, for example 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. Preference is given to alkali metal and alkaline earth metal hydrides, particularly preferably sodium hydride. The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.

The starting materials are generally reacted with one another in equimolar amounts.

From the compounds of formula IV, the corresponding acid of formula V is released. This reaction is usually carried out at temperatures from -78 ⁰ C to 12O ⁰ C, preferably -2O ⁰ C and 5O ⁰ C, in an inert organic solvent in the presence of a base (see FIG. Bioorganic and Medicinal Chemistry Letters (2006) Vol. 16 ( 3), 718-721).

Suitable solvents are water, alcohols such as methanol, ethanol, iso-propanol, 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, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, DMF and dimethylacetamide, particularly preferably halogenated Hydrocarbons such as methylene chloride, chloroform and chlorobenzene. 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 hydrogencarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyl lithium and phenyl lithium, alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethanolate, potassium ethoxide, potassium tert-butoxide and Dimethoxymagnesium, also organic bases, for example 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. Preference is given to alkali metal and alkaline earth metal Hydroxides are particularly preferred. The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.

The compounds of the formula V are activated by introducing a leaving group L ¹ . Suitable leaving groups L ¹ are generally those groups which increase the electrophilicity of the carbonyl group, for example O-alkyl, O-aryl, halides, activated esters or aldehydes (such as, for example, Weinreb amide), in particular pentafluorophenoxy.

This reaction is usually carried out at temperatures from -78 ⁰ C to 12O ⁰ C, preferably -2O ⁰ C to 5O ⁰ C, in an inert organic solvent in the presence of a base such as. Triethylamine (see J. Agric and Food Chem., 1994, 42 (4), 1019-1025), a catalyst such as e.g. B. Dicyclohexylcarbodiimide (see Egyptian Journal of Chemistry 1994, 37 (3), 273-282) or other known coupling reagents. 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, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, DMF and dimethylacetamide, more preferably methylene chloride and toluene. Mixtures of the solvents mentioned can also be used.

Bases generally include 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, calcite 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 hydrogencarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyl lithium and phenyl lithium, alkylmagnesium halides such as methylmagnesium chloride and also alkali metal and alkaline earth metal alcoholates. te as sodium methoxide, sodium ethoxide, potassium, potassium tert-butoxide and Dimethoxymagnesium, also organic bases, such as tertiary amines such as tri- thylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration. Particular preference is given to alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate, calcium carbonate, cesium car- carbonate and rubidium carbonate. The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.

The starting materials are generally reacted with one another in equimolar amounts.

As agent HL ¹ are alcohols, optionally subst. Phenols, N, O-dialkylhydroxylamine, in particular pentafluorophenol or N, O-dimethylhydroxylamine in question.

The compounds of the formula VI are reacted with acetic acid derivatives of the formula VII to give the V

This reaction is usually carried out at temperatures of from -78 ° C to 120 ⁰ C, preferably from -20 ⁰ C to 50 ⁰ C, in an inert organic solvent in the presence of a base or a Lewis acid or a catalyst [cf.. Bioorganic & Medicinal Chemistry (2004) Vol. 12 (6), 1357-1366]. 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, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, DMF and dimethylacetamide, particularly preferably acetonitrile and DMF. Mixtures of the solvents mentioned can also be used.

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, calcium carbonate, cesium carbonate and rubidium carbonate and alkali metal hydrogencarbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, Butylli- thium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and dimethoxy magnesium, as well as organic Ba sen, for example 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. Prefers are alkali metal and alkaline earth metal alkoxides, more preferably potassium tert-butoxide.

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

The starting materials are generally reacted with one another in equimolar amounts.

The compounds of formula IX may be prepared by cleaving the protecting group from

Compounds of formula VIII are released. The reaction conditions depend on the nature of the protecting group SG; the splitting off of a possibly subst. Benzyl group succeeds z. B. with trifluoroacetic acid at temperatures of -78 ° C to 10O ⁰ C, preferably -20 ⁰ C to 50 ⁰ C, in an inert organic solvent [cf. Greene's Protective Groups in Organic Synthesis, Wiley].

The introduction of the non-oxygen groups X, or Y in the compounds of formula I, or their precursors, carried out by well-known methods.

The compounds of formula IX and their precursors can exist in two tautomeric forms. The invention relates to both tautomers. For the sake of clarity, only one tautomer is mentioned in the description.

Tautomer 1 tautomer 2

The compounds of the formula IX can be converted by cyclization into compounds of the formula I. The cyclization succeeds z. B. with ges. Brine and an organic solvent at temperatures from -30 ⁰ C to 150 ⁰ C, preferably 30 ° C to 100 ° C.

This reaction is usually carried out at temperatures of -78 ° C to 120 ⁰ C, preferably -20 ⁰ C to 50 ° C.

Suitable solvents are water, alcohols such as methanol, ethanol, iso-propanol, 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, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide, DMF and dimethylacetamide, particularly preferably halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene. It is also possible to use mixtures of the solvents mentioned.

The sulfurization of the compounds of formula I is carried out under known conditions with a Schwefelungsagenz [S], it is usually at temperatures from 0 ⁰ C to 180 ⁰ C, preferably 20 ⁰ C to 140 ⁰ C, in an inert organic

I (X = S; R ¹ = OH) I (X = S; R ⁱ = OH)

Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-XyIoI, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane , Anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, and dimethyl sulfoxide, particularly preferably toluene and tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned. Suitable sulfurizing agents are, for example, phosphorus pentasulfide or La wesson's reagent.

The introduction of the groups NR ³ into the compounds of the formula I, or of R ¹ or R ^A is carried out under generally known conditions. The compounds of the formula I in which R ^{1 represents} a group bonded via S can be obtained, for example, via a reaction sequence according to Newman-Kwart starting from chlorothiocarbonyl compounds [cf.: J. Org. Chem., Vol. 59 (21), p 6318-21 (1994)].

The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and optionally chromatographic purification of the crude products. Some of the intermediate and end products are in the form of colorless or pale brownish, viscous oils which are obtained under reduced pressure and moderately elevated temperature of volatile fractions freed or cleaned. 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, unless isomeric mixtures are involved in the synthesis, separation is not necessarily required because the individual isomers can partially interconvert during processing for application or application (e.g., under light, acid, or base action). Corresponding conversions can also take place after use, for example in the treatment of plants in the treated plant or in the harmful plant to be controlled.

All organic hydrocarbon moieties, such as alkyl, halo (gen) alkyl, alkenyl, alkynyl, and the alkyl moieties and alkenyl moieties in alkoxy, halo (gen) are all collective groups for the substituents of the compounds of the invention. 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 can be 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. In addition, for example, alkyl and the alkyl moieties are, for example, 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-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl , 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2 Trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl. In one embodiment of the invention, alkyl is small alkyl groups 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 whose hydrogen atoms are partially or fully substituted by halogen atoms such as fluorine, chlorine, bromine and / or iodine, for example chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl , Dichlorofluoro-methyl, 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-pentafluoro propyl, 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- butenyl, 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 carbonyl hydrogen groups with two or more C 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.

Depending on the substitution pattern, the compounds of the formula I may contain one or more further chiral centers. The compounds according to the invention can therefore be present as pure enantiomers or diastereomers or as mixtures of enantiomers or diastereomers. The invention relates to both the pure enantiomers or diastereomers and mixtures thereof. 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 the cation, where, 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, or hydroxy-C 1 -C ₄ -alkyl. C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl may be replaced, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-1-oxy) eth-1 -ylammonium, di (2-hydroxyeth -1-yl) ammonium, trimethylbenzylammonium. As ammonium cation also comes the quaternized by alkylation or arylation pyridine nitrogen of the formula I in question. 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 a first preferred embodiment of the invention, R ^{1 is} OR ^A. In a further preferred embodiment of the invention, R ^{1 is} S (O) _n -R ^A , where n is preferably 0 or 2, in particular 0.

R ^A stands in particular for H, d-Ce-alkylcarbonyl, such as C (O) CH ₃ , C (O) CH ₂ CH ₃ , C (O) CH (CHs) ₂ or C (O) C (CH ₃ ) S ; C ₁ -C ₆ -cycloalkylcarbonyl, such as cyclopropylcarbonyl, cyclopentylcarbonyl or cyclohexylcarbonyl; C ₂ -C 6 alkenylcarbonyl, such as C (O) CH = CH ₂ or C (O) CH ₂ CH = CH ₂ , optionally subst. Benzoyl, such as C (O) C ₆ H ₅ ,

C (O) P -CH ₃ -C ₆ H ₄ ], C (O) P -CH ₃ -C ₆ H ₄ ], C (O) [2-FC ₆ H ₄ ], C (O) 4 FC ₆ H ₄ ], or subst. Heteroaryl, such as pyridine, which is bonded via a carbonyl group.

In a further preferred embodiment, R ^{A is} H, Ci-Cβ-alkyl, optionally substituted. Phenyl, di-C 1 -C 6 -alkylaminocarbonyl, C 1 -C 6 -alkylcarbonyl or benzoyl. With particular preference R ^{A is} H or C 1 -C 6 -alkylcarbonyl.

In a further preferred embodiment of the invention, R ^{A is} a 5- or 6-membered heterocycle optionally substituted by R ^b as defined above, which is preferably either 1, 2, 3 or 4 nitrogen atoms or 1 oxygen or 1 sulfur atom and optionally 1 or 2 has nitrogen atoms as ring members and which is unsubstituted or may have 1 or 2 substituents selected from R ^b . Preference is given to saturated or unsaturated groups which are bonded via N, for example:

Heteroaromatic groups: pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazine-2-yl, 2-furyl, 3-furyl, 2-thienyl , 3-Thienyl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazole-4 -yl, isothiazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, thiazol-2-yl , Thiazol-4-yl and thiazol-5-yl. In another embodiment, R ^{A is} a C-bonded heteroaromatic group such as pyrazol-3-yl, imidazol-5-yl, oxazol-2-yl, thiazol-2-yl, thiazol-4-yl, thiazole-5 yl, pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidine-5-yl, pyridazin-4-yl, pyrazine-2-yl yl, [1 H] -tetrazol-5-yl and [2H] -tetrazol-5-yl, where the heterocycles 1 or 2 mentioned here by way of example from R ^{b may have} selected substituents. Preferred groups R ^b are in particular F, Cl, CN, NO ₂ , CH ₃ , C ₂ H ₅ , OCH ₃ , OC ₂ H ₅ , OCHF ₂ , OCF ₃ and CF ₃ .

In a further preferred embodiment, R ^{2 is} phenyl which is unsubstituted or partially or completely substituted by groups R ^b . Particularly preferred are those compounds in which a group R ^{b is} in the ortho position.

Such compounds of the formula I are described by the formula I.A .:

In formula IA, the subscript n is an integer from zero to four, preferably 0, 1 or 2, in particular 0 or 1. R ⁵ and R ⁶ are groups R ^b , as defined above, preferably halogen, NO 2 C 1 -C ₄ -alkyl, C 1 -C ₂ -haloalkyl and C 1 -C ₄ -alkoxy. A group R ⁶ is preferably in position 5.

In a preferred embodiment, X is O. In another embodiment, X is S.

In another embodiment, X is NR ³ .

R ³ is preferably H, C ₁ -C ₆ -alkyl, such as CH ₃ , C ₂ H ₅ , nC ₃ H ₇ , CH (CHs) ₂ , nC ₃ H ₉ , or C (CHs) ₃ ; Cs-C ₆ -cycloalkyl-Ci-C ₄ -alkyl, such as cyclopropylmethyl, C ₃ -C ₆ -alkenyl, such as CH ₂ CH = CH ₂ , CH ₂ C (CHs) = CH ₂ , CH ₂ CH ₂ CH = CH ₂ , CH ₂ CH ₂ C (CHs) = CH ₂ , CH ₂ CH ₂ CH ₂ CH = CH ₂ , CH ₂ CH ₂ CH ₂ C (CHs) = CH ₂ , or optionally subst. Phenyl, such as C ₆ H ₅ , 4 -CH ₃ -C ₆ H ₄ , 4-FC ₆ H ₄ or S (O) _n -R ^N , wherein R ^{N is} C ₁ -C ₆ -haloalkyl, such as CH ₂ CF. _3, CH ₂ CHF. ₂ Particularly preferably, R ^{3 is} not hydrogen. In particular, R ³ is preferably C ₁ -C ₆ -haloalkyl, such as CH ₂ CF ₃ or CH ₂ CHF ₂ .

In a preferred embodiment, Y is O.

In another embodiment Y stands for S.

Another embodiment relates to compounds of the formula I in which R ^b1 and R ^{b2 are} each hydrogen.

A further embodiment relates to the N-oxides of the compounds of the formula I. A further embodiment relates to salts of the compounds of the formula I, especially those obtainable by quaternization of at least one pyrazine nitrogen atom, which can preferably be effected by alkylation or arylation of the compounds of the formula I. Accordingly, preferred salts of the compounds are the N-alkyl, in particular the N-methyl, or the N-phenyl salts. In particular, with regard to their use, the compounds of the formula I which are compiled in the following tables and correspond to the formula IA, in which R ^b1 and R ^{b2 are} each hydrogen (formula I.A.A.),

prefers. The groups mentioned in the tables for a substituent are also considered individually, regardless of the combination in which they are mentioned, a particularly preferred embodiment of the substituent in question.

Table 1

Compounds of the formula I in which X and Y are O and the combination of R ¹ , R ⁵ and (R ⁶ ) _n for each compound corresponds to one row of Table A.

Table 2

Compounds of the formula I in which X is O and Y is S and the combination of R ¹ , R ⁵ and (R ⁶ ) _n for each compound corresponds to one row of Table A.

Table 3

Compounds of the formula I in which X and Y are S and the combination of R ¹ , R ⁵ and (R ⁶ ) _n for each compound corresponds to one row of Table A.

Table 4 Compounds of the formula I in which X is S and Y0 and the combination of R ¹ , R ⁵ and (R ⁶ ) _n for each compound corresponds to one row of Table A.

Table A

Compounds of the formula I which correspond to the formula IA, in which R ^b1 and R ^b2 are each hydrogen (Formula I AA)

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. vulgar), 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 way 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. No. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, 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 as. Glyphosate (see, for example, WO 92/00377), glutamine synthetase (GS) inhibitors, such as, for example, 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. Using genetic engineering methods, crop plants such as soybean, produces cotton, corn, beets and rape, which are resistant to glyphosate or glufosinate, and sold under the trade name RoudupReady ^® (glyphosate) and Liberty Link ^® (glufosinate) are available.

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), e.g. 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 as 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 as. 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) Hercu- lex ^® RW (corn cultivars produce the toxins Cry34Ab1, Cry35Ab1 and the enzyme phosphinothricin N-acetyltransferase [PAT]); NuCOTN ^® 33B (cotton cultivars producing the toxin CrylAc), Bollgard ^® I (cotton cultivars producing the toxin CrylAc), Bollgard ^® Il (cotton cultivars producing the toxins CrylAc and Cry2Ab2); VIPCOT ^® (cotton varieties that produce a VIP toxin); NewLeaf ^® (potato cultivars producing the Cry3A toxin); Bt Xtra ^®, NatureGard® ^®, KnockOut ^®, BITE Gard ^®, Protecta ^®, bt 11 (z. B. Agrisure ^® CB) and Bt176 from Syngenta Seeds SAS, France (corn varieties which the toxin CrylAb and the PAT Producing enzyme), MIR604 from Syngenta Seeds SAS, France (maize varieties producing a modified version of the toxin Cry3A, see WO 03/018810), MON 863 from Monsanto Europe SA, Belgium (maize varieties producing the toxin Cry3Bb1), IPC 531 from Monsanto Europe SA, Belgium (cotton varieties that produce a modified version of the toxin CrylAc) and 1507 from Pioneer Overseas Corporation, Belgium (maize varieties that produce 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. B. the profitability (eg. Biomass, grain yield, starch, oil or protein content), increased tolerance to drought, salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral pathogens. 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 dehydration of the aerial parts of crop plants such as potato, oilseed rape, sunflower and soybean but also cereals. This enables a completely mechanical harvesting of these important crops.

Of economic interest is also the harvest relief, which is made possible by the time-concentrated dropping or reducing the adhesion to the tree in citrus fruits, olives or other types and varieties of pome, stone and peel fruit. The same mechanism, i.e. promoting the formation of release webs 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, also high-percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules by spraying , Misting, dusting, scattering, pouring or treatment of the seed or mixing with the seed. The application forms 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 pesticides.

Examples of the Formulation of Pesticides Commonly used adjuvants are auxiliaries, solid carriers, surfactants (such as dispersants

Protective colloids, emulsifiers, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze, antifoams, 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 antifoam agents 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) and 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 cyclohanol exanone or strongly polar solvents, e.g. 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. Surfactants (adjuvants, wetting agents, tackifiers, dispersants and emulsifiers) are the alkali metal, alkaline earth metal, ammonium salts of aromatic sulfonic acids, e.g. Ligninsulfonsäuren (eg Borrespers types, Borregaard), phenolsulfonic acids, naphthalene sulfonic acids (Morwet types, Akzo Nobel) and dibutylnaphthalenesulfonic acid (Nekal types, BASF SE), as well as fatty acids, alkyl and alkylaryl sulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and 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 naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octyl phenol ethers, ethoxylated isooctyl-, octyl- or nonylphenol, Alkylphenyl, tributylphenyl polyglycol ethers, alkylarylpolyether alcohols, isotridecylalcohol, fatty alcohol ethylenoxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin sulphite precipitates and proteins, denatured proteins, polysaccharides (eg Methylcellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol type Clariant), polycarboxylates (BASF SE, Sokalan types), polyalkoxylates, polyvinylamine (BASF SE, lupamine types), polyethylenimine (BASF SE, Lupasol types), polyvinylpyrrolidone and their copolymers into consideration.

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 preparations 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, at least of an active substance. 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 auxiliaries 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 to water by means of an emulsifying machine (e.g., Ultraturax) in 30 parts by weight and made into a homogeneous emulsion. 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 dispersing 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. In the dilution In water gives 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 carrier substances. 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, e.g. XyIoI solved. 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 take place in the pre-emergence, post-emergence or together with the seed of a crop. It is also possible to apply the herbicidal compositions or active ingredients characterized in that with the herbicidal agents or active ingredients pretreated seed of a crop plant 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 crops as far as 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, such as 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 acids and derivatives thereof, benzothiadiazinones, 2- (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 derivatives thereof, dihydrobenzofurans, Dihydro-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-phenyl- nylpropionic acid and derivatives thereof, pyrazoles, phenylpyrazoles, pyridazines, pyridinecarboxylic acid and derivatives thereof, 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 that 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-propar - gyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop-methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop-butyl, fluoride-P, fluazifop-p-butyl , Haloxyfop, Haloxyfopmethyl, Haloxyfop-P, Haloxyfop-P-methyl, Metamifop, Pinoxaden, Profoxydim, Propaquizafop, Quizalofop, Quizalofopethyl, Quizalofop-tefuryl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop-P-tefuryl .

Sethoxydim, tepraloxydim, tralkoxydim, benfuresate, 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, foramysulfuron, 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, pyra- zosulfuron, pyrazosulfuron-ethyl, pyribenzoxime, pyrimisulfan, pyriftalid, pyriminobac, pyriminobac-methyl, pyrithiobac, pyrith iobac-sodium, pyroxsulam, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, 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, chlorotoluene ron, chloroxuron, cyanazine, desmedipham, desmetryn, dimefuron, dimethametryn, diquat, diquat-dibromide, diuron, fluometuron, hexazinone, loxynil and its salts and esters, isoproturon, isourone, carbutilate, lenacil, linuron, metamitron, methabenzthiazirron, metobenzuron , Metoxuron, metribuzin, monolinuron, neburon, paraquat, paraquat-dichloride, paraquat-dimetilsulfate, pentanochlor, phenmedipham, phenmediphamethyl, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil , Terbumone, 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, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr- ethyl, flumiclorac, flumiclorac-pentyl, flumioxazine, fluoroglycofen, fluoroglycofenethyl, fluthiacet, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazole, pyraclonil, pyraflufen, pyraflufen- ethyl, saflufenacil, sulfentrazone, thidiazimine, 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-tetrahydropyrimidin-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-1H-pyrazole-1-carboxamide (B-3; CAS 452098-92-9), N-Tetrah ydrofurfuryl-3- (2,6-dichloro-4-trifluoromethylphenoxy) -5-methyl-1H-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 45100-03-7 ); 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, Pretila-5-Chloro, Propachlor , Propisochlor, pyroxasulfone (KIH-485) and thenylchloro;

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. 2 have in particular the following meanings:

R where # is the bond to the molecular skeleton; and 5 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, CrC ₄ - alkyl, Ci-C ₄ haloalkyl or _{Ci-C4-haloalkoxy;} m is 0, 1, 2 or 3; X oxygen; n 0 or 1.

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-difluoro-ethoxy) -1-methyl-3-tri-5-fluoromethyl-1H-pyrazol-4-yl] -fluoro-methanesulfonyl} -5,5-dimethyl-4, 5-dihydroisoxazole (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-difluoro-ethoxy) -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-dihydro-isoxazole (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-metylsulfates, 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 hydrazide, Mefluidide, Metam, methyl azide, methyl bromide, methyl -dymron, methyl iodide. 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 ingredients are known from WO 96/26202, WO 97/41 116, WO 97/411 17, WO 97/411 18, WO 01 / 83459 and WO 2008/074991 and W. Krämer et al. (ed.) "Modern Crop Protection Compounds", Vol. 1, Wiley VCH, 2007 and the literature cited therein. The invention also relates to compositions in the form of a crop protection agent formulated as a 1-component composition comprising a combination of active substances comprising at least one pyridine compound of the formula I and at least one further active ingredient, preferably selected from the active substances of groups b1 to b15, and at least one solid or liquid carrier and / or one or more surface-active substances and, if desired, one or more further auxiliaries customary for crop protection agents.

The invention also relates to compositions in the form of a plant protection composition formulated as a 2-component composition comprising a first component containing at least one pyridine compound of the formula I, a solid or liquid carrier and / or one or more surface-active substances, and a second component containing at least one further active ingredient selected from the active substances of groups b1 to b15, a solid or liquid carrier and / or one or more surface-active substances, wherein in addition both components may also contain further adjuvants customary for crop protection agents.

In binary compositions containing at least one compound of the formula I as component A and at least one herbicide B, the weight ratio of the active compounds A: B is generally in the range from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and particularly preferably in the range of 1: 75 to 75: 1.

In binary compositions which comprise at least one compound of the formula I as component A and at least one safener C, the weight ratio of the active compounds A: C is generally in the range from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and particularly preferably in the range of 1: 75 to 75: 1.

In ternary compositions containing both at least one compound of the formula I as component A, at least one herbicide B and at least one safener C, the relative proportions by weight of the components A: B are generally in the range from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range from 1: 250 to 250: 1 and more preferably in the range from 1: 75 to 75: 1, the weight ratio of component A: C is generally in the range of 1: 1000 to 1000: 1, preferably in the range of 1: 500 to 500: 1, in particular in the range of 1: 250 to 250: 1 and more preferably in the range of 1: 75 to 75: 1, and the weight ratio of the components B: C is generally in the range from 1: 1000 to 1000: 1, preferably in the range from 1: 500 to 500: 1, in particular in the range from 1: 250 to 250: 1 and particularly preferably in the range from 1: 75 to 75: 1st The weight ratio of components A + B to component C is preferably in the range from 1: 500 to 500: 1, in particular in the range from 1: 250 to 250: 1 and particularly preferably in the range from 1: 75 to 75: 1.

Examples of particularly preferred compositions according to the invention, containing in each case an individualized compound of the formula I and a mixture of partner, or a mixture partner combination are given in Table B below.

A further embodiment of the invention relates to the compositions B-1 to B-1235 listed in Table B, wherein in each case one row of Table B corresponds to a herbicidal composition comprising an individualized in the present specification compounds of formula I (component 1) and the further active ingredient from groups b1) to b15) and / or safener C (component 2) respectively indicated in the relevant line. The active ingredients in the described compositions are each preferably present in synergistically effective amounts.

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 those 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 pyrazine 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 were used with appropriate modification of the starting compounds to obtain further compounds I. 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 masses determined by MS spectrometry [m / z] (M + H) (quadrupole electrospray ionization, 80 V positive mode).

Example 1: Preparation of 8-hydroxy-7-o-tolyl-pyrano [2,3-b] pyrazine-6-one [I-2]

Step 1: 3- (4-Methoxy-benzyloxy) -pyrazine-2-carboxylic acid

A solution of 10 g 3-Hydroxy-pyrazin-2-carbonsäuremethylester in DMF was stirred after addition of 12.2 g of p-methoxy-benzyl chloride and 84,7g Cs2CO3 at 20 ⁰ C for approximately 14 hours.. After filtration, the filtrate was washed with saturated NaCl solution, extracted with ethyl acetate, the organic phase was freed from solvent after drying. 8g crude 3- (4-methoxy-benzyloxy) -pyrazin- 2-carbonsäuremethylester dissolved in methanol / water 2 were from the residue. Was added 1, treated with 81.4g of LiOH and at 20-25 ⁰ C for 2 h was stirred. After distilling off the methanol, the solution was adjusted to pH 3-4 and extracted with ethyl acetate. After distilling off the solvent, 5.54 g of the title compound were obtained.

Step 2: 3-Hydroxy-3- [3- (4-methoxy-benzyloxy) -pyrazino-2-yl] -2- (2-trifluoromethylphenyl) -acrylic acid methyl ester

5.2 g of the carboxylic acid from step 1 was dissolved in DMF, carbonyldiimidazole was added and the solution stirred 30 minutes at 20-25 ⁰ C. After addition of 4.8 g of methyl 2-trifluoromethylphenylacetate and 1.6 g of 60% NaH, stirring was continued for a further 2 hours, then sat. NH4Cl solution added. After extraction with ethyl acetate, the organic phase was washed with NaCl solution, dried and freed from the solvent. Chromatography of the residue on silica gel gave 2.5 g of the title compound of mass (m / z) 461. Step 3: 3-Hydroxy-3- (3-hydroxy-pyrazin-2-yl) -2- (2-trifluoromethyl -phenyl) - acrylic acid methyl ester

2.5 g of the ester from stage 2 were stirred in trifluoroacetic acid at 40 ° C. for about 14 hours, evaporated and chromatographed on silica gel. This gave 1, 0g of the title compound. Step 4: 8-hydroxy-7-o-tolyl-pyrano [2,3-b] pyrazine-6-one

1.0g of the ester from Step 3 was dissolved in 5ml of a mixture of DMSO / sat. aq. NaCl solution (5: 1) at 100 ° C for 2 hours. After washing with HCl / NaCl solution was extracted with ethyl acetate. After drying, the organic phase was freed from the solvent and the residue was purified by preparative HPLC. 135 mg of the title compound were obtained.

¹ H NMR (MeOD; 400MHz): δ 8.69-8.64 (d, J = 2.4Hz, 2H), 7.81 (d, J = 8Hz, 1H), 7.71 (d, J = 8Hz, 1H), 7.61 (d, J = 8Hz, 1H), 7.44 (d, J = 8Hz, 1H).

Table I: Compounds of the formula I which correspond to the formula I.AA:

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 rating was based on a scale of 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts and 0 no damage or normal growth course. 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.

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

1) The active ingredients 1-1, I-2, I-3, and I-4 showed at a rate of 0.5 kg / ha postemergence against CHEAL a very good herbicidal activity.

2) The active compounds 1-1, and I-2 showed at a rate of 0.5 kg / ha postemergence against ECHCG a good herbicidal activity.

3) The active compounds 1-1, and I-2 showed at a rate of 0.5 kg / ha postemergence against SETVI a very good herbicidal activity.

Claims

claims:

1. pyrazine compounds of the formula I.

wherein the variables have the following meaning

R ¹ OR ^A , S (O) _n -R ^A or OS (O) _n -R ^A ;

R ^{A is} hydrogen, C 1 -C ₄ -alkyl, ZC ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -haloalkyl, C ₂ -C ₆ -alkenyl, ZC ₃ -C ₆ -cycloalkenyl, C ₂ -C ₆ -alkl kinyl, Z- (tri-Ci-C ₄ alkyl) silyl, ZC (= O) -R ^a, ZP (= O) (R ^a) _2, via C or N-linked 3- to 7-limbs 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, Ci-C ₈ -alkyl, C ₄ haloalkyl, ZC ₃ -C ₆ -CyCIo- alkyl, C ₂ -C ₈ alkenyl, ZC ₅ -C ₆ cycloalkenyl, C ₂ -C ₈ -alkynyl, Zd-

C ₆ alkoxy, Z-Ci-C ₄ haloalkoxy, ZC ₃ -C ₈ alkenyloxy, ZC ₃ -C ₈ alkynyloxy, NR ¹ R ", Ci-C ₆ alkylsulfonyl, Z- (Tn-Ci-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 substituted by 1, 2, 3 or 4 groups R ^b , 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;

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;

Z is a covalent bond or C 1 -C ₄ -alkylene; n is O, 1 or 2; R ^{2 is} phenyl, naphthyl or and 5- or 6-membered monocyclic or 9- or

10-membered bicyclic aromatic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S, wherein the cyclic

Groups are unsubstituted or substituted by 1, 2, 3 or 4 groups R ^b , means;

R ^b is independently Z-CN, Z-OH, Z-NO _2, Z is halogen, Ci-C ₈ -Al- -alkyl, Ci-C ₄ haloalkyl, C ₂ -C ₈ -alkenyl, C ₂ -C ₈ -alkynyl, Z-C 1 -C ₈ -alkoxy, ZCi-Cs-haloalkoxy, Z-Cs -do-cycloalkyl, O-ZC ₃ -Cio-cycloalkyl, ZC (= O) -R ^a , NR ¹ R ", Z- (tri-C 1 -C ₄ -alkyl) silyl , Z-phenyl and S (O) _n R ^bb , wherein R ^{bb is} Ci-C ₈ -alkyl and Ci-C ₆ -haloalkyl and n is 0, 1 or 2; R ^b1 , R ^{b2 is} one of those in R ^b mentioned groups;

R ^b , R ^b1 , R ^b2 can also independently together with the bonded to the adjacent carbon atom group R ^b , R ^b1 or R ^{b2 form} a five- or six-membered saturated, partially or fully unsaturated ring, which in addition to carbon , 2 or 3 heteroatoms selected from O, N and S may contain;

YO or S; X is O, S or NR ^3;

R ³ is hydrogen, Ci-C ₆ alkyl, Ci-C ₄ haloalkyl, C ₂ -C ₆ alkenyl, C ₃ -C ₆ -Alki- nyl, Z-Cs-C-io-cycloalkyl, Ci-C ₆ Alkoxy-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -cyanoalkyl, Z-phenyl, ZC (= O) -R a ² and tri-C 1 -C ₄ -alkylsilyl;

R ^a2 is C ₁ -C ₆ -alkyl, C ₁ -C ₄ -haloalkyl, Z-C ₁ -C ₆ -alkoxy, Z-C ¹ -C ₄ -haloalkoxy and NR ¹ R ", where in groups R ^A , R ² , R ³ and their sub-substituents, the carbon chains and / or the cyclic groups may be partially or completely substituted by groups R ^a , and their N-oxides and agriculturally suitable salts.

2. Compounds according to claim 1, wherein Y is O.

3. Compounds according to claim 1, wherein Y is S.

4. Compounds according to any one of claims 1 to 3, wherein R ^{A is} hydrogen or Ci-Cβ-alkylcarbonyl.

5. Compounds of formula I according to any one of claims 1 to 4, wherein X is O.

6. Compounds of the formula I according to one of claims 1 to 4, in which X is S.

7. Compounds of formula I according to any one of claims 1 to 6, which correspond to the formula LA,

LA in which R ⁵ and R ^{6 are} groups R ^b and n is an integer from zero to four.

8. A process for the preparation of the compounds of the formula I according to any one of claims 1 to 7 by reaction of pyrazinecarboxylic acids of the formula II

under basic conditions with carbonyl compounds of the formula in the Hal represents a halogen atom or another suitable nucleophilic leaving group, to compounds of the formula IV,

which with agents HL ¹ , wherein L ^{1 is} a nucleophilic leaving group, to compounds of formula V

which are converted under basic conditions into compounds of the

Formula I are cyclized.

9. A process for the preparation of the compounds of the formula I according to one of claims 1 to 7 by reacting pyrazinecarboxylic acids of the formula II according to claim 8 with an agent HL ¹ according to claim 8 to pyrazinecarboxylic acid derivatives of the formula VI,

which are reacted under basic conditions with carbonyl compounds of the formula III according to claim 8 to compounds of the formula V according to claim 8, which are cyclized under basic conditions to give compounds of the formula I.

10. A composition comprising a herbicidally effective amount of at least one pyrazine compound of the formula I or an agriculturally suitable salt thereof according to any one of claims 1 to 7 and for the formulation of pesticides customary auxiliaries.

1 1. A composition according to claim 10, containing at least one further active ingredient.

12. Composition according to claim 10 or 11, containing two further active compounds from the group of herbicides and / or safeners.

13. A method for controlling undesired plant growth, characterized in that a herbicidally effective amount of at least one pyrazine compound of the formula I or an agriculturally useful salt thereof according to one of claims 1 to 7 on plants, their seeds and / or their Habitat acts.