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EP2437605A1 - Substituted pyridopyrazines with a herbicidal action - Google Patents

Substituted pyridopyrazines with a herbicidal action

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Publication number
EP2437605A1
EP2437605A1 EP10724420A EP10724420A EP2437605A1 EP 2437605 A1 EP2437605 A1 EP 2437605A1 EP 10724420 A EP10724420 A EP 10724420A EP 10724420 A EP10724420 A EP 10724420A EP 2437605 A1 EP2437605 A1 EP 2437605A1
Authority
EP
European Patent Office
Prior art keywords
formula
alkyl
compounds
methyl
haloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10724420A
Other languages
German (de)
French (fr)
Inventor
Dschun Song
Julia Major
Johannes Hutzler
Trevor William Newton
Matthias Witschel
William Karl Moberg
Liliana Parra Rapado
Tao QU
Frank Stelzer
Anna Aleksandra Michrowska
Thomas Seitz
Thomas Ehrhardt
Klaus Kreuz
Klaus Grossmann
Bernd Sievernich
Anja Simon
Ricarda Niggeweg
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BASF SE
Original Assignee
BASF SE
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Application filed by BASF SE filed Critical BASF SE
Priority to EP10724420A priority Critical patent/EP2437605A1/en
Publication of EP2437605A1 publication Critical patent/EP2437605A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system

Definitions

  • the present invention relates to substituted pyrazines of the formula I.
  • 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 Alkynyl, Z- (tri-C 1 -C 4 -alkyl) silyl,
  • 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-Ci-C 6 -alkoxy, Z-Ci-C 4 -haloalkoxy, ZC 3 -C 8 -alkenyloxy, ZC 3 -C 8 -alkynyloxy, NR 1 R ", d-Ce-alkylsulfonyl, Z- (tri-Ci-C 4 alkyl) silyl, Z-phenyl, Z-phenoxy-phenylamino Z and 5- or 6-membered monocyclic or 9- or
  • 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
  • n 0, 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,
  • R b1 , R b2 is one of the groups mentioned for R b ;
  • 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;
  • 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,
  • 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 also their N-oxides and agriculturally suitable salts; with the proviso that R 1 does not represent 0R A or OS (O) n -R A when X is O.
  • 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, which comprises allowing a herbicidally effective amount of at least one pyrazine compound of the formula I or a agriculturally useful salt of I to act on plants, their seeds and / or their habitat.
  • 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.
  • 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.
  • the compounds according to the invention can be prepared by standard methods of organic chemistry, for example according to the following synthesis route:
  • 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, particularly preferably halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene ,
  • 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 carbonate.
  • 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
  • bonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides 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, as well as 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. 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
  • the starting materials are generally reacted with one another in equimolar amounts.
  • 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 Methylene chloride
  • 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 phenyl lithium, alkylmagnesium halides such as methylmagnesium chloride and also alkali metal and alkaline earth metal alcoholates.
  • alkali metal and alkaline earth metal hydroxides such as lithium hydro
  • te as sodium methoxide, sodium, potassium, potassium tert-butoxide and Dimethoxymagnesium
  • 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.
  • 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.
  • alkali metal and alkaline earth metal hydroxides particularly preferably lithium hydroxide.
  • the bases are generally used in catalytic amounts, but they can also be used e
  • 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 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 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.
  • 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.
  • alkali metal and alkaline earth metal hydroxides such as
  • tertiary amines such as trisodium methylamine, triethylamine, tributylamine, di-isopropylethylamine and N-methylpiperidine
  • pyridine substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration.
  • alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, calcium carbonate, cesium 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.
  • agent HL 1 are alcohols, optionally subst. Phenols, N, O-dialkylhydroxylamine, in particular pentafluorophenol or N, O-dimethylhydroxylamine in question.
  • the compounds of formula VI are with acetic acid derivatives of the formula VII to the
  • 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, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide,
  • 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 the formula IX can be liberated by cleaving the protective group from the compounds of the formula VIII.
  • 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 100 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 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.
  • 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 ° C to 150 ° C, preferably 30 ° 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 Methylene chloride
  • the sulfurization of the compounds of formula X is carried out under known conditions with a Schwefelungsagenz [S], it is usually carried out at temperatures of 0 0 C to 180 0 C, preferably 20 ° C to 140 ° C, in an inert organi ⁇
  • 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 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 slightly brownish, viscous oils which are freed from volatile constituents under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.
  • 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.
  • halogenated substituents preferably carry one to five identical or different halogen atoms, in particular fluorine atoms or chlorine atoms.
  • 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-methyl
  • 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-C ⁇ -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-fluor
  • Cycloalkyl and the cycloalkyl moieties for example in cycloalkoxy or cycloalkyl carbonyl: monocyclic saturated hydrocarbon groups having three or more carbon atoms, for example 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. B.
  • 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 , 2-dimethyl-2
  • 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,
  • Alkoxy alkyl, as defined above, which is bonded via an oxygen atom: z.
  • 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 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.
  • 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.
  • ammonium can be used as cation, whereby here optionally one to four hydrogen atoms by C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkoxy-C 1 -C 4 -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) ammoni
  • ammonium cation is the pyridine nitrogen atom of the formula I quaternized by alkylation or arylation.
  • 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.
  • 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:
  • 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.
  • Benzoyl such as C (O) C 6 H 5 ,
  • R A is H, Ci-C ⁇ -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.
  • 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 .
  • 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
  • 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 ,
  • 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 .:
  • 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.
  • X is S. In another embodiment, X is NR 3 . Both groups R 3 may be the same or different.
  • 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
  • R 3 is not hydrogen.
  • R 3 is preferably C 1 -C 6 -haloalkyl, such as CH 2 CF 3 or CH 2 CHF 2 .
  • Another embodiment relates to compounds of the formula I in which R b1 and R b2 are each hydrogen.
  • Another 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 N-phenyl salts.
  • R 3 ⁇ is preferred.
  • 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.
  • 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 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.
  • the following cultures may be considered:
  • 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).
  • one or more genes are integrated into the genome of the plant in order to improve the properties of the plant.
  • 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.
  • 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.
  • EPSPS enolpyruvylshikimate-3-phosphate synthase
  • 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).
  • GS glutamine synthetase
  • 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.
  • VIPs vegetative insecticidal proteins
  • 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
  • RIPs Ribosome Inactivating Proteins
  • Enzymes e.g. 3-hydroxysteroid oxidase, ecdysteroid IDP glycosyltransferase, cholesterol oxidase, ecdysone inhibitors or HMG-CoA reductase; ion channel blockers, z. 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.
  • 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
  • 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
  • MON 863 from Monsanto Europe SA, Belgium
  • IPC 531 from Monsanto Europe SA, Belgium
  • cottons producing a modified version of the toxin CrylAc 1507 from Pioneer Overseas Corporation, Belgium (maize varieties producing the toxin Cryl F and the PAT enzyme).
  • 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).
  • PR proteins pathogenesis-related proteins
  • resistance proteins eg, potato varieties that produce two resistance genes against Phytophthora infestans from the Mexican wild potato Solanum bulbocastanum
  • T4 lysozyme z. Potato varieties resistant to bacteria such as Erwinia amylvora by the production of this protein.
  • crops thus also includes plants whose productivity has been improved by means of genetic engineering methods by z. For example, the productivity (eg biomass, grain yield, starch
  • crops also includes plants whose ingredients have been modified in particular to improve the human or animal diet using genetic engineering methods by z.
  • oil plants can produce health-promoting long-chain omega-3 fatty acids or monounsaturated omega-9 fatty acids (eg Nexera ® oilseed rape).
  • crops also includes plants that have been modified for the improved production of raw materials by means of genetic engineering methods by z.
  • the amylopectin content of potatoes (Amflora ® potato) was increased.
  • 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.
  • 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.
  • 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 application form depending 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.
  • auxiliaries include 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 ,
  • thickeners ie, compounds which impart modified flowability to the formulation, ie, high-level at low viscosity and low viscosity in the agitated state
  • 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).
  • antifoams examples include 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.
  • 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)
  • antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol.
  • 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, aeid red 51, aeid red 52, aeid red 14, aeid blue 9, aeid yellow 23, basic red 10, basic red 108.
  • adhesives are polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol and
  • 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, for example 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.
  • surface-active substances adjuvants, wetting, adhesion, dispersing and emulsifying agents
  • the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g.
  • Ligninsulfon Acid eg Borrespers types, Borregaard
  • phenolsulfonic acids naphthalene sulfonic acids
  • naphthalene sulfonic acids Methoxylated isooctyl-, octyl
  • 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 by
  • Binding of the active ingredients to solid carriers are produced.
  • Aqueous application forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
  • 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.
  • concentrates consisting of active substance, wetting, adhesion, dispersing or emulsifying agent and possibly solvent or oil, which are suitable for dilution with water.
  • 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, 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:
  • active compound 20 parts by weight 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.
  • a dispersant e.g. Polyvinylpyrrolidone dissolved. Dilution in water gives a dispersion.
  • the active ingredient content is 20% by weight
  • active compound 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.
  • active compound 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).
  • organic solvent for example alkylaromatics
  • 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.
  • active compound 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.
  • 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.
  • active compound 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.
  • 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.
  • 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).
  • the application of the compounds of the formula I or of the herbicidal compositions can be carried out by treating seed.
  • seed dressing seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping, and seed pelleting
  • seed dressing seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping, and seed pelleting
  • seed film coating seed multilayer coating
  • seed encrusting seed dripping
  • seed pelleting seed pelleting
  • seed includes seeds of all kinds, such as grains, seeds, fruits, tubers, cuttings and similar forms.
  • 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.
  • 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.).
  • the compounds I are usually used in amounts of 0.001 to 10 kg per 100 kg of seed.
  • 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- ⁇ -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-phenylcarba
  • 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.
  • Glyphosate, glyphosate isopropylammonium and glyphosate trimesium sulfosate
  • 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.
  • Particularly preferred compounds of the formula 2 are:
  • 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 and W. Krämer et al. (ed.) "Modern Crop Protection Compounds", Vol.
  • 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
  • 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.
  • 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.
  • 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.
  • 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
  • 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
  • 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.
  • 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.
  • Step 1 3- (4-methoxy-benzyloxy) -pyridine-2-carbonklaremethylester
  • a solution of 15.2 g of 3-hydroxy-pyridin-2-methylester in 200 ml DMF was added 4g NaH and 30 min at 20-25 0 C stirred.
  • 15.4 g of para-methoxybenzyl chloride was added.
  • the mixture was stirred at 40 ° C. for about 15 hours and then poured into water. After extraction with ethyl acetate, phase separation and washing of the combined organic phases with water and sat. NaCl solution, then drying and removal of the solvent, the residue was subjected to column chromatography. 20 g of the title compound were obtained as a yellow oil.
  • Step 2 3- (4-Methoxy-benzyloxy) -pyridine-2-carboxylic acid
  • a solution of 7g of the ester of Step 1 and 2.2g of LiOH in 60ml of methanol and 40ml of water was stirred at 20-25 ° C for approximately 15h. touched. Then, 100 ml of water and 7 ml of acetic acid were added. The mixture was extracted with ethyl acetate. The combined organic phases were dried and freed from the solvent. 5 g of the title compound were obtained as a yellowish solid.
  • Step 3 3- (4-Methoxy-benzyloxy) -pyridine-2-carboxylic acid pentafluorophenyl ester
  • Step 4 Methyl 3- [3- (4-methoxy-benzyloxy) -pyridin-2-yl] -3-oxo-2- (2-trifluoromethyl-phenyl) -propionate
  • Step 5 3- (3-Hydroxy-pyridin-2-yl) -3-oxo-2- (2-trifluoromethyl-phenyl) -propionic acid methyl ester
  • Step 6 8-Hydroxy-7- (2-trifluoromethyl-phenyl) -pyrano [2,3-b] pyrazine-6-one 350 mg of Step 5 was dissolved in 7 ml of DMSO / sat. Saline solution dissolved. The mixture was stirred at 100 0 C for 2 h. Subsequently, the reaction solution was diluted with 70 ml of 2N HCl and extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate. After removal of the solvent in vacuo and purification by prep. HPLC gave 83 mg of the title compound.
  • 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.
  • 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.
  • test plants were, depending on the growth habit, first grown to a height of from 3 to 15 cm and then treated with the active ingredients suspended or emulsified in water.
  • 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 from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts and 0 none
  • a good herbicidal activity is at Wer- at least 70 and a very good herbicidal activity is given at values of at least 85.
  • the plants used in the greenhouse experiments are composed of the following species:
  • Example 1 The active ingredient from Example 1 showed at a rate of 3.0 kg / ha in the pre-emergence against SETIT a very good herbicidal activity.
  • Example 2 The active ingredient from Example 1 showed at a rate of 3.0 kg / ha postemergence against ABUTH, AVEFA, or SETFA a very good herbicidal activity.

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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), agents 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

SUBSTITUIERTE PYRIDOPYRAZINE MIT HERBIZIDER WIRKUNG SUBSTITUTED PYRIDOPYRACINES WITH HERBICIDAL EFFECT
Beschreibungdescription
Die vorliegende Erfindung betrifft substituierte Pyrazine der Formel IThe present invention relates to substituted pyrazines of the formula I.
worin die Variablen folgende Bedeutung haben R1 O-RA, S(O)n-RA oder OS(O)n-RA; wherein the variables have the following meaning R 1 OR A , S (O) n -R A or OS (O) n -R A ;
RA Wasserstoff, Ci -C4-Al kyl, Z-C3-C6-Cycloalkyl, Ci-C4-Haloalkyl, C2-C6-Al- kenyl, Z-C3-C6-Cycloalkenyl, C2-C6-Al kinyl, Z-(Tri-Ci-C4-alkyl)silyl,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,
Z-C(=O)-Ra, Z-P(=O)(Ra)2, über C oder N gebundener 3- bis 7-gliedriger monocyclischer oder 9- oder 10-gliedriger bicyclischer gesättigter, ungesättigter oder aromatischer Heterocyclus, enthaltend 1 , 2, 3 oder 4 Heteroatome ausgewählt aus O, N und S, der teilweise oder vollständig durch Gruppen Ra und/oder Rb substituiert sein kann,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 ,
Ra Wasserstoff, OH, Ci-C8-Al kyl, Ci-C4-Haloalkyl, Z-C3-C6-Cycloalkyl, C2-C8-Al kenyl, Z-C5-C6-Cycloalkenyl, C2-C8-Al kinyl, Z-Ci-C6-Alkoxy, Z-Ci-C4-Haloalkoxy, Z-C3-C8-Alkenyloxy, Z-C3-C8-Alkinyloxy, NR1R", d-Ce-Alkylsulfonyl, Z-(Tri-Ci-C4-alkyl)silyl, Z-Phenyl, Z-Phenoxy, Z-Phenylamino und 5- oder 6-gliedriger monocyclischer oder 9- oderR 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-Ci-C 6 -alkoxy, Z-Ci-C 4 -haloalkoxy, ZC 3 -C 8 -alkenyloxy, ZC 3 -C 8 -alkynyloxy, NR 1 R ", d-Ce-alkylsulfonyl, Z- (tri-Ci-C 4 alkyl) silyl, Z-phenyl, Z-phenoxy-phenylamino Z and 5- or 6-membered monocyclic or 9- or
10-gliedriger bicyclischer Heterocyclus, enthaltend 1 , 2, 3 oder 4 Heteroatome ausgewählt aus O, N und S, wobei die cyclischen Gruppen unsubstituiert oder durch 1 , 2, 3 oder 4 Gruppen Rb substituiert sind, bedeutet; R',R" unabhängig voneinander Wasserstoff, Ci-C8-Alkyl, Ci-C4-HaIo- alkyl, C3-C8-Al kenyl, C3-C8-Al kinyl, Z-C3-C6-Cycloalkyl, Z-Ci-C8- Alkoxy, Z-Ci-C8-Haloalkoxy;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 ', R "are independently hydrogen, Ci-C 8 alkyl, Ci-C 4 -HaIo- alkyl, C 3 -C 8 -alkenyl -alkyl, C 3 -C 8 -alkyl kinyl, ZC 3 -C 6 cycloalkyl , Z-C 1 -C 8 -alkoxy, Z-C 1 -C 8 -haloalkoxy;
R1 und R" können auch gemeinsam mit dem N-Atom, an das sie gebunden sind, einen 5- oder 6-gliedrigen monocyclischen oder 9- oder 10-gliedrigen bicyclischer Heterocyclus bilden, enthaltend 1 , 2, 3 oderR 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 Heteroatome ausgewählt aus O, N und S; Z eine kovalente Bindung oder Ci-C4-Alkylen; n 0, 1 oder 2;4 heteroatoms selected from O, N and S; Z is a covalent bond or C 1 -C 4 -alkylene; n is 0, 1 or 2;
R2 Phenyl, Naphthyl oder und 5- oder 6-gliedriger monocyclischer oder 9- oder 10- gliedriger bicyclischer aromatischer Heterocyclus, enthaltend 1 , 2, 3 oder 4 Heteroatome ausgewählt aus O, N und S, wobei die cyclischen Gruppen unsubstituiert oder durch 1 , 2, 3 oder 4 Gruppen Rb substituiert sind, bedeutet; Rb unabhängig voneinander Z-CN, Z-OH, Z-NO2, Z-Halogen, Ci -C8-Al kyl, d- C4-Haloalkyl, C2-C8-Al kenyl, C2-C8-Al kinyl, Z-Ci-C8-Alkoxy, Z-Ci-C8-HaIo- alkoxy, Z-C3-Cio-Cycloalkyl, 0-Z-C3-Cio-Cycloalkyl, Z-C(=0)-Ra, NR1R", Z-(Tri-Ci-C4-alkyl)silyl, Z-Phenyl und S(O)nRbb, wobei Rbb Ci-C8-Alkyl und Ci-C6-Haloalkyl bedeutet und n für O, 1 oder 2 steht;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 -HaIo alkoxy, ZC 3 -Cio-Cycloalkyl, 0-ZC 3 -Cio-Cycloalkyl, ZC (= 0) -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 O, 1 or 2;
Rb1, Rb2 eine der bei Rb genannten Gruppen;R b1 , R b2 is one of the groups mentioned for R b ;
Rb, Rb1, Rb2 können unabhängig voneinander auch gemeinsam mit der an das benachbarte C-Atom gebundene Gruppe Rb, Rb1 oder Rb2 einen fünf- oder sechsgliedrigen gesättigten, teilweise oder vollständig ungesättigten Ring bilden, der neben Kohlenstoff- 1 , 2 oder 3 Heteroatome ausgewählt aus O, N und S enthalten kann; X O, S oder N-R3; R3 Wasserstoff, Ci-C6-Alkyl, Ci-C4-Haloalkyl, C2-C6-Alkenyl, C3-C6-Al kinyl,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; 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,
Z-C3-Cio-Cycloalkyl, d-Ce-Alkoxy-d-Ce-alkyl, Ci-C6-Cyanoalkyl, Z-Phenyl, Z-C(=O)-Ra2 und Tri-Ci-C4-alkylsilyl;ZC 3 -Cio cycloalkyl, d-Ce-alkoxy-d-Ce-alkyl, Ci-C 6 cyanoalkyl, phenyl-Z, Z is C (= O) -R 2 and a tri-Ci-C4-alkylsilyl;
Ra2 Ci-C6-Alkyl, Ci-C4-Haloalkyl, Z-Ci-C6-Alkoxy, Z-Ci-C4-Haloalkoxy undR 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
NR1R"; wobei in Gruppen RA, R2, R3 und deren Untersubstituenten die Kohlenstoffketten und/oder die cyclischen Gruppen teilweise oder vollständig durch Gruppen Ra sub- stituiert sein können, sowie deren N-Oxide und landwirtschaftlich geeignete Salze; mit der Maßgabe, dass R1 nicht 0RA oder OS(O)n-RA bedeutet, wenn X für O steht.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 also their N-oxides and agriculturally suitable salts; with the proviso that R 1 does not represent 0R A or OS (O) n -R A when X is O.
Außerdem betrifft die Erfindung Verfahren und Zwischenprodukte zur Herstellung der Pyrazine der Formel I und deren N-Oxide, deren landwirtschaftlich brauchbaren Salze, sowie sie enthaltende Wirkstoffkombinationen, sie enthaltende Mittel und deren Verwendung als Herbizide, d.h. zur Bekämpfung von Schadpflanzen, sowie ein Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs, bei dem man eine herbizid wirksame Menge mindestens einer Pyrazinverbindung der Formel I oder eines land- wirtschaftlich brauchbaren Salzes von I auf Pflanzen, deren Samen und/oder deren Lebensraum einwirken läßt.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, which comprises allowing a herbicidally effective amount of at least one pyrazine compound of the formula I or a agriculturally useful salt of I to act on plants, their seeds and / or their habitat.
Weitere Ausführungsformen der vorliegenden Erfindung sind den Ansprüchen, der Beschreibung und den Beispielen zu entnehmen. Es versteht sich, dass die vorstehend genannten und die nachstehend noch zu erläuternden Merkmale des erfindungsgemä- ßen Gegenstandes nicht nur in der jeweils angegebenen Kombination, sondern auch in anderen Kombinationen verwendbar sind, ohne den Rahmen der Erfindung zu verlassen.Further embodiments of the present invention can be taken from the claims, the description and the examples. It goes without saying that the features mentioned above and those still to be explained below of the article according to the invention can be used not only in the respectively indicated combination but also in other combinations without departing from the scope of the invention.
In WO 2008/009908 und WO 2008/071918 werden herbizide Pyrazine beschrieben, ihre herbizide Wirkung bei niedrigen Aufwandmengen, bzw. Verträglichkeit gegenüber Kulturpflanzen bleibt jedoch verbesserungsbedürftig. Eine Aufgabe der vorliegenden Erfindung ist die Bereitstellung von Verbindungen mit herbizider Wirkung. Insbesondere sollen Wirkstoffe zur Verfügung gestellt werden, die eine hohe herbizide Wirkung, insbesondere bereits bei niedrigen Aufwandmengen, aufweisen und deren Verträglichkeit gegenüber Kulturpflanzen für eine kommerzielle Verwertung hinreichend ist.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, 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.
Diese und weitere Aufgaben werden durch die eingangs definierten Verbindungen der Formel I und durch ihre N-Oxide, sowie deren landwirtschaftlich geeigneten Salze gelöst.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.
Die erfindungsgemäßen Verbindungen können nach Standardverfahren der organischen Chemie hergestellt werden, beispielsweise nach der folgenden Syntheseroute:The compounds according to the invention can be prepared by standard methods of organic chemistry, for example according to the following synthesis route:
Pyridincarbonsäuren der Formel Il können mit Verbindungen der Formel III zu Verbindungen der Formel IV umgesetzt werden. In Formeln Il und III haben die Variablen die für Formel I angegebene Bedeutung. Die Gruppe R' steht für CrC4-AIkOXy, HaI steht für ein Halogenatom oder eine andere geeignete nukleophile Abgangsgruppe, wie Alkoxy oder Phenoxy und SG bedeutet eine die Reaktivität von Y vermindernde Schutzgruppe, wie beispielsweise ggf. subst. Benzyl.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 C 1 -C 4 -alkoxy, Hal is a halogen atom or another suitable nucleophilic leaving group, such as alkoxy or phenoxy, and SG is a protective group which reduces the reactivity of Y, for example optionally subst. Benzyl.
Diese Umsetzung erfolgt üblicherweise bei Temperaturen von -78 0C bis 12O0C, vorzugsweise -2O0C bis 5O0C, in einem inerten organischen Lösungsmittel in Gegenwart einer Base (vgl. Greene's Protective Groups in Organic Synthesis, Wiley). 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).
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p- XyIoI, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethyl- keton, Diethylketon und tert.-Butylmethylketon, sowie Dimethylsulfoxid, Dimethylform- amid (DMF) und Dimethylacetamid, besonders bevorzugt halogenierte Kohlenwasser- Stoffe wie Methylenchlorid, Chloroform und Chlorbenzol. Es können auch Gemische der genannten Lösungsmittel verwendet werden.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, particularly preferably halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene , It is also possible to use mixtures of the solvents mentioned.
Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid und CaI- ziumhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, CaI- ziumoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Calziumhydrid, Alkalimetallamide wie Lithium- amid, Natriumamid und Kaliumamid, Alkalimetall- und Erdalkalimetallcarbonate wie Lithiumcarbonat, Kaliumcarbonat und Calziumcarbonat sowie Alkalimetallhydrogencar- bonate wie Natriumhydrogencarbonat, metallorganische Verbindungen, insbesondere Alkalimetallalkyle wie Methyllithium, Butyllithium und Phenyllithium, Alkylmagnesiumha- logenide wie Methylmagnesiumchlorid sowie Alkalimetall- und Erdalkalimetallalkohola- te wie Natriummethanolat, Natriumethanolat, Kaliumethanolat, Kalium- tert.-Butanolat und Dimethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Tri- methylamin, Triethylamin, Tributylamin, Di-isopropylethylamin und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethylaminopyridin sowie bicyclische Amine in Betracht. Bevorzugt werden Alkalimetall- und Erdalkalimetallhydride, besonders bevorzugt Natriumhydrid. Die Basen werden im allgemeinen in kataly- tischen Mengen eingesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.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 carbonate. bonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides 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, as well as 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. 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.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt.The starting materials are generally reacted with one another in equimolar amounts.
Aus den Verbindungen der Formel IV wird die entsprechende Säure der Formel V freigesetzt. Diese Umsetzung erfolgt üblicherweise bei Temperaturen von -78 0C bis 12O0C, vorzugsweise -2O0C bis 5O0C, in einem inerten organischen Lösungsmittel in Gegenwart einer Base (vgl. Bioorganic and Medicinal Chemistry Letters (2006) Bd. 16(3), 718 - 721 ). Geeignete Lösungsmittel sind Wasser, Alkohole wie Methanol, Ethanol, iso-Propa- nol, aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.- Butylmethylketon, sowie Dimethylsulfoxid, DMF und Dimethylacetamid, besonders bevorzugt halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol. Es können auch Gemische der genannten Lösungsmittel verwendet werden.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 Methylene chloride, chloroform and chlorobenzene. It is also possible to use mixtures of the solvents mentioned.
Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid und CaI- ziumhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, CaI- ziumoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Calziumhydrid, Alkalimetallamide wie Lithium- amid, Natriumamid und Kaliumamid, Alkalimetall- und Erdalkalimetallcarbonate wie Lithiumcarbonat, Kaliumcarbonat und Calziumcarbonat sowie Alkalimetallhydrogencar- bonate wie Natriumhydrogencarbonat, metallorganische Verbindungen, insbesondere Alkalimetallalkyle wie Methyllithium, Butyllithium und Phenyllithium, Alkylmagnesiumha- logenide wie Methylmagnesiumchlorid sowie Alkalimetall- und Erdalkalimetallalkohola- te wie Natriummethanolat, Natriumethanolat, Kaliumethanolat, Kalium- tert.-Butanolat und Dimethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Tri- methylamin, Triethylamin, Tributylamin, Di-isopropylethylamin und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethylaminopyridin sowie bicyclische Amine in Betracht. Bevorzugt werden Alkalimetall- und Erdalkalimetall- hydroxide besonders bevorzugt Lithiumhydroxid. Die Basen werden im allgemeinen in katalytischen Mengen eingesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.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 phenyl lithium, alkylmagnesium halides such as methylmagnesium chloride and also alkali metal and alkaline earth metal alcoholates. te as sodium methoxide, sodium, potassium, 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, particularly preferably lithium hydroxide. The bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
Die Verbindungen der Formel V werden durch Einführung einer Abgangsgruppe L1 aktiviert. Als Abgangsgruppen L1 kommen allgemein solche Gruppen in Frage, die die Elektrophilie der Carbonylgruppe erhöhen, beispielsweise O-Alkyl, O-Aryl, Halogenide, aktivierte Ester oder Aldehyde (wie z. B. Weinreb-Amid), insbesondere Pentafluorphen- oxy.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.
Diese Umsetzung erfolgt üblicherweise bei Temperaturen von -78 0C bis 12O0C, vor- zugsweise -2O0C bis 5O0C, in einem inerten organischen Lösungsmittel in Gegenwart einer Base wie z. B. Triethylamin (vgl. J. Agric. and Food Chem. 1994, 42(4), 1019 - 1025.), eines Katalysators wie z. B. Dicyclohexylcarbodiimid (vgl. Egyptian Journal of Chemistry 1994, 37(3), 273-282) oder anderer bekannter Kupplungsreagenzien. Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p- XyIoI, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethyl- keton, Diethylketon und tert.-Butylmethylketon, sowie Dimethylsulfoxid, DMF und Di- methylacetamid, besonders bevorzugt Methylenchlorid und Toluol Es können auch Gemische der genannten Lösungsmittel verwendet werden.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 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.
Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid und Calzi- umhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, Calzi- umoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Calziumhydrid, Alkalimetallamide wie Lithium- amid, Natriumamid und Kaliumamid, Alkalimetall- und Erdalkalimetallcarbonate wie Lithiumcarbonat, Kaliumcarbonat und Calziumcarbonat sowie Alkalimetallhydrogencar- bonate wie Natriumhydrogencarbonat, metallorganische Verbindungen, insbesondere Alkalimetallalkyle wie Methyllithium, Butyllithium und Phenyllithium, Alkylmagnesiumha- logenide wie Methylmagnesiumchlorid sowie Alkalimetall- und Erdalkalimetallalkohola- te wie Natriummethanolat, Natriumethanolat, Kaliumethanolat, Kalium- tert.-Butanolat und Dimethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Tri- methylamin, Triethylamin, Tributylamin, Di-isopropylethylamin und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethylaminopyridin sowie bicyclische Amine in Betracht. Besonders bevorzugt werden Alkalimetall- und Erdalka- limetallcarbonate wie Lithiumcarbonat, Kaliumcarbonat, Calziumcarbonat, Cäsiumcar- bonat und Rubidiumcarbonat. Die Basen werden im allgemeinen in katalytischen Mengen eingesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden.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. 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 trisodium methylamine, 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 alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, calcium carbonate, cesium 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.
Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt.The starting materials are generally reacted with one another in equimolar amounts.
Als Agenz H-L1 kommen Alkohole, ggf. subst. Phenole, N,O-Dialkylhydroxylamin, insbesondere Pentafluorphenol oder N,O-Dimethylhydroxylamin in Frage.As agent HL 1 are alcohols, optionally subst. Phenols, N, O-dialkylhydroxylamine, in particular pentafluorophenol or N, O-dimethylhydroxylamine in question.
Die Verbindungen der Formel VI werden mit Essigsäurederivaten der Formel VII zu denThe compounds of formula VI are with acetic acid derivatives of the formula VII to the
Diese Umsetzung erfolgt üblicherweise bei Temperaturen von -78°C bis 1200C, vorzugsweise -200C bis 500C, in einem inerten organischen Lösungsmittel in Gegenwart einer Base, bzw. einer Lewissäure oder eines Katalysators [vgl. Bioorganic & Medicinal Chemistry (2004) Bd. 12(6), 1357-1366]. Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p- XyIoI, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethyl- keton, Diethylketon und tert.-Butylmethylketon, sowie Dimethylsulfoxid, DMF und Di- methylacetamid, besonders bevorzugt Acetonitril und DMF Es können auch Gemische der genannten Lösungsmittel verwendet werden. 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.
Als Basen kommen allgemein anorganische Verbindungen wie Alkalimetall- und Erdalkalimetallhydroxide wie Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid und CaI- ziumhydroxid, Alkalimetall- und Erdalkalimetalloxide wie Lithiumoxid, Natriumoxid, CaI- ziumoxid und Magnesiumoxid, Alkalimetall- und Erdalkalimetallhydride wie Lithiumhydrid, Natriumhydrid, Kaliumhydrid und Calziumhydrid, Alkalimetallamide wie Lithium- amid, Natriumamid und Kaliumamid, Alkalimetall- und Erdalkalimetallcarbonate wie Lithiumcarbonat, Kaliumcarbonat, Calziumcarbonat, Cäsiumcarbonat und Rubidiumcarbonat sowie Alkalimetallhydrogencarbonate wie Natriumhydrogencarbonat, metall- organische Verbindungen, insbesondere Alkalimetallalkyle wie Methyllithium, Butylli- thium und Phenyllithium, Alkylmagnesiumhalogenide wie Methylmagnesiumchlorid sowie Alkalimetall- und Erdalkalimetallalkoholate wie Natriummethanolat, Natriumetha- nolat, Kaliumethanolat, Kalium- tert.-Butanolat und Dimethoxymagnesium, außerdem organische Basen, z.B. tertiäre Amine wie Trimethylamin, Triethylamin, Tributylamin, Di-isopropylethylamin und N-Methylpiperidin, Pyridin, substituierte Pyridine wie Collidin, Lutidin und 4-Dimethylaminopyridin sowie bicyclische Amine in Betracht. Bevorzugt werden Alkalimetall- und Erdalkalimetallalkoholate, besonders bevorzugt Kalium- tert.- Butanolat.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, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium nolate, potassium, 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 alcoholates, particularly preferably potassium tert-butoxide.
Die Basen werden im allgemeinen in katalytischen Mengen eingesetzt, sie können aber auch äquimolar, im Überschuß oder gegebenenfalls als Lösungsmittel verwendet werden. Die Edukte werden im allgemeinen in äquimolaren Mengen miteinander umgesetzt.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.
Die Verbindungen der Formel IX können durch Abspalten der Schutzgruppe aus den Verbindungen der Formel VIII freigesetzt werden. Die Reaktionsbedingungen hängen von der Natur der Schutzgruppe SG ab; die Abspaltung einer ggf. subst. Benzylgruppe gelingt z. B. mit Trifluoressigsäure bei Temperaturen von -78°C bis 1000C, vorzugsweise -200C bis 500C, in einem inerten organischen Lösungsmittel [vgl. Greene's Protecti- ve Groups in Organic Synthesis, Wiley].The compounds of the formula IX can be liberated by cleaving the protective group from the compounds of the formula VIII. 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 100 0 C, preferably -20 0 C to 50 0 C, in an inert organic solvent [cf. Greene's Protective Groups in Organic Synthesis, Wiley].
Die Einführung der von Sauerstoff verschiedenen Gruppen X, bzw. Y in die Verbin- düngen der Formel I, bzw. ihrer Vorstufen, erfolgt nach allgemein bekannten Methoden.The introduction of the non-oxygen groups X, or Y into the compounds of the formula I or their precursors, takes place according to generally known methods.
Die Verbindungen der Formel IX und ihre Vorstufen können in zwei tautomeren Formen vorliegen. Die Erfindung betrifft beide Tautomere. Nur der Übersichtlichkeit wegen wird in der Beschreibung generell nur ein Tautomer erwähnt.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.
Die Verbindungen der Formel IX können durch Cycliserung in Verbindungen der Formel I umgesetzt werden. Die Cyclisierung gelingt z. B. mit ges. Kochsalzlösung und einem organischen Lösungsmittel bei Temperaturen von -30°C bis 150°C, vorzugswei- se 30° bis 100°C. 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 ° C to 150 ° C, preferably 30 ° to 100 ° C.
Diese Umsetzung erfolgt üblicherweise bei Temperaturen von -78°C bis 1200C, vorzugsweise -200C bis 50°C.This reaction is usually carried out at temperatures of -78 ° C to 120 0 C, preferably -20 0 C to 50 ° C.
Geeignete Lösungsmittel sind Wasser, Alkohole wie Methanol, Ethanol, iso-Propa- nol, aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m- und p-Xylol, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, Ketone wie Aceton, Methylethylketon, Diethylketon und tert.- Butylmethylketon, sowie Dimethylsulfoxid, DMF und Dimethylacetamid, besonders bevorzugt halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol. Es können auch Gemische der genannten Lösungsmittel verwendet werden.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 Methylene chloride, chloroform and chlorobenzene. It is also possible to use mixtures of the solvents mentioned.
Die Schwefelung der Verbindungen der Formel X erfolgt unter an sich bekannten Bedingungen mit einem Schwefelungsagenz [S], sie erfolgt üblicherweise bei Temperaturen von 00C bis 1800C, vorzugsweise 20°C bis 140°C, in einem inerten organi¬The sulfurization of the compounds of formula X is carried out under known conditions with a Schwefelungsagenz [S], it is usually carried out at temperatures of 0 0 C to 180 0 C, preferably 20 ° C to 140 ° C, in an inert organi¬
Geeignete Lösungsmittel sind aliphatische Kohlenwasserstoffe wie Pentan, Hexan, Cyclohexan und Petrolether, aromatische Kohlenwasserstoffe wie Toluol, o-, m-und p- XyIoI, halogenierte Kohlenwasserstoffe wie Methylenchlorid, Chloroform und Chlorbenzol, Ether wie Diethylether, Diisopropylether, tert.-Butylmethylether, Dioxan, Anisol und Tetrahydrofuran, Nitrile wie Acetonitril und Propionitril, sowie Dimethylsulfoxid, besonders bevorzugt Toluol und Tetrahydrofuran. Es können auch Gemische der genannten Lösungsmittel verwendet werden.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.
Als Schwefelungsagenzien kommen beispielsweise Phosphorpentasulfid oder La- wesson-Reagenz in Betracht.Suitable sulfurizing agents are, for example, phosphorus pentasulfide or La wesson's reagent.
Die Einführung der Gruppen N-R3 in die Verbindungen der Formel I oder X, bzw. von R1, bzw. RA erfolgt unter allgemein bekannten Bedingungen.The introduction of the groups NR 3 into the compounds of the formula I or X, or of R 1 or R A is carried out under generally known conditions.
Die Verbindungen der Formel I, worin R1 eine über S gebundene Gruppe darstellt, können beispielsweise über eine Reaktionsfolge gemäß Newman-Kwart ausgehend von Chlorthiocarbonyl-Verbindungen erhalten werden [vgl: J. Org. Chem., Bd. 59(21), S. 6318-21 (1994)]. Die Reaktionsgemische werden in üblicher weise aufgearbeitet, z.B. durch Mischen mit Wasser, Trennung der Phasen und gegebenenfalls chromatographische Reinigung der Rohprodukte. Die Zwischen- und Endprodukte fallen z.T. in Form farbloser oder schwach bräunlicher, zäher Öle an, die unter vermindertem Druck und bei mäßig er- höhter Temperatur von flüchtigen Anteilen befreit oder gereinigt werden. Sofern die Zwischen- und Endprodukte als Feststoffe erhalten werden, kann die Reinigung auch durch Umkristallisieren oder Digerieren erfolgen.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 slightly brownish, viscous oils which are freed from volatile constituents under reduced pressure and at a moderately elevated temperature. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.
Sofern einzelne Verbindungen I nicht auf den voranstehend beschriebenen Wegen zugänglich sind, können sie durch Derivatisierung anderer Verbindungen I hergestellt werden.If individual compounds I are not accessible in the above-described ways, they can be prepared by derivatization of other compounds I.
Sofern bei der Synthese Isomerengemische anfallen, ist im allgemeinen jedoch eine Trennung nicht unbedingt erforderlich, da sich die einzelnen Isomere teilweise während der Aufbereitung für die Anwendung oder bei der Anwendung (z.B. unter Licht-, Säureoder Baseneinwirkung) ineinander umwandeln können. Entsprechende Umwandlungen können auch nach der Anwendung, beispielsweise bei der Behandlung von Pflanzen in der behandelten Pflanze oder in der zu bekämpfenden Schadpflanze erfolgen.However, unless isomeric mixtures are involved in the synthesis, separation is not necessarily required because the individual isomers can partially interconvert during processing for use or in use (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.
Die für die Substituenten der erfindungsgemäßen Verbindungen genannten organischen Molekülteile stellen Sammelbegriffe für individuelle Aufzählungen der einzelnen Gruppenmitglieder dar. Sämtliche Kohlenwasserstoffketten, wie Alkyl, Halo(gen)alkyl, Alkenyl, Alkinyl, sowie die Alkylteile und Alkenylteile in Alkoxy, Halo(gen)alkoxy, Alkyl- amino, Dialkylamino, N-Alkylsulfonylamino, Alkenyloxy, Alkinyloxy, Alkoxyamino, Alkyl- aminosulfonylamino, Dialkylaminosulfonylamino, Alkenylamino, Alkinylamino, N-(Alke- nyl)-N-(alkyl)-amino, N-(Alkinyl)-N-(alkyl)-amino, N-(Alkoxy)-N-(alkyl)-amino, N-(Alke- nyl)-N-(alkoxy)-amino oder N-(Alkinyl)-N-(alkoxy)-amino können geradkettig oder verzweigt sein.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.
Das Präfix Cn-Cm- gibt die jeweilige Kohlenstoffzahl der Kohlenwasserstoffeinheit an. Sofern nicht anders angegeben tragen halogenierte Substituenten vorzugsweise ein bis fünf gleiche oder verschiedene Halogenatome, insbesondere Fluoratome oder Chloratome.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.
Die Bedeutung Halogen steht jeweils für Fluor, Chlor, Brom oder lod. Ferner bedeuten beispielsweise:The meaning halogen in each case represents fluorine, chlorine, bromine or iodine. Furthermore, for example:
Alkyl sowie die Alkylteile beispielsweise in Alkoxy, Alkylamino, Dialkylamino, N-Alkylsulfonylamino, Alkylaminosulfonylamino, Dialkylaminosulfonylamino, N-(Alkenyl)-N- (alkyl)-amino, N-(Alkinyl)-N-(alkyl)-amino, N-(Alkoxy)-N-(alkyl)-amino: gesättigte, ge- radkettige oder verzweigte Kohlenwasserstoffreste mit einem oder mehr C-Atomen, z.B. 1 bis 2, 1 bis 4, oder 1 bis 6 Kohlenstoffatomen, z.B. Ci-C6-Alkyl wie 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-Methylpen- tyl, 4-Methylpentyl, 1 ,1-Dimethylbutyl, 1 ,2-Dimethylbutyl, 1 ,3-Dimethylbutyl, 2,2-Di- methylbutyl, 2,3-Dimethylbutyl, 3,3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1 ,1 ,2-Tri- methylpropyl, 1 ,2,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl, 1-Ethyl-2-methylpropyl. In einer erfindungsgemäßen Ausführungsform steht Alkyl für kleine Alkylgruppen wie d- C4-Alkyl. In einer anderen erfindungsgemäßen Ausführungsform steht Alkyl für größere Alkylgruppen wie Cs-Cβ-Alkyl. Halogenalkyl (auch als Haloalkyl bezeichnet): einen Alkylrest wie vorstehend genannt, dessen Wasserstoffatome partiell oder vollständig durch Halogenatome wie Fluor, Chlor, Brom und/oder lod substituiert sind, z.B. Chlormethyl, Dichlormethyl, Tri- chlormethyl, Fluormethyl, Difluormethyl, Trifluormethyl, Chlorfluormethyl, Dichlorfluor- methyl, Chlordifluormethyl, 2-Fluorethyl, 2-Chlorethyl, 2-Bromethyl, 2-lodethyl, 2,2-Di- fluorethyl, 2,2,2-Trifluorethyl, 2-Chlor-2-fluorethyl, 2-Chlor-2,2-difluorethyl, 2,2-Dichlor- 2-fluorethyl, 2,2,2-Trichlorethyl, Pentafluorethyl, 2-Fluorpropyl, 3-Fluorpropyl, 2,2-Di- fluorpropyl, 2,3-Difluorpropyl, 2-Chlorpropyl, 3-Chlorpropyl, 2,3-Dichlorpropyl, 2-Brom- propyl, 3-Brompropyl, 3,3,3-Trifluorpropyl, 3,3,3-Trichlorpropyl, 2,2,3,3,3-Pentafluor- propyl, Heptafluorpropyl, 1-(Fluormethyl)-2 -fluorethyl, 1-(Chlormethyl)-2-chlorethyl, 1- (Brommethyl)-2-bromethyl, 4-Fluorbutyl, 4-Chlorbutyl, 4-Brombutyl und Nonafluorbutyl.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-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-tri- methylpropyl, 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 sowie die Cycloalkylteile beispielsweise in Cycloalkoxy oder Cycloalkyl- carbonyl: monocyclische, gesättigte Kohlenwasserstoffgruppen mit drei oder mehr C- Atomen, z.B. 3 bis 6 Kohlenstoffringgliedern, wie Cyclopropyl, Cyclobutyl, Cyclopentyl und Cyclohexyl. Alkenyl sowie Alkenylteile beispielsweise in Alkenylamino, Alkenyloxy, N-(Alkenyl)- N-(alkyl)-amino, N-(Alkenyl)-N-(alkoxy)-amino: einfach ungesättigte, geradkettige oder verzweigte Kohlenwasserstoffreste mit zwei oder mehr C-Atomen, z. B. 2 bis 4, 2 bis 6 oder 3 bis 6 Kohlenstoffatomen und einer Doppelbindung in einer beliebigen Position, z.B. C2-C6-Alkenyl wie 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-but- enyl, 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-Di- methyl-2-propenyl, 1 ,2-Dimethyl-1-propenyl, 1 ,2-Dimethyl-2-propenyl, 1-Ethyl-1-prop- enyl, 1-Ethyl-2-propenyl, 1-Hexenyl, 2-Hexenyl, 3-Hexenyl, 4-Hexenyl, 5-Hexenyl, 1-Methyl-1-pentenyl, 2-Methyl-1-pentenyl, 3-Methyl-1-pentenyl, 4-Methyl-1-pentenyl, 1-Methyl-2-pentenyl, 2-Methyl-2-pentenyl, 3-Methyl-2-pentenyl, 4-Methyl-2-pentenyl, 1-Methyl-3-pentenyl, 2-Methyl-3-pentenyl, 3-Methyl-3-pentenyl, 4-Methyl-3-pentenyl, 1-Methyl-4-pentenyl, 2-Methyl-4-pentenyl, 3-Methyl-4-pentenyl, 4-Methyl-4-pentenyl, 1 ,1-Dimethyl-2-butenyl, 1 ,1-Dimethyl-3-butenyl, 1 ,2-Dimethyl-1-butenyl, 1 ,2-Dimethyl- 2-butenyl, 1 ,2-Dimethyl-3-butenyl, 1 ,3-Dimethyl-1-butenyl, 1 ,3-Dimethyl-2-butenyl, 1 ,3-Dimethyl-3-butenyl, 2,2-Dimethyl-3-butenyl, 2,3-Dimethyl-1-butenyl, 2,3-Dimethyl- 2-butenyl, 2,3-Dimethyl-3-butenyl, 3,3-Dimethyl-1-butenyl, 3,3-Dimethyl-2-butenyl, 1-Ethyl-1-butenyl, 1-Ethyl-2-butenyl, 1-Ethyl-3-butenyl, 2-Ethyl-1-butenyl, 2-Ethyl-2-but- 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: monocyclische, einfach ungesättigte Kohlenwasserstoffgruppen mit 3 bis 6, vorzugsweise 5 bis 6 Kohlenstoffringgliedern, wie Cyclopenten-1-yl, Cyclopen- ten-3-yl, Cyclohexen-1-yl, Cyclohexen-3-yl, Cyclohexen-4-yl.Cycloalkyl and the cycloalkyl moieties, for example in cycloalkoxy or cycloalkyl carbonyl: monocyclic saturated hydrocarbon groups having three or more carbon atoms, for example 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. B. 2 to 4, 2 to 6 or 3 to 6 carbon atoms and a double bond in any position, for example 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-meth yl-4-pentenyl, 4-methyl-4-pentenyl, 1, 1-dimethyl-2-butenyl, 1, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl 2-butenyl, 1, 2-dimethyl-3-butenyl, 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 2,2-dimethyl 3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl 2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl 3-butenyl, 1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl, 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 ,
Alkinyl sowie Alkinylteile beispielsweise in Alkinyloxy, Alkinylamino, N-(Alkinyl)-N-(al- kyl)-amino oder N-(Alkinyl)-N-(alkoxy)-amino: geradkettige oder verzweigte Kohlenwasserstoffgruppen mit zwei oder mehr C-Atomen, z. B. 2 bis 4, 2 bis 6, oder 3 bis 6 Kohlenstoffatomen und einer Dreifachbindung in beliebiger Position, z. B. C2-C6-Alkinyl wie Ethinyl, 1-Propinyl, 2-Propinyl, 1-Butinyl, 2-Butinyl, 3-Butinyl, 1-Methyl-2-propinyl, 1-Pentinyl, 2-Pentinyl, 3-Pentinyl, 4-Pentinyl, 1-Methyl-2-butinyl, 1 -Methyl-3-butinyl, 2-Methyl-3-butinyl, 3-Methyl-1 -butinyl, 1 ,1-Dimethyl-2-propinyl, 1 -Ethyl-2-propinyl,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-Hexinyl, 2-Hexinyl, 3-Hexinyl, 4-Hexinyl, 5-Hexinyl, 1-Methyl-2-pentinyl, 1 -Methyl-3- pentinyl, 1-Methyl-4-pentinyl, 2-Methyl-3-pentinyl, 2-Methyl-4-pentinyl, 3-Methyl-1-pen- tinyl, 3-Methyl-4-pentinyl, 4-Methyl-1-pentinyl, 4-Methyl-2-pentinyl, 1 ,1-Dimethyl-2-but- inyl, 1 ,1-Dimethyl-3-butinyl, 1 ,2-Dimethyl-3-butinyl, 2,2-Dimethyl-3-butinyl, 3,3-Dime- thyl-1 -butinyl, 1 -Ethyl-2-butinyl, 1 -Ethyl-3-butinyl, 2-Ethyl-3-butinyl, 1 -Ethyl-1 -methyl-2- propinyl.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- pentinyl, 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-butynyl, 1 - Ethyl 2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl.
Alkoxy: Alkyl, wie vorstehend definiert, das über ein O-Atom gebunden ist: z. B. Me- thoxy, Ethoxy, n-Propoxy, 1 -Methylethoxy, Butoxy, 1-Methylpropoxy, 2-Methylpropoxy oder 1 ,1-Dimethylethoxy, Pentoxy, 1-Methylbutoxy, 2-Methylbutoxy, 3-Methylbutoxy, 1 ,1-Dimethylpropoxy, 1 ,2-Dimethylpropoxy, 2,2-Dimethylpropoxy, 1-Ethylpropoxy, Hex- oxy, 1-Methylpentoxy, 2-Methylpentoxy, 3-Methylpentoxy, 4-Methylpentoxy, 1 ,1 -Di- methylbutoxy, 1 ,2-Dimethylbutoxy, 1 ,3-Dimethylbutoxy, 2,2-Dimethylbutoxy, 2,3-Di- methylbutoxy, 3,3-Dimethylbutoxy, 1-Ethylbutoxy, 2-Ethylbutoxy, 1 ,1 ,2-Trimethylprop- oxy, 1 ,2,2-Trimethylpropoxy, 1 -Ethyl-1 -methylpropoxy oder 1-Ethyl-2-methylpropoxy. 5- oder 6-gliedriger Heterocyclus: eine cyclische Gruppe, die 5 oder 6 Ringatome aufweist wobei 1 , 2, 3 oder 4 Ringatome Heteroatome sind, die ausgewählt sind aus O, S und N, wobei die cyclische Gruppe gesättigt, partiell ungesättigt oder aromatisch ist.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.
Die Verbindungen der Formel I können, je nach Substitutionsmuster, ein oder meh- rere weitere Chiralitätszentren enthalten. Die erfindungsgemäßen Verbindungen können daher als reine Enantiomere oder Diastereomere oder als Enantiomeren- oder Diastereomerengemische vorliegen. Gegenstand der Erfindung sind sowohl die reinen Enantiomeren oder Diastereomeren als auch deren Gemische.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.
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.
Es kommen als Kationen insbesondere Ionen der Alkalimetalle, vorzugsweise Lithi- um, Natrium oder Kalium, der Erdalkalimetalle, vorzugsweise Calcium oder Magnesium, und der Übergangsmetalle, vorzugsweise Mangan, Kupfer, Zink oder Eisen in Betracht. Ebenso kann als Kation Ammonium verwendet werden, wobei hier gewünsch- tenfalls ein bis vier Wasserstoffatome durch Ci-C4-AIkVl, Hydroxy-Ci-C4-alkyl, C1-C4- Alkoxy-Ci-C4-alkyl, Hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, Phenyl oder Benzyl ersetzt sein können, vorzugsweise Ammonium, Dimethylammonium, Diisopropylammonium, Tetramethylammonium, Tetrabutylammonium, 2-(2-Hydroxyeth-1 -oxy)eth-1 -ylammonium, Di(2-hydroxyeth-1-yl)ammonium, Trimethylbenzylammonium. Als Ammoniumkation kommt auch das durch Alkylierung oder Arylierung quaternisierte Pyridin-Stickstoffatom der Formel I in Frage. Des Weiteren kommen Phosphoniumionen, Sulfoniumionen, vorzugsweise Tri(Ci-C4-alkyl)sulfonium oder Sulfoxoniumionen, vorzugsweise Tri(Ci- C4-alkyl)sulfoxonium, in Betracht. Anionen von brauchbaren Säureadditionsalzen sind in erster Linie Chlorid, Bromid, Fluorid, Hydrogensulfat, Sulfat, Dihydrogenphosphat, Hydrogenphosphat, Nitrat, Hydrogencarbonat, Carbonat, Hexafluorosilikat, Hexafluorophosphat, Benzoat sowie die Anionen von Ci-C4-Alkansäuren, vorzugsweise Formiat, Acetat, Propionat, Butyrat oder Trifluoracetat.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. Likewise ammonium can be used as cation, whereby here optionally one to four hydrogen atoms by C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkoxy-C 1 -C 4 -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. 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.
Die besonders bevorzugten Ausführungsformen der Zwischenprodukte in Bezug auf die Variablen entsprechen denen der Gruppen der Formel I.The particularly preferred embodiments of the intermediates with respect to the variables correspond to those of the groups of the formula I.
In einer besonderen Ausführungsform haben die Variablen der Verbindungen der Formel I folgende Bedeutungen, wobei diese sowohl für sich allein betrachtet als auch in Kombination miteinander besondere Ausgestaltungen der Verbindungen der Formel I darstellen: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 einer ersten bevorzugten Ausführungsform der Erfindung steht R1 für O-RA. In einer weiteren bevorzugten Ausführungsform der Erfindung steht R1 für S(O)n-RA, darin steht n bevorzugt für 0 oder 2, insbesondere für 0.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.
RA steht insbesondere für H, d-Ce-Alkylcarbonyl, wie C(O)CH3, C(O)CH2CH3, C(O)CH(CHs)2 oder C(O)C(CH3)S; d-Ce-Cycloalkylcarbonyl, wie Cyclopropylcarbonyl, Cyclopentylcarbonyl oder Cyclohexylcarbonyl; wie C(O)CH=CH2 oder C(O)CH2CH=CH2, ggf. subst. Benzoyl, wie C(O)C6H5,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 ; d-Ce-cycloalkylcarbonyl such as cyclopropylcarbonyl, cyclopentylcarbonyl or cyclohexylcarbonyl; 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-CH3-C6H4], C(O)P-CH3-C6H4], C(O)[2-F-C6H4], C(O)[4-F-C6H4], oder ggf. subst. Heteroaryl, wie Pyridin, welches über eine Carbonylgruppe gebunden ist.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 einer weiteren bevorzugten Ausgestaltung steht RA für H, Ci-Cβ-Alkyl, ggf. subst. Phenyl, Di-Ci-Cβ-alkylaminocarbonyl, d-Cβ-Alkylcarbonyl oder Benzoyl. Besonders bevorzugt steht RA für H oder C-i-Cβ-Alkylcarbonyl.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 einer weiteren bevorzugten Ausführungsform der Erfindung steht RA für einen ggf. durch Rb substituierten 5- oder 6-gliedrigen Heterocyclus wie zuvor definiert, der vorzugsweise entweder 1 , 2, 3 oder 4 Stickstoffatome oder 1 Sauerstoff oder 1 Schwefelatom und gegebenenfalls 1 oder 2 Stickstoffatome als Ringlieder aufweist und die un- substituiert ist oder 1 oder 2 aus Rb ausgewählte Substituenten aufweisen kann. Bevorzugt sind über N gebundene gesättigte oder ungesättigte Gruppen, wie z.B.: Heteroaromatische Gruppen: Pyridazin-3-yl, Pyridazin-4-yl, Pyrimidin-2-yl, Pyrimidin- 4-yl, Pyrimidin-5-yl, Pyrazin-2-yl, 2-Furyl, 3-Furyl, 2-Thienyl, 3-Thienyl, Pyrazol-1-yl, Pyrazol-3-yl, Pyrazol-4-yl, lsoxazol-3-yl, lsoxazol-4-yl, lsoxazol-5-yl, lsothiazol-3-yl, lsothiazol-4-yl, lsothiazol-5-yl, lmidazol-1-yl, lmidazol-2-yl, lmidazol-4-yl, Oxazol-2-yl, Oxazol-4-yl, Oxazol-5-yl, Thiazol-2-yl, Thiazol-4-yl und Thiazol-5-yl.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 einer anderen Ausgestaltung steht RA für eine über C-gebundene heteroaromatische Gruppe wie Pyrazol-3-yl, lmidazol-5-yl, Oxazol-2-yl, Thiazol-2-yl, Thiazol-4-yl, Thiazol-5-yl, Pyridin-2-yl, Pyridin-3-yl, Pyridin-4-yl, Pyrimidin-2-yl, Pyrimidin-4-yl, Pyri- midin-5-yl, Pyridazin-4-yl, Pyrazin-2-yl, [1 H]-Tetrazol-5-yl und [2H]-Tetrazol-5-yl, wobei die hier exemplarisch genannten Heterocyclen 1 oder 2 aus Rb ausgewählte Substi- tuenten aufweisen können. Bevorzugte Gruppen Rb sind insbesondere F, Cl, CN, NO2, CH3, C2H5, OCH3, OC2H5, OCHF2, OCF3 und CF3.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 einer weiteren bevorzugten Ausgestaltung steht R2 für Phenyl, welches unsubsti- tuiert ist oder teilweise oder vollständig durch Gruppen Rb substituiert ist. Besonders bevorzugt sind solche Verbindungen, in denen eine Gruppe Rb in ortho-Position steht. Solche Verbindungen der Formel I werden durch die Formel I. A beschrieben: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 Formel I.A steht der Index n für eine ganze Zahl von Null bis vier, bevorzugt für O, 1 oder 2, insbesondere for 0 oder 1. R5 und R6 stehen für Gruppen Rb, wie eingangs definiert, bevorzugt für Halogen, NO2, Ci-C4-AIkVl, Ci-C2-Halogenalkyl und C1-C4- Alkoxy. Eine Gruppe R6 steht bevorzugt in Position 5.In formula IA, the subscript n is an integer from zero to four, preferably O, 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 einer bevorzugten Ausführungsform steht X für S. In einer weiteren Ausführungsform steht X für NR3. Beide Gruppen R3 können gleich oder verschieden sein.In a preferred embodiment, X is S. In another embodiment, X is NR 3 . Both groups R 3 may be the same or different.
R3 steht bevorzugt für H, Ci -C6-Al kyl, wie CH3, C2H5, n-C3H7, CH(CHs)2, n-C3H9, oder C(CH3)3; C3-C6-Cycloalkyl-Ci-C4-alkyl, wie Cyclopropylmethyl, C3-C6-Al kenyl, wie CH2CH=CH2, CH2C(CHs)=CH2, CH2CH2CH=CH2, CH2CH2C(CHs)=CH2,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 (CH 3 ) 3 ; C 3 -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 (CH) = CH 2 , CH 2 CH 2 CH = CH 2 , CH 2 CH 2 C (CHs) = CH 2 ,
CH2CH2CH2CH=CH2, CH2CH2CH2C(CHs)=CH2, oder ggf. subst. Phenyl, wie C6H5, 4-CH3-C6H4, 4-F-C6H4 oder S(O)n-RN, worin RN für Ci-C6-Halogenalkyl steht, wie CH2CF3, CH2CHF2. Besonders bevorzugt steht R3 nicht für Wasserstoff. Insbesondere bevorzugt steht R3 für Ci-C6-Haloalkyl, wie CH2CF3 oder CH2CHF2.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 .
Eine weitere Ausführungsform betrifft Verbindungen der Formel I, in denen Rb1 und Rb2 jeweils für Wasserstoff stehen.Another embodiment relates to compounds of the formula I in which R b1 and R b2 are each hydrogen.
Eine weitere Ausführungsform betrifft die N-Oxide der Verbindungen der Formel I. Eine weitere Ausführungsform betrifft Salze der Verbindungen der Formel I, insbesondere solche erhältlich durch Quaternisierung mindestens eines Pyrazin-Stickstoff- atoms, die bevorzugt erfolgen kann durch Alkylierung oder Arylierung der Verbindungen der Formel I. Entsprechend sind bevorzugte Salze der Verbindungen die N-Alkyl-, insbesondere die N-Methyl-, bzw. die N-Phenyl-Salze.Another 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 N-phenyl salts.
Insbesondere sind im Hinblick auf ihre Verwendung die in den folgenden Tabellen zusammengestellten Verbindungen der Formel I, welche der Formel I.A entsprechen, in der Rb1 und Rb2 jeweils für Wasserstoff steht (Formel I.AA),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.AA),
l NλNlyX R5 I AA l NλNl y XR 5 I AA
R3 κ bevorzugt. Die in den Tabellen für einen Substituenten genannten Gruppen stellen außerdem für sich betrachtet, unabhängig von der Kombination, in der sie genannt sind, eine besonders bevorzugte Ausgestaltung des betreffenden Substituenten dar.R 3 κ is preferred. 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.
Tabelle 1Table 1
Verbindungen der Formel I, in denen X O und R3 H bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile A-1 bis A-48 der Tabelle A entspricht Tabelle 2 Verbindungen der Formel I, in denen X O und R3 CH3 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile A- 1 bis A-48 der Tabelle A entsprichtCompounds of the formula I in which X is O and R 3 is H and the combination of R 1 , R 5 and (R 6 ) n for a compound corresponds in each case to one line A-1 to A-48 of Table A. Table 2 Compounds of the formula In which X is O and R 3 is CH 3 and the combination of R 1 , R 5 and (R 6 ) n for a compound corresponds in each case to one row A-1 to A-48 of Table A.
Tabelle 3 Verbindungen der Formel I, in denen X O und R3 C2H5 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile A- 1 bis A-48 der Tabelle A entsprichtTable 3 Compounds of the formula I in which X is O and R 3 is C 2 H 5 and the combination of R 1 , R 5 and (R 6 ) n for a compound corresponds in each case to one row A-1 to A-48 of Table A.
Tabelle 4Table 4
Verbindungen der Formel I, in denen X O und R3 n-C3H7 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile A-1 bis A-48 der Tabelle A entspricht Tabelle 5Compounds of the formula I in which XO and R 3 denote n-C3H 7 and the combination of R 1 , R 5 and (R 6 ) n for a compound corresponds in each case to one row A-1 to A-48 of Table A corresponds to Table 5
Verbindungen der Formel I, in denen X O und R3 CH(CH3)2 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile A-1 bis A-48 der Tabelle A entspricht Tabelle 6Compounds of the formula I in which X is O and R 3 is CH (CH 3 ) 2 and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one line A-1 to A-48 of Table A Table 6
Verbindungen der Formel I, in denen X O und R3 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile A-1 bis A-48 der Tabelle A entspricht Tabelle 7Compounds of the formula I in which X is O and R 3 and the combination of R 1 , R 5 and (R 6 ) n for a compound corresponds in each case to one row A-1 to A-48 of Table A. Table 7
Verbindungen der Formel I, in denen X O und R3 CH2CH=CH2 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile A-1 bis A-48 der Tabelle A entspricht Tabelle 8Compounds of the formula I in which X is O and R 3 is CH 2 CH = CH 2 and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one line A-1 to A-48 of Table A corresponds to Table 8
Verbindungen der Formel I, in denen X O und R3 CH2C≡CH bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile A-1 bis A-48 der Tabelle A entsprichtCompounds of the formula I in which X is O and R 3 is CH 2 C≡CH and the combination of R 1 , R 5 and (R 6 ) n for a compound corresponds in each case to one row A-1 to A-48 of Table A.
Tabelle 9 Verbindungen der Formel I, in denen X O und R3 CH2CN bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile A- 1 bis A-48 der Tabelle A entsprichtTable 9 Compounds of the formula I in which X is O and R 3 is CH 2 CN and the combination of R 1 , R 5 and (R 6 ) n for a compound corresponds in each case to one row A-1 to A-48 of Table A.
Tabelle 10Table 10
Verbindungen der Formel I, in denen X O und R3 CH2CF3 bedeuten und die Kombinati- on von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile A- 1 bis A-48 der Tabelle A entsprichtCompounds of the formula I in which X is O and R 3 is CH 2 CF 3 and the combination of R 1 , R 5 and (R 6 ) n for a compound corresponds in each case to one row A-1 to A-48 of Table A.
Tabelle nTable n
Verbindungen der Formel I, in denen X O und R3 CH2CHF2 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile A-1 bis A-48 der Ta- belle A entsprichtCompounds of the formula I in which X is O and R 3 is CH 2 CHF 2 and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row A-1 to A-48 of Table A.
Tabelle 12Table 12
Verbindungen der Formel I, in denen X O und R3 CH2CeH5 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile A- 1 bis A-48 der Tabelle A entspricht Tabelle 13Compounds of the formula I in which X is O and R 3 is CH 2 CeH 5 and the combination of R 1 , R 5 and (R 6 ) n for a compound corresponds in each case to one row A-1 to A-48 of Table A corresponds to Table 13
Verbindungen der Formel I, in denen X S und R3 H bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which XS and R 3 are H and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row of Table A.
Tabelle nTable n
Verbindungen der Formel I, in denen X S und R3 CH3 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S and R 3 is CH 3 and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row of Table A.
Tabelle 15Table 15
Verbindungen der Formel I, in denen X S und R3 C2H5 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S and R 3 is C 2 H 5 and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row of Table A.
Tabelle 16 Verbindungen der Formel I, in denen X S und R3 n-C3H7 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtTable 16 Compounds of the formula I in which XS and R 3 denote nC 3 H 7 and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row of Table A.
Tabelle 17Table 17
Verbindungen der Formel I, in denen X S und R3 CH(CH3)2 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile der Tabelle A ent- spricht Tabelle 18Compounds of the formula I in which X is S and R 3 is CH (CH 3 ) 2 and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row of Table A. Table 18
Verbindungen der Formel I, in denen X S und R3 n-C4H9 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which XS and R 3 denote nC 4 H 9 and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row of Table A.
Tabelle 19Table 19
Verbindungen der Formel I, in denen X S und R3 CH2CH=CH2 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S and R 3 is CH 2 CH = CH 2 and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row of Table A.
Tabelle 20Table 20
Verbindungen der Formel I, in denen X S und R3 CH2C≡CH bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S and R 3 is CH 2 C≡CH and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row of Table A.
Tabelle 21Table 21
Verbindungen der Formel I, in denen X S und R3 CH2CN bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S and R 3 is CH 2 CN and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row of Table A.
Tabelle 22Table 22
Verbindungen der Formel I, in denen X S und R3 CH2CF3 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S and R 3 is CH 2 CF 3 and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row of Table A.
Tabelle 23Table 23
Verbindungen der Formel I, in denen X S und R3 CH2CHF2 bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which X is S and R 3 is CH 2 CHF 2 and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row of Table A.
Tabelle 24Table 24
Verbindungen der Formel I, in denen X S und R3 CH2CeHs bedeuten und die Kombination von R1, R5 und (R6)n für eine Verbindung jeweils einer Zeile der Tabelle A entsprichtCompounds of the formula I in which XS and R 3 are CH 2 CeHs and the combination of R 1 , R 5 and (R 6 ) n for each compound corresponds to one row of Table A.
Tabelle ATable A
Verbindungen der Formel I, welche der Formel I.A entsprechen, in der Rb1 und Rb2 jeweils für Wasserstoff steht (Formel I. AA)Compounds of the formula I which correspond to the formula IA, in which R b1 and R b2 are each hydrogen (Formula I. AA)
Die Verbindungen I und deren landwirtschaftlich brauchbaren Salze eignen sich - sowohl als Isomerengemische als auch in Form der reinen Isomeren - als Herbizide. Sie eignen sich als solche oder als entsprechend formuliertes Mittel. Die herbiziden Mittel, die die Verbindung I, insbesondere die bevorzugten Ausgestaltungen davon, enthalten, bekämpfen Pflanzenwuchs auf Nichtkulturflächen sehr gut, besonders bei hohen Aufwandmengen. In Kulturen wie Weizen, Reis, Mais, Soja und Baumwolle wirken sie gegen Unkräuter und Schadgräser, ohne die Kulturpflanzen nennenswert zu schädigen. Dieser Effekt tritt vor allem bei niedrigen Aufwandmengen auf.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.
In Abhängigkeit von der jeweiligen Applikationsmethode können die Verbindungen I, insbesondere die bevorzugten Ausgestaltungen davon, bzw. sie enthaltende Mittel noch in einer weiteren Zahl von Kulturpflanzen zur Beseitigung unerwünschter Pflanzen eingesetzt werden. In Betracht kommen beispielsweise folgende Kulturen: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, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena sati- va, Beta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Brassica oleracea, Brassica nigra, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus Ii- mon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea liberica), Cucumis sa- tivus, Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgäre, Humulus lupulus, Ipomoea batatas, Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec, Manihot esculenta, Medicago sativa, Musa spec, Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec, Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis und prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Seeale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (s. vulgäre), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.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, sea ale cereale, Sinapis alba, Solanum tuberosum, Sorghum bicolor (see vulgaris), Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticale, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.
Der Begriff Kulturpflanzen schließt auch solche ein, die durch Züchtung, Mutagenese oder gentechnische Methoden verändert wurden. Gentechnisch veränderte Pflanzen sind Pflanzen, deren genetisches Material in einer Weise verändert worden ist, wie sie unter natürlichen Bedingungen durch Kreuzen, Mutationen oder natürliche Rekombination (d.h. Neuzusammenstellung der Erbinformation) nicht vorkommt. Dabei werden in der Regel ein oder mehrere Gene in das Erbgut der Pflanze integriert, um die Eigenschaften der Pflanze zu verbessern.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.
Der Begriff Kulturpflanzen umfasst somit auch Pflanzen, die durch züchterische und gentechnische Maßnahmen eine Toleranz gegen bestimmter Herbizidklassen, wie Hydroxyphenylpyruvat-Dioxygenase (HPPD)-Inhibitoren, Acetolactat-Synthase (ALS)- Inhibitoren, wie z. B. Sulfonylharnstoffe (EP-A 257 993, US 5,013,659) oder Imidazoli- none (siehe z. B. US 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), Enolpyruvylshikimat-3-Phosphat- Synthase (EPSPS)-lnhibitoren wie z. B. Glyphosat (siehe z. B. WO 92/00377), Gluta- minsynthetase (GS)-lnhibitoren wie z. B. Glufosinat (siehe z. B. EP-A 242 236, EP-A 242 246) oder Oxynil-Herbizide (siehe z. B. US 5,559,024) erworben haben.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).
Mit Hilfe klassischer Züchtungsmethoden (Mutagenese) wurden zahlreiche Kulturpflanzen, z. B. Clearfield®-Raps, erzeugt, die eine Toleranz gegen Imidazolinone, z. B. Imazamox, haben. Mit Hilfe gentechnischer Methoden wurden Kulturpflanzen, wie So- ja, Baumwolle, Mais, Rüben und Raps, erzeugt, die resistent gegen Glyphosat oder Glufosinat sind, erzeugt, welche unter den Handelsnamen RoudupReady® (Glyphosat) und Liberty Link® (Glufosinat) erhältlich sind.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 Crop plants were as solar yes, produces cotton, corn, beet and oilseed rape, against glyphosate or glufosinate resistant, produced under the trade name RoudupReady ® (glyphosate) and Liberty Link ® (glufosinate) have ,
Der Begriff Kulturpflanzen umfasst somit auch Pflanzen, die mit Hilfe gentechnischer Maßnahmen ein oder mehrere Toxine, z. B. solche aus dem Bakterienstamm Bacillus ssp., produzieren. Toxine, die durch solche gentechnisch veränderten Pflanzen hergestellt werden, umfassen z. B. insektizide Proteine von Bacillus spp., insbesondere von B. thuringiensis, wie die Endotoxine CrylAb, CrylAc, Cryl F, Cry1 Fa2, Cry2Ab, Cry3A, Cry3Bb1 , Cry9c, Cry34Ab1 oder Cry35Ab1 ; oder vegetative insektizide Proteine (VIPs), z. B. VIP1 , VIP2, VIP3, oder VIP3A; insektizide Proteine von Nematoden- kolonisierenden Bakterien, z. B. Photorhabdus spp. oder Xenorhabdus spp.; Toxine aus tierischen Organismen, z. B. Wepsen,-, Spinnen- oder Skorpionstoxine; pilzliche Toxine, z. B. aus Streptomyceten; pflanzliche Lektine, z. B. aus Erbse oder Gerste; Agglutinine; Proteinase-Inhibitoren, z. B. Trypsin-Inhibitoren, Serinprotease-Inhibitoren, Patatin, Cystatin oder Papain-Inhibitoren; Ribosomen-inaktivierende Proteine (RIPs), z. B. Ricin, Mais-RIP, Abrin, Luffin, Saporin oder Bryodin; Steroid-metabolisierendeThe 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
Enzyme, z. B. 3-Hydroxysteroid-Oxidase, Ecdysteroid-IDP-Glycosyl-Transferase, Cho- lesterinoxidase, Ecdyson-Inhibitoren oder HMG-CoA-Reduktase; lonenkanalblocker, z. B. Inhibitoren von Natrium- oder Calziumkanälen; Juvenilhormon-Esterase; Rezeptoren für das diuretischen Hormon (Helicokininrezeptoren); Stilbensynthase, Bibenzyl- synthase, Chitinasen und Glucanasen. Diese Toxine können in den Pflanzen auch als Prätoxine, Hybridproteine, verkürzte oder anderweitig modfizierte Proteine produziert werden. Hybridproteine zeichnen sich durch eine neue Kombination von verschiedenen Proteindomänen aus (siehe z. B. WO 2002/015701). Weitere Besipiele für derartige Toxine oder gentechnisch veränderte Pflanzen, die diese Toxine produzieren sind in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073 offenbart. Die Methoden zur Herstellung dieser gentechnisch veränderten Pflanzen sind dem Fachmann bekannt und z. B. in den oben erwähnten Publikationen dargelegt. Zahlreiche der zuvor genannten Toxine verleihen den Pflanzen, die diese produzieren, eine Toleranz gegen Schädlinge aus allen taxo- nomischen Arthropodenklassen, insbesondere gegen Käfer (Coeleropta), Zweiflügler (Diptera) und Schmetterlinge (Lepidoptera) und gegen Nematoden (Nematoda). Gentechnisch veränderte Pflanzen, die ein oder mehrere Gene, die für insektizide Toxine kodieren, produzieren sind z. B. in den oben erwähnten Publikationen beschrieben und zum Teil kommerziell erhältlich, wie z. B. YieldGard® (Maissorten, die das Toxin CrylAb produzieren), YieldGard® Plus (Maissorten, die die Toxine CrylAb und Cry3Bb1 produzieren), Starlink® (Maissorten, die das Toxin Cry9c produzieren), Herculex® RW (Maissorten, die die Toxine Cry34Ab1 , Cry35Ab1 und das EnzymEnzymes, e.g. 3-hydroxysteroid oxidase, ecdysteroid IDP glycosyltransferase, cholesterol oxidase, ecdysone inhibitors or HMG-CoA reductase; ion channel blockers, z. 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 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), Herculex ® RW (corn cultivars toxins which Cry34Ab1, Cry35Ab1 and the enzyme
Phosphinothricin-N-Acetyltransferase [PAT] produzieren); NuCOTN® 33B (Baumwollsorten, die das Toxin CrylAc produzieren), Bollgard® I (Baumwollsorten, die das Toxin CrylAc produzieren), Bollgard® Il (Baumwollsorten, die die Toxine CrylAc und Cry2Ab2 produzieren); VIPCOT® (Baumwollsorten, die ein VIP-Toxin produzieren); NewLeaf® (Kartoffelsorten, die das Toxin Cry3A produzieren); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt11 (z. B. Agrisure® CB) und Bt176 von Syngenta Seeds SAS, Frankreich, (Maissorten, die das Toxin CrylAb und das PAT-Enyzm produzieren), MIR604 von Syngenta Seeds SAS, Frankreich (Maissorten, die ein modifizierte Version des Toxins Cry3A produzieren, siehe hierzu WO 03/018810), MON 863 von Monsanto Europe S.A., Belgien (Maissorten, die das Toxin Cry3Bb1 produzieren), IPC 531 von Monsanto Europe S.A., Belgien (Baumwollsorten, die eine modifizierte Version des Toxins CrylAc produzieren) und 1507 von Pioneer Overseas Corporation, Belgien (Maissorten, die das Toxin Cryl F und das PAT-Enyzm produzieren). Der Begriff Kulturpflanzen umfasst somit auch Pflanzen, die mit Hilfe gentechnischer Maßnahmen ein oder mehrere Proteine produzieren, die eine erhöhte Resistenz oder Widerstandfähigkeit gegen bakterielle, virale oder pilzliche Pathogene bewirken, wie z. B. sogenannte Pathogenesis-related-Proteine (PR-Proteine, siehe EP-A 392 225), Resistenzproteine (z. B. Kartoffelsorten, die zwei Resistenzgene gegen Phytophthora infestans aus der mexikanischen Wildkartoffel Solanum bulbocastanum produzieren) oder T4-Lysozym (z. B. Kartoffelsorten, die durch die Produktion diese Proteins resistent gegen Bakterien wie Erwinia amylvora ist). Der Begriff Kulturpflanzen umfasst somit auch Pflanzen, deren Produktivität mit Hilfe gentechnischer Methoden verbessert wurde, indem z. B. die Ertragsfähigkeit (z. B. Biomasse, Kornertrag, Stärke-, Öl- oder Proteingehalt), die Toleranz gegenüber Trockenheit, Salz oder anderen begrenzenden Umweltfaktoren oder die Widerstandsfä- higkeit gegenüber Schädlingen und pilzlichen, bakteriellen und viralen Pathogenen gesteigert wird.Producing 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 ®, 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 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 (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, the productivity (eg biomass, grain yield, starch, oil or protein content), the tolerance to drought, salt or other limiting environmental factors, or the resistance to pests and fungal, bacterial and viral pathogens can be increased.
Der Begriff Kulturpflanzen umfasst auch Pflanzen, deren Inhaltsstoffe insbesondere zur Verbesserung der menschlichen oder tierischen Ernährung mit Hilfe gentechnischer Methoden verändert wurden, indem z. B. Ölpflanzen gesundheitsfördernde lang- kettige Omega-3-Fettsäuren oder einfach ungesättigte Omega-9-Fettsäuren (z. B. Ne- xera®-Raps) produzieren.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).
Der Begriff Kulturpflanzen umfasst auch Pflanzen, die zur verbesserten Produktion von Rohstoffen mit Hilfe gentechnischer Methoden verändert wurden, indem z. B. der Amylopektin-Gehalt von Kartoffeln (Amflora®-Kartoffel) erhöht wurde. Des Weiteren wurde gefunden, dass die Verbindungen der Formel I auch zur Defoli- ation und/oder Desikkation von Pflanzenteilen geeignet ist, wofür Kulturpflanzen wie Baumwolle, Kartoffel, Raps, Sonnenblume, Sojabohne oder Ackerbohnen, insbesondere Baumwolle, in Betracht kommen. Diesbezüglich wurden Mittel zur Desikkation und /oder Defoliation von Pflanzen, Verfahren zur Herstellung dieser Mittel und Verfahren zur Desikkation und/oder Defoliation von Pflanzen mit der Verbindungen der Formel I gefunden.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.
Als Desikkantien eignen sich die Verbindungen der Formel I insbesondere zur Austrocknung der oberirdischen Teile von Kulturpflanzen wie Kartoffel, Raps, Sonnenblume und Sojabohne aber auch Getreide. Damit wird ein vollständig mechanisches Be- ernten dieser wichtigen Kulturpflanzen ermöglicht.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.
Von wirtschaftlichem Interesse ist ferner die Ernteerleichterung, die durch das zeitlich konzentrierte Abfallen oder Vermindern der Haftfestigkeit am Baum bei Zitrusfrüchten, Oliven oder bei anderen Arten und Sorten von Kern-, Stein- und Schalenobst er- möglicht wird. Derselbe Mechanismus, d.h., die Förderung der Ausbildung von Trenngewebe zwischen Frucht- oder Blatt- und Sprossteil der Pflanzen ist auch für ein gut kontrollierbares Entblättern von Nutzpflanzen, insbesondere Baumwolle, wesentlich. Außerdem führt die Verkürzung des Zeitintervalls, in dem die einzelnen Baumwollpflanzen reif werden, zu einer erhöhten Qualität der Faser nach der Ernte.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, 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.
Die Verbindungen I bzw. die sie enthaltenden herbiziden Mittel können beispielsweise in Form von direkt versprühbaren wäßrigen Lösungen, Pulvern, Suspensionen, auch hochprozentigen wäßrigen, öligen oder sonstigen Suspensionen oder Dispersionen, Emulsionen, Öldispersionen, Pasten, Stäubemitteln, Streumitteln oder Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen, Gießen oder Behandlung des Saatgutes bzw. Mischen mit dem Saatgut angewendet werden. Die Anwendungsfor- men richten sich nach den Verwendungszwecken; sie sollten in jedem Fall möglichst die feinste Verteilung der erfindungsgemäßen Wirkstoffe gewährleisten.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 application form depending on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.
Die herbiziden Mittel enthalten eine herbizid wirksame Menge mindestens einer Verbindung der Formel I oder eines landwirtschaftlich brauchbaren Salzes von I und für die Formulierung von Pflanzenschutzmitteln übliche Hilfsstoffe.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.
Beispiele für die Formulierung von Pflanzenschutzmitteln übliche Hilfsmittel sind i- nerte Hilfsstoffe, feste Trägerstoffe, oberflächenaktive Stoffe (wie Dispergiermittel Schutzkolloide, Emulgatoren, Netzmittel und Haftmittel), organische und anorganische Verdicker, Bakterizide, Frostschutzmittel, Entschäumer ggf. Farbstoffe und für Saatgut- formulierungen Kleber.Examples of the Formulation of Pesticides Commonly used auxiliaries include 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 ,
Beispiele für Verdicker (d.h. Verbindungen, die der Formulierung ein modifiziertes Fließverhalten verleihen, d.h. hohe Viskosität im Ruhezustand und niedrige Viskosität im bewegten Zustand) sind Polysaccharide wie Xanthan Gum (Kelzan® der Fa. Kelco), Rhodopol® 23 (Rhone Poulenc) oder Veegum® (Firma R. T. Vanderbilt) sowie organi- sehe und anorganische Schichtmineralienwie Attaclay® (Firma Engelhardt).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).
Beispiele für Antischaummittel sind Silikonemulsionen (wie z.Bsp. Silikon® SRE, Firma Wacker oder Rhodorsil® der Firma Rhodia ), langkettige Alkohole, Fettsäuren, Salze von Fettsäuren, fluororganische Verbindungen und deren Gemische.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.
Bakterizide können zur Stabilisierung der wäßrigen Herbizid-Formulierung zugesetzt werden. Beispiele für Bakterizide sind Bakterizide basierend auf Diclorophen und Ben- zylalkoholhemiformal (Proxel® der Fa. ICI oder Acticide® RS der Fa. Thor Chemie und Kathon® MK der Firma Rohm & Haas) sowie Isothiazolinonderivaten wie Alkylisothia- zolinonen und Benzisothiazolinonen (Acticide MBS der Fa. Thor Chemie)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)
Beispiele für Frostschutzmittel sind Ethylenglycol, Propylenglycol, Harnstoff oder Glycerin.Examples of antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol.
Beispiele für Farbmittel sind sowohl in Wasser wenig lösliche Pigmente als auch in Wasser lösliche Farbstoffe. Als Beispiele genannt seien die unter den Bezeichnungen Rhodamin B, Cl. Pigment Red 112 und Cl. Solvent Red 1 bekannten Farbstoffe, sowie pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pig- ment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, 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, aeid red 51 , aeid red 52, aeid red 14, aeid blue 9, aeid yellow 23, basic red 10, basic red 108. Beispiele für Kleber sind Polyvinylpyrrolidon, Polyvinylacetat, Polyvinylalkohol undExamples 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, aeid red 51, aeid red 52, aeid red 14, aeid blue 9, aeid yellow 23, basic red 10, basic red 108. Examples of adhesives are polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol and
Tylose.Tylose.
Als inerte Zusatzstoffe kommen beispielsweise in Betracht: Mineralölfraktionen von mittlerem bis hohem Siedepunkt, wie Kerosin oder Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Paraffin, Tetrahydronaphthalin, alkylierte Naphthaline oder deren Derivate, alkylierte Benzole oder deren Derivate, Alkohole wie Methanol, Ethanol, Propanol, Butanol, Cyclohexanol, Ketone wie Cycloh- exanon oder stark polare Lösungsmittel, z. B. Amine wie N-Methylpyrrolidon oder Wasser.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, for example 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.
Feste Trägerstoffe sind Mineralerden wie Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Trägerstoffe. Als oberflächenaktive Stoffe (Adjuvantien, Netz-, Haft-, Dispergier- sowie Emulgiermittel) kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäu- ren, z.B. Ligninsulfonsäuren (z.B. Borrespers-Typen, Borregaard), Phenolsulfonsäuren, Naphthalinsulfonsäuren (Morwet-Typen, Akzo Nobel) und Dibutylnaphthalinsulfonsäure (Nekal-Typen, BASF SE), sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Laurylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octa- decanolen sowie von Fettalkoholglykolether, Kondensationsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxyethylen- octylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tribu- tylphenylpolyglykolether, Alkylarylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethy- lenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylenalkylether oder Polyoxy- propylenalkylether, Laurylalkoholpolyglykoletheracetat, Sorbitester, Lignin-Sulfitablau- gen sowie Proteine, denaturierte Proteine, Polysaccharide (z.B. Methylcellulose), hydrophob modifizierte Stärken, Polyvinylalkohol (Mowiol typen Clariant), Polycarboxylate (BASF SE, Sokalan-Typen), Polyalkoxylate, Polyvinylamin (BASF SE, Lupamin-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, adhesion, dispersing and emulsifying agents), the alkali, alkaline earth, 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 types Clariant), polycarboxylates (BASF SE, Sokalan types), polyalkoxylates, polyvinylamine (BASF SE, lupamin
Typen), Polyethylenimin (BASF SE, Lupasol-Typen) , Polyvinylpyrrolidon und deren Copolymere in Betracht.Types), polyethylenimine (BASF SE, Lupasol types), polyvinylpyrrolidone and copolymers thereof.
Pulver-, Streu- und Stäubemittel können durch Mischen oder gemeinsames Vermählen der wirksamen Substanzen mit einem festen Trägerstoff hergestellt werden. Granulate, z.B. Umhüllungs-, Imprägnierungs- und Homogengranulate können durchPowders, 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 by
Bindung der Wirkstoffe an feste Trägerstoffe hergestellt werden.Binding of the active ingredients to solid carriers are produced.
Wässrige Anwendungsformen können aus Emulsionskonzentraten, Suspensionen, Pasten, netzbaren Pulvern oder wasserdispergierbaren Granulaten durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pasten oder Öldispersionen können die Verbindungen der Formel I oder Ia als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermittel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz, Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind. Die Konzentrationen der Verbindungen der Formel I in den anwendungsfertigen Zubereitungen können in weiten Bereichen variiert werden. Die Formulierungen enthalten im Allgemeinen 0,001 bis 98 Gew.-%, vorzugsweise 0,01 bis 95 Gew.-%, mindestens eines Wirkstoffs. Die Wirkstoffe werden dabei in einer Reinheit von 90% bis 100%, vorzugsweise 95% bis 100% (nach NMR-Spektrum) eingesetzt.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, 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).
Die erfindungsgemäßen Verbindungen I können beispielsweise wie folgt formuliert werden:The compounds I according to the invention can be formulated, for example, as follows:
1. Produkte zur Verdünnung in Wasser A Wasserlösliche Konzentrate1. Products for dilution in water A Water-soluble concentrates
10 Gew.-Teile Wirkstoff werden mit 90 Gew.-Teilen Wasser oder einem wasserlöslichen Lösungsmittel gelöst. Alternativ werden Netzmittel oder andere Hilfsmittel zuge- fügt. Bei der Verdünnung in Wasser löst sich der Wirkstoff. Man erhält auf diese Weise eine Formulierung mit 10 Gew.-% Wirkstoffgehalt.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 Dispergierbare KonzentrateB Dispersible concentrates
20 Gew.-Teile Wirkstoff werden in 70 Gew.-Teilen Cyclohexanon unter Zusatz von 10 Gew.-Teilen eines Dispergiermittels z.B. Polyvinylpyrrolidon gelöst. Bei Verdünnung in Wasser ergibt sich eine Dispersion. Der Wirkstoffgehalt beträgt 20 Gew.-%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 Emulgierbare KonzentrateC Emulsifiable concentrates
15 Gew.-Teile Wirkstoff werden in 75 Gew.-Teilen eines organisches Lösungsmittels (z.B. Alkylaromaten)-unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxy- lat (jeweils 5 Gew.-Teile) gelöst. Bei der Verdünnung in Wasser ergibt sich eine Emul- sion. Die Formulierung hat 15 Gew.-% Wirkstoffgehalt.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 EmulsionenD emulsions
25 Gew.-Teile Wirkstoff werden in 35 Gew.-Teilen eines organisches Lösungsmittels (z.B. Alkylaromaten) unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxy- lat (jeweils 5 Gew.-Teile) gelöst. Diese Mischung wird mittels einer Emulgiermaschine (z.B. Ultraturax) in 30 Gew.Teile Wasser gegeben und zu einer homogenen Emulsion gebracht. Bei der Verdünnung in Wasser ergibt sich eine Emulsion. Die Formulierung hat einen Wirkstoffgehalt von 25 Gew.-%.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 SuspensionenE suspensions
20 Gew.-Teile Wirkstoff werden unter Zusatz von 10 Gew.-Teilen Dispergier- und Netzmitteln und 70 Gew.-Teilen Wasser oder einem organischen Lösungsmittel in einer Rührwerkskugelmühle zu einer feinen Wirkstoffsuspension zerkleinert. Bei der Verdünnung in Wasser ergibt sich eine stabile Suspension des Wirkstoffs. Der Wirkstoffgehalt in der Formulierung beträgt 20 Gew.-% .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 Wasserdispergierbare und wasserlösliche Granulate 50 Gew.-Teile Wirkstoff werden unter Zusatz von 50 Gew-Teilen Dispergier- und Netzmitteln fein gemahlen und mittels technischer Geräte (z.B. Extrusion, Sprühturm, Wirbelschicht) als wasserdispergierbare oder wasserlösliche Granulate hergestellt. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs. Die Formulierung hat einen Wirkstoffgehalt von 50 Gew.-%. G Wasserdispergierbare und wasserlösliche PulverF 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 Gew.-Teile Wirkstoff werden unter Zusatz von 25 Gew.-Teilen Dispergier- und Netzmitteln sowie Kieselsäuregel in einer Rotor-Strator Mühle vermählen. Bei der Verdün- nung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs. Der Wirkstoffgehalt der Formulierung beträgt 75 Gew.-%.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 GelformulierungenH gel formulations
In einer Kugelmühle werden 20 Gew.-Teile Wirkstoff, 10 Gew.-Teile Dispergiermittel, 1 Gew.-Teil Geliermittel und 70 Gew.-Teile Wasser oder eines organischen Lösungsmittels zu einer feinen Suspension vermählen. Bei der Verdünnung mit Wasser ergibt sich eine stabile Suspension mit 20 Gew.-% Wirkstoffgehalt.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. Produkte für die Direktapplikation I Stäube2. Products for direct application I dusts
5 Gew.-Teile Wirkstoff werden fein gemahlen und mit 95 Gew.-Teilen feinteiligem Kaolin innig vermischt. Man erhält dadurch ein Stäubemittel mit 5 Gew.-% Wirkstoffgehalt.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 Granulate (GR, FG, GG, MG)J Granules (GR, FG, GG, MG)
0,5 Gew-Teile Wirkstoff werden fein gemahlen und mit 99,5 Gewichtsteilen Träger- Stoffe verbunden. Gängige Verfahren sind dabei die Extrusion, die Sprühtrocknung oder die Wirbelschicht. Man erhält dadurch ein Granulat für die Direktapplikation mit 0,5 Gew.-% Wirkstoffgehalt.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- Lösungen (UL)K ULV solutions (UL)
10 Gew.-Teile Wirkstoff werden in 90 Gew.-Teilen eines organischen Lösungsmittels z.B. XyIoI gelöst. Dadurch erhält man ein Produkt für die Direktapplikation mit 10 Gew.- % Wirkstoffgehalt.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.
Die Applikation der Verbindungen I oder der sie enthaltenden herbiziden Mittel kann im Vorauflauf-, im Nachauflaufverfahren oder zusammen mit dem Saatgut einer Kultur- pflanze erfolgen. Es besteht auch die Möglichkeit, die herbiziden Mittel bzw. Wirkstoffe dadurch zu applizieren, dass mit den herbiziden Mitteln bzw. Wirkstoffen vorbehandeltes Saatgut einer Kulturpflanze ausgebracht wird. Sind die Wirkstoffe für gewisse Kulturpflanzen weniger verträglich, so können Ausbringungstechniken angewandt werden, bei welchen die herbiziden Mittel mit Hilfe der Spritzgeräte so gespritzt werden, daß die Blätter der empfindlichen Kulturpflanzen nach Möglichkeit nicht getroffen werden, während die Wirkstoffe auf die Blätter darunter wachsender unerwünschter Pflanzen oder die unbedeckte Bodenfläche gelangen (post-directed, lay-by).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 einer weiteren Ausführungsform kann die Applikation der Verbindungen der For- mel I bzw. der herbiziden Mittel durch Behandlung von Saatgut erfolgen.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.
Die Behandlung von Saatgut umfasst im Wesentlichen alle dem Fachmann geläufigen Techniken (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping, und seed pelleting) basierend auf den erfindungsgemäßen Verbindungen der Formel I bzw. daraus herge- stellten Mitteln. Hierbei können die herbiziden Mittel verdünnt oder unverdünnt aufgetragen werden. Der Begriff Saatgut umfasst Saatgut aller Arten, wie z.B. Körner, Samen, Früchte, Knollen, Stecklinge und ähnliche Formen. Bevorzugt beschreibt der Begriff Saatgut hier Körner und Samen.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.
Als Saatgut kann Saatgut der oben erwähnten Nutzpflanzen aber auch das Saatgut transgener oder durch herkömmliche Züchtungsmethoden erhaltener Pflanzen eingesetzt werden.Seeds of the abovementioned crops but also the seeds of transgenic or obtained by conventional breeding methods plants can be used as seeds.
Die Aufwandmengen an Wirkstoff betragen je nach Bekämpfungsziel, Jahreszeit, Zielpflanzen und Wachstumsstadium 0.001 bis 3.0, vorzugsweise 0.01 bis 1.0 kg/ha aktive Substanz (a. S.). Zur Saatgutbehandlung werden die Verbindungen I üblicherweise in Mengen von 0,001 bis 10 kg pro 100 kg Saatgut eingesetzt.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.
Es kann auch von Vorteil sein, die Verbindungen der Formel I in Kombination mit Safenern zu verwenden. Safener sind chemische Verbindungen, die Schaden an Nutz- pflanzen verhindern oder reduzieren, ohne die herbizide Wirkung der Verbindungen der Formel I auf unerwünschte Pflanzen wesentlich zu beeinflussen. Sie können sowohl vor der Aussaat (beispielsweise bei Saatgutbehandlungen, bei Stecklingen oder Setzlingen) als auch im Vor- oder Nachauflauf der Nutzpflanze verwendet werden. Die Safener und die Verbindungen der Formel I können gleichzeitig oder nacheinander verwendet werden. Geeignete Safener sind beispielsweise (Chinolin-δ-oxy)essig- säuren, 1-Phenyl-5-haloalkyl-1 H-1 ,2,4-triazol-3-carbonsäuren, 1-Phenyl-4,5-dihydro-5- alkyl-1 H-pyrazol-3,5-dicarbonsäuren, 4,5-Dihydro-5,5-diaryl-3-isoxazolcarbonsäuren, Dichloroacetamide, alpha-Oximinophenylacetonitrile, Acetophenonoxime, 4,6-Dihalo-2- phenylpyrimidine, N-[[4-(Aminocarbonyl)phenyl]sulfonyl]-2-benzoesäureamide, 1 ,8- Naphthalsäureanhydrid, 2-Halo-4-(haloalkyl)-5-thiazolcarbonsäuren, Phosphorthiolate und N-Alkyl-O-phenylcarbamate sowie ihre landwirtschaftlich brauchbaren Salze, und vorausgesetzt sie haben eine Säurefunktion, ihre landwirtschaftlich brauchbaren Derivate, wie Amide, Ester und Thioester. Zur Verbreiterung des Wirkungsspektrums und zur Erzielung synergistischer Effekte können die Verbindungen der Formel I mit zahlreichen Vertretern anderer herbizider oder wachstumsregulierender Wirkstoffgruppen oder mit Safenern gemischt und gemeinsam ausgebracht werden. Beispielsweise kommen als Mischungspartner 1 ,2,4- Thiadiazole, 1 ,3,4-Thiadiazole, Amide, Aminophosphorsäure und deren Derivate, Ami- notriazole, Anilide, Aryloxy-/Heteroaryloxyalkansäuren und deren Derivate, Benzoesäu- re und deren Derivate, Benzothiadiazinone, 2-(Hetaroyl/Aroyl)-1 ,3-cyclohexandione, Heteroaryl-Aryl-Ketone, Benzylisoxazolidinone, meta-CF3-Phenylderivate, Carbamate, Chinolincarbonsäure und deren Derivate, Chloracetanilide, Cyclohexenonoximetherde- rivate, Diazine, Dichlorpropionsäure und deren Derivate, Dihydrobenzofurane, Dihydro- furan-3-one, Dinitroaniline, Dinitrophenole, Diphenylether, Dipyridyle, Halogencarbon- säuren und deren Derivate, Harnstoffe, 3-Phenyluracile, Imidazole, Imidazolinone, N- Phenyl-3,4,5,6-tetrahydrophthalimide, Oxadiazole, Oxirane, Phenole, Aryloxy- und He- teroaryloxyphenoxypropionsäureester, Phenylessigsäure und deren Derivate, 2-Phe- nylpropionsäure und deren Derivate, Pyrazole, Phenylpyrazole, Pyridazine, Pyridincar- bonsäure und deren Derivate, Pyrimidylether, Sulfonamide, Sulfonylharnstoffe, Triazi- ne, Triazinone, Triazolinone, Triazolcarboxamide, Uracile sowie Phenylpyrazoline und Isoxazoline und deren Derivate in Betracht. Außerdem kann es von Nutzen sein, die Verbindungen I allein oder in Kombination mit anderen Herbiziden oder auch noch mit weiteren Pflanzenschutzmitteln gemischt, gemeinsam auszubringen, beispielsweise mit Mitteln zur Bekämpfung von Schädlingen oder phytopathogenen Pilzen bzw. Bakterien. Von Interesse ist ferner die Mischbarkeit mit Mineralsalzlösungen, welche zur Behebung von Ernährungs- und Spurenelement- mangeln eingesetzt werden. Es können auch weitere Additve wie nicht phytotoxische Öle und Ölkonzentrate zugesetzt werden.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.
Beispiele für Herbizide, die in Kombination mit den Pyridinverbindungen der Formel I gemäß der vorliegenden Erfindung verwendet werden können, sind: b1) aus der Gruppe der Lipid-Biosynthese-Inhibitoren: Alloxydim, Alloxydim-natrium, Butroxydim, Clethodim, Clodinafop, Clodinafop-propar- gyl, Cycloxydim, Cyhalofop, Cyhalofop-butyl, Diclofop, Diclofop-methyl, Fenoxaprop, Fenoxaprop-ethyl, Fenoxaprop-P, Fenoxaprop-P-ethyl, Fluazifop, Fluazifop-butyl, FIu- azifop-P, Fluazifop-P-butyl, Haloxyfop, Haloxyfop-methyl, Haloxyfop-P, Haloxyfop-P- methyl, Metamifop, Pinoxaden, Profoxydim, Propaquizafop, Quizalofop, Quizalofop- ethyl, Quizalofop-tefuryl, Quizalofop-P, Quizalofop-P-ethyl, Quizalofop-P-tefuryl,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, Benfuresat, Butylat, Cycloat, Dalapon, Dime- piperat, EPTC, Esprocarb, Ethofumesat, Flupropanat, Molinat, Orbencarb, Pebulat, Prosulfocarb, TCA, Thiobencarb, Tiocarbazil, Triallat und Vernolat; b2) aus der Gruppe der ALS-Inhibitoren: Amidosulfuron, Azimsulfuron, Bensulfuron, Bensulfuron-methyl, Bispyribac, Bispyribac- natrium, Chlorimuron, Chlorimuron-ethyl, Chlorsulfuron, Cinosulfuron, Cloransulam, Cloransulam-methyl, Cyclosulfamuron, Diclosulam, Ethametsulfuron, Ethametsulfuron- methyl, Ethoxysulfuron, Flazasulfuron, Florasulam, Flucarbazon, Flucarbazon-natrium, Flucetosulfuron, Flumetsulam, Flupyrsulfuron, Flupyrsulfuron-methyl-natrium, Foram- sulfuron, Halosulfuron, Halosulfuron-methyl, Imazamethabenz, Imazamethabenz- methyl, Imazamox, Imazapic, Imazapyr, Imazaquin, Imazethapyr, Imazosulfuron, lodo- sulfuron, lodosulfuron-methyl-natrium, Mesosulfuron, Metosulam, Metsulfuron, Metsul- furon-methyl, Nicosulfuron, Orthosulfamuron, Oxasulfuron, Penoxsulam, Primisulfuron, Primisulfuron-methyl, Propoxycarbazon, Propoxycarbazon-natrium, Prosulfuron, Pyra- zosulfuron, Pyrazosulfuron-ethyl, Pyribenzoxim, Pyrimisulfan, Pyriftalid, Pyriminobac, Pyriminobac-methyl, Pyrithiobac, Pyrithiobac-natrium, Pyroxsulam, Rimsulfuron, SuI- fometuron, Sulfometuron-methyl, Sulfosulfuron, Thiencarbazon, Thiencarbazon-methyl, Thifensulfuron, Thifensulfuron-methyl, Triasulfuron, Tribenuron, Tribenuron-methyl, Trifloxysulfuron, Triflusulfuron, Triflusulfuron-methyl und Tritosulfuron; b3) aus der Gruppe der Photosynthese-Inhibitoren: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, Amicarbazon, Atrazin, Bentazon, Bentazon-natrium, Bromacil, Bromofeno- xim, Bromoxynil und seine Salze und Ester, Chlorobromuron, Chloridazon, Chlorotolu- ron, Chloroxuron, Cyanazin, Desmedipham, Desmetryn, Dimefuron, Dimethametryn, Diquat, Diquat-dibromid, Diuron, Fluometuron, Hexazinon, loxynil und seine Salze und Ester, Isoproturon, Isouron, Karbutilat, Lenacil, Linuron, Metamitron, Methabenzthiazu- ron, Metobenzuron, Metoxuron, Metribuzin, Monolinuron, Neburon, Paraquat, Para- quat-dichlorid, Paraquat-dimetilsulfat, Pentanochlor, Phenmedipham, Phenmedipham- ethyl, Prometon, Prometryn, Propanil, Propazin, Pyridafol, Pyridat, Siduron, Simazin, Simetryn, Tebuthiuron, Terbacil, Terbumeton, Terbuthylazin, Terbutryn, Thidiazuron und Trietazin; b4) aus der Gruppe der Protoporphyrinogen-IX-Oxidase-Inhibitoren: Acifluorfen, Acifluorfen-natrium, Azafenidin, Bencarbazon, Benzfendizon, Bifenox, Bu- tafenacil, Carfentrazon, Carfentrazon-ethyl, Chlomethoxyfen, Cinidon-ethyl, Fluazolat, Flufenpyr, Flufenpyr-ethyl, Flumiclorac, Flumiclorac-pentyl, Flumioxazin, Fluoroglyco- fen, Fluoroglycofen-ethyl, Fluthiacet, Fluthiacet-methyl, Fomesafen, Halosafen, Lacto- fen, Oxadiargyl, Oxadiazon, Oxyfluorfen, Pentoxazon, Profluazol, Pyraclonil, Pyraflu- fen, Pyraflufen-ethyl, Saflufenacil, Sulfentrazon, Thidiazimin, 2-Chlor-5-[3,6-dihydro-3- methyl-2,6-dioxo-4-(trifluormethyl)-1 (2H)-pyrimidinyl]-4-fluor-N-[(isopropyl)methylsulf- amoyl]benzamid (B-1 ; CAS 372137-35-4), [3-[2-Chlor-4-fluor-5-(1-methyl-6-trifluor- methyl-2,4-dioxo-1 ,2,3,4,-tetrahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]essigsäure- ethylester (B-2; CAS 353292-31-6), N-Ethyl-3-(2,6-dichlor-4-trifluormethylphenoxy)-5- methyl-1 H-pyrazol-1-carboxamid (B-3; CAS 452098-92-9), N-Tetrahydrofurfuryl-3-(2,6- dichlor-4-trifluormethylphenoxy)-5-methyl-1 H-pyrazol-1-carboxamid (B-4; CAS 915396- 43-9), N-Ethyl-3-(2-chlor-6-fluor-4-trifluormethylphenoxy)-5-methyl-1 H-pyrazol-1 -carb- oxamid (B-5; CAS 452099-05-7) und N-Tetrahydrofurfuryl-3-(2-chlor-6-fluor-4-trifluor- methylphenoxy)-5-methyl-1 H-pyrazol-1-carboxamid (B-6; CAS 45100-03-7); b5) aus der Gruppe der Bleacher-Herbizide: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, Amitrol, Beflubutamid, Benzobicyclon, Benzofenap, Clomazon, Diflufeni- can, Fluridon, Flurochloridon, Flurtamon, Isoxaflutol, Mesotrion, Norflurazon, Picolina- fen, Pyrasulfutol, Pyrazolynat, Pyrazoxyfen, Sulcotrion, Tefuryltrion, Tembotrion, Top- ramezon, 4-Hydroxy-3-[[2-[(2-methoxyethoxy)methyl]-6-(trifluormethyl)-3-pyridyl]car- bonyl]bicyclo[3.2.1]oct-3-en-2-one (B-7; CAS 352010-68-5) und 4-(3-Trifluormethyl- phenoxy)-2-(4-trifluormethylphenyl)pyrimidin (B-8; CAS 180608-33-7); b6) aus der Gruppe der EPSP-Synthase-lnhibitoren: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:
Glyphosat, Glyphosat-isopropylammonium und Glyphosat-trimesium (Sulfosat); b7) aus der Gruppe der Glutamin-Synthase-Inhibitoren: Bilanaphos (Bialaphos), Bilanaphos-natrium, Glufosinat und Glufosinat-ammonium; b8) aus der Gruppe der DHP-Synthase-Inhibitoren: Asulam; b9) aus der Gruppe der Mitose-Inhibitoren: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, Butralin, Carbetamid, Chlorpropham, Chlorthal, Chlorthal-dimethyl, Dinitramin, Dithiopyr, Ethalfluralin, FIu- chloralin, Oryzalin, Pendimethalin, Prodiamin, Propham, Propyzamid, Tebutam, Thia- zopyr und Trifluralin; b10) aus der Gruppe der VLCFA-lnhibitoren: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, Dimethanamid, Dimethenamid-P, Diphenamid, Fentrazamid, Flufenacet, Mefenacet, Metazachlor, Me- tolachlor, Metolachlor-S, Naproanilid, Napropamid, Pethoxamid, Piperophos, Pretila- 5 chlor, Propachlor, Propisochlor, Pyroxasulfon (KIH-485) und Thenylchlor;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;
Verbindungen der Formel 2:Compounds of the formula 2:
worin die Variablen folgende Bedeutungen haben: wherein the variables have the following meanings:
Y Phenyl oder 5- oder 6-gliedriges Heteroaryl wie eingangs definiert, welche durch0 eine bis drei Gruppen Raa substituiert sein können; R21, R22, R23, R24 H, Halogen, oder Ci-C4-Alkyl; X O oder NH; n 0 oder 1. 2 weisen insbesondere die folgenden Bedeutungen auf: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 wobei # die Bindung zu dem Molekülgerüst bedeutet; und 5 R21, R22, R23, R24 H, Cl, F oder CH3; R25 Halogen, d-C4-Alkyl oder Ci-C4-Haloalkyl; R26 Ci-C4-Alkyl; R27 Halogen, Ci-C4-Alkoxy oder Ci-C4-Haloalkoxy; R28 H, Halogen, CrC4- Alkyl, Ci-C4-Haloalkyl oder Ci-C4-Haloalkoxy; m 0, 1 , 2 oder 3; X Sauerstoff; n 0 oder 1.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.
R21 H; R22, R23 F; R24 H oder F; X Sauerstoff; n 0 oder 1 .R 21 H; R 22, R 23 F; R 24 H or F; X oxygen; n 0 or 1.
Besonders bevorzugte Verbindungen der Formel 2 sind:Particularly preferred compounds of the formula 2 are:
3-[5-(2,2-Difluor-ethoxy)-1 -methyl-3-trifluormethyl-1 H-pyrazol-4-ylmethansulfonyl]-4- fluor-5,5-dimethyl-4,5-dihydro-isoxazol (2-1 ); 3-{[5-(2,2-Difluor-ethoxy)-1 -methyl-3-tri-5 fluormethyl-1 H-pyrazol-4-yl]-fluor-methansulfonyl}-5,5-dimethyl-4,5-dihydro-isoxazol (2- 2); 4-(4-Fluor-5,5-dimethyl-4,5-dihydro-isoxazol-3-sulfonylmethyl)-2-methyl-5-trifluor- methyl-2H-[1 ,2,3]triazol (2-3); 4-[(5,5-Dimethyl-4,5-dihydro-isoxazol-3-sulfonyl)-fluor- methyl]-2-methyl-5-trifluormethyl-2H-[1 ,2,3]triazol (2-4); 4-(5,5-Dimethyl-4,5-dihydro- isoxazol-3-sulfonylmethyl)-2-methyl-5-trifluormethyl-2H-[1 ,2,3]triazol (2-5); 3-{[5-(2,2-0 Difluor-ethoxy)-1 -methyl-3-trifluormethyl-1 H-pyrazol-4-yl]-difluor-methansulfonyl}-5,5- dimethyl-4,5-dihydro-isoxazol (2-6); 4-[(5,5-Dimethyl-4,5-dihydro-isoxazol-3-sulfonyl)- difluor-methyl]-2-methyl-5-trifluormethyl-2H-[1 ,2,3]triazol (2-7); 3-{[5-(2,2-Difluor- ethoxy)-1 -methyl-3-trifluormethyl-1 H-pyrazol-4-yl]-difluor-methansulfonyl}-4-fluor-5,5- dimethyl-4,5-dihydro-isoxazol (2-8); 4-[Difluor-(4-fluor-5,5-dimethyl-4,5-dihydro- isoxazol-3-sulfonyl)-methyl]-2-methyl-5-trifluormethyl-2H-[1 ,2,3]triazol (2-9); b1 1) aus der Gruppe der Cellulose-Biosynthese-Inhibitoren: Chlorthiamid, Dichlobenil, Flupoxam und Isoxaben; b12) aus der Gruppe der Entkoppler-Herbizide: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 und DNOC und seine Salze; b13) aus der Gruppe der Auxin-Herbizide:Dinoseb, Dinoterb and DNOC and its salts; b13) from the group of auxin herbicides:
2,4-D und seine Salze und Ester, 2,4-DB und seine Salze und Ester, Aminopyralid und seine Salze wie Aminopyralid-tris(2-hydroxypropyl)ammonium und seine Ester, Benazolin, Benazolin-ethyl, Chloramben und seine Salze und Ester, Clomeprop, Clopy- ralid und seine Salze und Ester, Dicamba und seine Salze und Ester, Dichlorprop und seine Salze und Ester, Dichlorprop-P und seine Salze und Ester, Fluroxypyr, Fluroxy- pyr-butometyl, Fluroxypyr-meptyl, MCPA und seine Salze und Ester, MCPA-thioethyl, MCPB und seine Salze und Ester, Mecoprop und seine Salze und Ester, Mecoprop-P und seine Salze und Ester, Picloram und seine Salze und Ester, Quinclorac, Quinme- rac, TBA (2,3,6) und seine Salze und Ester, Triclopyr und seine Salze und Ester, und 5,6-Dichlor-2-cyclopropyl-4-pyrimidincarbonsäure (B-9; CAS 858956-08-8) und seine Salze und Ester; b14) aus der Gruppe der Auxin-Transport-Inhibitoren: Diflufenzopyr, Diflufenzopyr- natrium, Naptalam und Naptalam-natrium; b15) aus der Gruppe der sonstigen Herbizide: Bromobutid, Chlorflurenol, Chlor- flurenol-methyl, Cinmethylin, Cumyluron, Dalapon, Dazomet, Difenzoquat, Difenzo- quat-metilsulfate, Dimethipin, DSMA, Dymron, Endothal und seine Salze, Etobenzanid, Flamprop, Flamprop-isopropyl, Flamprop-methyl Flamprop-M-isopropyl, Flamprop-M- methyl, Flurenol, Flurenol-butyl, Flurprimidol, Fosamin, Fosamine-ammonium, Indano- fan, Maleinsäure-hydrazid, Mefluidid, Metam, Methylazid, Methylbromid, Methyl-dym- ron, Methyljodid. MSMA, Ölsäure, Oxaziclomefon, Pelargonsäure, Pyributicarb, Quino- clamin, Triaziflam, Tridiphan und 6-Chlor-3-(2-cyclopropyl-6-methylphenoxy)-4-pyrida- zinol (B-10; CAS 499223-49-3) und seine Salze und Ester. Beispiele für bevorzugte Safener C sind Benoxacor, Cloquintocet, Cyometrinil, Cy- prosulfamid, Dichlormid, Dicyclonon, Dietholate, Fenchlorazol, Fenclorim, Flurazol, FIu- xofenim, Furilazol, Isoxadifen, Mefenpyr, Mephenat, Naphthalsäureanhydrid, Oxabetri- nil, 4-(Dichloracetyl)-1-oxa-4-azaspiro[4.5]decan (B-1 1 ; MON4660, CAS 71526-07-3) und 2,2,5-Trimethyl-3-(dichloracetyl)-1 ,3-oxazolidin (B-12; R-29148, CAS 52836-31-4). Die Wirkstoffe der Gruppen b1 ) bis b15) und die Safener C sind bekannte Herbizide und Safener, siehe z. B. The Compendium of Pesticide Common Names (http://www.alanwood.net/pesticides/); B. Hock, C. Fedtke, R. R. Schmidt, Herbizide, Georg Thieme Verlag, Stuttgart 1995. Weitere herbizide Wirkstoffe sind aus WO 96/26202, WO 97/411 16, WO 97/41 117, WO 97/411 18, WO 01/83459 und WO 2008/074991 sowie aus W. Krämer et al. (ed.) "Modern Crop Protection Compounds", Vol. 1 , Wiley VCH, 2007 und der darin zitierten Literatur bekannt. Die Erfindung betrifft auch Zusammensetzungen in Form eines als 1 -Komponentenzusammensetzung formulierten Pflanzenschutzmittels, enthaltend eine Wirkstoffkombination, die wenigstens eine Pyridinverbindung der Formel I und wenigstens einen weiteren Wirkstoff, bevorzugt ausgewählt aus den Wirkstoffen der Gruppen b1 bis b15, und wenigstens einen festen oder flüssigen Träger und/oder eine oder mehrere grenzflächenaktive Substanzen und gewünschtenfalls einen oder mehrere für Pflanzenschutzmittel übliche weitere Hilfsstoffe.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 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 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.
Die Erfindung betrifft auch Zusammensetzungen in Form eines als 2-Komponenten- zusammensetzung formulierten Pflanzenschutzmittels, umfassend eine erste Kompo- nente, enthaltend wenigstens eine Pyridinverbindung der Formel I, einen festen oder flüssigen Träger und/oder eine oder mehrere grenzflächenaktive Substanzen, und eine zweite Komponente, enthaltend wenigstens einen weiteren Wirkstoff, ausgewählt aus den Wirkstoffen der Gruppen b1 bis b15, einem festen oder flüssigen Träger und/oder eine oder mehrere grenzflächenaktive Substanzen, wobei zusätzlich beide Komponen- ten auch weitere, für Pflanzenschutzmittel üblichen Hilfsmittel enthalten können.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 binären Zusammensetzungen, die wenigstens eine Verbindung der Formel I als Komponente A und wenigstens ein Herbizid B enthalten, liegt das Gewichtsverhältnis der Wirkstoffe A:B in der Regel im Bereich von 1 :1000 bis 1000:1 , vorzugsweise im Bereich von 1 :500 bis 500:1 , insbesondere im Bereich von 1 :250 bis 250:1 und besonders bevorzugt im Bereich von 1 :75 bis 75:1.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 binären Zusammensetzungen, die wenigstens eine Verbindung der Formel I als Komponente A und wenigstens einen Safener C enthalten, liegt das Gewichtsverhältnis der Wirkstoffe A:C in der Regel im Bereich von 1 :1000 bis 1000:1 , vorzugsweise im Bereich von 1 :500 bis 500:1 , insbesondere im Bereich von 1 :250 bis 250:1 und besonders bevorzugt im Bereich von 1 :75 bis 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 ternären Zusammensetzungen, die sowohl wenigstens eine Verbindung der Formel I als Komponente A, wenigstens ein Herbizid B und wenigstens einen Safener C enthalten, liegen die relativen Gewichtsanteile der Komponenten A:B in der Regel im Bereich von 1 :1000 bis 1000:1 , vorzugsweise im Bereich von 1 :500 bis 500:1 , insbesondere im Bereich von 1 :250 bis 250:1 und besonders bevorzugt im Bereich von 1 :75 bis 75:1 , das Gewichtsverhältnis der Komponente A:C in der Regel im Bereich von 1 :1000 bis 1000:1 , vorzugsweise im Bereich von 1 :500 bis 500:1 , insbesondere im Bereich von 1 :250 bis 250:1 und besonders bevorzugt im Bereich von 1 :75 bis 75:1 , und das Gewichtsverhältnis der Komponenten B:C in der Regel im Bereich von 1 :1000 bis 1000:1 , vorzugsweise im Bereich von 1 :500 bis 500:1 , insbesondere im Bereich von 1 :250 bis 250:1 und besonders bevorzugt im Bereich von 1 :75 bis 75:1. Vorzugsweise liegt das Gewichtsverhältnis der Komponenten A + B zur Komponente C im Bereich von 1 :500 bis 500:1 , insbesondere im Bereich von 1 :250 bis 250:1 und besonders bevorzugt im Bereich von 1 :75 bis 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.
Beispiele für besonders bevorzugte erfindungsgemäße Zusammensetzungen, enthaltend jeweils eine individualisierte Verbindung der Formel I und einen Mischungs- partner, bzw. eine Mischungspartnerkombination sind in der folgenden Tabelle B angegeben.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.
Einer weitere Ausgestaltung der Erfindung betrifft die in der Tabelle B aufgeführten Zusammensetzungen B-1 bis B-1235, wobei jeweils eine Zeile der Tabelle B einer her- biziden Zusammensetzung entspricht, umfassend eine in der vorliegenden Beschreibung individualisierten Verbindungen der Formel I (Komponente 1 ) und den jeweils in der betreffenden Zeile angegebenen weiteren Wirkstoff aus den Gruppen b1 ) bis b15) und/oder Safener C (Komponente 2). Die Wirkstoffe in den beschriebenen Zusammensetzungen liegen jeweils vorzugsweise in synergistisch wirksamen Mengen vor.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.
Die Verbindungen I und die erfindungsgemäßen Zusammensetzungen können auch eine pflanzenstärkende Wirkung aufweisen. Sie eigenen sich daher zu Mobilisierung pflanzeneigener Abwehrkräfte gegen Befall durch unerwünschte Mikroorganismen, wie Schadpilze, aber auch Viren und Bakterien. Unter pflanzenstärkenden (resistenzinduzierenden) Stoffen sind in diesem Zusammenhang solche Substanzen zu verstehen, die in der Lage sind, das Abwehrsystem von behandelten Pflanzen so zu stimulieren, dass diese bei nachfolgender Inokulation mit unerwünschten Mikroorganismen weitgehende Resistenz gegen diese Mikroorganismen entfalten. Die Verbindungen I können eingesetzt werden, um Pflanzen innerhalb eines gewissen Zeitraumes nach der Behandlung gegen den Befall durch unerwünschte Mikroorganismen zu schützen. Der Zeitraum, innerhalb dessen Schutz herbeigeführt wird, erstreckt sich im Allgemeinen auf 1 bis 28 Tage, vorzugsweise 1 bis 14 Tage nach der Behandlung der Pflanzen mit den Verbindungen I bzw. nach Behandlung des Saatguts, auf bis zu 9 Monate nach Aussaat.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.
Die Verbindungen I und die erfindungsgemäßen Zusammensetzungen eignen sich auch zur Steigerung des Ernteertrages.The compounds I and the compositions according to the invention are also suitable for increasing crop yield.
Sie sind außerdem mindertoxisch und weisen eine gute Pflanzenverträglichkeit auf. Im Folgenden wird die Herstellung von Pyrazinverbindungen der Formel I anhand von Beispielen erläutert.They are also low toxicity and have good plant tolerance. The preparation of pyrazine compounds of the formula I is explained below by way of examples.
Synthesebeispiele Die in den nachstehenden Synthesebeispielen wiedergegebenen Vorschriften wurden unter entsprechender Abwandlung der Ausgangsverbindungen zur Gewinnung von Verbindungen der Formel I benutzt.Synthesis Examples The instructions given in the Synthesis Examples below were used with appropriate modification of the starting compounds to obtain compounds of formula I.
Beispiel 1 : Herstellung von 3-(3-Hydroxy-pyridin-2-yl)-3-oxo-2-(2-trifluormethyl- phenyl)-propionsäuremethylester (nicht erfindungsgemäß)Example 1 Preparation of 3- (3-Hydroxy-pyridin-2-yl) -3-oxo-2- (2-trifluoromethyl-phenyl) -propionic acid methyl ester (not according to the invention)
Stufe 1 : 3-(4-Methoxy-benzyloxy)-pyridin-2-carbonsäuremethylester Eine Lösung von 15,2g 3-Hydroxy-pyridin-2-methylester in 200 ml DMF wurde mit 4g NaH versetzt und 30 min bei 20-250C gerührt. Dann wurden 15,4g Para-methoxy- benzylchlorid hinzugefügt. Die Mischung wurde bei 400C etwa 15 Std. gerührt und an- schließend in Wasser gegeben. Nach Extraktion mit Ethylacetat, Phasentrennung und Waschen der vereinigten organischen Phasen mit Wasser und ges. NaCI-Lösung, dann Trocknen und Entfernen des Lösungsmittels wurde der Rückstand einer Säulenchromatographie unterworfen. Man erhielt 20g der Titelverbindung als gelbes Öl. Stufe 2: 3-(4-Methoxy-benzyloxy)-pyridin-2-carbonsäure Eine Lösung von 7g des Esters aus Stufe 1 und 2,2g LiOH in 60 ml Methanol und 40ml Wasser wurde bei 20-25°C etwa 15 Std. gerührt. Dann wurden 100 ml Wasser und 7ml Essigsäure zugegeben. Die Mischung wurde mit Ethylacetat extrahiert. Die vereining- ten organischen Phasen wurden getrocknet und vom Lösungsmittel befreit. Es wurden 5g der Titelverbindung als gelblicher Feststoff erhalten. Stufe 3: 3-(4-Methoxy-benzyloxy)-pyridin-2-carbonsäurepentafluorphenylesterStep 1: 3- (4-methoxy-benzyloxy) -pyridine-2-carbonsäuremethylester A solution of 15.2 g of 3-hydroxy-pyridin-2-methylester in 200 ml DMF was added 4g NaH and 30 min at 20-25 0 C stirred. Then, 15.4 g of para-methoxybenzyl chloride was added. The mixture was stirred at 40 ° C. for about 15 hours and then poured into water. After extraction with ethyl acetate, phase separation and washing of the combined organic phases with water and sat. NaCl solution, then drying and removal of the solvent, the residue was subjected to column chromatography. 20 g of the title compound were obtained as a yellow oil. Step 2: 3- (4-Methoxy-benzyloxy) -pyridine-2-carboxylic acid A solution of 7g of the ester of Step 1 and 2.2g of LiOH in 60ml of methanol and 40ml of water was stirred at 20-25 ° C for approximately 15h. touched. Then, 100 ml of water and 7 ml of acetic acid were added. The mixture was extracted with ethyl acetate. The combined organic phases were dried and freed from the solvent. 5 g of the title compound were obtained as a yellowish solid. Step 3: 3- (4-Methoxy-benzyloxy) -pyridine-2-carboxylic acid pentafluorophenyl ester
Zu einer Lösung von 5g der Säure aus Stufe 2 und 3,5g Pentafluorphenol in 100ml CH2CI2 wurden 2,4g N,N'-Diisopropylcarbodiimid tropfenweise zugesetzt. Die Mischung wurde bei 20-250C etwa 1 Std. gerührt, dann mit ges. NaCI-Lösung gewaschen und im Vakuum eingeengt. Nach säulenchromatographischer Reinigung des Rückstandes (Petrolether: Ethylacetat 5:1 ) wurden 4,6g der Titelverbindung erhalten.To a solution of 5 g of the acid from Step 2 and 3.5 g of pentafluorophenol in 100 ml of CH 2 Cl 2, 2.4 g of N, N'-diisopropylcarbodiimide was added dropwise. The mixture was stirred at 20-25 0 C for about 1 hr, then with sat. NaCl solution and concentrated in vacuo. After purification by column chromatography on the residue (petroleum ether: ethyl acetate 5: 1), 4.6 g of the title compound were obtained.
Stufe 4: 3-[3-(4-Methoxy-benzyloxy)-pyridin-2-yl]-3-oxo-2-(2-trifluormethyl-phenyl)- propionsäuremethylesterStep 4: Methyl 3- [3- (4-methoxy-benzyloxy) -pyridin-2-yl] -3-oxo-2- (2-trifluoromethyl-phenyl) -propionate
Zu einer Lösung von 1 ,2g des Esters aus Stufe 3 in 10ml DMF wurden 0,74g Kalium- tert-Butanolat zugegeben. Die Mischung wurde bei 20-25°C etwa 30min gerührt. An- schließend wurde eine Lösung von 2,25g (2-Trifluormethyl-phenyl)-essigsäuremethyl- ester in 5ml DMF zugegeben. Nach 30 min rühren bei 20-25°C wurde die Reaktion durch Zugabe von ges. NH4CI-Lösung beendet. Die Mischung wurde mit Ethylacetat extrahiert. Die vereiningten organischen Phasen wurden mit ges. NaCI-Lösung gewaschen, dann getrocknet und vom Lösungsmittel befreit. Nach säulenchromato- graphischer Reinigung des Rückstandes (PetroletheπEthylacetat 5:1 ) wurden 0,23g der Titelverbindung erhalten. Stufe 5: 3-(3-Hydroxy-pyridin-2-yl)-3-oxo-2-(2-trifluormethyl-phenyl)-propionsäure- methylesterTo a solution of 1.2 g of the ester from Step 3 in 10 ml of DMF was added 0.74 g of potassium tert-butoxide. The mixture was stirred at 20-25 ° C for about 30 minutes. Subsequently, a solution of 2,25g (2-trifluoromethyl-phenyl) -acetic acid methyl ester in 5 ml of DMF was added. After stirring for 30 min at 20-25 ° C, the reaction by addition of sat. NH4CI solution ended. The mixture was extracted with ethyl acetate. The unified organic phases were washed with sat. NaCl solution, then dried and freed from the solvent. After purification by column chromatography of the residue (petroleum ether: ethyl acetate 5: 1), 0.23 g of the title compound were obtained. Step 5: 3- (3-Hydroxy-pyridin-2-yl) -3-oxo-2- (2-trifluoromethyl-phenyl) -propionic acid methyl ester
160mg des Esters aus Stufe 4 wurden mit 1 ml Trifluoressigsäure bei 00C versetzt und die Reaktionsmischung wurde 20 min bei 00C gerührt. Anschließend wurde ges. NaHCθ3-Lösung zugegeben. Nach Extraktion mit Ethylacetat, Entfernen des Lösungsmittels im Vakuum und präparativer HPLC wurden 83mg des Esters erhalten.160mg of the ester from step 4 were treated with 1 ml of trifluoroacetic acid at 0 0 C and the reaction mixture was stirred for 20 min at 0 0 C. Subsequently, sat. NaHCO 3 solution added. After extraction with ethyl acetate, removal of the solvent in vacuo and preparative HPLC, 83 mg of the ester were obtained.
1H NMR (CDCI3): 6 1 1 ,05 (bre, 1 H); 8,26-8,24 (m, 1 H); 7,73 (d, 1 H); 7,61-7,58 (m, 2H); 7,48-7,34 (m, 3H); 6,64 (s, 1 H); 3,76 (s, 3H). 1 H NMR (CDCl 3 ): 6 1 1, 05 (bre, 1H); 8.26-8.24 (m, 1H); 7.73 (d, 1H); 7.61-7.58 (m, 2H); 7.48-7.34 (m, 3H); 6.64 (s, 1H); 3.76 (s, 3H).
Stufe 6: 8-Hydroxy-7-(2-trifluoromethyl-phenyl)-pyrano[2,3-b]pyrazin-6-one350 mg der Stufe 5 wurden in 7ml DMSO/ges. Kochsalzlösung gelöst. Die Mischung wurde bei 100 0C 2 h gerührt. Anschließend wurde die Reaktionslösung mit 70ml 2N HCl verdünnt und mit Ethylacetat extrahiert. Die vereinigten organischen Phasen wurden über Natriumsulfat getrocknet. Nach Entfernen des Lösungmittels im Vakuum und Reinigung mittels präp. HPLC wurden 83mg der Titelverbindung erhalten. 1H NMR (MeOD): δ 8,64-8,69 (m, 2H), 7,82 (d, 1 H, J = 8Hz), 7,71 (t, 1 H, J = 8Hz), 7,61 (t, 1 H, J = 8Hz), 7,45 (d, 1 H, J = 8Hz).Step 6: 8-Hydroxy-7- (2-trifluoromethyl-phenyl) -pyrano [2,3-b] pyrazine-6-one 350 mg of Step 5 was dissolved in 7 ml of DMSO / sat. Saline solution dissolved. The mixture was stirred at 100 0 C for 2 h. Subsequently, the reaction solution was diluted with 70 ml of 2N HCl and extracted with ethyl acetate. The combined organic phases were dried over sodium sulfate. After removal of the solvent in vacuo and purification by prep. HPLC gave 83 mg of the title compound. 1H NMR (MeOD): δ 8.64-8.69 (m, 2H), 7.82 (d, 1H, J = 8Hz), 7.71 (t, 1H, J = 8Hz), 7, 61 (t, 1H, J = 8Hz), 7.45 (d, 1H, J = 8Hz).
Anwendungsbeispieleapplications
Die herbizide Wirkung der Verbindungen der Formel I ließ sich durch Gewächshaus- versuche zeigen:The herbicidal activity of the compounds of the formula I was demonstrated by greenhouse experiments:
Als Kulturgefäße dienten Plastiktöpfe mit lehmigem Sand mit etwa 3,0% Humus als Substrat. Die Samen der Testpflanzen wurden nach Arten getrennt eingesät.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.
Bei Vorauflaufbehandlung wurden die in Wasser suspendierten oder emulgierten Wirkstoffe direkt nach Einsaat mittels fein verteilender Düsen aufgebracht. Die Gefäße wurden leicht beregnet, um Keimung und Wachstum zu fördern, und anschließend mit durchsichtigen Plastikhauben abgedeckt, bis die Pflanzen angewachsen waren. Diese Abdeckung bewirkt ein gleichmäßiges Keimen der Testpflanzen, sofern dies nicht durch die Wirkstoffe beeinträchtigt wurde.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.
Zum Zweck der Nachauflaufbehandlung wurden die Testpflanzen je nach Wuchs- form erst bis zu einer Wuchshöhe von 3 bis 15 cm angezogen und dann mit den in Wasser suspendierten oder emulgierten Wirkstoffen behandelt. Die Testpflanzen wurden dafür entweder direkt gesät und in den gleichen Gefäßen aufgezogen oder sie wurden erst als Keimpflanzen getrennt angezogen und einige Tage vor der Behandlung in die Versuchsgefäße verpflanzt. Die Pflanzen wurden artenspezifisch bei Temperaturen von 10 - 25°C bzw. 20 - 35°C gehalten. Die Versuchsperiode erstreckte sich über 2 bis 4 Wochen. Während dieser Zeit wurden die Pflanzen gepflegt, und ihre Reaktion auf die einzelnen Behandlungen wurde ausgewertet.For the purpose of the postemergence treatment, the test plants were, depending on the growth habit, first grown to a height of from 3 to 15 cm and then treated with the active ingredients suspended or emulsified in water. 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.
Bewertet wurde nach einer Skala von 0 bis 100. Dabei bedeutet 100 kein Aufgang der Pflanzen bzw. völlige Zerstörung zumindest der oberirdischen Teile und 0 keineThe rating was based on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the above-ground parts and 0 none
Schädigung oder normaler Wachstumsverlauf. Eine gute herbizide Aktivität ist bei Wer- ten von wenigstens 70 und eine sehr gute herbizide Aktivität ist bei Werten von wenigstens 85 gegeben.Damage or normal growth course. A good herbicidal activity is at Wer- at least 70 and a very good herbicidal activity is given at values of at least 85.
Die in den Gewächshausversuchen verwendeten Pflanzen setzten sich aus folgen- den Arten zusammen:The plants used in the greenhouse experiments are composed of the following species:
1 ) Der Wirkstoff aus Beispiel 1 zeigte bei einer Aufwandmenge von 3,0 kg/ha im Vorauflauf gegen SETIT eine sehr gute herbizide Wirkung.1) The active ingredient from Example 1 showed at a rate of 3.0 kg / ha in the pre-emergence against SETIT a very good herbicidal activity.
2) Der Wirkstoff aus Beispiel 1 zeigte bei einer Aufwandmenge von 3,0 kg/ha im Nachauflauf gegen ABUTH, AVEFA, bzw. SETFA eine sehr gute herbizide Wirkung. 2) The active ingredient from Example 1 showed at a rate of 3.0 kg / ha postemergence against ABUTH, AVEFA, or SETFA a very good herbicidal activity.

Claims

Patentansprüche: claims:
1. Pyrazinverbindungen der Formel1. pyrazine compounds of the formula
worin die Variablen folgende Bedeutung haben wherein the variables have the following meaning
R1 O-RA, S(O)n-RA oder OS(O)n-RA;R 1 OR A , S (O) n -R A or OS (O) n -R A ;
RA Wasserstoff, Ci -C4-Al kyl, Z-C3-C6-Cycloalkyl, Ci-C4-Haloalkyl, C2-C6- Alkenyl, Z-C3-C6-Cycloalkenyl, C2-C6-Al kinyl, Z-(Tri-Ci-C4-alkyl)silyl, Z-C(=O)-Ra, Z-P(=O)(Ra)2, über C oder N gebundener 3- bis 7-glied- riger monocyclischer oder 9- oder 10-gliedriger bicyclischer gesättigter, ungesättigter oder aromatischer Heterocyclus, enthaltend 1 , 2, 3 oder 4 Heteroatome ausgewählt aus O, N und S, der teilweise oder vollständig durch Gruppen Ra und/oder Rb substituiert sein kann, Ra Wasserstoff, OH, Ci-C8-Al kyl, Ci-C4-Haloalkyl, Z-C3-C6-CyCIo- alkyl, C2-C8-Alkenyl, Z-C5-C6-Cycloalkenyl, C2-C8-Al kinyl, Z-d-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-
C6-Alkoxy, Z-Ci-C4-Haloalkoxy, Z-C3-C8-Alkenyloxy, Z-C3-C8-Al- kinyloxy, NR1R", Ci-C6-Alkylsulfonyl, Z-(Tri-Ci-C4-alkyl)silyl, Z-Phenyl, Z-Phenoxy, Z-Phenylamino und 5- oder 6-gliedriger monocyclischer oder 9- oder 10-gliedriger bicyclischer Hetero- cyclus, enthaltend 1 , 2, 3 oder 4 Heteroatome ausgewählt ausC 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-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 und S, wobei die cyclischen Gruppen unsubstituiert oder durch 1 , 2, 3 oder 4 Gruppen Rb substituiert sind, bedeutet; R1, R" unabhängig voneinander Wasserstoff, Ci-C8-Alkyl, Ci-C4-HaIo- alkyl, C3-C8-Al kenyl, C3-C8-Al kinyl, Z-C3-C6-Cycloalkyl, Z-Ci-C8- Alkoxy, Z-Ci-C8-Haloalkoxy;O, N and S, wherein the cyclic groups are 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-C 1 -C 8 -alkoxy, Z-C 1 -C 8 -haloalkoxy;
R1 und R" können auch gemeinsam mit dem N-Atom, an das sie gebunden sind, einen 5- oder θ-gliedrigen monocyclischen oder 9- oder 10-gliedrigen bicyclischer Heterocyclus bilden, enthaltend 1 , 2, 3 oder 4 Heteroatome ausgewählt aus O, N und S; Z eine kovalente Bindung oder Ci-C4-Alkylen; n O, 1 oder 2;R 1 and R "can 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;
R2 Phenyl, Naphthyl oder und 5- oder 6-gliedriger monocyclischer oder 9- oder 10-gliedriger bicyclischer aromatischer Heterocyclus, enthaltend 1 , 2, 3 o- der 4 Heteroatome ausgewählt aus O, N und S, wobei die cyclischen Gruppen unsubstituiert oder durch 1 , 2, 3 oder 4 Gruppen Rb substituiert sind, bedeutet;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;
Rb unabhängig voneinander Z-CN, Z-OH, Z-NO2, Z-Halogen, Ci-C8-Al- kyl, Ci-C4-Haloalkyl, C2-C8-Al kenyl, C2-C8-Al kinyl, Z-Ci-C8-Alkoxy, Z-C-i-Cs-Haloalkoxy, Z-Cs-do-Cycloalkyl, 0-Z-C3-Cio-Cycloalkyl, Z-C(=O)-Ra, NR1R", Z-(Tri-Ci-C4-alkyl)silyl, Z-Phenyl und S(O)nRbb, wobei Rbb Ci-C8-Alkyl und Ci-C6-Haloalkyl bedeutet und n für 0, 1 oder 2 steht; Rb1, Rb2 eine der bei Rb genannten Gruppen;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;
Rb, Rb1, Rb2 können unabhängig voneinander auch gemeinsam mit der an das benachbarte C-Atom gebundene Gruppe Rb, Rb1 oder Rb2 einen fünf- oder sechsgliedrigen gesättigten, teilweise oder vollständig ungesättigten Ring bilden, der neben Kohlenstoff- 1 , 2 oder 3 Heteroatome ausgewählt aus O, N und S enthalten kann;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;
X O, S oder N-R3; R3 Wasserstoff, Ci-C6-Alkyl, Ci-C4-Haloalkyl, C2-C6-Alkenyl, C3-C6-Alkinyl,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 alkynyl,
Z-C3-Cio-Cycloalkyl, Ci-C6-Alkoxy-Ci-C6-alkyl, Ci-C6-Cyanoalkyl, Z-Phenyl, Z-C(=O)-Ra2 und Tri-Ci-C4-alkylsilyl; Ra2 d-Ce-Alkyl, Ci-C4-Haloalkyl, Z-Ci-C6-Alkoxy, Z-Ci-C4-Haloalk- oxy und NR1R"; wobei in Gruppen RA, R2, R3 und deren Untersubstituenten die Kohlenstoffketten und/oder die cyclischen Gruppen teilweise oder vollständig durch Gruppen Ra substituiert sein können, sowie deren N-Oxide und landwirtschaftlich geeignete Salze; mit der Maßgabe, dass R1 nicht ORA oder OS(O)n-RA bedeutet, wenn X für O steht.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 d-Ce-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; with the proviso that R 1 is not OR A or OS (O) n - R A means if X stands for O.
2. Verbindungen der Formel I gemäß Anspruch 1 , worin R1 für S(O)n-RA steht.2. Compounds of formula I according to claim 1, wherein R 1 is S (O) n -R A.
3. Verbindungen der Formel I gemäß Anspruch 1 , worin R1 für ORA oder OS(O)n-RA steht.3. Compounds of formula I according to claim 1, wherein R 1 is OR A or OS (O) n -R A.
4. Verbindungen der Formel I gemäß einem der Ansprüche 1 bis 3, worin RA H oder d-Ce-Alkylcarbonyl bedeutet.4. Compounds of formula I according to any one of claims 1 to 3, wherein R A is H or d-Ce-alkylcarbonyl.
5. Verbindungen der Formel I gemäß einem der Ansprüche 1 , 3 oder 4, worin X ür O steht.5. Compounds of formula I according to any one of claims 1, 3 or 4, wherein X is O.
6. Verbindungen der Formel I gemäß einem der Ansprüche 1 bis 4, worin X für S steht.6. Compounds of formula I according to any one of claims 1 to 4, wherein X is S.
7. Verbindungen der Formel I gemäß einem der Ansprüche 1 bis 6, worin R3 für d-7. Compounds of the formula I according to any one of claims 1 to 6, wherein R 3 is for d-
Ce-Alkyl, Ci-C6-Halogenalkyl, C3-C6-Cycloalkyl-Ci-C4-alkyl, C3-C6-Alkenyl, ggf. subst. Phenyl, oder S(O)n-RN steht und RN für d-Ce-Halogenalkyl bedeutet. Ce-alkyl, Ci-C 6 haloalkyl, C 3 -C 6 cycloalkyl-Ci-C 4 alkyl, C 3 -C 6 alkenyl, unsubstituted or substituted. Phenyl, or S (O) n -R N and R N is d-Ce-haloalkyl.
8. Verbindungen der Formel I gemäß einem der Ansprüche 1 bis 7, welche der Formel LA entsprechen,8. Compounds of formula I according to any one of claims 1 to 7, which correspond to the formula LA,
in der R5 und R6 für Gruppen Rb und n für eine ganze Zahl von Null bis vier ste- hen. in which R 5 and R 6 are groups R b and n is an integer from zero to four.
9. Verbindungen der Formel I gemäß Anspruch 8, worin R5 für Ci-C2-Halogenalkyl steht.9. Compounds of formula I according to claim 8, wherein R 5 is Ci-C2-haloalkyl.
10. Verbindungen der Formel I gemäß einem der Ansprüche 1 bis 8, worin die Sub- stituenten Rb ausgewählt sind aus Halogen, NO2, Ci-C4-AIkVl, Ci-C2-Halogenalkyl und CrC4-AIkOXy.10. Compounds of the formula I according to one of claims 1 to 8, in which the substituents R b are selected from halogen, NO 2, C 1 -C 4 -alkyl, C 1 -C 2 -haloalkyl and C 1 -C 4 -alkoxy.
1 1. Mittel, enthaltend eine herbizid wirksame Menge mindestens einer Pyrazin- Verbindung der Formel I oder eines landwirtschaftlich geeigneten Salzes davon nach einem der Ansprüche 1 bis 10 und für die Formulierung von Pflanzenschutzmitteln übliche Hilfsmittel.1 1. An agent containing 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 10 and for the formulation of pesticides customary auxiliaries.
12. Mittel gemäß Anspruch 1 1 , enthaltend mindestens einen weiteren Wirkstoff.12. Composition according to claim 1 1, containing at least one further active ingredient.
13. Mittel gemäß Anspruch 12 oder 13, enthaltend zwei weitere Wirkstoffe aus der Gruppe der Herbizide und/oder Safener.13. Composition according to claim 12 or 13, containing two further active ingredients from the group of herbicides and / or safeners.
14. Verfahren zur Bekämpfung von unerwünschtem Pflanzenwuchs, dadurch ge- kennzeichnet, dass man eine herbizid wirksame Menge mindestens einer Pyra- zinverbindung der Formel I oder eines landwirtschaftlich brauchbaren Salzes davon nach einem der Ansprüche 1 bis 10 auf Pflanzen, deren Samen und/oder deren Lebensraum einwirken lässt. 14. 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 10 on plants, their seeds and / or their Habitat acts.
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AR081526A1 (en) 2010-03-23 2012-10-03 Basf Se PIRIDAZINAS REPLACED THAT HAVE HERBICITY ACTION
JP2013522336A (en) 2010-03-23 2013-06-13 ビーエーエスエフ ソシエタス・ヨーロピア Pyridothiazine with herbicidal activity
US20130012389A1 (en) * 2010-03-23 2013-01-10 Basf Se Substituted Pyridazines Having Herbicidal Action
CN102906096A (en) 2010-03-23 2013-01-30 巴斯夫欧洲公司 Substituted pyridines having herbicidal action
BR112012023936A2 (en) 2010-03-23 2015-09-15 Basf Se substituted pyridazine of formula i, compound for formula i, composition and method for controlling unwanted vegetation
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Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2046167T3 (en) 1985-12-13 1994-02-01 American Cyanamid Company PROCEDURE FOR THE PREPARATION OF HERBICIDE COMPOSITIONS OF CONDENSED (2-IMIDAZOLIN-2-IL) -HETEROPYRIDINE.
DE4131029A1 (en) * 1991-09-18 1993-07-29 Basf Ag SUBSTITUTED PYRIDO (2,3-D) PYRIMIDINE AS ANTIDOTS
US5563280A (en) 1994-07-25 1996-10-08 American Cyanamid Co. 4-Phenoxycoumarins as herbicidal agents
US5801183A (en) 1995-01-27 1998-09-01 State Of Oregon, Acting By And Through The Oregon State Board Of Higher Education, Acting For And On Behalf Of The Oregon Health Sciences University And The University Of Oregon Aza and aza (N-oxy) analogs of glycine/NMDA receptor antagonists
US7470709B2 (en) 2002-08-23 2008-12-30 Novartis Vaccines And Diagnostics, Inc. Benzimidazole quinolinones and uses thereof
US20040097492A1 (en) 2002-11-01 2004-05-20 Pratt John K Anti-infective agents
WO2005010000A2 (en) 2003-07-18 2005-02-03 Basf Aktiengesellschaft Aryl-condensed 3-arylpyridine compounds and use thereof for controlling pathogenic fungi
GB0614471D0 (en) 2006-07-20 2006-08-30 Syngenta Ltd Herbicidal Compounds
GB0624760D0 (en) * 2006-12-12 2007-01-17 Syngenta Ltd Herbicidal compounds
GB0800855D0 (en) 2008-01-17 2008-02-27 Syngenta Ltd Herbicidal compounds
GB0800856D0 (en) * 2008-01-17 2008-02-27 Syngenta Ltd Herbicidal compounds
GB0816880D0 (en) * 2008-09-15 2008-10-22 Syngenta Ltd Improvements in or relating to organic compounds
CN102203091B (en) 2008-10-29 2014-08-13 巴斯夫欧洲公司 Substituted pyridines having a herbicidal effect
US20130012389A1 (en) * 2010-03-23 2013-01-10 Basf Se Substituted Pyridazines Having Herbicidal Action

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010139658A1 *

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