Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
  • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
  • C07C255/41—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by carboxyl groups, other than cyano groups
• • 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
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/34—Nitriles
• • 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
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
  • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
  • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
  • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
• • 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
  • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
  • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
  • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C255/00—Carboxylic acid nitriles
  • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C255/57—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and carboxyl groups, other than cyano groups, bound to the carbon skeleton

Definitions

• the present invention relates to substituted cyanobutyrates of the formula I.
• R is halogen, cyano, nitro, C -C alkyl 4 -alkyl, Ci-C 4 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 -alkyl kinyl,
• R a is hydrogen, OH, Ci-C 8 -alkyl, C 4 haloalkyl, ZC 3 -C 6 cycloalkyl, C 2 -C 8 - alkenyl, ZC 5 -C 6 cycloalkenyl, C 2 -C 8 Alkynyl, Z-Ci-C 6 alkoxy, Z-CrC 4 - haloalkoxy, ZC 3 -C 8 alkenyloxy, ZC 3 -C 8 alkynyloxy, NR 1 R ", Ci-C 6 alkyl sulfonyl, Z- (tri-C 1 -C 4 -alkyl) silyl, Z-phenyl, Z-phenoxy, Z-phenylamino and
• R 1 , R "independently of one another are hydrogen, C 1 -C 8 -alkyl, C 1 -C 4 -haloalkyl,
• R 1 and R can also together with the N-atom to which they are bonded form a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle containing 1, 2, 3 or 4 heteroatoms selected from O, N and S;
• R b independently of one another Z-CN, Z-OH, Z-NO 2 , Z-halogen, Ci-C 8 -
• R bb is C 1 -C 8 -alkyl and C 1 -C 6 -haloalkyl
• n 0, 1 or 2;
• R b can also form, together with the group R b attached to the adjacent carbon atom, a five- or six-membered saturated, partially or completely unsaturated ring which, in addition to carbon atoms, can contain 1, 2 or 3 heteroatoms selected from O, N and S. ;
• Z is a covalent bond or Ci-Cs-alkylene
• n 0, 1, 2, 3, 4 or 5;
• R 2 , R 3 independently of one another are halogen, cyano, nitro, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy,
• R 2 and R 3 may also together form a five- or six-membered saturated, partially or completely unsaturated mono- or bicyclic ring which may contain, in addition to carbon, 1, 2 or 3 heteroatoms selected from O, N and S and groups R b may be substituted;
• groups R and R 1 and their sub-substituents the carbon chains and / or the cyclic groups may be partially or completely substituted by groups R a and / or R b ,
• R 2 and R 3 are chlorine when R is hydrogen and R 1 is ethyl or allyl;
• the invention relates to processes and intermediates for the preparation of the compounds of formula I and their N-oxides, their agriculturally useful salts, agents containing them and their use as herbicides, i. for controlling harmful plants, and a method for controlling undesired plant growth, comprising allowing a herbicidally effective amount of at least one compound of formula I or an agriculturally useful salt thereof to act on plants, their seeds and / or their habitat.
• EP-A 5 341, EP-A 266 725, EP-A 270 830, JP 04/297 454, JP 04/297 455 and JP 05/058 979 disclose herbicidal cyanobutyrates, their herbicidal action, in particular at low levels
• 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 analogously to the synthetic routes described in the cited documents by standard methods of organic chemistry, for example according to the following synthesis route:
• Phenylacetonitrile derivatives of the formula II can be reacted with cinnamate derivatives of the formula III in the sense of a Michael addition to give compounds of the formula I.
• the variables have the meaning given for formula I.
• This reaction is usually carried out at temperatures of -100 0 C to 150 0 C, preferably -78 ° C to 50 0 C, in a solvent in the presence of a base and / or a catalyst [see. J. Chem. Soc. (1945), p. 438].
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane , Anisole and tetrahydrofuran (THF), nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert. Butanol, and dimethyl sulfox
• Bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, Alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydrogen carbonates such as sodium hydrogencarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides such as methylmagnesium chloride and also alkali metal and alkaline earth metal alkoxides such as sodium methoxide, sodium ethanolate, potassium
• the bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
• Acid catalysts include inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, ferric chloride, tin IV chloride, titanium IV chloride, scandium III triflate and zinc -ll-chloride, and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid,
• Camphorsulfonic acid, citric acid and trifluoroacetic acid use.
• the acids are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
• the compounds of formula I can also be obtained by U-esterification of other Cyanobutyrate be obtained. This can be done by various methods, for example according to the following:
• the transesterification can be carried out in the presence of molecular sieve in an alcohol R 1 -OH, optionally in an aprotic solvent.
• This reaction is usually carried out at temperatures of 0 0 C to 180 ° C, preferably 20 0 C to 80 0 C in the presence of a Lewis or Branstedtklare or an enzyme [cf.. J. Org. Chem. 2002, 67, 431].
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and THF, nitriles such as acetonitrile and propionitrile, ketones, as well as dimethyl sulfoxide, dimethylformamide and dimethylacetamide, more preferably alcohol R 1 -OH.
• aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether
• aromatic hydrocarbons such as toluene, o-, m- and p-xylene
• transesterification may be by acid or base saponification of other cyanobutyrates (a), followed by reaction with an alcohol R 1 -OH.
• a cyanobutyrate
• These reactions are usually carried out at temperatures of from 0 C to 12O 0 C, preference example, 2O 0 C to 5O 0 C in the presence of a base, or an acid and / or a catalyst [see. J. Am. Chem. Soc. 2007, 129 (43), 13321; J. Org. Chem. 1984, 49 (22), 4287.].
• Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane , Anisole and THF, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, and dimethyl sulfoxide, dimethylformamide and Dimethyl
• Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and Calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate and alkali metal hydrogen carbonates such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls such as methyllithium, butyllithium and phenyllithium, Alkylmeas- siumhalogenide such as methylmagnesium chloride and alkali metal and Alkaline earth metal alkoxides such as sodium methoxide, sodium ethoxid
• acids and acidic catalysts are inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, Lewis acids such as boron trifluoride, aluminum trichloride, ferric chloride, stannic chloride, titanium IV chloride and zinc II chloride , and organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and trifluoroacetic acid use.
• inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid
• Lewis acids such as boron trifluoride, aluminum trichloride, ferric chloride, stannic chloride, titanium IV chloride and zinc II chloride
• organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, tolu
• the acids are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
• the starting materials required for the preparation of the compounds I are known in the literature or can be prepared according to the cited literature.
• the reaction mixtures are worked up in the usual way, e.g. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products.
• the intermediate and end products are z.T. in the form of colorless or pale brownish, viscous oils, which are freed or purified under reduced pressure and at moderately elevated temperature from volatile constituents. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.
• 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-N
• 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.
• 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
• Haloalkyl also referred to as haloalkyl: an alkyl radical as mentioned above, the hydrogen atoms of which are partially or completely substituted by halogen atoms such as fluorine, chlorine, bromine and / or iodine, e.g.
• Cycloalkyl and the cycloalkyl moieties for example, in cycloalkoxy or cycloalkylcarbonyl: monocyclic, saturated hydrocarbon groups having three or more C atoms, e.g. 3 to 6 carbon ring members such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
• Alkenyl and alkenyl moieties for example, in alkenylamino, alkenyloxy, N- (alkenyl) -N- (alkyl) -amino, N- (alkenyl) -N- (alkoxy) -amino: monounsaturated, straight-chain or branched hydrocarbon radicals having two or more carbon atoms. Atoms, z. 2 to 4, 2 to 6 or 3 to 6 carbon atoms and a double bond in any position, e.g.
• C2-C6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1 Methyl 2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3 Methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl 3-butenyl, 1, 1-dimethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-1
• Cycloalkenyl monocyclic, monounsaturated hydrocarbon groups having 3 to 6, preferably 5 to 6 carbon ring members, such as cyclopenten-1-yl, cyclopentene-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl ,
• Alkynyl and alkynyl moieties for example in alkynyloxy, alkynylamino, N- (alkynyl) -N- (alkyl) -amino or N- (alkynyl) -N- (alkoxy) -amino: straight-chain or branched hydrocarbon groups having two or more carbon atoms , z. B. 2 to 4, 2 to 6, or 3 to 6 carbon atoms and a triple bond in any position, for.
• C 2 -C 6 -alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl 2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2- Methyl-3-pentynyl, 2-methyl
• 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 formula I contain two chiral centers and, depending on the substitution pattern, may contain one or more others.
• the compounds according to the invention can therefore be present as pure enantiomers or diastereomers or as enantiomer or diastereomer mixtures.
• the invention relates to both the pure enantiomers or diastereomers and mixtures thereof.
• 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. It is likewise possible to use ammonium as cation, in which case, if desired, one to four hydrogen atoms are represented by C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, hydroxyC 1 -C 4 alkoxy-C 1 -C 4 -alkyl, phenyl or benzyl, preferably ammonium, dimethylammonium, diisopropylammonium, tetramethylammonium, tetrabutylammonium, 2- (2-hydroxyeth-1-oxy) eth-1-ylammonium, di (2-hydroxyethyl) 1-yl)
• ammonium 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:
• the subscript n stands for a value of 0 to 3, preferably for 0 or 1, in particular for 1. In another embodiment, it stands for 0. If at least one group R is present, it stands preferably in the positions 3, 4 and / or 5, in particular 3 or 4. If the index n is 2, the groups R are preferably in positions 2.5 or 3.4.
• Embodiments of the group (s) R concern halogen, in particular chlorine or fluorine. Further embodiments of the group (s) R concern cyano or nitro, in particular cyano. Particularly preferred embodiments of the group R n include the following:
• Preferred embodiments of the group R 1 relate to hydrogen, C 1 -C 6 -alkyl, cyano-C 1 -C 4 -alkyl, C 3 -C 6 -alkynyl, C 3 -C 6 -alkynyl, C 1 -C 8 -haloalkyl, if appropriate subst.
• Particularly preferred embodiments of the group R 1 relate to hydrogen, C 1 -C 4 -alkyl, cyanomethyl, allyl, propargyl, C 1 -C 4 -haloalkyl containing preferably 1 to 3 halogen atoms, phenyl or benzyl, which aromatic groups may be partially or completely substituted.
• Particularly preferred embodiments for R 1 include the following: H, CH 3 , C 2 H 5 , CH 2 CN, CH 2 C ⁇ CH, CH 2 CH 2 F, CH 2 CHF 2 , CH 2 CF 3 , CH 2 OCH 3 ,
• Preferred embodiments of the group R 2 relate to halogen, cyano, nitro, C T C 4 - AI alkyl, Ci-C 4 alkoxy, S (O) m R bb, NR 1 R "Ci-C 4 haloalkyl, Ci- C 4 haloalkoxy
• Particularly preferred embodiments of the group R 2 include halogen, CN, NO 2 , CH 3 , CHF 2 , CF 3 , OCHF 2 , OCF 3.
• Particularly preferred embodiments of the group R 2 are selected from fluorine, chlorine, bromine and more preferably, R 2 is not chlorine.
• R 2 is fluorine
• R 2 is bromine
• R 2 is iodine.
• Preferred embodiments of the group R 3 relate to halogen, cyano, nitro, Ci-C 4 - AI alkyl, Ci-C 4 alkoxy, S (O) m R bb, NR 1 R "Ci-C 4 haloalkyl, Ci- C 4 haloalkoxy
• Particularly preferred embodiments of the group R 3 relate to halogen, CN, NO 2 , CH 3 , CHF 2 , CF 3 , OCHF 2 , OCF 3.
• Particularly preferred embodiments of the group R 3 are selected from fluorine, chlorine, bromine and iodine, more preferably R 3 is not chlorine.
• R 3 is fluorine
• R 3 is bromine
• R 3 is iodine.
• 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.
• 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:
• crops also includes those that have been modified by breeding, mutagenesis or genetic engineering methods.
• Genetically engineered plants are plants whose genetic material has been altered in a manner that does not occur under natural conditions by crossing, mutations or natural recombination (i.e., rearrangement of genetic information).
• 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. Nos. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, US Pat.
• HPPD hydroxyphenylpyruvate dioxygenase
• ALS acetolactate synthase
• Sulfonylureas EP-A 257 993, US Pat. No. 5,013,659
• imidazolinones see, for example, US Pat. Nos. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, US Pat.
• WO 03/13225, WO 03/14356, WO 04/16073), enolpyruvylshikimate-3-phosphate synthase (EPSPS) -inhibitors such. Glyphosate (see, for example, WO 92/00377), glutamine synthetase (GS) inhibitors such as. Glufosinate (see eg EP-A 242 236, EP-A 242 246) or oxynil herbicides (see eg US 5,559,024).
• crops eg. As Clearfield® rapeseed, which produces a tolerance to imidazolinones, z. As imazamox, have.
• crops such as soybean generated yes, cotton, corn, beets and rape, which are resistant to glyphosate or glufosinate, which under the trade names RoudupReady ® (glyphosate) and Liberty Link ® (glufosinate) can be obtained.
• crops thus also includes plants that use genetic engineering measures one or more toxins, eg. As those from the bacterial strain Bacillus ssp., Produce.
• Toxins produced by such genetically engineered plants include e.g. Insecticidal proteins of Bacillus spp., In particular B. thuringiensis such as the endotoxins CrylAb, CrylAc, CrylF, Cry1Fe2, Cry2Ab, Cry3A, Cry3Bb1, Cry9c, Cry34Ab1 or Cry35Ab1; or vegetative insecticidal proteins (VIPs) 1 eg VIP1, VIP2, VIP3, or VIP3A; insecticidal proteins of nematode-colonizing bacteria, e.g.
• RIPs Ribosome Inactivating Proteins
• Steroid metabolizing enzymes e.g. 3-hydroxysteroid oxidase, ecdysteroid IDP glycosyltransferase, cholesterol oxidase, ecdysone inhibitors or HMG-CoA reductase
• ion channel blocker e.g.
• 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,
• 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).
• 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.
• 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.
• yield eg biomass, grain yield, starch, oil or protein content
• tolerance to drought salt or other limiting environmental factors or resistance to pests and fungal, bacterial and viral pathogens may be increased.
• 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 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 drying the aerial parts of crop plants such as potato, rape, sunflower and soybean but also cereals. This enables a completely mechanical harvesting of these important crops. Of economic interest is also the relief of the crop, which is made possible by the time-concentrated drop or decrease in the adhesion to the tree in citrus fruits, olives or other types and varieties of pome, stone and peel fruit.
• the same mechanism that is, the promotion of the formation of release tissue between fruit or leaf and shoot part of the plants is also essential for a well controllable defoliation of crops, especially cotton.
• shortening the time interval in which the individual cotton plants ripen results in increased fiber quality after harvest.
• the compounds I or the herbicidal compositions containing them can, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, even high-percentage aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents or granules by spraying, atomizing , Dusting, scattering, pouring or treatment of the seed or mixing with the seed.
• the forms of application depend on the intended use; In any case, they should ensure the finest possible distribution of the active compounds according to the invention.
• the herbicidal compositions contain a herbicidally effective amount of at least one compound of the formula I or an agriculturally useful salt of I and auxiliaries customary for the formulation of crop protection agents.
• auxiliaries are preferred auxiliaries, solid carriers, surface-active substances (such as dispersants, protective colloids, emulsifiers, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if necessary, dyes and for seed formulations adhesives.
• surface-active substances such as dispersants, protective colloids, emulsifiers, wetting agents and adhesives
• organic and inorganic thickeners such as 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) as well as 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, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
• adhesives examples include polyvinyl pyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose.
• Suitable inert additives are, for example:
• Mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, eg. As amines such as N-methylpyrrolidone or water.
• 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.
• 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
• alkali alkaline earth
• ammonium salts of aromatic sulfonic acids eg lignosulfonic acids (eg Borrespers types, Borregaard), phenolsulfonic acids, naphthalenesulfonic acids (Morwet types , Akzo Nobel) and dibutylnaphthalenesulfonic acid (Nekal types, BASF SE)
• fatty acids alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene
• Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.
• Granules e.g. Coating, impregnation and homogeneous granules can be prepared by binding the active compounds to solid carriers.
• Aqueous application forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water.
• 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.
• concentrates consisting of active substance, wetting, adhesion, dispersing or emulsifying agent and possibly solvent or oil, which are suitable for dilution with water.
• the concentrations of the compounds of the formula I in the ready-to-use formulations can be varied within wide limits.
• the formulations generally contain from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight, of at least one active ingredient.
• the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
• the compounds I according to the invention can be formulated, for example, as follows:
• 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 by means of an emulsifying machine (eg Ultraturax) in 30 parts by weight of water and a homogeneous emulsion brought. Dilution in water results in an emulsion.
• the formulation has an active ingredient content of 25% by weight.
• 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.
• active compound 50 parts by weight are finely ground with the addition of 50 parts by weight of dispersants and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
• the formulation has an active ingredient content of 50% by weight.
• 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. Dilution in water results in a stable dispersion or solution of the active ingredient.
• the active ingredient content of the formulation is 75% by weight.
• 0.5 parts by weight of active compound are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying or fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.
• the application of the compounds I or the herbicidal compositions containing them can be carried out in the pre-emergence, postemergence or together with the seed of a crop. It is also possible, the herbicidal agents or agents in that seed of a crop plant pretreated with the herbicidal agents or active substances is applied. If the active ingredients are less compatible with certain crops, then application techniques may be employed whereby the herbicidal agents are sprayed by the sprayers so as not to hit the leaves of the sensitive crop if possible, while the active ingredients affect the leaves underneath growing undesirable plants or the uncovered floor surface (post-directed, lay-by).
• the application of the compounds of the formula I or of the herbicidal compositions can be carried out by treating seed.
• the treatment of seed comprises essentially all techniques familiar to the skilled worker (seed dressing, seed coating, seed dusting, seed soaking, seed film coating, seed multilayer coating, seed encrusting, seed dripping and seed pelleting) based on the compounds of the formula according to the invention I or funds produced therefrom.
• the herbicidal agents can be diluted or applied undiluted.
• seed includes seeds of all kinds, e.g. 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.
• herbicides which can be used in combination with the pyridine compounds of the formula I according to the present invention are:
• Bilanaphos (bialaphos), bilanaphos-sodium, glufosinate and glufosinate-ammonium; b8) from the group of DHP synthase inhibitors: asulam;
• 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.
• R 21 , R 22 , R 23 , R 24 are H, Cl, F or CH 3 ;
• R 25 is halogen, C 1 -C 4 -alkyl or C 1 -C 4 -haloalkyl;
• R 26 is C 1 -C 4 -alkyl;
• R 27 is halogen, C 1 -C 4 -alkoxy or C 1 -C 4 -haloalkoxy;
• R 28 is H, halogen, Ci-C 4 - alkyl, Ci-C 4 haloalkyl or Ci-C4-haloalkoxy;
• m is 0, 1, 2 or 3;
• Preferred compounds of the formula 2 have the following meanings:
• Particularly preferred compounds of the formula 2 are:
• auxin transport inhibitors diflufenzopyr, diflufenzopyrsodium, naptalam and naptalam sodium;
• 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
• 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
• 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 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.
• HPLC-MS High Performance Liquid Chromatography combined with mass spectrometry
• 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 grown depending on the growth form only to a height of from 3 to 15 cm and then treated with the suspended or emulsified in water agents.
• the test plants were either sown directly and grown in the same containers or they were first grown separately as seedlings and transplanted into the test containers a few days before the treatment.
• the plants were kept species-specific at temperatures of 10 - 25 ° C and 20 - 35 ° C, respectively.
• the trial period lasted for 2 to 4 weeks. During this time, the plants were cared for, and their response to each treatment was evaluated.
• the plants used in the greenhouse experiments are composed of the following species:
• the scale was rated from 0 to 100. 100 means no plants rising or completely destroying at least the above-ground parts and 0 means no damage or normal growth. A good herbicidal activity is at values of at least 70 and a very good herbicidal activity is given at values of at least 85.
• the active ingredient 1-105 showed at a rate of 0.125 kg / ha in the wake of ALOMY a good and the active ingredients I-94, I-99, 1-1 14, 1-1 19, 1-120, resp I-
• the active ingredient 1-100 showed at a rate of 0.25 kg / ha postemergence against ALOMY a good and the active ingredients I-87, I-88, I-89, 1-101, 1-102, 1-174 , I-224, I-226, I-227, and I-228 a very good herbicidal activity.
• the active compounds 1-1 18, or 1-154 showed at a rate of 0, 125 kg / ha post-emergence against POLCO a good and the active ingredients I-32, I-76, I-94, I-96, 1-105, 1-106, 1-107, 1-108, 1-109, 1-112, 1-113, 1-119, 1-120, 1-122, 1-124, 1-144, 1- 150, I-151, 1-152, 1-153, 1-155, 1-156, 1-159, 1-171, and 1-192, respectively, has a very good herbicidal activity.
• the active ingredients I-87, I-95, 1-130, 1-215, and 1-216 showed at a rate of 0.25 kg / ha post-emergence against POLCO a good and the active ingredients I-79, I -88, 1-102, 1-126, 1-143, 1-164, 1-165, 1-166, 1-167, 1-168, 1-169, 1-170, 1-172, 1-173 , I-174, 1-175, 1-178, 1-179, 1-180, 1-181, 1-196, I-205, I-206, I-207, I-208, I-209, 1 -210, I-211, 1-212, 1-213, 1-214, 1-217, 1-218, 1-219, 1-220, and 1-221 a very good herbicidal activity.

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• 2010
  • 2010-06-29 WO PCT/EP2010/059185 patent/WO2011003776A2/de active Application Filing
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