Classifications

• • 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
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
  • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
  • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
  • C07D213/79—Acids; Esters

Definitions

• the present invention relates to novel, herbicidally active 6- (2-aminophenyl) picoline derivatives and to processes for their preparation.
• Another object of the present invention is its use as a herbicide, in particular as a herbicide for the selective control of harmful plants in crops, and as a plant growth regulator alone or in combination with safeners and / or in admixture with other herbicides. It is known from various publications that similarly substituted picoline derivatives have herbicidal or pesticidal properties:
• WO 2001/51468 and WO 2006/062979 describe herbicidally active derivatives of picolinic acids. However, in contrast to the present invention, these compounds have no phenyl substituent in the 6-position.
• WO 2003/011853, WO 2007/082098, WO 2007/092184 and WO 2009/046090 likewise describe herbicidally active, differently substituted 6-phenyl picolinates. However, in contrast to the present invention, these references do not disclose 6- (2-aminophenyl) substituted picolinates.
• WO 2010/099279 discloses exclusively N-alkoxyamide derivatives of 6-phenyl-substituted picolinic acids. However, the prior art does not disclose 6- (2-aminophenyl) substituted picolinic acid derivatives.
• WO 2010/060581 discloses 6-phenyl picolinates and their use as herbicides.
• n is an integer selected from 0, 1, 2, 3, 4;
• R 1 is selected from the group consisting of hydrogen, halogen, cyano, nitro, amino, hydroxy, (Ci-C 6 ) alkyl, (Ci-C 6 ) haloalkyl, (Ci-C 4 ) hydroxyalkyl, (C 2 -C 6 ) alkoxyalkyl, (C 2 -C 6 ) haloalkoxyalkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) haloalkenyl, (C 2 -
• R 2 is hydrogen, halogen, cyano, nitro, (Ci-C 6) alkyl, (Ci-C 6) haloalkyl, (C 1 - C 6) alkoxy, (Ci-C 6) alkylamino, (Ci-C 6) dialkylamino, (Ci-C6) thioalkoxy, (C 2 - C 6) alkenyl, (C 2 -C 6) haloalkenyl, (C 2 -C 6) alkynyl;
• R 4 is hydrogen, (C 1 -C 4 ) alkyl optionally substituted with one or two radicals
• R 5 is hydrogen, halogen, cyano, nitro, formyl, (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 2 -C 6 ) alkynyl, (C 1 -C 6 ) haloalkyl, (C 2 -C 6) haloalkenyl, (Ci-C 6) alkoxy, (Ci-C6) thioalkoxy, (C 2 -C 6) alkoxyalkyl, (C 2 -C 6) thioalkoxyalkyl;
• R 9 is hydrogen, (Ci-C 4) alkyl, (Ci-C 4) haloalkyl, (Ci-C 4) alkoxy, phenyl,
• R 10 is hydrogen, (C 1 -C 4 ) alkyl, (C 1 -C 3 ) haloalkyl or CHR 22 C (O) OR 23 ;
• R 11 is (C 1 -C 4) alkyl, (C 1 -C 4) haloalkyl or phenyl optionally substituted by one, two or three radicals independently selected from CH 3 ,
• R 13 is hydrogen or (C 1 -C 4 ) alkyl
• R 14 is hydrogen, (C 1 -C 4) alkyl or phenyl optionally substituted with one, two or three radicals independently selected from CH 3 , Cl or OCH 3 ;
• R 15 is hydrogen or (Ci-C4) alkyl; or R 14 and R 15 together form a -
• R 16 is independently halogen, (CiC 3 ) alkyl, (Ci-C 3 ) alkoxy, (CiC 3 ) halo alkoxy, (CC 3 ) alkylthio, (Ci-C 3 ) haloalkylthio, amino, (Ci-C 3 ) Alkylamino, (C 2 -
• R 17 is hydrogen or (Ci-C 4 ) alkyl
• R 20 is hydrogen or (C 1 -C 4 ) alkyl
• R 21 is (C 1 -C 4 ) alkyl;
• R " is hydrogen, (C 1 -C 4 ) alkyl, (C 1 -C 3 ) haloalkyl, (C 1 -C 4 ) alkoxy, phenyl, phenoxy or benzyloxy;
• R 23 is hydrogen, (C 1 -C 4 ) alkyl or (C 1 -C 4 ) alkoxy;
• R 24 is hydrogen, C 1 -C 4 alkyl or benzyl
• R 25 is independently halogen, cyano, nitro, (C 1 -C 6 ) alkyl, (C 1 -C 6 ) haloalkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) haloalkenyl, (C 3 -C 4 ) alkynyl, (C 3 - C 4) haloalkynyl, (Ci-C 4) alkoxy, (Ci-C 4) haloalkoxy, (Ci-C 4) alkylthio, (Ci- C4) haloalkylthio, (Ci-C4) alkylsulphinyl , (Ci-C 4) alkylsulfonyl, (Ci-C 4) alkylamino, (C 2 -C 8) dialkylamino, (C 2 -C 4) alkylcarbonyl, (C 2 -C 6) alkoxycarbonyl, (C 2
• a dimethylaminocarbonyl radical is a C3 radical.
• agrochemically suitable derivatives which is used to describe the variations of the carboxylic acid function according to the invention in the 2-position, denotes any esters, acylhydrazides, imidates, thioimidates, amidines, amides, orthoesters, acyl cyanides, acyl halides, thioesters, thionoesters, dithiol esters, Nitriles or other carboxylic acid derivatives known in the art, which
• Preferred agrochemically suitable derivatives of the picolinic acids of the formula (I) are therefore salts, amides and esters.
• agrochemically suitable derivatives also describes any silylamines, phosphorylamines, phosphinimines, phosphoramidates, sulfonamides, sulfilimides, sulfoximines, aminals, hemiaminals, amides, thioamides, carbamates, thiocarbamates, amidines, ureas, imines, nitro , Nitroso, azido or other nitrogen-containing derivatives, which in the state of Technique are described and
• Preferred agrochemically suitable derivatives with respect to the amino groups are therefore salts, amides, sulfonamides and carbamates.
• radicals have the following meanings X is selected from O, S, N H and N R ", where R" ei ne
• C4) is alkyl group
• n 0 or 1
• Y is selected from halogen, O, S and N;
• q 0, 1 or 2;
• p 1, 2 or 3
• R ' is selected from hydrogen, halogen, (Ci-C4) alkyl, (Cr C4) haloalkyl, (C 2 -C 4) alkoxyalkyl, (C 2 -C 4) alkylthioalkyl, (C 2 -C 4) alkenyl, oxiranyl, (Ci-C 4) Alkyloxiranyl, oxiranyl (Ci-C 4) alkyl, (C 2 -C 4) alkenyl halo, 2-Halooxiranyl, 3-Halooxiranyl, 2,3-Dihalooxiranyl, (C3- C6 ) Alkoxyalkenyl, (C 3 -C 6 ) alkylthioalkenyl, (C 2 -C 4 ) alkynyl, (C 2 -C 4 ) haloalkynyl, formyl, (C 2 -C 4 ) alkylcarbonyl, (C 2
• X is selected from O or S
• Q is 0 or 1
• M + has the meaning of a cation, particularly preferred are the sodium, potassium and ammonium salts of the compounds of formula (I) according to the invention.
• Fo rmel (l-c) represents salt-like derivatives of the compounds of the formula (I) according to the invention.
• Salt formation can in a known manner, for. B. by the action of a base on compounds of formula (I).
• Suitable bases are, for example, organic amines, such as trialkylamines, morpholine, piperidine or pyridine, and ammonia, ammonium, alkali metal or alkaline earth metal hydroxides, carbonates and bicarbonates, in particular sodium and potassium hydroxide, sodium and potassium carbonate and sodium and potassium bicarbonate.
• salts are compounds in which the acidic hydrogen is replaced by an agriculturally suitable cation, for example metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or salts with organic amines or ammonium salts, for example with ammonium ions of the formula [NRR 'R “R”'] +, wherein R, R ', R “and R'” are each independently H or an organic radical, in particular (C C6) alkyl, (C 6 -C 0) aryl, (C 7 -C 2 o) aralkyl or (C 7 -C 2 o) represent alkylaryl.
• an agriculturally suitable cation for example metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or salts with organic amines or ammonium salts, for example with ammonium ions of the formula [NRR 'R “R”'] +, wherein R, R
• Examples are [NH 4 ] ⁇ [NH 3 CH 3 ] + , [NH 2 (CH 3 ) 2 ] + , [NH (CH 3 ) 3 ] + , [N (CH 3 ) 4 ] + , [NH 2 CH 3 C 2 H 5 ] + or [NH 2 CH 3 C6H 5 ] + .
• alkylsulfonium and alkylsulfoxonium salts such as (C 1 -C 4) -trialkylsulfonium and (C 1 -C 4) -trialkylsulfoxonium salts.
• n is an integer selected from 0, 1, 2, 3 and 4;
• R 1 is independently selected from hydrogen, halogen, cyano, nitro, amino, (Ci-C 6) alkyl, (Ci-C 6) haloalkyl, (C 2 -C 6) alkoxyalkyl, (C 2 - C 6) haloalkoxyalkyl , (C 2 -C 6) alkenyl, (C 2 -C 6) haloalkenyl, (C 2 -C 6) alkynyl, (Ci- C 6) alkoxy, (Ci-C 6) haloalkoxy, (C 2 -C 6 ) haloalkenyloxy, (Ci-C 6) alkylthio, (C 2 - C 6) alkylthioalkyl, (Ci-C 6) haloalkylthio, (Ci-C 6) alkylsulfonyl, (CC 6) haloalkylsulfonyl, (C 2 -C 6)
• R 2 is hydrogen, halogen, cyano
• R 3 and R 4 together form a - (CH 2 ) 4 -, - (CH 2 ) 5 , - (CH 2 ) 20 (CH 2 ) - or
• Each R 6 is independently halo, (Ci-C3) alkoxy, (Cr C3) haloalkoxy, (Ci-C 3) alkylthio, (Ci-C 3) haloalkylthio, amino, (Ci-
• R a is independently hydrogen, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, (C 1 -C 4 ) alkoxy, phenyl, phenoxy, benzyl or benzyloxy;
• R 10 is hydrogen, (C 1 -C 4 ) alkyl or (C 1 -C 3 ) haloalkyl;
• R 11 is (C 1 -C 4) alkyl or phenyl optionally substituted with one, two or three radicals independently selected from CH 3 , Cl or OCH 3 ;
• R 13 is hydrogen or (C 1 -C 4 ) alkyl
• R 14 is hydrogen or (Ci-C 4 ) alkyl
• R 15 is hydrogen or (Ci-C 4 ) alkyl
• R 14 and R 15 together form a - (CH 2 ) 4 - or - (CH 2 ) 5 group;
• R 17 is hydrogen or (Ci-C 4 ) alkyl
• R 18 and R 19 are independently hydrogen or (C 1 -C 4 ) alkyl
• R 24 is hydrogen, C 1 -C 4 alkyl or benzyl.
• n is an integer selected from 0, 1, 2, 3 and 4
• R 1 with is independently selected from hydrogen, fluorine, chlorine,
• Methylthio, methoxycarbonyl, dimethylamino, R 2 is hydrogen, fluorine or chlorine;
• R 5 is hydrogen, fluorine or chlorine.
• carbonyl compounds may be present in both the keto form and the enol form, both of which are encompassed by the definition of the compound of formula (I).
• the compounds of the general formula (I) can exist as stereoisomers.
• the possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z and E isomers, geometric isomers and atropisomers, and mixtures thereof are all encompassed by formula (I).
• diastereomers Z and E isomers
• asymmetric carbon atoms asymmetrically substituted carbon atoms
• asymmetric sulfur atoms in the form of sulfoxides which may exist in two enantiomeric forms
• enantiomers and diastereomers may occur.
• Stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation methods.
• stereoisomers can be selectively prepared by using stereoselective reactions using optically active starting and / or adjuvants.
• the invention thus also relates to all Stereoisomers encompassed by the general formula (I) but not specified with their specific stereoform and mixtures thereof.
• the “ee” can be determined by various physical methods, such as chromatography on chiral sorbents in the liquid as well as the gas phase, NMR measurements with chiral derivatives, or by determination of the specific rotation, which, however, requires the specific rotation the pure enantiomer is known, the optical purity p
• optical yield P optical purity multiplied by 100
• ee optical purity multiplied by 100
• the compounds of formula (I) can form salts. Salt formation can through Effect of a base on such compounds of the formula (I) take place, which carry an acidic hydrogen atom, for example, in the case of a COOH group or a sulfonamide group -NHSO2- is contained.
• Suitable bases are, for example, organic amines such as trialkylamines, morpholine, piperidine or pyridine and ammonium, alkali metal or alkaline earth metal hydroxides, carbonates and bicarbonates, in particular sodium and potassium hydroxide, sodium and potassium carbonate and sodium and potassium bicarbonate.
• salts are compounds in which the acidic hydrogen is replaced by an agriculturally suitable cation, for example metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or else ammonium salts, salts with organic amines or quaternary ammonium salts
• metal salts in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or else ammonium salts, salts with organic amines or quaternary ammonium salts
• R 1 to R '" each independently of one another represent an organic radical, in particular alkyl, aryl, aralkyl or alkylaryl.
• suitable are also alkylsulfonium and alkylsulfoxonium salts, such as (Ci -C4) trialkylsulfonium and (C 1 -C 4) trialkylsulfoxonium salts.
• the compounds of formula (I) may be prepared by addition of a suitable inorganic or organic acid such as, for example, mineral acids such as HCl, HBr, H 2 SO 4 , H 3 PO 4 or HNO 3 , or organic acids, e.g.
• a suitable inorganic or organic acid such as, for example, mineral acids such as HCl, HBr, H 2 SO 4 , H 3 PO 4 or HNO 3 , or organic acids, e.g.
• carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicylic acid or sulfonic acids such as p-toluenesulfonic acid to form a basic group such as amino, alkylamino, dialkylamino, piperidino, morpholino or pyridino, salts.
• These salts then contain the conjugate base of the acid as an anion.
• Suitable substituents which are in deprotonated form e.g. Sulfonic acids or carboxylic acids, may form internal salts with their turn protonatable groups, such as amino groups.
• An inorganic radical is a radical without carbon atoms, preferably halogen, OH and its inorganic salts, in which the hydrogen is replaced by a cation, for example alkali metal salts and alkaline earth metal salts, -NH 2 and its ammonium salts with (inorganic) Acids, for example mineral acids, -N 3 (azide), -N 2 + A " (diazonium group, where A " represents an anion), -NO, -NHOH, -NHNH 2 , -NO 2 , -ONO, -ONO 2 , -SH, SOH (sulfenic acid group), S (O) OH (sulfinic acid group), S (O) 2 OH (or also short SO 3 H, sulfonic acid group), -O-SO 2 H (sulfite Group), -O-SO 3 H (sulfate group), -SO 2 NH 2 (sulfamoyl group), -SO 2
• organic radical here preferably does not include pseudohalogen groups such as CN, SCN, organic metal complexes, carbonate or COOH, which are better assigned to the organic radicals because of the content of carbon atoms.
• halogen means, for example, fluorine, chlorine, bromine or iodine.
• halogen means, for example, a fluorine, chlorine, bromine or iodine atom.
• Alkyl is a straight-chain, branched or cyclic hydrocarbon radical.
• the term "(C 1 -C 4) -alkyl” denotes, for example, a short notation for alkyl having one to 4 carbon atoms corresponding to the range indicated for C atoms and includes, for example, the radicals methyl, ethyl, 1-propyl, 2- Propyl, 1-butyl, 2-butyl, 2-methylpropyl, tert-butyl, cyclopropyl and cyclobutyl.
• General alkyl radicals having a larger specified range of carbon atoms eg. B.
• (Ci-C6) alkyl correspondingly include straight-chain, branched or cyclic alkyl radicals having a larger number of carbon atoms, ie according to Example, the alkyl radicals having 5 and 6 carbon atoms.
• hydrocarbon radicals such as alkyl, alkenyl and alkynyl radicals, even in assembled radicals, are the lower carbon skeletons, e.g. with 1 to 6 C atoms or with unsaturated groups having 2 to 6 C atoms, preferred.
• Preferred cyclic alkyl radicals preferably have 3-8 ring C atoms, e.g. Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
• cyclic systems are included with substituents, wherein substituents having a double bond on the cyclic alkyl radical, for.
• an alkylidene group such as methylidene, are included.
• polycyclic aliphatic systems are also included, such as bicyclo [1.1.0] butan-1-yl, bicyclo [1.1.0] butan-2-yl, bicyclo [2.1.0] pentan-1-yl , Bicyclo [2.1.0] pentan-2-yl, bicyclo [2.1.0] pentan-5-yl, bicyclo [2.2.1] hept-2-yl (norbornyl), adamantan-1-yl and adamantan-2 yl.
• spirocyclic aliphatic systems are also included, such as spiro [2.2] pent-1-yl, spiro [2.3] hex-1-yl, spiro [2.3] hex-4-yl, 3-spiro [ 2.3] hex-5-yl.
• Alkenyl and alkynyl radicals have the meaning of the possible unsaturated straight-chain, branched or cyclic radicals corresponding to the alkyl radicals, wherein at least one double bond or triple bond is contained. Preference is given to radicals having a double bond or having a triple bond.
• Alkenyl also includes straight-chain, branched or cyclic hydrocarbon radicals having more than one double bond, such as 1, 3-butadienyl, 1, 4-pentadienyl or cyclohexadienyl, but also allenyl or cumulenyl radicals having one or more cumulative double bonds, such as allenyl (1,2-propadienyl), 1,2-butadienyl and 1,2,3-pentatrienyl.
• Alkynyl also includes straight-chain, branched or cyclic hydrocarbon radicals having more than one triple bond or else having one or more triple bonds and one or more double bonds, for example 1,3-butatrienyl or 3-penten-1-yn-1-yl.
• Alkenyl means e.g. Vinyl, which may be substituted by further alkyl radicals k n, for.
• (C 2 -C 6) -alkynyl is, for example, ethinyl, propargyl, 1-methyl-prop-2-yn-1-yl, 2-butynyl, 2-pentynyl or 2-hexynyl, preferably propargyl, but-2-yn-1 yl, but-3-yn-1-yl or 1-methyl-but-3-yn-1-yl.
• Cyclic alkenyl radicals represent a carbocyclic, non-aromatic, partially unsaturated ring system preferably having 4-8 C atoms, e.g.
• Alkylidene e.g. B. also in the form (Ci-Cio) alkylidene, means the radical of a straight-chain, branched or cyclic hydrocarbon radical, which is bonded via a double bond.
• Aryl is a mono-, bi- or polycyclic aromatic system having preferably 6 to 14, in particular 6 to 10 ring C atoms, for example phenyl, naphthyl, anthryl, phenanthrenyl, and the like, preferably phenyl.
• aryl In the case of optionally substituted aryl, more cyclic systems, such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenylyl, are included, the binding site being on the aromatic system.
• aryl is also encompassed by the term "optionally substituted phenyl”.
• substituted by one or more radicals means, independently of one another, one or more identical or different radicals, it being possible for two or more radicals to form one or more rings on one cycle as main body.
• Substituted radicals such as a substituted alkyl, alkenyl, alkynyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radical, are, for example, a substituted radical derived from the unsubstituted radical, where the substituents are, for example, one or more, preferably 1, 2 or 3 radicals selected from the group consisting of halogen, alkoxy, alkylthio, hydroxy, amino, nitro, carboxy or a carboxy group equivalent group, cyano, isocyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as Acylamino, mono- and dialkylamino, trialkylsilyl and optionally substituted cyclic alkyl, optionally substituted aryl, optionally substituted heterocyclyl, wherein each of the latter cyclic groups may also be
• substituents in addition to the said saturated hydrocarbon-containing radicals corresponding unsaturated aliphatic and aromatic radicals such as optionally substituted alkenyl, alkynyl, alkenyloxy, alkynyloxy, alkenylthio, Alkynylthio, alkenyloxycarbonyl, alkynyloxycarbonyl, alkenylcarbonyl, alkynylcarbonyl, mono- and dialkenylaminocarbonyl, mono- and dialkynylaminocarbonyl, mono- and dialkenylamino, mono- and dialkynylamino, trialkenylsilyl, trialkynylsilyl, phenyl, phenoxy, etc., included.
• cyclic systems are also included having such substituents attached to the ring by a double bond, e.g. B. substituted with an alkylidene group such as methylidene or ethylidene or an oxo group, imino group or substituted imino group.
• an alkylidene group such as methylidene or ethylidene or an oxo group, imino group or substituted imino group.
• two or more radicals form one or more rings, these may be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, for example also aromatic and optionally further substituted.
• the fused rings are preferably 5- or 6-membered rings, particularly preferred are benzo-fused rings.
• first substituent level if they contain hydrocarbon-containing moieties, may optionally be further substituted there (“second substituent plane"), for example by one of the substituents as defined for the first substituent level.
• second substituent plane corresponds further substituent levels.
• substituted radical includes only one or two substituent levels.
• substituents for the substituent levels are, for example, amino, hydroxy, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxy, carbonamide, SF 5 , aminosulfonyl, alkyl, alkenyl, alkynyl, monoalkylamino, dialkylamino, N-alkanoylamino , Alkoxy, alkenyloxy, alkynyloxy, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryloxycarbonyl, alkanoyl, alkenyl carbonyl, alkynylcarbonyl, arylcarbonyl, alkylthio, alkenylthio, alkynylthio, alkylsulfenyl, alkylsulfinyl, wherein both enantiomers of the alkylsulfinyl group are included, alkyl
• Substituents which are composed of several substituent levels are preferably, for example, alkoxyalkyl, such as monoalkoxyalkyl or dialkoxyalkyl, alkylthioalkyl, alkylthioalkoxy, alkoxyalkoxy, such as monoalkoxyalkoxy or dialkoxyalkoxy, benzyl, phenethyl, benzyloxy, haloalkyl, haloalkoxy, haloalkylthio, haloalkanoyl, haloalkylcarbonyl, haloalkoxycarbonyl, haloalkoxyalkoxy, Haloalkoxyalkylthio, haloalkoxyalkanoyl, haloalkoxyalkyl, alkanoylalkyl, haloalkanoylalkyl, alkanoyloxyalkyl.
• radicals with carbon atoms preference is given to those having 1 to 6 C atoms, preferably 1 to 4 C atoms, in particular 1 or 2 C atoms.
• substituents from the group halogen for example fluorine and chlorine, (C 1 -C 4 ) -alkyl, preferably methyl or ethyl, (C 1 -C 4 ) -haloalkyl, preferably trifluoromethyl, (C 1 -C 4 ) -alkoxy, preferably methoxy or ethoxy, ( Ci-C4) haloalkoxy, nitro and cyano.
• substituents methyl, methoxy, fluorine and chlorine are particularly preferred.
• Substituted amino such as mono- or disubstituted amino means a radical from the group of substituted amino radicals which are N-substituted, for example by one or two identical or different radicals from the group alkyl, hydroxy, amino, alkoxy, acyl and aryl; preferably mono- and dialkylamino, mono- and diarylamino, such as optionally substituted anilines, acylamino, N, N-diacyl amino, N-alkyl-N-arylamino, N-alkyl-N-acylamino and saturated N-heterocycles; while alkyl radicals having 1 to 4 carbon atoms are preferred;
• Aryl is preferably phenyl or substituted phenyl; for acyl, the below applies mentioned definition, preferably (Ci-C4) alkanoyl. The same applies to substituted hydroxylamino or hydrazino.
• Substituted amino also includes quaternary ammonium compounds (salts) having four organic substituents on the nitrogen atom.
• a group equivalent to carboxy group means an alkyl ester, aryl ester, O-alkyl thioester, S-alkyl dithioester, S-alkyl thioester, carboximide ester, carboximide thioester; 5,6-dihydro-1,2,4-dioxazin-3-yl; 5,6-dihydro-1,2,4-oxathiazin-3-yl, trialkylorthoesters, dialkoxyalkylamino esters, dialkylaminoalkoxyesters, trialkylamino esters, amidines, dialkoxyketene acetals or dialkyldithioketene acetals.
• Optionally substituted phenyl is preferably phenyl which is unsubstituted or mono- or polysubstituted, preferably up to three times by identical or different radicals from the group halogen, (C 1 -C 4 ) -alkyl, (C 1 -C 4 ) -alkoxy, (C 1 -C 4 ) -alkoxy - (Ci-C 4 ) alkoxy, (Ci-C 4 ) alkoxy- (Ci-C 4 ) alkyl, (Ci-C 4 ) haloalkyl, (CiC 4 ) haloalkoxy, (CiC 4 ) alkylthio, (Ci-C 4 ) Haloalkylthio, cyano, isocyano and nitro, for example, o-, m- and p-tolyl, dimethylphenols, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-fluorophenyl, 2-,
• Optionally substituted cycloalkyl is preferably cycloalkyl which is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group halogen, cyano, (CiC 4) alkyl, (CiC 4) alkoxy, (CiC 4 ) alkoxy- (CiC 4) alkoxy, (CiC 4) alkoxy- (CiC 4) alkyl, (CiC 4) haloalkyl and (CiC 4) haloalkoxy, in particular by one or two (CiC 4 ) alkyl radicals is substituted,
• Optionally substituted heterocyclyl is preferably heterocyclyl is unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by identical or different radicals from the group halogen, cyano, (CiC 4) alkyl, (CiC 4) alk oxy, (CiC 4 ) alkoxy (Ci-C 4) alkoxy, (Ci-C 4) alkoxy (Ci-C 4) alkyl, (Ci-C 4) haloalkyl, (Ci-C4) haloalkoxy, nitro and oxo is substituted, in particular one or more times by radicals from the group halogen, (Ci-C4) alkyl, (Ci-C4) alkoxy, (Ci-C4) haloalkyl and oxo, very particularly is substituted by one or two (Ci-C-4) alkyl radicals.
• monohaloalkyl such as CH 2 CH
• An organic acid residue means a residue of an oxo acid or thioacid of the general formula
• R is an organic residue
• E is an atom from the group C, S, P,
• R ' is independently a hydrogen atom, alkyl, haloalkyl, alkoxyalkyl or optionally aryl.
• z is a natural number or zero.
• the organic acid radical is formally formed by separating a hydroxy group on the acid function, wherein the organic radical R in the acid can also be connected via one or more heteroatoms with the acid function:
• organic acid radicals derived from the oxo acids or thio acids of sulfur are S (O) OCH 3 , SO 2 OH, SO 2 OCH 3 or SO 2 NHR (N-substituted sulfonamide acids).
• alkylsulfonyl and alkylsulfinyl radicals such as (H 3 C) S (O) 2 , (F 3 C) S (O) 2 , p-tolylS (O) 2 , (H 3 C) S (O) (NH-nC 4 H 9) (C 6 H 5) S (S) (O) or (C 6 H 5) S (O) with covers.
• alkylphosphinyl and alkylphosphonyl radicals such as (H 3 C) 2 P (O), (C 6 H 5 ) 2 P (O), (H 3 C) (C 6 H 5 ) P (O); (H 3 C) P (O) OCH 3 , (H 5 C 2 ) P (O) (OC 2 H 5 ), (C 6 H 5 ) P (O) (OC 2 H 5 ), (C 2 H 5 ) P (O) (SC 6 H 5 ), (H 3 C) P (O) NH (C 6 H 5 ), (H 3 C) P (S) (NH-iC 3 H 7 ), (C 6 H 5 ) P (S) (OC 2 H 5 ) or (C 6 H 5 ) P (S) (SC 2 H 5 ).
• acyl are the radical -CO-R of a carboxylic acid HO-CO- R and residues thereof derived acids or the residue of carbonic acid monoesters or N-substituted carbamic acids and carbonates and their esters.
• Acyl for example, formyl, oxalyl (ester), alkylcarbonyl as [(C 1 -C 4) alkyl] carbonyl, haloalkylcarbonyl, phenylcarbonyl, alkyloxycarbonyl, especially tert-butyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, fluorenyloxycarbonyl, N-alkyl-1-iminoalkyl, N-alkyl and N, N-dialkylcarbamoyl.
• the radicals may each be further substituted in the alkyl or phenyl part, for example in the alkyl part by one or more radicals from the group halogen, cyano, alkoxy, phenyl and phenoxy;
• substituents in the phenyl moiety are the substituents already mentioned above generally for substituted phenyl.
• Acyl is preferably an acyl radical in the strictest sense, ie a radical of an organic acid in which the acid group is bonded directly to the C atom of an organic radical, for example alkanoyl, such as formyl and acetyl, aroyl, such as phenylcarbonyl, and other radicals of saturated or unsaturated organic acids.
• Aroyl means an aryl radical as defined above bonded through a carbonyl group, e.g. the benzoyl group.
• the present invention also provides methods for the preparation of the compounds according to the invention.
• the compounds of the invention may alternatively be prepared by various methods.
• inert solvents respectively designate solvents which are inert under the respective reaction conditions, but which need not be inert under any desired reaction conditions.
• the reaction can be carried out, for example, in various solvents such as water, methanol, ethanol, tetrahydrofuran, dioxane, diethyl ether, dichloromethane, dichloroethane, acetonitrile, toluene or other suitable solvents or corresponding mixtures.
• the reaction temperatures are generally between 0 ° C and 100 ° C.
• compounds of the formula (II) react with the compounds of the formula (III) using a suitable base such as, for example, triethylamine, potassium tert-butylate, potassium carbonate, potassium acetate, potassium phosphate, sodium bicarbonate, sodium carbonate, barium hydroxide, sodium hydroxide, cesium carbonate or cesium fluoride, and a suitable palladium catalyst such.
• a suitable base such as, for example, triethylamine, potassium tert-butylate, potassium carbonate, potassium acetate, potassium phosphate, sodium bicarbonate, sodium carbonate, barium hydroxide, sodium hydroxide, cesium carbonate or cesium fluoride, and a suitable palladium catalyst such.
• Pd (PPh 3) 4, Pd (OAc) 2, Pd (dppf) 2Cl2, or Pd2 (dba) 3 The addition of further ligands such as X-Phos, S-Phos, Ru-Phos, P (iBu) 3 , P (Cy) 3, P (o-Tol) 3 leads in some cases to improved yields or allows the reaction at all.
• Suitable solvents for these reactions are, for example, methanol, ethanol, toluene, dimethylformamide, dimethyl sulfoxide, dioxane, tetrahydrofuran, dimethoxyethane, ethylene glycol and water; It is also possible to use different solvent mixtures.
• the reactions are usually carried out at a temperature between 20 ° C and 200 ° C. Especially at higher temperatures, the use of microwave technology is suitable (see, for example: “Microwaves in Organic and Medicinal Chemistry", CO cap and A. Stadler, Verlag Wiley, 2005)
• One possibility for the preparation of compounds of the formula (III) is the reaction of ortho-halogenated anilines of the formula (V) with boronates of the formula (VI) or diboranes of the formula (VII).
• a suitable base such as.
• triethylamine, potassium tert-butylate, potassium acetate, potassium phosphate, sodium carbonate or cesium fluoride, and a suitable palladium catalyst such.
• the boronic esters of formula (III) can be generated.
• Suitable solvents for this reaction are, for example, toluene, dimethylformamide, dimethyl sulfoxide, dioxane, tetrahydrofuran, dimethoxyethane or ethylene glycol.
• the implementations usually run at a temperature between 20 ° C and 200 ° C.
• Collections of compounds according to the invention which can be synthesized after the abovementioned reactions can also be prepared in a parallelized manner
• the preparation of compounds according to the invention can be carried out completely or partially by methods supported by solid phases. Both solid and liquid phases can be supported by the implementation of single or multiple synthetic steps through the use of microwave technology. A number of experimental protocols are described in the specialist literature, for example in Microwaves in Organic and Medicinal Chemistry (publishers C. O. Kappe and A. Stadler), Verlag Wiley, 2005.
• Compounds of the invention are excellent in their herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous weeds, as well as perennial weed pests which are difficult to control and which drive out of rhizomes, rhizomes or other permanent organs.
• the present invention therefore also provides a process for controlling undesirable plants or for regulating the growth of plants, preferably in plant crops, wherein one or more compounds of the invention are applied to the plants (eg harmful plants such as monocotyledonous or dicotyledonous weeds or unwanted crops), the seeds (eg grains, seeds or vegetative propagules such as tubers or sprout parts with buds) or the area on which the plants grow (eg the acreage) are applied.
• the compounds of the invention may be e.g. in pre-sowing (possibly also by incorporation into the soil), pre-emergence or Nachauflaufmaschinen be applied.
• some representatives of the monocotyledonous and dicotyledonous weed flora may be mentioned, which can be controlled by the compounds according to the invention, without the intention of being restricted to certain species.
• the compounds according to the invention are applied to the surface of the earth before germination, then either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then cease their growth and finally die off completely after a lapse of three to four weeks.
• the compounds of the invention have excellent herbicidal activity against mono- and dicotyledonous weeds, crops of economically important crops, e.g. dicotyledonous cultures of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Miscanthus, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous cultures of the genera Allium, Pineapple , Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Seeale, Sorghum, Triticale, Triticum, Zea, especially Zea and Triticum, depending on the structure of the respective compound of the invention and their application rate only insignificantly or not at all damaged.
• the present compounds are very well suited for the selective control of undesired plant growth in crops such as agricultural crops or ornament
• the compounds of the invention (depending on their respective structure and the application rate applied) excellent growth-regulatory properties in crop plants. They regulate the plant's metabolism and can thus be used to specifically influence plant ingredients and facilitate harvesting, eg by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops, since, for example, storage formation can thereby be reduced or completely prevented.
• the active compounds can also be used for controlling harmful plants in crops of known or yet to be developed genetically modified plants.
• the transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
• Other special properties concern e.g. the crop in terms of quantity, quality, shelf life, composition and special ingredients.
• transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.
• Other particular properties may include tolerance or resistance to abiotic stressors, e.g. Heat, cold, drought, salt and ultraviolet radiation are present.
• the compounds of the formula (I) can be used as herbicides in crops which are resistant to the phytotoxic effects of the herbicides or have been made genetically resistant.
• transgenic crops which are resistant to certain glufosinate-type herbicides (cf., for example, EP 0242236 A, EP 0242246 A) or glyphosate (WO 92/000377 A) or the sulfonylureas (EP 0257993 A, US Pat. No. 5,013,659) or to combinations or mixtures of these herbicides "Gene stacking" are resistant, such as transgenic crops such as corn or soybean with the
• Transgenic crops such as cotton, with the ability to produce Bacillus thuringiensis toxins (Bt toxins), which make the plants resistant to certain pests (EP 0142924 A, EP 0193259 A).
• Bacillus thuringiensis toxins Bacillus thuringiensis toxins
• transgenic crops characterized by a combination of e.g. the o. g. characterize new properties ("gene stacking")
• nucleic acid molecules can be introduced into plasmids that allow mutagenesis or sequence alteration by recombination of DNA sequences.
• Base exchanges are made, partial sequences removed or natural or synthetic sequences added.
• For the connection of the DNA fragments with one another adapters or linkers can be attached to the fragments, see e.g. Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd Ed. Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY; or Winnacker "Genes and Clones", VCH Weinheim 2nd edition 1996
• the production of plant cells having a reduced activity of a gene product can be achieved, for example, by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a cosuppression effect, or the expression of at least one appropriately engineered ribozyme which specifically cleaves transcripts of the above gene product.
• DNA molecules can be used which contain the entire coding sequence of a gene product, including any genes flanking sequences, as well as DNA molecules comprising only parts of the coding sequence, which parts must be long enough to cause an antisense effect in the cells. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product but are not completely identical.
• the synthesized protein may be located in any compartment of the plant cell.
• the coding region is linked to DNA sequences which ensure localization in a particular compartment.
• sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad., U.S.A. 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106).
• the expression of the nucleic acid molecules can also take place in the organelles of the plant cells.
• the transgenic plant cells can be regenerated to whole plants by known techniques.
• the transgenic plants may, in principle, be plants of any plant species, that is, both monocotyledonous and dicotyledonous plants.
• the compounds (I) according to the invention can be used in transgenic cultures which are resistant to growth substances, such as 2,4 D, dicamba or herbicides, the essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD) inhibit, respectively against herbicides from the group of Sulfonylureas, the glyphosate, glufosinate or Benzoylisoxazole and analogous drugs, or against any combination of these agents, resistant.
• the essential plant enzymes for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD) inhibit, respectively against herbicides from the group of Sulfonylureas, the glyphosate, glufosinate or Benzoylisoxazole and analogous drugs, or against
• the compounds according to the invention can particularly preferably be used in transgenic crop plants which are resistant to a combination of glyphosates and glufosinates, glyphosates and sulfonylureas or imidazolinones. Most preferably, the compounds of the invention in transgenic crops such. As corn or soybean with the trade name or the name Optimum TM GAT TM (Glyphosate ALS Tolerant) are used.
• the invention therefore also relates to the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
• the compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations.
• the invention therefore also relates to herbicidal and plant growth-regulating agents which contain the compounds according to the invention.
• the compounds according to the invention can be formulated in various ways, depending on which biological and / or chemical-physical Parameter specified si nd.
• Possible formulation options are, for example, wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions , sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), mordants, granules for litter and soil application, granules (GR) in the form of micro-, spray -, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
• WP wettable powders
• SP water-soluble powders
• EC emul
• Injectable powders are preparations which are uniformly dispersible in water and contain surfactants of the ionic and / or nonionic type (wetting agents, dispersants), eg polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ethersulfates, alkanesulfonates, alkylbenzenesulfonates in addition to the active substance except a diluent or inert substance.
• surfactants of the ionic and / or nonionic type (wetting agents, dispersants), eg polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ethersulfates, alkanesulfonates, alkylbenzenesulfonates in addition to the active substance except a
• the herbicidal active compounds are finely ground, for example in customary apparatus such as hammer mills, blower mills and air jet mills, and mixed simultaneously or subsequently with the formulation auxiliaries.
• Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers).
• organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents.
• alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers
• fatty acid polyglycol esters alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensation products
• alkyl polyethers sorbitan esters such as e.g. Sorbitan fatty acid esters or polyoxethylenesorbitan esters such as e.g. Polyoxyethylene sorbitan fatty acid ester.
• Dusts are obtained by milling the active ingredient with finely divided solids, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
• Suspension concentrates may be water or oil based. They can be prepared, for example, by wet grinding by means of commercially available bead mills and, if appropriate, addition of surfactants, as already listed above, for example, in the other formulation types.
• Emulsions for example oil-in-water emulsions (EW)
• EW oil-in-water emulsions
• Granules can either be prepared by atomizing the active ingredient on adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils, on the surface of carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the manufacture of fertilizer granules, if desired in admixture with fertilizers. Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
• the agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention.
• the active ingredient concentration is, for example, about 10 to 90 wt .-%, the remainder to 1 00 wt .-% consists of conventional formulation components. at emulsifiable concentrates, the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%.
• Dust-like formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% active ingredient.
• the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used. In the case of the water-dispersible granules, the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
• the active substance formulations mentioned optionally contain the customary adhesion, wetting, dispersing, emulsifying, penetrating, preserving, antifreeze and solvent, fillers, carriers and dyes, antifoams, evaporation inhibitors and the pH and the Viscosity-influencing agent.
• the compounds according to the invention can be combined with further fungicidal, insecticidal, nematicidal or herbicidal active substances or with safeners.
• combination partners for the compounds according to the invention in mixture formulations or in the tank mix are known active compounds which are based on inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase , p-hydroxyphenylpyruvate dioxygenase, phytoene desaturase, photosystem I, photosystem II, protoporphyrinogen oxidase are based, can be used, for example from Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 15th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2006 and cited therein.
• Examples of known herbicides or plant growth regulators which can be combined with the compounds according to the invention are the following active substances (the compounds are either with the "common name” according to the International Organization for Standardization (ISO) or with the chemical name or with the code number designated) and always include all forms of application such as acids, salts, esters and isomers such as stereoisomers and optical isomers.
• ISO International Organization for Standardization
• plant growth regulators as possible mixing partners are:
• Dichlorophenylpyrazoline-3-carboxylic acid type compounds (S1 a ), preferably compounds such as
• Dichlorophenylpyrazolecarboxylic acid derivatives (S1 b), preferably compounds such as 1 - (2,4-dichlorophenyl) -5-methylpyrazole-3-carboxylate (S1-2), 1- (2,4-dichlorophenyl) -5-isopropylpyrazol-3- carboxylic acid ethyl ester (S1-3), 1- (2,4-dichlorophenyl) -5- (1, 1-dimethyl-ethyl) pyrazole-3-carboxylic acid ethyl ester (S1-4) and related compounds as described in EP-A 333,131 and EP-A-269,806 are described;
• 1, 5-diphenylpyrazole-3-carboxylic acid S1 c
• compounds such as 1 - (2,4-dichlorophenyl) -5-phenylpyrazole-3-carboxylic acid ethyl ester (S1-5), 1- (2-chlorophenyl ) -5-phenylpyrazole-3-carboxylic acid methyl ester (S1-6) and related compounds as described, for example, in EP-A-268554;
• Verbi ndgen the type de r (5-chloro-8-quinolinoxy) malonic acid (S2 b ), preferably compounds such as diethyl (5-chloro-8-quinolinoxy) malonate, (5-chloro-8-quinolinoxy) malonate, (5-chloro-8-chino-linoxy) -malonic acid methyl ethyl ester and related compounds, as described in EP-A-0 582 198. S3) Active substances of the dichloroacetamide type (S3), which are often used as pre-emergence safener (soil-active safener), such as. B.
• R A 2 is halogen, (Ci-C 4) alkyl, (Ci-C 4) alkoxy, CF 3;
• v A 0, 1, 2 or 3;
• R B 3 is halogen, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl or (C 1 -C 4 ) alkoxy and m B is 1 or 2, for example those in which
• R B 1 cyclopropyl
• R B 2 hydrogen
• (R B 3 ) 2-OMe (S4-1, "Cyprosulfamide",)
• R B 1 isopropyl
• n D is an integer from 0 to 2.
• R E 1 is halogen, (C 1 -C 4 ) alkyl, methoxy, nitro, cyano, CF 3 , OCF 3
• n E is an integer from 0 to 4,
• R E 2 is (C 1 -C 6 ) alkyl, (C 2 -C 6 ) alkenyl, (C 3 -C 6 ) cycloalkyl, aryl; Benzyl, halobenzyl, R E 3 is hydrogen or (Ci-C 6 ) alkyl.
• “Oxabetrinil” ((Z) -1, 3-dioxolan-2-ylmethoxyimino- (phenyl) acetonitrile) (S1 1-1), which is known as millet safener for millet against damage by metolachlor
• "FI uxof enim” (1- (4-chlorophenyl) -2,2,2-trifluoro-1-ethanone-O- (1,3-dioxolan-2-ylmethyl) -oxime) (S11-2), which was used as a Seed pickling safener for millet is known against damage from metolachlor, and
• Naphthalene anhydride (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as a seed safener for corn against damage by thiocarbamate herbicides.
• MG 191 (CAS Reg. No. 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as safener for corn,
• Mephenate (4-chlorophenyl methylcarbamate) (S13-9).
• S14) active substances which, in addition to a herbicidal action against harmful plants, also have safener action on crop plants such as rice, such as rice.
• B. "Dimepiperate” or “MY-93” (S-1-methyl-1-phenylethyl-piperidine-1-carbothioate), which is known as a safener for rice against damage by the herbicide Molinate,
• NK 049 3,3'-dimethyl-4-methoxy-benzophenone
• COD (1-bromo-4- (chloromethylsulfonyl) benzene) by Kumiai, (CAS No. 54091-06-4), which is known as a safener against damage of some herbicides in rice.
• R H 1 is a (Ci-C6) haloalkyl radical
• R H 2 is hydrogen or halogen
• R H 3 , R H 4 independently of one another are hydrogen, (Ci-Ci6) alkyl, (C-2-C-i6) alkenyl or (C 2 -C 6 ) alkynyl,
• each of the last-mentioned 3 radicals is unsubstituted or substituted by one or more radicals from the group halogen, hydroxy, cyano,
• each of the last-mentioned 4 radicals is unsubstituted or substituted by one or more radicals from the group halogen, hydroxy, cyano,
• R is H 3 (C 1 -C 4 ) alkoxy, (C 2 -C 4 ) alkenyloxy, (C 2 -C 6 ) alkynyloxy or (C 2 -C 4 ) haloalkoxy and
• R H 4 is hydrogen or (Ci-C 4 ) -alkyl or
• R H 3 and R H 4 together with the directly bonded N atom, a four- to eight-membered heterocyclic ring, which may contain in addition to the N-atom also further hetero atoms, preferably up to two other heteroargum from the group N, O and S, and unsubstituted or substituted by one or more radicals from the group halogen, cyano, nitro, (Ci-C4) alkyl,
• (Ci-C 4 ) haloalkyl, (Ci-C 4 ) alkoxy, (Ci-C 4 ) haloalkoxy and (Ci-C 4 ) alkylthio is substituted, means.
• Some of the safeners are also known as herbicides and thus, in addition to the herbicidal action in harmful plants, at the same time also have a protective effect on the crop plants.
• the weight ratio of herbicide (mixture) to safener generally depends on the application rate of herbicide and the effectiveness of the particular safener and can vary within wide limits, for example in the range from 200: 1 to 1: 200, preferably 100: 1 to 1: 100, in particular 20: 1 to 1:20.
• the safeners can be formulated analogously to the compounds according to the invention or mixtures thereof with further pesticides and can be provided and used as finished formulation or tank mixture with the compounds according to the invention.
• the formulations present in commercially available form are optionally diluted in a customary manner, for.
• emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dust-like preparations, ground or scattered granules and sprayable solutions are usually no longer diluted with other inert substances before use.
• the required application rate of the compounds of the invention varies. It can vary within wide limits, eg. B. between 0.001 and 10.0 kg / ha or more active substance, but it is preferably between 0.005 and 5 kg / ha. Examples
• the reaction mixture is degassed with nitrogen, the catalyst Pd (PPh 3 ) 4 added (0.05 equivalent) and heated in the closed vessel for 2 hours in the microwave to 130 ° C.
• the mixture is then treated with ethyl acetate and water, the organic phase is separated, dried over magnesium sulfate and concentrated in vacuo.
• the resulting crude product is purified by chromatography on silica gel with various eluents (preferably a mixture of ethyl acetate / n-heptane or methanol / dichloromethane) or recrystallized to give the pure product.
• the resulting crude product is purified by chromatography on silica gel with various eluents (preferably a mixture of ethyl acetate / n-heptane or methanol / dichloromethane) or / and recrystallized to give the pure product.
• various eluents preferably a mixture of ethyl acetate / n-heptane or methanol / dichloromethane
• the methyl ester obtained from Synthesis Instructions (A) or (B) (1.0 equivalent) is dissolved in tetrahydrofuran (3 ml / mmol of the methyl ester used) and sodium hydroxide solution (1.2 equivalents, 0.5 molar) was added. It is stirred for four hours at room temperature and then acidified with 10% sulfuric acid. The mixture is extracted several times with ethyl acetate, the organic phases dried with magnesium sulfate and concentrated in vacuo. The resulting crude product is purified by preparative HPLC or recrystallized to give the pure product.
• the substance is prepared analogously to general synthesis instructions (A).
• the substance is prepared analogously to general synthesis instructions (A).
• the substance is prepared analogously to general synthesis instructions (A).
• Methyl 4-amino-6- (2-amino-4-chlorophenyl) -3-chloro-5-fluoropyridine-2-carboxylate (Ex. No. 62) is dissolved in acetonitrile and N-chlorosuccinimide (3.0 equivalents) added. The mixture is refluxed for two hours, added to diethyl ether and then washed with water. The organic
• the substance is prepared analogously to general synthesis instructions (B).
• the substance is prepared analogously to general synthesis instructions (B).
• Methyl 4-amino-6- (2-amino-3-chloro-5-fluorophenyl) -3-chloropyridine-2-carboxylate (Ex. No. 638) is dissolved in acetonitrile and N-chlorosuccinimide (1.1 eq.) Is added. The mixture is stirred for 48 hours at room temperature, added to ethyl acetate and then washed with water. The organic Phase is dried over magnesium sulfate, concentrated and
• the substance is prepared analogously to general synthesis instructions (B).
• the substance is prepared analogously to general synthesis instructions (B).
• the substance is prepared analogously to general synthesis instructions (B).
• Methyl 4-amino-6- (2-amino-4- (trifluoromethyl) -5-chlorophenyl) -3-chloropyridine-2-carboxylate (Ex. No. 648) is dissolved in tetrahydrofuran and N-chlorosuccinimide (2.0 equivalents) added. The mixture is added for 48 hours
• the substance is prepared analogously to general synthesis instructions (B).
• the substance is prepared analogously to general synthesis instructions (B).
• Synthesis protocol (A) first prepared the Boc-protected Derviat. The yield of this Suzuki coupling is 51%. The subsequent removal of the Boc protective group is carried out by dissolving the crude product in dichloromethane, adding trifluoroacetic acid, subsequent neutralization by means of aqueous sodium bicarbonate solution and extraction from the aqueous phase. It is recrystallized from ethyl acetate / heptane. The yield is 63%.
• the substance is prepared analogously to general synthesis instructions (B).
• the substance is prepared analogously to general synthesis instructions (B).
• the substance is prepared analogously to general synthesis instructions (B).

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  • 2011-12-15 AR ARP110104713A patent/AR084317A1/es unknown
• 2013
  • 2013-05-29 ZA ZA2013/03920A patent/ZA201303920B/en unknown

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