Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
  • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
  • C07D513/04—Ortho-condensed systems
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
  • A01P13/00—Herbicides; Algicides
  • A01P13/02—Herbicides; Algicides selective

Definitions

• Substituted thiazolopyridines, salts thereof and their use as herbicidally active substancesrelates to the technical field of crop protection agents, in particular that of herbicides for the selective control of broad-leaved weeds and weed grasses in crops of useful plants.
• the present inventionrelates to substituted thiazolopyridines and salts thereof, to processes for their preparation and to their use as herbicides.
• crop protection agents known to date for the selective control of harmful plants in crops of useful plants or active compounds for controlling unwanted vegetationsometimes have disadvantages, be it (a) that they have no or insufficient herbicidal activity against particular harmful plants, (b) that the spectrum of harmful plants which can be controlled with an active compound is not broad enough, (c) that their selectivity in crops of useful plants is too low and/or (d) that they have a toxicologically unfavourable profile.
• active compounds which can be used as plant growth regulators for a number of useful plantscause unwanted reduced harvest yields in other useful plants or are not compatible with the crop plant, or only within a narrow application rate range.
• WO2019/089580discloses that substituted thiazolopyridines or pharmaceutically acceptable salts thereof can be used as a method for treating haematological disorders and solid malignant tumours via inhibition of IRAK4 and BCL-2 kinases.
• WO2018/178947concerns the preparation of substituted thiazolopyridines and their use for the treatment of acute myeloid leukaemia.
• WO2017/153601relates to substituted thiazolopyridines and their use as a treatment for diseases that involve the build-up of amyloid-like proteins, such as Parkinson’s disease.
• WO 2010/135524discloses substituted thiazolopyridines inhibitors of phosphatidylinositol 3-kinase (PI3K ⁇ ) that can be used against proliferative diseases.
• PI3K ⁇phosphatidylinositol 3-kinase
• Several documents(WO2016/087373, WO2014/125651, WO2013/018928, EP1000946, WO2012/086848 and JP2019/112369) describe that substituted thiazolopyridines and acceptable salts thereof can be used as effective pest control agents.
• WO2003/006470 and WO2017/110863reports that substituted thiazolopyridines can be potent fungicidal agents.
• WO2010/016846describes that substituted thiazolopyridines and related compounds are able to modulate TGR5. This modulation of TGR5 could represent a new opportunity to treat patients suffering from metabolic syndrome (Syndrome X).
• the publication entitled “Synthesis of Thiazolo[4,5- d]pyridines”shows various methods to prepare compounds containing a thiazolopyridine core.
• the substituted thiazolopyridines or salts thereof reported hereinhave not been previously described as herbicidally active compounds. Surprisingly, it has now been found that substituted thiazolopyridines or salts thereof are particularly suitable as herbicides.
• herbicides that are known to date for controlling harmful plants in crops of useful plants or herbicides for controlling unwanted vegetationsometimes have disadvantages, be it (a) that they have no or insufficient herbicidal activity against particularly harmful plants, (b) that the spectrum of harmful plants which can be controlled with an active compound is not broad enough, and/or (c) that the selectivity of the herbicides in and their compatibility with crop plants is too low, thereby causing unwanted damage and/or unwanted reduced harvest yields of the crops.
• herbicidesin particular highly active herbicides that are useful at low application rates and/or having good compatibility with crop plants, for the selective application in plant crops or use on non-crop land.
• the present inventionprovides substituted thiazolopyridines of the general formula (I) or salts thereof in which R 1 represents (C 3 -C 8 )-cycloalkyl, (C 3 -C 8 )-cycloalkenyl, (C 3 -C 8 )-cycloalkoxy, aryl, heteroaryl, heterocyclyl, a bicyclic or a heterobicyclic residue, wherein each of the previously mentioned eight residues is unsubstituted or is independently substituted by one or more residues selected from the group R 5 , R 2 represents hydrogen, halogen, formyl, hydroxy, hydrothio, hydroxycarbonyl, aminocarbonyl, aminothiocarbonyl, (C 1 -C 8 )-alkyl, (C 1 -C 8 )-haloalkyl, (C 2 -C 8 )-alkenyl, (C 2 -C 8 )-haloalkenyl, (C 2 -C 8 )-hal
• the compounds of the general formula (I)can form salts by addition of a suitable inorganic or organic acid, for example mineral acids, for example HCl, HBr, H 2 SO 4 , H 3 PO 4 or HNO 3 , or organic acids, for example carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, lactic acid or salicylic acid or sulfonic acids, for example p-toluenesulfonic acid, onto a basic group, for example amino, alkylamino, dialkylamino, piperidino, morpholino or pyridino.
• these saltswill comprise the conjugated base of the acid as the anion.
• Suitable substituents in deprotonated formare capable of forming internal salts with groups, such as amino groups, which are themselves protonatable. Salts may also be formed by action of a base on compounds of the general formula (I).
• Suitable basesare, for example, organic amines such as trialkylamines, morpholine, piperidine and pyridine, and the hydroxides, carbonates and bicarbonates of ammonium, alkali metals or alkaline earth metals, especially sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
• saltsare compounds in which the acidic hydrogen is replaced by an agriculturally suitable cation, for example metal salts, especially 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, for example with cations of the formula [NR a R b R c R d ] + in which R a to R d are each independently an organic radical, especially alkyl, aryl, arylalkyl or alkylaryl.
• an agriculturally suitable cationfor example metal salts, especially 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, for example with cations of the formula [NR a R b R c R d ] + in which R a to R d are each independently an organic radical, especially alkyl, aryl,
• alkylsulfonium and alkylsulfoxonium saltssuch as (C 1 -C 4 )-trialkylsulfonium and (C 1 -C 4 )- trialkylsulfoxonium salts.
• the substituted thiazolopyridines of the general formula (I) according to the inventioncan, depending on external conditions such as pH, solvent and temperature, be present in various tautomeric structures, all of which are embraced by the general formula (I).
• the compounds of the formula (I) used in accordance with the invention and salts thereofare also referred to hereinafter as "compounds of the general formula (I)".
• the inventionpreferably provides compounds of the general formula (I) in which R 1 represents (C 3 -C 6 )-cycloalkyl, (C 3 -C 6 )-cycloalkenyl, (C 3 -C 6 )-cycloalkoxy, aryl, heteroaryl, heterocyclyl, a bicyclic or a heterobicyclic residue, wherein each of the previously mentioned eight residues is unsubstituted or is independently substituted by one or more residues selected from the group R 5 , R 2 represents hydrogen, halogen, formyl, hydroxy, hydrothio, hydroxycarbonyl, aminocarbonyl, aminothiocarbonyl, (C 1 -C 6 )-alkyl, (C 1 -C 6 )-haloalkyl, (C 2 -C 6 )-alkenyl, (C 2 -C 6 )-haloalkenyl, (C 2 -C 6 )-alkynyl, (C 2 -C 6
• the inventionmore preferably provides compounds of the general formula (I) in which R 1 represents (C 3 -C 6 )-cycloalkyl, (C 3 -C 6 )-cycloalkenyl, (C 3 -C 6 )-cycloalkoxy, aryl, heteroaryl, heterocyclyl, a bicyclic or a heterobicyclic residue, wherein each of the previously mentioned eight residues is unsubstituted or is independently substituted by one or more residues selected from the group R 5 , R 2 represents hydrogen, halogen, formyl, hydroxy, hydrothio, hydroxycarbonyl, aminocarbonyl, aminothiocarbonyl, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-haloalkyl, (C 2 -C 4 )-alkenyl, (C 2 -C 4 )-haloalkenyl, (C 2 -C 4 )-alkynyl, (C 2 -C
• the inventionparticularly provides compounds of the general formula (I) in which R 1 represents phenyl, furyl, pyrrolyl, thienyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thiazolyl, isothiazolyl, thiadiazolyl, oxazolyl, isoxazolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, cyclopentenyl, cyclohexenyl or an oxabicycloheptanyl residue, wherein each of the previously mentioned 20 residues is unsubstituted or is independently substituted by one or more residues selected from the group R 5 , R 2 represents hydrogen, halogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-haloalkyl, (C 2 -C 4 )-alkenyl, (C 2 -C 4 )
• the inventionmore particularly provides compounds of the general formula (I) in which R 1 represents phenyl, 2-thienyl, 3-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, oxazolyl; thiadiazolyl, isothiazolyl, cyclopentene-1-yl, cyclohexen-1-yl or 7-oxabicyclo[4.1.0]heptan-1-yl, wherein each of the previously mentioned nine residues is unsubstituted or is optionally substituted by one or more residues selected from the group R 5 , R 2 represents hydrogen, halogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-haloalkyl, (C 2 -C 4 )-alkenyl, (C 2 -C 4 )- haloalkenyl, (C 1 -C 4 )-alkoxy, (C 1 -C 4 ) haloalk
• the inventionmore particularly provides compounds of the general formula (I) in which R 1 represents phenyl, 2-thienyl, 3-thienyl, oxazolyl or thiadiazolyl, wherein each of the previously mentioned five residues is unsubstituted or is optionally substituted by one or more residues selected from the group R 5 ,
• R 2represents hydrogen, halogen, (C 1 -C 4 )-alkyl, (C 2 -C 4 )-alkenyl, (C 1 -C 4 )-alkoxy, (C 1 -C 4 )-alkoxy- (C 1 -C 4 )-alkyl or (C 3 -C 6 )-cycloalkyl-(C 1 -C 4 )-alkyl,
• R 3is hydrogen
• R 4represents hydrogen or hydrothio
• R 5represents halogen, (C 1 -C 4 )-alkyl or (C 1 -C 4 )-alkoxy.
• the inventionespecially provides compounds of the general formula (I) in which R 1 represents phenyl, 2-fluorophenyl, 3-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-bromo-6- fluorophenyl, 2-ethylphenyl, 2-methoxyphenyl, 2-fluoro-3-methylphenyl, 2,3-dimethylphenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,4,5-trifluorophenyl, 3-chloro-2-fluorophenyl, 2- thienyl, 3-fluoro-2-thienyl, 3-bromo-2-thienyl, 3-methyl-2-thienyl, 2-bromo-3-thienyl, 4- methyl-2-thienyl, 3-thienyl, 4-fluoro-3-thienyl, 2,4-dimethyl-3-thienyl, 3,5-dimethyl-1,2- oxa
• the inventionmore especially provides compounds of the general formula (I) in which R 1 represents phenyl, 2-fluorophenyl, 3-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-fluoro-3-methylphenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,4,5- trifluorophenyl, 3-chloro-2-fluorophenyl, 2-thienyl, 2-bromo-3-thienyl, 3-fluoro-2-thienyl, 3-bromo-2-thienyl, 3-methyl-2-thienyl, 4-methyl-2-thienyl or 3-thienyl, R 2 represents hydrogen, fluorine, bromine, methyl, ethyl, allyl, methoxy, ethoxy or cyclopropylmethyl, R 3 represents hydrogen, and R 4 represents hydrogen or hydrothio.
• R 1represents phenyl, 2-flu
• radicals listed above in general terms or within areas of preferenceapply both to the end products of the general formula (I) and correspondingly to the starting materials or intermediates required for preparation in each case. These radical definitions can be combined with one another as desired, i.e. including combinations between the given preferred ranges.
• compounds of the abovementioned general formula (I) according to the invention or their salts or their use according to the inventionare of particular interest in which individual radicals have one of the preferred meanings already specified or specified below, or in particular those in which one or more of the preferred meanings already specified or specified below occur in combination.
• alkylsulfonylalone or as part of a chemical group - refers to straight- chain or branched alkylsulfonyl, preferably having 1 to 8 or 1 to 6 carbon atoms, for example (but not limited to) (C 1 -C 6 )-alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethyl- sulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1,1-dimethyl- propylsulfonyl, 1,
• alkylthio- alone or as part of a chemical group - denotes straight-chain or branched S-alkyl, preferably having 1 to 8 or 1 to 6 carbon atoms, such as (C 1 -C 10 )-, (C 1 -C 6 )- or (C 1 -C 4 )- alkylthio, for example (but not limited to) (C 1 -C 6 )-alkylthio such as methylthio, ethylthio, propylthio, 1- methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropyl- thio, 2,2-dimethylpropylthio, 1-eth
• Alkoxydenotes an alkyl radical bonded via an oxygen atom, for example (but not limited to) (C 1 -C 6 )- alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methyl- pentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethyl- butoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-e
• Alkenyloxydenotes an alkenyl radical attached via an oxygen atom
• alkynyloxydenotes an alkynyl radical attached via an oxygen atom
• alkenyloxydenotes an alkenyl radical attached via an oxygen atom
• alkynyloxydenotes an alkynyl radical attached via an oxygen atom
• “Cycloalkoxy”denotes a cycloalkyl radical attached via an oxygen atom
• cycloalkenyloxydenotes a cycloalkenyl radical attached via an oxygen atom.
• the number of the carbon atomsrefers to the alkyl radical in the alkylcarbonyl group.
• alkenylcarbonyl and “alkynylcarbonyl”, unless defined differently elsewhere, in accordance with the invention, respectively represent alkenyl and alkynyl radicals attached to the skeleton via -C(O)-, such as (C 2 -C 10 )-, (C 2 -C 6 )- or (C 2 -C 4 )-alkenylcarbonyl and (C 2 -C 10 )-, (C 2 -C 6 )- or (C 2 -C 4 )-alkynylcarbonyl.
• the number of the carbon atomsrefers to the alkenyl or alkynyl radical in the alkenyl or alkynyl group.
• the number of the carbon atomsrefers to the alkyl radical in the alkoxycarbonyl group.
• alkenyloxycarbonyl and “alkynyloxycarbonyl”, unless defined differently elsewhere, in accordance with the invention, respectively represent alkenyl and alkynyl radicals attached to the skeleton via -O-C(O)-, such as (C 2 -C 10 )-, (C 2 -C 6 )- or (C 2 -C 4 )-alkenyloxycarbonyl and (C 3 -C 10 )-, (C 3 -C 6 )- or (C 3 -C 4 )-alkynyloxycarbonyl.
• the number of the carbon atomsrefers to the alkenyl or alkynyl radical in the alkenyloxycarbonyl or alkynyloxycarbonyl group.
• aryldenotes an optionally substituted mono-, bi- or polycyclic aromatic system having preferably 6 to 14, especially 6 to 10, ring carbon atoms, for example phenyl, naphthyl, anthryl, phenanthrenyl and the like, preferably phenyl.
• optionally substituted arylalso embraces polycyclic systems, such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenylyl, where the bonding site is on the aromatic system.
• arylis generally also encompassed by the term “optionally substituted phenyl”.
• Preferred aryl substituents hereare, for example, hydrogen, halogen, alkyl, cycloalkyl, cycloalkylalkyl, cycloalkenyl, halocycloalkyl, alkenyl, alkynyl, aryl, arylalkyl, arylalkenyl, heteroaryl, heteroarylalkyl, heterocyclyl, heterocyclylalkyl, alkoxyalkyl, alkylthio, haloalkylthio, haloalkyl, alkoxy, haloalkoxy, cycloalkoxy, cycloalkylalkoxy, aryloxy, heteroraryloxy, alkoxyalkoxy, alkynylalkoxy, alkenyloxy, dialkylamino- alkoxy, tris-[alkyl]silyl, di-[alkyl
• optionally substituted heterocyclylpolycyclic systems are also included, for example 8-azabicyclo[3.2.1]octanyl, 8-azabicyclo[2.2.2]octanyl or 1-azabicyclo[2.2.1]heptyl.
• Optionally substituted heterocyclylalso includes spirocyclic systems, such as, for example, 1-oxa-5-aza-spiro[2.3]hexyl.
• the heterocyclic ringpreferably contains 3 to 9 ring atoms, in particular 3 to 6 ring atoms, and one or more, preferably 1 to 4, in particular 1, 2 or 3 heteroatoms in the heterocyclic ring, preferably from the group N, O and S, where, however, two oxygen atoms must not be directly adjacent to one another, for example having one heteroatom from the group consisting of N, O and S 1- or 2- or 3-pyrrolidinyl, 3,4-dihydro-2H-pyrrol-2- or -3-yl, 2,3-dihydro-1H-pyrrol-1- or -2- or -3- or -4- or -5-yl; 2,5-dihydro-1H-pyrrol-1- or -2- or -3-yl, 1- or 2- or 3- or 4-piperidinyl; 2,3,4,5-tetrahydropyridin-2- or -3- or -4- or -5-yl or -6-yl; 1,2,3,6- tetra
• Preferred 3-membered and 4-membered heterocyclesare, for example, 1- or 2-aziridinyl, oxiranyl, thiiranyl, 1- or 2- or 3-azetidinyl, 2- or 3-oxetanyl, 2- or 3- thietanyl, 1,3-dioxetan-2-yl.
• heterocyclylare a partially or fully hydrogenated heterocyclic radical having two heteroatoms from the group of N, O and S, for example 1- or 2- or 3- or 4-pyrazolidinyl; 4,5-dihydro-3H-pyrazol-3- or -4- or -5-yl; 4,5-dihydro-1H-pyrazol-1- or -3- or -4- or -5- yl; 2,3-dihydro-1H-pyrazol-1- or -2- or -3- or -4- or -5-yl; 1- or -2- or -3- or -4-imidazolidinyl; 2,3- dihydro-1H-imidazol-1- or -2- or -3- or -4-yl; 2,5-dihydro-1H-imidazol-1- or -2- or -4- or -5-yl; 4,5- dihydro-1H-imidazol-1- or -2- or -4- or -5-yl; 4,5- di
• heterocyclylare a partially or fully hydrogenated heterocyclic radical having 3 heteroatoms from the group of N, O and S, for example 1,4,2-dioxazolidin-2- or -3- or -5-yl; 1,4,2-dioxazol-3- or -5-yl; 1,4,2-dioxazinan-2- or -3- or -5- or -6-yl; 5,6-dihydro-1,4,2-dioxazin-3- or -5- or -6-yl; 1,4,2-dioxazin-3- or -5- or -6-yl; 1,4,2-dioxazepan-2- or - 3- or -5- or -6- or -7-yl; 6,7-dihydro-5H-1,4,2-dioxazepin-3- or -5- or -6- or -7-yl; 2,3-dihydro-7H-1,4,2- dioxazepin-2- or -3- or -5- or -5-
• heterocycles listed aboveare preferably substituted, for example, by hydrogen, halogen, alkyl, haloalkyl, hydroxyl, alkoxy, cycloalkoxy, aryloxy, alkoxyalkyl, alkoxyalkoxy, cycloalkyl, halocycloalkyl, aryl, arylalkyl, heteroaryl, heterocyclyl, alkenyl, alkylcarbonyl, cycloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl, alkoxycarbonyl, hydroxycarbonyl, cycloalkoxycarbonyl, cycloalkylalkoxycarbonyl, alkoxycarbonylalkyl, arylalkoxycarbonyl
• substituents for a substituted heterocyclic radicalare the substituents specified further down, and additionally also oxo and thioxo.
• the oxo group as a substituent on a ring carbon atomis then, for example, a carbonyl group in the heterocyclic ring.
• lactones and lactamsare preferably also included.
• the oxo groupmay also occur on the ring heteroatoms, which may exist in different oxidation states, for example in the case of N and S, and in that case form, for example, the divalent -N(O)-, - S(O)- (also SO for short) and -S(O) 2 - (also SO 2 for short) groups in the heterocyclic ring.
• a heteroarylrefers to heteroaromatic compounds, i.e.
• heteroarylsare, for example, 1H-pyrrol-1-yl; 1H-pyrrol-2-yl; 1H-pyrrol-3-yl; furan-2-yl; furan-3-yl; thien-2-yl; thien-3-yl, 1H-imidazol-1-yl; 1H-imidazol-2-yl; 1H-imidazol-4-yl; 1H-imidazol-5-yl; 1H-pyrazol-1-yl; 1H-pyrazol-3-yl; 1H-pyrazol-4-yl; 1H-pyrazol-5-yl, 1H-1,2,3-triazol-1-yl, 1H-1,2,3-triazol-4-yl, 1H-1,2,3-triazol-5-yl, 2H
• heteroaryl groups according to the inventionmay also be substituted by one or more identical or different radicals. If two adjacent carbon atoms are part of a further aromatic ring, the systems are fused heteroaromatic systems, such as benzofused or polyannealed heteroaromatics.
• Preferred examplesare quinolines (e.g. quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl); isoquinolines (e.g.
• heteroarylare also 5- or 6-membered benzofused rings from the group of 1H-indol-1-yl, 1H-indol-2-yl, 1H-indol-3-yl, 1H-indol-4-yl, 1H-indol-5-yl, 1H-indol-6-yl, 1H-indol-7-yl, 1-benzofuran-2-yl, 1-benzofuran-3-yl, 1-benzofuran-4-yl, 1-benzofuran-5-yl, 1-benzofuran-6-yl, 1-benzofuran-7-yl, 1-benzothiophen-2-yl, 1-benzothiophen-3-yl, 1-benzothiophen-4-yl, 1-benzothiophen-5-yl, 1-benzothiophen-6-yl, 1-benzothiophen-7-yl, 1H-indazol-1-yl, 1H-indazol-3-yl,
• halogendenotes, for example, fluorine, chlorine, bromine or iodine. If the term is used for a radical, "halogen” denotes, for example, a fluorine, chlorine, bromine or iodine atom.
• alkyldenotes a straight-chain or branched open-chain, saturated hydrocarbon radical which is optionally mono- or polysubstituted, and in the latter case is referred to as "substituted alkyl".
• Preferred substituentsare halogen atoms, alkoxy, haloalkoxy, cyano, alkylthio, haloalkylthio, amino or nitro groups, particular preference being given to methoxy, methyl, fluoroalkyl, cyano, nitro, fluorine, chlorine, bromine or iodine.
• the prefix “di”includes the combination of equal or different alkyl radicals, e.g. dimethyl or methyl(ethyl) or ethyl(methyl).
• Haloalkyl"-alkenyl” and “-alkynyl” respectively denote alkyl, alkenyl and alkynyl partially or fully substituted by identical or different halogen atoms, for example monohaloalkyl such as CH 2 CH 2 Cl, CH 2 CH 2 Br, CHClCH 3 , CH 2 Cl, CH 2 F; perhaloalkyl such as CCl 3 , CClF 2 , CFCl 2 , CF 2 CClF 2 , CF 2 CClFCF 3 ; polyhaloalkyl such as CH 2 CHFCl, CF 2 CClFH, CF 2 CBrFH, CH 2 CF 3 ; the term perhaloalkyl also encompasses the term perfluoroalkyl.
• monohaloalkylsuch as CH 2 CH 2 Cl, CH 2 CH 2 Br, CHClCH 3 , CH 2 Cl, CH 2 F
• perhaloalkylsuch as CCl 3 , CC
• Haloalkoxyis, for example, OCF 3 , OCHF2, OCH 2 F, OCF 2 CF 3 , OCH 2 CF 3 and OCH 2 CH 2 Cl; this applies correspondingly to haloalkenyl and other halogen-substituted radicals.
• the expression "(C 1 -C 4 )-alkyl” mentioned here by way of exampleis a brief notation for straight-chain or branched alkyl having one to 4 carbon atoms according to the range stated for carbon atoms, i.e. encompasses the methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radicals.
• Alkyl radicalsincluding in composite radicals such as alkoxy, haloalkyl, etc., are, for example, methyl, ethyl, n-propyl or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls such as n-hexyl, i-hexyl and 1,3- dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl; alkenyl and alkynyl radicals are defined as the possible unsaturated radicals corresponding to the alkyl radicals, where at least one double bond or triple bond is present.
• radicals having one double bond or triple bondPreference is given to radicals having one double bond or triple bond.
• alkenylalso includes, in particular, straight-chain or branched open-chain hydrocarbon radicals having more than one double bond, such as 1,3-butadienyl and 1,4-pentadienyl, but also allenyl or cumulenyl radicals having one or more cumulated double bonds, for example allenyl (1,2- propadienyl), 1,2-butadienyl and 1,2,3-pentatrienyl.
• Alkenyldenotes, for example, vinyl which may optionally be substituted by further alkyl radicals, for example (but not limited thereto) (C 2 -C 6 )-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-d
• alkynylalso includes, in particular, straight-chain or branched open-chain 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.
• (C 2 -C 6 )-Alkynyldenotes, for example, 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- pent
• cycloalkyldenotes a carbocyclic saturated ring system having preferably 3-8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, which optionally has further substitution, preferably by hydrogen, alkyl, alkoxy, cyano, nitro, alkylthio, haloalkylthio, halogen, alkenyl, alkynyl, haloalkyl, amino, alkylamino, dialkylamino, alkoxycarbonyl, hydroxycarbonyl, arylalkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl.
• cyclic systems with substituentsare included, also including substituents with a double bond on the cycloalkyl radical, for example an alkylidene group such as methylidene.
• polycyclic aliphatic systemsare also included, for example bicyclo[1.1.0]butan-1-yl, bicyclo[1.1.0]butan-2-yl, bicyclo[2.1.0]pentan-1-yl, bicyclo[1.1.1]pentan-1-yl, bicyclo[2.1.0]pentan-2-yl, bicyclo[2.1.0]pentan-5-yl, bicyclo[2.1.1]hexyl, bicyclo[2.2.1]hept-2-yl, bicyclo[2.2.2]octan-2-yl, bicyclo[3.2.1]octan-2-yl, bicyclo[3.2.2]nonan-2-yl, a
• (C3-C7)-cycloalkylis a brief notation for cycloalkyl having three to 7 carbon atoms, corresponding to the range specified for carbon atoms.
• substituted cycloalkylspirocyclic aliphatic systems are also included, for example 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, spiro[3.3]hept-1-yl, spiro[3.3]hept-2-yl.
• Cycloalkenyldenotes a carbocyclic, nonaromatic, partially unsaturated ring system having preferably 4-8 carbon atoms, e.g.1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclo- pentenyl, or 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1,3-cyclohexadienyl or 1,4-cyclohexa- dienyl, also including substituents with a double bond on the cycloalkenyl radical, for example an alkylidene group such as methylidene.
• haloalkylthioon its own or as constituent part of a chemical group - represents straight-chain or branched S-haloalkyl, preferably having 1 to 8, or having 1 to 6 carbon atoms, such as (C 1 -C 8 )-, (C 1 -C 6 )- or (C 1 -C 4 )-haloalkylthio, for example (but not limited thereto) trifluoromethylthio, pentafluoroethylthio, difluoromethyl, 2,2-difluoroeth-1-ylthio, 2,2,2-difluoroeth-1- ylthio, 3,3,3-prop-1-ylthio.
• Halocycloalkyl and halocycloalkenyldenote cycloalkyl and cycloalkenyl, respectively, which are partially or fully substituted by identical or different halogen atoms, such as F, Cl and Br, or by haloalkyl, such as trifluoromethyl or difluoromethyl, for example 1-fluorocycloprop-1-yl, 2-fluoro- cycloprop-1-yl, 2,2-difluorocycloprop-1-yl, 1-fluorocyclobut-1-yl, 1-trifluoromethylcycloprop-1-yl, 2-trifluoromethylcycloprop-1-yl, 1-chlorocycloprop-1-yl, 2-chlorocycloprop-1-yl, 2,2- dichlorocycloprop-1-yl, 3,3-difluorocyclobutyl.
• “trialkylsilyl” - on its own or as constituent part of a chemical group -represents straight-chain or branched Si-alkyl, preferably having 1 to 8, or having 1 to 6 carbon atoms, such as tri[(C 1 -C 8 )-, (C 1 -C 6 )- or (C 1 -C 4 )-alkyl]silyl, for example (but not limited thereto) trimethylsilyl, triethylsilyl, tri(n-propyl)silyl, tri(isopropyl)silyl, tri(n-butyl)silyl, tri(1-methylprop-1-yl)silyl, tri(2-methylprop-1-yl)silyl, tri(1,1-dimethyleth-1-yl)silyl, tri(2,2-dimethyleth-1-yl)silyl.
• the compoundscan form, through a hydrogen shift, tautomers whose structure is not formally covered by the general formula (I), these tautomers are nevertheless covered by the definition of the inventive compounds of the general formula (I), unless a particular tautomer is under consideration.
• many carbonyl compoundsmay be present both in the keto form and in the enol form, both forms being encompassed by the definition of the compound of the general formula (I).
• the compounds of the general formula (I)may be present as stereoisomers.
• the general formula (I)embraces all possible stereoisomers defined by the specific three-dimensional form thereof, such as enantiomers, diastereomers, Z and E isomers.
• stereoisomerscan be obtained from the mixtures obtained in the preparation by customary separation methods. The chromatographic separation can be affected either on the analytical scale to find the enantiomeric excess or the diastereomeric excess, or else on the preparative scale to produce test specimens for biological testing. It is likewise possible to selectively prepare stereoisomers by using stereoselective reactions with use of optically active starting materials and/or auxiliaries.
• the inventionthus also relates to all stereoisomers which are embraced by the general formula (I) but are not shown in their specific stereomeric form, and to mixtures thereof. If the compounds are obtained as solids, the purification can also be carried out by recrystallization or digestion. If individual compounds of general formula (I) cannot be obtained in a satisfactory manner by the routes described below, they can be prepared by derivatization of other compounds of general formula (I).
• Suitable isolation methods, purification methods and methods for separating stereoisomers of compounds of the general formula (I)are methods generally known to the person skilled in the art from analogous cases, for example by physical processes such as crystallization, chromatographic methods, in particular column chromatography and HPLC (high pressure liquid chromatography), distillation, optionally under reduced pressure, extraction and other methods, any mixtures that remain can generally be separated by chromatographic separation, for example on chiral solid phases.
• Suitable for preparative amounts or on an industrial scaleare processes such as crystallization, for example of diastereomeric salts which can be obtained from the diastereomer mixtures using optically active acids and, if appropriate, provided that acidic groups are present, using optically active bases.
• the substituted thiazolopyridines of the general formula (I)can be prepared using known processes.
• the synthesis routes used and examinedproceed from commercially available or easily synthesised substituted thiazoles or substituted pyridines.
• the groups R 1 , R 2 , R 3 and R 4 of the general formula (I)have the meanings defined above, unless exemplary, but not limiting definitions are given.
• the first synthesis route for substituted thiazolopyridines of the general formula (I)proceeds via an optionally substituted Boc-protected aminothiazole (II) (Scheme 1).
• a suitable nucleophilic reagente.g. lithium aluminium hydride or methylmagnesium chloride
• a basee.g. potassium tert- butoxide
• TFAtrifluoroacetic acid
• a suitable polar-aprotic solvente.g. dichloromethane
• a suitable palladium complexe.g. Pd(dppf)Cl2
• an appropriate basee.g. potassium carbonate
• Reagents that can accomplish the formamide deprotectioninclude a mixture of potassium hydroxide, lithium hydroxide and lithium aluminium hydride (cf. Chem. Eur. J., 2018, 24, 4864-487; WO2016/120403).
• cyclisation using an appropriate reaction partnere.g. triethyl orthoformate
• R 4by way of example, but not by limitation represents hydrogen.
• a suitable reagente.g.
• a polar solvente.g. acetonitrile
• a metale.g. Zn or Fe
• a protic solvent or a mixture containing protic reagentse.g an organic acid such as acetic acid
• alkylation of the sulfur atom with an alkylating agente.g. methyl iodide
• an appropriate basee.g. potassium carbonate
• Displacement of the sulfone group using a suitable nucleophilee.g. sodium borohydride
• a palladium cross coupling reaction of a boronic acid coupling using an appropriate palladium complexe.g.
• XXIa3,5-dibromo-6-(2-fluoro-3-chlorophenyl)pyridin-2-amine
• acetonitrile140 mL
• N-bromosuccinimide17.79 g, 99.99 mmol, 2.2 eq.
• the reaction mixturewas diluted with water and the resulting solid was removed by filtration washing with water and then dried under reduced pressure to afford compound XXIa (16.75 g, 95% yield) as a dark orange solid.
• I-0315-(2-fluoro-3-chlorophenyl)-6-methyl-[1,3]thiazolo[4,5-b]pyridine To a stirred mixture of compound I-029 (2.87 g, 6.27 mmol, 1.0 eq.), methyl boronic acid (1.55 g, 25.06 mmol, 4.0 eq.) and potassium phosphate (2.66 g, 12.53 mmol, 2.0 eq.) in abs.
• PhMe (60 mL) at RT under an atmosphere of argonwas added palladium(II)acetate (141 mg, 0.63 mmol, 0.1 eq.) and 2-dicyclohexylphosphino-2’,6’-dimethoxybiphenyl (795 mg, 1.88 mmol, 0.3 eq.).
• the resulting mixturewas stirred at reflux for 3.5 h.
• the reaction mixturewas allowed to cool to RT, diluted with water (100 mL) and PhMe (20 mL) followed by the addition of ammonium-pyrrolidine dithiocarbamate (451 mg, 2.75 mmol, 0.44 eq.).
• XXb6-(2-ethylphenyl)pyridin-2-amine
• 6-bromopyridin-2-amine6.00 g, 34.13 mmol, 1.00 eq.
• 2-ethyylphenylboronic acid10.55 g, 68.26 mmol, 2.00 eq.
• Na 2 CO 39.43 g, 68.26 mmol, 2.00 eq.
• Pd(dppf)Cl 2(1.25 g, 1.71 mmol, 0.05 eq.
• I-0145-(2-ethylphenyl)-6-methyl-[1,3]thiazolo[4,5-b]pyridine
• methyl boronic acid705 mg, 12.53 mmol, 2.0 eq.
• potassium phosphate5.32 g, 25.06 mmol, 4.0 eq.
• palladium(II)acetate141 mg, 0.63 mmol, 0.1 eq.
• 2- dicyclohexylphosphino-2’,6’-dimethoxybiphenyl514 mg, 1.25 mmol, 0.2 eq.
• XXIIIa2-fluoro-1-phenyl-3-(dimethylamino)prop-2-en-1-one
• a mixture of 2-fluoro-1-phenylethanone (280 mg, 2.00 mmol) in DMF.DMA (2 mL) at RTwas stirred at 120 °C for 1.5 h. The resulting mixture was allowed to cool to RT and was concentrated under reduced pressure to afford compound XXIIIa, which was used directly in the next step without further purification.
• No. I-0116-fluoro-5-phenyl-thiazolo[4,5-b]pyridine and No.
• Spectroscopic data of selected table examplesThe spectroscopic data listed hereinafter for selected table examples were evaluated via conventional 1 H-NMR interpretation or via NMR peak list methods.
• I-0021 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.68 (s, 1H), 8.02 (s, 1H), 7.52-7.49 (m, 1H), 7.44-7.38 (m, 2H), 7.34-7.31 (m, 1H).
• I-0031 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.29 (s, 1H), 8.24 (s, 1H), 7.48 (t, 1H), 6.86 (dd, 1H), 2.48 (d, 3H).
• I-0041 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.35 (s, 1H), 8.40 (d, 1H), 7.46 (d, 1H), 6.86 (dd, 1H), 2.68 (s, 3H), 2.54 (s, 3H).
• I-0051 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.22 (s, 1H), 8.19 (s, 1H), 7.38 (d, 1H), 7.05 (t, 1H), 3.08 (q, 2H), 2.33 (d, 3H), 1.38 (t, 3H).
• I-0061 H-NMR (400 MHz, CDCl3) ⁇ H 9.26 (s, 1H), 8.26 (s, 1H), 7.32 (d, 1H), 6.94 (d, 1H), 2.78 (q, 2H), 2.14 (s, 3H), 1.20 (t, 3H).
• I-0071 H-NMR (600 MHz, CDCl 3 ) ⁇ H 9.41 (s, 1H), 8.49 (d, 1H), 7.75 (d, 1H), 3.07 (s, 3H).
• I-0091 H-NMR (400 MHz, CDCl3) ⁇ H 9.36 (s, 1H), 8.34 (s, 1H), 7.51-7.44 (m, 2H), 7.28 (m, 1H), 7.19 (t, 1H), 5.85 (m, 1H), 5.13 (m, 1H), 5.03 (m, 1H), 3.47 (m, 2H).
• I-0101 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.32 (s, 1H), 8.58 (s, 1H), 7.55 (m, 1H), 7.46 (m, 1H), 7.30 (m, 1H), 7.17 (m, 1H), 4.51 (s, 2H), 3.38 (s, 3H).
• I-0111 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.28 (s, 1H), 8.13-8.09 (m, 3H), 7.55-7.46 (m, 3H).
• I-0121 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.32 (s, 1H), 8.44 (s, 1H), 7.83 (m, 2H), 7.53-7.46 (m, 3H).
• I-0131 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.12 (s, 1H), 8.03 (m, 2H), 7.83 (s, 1H), 7.50-7.43 (m, 3H), 3.96 (s, 3H).
• I-0161 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.28 (s, 1H), 8.58 (s, 1H), 7.47-7.43 (m, 1H), 7.38-7.36 (m, 1H), 7.11-7.17 (m, 1H), 7.02-7.00 (d, 1H), 3.80 (s, 3H).
• I-0191 H-NMR (400 MHz, CDCl3) ⁇ H 9.24 (s, 1H), 8.22 (s, 1H), 7.55 (dd, 1H), 7.48 (dd, 1H), 7.15 (dd, 1H), 3.10 (q, 2H), 1.39 (t, 3H).
• I-0201 H-NMR (400 MHz, CDCl3) ⁇ H 9.23 (s, 1H), 8.17 (d, 1H), 7.64 (dd, 1H), 7.48 (dd, 1H), 7.16 (dd, 1H), 2.75 (d, 3H).
• I-0211 H-NMR (400 MHz, CDCl3) ⁇ H 9.23 (s, 1H), 8.19 (d, 1H), 7.73 (dd, 1H), 7.63 (dd, 1H), 7.42 (dd, 1H), 2.64 (d, 3H).
• I-0221 H-NMR (400 MHz, CDCl3) ⁇ H 9.25 (s, 1H), 8.24 (s, 1H), 7.65 (dd, 1H), 7.50 (dd, 1H), 7.41 (dd, 1H), 2.95 (q, 2H), 1.29 (t, 3H).
• I-0231 H-NMR (400 MHz, CDCl3) ⁇ H 9.13 (s, 1H), 7.83 (s, 1H), 7.63 (m, 1H), 7.43 (m, 1H), 7.27 (m, 1H), 7.15 (m, 1H), 3.94 (s, 3H).
• I-0241 H-NMR (400 MHz, CDCl3) ⁇ H 9.36 (s, 1H), 8.40 (d, 1H), 7.77 (d, 1H), 7.72-7.70 (m, 2H), 7.45 (m, 1H), 7.30 (m, 1H), 7.15 (m, 1H).
• I-0251 H-NMR (400 MHz, CDCl3) ⁇ H 9.26 (s, 1H), 8.23 (d, 1H), 7.68 (m, 1H), 7.44 (m, 1H), 7.37 (m, 1H), 7.30 (m, 1H), 2.32 (d, 3H).
• I-0261 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.27 (s, 1H), 8.52 (s, 1H), 7.51-7.40 (m, 2H), 7.27 (m, 1H), 7.15 (m, 1H), 2.62 (d, 2H), 0.92 (m, 1H), 0.55 (m, 2H), 0.14 (m, 2H).
• I-0271 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.30 (s, 1H), 8.13 (d, 1H), 7.76 (m, 1H), 7.49 (m, 1H), 7.32 (m, 1H), 7.21 (m, 1H).
• I-0291 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.34 (s, 1H), 8.65 (s, 1H), 7.55-7.51 (m, 1H), 7.43-7.39 (m, 1H), 7.25-7.21 (m, 1H).
• I-0301 H-NMR (400 MHz, CDCl 3 ) ⁇ H 9.25 (s, 1H), 8.22 (s, 1H), 7.32-7.28 (m, 1H), 7.27-7.22 (m, 1H), 7.18-7.14 (m, 1H), 2.35 (s, 3H).
• I-0311 H-NMR (400 MHz, CDCl3) ⁇ H 9.27 (s, 1H), 8.25 (s, 1H), 7.53-7.48 (m, 1H), 7.44-7.40 (m, 1H), 7.25-7.21 (m, 1H), 2.40 (s, 3H).
• I-0321 H-NMR (400 MHz, CDCl3) ⁇ H 9.30 (s, 1H), 8.30 (s, 1H), 6.81 (dd, 1H), 2.28 (s, 3H), 2.22 (s, 3H), 1.96 (d, 3H).
• I-0331 H-NMR (400 MHz, CDCl3) ⁇ H 9.18 (s, 1H), 7.83 (d, 1H), 7.63 (m, 1H), 7.44 (m, 1H), 7.27 (m, 1H), 7.15 (m, 1H), 4.17 (q, 2H), 1.41 (t, 3H).
• I-0341 H-NMR (400 MHz, CDCl3) ⁇ H 9.25 (s, 1H), 8.22 (d, 1H), 7.36 (dd, 1H), 6.89 (d, 1H), 2.57 (d, 3H).
• the peak list of an examplehas therefore the form: ⁇ 1 (intensity 1 ); ⁇ 2 (intensity 2 );........; ⁇ i (intensity i ); hence; ⁇ n (intensity n )
• Intensity of sharp signalscorrelates with the height of the signals in a printed example of a NMR spectrum in cm and shows the real relations of signal intensities. From broad signals several peaks or the middle of the signal and their relative intensity in comparison to the most intensive signal in the spectrum can be shown.
• tetramethylsilane peakcan occur but not necessarily.
• the 1 H-NMR peak listsare similar to classical 1 H-NMR prints and contains therefore usually all peaks, which are listed at classical NMR-interpretation. Additionally they can show like classical 1 H-NMR prints signals of solvents, stereoisomers of the target compounds, which are also object of the invention, and/or peaks of impurities.
• peaks of solventsfor example peaks of DMSO in DMSO-D 6 and the peak of water are shown in our 1 H-NMR peak lists and have usually on average a high intensity .
• the peaks of stereoisomers of the target compounds and/or peaks of impuritieshave usually on average a lower intensity than the peaks of target compounds (for example with a purity >90%).
• Such stereoisomers and/or impuritiescan be typical for the specific preparation process. Therefore, their peaks can help to recognize the reproduction of our preparation process via “side-products-fingerprints”.
• the present inventionfurthermore provides the use of one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (I-001) to (I-041) and/or salts thereof, in each case as defined above, as herbicide and/or plant growth regulator, preferably in crops of useful plants and/or ornamental plants.
• the present inventionfurthermore provides a method for controlling harmful plants and/or for regulating the growth of plants, characterized in that an effective amount - of one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (I-001) to (I-041) and/or salts thereof, in each case as defined above, or - of a composition according to the invention, as defined below, is applied to the (harmful) plants, seeds of (harmful) plants, the soil in which or on which the (harmful) plants grow or the area under cultivation.
• the present inventionalso provides a method for controlling unwanted plants, preferably in crops of useful plants, characterized in that an effective amount - of one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (I-001) to (I-041) and/or salts thereof, in each case as defined above, or - of a composition according to the invention, as defined below, is applied to unwanted plants (for example harmful plants such as mono- or dicotyledonous weeds or unwanted crop plants), the seed of the unwanted plants (i.e.
• plant seedsfor example grains, seeds or vegetative propagation organs such as tubers or shoot parts with buds
• the soil in which or on which the unwanted plants growfor example the soil of crop land or non-crop land
• the area under cultivationi.e. the area on which the unwanted plants will grow.
• the present inventionfurthermore also provides methods for regulating the growth of plants, preferably of useful plants, characterized in that an effective amount - of one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (I-001) to (I-041) and/or salts thereof, in each case as defined above, or - of a composition according to the invention, as defined below, is applied to the plant, the seed of the plant (i.e.
• the compounds according to the invention or the compositions according to the inventioncan be applied for example by pre-sowing (if appropriate also by incorporation into the soil), pre- emergence and/or post-emergence processes.
• Specific examples of some representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the compounds according to the inventionare as follows, though there is no intention to restrict the enumeration to particular species.
• one or more compounds of the general formula (I) and/or salts thereofare preferably employed for controlling harmful plants or for regulating growth in crops of useful plants or ornamental plants, where in a preferred embodiment the useful plants or ornamental plants are transgenic plants.
• the compounds of the general formula (I) according to the invention and/or their saltsare suitable for controlling the following genera of monocotyledonous and dicotyledonous harmful plants: Monocotyledonous harmful plants of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.
• the compounds according to the inventionare applied to the soil surface before germination of the harmful plants (weed grasses and/or broad-leaved weeds) (pre-emergence method)
• either the seedlings of the weed grasses or broad-leaved weedsare prevented completely from emerging or they grow until they have reached the cotyledon stage, but then stop growing and eventually, after three to four weeks have elapsed, die completely.
• the active compoundsare applied post-emergence to the green parts of the plants, growth stops after the treatment, and the harmful plants remain at the growth stage at the time of application, or they die completely after a certain time, so that in this manner competition by the weeds, which is harmful to the crop plants, is eliminated very early and in a sustained manner.
• the compounds according to the inventiondisplay an outstanding herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, for example dicotyledonous crops of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Miscanthus, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous crops of the genera Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, triticale, triticum, Zea, are damaged only to an insignificant extent, or not at all, depending on the structure of the respective compound according to the invention and its application rate.
• the present compoundsare very suitable for selective control of unwanted plant growth in plant crops such as agriculturally useful plants or ornamental plants.
• the compounds of the invention(depending on their particular structure and the application rate deployed) have outstanding growth-regulating properties in crop plants. They intervene in the plants’ own metabolism with regulatory effect and can thus be used for the controlled influencing of plant constituents and to facilitate harvesting, for example by triggering desiccation and stunted growth.
• theyare also suitable for the general control and inhibition of unwanted vegetative growth without killing the plants in the process. Inhibition of vegetative growth plays a major role for many mono- and dicotyledonous crops since, for example, this can reduce or completely prevent lodging.
• the active compoundscan also be used to control harmful plants in crops of genetically modified plants or plants modified by conventional mutagenesis.
• the transgenic plantsare characterized by particular advantageous properties, for example by resistances to certain pesticides, in particular certain herbicides, resistances to plant diseases or pathogens of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses.
• Other specific characteristicsrelate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents. For instance, there are known transgenic plants with an elevated starch content or altered starch quality, or those with a different fatty acid composition in the harvested material.
• transgenic cropsit is preferred with a view to transgenic crops to use the compounds according to the invention and/or their salts in economically important transgenic crops of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, millet, rice and corn or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetables.
• cerealssuch as wheat, barley, rye, oats, millet, rice and corn or else crops of sugar beet, cotton, soybean, oilseed rape, potato, tomato, peas and other vegetables.
• the compounds according to the inventionas herbicides in crops of useful plants which are resistant, or have been made resistant by recombinant means, to the phytotoxic effects of the herbicides.
• the active compoundscan also be used to control harmful plants in crops of genetically modified plants which are known or are yet to be developed.
• the transgenic plantsare characterized by particular advantageous properties, for example by resistances to certain pesticides, in particular certain herbicides, resistances to plant diseases or pathogens of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses.
• Other specific characteristicsrelate, for example, to the harvested material with regard to quantity, quality, storability, composition and specific constituents.
• transgenic plants with an elevated starch content or altered starch quality, or those with a different fatty acid composition in the harvested materialmay be tolerance or resistance to abiotic stressors, for example heat, cold, drought, salinity and ultraviolet radiation.
• the compounds of the general formula (I)can preferably be used as herbicides in crops of useful plants which are resistant, or have been made resistant by recombinant means, to the phytotoxic effects of the herbicides.
• Conventional ways of producing novel plants which have modified properties in comparison to existing plantsconsist, for example, in traditional cultivation methods and the generation of mutants.
• novel plants with altered propertiescan be generated with the aid of recombinant methods.
• a large number of molecular-biological techniques by means of which novel transgenic plants with modified properties can be generatedare known to the person skilled in the art.
• nucleic acid molecules which allow mutagenesis or sequence alteration by recombination of DNA sequencescan be introduced into plasmids.
• base exchangesremove parts of sequences or add natural or synthetic sequences.
• adapters or linkersmay be added to the fragments.
• the generation of plant cells with a reduced activity of a gene productcan be achieved by expressing at least one corresponding antisense RNA, a sense RNA for achieving a cosuppression effect, or by expressing at least one suitably constructed ribozyme which specifically cleaves transcripts of the abovementioned gene product.
• DNA molecules which encompass the entire coding sequence of a gene product inclusive of any flanking sequences which may be presentand also DNA molecules which only encompass portions of the coding sequence, in which case it is necessary for these portions to be long enough to have an antisense effect in the cells.
• DNA sequences which have a high degree of homology to the coding sequences of a gene product but are not completely identical to themmay be localized in any desired compartment of the plant cell. However, to achieve localization in a particular compartment, it is possible, for example, to join the coding region to DNA sequences which ensure localization in a particular compartment. Such sequences are known to those skilled in the art (see, for example, Braun et al., EMBO J.11 (1992), 3219-3227).
• the nucleic acid moleculescan also be expressed in the organelles of the plant cells.
• the transgenic plant cellscan be regenerated by known techniques to give rise to entire plants.
• the transgenic plantsmay be plants of any desired plant species, i.e. not only monocotyledonous but also dicotyledonous plants.
• the compounds (I) according to the inventionare preferred to employ in transgenic crops which are resistant to growth regulators such as, for example, dicamba, or to herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or to herbicides from the group of the sulfonylureas, glyphosate, glufosinate or benzoylisoxazoles and analogous active compounds.
• growth regulatorssuch as, for example, dicamba, or to herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or to herbicides from the group of the sulfonylureas, glyphosate, glufosinate or benzoyliso
• the active compounds of the inventionare employed in transgenic crops, not only do the effects toward harmful plants observed in other crops occur, but frequently also effects which are specific to application in the particular transgenic crop, for example an altered or specifically widened spectrum of weeds which can be controlled, altered application rates which can be used for the application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and influencing of growth and yield of the transgenic crop plants.
• the inventiontherefore also relates to the use of the compounds of the general formula (I) according to the invention and/or their salts as herbicides for controlling harmful plants in crops of useful plants or ornamentals, optionally in transgenic crop plants.
• the use according to the invention for the control of harmful plants or for growth regulation of plantsalso includes the case in which the active compound of the general formula (I) or its salt is not formed from a precursor substance (“prodrug”) until after application on the plant, in the plant or in the soil.
• the inventionalso provides for the use of one or more compounds of the general formula (I) or salts thereof or of a composition according to the invention (as defined below) (in a method) for controlling harmful plants or for regulating the growth of plants which comprises applying an effective amount of one or more compounds of the general formula (I) or salts thereof onto the plants (harmful plants, if appropriate together with the useful plants), plant seeds, the soil in which or on which the plants grow or the area under cultivation.
• the inventionalso provides a herbicidal and/or plant growth-regulating composition, characterized in that the composition comprises (a) one or more compounds of the general formula (I) and/or salts thereof, as defined above, preferably in one of the embodiments identified as preferred or particularly preferred, in particular one or more compounds of the formulae (I-001) to (I-041) and/or salts thereof, in each case as defined above, and (b) one or more further substances selected from groups (i) and/or (ii): (i) one or more further agrochemically active substances, preferably selected from the group consisting of insecticides, acaricides, nematicides, further herbicides (i.e.
• component (i) of a composition according to the inventionare preferably selected from the group of substances mentioned in "The Pesticide Manual", 16th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2012.
• a herbicidal or plant growth-regulating composition according to the inventioncomprises preferably one, two, three or more formulation auxiliaries (ii) customary in crop protection selected from the group consisting of surfactants, emulsifiers, dispersants, film-formers, thickeners, inorganic salts, dusting agents, carriers solid at 25 °C and 1013 mbar, preferably adsorbent granulated inert materials, wetting agents, antioxidants, stabilizers, buffer substances, antifoam agents, water, organic solvents, preferably organic solvents miscible with water in any ratio at 25 °C and 1013 mbar.
• formulation auxiliariescustomary in crop protection selected from the group consisting of surfactants, emulsifiers, dispersants, film-formers, thickeners, inorganic salts, dusting agents, carriers solid at 25 °C and 1013 mbar, preferably adsorbent granulated inert materials, wetting agents, antioxidants, stabilizers, buffer
• the compounds of general formula (I) according to the inventioncan be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting products or granules in the customary formulations.
• the inventiontherefore also provides herbicidal and plant growth-regulating compositions which comprise compounds of the general formula (I) and/or salts thereof.
• the compounds of the general formula (I) and/or salts thereofcan be formulated in various ways according to which biological and/or physicochemical parameters are required.
• Possible formulationsinclude, 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), dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS), dusting products (DP), dressings, granules for scattering and soil application, granules (GR) in the form of microgranules, spray granules, absorption and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
• WPwettable powders
• SPwater-soluble powders
• ECemulsifiable concentrates
• EWemulsions
• SCsuspension concentrates
• CScapsule suspension
• Wettable powdersare preparations which can be dispersed uniformly in water and, in addition to the active compound, apart from a diluent or inert substance, also comprise surfactants of the ionic and/or nonionic type (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6'- disulfonate, sodium dibutylnaphthalenesulfonate or else sodium oleoylmethyltaurate.
• surfactants of the ionic and/or nonionic typefor example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxye
• the herbicidally active compoundsare finely ground, for example in customary apparatuses such as hammer mills, blower mills and air-jet mills, and simultaneously or subsequently mixed with the formulation auxiliaries.
• Emulsifiable concentratesare produced by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene, or else relatively high-boiling aromatics or hydrocarbons or mixtures of the organic solvents, with addition of one or more ionic and/or nonionic surfactants (emulsifiers).
• emulsifierswhich may be used are: calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.
• calcium alkylarylsulfonatessuch as calcium dodecylbenzenesulfonate
• nonionic emulsifierssuch as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid est
• Dusting productsare obtained by grinding the active compound with finely distributed solids, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
• Suspension concentratesmay be water- or oil-based. They may be prepared, for example, by wet- grinding by means of commercial bead mills and optional addition of surfactants as have, for example, already been listed above for the other formulation types.
• Emulsionsfor example oil-in-water emulsions (EW)
• EWoil-in-water emulsions
• Granulescan be produced either by spraying the active compound onto adsorptive granular inert material or by applying active compound concentrates to the surface of carriers, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or else mineral oils.
• Suitable active compoundscan also be granulated in the manner customary for the production of fertilizer granules - if desired as a mixture with fertilizers.
• Water-dispersible granulesare produced generally by the customary processes such as spray-drying, fluidized-bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material.
• the agrochemical preparations, preferably herbicidal or plant growth-regulating compositions, of the present inventionpreferably comprise a total amount of from 0.1 to 99% by weight, preferably 0.5 to 95% by weight, particularly preferably 1 to 90% by weight, especially preferably 2 to 80% by weight, of active compounds of the general formula (I) and their salts.
• the active compound concentrationis, for example, about 10 to 90% by weight, the remainder to 100% by weight consisting of customary formulation constituents.
• the active compound concentrationmay be about 1% to 90% and preferably 5% to 80% by weight.
• Formulations in the form of dustscomprise 1% to 30% by weight of active compound, preferably usually 5% to 20% by weight of active compound; sprayable solutions contain about 0.05% to 80% by weight, preferably 2% to 50% by weight of active compound.
• the active compound contentdepends partially on whether the active compound is in liquid or solid form and on which granulation auxiliaries, fillers, etc., are used.
• the content of active compoundis, for example, between 1% and 95% by weight, preferably between 10% and 80% by weight.
• the active compound formulations mentionedoptionally comprise the respective customary stickers, wetters, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents which influence the pH and the viscosity.
• formulation auxiliariesare described inter alia in “Chemistry and Technology of Agrochemical Formulations”, ed. D.A. Knowles, Kluwer Academic Publishers (1998).
• the compounds of the general formula (I) or salts thereofcan be used as such or in the form of their preparations (formulations) in a combination with other pesticidally active substances, for example insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and/or growth regulators, for example in the form of a finished formulation or of a tank mix.
• pesticidally active substancesfor example insecticides, acaricides, nematicides, herbicides, fungicides, safeners, fertilizers and/or growth regulators, for example in the form of a finished formulation or of a tank mix.
• the combination formulationscan be prepared on the basis of the abovementioned formulations, while taking account of the physical properties and stabilities of the active compounds to be combined.
• Active compounds which can be employed in combination with the compounds of general formula (I) according to the invention in mixture formulations or in a tank mixare, for example, known active compounds based on inhibition of, for example, acetolactate synthase, acetyl-CoA carboxylase, cellulose synthase, enolpyruvylshikimate-3-phosphate synthase, glutamine synthetase, p- hydroxyphenylpyruvate dioxygenase, phytoendesaturase, photosystem I, photosystem II, protoporphyrinogen oxidase, as described, for example, in Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 16th edition, The British Crop Protection Council and the Royal Soc.
• the safenerswhich are used in an antidotically effective amount, reduce the phytotoxic side effects of the herbicides/pesticides employed, for example in economically important crops, such as cereals (wheat, barley, rye, corn, rice, millet), sugarbeet, sugarcane, oilseed rape, cotton and soybeans, preferably cereals.
• the weight ratios of herbicide (mixture) to safenerdepend generally on the herbicide application rate and the efficacy of the safener in question and may 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 safenerscan be formulated with further herbicides/pesticides and be provided and employed as a finished formulation or tank mix with the herbicides.
• the herbicide or herbicide/safener formulations present in commercial formare, if appropriate, diluted in a customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules with water. Dust-type preparations, granules for soil application or granules for scattering and sprayable solutions are not normally diluted further with other inert substances prior to application.
• the application rate of the compounds of the general formula (I) and/or their saltsis affected to a certain extent by external conditions such as temperature, humidity, etc.
• the application ratemay vary within wide limits.
• the total amount of compounds of the general formula (I) and/or their saltsis preferably in the range from 0.001 to 10.0 kg/ha, with preference in the range from 0.005 to 5 kg/ha, more preferably in the range from 0.01 to 1.5 kg/ha, in particular preferably in the range from 0.05 to 1 kg/ha. This applies both to the pre-emergence and the post-emergence application.
• the total application rateis preferably in the range of from 0.001 to 2 kg/ha, preferably in the range of from 0.005 to 1 kg/ha, in particular in the range of from 10 to 500 g/ha, very particularly in the range from 20 to 250 g/ha. This applies both to the pre- emergence and the post-emergence application.
• the application as culm stabilizermay take place at various stages of the growth of the plants.
• application as plant growth regulatoris also possible by treating the seed, which includes various techniques for dressing and coating seed.
• the application ratedepends on the particular techniques and can be determined in preliminary tests.
• Active compounds which can be employed in combination with the compounds of the general formula (I) according to the invention in compositions according to the inventionare, for example, known active compounds which are based on the 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, as are described in, for example, Weed Research 26 (1986) 441-445 or "The Pesticide Manual", 16th edition, The British Crop Protection Council and the Royal Soc.
• herbicides or plant growth regulatorswhich can be combined with the compounds according to the invention are, for example, the following active compounds, where the compounds are designated either with the "common name” in accordance with the International Organization for Standardization (ISO) or with the chemical name or with the code number. They always encompass all of the application forms such as, for example, acids, salts, esters and also all isomeric forms such as stereoisomers and optical isomers, even if not explicitly mentioned.
• herbicidal mixing partnersare: Acetochlor, acifluorfen, acifluorfen-methyl, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6- (4-chloro-2-fluoro-3-methylphenyl)-5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralid, aminopyralid- dimethylammonium, aminopyralid-tripromine, amitrole, ammoniumsulfamate, anilofos, asulam, asulam-potassium, asulam sodium, atrazine, azafenidin, azimsulfuron, beflubutamid, (S)-(
• dicamba-biproaminedicamba-N,N-Bis(3-aminopropyl)methylamine, dicamba-butotyl, dicamba-choline, dicamba-diglycolamine, dicamba-dimethylammonium, dicamba- diethanolaminemmonium, dicamba-diethylammonium, dicamba-isopropylammonium, dicamba-methyl, dicamba-monoethanolaminedicamba-olamine, dicamba-potassium, dicamba-sodium, dicamba- triethanolamine, dichlobenil, 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, 2-(2,5- dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, dichlorprop, dichlorprop-butotyl, dichlroprop- dimethylammonium, dichhlorprop-etexyl
• plant growth regulatorsas possible mixing partners are: Abscisic acid, acibenzolar, acibenzolar-S-methyl, 1-aminocyclopro-1-yl carboxylic acid and derivatives thereof,5-Aminolävulin Textre, ancymidol, 6-benzylaminopurine, bikinin, brassinolide, brassinolide-ethyl, catechin, chitooligosaccharides (CO; COs differ from LCOs in that they lack the pendant fatty acid chain that is characteristic of LCOs.
• COssometimes referred to as N-acetylchitooligosaccharides, are also composed of GlcNAc residues but have side chain decorations that make them different from chitin molecules [(C8H13NO5)n, CAS No.1398-61-4] and chitosan molecules [(C5H11NO4)n, CAS No.
• chitinous compoundschlormequat chloride, cloprop, cyclanilide, 3-(Cycloprop-1- enyl)propionic acid, daminozide, dazomet, dazomet-sodium, n-decanol, dikegulac, dikegulac-sodium, endothal, endothal-dipotassium, -disodium, and mono(N,N-dimethylalkylammonium), ethephon, flumetralin, flurenol, flurenol-butyl, flurenol-methyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indol-3-acetic acid (IAA), 4-indol-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, Jasmonic acid or derivatives thereof (e.g.
• LCOlipo-chitooligosaccharides
• Nodsymbiotic nodulation
• Myc factorsconsist of an oligosaccharide backbone of ⁇ -l,4-linked N-acetyl-D-glucosamine (“GlcNAc”) residues with an N-linked fatty acyl chain condensed at the non-reducing end.
• LCOsdiffer in the number of GlcNAc residues in the backbone, in the length and degree of saturation of the fatty acyl chain and in the substitutions of reducing and non-reducing sugar residues), linoleic acid or derivatives thereof, linolenic acid or derivatives thereof, maleic hydrazide, mepiquat chloride, mepiquat pentaborate, 1-methylcyclopropene, 3’-methyl abscisic acid, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2- naphthyloxyacetic acid, nitrophenolate-mixture, 4-Oxo-4[(2-phenylethyl)amino]butyric acid, paclobutrazol, 4-phenylbutyric acid, N-phenylphthalamic acid, prohexadione, prohexadione-calcium, prohydrojasmon, salicylic acid, salicylic
• Suitable combination partners for the compounds of the general formula (I) according to the inventionalso include, for example, the following safeners: S1) Compounds from the group of heterocyclic carboxylic acid derivatives: S1 a ) Compounds of the dichlorophenylpyrazoline-3-carboxylic acid type (S1 a ), preferably compounds such as 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl 1- (2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (S1-1) ("mefenpyr-diethyl”), and related compounds as described in WO-A-91/07874; S1 b ) Derivatives of dichlorophenylpyrazolecarboxylic acid (S1 b ), preferably compounds such as ethyl 1-(2,4-dichlor
• S2 aCompounds from the group of the 8-quinolinoxy derivatives (S2): S2 a ) Compounds of the 8-quinolinoxyacetic acid type (S2 a ), preferably 1-methylhexyl (5-chloro-8- quinolinoxy)acetate ("cloquintocet-mexyl") (S2-1), 1,3-dimethylbut-1-yl (5-chloro-8- quinolinoxy)acetate (S2-2), 4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate (S2-3), 1- allyloxyprop-2-yl (5-chloro-8-quinolinoxy)acetate (S2-4), ethyl (5-chloro-8-quinolinoxy)acetate (S2-5), methyl 5-chloro-8-quinolinoxyacetate (S2-6), allyl (5-chloro-8-quinolinoxy)acetate (S2- 7), 2-(2-propylideneiminoxy)-1-eth
• S3Active compounds of the dichloroacetamide type (S3), which are frequently used as pre- emergence safeners (soil-acting safeners), for example "dichlormid” (N,N-diallyl-2,2-dichloroacetamide) (S3-1), "R-29148” (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2), "R-28725" (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) from Stauffer (S3-3), "benoxacor” (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4), "PPG-1292” (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide) from PPG Industries (S3-5), "DKA-24" (N-ally
• S4 aN-Acylsulfonamides of the formula (S4 a ) and salts thereof, as described in WO-A-97/45016, O in which R A 1 is (C 1 -C 6 )-alkyl, (C 3 -C 6 )-cycloalkyl, where the 2 latter radicals are substituted by v A substituents from the group of halogen, (C 1 -C 4 )-alkoxy, (C 1 -C 6 )-haloalkoxy and (C 1 -C 4 )- alkylthio and, in the case of cyclic radicals, also by (C 1 -C 4 )-alkyl and (C 1 -C 4 )-haloalkyl; R A 2 is halogen, (C 1 -C 4 )-alkyl, (C 1 -C 4 )-alkoxy,
• Active compounds from the class of the hydroxyaromatics and the aromatic-aliphatic carboxylic acid derivatives (S5)for example ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4- hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2-hydroxycinnamic acid, 2,4-dichlorocinnamic acid, as described in WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001.
• S6Active compounds from the class of the 1,2-dihydroquinoxalin-2-ones (S6), for example 1- methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, 1-methyl-3-(2-thienyl)-1,2- dihydroquinoxaline-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one hydrochloride, 1-(2-methylsulfonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, as described in WO-A-2005/112630.
• S7Compounds from the class of the diphenylmethoxyacetic acid derivatives (S7), e.g. methyl diphenylmethoxyacetate (CAS Reg. No.41858-19-9) (S7-1), ethyl diphenylmethoxyacetate or diphenylmethoxyacetic acid, as described in WO-A-98/38856.
• S7diphenylmethoxyacetic acid derivatives
• S9 active compoundsfrom the class of the 3-(5-tetrazolylcarbonyl)-2-quinolones (S9), for example 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No.219479- 18-2), 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No.
• R E 1is halogen, (C 1 -C 4 )-alkyl, methoxy, nitro, cyano, CF 3 , OCF 3 Y E , Z E are independently O or S
• n Eis an integer from 0 to 4
• R E 2is (C 1 -C 16 )-alkyl, (C 2 -C 6 )-alkenyl, (C 3 -C 6 )-cycloalkyl, aryl; benzyl, halobenzyl, R E 3 is hydrogen or (C 1 -C 6 )-alkyl.
• S11Active compounds of the oxyimino compound type (S11), which are known as seed-dressing agents, for example “oxabetrinil” ((Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1), which is known as a seed-dressing safener for millet/sorghum against metolachlor damage, "fluxofenim” (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone O-(1,3-dioxolan-2- ylmethyl)oxime) (S11-2), which is known as a seed-dressing safener for millet/sorghum against metolachlor damage, and “cyometrinil” or “CGA-43089” ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), which is known as a seed-dressing safener for millet
• S12active compounds from the class of the isothiochromanones (S12), for example methyl [(3-oxo- 1H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS Reg. No.205121-04-6) (S12-1) and related compounds from WO-A-1998/13361.
• S13One or more compounds from group (S13): “naphthalic anhydride” (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as a seed-dressing safener for corn against thiocarbamate herbicide damage, "fenclorim” (4,6-dichloro-2-phenylpyrimidine) (S13-2), which is known as a safener for pretilachlor in sown rice, "flurazole” (benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3), which is known as a seed-dressing safener for millet/sorghum against alachlor and metolachlor damage, "CL 304415” (CAS Reg.
• Preferred safeners in combination with the compounds of the general formula (I) according to the invention and/or salts thereof, in particular with the compounds of the formulae (I-001) to (I-041) and/or salts thereof,are: cloquintocet-mexyl, cyprosulfamide, fenchlorazole-ethyl, isoxadifen-ethyl, mefenpyr- diethyl, fenclorim, cumyluron, S4-1 and S4-5, and particularly preferred safeners are: cloquintocet- mexyl, cyprosulfamide, isoxadifen-ethyl and mefenpyr-diethyl.
• Biological examplesThe following abbreviations are used in the examples and tables below: Tested harmful plants: ABUTH: Abutilon theophrasti ALOMY: Alopecurus myosuroides AMARE Amaranthus retroflexus DIGSA: Digitaria sanguinalis ECHCG: Echinochloa crus-galli KCHSC: Kochia scoparia LOLRI: Lolium rigidum MATIN: Matricaria inodora POAAN: Poa annua SETVI: Setaria viridis STEME: Stellaria media VERPE: Veronica persica
• WPwettable powders
• ECemulsifiable concentrates
• Tables B1 to B12show the effects of selected compounds of the general formula (I) according to Table 1 on various harmful plants and an application rate corresponding to 1280 g/ha obtained by the experimental procedure mentioned above.
• Table B1 Table B2Table B3
• Table B4Table B5
• Table B6Table B7
• Table B8Table B9
• Table B10Table B11
• Tables D1 to D10show the effects of selected compounds of the general formula (I) according to Table 1 on various harmful plants and an application rate corresponding to 320 g/ha obtained by the experimental procedure mentioned above.
• Table D1 Table D2Table D3
• Table D4Table D5
• Table D6Table D6

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