Patent Application
20240174618
The invention relates to the technical field of crop protection products, in particular that of herbicides for selective control of broad-leaved weeds and weed grasses in crops of useful plants.
Specifically, the present invention relates to substituted (2-heteroaryloxyphenyl)sulfonates and salts thereof, to processes for their preparation and to their use as herbicides.
In their application, crop protection products known to date for the selective control of harmful plants in crops of useful plants or active ingredients for controlling unwanted vegetation sometimes have disadvantages, whether (a) that they have insufficient herbicidal activity, if any, against particular harmful plants, (b) that the spectrum of harmful plants which can be controlled with an active ingredient is not wide enough, (c) that their selectivity in crops of useful plants is too low and/or (d) that they have a toxicologically unfavorable profile. Furthermore, some active ingredients which can be used as plant growth regulators for a number of useful plants cause undesirably reduced harvest yields in other useful plants or are compatible with the crop plant only within a narrow application rate range, if at all. Some of the known active ingredients cannot be produced economically on an industrial scale owing to precursors and reagents which are difficult to obtain, or they have only insufficient chemical stabilities. In the case of other active ingredients, the activity is too highly dependent on environmental conditions, such as weather and soil conditions.
The herbicidal action of these known compounds, especially at low application rates, and/or the compatibility thereof with crop plants is still in need of improvement.
WO 2017/011288 describes, as herbicides, various pyrimidinyloxybenzenes that bear an ether group in the 2 position of the benzene. In addition, documents WO 2016/196606 and WO2016/010731 describe further pyrimidinyloxybenzenes, and documents WO2020/002087 and WO2020/002085 describe heteroaryloxypyridines, as herbicides.
By contrast, there is still no description of heteroaryloxybenzenes substituted by a sulfonate group in the 2 position of the benzene, and salts thereof.
It has now been found that, surprisingly, (2-heteroaryloxyphenyl)sulfonates and/or salts thereof are of particularly good suitability as active herbicidal ingredients.
The present invention thus provides substituted (2-heteroaryloxyphenyl)sulfonates of the general formula (I) or salts thereof
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, H2SO4, H3PO4 or HNO3, 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 salts then contain the conjugate base of the acid as anion. Suitable substituents in deprotonated form, for example sulfonic acids, particular sulfonamides or carboxylic acids, are 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 bases are, for example, organic amines such as trialkylamines, morpholine, piperidine and pyridine, and the hydroxides, carbonates and hydrogencarbonates of ammonium, alkali metals or alkaline earth metals, especially sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate. These salts are 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 [NRaRbRcRd]+ in which Ra to Rd are each independently an organic radical, especially alkyl, aryl, arylalkyl or alkylaryl. Also useful are alkylsulfonium and alkylsulfoxonium salts, such as (C1-C4)-trialkylsulfonium and (C1-C4)-trialkylsulfoxonium salts.
The heteroaryloxypyridines of the general formula (I) having substitution in accordance with the invention may, 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 thereof are referred to hereinafter as “compounds of the general formula (I)”.
The invention preferably provides compounds of the general formula (I) in which
The invention more preferably provides compounds of the general formula (I) in which
The invention very particularly preferably provides compounds of the general formula (I) in which
The invention most preferably provides compounds of the general formula (I) in which
The definitions of radicals listed above in general terms or within areas of preference apply 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.
Of particular interest, primarily for reasons of higher herbicidal activity, better selectivity and/or better preparability, are inventive compounds of the general formula (I) given or salts thereof or the inventive use thereof 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.
With regard to the compounds of the invention, the terms used above and further down will be elucidated. These are familiar to the person skilled in the art and especially have the definitions elucidated hereinafter:
Unless defined differently, names of chemical groups are generally to be understood such that attachment to the skeleton or the remainder of the molecule is via the structural element of the relevant chemical group mentioned last, i.e. for example in the case of (C1-C4)-alkoxy via the oxygen atom and in the case of carboxy-(C1-C4)-alkyl or (C1-C4)-alkoxy-(C1-C4)-alkyl in each case via the carbon atom of the alkyl group.
According to the invention, “alkylsulfonyl”—on its own or as part of a chemical group—represents straight-chain or branched alkylsulfonyl, preferably having 1 to 4 carbon atoms, for example (but not limited to) (C1-C4)-alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl.
According to the invention, “alkylthio”—on its own or as part of a chemical group—represents straight-chain or branched S-alkyl, preferably having 1 to 4 carbon atoms, such as (C1-C4)-alkylthio, for example (but not limited to) (C1-C4)-alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio.
According to the invention, “alkylsulfinyl (alkyl-S(═O)—)”, unless otherwise defined elsewhere, represents alkyl radicals bonded to the skeleton via —S(═O)—, such as (C1-C4)-alkylsulfinyl, for example (but not limited to) (C1-C4)-alkylsulfinyl such as methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl.
“Alkoxy” denotes an alkyl radical bonded via an oxygen atom, for example (but not limited to) (C1-C4)-alkoxy such as methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy.
According to the invention, “alkylcarbonyl” (alkyl-C(═O)—), unless otherwise defined elsewhere, represents alkyl radicals bonded to the skeleton via —C(═O)—, such as (C1-C4)-alkylcarbonyl. The number of the carbon atoms here relates to the alkyl radical in the alkylcarbonyl group.
According to the invention, “alkylaminocarbonyl” (alkyl-NH—C(═O)—), unless defined differently elsewhere, represents alkyl radicals bonded to the skeleton by the carbon via —NH—C(═O)—, such as (C1-C4)-alkylaminocarbonyl. The number of the carbon atoms here relates to the alkyl radical in the alkylaminocarbonyl group.
According to the invention, “alkylaminocarbonylamino” (alkyl-NH—C(═O)—NH), unless defined differently elsewhere, represents alkyl radicals bonded to the skeleton by the nitrogen via —NH—C(═O)—NH—, such as (C1-C4)-alkylaminocarbonylamino. The number of the carbon atoms here relates to the alkyl radical in the alkylaminocarbonylamino group.
“Alkoxycarbonyl (alkyl-O—C(═O)—)”, unless defined differently elsewhere: alkyl radicals bonded to the skeleton via —O—C(═O)—, such as (C1-C4)-alkoxycarbonyl. The number of the carbon atoms here relates to the alkyl radical in the alkoxycarbonyl group.
“Alkoxycarbonylamino” (alkyl-O—C(═O)—NH), unless defined differently elsewhere: alkyl radicals bonded to the skeleton by the nitrogen via —O—C(═O)—NH, such as (C1-C4)-alkoxycarbonylamino. The number of the carbon atoms here relates to the alkyl radical in the alkoxycarbonylamino group.
“Alkylcarbonyloxy” (alkyl-C(═O)—O—), unless defined differently elsewhere: alkyl radicals bonded to the skeleton by the oxygen via a carbonyloxy group (—C(═O)—O—), such as (C1-C4)-alkylcarbonyloxy. The number of the carbon atoms here relates to the alkyl radical in the alkylcarbonyloxy group.
“Alkylcarbonylamino” (alkyl-C(═O)—NH—), unless defined differently elsewhere: alkyl radicals bonded to the skeleton by the nitrogen via a carbonylamino group (—C(═O)—NH—), such as (C1-C4)-alkylcarbonylamino. The number of the carbon atoms here relates to the alkyl radical in the alkylcarbonylamino group.
The term “halogen” denotes, 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.
According to the invention, “alkyl” means 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 substituents are halogen atoms, alkoxy, haloalkoxy, cyano, alkylthio, haloalkylthio, amino or nitro groups, particular preference being given to methoxy, fluoroalkyl, cyano, nitro, fluorine, chlorine, bromine or iodine. The prefix “bis” also includes the combination of different alkyl radicals, e.g. methyl(ethyl) or ethyl(methyl).
“Haloalkyl”, “-alkenyl” and “-alkynyl” respectively denote alkyl, alkenyl and alkynyl partly or fully substituted by identical or different halogen atoms, for example monohaloalkyl such as CH2CH2Cl, CH2CH2Br, CHClCH3, CH2Cl, CH2F; dihaloalkyl such as CHF2, CHCl2; perhaloalkyl such as CF3, CCl3, CClF2, CBrF2, CFCl2, CF2CClF2, CF2CClFCF3; polyhaloalkyl such as CH2CHFCl, CF2CClFH, CF2CBrFH, CH2CF3; the term perhaloalkyl also encompasses the term perfluoroalkyl.
“Haloalkoxy” is, for example, OCF3, OCHF2, OCH2F, OCF2CF3, OCH2CF3 and OCH2CH2Cl; this applies correspondingly to haloalkenyl and other halogen-substituted radicals.
The expression “(C1-C4)-alkyl” mentioned here by way of example is 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.
Unless stated specifically, in the case of the hydrocarbon radicals such as alkyl, alkenyl and alkynyl radicals, including in composite radicals, preference is given to the lower carbon skeletons, for example having from 1 to 6 carbon atoms, or having from 2 to 6 carbon atoms in the case of unsaturated groups. Alkyl radicals, including 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; 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. Preference is given to radicals having one double bond or triple bond.
The term “alkenyl” also 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) and 1,2-butadienyl. Alkenyl denotes, for example, vinyl, which can optionally be substituted by further alkyl radicals, for example (but not limited to) (C2-C4)-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.
The term “alkynyl” also 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. (C2-C4)-Alkynyl denotes, for example, ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl.
The term “cycloalkyl” refers to a carbocyclic saturated ring system having preferably 3-6 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, bisalkylamino, alkoxycarbonyl, hydroxycarbonyl, arylalkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl. In the case of optionally substituted cycloalkyl, cyclic systems with substituents are included, also including substituents with a double bond on the cycloalkyl radical, for example an alkylidene group such as methylidene. In the case of optionally substituted cycloalkyl, polycyclic aliphatic systems are 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 and bicyclo[2.1.1]hexyl, but also systems such as 1,1′-bi(cyclopropyl)-1-yl, 1,1′-bi(cyclopropyl)-2-yl. The expression “(C3-C6)-cycloalkyl” is a brief notation for cycloalkyl having three to 6 carbon atoms, corresponding to the range specified for carbon atoms.
In the case of substituted cycloalkyl, spirocyclic 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.
“Cycloalkenyl” denotes a carbocyclic, nonaromatic, partly unsaturated ring system having preferably 4-6 carbon atoms, e.g. 1-cyclobutenyl, 2-cyclobutenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, or 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, 1,3-cyclohexadienyl or 1,4-cyclohexadienyl, also including substituents with a double bond on the cycloalkenyl radical, for example an alkylidene group such as methylidene. In the case of optionally substituted cycloalkenyl, the elucidations for substituted cycloalkyl apply correspondingly.
According to the invention, “haloalkylthio”—on its own or as part of a chemical group—represents straight-chain or branched S-haloalkyl, preferably having 1 to 4 carbon atoms, such as (C1-C4)-haloalkylthio, for example (but not limited to) trifluoromethylthio, pentafluoroethylthio, difluoromethyl, 2,2-difluoroeth-1-ylthio, 2,2,2-difluoroeth-1-ylthio, 3,3,3-prop-1-ylthio.
“Halocycloalkyl” denotes cycloalkyl which is 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-fluorocycloprop-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.
According to the invention, “trialkylsilyl”—on its own or as part of a chemical group—represents straight-chain or branched Si-alkyl, preferably having 1 to 6 carbon atoms, such as tri-[(C1-C2)-alkyl]silyl, for example (but not limited to) trimethylsilyl, triethylsilyl.
If a collective term for a substituent, for example C1-C4-alkyl, is at the end of a composite substituent, as for example in C3-C6-cycloalkyl-C1-C4-alkyl, the constituent at the start of the composite substituent, for example the C3-C6-cycloalkyl, may be mono- or polysubstituted identically or differently and independently by the latter substituent, C1-C4-alkyl.
Unless defined differently, the definition for collective terms also applies to these collective terms in composite substituents. Example: The definition of (C1-C4)-alkyl also applies to (C1-C4)-alkyl as component of a composite substituent such as, for example, (C3-C6)-cycloalkyl-(C1-C4)-alkyl.
If the compounds can form, through a hydrogen shift, tautomers whose structure would not formally be covered by the general formula (I), these tautomers are nevertheless encompassed by the definition of the inventive compounds of the general formula (I), unless a particular tautomer is under consideration. For example, many carbonyl compounds may 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).
Depending on the nature of the substituents and the manner in which they are attached, the compounds of the general formula (I) may be present as stereoisomers. The possible stereoisomers defined by the specific three-dimensional form thereof, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the general formula (I). If, for example, one or more alkenyl groups are present, diastereomers (Z and E isomers) may occur. If, for example, one or more asymmetric carbon atoms are present, enantiomers and diastereomers may occur. Stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods. The chromatographic separation can be effected 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 invention thus 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 (I) cannot be obtained in a satisfactory manner by the routes described below, they can be prepared by derivatization of other compounds (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 scale are 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 present invention also claims processes for preparing the inventive compounds of the general formula (I).
The inventive compounds of the general formula (I) can be prepared, inter alia, using known processes.
The synthesis routes used and examined proceed from commercially available or easily preparable building blocks. In the schemes which follow, the moieties R1, R2, R3, R4, X and Y in the general formula (I) have the meanings defined above, unless illustrative but non-limiting definitions are given. Inventive compounds of the general formula (I) may be prepared, for example, by the method specified in
scheme 1.
The (2-heteroaryloxyphenyl)sulfonates of the general formula (I) can be prepared via a reaction of the phenols (E-I) with sulfonyl chlorides (E-II) in the presence of bases. The base may be an amine base (for example 1-methylimidazole or triethylamine). The reactions are generally conducted in an organic solvent, for example dichloroethane or acetonitrile, at temperatures between 0° C. and the boiling point of the solvent.
The phenols of the general formula (E-I) can be prepared via an alkylation of the 1,2-dihydroxybenzenes (E-III) in the presence of bases with the pyridine, pyrimidine or pyrazine (E-IV), where LG is a leaving group (scheme 2).
The base may be a carbonate salt of an alkali metal (for example sodium, potassium or cesium), or an amine base (for example N,N-diisopropylethylamine). The reactions are generally conducted in an organic solvent, for example acetonitrile, butyronitrile, dimethylformamide or chlorobenzene, at temperatures between 0° C. and the boiling point of the solvent.
For a suitable regioselectivity, the phenols (E-1) may be synthesized as described in scheme 3: The oxidation reactions of the methoxybenzaldehyde derivatives may be conducted with m-chloroperoxybenzoic acid in dichloromethane under standard reaction conditions. Directly after workup, the intermediate may be admixed with methanol and an amine base, for example triethylamine, tributylamine or N,N-diisopropylethylamine. The resultant phenol (E-VI), after evaporation of the solvents, can be arylated as described in scheme 2. By reaction with, for example, boron tribromide in DCM, boron trichloride or hydrogen bromide, it is then possible to obtain the phenol derivative E-I which is suitable for sulfonation (scheme 3).
A mixture of catechol (4.00 g, 36.3 mmol), 2,5-dichloropyrimidine (4.87 ml, 32.7 mmol) and N,N-diisopropylethylamine (6.96 ml, 40.0 mmol) in 15 ml of chlorobenzene was heated at 140° C. for 9 h. The resulting reaction mixture was cooled down to room temperature, diluted with water and extracted repeatedly with ethyl acetate. The combined organic phases were then washed with water, dried over magnesium sulfate, filtered and concentrated. By subsequent purification of the resulting crude product by column chromatography (ethyl acetate/heptane gradient), 2-(5-chloropyrimidin-2-yl)oxyphenol was isolated.
The yield was 4.33 g (53% of theory).
A mixture of 2-(5-chloropyrimidin-2-yl)oxyphenol (intermediate A-01, 150 mg, 0.67 mmol) and 1-methylimidazole (160 μl, 2.02 mmol) in 8 ml of dichloroethane was cooled down to 0° C., and isobutanesulfonyl chloride (114 μl, 0.88 mmol) was added. The mixture was stirred at room temperature for 18 hours. The resulting reaction mixture was concentrated, diluted with 30 ml of water and 4 equivalents of 6M HCl, and then extracted repeatedly with ethyl acetate. The combined organic phases were then dried over magnesium sulfate, filtered and concentrated. In this way, [2-(5-chloropyrimidin-2-yl)oxyphenyl] 2-methylpropane-1-sulfonate (synthesis example no. I-7) was isolated.
The yield was 200 mg (86% of theory).
A mixture of 2-methoxy-3-methylbenzaldehyde (4.00 g, 26.6 mmol) in 80 ml of dichloromethane was cooled down to 0° C., and m-CPBA 77% (8.95 g, 39.9 mmol) was added. The mixture was stirred at room temperature for 18 hours. The resulting reaction mixture was concentrated, diluted with 100 ml of dichloromethane and a mixture of saturated NaHCO3/saturated Na2S2O3 solution 1:1 (1×200 ml), and then extracted repeatedly with dichloromethane. The combined organic phases were washed with water and saturated NaCl solution, dried over magnesium sulfate, filtered and concentrated. The intermediate was dissolved in 60 ml of methanol, and triethylamine was added. The mixture was stirred at room temperature for 48 hours and then concentrated. By subsequent purification of the resulting crude product by column chromatography (acetone/heptane gradient), 2-methoxy-3-methylphenol was isolated.
The yield was 3.45 g (89% of theory).
A mixture of intermediate A02 (1.10 g, 7.96 mmol), 2,5-dichloropyrimidine (1.30 ml, 8.75 mmol) and potassium carbonate (2.75 g, 19.9 mmol) in 10 ml of dimethylformamide was heated at 80° C. for 2 h. The resulting reaction mixture was cooled down to room temperature, diluted with water and extracted repeatedly with tert-butyl methyl ether. The combined organic phases were then washed with water, dried over magnesium sulfate, filtered and concentrated. By subsequent purification of the resulting crude product by column chromatography (acetone/heptane gradient), 5-chloro-2-(2-methoxy-3-methylphenoxy)pyrimidine was isolated.
The yield was 1.88 g (84% of theory).
A mixture of 5-chloro-2-(2-methoxy-3-methylphenoxy)pyrimidine A03 (1.80 g, 7.18 mmol) in 20 ml of dichloromethane was cooled down to −78° C. under nitrogen, and boron tribromide (1M in dichloromethane) (21.50 ml, 21.50 mmol) was cautiously added dropwise at −78° C. The mixture was then allowed to come to room temperature, and stirring was continued at room temperature. The resulting reaction mixture was diluted with ice-water and subsequently extracted repeatedly with dichloromethane. The combined organic phases were then washed with water and saturated NaCl solution, dried over magnesium sulfate, filtered and concentrated. 2-[(5-Chloropyrimidin-2-yl)oxy]-6-methylphenol was isolated without further purification. The yield was 1.59 g (79% of theory).
A mixture of 2-[(5-chloropyrimidin-2-yl)oxy]-6-methylphenol (intermediate A-04, 150 mg, 0.63 mmol) and 1-methylimidazole (202 μl, 2.53 mmol) in 5 ml of dichloroethane was cooled down to 0° C., and 4,4,4-trifluorobutane-1-sulfonyl chloride (182 μl, 1.26 mmol) was added. The mixture was stirred at room temperature for 18 hours. The resulting reaction mixture was concentrated, diluted with 30 ml of water and 4 equivalents of 6M HCl, and then extracted repeatedly with ethyl acetate. The combined organic phases were then dried over magnesium sulfate, filtered and concentrated. Subsequent purification of the resulting crude product by column chromatography (acetone/heptane gradient) resulted in isolation of 2-[(5-chloropyrimidin-2-yl)oxy]-6-methylphenyl 4,4,4-trifluorobutane-1-sulfonate (synthesis example no. I-28).
The yield was 145 mg (54% of theory).
In analogy to the preparation examples cited above and recited at the appropriate point, the inventive compounds of the general formula (I) specified hereinafter and shown in table 1 are obtained.
Selected detailed synthesis examples for the inventive compounds of the general formula (I) are adduced below. The 1H NMR spectroscopic data given for the chemical examples described in the following sections (400 MHz for 1H NMR, solvent CDCl3 or d6-DMSO, internal standard: tetramethylsilane δ=0.00 ppm) were obtained on a Bruker instrument, and the signals listed have the meanings given below: br=broad; s=singlet, d=doublet, t=triplet, dd=doublet of doublets, ddd=doublet of a doublet of doublets, m=multiplet, q=quartet, quint=quintet, sext=sextet, sept=septet, dq=doublet of quartets, dt=doublet of triplets. In the case of diastereomer mixtures, what is reported is either the significant signals for each of the two diastereomers or the characteristic signal of the main diastereomer.
1H NMR (400 MHz, CDCl3 δ, ppm) 8.49 (s, 2H), 7.50-7.32 (m, 4H), 3.17 (s, 3H).
1H NMR (400 MHz, d6-DMSO δ, ppm) 8.79 (s, 2H), 7.52-7.37 (m, 4H), 3.70 (tr, 2H), 3.60 (tr, 2H), 2.14 (m, 2H).
1H NMR (400 MHz, d6-DMSO δ, ppm) 8.79 (s, 2H), 7.50-7.37 (m, 4H), 3.45 (tr, 2H), 1.70 (m, 2H), 0.94 (tr, 3H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.48-7.26 (m, 4H), 4.18 (qu, 2H).
1H NMR (400 MHz, d6-DMSO δ, ppm) 8.77 (s, 2H), 7.52-7.37 (m, 4H), 3.70 (tr, 2H), 3.60 (tr, 2H), 2.14 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.49 (s, 2H), 7.51-7.31 (m, 4H), 3.26 (tr, 2H), 1.83 (m, 2H), 1.46 (m, 2H), 0.94 (tr, 3H).
1H NMR (400 MHz, d6-DMSO δ, ppm) 8.79 (s, 2H), 7.51-7.37 (m, 4H), 3.39 (d, 2H), 2.10 (m, 1H), 0.98 (d, 6H).
1H NMR (400 MHz, d6-DMSO δ, ppm) 8.79 (s, 2H), 7.55-7.38 (m, 4H), 3.85 (m, 2H), 2.81 (m, 2H).
1H NMR (400 MHz, d6-DMSO δ, ppm) 8.79 (s, 2H), 7.56-7.39 (m, 4H), 5.57 (s, 2H).
1H NMR (400 MHz, d6-DMSO δ, ppm) 8.79 (s, 2H), 7.52-7.38 (m, 4H), 3.63 (tr, 2H), 2.41 (m, 2H), 1.88 (m, 2H).
1H NMR (400 MHz, d6-DMSO δ, ppm) 8.79 (s, 2H), 7.35-7.26 (m, 3H), 3.69 (m, 4H), 2.36 (s, 3H), 2.13 (m, 2H).
1H NMR (400 MHz, d6-DMSO δ, ppm) 8.78 (s, 2H), 7.36-7.29 (m, 3H), 3.70 tr, 2H), 3.59 (tr, 2H), 2.16 (s, 3H), 2.10 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.33-7.18 (m, 3H), 3.70 (m, 2H), 3.50 (m, 2H), 2.40 (m, 2H).
1H NMR (400 MHz, d6-DMSO δ, ppm) 8.82 (s, 2H), 7.52-7.34 (m, 3H), 3.71 (m, 4H), 2.18 (m, 2H).
1H NMR (400 MHz, d6-DMSO δ, ppm) 8.79 (s, 2H), 7.51-7.37 (m, 4H), 3.65 (m, 2H), 3.56 (m, 2H), 1.81 (m, 4H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.49 (s, 2H), 7.52-7.30 (m, 4H), 3.30 (qu, 2H), 1.45 (tr, 3H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.47 (s, 2H), 7.27 (m, 1H), 7.11 (m, 1H), 6.96 (m, 1H), 3.79 (s, 3H), 3.28 (m, 2H), 1.84 (m, 2H), 1.45 (m, 2H), 0.93 tr, 3H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.48 (s, 2H), 7.52-7.29 (m, 4H), 3.48 (m, 1H), 1.43 (d, 6H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.54-7.28 (m, 4H), 3.72 (m, 1H), 2.08 (m, 4H), 1.76 (m, 2H), 1.63 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.49 (s, 2H), 7.52-7.30 (m, 4H), 3.83 (tr, 2H), 3.56 (tr, 2H), 3.36 (s, 3H).
1H NMR (400 MHz, CDCl3, ppm) 8.48 (s, 2H), 7.50-7.30 (m, 4H), 2.69 (m, 1H), 1.13 (m, 4H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.49 (s, 2H), 7.53-7.28 (m, 4H), 3.24 (m, 1H), 2.06 (m, 1H), 1.64 (m, 1H), 1.42 (d, 3H), 1.02 (tr, 3H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.48 (s, 2H), 7.53-7.30 (m, 4H), 3.20 (d, 2H), 1.22 (m, 1H), 0.72 (m, 2H), 0.41 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.48 (s, 2H), 7.51-7.29 (m, 4H), 3.25 (m, 2H), 1.85 (m, 2H), 1.38 (m, 4H), 0.92 (m, 3H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.48 (s, 2H), 7.51-7.30 (m, 4H), 3.25 (m, 2H), 1.73 (m, 3H), 0.95 (m, 6H).
1H NMR (400 MHz, d6-DMSO, δ, ppm): 8.18 (s, 1H), 8.02-7.99 (m, 1H), 7.49-7.38 (m, 4H), 7.34-7.16 (m, 1H), 3.63-3.59 (m, 2H), 2.47-2.35 (m, 2H), 1.92-1.84 (m, 2H).
1H NMR (400 MHz, d6-DMSO, δ, ppm): 8.18 (s, 1H), 8.02-7.90 (m, 1H), 7.48-7.36 (m, 4H), 7.34-7.18 (m, 1H), 3.71-3.68 (m, 2H), 3.59-3.57 (m, 2H), 2.17-2.10 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.48 (s, 2H), 7.29-7.25 (m, 1H), 7.22-7.20 (m, 1H), 7.16-7.13 (m, 1H), 3.55-3.53 (m, 2H), 2.46 (s, 3H), 2.40-2.29 (m, 2H), 2.22-2.12 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.49 (s, 2H), 7.30-7.28 (m, 1H), 7.21-7.16 (m, 2H), 3.70-3.66 (m, 2H), 2.80-2.73 (m, 2H), 2.45 (s, 3H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.49 (s, 2H), 7.59-7.56 (m, 1H), 7.32-7.24 (m, 2H), 3.63-3.59 (m, 2H), 2.39-2.29 (m, 2H), 2.25-2.17 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.58-7.56 (m, 1H), 7.35-7.25 (m, 2H), 3.77-3.73 (m, 2H), 2.87-2.78 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.59 (s, 2H), 7.43-7.41 (m, 1H), 7.35-7.28 (m, 2H), 3.73-3.69 (m, 2H), 2.84-2.78 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.58 (s, 2H), 7.30-7.28 (m, 1H), 7.21-7.16 (m, 2H), 3.70-3.66 (m, 2H), 2.80-2.73 (m, 2H), 2.45 (s, 3H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.58 (s, 2H), 7.43-7.41 (m, 1H), 7.34-7.25 (m, 2H), 3.60-3.56 (m, 2H), 2.38-2.31 (m, 2H), 2.25-2.19 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.56 (s, 2H), 7.30-7.27 (m, 1H), 7.23-7.21 (m, 1H), 7.17-7.14 (m, 1H), 3.56 (tr, 2H), 2.47 (s, 3H), 2.41-2.30 (m, 2H), 2.21-2.13 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.49 (s, 2H), 7.51-7.48 (m, 1H), 7.39-7.30 (m, 3H), 5.91-5.83 (m, 1H), 5.49-5.44 (m, 2H), 4.01-3.99 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.48 (s, 2H), 7.49-7.41 (m, 1H), 7.41-7.27 (m, 3H), 6.73 (dd, 1H), 6.30 (dd, 1H), 6.13 (dd, 1H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.43-7.41 (m, 1H), 7.35-7.28 (m, 2H), 3.73-3.69 (m, 2H), 2.84-2.78 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.43-7.41 (m, 1H), 7.34-7.28 (m, 2H), 3.60-3.56 (m, 2H), 2.38-2.31 (m, 2H), 2.25-2.19 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.59 (s, 2H), 7.39-7.33 (m, 1H), 7.20-7.15 (m, 2H), 3.63-3.59 (m, 2H), 2.83-2.77 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.58 (s, 2H), 7.37-7.32 (m, 1H), 7.20-7.13 (m, 2H), 3.50-3.47 (m, 2H), 2.38-2.31 (m, 2H), 2.25-2.19 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.42 (s, 2H), 7.37-7.32 (m, 1H), 7.19-7.13 (m, 2H), 3.51-3.47 (m, 2H), 2.38-2.31 (m, 2H), 2.24-2.19 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.43 (s, 2H), 7.58-7.55 (m, 1H), 7.35-7.33 (m, 1H), 7.29-7.25 (m, 1H), 3.77-3.73 (m, 2H), 2.84-2.78 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.42 (s, 2H), 7.58-7.56 (m, 1H), 7.33-7.30 (m, 1H), 7.28-7.24 (m, 1H), 3.63-3.60 (m, 2H), 2.38-2.31 (m, 2H), 2.24-2.18 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.43 (s, 2H), 7.30-7.28 (m, 1H), 7.21-7.17 (m, 2H), 3.71-3.67 (m, 2H), 2.80-2.73 (m, 2H), 2.45 (s, 3H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.41 (s, 2H), 7.29-7.25 (m, 1H), 7.22-7.19 (m, 1H), 7.16-7.14 (m, 1H), 3.58-3.54 (m, 2H), 2.46 (s, 3H), 2.38-2.31 (m, 2H), 2.19-2.13 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.43 (s, 2H), 7.38-7.33 (m, 1H), 7.18-7.15 (m, 2H), 3.63-3.59 (m, 2H), 2.83-2.77 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.51 (s, 2H), 7.38-7.34 (m, 1H), 7.19-7.16 (m, 2H), 3.62-3.59 (m, 2H), 2.84-2.76 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.37-7.33 (m, 1H), 7.19-7.14 (m, 2H), 3.50-3.47 (m, 2H), 2.38-2.30 (m, 2H), 2.24-2.19 (m, 2H).
1H NMR (600 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.35-7.31 (m, 1H), 7.18-7.12 (m, 2H), 5.85-5.78 (m, 1H), 5.18-5.11 (m, 2H), 3.47-3.44 (m, 2H), 2.68-2.64 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.51 (s, 2H), 7.37-7.32 (m, 1H), 7.19-7.13 (m, 2H), 3.63-3.55 (m, 2H), 2.21-2.14 (m, 2H), 1.81-1.76 (m, 1H), 1.71-1.66 (m, 1H), 1.25-1.20 (m, 1H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.34-7.30 (m, 1H), 7.18-7.12 (m, 2H), 3.88-3.85 (m, 2H), 3.69-3.66 (m, 2H), 3.36 (s, 3H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.51 (s, 2H), 7.37-7.32 (m, 1H), 7.19-7.13 (m, 2H), 3.59 (d, 2H), 2.95-2.73 (m, 3H), 2.54-2.42 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.49 (s, 2H), 7.36-7.30 (m, 1H), 7.18-7.11 (m, 2H), 4.41-4.37 (m, 1H), 3.90-3.85 (m, 1H), 3.80-3.75 (m, 1H), 3.72-3.67 (m, 1H), 3.53-3.48 (m, 1H), 2.25-2.17 (m, 1H), 1.98-1.90 (m, 2H), 1.80-1.71 (m, 1H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.36-7.30 (m, 1H), 7.19-7.12 (m, 2H), 3.50-3.46 (m, 2H), 1.84-1.78 (m, 2H), 0.86-0.78 (m, 1H), 0.55-0.50 (m, 2H), 0.17-0.13 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.37-7.31 (m, 1H), 7.19-7.12 (m, 2H), 6.02-5.74 (m, 1H), 3.49-3.45 (m, 2H), 2.15-2.02 (m, 4H).
1H NMR (400 MHz, d6-DMSO δ, ppm) 8.81 (s, 2H), 7.52-7.41 (m, 2H), 7.38-7.35 (m, 1H), 4.11-4.05 (m, 1H), 3.74-3.69 (m, 1H), 2.10-1.93 (m, 2H), 1.62-1.58 (m, 1H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.46 (s, 1H), 8.45 (d, 1H), 8.15 (d, 1H), 7.46-7.20 (m, 4H), 3.64 (tr, 2H), 3.43 (tr, 2H), 2.24-2.18 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.23 (s, 1H), 8.01 (s, 1H), 7.39-7.31 (m, 4H), 3.69 (tr, 2H), 3.48 (tr, 2H), 2.42-2.35 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 7.81 (s, 1H), 7.51 (d, 1H), 7.37-7.25 (m, 4H), 3.68 (tr, 2H), 3.44 (tr, 2H), 2.42-2.32 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.80 (s, 1H), 8.33 (d, 1H), 7.51-7.26 (m, 4H), 3.66 (tr, 2H), 3.44 (tr, 2H), 2.38-2.33 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 9.00 (s, 1H), 8.51 (d, 1H), 7.35 (d, 1H), 7.33-7.25 (m, 3H), 7.12 (d, 1H), 3.61 (tr, 2H), 3.37 (tr, 2H), 2.31-2.27 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.44 (d, 1H), 7.96 (d, 1H), 7.55 (d, 1H), 7.38-7.27 (m, 3H), 7.12 (d, 1H), 3.62 (tr, 2H), 3.41 (tr, 2H), 2.34-2.29 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 7.86 (d, 1H), 7.53 (d, 1H), 7.37-7.25 (m, 4H), 3.63 (tr, 2H), 3.43 (tr, 2H), 2.35-2.31 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 7.96 (d, 1H), 7.69 (d, 1H), 7.38-7.26 (m, 4H), 3.67 (tr, 2H), 3.44 (tr, 2H), 2.37-2.34 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.12 (s, 1H), 7.99 (s, 1H), 7.51-6.99 (m, 4H), 3.66 (tr, 2H), 3.48 (tr, 2H), 2.37-2.32 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.49 (s, 2H), 7.60-7.58 (m, 1H), 7.34-7.25 (m, 2H), 3.64 (tr, 2H), 2.35-2.24 (m, 4H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.51 (s, 2H), 7.39-7.33 (m, 1H), 7.21-7.14 (m, 2H), 3.51 (tr, 2H), 2.35-2.28 (m, 4H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.47 (s, 2H), 7.29-7.27 (m, 1H), 7.25-7.13 (m, 2H), 3.56 (tr, 2H), 2.46 (s, 3H), 2.31-2.19 (m, 4H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.38-7.33 (m, 1H), 7.19-7.13 (m, 2H), 3.62-3.58 (m, 2H), 3.01-2.92 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.48 (s, 2H), 7.29-7.25 (m, 1H), 7.21-7.14 (m, 2H), 3.70-3.66 (m, 2H), 2.97-2.80 (m, 2H), 2.46 (s, 3H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.58-7.56 (m, 1H), 7.33-7.24 (m, 2H), 3.76-3.72 (m, 2H), 3.02-2.93 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.43-7.41 (m, 1H), 7.35-7.27 (m, 2H), 3.72-3.69 (m, 2H), 3.02-2.94 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.29-7.27 (m, 1H), 7.22-7.14 (m, 2H), 3.66 (d, 2H), 2.90-2.83 (m, 3H), 2.48-2.42 (m, 5H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.58-7.56 (m, 1H), 7.33-7.23 (m, 2H), 3.72 (d, 2H), 2.90-2.82 (m, 3H), 2.51-2.46 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.49 (s, 2H), 7.30-7.28 (m, 1H), 7.22-7.15 (m, 2H), 4.11-4.06 (m, 1H), 3.37-3.31 (m, 1H), 2.47 (s, 3H), 2.09-2.02 (m, 1H), 1.90-1.85 (m, 1H), 1.58-1.54 (m, 1H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.58-7.56 (m, 1H), 7.33-7.24 (m, 2H), 4.17-4.12 (m, 1H), 3.44-3.38 (m, 1H), 2.16-2.08 (m, 1H), 1.90-1.85 (m, 1H), 1.61-1.59 (m, 1H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.51 (s, 2H), 7.65-7.62 (m, 1H), 7.52-7.48 (m, 2H), 4.14-4.09 (m, 1H), 3.50-3.44 (m, 1H), 2.21-2.16 (m, 1H), 1.93-1.89 (m, 1H), 1.63-1.59 (m, 1H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.51 (s, 2H), 7.64-7.62 (m, 2H), 7.51-7.47 (m, 1H), 3.59 (d, 2H), 2.95-2.84 (m, 3H), 2.56-2.44 (m, 2H).
1H NMR (400 MHz, d6-DMSO δ, ppm): 8.51 (s, 2H), 7.65-7.61 (m, 2H), 7.51-7.47 (m, 1H), 3.73-3.69 (m, 4H), 2.50-2.43 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.65-7.62 (m, 2H), 7.52-7.48 (m, 1H), 3.62 (tr, 2H), 2.42-2.23 (m, 4H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.51 (s, 2H), 7.66-7.63 (m, 2H), 7.53-7.49 (m, 1H), 3.77-3.73 (m, 2H), 2.89-2.82 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.51 (s, 2H), 7.31-7.28 (m, 1H), 7.23-7.16 (m, 2H), 6.08 (tr, 1H), 4.34 (d, 2H), 2.46 (s, 3H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.58-7.56 (m, 1H), 7.33-7.24 (m, 2H), 6.11 (tr, 1H), 4.40 (d, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.51 (s, 2H), 7.38-7.32 (m, 1H), 7.20-7.14 (m, 2H), 6.10 (tr, 1H), 4.27 (d, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.42 (s, 2H), 7.37-7.31 (m, 1H), 7.19-7.13 (m, 2H), 4.14 (tr, 2H), 3.53 (tr, 2H), 2.37-2.31 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.48 (s, 2H), 7.29-7.14 (m, 3H), 4.15 (tr, 2H), 3.59 (tr, 2H), 2.47 (s, 3H), 2.33-2.30 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.50 (s, 2H), 7.43-7.40 (m, 1H), 7.34-7.28 (m, 2H), 4.14 (tr, 2H), 3.62 (tr, 2H), 2.36-2.33 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.51 (s, 2H), 7.39-7.33 (m, 1H), 7.20-7.15 (m, 2H), 3.56 (tr, 2H), 2.66 (tr, 2H), 2.37-2.30 (m, 2H).
1H NMR (400 MHz, CDCl3 δ, ppm) 8.51 (s, 2H), 7.36-7.32 (m, 1H), 7.19-7.14 (m, 2H), 4.14 (tr, 2H), 3.53 (tr, 2H), 2.36-2.33 (m, 2H).
The present invention further provides for 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 (1-1) to (1-90) 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 ornamentals.
The present invention further provides a method of controlling harmful plants and/or for regulating the growth of plants, characterized in that an effective amount
The present invention also provides a method for controlling unwanted plants, preferably in crops of useful plants, characterized in that an effective amount
The present invention also further provides a method for controlling for regulating the growth of plants, preferably of useful plants, characterized in that an effective amount
In this context, the inventive compounds or the inventive compositions can 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 of the invention are as follows, though there is no intention to restrict the enumeration to particular species.
In a method of the invention for controlling harmful plants or for regulating the growth of plants, preference is given to using one or more compounds of the general formula (I) and/or salts thereof for control of harmful plants or for regulation of growth in crops of useful plants or ornamental plants, where the useful plants or ornamental plants in a preferred configuration are transgenic plants.
The inventive compounds of the general formula (I) and/or salts thereof are suitable for controlling the following genera of monocotyledonous and dicotyledonous harmful plants:
When the inventive compounds of the general formula (I) are 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 weeds are 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.
If the active ingredients of the general formula (I) are 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.
Although the inventive compounds of the general formula (I) display 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 inventive compound and its application rate. For these reasons, the present compounds are very suitable for selective control of unwanted plant growth in plant crops such as agriculturally useful plants or ornamental plants.
In addition, the inventive compounds of the general formula (I) (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. Furthermore, they are 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.
By virtue of their herbicidal and plant growth regulatory properties, the active ingredients of the general formula (I) can also be used to control harmful plants in crops of genetically modified plants or plants modified by conventional mutagenesis. In general, the transgenic plants are 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 characteristics relate, 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.
It is preferred with a view to transgenic crops to use the inventive compounds of the general formula (I) and/or salts thereof 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.
It is preferable to employ the inventive compounds of the general formula (I) also 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.
By virtue of their herbicidal and plant growth regulatory properties, the inventive compounds of the general formula (I) can also be used to control harmful plants in crops of genetically modified plants which are known or are yet to be developed. In general, the transgenic plants are 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 characteristics relate, 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. Further special properties may be tolerance or resistance to abiotic stressors, for example heat, cold, drought, salinity and ultraviolet radiation.
Preference is given to the use of the inventive compounds of the general formula (I) or salts thereof in economically important transgenic crops of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, triticale, millet, rice, cassava and corn, or else crops of sugar beet, cotton, soybean, oilseed rape, potatoes, tomatoes, peas and other vegetables.
It is preferable to employ the compounds of the general formula (I) 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 plants consist, for example, in traditional cultivation methods and the generation of mutants. Alternatively, novel plants with altered properties can 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 generated are known to the person skilled in the art. For such genetic manipulations, nucleic acid molecules which allow mutagenesis or sequence alteration by recombination of DNA sequences can be introduced into plasmids. With the aid of standard methods, it is possible, for example, to undertake base exchanges, remove part sequences or add natural or synthetic sequences. To connect the DNA fragments to each other, adapters or linkers may be added to the fragments.
For example, the generation of plant cells with a reduced activity of a gene product can 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.
To this end, it is firstly possible to use DNA molecules which encompass the entire coding sequence of a gene product inclusive of any flanking sequences which may be present, and 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. 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 to them.
When expressing nucleic acid molecules in plants, the protein synthesized may 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. Sequences of this kind are known to the person skilled in the art (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227). The nucleic acid molecules can also be expressed in the organelles of the plant cells.
The transgenic plant cells can be regenerated by known techniques to give rise to entire plants. In principle, the transgenic plants may be plants of any desired plant species, i.e. not only monocotyledonous but also dicotyledonous plants.
Obtainable in this way are transgenic plants having properties altered by overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences or expression of heterologous (=foreign) genes or gene sequences.
The inventive compounds of the general formula (I) can preferably also be used in transgenic crops which are resistant to growth regulators, for example dicamba, or to herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS), hydroxyphenylpyruvate dioxygenases (HPPD), or protoporphyrinogen oxidase (PPO), or to herbicides from the group of the sulfonylureas, the glyphosates, glufosinates or benzoylisoxazoles and analogous active ingredients.
When the inventive compounds of the general formula (I) are 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 invention therefore also relates to the use of the inventive compounds of the general formula (I) and/or salts thereof as herbicides for controlling harmful plants in crops of useful plants or ornamentals, optionally in transgenic crop plants.
Preference is given to the use of compounds of the general formula (I) in cereals, here preferably corn, wheat, barley, rye, oats, millet or rice, by the pre- or post-emergence method.
Preference is also given to the use of compounds of the general formula (I) in soybean by the pre-emergence or post-emergence method.
The use of inventive compounds of the formula (I) for the control of harmful plants or for growth regulation of plants also includes the case in which a 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 invention also provides 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 invention also provides a herbicidal and/or plant growth-regulating composition, characterized in that the composition comprises
The further agrochemically active substances of component (i) of a composition of the invention are 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 of the invention comprises 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 that are solid at 25° C. and 1013 mbar, preferably adsorptive 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.
The inventive compounds of the general formula (I) can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting products or granules in the customary formulations. The invention therefore also provides herbicidal and plant growth-regulating compositions which comprise compounds of the general formula (I) and/or salts thereof.
The inventive compounds of the general formula (I) and/or salts thereof can be formulated in various ways according to which biological and/or physicochemical parameters are specified. Possible formulations include, 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.
These individual formulation types and the formulation auxiliaries, such as inert materials, surfactants, solvents and further additives, are known to the person skilled in the art and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd ed., Darland Books, Caldwell N.J., H. v. Olphen, “Introduction to Clay Colloid Chemistry”, 2nd ed., J. Wiley & Sons, N.Y., C. Marsden, “Solvents Guide”, 2nd ed., Interscience, N.Y. 1963, McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood N.J., Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., N.Y. 1964, Schönfeldt, “Grenzflächenaktive Athylenoxidaddukte” [Interface-active Ethylene Oxide Adducts], Wiss. Verlagsgesellschaft, Stuttgart 1976, Winnacker-Küchler, “Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th ed. 1986.
Wettable powders are preparations which can be dispersed uniformly in water and, in addition to the active ingredient, 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. To produce the wettable powders, the active herbicidal ingredients are 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 concentrates are produced by dissolving the active ingredient 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). Examples of emulsifiers which may be used are: calcium alkylarylsulfonate salts, for example 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.
Dusting products are obtained by grinding the active ingredient with finely distributed solids, for example talc, natural clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
Suspension concentrates may be water- or oil-based. They may be produced, for example, by wet-grinding by means of commercial bead mills and optional addition of surfactants as already listed above, for example, for the other formulation types.
Emulsions, for example oil-in-water emulsions (EW), can be produced, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and optionally surfactants as already listed above, for example, for the other formulation types.
Granules can be produced either by spraying the active ingredient onto granular inert material capable of adsorption or by applying active ingredient concentrates to the surface of carrier substances, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or else mineral oils. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules—if desired as a mixture with fertilizers.
Water-dispersible granules are 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.
For the production of pan granules, fluidized bed granules, extruder granules and spray granules, see, for example, processes in “Spray-Drying Handbook” 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning, “Agglomeration”, Chemical and Engineering 1967, pages 147 ff.; “Perry's Chemical Engineer's Handbook”, 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.
For further details regarding the formulation of crop protection compositions, see, for example, G. C. Klingman, “Weed Control as a Science”, John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J. D. Freyer, S. A. Evans, “Weed Control Handbook”, 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.
The agrochemical preparations, preferably herbicidal or plant growth-regulating compositions, of the present invention preferably comprise a total amount of 0.1 to 99% by weight, preferably 0.5 to 95% by weight, more preferably 1 to 90% by weight, especially preferably 2 to 80% by weight, of active ingredients of the general formula (I) and salts thereof.
In wettable powders, the active ingredient concentration is, for example, about 10% to 90% by weight, the remainder to 100% by weight consisting of customary formulation constituents. In emulsifiable concentrates, the active ingredient concentration may be about 1% to 90% and preferably 5% to 80% by weight. Formulations in the form of dusts comprise 1% to 30% by weight of active ingredient, preferably usually 5% to 20% by weight of active ingredient; sprayable solutions contain about 0.05% to 80% by weight, preferably 2% to 50% by weight of active ingredient. In the case of water-dispersible granules, the active ingredient content depends partly on whether the active ingredient is in liquid or solid form and on which granulation auxiliaries, fillers, and so forth are used. In 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.
In addition, the active ingredient formulations mentioned optionally 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. Examples of formulation auxiliaries are described, inter alia, in “Chemistry and Technology of Agrochemical Formulations”, ed. D. A. Knowles, Kluwer Academic Publishers (1998).
The inventive compounds of the general formula (I) or salts thereof can 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 tankmix. The combination formulations can be produced on the basis of the abovementioned formulations, taking account of the physical properties and stabilities of the active ingredients to be combined.
Combination partners usable for the inventive compounds of the general formula (I) in mixed formulations or in a tankmix are, for example, known active ingredients 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, 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. of Chemistry, 2012, and the literature cited therein.
Of particular interest is the selective control of harmful plants in crops of useful plants and ornamentals. Although the inventive compounds of the general formula (I) have already demonstrated very good to adequate selectivity in a large number of crops, in principle, in some crops and in particular also in the case of mixtures with other, less selective herbicides, phytotoxicities on the crop plants may occur. In this connection, combinations of inventive compounds (I) that are of particular interest are those which comprise the compounds of the general formula (I) or their combinations with other herbicides or pesticides and safeners. The safeners, which 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 safener depend 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. Analogously to the compounds of the general formula (I) or mixtures thereof, the safeners can be formulated with further herbicides/pesticides and be provided and employed as a finished formulation or tank mix with the herbicides.
For application, the herbicide formulations or herbicide-safener formulations in the commercial form are diluted if appropriate in a customary manner, for example with water in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Preparations in dust form, 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 salts is affected to a certain extent by external conditions such as temperature, humidity, etc. The application rate may vary within wide limits. For the application as a herbicide for controlling harmful plants, the total amount of compounds of the general formula (I) and their salts is 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, particularly preferably in the range from 0.05 to 1 kg/ha. This applies both to pre-emergence and to post-emergence application.
When the inventive compounds of the general formula (I) and/or salts thereof are used as plant growth regulator, for example as culm stabilizer for crop plants like those mentioned above, preferably cereal plants, such as wheat, barley, rye, triticale, millet, rice or corn, the total application rate is 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 preferably in the range from 20 to 250 g/ha. This applies both to pre-emergence and to post-emergence application.
The application as culm stabilizer may take place at various stages of the growth of the plants. Preferred is, for example, the application after the tillering phase, at the beginning of the longitudinal growth.
As an alternative, application as plant growth regulator is also possible by treating the seed, which includes various techniques for dressing and coating seed. The application rate depends on the particular techniques and can be determined in preliminary tests.
Combination partners usable for the inventive compounds of the general formula (I) in compositions of the invention (e.g. mixed formulations or in a tankmix) are, for example, known active ingredients 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 or protoporphyrinogen oxidase, as described, for example, from Weed Research 26 (1986) 441-445 or “The Pesticide Manual”, 16th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2012, and literature cited therein. Known herbicides or plant growth regulators which can be combined with the compounds of the invention are, for example, the following, where said active ingredients are referred to either by their “common name” in accordance with the International Organization for Standardization (ISO) or by the chemical name or by the code number. They always encompass all the use forms, for example acids, salts, esters and also all isomeric forms such as stereoisomers and optical isomers, even if they are not mentioned explicitly.
Examples of such herbicidal mixing partners are:
Examples of plant growth regulators as possible mixing partners are:
Useful combination partners for the inventive compounds of the general formula (I) also include, for example, the following safeners:
Preferred safeners in combination with the inventive compounds of the general formula (I) and/or salts thereof, especially with the compounds of the formulae (I-1) to (I-90) and/or salts thereof, are: cloquintocet-mexyl, cyprosulfamide, fenchlorazole ethyl ester, isoxadifen-ethyl, mefenpyr-diethyl, fenclorim, cumyluron, 54-1 and S4-5, and particularly preferred safeners are: cloquintocet-mexyl, cyprosulfamide, isoxadifen-ethyl and mefenpyr-diethyl.
The following abbreviations are used in the examples below and the tables:
Harmful Plants Tested:
Useful Plants Tested
A. Herbicidal Pre-Emergence Efficacy
Seeds of mono- and dicotyledonous weed plants were placed in plastic pots in sandy loam soil (doubly sown with one species each of mono- or dicotyledonous weed plants per pot) and covered with soil. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), were then applied onto the surface of the covering soil as aqueous suspension or emulsion with addition of 0.5% additive at a water application rate of 600 liters per hectare (converted). After the treatment, the pots were placed in a greenhouse and kept under good growth conditions for the test plants. After about 3 weeks, the efficacy of the preparations was scored visually in comparison with untreated controls as percentages.
For example,
Tables A1a to A12c below show the effects of selected compounds of the general formula (I) according to table 1 on various harmful plants at an application rate corresponding to 1280 g/ha or less, which were obtained by the experimental procedure mentioned above.
As shown by way of example by the results from tables A1a-A12c, the inventive compounds of the formula I in the case of pre-emergence treatment showed very good herbicidal efficacy against the harmful plants Abutilon theophrasti (ABUTH), Alopecurus myosuroides (ALOMY), Amaranthus retroflexus (AMARE), Echinochloa crus-galli (ECHCG), Bassia scoparia (KCHSC), Lolium rigidum (LOLRI), Poa annua (POAAN), Setaria viridis (SETVI), Stellaria media (STEME) and Veronica persica (VERPE) at an application rate of 1280 g or less of active substance per hectare.
B. Herbicidal Post-Emergence Efficacy
Seeds of mono- and dicotyledonous weed plants were placed in plastic pots in sandy loam soil (doubly sown with in each case one species of mono- or dicotyledonous weed plants per pot), covered with soil and cultivated in a greenhouse under controlled growth conditions. 2 to 3 weeks after sowing, the test plants were treated at the one-leaf stage. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), were applied onto the green parts of the plants as aqueous suspension or emulsion with addition of 0.5% additive at a water application rate of 600 liters per hectare (converted). After the test plants had been kept in the greenhouse under optimum growth conditions for about 3 weeks, the activity of the preparations was rated visually in comparison to untreated controls.
For example,
Tables B1a to B12c below show the effects of selected inventive compounds of the general formula (I) according to table 1 on various harmful plants at an application rate corresponding to 1280 g/ha or less, which were obtained by the experimental procedure mentioned above.
As shown by the results from tables B1a-B12c by way of example, the inventive compounds of the formula I in the case of post-emergence treatment showed very good herbicidal efficacy against the harmful plants Abutilon theophrasti (ABUTH), Alopecurus myosuroides (ALOMY), Amaranthus retroflexus (AMARE), Echinochloa crus-galli (ECHCG), Bassia scoparia (KCHSC), Lolium rigidum (LOLRI), Poa annua (POAAN), Setaria viridis (SETVI), Stellaria media (STEME) and Veronica persica (VERPE) at an application rate of 1280 g or less of active substance per hectare.
C. Herbicidal Pre-Emergence Efficacy
Seeds of monocotyledonous and dicotyledonous weed plants and crop plants were placed in plastic or organic planting pots and covered with soil. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), were then applied to the surface of the covering soil as aqueous suspension or emulsion with addition of 0.5% additive at a water application rate equivalent to 600 l/ha (converted). After the treatment, the pots were placed in a greenhouse and kept under good growth conditions for the test plants. After about 3 weeks, the efficacy of the preparations was scored visually in comparison with untreated controls as percentages. For example,
Tables C1a to C14b below show the effects of selected compounds of the general formula (I) according to table 1 on various harmful plants at an application rate corresponding to 320 g/ha or less, which were obtained by the experimental procedure mentioned above.
As shown by way of example by the results from tables C1a-C14b, the inventive compounds of the formula I in the case of pre-emergence treatment showed very good herbicidal efficacy against the harmful plants Abutilon theophrasti (ABUTH), Alopecurus myosuroides (ALOMY), Amaranthus retroflexus (AMARE), Avena fatua (AVEFA), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Kochia scoparia (KCHSC), Lolium rigidum (LOLRI), Matricaria inodora (MATIN), Pharbitis purpurea (PHBPU), Polygonum convolvulus (POLCO), Setaria viridis (SETVI), Veronica persica (VERPE) and Viola tricolor (VIOTR) at an application rate of 320 g or less of active substance per hectare.
D. Pre-Emergence Effect on Useful Plants
Tables D1a to D5b below show the effects of selected compounds of the general formula (I) according to table 1 on various useful plants at an application rate corresponding to 320 g/ha or less, which were obtained by the experimental procedure mentioned above.
As shown by way of example by the results from tables D1a-D5b, the inventive compounds of the formula I in the case of pre-emergence treatment have only a small harmful effect, if any, on crop plants such as Triticum aestivum (TRZAS), Zea Mays (ZEAMX), Oryza sativa (ORYSA), Glycine max (GLXMA) and Brassica napus (BRSNW).
E. Herbicidal Post-Emergence Efficacy
Seeds of monocotyledonous and dicotyledonous weeds and crop plants were placed in sandy loam in plastic or organic planting pots, covered with soil and cultivated in a greenhouse under controlled growth conditions. 2 to 3 weeks after sowing, the test plants were treated at the one-leaf stage. The compounds of the invention, formulated in the form of wettable powders (WP) or as emulsion concentrates (EC), were then sprayed onto the green parts of the plants as aqueous suspension or emulsion with addition of 0.5% additive at a water application rate of 600 l/ha (converted). After the test plants had been kept in the greenhouse under optimum growth conditions for about 3 weeks, the activity of the preparations was rated visually in comparison to untreated controls.
For example,
Tables E1a to E12b below show the effects of selected compounds of the general formula (I) according to table 1 on various harmful plants at an application rate corresponding to 320 g/ha or less, which were obtained by the experimental procedure mentioned above.
As shown by way of example by the results from tables Ela-E12b, the inventive compounds of the formula I in the case of post-emergence treatment showed very good herbicidal efficacy against the harmful plants Abutilon theophrasti (ABUTH), Alopecurus myosuroides (ALOMY), Amaranthus retroflexus (AMARE), Digitaria sanguinalis (DIGSA), Echinochloa crus-galli (ECHCG), Kochia scoparia (KCHSC), Lolium rigidum (LOLRI), Pharbitis purpurea (PHBPU), Polygonum convolvulus (POLCO), Setaria viridis (SETVI), Veronica persica (VERPE) and Viola tricolor (VIOTR) at an application rate of 320 g or less of active substance per hectare.
F. Post-Emergence Effect on Useful Plants
Tables F1a to F4 below show the effects of selected compounds of the general formula (I) according to table 1 on various useful plants at an application rate corresponding to 320 g/ha or less, which were obtained by the experimental procedure mentioned above.
As shown by way of example by the results from tables Fla-F4, the inventive compounds of the formula I in the case of post-emergence treatment have only a small harmful effect, if any, on useful plants such as Triticum aestivum (TRZAS), Zea Mays (ZEAMX), Oryza sativa (ORYSA) and Glycine max (GLXMA).
| Number | Date | Country | Kind |
|---|---|---|---|
| 21155250.0 | Feb 2021 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/052021 | 1/28/2022 | WO |
