[(1,5-DIPHENYL-1H-1,2,4-TRIAZOL-3-YL)OXY]ACETIC ACID DERIVATIVES AND SALTS THEREOF, CROP PROTECTION COMPOSITIONS COMPRISING THEM, METHODS FOR PRODUCING THEM AND USE THEREOF AS SAFENERS

Abstract

The present invention relates to useful plant-protecting compounds and compositions comprising specific compounds as safeners for reduction of phytotoxic effects of agrochemicals, especially of herbicides.

More particularly, the invention relates to particular [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetic acid derivatives of the general formula (I)

##STR00001##

and salts thereof, to processes for preparation thereof and to their use as useful plant-protecting compounds (safeners).

Claims

1. A compound of formula (I) or salt thereof ##STR00117## in which R.sup.1 and R.sup.2 are independently hydrogen, halogen, cyano, nitro, (C.sub.1-C.sub.6)alkyl, (C.sub.2-C.sub.6)alkenyl, (C.sub.2-C.sub.6)alkynyl, (C.sub.3-C.sub.8)cycloalkyl, (C.sub.3-C.sub.8)cycloalkenyl, (C.sub.1-C.sub.6)alkoxy or (C.sub.1-C.sub.6)alkylS(O).sub.p, where the latter seven radicals are unsubstituted or substituted by one already more radicals from the group of halogen, cyano, (C.sub.1-C.sub.6)alkoxy and (C.sub.1-C.sub.6)alkylS(O).sub.p, R.sup.3 is hydrogen or (C.sub.1-C.sub.6)alkyl, R.sup.4 is hydrogen, (C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)haloalkyl, (C.sub.1-C.sub.18)cyanoalkyl, (C.sub.2-C.sub.18)alkenyl, (C.sub.2-C.sub.18)alkynyl, (C.sub.3-C.sub.12)cycloalkyl, (C.sub.3-C.sub.12)cycloalkenyl, aryl, heteroaryl, (C.sub.1-C.sub.18)alkoxy-(C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)haloalkoxy-(C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)alkoxy-(C.sub.1-C.sub.18)haloalkyl, (C.sub.1-C.sub.18)alkylthio-(C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)haloalkylthio-(C.sub.1-C.sub.18)alkyl, (C.sub.2-C.sub.18)haloalkenyl, (C.sub.2-C.sub.18)haloalkynyl, heterocyclyl-(C.sub.1-C.sub.18)alkyl, aryl-(C.sub.1-C.sub.18)alkyl, (C.sub.3-C.sub.12)cycloalkyl-(C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)alkoxycarbonyl-(C.sub.1-C.sub.18)alkyl, and (C.sub.1-C.sub.18)alkoxycarbonyl-(C.sub.3-C.sub.12)cycloalkyl-(C.sub.1-C.sub.18)alkyl, or a radical of the formula —NR.sup.aR.sup.b or —N═CR.sup.cR.sup.d, where, in the former 2 radicals, each of the R.sup.a, R.sup.b, R.sup.c and R.sup.d radicals is independently hydrogen, (C.sub.1-C.sub.4)alkyl, (C.sub.2-C.sub.4)alkenyl, (C.sub.2-C.sub.4)alkynyl, benzyl, substituted benzyl, phenyl or substituted phenyl or R.sup.a and R.sup.b together with the nitrogen atom form a 3- to 8-membered heterocycle which, in addition to the nitrogen atom, may contain one or two further ring heteroatoms from the group of N, O and S and which is unsubstituted or substituted by one or more radicals from the group of (C.sub.1-C.sub.4)-alkyl and (C.sub.1-C.sub.4)-haloalkyl, or R.sup.c and R.sup.d together with the carbon atom form a 3- to 8-membered carbocyclic or heterocyclic radical which may contain 1 to 3 ring heteroatoms from the group of N, O and S, where the carbocyclic or heterocyclic radical is unsubstituted or substituted by one or more radicals from the group of (C.sub.1-C.sub.4)-alkyl and (C.sub.1-C.sub.4)-haloalkyl, n and m are independently a number from 0 to 5, and p is 0, 1 or 2, excluding ethyl [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetate (CAS [931426-67-4]).

2. The compound of formula (I) as claimed in claim 1 or salt thereof, in which R.sup.1 and R.sup.2 are independently hydrogen, halogen, cyano, nitro, (C.sub.1-C.sub.4)alkyl, (C.sub.2-C.sub.4)alkenyl, (C.sub.2-C.sub.4)alkynyl, (C.sub.3-C.sub.6)cycloalkyl, (C.sub.3-C.sub.6)cycloalkenyl, (C.sub.1-C.sub.4)alkoxy or (C.sub.1-C.sub.4)alkylS(O).sub.p, where the latter seven radicals are unsubstituted or substituted by one already more radicals from the group of halogen, cyano, (C.sub.1-C.sub.4)alkoxy and (C.sub.1-C.sub.4)alkylS(O).sub.p, R.sup.3 is hydrogen or (C.sub.1-C.sub.4)alkyl, R.sup.4 is hydrogen, (C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)haloalkyl, (C.sub.1-C.sub.18)cyanoalkyl, (C.sub.2-C.sub.18)alkenyl, (C.sub.2-C.sub.18)alkynyl, (C.sub.3-C.sub.12)cycloalkyl, (C.sub.3-C.sub.12)cycloalkenyl, aryl, hetero aryl, (C.sub.1-C.sub.18)alkoxy-(C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)haloalkoxy-(C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)alkoxy-(C.sub.1-C.sub.18)haloalkyl, (C.sub.1-C.sub.18)alkylthio-(C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)haloalkylthio-(C.sub.1-C.sub.18)alkyl, (C.sub.2-C.sub.18)haloalkenyl, (C.sub.2-C.sub.18)haloalkynyl, heterocyclyl-(C.sub.1-C.sub.18)alkyl, aryl-(C.sub.1-C.sub.18)alkyl, (C.sub.3-C.sub.12)cycloalkyl-(C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)alkoxycarbonyl-(C.sub.1-C.sub.18)alkyl, or (C.sub.1-C.sub.18)alkoxycarbonyl-(C.sub.3-C.sub.12)cycloalkyl-(C.sub.1-C.sub.18)alkyl, n and m are independently a number from 0 to 4, and p is 0, 1 or 2, excluding ethyl [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetate.

3. The compound of formula (I) as claimed in claim 1 or salt thereof, in which R.sup.1 and R.sup.2 are independently hydrogen, halogen, cyano, methyl, CF.sub.3, CH.sub.2F, CHF.sub.2, OCH.sub.3, OCF.sub.3, SCH.sub.3 or SCF.sub.3, R.sup.3 is hydrogen, CH.sub.2CH.sub.3 or CH.sub.3, R.sup.4 is hydrogen, (C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)haloalkyl, (C.sub.1-C.sub.18)cyanoalkyl, (C.sub.2-C.sub.18)alkenyl, (C.sub.2-C.sub.18)alkynyl, (C.sub.3-C.sub.12)cycloalkyl, (C.sub.3-C.sub.12)cycloalkenyl, aryl, heteroaryl, (C.sub.1-C.sub.18)alkoxy-(C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)haloalkoxy-(C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)alkoxy-(C.sub.1-C.sub.18)haloalkyl, (C.sub.1-C.sub.18)alkylthio-(C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)haloalkylthio-(C.sub.1-C.sub.18)alkyl, (C.sub.2-C.sub.18)haloalkenyl, (C.sub.2-C.sub.18)haloalkynyl, heterocyclyl-(C.sub.1-C.sub.18)alkyl, aryl-(C.sub.1-C.sub.18)alkyl, (C.sub.3-C.sub.12)cycloalkyl-(C.sub.1-C.sub.18)alkyl, (C.sub.1-C.sub.18)alkoxycarbonyl-(C.sub.1-C.sub.18)alkyl, or (C.sub.1-C.sub.18)alkoxycarbonyl-(C.sub.3-C.sub.12)cycloalkyl-(C.sub.1-C.sub.18)alkyl, n and m are independently a number 0, 1, 2 or 3, excluding ethyl [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetate.

4. The compound of formula (I) as claimed in claim 1 or salt thereof, in which R.sup.1 and R.sup.2 are independently hydrogen, fluorine, chlorine, bromine, iodine, CN, methyl, CF.sub.3, CH.sub.2F, CHF.sub.2, OCH.sub.3, OCF.sub.3, SCH.sub.3 or SCF.sub.3, R.sup.3 is hydrogen or CH.sub.3, R.sup.4 is hydrogen, (C.sub.1-C.sub.10)alkyl, (C.sub.1-C.sub.10)haloalkyl, (C.sub.1-C.sub.10)cyanoalkyl, (C.sub.2-C.sub.10)alkenyl, (C.sub.2-C.sub.10)alkynyl, (C.sub.3-C.sub.9)cycloalkyl, (C.sub.3-C.sub.9)cycloalkenyl, aryl, heteroaryl, (C.sub.1-C.sub.10)alkoxy-(C.sub.1-C.sub.10)alkyl, (C.sub.1-C.sub.10)haloalkoxy-(C.sub.1-C.sub.10)alkyl, (C.sub.1-C.sub.10)alkoxy-(C.sub.1-C.sub.10)haloalkyl, (C.sub.1-C.sub.10)alkylthio-(C.sub.1-C.sub.10)alkyl, (C.sub.1-C.sub.10)haloalkylthio-(C.sub.1-C.sub.10)alkyl, (C.sub.2-C.sub.18)haloalkenyl, (C.sub.2-C.sub.18)haloalkynyl, heterocyclyl-(C.sub.1-C.sub.10)alkyl, aryl-(C.sub.1-C.sub.10)alkyl, (C.sub.3-C.sub.9)cycloalkyl-(C.sub.1-C.sub.10)alkyl, (C.sub.1-C.sub.10)alkoxycarbonyl-(C.sub.1-C.sub.10)alkyl or (C.sub.1-C.sub.10)alkoxycarbonyl-(C.sub.3-C.sub.9)cycloalkyl-(C.sub.1-C.sub.10)alkyl, n and m are independently a number 0, 1, 2 or 3, excluding ethyl [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetate.

5. The compound of formula (I) as claimed in claim 1 or salt thereof, in which R.sup.1 and R.sup.2 are independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, methyl, CF.sub.3, CH.sub.2F, CHF.sub.2, OCH.sub.3, OCF.sub.3, SCH.sub.3 or SCF.sub.3, R.sup.3 is hydrogen, R.sup.4 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, n-pentyl, phenyl, benzyl, CH.sub.2(4-Cl-Ph), CH.sub.2(4-F-Ph), CH.sub.2(4-OMe-Ph), 2-methoxyethyl, tetrahydrofuran-2-yl-methyl, tetrahydrofuran-3-ylmethyl, tetrahydropyran-2-ylmethyl, tetrahydropyran-3-ylmethyl, tetrahydropyran-4-ylmethyl, methylpropionate-3-yl, ethylpropionate-3-yl, methylacetate-2-yl, ethylacetate-2-yl, methylpivalate-2-yl, ethylpivalate-3-yl, methyl-2-methylpropanoate-3-yl, methyl-2,2-dimethylpropanoate-3-yl, ethyl-2-methylpropanoate-3-yl, methyl-2-propanoate-2-yl, ethyl-2-propanoate-2-yl, methylacetate-2-yl, ethylacetate-2-yl, methyl-1-methylcyclopropanecarboxylate-2-yl, ethyl-1-methylcyclopropanecarboxylat-2-yl, 2-(dimethylamino)ethyl, oxetan-3-yl, (3-methyloxetan-3-yl)methyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2-fluoroethyl, 2,2,3,3,3-pentafluoropropyl, cyclopropylmethyl, 1-cyclopropylethyl, (1-methylcyclopropyl)methyl, (2,2-dichlorocyclopropyl)methyl, (2,2-dimethylcyclopropyl)methyl, allyl, propargyl (prop-2-yn-1-yl), 2-chloroprop-2-en-1-yl, 3-phenylprop-2-yn-1-yl, 3,3-dichloroprop-2-en-1-yl, 3,3-dichloro-2-fluoroprop-2-en-1-yl, methylprop-2-yn-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, but-2-yn-1-yl, but-3-yn-1-yl, 4-chlorobut-2-yn-1-yl, 3-methylbut-2-en-1-yl, 3-methylbut-1-en-1-yl, 1-(2E)-1-methylbut-2-en-1-yl, (E)-pent-3-en-2-yl or (Z)-pent-3-en-2-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, heptan-2-yl, isobutyl, 1,3-dioxolan-2-ylmethyl or 1-ethyl-5-methyl-1H-pyrazole-4-methyl, n and m are independently a number 0, 1, 2 or 3, excluding ethyl [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetate.

6. The compound of formula (I) as claimed in claim 1 or salt thereof, in which (R.sup.1).sub.n-phenyl is the Q-1.1 to Q-1.53 groups ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## (R.sup.2).sub.m-phenyl is the Q-2.1 to Q-2.53 groups ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## R.sup.3 is hydrogen, and R.sup.4 is hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, n-pentyl, phenyl, benzyl, CH.sub.2(4-Cl-Ph), CH.sub.2(4-F-Ph), CH.sub.2(4-OMe-Ph), 2-methoxyethyl, tetrahydrofuran-2-yl-methyl, tetrahydrofuran-3-ylmethyl, tetrahydropyran-2-ylmethyl, tetrahydropyran-3-ylmethyl, tetrahydropyran-4-ylmethyl, methylpropionate-3-yl, ethylpropionate-3-yl, methylacetate-2-yl, ethylacetate-2-yl, methylpivalate-2-yl, ethylpivalate-3-yl, methyl-2-methylpropanoate-3-yl, methyl-2,2-dimethylpropanoate-3-yl, ethyl-2-methylpropanoate-3-yl, methyl-2-propanoate-2-yl, ethyl-2-propanoate-2-yl, methylacetate-2-yl, ethylacetate-2-yl, methyl-1-methylcyclopropanecarboxylate-2-yl, ethyl-1-methylcyclopropanecarboxylat-2-yl, 2-(dimethylamino)ethyl, oxetan-3-yl, (3-methyloxetan-3-yl)methyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, 2-fluoroethyl, 2,2,3,3,3-pentafluoropropyl, cyclopropylmethyl, 1-cyclopropylethyl, (1-methylcyclopropyl)methyl, (2,2-dichlorocyclopropyl)methyl, (2,2-dimethylcyclopropyl)methyl, allyl, propargyl (prop-2-yn-1-yl), 2-chloroprop-2-en-1-yl, 3-phenylprop-2-yn-1-yl, 3,3-dichloroprop-2-en-1-yl, 3,3-dichloro-2-fluoroprop-2-en-1-yl, methylprop-2-yn-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, but-2-yn-1-yl, but-3-yn-1-yl, 4-chlorobut-2-yn-1-yl, 3-methylbut-2-en-1-yl, 3-methylbut-1-en-1-yl, 1-(2E)-1-methylbut-2-en-1-yl, (E)-pent-3-en-2-yl or (Z)-pent-3-en-2-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, heptan-2-yl, isobutyl, 1,3-dioxolan-2-ylmethyl or 1-ethyl-5-methyl-1H-pyrazole-4-methyl, excluding ethyl [(1,5-diphenyl-1H-1,2,4-triazol-3-yl)oxy]acetate.

7. A useful plant- or crop plant-protecting composition, comprising a content of at least one compound of formula (I) or salt thereof as claimed in claim 1 in combination with one or more further agrochemicals and optionally one or more formulation auxiliaries.

8. The composition as claimed in claim 7, comprising at least one herbicide.

9. A method of reducing phytotoxic effects of one or more pesticides on one or more useful plants or crop plants comprising using one or more compounds of claim 1 or a composition thereof.

10. A method of reducing phytotoxic effects of one or more pesticides on one or more useful plants or crop plants, comprising employing one or more compounds of formula (I) as claimed in claim 1 for joint use with one or more pesticides deployed simultaneously or in any sequence with the one or more pesticides.

11. The method as claimed in claim 10, wherein the pesticides are one or more herbicides.

12. The method as claimed in claim 10, wherein one or more compounds of formula (I) or salts thereof as claimed in claims 1 are applied to one or more plants, one or more parts of plants, and/or seeds or seed material thereof.

Description

EXAMPLES

1. Formulation Examples

[0280] 1.1 Dusting Product

[0281] A dusting product is obtained by mixing 10 parts by weight of a compound of the general formula (I) (safener) or of an active ingredient mixture composed of a pesticide (e.g. a herbicide) and a safener of the general formula (I) and 90 parts by weight of talc as inert substance, and comminuting in a bead mill.

[0282] 1.2 Water-Dispersible Powder

[0283] A readily water-dispersible wettable powder is obtained by mixing 25 parts by weight of a compound of the general formula (I) or of an active ingredient mixture of a pesticide (e.g. a herbicide) and a safener of the general formula (I), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as a wetting agent and dispersant, and grinding the mixture in a pinned-disk mill.

[0284] 1.3 Water-Dispersible Concentrate

[0285] A water-dispersible dispersion concentrate is obtained by mixing 20 parts by weight of a compound of the general formula (I) or of an active ingredient mixture of a pesticide (e.g. a herbicide) and a safener of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether and 71 parts by weight of paraffinic mineral oil, and grinding in a friction ball mill to a fineness below 5 microns.

[0286] 1.4 Emulsifiable Concentrate

[0287] An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the general formula (I) or of an active ingredient mixture composed of a pesticide (e.g. a herbicide) and a safener of the general formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.

[0288] 1.5 Water-Dispersible Granules

[0289] Water-dispersible granules are obtained by mixing [0290] 75 parts by weight of a safener of the general formula (I) or a mixture of a pesticide and a safener of the general formula (I), [0291] 10 ″ of calcium lignosulfonate, [0292] 5 ″ of sodium laurylsulfate, [0293] 3 ″ of polyvinyl alcohol and [0294] 7 ″ of polyvinyl alcohol and [0295] 7 ″ of kaolin,

[0296] grinding the mixture in a pinned-disk mill, and granulating the powder in a fluidized bed by spray application of water as a granulating liquid.

[0297] Water-dispersible granules are also obtained by homogenizing and comminuting, in a colloid mill, [0298] 25 parts by weight of a safener of the general formula (I) or a mixture of a pesticide and a safener of the general formula (I), [0299] 5 ″ of sodium 2,2′-dinaphthylmethane-6,6′-disulfonate, [0300] 2 ″ of sodium oleoylmethyltaurinate, [0301] 17 ″ of calcium carbonate, [0302] 50 ″ of water and [0303] 1 part by weight of polyvinyl alcohol,

[0304] then grinding the mixture in a bead mill and atomizing and drying the suspension thus obtained in a spray tower by means of a one-phase nozzle.

2. Biological Examples

[0305] 2.1 Absolute Action of Selected Compounds of the Invention Using the Example of Reduction of Damage by Mesosulfuron-Methyl on Summer Wheat (TRZAS)

[0306] The seeds of the crop plants to be treated are laid out in sandy loam in wood fiber or plastic pots (diameter ˜4 cm), covered with soil and grow in a greenhouse under good conditions for germination and growth. The trial plants were treated at the early leaf stage (BBCH.sub.10-BBCH.sub.12). In the course of this, the inventive compounds of the general formula (I) formulated in the form of wettable powders (WP) were sprayed onto the above-ground parts of the plants as an aqueous suspension with a water application rate corresponding to 800 l/ha with addition of wetting agent (e.g. 0.2% agrotin) in the specified dose.

[0307] This was followed by the application of the herbicide. For this purpose, mesosulfuron-methyl, formulated in the form of water-dispersible granules (WG), was sprayed onto the above-ground parts of the plants in the form of an aqueous dispersion with a water application rate corresponding to 800 l/ha with addition of wetting agent (e.g. 0.2% agrotin) in a dose of 20 g/ha. The dose of the herbicide was chosen here such that it causes visually apparent damage (min. 30%, max. 75%) compared to untreated crop plants at the evaluation time on a control group of crop plants without safener treatment that were included in the same trial.

[0308] After application, the plants were cultivated under good growth conditions in a greenhouse. The damage was visually assessed 14-21 days after application.

[0309] The damage effect was assessed visually on a scale of 0-100% by comparison with untreated control plants, and averaged over 2-3 repeats per treatment. Examples: [0310] 0%=no noticeable effect compared to the untreated plant [0311] 20%=the treated plant population has 20% damage compared to the untreated control population (e.g. growth height, leaf damage, etc.) [0312] 100%=treated plants completely damaged/killed.

[0313] The trials show that damage to the summer wheat crop plant (TRZAS; cv. Triso) caused by the herbicide mesosulfuron-methyl (=herbicide damage without compound of the formula (I) in the table below) is significantly reduced by treatment with substances of the invention herbicide damage with compound of the formula (I) in the table below):

TABLE-US-00003 Dose of the Herbicide Herbicide safener damage damage of the without with Absolute formula compound compound redaction Example (I) Crop of the of the in damage No. (g/ha) plant formula (I) formula (I) (difference) I.11-38 TRZAS 50 30 20 I.2-38  1000 g/ha TRZAS 50 30 20 I.2-4   1000 g/ha TRZAS 50 30 20 I.3-4   1000 g/ha TRZAS 50 23 27 I.3-4    250 g/ha TRZAS 50 30 20 I.54-38 1000 g/ha TRZAS 50 30 20 I.21-38 1000 g/ha TRZAS 43 20 23 I.53-4  1000 g/ha TRZAS 43 23 20 I.54-4   250 g/ha TRZAS 43 20 23 I.53-38 1000 g/ha TRZAS 43 23 20 I.12-7   250 g/ha TRZAS 43 20 23 I.53-7   250 g/ha TRZAS 43 10 33 I.42-7   250 g/ha TRZAS 43  0 43 I.41-7   250 g/ha TRZAS 43 20 23 I.3-7   1000 g/ha TRZAS 43 10 33 I.3-7    250 g/ha TRZAS 43 20 23 I.20-1  1000 g/ha TRZAS 43  7 36 I.20-1   250 g TRZAS 43 13 30 a.i./ha I.5-49   125 g TRZAS 67 13 54 a.i./ha I.6-49   250 g TRZAS 57 27 30 a.i./ha I.5-32  1000 g TRZAS 57 30 27 a.i./ha I.6-38   125 g TRZAS 67 17 50 a.i./ha I.47-38  125 g TRZAS 40 13 27 a.i./ha I.47-32  500 g TRZAS 57 13 44 a.i./ha I.47-32  125 g TRZAS 57 23 34 a.i./ha I.47-49  125 g TRZAS 60 30 30 a.i./ha I.48-38  125 g TRZAS 60 30 30 a.i./ha I.48-32  500 g TRZAS 60 23 37 a.i./ha I.48-32  125 g TRZAS 60 30 30 a.i./ha I.48-49  500 g TRZAS 60 20 40 a.i./ha I.48-49  125 g TRZAS 60 23 37 a.i./ha I.44-32  500 g TRZAS 63  7 56 a.i./ha I.44-32  125 g TRZAS 63 10 53 a.i./ha I.45-38  500 g TRZAS 63 20 43 a.i./ha I.45-38  125 g TRZAS 63 30 33 a.i./ha I.45-32  500 g TRZAS 63 33 30 a.i./ha I.45-32  125 g TRZAS 63 40 23 a.i./ha I.45-49  500 g TRZAS 63 40 23 a.i./ha I.45-49  125 g TRZAS 63 43 20 a.i./ha I.48-2   125 g TRZAS 30 3 27 a.i./ha I.45-2   500 g TRZAS 50 30 20 a.i./ha I.44-38  500 g TRZAS 63  3 60 a.i./ha I.44-38  125 g TRZAS 63 10 53 a.i./ha I.44-49  500 g TRZAS 53  7 46 a.i./ha I.44-49  125 g TRZAS 53 10 43 a.i./ha I.24-2   500 g TRZAS 50 30 20 a.i./ha 1.43-49  500 g TRZAS 63 23 40 a.i./ha I.43-49  125 g TRZAS 63 27 36 a.i./ha I.46-38  125 g TRZAS 63 30 33 a.i./ha I.43-32  500 g TRZAS 63 20 43 a.i./ha I.43-32  125 g TRZAS 63 30 33 a.i./ha I.43-38  500 g TRZAS 63 30 33 a.i./ha I.43-38  125 g TRZAS 63 33 30 a.i./ha I.46-32  500 g TRZAS 53  7 46 a.i./ha I.46-32  125 g TRZAS 53 10 43 a.i./ha I.46-49  125 g TRZAS 53 10 43 a.i./ha I.46-2   125 g TRZAS 53  7 46 a.i./ha I.4-38   125 g TRZAS 57 30 27 a.i./ha I.4-49   125 g TRZAS 57 17 40 a.i./ha I.4-32   500 g TRZAS 57 10 47 a.i./ha I.4-32   125 g TRZAS 57 23 34 a.i./ha

[0314] 2.2 Absolute Action of Selected Compounds of the Invention Using the Example of Reduction of Damage by Mesosulfuron-Methyl on Summer Barley (HORVS)

[0315] The seeds of the crop plants to be treated are aid out in sandy loam in wood fiber or plastic pots (diameter ˜4 cm), covered with soil and grown in a greenhouse under good conditions for germination and growth. The trial plants were treated at the early leaf stage (BBCE10-BBCH.sub.12). In the course of this, the inventive compounds of the general formula (I) formulated in the form of wettable powders (WP) were sprayed onto the above-ground parts of the plants as an aqueous suspension with a water application rate corresponding to 800 l/ha with addition of wetting agent (e.g. 0.2% agrotin) in the specified dose.

[0316] This was followed by the application of the herbicide. For this purpose, mesosulfuron-methyl, formulated in the form of water-dispersible granules (WG), was sprayed onto the above-ground parts of the plants in the form of an aqueous dispersion with a water application rate corresponding to 800 l/ha with addition of wetting agent (e.g. 0.2% agrotin) in a dose of 20 g/ha. The dose of the herbicide was chosen here such that it causes visually apparent damage (min. 30%, max. 75%) compared to untreated crop plants at the evaluation time on a control group of crop plants without safener treatment that were included in the same trial.

[0317] After application, the plants were cultivated under good growth conditions in a greenhouse. The damage was visually assessed 14-21 days after application.

[0318] The damage effect was assessed visually on a scale of 0-100% by comparison with untreated control plants, and averaged over 2-3 repeats per treatment. Examples: [0319] 0%=no noticeable effect compared to the untreated plant [0320] 20%=the treated plant population has 20% damage compared to the untreated control population (e.g.: growth height, leaf damage, etc.) [0321] 100%=treated plants completely damaged/killed.

[0322] The trials show that damage to the summer barley crop plant (HORVS; cv. Montoya) caused by the herbicide mesosulfuron-methyl (=herbicide damage without compound of the formula (I) in the table below) is significantly reduced by treatment with substances of the invention (=herbicide damage with compound of the formula (I) in the table below):

TABLE-US-00004 Herbicide Herbicide damage damage without with compound compound Absolute Dose of the of the of the reduction Example safener of the Crop formula (I) formula (I) in damage No. formula (I) plant (%) (%) (difference) I.41-38 1000 g a.i./ha HORVS 53 30 23 I.41-38  250 g a.i./ha HORVS 53 30 23 I.54-38 1000 g a.i./ha HORVS 53 20 33 I.54-38  250 g a.i./ha HORVS 53 30 23 I.21-38 1000 g a.i./ha HORVS 60 20 40 I.21-38  250 g a.i./ha HORVS 60 30 30 I.53-4   250 g a.i./ha HORVS 60 33 27 I.54-4   250 g a.i./ha HORVS 60 37 23 I.53-38 1000 g a.i./ha HORVS 60 20 40 I.53-38  250 g a.i./ha HORVS 60 30 30 I.12-7  1000 g a.i./ha HORVS 60 40 20 I.53-7   250 g a.i./ha HORVS 60 20 40 I.42-7   250 g a.i./ha HORVS 60  0 60 I.41-7  1000 g a.i./ha HORVS 60 20 40 I.3-7    250 g a.i./ha HORVS 60 40 20 I.5-49   500 g a.i./ha HORVS 73 17 56 I.5-49   125 g a.i./ha HORVS 73 23 50 I.6-49  1000 g a.i./ha HORVS 60 30 30 I.6-49   250 g a.i./ha HORVS 60 40 20 I.6-32   250 g a.i./ha HORVS 60 40 20 I.6-38   125 g a.i./ha HORVS 73 20 53 I.47-38  500 g a.i./ha HORVS 57 10 47 I.47-38  125 g a.i./ha HORVS 57 17 40 I.47-32  500 g a.i./ha HORVS 57 10 47 I.47-49  125 g a.i./ha HORVS 60 10 50 I.48-38  125 g a.i./ha HORVS 60 10 50 I.48-32  500 g a.i./ha HORVS 60 10 50 I.48-32  125 g a.i./ha HORVS 60 20 40 I.48-49  500 g a.i./ha HORVS 60  0 60 I.48-49  125 g a.i./ha HORVS 60 20 40 I.44-32  500 g a.i./ha HORVS 60 13 47 I.44-32  125 g a.i./ha HORVS 60 27 33 I.45-38  500 g a.i./ha HORVS 60 20 40 I.45-38  125 g a.i./ha HORVS 60 30 30 I.45-49  500 g a.i./ha HORVS 60 30 30 I.45-49  125 g a.i./ha HORVS 60 40 20 I.48-2   500 g a.i./ha HORVS 47 20 27 I.48-2   125 g a.i./ha HORVS 47 27 20 I.44-38  500 g a.i./ha HORVS 60 10 50 I.44-38  125 g a.i./ha HORVS 60 17 43 I.44-49  125 g a.i./ha HORVS 60 30 30 I.43-49  500 g a.i./ha HORVS 63 30 33 I.43-49  125 g a.i./ha HORVS 63 33 30 I.46-38  500 g a.i./ha HORVS 63 20 43 I.46-38  125 g a.i./ha HORVS 63 23 40 I.43-32  500 g a.i./ha HORVS 63 30 33 I.43-32  125 g a.i./ha HORVS 63 37 26 I.43-38  125 g a.i./ha HORVS 63 37 26 I.46-32  500 g a.i./ha HORVS 60 27 33 I.46-32  125 g a.i./ha HORVS 60 33 27 I.46-49  500 g a.i./ha HORVS 60 17 43 I.46-49  125 g a.i./ha HORVS 60 20 40 I.46-2   500 g a.i./ha HORVS 60 27 33 I.46-2   125 g a.i./ha HORVS 60 37 23 I.4-38   500 g a.i./ha HORVS 57  7 50 I.4-49   500 g a.i./ha HORVS 57 10 47 I.4-49   125 g a.i./ha HORVS 57 13 44 I.4-32   500 g a.i./ha HORVS 57 13 44 I.4-32   125 g a.i./ha HORVS 57 37 20

[0323] 2.3 Relative Action of Selected Compounds of the Invention Using the Example of Reduction of Damage by Mesosulfuron-Methyl on Summer Wheat (TRZAS)

[0324] The seeds of the crop plants to be treated are laid out in sandy loam in plastic pots (diameter ˜4 cm), covered with soil and grown in a greenhouse under good conditions for germination and growth. The trial plants were treated at the early leaf stage (BBCH.sub.10-BBCH.sub.12). In the course of this, the inventive compounds of the general formula (I) formulated in the form of wettable powders (WP) were sprayed onto the above-ground parts of the plants as an aqueous suspension with a water application rate corresponding to 800 l/ha with addition of wetting agent (e.g. 0.2% Genapol-LRO or 0.2% Mero) in the specified dose.

[0325] This was followed by the application of the herbicide. For this purpose, mesosulfuron-methyl, formulated in the form of water-dispersible granules (WG), was sprayed onto the above-ground parts of the plants in the form of an aqueous dispersion with a water application rate corresponding to 800 l/ha with addition of wetting agent (e.g. 0.2% Genapol-LRO or 1 l/ha Biopower) in a dose of 40-60 g/ha. The dose of the herbicide was chosen here such that it causes visually apparent damage (min. 30%, max. 75%) compared to untreated crop plants at the evaluation time on a control group of crop plants without safener treatment that were included in the same trial.

[0326] After application, the plants were cultivated under good growth conditions in a greenhouse. 9-13 days after application, the efficacy of the test compounds was assessed visually. For this purpose, the appearance of the plants treated with the test compound and herbicide was compared to the corresponding herbicide controls (without safener; with clearly visible damage) and the untreated controls (without damage). The damage-reducing effect of the test compounds was expressed here in graded efficacy codes according to the following scheme:

[0327] 0: no reduction in damage (appearance corresponding to the herbicide control)

[0328] 1: slight reduction in damage

[0329] 2: distinct reduction in damage

[0330] 3: significant reduction in damage

[0331] 4: complete reduction in damage (appearance corresponding to the untreated control)

[0332] The trials show clear efficacy of the substances of the invention with regard to the reduction in damage to the summer wheat crop plant (TRZAS; cv. Triso) caused by the herbicide mesosulfuron-methyl:

TABLE-US-00005 Dose of the Efficacy of Example safener of the Crop the safener No. formula (1) plant (efficacy code) I.40-49 500 TRZAS 4 I.40-49 100 TRZAS 4 I.40-7  500 TRZAS 4 I.40-7  100 TRZAS 4 I.42-49 500 TRZAS 2 I.42-49 100 TRZAS 2 I.55-2  500 TRZAS 2 I.55-2  100 TRZAS 2 I.55-49 500 TRZAS 2 I.55-49 100 TRZAS 2 I.57-2  500 TRZAS 2 I.57-2  100 TRZAS 2 I.57-43 500 TRZAS 2 I.61-49 100 TRZAS 2 I.62-49 500 TRZAS 2 I.62-49 100 TRZAS 2 I.62-7  100 TRZAS 3 I.63-49 100 TRZAS 2 I.64-49 100 TRZAS 2 I.67-49 500 TRZAS 2 I.67-49 100 TRZAS 2 I.67-7  100 TRZAS 3 I.41-49 100 TRZAS 2 I.3-43  500 TRZAS 2 I.3-43  100 TRZAS 2 I.57-43 500 TRZAS 2 I.48-43 500 TRZAS 2 I.42-43 500 TRZAS 2 I.42-43 100 TRZAS 2 I.66-49 100 TRZAS 2 I.68-49 100 TRZAS 2 I.69-49 100 TRZAS 2 I.73-49 100 TRZAS 2 I.40-48 100 TRZAS 2 I.41-49 100 TRZAS 2 I.67-48 100 TRZAS 2 I.61-48 100 TRZAS 2

[0333] 2.4 Relative Action of Selected Compounds of the Invention Using the Example of Reduction of Damage by Mesosulfuron-Methyl on Summer Barley (HORVS)

[0334] The seeds of the crop plants to be treated are laid out in sandy loam in plastic pots (diameter ˜4 cm), covered with soil and grown in a greenhouse under good conditions for germination and growth. The trial plants were treated at the early leaf stage (BBCH.sub.10-BBCH.sub.12). In the course of this, the inventive compounds of the general formula (I) formulated in the form of wettable powders (WP) were sprayed onto the above-ground parts of the plants as an aqueous suspension with a water application rate corresponding to 800 l/ha with addition of wetting agent (e.g. 0.2% Genapol-LRO or 0.2% Mero) in the specified dose.

[0335] This was followed by the application of the herbicide. For this purpose, mesosulfuron-methyl, formulated in the form of water-dispersible granules (WG), was sprayed onto the above-ground parts of the plants in the form of an aqueous dispersion with a water application rate corresponding to 800 l/ha with addition of wetting agent (e.g. 0.2% Genapol-LRC) or 1 l/ha Biopower) in a dose of 40-60 g/ha. The dose of the herbicide was chosen here such that it causes visually apparent damage (min. 30%, max. 75%) compared to untreated crop plants at the evaluation time on a control group of crop plants without safener treatment that were included in the same trial.

[0336] After application, the plants were cultivated under good growth conditions in a greenhouse. 9-13 days after application, the efficacy of the test compounds was assessed visually. For this purpose, the appearance of the plants treated with the test compound and herbicide was compared to the corresponding herbicide controls (without safener; with clearly visible damage) and the untreated controls (without damage). The damage-reducing effect of the test compounds was expressed here separately for 2 repeats in graded efficacy codes according to the following scheme:

[0337] 0: no reduction in damage (appearance corresponding to the herbicide control)

[0338] 1: slight reduction in damage

[0339] 2: distinct reduction in damage

[0340] 3: significant reduction in damage

[0341] 4: complete reduction in damage (appearance corresponding to the untreated control)

[0342] The trials show clear efficacy of the substances of the invention with regard to the reduction in damage to the summer barley crop plant (HORVS; cv. Montoya) caused by the herbicide mesosulfuron-methyl:

TABLE-US-00006 Dose of the safener of the Efficacy of Example formula (I) Crop the safener No. (g/ha) plant (efficacy code) I.40-49 500 HORVS 4 I.40-49 100 HORVS 4 I.40-7  500 HORVS 4 I.40-7  100 HORVS 2 I.42-49 500 HORVS 3 I.42-49 100 HORVS 2 I.55-49 500 HORVS 2 I.55-49 100 HORVS 2 I.57-49 500 HORVS 2 I.57-49 100 HORVS 2 I.61-49 100 HORVS 2 I.62-49 500 HORVS 2 I.62-49 100 HORVS 2 I.62-7  500 HORVS 2 I.62-7  100 HORVS 2 I.63-49 100 HORVS 2 I.64-49 100 HORVS 2 I.67-49 500 HORVS 2 I.67-49 100 HORVS 2 I.67-7  500 HORVS 2 I.67-7  100 HORVS 2 I.41-49 100 HORVS 2 I.3-43  500 HORVS 2 I.3-43  100 HORVS 2 I.57-43 500 HORVS 2 I.48-43 500 HORVS 2 I.42-43 500 HORVS 2 I.42-43 100 HORVS 2 I.66-49 100 HORVS 2 I.68-49 100 HORVS 2 I.69-49 100 HORVS 2 I.73-49 100 HORVS 2 I.40-48 100 HORVS 2 I.41-49 100 HORVS 2 I.67-48 100 HORVS 2 I.61-48 100 HORVS 2