US 2007002 1303A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2007/0021303 A1 Rosinger et al. (43) Pub. Date: Jan. 25, 2007

(54) SAFENING METHOD Publication Classification (76) Inventors: Christopher Rosinger, Hofheim (DE); (51) Int. Cl. Jan Van Den Berg, Heythuysen (NL); AOIN 25/32 (2006.01) Bart Geraats, Weert (NL) (52) U.S. Cl...... SO4/105 Correspondence Address: FROMMER LAWRENCE & HAUG (57) ABSTRACT 745 FIFTHAVENUE- 1 OTH FL. NEW YORK, NY 10151 (US) The invention relates to the sue of a compound (B) as (21) Appl. No.: 11/183,661 safener for reducing or avoiding phytotoxic side-effects of a pesticide (A) in useful plants selected from the plant order (22) Filed: Jul. 18, 2005 Liliflorae, wherein (A) is one or more pesticides, and (B) is one or more Safeners selected from the group consisting of (30) Foreign Application Priority Data safeners (B1) to (B19) as defined in claim 1. The safener can be applied by various methods including spraying tech Jul. 20, 2004 (DE)...... 10 2004 O35 136.8 niques and seed treatment. US 2007/002 1303 A1 Jan. 25, 2007

SAFENING METHOD thyl-2-pyrazoline-3-carboxylate (B1-1) (“Mefenpyr-di 0001. The invention relates to the technical field of crop ethyl”. PM, pp. 622-623) and related compounds as they protection compositions and safening of crops against phy are described in WO 91/07874; totoxic effects of pesticides, in particular safening of crops 0011 (B2) dichlorophenylpyrazolecarboxylic acid of Some useful plants selected from a specific plant order derivatives, preferably compounds such as ethyl 1-(2,4- against pesticides which are highly suitable for use against dichlorophenyl)-5-methylpyrazole-3-carboxylate (B2-1), harmful organisms in said crops. ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-car 0002 The application of pesticides such as herbicides boxylate (B2-2), ethyl 1-(2,4-dichlorophenyl)-5-(1,1- and also fungicides and insecticides against harmful organ dimethylethyl)pyrazole-3-carboxylate (B2-3), ethyl 1-(2, isms in crops of useful plants is often limited by phytotoxic 4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate effects of the pesticides in said crops. As a result the (B2-4) and related compounds as they are described in application of the particular pesticide in said crop is not EP-A-333 131 and EP-A-269 806; possible at all or possible only at an application rate where 0012 (B3) compounds of the triazolecarboxylic acids the desired effect against harmful organisms is insufficient. type, preferably compounds Such as fenchlorazol and its 0003 For example, it is known that many herbicides ethyl ester, i.e. ethyl 1-(2,4-dichlorophenyl)-5-trichlorom injure crop plants at herbicide application rates needed to ethyl-(1H)-1,2,4-triazole-3-carboxylate (B3-1), and control weed growth. This renders many herbicides unsuit related compounds (see EP-A-174 562 and EP-A-346 able for controlling weeds in the presence of certain crops. 620): Where weed growth in crops is uncontrolled however, this 0013 (B4) compounds of the 5-benzyl- or 5-phenyl-2- results in lower crop yield and reduced crop quality, as isoxazoline-3-carboxylic acid type or the 5,5-diphenyl-2- weeds will compete with crops for nutrients, light and water. isoxazoline-3-carboxylic acid, preferably compounds Reduction in herbicidal injury to crops without an unaccept such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-car able reduction in the herbicidal action can be accomplished boxylate (B4-1) or ethyl 5-phenyl-2-isoxazoline-3-car by use of crop protectants known as “safeners', also some boxylate (B4-2) and related compounds as they are times referred to as “antidotes' or “antagonists’. The safen described in WO91/08202, or ethyl 5,5-diphenyl-2-isox ing effect of a compound is generally more or less specific azoline-3-carboxylate (B4-3) (“isoxadifen-ethyl”. PM, p. to the herbicidal partner and the crop where the active 588) or n-propyl 5,5-diphenyl-2-isoxazoline-3-carboxy ingredients are applied. late (B4-4) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isox 0004. Likewise some crops can be protected by specific azoline-3-carboxylate (B4-5), as they are described in safeners or antidots which are able to reduce or avoid the German Patent Application (WO-A-95/07897); phytotoxicity of other pesticides Such as fungicides or pesticides against harmful animals, such as insecticides, 0014 (B5) compounds of the 8-quinolinoxyacetic acid acaricides, nematicides, molluscicides or miticides (in short type, preferably 1-methylhex-1-yl (5-chloro-8-quinoli together also called just “insecticides') towards the crops noxy)acetate (common name "cloquintocet-mexyl) (B5 without reducing or substantially reducing the desired effect 1) (see PM, pp. 196-197) of the pesticides against harmful organisms. 0015 1,3-dimethylbut-1-yl(5-chloro-8-quinolinoxy)ac 0005 Various commercial safeners have been developed etate (B5-2), for major cereal crops including maize, mainly for Safening the crops against damage of herbicides. The use of Safeners 0016 4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate against damage of pesticides in other culture crops such as (B5-3), vegetable crops is relatively rare. 00.17 1-allyloxyprop-2-yl(5-chloro-8-quinolinoxy)ac 0006 We have now shown that, surprisingly, some crop etate (B5-4), plants selected from useful plants of the order Liliflorae can ethyl(5-chloro-8-quinolinoxy)acetate (B5-5), be effectively protected against undesirable damage by 0.018 pesticides if the pesticides are applied together with certain 0019) methyl(5-chloro-8-quinolinoxy)acetate (B5-6), compounds acting as Safeners to the crop plants. allyl (5-chloro-8-quinolinoxy)acetate (B5-7), 0007 Accordingly, the present invention provides a use 0020 of a compound (B) as safener for reducing or avoiding 0021 2-(2-propylideneiminooxy)-1-ethyl(5-chloro-8- phytotoxic side-effects of a pesticide (A) in useful plants quinolinoxy)acetate (B5-8), selected from the plant order Liliflorae, wherein 0022 2-oxoprop-1-yl(5-chloro-8-quinolinoxy)acetate 0008 (A) is one or more pesticides, preferably selected (B5-9), from herbicides, insecticides and fungicides, or agricul turally acceptable salts thereof, and and related compounds as are described in EP-A-86 750, EP-A-94 349 and EP-A-191 736 or EP-A-0 492 366; 0009 (B) is one or more safeners selected from the group consisting of (abbreviation “PM used herein means “The 0023 (B6) compounds of the (5-chloro-8-quinolinoxy )malonic acid type, preferably compounds Such as Pesticide Manual, 13th edition): diethyl(5-chloro-8-quinolinoxy)malonate, diallyl 0010 (B1) compounds of the dichlorophenylpyrazoline (5-chloro-8-quinolinoxy)malonate, methylethyl(5-chloro 3-carboxylic acid type, preferably compounds such as 8-quinolinoxy)malonate and related compounds as are ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-me described in EP-A-0 582 198: US 2007/002 1303 A1 Jan. 25, 2007

0024 (B7) active substances of the phenoxyacetic or 0047 (B13) active substances of the naphthalenedicar phenoxypropionic acid derivatives type or of the aromatic boxylic acid derivatives type, Such as, for example, carboxylic acids type. Such as, for example, 0048) “naphthalic anhydride” (PM, p. 1083) (= 1,8-naph 0.025 2,4-dichlorophenoxyacetic acids (and its esters) thalenedicarboxylic anhydride) (B13-1), (2,4-D), 0049 (B14) active substances of the chromanacetic acid 0026 4-chloro-2-methylphenoxypropionic esters (meco derivatives type. Such as, for example, prop), MCPA or 0050 “CL 304415” (CAS Reg. No. 31541-57-8) (=2-(4- 0027 3,6-dichloro-2-methoxybenzoic acid (and its carboxychroman-4-yl)acetic acid by American Cyana esters) (); mid), 0028 (B8) active substances of the pyrimidines type 0051 (B15) active substances which, in addition to a which are employed in rice as soil-acting safeners, such herbicidal action against harmful plants, also exhibit a as, for example, safeneraction in connection with crop plants for example, 0029) “fenclorim' (PM, pp. 406) (=4,6-dichloro-2-phe 0.052 “dimepiperate” or “MY-93” (PM, pp. 316-317) nylpyrimidine), (=S-1-methyl-1-phenylethyl piperidine-1-carbothioate), 0030 (B9) active substances of the dichloroacetamides 0.053 “daimuron” or “SK 23” (PM, p. 259) (=1-(1- type. Such as methyl-1-phenylethyl)-3-p-tolylurea), 0031) “dichlormid' (PM, pp. 284) (=N,N-diallyl-2.2- dichloroacetamide), 0054) “cumyluron’=“JC-940” (=3-(2-chlorophenylm ethyl)-1-(1-methyl-1-phenyl-ethyl)urea, See JP-A- 0032) “R-29148” (=3-dichloroacetyl-2.2.5-trimethyl-1,3- 60087254), oxazolidine, by Stauffer), 0.055 “methoxyphenone' or “NK 049” (=3,3'-dimethyl 0033) “benoxacor” (PM, pp. 72-73) (=4-dichloroacetyl 4-methoxybenzophenone), “CSB' (=1-bromo-4-(chlo 3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (B9-1), romethylsulfonyl)benzene) (CAS Reg. No. 54091-06-4, 0034) “PPG-1292 (=N-allyl-N-(1,3-dioxolan-2-yl)m- by Kumiai), ethyldichloroacetamide by PPG Industries), 0056 (B16) N-acylsulfonamides of the formula (S3) and 0035) “DK-24” (=N-allyl-N-(allylaminocarbonyl)m- their salts ethyldichloroacetamide by Sagro-Chem), 0036) “AD-67 or “MON 4660 (=3-dichloroacetyl-1- (S3) oxa-3-azaspiro4.5decane by Nitrokemia and Monsanto, respectively), R! N S-N 0037) “diclonon” or “BAS145138” or “LAB145138” N / o (=3-dichloroacetyl-2.5.5-trimethyl-1,3-diazabicyclo O 4.3.0nonane by BASF) and O (R) 0038) “furilazol” or “MON 13900” (see PM, 507) (=(RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazo lidine); 0057) as are described in WO-A-97/.45016: 0039 (B10) active substances of the dichloroacetone 0.058 (B17) acylsulfamoylbenzamides of the formula derivatives type, such as, for example, (S4), if appropriate also in salt form, 0040) “MG 191” (CAS Reg. No. 96420-72-3) (=2- dichloromethyl-2-methyl-1,3-dioxolane by Nitrokemia), (S4) 0041 (B11) active substances of the oxyimino com R O O O pounds type, such as, for example, N-G V 1S 0042 “oxabetrinil (PM, pp. 724-725) (=(Z)-1,3-diox olan-2-ylmethoxyimino(phenyl)-acetonitrile) (B11-1), k \ / t"X (R) 0043 “fluxofenim” (PM, pp. 490) (=1-(4-chlorophenyl)- 2.2.2-trifluoro-1-ethanone O-(1,3-dioxolan-2-ylmethy l)oxime (B11-2), and as are described in WO-A-99/16744); 0044) “cyometrinily or “-CGA-43089 (PM, pp. 1056 0059 (B18) dietholate (no ISO common name, approved (=(Z)-cyanomethoxy-imino(phenyl)acetonitrile), by the Weed Society of America), i.e. O,O-diethyl O-phe 0045 (B12) active substances of the thiazolecarboxylic nyl phosphorothioate, and ester type, for example, 0060 (B19) mephenate (no ISO common name, 0046) “flurazole” (PM, pp. 473–474) (=benzyl 2-chloro approved by the Weed Society of America), i.e 4-chlo 4-trifluoromethyl-1,3-thiazole-5-carboxylate), rophenyl methyl carbamate, US 2007/002 1303 A1 Jan. 25, 2007 including the stereoisomers and the salts conventionally 0071 (B3.1) compounds of the triazolecarboxylic acid used in agriculture. type, for example of the formula (III): 0061 Amongst the safeners mentioned, those which are of particular interest are (B1-1), (B4-3), (B5-1), (B13-1) and (III) safeners of the group (B17). Also of interest are (B9-1), (B11-1) and (B11-2). (R)n 1N 0062 Preference is given to herbicide-safener combina 2 N -N O tions comprising one or more compounds (A) and an effec \ tive amount of one or more compounds (B) selected from the group consisting of R3 us N R2 0063 (B1.1) compounds of the phenylpyrazolin-3-car boxylic acid type, for example of the formula (I): in which 0072) R', n, R and R are as defined under formula (I), (I) preferably fenchlorazole(ethyl ester), i.e. ethyl 1-(2,4- dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3- (R)n 1N carboxylate (B3-1) and related compounds as described in 21 N -N. O EP-A-174562 and EP-A-346 620, \ 0073 (B4.1) compounds of the 5-benzyl-, 5-phenyl- or R3 R2 5,5-diphenyl-2-isoxazoline-3-carboxylic acid type, for COOR example of the formula (IV): in which (IV) 0064) R' are identical or different and are halogen, (C- Cl)-alkyl, (C-C)-alkoxy, nitro or (C-C)-haloalkyl, 0065 n is an integer from 0 to 5, preferably from 0 to 3, 0.066 R is OR, SR or NR'R' or a saturated or unsat urated 3- to 7-membered heterocycle having at least one nitrogen atom and up to 3 heteroatoms, preferably in which Selected from the group consisting of O and S, which is 0074) R', n and R are as defined under formula (I) and attached to the carbonyl group in formula (I) via the R" is hydrogen, (C-Cs)-alkyl, (C-Cs)-haloalkyl, (C- nitrogenatom and which is unsubstituted or substituted by C)-cycloalkyl or Substituted or unsubstituted phenyl and radicals selected from the group consisting of (C-C)- alkyl, (C-C)-alkoxy and unsubstituted or substituted 0075) m is 0 or 1, phenyl, preferably a radical of the formula OR, NHR' or N(CH3)2, in particular of the formula OR, preferably compounds such as 0076 ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-car 0067 R is hydrogen, (C-C)-alkyl, (C-C)-haloalkyl, boxylate or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (C-C)-cycloalkyl or Substituted or unsubstituted phe (B1.4.2) and related compounds as described in WO nyl, 91/08202, or 0068) R' is hydrogen, (C-Cs)-alkyl, (C-Cs)-haloalkyl, 0077 ethyl 5,5-diphenyl-2-isoxazolinecarboxylate (B4 (C-C)-alkoxy-(C-C)-alkyl, (C-C)-hydroxyalkyl, 3) (“isoxadifen-ethyl) or the n-propyl ester or (C-C)-cycloalkyl or tri-(C-C)-alkyl-silyl, 0078 ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline 0069. R. R. R7 independently of one another are hydro 3-carboxylate as described in WO-A-95/07897, gen or an unsubstituted or Substituted aliphatic hydrocar 0079 (B5) compounds of the 8-quinolinoxyacetic acid bon radical, preferably having a total of 1 to 18 carbon type, preferably 1-methylhex-1-yl (5-chloro-8-quinoli atoms, and noxy)acetate (common name "cloquintocet-mexyl) (B5 0070 R is hydrogen, (C-C)-alkyl, (C-C)-alkoxy or 1) (see PM, pp. 196-197) substituted or unsubstituted phenyl, 0080) 1,3-dimethylbut-1-yl(5-chloro-8-quinolinoxy)ac preferably compounds Such as ethyl 1-(2,4-dichlorophenyl)- etate (B5-2), 5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (B1-1) (“Mefenpyr-diethyl, see “The Pesticide Manual”, 0081 4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate 13th edition 2003, pp. 622-623), and related compounds (B5-3), as described in WO 91/07874, 0082) 1-allyloxyprop-2-yl(5-chloro-8-quinolinoxy)ac (“The Pesticide Manual, 13th edition, is hereinbelow also etate (B5-4), abbreviated “PM), 0083) ethyl(5-chloro-8-quinolinoxy)acetate (B5-5), US 2007/002 1303 A1 Jan. 25, 2007

0084) methyl(5-chloro-8-quinolinoxy)acetate (B5-6), 0099 R is a hydrocarbon radical or a heterocyclyl radi allyl (5-chloro-8-quinolinoxy)acetate (B5-7), cal, where each of the two last-mentioned radicals is 0085 unsubstituted or substituted by one or more identical or 0.086 2-(2-propylideneiminooxy)-1-ethyl(5-chloro-8- different radicals selected from the group consisting of quinolinoxy)acetate (B5-8), halogen, cyano, nitro, amino, hydroxyl, mono- and di (C-C)-alkylamino, or an alkyl radical in which a 0087 2-oxoprop-1-yl(5-chloro-8-quinolinoxy)acetate plurality, preferably 2 or 3, of non-adjacent CH2 groups (B5-9), are in each case replaced by an oxygen atom, and related compounds as are described in EP-A-86 750, 0100 R.R are identical or different and are a hydrocar EP-A-94 349 and EP-A-191 736 or EP-A-O 492 366; bon radical or a heterocyclyl radical, where each of the 0088 (B12) active compounds of the thiazolecarboxylic two last-mentioned radicals is unsubstituted or substituted esters type which are known as seed dressings, such as, by one or more identical or different radicals selected for example, “flurazole” (PM, pp. 450-451) (=benzyl from the group consisting of halogen, cyano, nitro, amino, 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate), hydroxyl, phosphoryl, halo-(C-C)-alkoxy, mono- and which is known as a seed-dressing safener for millet di-(C-C)-alkylamino, or an alkyl radical in which a against and damage, plurality, preferably 2 or 3, of non-adjacent CH2 groups 0089 (B13) active substances of the naphthalenedicar are in each replaced by an oxygen atom, boxylic acid derivatives type, Such as, for example, 0101 Z is a divalent group of the formula O, S, CO, CS, 0090 “naphthalic anhydride” (PM, p. 1083) (= 1,8-naph CO-O, CO S, O CO, S CO, SO, SO, NR*, CO NR*, NR* CO, SO NR* or NR* SO, where thalenedicarboxylic anhydride) (B13-1), the bond indicated on the right-hand side of the divalent 0.091 (B16) N-acyl-N-benzoyl-aminobenzolsulfona group in question is the bond to the radical R and where mides of the formula (V) and their salts: the radicals R* in the 5 last-mentioned radicals indepen dently of one another are in each case H., (C-C)-alkyl or halo-(C-C)-alkyl, (V) 0102) Z.Z independently of one another are a direct bond or a divalent group of the formula O, S, CO, CS, RI N S-N CO-O, CO S, O CO, S CO, SO, SO, NR*, SO, \ A o NR*, NR* SO, CO. NR* or NR* CO, where in the O case of assymetrical divalent groups the atom located on O (R), the right-hand side is attached to the radical R or R, and where the radicals R* in the 5 last-mentioned radicals independently of one another are in each case H. (C- as described in WO-A-97/.45016, in which Cl)-alkyl or halo-(C-C)-alkyl, 0092) R' is hydrogen, a hydrocarbon radical, a hydrocar 0.103 n is an integer from 0 to 4, preferably 0, 1 or 2, in bon-oxy radical, a hydrocarbon-thio radical or a hetero particular 0 or 1, and cyclyl radical, which is preferably attached via a carbon atom, where each of the 4 last-mentioned radicals is 0.104 m is an integer from 0 to 5, preferably 0, 1, 2 or 3, unsubstituted or substituted by one or more identical or in particular 0, 1 or 2, different radicals selected from the group consisting of for example the compound 1-(4-(N-2-methoxybenzoylsul halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl, famoyl)phenyl)-3-methylurea, i.e. formula (V) in which carboxamide, Sulfonamide and radicals of the formula R=CH-NH-, R=H, n=0, R=H and (R)=2-meth Z-R, oxy (B3.1.1), 0093 where each hydrocarbon moiety has preferably 1 to 0105 (B17) acylsulfamoylbenzamides of the formula 20 carbon atoms and a carbon-containing radical R', (VI), if appropriate also in salt form, including substituents, has preferably 1 to 30 carbon atOmS, 0094) R is hydrogen or (C-C)-alkyl, preferably hydro (VI) gen, Or 0095) R' and R together with the group of the formula "V O 1s —CO N– are the radical of a 3- to 8-membered Saturated or unsaturated ring, k {)- t X R 0096). Rare identical or different and are halogen, cyano, (R), nitro, amino, hydroxyl, carboxyl, formyl, CONH, SONH, or a radical of the formula Zb-Rb, as described in the International Application No. PCT/EP98/ 0097) R' is hydrogen or (C-C)-alkyl, preferably hydro 06097 (WO-A-99/16744), in which gen, 0098 Rare identical or different and are halogen, cyano, 0106 X is CH or N, nitro, amino, hydroxyl, carboxyl, CHO, CONH, SONH, 0107) R' is hydrogen, heterocyclyl or a hydrocarbon or a radical of the formula Z-R, radical, where the two last-mentioned radicals are unsub US 2007/002 1303 A1 Jan. 25, 2007

stituted or substituted by one or more identical or different 0.120. Also preferred are safeners from the groups: radicals selected from the group consisting of halogen, 0121 (B9) active substances of the dichloroacetamides cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH2, type. Such as SONH, and Zd-Rd, 0122) “benoxacor” (PM, pp. 72-73) (=4-dichloroacetyl 0108) R is hydrogen, hydroxyl, (C-C)-alkyl, (C-C)- 3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (B9-1), and alkenyl, (C-C)-alkynyl, (C-C)-alkoxy, (C-C)-alk 0123 (B11) active substances of the oxyimino com enyloxy, where the five last-mentioned radicals are unsub pounds type, such as, for example, stituted or substituted by one or more identical or different 0.124 “oxabetrinil (PM, pp. 724-725) (=(Z)-1,3-diox radicals selected from the group consisting of halogen, olan-2-ylmethoxyimino(phenyl)-acetonitrile) (B11-1), hydroxyl, (C-C)-alkyl, (C-C)-alkoxy and (C-C)- alkylthio, or 0.125 “fluxofenim” (PM, pp. 490) (=1-(4-chlorophenyl)- 2.2.2-trifluoro-1-ethanone O-(1,3-dioxolan-2-ylmethy 0109) R' and R together with the nitrogen atom that 1)oxime (B11-2), and carries them are a 3- to 8-membered saturated or unsat 0126) “cyometrinil” or “-CGA-43089” (PM, p. 1056) urated ring, (=(Z)-cyanomethoxy-imino(phenyl)acetonitrile), 0110) Rare identical or different and are halogen, cyano, 0127. Some of the safeners are already known as herbi nitro, amino, hydroxyl, carboxyl, CHO, CONH, SONH, cides or pesticides and therefore simultaneously display a or Z-R, protective action in connection with the crop plants in addition to the herbicidal action or pesticidal action in 0111) R' is hydrogen, (C-C)-alkyl, (C-C)-alkenyl or connection with harmful plants or other harmful organisms, (C-C)-alkynyl, respectively. 0112) Rare identical or different and are halogen, cyano, 0128. The safeners (B) used in the combinations of the nitro, amino, hydroxyl, carboxyl, phosphoryl, CHO, present invention are understood to embrace all stereoiso CONH, SONH, or Z-R, mers and mixtures thereof, as well as their salts. 0129. The advantageous safener effects are observed 0113) R' is a (C-Co)-alkyl radical whose carbon chain when the active compounds (A) and (B) are applied simul is interrupted once or a plurality of times by oxygen taneously, however, they can also frequently be observed atoms, is heterocyclyl or a hydrocarbon radical, where the when the active compounds are applied at different times two last-mentioned radicals are unsubstituted or Substi (splitting). It is also possible to apply the active compounds tuted by one or more identical or different radicals in a plurality of portions (sequential application), for Selected from the group consisting of halogen, cyano, example after pre-emergence applications, followed by post nitro, amino, hydroxy, mono- and di-(C-C)-alkyl emergence applications or after early post-emergence appli amino; cations, followed by medium or late post-emergence appli 0114) R, R are identical or different and area (C-C)- cations. It is also possible to use the safeners as a dressing alkyl radical whose carbon chain is interrupted once or a or coating for pre-treating the seeds of the crop plants or plurality of times by oxgen atoms, or are heterocyclyl or plant seedlings. In case of Some pesticides Such as insecti a hydrocarbon radical, where the two last-mentioned cides or fungicides the pre-treatment of seeds with Safener radicals are unsubstituted or substituted by one or more can be combined with the pre-treatment with such a pesti identical or different radicals selected from the group cide. consisting of halogen, cyano, nitro, amino, hydroxyl, 0.130. The active compounds of the combination in ques phosphoryl, (C-C)-haloalkoxy, mono- and di-(C-C)- tion are preferably supplied jointly or within a short interval. alkylamino, Preferred is also the seed dressing of the crop plant seeds 0115) Z is a divalent unit selected from the group con with compound (B) and later application of compound (A), sisting of O, S, CO, CS, C(O)O, C(O)S, SO, SO, NR*, or treatment of the seeds with a combination of (B) and C(O)NR* or SONR*, compounds (A) selected from fungicides and insecticides. 0131 The pesticide-safener combinations reduce or 0116) Z, Zare identical or different and are a direct bond eliminate phytotoxic effects which can occur when the or a divalent unit selected from the group consisting of O, pesticidally active compounds (A) are used in useful plants, S, CO, CS, C(O)O, C(O)S, SO, SO, NR*, SONR* or without having any substantial detrimental effect on the C(O)NR*, activity of these active compounds against harmful organ 0117 R* is hydrogen, (C-C)-alkyl or (C-C)-ha isms. They permit a higher dosage (application rate) of the loalkyl, pesticide compared to the individual application of the pesticide in crops of useful plants, and thus a more effective 0118 n is an integer from 0 to 4, and control of the harmful organisms, e.g. competing harmful plants. In case of a herbicide as a pesticide the higher 0119 m is, in the case that X is CH, an integer from 0 to efficacy permits the control of weed species which are as yet 5 and, in the case that X is N, an integer from 0 to 4, uncontrolled (gaps), an extension of the period of applica for example the compound 4-(2-methoxybenzoylsulfa tion and/or a reduction in the number of individual appli moyl)-N-cyclopropylbenzamide (B17-1), and cations required and 0132) as a result for the user weed control systems including the Stereoisomers and the agriculturally useful which are more advantageous economically and eco salts thereof. logically. US 2007/002 1303 A1 Jan. 25, 2007

0133. It has hitherto not been known and is also surpris after the application of a pesticide, or used for the pretreat ing that the phytotoxicity of the pesticides (A) at said type ment of seed, i.e., for example, for dressing the seed of the of monocotyledonous plants can be reduced effectively or useful plants. eliminated with the aid of safeners (B). In general, said 0.138. The advantageous actions of the compounds (B) plants are much different in the biological response to the according to the invention are observed when they are used application of pesticides compared with commercially together with the pesticides by the pre-emergence method or important cereal plants. Thus, an effect of the Safeners in the post-emergence method, for example in the case of combination with pesticides on Such plants would not have simultaneous application as a tank mix or a coformulation or been predicted in a similar fashion. in the case of a separate application, in parallel or in 0134) The safeners together with pesticides are suitable Succession (split application). It is also possible to repeat the for the selective control of harmful organisms in a number application a number of times. In some cases, it may be of useful plants selected from monocotyledonous plants of expedient to combine a pre-emergence application with a the plant order Liliiflorae, for example the plant families post-emergence application. One option is a post-emergence Liliaceae, Amaryllidaceae, Iridaceae and Juncadeae, prefer application of compounds (B) to the useful plant or crop ably plants of the plant family Liliaceae, such as monocoty plant together with a simultaneous or later application of the ledonous vegetables, ornamentals and flowers of said plant pesticide. Also possible is the use of the compounds (B) family, such as plants from the genera Tofieldia, Narthecium, according to the invention for seed dressing, for (dip) Veratrum, Colchicum, Anthericum, Hemerocallis, Gagea, treatment of seedlings or for the treatment of other propa Allium, Lilium, Fritillaria, Tulipa, Lloydia, Scilla, Orni gation material Such as plantlets, bulbs, and Somatic thogalum, Muscari, Asparagus, Ruscus, Maianthemum, embryos. Polygonatum, Streptopus, Convallaria, Paris, more prefer 0.139. In the seed dressing method the seed can be ably plants from the genera Allium or Asparagus. More employed as normal seed or seed which has been pre-treated preferred are crop plants such as leeks (e.g. Allium porrum), to enhance growth, such as seed enhanced by steeping, onions (e.g. Allium cepa, Allium fistulosum), garlic (Allium priming or elsewise. sativum), chives (Allium Schoenoprasum), shallots (Allium ascalonicum), or asparagus (e.g. Asparagus officinalis). 0140 Preferred is the application of the compounds (B) Most preferred are leeks and onions. together with the pesticide (A) or prior to the application of pesticide (A). It is also preferred to apply compound (B) by 0135 Also of interest are mutant crops which are par the seed dressing method, optionally combined with an tially tolerant or insufficiently tolerant to some pesticides or application of an appropriate compound (A) in the seed transgenic crops which are partially or insufficiently toler dressing method. ant, for example crops resistant to , or herbicidal imidazolinones. However, the particular advan 0.141. When using the compounds (B) according to the tage of the novel use of the safeners is their effective action invention in combination with pesticides, e.g. herbicides, in in crops which are normally not sufficiently tolerant to the addition to the Safener action, enhanced action, e.g. herbi pesticides mentioned. cidal action, against harmful plants is frequently also observed. Furthermore, in many cases, there is an improved 0136. For the joint use with pesticides, the compounds of growth of the useful plants, and it is possible to increase the the formula (I) according to the invention can be applied harvest yields. simultaneously with the active compounds or in any order, and they are then capable of reducing or completely elimi 0142. The compositions according to the invention may nating harmful side effects of these active compounds in comprise one or more pesticides. Suitable pesticides are, for crop plants, without negatively affecting or Substantially example, herbicides, fungicides, pesticides against harmful reducing the activity of these active compounds against animals, such as insecticides, acaricides, nematicides, mol unwanted harmful organisms. Here, even damage caused by luscicides and miticides, which, when used on their own, using a plurality of pesticides, for example a plurality of would cause phytotoxic damage to the crop plants or would herbicides, insecticides or fungicides or herbicides in com probably cause damage. Of particular interest are corre bination with insecticides or fungicides, can be reduced sponding pesticidally active compounds from the groups of Substantially or eliminated completely. In this manner, it is the herbicides, insecticides, acaricides, nematicides, miti possible to extend the field of use of conventional pesticides cides and fungicides, in particular herbicides. considerably. 0.143. The safeners (B) can be used in the customary manner, separately or together with agrochemicals, e.g. 0137 If the compositions according to the invention pesticides, fertilizers and/or formulation auxiliaries. Accord comprise pesticides, these compositions are, after appropri ingly, the present invention also provides the usefull-plant ate dilution, applied either directly to the area under culti protecting or crop-plant-protecting compositions. Vation, to the already germinated harmful and/or useful plants or to the already emerged harmful and/or useful 0144. Herbicides whose phytotoxic side effects on crop plants. If compositions of single formulated compounds (B) plants can be reduced using compounds (B) can be from are used the compositions according to the invention con entirely different structural classes and have entirely differ taining active ingredients (A) and (B) can be prepared by the ent mechanisms of action. Preference is given to commer tank mix method—i.e. the user mixes and dilutes the sepa cially available herbicides as described, for example, in the rately available products (=the pesticide and the agent handbook “The Pesticide Manual, 13th Edition 2003, The protecting the useful plants) immediately prior to application British Crop Protection Council (abbreviation herein “PM), to the area to be treated. The application of compound (B) and the e-Pesticide Manual Version 3. The British Crop can also be made prior to the application of pesticide (A), or Protection Council 2003, or else trade names and common US 2007/002 1303 A1 Jan. 25, 2007

names which are referred to in the “Compendium of Pesti esters, for example -butyl and fluazifop-P-butyl: cide Common Names' (searchable via the Internet) and in fluazolate, flucarbazone(-sodium); flucetosulfuron, fluchlo literature quoted therein. The herbicides and plant growth ralin; flufenacet (FOE 5043), flufenpyr, flumetsulam; flu regulators mentioned hereinbelow by way of example are in meturon; flumiclorac(-pentyl); flumioxazin (S482); flumi each case referred to by their standardized common active propyn; fluometuron; fluorochloridone, fluorodifen; compound name according to the “International Organiza fluoroglycofen(-ethyl); flupoxam (KNW-739); flupropacil tion for Standardization’ (ISO), or by the chemical name or (UBIC-4243); fluproanate, flupyrsulfuron(-methyl, or -so the code number. Examples of active compounds whose dium); flurenol (-butyl); fluridone; flurochloridone; fluroxy phytotoxic action in crop plants and useful plants can be pyr(-meptyl); flurprimidol, flurtamone; fluthiacet(-methyl); reduced by the compounds (I) according to the invention fluthiamide (also known as flufenacet); fomesafen; foram a. sulfuron; fosamine; furilazole (MON 13900), furyloxyfen; 0145 ; (-sodium); ; AKH glufosinate (-ammonium); glyphosate(-isopropylammo 7088, i.e. 1-5-2-chloro-4-(trifluoromethyl)phenoxy-2- nium); halosafen; halosulfuron(-methyl) and its esters (for nitrophenyl-2-methoxyethylideneaminoloxyacetic acid example the methyl ester, NC-319); haloxyfop and its esters: and its methyl ester, alachlor; alloxydim(-Sodium); ametryn; haloxyfop-P(=R-haloxyfop) and its esters; HC-252 (diphe amicarbaZone, amidochlor, amidosulfuron; , nyl ether), ; imazamethabenZ(-methyl); amitrol: AMS, i.e. ammonium sulfamate; anilofos; ; imaZamethapyr; imaZamoX; , ; imaZaquin ; azafenidin; azimsulfuron (DPX-A8947); aziprot and salts such as the ammonium salts; imazethamethapyr; ryn; barban; BAS 516H, i.e. 5-fluoro-2-phenyl-4H-3,1-ben imazethapyr, imaZoSulfuron; indanofan; iodosulfuron-(me Zoxazin-4-one; beflubutamid; benazolin(-ethyl); ; thyl)-(sodium), ioxynil; isocarbamid; isopropalin; isoprotu benfuresate; bensulfuron(-methyl); ; bentazone(- ron; isouron; isoxaben; isoxachlortole; isoxaflutole; isox Sodium); benzfendizone, benzobicyclone; benzofenap; ben apyrifop: karbutilate; ; lenacil; : MCPA: Zofluor; benzoylprop(-ethyl); benzthiazuron; bialaphos MCPA-thioethyl, MCPB: (-P); mefenacet; meflui (bilanafos); ; bispyribac(-sodium); bromacil; bro did; mesosulfuron(-methyl); ; metam, metami mobutide; bromofenoxim; ; bromuron; bumin fop, metamitron; metaZachlor; methabenzthiazuron; meth afos; busoxinone; ; ; butamifos; buten azole; methoxyphenone; methyldymron; metobenzuron, achlor; buthidazole; butralin; butroxydim; butylate: metobromuron; (S-)metolachlor; metosulam (XRD 511); cafenstrole (CH-900); carbetamide; carfentraZone(-ethyl); metoxuron; ; metsulfuron-methyl; MK-616: caloxydim, CDAA, i.e. 2-chloro-N,N-di-2-propenylaceta molinate; monalide; monocarbamide dihydrogensulfate: mide: CDEC, i.e. 2-chloroallyl diethyldithiocarbamate; ; monuron; MT 128, i.e. 6-chloro-N-(3-chloro chlomethoxyfen; chloramben; chlorazifop-butyl; chlorbro 2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine; MT muron; chlorbufam; chlorfenac; chlorfenprop, chlorflure 5950, i.e. N-3-chloro-4-(1-methylethyl)-phenyl-2-methyl nol-methyl; chloridazon; chlorimuron(-ethyl); chlornitrofen; pentanamide; naproanilide; napropamide; naptalam; NC chlorotoluron; ; chlorpropham; chlorSulfuron; 310, i.e. 4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxy chlorthal-dimethyl; chlorthiamid; , cinidon-(- pyrazole; neburon; nicosulfuron; nipyraclophen; nitralin; methyl or -ethyl), cinmethylin; cinosulfuron; clethodim; ; nitrofluorfen: norflurazon; orbencarb; oryzalin; clefoxydim, clodinafop and its ester derivatives (for oxadiargyl (RP-020630); oxadiazone; oxasulfuron; oxazi example clodinafop-propargyl); ; clomeprop; clo clomefone; oxyfluorfen: , pebulate; pelargonic acid; prop, cloproxydim; ; clopyrasulfuron(-methyl); ; penoXulam, pentanochlor, pentoxazone; per cloranSulam(-methyl); cumyluron (JC 940); ; fluidone; pethoxamid, phenisopham; phenmedipham; piclo cycloate; cyclosulfamuron (AC 104); cycloxydim; cycluron; ram, picolinafen; pinoxaden, piperophos; piributicarb; pir cyhalofop and its ester derivatives (for example butyl ester, ifenop-butyl: pretilachlor; primisulfuron(-methyl); DEH-112); cyperquat, cyprazine; cyprazole; daimuron; 2,4- procarbaZone(-Sodium); procyazine; prodiamine; proflua D; 2,4-DB; dalapon; dazomet, desmedipham; desmetryn; Zole, profluralin; proglinazine(-ethyl); ; prom di-allate; dicamba; dichlobenil; (-P); diclofop etryn; ; ; propaquizafop; propazine; and its esters such as diclofop-methyl; dicloSulam, propham; propisochlor, propoxycarbaZone(-Sodium), pro diethatyl(-ethyl); difenoxuron; difenzoquat; diflufenican; pyZamide; prosulfalin; prosulfocarb; prosulfuron (CGA diflufenzopyr; dimefuron; dimepiperate; dimethachlor; 152005); prynachlor; pyraclonil, pyraflufen(-ethyl); pyrazo dimethametryn; (SAN-582H); dimethena linate; pyrazon; pyrazosulfuron(-ethyl); pyrazoxyfen; mid(-P); dimethaZone, dimethipin; dimexyflam, dimetrasul ; pyributicarb: pyridafol; pyridate; pyriftalid, furon, dinitramine; ; dinoterb; diphenamid; dipro pyrimidobacG-methyl); pyrithiobacG-sodium) (KIH-2031); petryn; diguat; ; diuron; DNOC: eglinazine-ethyl: pyroxofop and its esters (for example propargyl ester); EL 77, i.e. 5-cyano-1-(1,1-dimethylethyl)-N-methyl-1H ; quinmerac; quinoclamine, quinofop and its ester pyrazole-4-carboxamide; endothal; epoprodan, EPTC, esp derivatives, quizalofop and quizalofop-P and their ester rocarb; ethalfluralin; ethametsulfuron-methyl; ethidimuron; derivatives, for example quizalofop-ethyl; quizalofop-P- ethiozin; ethofumesate; ethoxyfen and its esters (for tefuryl and -ethyl; renriduron; rimsulfuron (DPX-E 9636); S example ethyl ester, HC-252), ethoxysulfuron, etobenzanid 275, i.e. 2-4-chloro-2-fluoro-5-(2-propynyloxy)phenyl-4, (HW 52); F5231, i.e. N-(2-chloro-4-fluoro-5-4-(3-fluoro 5,6,7-tetrahydro-2H-indazole; secbumeton; ; propyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl-phenyl siduron; ; simetryn: SN 106279, i.e. 2-7-2- ethanesulfonamide; ; fenoxan, fenoxaprop and chloro-4-(trifluoromethyl)phenoxy-2-naphthalenyloxy fenoxaprop-P and their esters, for example fenoxaprop-P- propanoic acid and its methyl ester, Sulcotrione, Sulfentra ethyl and fenoxaprop-ethyl; fenoxydim; fentraZamide; fenu Zone (FMC-97285, F-6285); sulfazuron; sulfometuron(- ron; flamprop?-methyl or -isopropyl or -isopropyl-L); flaza methyl); sulfosate (ICI-A0224); sulfosulfuron; TCA: sulfuron; florasulam; fluazifop and fluazifop-P and their tebutam (GCP-5544); ; tepraloxydim; terbacil; US 2007/002 1303 A1 Jan. 25, 2007

terbucarb: terbuchlor; terbumeton; ; ter 0152 propargyl 2-(4-(3,5-dichloropyridyl-2-oxy)phe butryn: TFH 450, i.e. N,N-diethyl-3-(2-ethyl-6-methylphe noxy)propionate (EP-A 0 003 114), nyl)sulfonyl)-1H-1,2,4-triazole-1-carboxamide; thenylchlor 0.153 methyl(RS)- or (R)-2-(4-(3-chloro-5-trifluorom (NSK-850); thiafluamide; thiazafluron; thiazopyr (Mon ethyl-2-pyridyloxy)phenoxy)propionate (haloxyfop-me 13200); thidiazimin (SN-24085); thidiaZuron, thifensulfu ron(-methyl); thiobencarb: tiocarbazil; tralkoxydim; tri-al thyl or haloxyfop-P-methyl), late; triasulfuron; triaziflam; triazofenamide; tribenuron(- 0154) ethyl 2-(4-(3-chloro-5-trifluoromethyl-2-pyridy methyl); 2.3,6-trichlorobenzoic acid (2.3.6-TBA), ; loxy)phenoxy)propionate (EP-A 0 003 890), tridiphane; trietazine; trifloxysulfuron(-sodium), ; triflusulfuron and esters (e.g. methyl ester, DPX-66037): 0.155 propargyl 2-(4-(5-chloro-3-fluoro-2-pyridylox trimeturon; tritosulfuron; tsitodef vernolate; WL 110547, y)phenoxy)propionate (clodinafoppropargyl), i.e. 5-phenoxy-1-3-(trifluoromethyl)phenyl)-1H-tetrazole; 0156 butyl(RS)- or (R)-2-(4-(5-trifluoromethyl-2-py UBH-509: D-489; LS 82-556; KPP-300; NC-324; NC-330; ridyloxy)phenoxy)propionate (fluazifop-butyl or fluazi KH-218: DPX-N8189: SC-0774; DOWCO-535; DK-8910; fop-P-butyl), V-53482; PP-600; MBH-001; KIH-9201: ET-751; KIH 6127; KIH-2023 and KIH5996. 0157 (R)-2-[4-(3-chloro-5-trifluoromethyl-2-pyridylox y)phenoxypropionic acid 0146 Herbicides, whose phytotoxic side effects on crop plants can be reduced using compounds of the formula I are, 0158 (A1.3) “bicyclic heteroaryloxyphenoxyalkan for example, herbicides from the group of the carbamates, ecarboxylic acid derivatives, for example thiocarbamates, haloacetanilides, Substituted phenoxy-, naphthoxy- and phenoxyphenoxycarboxylic acid derivatives 0159 methyl and ethyl(RS)- or (R)-2-(4-(6-chloro-2-qui and heteroaryloxyphenoxyalkanecarboxylic acid deriva noxalyloxy)phenoxy)propionate (quizalofop-methyl and tives, such as quinolyloxy-, quinoxalyloxy-, pyridyloxy-, -ethyl or quizalofop-P-methyl and -P-ethyl), benzoxazolyloxy- and benzothiazolyloxyphenoxyal 0.160 methyl 2-(4-(6-fluoro-2-quinoxalyloxy)phenox kanecarboxylic acid esters, cyclohexanedione oximes, ben y)propionate (see J. Pest. Sci. Vol. 10, 61 (1985)), Zoylcyclohexanediones, benzoylisoxazoles, benzoylpyra Zoles, imidazolinones, pyrimidinyloxypyridinecarboxylic 0.161 2-isopropylidenaminooxyethyl(R)-2-(4-(6-chloro acid derivatives, pyrimidyloxybenzoic acid derivatives, Sul 2-quinoxalyloxy)phenoxy)propionate (propaquizafop), fonylureas, sulfonylaminocarbonyltriazolinones, triazolopy 0162 ethyl(RS)- or (R)-2-(4-(6-chlorobenzoxazol-2- rimidinesulfonamide derivatives, phosphinic acid deriva yloxy)phenoxy)propionate (fenoxaprop-ethyl or fenox tives and salts thereof glycine derivatives, triazolinones, aprop-P-ethyl), triazinones and also S-(N-aryl-N-alkylcarbamoylmeth yl)dithiophosphoric esters, pyridinecarboxylic acids, 0.163 ethyl 2-(4-(6-chlorobenzthiazol-2-yloxy)phenox pyridines, pyridinecarboxamides, 1,3,5-triazines, hydroxy y)propionate (DE-A-26 40 730), benzonitriles, dinitroanilides, ureas, diphenylethers, oxadia 0.164 tetrahydro-2-furylmethyl(RS)- or (R)-2-(4-(6-chlo Zoles, benzamides, bispyridylium derivatives and others. roquinoxalyloxy)phenoxy) propionate (EP-A-0 323 727); 0147 Herbicides which are suitable for combination with 0.165 (A2) herbicides from the group of the sulfony the Safeners (B) according to the invention are, for example: lureas, such as pyrimidinyl- or triazinylaminocarbonyl 0148 (A1) herbicides of the type of the phenoxyphe benzene-, -pyridine-, -pyrazole-, -thiophene- and -(alkyl noxy- and heteroaryloxyphenoxycarboxylic acid deriva sulfonyl)alkylaminosulfamides. Preferred substituents tives, such as on the pyrimidine ring or the triazine ring are alkoxy, alkyl, haloalkoxy, haloalkyl, halogen or dimethylamino, it 0149 (A1.1) phenoxyphenoxy- and benzyloxyphenoxy being possible to combine all Substituents independently carboxylic acid derivatives, for example methyl 2-(4-(2, of one another. Preferred substituents in the benzene, 4-dichlorophenoxy)phenoxy)propionate (diclofop-me pyridine, pyrazole, thiophene or (alkylsulfonyl)alky thyl), methyl 2-(4-(4-bromo-2- lamino moiety are alkyl, alkoxy, halogen, nitro, alkoxy chlorophenoxy)phenoxy)propionate (DE-A 26 01 548), carbonyl, aminocarbonyl, alkylaminocarbonyl, dialky methyl 2-(4-(4-bromo-2-fluorophenoxy)phenoxy)propi laminocarbonyl, alkoxyaminocarbonyl, haloalkoxy, onate (U.S. Pat. No. 4,808,750), methyl 2-(4-(2-chloro haloalkyl, alkylcarbonyl, alkoxyalkyl, (alkanesulfonyl)a- 4-trifluoromethylphenoxy)phenoxy)propionate (DE-A 24 lkylamino. Such suitable Sulfonylureas are, for example, 33 067), methyl 2-(4-(2-fluoro-4-trifluoromethylphenox y)phenoxy)propionate (U.S. Pat. No. 4,808,750), methyl 0166 (A2.1) phenyl- and benzylsulfonylureas and 2-(4-(2,4-dichlorobenzyl)phenoxy)propionate (DE-A 24 related compounds, for example 17 487), ethyl 4-(4-(4-trifluoromethylphenoxy)phenox y)pent-2-enoate, methyl 2-(4-(4-trifluoromethylphenox 0.167 1-(2-chlorophenylsulfonyl)-3-(4-methoxy-6-me y)phenoxy)propionate (DE-A 24 33 067), butyl(R)-2-4- thyl-1,3,5-triazin-2-yl)urea (chlorsulfuron), (4-cyano-2-fluorophenoxy)phenoxypropionate 0168 1-(2-ethoxycarbonylphenylsulfonyl)-3-(4-chloro (cyhalofop-butyl) 6-methoxypyrimidin-2-yl)urea (chlorimuron-ethyl), 0150 (A1.2) “monocyclic heteroaryloxyphenoxyalkan 0.169 1-(2-methoxyphenylsulfonyl)-3-(4-methoxy-6- ecarboxylic acid derivatives, for example methyl-1,3,5-triazin-2-yl)urea (metsulfuron-methyl), 0151 ethyl 2-(4-(3,5-dichloropyridyl-2-oxy)phenox 0170 1-(2-chloroethoxyphenylsulfonyl)-3-(4-methoxy y)propionate (EP-A 0002925), 6-methyl-1,3,5-triazin-2-yl)urea (Triasulfuron),

US 2007/002 1303 A1 Jan. 25, 2007

0216 cycloate, dimepiperate, esprocarb, molinate, 0241 2',4'-dichloro-5'-(4-difluoromethyl-4,5-dihydro-3- orbencarb, pebulate, prosulfocarb, thiobencarb, tiocarba methyl-5-oxo-1H-1,2,4-triazol-1-yl)-methanesulfonanil Zil and tri-allate; ide (); 0217 (A5) cyclohexanedione oximes, for example 0242 (A13) phosphinic acids and derivatives, for example 0218 alloxydim, butroxydim, clethodim, cloproxydim, cycloxydim, protoxydim, Sethoxydim, tepraloxydim and 0243 4-hydroxy(methyl)phosphinoyl-L-homoalanyl tralkoxydim; L-alanyl-L- (bilanafos), 0219 (A6) imidazolinones, for example 0244 DL-homoalanin-4-yl(methyl)phosphinic acid ammonium salt (glufosinate-ammonium); 0220 imazamethabenz-methyl, imazapic, imaZamox, imazapyr, imaZaquin and imazethapyr; 0245 (A14) glycine derivatives, for example 0221 (A7) triazolopyrimidinesulfonamide derivatives, 0246 N-(phosphonomethyl)glycine and its salts (glypho for example sate and salts, for example the Sodium salt or the isopro pylammonium salt), 0222 chloransulam-methyl, diclosulam, florasulam, flu metSulam, metoSulam and penoXulam; 0247 N-(phosphonomethyl)glycine trimesium salt (sul fosate); 0223 (A8) benzoylcyclohexanediones, for example 0248 (A15) pyrimidinyloxypyridinecarboxylic acid 0224 2-(2-chloro-4-methylsulfonylbenzoyl)cyclo derivatives and pyrimidinyloxybenzoic acid derivatives, hexane-1,3-dione (SC-0051, sulcotrione), for example 0225 2-(2-nitrobenzoyl)-4,4-dimethylcyclohexane-1,3- 0249 benzyl 3-(4,6-dimethoxypyrimidin-2-yl)oxypyri dione (EP-A 0 274 634), dine-2-carboxylate (EP-A 0 249 707), 0226, 2-(2-nitro-3-methylsulfonylbenzoyl)-4,4-dimeth 0250 methyl 3-(4,6-dimethoxypyrimidin-2-yl)oxypyri ylcyclohexane-1,3-dione (WO 91/13548), dine-2-carboxylate (EP-A 0 249 707), 0227 2-4-(methylsulfonyl)-2-nitrobenzoyl-1,3-cyclo 0251 1-(ethoxycarbonyloxyethyl)2,6-bis(4,6- hexanedione (mesotrione); dimethoxypyrimidin-2-yl)oxybenzoate (EP-A 0 472 0228 (A9) benzoylisoxazoles, for example 113), 0229 5-cyclopropyl-2-(methylsulfonyl)-4-(trifluorom 0252) 2,6-bis(4,6-dimethoxypyrimidin-2-yl)oxyben ethyl)benzoylisoxazole (isoxaflutole); Zoic acid (bispyribac-Sodium), 0253 pyribenzoxim, pyriftalid, pyriminobac-methyl and 0230 (A10) benzoylpyrazoles, for example pyrithiobac-Sodium; 0231 2-4-(2,4-dichloro-m-toluyl)-1,3-dimethylpyrazol 0254 (A16) S-(N-aryl-N-alkylcarbamoylmeth 5-yloxy-4-methylacetophenone (benzofenap), yl)dithiophosphonic acid esters, such as S-N-(4-chlo 0232 4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol-5-yl rophenyl)-N-isopropylcarbamoylmethylO.O-dimethyl toluene-4-Sulfonate (pyrazolynate), dithiophosphate (anilophos); 0233 2-4-(2,4-dichlorobenzoyl)-1,3-dimethylpyrazol 0255 (A17) triazinones, for example 5-yloxyacetophenone (pyrazoxyfen); 0256 3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-tri 0234 (A11) Sulfonylaminocarbonyltriazolinones, for azine-2,4-(1H.3H)-dione (hexazinone), example 0257 4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-tri 0235 4.5-dihydro-3-methoxy-4-methyl-5-oxo-N-(2-trif aZin-5-one (metamitron), luoromethoxyphenylsulfonyl)-1H-1,2,4-triazole-1-car 0258 4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1, boxamide Sodium salt (flucarbazone-sodium), 2,4-triazin-5-one (metribuzin); 0236 methyl 2-(4,5-dihydro-4-methyl-5-oxo-3-propoxy 1H-1,2,4-triazol-1-yl)carboxamidosulfonylbenzoate 0259 (A18) pyridinecarboxylic acids, for example Sodium salt (propoxycarbazone-Na); 0260) clopyralid, , and triclopyr; 0237 (A12) triazolinones, for example 0261) (A19) pyridines, for example 0238 4-amino-N-tert-butyl-4,5-dihydro-3-isopropyl-5- 0262) dithiopyr and thiazopyr; OXo-1,2,4-1H-triazole-1-carboxamide (amicarbazone), 0263 (A20) pyridinecarboxamides, for example 0239 2-(2,4-dichloro-5-prop-2-ynyloxyphenyl)-5,6,7,8- tetrahydro-1,2,4-triazolo 4,3-alpyridin-3(2H)-one 0264) diflufenican and picolinafen; (azafenidin), 0265 (A21) 1,3,5-triazines, for example 0240 ethyl(RS)-2-chloro-3-2-chloro-5-(4-difluorom 0266 ametryn, atrazine, cyanazine, dimethametrin, ethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1- prometon, prometryn, propazine, simazine, Symetryn, ter yl)-4-fluorophenylpropionate (carfentraZone-ethyl), bumeton, terbuthylazine, terbutryn and trietazine; US 2007/002 1303 A1 Jan. 25, 2007

0267 (A22) hydroxybenzonitriles, for example dinocap: diphenylamine; dipyrithione; ditalimfos; 0268 bromoxynil (3,5-dibromo-4-hydroxybenzonitrile), dithianon; dodine; draZOXolon; edifenphos; epoxiconazole; bromoxynil-octanoate, bromoxynil-heptanoate, bro ethaboxam, ethirimol; etridiazole; famoxadone; fenami moxynil-octanoate/heptanoate, bromoxynil-potassium, done; fenapanil; fenarimol; fenbuconazole; fenfuram; fen ioxynil (4-hydroxy-3,5-di-iodobenzonitrile), ioxynil-oc hexamid; fenitropan; fenoxanil; fempiclonil; fempropidin; fenpropimorph: ferbam; fluazinam; flubenzimine; fludiox tanoate, ioxynil-sodium, onil; flumetover; flumorph; fluoromide; fluoxastrobin: flu 0269 (A23) dinitroanilides such as trifluralin and pen quinconazole; flurprimidol; flusilazole; flusulfamide; fluto dimethalin, lanil; flutriafol; folpet; fosetyl-Al; fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; furcarbanil; furmecy 0270 (A24) carbamates such as chlorpropham, clox, guaZatine; hexachlorobenzene; hexaconazole; hymex 0271 (A25) ureas such as metabenthiazuron, linuron and aZol; imazalil; imibenconazole; iminoctadine triacetate; imi monolinuron, noctadine tris(albesilate); iodocarb; ipconazole, iprobenfos; iprodione, iprovalicarb; irumamycin; isoprothiolane; isov 0272 (A26) nitrodiphenylethers such as oxyfluorfen, aledione; kasugamycin; kresoxim-methyl; mancoZeb; 0273 (A27) oxydiazoles such as oxadiazon and oxadiar maneb, meferim Zone; mepanipyrim, mepronil; metalaxyl; gyl. metalaxyl-M; metconazole; methasulfocarb; methfuroxam; methyl 1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H 0274 (A28) benzofurans such as ethofumesate, imidazole-5-carboxylate; methyl 2-cyclopropyl (4-meth 0275 (A29) benzamides such as isoxaben, and oxyphenyl)iminomethylthiomethyl)-alpha.-(methoxym ethylene)benzeneacetate; methyl 2-2-3-(4-chlorophenyl)- 0276 (A30) bypyridylium derivatives such as paraquat 1-methylallylideneaminooxymethylphenyl-3- dichloride. methoxyacrylate; metiram; metominostrobin: metrafenone; 0277. The herbicides of groups (A1) to (A30) are known, metSulfovax, mildiomycin; monopotassium carbonate; for example, from the respective abovementioned publica myclobutanil; myclozolin: nabam, N-(3-ethyl-3,5,5-trimeth tions and from “The Pesticide Manual”. The British Crop ylcyclohexyl)-3-formylamino-2-hydroxybenzamide, N-(6- Protection Council, 13th Edition, 2003 (="PM), or the methoxy-3-pyridinyl)cyclopropanecarboxamide: N-butyl-8- e-Pesticide Manual, Version 3.0, British Crop Protection (1,1-dimethylethyl)-1-oxaspiro4.5decan-3-amine; Council 2003. natamycin; nitrothal-isopropyl; noviflumuron; nuarimol; ofurace; orysastrobin, oxadixyl; OXolinic acid; Oxpocona 0278 Preferred herbicides are selected from the group Zole; oxycarboxin; oxyfenthiin, paclobutraZol; pefurazoate; consisting of chloroacetic acid, chlorpropham, chlorthal penconazole; pencycuron; penthiopyrad; phosdiphen; dimethyl, clopyralid, cyanamide, ethofumesate, formasulfu phthalide, picobenzamid; picoxystrobin; piperalin; polyox ron, haloxyflop, haloxyfop-P hydroxybenzonitrils (such as ins; polyoxorim; probenazole; prochloraz; procymidone; bromoxynil and ioxynil), isoxaben, linuron, mesosulfuron, propamocarb; propanosine-sodium; propiconazole; metaZachlor, methabenzthiaZuron, metribuzin, monolinu propineb; produinazid; prothioconazole; pyraclostrobin; ron, oxadiazon, oxyfluorfen, paraquat dichloride, pen pyrazophos; pyrifenox, pyrimethanil; pyroquilon; pyroxy dimethalin, prometryn, propachlor, propisochlor, Sethoxy fur; pyrrolnitrine; quinconazole; quinoxyfen, quintoZene; dim, simazine, trifluralin. silthiofam; Simeconazole; sodium tetrathiocarbonate; 0279 Preferred plant growth regulators are selected from spiroxamine; Sulfur, tebuconazole; tecloftalam, tecnaZene; the group consisting of maleic hydrazide and mepiduat tetcyclacis; tetraconazole; thiabendazole; thicyofen; thi chloride. fluZamide; thiophanate-methyl; thiram; tiadinil; tioxymid; tolclofos-methyl; tolylfluanid; triadimefon: triadimenol; tri 0280 Fungicidally active compounds which can be used azbutil; triazoxide; tricyclamide: tricyclazole; tridemorph; in combination with the crop-plant-protecting compounds trifloxystrobin; triflumizole; triforine; triticonazole; uni (I) according to the invention are preferably commercially conazole; validamycin A; VincloZolin; Zineb, Ziram; ZOxa available active compounds, for example (analogously to the mide; (2S)-N-2-4-3-(4-chlorophenyl)-2-propynyloxy herbicides, the compounds are generally referred to by their 3-methoxyphenylethyl-3-methyl-2- common names): 2-phenylphenol; 8-hydroxyquinoline Sul (methylsulfonyl)amino-butanamide: 1-(1-naphthalenyl)- fate; acibenzolar-5-methyl; actinovate; aldimorph; amidof 1H-pyrrole-2,5-dione: 2,3,5,6-tetrachloro-4- lumet, ampropylfos; ampropylfos-potassium; andoprim; (methylsulfonyl)pyridine: 2,4-dihydro-5-methoxy-2- anilazine; azaconazole; azoxystrobin; benalaxyl; benodanil; methyl-4-1-3-(trifluoromethyl)phenylethylidene benomyl; benthiavalicarb-isopropyl; benzamacril; ben aminooxymethylphenyl-3H-1,2,3-triazol-3-one: Zamacril-isobutyl; binapacryl; biphenyl; bitertanol; blastici 2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide: din-S; boscalid; bromuconazole; bupirimate; buthiobate: 2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3- butylamine; calcium polysulfide; capsimycin; captafol; cap pyridinecarboxamide: 3,4,5-trichloro-2,6-pyridinedicarbo tan; carbendazim; carboxin; carpropamid; carvone; chi nitrile; 3-(3-bromo-6-fluoro-2-methyl-1H-indol-1-yl)sulfo nomethionat; chlobenthiazone; chlorfenazole; chloroneb; nyl-N,N-dimethyl-1H-1,2,4-triazole-1-sulfonamide: chlorothalonil; chlozolinate; cis-1-(4-chlorophenyl)-2-(1H copper salts and copper preparations, such as Bordeaux 1,2,4-triazol-1-yl)cycloheptanol; cloZylacon; cyaZofamid; mixture; copper hydroxide; copper naphthenate; copper cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cypro oxychloride; copper Sulfate; cufraneb; copper(I) oxide; man furam; Dagger G; debacarb; dichlofluanid; dichlone; dichlo copper; Oxine-copper, rophen; diclocymet; diclomeZine; dicloran; diethofencarb; difenoconazole; diflumetorim; dimethirimol; dimetho 0281 Of particular interest are fungicides selected from morph; dimoxystrobin, diniconazole; diniconazole-M; the group consisting of benalaxyl, bitertanol, bromuconazol. US 2007/002 1303 A1 Jan. 25, 2007 captafol, carbendazim, carpropamid, cyaZofamid, cypro dane, endosulfan, gamma-HCH, HCH, heptachlor, lindane, conazol, diethofencarb, edifenphos, fenpropimorph, fentine, methoxychlor spinosad, acetoprole, ethiprole, fipronil. fluguinconazol, fosetyl, fluoroimide, folpet, iminoctadine, Vaniliprole, avermectin, emamectin, emamectin-benzoate, iprodionem, iprovalicarb, kasugamycin, maneb, nabam, ivermectin, milbemycin, diofenolan, epolfenonane, fenoxy pencycuron, prochloraz, propamocarb, propineb, pyrimetha carb, hydroprene, kinoprene, methoprene, pyriproxifen, tri nil, Sprioxamine, quintoZene, tebuconazole, tolylfluanid, tri prene, chromafenozide, halofenozide, methoxyfenozide, adimefon, triadimenol, trifloxystrobin, Zineb. tebufenozide, bistrifluron, chlofluaZuron, diflubenzuron, fluaZuron, flucycloXuron, flufenoXuron, hexaflumuron, 0282 Preferred fungicides are selected from the group lufenuron, novaluron, noviflumuron, penfluron, teflubenzu consisting of benalaxyl, captafol, cyaZofamid, diethofen ron, triflumuron, buprofezin, cyromazine, diafenthiuron, carb, fenpropimorph, fluoroimide, folpet, iminoctadine, aZocyclotin, cyhexatin, fenbutatin-oxide, chlorfenapyr, kasugamycin, maneb, nabam, quintoZene, Zineb. binapacyri, dinobuton, dinocap, DNOC, fenaZaquin, fenpy 0283 Pesticides against harmful animals (such as insec roximate, pyrimidifen, pyridaben, tebufenpyrad, tolfen ticidally, acaricidally and similarly active active compounds, pyrad, hydramethylnon, dicofol, rotenone, acequinocyl, flu in short “insecticides) are, for example (analogously to the acrypyrim, Bacillus thuringiensis strains, spirodiclofen, herbicides and fungicides, compounds are, if possible, spiromesifen, 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1- referred to by their common names): azaspiro4.5dec-3-en-4-yl ethyl carbonate (alias: carbonic acid, 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-1-azaspiro 0284 alanycarb, aldicarb, aldoxycarb, allyxycarb, ami 4.5dec-3-en-4-yl ethyl ester, CAS-Reg.-No. 382608-10-8) nocarb, bendiocarb, benfuracarb, bufencarb, butacarb, buto and carbonic acid, cis-3-(2,5-dimethylphenyl)-8-methoxy carboxim, butoxycarboxim, carbaryl, carbofuran, carbosul 2-oxo-1-azaspiro4.5dec-3-en-4-yl ethyl ester (CAS-Reg fan, cloethocarb, dimetilan, ethiofencarb, fenobucarb, No.: 203313-25-1), flonicamid, amitraz, propargite, N2-1, fenothiocarb, formetanate, furathiocarb, isoprocarb, metam 1-dimethyl-2-(methylsulfonyl)ethyl-3-iodo-N1-(2-methyl Sodium, methiocarb, methomyl, metolcarb, oxamyl, pirimi 4-1.2.2.2-tetrafluoro-1-(trifluoromethyl)ethylphenyl-1,2- carb, promecarb, propoXur, thiodicarb, thiofanox, trimethac benzenedicarboxamide (CAS-Reg.-No. 272451-65-7), arb. XMC, Xylylcarb, acephate, azamethiphos, azinphos thiocyclam hydrogen oxalate, thiosultap-sodium, azadirach (-methyl, -ethyl), bromophos-ethyl, bromfenvinfos (-me tin, Bacillus spec. Beauveria spec., codilemone, Metarrhi thyl), butathiofos, cadusafos, carbophenothion, chlorethoxy Zium spec. Paecilomyces spec., thuringiensin, Verticillium fos, chlorfenvinphos, chlormephos, chlorpyrifos (-methyl/- spec., aluminum phosphide, methyl bromide, Sulfuryl fluo ethyl), coumaphos, cyanofenphos, cyanophos, ride, cryolite, flonicamid, pymetrozine, clofentezine, etox chlorfenvinphos, demeton-5-methyl, demeton-5-methylsul azole, hexythiaZOX, amidoflumet, benclothiaz, benzoximate, phon, dialifos, diazinon, dichlofenthion, dichlorvos/DDVP. bifenazate, bromopropylate, buprofezin, chinomethionat, dicrotophos, dimethoate, dimethylvinphos, dioxabenzofos, chlordimeform, chlorobenzilate, chloropicrin, clothiazoben, disulfoton, EPN, ethion, ethoprophos, etrimfos, famphur, cycloprene, dicyclanil, fenoxacrim, fentrifanil, flubenz fenamiphos, fenitrothion, fensulfothion, fenthion, flupyra imine, flufenerim, flutenZin, gossyplure, hydramethylnone, Zofos, fonofos, formothion, foSmethilan, fosthiazate, hep tenophos, iodofenphos, iprobenfos, isazofoS, isofenphos, japonilure, metoxadiaZone, petroleum, piperonyl butoxide, isopropyl O-Salicylate, isoxathion, malathion, mecarbam, potassium oleate, pyridalyl, Sulfluramid, tetradifon, tetrasul, methacrifos, methamidophos, methidathion, mevinphos, triarathene, verbutin. monocrotophos, naled, omethoate, Oxydemeton-methyl, par 0285 Insecticides which, on their own or together with athion (-methyl/-ethyl), phenthoate, phorate, phosalone, herbicides, can cause damage to plants include, for example: phosmet, phosphamidon, phosphocarb, phoxim, pirimiphos 0286 acetamiprid, acrinathrin, aldicarb, amitraz, acin (-methyl/-ethyl), profenofos, propaphos, propetamphos, phos-methyl, cyfluthrin, carbaryl, cypermethrin, delta prothiofos, prothoate, pyraclofos, pyridaphenthion, pyri methrin, endosulfan, ethoprophos, fenamiphos, fenthion, dathion, quinalphos, Sebufos, Sulfotep, Sulprofos, tebupirim fipronil, imidacloprid, methamidophos, methiocarb, niclosa fos, temephos, terbufos, tetrachlorvinphos, thiometon, tria mide, Oxydemeton-methyl, prothiophos, Silafluofen, thiaclo Zophos, triclorfon, vamidothion, acrinathrin, allethrin (d-cis trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin, prid, thiodicarb, tralomethrin, triazophos, trichlorfon, triflu bioallethrin-5-cyclopentyl-isomer, bioethanomethrin, biop muron, terbufos, fonofos, phorate, chlorpyriphos, ermethrin, bioresmethrin, chlovaporthrin, cis-cypermethrin, carbofuran and tefluthrin. cis-resmethrin, cis-permethrin, clocythrin, cycloprothrin, 0287. Of particular interest are also organophosphates, cyfluthrin, cyhalothrin, cypermethrin (alpha-, beta-, theta-, for example terbufos (CounterR), fonofos (Dyfonate(R). Zeta-), cyphenothrin, deltamethrin, empenthrin (1R-isomer), phorate (Thimet(R), chlorpyriphos (Reldan R), carbamates, esfenvalerate, etofemproX, fenfluthrin, fenpropathrin, fenpy Such as carbofuran (Furadan R), pyrethroid insecticides, rithrin, fenvalerate, flubrocythrinate, flucythrinate, flufen such as tefluthrin (Force(R), deltamethrin (Decis(R) and proX, flumethrin, fluvalinate, fubfenproX, gamma-cyhalo tralomethrin (Scout.R.), and other insecticidal agents having thrin, imiprothrin, kadethrin, lambda-cyhalothrin, a different mechanism of action. metofluthrin, permethrin (cis-, trans-), phenothrin (1R-trans 0288 Preferred insecticides are selected from the group isomer), prallethrin, profluthrin, protrifenbute, pyres consisting of aldicarb, mecarbam, mecurous chloride, methrin, resmethrin, RU 15525, silafluofen, tau-fluvalinate, metam and terbufos. tefluthrin, terallethrin, tetramethrin (-1R-isomer), tralom ethrin, transfluthrin, ZXI 8901, pyrethrins (pyrethrum), 0289 Among the safeners mentioned, those of group DDT, indoxacarb, acetamiprid, clothianidin, dinotefuran, (B1.1) are preferred. Also preferred are the safeners mefen imidacloprid, nitenpyram, nithiazine, thiacloprid, thia pyr-diethyl (B1-1), isoxadifen-ethyl (B4-3), cloquintocet methoxam, nicotine, benSultap, cartap, camphechlor, chlor mexyl (B5-1), benoxacor (B9-1), oxabetrinil (B11-1), flux

US 2007/002 1303 A1 Jan. 25, 2007

cides, miticides, herbicides, fungicides, Safeners, fertilizers wide limits also, and is, for example, in the range from and/or growth regulators, for example in the form of a 1000:1 to 1:1, preferably from 500:1 to 10:1, most prefer finished formulation or tank mixes. The preferred additional ably from 200:1 to 10:1. The amounts of pesticidally active active compounds are herbicides. compound and safener which are optimal in each case depend on the active compound (A) and the Safener (B) in 0329. Also preferred according to the invention are those question and on the type of crops to be treated, and they can combinations in which one or more further active com be determined in each case by appropriate preliminary pounds of a different structure active compounds (C) are experiments. added, such as: 0336 Depending on their properties, the safeners may be (A)+(B)+(C), wherein (C) is one or more other active used for pre-treating the seed of the crop plant (seed dress compounds. ing) or the seedlings, plantlets, bulbs or somatic embryos or 0330 Suitable active compounds (C) which can be com be incorporated into the seed furrow prior to sowing. In the bined with the active compounds according to the invention pretreatment of seedlings it is possible, for example, to spray in mixed formulations or in a tank mix are, for example, the roots or the entire seedling with a solution of the safener known active compounds, for example herbicides, insecti or to dip them into Such a solution. The use of one or more cides and fungicides, preferably herbicides, as described pesticides can then be carried out by the pre-emergence or already above for the compounds (A). post-emergence method. Pesticides such as fungicides or insecticides can often also be applied by seed treatment and 0331 In individual cases, it may be advantageous to can thus also be combined with the safener in the seed combine one or more compounds (A) with a plurality of compounds (B). treatment. 0337 Alternatively, it is possible to apply the safeners 0332 The application rate of the herbicides (A) can be together with the pesticides, before or after emergence of the varied within wide limits, the optimum amount depending plants. Pre-emergence treatment includes both the treatment on the herbicide in question, the spectrum of harmful plants of the area under cultivation prior to Sowing and the treat and the crop plants. In general, the application rate for spray ment of the areas under cultivation where the crops have application is in the range from 0.001 g to 12 kg, preferably been sown but not yet emerged. Preferred is also a sequential 1 g to 3 kg, very particularly 5 g to 2 kg of active compound procedure, where the treatment with safener is carried out (a.i.) per ha, depending on efficacy of the individual com first followed, preferably closely, by application of the pound (A) pesticide. 0333. The amount of safener used varies according to a 0338. In general, simultaneous application of safener and number of parameters including the particular safener pesticide in the form of tank mixes or finish formulations is employed, the crop to be protected, the amount and rate of preferred. Also preferred is the seed treatment with the herbicide applied, the Soil type and climatic conditions safener (B), followed by sowing of the crop and application prevailing. Also, the selection of the specific safener for use of the pesticide (A), preferrably in case of herbicides, during in the method of the invention, the manner in which it is to pre-emergence or post-emergence of the crop. Also pre be applied and the determination of the activity which is ferred is the seed treatment with a combination of the safener non-phytotoxic but antidotally effective, can be readily (B) and a pesticide (A) selected from fungicides and pesti performed in accordance with common practice in the art. cides against harmful animals. The application rate of safener can vary within wide limits 0339 Accordingly, the invention also provides a method and is generally in the range from 0.001 g to 2 kg, preferably for protecting crop plants against phytotoxic side effects of from 0.005 to 1 kg, more preferably from 0.005 g to 500 g a pesticide (A), which method comprises the application of of safener (a.i.) per hectare. For seed treatment the use is, for an amount, acting as an antidote, of one or more Safeners (B) example, from 0.001 g to 1 kg ai. Safener per kg seed, before, after or simultaneously with the pesticide (A) to the preferably 0.05 g to 500 g ai. Safener per kg seed, in plants, parts of plants, plant seeds or the area under culti particular 0.1 g to 250 ga.i. Safener per kg seed. Vation. 0334. If solutions of safener (B) are used for seed dress ing and the seeds or seedlings are wetted with the Solutions, 0340. The pesticide-safener combinations according to the Suitable concentration is generally in the range from 0.1 the invention (i.e. the herbicidal compositions) have excel to 100000 ppm, preferably 1 to 10 000 ppm, more preferably lent pesticidal activity against a broad spectrum of economi from 100 to 1000 ppm, based on the weight. The amounts cally important harmful organisms. and weight ratios required for a successful treatment can be 0341 In case the pesticide (A) is a herbicide the herbi determined by simple preliminary experiments. cidal effects of the combinations aginst weeds are similar to 0335 The pesticidally active compounds and the safeners those of the herbicides (A) when used alone at comparable can be applied together (as finished formulation or by the application rates. tank-mix method) or sequentially in any order. The weight 0342. Owing to their herbicidal and plant growth-regu ratio pesticide (A): safener (B) can vary within wide limits latory properties, the combinations can be employed for and is, for example, in the range from 1:200 to 200:1, controlling harmful plants in known crops or in still to be preferably from 1:100 to 100:1, in particular from 1:20 to developed genetically engineered plants. Transgenic plants 20:1, most preferably from 1:10 to 10:1, preferably when generally have particularly advantageous properties, for applied by the spraying technique in pre-emergence or the example resistance to certain pesticides, above all certain post-emergence application. If the Safener is used in seed herbicides, resistance to plant diseases or causative organ treatment the ratio of pesticide to safener may vary within isms of plant diseases, such as certain insects or microor US 2007/002 1303 A1 Jan. 25, 2007

ganisms such as fungi, bacteria or viruses. Other particular the active compound and as well as a diluent or inert properties relate, for example, to the quantity, quality, Stor Substance, Surfactants of ionic or nonionic type (wetting age-stability, composition and to specific ingredients of the agents, dispersants), for example polyethoxylated alkylphe harvested product. Thus, transgenic plants having an nols, polyethoxylated fatty alcohols, polyethoxylated fatty increased starch content or a modified quality of the starch amines, alkanesulfonates, alkylbenzenesulfonates, sodium or those having a different fatty acid composition of the ligninsulfonate, Sodium 2,2'-dinaphthylmethane-6,6'-disul harvested product are known. fonate, Sodium dibutyinaphthalene-Sulfonate or else sodium 0343. The combinations according to the invention are oleoylmethyltaurinate. preferably employed in economically important transgenic 0350 Emulsifiable concentrates are prepared by dissolv crops of useful and ornamental plants, for example of leeks ing the active compound in an organic solvent, for example and onions. butanol, cyclohexanone, dimethylformamide, Xylene or else 0344) The invention also provides the use of the pesti relatively high-boiling aromatic compounds or hydrocar cidal compositions comprising combinations of (A)+(B) for bons with the addition of one or more surfactants of ionic or controlling harmful organisms, preferably in plant crops. nonionic type (emulsifiers). Examples of emulsifiers which can be used are calcium alkylarylsulfonates, such as Ca 0345 The active compound combinations according to dodecylbenzenesulfonate, or nonionic emulsifiers, such as the invention can be present both as mixed formulations of fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty the two components, if appropriate with other active com alcohol polyglycol ethers, propylene oxide-ethylene oxide pounds, additives and/or customary formulation auxiliaries, condensation products, alkyl polyethers, Sorbitan fatty acid which are then applied in a customary manner diluted with esters, polyoxyethylene Sorbitan fatty acid esters or poly water, or be prepared as so-called tank mixes by joint oxyethylene Sorbitan esters. dilution of the separately formulated or partially separately formulated components with water. 0351 Dusts are obtained by grinding the active com 0346) The compounds (A) and (B) or their combinations pound with finely divided solid substances, for example talc, can be formulated in various ways depending on the pre natural clays, such as kaolin, bentonite and pyrophyllite, or Vailing biological and/or chemico-physical parameters. diatomaceous earth. Examples of suitable formulation options are: wettable 0352 Granules can be prepared either by spraying the powders (WP), emulsifiable concentrates (EC), aqueous active compound onto adsorptive, granulated inert material solutions (SL), emulsions (EW), such as oil-in-water and or by applying active-compound concentrates to the surface water-in-oil emulsions, sprayable Solutions or emulsions, of carriers such as sand, kaolinites or granulated inert oil- or water-based dispersions, Suspoemulsions, dusts (DP). material, by means of adhesive binders, for example poly seed-dressing compositions, granules for broadcasting and vinyl alcohol, Sodium polyacrylate or else mineral oils. soil application, or water-dispersible granules (WG), ULV Suitable active compounds can also be granulated in the formulations, micro-capsules or waxes. manner which is customary for the preparation of fertilizer 0347 The individual formulation types are known in granules, if desired as a mixture with fertilizers. Water principle and are described, for example, in Winnacker dispersible granules are generally prepared by processes Kuchler, “Chemische Technologie'Chemical Technology). Such as spray-drying, fluidized-bed granulation, disk granu Volume 7, C. Hanserverlag Munich, 4th. Edition 1986; van lation, mixing using high-speed mixers, and extrusion with Valkenburg, “Pesticides Formulations’, Marcel Dekker, out solid inert material. N.Y., 1973; K. Martens, “Spray Drying Handbook'', 3rd Ed. 0353. The agrochemical formulations generally contain 1979, G. Goodwin Ltd. London. The necessary formulation from 0.1 to 99% by weight, in particular from 2 to 95% by auxiliaries, such as inert materials, Surfactants, solvents and weight, of active compounds of types A and/or B, the other additives, are likewise known and are described, for following concentrations being customary, depending on the example, in Watkins, “Handbook of Insecticide Dust Dilu type of formulations: In wettable powders the concentration ents and Carriers', 2nd Ed., Darland Books, Caldwell N.J., of active compound is, for example, from about 10 to 95% H. V. Olphen, “Introduction to Clay Colloid Chemistry’; 2nd by weight, the remainder to 100% by weight consisting of Ed., J. Wiley & Sons, N.Y.: C. Marsden, “Solvents Guide': customary formulation constituents. In emulsifiable concen 2nd Ed., Interscience, N.Y. 1950; McCutcheon’s “Deter trates the concentration of active compound can be, for gents and Emulsifiers Annual, MC Publ. Corp., Ridgewood example, from 5 to 80% by weight. N.J.; Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., N.Y. 1964: Schönfeldt, 0354 Formulations in the form of dusts usually contain “Grenzfláchenaktive Athylenoxidaddukte'Surface-active from 5 to 20% by weight of active compound, while ethylene oxide adducts, Wiss. Verlagsgesellschoft, Stuttgart sprayable solutions contain from about 0.2 to 25% by weight 1976: Winnacker-Kuchler, “Chemische Technologie' of active compound. Chemical Technology, Volume 7, C. Hanser Verlag 0355. In the case of granules, such as dispersible gran Munich, 4th Edition 1986. ules, the content of active compound depends partly on 0348 Based on these formulations it is also possible to whether the active compound is in liquid or solid form and produce combinations with other pesticidally active sub on which granulation auxiliaries and fillers that are used. In stances, such as other herbicides, fungicides or insecticides, water-dispersible granules the content is generally between and also with Safeners, fertilizers and/or growth regulators, 10 and 90% by weight. for example in the form of a ready-mix or tank mix. 0356. In addition, said formulations of active compound 0349 Wettable powders are preparations which are uni may comprise the tackifiers, wetting agents, dispersants, formly dispersible in water and which contain, in addition to emulsifiers, preservatives, antifreeze agents and solvents, US 2007/002 1303 A1 Jan. 25, 2007 fillers, colorants and carriers, antifoams, evaporation inhibi 0366 Pelleting and encrustment in which the safener tors, pH and Viscosity regulators, thickeners and/or fertiliz formulations are mixed with or (film) coated on top of the ers which are customary in each case. pellet encrustment. Pelleting and encrustment involve the same processing steps, comprising build-up, drying, and 0357 For use, the formulations, which are in commer size-grading. Seed contained in revolving pans or drums cially available form, are, if appropriate, diluted in a cus of various designs is wetted and a blend of powdered tomary manner, for example using water in the case of materials is progressively added, along with more water wettable powders, emulsifiable concentrates, dispersions or glue, until the desired weight or size increase is and water-dispersible granules. Preparations in the form of reached. Encrustments and pellets distinguish themselves dusts, soil granules, granules for spreading and sprayable by the amount of inert material stuck to the seeds. In solutions are conventionally not diluted any further with encrusted seeds the shape of the seed is still distinguish other inert Substances prior to use. able and the major purpose of the encrustment is weight 0358. The pesticidal compounds can be applied to the increase. Pelleted seeds are typically oval or round and the plants, parts of the plants, seeds of the plants or the area original seed size is no longer distinguishable. The typical under cultivation (tilled soil), preferably to the green plants purpose of pellets is weight increase and a uniform pellets and parts of the plants and, if desired, additionally to the size. Both encrusted and pelleted seeds are used for tilled soil. enhanced sowing characteristics. 0359 A possible use is the joint application of the active 0367. Seed application of safeners can be done on con compounds in the form of tank mixes, where the concen ventional seeds or seeds that have been enhanced by seed trated formulations of the individual active substances, in enhancement technologies Such as steeping and priming the form of their optimal formulations, are mixed jointly (“Enhancing Seed Performance' pp. 255-372, Sheffield with water in the tank, and the resulting spray mixture is Academic Press, Sheffield, UK, 419 pp. ISBN 0-8493-9749 applied. Also preferred is the application of the safener by 9, subsection “Seed Technology and its Biological Basis', seed treatment. Such as seed coating or seed dressing. The ed. Michael Black and J. Derek Bewley, especially chapter treated seed of useful plants can then be used to grow the 9 by Miller MacDonald pp. 287-325). Or the safeners can be respective crop, and the crop is then safened against damage applied to artificial seeds. Such as somatic embryos (see otherwise occurring after application of pesticides to the “Enhancing Seed Performance' mentioned above, subsec crop plants. tion “Seed Technology and its Biological Basis', chapter 10 by David R. Cyr pp. 326-372). 0360 A joint pesticidal formulation of the combination according to the invention of the active compounds (A) and 0368 A further object of the invention are thus seeds or (B) has the advantage that it can be applied more easily seedlings treated with compounds (B) or combinations of because the amounts of the components have already been (A) and (B), e.g. prepared by the techniques mentioned Such adjusted to one another in the correct ratio. Moreover, the as the seed coating or dressing techniques, wherein the seeds auxiliaries of the formulation can be selected to suit each or seedlings are selected from seeds of those plants as other in the best possible way, while a tank mix of various defined above, preferably leek and onion. formulations may result in undesirable combinations of A. GENERAL FORMULATION EXAMPLES auxiliaries. 0369 a) A dust is obtained by mixing 10 parts by weight 0361. Another object of the invention are thus novel of an active compound/active compound mixture and 90 compositions containing (A) and (B). parts by weight of talc as inert Substance and comminuting 0362. When the safeners (B) are applied as a seed treat the mixture in a hammer mill. ment they can be applied by, but not limited to, the seed 0370 b) A wettable powder which is readily dispersible application technologies that are commonly used within the in water is obtained by mixing 25 parts by weight of an seed industry, or a combination thereof, as outlined in the active compound/active compound mixture, 64 parts by book “Enhancing Seed Performance' pp. 255-372, Sheffield weight of kaolin-containing quartz as inert Substance, 10 Academic Press, Sheffield, UK, 419 pp. ISBN 0-8493-9749 parts by weight of potassium lignoSulfonate and 1 part by 9, subsection “Seed Technology and its Biological, ed. weight of sodium oleoylmethyltaurinate as wetting agent Michael Black and J. Derek Bewley, Sheffield Academic and dispersant, and grinding the mixture in a pinned-disk Press, Sheffield, UK, 419 pp. ISBN 0-8493-9749-9, espe mill. cially chapter 8 by Peter Halmer, pp. 257-286. These seed applications technologies are: 0371 c) A dispersion concentrate which is readily dis persible in water is obtained by mixing 20 parts by weight 0363 Applications directly to the seed using formula of an active compound/active compound mixture with 6 tions such as dry powders, Solutions, slurried wettable or parts by weight of alkylphenol polyglycol ether (RTriton X water-dispersible powders, or flowable concentrates 207), 3 parts by weight of isotridecanol polyglycol ether (8 (emulsion or micro-encapsulated formulations) EO) and 71 parts by weight of paraffinic mineral oil (boiling range for example approximately 255 to 277 C.) and 0364 Soaking the seeds in a (aqueous) solution contain grinding the mixture in a ball mill to a fineness of below 5 ing the safener (B) microns. 0365 Film coating in which the safener formulation is 0372 d) An emulsifiable concentrate is obtained from 15 premixed in aqueous Suspension with a binder, adjuvants, parts by weight of an active compound/active compound pigments and opacifiers, and sprayed onto the moving mixture, 75 parts by weight of cyclohexanone as solvent and seeds in a filmcoating equipment 10 parts by weight of ethoxylated nonylphenol as emulsifier. US 2007/002 1303 A1 Jan. 25, 2007

0373) e) Water-dispersible granules are obtained by mix ment—a tank-mix of the herbicide and a safener (using same ing basic formulation in each case) was applied to the green 0374 75 parts by weight of an active compound/active parts of the plants and the uncovered part of the soil surface compound mixture, with a spray bar using a water application rate of 300 liters per hectare. 0375) 10 parts by weight of calcium lignoSulfonate, 0376 5 parts by weight of sodium lauryl sulfate, 0390 The pots were placed in a greenhouse under favor able growth conditions. Visual scoring of the herbicidal 0377 3 parts by weight of polyvinyl alcohol and action was carried out 21 or 40 days after treatment with the 0378 7 parts by weight of kaolin, herbicide or the tank-mix, respectively. Evaluation was carried out on a percentage basis by comparison with grinding the mixture in a pinned-disk mill and granulating the powder in a fluidized bed by spraying on water as untreated control plants (0%=no noticeable effect compared granulation liquid. with the untreated plant, 100%=treated plant dies). The results are summarized in the table 1 below. 0379 f) Water-dispersible granules are also obtained by homogenizing and precomminuting, in a colloid mill, TABLE 1. 0380 25 parts by weight of an active compound/active Post-emergence application of leek compound mixture, Application 0381 5 parts by weight of sodium 2,2'-dinaphthyl Active rate Scoring Damage to leek (in 90 methane-6,6'-disulfonate, ingredients ga.i./hal DAT variety Kenton variety Harston 0382 2 parts by weight of sodium oleoylmethyltaurinate, H1 600 40 55% 40% 0383) 1 part by weight of polyvinyl alcohol, H1 - S1 600 + 100 40 10% 10% H1 - S2 600 + 100 40 10% 10% 0384) 17 parts by weight of calcium carbonate and H2 250 40 20% 20% H2 - S1 2SO - 1 OO 40 O% O% 0385) 50 parts by weight of water, H2 + S2 2SO - 1 OO 40 O% O% H3 50 40 45% SO% Subsequently grinding the mixture in a bead mill and atom H3 - S1 SO - 100 40 O% O% izing and drying the resulting Suspension in a spray tower H4 50 21 SO% SO% by means of a single-substance nozzle. H4 - S1 SO - 100 21 O% 10% Abbreviations in Table 1: B. BIOLOGICAL, EXAMPLES H1 = ioxynil H2 = linuron 0386 The following non-limiting Examples illustrate the H3 = mesosulfuron (Oder mesosulfuron-methyl) invention. H4 = foramsulfuron S1 = mefenpyr-diethyl 1. Herbicide and Safener Pre-Emergence Application by the S2 = isoxadifen-ethyl Tank Mix Method DAT = days after treatment a.i. = active ingredient (calculated on 100% active ingredient) 0387 Seeds of various vegetable crop plants and weed species were sown in Sandy loam soil in round plastic pots of a diameter of 13 cm and covered with a layer of sandy 3. Post-Emergence Application of Herbicide and Safener by loam of a thickness of about 1 cm. Herbicides and safeners the Tank Mix Method. in the form of liquid (for example emulsion concentrates) or dry (for example water-dispersible powders) formulations 0391) Seeds of onion plants were sown in sandy loam soil were diluted with deionized water to the required concen in round plastic pots of a diameter of 7 cm and covered with tration and applied to the surface of the soil with a spray bar a layer of sandy loam of a thickness of about 0.2 cm. The using a water application rate of 300 liters per hectare. pots were placed in a greenhouse under favorable growth 0388. The pots were placed in a greenhouse under favor conditions for until the plants had reached the 2-leaves able growth conditions. Visual scoring of the herbicidal growth stage. Then, a herbicide or in a parallel experi action was carried out four weeks after the herbicide appli ment—a tank-mix of the herbicide and a safener (using same cation. Evaluation was carried out on a percentage basis by basic formulation in each case) was applied to the green comparison with untreated control plants (0%=no noticeable parts of the plants and the uncovered part of the soil surface effect compared with the untreated plant, 100%=treated with a spray bar using a water application rate of 300 liters plant dies). per hectare. 2. Post-Emergence Application of Herbicide and Safener by 0392 The pots were placed in a greenhouse under favor the Tank Mix Method. able growth conditions. Visual scoring of the herbicidal 0389. Seeds of leek plants were sown in sandy loam soil action was carried out 21 or 40 days after treatment with the in round plastic pots of a diameter of 7 cm and covered with herbicide or the tank-mix, respectively. Evaluation was a layer of sandy loam of a thickness of about 0.2 cm. The carried out on a percentage basis by comparison with pots were placed in a greenhouse under favorable growth untreated control plants (0%=no noticeable effect compared conditions for until the plants had reached the 2-leaves with the untreated plant, 100%=treated plant dies). The growth stage. Then, a herbicide or in a parallel experi results are summarized in the table 2 below. US 2007/002 1303 A1 Jan. 25, 2007 18

TABLE 2 TABLE 3 Seed treatment of leek with safener, early post-emergence Post-emergence application of onion application of herbicide (encrustment method Active Application rate Application time Damage to leek Damage to onion (in 96) ingredients ga.i./hal after seeding (in %) 6 DAT Active Application rate Scoring variety Blanco variety H 1200 9 days 52% ST - H ST1 - 1200 9 days 26% ingredients gai?ha DAT Duro Brioso ST - H ST2 - 1200 9 days 2%

Abbreviations in Table 3: H1 600 21 55% 45% H = herbicide ioxynil H1 - S1 600 + 100 40 20% O% ST = seed treatment with mefenpyr-diethyl H2 250 40 100% 30% ST1 = seed treatment of leek seed with 0.4 ga.i./kg mefenpyr-diethyl ST2 = seed treatment of leek seed with 2 ga.i./kg mefenpyr-diethyl H2 + S2 2SO - 1 OO 40 40% 10% DAT = days after treatment H3 50 40 70% SO% H3 - S1 SO - 100 40 20% 5. Seed Treatment of Onion with Safener Followed by Early H3 - S2 SO - 100 40 30% Post-Emergence Treatment with Herbicide H4 50 21 10% 30% Materials and Methods H4 - S1 SO - 100 21 O% 10% 0397 Onion (Allium cepa var. Brioso) seeds were Abbreviations in Table 2: encrusted in a commercial seed coating machine. Approxi mately 1 ml of binder was added. Subsequently, a small 1 = ioxynil amount of encrustment powder (X % Naphthalic Anhy H2 = linuron dride+100-X% inert filler material) was added. Binder 3 = mesosulfuron-methyl was added again and this procedure was repeated until all 4 = foramsulfuron encrustment powder was stuck to the seeds. Seeds were S1 = mefenpyr-diethyl dried subsequently. S2 = isoxadifen-ethyl 0398. The differently-treated seeds were sown in trays. DAT = days after treatment After 9 days, the seedlings were sprayed with 1.0 g/l ioxynil a.i. = active ingredient (calculated on 100% active ingredient) using an atomizer. A dosage of 3 ml per tray was applied, equalizing 300 g.a.i./hectare. At 3 days after spraying the 4. Seed Treatment of Leek with Safener Followed by Early number of collapsed seedlings was counted. Post-Emergence Treatment with Herbicide Results Materials and Methods 0399. Severe symptoms were observed after 3 days already. Almost 60% of the control-treated seedlings had 0393 Leek (allium porrum var. Parton) seeds were put in collapsed, whereas all naphthalic anhydride-treated seed an erlenmeyer flask with a spinning stirring magnet. A lings showed significantly less damage (see Table 4). droplet of binder (glue) was added and distributed evenly amongst the seeds. Subsequently, a Small amount of encrust TABLE 4 ment powder (X% mefenpyr-diethyl--100-X% inert filler material) was added and mixed through the seeds using the Seed treatment of onion with Safener, early post-emergence stirring magnet. A droplet of binder was added again and this application of herbicide (encrustment with rotostat procedure was repeated until all encrustment powder was Active Application rate Application time Damage to onion stuck to the seeds. Seeds were dried subsequently. ingredients ga.i./hal after seeding (in %) 3 DAT H 300 9 days 57% 0394 The differently-treated seeds were sown in trays. ST - H ST1 - 300 9 days 39% After 9 days, the seedlings were sprayed with 4.0 g/l ioxynil ST - H ST2 - 300 9 days 26% using an atomizer. A dosage of 3 ml per tray was applied, Abbreviations in Table 4: equalizing 1200 g.a.i./hectare. At 6 days after spraying the H = herbicide ioxynil ST = seed treatment number of collapsed seedlings was counted. ST1 = Seed treatment of Onion seed with 10 ga.i./kg naphthalic anhydride ST2 = seed treatment of Onion seedwith 50 ga.i./kg naphthalic anhydride Results DAT = days after treatment 0395. At 6 days after application, more than 50% of the control-treated seedlings were collapsed, whereas the 6. Seed Treatment of Leek with Safener Followed by Early mefenpyr-treated seedlings showed significantly less dam Post-Emergence Treatment with Herbicide age. Materials and Methods 0396 The results are summarized in Table 3. Similar 04.00 Leek (allium porrum var. Shelton) seeds were results were found with another leek variety (i.e. Shelton). coated in a commercial seed coating machine. Gradually, US 2007/002 1303 A1 Jan. 25, 2007

binder solution with X g of mefenpyr-diethyl was added. evaluated as described in Example 6 with the difference that Seeds were dried subsequently. the herbicide is prometryn. Details of application rate, 04.01 The differently-treated seeds were sown in the field application time and results are set forth in table 7 below. using commercial Sowing equipment. After 25 days, the seedlings were sprayed with a standard formulation of TABLE 7 ioxynil (RTotril) at an application rate of 112 ga.i./ha ioxynil. At 15 days after spraying the number of collapsed Fluxofenin Safening oxynil damage in leek seedlings was counted. Application Damage Safener rate application time to seedling Results ga.i./kg of herbicide H after seeding (% collapsed) Variety seed ga.i./hal days at SDAT 0402. The percentage collapsed control-treated plants in the field was approximately 6% at 15 days after herbicide Shelton O 112 10 16 application (see Table 5). Application of the highest rate of Shelton 1 112 10 10 mefenpyr-diethyl (2.0 g.a.i./kg) significantly reduced the Shelton 2 112 10 6 amount of damage (see Table 5). Abbreviations in Table 7: H = herbicide ioxynil (used as standard formulation (R) Totril) Safener = fluxofenim TABLE 5 DAT = days after treatment Seed treatment of leek with safener, early post-emergence application of herbicide (Seed coating with rotostat System 9. Seed Treatment of Leek with Safener Followed by Early Active Application rate Application time Damage to leek Post-Emergence Treatment with Herbicide ingredients ga.i./hal after seeding (in %) 15 DAT 04.05 Leek seeds (allium porrum, var. Shelton) were H 112 25 days 6% ST - H ST1 - 112 25 days 6% treated with safener, sown, treated with a herbicide and ST - H ST2 - 112 25 days 4.7% evaluated as described in Example 6 with the difference that ST - H ST3 - 112 25 days 1.2% the herbicide is prometryn. Details of application rate, Abbreviations in Table 5: application time and results are set forth in table 8 below. H = herbicide ioxynil ST = seed treatment with mefenpyr-diethyl TABLE 8 ST1 = seed treatment of leek seed with 0.4 ga.i./kg mefenpyr-diethyl ST2 = seed treatment of leek seed with 1.0 ga.i./kg mefenpyr-diethyl Oxabetrinil Safening oxynil damage in leek ST3 = seed treatment of leek seed with 2.0 ga.i./kg mefenpyr-diethyl DAT = days after treatment Application Damage Safener rate application time to seedling ga.i./kg of herbicide H after seeding (% collapsed) 7. Seed Treatment of Leek with Safener Followed by Early Variety seed ga.i./hal days at 7 DAT Post-Emergence Treatment with Herbicide Shelton O 112 10 45 0403 Leek seeds (allium porrum, var. Shelton or Parton) Shelton 1 112 10 25 were treated with safener, sown, treated with a herbicide and Shelton 2 112 10 27 evaluated as described in Example 6 with the difference that Shelton 4 112 10 13 the herbicide is prometryn. Details of application rate, Abbreviations in Table 8: application time and results are set forth in table 6 below. H = herbicide ioxynil (used as standard formulation (R) Totril) Safener = oxabetrinil TABLE 6 DAT = days after treatment Mefenpyr safening Prometryn damage in leek 10. Seed Treatment of Onion with Safener Followed by Application Damage Early Post-Emergence Treatment with Herbicide Safener rate application time to seedling ga.i./kg of herbicide H5 after seeding (% collapsed) 0406) Onion (Allium cepa var. Diamante) were treated Variety seed ga.i./hal days at 6 DAT with safener, sown, treated with a herbicide and evaluated as Shelton O 750 10 11 described in Example 5 with the difference that the herbicide Shelton 1 750 10 2 is oxyfluorfen and the safener is mefenpyr-diethyl. Details of Shelton 2 750 10 1 application rate, application time and results are set forth in Parton O 750 10 9 Parton 1 750 10 3 table 9 below. Parton 2 750 10 1 TABLE 9 Abbreviations in Table 6: H5 = herbicide prometryn (used as standard formulation (R) Gesagard) Mefenpyr Safening oxyfluorfen damage in onion Safener = mefenpyr-diethyl DAT = days after treatment Application application Damage Safener rate time to seedling ga.i./kg of herbicide H6 after seeding (% collapsed) 8. Seed Treatment of Leek with Safener Followed by Early Variety seed ga.i./hal days at SDAT Post-Emergence Treatment with Herbicide Diamante O 7.5 9 83 0404 Leek seeds (allium porrum, var. Shelton) were Diamante 2 7.5 9 64 treated with safener, sown, treated with a herbicide and US 2007/002 1303 A1 Jan. 25, 2007 20

(B5) compounds of the 8-quinolinoxyacetic acid type, TABLE 9-continued (B6) compounds of the (5-chloro-8-quinolinoxy)malonic Mefenpyr Safening oxyfluorfen damage in onion acid type, Application application Damage (B7) active substances of the phenoxyacetic or phenox Safener rate time to seedling ypropionic acid derivatives type or of the aromatic ga.i./kg of herbicide H6 after seeding (% collapsed) carboxylic acids type, Variety seed ga.i./hal days at SDAT (B8) active substances of the pyrimidines type, Diamante 4 7.5 9 49 Diamante 8 7.5 9 39 (B9) active substances of the dichloroacetamides type, Abbreviations in Table 9: (B10) active substances of the dichloroacetone deriva H6 = herbicide oxyfluorfen (used as standard formulation (R) Goal) tives type, Safener = mefenpyr-diethyl DAT = days after treatment (B11) active Substances of the oxyimino compounds type, (B12) active substances of the thiazolecarboxylic ester 11. Seed Treatment of Onion with Safener Followed by type, Early Post-Emergence Treatment with Herbicide (B13) active substances of the naphthalenedicarboxylic 0407 Onion (Allium cepa var. Diamante) were treated acid derivatives type, with safener, sown, treated with a herbicide and evaluated as described in Example 5 with the difference that the herbicide (B14) active substances of the chromanacetic acid deriva is bromoxynil-octanoate and the safener is benoxacor. tives type, Details of application rate, application time and results are (B15) active substances which, in addition to a herbicidal set forth in table 10 below. action against harmful plants, also exhibit a safener action in connection with crop plants, TABLE 10 (B16) N-acylsulfonamides of the formula (S3) and their Benoxacor safening bronoxynil damage in onion salts Application application Damage Safener rate time to seedling ga.i./kg of herbicide H7 after seeding (% collapsed) (S3) Variety seed ga.i./hal days at SDAT R2 O R. O 5 Diamante O 25 10 19 o y- (R)m Diamante 1 25 10 7 Diamante 2 25 10 O \ / o O Abbreviations in Table 10: O (R), H7 = herbicide bromoxynil-octanoate (used as standard formulation (R) Buctril) Safener = benoxacor DAT = days after treatment (B17) acylsulfamoylbenzamides of the formula (S4), if appropriate also in Salt form,

What is claimed is: (S4) 1. A method for reducing or avoiding phytotoxic side effects of a pesticide (A) in useful plants selected from the R O O O plant order Liliflorae, which comprises application of an N-G V 1s effective amount of a compound (B) as a safener before, (R) after or simultaneously with the application of the pesticide k & it X - (A) to the plants, part of the plants, plant seeds or the area (R), under cultivation, wherein (A) is one or more pesticides or agriculturally acceptable (B18) dietholate, and salts thereof, and (B19) mephenate, (B) is one or more Safeners selected from the group consisting of or salts of the compounds mentioned. 2. The method as claimed in claim 1, characterized by a (B1) compounds of the dichlorophenylpyrazoline-3-car compound (B) being one or more Safeners selected from the boxylic acid type, group consisting of mefenpyr-diethyl, fenchlorazol-ethyl, isoxadifen-ethyl, cloquintocet-mexyl, fenclorim, dichlor (B2) dichlorophenylpyrazolecarboxylic acid derivatives, mid, R-29148, benoxacor, PPG-1292, DK-24, AD-67, MON (B3) compounds of the triazolecarboxylic acids type, 4660, diclonon, BAS145138, LAB 145138, furilaZol, MG 191, oxabetrinil, fluxofenim, cyometrinil, flurazole, naph (B4) compounds of the 5-benzyl- or 5-phenyl-2-isoxazo thalic anhydride, CL 304415, dimepiperate, daimuron, line-3-carboxylic acid type or the 5,5-diphenyl-2-isox cumyluron, methoxyphenone, Safeners of the group of acyl aZoline-3-carboxylic acid, sulfamoylbenzamides, CSB, dietholate and mephenate. US 2007/002 1303 A1 Jan. 25, 2007

3. The method as claimed in claim 1, characterized by a 10. The method as claimed in claim 9, characterized by compound (B) being one or more Safeners selected from the the ratio of pesticide (A) and safener (B) being in a weight group consisting of mefenpyr-diethyl, fenchlorazol-ethyl, ratio of from 1000:1 to 1:1, isoxadifen-ethyl, cloquintocet-mexyl, fenclorim, dichlor 11. A method as claimed in claim 1 characterized by the mid, benoxacor, AD-67, furilazole, oxabetrinil, fluxofenim, crop plant being onion. cyometrinil, flurazole, naphthalic anhydride, dimepiperate, 12. A method for selective control of harmful organisms daimuron, cumyluron, methoxyphenone and Safeners of the in useful plants selected from the plant order Liliiflorae group of acylsulfamoylbenzamides. which comprises applying a pesticidally effective amount of 4. The method as claimed in any of claim 1, characterized one or more pesticides (A) and an crop-safening effective by the compound (A) being selected from the group con amount of one or more safeners (B) before, after or simul sisting of chloroacetic acid, chlorpropham, chlorthaldim taneous with the application of pesticide (A) to the plants, ethyl, clopyralid, cyanamide, ethofumesate, foramsulfuron, parts of plants, plant seeds or the area under cultivation, haloxyfop, haloxyfop-P hydroxybenzonitrils, isoxaben, pesticide (A) and safener (B) and plants being defined as in linuron, mesosulfuron, metaZachlor, methabenzthiazuron, claim 1. metribuzin, monolinuron, oxadiazon, oxyfluorfen, paraquat 13. Seed of useful plants selected from the plant order dichloride, pendimethalin, prometryn, propachlor, prop Liliflorae, characterized by the seed being treated with an isochlor, Sethoxydim, simazine and trifluralin. effective crop-safening amount of one or more safeners (B) 5. The method as claimed in claim 1, characterized by the as defined in claim 1. crop plant being selected from the group consisting of plant 14. Seed as claimed in claim 13, characterized by the seed families Liliaceae, Amaryllidaceae, Iridaceae and being treated according to a technique selected from seed Juncadeae. dressing, seed coating, seed soaking, seed pelleting and seed 6. The method as claimed in claim 1, characterized by the crop plant being leek. encrusment. 7. The method as claimed in claim 1, characterized by a 15. Seed as claimed in claim 13, characterized by the crop safener selected from the group consisting of mefenpyr plant being leek. diethyl, isoxadifen-ethyl, cloquintocet-mexyl, naphthalic 16. Seed as claimed in claim 13, characterized by the crop anhydride, benoxacor, oxabetrinil, fluxofenim and Safeners plant being onion. of the group of acylsulfamoylbenzamides. 17. Process for preparing seeds as defined in claim 13, 8. The method as claimed in claim 1, characterized by the characterized in that seeds of useful plants selected from the ratio of pesticide (A) and safener (B) being in a weight ratio plant order Liliflorae are treated with an effective crop of from 200:1 to 1:200. safening amount of one or more Safeners (B). 9. The method as claimed in claim 1, characterized by seed treatment of the crop seed with safener (B). k k k k k