CA2085148A1 - Combination of als inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agents - Google Patents
Combination of als inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agentsInfo
- Publication number
- CA2085148A1 CA2085148A1 CA 2085148 CA2085148A CA2085148A1 CA 2085148 A1 CA2085148 A1 CA 2085148A1 CA 2085148 CA2085148 CA 2085148 CA 2085148 A CA2085148 A CA 2085148A CA 2085148 A1 CA2085148 A1 CA 2085148A1
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- alkoxy
- hydrogen
- halogen
- radicals
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000002917 insecticide Substances 0.000 title claims abstract description 27
- 239000003112 inhibitor Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000003223 protective agent Substances 0.000 title abstract description 4
- 239000004009 herbicide Substances 0.000 claims abstract description 65
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 230000002363 herbicidal effect Effects 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 244000038559 crop plants Species 0.000 claims abstract description 16
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical class OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229940100389 Sulfonylurea Drugs 0.000 claims abstract description 6
- CAAMSDWKXXPUJR-UHFFFAOYSA-N 3,5-dihydro-4H-imidazol-4-one Chemical compound O=C1CNC=N1 CAAMSDWKXXPUJR-UHFFFAOYSA-N 0.000 claims abstract description 5
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims abstract description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims description 73
- 229910052739 hydrogen Inorganic materials 0.000 claims description 73
- 150000002431 hydrogen Chemical class 0.000 claims description 57
- 229910052736 halogen Inorganic materials 0.000 claims description 53
- 150000002367 halogens Chemical class 0.000 claims description 53
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 42
- -1 C3-C12-cycloalkyl Chemical group 0.000 claims description 41
- 239000013543 active substance Substances 0.000 claims description 33
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 31
- 150000003254 radicals Chemical class 0.000 claims description 31
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 20
- XLNZEKHULJKQBA-UHFFFAOYSA-N terbufos Chemical compound CCOP(=S)(OCC)SCSC(C)(C)C XLNZEKHULJKQBA-UHFFFAOYSA-N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 240000008042 Zea mays Species 0.000 claims description 15
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims description 14
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 14
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 14
- 235000009973 maize Nutrition 0.000 claims description 14
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 241000196324 Embryophyta Species 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 7
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 7
- 125000004769 (C1-C4) alkylsulfonyl group Chemical group 0.000 claims description 6
- UPMXNNIRAGDFEH-UHFFFAOYSA-N 3,5-dibromo-4-hydroxybenzonitrile Chemical compound OC1=C(Br)C=C(C#N)C=C1Br UPMXNNIRAGDFEH-UHFFFAOYSA-N 0.000 claims description 6
- 239000005476 Bentazone Substances 0.000 claims description 6
- 239000005489 Bromoxynil Substances 0.000 claims description 6
- 239000005586 Nicosulfuron Substances 0.000 claims description 6
- ZOMSMJKLGFBRBS-UHFFFAOYSA-N bentazone Chemical compound C1=CC=C2NS(=O)(=O)N(C(C)C)C(=O)C2=C1 ZOMSMJKLGFBRBS-UHFFFAOYSA-N 0.000 claims description 6
- CNBGNNVCVSKAQZ-UHFFFAOYSA-N benzidamine Natural products C12=CC=CC=C2C(OCCCN(C)C)=NN1CC1=CC=CC=C1 CNBGNNVCVSKAQZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001188 haloalkyl group Chemical group 0.000 claims description 6
- RTCOGUMHFFWOJV-UHFFFAOYSA-N nicosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CN=2)C(=O)N(C)C)=N1 RTCOGUMHFFWOJV-UHFFFAOYSA-N 0.000 claims description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- JCXJVPUVTGWSNB-UHFFFAOYSA-N Nitrogen dioxide Chemical group O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 5
- 239000000729 antidote Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000004094 surface-active agent Substances 0.000 claims description 5
- 125000005208 trialkylammonium group Chemical group 0.000 claims description 5
- 125000004767 (C1-C4) haloalkoxy group Chemical group 0.000 claims description 4
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 claims description 4
- 125000006650 (C2-C4) alkynyl group Chemical group 0.000 claims description 4
- 125000004648 C2-C8 alkenyl group Chemical group 0.000 claims description 4
- 125000004649 C2-C8 alkynyl group Chemical group 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- MZZBPDKVEFVLFF-UHFFFAOYSA-N cyanazine Chemical compound CCNC1=NC(Cl)=NC(NC(C)(C)C#N)=N1 MZZBPDKVEFVLFF-UHFFFAOYSA-N 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- MEFOUWRMVYJCQC-UHFFFAOYSA-N rimsulfuron Chemical compound CCS(=O)(=O)C1=CC=CN=C1S(=O)(=O)NC(=O)NC1=NC(OC)=CC(OC)=N1 MEFOUWRMVYJCQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 125000006766 (C2-C6) alkynyloxy group Chemical group 0.000 claims description 3
- RFEBDZANCVHDLP-UHFFFAOYSA-N 3-[(4-cyanophenyl)methylamino]-6-(trifluoromethyl)quinoxaline-2-carboxylic acid Chemical compound OC(=O)C1=NC2=CC=C(C(F)(F)F)C=C2N=C1NCC1=CC=C(C#N)C=C1 RFEBDZANCVHDLP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004399 C1-C4 alkenyl group Chemical group 0.000 claims description 3
- 229910003827 NRaRb Inorganic materials 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- KVGLBTYUCJYMND-UHFFFAOYSA-N fonofos Chemical compound CCOP(=S)(CC)SC1=CC=CC=C1 KVGLBTYUCJYMND-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- BULVZWIRKLYCBC-UHFFFAOYSA-N phorate Chemical compound CCOP(=S)(OCC)SCSCC BULVZWIRKLYCBC-UHFFFAOYSA-N 0.000 claims description 3
- 230000000885 phytotoxic effect Effects 0.000 claims description 3
- 150000003918 triazines Chemical class 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 125000004455 (C1-C3) alkylthio group Chemical group 0.000 claims description 2
- 125000006677 (C1-C3) haloalkoxy group Chemical group 0.000 claims description 2
- 125000004191 (C1-C6) alkoxy group Chemical group 0.000 claims description 2
- 125000004793 2,2,2-trifluoroethoxy group Chemical group FC(CO*)(F)F 0.000 claims description 2
- YQTCQNIPQMJNTI-UHFFFAOYSA-N 2,2-dimethylpropan-1-one Chemical group CC(C)(C)[C]=O YQTCQNIPQMJNTI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003666 Amidosulfuron Substances 0.000 claims description 2
- CTTHWASMBLQOFR-UHFFFAOYSA-N Amidosulfuron Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)N(C)S(C)(=O)=O)=N1 CTTHWASMBLQOFR-UHFFFAOYSA-N 0.000 claims description 2
- ZOUTYVWHWSUKPL-NOZJJQNGSA-N C[C@H](CS)C(=O)N[C@H](Cc1c[nH]c2ccccc12)C(O)=O Chemical compound C[C@H](CS)C(=O)N[C@H](Cc1c[nH]c2ccccc12)C(O)=O ZOUTYVWHWSUKPL-NOZJJQNGSA-N 0.000 claims description 2
- 239000005944 Chlorpyrifos Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- 125000005160 aryl oxy alkyl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005046 dihydronaphthyl group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000001624 naphthyl group Chemical group 0.000 claims description 2
- 231100000208 phytotoxic Toxicity 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000006413 ring segment Chemical group 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- AHTPATJNIAFOLR-UHFFFAOYSA-N thifensulfuron-methyl Chemical group S1C=CC(S(=O)(=O)NC(=O)NC=2N=C(OC)N=C(C)N=2)=C1C(=O)OC AHTPATJNIAFOLR-UHFFFAOYSA-N 0.000 claims description 2
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims 18
- FRZNJFWQVYAVCE-UHFFFAOYSA-N 1-[5-tert-butyl-2-(4-methylphenyl)pyrazol-3-yl]-3-[4-(2-morpholin-4-ylethoxy)phenyl]urea Chemical compound C1=CC(C)=CC=C1N1C(NC(=O)NC=2C=CC(OCCN3CCOCC3)=CC=2)=CC(C(C)(C)C)=N1 FRZNJFWQVYAVCE-UHFFFAOYSA-N 0.000 claims 2
- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 claims 2
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 125000000171 (C1-C6) haloalkyl group Chemical group 0.000 claims 1
- 239000005631 2,4-Dichlorophenoxyacetic acid Substances 0.000 claims 1
- XTFNPKDYCLFGPV-OMCISZLKSA-N Bromofenoxim Chemical compound C1=C(Br)C(O)=C(Br)C=C1\C=N\OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O XTFNPKDYCLFGPV-OMCISZLKSA-N 0.000 claims 1
- 125000003320 C2-C6 alkenyloxy group Chemical group 0.000 claims 1
- 239000005504 Dicamba Substances 0.000 claims 1
- FMGZEUWROYGLAY-UHFFFAOYSA-N Halosulfuron-methyl Chemical compound ClC1=NN(C)C(S(=O)(=O)NC(=O)NC=2N=C(OC)C=C(OC)N=2)=C1C(=O)OC FMGZEUWROYGLAY-UHFFFAOYSA-N 0.000 claims 1
- 239000005606 Pyridate Substances 0.000 claims 1
- JTZCTMAVMHRNTR-UHFFFAOYSA-N Pyridate Chemical compound CCCCCCCCSC(=O)OC1=CC(Cl)=NN=C1C1=CC=CC=C1 JTZCTMAVMHRNTR-UHFFFAOYSA-N 0.000 claims 1
- 125000004466 alkoxycarbonylamino group Chemical group 0.000 claims 1
- IWEDIXLBFLAXBO-UHFFFAOYSA-N dicamba Chemical compound COC1=C(Cl)C=CC(Cl)=C1C(O)=O IWEDIXLBFLAXBO-UHFFFAOYSA-N 0.000 claims 1
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 claims 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims 1
- ZTMKADLOSYKWCA-UHFFFAOYSA-N lenacil Chemical compound O=C1NC=2CCCC=2C(=O)N1C1CCCCC1 ZTMKADLOSYKWCA-UHFFFAOYSA-N 0.000 claims 1
- ZTYVMAQSHCZXLF-UHFFFAOYSA-N methyl 2-[[4,6-bis(difluoromethoxy)pyrimidin-2-yl]carbamoylsulfamoyl]benzoate Chemical group COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(OC(F)F)=CC(OC(F)F)=N1 ZTYVMAQSHCZXLF-UHFFFAOYSA-N 0.000 claims 1
- 230000006378 damage Effects 0.000 abstract description 10
- 239000011814 protection agent Substances 0.000 abstract description 6
- 229940000425 combination drug Drugs 0.000 abstract 1
- 230000007246 mechanism Effects 0.000 abstract 1
- 239000008187 granular material Substances 0.000 description 17
- 238000009472 formulation Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- GPGLBXMQFQQXDV-UHFFFAOYSA-N Primisulfuron Chemical compound OC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(OC(F)F)=CC(OC(F)F)=N1 GPGLBXMQFQQXDV-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 239000004495 emulsifiable concentrate Substances 0.000 description 6
- 239000003995 emulsifying agent Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000080 wetting agent Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 229920000151 polyglycol Polymers 0.000 description 5
- 239000010695 polyglycol Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002191 fatty alcohols Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 229940075522 antidotes Drugs 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000010410 dusting Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
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- 239000000047 product Substances 0.000 description 3
- 238000009331 sowing Methods 0.000 description 3
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- RXCPQSJAVKGONC-UHFFFAOYSA-N Flumetsulam Chemical compound N1=C2N=C(C)C=CN2N=C1S(=O)(=O)NC1=C(F)C=CC=C1F RXCPQSJAVKGONC-UHFFFAOYSA-N 0.000 description 2
- 240000005979 Hordeum vulgare Species 0.000 description 2
- 235000007340 Hordeum vulgare Nutrition 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- OWZREIFADZCYQD-NSHGMRRFSA-N deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000000749 insecticidal effect Effects 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002728 pyrethroid Substances 0.000 description 2
- 150000003230 pyrimidines Chemical class 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 230000009528 severe injury Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000004562 water dispersible granule Substances 0.000 description 2
- ZFHGXWPMULPQSE-SZGBIDFHSA-N (Z)-(1S)-cis-tefluthrin Chemical compound FC1=C(F)C(C)=C(F)C(F)=C1COC(=O)[C@@H]1C(C)(C)[C@@H]1\C=C(/Cl)C(F)(F)F ZFHGXWPMULPQSE-SZGBIDFHSA-N 0.000 description 1
- HKELWJONQIFBPO-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-5-(trichloromethyl)-1,2,4-triazole-3-carboxylic acid Chemical compound N1=C(C(=O)O)N=C(C(Cl)(Cl)Cl)N1C1=CC=C(Cl)C=C1Cl HKELWJONQIFBPO-UHFFFAOYSA-N 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- 125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- GTODOEDLCNTSLG-UHFFFAOYSA-N 2h-triazole-4-carboxylic acid Chemical compound OC(=O)C1=CNN=N1 GTODOEDLCNTSLG-UHFFFAOYSA-N 0.000 description 1
- 125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 description 1
- WVQFVFHYUXCSBD-UHFFFAOYSA-N 4-(2,3-dichlorophenyl)-1h-pyrazole-5-carboxylic acid Chemical class N1N=CC(C=2C(=C(Cl)C=CC=2)Cl)=C1C(=O)O WVQFVFHYUXCSBD-UHFFFAOYSA-N 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 108010000700 Acetolactate synthase Proteins 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- QDQRXAIFVSGJTJ-UHFFFAOYSA-N ClC1(C(C(=NO1)C(=O)O)CC1=CC=CC=C1)Cl Chemical compound ClC1(C(C(=NO1)C(=O)O)CC1=CC=CC=C1)Cl QDQRXAIFVSGJTJ-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000005892 Deltamethrin Substances 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- JNCMHMUGTWEVOZ-UHFFFAOYSA-N F[CH]F Chemical compound F[CH]F JNCMHMUGTWEVOZ-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 108010081348 HRT1 protein Hairy Proteins 0.000 description 1
- 102100021881 Hairy/enhancer-of-split related with YRPW motif protein 1 Human genes 0.000 description 1
- 239000005981 Imazaquin Substances 0.000 description 1
- XVOKUMIPKHGGTN-UHFFFAOYSA-N Imazethapyr Chemical compound OC(=O)C1=CC(CC)=CN=C1C1=NC(C)(C(C)C)C(=O)N1 XVOKUMIPKHGGTN-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000209504 Poaceae Species 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000005616 Rimsulfuron Substances 0.000 description 1
- 235000007238 Secale cereale Nutrition 0.000 description 1
- 244000082988 Secale cereale Species 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000005939 Tefluthrin Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000005133 alkynyloxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HRBKVYFZANMGRE-UHFFFAOYSA-N chlorpyrifos-methyl Chemical compound COP(=S)(OC)OC1=NC(Cl)=C(Cl)C=C1Cl HRBKVYFZANMGRE-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- ICJSJAJWTWPSBD-UHFFFAOYSA-N cloquintocet Chemical compound C1=CN=C2C(OCC(=O)O)=CC=C(Cl)C2=C1 ICJSJAJWTWPSBD-UHFFFAOYSA-N 0.000 description 1
- 239000007931 coated granule Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229960002483 decamethrin Drugs 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- ZJULYDCRWUEPTK-UHFFFAOYSA-N dichloromethyl Chemical compound Cl[CH]Cl ZJULYDCRWUEPTK-UHFFFAOYSA-N 0.000 description 1
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- XQTFGOSTLPHBRA-UHFFFAOYSA-N ethyl 1-(2,4-dichlorophenyl)-5-propan-2-ylpyrazole-3-carboxylate Chemical compound N1=C(C(=O)OCC)C=C(C(C)C)N1C1=CC=C(Cl)C=C1Cl XQTFGOSTLPHBRA-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- VUWZPRWSIVNGKG-UHFFFAOYSA-N fluoromethane Chemical compound F[CH2] VUWZPRWSIVNGKG-UHFFFAOYSA-N 0.000 description 1
- 125000004785 fluoromethoxy group Chemical group [H]C([H])(F)O* 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 208000037824 growth disorder Diseases 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 208000006278 hypochromic anemia Diseases 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000017066 negative regulation of growth Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical class CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical compound CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000003090 pesticide formulation Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001522 polyglycol ester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 1
- 239000004550 soluble concentrate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000004546 suspension concentrate Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YWSCPYYRJXKUDB-KAKFPZCNSA-N tralomethrin Chemical compound CC1(C)[C@@H](C(Br)C(Br)(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 YWSCPYYRJXKUDB-KAKFPZCNSA-N 0.000 description 1
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000004563 wettable powder Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Abstract Combination of ALS inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agents.
The invention relates to mixtures or application combina-tions which contain ALS inhibitor herbicides and other plant-protection agents such as insecticides or her-bicides having different mechanisms of action, indepen-dently of whether these preparations are applied together or in succession, in particular one or more herbicides from the sulfonylurea, imidazolinone and pyrimidine or triazine derivative group and other agents such as insecticides and herbicides and one or more compounds of the formulae B1 and B2, (B1) (B2) in which the radicals are as defined in the description.
It has been found that damage to the crop plants can be reduced or entirely prevented if these mixtures or application combinations are applied.
The invention relates to mixtures or application combina-tions which contain ALS inhibitor herbicides and other plant-protection agents such as insecticides or her-bicides having different mechanisms of action, indepen-dently of whether these preparations are applied together or in succession, in particular one or more herbicides from the sulfonylurea, imidazolinone and pyrimidine or triazine derivative group and other agents such as insecticides and herbicides and one or more compounds of the formulae B1 and B2, (B1) (B2) in which the radicals are as defined in the description.
It has been found that damage to the crop plants can be reduced or entirely prevented if these mixtures or application combinations are applied.
Description
208~48 HOECHST AXTIENGESELLSCHAFT HOE 91tF 391 Dr. AB/PL
Description Combination of ALS inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agents The invention relates to the technical field of plant-protection agents, in particular combinations of herbi-cides of the ALS inhibitor type with insecticides or other foliar-active herbicides.
German Patent Application P 40 41 120.6 has proposed to make available acetolactate synthase tALS) inhibitors, which could formerly not be employed selectively in gramineous crops such as cereals or maize, in combination with certain herbicide safeners tantidotes) for selective use in such crops.
Surprisingly, it has now been found that these antidotes can also prevent the damage to crop plants which arises when ALS inhibitors and other plant-protection agents, such as insecticides and herbicides, are applied together or in succession to a crop plant population.
Novel herbicides from the sulfonylurea group tALS
inhibitors) are increasingly also employed in maize crops for the selective control of weeds and weed grasses, since they have already been of importance for years in cereal and rice crops. Such herbicides are, for example, primisulfuron, nicosulfuron, DPX-E-9636 rimsulfuron and other sulfonylurea derivatives, or mixtures of these compounds with one another.
Although the selectivity of these herbicides in maize cultures is normally good, their use can lead to damage of the crop plants if these are treated beforehand or at - 2 - 2~
the same time or afterwards with an insecticide, such as, for example, terbufos, or other insecticides from the org~nophosphate, pyrethroid or carbamate groups. Even if such treatments are up to 20 days or more apart, damage to the crop plants can still ari~e. Herbicides, such as, for example, bentazone or bromoxynil, can also cause damage if maize crops or other crops are treated together or alternatively at separate tLmes with such compounds and sulfonylurea herbicides. In this case, the type of treatment i8 not important, it can be spraying of the leaves or soil, or the insecticides or herbicides can be applied to the seed as granules on or in the soil, or the seed~ can be dressed. It is only crucial that when all is said and done the various active substances act in the crop plant or begin to interact there in the plant metabolism. The presence of these compounds prevents or reduces the plant metabolism of ALS inhibitor (sulfonylurea) herbicides, so that discolorations, chloroses or even leaf deformations and severe growth disorders occur, which can also severely damage the yield of the crop plants.
The mentioned incompatibilities are an economic problem for the user, since he must not apply various agents together or must not treat crop plants, such as, for example, maize, with certain preparations which, for example, are very effective or very good value.
Surprisingly, however, it has now been found that ~uch damage to crop plants can be reduced or entixely pre-vented if, at the s~me time as the herbicide or ALS
inhibitor, plant-protecting agent~ are app ied such as have been proposed in German Patent Application P 40 41 120.6, which act as antidotes or safeners.
The invention therefore relates to mixtures or applica-tion combinations which contain ~ 3 - 208S~8 A) ALS inhibitor herbicides and other plant-protection agents such as insecticides or herbicides with different mechani~ms of action, independently of whether these preparations are applied together or S in succession, in particular one or more herbicides from the sulfonylurea, imidazolinone and pyrimidine or triazine derivative group and other agents such as insecticides and herbicides and B) one or more compounds of the formulae B1 and B2 (X)n ~ W ~`Z (B1) ~( X )n (B2) O~ "C O
in which X is hydrogen, halogen, C1-C4-alkyl, Cl-C4-alkoxy, nitro or C1-C4-haloalkyl, 15 Z is OR1, SR1, NR1R, where R is H, C1-C~-alkyl, C1-C6-alkoxy or optionally ~ubstituted phenyl, or a saturated or unsaturatQd 3- to 7-membered hetero-cycle having at least one nitrogen atom and up to 3 hetero atoms, which is bonded to the carbonyl group 2 0 via the nitrogen atom and is unsub6tituted or substituted by radicals from the group comprising C1-C4-alkyl, C1-C4-alkoxy and optionally sub6tituted phenyl, preferably a radical of the formula OR1, NHR
or N(CH3), in particular of the formula OR1, _ 4 _ 208~8 R is a Cl-C2-alkylene chain which can additionally be substituted by one or two C1-C4-alkyl radicals, preferably -CH2-, Rl is hydrogen, Cl-Cl8-alkyl, C3-Cl2-cycloalkyl, C2-C8-alkenyl or C2-C8-alkynyl, where the above carbon-containing radicals are unsubsituted or mono- or polysubstituted by radicals from the group compri~ing halogen, hydroxyl, C1-CB-a1kOXY~ C1-C8_a1kY1thiO, C2-C8-a1k~nY1thiO, C2-C8-alkynylthio, C2-CB-alkenyloxy, C2-C8-alXynyloxy, C3-C7-cycloalkyl, C3-C7-cycloalkoxy, cyano, mono~ and di-Cl-C4-alkylamino, Cl-C8-alkoxycarbonyl, C2-C8-alkenyloxycarbonyl, Cl-C8-alkylthiocarbonyl, C2-C8-alkynyloxycarbonyl, Cl-C8-alkylcarbonyl, C2-C8-alkenylcarbonyl, C2-C8-alkynylcarbonyl, Cl-C8-alkylcarbonylamino,C2-C8-alkenylcarbonylamino, C2-C8-alkynylcarbonylamino, aminocarbonyl, Cl-C8-alkylaminocarbonyl, Di-Cl-C6-alkylaminocarbonyl, C2-C6-alkenylaminocarbonyl, C2-C6-alkynylamino-c arbonyl, C1-C8- alkoxyc arbonyl amino, Cl-C8-alkylaminocarbonylamino,Cl-C6-alkylcarbonyloxy which is unsubstituted or substituted by halogen, NO2, Cl-C4-alkoxy or optionally substituted phenyl, C2-C6-alkenylcarbonyloxy, C2-C6-alkynylcarbonyloxy, C1-C8-alkylsulfonyl, phenyl, phenyl-C1-C6-alkoxy, phenyl-C1-C6-alkoxycarbonyl, phenoxy, phenoxy-C1-C6-alkoxy, phenoxy-C1-C6-alkoxycarbonyl, phenylcar-bonyloxy, phenylcarbonylamino, phenyl-Cl-C6-alkyl-carbonylamino, where the last-mentioned 9 radicals in the phenyl ring are unsubstituted or mono- or polysubstituted by radicals from the group com-prising halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloa:lkoxy and nitro, and radicals of the formulae -SiR'3, -O-SIR'3, (R')3Si-C1-C6-alkoxy, -CO-O-NR' 2 ~ _O-N=cR ~ 2 ~ -N=CR' 2 ~
-O-NR~2-CH(OR~ )2 and -O-~CH2)m-CH(OR'2)2, in which R' in said formulae independently of one another are 20~5~4~
hydrogen, C1-C4-alkyl, phenyl which is unsubstituted or mono- or polysubstituted by radicals from the group comprising halogen, Cl-C4-alkyl, C~-C4-alkoxy, C1-C4-haloalkoxy and nitro, or in pairs are a C2-C6-alkylene chain and m = 0 to 6, and a radical of the formula R"O-CHR (OR")-Cl-C6-alkoxy, in which the radicals R" independently of one another are C1-C4-alkyl or together are a C1-C6-alkylene radical and R is hydrogen or C1-C4-alkyl, 10 n is an integer from 1 to 5, preferably 1 to 3, W is a divalent heterocyclic radical having 5 ring atoms, of the formula Wl to W4 ~N~ N~
R2 ~J
CooR3 (W1) (W2) N/ \
N - CH
(W3) (W4) in which R2 is hydrogen, C1-C~-alkyl, C1-Ca-haloalkyl, C3-C12-cycloalkyl or optionally substituted phenyl and R3 is hydrogen, C1-C3-alkyl, Cl-Ca-haloalkyl, Cl-C4-alkoxy-Cl-C4-alkylI Cl-C6-hydroxyalkyl, C3-Cl2-20cycloalkyl or tri-(C1-C4-alkyl)silyl, or the salts of said compounds.
- 6 - 6~
Herbicidal agents according to the invention of par-ticular interest are those where, in the compounds of the formulae Bl and B2, Rl is hydrogen, C1-C12-alkyl or C3-C7-cycloalkyl, C2-C8-alkenyl or C2-C8-alkynyl, where the above carbon-containing radicals are unsubstituted or mono- or polysubstituted by halogen or mono- or disubsti-tuted, preferably monosubstituted by radicals from the group comprising hydroxyl, Cl-C4-alkoxy, Cl-C4-alkylthio, C2-C4-alkenyloxy, C2-C6-alkynyloxy, mono-and di-(Cl-C2-alkyl)-amino, (Cl-C4-alkoxy)carbonyl, C2-C4-alkenyloxycarbonyl, C2-C4-alkynyloxycarbonyl, Cl-C4-alkylcarbonyl, C2-C4-alkenylcarbonyl, C2-C4-alkynylcarbonyl,C1-C4-alkylsulfonyl, phenyl,phenyl-C1-C4-alkoxycarbonyl, phenoxy, phenoxy-Cl-C4-alkoxy, phenoxy-(Cl-C4-alkoxy)carbonyl, where the last-mentioned 6 radicals in the phenyl ring are unsub-stituted or mono- or polysubstituted by radicals from the group comprising halogen, Cl-C2-alkyl, Cl-C2-alkoxy, Cl-C2-haloalkyl, C1-C2-haloalkoxy and nitro, and radicals of the formulae -SIR'3, -O-N=CR'2, -N=CR~2, -N=CR'2 and -O-NR'2, in which the R' in said formulae independently of one another are hydrogen, Cl-C2-alkyl, phenyl which is unsubstituted or mono-or polysubstituted by radicals from the group comprising halogen, Cl-C2-alkyl, Cl-C2-alkoxy, Cl-C2-haloalkyl, Cl-C2-haloalkoxy and nitro, or in ~airs are a C4-C5-alkanediyl chain.
Herbicidal agent~ according to the invention also of particular interest are those where, in the compounds of the formulae Bl and B2, X i6 hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or Cl-C2-haloalkyl, preferably hydrogen, halogen or Cl-C2-haloalkyl.
- 7 - 2~8~$~
Preferred herbicidal agents according to th~ invention are those where, in the compounds of the formula Bl, X is hydrogen, halogen, nitro or Cl-C4-haloalkyl, n is a number from 1 to 3, Z is a radical of the formula ORl, R1 is hydrogen, C1-C8-alkyl or C3-C7-cycloalkyl, where the above C-containing radicals are unsub-stituted or mono- or polys~bstituted by radicals from the group comprising halogen or mono- or disubstituted, preferably unsubstituted or monosub-stituted, by radicals from the group comprising hydroxyl, Cl-C4-alkoxy, (C1-C4-alkoxy)carbonyl, C2-C6-alkenyloxycarbonyl, (C2-C6~alkynyloxy)carbonyl and radicals of the formulae -SiR'3, -O-N=CR'2, -N=CR'2 and -O-NR'2, in which the radicals R' in said formulae independently of one another are hydrogen or Cl-C4-alkyl or in pairs are a C4-C5-alkylene chain, R2 is hydrogen, Cl-Ce-alkyl, Cl-C6-haloalkyl, C3-C7-cycloalkyl or phenyl and 0 R3 is hydrogen, Cl-C8-alkyl, Cl-C8-haloalkyl, (Cl-C4-alkoxy)-Cl-C4-alkyl, Cl-C6-hydroxyalkyl, C3-C7-cyclo-alkyl or tri-(Cl-C4-alkyl)silyl.
Preferred herbicidal agents according to the invention are also those where, in the compounds of the formula B2, X is hydrogen, halogen or Cl-C4-haloalkyl and n is a number from 1 to 3, pxeferably (X)n = 5-Cl, Z is a radical of the formuls OR1, R is CH2 and Rl is hydrogen, Cl-C8-alkyl, Cl-C8-haloalkyl, (Cl-C4-alkoxy)-Cl-C4-alkyl or ~Cl-C4-alkenyloxy)-Cl-C4-alkyl, prefexably Cl-C8-alkyl.
Particularly preferred herbicidal agent~ according to the invention are those containing compounds of the formula ~1, in which 208~ ~%
W is Wl, X is H, halogen or C1~C2-haloalkyl and n = 1 - 3, in particular (X) n = 2 ~ 4 -C12 ~
Z is a radical of the formula OR1, R1 is hydrogen, C1-C8-alkyl, C1-C4-haloalkyl, Cl-C4-hydroxyalkyl, C3-C7-cycloalkyl, (cl-c4-alkoxy)-cl-c4-alkyl or tri-(C1-C2-alkyl)-silyl, preferably Cl-C4-alkyl, R2 is hydrogen, C1-C~-alkyl, C1-C4-haloalkyl or C3-C7-cycloalkyl, preferably hydrogen or C1-C4-alkyl, and R3 is hydrogen, C1-CB-alkyl, C1-C4-haloalkyl, C1-C4-hydroxyalkyl, C3-C7-cycloalkyl, (C1-C4-alkoxy)-C1-C4-alkyl or tri-(C1-C2-alkyl)silyl, preferably hydrogen or C1-C4-alkyl.
15 Particularly preferred herbicidal agents according to the invention are also those containing compounds of the formula Bl, in which W is W2~
X is H, halogen or C1-C2-haloalkyl and n = 1 - 3, in particular (X) n = 2~4 -C12, Z is a radical of the formula OR1, R1 is hydrogen, C1-C~-alkyl, C1-C4-haloalkyl, C1-C4-hydroxyalkyl, C3-C7-cycloalkyl, (C1-C4-alkoxy)-C1-C4-alkyl or tri-(C1-C2-alkyl)silyl, preferably C1-C4-alkyl and R2 is hydrogen, C1-C~-alkyl, C1-C4-haloalkyl, C3-C7-cycloalkyl or phenyl, preferably hydrogen or Cl-C4-alkyl.
Particularly preferred herbicidal agents according to the invention are also those containing compounds of the formula Bl, in which W is W3, X is H, halogen or C1-C2-haloalkyl and n = 1 - 3, in particular (X) n = 2 ~ 4-Cl2 ~ 5 Z is a radical of the formula OR1, 208~ 48 Rl is hydrogen, C~-C8-alkyl, C1-C4-haloalkyl, Cl-C4-hydroxyalkyl, C3-C7-cycloalkyl, (Cl-C4-alkoxy)-Cl-C4-alkyl or tri-(Cl-C2-alkyl)silyl, preferably Cl-C4-alkyl and R2 is Cl-C8-alkyl or Cl-C4-haloalkyl, preferably Cl-haloalkyl.
Particularly preferred herbicidal agents a~cording to the invention are also those containing compounds of the formula B1, in which W is W4, X is hydrogen~ halogen, nitro, Cl-C4-alkyl or Cl-C2-haloalkyl, preferably CF3, or Cl-C4-alkoxy, n is l to 3, Z is a radical of the formula ORl, 5 R1 is hydrogen, Cl-C4-alkyl or (C1-C4-alkoxy)carbonyl-Cl-C4-alkyl, preferably (cl-c4-alkoxy)-co-cH2-~( alkoxy)-CO-C(CH3)H-, HO-CO-CH2- or HO-CO-C(CH3)H-.
In the formulae, alkyl, alkenyl and alkynyl are straight-chain or branched; the same applies to substituted alkyl, alkenyl and alkynyl radicals such a haloalkyl, hydroxy-alkyl, alkoxycarbonyl etc.; alkyl is, for example, methyl, ethyl, n- and i-propyl, n-, i-, t- and 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1,3-di-methylbutyl, heptyls, such as n-heptyl, l-methylhexyl and 1,4-dimethylpentyl; alkenyl is, for example, allyl, l-methylprop-2-en-l-yl, but-2-en-l-yl, but-3-en-1-yl, l-methylbut-3-ene and 1-methylbut-2-ene; alkynyl i~, for example, propargyl, but-2-yn-1-yl, but 3-yn-l-yl, l-methyl-but-3-yne; halogen iB fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine; haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl or alkynyl substituted by halogen, for example such as CF3, CHF2, CH2F, CF3CF2, CH2FCHCl, CCl3, CHCl2, CH2CH2Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F, CF3CF20, CF3CH20;
optionally substituted phenyl is, for example, phenyl 2a~ 8 which is unsubstituted or mono- or polysubstituted by radicals from the group comprising halogen, Cl-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3-and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, and o-, m- and p-methoxyphenyl.
The compounds of the formula Bl are disclosed in EP-A-333 131, EP-A-269 806, EP-A-346 620, International Patent Application PCT/EP gO/01966 and International Application No. PCT/EP 90/02020 and literature cited therein or can be prepared by or analogously to the processes described therein. The compounds of the formula B2 are disclosed in EP-A-86 750, EP-A-94 349 and EP-A-l91 736 and literature cited therein or can be prepared by or analogously to the processes described therein. ~hey are additionally proposed in German Patent Application P 40 41 121.4.
Suitable mixed combinations of the type A are ALS in-hibitor herbicides according to the invention, such as sulfonylureas and imidazolinones, as well as substituted pyrimidines and triazones which can be employed in a mixture or applied separately with other plant-protection agents, such as insecticides, for example organo-phosphates, or herbicides.
Such ALS inhibitors of the 6ulfonylurea type are, forexample, the known compounds priml~ulfuron-methyl, nicosulfuron, DPX-E-9636, amidosulfuron, thiameturon-methyl, NC319 (EP-A-282 613) and other disclosed active substances and pyridylsulfonylureas (German Patent Application P 40 30 577.5) and alkoxyphenoxysulfonylureas (EP-A-342 569) and mixtures of said active substances with one another.
~8~
Suitable compounds are pyridylsulfonylureas of the formula Al or their salts, R~
~ ~ R R6 Rs ~ //\\ ~ ~ ~ ~ (A1) in which R is hydrogen, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or ~rialkylammonium, E is CH or nitrogen, R4 is halogen or NR9R10, R5 is hydrogen, halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy,C1-C3-haloalkyl,C1-C3-haloalkoxy,C1-C3-alkyl-thio, (C1-C3-alkoxy)-C1-C3-alkyl, (C1-C3-alkoxy)carbonyl, mono- or di(C1-C3-alkyl)amino, Cl-C3-alkylsulfinyl or sulfonyl, SO2-NR4Rb or CO-NRaRb, R6 is hydrogen or CH3, R7 is halogen, C1-C2-alkyl,Cl-C2-alkoxy, C1-C2-haloalkyl, C1-C2-haloalkoxy or OCH2CF3, R8 is C1-C2-alkyl, C1-C2-haloalkoxy or C1-C2-alkoxy and R9 is Cl-C4-alkyl and R10 is C1-C4-alkylsulfonyl or R9 and Rl together are a chain of the formula -(CH2)3S02- or -(CHz)4SO2-r or alkoxyphenoxysulfonylureas of the formula A2 or their salts, Rl4 ( R 1 2 ) ~ ~S~ ~ 1N--1R 15 1.... 1,~
R R
in which 12 2~8~8 R"" is hydrogen, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium, E is CH or nitrogen, Rl1 is methoxy, ethoxy, propoxy, isopropoxy or Cl-C4-alkoxycarbonyl, RlZ is hydrogen, halogen, NO2, CF3, CN, C1-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio or (Cl-C3-alkoxy)-carbonyl, n is 1, 2 or 3, Rl3 is hydrogen, Cl-C4-alkyl or C3-C4-alkenyl, R14 and Rl5 independently of one another are halogen, Cl-C2-alkyl, Cl-Cz-alkoxy, Cl-C~-haloalkyl, Cl-C2-halo-alkoxy or (Cl-C2-alkXY)-cl-c2-al~yl-ALS inhibitors of the imidazolinone type are imazethapyr, 15 imazaquin, imazethamethapyr (AC-263222) and other related compounds and mixtures thereof.
Suitable substituted pyrimidines and triazines have the formula C
N ~ R2~
N ~ (C) in which X' is oxygén, sulfur or NR24, Y' is nitrogen or CH, R22 and R23 independently of one another are hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, Cl-C4-alkylmer-25 capto, C~-C4-alkylamino or di-Cl-C4-alkylamino, R2l is a substituted aryl or heteroaryl radical of the formula - 13 - 20~4~
R 2 s~( w ) n ~R26 or ~ ~ ~ ~502R
n~ is 0 or 1, W' is -O-, -NR24-, -S-, -ON(R31)- or -o-N=C(R31), X' is N, N~O or CR24, S R24 is defined as R22 or R23, RZ5 is halogen, cyanor nitro, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Cl-C4-alkoxy, haloalkyl or haloalkoxy, R26 is C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, alkali metal or 1 equivalent of alkaline earth metal, alkylammonium, aryl, CF3 or (CHR33)m.CHR27R2B where m' = 0 or 1, R27 and R33 independently of one another are hydrogen, Cl-C4-alkyl or Cl-C4-alkoxy, R2~ is C1-C4-alkoxycarbonyl, cyano, halogen, acetyl, pivaloyl, benzoyl, C1-C4-alkoxy, aryloxy, halo-acetoxy, methanesulfonyloxy, hydroxyl, C1-C4-alkyl-mercapto,C1-C4-alkylsulfonyl,arylmercapto,di-C1-C4-alkylamino, pyridyl, aryl or CoNR2aR30, R29 and R30 independently of one another are hydrogen, C1-C4-alkyl, C~-C4-alkenyl, aryl or benzyl, R31 is hydrogen ox C1-C4-alkyl or R26 and R31 together are methylene, ethanediyl or pro-panediyl and aryl i8 phenyl or naphthyl, each of which i~ unsubsti-tuted or mono- or disubstituted by halogen, Cl-C4-alkyl, C1-C4-alkoxy, phenoxy, nitro and/or C1-C4-alkoxycarbonyl, or R11 is a radical of the formula 2085~48 - ~4 -R~200~ ~ or ~ ~9 R34 iB hydrogen, halogen, halo-Cl-C4-alkyl, C1-C4-cyclo-alkyl, Cl-C4-alkylmercapto-C1-C4-alkyl, hydroxyl-Cl-C4-alkyl, hydroxyl, cyano, aryloxyalkyl, thienyl, aryl, dihydronaphthyl or ,R
( CH2 )m~
where aryl is as defined above, R40 is hydrogen, halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy or S(O)p.R , R41 is alkyl, p' is a 0, 1 or 2, m" is a 0, 1 or 2, R3s and R36 independently of one another are hydrogen or C1-C4-alkyl, or these, together with the carbon atom, are a 3-, 4-, 5- or 6-membered cycloalkane ring, in which a methylene group can be replaced by oxygen and which can be substituted by one or two C1-C4-alkyl groups, R37 and R3~ independently of one another are hydrogen or Cl-C4-alkyl, R39 is Cl-C4-alkyl or phenyl, or R38 and R3~ are -(CH2)l- where l = 3 or 4, which can be substituted by one or two C1-C4-alkyl groups, R42 is hydrogen, C1-C4-alkyl,C1-C4-alkenyl, C1-C4-alkynyl, phenyl, C1-C4-alkylidenamino, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, halo-C1-C4-- 15 _ 2~8~ ~ ~8 alkyl, cycloalkyl, nitro-substituted phenylmercapto-Cl-C4-alkyl, halogen or benzyl which can be substi-tuted by Cl-C4-alkyl or Cl-C4-alkoxy, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium.
The various types of ALS inhibitors can also be mixed with one another. Other active substance structures which inhibit the enzyme ALS, for example herbicidal sulfona-mides such as flumetsulam (DE-498) and the like are also possible here. Possible combination components in the ~mixture~ of the type A are the following plant-protec-tion agents, where the indiYidual components can be applied toge~her or separately from one another at an interval of time of up to several weeks:
1.) Insecticidal preparations such as organophosphates, for example terbufos (~Counter~, fonofos (~Dyfonate), phorate (~Thimet), chlorpyrifos (Reldan) and other rela~éd active substances, insecticidal carbamates such as, for example, carbofuran (0Furadan) and others; as well as pyrethroid insecticides such as, for example, tefluthrin (~Force), deltamethrin (~Decis) and tralomethrin (Scout) and others; as well as other insecticidal agents having a different mechanism of action.
5 2.) Herbicides which are employed as components, in order to widen the spectrum of action of ALS
inhibitors and to improve the activity, such a~, for example, bentazone, cyanazine, bromoxynil or other herbicides which are absorbed through the leaf.
The following groups of compounds have proven suitable as safeners for the abovementioned product combinations:
a) Compounds of the dichlorophenylpyrazoline-3-car-boxylic acid type (i.e. of the formula ~1, in which - 16 - ~8~8 W = Wl and (X)n = 2,4-Cl2), preferably compounds such as ethyl l-(2,4-dichlorophenyl)-5-(ethoxycarbonyl-5-methyl-2-pyrazoline-3-carboxylate (Bl-l) and related compounds, such as are described in Inter-national Application PCT/EP 90/02020, b3 Derivatives of dichlorophenylpyrazolcarboxylic acid (i.e. of the formula Bl, in which W = W2 and (X)n =
2,4-C12), preferably compounds ~uch as ethyl l-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (B1-2), ethyl 1-(2,4-dichlorphenyl)-5-isopropyl-pyrazole-3-carboxylate (Bl-3), ethyl l-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (B1-4), ethyl 1~(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate ~Bl-5) and related compounds, such as are described in EP-A-0 333 131 and EP-A-0 269 806.
c) Compounds of the triazolecarboxylic acid type (i.e.
of the formula B1 in which W = W3 and (X)n =
2~4-Clz)~ preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-(lH)-1,2,4-tria-zole-carboxylate (Bl-6, fenchlorazole) and related compounds (see EP-A-0 174 562 and EP-A-0 346 620);
d) Compounds of the dichlorobenzyl-2-isoxazoline-3-carboxylic acid type (i.e. of the formula B1, in which W = W4 and (X)~ = 2,4-Cl2), preferably com-pounds such as ethyl 5-(2,4-dichlorohenzyl)-2-iso-axazoline-3-carboxylate (B1-7) and related com-pounds, such as are described in International Application PCT/EP 90/01966.
0 e) Compounds of the (5-chloro-8-quinolinoxy)acetic acid type (i.e. of the formula B2, in which (X)n = 5-Cl, Z = OR1, R = CH2), preferably compounds such as l-methylhex-l-yl (5-chloro-8-quinolihoxy)acetate (B2-l), 1,3-dimethylbut-1-yl (5-chloro-8-quino-- 17 _ 2~ 8 linoxy)acetate (B2-2), 2-allyloxy-1-methylethyl (5-chloro-8-quinolinoxy)acetate (B2-3) and related compounds, such as are described or have been proposed in EP-A-86 750, EP-A-94 349 and EP-A-l91 736 and German Patent Application P 40 41 121.4.
The safeners (antidotes) of the above groups a) to e) reduce or suppress phytotoxic effects which can occur when using the product combinations in productive plant crops, without impairing the activity of the herbicides against harmful plants. By this means, the field of use of the mixtures can be very considerably widened and extended, for example, to crops such as maize, wheat, barley and other gramineous crops in which until now use 1~ of the combinations has not been possible or only restri-ctively possible, i.e. at low doses with not very wide action.
The herbicidal ALS inhibitors and their combination components and the safeners mentioned can be applied together (as a finished formulation or in a tank-mix process) or in any desired sequence in succession. The weight ratio safener: herbicide (ALS inhibitor) can vary within wide limits and is preferably in the range from 1:10 to 10:1, in particular from 1:10 to S:l. The optimum amounts of herbicide and safener in each case are depen-dent on the type of herbicide used or on the safener used and on the nature of the plant population to be treated and can be determined from case to case by appxopriate preliminary experiments. The application rate of the insecticide or herbicide additionally employed is depen-dent on its activity alone and corresponds to the general product recommendations.
Principal fields of use for the application of the safeners are, in particular, maize and cereal crops, (wheat, rye, barley, oats), rice and sorghum, but also - 18 ~ 8 cotton and soybean, preferably maize.
Depending on their properties, the safeners of the type B can be used for the pretreatment of the seeds of the crop plant (dressing of the seeds) or introduced into the seed furrows before the seed or applied together with the herbicide before or after the emergence of the plants.
Pre-emergence treatment includes both the treatment of the cultivation areas before sowing and the treatment of the sown, but not yet covered cultivation surfaces.
Application together with the herbicide is preferred, i.e. with the ALS inhibitor. Tank mixtures or finished formulations can be employed for this.
The required application rates of the safeners can vary within wide limits depending on the indication and herbicide used and are as a rule in the range from 0.001 to l kg, preferably 0.005 to 0.2 kg, of acti~e substance per hectare.
The present invention therefore also relates to a process for the protection of crop plants from phytotoxic side effects of herbicide combinations, which comprises applying to the plants, plant seeds or the cultivation surface an effective amount of a compound of said type B) before, after or at the same time as the herbicide of said type A) in combination with an insecticide or herbicide.
The compounds of the type B) and their combinations with one or more of said herbicides (ALS inhibitors) can be formulated in various ways, depending on which biological and/or chemico-physical parameters are specified. Suit-able formulation possibilities are, for example:
Wettable powders (WP), emulsifiable concentrates (EC),water-soluble powders (SP), water-soluble concentrates (SL), concentrated emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions or 2~8~48 emulsions, capsule suspensions (CS), dispersions on an oil or water basis (SC), suspoemulsions, suspension concentrates, dusting agents (DP), oil-miscible solutions (OL), dressing agents, granules (GR) in the form of micro granules, spray granules, coated granules and adsorption granules, granules for application to the soil or scat-tering, water-soluble granules (SG), water-dispersible granules (NG), ULV formulations, microcapsules and waxes.
These individual formulation types are known in principle and are described, for example, in: Winnacker-Ruchler, "Chemische Technologie~ (Chemical Technology) Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986; Wade van Valkenburg, "Pesticide Formulations~, Marcel Dekker N.Y., 1973; K. Martens, "Spray Drying Handbook~, 3rd Ed. 1979, G. Goodwin Ltd. London.
The required formulation auxiliaries such as inert materials, surfactants, solvents and other additives are likewise known and are described, for example, in:
Watkins, ~Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.;
H.v. Olphen ~'Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y., Marsden "Solvents Guide", 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.;
Sisley and Wood, "Encyclopedia of Surface Active Agents~, Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzflach-enaktive Athylenoxidaddukte" (Surface-active Ethylene Oxide Adducts), Wiss. Verlagsgesell., Stuttgart 1976;
Winnacker-Kuchler "Chemische Technologie" tChemical Technology) Vol./4th Ed, 7, C. Hauser Verlag Munich, 1986.
On the basis of these formulations, combinations with other pesticidally active substances, such as insecticides, fungicides, fertilizers and/or growth regulators, can be prepared, for example in the form of ~o~ 8 a finished formulation or as a tank-mix.
Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substance, also contain wetting agents, for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols and fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates or alkylarylsulfonates and dispersing agents, for example sodium ligninsulfonate, sodium 2,2-dinaphthylmethane-6-6~-disulfonate, sodium dibutylnaphthalenesulfonate or alternatively sodium oleoylmethyltauride in addition to a diluent or inert substance.
Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or alternatively higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. Examples of emulsifiers which can be used are: alkylarylsulfonic acid calcium salts such as Ca dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide conden-sation products ~for example block polymers), alkyl polyethers, sorbitan fatty acid estars, polyoxyethylene-sorbitan fatty acid esters of polyoxyethylenesorbitolesters.
Dusting agents can be obtained by grinding the active substance with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophillite, or diatomaceous earth.
Granules can be produced either by spraying the active substance onto adsorptive, granulated inert material or by applying active substance concentrates to the surface of carriers, such as sand, kaolinites or granulated inert - 21 - 208~48 material, by means of binders, for example polyvinyl alcohol, sodium polyacrylate or alternatively mineral oils. Suitable active substances can also be granulated in the manner which is customary for the production of fertilizer granules, if desired in a mixture with fer-tilizers.
The agrochemical preparations as a rule contain 0.1 to 99 ~ by weight, in particular 0.1 to 95 % by weight, of active substances of type B) or of antidote/herbicide active substance mixture A) and B) and 1 to 99.9 % by weight, in particular 5 to g9.~ % by weight, of a solid or liquid additive and 0 to 25 % by weight, in particular 0.1 to 25 % by weight, of a surfactant.
The concentration of active substance in wettable powders is, for example, about 10 to 90 % by weight; the remainder to 100 % by weight is composed of customary formulation component In the case of emulsifiable concentrates, the active substance concentration is about 1 to 80 ~ by weight of active substances. Formulations in the form of dusts contain about 1 to 20 % by weight of active substances, sprayable solutions about 0.2 to 20 %
by weight of active substances. In the case of granules such as water-dispersable granules, the active substance content depends partly on whether the active substance is liquid or solid. As a rule, the contents in the case of the water-dispersable granules is between 10 and 90 % by weight.
In addition, said active sub~tance formulations optionally contain the tackifiers, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers customary in each case.
For use, the formulations, present in commercially available form, are diluted, i~ appropriate, in a customary manner, for example by means of water in the 2~
case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Preparations in the form of dusts, granules and sprayable solutions are customarily not further diluted with other inert substances before use. Particularly good activitieæ of the agents according to the invention can be achieved if other wetting agents in concentrations of 0.1 to 0.5 % by weight are added in the tank-mix process to the surfac-tants contained in the formulations, for example nonionic wetting agents or wetting agents of the fatty alcohol polyol ether sulfate type (see, for example, German Patent Application P 40 29 304.1). The required applica-tion rate of the "safener" varies with the external conditions such as temperature, humidity, the nature of the herbicide used and the like.
The following examples serve to illustrate the invention without restricting it thereto:
A. Formulation examples a) A dusting agent is obtained by mixing 10 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B) and 90 parts by weight of talc as inert substance and comminuting the mixture in a hammer mill.
b) A wettable powder which is readily dispersible in water is obtained by mixing 25 part~ by weight of a substance of type B) or of an active substance mixture type A) and a safener of type B), 64 parts by weight o~ kaolin-containing quartz as inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltauride as a wetting and dispersing agent and grinding the mixture in a pinned-disk mill.
2 ~
c) A dispersion concentrate which is readily disper-sible in water is obtained by mixing 20 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B), 6 parts by weight of alkylphenol polyglycol ether ~registered trademark ~Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 E0) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to over 277C), and grinding the mixture in a ball mill to a fineness of less than 5 microns.
d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B), 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of ethoxylated nonyl-phenol as an emulsifier.
e) Water-dispersable granules are obtained by mixing 75 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B), 10 " of calcium ligninsulfonate, 5 " of sodium lauryl sulfate 25 3 " of polyvinyl alcohol and 7 " of kaolin, grinding the mixture in a pinned-di0k mill and granulating the powder in a fluidized bed by spraying water as a granulating fluid.
0 f) Water-dispersable granules are also obtained by homogenizing 25 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type 2a8~8 B), o f s o d i u m 2 , 2 ~ -dinaphthylmethane-6,6'-disulfonate, 2 parts by weight of sodium oleoylmethyltauride, 1 " of polyvinyl alcohol, 17 ~I of calcium carbonate and 50 " of water in a colloid mill and precomminuting, then grinding the mixture in a bead mill and atomizing and drying the suspension thus obtained in a spray tower by means of a single substance nozzle.
The insecticides or herbicides additionally used can be added both in the tank-mix process, or applied separately from the finished formulation composed of ALS inhibitor and safener of the type B.
The active substance mixture A is in each case composed of an ALS inhibitor and an insecticide and/or another herbicide.
B. Biological examples The crop plants were cultivated up to the 4-leaf stage in open ground or in a greenhouse in plastic pots and then treated according to the invention with compoundæ of type A) and B) post-emergence. The compounds of type A) and B) were in this case applied in the form of aqueous suspensions br emulsions at a water application rate of, after conversion, 300 l/ha. 4 week~ after treatment, the plant6 were visually as6e~sed for any typ~ of damage due to the applied herbicides, the extent of prolonged inhibition of growth being taken particularly into account. Assessment was carried out in percentage values in comparison with untreated controls.
The result~ in the following tables illustrate that the compounds of type B) employed according to the invention 2~8~
can effectively reduce severe damage to crop plants. Even very severe damage is markedly reduced and slight damage is completely abolished. Combinations of ALS inhibitors and mixture components and compounds of type B) are therefore outstandingly suitable for the selective control of weeds in maize.
Example 1 Type A Type B Type A Type B
Herbicide combination Safener g of AS/ha g of AS/ha X damage (ALS inhibitor) to thQ
crop plant maize Hl + terbufos - 25 + 500 0 100 12 + 500 0 80 primisulfuron - 100 + 500 0 100 + terbufos 50 + 500 0 70 nicosulfuron - 200 + 500 0 90 + terbufos 100 + 500 0 80 terbufos - 500 0 0 primisulfuron B2-1 100 + 500 100 70 50 + 500 50 40 Hl + terbufos B2-2 25 + 500 25 50 12 + 500 12 20 nicosulfuron B2-3 200 + 500 200 40 + terbufos 100 + 500 100 30 Hl ~ 25 0 40 primisulfuron - 100 0 50 nicosulfuron - 200 0 30 Greenhouse experiment with 4 repetitions.
2o8~8 Sowing of maize in a pure sand culture. Terbufos was scattered on the soil surface as granules immediately after sowing. All other treatments were carried out in the 4-leaf stage. Naize variety "~FELIX".
H1 = CH
1 ~
CO/ ~<N~
S Example 2:
OCH~
Type AS~ha ~ damag~ to maize varieties FELIX DEA
bentazone 2.0 0 0 1.0 0 0 0.5 0 0 bromoxynil 1.0 20 30 0.5 20 30 0.25 10 15 15 primisulfurone 0.100 25 20 0.050 10 8 0.025 5 5 bentazone + 2.0 + 0.05 30 35 + prlmisulfuron 1.0 -~ 0.05 15 20 20 bentazone + 2.0 ~ 0.05 + 0.1 10 15 + primisulfuron 1.0 + 0.05 + 0.1 0 5 + Hl bromoxynil + 1.0 + 0.05 55 50 + primisulfuron 0.5 + 0.05 40 35 20~5~48 bromoxynil + 1.0 + 0.05 + 0.1 lS 15 + primisulfuron 0.5 + 0.05 + 0.1 5 0 + Hl Application in the 4-leaf stage cf the maize, height 23 - 26 cm.
Assessment: 4 weeks aftsr treatment
Description Combination of ALS inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agents The invention relates to the technical field of plant-protection agents, in particular combinations of herbi-cides of the ALS inhibitor type with insecticides or other foliar-active herbicides.
German Patent Application P 40 41 120.6 has proposed to make available acetolactate synthase tALS) inhibitors, which could formerly not be employed selectively in gramineous crops such as cereals or maize, in combination with certain herbicide safeners tantidotes) for selective use in such crops.
Surprisingly, it has now been found that these antidotes can also prevent the damage to crop plants which arises when ALS inhibitors and other plant-protection agents, such as insecticides and herbicides, are applied together or in succession to a crop plant population.
Novel herbicides from the sulfonylurea group tALS
inhibitors) are increasingly also employed in maize crops for the selective control of weeds and weed grasses, since they have already been of importance for years in cereal and rice crops. Such herbicides are, for example, primisulfuron, nicosulfuron, DPX-E-9636 rimsulfuron and other sulfonylurea derivatives, or mixtures of these compounds with one another.
Although the selectivity of these herbicides in maize cultures is normally good, their use can lead to damage of the crop plants if these are treated beforehand or at - 2 - 2~
the same time or afterwards with an insecticide, such as, for example, terbufos, or other insecticides from the org~nophosphate, pyrethroid or carbamate groups. Even if such treatments are up to 20 days or more apart, damage to the crop plants can still ari~e. Herbicides, such as, for example, bentazone or bromoxynil, can also cause damage if maize crops or other crops are treated together or alternatively at separate tLmes with such compounds and sulfonylurea herbicides. In this case, the type of treatment i8 not important, it can be spraying of the leaves or soil, or the insecticides or herbicides can be applied to the seed as granules on or in the soil, or the seed~ can be dressed. It is only crucial that when all is said and done the various active substances act in the crop plant or begin to interact there in the plant metabolism. The presence of these compounds prevents or reduces the plant metabolism of ALS inhibitor (sulfonylurea) herbicides, so that discolorations, chloroses or even leaf deformations and severe growth disorders occur, which can also severely damage the yield of the crop plants.
The mentioned incompatibilities are an economic problem for the user, since he must not apply various agents together or must not treat crop plants, such as, for example, maize, with certain preparations which, for example, are very effective or very good value.
Surprisingly, however, it has now been found that ~uch damage to crop plants can be reduced or entixely pre-vented if, at the s~me time as the herbicide or ALS
inhibitor, plant-protecting agent~ are app ied such as have been proposed in German Patent Application P 40 41 120.6, which act as antidotes or safeners.
The invention therefore relates to mixtures or applica-tion combinations which contain ~ 3 - 208S~8 A) ALS inhibitor herbicides and other plant-protection agents such as insecticides or herbicides with different mechani~ms of action, independently of whether these preparations are applied together or S in succession, in particular one or more herbicides from the sulfonylurea, imidazolinone and pyrimidine or triazine derivative group and other agents such as insecticides and herbicides and B) one or more compounds of the formulae B1 and B2 (X)n ~ W ~`Z (B1) ~( X )n (B2) O~ "C O
in which X is hydrogen, halogen, C1-C4-alkyl, Cl-C4-alkoxy, nitro or C1-C4-haloalkyl, 15 Z is OR1, SR1, NR1R, where R is H, C1-C~-alkyl, C1-C6-alkoxy or optionally ~ubstituted phenyl, or a saturated or unsaturatQd 3- to 7-membered hetero-cycle having at least one nitrogen atom and up to 3 hetero atoms, which is bonded to the carbonyl group 2 0 via the nitrogen atom and is unsub6tituted or substituted by radicals from the group comprising C1-C4-alkyl, C1-C4-alkoxy and optionally sub6tituted phenyl, preferably a radical of the formula OR1, NHR
or N(CH3), in particular of the formula OR1, _ 4 _ 208~8 R is a Cl-C2-alkylene chain which can additionally be substituted by one or two C1-C4-alkyl radicals, preferably -CH2-, Rl is hydrogen, Cl-Cl8-alkyl, C3-Cl2-cycloalkyl, C2-C8-alkenyl or C2-C8-alkynyl, where the above carbon-containing radicals are unsubsituted or mono- or polysubstituted by radicals from the group compri~ing halogen, hydroxyl, C1-CB-a1kOXY~ C1-C8_a1kY1thiO, C2-C8-a1k~nY1thiO, C2-C8-alkynylthio, C2-CB-alkenyloxy, C2-C8-alXynyloxy, C3-C7-cycloalkyl, C3-C7-cycloalkoxy, cyano, mono~ and di-Cl-C4-alkylamino, Cl-C8-alkoxycarbonyl, C2-C8-alkenyloxycarbonyl, Cl-C8-alkylthiocarbonyl, C2-C8-alkynyloxycarbonyl, Cl-C8-alkylcarbonyl, C2-C8-alkenylcarbonyl, C2-C8-alkynylcarbonyl, Cl-C8-alkylcarbonylamino,C2-C8-alkenylcarbonylamino, C2-C8-alkynylcarbonylamino, aminocarbonyl, Cl-C8-alkylaminocarbonyl, Di-Cl-C6-alkylaminocarbonyl, C2-C6-alkenylaminocarbonyl, C2-C6-alkynylamino-c arbonyl, C1-C8- alkoxyc arbonyl amino, Cl-C8-alkylaminocarbonylamino,Cl-C6-alkylcarbonyloxy which is unsubstituted or substituted by halogen, NO2, Cl-C4-alkoxy or optionally substituted phenyl, C2-C6-alkenylcarbonyloxy, C2-C6-alkynylcarbonyloxy, C1-C8-alkylsulfonyl, phenyl, phenyl-C1-C6-alkoxy, phenyl-C1-C6-alkoxycarbonyl, phenoxy, phenoxy-C1-C6-alkoxy, phenoxy-C1-C6-alkoxycarbonyl, phenylcar-bonyloxy, phenylcarbonylamino, phenyl-Cl-C6-alkyl-carbonylamino, where the last-mentioned 9 radicals in the phenyl ring are unsubstituted or mono- or polysubstituted by radicals from the group com-prising halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloa:lkoxy and nitro, and radicals of the formulae -SiR'3, -O-SIR'3, (R')3Si-C1-C6-alkoxy, -CO-O-NR' 2 ~ _O-N=cR ~ 2 ~ -N=CR' 2 ~
-O-NR~2-CH(OR~ )2 and -O-~CH2)m-CH(OR'2)2, in which R' in said formulae independently of one another are 20~5~4~
hydrogen, C1-C4-alkyl, phenyl which is unsubstituted or mono- or polysubstituted by radicals from the group comprising halogen, Cl-C4-alkyl, C~-C4-alkoxy, C1-C4-haloalkoxy and nitro, or in pairs are a C2-C6-alkylene chain and m = 0 to 6, and a radical of the formula R"O-CHR (OR")-Cl-C6-alkoxy, in which the radicals R" independently of one another are C1-C4-alkyl or together are a C1-C6-alkylene radical and R is hydrogen or C1-C4-alkyl, 10 n is an integer from 1 to 5, preferably 1 to 3, W is a divalent heterocyclic radical having 5 ring atoms, of the formula Wl to W4 ~N~ N~
R2 ~J
CooR3 (W1) (W2) N/ \
N - CH
(W3) (W4) in which R2 is hydrogen, C1-C~-alkyl, C1-Ca-haloalkyl, C3-C12-cycloalkyl or optionally substituted phenyl and R3 is hydrogen, C1-C3-alkyl, Cl-Ca-haloalkyl, Cl-C4-alkoxy-Cl-C4-alkylI Cl-C6-hydroxyalkyl, C3-Cl2-20cycloalkyl or tri-(C1-C4-alkyl)silyl, or the salts of said compounds.
- 6 - 6~
Herbicidal agents according to the invention of par-ticular interest are those where, in the compounds of the formulae Bl and B2, Rl is hydrogen, C1-C12-alkyl or C3-C7-cycloalkyl, C2-C8-alkenyl or C2-C8-alkynyl, where the above carbon-containing radicals are unsubstituted or mono- or polysubstituted by halogen or mono- or disubsti-tuted, preferably monosubstituted by radicals from the group comprising hydroxyl, Cl-C4-alkoxy, Cl-C4-alkylthio, C2-C4-alkenyloxy, C2-C6-alkynyloxy, mono-and di-(Cl-C2-alkyl)-amino, (Cl-C4-alkoxy)carbonyl, C2-C4-alkenyloxycarbonyl, C2-C4-alkynyloxycarbonyl, Cl-C4-alkylcarbonyl, C2-C4-alkenylcarbonyl, C2-C4-alkynylcarbonyl,C1-C4-alkylsulfonyl, phenyl,phenyl-C1-C4-alkoxycarbonyl, phenoxy, phenoxy-Cl-C4-alkoxy, phenoxy-(Cl-C4-alkoxy)carbonyl, where the last-mentioned 6 radicals in the phenyl ring are unsub-stituted or mono- or polysubstituted by radicals from the group comprising halogen, Cl-C2-alkyl, Cl-C2-alkoxy, Cl-C2-haloalkyl, C1-C2-haloalkoxy and nitro, and radicals of the formulae -SIR'3, -O-N=CR'2, -N=CR~2, -N=CR'2 and -O-NR'2, in which the R' in said formulae independently of one another are hydrogen, Cl-C2-alkyl, phenyl which is unsubstituted or mono-or polysubstituted by radicals from the group comprising halogen, Cl-C2-alkyl, Cl-C2-alkoxy, Cl-C2-haloalkyl, Cl-C2-haloalkoxy and nitro, or in ~airs are a C4-C5-alkanediyl chain.
Herbicidal agent~ according to the invention also of particular interest are those where, in the compounds of the formulae Bl and B2, X i6 hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or Cl-C2-haloalkyl, preferably hydrogen, halogen or Cl-C2-haloalkyl.
- 7 - 2~8~$~
Preferred herbicidal agents according to th~ invention are those where, in the compounds of the formula Bl, X is hydrogen, halogen, nitro or Cl-C4-haloalkyl, n is a number from 1 to 3, Z is a radical of the formula ORl, R1 is hydrogen, C1-C8-alkyl or C3-C7-cycloalkyl, where the above C-containing radicals are unsub-stituted or mono- or polys~bstituted by radicals from the group comprising halogen or mono- or disubstituted, preferably unsubstituted or monosub-stituted, by radicals from the group comprising hydroxyl, Cl-C4-alkoxy, (C1-C4-alkoxy)carbonyl, C2-C6-alkenyloxycarbonyl, (C2-C6~alkynyloxy)carbonyl and radicals of the formulae -SiR'3, -O-N=CR'2, -N=CR'2 and -O-NR'2, in which the radicals R' in said formulae independently of one another are hydrogen or Cl-C4-alkyl or in pairs are a C4-C5-alkylene chain, R2 is hydrogen, Cl-Ce-alkyl, Cl-C6-haloalkyl, C3-C7-cycloalkyl or phenyl and 0 R3 is hydrogen, Cl-C8-alkyl, Cl-C8-haloalkyl, (Cl-C4-alkoxy)-Cl-C4-alkyl, Cl-C6-hydroxyalkyl, C3-C7-cyclo-alkyl or tri-(Cl-C4-alkyl)silyl.
Preferred herbicidal agents according to the invention are also those where, in the compounds of the formula B2, X is hydrogen, halogen or Cl-C4-haloalkyl and n is a number from 1 to 3, pxeferably (X)n = 5-Cl, Z is a radical of the formuls OR1, R is CH2 and Rl is hydrogen, Cl-C8-alkyl, Cl-C8-haloalkyl, (Cl-C4-alkoxy)-Cl-C4-alkyl or ~Cl-C4-alkenyloxy)-Cl-C4-alkyl, prefexably Cl-C8-alkyl.
Particularly preferred herbicidal agent~ according to the invention are those containing compounds of the formula ~1, in which 208~ ~%
W is Wl, X is H, halogen or C1~C2-haloalkyl and n = 1 - 3, in particular (X) n = 2 ~ 4 -C12 ~
Z is a radical of the formula OR1, R1 is hydrogen, C1-C8-alkyl, C1-C4-haloalkyl, Cl-C4-hydroxyalkyl, C3-C7-cycloalkyl, (cl-c4-alkoxy)-cl-c4-alkyl or tri-(C1-C2-alkyl)-silyl, preferably Cl-C4-alkyl, R2 is hydrogen, C1-C~-alkyl, C1-C4-haloalkyl or C3-C7-cycloalkyl, preferably hydrogen or C1-C4-alkyl, and R3 is hydrogen, C1-CB-alkyl, C1-C4-haloalkyl, C1-C4-hydroxyalkyl, C3-C7-cycloalkyl, (C1-C4-alkoxy)-C1-C4-alkyl or tri-(C1-C2-alkyl)silyl, preferably hydrogen or C1-C4-alkyl.
15 Particularly preferred herbicidal agents according to the invention are also those containing compounds of the formula Bl, in which W is W2~
X is H, halogen or C1-C2-haloalkyl and n = 1 - 3, in particular (X) n = 2~4 -C12, Z is a radical of the formula OR1, R1 is hydrogen, C1-C~-alkyl, C1-C4-haloalkyl, C1-C4-hydroxyalkyl, C3-C7-cycloalkyl, (C1-C4-alkoxy)-C1-C4-alkyl or tri-(C1-C2-alkyl)silyl, preferably C1-C4-alkyl and R2 is hydrogen, C1-C~-alkyl, C1-C4-haloalkyl, C3-C7-cycloalkyl or phenyl, preferably hydrogen or Cl-C4-alkyl.
Particularly preferred herbicidal agents according to the invention are also those containing compounds of the formula Bl, in which W is W3, X is H, halogen or C1-C2-haloalkyl and n = 1 - 3, in particular (X) n = 2 ~ 4-Cl2 ~ 5 Z is a radical of the formula OR1, 208~ 48 Rl is hydrogen, C~-C8-alkyl, C1-C4-haloalkyl, Cl-C4-hydroxyalkyl, C3-C7-cycloalkyl, (Cl-C4-alkoxy)-Cl-C4-alkyl or tri-(Cl-C2-alkyl)silyl, preferably Cl-C4-alkyl and R2 is Cl-C8-alkyl or Cl-C4-haloalkyl, preferably Cl-haloalkyl.
Particularly preferred herbicidal agents a~cording to the invention are also those containing compounds of the formula B1, in which W is W4, X is hydrogen~ halogen, nitro, Cl-C4-alkyl or Cl-C2-haloalkyl, preferably CF3, or Cl-C4-alkoxy, n is l to 3, Z is a radical of the formula ORl, 5 R1 is hydrogen, Cl-C4-alkyl or (C1-C4-alkoxy)carbonyl-Cl-C4-alkyl, preferably (cl-c4-alkoxy)-co-cH2-~( alkoxy)-CO-C(CH3)H-, HO-CO-CH2- or HO-CO-C(CH3)H-.
In the formulae, alkyl, alkenyl and alkynyl are straight-chain or branched; the same applies to substituted alkyl, alkenyl and alkynyl radicals such a haloalkyl, hydroxy-alkyl, alkoxycarbonyl etc.; alkyl is, for example, methyl, ethyl, n- and i-propyl, n-, i-, t- and 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1,3-di-methylbutyl, heptyls, such as n-heptyl, l-methylhexyl and 1,4-dimethylpentyl; alkenyl is, for example, allyl, l-methylprop-2-en-l-yl, but-2-en-l-yl, but-3-en-1-yl, l-methylbut-3-ene and 1-methylbut-2-ene; alkynyl i~, for example, propargyl, but-2-yn-1-yl, but 3-yn-l-yl, l-methyl-but-3-yne; halogen iB fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine; haloalkyl, -alkenyl and -alkynyl are alkyl, alkenyl or alkynyl substituted by halogen, for example such as CF3, CHF2, CH2F, CF3CF2, CH2FCHCl, CCl3, CHCl2, CH2CH2Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F, CF3CF20, CF3CH20;
optionally substituted phenyl is, for example, phenyl 2a~ 8 which is unsubstituted or mono- or polysubstituted by radicals from the group comprising halogen, Cl-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3-and 4-chlorophenyl, 2-, 3- and 4-trifluoro- and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, and o-, m- and p-methoxyphenyl.
The compounds of the formula Bl are disclosed in EP-A-333 131, EP-A-269 806, EP-A-346 620, International Patent Application PCT/EP gO/01966 and International Application No. PCT/EP 90/02020 and literature cited therein or can be prepared by or analogously to the processes described therein. The compounds of the formula B2 are disclosed in EP-A-86 750, EP-A-94 349 and EP-A-l91 736 and literature cited therein or can be prepared by or analogously to the processes described therein. ~hey are additionally proposed in German Patent Application P 40 41 121.4.
Suitable mixed combinations of the type A are ALS in-hibitor herbicides according to the invention, such as sulfonylureas and imidazolinones, as well as substituted pyrimidines and triazones which can be employed in a mixture or applied separately with other plant-protection agents, such as insecticides, for example organo-phosphates, or herbicides.
Such ALS inhibitors of the 6ulfonylurea type are, forexample, the known compounds priml~ulfuron-methyl, nicosulfuron, DPX-E-9636, amidosulfuron, thiameturon-methyl, NC319 (EP-A-282 613) and other disclosed active substances and pyridylsulfonylureas (German Patent Application P 40 30 577.5) and alkoxyphenoxysulfonylureas (EP-A-342 569) and mixtures of said active substances with one another.
~8~
Suitable compounds are pyridylsulfonylureas of the formula Al or their salts, R~
~ ~ R R6 Rs ~ //\\ ~ ~ ~ ~ (A1) in which R is hydrogen, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or ~rialkylammonium, E is CH or nitrogen, R4 is halogen or NR9R10, R5 is hydrogen, halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy,C1-C3-haloalkyl,C1-C3-haloalkoxy,C1-C3-alkyl-thio, (C1-C3-alkoxy)-C1-C3-alkyl, (C1-C3-alkoxy)carbonyl, mono- or di(C1-C3-alkyl)amino, Cl-C3-alkylsulfinyl or sulfonyl, SO2-NR4Rb or CO-NRaRb, R6 is hydrogen or CH3, R7 is halogen, C1-C2-alkyl,Cl-C2-alkoxy, C1-C2-haloalkyl, C1-C2-haloalkoxy or OCH2CF3, R8 is C1-C2-alkyl, C1-C2-haloalkoxy or C1-C2-alkoxy and R9 is Cl-C4-alkyl and R10 is C1-C4-alkylsulfonyl or R9 and Rl together are a chain of the formula -(CH2)3S02- or -(CHz)4SO2-r or alkoxyphenoxysulfonylureas of the formula A2 or their salts, Rl4 ( R 1 2 ) ~ ~S~ ~ 1N--1R 15 1.... 1,~
R R
in which 12 2~8~8 R"" is hydrogen, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium, E is CH or nitrogen, Rl1 is methoxy, ethoxy, propoxy, isopropoxy or Cl-C4-alkoxycarbonyl, RlZ is hydrogen, halogen, NO2, CF3, CN, C1-C4-alkyl, Cl-C4-alkoxy, Cl-C4-alkylthio or (Cl-C3-alkoxy)-carbonyl, n is 1, 2 or 3, Rl3 is hydrogen, Cl-C4-alkyl or C3-C4-alkenyl, R14 and Rl5 independently of one another are halogen, Cl-C2-alkyl, Cl-Cz-alkoxy, Cl-C~-haloalkyl, Cl-C2-halo-alkoxy or (Cl-C2-alkXY)-cl-c2-al~yl-ALS inhibitors of the imidazolinone type are imazethapyr, 15 imazaquin, imazethamethapyr (AC-263222) and other related compounds and mixtures thereof.
Suitable substituted pyrimidines and triazines have the formula C
N ~ R2~
N ~ (C) in which X' is oxygén, sulfur or NR24, Y' is nitrogen or CH, R22 and R23 independently of one another are hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, Cl-C4-alkylmer-25 capto, C~-C4-alkylamino or di-Cl-C4-alkylamino, R2l is a substituted aryl or heteroaryl radical of the formula - 13 - 20~4~
R 2 s~( w ) n ~R26 or ~ ~ ~ ~502R
n~ is 0 or 1, W' is -O-, -NR24-, -S-, -ON(R31)- or -o-N=C(R31), X' is N, N~O or CR24, S R24 is defined as R22 or R23, RZ5 is halogen, cyanor nitro, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Cl-C4-alkoxy, haloalkyl or haloalkoxy, R26 is C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, alkali metal or 1 equivalent of alkaline earth metal, alkylammonium, aryl, CF3 or (CHR33)m.CHR27R2B where m' = 0 or 1, R27 and R33 independently of one another are hydrogen, Cl-C4-alkyl or Cl-C4-alkoxy, R2~ is C1-C4-alkoxycarbonyl, cyano, halogen, acetyl, pivaloyl, benzoyl, C1-C4-alkoxy, aryloxy, halo-acetoxy, methanesulfonyloxy, hydroxyl, C1-C4-alkyl-mercapto,C1-C4-alkylsulfonyl,arylmercapto,di-C1-C4-alkylamino, pyridyl, aryl or CoNR2aR30, R29 and R30 independently of one another are hydrogen, C1-C4-alkyl, C~-C4-alkenyl, aryl or benzyl, R31 is hydrogen ox C1-C4-alkyl or R26 and R31 together are methylene, ethanediyl or pro-panediyl and aryl i8 phenyl or naphthyl, each of which i~ unsubsti-tuted or mono- or disubstituted by halogen, Cl-C4-alkyl, C1-C4-alkoxy, phenoxy, nitro and/or C1-C4-alkoxycarbonyl, or R11 is a radical of the formula 2085~48 - ~4 -R~200~ ~ or ~ ~9 R34 iB hydrogen, halogen, halo-Cl-C4-alkyl, C1-C4-cyclo-alkyl, Cl-C4-alkylmercapto-C1-C4-alkyl, hydroxyl-Cl-C4-alkyl, hydroxyl, cyano, aryloxyalkyl, thienyl, aryl, dihydronaphthyl or ,R
( CH2 )m~
where aryl is as defined above, R40 is hydrogen, halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy or S(O)p.R , R41 is alkyl, p' is a 0, 1 or 2, m" is a 0, 1 or 2, R3s and R36 independently of one another are hydrogen or C1-C4-alkyl, or these, together with the carbon atom, are a 3-, 4-, 5- or 6-membered cycloalkane ring, in which a methylene group can be replaced by oxygen and which can be substituted by one or two C1-C4-alkyl groups, R37 and R3~ independently of one another are hydrogen or Cl-C4-alkyl, R39 is Cl-C4-alkyl or phenyl, or R38 and R3~ are -(CH2)l- where l = 3 or 4, which can be substituted by one or two C1-C4-alkyl groups, R42 is hydrogen, C1-C4-alkyl,C1-C4-alkenyl, C1-C4-alkynyl, phenyl, C1-C4-alkylidenamino, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, halo-C1-C4-- 15 _ 2~8~ ~ ~8 alkyl, cycloalkyl, nitro-substituted phenylmercapto-Cl-C4-alkyl, halogen or benzyl which can be substi-tuted by Cl-C4-alkyl or Cl-C4-alkoxy, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium.
The various types of ALS inhibitors can also be mixed with one another. Other active substance structures which inhibit the enzyme ALS, for example herbicidal sulfona-mides such as flumetsulam (DE-498) and the like are also possible here. Possible combination components in the ~mixture~ of the type A are the following plant-protec-tion agents, where the indiYidual components can be applied toge~her or separately from one another at an interval of time of up to several weeks:
1.) Insecticidal preparations such as organophosphates, for example terbufos (~Counter~, fonofos (~Dyfonate), phorate (~Thimet), chlorpyrifos (Reldan) and other rela~éd active substances, insecticidal carbamates such as, for example, carbofuran (0Furadan) and others; as well as pyrethroid insecticides such as, for example, tefluthrin (~Force), deltamethrin (~Decis) and tralomethrin (Scout) and others; as well as other insecticidal agents having a different mechanism of action.
5 2.) Herbicides which are employed as components, in order to widen the spectrum of action of ALS
inhibitors and to improve the activity, such a~, for example, bentazone, cyanazine, bromoxynil or other herbicides which are absorbed through the leaf.
The following groups of compounds have proven suitable as safeners for the abovementioned product combinations:
a) Compounds of the dichlorophenylpyrazoline-3-car-boxylic acid type (i.e. of the formula ~1, in which - 16 - ~8~8 W = Wl and (X)n = 2,4-Cl2), preferably compounds such as ethyl l-(2,4-dichlorophenyl)-5-(ethoxycarbonyl-5-methyl-2-pyrazoline-3-carboxylate (Bl-l) and related compounds, such as are described in Inter-national Application PCT/EP 90/02020, b3 Derivatives of dichlorophenylpyrazolcarboxylic acid (i.e. of the formula Bl, in which W = W2 and (X)n =
2,4-C12), preferably compounds ~uch as ethyl l-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (B1-2), ethyl 1-(2,4-dichlorphenyl)-5-isopropyl-pyrazole-3-carboxylate (Bl-3), ethyl l-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (B1-4), ethyl 1~(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate ~Bl-5) and related compounds, such as are described in EP-A-0 333 131 and EP-A-0 269 806.
c) Compounds of the triazolecarboxylic acid type (i.e.
of the formula B1 in which W = W3 and (X)n =
2~4-Clz)~ preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-(lH)-1,2,4-tria-zole-carboxylate (Bl-6, fenchlorazole) and related compounds (see EP-A-0 174 562 and EP-A-0 346 620);
d) Compounds of the dichlorobenzyl-2-isoxazoline-3-carboxylic acid type (i.e. of the formula B1, in which W = W4 and (X)~ = 2,4-Cl2), preferably com-pounds such as ethyl 5-(2,4-dichlorohenzyl)-2-iso-axazoline-3-carboxylate (B1-7) and related com-pounds, such as are described in International Application PCT/EP 90/01966.
0 e) Compounds of the (5-chloro-8-quinolinoxy)acetic acid type (i.e. of the formula B2, in which (X)n = 5-Cl, Z = OR1, R = CH2), preferably compounds such as l-methylhex-l-yl (5-chloro-8-quinolihoxy)acetate (B2-l), 1,3-dimethylbut-1-yl (5-chloro-8-quino-- 17 _ 2~ 8 linoxy)acetate (B2-2), 2-allyloxy-1-methylethyl (5-chloro-8-quinolinoxy)acetate (B2-3) and related compounds, such as are described or have been proposed in EP-A-86 750, EP-A-94 349 and EP-A-l91 736 and German Patent Application P 40 41 121.4.
The safeners (antidotes) of the above groups a) to e) reduce or suppress phytotoxic effects which can occur when using the product combinations in productive plant crops, without impairing the activity of the herbicides against harmful plants. By this means, the field of use of the mixtures can be very considerably widened and extended, for example, to crops such as maize, wheat, barley and other gramineous crops in which until now use 1~ of the combinations has not been possible or only restri-ctively possible, i.e. at low doses with not very wide action.
The herbicidal ALS inhibitors and their combination components and the safeners mentioned can be applied together (as a finished formulation or in a tank-mix process) or in any desired sequence in succession. The weight ratio safener: herbicide (ALS inhibitor) can vary within wide limits and is preferably in the range from 1:10 to 10:1, in particular from 1:10 to S:l. The optimum amounts of herbicide and safener in each case are depen-dent on the type of herbicide used or on the safener used and on the nature of the plant population to be treated and can be determined from case to case by appxopriate preliminary experiments. The application rate of the insecticide or herbicide additionally employed is depen-dent on its activity alone and corresponds to the general product recommendations.
Principal fields of use for the application of the safeners are, in particular, maize and cereal crops, (wheat, rye, barley, oats), rice and sorghum, but also - 18 ~ 8 cotton and soybean, preferably maize.
Depending on their properties, the safeners of the type B can be used for the pretreatment of the seeds of the crop plant (dressing of the seeds) or introduced into the seed furrows before the seed or applied together with the herbicide before or after the emergence of the plants.
Pre-emergence treatment includes both the treatment of the cultivation areas before sowing and the treatment of the sown, but not yet covered cultivation surfaces.
Application together with the herbicide is preferred, i.e. with the ALS inhibitor. Tank mixtures or finished formulations can be employed for this.
The required application rates of the safeners can vary within wide limits depending on the indication and herbicide used and are as a rule in the range from 0.001 to l kg, preferably 0.005 to 0.2 kg, of acti~e substance per hectare.
The present invention therefore also relates to a process for the protection of crop plants from phytotoxic side effects of herbicide combinations, which comprises applying to the plants, plant seeds or the cultivation surface an effective amount of a compound of said type B) before, after or at the same time as the herbicide of said type A) in combination with an insecticide or herbicide.
The compounds of the type B) and their combinations with one or more of said herbicides (ALS inhibitors) can be formulated in various ways, depending on which biological and/or chemico-physical parameters are specified. Suit-able formulation possibilities are, for example:
Wettable powders (WP), emulsifiable concentrates (EC),water-soluble powders (SP), water-soluble concentrates (SL), concentrated emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions or 2~8~48 emulsions, capsule suspensions (CS), dispersions on an oil or water basis (SC), suspoemulsions, suspension concentrates, dusting agents (DP), oil-miscible solutions (OL), dressing agents, granules (GR) in the form of micro granules, spray granules, coated granules and adsorption granules, granules for application to the soil or scat-tering, water-soluble granules (SG), water-dispersible granules (NG), ULV formulations, microcapsules and waxes.
These individual formulation types are known in principle and are described, for example, in: Winnacker-Ruchler, "Chemische Technologie~ (Chemical Technology) Volume 7, C. Hauser Verlag Munich, 4th Ed. 1986; Wade van Valkenburg, "Pesticide Formulations~, Marcel Dekker N.Y., 1973; K. Martens, "Spray Drying Handbook~, 3rd Ed. 1979, G. Goodwin Ltd. London.
The required formulation auxiliaries such as inert materials, surfactants, solvents and other additives are likewise known and are described, for example, in:
Watkins, ~Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J.;
H.v. Olphen ~'Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y., Marsden "Solvents Guide", 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.;
Sisley and Wood, "Encyclopedia of Surface Active Agents~, Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzflach-enaktive Athylenoxidaddukte" (Surface-active Ethylene Oxide Adducts), Wiss. Verlagsgesell., Stuttgart 1976;
Winnacker-Kuchler "Chemische Technologie" tChemical Technology) Vol./4th Ed, 7, C. Hauser Verlag Munich, 1986.
On the basis of these formulations, combinations with other pesticidally active substances, such as insecticides, fungicides, fertilizers and/or growth regulators, can be prepared, for example in the form of ~o~ 8 a finished formulation or as a tank-mix.
Wettable powders are preparations which are uniformly dispersible in water and which, besides the active substance, also contain wetting agents, for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols and fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates or alkylarylsulfonates and dispersing agents, for example sodium ligninsulfonate, sodium 2,2-dinaphthylmethane-6-6~-disulfonate, sodium dibutylnaphthalenesulfonate or alternatively sodium oleoylmethyltauride in addition to a diluent or inert substance.
Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or alternatively higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. Examples of emulsifiers which can be used are: alkylarylsulfonic acid calcium salts such as Ca dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide conden-sation products ~for example block polymers), alkyl polyethers, sorbitan fatty acid estars, polyoxyethylene-sorbitan fatty acid esters of polyoxyethylenesorbitolesters.
Dusting agents can be obtained by grinding the active substance with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite and pyrophillite, or diatomaceous earth.
Granules can be produced either by spraying the active substance onto adsorptive, granulated inert material or by applying active substance concentrates to the surface of carriers, such as sand, kaolinites or granulated inert - 21 - 208~48 material, by means of binders, for example polyvinyl alcohol, sodium polyacrylate or alternatively mineral oils. Suitable active substances can also be granulated in the manner which is customary for the production of fertilizer granules, if desired in a mixture with fer-tilizers.
The agrochemical preparations as a rule contain 0.1 to 99 ~ by weight, in particular 0.1 to 95 % by weight, of active substances of type B) or of antidote/herbicide active substance mixture A) and B) and 1 to 99.9 % by weight, in particular 5 to g9.~ % by weight, of a solid or liquid additive and 0 to 25 % by weight, in particular 0.1 to 25 % by weight, of a surfactant.
The concentration of active substance in wettable powders is, for example, about 10 to 90 % by weight; the remainder to 100 % by weight is composed of customary formulation component In the case of emulsifiable concentrates, the active substance concentration is about 1 to 80 ~ by weight of active substances. Formulations in the form of dusts contain about 1 to 20 % by weight of active substances, sprayable solutions about 0.2 to 20 %
by weight of active substances. In the case of granules such as water-dispersable granules, the active substance content depends partly on whether the active substance is liquid or solid. As a rule, the contents in the case of the water-dispersable granules is between 10 and 90 % by weight.
In addition, said active sub~tance formulations optionally contain the tackifiers, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers customary in each case.
For use, the formulations, present in commercially available form, are diluted, i~ appropriate, in a customary manner, for example by means of water in the 2~
case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. Preparations in the form of dusts, granules and sprayable solutions are customarily not further diluted with other inert substances before use. Particularly good activitieæ of the agents according to the invention can be achieved if other wetting agents in concentrations of 0.1 to 0.5 % by weight are added in the tank-mix process to the surfac-tants contained in the formulations, for example nonionic wetting agents or wetting agents of the fatty alcohol polyol ether sulfate type (see, for example, German Patent Application P 40 29 304.1). The required applica-tion rate of the "safener" varies with the external conditions such as temperature, humidity, the nature of the herbicide used and the like.
The following examples serve to illustrate the invention without restricting it thereto:
A. Formulation examples a) A dusting agent is obtained by mixing 10 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B) and 90 parts by weight of talc as inert substance and comminuting the mixture in a hammer mill.
b) A wettable powder which is readily dispersible in water is obtained by mixing 25 part~ by weight of a substance of type B) or of an active substance mixture type A) and a safener of type B), 64 parts by weight o~ kaolin-containing quartz as inert substance, 10 parts by weight of potassium ligninsulfonate and 1 part by weight of sodium oleoylmethyltauride as a wetting and dispersing agent and grinding the mixture in a pinned-disk mill.
2 ~
c) A dispersion concentrate which is readily disper-sible in water is obtained by mixing 20 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B), 6 parts by weight of alkylphenol polyglycol ether ~registered trademark ~Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 E0) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to over 277C), and grinding the mixture in a ball mill to a fineness of less than 5 microns.
d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B), 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of ethoxylated nonyl-phenol as an emulsifier.
e) Water-dispersable granules are obtained by mixing 75 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type B), 10 " of calcium ligninsulfonate, 5 " of sodium lauryl sulfate 25 3 " of polyvinyl alcohol and 7 " of kaolin, grinding the mixture in a pinned-di0k mill and granulating the powder in a fluidized bed by spraying water as a granulating fluid.
0 f) Water-dispersable granules are also obtained by homogenizing 25 parts by weight of a compound of type B) or of an active substance mixture of type A) and a safener of type 2a8~8 B), o f s o d i u m 2 , 2 ~ -dinaphthylmethane-6,6'-disulfonate, 2 parts by weight of sodium oleoylmethyltauride, 1 " of polyvinyl alcohol, 17 ~I of calcium carbonate and 50 " of water in a colloid mill and precomminuting, then grinding the mixture in a bead mill and atomizing and drying the suspension thus obtained in a spray tower by means of a single substance nozzle.
The insecticides or herbicides additionally used can be added both in the tank-mix process, or applied separately from the finished formulation composed of ALS inhibitor and safener of the type B.
The active substance mixture A is in each case composed of an ALS inhibitor and an insecticide and/or another herbicide.
B. Biological examples The crop plants were cultivated up to the 4-leaf stage in open ground or in a greenhouse in plastic pots and then treated according to the invention with compoundæ of type A) and B) post-emergence. The compounds of type A) and B) were in this case applied in the form of aqueous suspensions br emulsions at a water application rate of, after conversion, 300 l/ha. 4 week~ after treatment, the plant6 were visually as6e~sed for any typ~ of damage due to the applied herbicides, the extent of prolonged inhibition of growth being taken particularly into account. Assessment was carried out in percentage values in comparison with untreated controls.
The result~ in the following tables illustrate that the compounds of type B) employed according to the invention 2~8~
can effectively reduce severe damage to crop plants. Even very severe damage is markedly reduced and slight damage is completely abolished. Combinations of ALS inhibitors and mixture components and compounds of type B) are therefore outstandingly suitable for the selective control of weeds in maize.
Example 1 Type A Type B Type A Type B
Herbicide combination Safener g of AS/ha g of AS/ha X damage (ALS inhibitor) to thQ
crop plant maize Hl + terbufos - 25 + 500 0 100 12 + 500 0 80 primisulfuron - 100 + 500 0 100 + terbufos 50 + 500 0 70 nicosulfuron - 200 + 500 0 90 + terbufos 100 + 500 0 80 terbufos - 500 0 0 primisulfuron B2-1 100 + 500 100 70 50 + 500 50 40 Hl + terbufos B2-2 25 + 500 25 50 12 + 500 12 20 nicosulfuron B2-3 200 + 500 200 40 + terbufos 100 + 500 100 30 Hl ~ 25 0 40 primisulfuron - 100 0 50 nicosulfuron - 200 0 30 Greenhouse experiment with 4 repetitions.
2o8~8 Sowing of maize in a pure sand culture. Terbufos was scattered on the soil surface as granules immediately after sowing. All other treatments were carried out in the 4-leaf stage. Naize variety "~FELIX".
H1 = CH
1 ~
CO/ ~<N~
S Example 2:
OCH~
Type AS~ha ~ damag~ to maize varieties FELIX DEA
bentazone 2.0 0 0 1.0 0 0 0.5 0 0 bromoxynil 1.0 20 30 0.5 20 30 0.25 10 15 15 primisulfurone 0.100 25 20 0.050 10 8 0.025 5 5 bentazone + 2.0 + 0.05 30 35 + prlmisulfuron 1.0 -~ 0.05 15 20 20 bentazone + 2.0 ~ 0.05 + 0.1 10 15 + primisulfuron 1.0 + 0.05 + 0.1 0 5 + Hl bromoxynil + 1.0 + 0.05 55 50 + primisulfuron 0.5 + 0.05 40 35 20~5~48 bromoxynil + 1.0 + 0.05 + 0.1 lS 15 + primisulfuron 0.5 + 0.05 + 0.1 5 0 + Hl Application in the 4-leaf stage cf the maize, height 23 - 26 cm.
Assessment: 4 weeks aftsr treatment
Claims (13)
1. A herbicidal agent, which comprises A) one or more herbicides from the sulfonylurea, im-idazolinone and pyrimidine or triazine derivative group and other agents such as insecticides and herbicides and B) one or more compounds of the formulae B1 and B2, (B1) (B2) in which X is hydrogen, halogen, C1-C4 alkyl, C1-C4-alkoxy, nitro or C1-C4-haloalkyl, Z is OR1, SR1, NR1R, where R is H, C1-C6-alkyl, C1-C6-alkoxy or optionally substituted phenyl, or a saturated or unsaturated 3- to 7-membered hetero-cycle having at least one nitrogen atom and up to 3 hetero atoms, which is bonded to the carbonyl group via the nitrogen atom and is unsubstituted or substituted by radicals from the group comprising C1-C4-alkyl, C1-C4-alkoxy and optionally substituted phenyl, R is a C1-C2-alkylene chain which can additionally be substituted by one or two C1-C4-alkyl radicals, R1 is hydrogen, C1-C18-alkyl, C3-C12-cycloalkyl, C2-C8-alkenyl or C2-C8-alkynyl, where the above carbon-containing radicals are unsubstituted or mono- or polysubstituted by radicals from the group comprising halogen, hydroxyl, C1-C8-alkoxy, C1-C8-alkylthio, C2-C8-alkenylthio, C2-C8-akynylthio, C2-C8-alkenyloxy, C2-C8-alkynyloxy, C3-C7-cycloalkyl, C3-C7-cycloalkoxy, cyano, mono- and di-C1-C4-alkylamino, C1-C8-alkoxycarbonyl, C2-C8-alkenyloxycarbonyl, C1-C8-alkylthiocarbonyl, C2-C8-alkynyloxycarbonyl, C1-C8-alkylcarbonyl, C2-C8-alkenylcarbonyl, C2-C8-alkynylcarbonyl, C1-C8-alkylcarbonylamino,C2-C8-alkenylcarbonylamino, C2-C8-alkynylcarbonylamino, aminocarbonyl, C1-C8-alkylaminocarbonyl, di-C1-C6-alkylaminocarbonyl, C2-C6-alkenylaminocarbonyl, C2-C6-alkynylamino-carbonyl, C1-C8 alkoxycarbonylamino, C1-C8-alkylaminocarbonylamino, C1-C6-alkylcarbonyloxy, which is unsubstituted or substituted by halogen, NO2, C1-C4-alkoxy or optionally substituted phenyl, C2-C6-alkenylcarbonyloxy, C2-C6-alkynylcarbonyloxy, C1-C8-alkylsulfonyl, phenyl, phenyl-C1-C6-alkoxy, phenyl-C1-C6-alkoxycarbonyl, phenoxy, phenoxy-C1-C6-alkoxy, phenoxy-C1-C6-alkoxycarbonyl, phenylcar-bonyloxy, phenylcarbonylamino, phenyl-C1-C6-alkylcar-bonylamino, where the last-mentioned 9 radicals in the phenyl ring are unsubstituted or mono- or poly-substituted by radicals from the group comprising halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy and nitro, and radicals of the formulae -SiR'3, -O-SiR'3, (R')3Si-C1-C6-alkoxy, -CO-O-NR'2, -O-N=CR'2, -N=CR'2, -O-NR'2-CH(OR')2 and -O-(CH2)m-CH(OR'2)2, in which the R' in said formulae independently of one another are hydrogen, C1-C4-alkyl, phenyl which is unsubstituted or mono- or polysubstituted by radicals from the group com-prising halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and nitro, or in pairs are a C2-C6-alkylene chain and m = O to 6, and a radical of the formula R"O-CHR'"(OR")-C1-C6-alkoxy, in which the radical R" independently of one another are C1-C4-alkyl or together are a C1-C6-alkylene radical and R'" is hydrogen or C1-C4-alkyl, n is an integer from 1 to 5, W is a divalent heterocyclic radical having 5 ring atoms, of the formula W1 to W4 (W1) (W2) (W3) (W4) in which R2 is hydrogen, C1-C8-alkyl, C1-C8-haloalkyl, C3-C12-cycloalkyl or optionally substituted phenyl and R3 is hydrogen, C1-Ca-alkyl, C1-C8-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C6-hydroxyalkyl, C3-C12-cycloalkyl or tri-(C1-C4-alkyl)silyl, or the salts of said compounds.
2. An agent as claimed in claim 1, wherein R1 is hydrogen, C1-C12-alkyl or C3-C7-cycloalkyl, C2-C8-alkenyl or C2-C8-alkynyl, where the above carbon-containing radicals are unsubstituted or mono- or polysubstituted by halogen or mono- or disubsti-tuted, preferably monosubstituted by radicals from the group comprising hydroxyl, C1-C4-alkoxy, C1-C4-alkylthio, C2-C4-alkenyloxy, C2-C6-alkynyloxy, mono-and di-(C1-C2-alkyl)-amino, (C1-C4-alkoxy)carbonyl, C2-C4-alkenyloxycarbonyl, C2-C4-alkynyloxycarbonyl, C1-C4-alkylcarbonyl, C2-C4-alkenylcarbonyl, C2-C4-alkynylcarbonyl, C1-C4-alkylsulfonyl, phenyl,phenyl-C1-C4-alkoxycarbonyl, phenoxy, phenoxy-C1-C4-alkoxy, phenoxy-(C1-C4-alkoxy)carbonyl, where the last-men-tioned 6 radicals in the phenyl ring are unsubsti-tuted or mono- or polysubstituted by radicals from the gxoup comprising halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl, C1-C2-haloalkoxy and nitro, and radicals of the formulae -SiR'3, -O-N=CR'2, -N=CR'2 and -O-NR'2, in which the R' in said formulae independently of one another are hydrogen, C1-C2-alkyl, phenyl which is unsubstituted or mono- or polysubstituted by radicals from the group com-prising halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl, C1-C2-haloalkoxy and nitro, or in pairs are a C4-C5-alkenyl chain.
3. An agent as claimed in claim 1 or 2, wherein in the compounds of the formula B1, X is hydrogen, halogen, nitro or C1-C4-haloalkyl, n is a number from 1 to 3, Z is a radical of the formula OR1, R1 is hydrogen, C1-C8-alkyl or C3-C7-cycloalkyl, where the above carbon-containing radicals are unsubstituted or mono- or polysubstituted by radicals from the group comprising halogen or mono-or disubstituted, preferably unsubstituted or monosubstituted, by radicals from the group comprising hydroxyl, C1-C4-alkoxy, (C1-C4)-alkoxy)carbonyl, C2-C6-alkenyloxy)carbonyl, (C2-C6-alkynyloxy)carbonyl and radicals of the formulae -SiR'3, -O-N=CR'2, -N=CR'2 and -O-NR'2, in which the radicals R' in said formulae independently of one another are hydrogen or C1-C4-alkyl or in pairs are a C4-C5-alkanediyl chain, R2 is hydrogen, C1-C8-alkyl, C1-C6-haloalkyl, C3-C7-cycloalkyl or phenyl and R3 is hydrogen, C1-C8-alkyl, C1-C8-haloalkyl, (C1-C4-alkoxy)-C1-C4-alkyl, C1-C6-hydroxyalkyl, C3-C7-cyclo-alkyl or tri-(C1-C4-alkyl)silyl.
4. An agent as claimed in one or more of claims 1 to 3, wherein in the compounds of the formula B2, X is hydrogen, halogen or C1-C4-haloalkyl and n is a number from 1 to 3, preferably (X)n = 5-Cl, Z is a radical of the formula OR1, R* is CH2 and R1 is hydrogen, C1-C8-alkyl, C1-C8-haloalkyl, (C1-C4-alkoxy)-Cl-C4-alkyl or (Cl-C4-alkenyloxy)-Cl-C4-alkyl, preferably C1-C8-alkyl.
5. An agent as claimed in one or more of claims 1 to 4, which contains one or more herbicides from the group c o m p r i s i n g p h e n y l s u l f o n y l u r e a s , thienylsulfonylureas, pyrazolsulfonylureas, sulfondiamide derivatives, pyridylsulfonylureas, alkoxyphenoxysulfonylureas, imidazolinones and pyrimidine or triazine derivatives in combination with other insecticides and herbicides.
6. An agent as claimed in one or more of claims 1 to 5, which contains one or more herbicides from the group comprising nicosulfuron, DPX-E-9636, amidosulfuron, thiameturon-methyl, NC 319, primisulfuron-methyl, pyridylsulfonylureas of the formula Al, (A1) in which R is hydrogen, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium, E is CH or nitrogen, R4 is halogen or NR9R10, R5 is hydrogen, halogen, cyano, C1-C3-alkyl, C1-C3-alkoxy,C1-C3-haloalkyl,C1-C3-haloalkoxy,C1-C3-alkyl-thio, (C1-C3-alkoxy)-C1-C3-alkyl, (C1-C3-alkoxy)carbonyl, mono- or di(C1-C3-alkyl)amino, C1-C3-alkylsulfinyl or sulfonyl, SO2-NRaRb or CO-NRaRb, R6 is hydrogen or CH3, R7 is halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl, C1-C2-haloalkoxy or OCH2CF3, R8 is C1-C2-alkyl, C1-C2-haloalkoxy or C1-C2-alkoxy and R9 is C1-C4-alkyl and R10 is C1-C4-alkylsulfonyl or R9 and R10 together are a chain of the formula -(CH2)3SO2- or -(CHZ)4SO2-, alkoxyphenoxysulfonylureas of the formula A2 (A2) in which R"" is hydrogen, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium, E is CH or nitrogen, R11 is ethoxy, propoxy or isopropoxy, R12 is hydrogen, halogen, NO2, CF3, CN, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio or (C1-C3-alkoxy)carbonyl, n is 1, 2 or 3, R13 is hydrogen, C1-C4-alkyl or C3-C4-alkenyl, R14 and R15 independently of one another are halogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-haloalkyl, C1-C2-halo-alkoxy or (C1-C2-alkoxy)-C1-C2-alkyl, or the salts of said compounds.
7. An agent as claimed in one or more of claims 1 to 6, which contains at least one active substance from the pyrimidine and triazine series, of the formula C
(C) in which X' is oxygen, sulfur or NR24, Y' is nitrogen or CH, R22 and R23 independently of one another are hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, C1-C4-alkylmer-capto, C1-C4-alkylamino or di-C1-C4-alkylamino, R21 is a substituted aryl or heteroaryl radical of the formula or n' is O or 1, W' is -O-, -NR24-, -S-, -oN(R31)- or -n-N=C(R31)-, Z' is N, N-O or CR24, R24 is defined as R22 or R23, R25 is halogen, cyano, nitro, C,-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4alkoxy, haloalkyl or haloalkoxy, R26 is C1-C4-alkyl, C2-C4alkenyl, C2-C4-alkynyl, alkali metal or 1 equivalent of alkaline earth metal, alkyl ammonium, aryl, CF3 or (CHR33)mCHR27R28 where m' = O
or 1, R27 and R33 independently of one another are hydrogen, C1-C4-alkyl or C1-C4-alkoxy, R28 is C1-C4-alkoxycarbonyl, cyano, halogen, acetyl, pivaloyl, benzoyl, C1-C4-alkoxy, aryloxy, halo-acetoxy, methanesulfonyloxy, hydroxyl, C1-C4-alkyl-mercapto,C1-C4-alkylsulfonyl,arylmercapto,di-C1-C4-alkylamino, pyridyl, aryl or CONR28R30, R29 and R30 independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, aryl or benzyl, R31 is hydrogen or C1-C4-alkyl or R26 and R31 together are methylene, ethanediyl or pro-panediyl and aryl is phenyl or naphthyl, each of which is unsubsti-tuted or mono- or disubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, phenoxy, nitro and/or C1-C4-alkoxycarbonyl, or R11 is a radical of the formula or R34 is hydrogen, halogen, halo-C1-C4-alkyl, C1-C4-cyclo-alkyl, C1-C4-alkylmercapto-C1-C4-alkyl, hydroxyl-C1-C4-alkyl, hydroxyl, cyano, aryloxyalkyl, thienyl, aryl, dihydronaphthyl or where aryl is as defined above, R40 is hydrogen, halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy or S(O)pR41, R41 is alkyl, P' is a 0, 1 or 2, m" is a 0, 1 or 2, R35 and R36 independently of one another are hydrogen or C1-C4-alkyl, or these, together with the carbon atom, are a 3-, 4-, 5- or 6-membered cycloalkane ring, in which a methylene group can be replaced by oxygen and which can be substituted by one or two C1-C4-alkyl groups, R37 and R38 independently of one another are hydrogen or C1-C4-alkyl, R39 is C1-C4-alkyl or phenyl, or R38 and R39 are -(CH2)1- where 1 = 3 or 4, which can be substituted by one or two C1-C4-alkyl groups, R42 is hydrogen, Cl-C4-alkyl, C1-C4-alkenyl, C1-C4-alkynyl, phenyl, C1-C4-alkylidenamino, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, halo-C1-C4-alkyl, cycloalkyl, nitro-substituted phenylmercapto-C1-C4-alkyl, halogen or benzyl which can be substi-tuted by C1-C4-alkyl or C1-C4-alkoxy, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium.
(C) in which X' is oxygen, sulfur or NR24, Y' is nitrogen or CH, R22 and R23 independently of one another are hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, C1-C4-alkylmer-capto, C1-C4-alkylamino or di-C1-C4-alkylamino, R21 is a substituted aryl or heteroaryl radical of the formula or n' is O or 1, W' is -O-, -NR24-, -S-, -oN(R31)- or -n-N=C(R31)-, Z' is N, N-O or CR24, R24 is defined as R22 or R23, R25 is halogen, cyano, nitro, C,-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4alkoxy, haloalkyl or haloalkoxy, R26 is C1-C4-alkyl, C2-C4alkenyl, C2-C4-alkynyl, alkali metal or 1 equivalent of alkaline earth metal, alkyl ammonium, aryl, CF3 or (CHR33)mCHR27R28 where m' = O
or 1, R27 and R33 independently of one another are hydrogen, C1-C4-alkyl or C1-C4-alkoxy, R28 is C1-C4-alkoxycarbonyl, cyano, halogen, acetyl, pivaloyl, benzoyl, C1-C4-alkoxy, aryloxy, halo-acetoxy, methanesulfonyloxy, hydroxyl, C1-C4-alkyl-mercapto,C1-C4-alkylsulfonyl,arylmercapto,di-C1-C4-alkylamino, pyridyl, aryl or CONR28R30, R29 and R30 independently of one another are hydrogen, C1-C4-alkyl, C2-C4-alkenyl, aryl or benzyl, R31 is hydrogen or C1-C4-alkyl or R26 and R31 together are methylene, ethanediyl or pro-panediyl and aryl is phenyl or naphthyl, each of which is unsubsti-tuted or mono- or disubstituted by halogen, C1-C4-alkyl, C1-C4-alkoxy, phenoxy, nitro and/or C1-C4-alkoxycarbonyl, or R11 is a radical of the formula or R34 is hydrogen, halogen, halo-C1-C4-alkyl, C1-C4-cyclo-alkyl, C1-C4-alkylmercapto-C1-C4-alkyl, hydroxyl-C1-C4-alkyl, hydroxyl, cyano, aryloxyalkyl, thienyl, aryl, dihydronaphthyl or where aryl is as defined above, R40 is hydrogen, halogen, nitro, C1-C4-alkyl, C1-C4-alkoxy or S(O)pR41, R41 is alkyl, P' is a 0, 1 or 2, m" is a 0, 1 or 2, R35 and R36 independently of one another are hydrogen or C1-C4-alkyl, or these, together with the carbon atom, are a 3-, 4-, 5- or 6-membered cycloalkane ring, in which a methylene group can be replaced by oxygen and which can be substituted by one or two C1-C4-alkyl groups, R37 and R38 independently of one another are hydrogen or C1-C4-alkyl, R39 is C1-C4-alkyl or phenyl, or R38 and R39 are -(CH2)1- where 1 = 3 or 4, which can be substituted by one or two C1-C4-alkyl groups, R42 is hydrogen, Cl-C4-alkyl, C1-C4-alkenyl, C1-C4-alkynyl, phenyl, C1-C4-alkylidenamino, C1-C4-alkoxycarbonyl-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, halo-C1-C4-alkyl, cycloalkyl, nitro-substituted phenylmercapto-C1-C4-alkyl, halogen or benzyl which can be substi-tuted by C1-C4-alkyl or C1-C4-alkoxy, alkali metal, 1 equivalent of alkaline earth metal, mono-, di- or trialkylammonium.
8. An agent as claimed in claims 1 to 7, which additionally contains insecticides such as terbufos, fonofos, phorate, chlorpyrifos or other insecticides and/or herbicides such as bentazone, cyanazine, bromoxynil, dicamba, pyridate, 2,4-D, bromofenoxim or other herbicides of different active substance classes, which can be selectively employed in maize, where insecticides and herbicides can both be applied together with the ALS inhibitors or separately from them at an earlier or later time.
9. An agent as claimed in one or more of claims 1 to 8, wherein the weight ratio safener: herbicide is in the range from 1 : 10 to 10 : 1.
10. An agent as claimed in one or more of claims 1 to 9, which contains 0.1 to 99 % by weight of active substances of the type B) or of the antidote/herbi-cide active substance mixture A) and B) and 1 to 99.9 % by weight of a solid or liquid additive and 0 to 25 % by weight of a surfactant.
11. A process for the protection of crop plants from phytotoxic side effects of herbicides, which com-prises applying an effective amount of one or more compounds (safeners) of the type B) defined in claim 1 before, after or at the same time as the herbicide of the type A) as claimed in claim 1 to the plants, plant seeds or the cultivation surface, an insecticide and/or a herbicide as claimed in claim 7 or 8 being co-applied beforehand, afterwards or at the same time.
12. The process as claimed in claim 11, wherein the safener of the type B) is applied at an application rate of 0.001 to 2 kg/ha of active substance and in a weight ratio safener: herbicide in the range from 1 : 10 to 10 : 1.
13. The process as claimed in claim 11 or 12, wherein the crop plants are maize plants.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4141247 | 1991-12-14 | ||
DEP4141247.8 | 1991-12-14 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2085148A1 true CA2085148A1 (en) | 1993-06-15 |
Family
ID=6447038
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA 2085148 Abandoned CA2085148A1 (en) | 1991-12-14 | 1992-12-11 | Combination of als inhibitors, insecticides and safeners, processes for their preparation and their use as plant-protecting agents |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0547546A1 (en) |
CA (1) | CA2085148A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5541148A (en) * | 1992-07-08 | 1996-07-30 | Ciba-Geigy Corporation | Selective safened herbicidal composition comprising 2-ethoxycarbonyl-3-(4,6-dimethoxypyrimidine-2-yl) oxy-pyridine and an acylsulfamoylphenyl-urea safener |
GB2334887A (en) * | 1998-03-05 | 1999-09-08 | Rhone Poulenc Agriculture | Antidotes for the herbicide pyribenzoxim [benzophenone O-(2,6-bis[(4,6-dimethoxy-2-pyrimidyl)oxy]benzoyl)oxime], especially cloquintocet & fenchlorazole |
WO2000003592A2 (en) * | 1998-07-16 | 2000-01-27 | Aventis Cropscience Gnbh | Herbicidal agents with substituted phenoxysulfonylureas |
US6201897B1 (en) | 1998-11-09 | 2001-03-13 | Earth Resource Mapping | Transformation and selective inverse transformation of large digital images |
DE102004035132A1 (en) * | 2004-07-20 | 2006-02-16 | Bayer Cropscience Ag | Insecticides based on selected insecticides and safeners |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE59109249D1 (en) * | 1990-12-21 | 2003-04-24 | Bayer Cropscience Gmbh | Mixtures of herbicides and antidotes |
CA2096527A1 (en) * | 1990-12-31 | 1992-07-01 | Brett H. Bussler | Reducing pesticidal interactions in crops |
-
1992
- 1992-12-11 CA CA 2085148 patent/CA2085148A1/en not_active Abandoned
- 1992-12-14 EP EP92121257A patent/EP0547546A1/en not_active Withdrawn
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EP0547546A1 (en) | 1993-06-23 |
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