MXPA06004954A - Agente herbicidamente activo - Google Patents
Agente herbicidamente activoInfo
- Publication number
- MXPA06004954A MXPA06004954A MXPA/A/2006/004954A MXPA06004954A MXPA06004954A MX PA06004954 A MXPA06004954 A MX PA06004954A MX PA06004954 A MXPA06004954 A MX PA06004954A MX PA06004954 A MXPA06004954 A MX PA06004954A
- Authority
- MX
- Mexico
- Prior art keywords
- esters
- liquid formulation
- oil
- weight
- methyl
- Prior art date
Links
- 150000002148 esters Chemical class 0.000 claims abstract description 46
- 239000011780 sodium chloride Substances 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 34
- 229940090121 Sulfonylureas for blood glucose lowering Drugs 0.000 claims abstract description 19
- XEJNEDVTJPXRSM-UHFFFAOYSA-N 1-(2,4-dichlorophenyl)-5-methyl-4H-pyrazole-3,5-dicarboxylic acid Chemical compound OC(=O)C1(C)CC(C(O)=O)=NN1C1=CC=C(Cl)C=C1Cl XEJNEDVTJPXRSM-UHFFFAOYSA-N 0.000 claims abstract description 7
- ICJSJAJWTWPSBD-UHFFFAOYSA-N 2-(5-chloroquinolin-8-yl)oxyacetic acid Chemical compound C1=CN=C2C(OCC(=O)O)=CC=C(Cl)C2=C1 ICJSJAJWTWPSBD-UHFFFAOYSA-N 0.000 claims abstract description 6
- LOQQVLXUKHKNIA-UHFFFAOYSA-N 3-[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)carbamoylsulfamoyl]thiophene-2-carboxylic acid Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C2=C(SC=C2)C(O)=O)=N1 LOQQVLXUKHKNIA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005626 Tribenuron Substances 0.000 claims abstract description 4
- BQZXUHDXIARLEO-UHFFFAOYSA-N tribenuron Chemical compound COC1=NC(C)=NC(N(C)C(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(O)=O)=N1 BQZXUHDXIARLEO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 112
- -1 soxadifen Chemical compound 0.000 claims description 63
- 241000196324 Embryophyta Species 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 34
- 239000012141 concentrate Substances 0.000 claims description 23
- 238000009472 formulation Methods 0.000 claims description 20
- ULUAUXLGCMPNKK-UHFFFAOYSA-L 2-sulfobutanedioate Chemical class OS(=O)(=O)C(C([O-])=O)CC([O-])=O ULUAUXLGCMPNKK-UHFFFAOYSA-L 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 13
- 239000012053 oil suspension Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 235000013311 vegetables Nutrition 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 240000005979 Hordeum vulgare Species 0.000 claims description 6
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 6
- 240000008529 Triticum aestivum Species 0.000 claims description 6
- 240000008042 Zea mays Species 0.000 claims description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 6
- 230000002605 anti-dotal Effects 0.000 claims description 6
- 235000021307 wheat Nutrition 0.000 claims description 6
- 240000007594 Oryza sativa Species 0.000 claims description 5
- 235000007164 Oryza sativa Nutrition 0.000 claims description 5
- 235000005822 corn Nutrition 0.000 claims description 5
- 235000005824 corn Nutrition 0.000 claims description 5
- 235000009566 rice Nutrition 0.000 claims description 5
- 239000000729 antidote Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- 235000007319 Avena orientalis Nutrition 0.000 claims description 3
- 244000075850 Avena orientalis Species 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 3
- 235000010469 Glycine max Nutrition 0.000 claims description 3
- 240000007842 Glycine max Species 0.000 claims description 3
- 240000006962 Gossypium hirsutum Species 0.000 claims description 3
- 235000007238 Secale cereale Nutrition 0.000 claims description 3
- 240000002057 Secale cereale Species 0.000 claims description 3
- 240000006394 Sorghum bicolor Species 0.000 claims description 3
- 235000011684 Sorghum saccharatum Nutrition 0.000 claims description 2
- 238000003306 harvesting Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- ITGSCCPVERXFGN-UHFFFAOYSA-N 5,5-diphenyl-4H-1,2-oxazole-3-carboxylic acid Chemical compound C1C(C(=O)O)=NOC1(C=1C=CC=CC=1)C1=CC=CC=C1 ITGSCCPVERXFGN-UHFFFAOYSA-N 0.000 abstract description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N Sulfuryl chloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 abstract 1
- 101710017512 A2.2 Proteins 0.000 description 992
- 101710017516 A1.2 Proteins 0.000 description 967
- 230000002363 herbicidal Effects 0.000 description 43
- 235000014113 dietary fatty acids Nutrition 0.000 description 42
- 239000000194 fatty acid Substances 0.000 description 42
- 230000001012 protector Effects 0.000 description 38
- YROXIXLRRCOBKF-UHFFFAOYSA-N sulfonylurea Chemical compound OC(=N)N=S(=O)=O YROXIXLRRCOBKF-UHFFFAOYSA-N 0.000 description 36
- 239000004009 herbicide Substances 0.000 description 28
- 150000004665 fatty acids Chemical class 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 229910052708 sodium Inorganic materials 0.000 description 21
- 239000011734 sodium Substances 0.000 description 21
- 239000008187 granular material Substances 0.000 description 19
- 239000003995 emulsifying agent Substances 0.000 description 18
- 239000004480 active ingredient Substances 0.000 description 17
- 239000003921 oil Substances 0.000 description 17
- 235000019198 oils Nutrition 0.000 description 15
- 235000019484 Rapeseed oil Nutrition 0.000 description 14
- 150000004702 methyl esters Chemical class 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 239000002270 dispersing agent Substances 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N oxane Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 12
- 239000002562 thickening agent Substances 0.000 description 12
- 235000015112 vegetable and seed oil Nutrition 0.000 description 12
- 239000008158 vegetable oil Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 11
- 125000004432 carbon atoms Chemical group C* 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000000839 emulsion Substances 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-Dichlorophenoxyacetic acid Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000004495 emulsifiable concentrate Substances 0.000 description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- OPGCOAPTHCZZIW-UHFFFAOYSA-N diethyl 1-(2,4-dichlorophenyl)-5-methyl-4H-pyrazole-3,5-dicarboxylate Chemical compound CCOC(=O)C1(C)CC(C(=O)OCC)=NN1C1=CC=C(Cl)C=C1Cl OPGCOAPTHCZZIW-UHFFFAOYSA-N 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 7
- DPUOLQHDNGRHBS-KTKRTIGZSA-N Erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 6
- OYHQOLUKZRVURQ-IXWMQOLASA-N Linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N Oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N Palmitic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Stearic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- MWKVXOJATACCCH-UHFFFAOYSA-N ethyl 5,5-diphenyl-4H-1,2-oxazole-3-carboxylate Chemical compound C1C(C(=O)OCC)=NOC1(C=1C=CC=CC=1)C1=CC=CC=C1 MWKVXOJATACCCH-UHFFFAOYSA-N 0.000 description 6
- 125000004494 ethyl ester group Chemical group 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000001681 protective Effects 0.000 description 6
- DTOSIQBPPRVQHS-PDBXOOCHSA-N α-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 6
- 239000005584 Metsulfuron-methyl Substances 0.000 description 5
- RSMUVYRMZCOLBH-UHFFFAOYSA-N Metsulfuron-methyl Chemical group COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(C)=NC(OC)=N1 RSMUVYRMZCOLBH-UHFFFAOYSA-N 0.000 description 5
- 239000005623 Thifensulfuron-methyl Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 125000005907 alkyl ester group Chemical group 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000004359 castor oil Substances 0.000 description 5
- 235000019438 castor oil Nutrition 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920000151 polyglycol Polymers 0.000 description 5
- 239000010695 polyglycol Substances 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000009331 sowing Methods 0.000 description 5
- 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 description 5
- FDDDEECHVMSUSB-UHFFFAOYSA-N Sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 4
- YMXOXAPKZDWXLY-QWRGUYRKSA-N Tribenuron Methyl Chemical group COC(=O)[C@H]1CCCC[C@@H]1S(=O)(=O)NC(=O)N(C)C1=NC(C)=NC(OC)=N1 YMXOXAPKZDWXLY-QWRGUYRKSA-N 0.000 description 4
- 239000000443 aerosol Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 239000002075 main ingredient Substances 0.000 description 4
- 239000004530 micro-emulsion Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 159000000001 potassium salts Chemical class 0.000 description 4
- 229960001663 sulfanilamide Drugs 0.000 description 4
- 150000003457 sulfones Chemical class 0.000 description 4
- VJYIFXVZLXQVHO-UHFFFAOYSA-N 1-(2-chlorophenyl)sulfonyl-3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)urea Chemical compound COC1=NC(C)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)Cl)=N1 VJYIFXVZLXQVHO-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- PZZYQPZGQPZBDN-UHFFFAOYSA-N Aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 3
- ZOGDSYNXUXQGHF-XIEYBQDHSA-N Butroxydim Chemical compound CCCC(=O)C1=C(C)C=C(C)C(C2CC(=O)C(\C(CC)=N\OCC)=C(O)C2)=C1C ZOGDSYNXUXQGHF-XIEYBQDHSA-N 0.000 description 3
- 239000005496 Chlorsulfuron Substances 0.000 description 3
- JHIVVAPYMSGYDF-UHFFFAOYSA-N Cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 3
- LQZZUXJYWNFBMV-UHFFFAOYSA-N Dodecanol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 3
- 108010000700 EC 2.2.1.6 Proteins 0.000 description 3
- 229960004488 Linolenic Acid Drugs 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- JNYAEWCLZODPBN-CTQIIAAMSA-N Sorbitan Chemical class OCC(O)C1OCC(O)[C@@H]1O JNYAEWCLZODPBN-CTQIIAAMSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- FPKOPBFLPLFWAD-UHFFFAOYSA-N Trinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1[N+]([O-])=O FPKOPBFLPLFWAD-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000010775 animal oil Substances 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 238000007046 ethoxylation reaction Methods 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000000749 insecticidal Effects 0.000 description 3
- 239000002917 insecticide Substances 0.000 description 3
- 235000020778 linoleic acid Nutrition 0.000 description 3
- 235000021313 oleic acid Nutrition 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N oxo-oxoalumanyloxy-[oxo(oxoalumanyloxy)silyl]oxysilane;dihydrate Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propanol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 244000045561 useful plants Species 0.000 description 3
- 239000003981 vehicle Substances 0.000 description 3
- BHZWBQPHPLFZSV-UHFFFAOYSA-N (2,6-dibromo-4-cyanophenyl) heptanoate Chemical compound CCCCCCC(=O)OC1=C(Br)C=C(C#N)C=C1Br BHZWBQPHPLFZSV-UHFFFAOYSA-N 0.000 description 2
- DQKWXTIYGWPGOO-UHFFFAOYSA-N (2,6-dibromo-4-cyanophenyl) octanoate Chemical compound CCCCCCCC(=O)OC1=C(Br)C=C(C#N)C=C1Br DQKWXTIYGWPGOO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N 1-Decanol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N 1-Nonanol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 239000005631 2,4-D Substances 0.000 description 2
- MAYMYMXYWIVVOK-UHFFFAOYSA-N 2-[(4,6-dimethoxypyrimidin-2-yl)carbamoylsulfamoyl]-4-(methanesulfonamidomethyl)benzoic acid Chemical compound COC1=CC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=C(CNS(C)(=O)=O)C=2)C(O)=O)=N1 MAYMYMXYWIVVOK-UHFFFAOYSA-N 0.000 description 2
- MPPOHAUSNPTFAJ-UHFFFAOYSA-N 2-[4-[(6-chloro-1,3-benzoxazol-2-yl)oxy]phenoxy]propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=NC2=CC=C(Cl)C=C2O1 MPPOHAUSNPTFAJ-UHFFFAOYSA-N 0.000 description 2
- 240000002791 Brassica napus Species 0.000 description 2
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 2
- UYISBQRLYUMVPG-UHFFFAOYSA-N CCCONNC(=O)N=N Chemical compound CCCONNC(=O)N=N UYISBQRLYUMVPG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000005493 Chloridazon (aka pyrazone) Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000005499 Clomazone Substances 0.000 description 2
- KIEDNEWSYUYDSN-UHFFFAOYSA-N Clomazone Chemical compound O=C1C(C)(C)CON1CC1=CC=CC=C1Cl KIEDNEWSYUYDSN-UHFFFAOYSA-N 0.000 description 2
- 239000005504 Dicamba Substances 0.000 description 2
- IWEDIXLBFLAXBO-UHFFFAOYSA-N Dicamba Chemical compound COC1=C(Cl)C=CC(Cl)=C1C(O)=O IWEDIXLBFLAXBO-UHFFFAOYSA-N 0.000 description 2
- QNXAVFXEJCPCJO-UHFFFAOYSA-N Diclosulam Chemical compound N=1N2C(OCC)=NC(F)=CC2=NC=1S(=O)(=O)NC1=C(Cl)C=CC=C1Cl QNXAVFXEJCPCJO-UHFFFAOYSA-N 0.000 description 2
- FDNBWBAHQKZDSN-UHFFFAOYSA-N F5231 Chemical compound C1=C(Cl)C(NS(=O)(=O)CC)=CC(N2C(N(CCCF)N=N2)=O)=C1F FDNBWBAHQKZDSN-UHFFFAOYSA-N 0.000 description 2
- PQKBPHSEKWERTG-UHFFFAOYSA-N Fenoxaprop ethyl Chemical group C1=CC(OC(C)C(=O)OCC)=CC=C1OC1=NC2=CC=C(Cl)C=C2O1 PQKBPHSEKWERTG-UHFFFAOYSA-N 0.000 description 2
- QZXATCCPQKOEIH-UHFFFAOYSA-N Florasulam Chemical compound N=1N2C(OC)=NC=C(F)C2=NC=1S(=O)(=O)NC1=C(F)C=CC=C1F QZXATCCPQKOEIH-UHFFFAOYSA-N 0.000 description 2
- FOUWCSDKDDHKQP-UHFFFAOYSA-N Flumioxazin Chemical compound FC1=CC=2OCC(=O)N(CC#C)C=2C=C1N(C1=O)C(=O)C2=C1CCCC2 FOUWCSDKDDHKQP-UHFFFAOYSA-N 0.000 description 2
- 239000005558 Fluroxypyr Substances 0.000 description 2
- MEFQWPUMEMWTJP-UHFFFAOYSA-N Fluroxypyr Chemical compound NC1=C(Cl)C(F)=NC(OCC(O)=O)=C1Cl MEFQWPUMEMWTJP-UHFFFAOYSA-N 0.000 description 2
- 239000005560 Foramsulfuron Substances 0.000 description 2
- 239000005562 Glyphosate Substances 0.000 description 2
- PMAAYIYCDXGUAP-UHFFFAOYSA-N Indanofan Chemical compound O=C1C2=CC=CC=C2C(=O)C1(CC)CC1(C=2C=C(Cl)C=CC=2)CO1 PMAAYIYCDXGUAP-UHFFFAOYSA-N 0.000 description 2
- JUJFQMPKBJPSFZ-UHFFFAOYSA-M Iodosulfuron-methyl-sodium Chemical compound [Na+].COC(=O)C1=CC=C(I)C=C1S(=O)(=O)[N-]C(=O)NC1=NC(C)=NC(OC)=N1 JUJFQMPKBJPSFZ-UHFFFAOYSA-M 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N Lauric acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- 239000005574 MCPA Substances 0.000 description 2
- 239000005577 Mesosulfuron Substances 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
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- 239000004576 sand Substances 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 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
- FUHMZYWBSHTEDZ-UHFFFAOYSA-M sodium;2,6-bis[(4,6-dimethoxypyrimidin-2-yl)oxy]benzoate Chemical compound [Na+].COC1=CC(OC)=NC(OC=2C(=C(OC=3N=C(OC)C=C(OC)N=3)C=CC=2)C([O-])=O)=N1 FUHMZYWBSHTEDZ-UHFFFAOYSA-M 0.000 description 1
- STAPBGVGYWCRTF-UHFFFAOYSA-M sodium;2-(4-chloro-2-methylphenoxy)acetate Chemical compound [Na+].CC1=CC(Cl)=CC=C1OCC([O-])=O STAPBGVGYWCRTF-UHFFFAOYSA-M 0.000 description 1
- JUNDBKFAZXZKRA-MAFYXNADSA-M sodium;2-[(E)-N-[(3,5-difluorophenyl)carbamoylamino]-C-methylcarbonimidoyl]pyridine-3-carboxylate Chemical compound [Na+].N=1C=CC=C(C([O-])=O)C=1C(/C)=N/NC(=O)NC1=CC(F)=CC(F)=C1 JUNDBKFAZXZKRA-MAFYXNADSA-M 0.000 description 1
- HLZCHRAMVPCKDU-UHFFFAOYSA-M sodium;3,6-dichloro-2-methoxybenzoate Chemical compound [Na+].COC1=C(Cl)C=CC(Cl)=C1C([O-])=O HLZCHRAMVPCKDU-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003381 solubilizing Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000707 stereoselective Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- PQTBTIFWAXVEPB-UHFFFAOYSA-N sulcotrione Chemical compound ClC1=CC(S(=O)(=O)C)=CC=C1C(=O)C1C(=O)CCCC1=O PQTBTIFWAXVEPB-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZDXMLEQEMNLCQG-UHFFFAOYSA-N sulfometuron methyl Chemical group COC(=O)C1=CC=CC=C1S(=O)(=O)NC(=O)NC1=NC(C)=CC(C)=N1 ZDXMLEQEMNLCQG-UHFFFAOYSA-N 0.000 description 1
- 239000004546 suspension concentrate Substances 0.000 description 1
- BCQMBFHBDZVHKU-UHFFFAOYSA-N terbumeton Chemical compound CCNC1=NC(NC(C)(C)C)=NC(OC)=N1 BCQMBFHBDZVHKU-UHFFFAOYSA-N 0.000 description 1
- IROINLKCQGIITA-UHFFFAOYSA-N terbutryn Chemical compound CCNC1=NC(NC(C)(C)C)=NC(SC)=N1 IROINLKCQGIITA-UHFFFAOYSA-N 0.000 description 1
- XZPMQCKVOWVETG-UHFFFAOYSA-J tetrasodium;2-[(3-carboxylato-3-sulfonatopropanoyl)-octadecylamino]butanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].CCCCCCCCCCCCCCCCCCN(C(CC([O-])=O)C([O-])=O)C(=O)CC(C([O-])=O)S([O-])(=O)=O XZPMQCKVOWVETG-UHFFFAOYSA-J 0.000 description 1
- GHTMQNZCRVHCQP-UHFFFAOYSA-J tetrasodium;4-[1,2-dicarboxyethyl(octadecyl)amino]-4-oxo-2-sulfobutanoate Chemical compound [Na+].[Na+].[Na+].[Na+].CCCCCCCCCCCCCCCCCCN(C(CC(O)=O)C(O)=O)C(=O)CC(C([O-])=O)S(O)(=O)=O.CCCCCCCCCCCCCCCCCCN(C(CC(O)=O)C(O)=O)C(=O)CC(C([O-])=O)S(O)(=O)=O.CCCCCCCCCCCCCCCCCCN(C(CC(O)=O)C(O)=O)C(=O)CC(C([O-])=O)S(O)(=O)=O.CCCCCCCCCCCCCCCCCCN(C(CC(O)=O)C(O)=O)C(=O)CC(C([O-])=O)S(O)(=O)=O GHTMQNZCRVHCQP-UHFFFAOYSA-J 0.000 description 1
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- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- KVEQCVKVIFQSGC-UHFFFAOYSA-N tritosulfuron Chemical compound FC(F)(F)C1=NC(OC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(F)(F)F)=N1 KVEQCVKVIFQSGC-UHFFFAOYSA-N 0.000 description 1
- CCPPLLJZDQAOHD-FLIBITNWSA-M vernolate Chemical compound CCCCCC1OC1C\C=C/CCCCCCCC([O-])=O CCPPLLJZDQAOHD-FLIBITNWSA-M 0.000 description 1
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Abstract
Una composición herbicidamente activa, que comprende (A) una o más sulfonilureas a partir del grupo que consiste de metsulfurona, tifensulfurona, tribenurona, clorsulfurona y sus sales yésteres, y (A) uno o más protectores a partir del grupo que consiste de mefenpyr, isoxadifen, cloquintocet, fenclorazol y sus sales yésteres.
Description
AGENTE HERBICIDAMENTE ACTIVO
MEMORIA DESCRIPTIVA
La invención se refiere al campo técnico, de composiciones para protección de cosecha, en particular a composiciones herbicidamente activas las cuales comprenden combinaciones de sulfonilurea/protector (combinaciones de compuesto activo y antídoto) y son altamente adecuadas para uso en contra de plantas dañinas competentes en cosechas de plantas útiles. Se conocen combinaciones de herbicidas las cuales inhiben a la enzima acetolactate sintasa (ALS) y a los protectores. Por lo tanto, EP 0 492 367 A2 describe combinaciones de diferentes inhibidores de ALS con diferentes protectores. No obstante, las combinaciones específicas descritas en estas publicaciones no son siempre satisfactorias, con respecto a la selectividad y espectro de actividad. Por consiguiente, fue un objetivo de la presente invención proveer composiciones herbicidamente activas con selectividad incrementada en cosechas vegetales importantes y, al mismo tiempo, alta actividad en contra de plantas dañinas. De manera sorprendente, este objetivo se logra por la composición herbicidamente activa de la presente invención. Por consiguiente, la invención provee una composición herbicidamente activa, que comprende (A) una o más sulfonilureas a partir del grupo que consiste de metsulfuron, thifensulfuron, tribenuron, chlorsulfuron y sus sales y esteres, preferiblemente en una cantidad herbicidamente efectiva, y (B) uno o más protectores a partir del grupo que consiste de mefenpyr, isoxadifen, cloquintocet, fenclorazol y sus sales y esteres, preferiblemente en una cantidad antídoto efectiva, preferiblemente mefenpyr, isoxadifen, cloquintocet y sus sales y esteres, particularmente preferiblemente mefenpyr, cloquintocet y sus sales y esteres, muy particularmente preferiblemente mefenpyr y sus sales y esteres. Las sulfonilureas A) y los protectores B) también pueden estar presentes en la forma de sus sales, por ejemplo como sales con contraiones inorgánicos y orgánicos. Estas sales son, por ejemplo, sales metálicas, en particular sales metálicas álcali o sales metálicas terreas alcalinas, en particular sales de sodio y sales de potasio, o cualesquiera sales de amonio y sales con aminas orgánicas. La formación de sal también puede tomar lugar mediante un ácido que forma un aducto con grupos básicos, tales como, por ejemplo, amino y alquilamino. Los ácidos adecuados para este propósito son ácidos fuertes ¡orgánicos y orgánicos, por ejemplo HCl, HBr, H2SO o HNO3. Las sales preferidas son las sales metálicas álcali, tales como las sales de sodio y sales de potasio. Las sulfonilureas A) pueden formar, por ejemplo, sales en las cuales el hidrógeno del grupo -SO2-NH- se reemplaza por un catión agriculturalmente adecuado, por ejemplo un ion metálico tal como un ion metálico álcali, preferiblemente un ion de sodio o un ion de potasio.
Las sulfonilureas A) y los protectores B) también pueden estar presentes en la forma de sus esteres, en particular en la forma de sus esteres alquílicos, tales como esteres alquílicos de C1-C10. Esteres metílicos y esteres etílicos son particularmente preferidos por las sulfonilureas A). Esteres metílicos y esteres etílicos y esteres metilhexílicos son particularmente preferidos por los protectores B). Las sulfonilureas (A) preferiblemente se seleccionan a partir del grupo que consiste de metsulfuron-metil (A1.1), thifensulfuron-metil (A2.1), tribenuron-metil (A3.1) y clorsulfuron (A4.1), incluyendo las sales usuales en agricultura, tales como las sales sódicas de metsulfuron-metílico-sódico (A1.2), thifensulfuron-metílico-sódico (A2.2), tribenuron- metílico-sódico (A3.2) y clorsulfuron-sódico (A4.2). La preferencia se da adicionalmente a la metsulfuron (A1.3), metsulfuron-sódico (A1.4), thifensulfuron (A2.3), thifensulfuron-sódico (A2.4), tribenuron (A3.3) y tribenuron-sódico (A3.4). Las sulfonilureas particularmente preferidas (A) son metsulfu ron-metílico (A1.1), thifensulfuron-metílico (A2.1 ), tribenuron-metílico (A3.1) y clorsulfuron (A4.1). Los protectores (B) preferiblemente se seleccionan a partir del grupo que consiste de 1-(2,4-diclorofenil)-5-(etoxicarbonil)-5-metil-2-pirazolin-3-carboxilato etílico (B1, mefenpyr-dietílico), 5,5-difenil-2-isoxazolina-3-carboxilato etílico (B2, isoxadifen-etílico), 1 -metilhex.il (5-c!oro-8-quinolineoxi)acetato (B3, cloquintocet-mexil), mefenpyr-dimetil (B4), mefenpyr (B5), isoxadifen (B6) y cloquintocet (B7), 1-(2,4-diclorofenil)-5-triclorometil-(1H)-1 ,2,4-triazol-3-carboxilato etílico (B8, fenclorazol-etílico) y fenclorazol (B9), incluyendo las sales usuales en agricultura, tales como las sales de potasio. Los protectores preferidos son (B1), (B2), (B3) y (B8), en particular (B1), (B2) y (B3). Particularmente los protectores preferidos son (B1 ) y (B2), y se da una preferencia muy particular a mefenpyr-dietílico (B1). Para el propósito de la invención, una cantidad herbicidamente efectiva es una cantidad de uno o más herbicidas adecuadas para tener un efecto negativo sobre el crecimiento vegetal. Para el propósito de la invención, una cantidad antídoto efectiva es una cantidad de uno o más protectores adecuada para neutralizar la acción fitotóxica de un herbicida o mezcla herbicida sobre una planta útil al menos parcialmente. Los compuestos (A) y (B) también abarcan todos los estereoisómeros en los cuales la unión de los átomos es topológicamente la misma, y las mezclas de ios mismos. Dichos compuestos contienen uno o más átomos de carbono asimétricos u otros enlaces dobles los cuales no se muestran específicamente en las fórmulas. Los posibles esteroisómeros definidos por su forma espacial específica, tales como enantiómeros, diaestereómeros, isómeros Z y E, se pueden obtener mediante métodos usuales a partir de las mezclas de los estereoisómeros, u otros preparados mediante reacciones estereoselectivas en combinación con el uso de materias primas estereoquímicamente puras. Las sulfonilureas (A) están comercialmente disponibles y se conocen, por ejemplo, a partir de "The Pesticide Manual", 12a edición (2000), The British Crop Protection Association, y a partir de US 4,370,480, EP 30138, US 4,701 ,535, EP 30142, EP 202830 y US 4,127,405 los cuales contienen información detallada sobre los procedimientos de preparación y materias primas. Estas publicaciones se incorporan expresamente, a manera de referencia, en esta descripción. Los protectores (B) están comercialmente disponibles y se conocen, por ejemplo, a partir de "The Pesticide Manual", 12a edición (2000), The British Crop Protection Association, y a partir de WO 91/7874, WO 95/7897, EP-A-94349 y EP-A-174562 los cuales contienen información detallada sobre los procedimientos de preparación y materias primas. Estas publicaciones se incorporan expresamente, a manera de referencia, en esta descripción. Los ejemplos de combinaciones preferidas de conformidad con la invención de sulfonilureas (A) y protectores (B) son: (A1.1) + (B1 ), (A1.1 ) + (B2), (A1.1) + (B3), (A1.1) + (B8), (A2.1 ) +
(B1 ), (A2.1) + (B2), (A2.1 ) + (B3), (A2.1) + (B8), (A3.1) + (B1 ), (A3.1) + (B2), (A3.1) + (B3), (A3.1 ) + (B8), (A4.1) + (B1), (A4.1) + (B2), (A4.1) + (B3), (A4.1) + (B8), (A1.2) + (B1 ), (A1.2) + (B2), (A1.2) + (B3), (A1.2) + (B8), (A2.2) + (B1 ), (A2.2) + (B2), (A2.2) + (B3), (A2.2) + (B8), (A3.2) + (B1 ), (A3.2) + (B2), (A3.2) + (B3), (A3.2) + (B8), (A4.2) + (B1), (A4.2) + (B2), (A4.2) + (B3), (A4.2) + (B8), (A1.3) + (B1), (A1.3) + (B2), (A1.3) + (B3), (A1.3) + (B8), (A2.3) + (B1), (A2.3) + (B2), (A2.3) + (B3), (A2.3) + (B8), (A3.3) + (B1), (A3.3) + (B2), (A3.3) + (B3), (A3.3) + (B8), (A1.4) + (B 1), (A1.4) + (B2), (A1.4) + (B3), (A1.4) + (B8), (A2.4) + (B1), (A2.4) + (B2), (A2.4) + (B3), (A2.4) + (B8), (A3.4) + (B1), (A3.4) + (B2), (A3.4) + (B3), (A3.4) + (B8); (A1.1 ) + (A1.2) + (B1), (A1.1) + (A2.1) + (B1), (A1.1) + (A2.2) + (B1), (A1.1) + (A3.1 ) + (B1 ), (A1.1) + (A3.2) + (B1), (A1.1) + (A4.1) + (B1 ), (A1.1) + (A4.2) + (B1 ); (A1.2) + (A2.1) + (B1), (A1.2) + (A2.2) + (B1 ), (A1.2) + (A3.1 ) + (B1), (A1.2) + (A3.2) + (B1), (A1.2) + (A4.1) + (B1), (A1.2) + (A4.2) + (B1); (A2.1 ) + (A2.2) + (B1 ), (A2.1 ) + (A3.1) + (B1), (A2.1 ) + (A3.2) + (B1), (A2.1 ) + (A4.1) + (B1), (A2.1) + (A4.2) + (B1); (A2.2) + (A3.1) + (B1), (A2.2) + (A3.2) + (B1), (A2.2) + (A4.1) +
(B1), (A2.2) + (A4.2) + (B1); (A3.1) + (A3.2) + (B1), (A3.1) + (A4.1) + (B1), (A3.1) + (A4.2) + (B1); (A3.2) + (A4.1) + (B1), (A3.2) + (A4.2) + (B1), (A4.1) + (A4.2) + (B1); (A1.1) + (A1.2) + (B2), (A1.1) + (A2.1) + (B2), (A1.1) + (A2.2) + (B2), (A1.1) + (A3.1 ) + (B2), (A1.1) + (A3.2) + (B2), (A1.1) + (A4.1 ) + (B2), (A1.1) + (A4.2) + (B2); (A1.2) + (A2.1) + (B2), (A1.2) + (A2.2) + (B2), (A1.2) + (A3.1 ) + (B2), (A1.2) + (A3.2) + (B2), (A1.2) + (A4.1) + (B2), (A1.2) + (A4.2) + (B2); (A2.1 ) + (A2.2) + (B2), (A2.1) + (A3.1) + (B2), (A2.1) + (A3.2) + (B2), (A2.1) + (A4.1) + (B2), (A2.1) + (A4.2) + (B2); (A2.2) + (A3.1) + (B2), (A2.2) + (A3.2) + (B2), (A2.2) + (A4.1 ) + (B2), (A2.2) + (A4.2) + (B2); (A3.1) + (A3.2) + (B2), (A3.1) + (A4.1) + (B2), (A3.1) + (A4.2) + (B2); (A3.2) + (A4.1) + (B2), (A3.2) + (A4.2) + (B2), (A4.1) + (A4.2) + (B2); (A1.1) + (A1.2) + (B3), (A1.1) + (A2.1) + (B3), (A1.1) + (A2.2) + (B3), (A1.1) + (A3.1) + (B3), (A1.1) + (A3.2) + (B3), (A1.1) + (A4.1) + (B3), (A1.1) + (A4.2) + (B3); (A1.2) + (A2.1) + (B3), (A1.2) + (A2.2) + (B3), (A1.2) + (A3.1) +
(B3), (A1.2) + (A3.2) + (B3), (A1.2) + (A4.1 ) + (B3), (A1.2) + (A4.2) + (B3); (A2.1) + (A2.2) + (B3), (A2.1) + (A3.1) + (B3), (A2.1) + (A3.2) + (B3), (A2.1) + (A4.1) + (B3), (A2.1) + (A4.2) + (B3); (A2.2) + (A3.1) + (B3), (A2.2) + (A3.2) + (B3), (A2.2) + (A4.1) + (B3), (A2.2) + (A4.2) + (B3); (A3.1) + (A3.2) + (B3), (A3.1) + (A4.1) + (B3), (A3.1) + (A4.2) + (B3); (A3.2) + (A4.1) + (B3), (A3.2) + (A4.2) + (B3), (A4.1) + (A4.2) + (B3); (A1.1) + (A1.2) + (B8), (A1.1) + (A2.1) + (B8), (A1.1) + (A2.2) + (B8), (A1.1) + (A3.1) + (B8), (A1.1) + (A3.2) + (B8), (A1.1) + (A4.1) + (B8), (A1.1) + (A4.2) + (B8); (A1.2) + (A2.1) + (B8), (A1.2) + (A2.2) + (B8), (A1.2) + (A3.1) + (B8), (A1.2) + (A3.2) + (B8), (A1.2) + (A4.1) + (B8), (A1.2) + (A4.2) + (B8); (A2.1) + (A2.2) + (B8), (A2.1) + (A3.1) + (B8), (A2.1) + (A3.2) + (B8), (A2.1) + (A4.1) + (B8), (A2.1) + (A4.2) + (B8); (A2.2) + (A3.1) + (B8), (A2.2) + (A3.2) + (B8), (A2.2) + (A4.1) +
(B8), (A2.2) + (A4.2) + (B8); (A3.1 ) + (A3.2) + (B8), (A3.1) + (A4.1 ) + (B8), (A3.1 ) + (A4.2) + (B8); (A3.2) + (A4.1) + (B8), (A3.2) + (A4.2) + (B8), (A4.1) + (A4.2) + (B8).
Los protectores (antídotos) del grupo (B) reducen o previenen los efectos fitotóxicos los cuales se pueden presentar cuando se utilizan los compuestos herbicidamente activos (A) en cosechas de plantas útiles sin afectar sustancialmente la actividad de estos compuestos herbicidamente activos en contra de plantas dañinas. Esto permite que el campo de aplicación de productos convencionales para protección de cosecha se amplié considerablemente y se extienda a, por ejemplo, cosechas tales como trigo, cebada, maíz, arroz y otras cosechas en las cuales el uso de los herbicidas fue hasta ahora imposible, o de posibilidad solamente limitada, es decir a bajas relaciones y con un espectro restringido. Las sulfonilureas (A) y los protectores (B) de las combinaciones de sulfonilurea/protector de conformidad con la invención se pueden aplicar juntos (por ejemplo como una mezcla preparada o mediante el método de mezclado en tanque) o en sucesión en cualquier secuencia deseada. La relación en peso de protectopsulfonilurea puede variar dentro de límites amplios y preferiblemente se encuentra dentro del intervalo de 1 :100 a 100:1, en particular de 1 :10 a 10:1. Las cantidades óptimas de sulfonilurea y protector dependen del tipo de la sulfonilurea utilizada o del protector utilizado y de las especies de la planta en pie a ser tratada y se puede determinar en cada caso individual mediante experimentos preliminares estándares simples. Los campos de aplicación principales para las combinaciones herbicidamente activas de conformidad con la invención son, en particular, cosechas de cereal (por ejemplo trigo, centeno, cebada, avena), arroz, maíz, sorgo, algodón y frijoles de soya, preferiblemente cereales, arroz y maíz. Dependiendo de sus propiedades, los protectores contenidos en la composición herbicidamente activa de conformidad con la invención se pueden utilizar para el pretratamiento de la semilla de la planta de cosecha (por ejemplo revestimiento de semilla), o se incorpora dentro de los surcos para la semilla antes de la siembra o se aplica junto con un herbicida, en particular una sulfonilurea (A), antes o después del surgimiento de las plantas.
El tratamiento de pre-surgimiento incluye tanto el tratamiento del área bajo cultivo antes de la siembra como del tratamiento de las áreas bajo cultivo en donde las semillas han sido sembradas pero las plantas aún no han surgido.
Se prefiere la aplicación conjunta con un hebicida. Para este fin, se pueden emplear las mezclas en tanque o mezclas preparadas. Las relaciones de aplicación de protectores requeridos pueden variar dentro de límites amplios dependiendo de la indicación y los compuestos herbicidamente activos utilizados y generalmente se encuentran en el intervalo de 0.001 a 5 kg, preferiblemente de 0.005 a 0.5 kg, de compuesto activo por hectárea. Las composiciones herbicidas de conformidad con la invención o combinaciones de sulfonilurea/protector también pueden comprender, si es apropiado, como componentes adicionales: (C) uno o más solventes, preferiblemente solventes orgánicos,
(D) uno o más sulfosuccinatos, (E) uno o más compuestos agroquímicamente activos diferentes a (A) y (B), y/o (F) auxiliares y aditivos usuales. Los solventes orgánicos opcionales adecuados (componente C) son, por ejemplo: 1) hidrocarburos, los cuales pueden ser no sustituidos o sustituidos, por ejemplo 1a) hidrocarburos aromáticos, por ejemplo • bencenos mono- o polialquil-sustituidos, tales como tolueno, xilenos, mesitileno, etiibenceno, o • naftalenos mono- o polialquil-sustituidos, tales como 1-metilnaftaleno, 2-metilnaftaleno o dimetilnaftaleno, u • otros hidrocarburos aromáticos derivados de benceno, tales como indano o Tetralin®, o • mezclas de los mismos, 1b) hidrocarburos alifáticos, por ejemplo • alifáticos de cadena recta o ramificados, por ejemplo de la fórmula CnH2n+2, tales como pentano, hexano, octano, 2-metilbutano o 2,2,4-trimetilpentano, o • alifáticos cíclicos, opcionalmente sustituidos con alquilo, tales como ciciohexano o metilciclopentano, o • mezclas de los mismos, tales como solventes de la serie Exxsol® D, serie Isopar® o serie Bayol®, por ejemplo Bayol® 82 (ExxonMobil Chemicals), o la serie Isane® IP o serie Hydroseal® G (TotalFinaElf), 1c) Mezclas de hidrocarburos aromáticos y alifáticos, tales como solventes de la serie Solvesso®, por ejemplo Solvesso® 100,
Solvesso® 150 o Solvesso® 200 (ExxonMobil Chemicals), de la serie
Solvarex®/Solvaro® (TotalFinaElf) o la serie Caromax®, por ejemplo Caromax® 28 (Petrochem Carless), o 1d) hidrocarburos halogenados, tales como hidrocarburos halogenados aromáticos y alifáticos, tales como clorobenceno o cloruro de metileno, o 2) solventes apróticos polares, tales como éteres, esteres de ácidos alcanóicos de C-i-C. los cuales pueden ser mono-, di- o polifuncionales, tales como sus mono-, di- o triésteres, por ejemplo con alcoholes de alquilo de C-I-C-IS, cetonas con una baja tendencia a tautomerizar, esteres de ácido fosfórico, amidas, nitritos o suifonas, por ejemplo diisobutil adipato, Rhodiasolv® RPDE (Rhodia), ciciohexanona, Jeffsol® PC (Huntsman), ?-butyrolactona, N-metilpirrolidona, dimetil sulfóxido, acetonitrilo, tributilphosphatam o la serie Hostarex® PO (Clariant), o 3) esteres de ácido graso, por ejemplo de origen natural, por ejemplo aceites naturales, tales como aceites animales o aceites vegetales, o de origen sintético, por ejemplo la serie Edenor®, por ejemplo Edenor® MEPa o Edenor® MESU, o la serie Agnique® ME o la serie Agnique® AE (Cognis), la serie Salim® ME (Salim), la serie Radia®, por ejemplo Radia® 30167 (ICI), la serie Prilube®, por ejemplo Prilube® 1530 (Petrofina), la serie Stepan® C (Stepan) o la serie Witconol® 23 (Witco). Los esteres de ácido graso preferiblemente son esteres de ácidos grasos de C-?0-C22, con preferencia de Ci2-C20-. Los esteres de ácido graso de C?0-C22 son, por ejemplo, esteres de ácidos grasos de C-?0-C22 insaturados o saturados, en particular aquellos que tienen un número par de átomos de carbono, por ejemplo ácido erúcico, ácido láurico, ácido palmítico, y en particular ácidos grasos de C-¡_, tales como ácido esteárico, ácido oléico, ácido linoléico o ácido linolénico. Los ejemplos de esteres de ácido graso tales como esteres de ácido graso de C10-C22 son glicerol y glicol esteres de ácidos grasos tales como ácidos grasos de C?o-C22, o productos de transesterificación de los mismos, por ejemplo esteres alquílicos de ácido graso tales como esteres alquílicos de C?-C2u del ácido graso-C-?0-C22, los cuales se pueden obtener, por ejemplo, mediante transesterificación del glicerol anteriormente mencionado o esteres glicólicos de ácido graso tales como esteres de ácido graso de C?_-C2 con alcoholes de CrC2. (por ejemplo metanol, etanol, propanol o butanol). La transesterificación se puede llevar a cabo mediante métodos conocidos, como se describe, por ejemplo, en Rómpp Chemie Lexikon, 9a edición, volumen 2, página 1343, Thieme Verlag Stuttgart. Los esteres alquílicos de ácido graso preferidos tales como esteres alquílicos de CrC2Cl de ácido graso C 0-C22 son esteres metílicos, esteres etílicos, esteres propíiicos, esteres butílicos, esteres 2-etilhexí!icos y esteres dodecílicos. Los glicoles preferidos y esteres glicerólicos de ácido graso tales como esteres de ácido graso de C-?o-C22 son los esteres glicólicos uniformes o mezclados y esteres glicerólicos de ácidos grasos de C-?o-C22, en particular de dichos ácidos grasos que tienen un número par de átomos de carbono, por ejemplo ácido erúcico, ácido láurico, ácido palmítico y en particular ácidos grasos de C-t8 tales como ácido esteárico, ácido oléico, ácido linoléico o ácido linolénico. Los aceites animales generalmente se conocen y están comercialmente disponibles. Para el propósito de la presente invención, el término "aceites animales" debe entenderse que significa, por ejemplo, aceites de origen animal tales como aceite de ballena, aceite de hígado de bacalao, aceite de cervatillo o aceite de visón. Los aceites vegetales generalmente se conocen y están comercialmente disponibles. Para el propósito de la presente invención, el término "aceites vegetales" debe entenderse que significa, por ejemplo, aceites de especies de plantas oleaginosas, tales como aceite de frijol de soya, aceite de colza, aceite de maíz, aceite de girasol, aceite de semilla de algodón, aceite de linaza, aceite de coco, aceite de palma, aceite de cardo, aceite de nuez, aceite de araquis, aceite de oliva o aceite de ricino, en particular aceite de colza, en donde los aceites vegetales también incluyen sus productos de transesterificación, por ejemplo alquil esteres, tales como aceite de metil éster de colza o aceite de etil éster de colza. Los aceites vegetales preferiblemente son esteres de C?0-C22) preferiblemente ácidos grasos de C?2-C2o. Los esteres de ácido graso de C?0-C22 son, por ejemplo, esteres de ácidos grasos de C-?o-C22 insaturados o saturados que tienen, en particular, un número par de átomos de carbono, por ejemplo ácido erúcico, ácido láurico, ácido palmítico y en particular ácidos grasos de C?8 tales como ácido esteárico, ácido oléico, ácido linoléico o ácido linolénico. Los ejemplos de aceites vegetales son esteres glicerólicos o glicólicos de ácido graso de C1.-C22 con ácidos grasos de C-?0-C22, o esteres alquílicos de C?-C2? de ácido graso C10-C22 los cuales se pueden obtener, por ejemplo, mediante transesterificación de los esteres glicerólicos o glicólicos de ácido graso de C-?.-C22 anteriormente mencionados con alcoholes de C?-C2_ (por ejemplo metanol, etanol, propanol o butanol). La transesterificación se puede llevar a cabo mediante métodos conocidos como se describe, por ejemplo, en Rómpp Chemie Lexikon, 9a edición, volumen 2, página 1343, Thieme Verlag Stuttgart. Los aceites vegetales pueden ser contenidos en las mezclas por ejemplo en la forma de aceites vegetales comercialmente disponible, en particular aceites de colza, tales como metil éster de aceite de colza, por ejemplo Phytorob® B (Novance, Francia), Edenor® MESU y la serie Agnique® ME (Cognis, Alemania) la serie Radia® (1CI), la serie Prilube® (Petrofina), o biodiesel o en la forma de aditivos para formulación que contienen aceite vegetal comercialmente disponibles, en particular aquellos basados en aceites de colza, tales como metil esteres de aceite de colza, por ejemplo Hasten® (Victoria Chemical Company, Australia, a continuación referido como Hasten, ingrediente principal: etil éster de aceite de colza), Actirob® B (Novance, Francia, a continuación referido como Actirob B, ingrediente principal: metil éster de aceite de colza), Rako-Binol® (Bayer AG, Alemania, a continuación referido como Rako-Binol®, ingrediente principal: aceite de colza), Renol® (Stefes, Alemania, a continuación referido como Renol, ingrediente de aceite vegetal: metil éster de aceite de colza) o stefes Mero® (Stefes, Alemania, a continuación referido como mero, ingrediente principal: metil éster de aceite de colza). Los ejemplos de esteres del ácido sintético son, por ejemplo, aquellos derivados a partir de ácidos grasos que tienen un número non de átomos de carbono, tales como esteres de ácido graso de C11-C21. Los solventes orgánicos preferidos son hidrocarburos, en particular hidrocarburos aromáticos y/o hidrocarburos alifáticos y esteres de ácido graso, tales como aceites vegetales, tales como triglicéridos de ácidos grasos que tienen de 10 a 22 átomos de carbono, los cuales pueden ser saturados o ya sea insaturados, de cadena recta o ramificada y los cuales pueden o pueden no portar grupos funcionales adicionales, tales como aceite de maíz, aceite de colza, aceite de girasol, aceite de semilla de algodón, aceite de linaza, aceite de frijol de soya, aceite de coco, aceite de palma, aceite de cardo o aceite de ricino, y sus productos de transesterificación, tales como esteres alquílicos de ácido graso, y mezclas de los mismos. Los solventes pueden estar presentes como tales o como una mezcla. El poder solubilizante del solvente o mezcla solvente utilizada para la sulfonilurea(s) utilizada (componente A) preferiblemente es bajo. La proporción total de solventes en las composiciones herbicidas de conformidad con la invención generalmente es entre 0 y 95% en peso, preferiblemente en el intervalo entre 20 y 80% en peso. La proporción de solventes polares tales como solventes apróticos polares generalmente es menor de 20% en peso, preferiblemente en el intervalo de 0 a 10% en peso. Los sulfosuccinatos (componente D) opcionalmente presentes en las composiciones herbicidas de conformidad con la invención pueden ser, por ejemplo, mono- o diésteres de ácido sulfosuccínico, preferiblemente aquellos de la fórmula (lll) R1-(X1)n-O-CO-CH2-CH(SO3M)-CO-O-(X2)m-R2 (lll) en la cual R1 es H o un radical hidrocarburo de CrC30 no sustituido o sustituido, tales como alquilo de C?-C3u o arilalquilo de C -C30, R2 es H o un radical hidrocarburo de C-?-C3o no sustituido o sustituido, tales como alquilo de C?-C3fJ o alquilarilo de C -C_0, o un catión, por ejemplo un catión metálico, tales como un catión metálico álcali o catión metálico terreo alcalino, o un catión de amonio, tales como NH4 o un catión alquilo, alquilarilo o poli(arilalquil)fenilamonio, X1, X2 son idénticos o diferentes e independientemente entre sí son una unidad espadadora, tales como una unidad de poliéter o una unidad de poliéster, n, m son idénticos o diferentes e independientemente entre sí son cero o 1 , preferiblemente cero, y M es un catión, por ejemplo un catión metálico, tales como un catión metálico álcali o catión metálico terreo alcalino, o un catión de amonio, tales como NH4 o un catión alquil-, alquilarilo- o poli(arilalquil)fenilamonio. Se da preferencia a sulfosuccinatos de la fórmula (lll) en los cuales R1 y R2 son idénticos o diferentes e independientemente entre sí son radicales alquilo de C1-C20, preferiblemente de C -C?s de cadena recta, ramificados o cíclicos, saturados o no saturados, tales como metilo, etilo, butilo, hexiio, ciciohexilo, octilo, tales como radicales 2-etilhexilo, decilo, tridecilo o octadecilo, o R1 y R2 son radicales alquilarilo de C7-C20, tales como nonilfenilo, 2,4,6-tri-sec-butilfenilo, 2,4,6-tris-(1-feniletil)fenilo, alquilbencilo o un radical hidroxicinámico, X y X2 son idénticos o diferentes e independientemente entre sí son unidades poliéter, tales como polietilenglicoles -(C2H4O)p- o poiipropilenglicoles -(C3HßO)p- en donde p = 1 a p = 20, en particular p = 1 a p = 12, o unidades de poliéster, tales como ácido polihidroxibutírico -(CH[CH3]-CH2-COO)q- o ácido poliláctico -(CH[CH3]-COO)q- en donde q = 1 a q = 15, en particular q = 1 a q = 8, n, m son idénticos o diferentes e independientemente entre sí son cero o 1 , preferiblemente cero, y M es un catión, por ejemplo un catión metálico, tales como un catión metálico álcali o catión metálico terreo alcalino, o un catión de amonio los cuales pueden estar sustituidos en alquilo.
Los ejemplos de sulfosuccinatos los cuales preferiblemente están presentes son a1) sulfosuccinato el cual se esterifica una vez o dos veces con alcoholes alifáticos, cicloalifáticos y/o aromáticos de cadena recta, cíclicos o ramificados, que tienen, por ejemplo, 1 a 22 átomos de carbono en el radical alquilo, preferiblemente sulfosuccinato de metal mono- o dialquílico, en particular sulfosuccinato mono- o disódico, el cual se esterifica una vez o dos veces con metanol, etanol, (iso)propanol, (iso)butanol, (iso)pentanol, (iso)hexanol, ciclohexanol, (iso)heptanol, (iso)octanol (en particular: etilhexanol), (iso)nonanol, (iso)decanol, (iso)undecanol, (iso)dodecanol o (iso)tridecanol, a2) sulfosuccinato el cual se esterifica una vez o dos veces con aducios de óxido de (poli)alquileno de alcoholes, que tienen, por ejemplo, de 1 a 22 átomos de carbono en el radical alquilo y de 1 a 200, preferiblemente de 2 a 200, unidades de óxido de alquileno en la porción óxido de (poli)alquileno, preferiblemente sulfosuccinato de metal mono- o diálcali, en particular sulfosuccinato de mono- o disódico, el cual se esterifica una vez o dos veces con dodecil/tetradecil alcohol +2-5 moles de óxido de etileno o con i-tridecíl+3 moles de óxido de etileno, a3) la sal metálica diálcali, preferiblemente la sal disódica, de anhídrido maléico la cual se ha hecho reaccionar con un equivalente de una amina o un aducto de óxido de (poli)alquileno amino-terminado de un alcohol, una amina, un ácido graso, un éster o una amida y posteriormente se sulfona, que tiene, por ejemplo, de 1 a 22 átomos de carbono en el radical alquilo y de 1 a 200, preferiblemente de 2 a 200, unidades de oxialquileno en la porción de óxido de (poli)alquileno, preferiblemente la sal disódica de anhídrido maléico la cual se ha hecho reaccionar con un equivalente de amina grasa de coco y posteriormente se sulfona, a4) la sal metálica diálcali, preferiblemente la sal disódica, de anhídrido maléico la cual se ha hecho reaccionar con un equivalente de una amida o un aducto de óxido de (poli)alquileno de una amida y posteriormente se sulfona, que tiene, por ejemplo, de 1 a 22 átomos de carbono en el radical alquilo y de 1 a 200, preferiblemente de 2 a 200, unidades de oxialquileno en la porción de óxido de (poli)alquileno, preferiblemente la sal disódica de anhídrido maléico la cual se ha hecho reaccionar con un equivalente de oleilamida + 2 moles de óxido de etileno y posteriormente se sulfona, y/o a5) la sal metálica tetraálcali, preferiblemente la sal tetrasódica, de N-(1 ,2-dicarboxietil)-N-octadecilsulfosuccinamato. Los ejemplos de sulfosuccinatos de los grupos a1) a a5) los cuales están comercialmente disponibles y se prefieren dentro del contexto de la presente invención se listan a continuación: a1) dialquilsulfosuccinato sódico, por ejemplo dialquilsulfo-succinato de (C -C18) sódico, tales como diisooc-tilsulfosuccinato sódico, preferiblemente di(2-etilhexil)sulfosuccinato sódico, comercialmente disponible, por ejemplo, en la forma de las marcas registradas Aerosol®
(Cytec), las marcas registradas Agrilan® o Lankropol® (Akzo Nobel), las marcas registradas Empimin® (Albright&Wilson), las marcas registradas Cropol® (Croda), las marcas registradas Lutensit® (BASF), las marcas registradas Tritón® (Union Carbide), las marcas registradas Geropon® (Rhodia) o las marcas registradas Imbirol®, Madeol® o Polirol® (Cesalpinia), a2) éter sulfosuccinato de poiietilenglicol alcohol sódico, comercialmente disponible, por ejemplo, en la forma de las marcas registradas Geropon® ACR (Rhodia), a3) Éter semisulfosuccinato de polietilen glicol alcohol disódico, comercialmente disponible, por ejemplo, en la forma de las marcas registradas Aerosol® (Cytec), las marcas registradas Mariinat® o Sermul® (Condea), las marcas registradas Empicol® (Albright&Wilson), las marcas registradas Secosol® (Stepan), las marcas registradas Geropon® (Rhodia), las marcas registradas Disponil® o Texapon® (Cognis) o las marcas registradas Rolpon® (Cesalpinia), a4) N-alquilsulfosuccinamato disódico, comercialmente disponible, por ejemplo, en la forma de las marcas registradas Aerosol® (Cytec), las marcas registradas Rewopol® o Rewoderm® (Rewo), las marcas registradas Empimin® (Albright&Wilson), las marcas registradas Geropon® (Rhodia) o las marcas registradas Polirol® (Cesalpinia), a-5) Éter semisulfosuccinato de polietilenglico! ácido graso amida disódico, comercialmente disponible, por ejemplo, en la forma de las marcas registradas Elfanol® o Lankropol® (Akzo Nobel), las marcas registradas Rewoderm®, Rewocid® o Rewopol® (Rewo), las marcas registradas Emcol® (Witco), las marcas registradas Standapol® (Cognis) o las marcas registradas Rolpon® (Cesalpinia), y a6) N-(1 ,2-dicarboxietil)-N-octadecilsulfosuccinamato tetrasódico, comercialmente disponible, por ejemplo, en la forma de Aerosol 22® (Cytec). Comercialmente, los sulfosuccinatos se obtienen, por ejemplo, como la serie Aerosol® (Cytec), Agrilan® o Lankropol® (Akzo Nobel),
Empimin® (Huntsman), Cropol® (Croda), Lutensit® (BASF), Tritón® GR
(UnionCarbide), lmbirol®/Madeol®/Polirol® (Cesalpinia); Geropon® AR serie o Geropon® SDS (Rhodia). Los sulfosuccinatos preferidos son, por ejemplo, las sales de sodio, potasio y amonio de bis(alquil)sulfosuccinatos, en donde los radicales alquilo pueden ser idénticos o diferentes y contienen de 4 a 16 átomos de carbono y preferiblemente son radicales butilo, hexilo, octilo, tales como 2-etilhexilo, o decilo los cuales pueden ser de cadena recta o ramificada. La proporción total de sulfosuccinato o sulfosuccinatos en las composiciones herbicidas de conformidad con la invención generalmente es entre 0 y 60% en peso, en particular en el intervalo entre 0.5 y 30% en peso. Los compuestos agroquímicamente activos opcionales adecuados (E) diferentes a (A) y (B) para las composiciones herbicidas de conformidad con la invención son, por ejemplo, compuestos activos conocidos, tales como herbicidas, insecticidas o fungicidas, como se describe, por ejemplo, en Weed Research 26, 441-445 (1986), o "The Pesticide Manual", 12a edición, The British Crop Protection Council, 2000, y la literatura citada en la presente invención, por ejemplo en formulaciones mezcladas o como un componente para una mezcla en tanque. Los siguientes compuestos activos, por ejemplo, se pueden mencionar como herbicidas conocidos a partir de la literatura los cuales pueden estar presentes en las composiciones herbicidas de conformidad con la invención. Los compuestos se refieren ya sea mediante el "nombre común" de the International Organization for Standardization (ISO) o mediante el nombre químico, si es apropiado junto con un número de código usual, e incluye en cada caso todas las formas posibles de uso, tales como ácidos, sales, esteres e isómeros, tales como setereoisómeros e isómeros ópticos: acetochlor; acifluorfen; aclonifen; AKH 7088, por ejemplo ácido [[[1-[5-[2-cloro-4-(trifluorometil)fenoxi]-2-nitrofenil]-2-metoxietiliden]amino]oxi]acético y su éster metílico; alachlor; alloxydim; ametryn; amidosulfuron; amitrol; AMS, por ejemplo sulfamato de amonio; anilofos; asulam; atrazine; azafenidine (DPX-R6447), azimsulfuron (DPX-A8947); aziprotryn; barban; BAS 516 H, por ejemplo 5-fluoro-2-fenil-4H-3,1-benzoxazin-4-ona; benazolin; benfluralin; benfuresate; bensulfuron-metílico; bensulide; bentazone; benzofluor; benzoylprop-etíüco; benztiazurona; bialaphos; bifenox; bispiribac-sódico (KIH-2023), bromacil; bromobutide; bromofenoxim; bromoxyni!, en particular bromoxynil-octanoato y bromoxynil-heptanoato; butachlor; butamifos; butenachlor; buthidazol; butralin; butroxydim (lCI-0500), butilato; cafenstrole (CH-900); carbetamide; cafentrazone; CDAA, por ejemplo 2-cloro-N,N-di-2-propeni!acetamida; CDEC, por ejemplo 2-cloroalil dietilditiocarbamato; clometoxifen; chloramben; chloransulam-metílico (XDE-565), chlorazifop-butilo, chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-metílico; chloridazon; chlorimuron etílico; chlomitrofen; chlorotoluron; chloroxuron; chlorprofam; chlortal-dimetílico; chlortiamida; cinidon-etílico, cinmethylin; cinosulfuron; clethodim; clodinafop y sus derivados éster (por ejemplo chlodinafop-propargyl); clomazone; clomeprop; cloproxydim; clopyralid; cumyluron (JC 940); cyanazine; cycloate; cyclosulfamuron (AC 014); cycloxiydim; cycluron; cyhalofop y sus derivados éster (por ejemplo butil éster, DEH-112); cyperquat; cyprazine; ciprazol; 2,4-D; 2,4-DB; dalapon; desmedipham; desmetryn; di-allate; dicamba; dichlobenil; dichlorprop; diclofop y sus esteres tales como diclofop-metílico; diclosulam (XDE-564), diethatyl; difenoxuron; difenzoquat; diflufenican; diflufenzopyr-sódico (SAN-835H), dimefuron; dimethachlor; dimethametryn; dimethenamide (SAN-582H); dimidazon, 5-(4,6-dimetilpirimidin-2-il-carbamoilsulfamoil)-1-(2-piridil)pirazole-4-carboxilato metílico (NC-330); triaziflam (IDH -1105), cinosulfon; dimethipin; dinitramina; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-etílico; EL 177, por ejemplo 5-ciano-1-(1 ,1-dimetiietil)-N-metil-1 H-pirazol-4-carboxamida; endothal; indanofan (MK-243), EPTC; esprocarb; ethalfluralin; ethametsulfuron-metílico; ethidimuron; ethiozin; ethofumesate; F5231 , por ejemplo N-[2-cloro-4-fluoro-5-[4-(3-fluoropropil)-4,5-dihidro-5-oxo-1 H-tetrazol-1-il]fenil]etansulfonamida; etoxifen y su éster (por ejemplo éster etílico, HN-252); etoxisulfuron (a partir de EP 342569); etobenzanid (HW 52); 3-(4-etoxi-6-et¡l-1 ,3,5-triazin-2-il)-1-(2,3-dihidro-1 )1- dioxo-2-metilbenzo[b]tiofen-7-sulfonil)urea (EP-A 079 683); 3-(4-etil-6-metoxi- 1 ,3,5-triazin-2-¡l)-1-(2,3-dihidro-1 ,1-dioxo-2-metilbenzo[b]tiofen-7-sulfonil)urea (EP-A 079 683); fenoprop; clomazone, fenoxaprop y fenoxaprop-P y sus esteres, por ejemplo fenoxaprop-P-etil y fenoxaprop-etil; butroxydim; fenuron; flamprop-metil; flazasulfuron; flufenacet (BAY-FOE-5043), fluazifop y fluazifop-P y sus esteres, por ejemplo fluazifop-butílico y fluazifop-P-butílico, florasulam (DE-570); fluchloralin; flumetsulam; flumeturon; flumiclorac y sus esteres (por ejemplo éster pentílico, S-23031); flumioxazin (S-482); flumipropyn; flupoxam (KNW-739); fluorodifen; fluoroglycofen-etil; flupropacil (UBlC-4243); flupyrsulfuron-metílico sódico (DPX-KE459), fluridone; flurochloridone; fluroxypyr; flurtamone; fluthiacet-metil (KIH-9201), fomesafen; fosamina; furyloxyfen; glufosinate; glyphosate; halosafen; halosulfuron y sus esteres (por ejemplo éster metílico, NC-319); haloxyfop y sus esteres; haloxyfop-P (= R-haloxyfop) y sus esteres; hexazinone; ¡mazamethabenz-metil; imazamox (AC-299263), imazapyr; imazaquin y sales tales como la sal de amonio; imazapic; imazethapyr; imazosulfuron; iodosulfuron-metílico-sódico (metil 4-iodo-2-[3-(4-metoxi-6-metil-1 ,3,5-triazin-2-il)ureidosulfoniljbenzoato, sal sódica, WO 92/13845); ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidid; metamitron; metazachior; methabenzthiazuron; metham; methazole; metoxiphenone; metildymron; metobenzuron, mesosulfuron-metil (WO 95/10507); metobenzuron; metobromuron; metolachlor; S-metolachlor, metosulam (XRD 511 ); metoxuron; metribuzin; hidrazida maléica; molinate;
monalide; monocarbamida dihidrogensulfato; monolinuron; monuron; MT 128, por ejemplo 6-cloro-N-(3-cloro-2-propenil)-5-metil-N-fenil-3-piridazinamina; MT 5950, por ejemplo N-[3-cloro-4-(1-metiletil)fenil]-2-metilpentanamida; foramsulfuron (WO 95/01344); naproanilide; napropamida; naptalam; NC 310, por ejemplo 4-(2,4-diclorobenzoil)-1-metil-5-benciloxipirazol; neburon; nicosulfuron; nipyraclofen; nitralin; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon; oxaziclomefone (MY-100), oxyfluorfen; oxasulfuron (CGA-277476), paraquat; pebulate; pendimethalin; pentoxazone (KPP-314), perfluidone; phenisopham; phenmedipham; picloram; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-metil; procyazine; prodiamina; profluralin; proglinazine-etil; prometon; prometryn; propachlor; propanil; propaquizafop y sus esteres; propazine; propham; propisochlor; propoxicarbazona-sódica; propyzamida; prosulfalin; prosulfocarb; prosulfuron (CGA-152005); prynachlor; pyraflufen-etílico (ET-751), chloridazon; pyrazosulfuron-etílico; pyrazoxyfen; pyribenzoxim, pyridate; pyriminobac-metílico (KIH-6127), pyrithiobac (KIH-2031); pyroxofop y sus esteres (por ejemplo éster propargílico); quinclorac; quinmerac; quizalofop y quizalofop-P y sus derivados éster, por ejemplo quizalofop-etílico; quizalofop-P-tefurílico y -etílico; rimsulfuron (DPX-E 9636); S 275, por ejemplo 2-[4-cloro-2-fluoro-5-(2-propiniioxi)fenil]-4,5,6,7-tetrahidro-2H-indazol; secbumeton; setoxidim; siduron; simazine; simetryn; SN 106279, por ejemplo ácido 2-[[7-[2-cloro-4-(trifluorometil)fenoxi]-2-naftalenil]oxi]propanóico y su éster metílico; sulfentrazone (FMC-97285, F- 6285); sulfazuron; sulfometuron-metil; glyphosate-trimesium (ICI-A0224); sulfosulfuron (MON-37500), TCA; tebutam (GCP-5544); tebuthiuron; tepraloxydim (BAS-620H), terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, por ejemplo N,N-dietil-3-[(2-etil-6-metilfenil)sulfonil]-1 H-1 ,2,4-triazol-1 -carboxamida; thenylchlor (NSK-850); thiazafluron; thiazopyr (Mon-13200); thidiazimin (SN-124085); thiobencarb; thiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamida; triclopyr; tridiphane; trietazine; trifluralin; triflusulfuron y esteres (por ejemplo éster metílico, DPX-66037); trimeturon; tsitodef; vernolate; WL 110547, por ejemplo 5-fenoxi-1-[3-(trifluorometil)fen¡l]-1 H-tetrazol; UBH-509; D-489; LS 82-556;
KPP-300; KPP-421 , MT-146, NC-324; butenachlor (KH-218); DPX-N8189; haloxyfop-etotyl (DOWCO-535); DK-8910; flumioxazin (V-53482); PP-600;
MBH-001 , amicarbazone, aminopyralid, beflubutamid, benzobicyclon, benzofenap, benzfendizone, butafenacil, chlorfenprop, cloprop, daimuron, dichIorprop-P, dimepipeate, dimethenamid-P, fentrazamida, flamprop-M, fluazolate, flucarbazone, flucetosulfuron, foramsulfuron, indanofan, isoxachlortole, isoxaflutole, MCPA-thioetil, mecoprop-P, mesosulfuron, mesotrione, metamifop, orthosulfamuron (IR-5878), penoxsulam, pethoxamid, picolinafen, pinoxaden, profluazol, profoxydim, propoxycarbazone, pyraclonil, pyrazolynate, pyridafol, pyriftalid, pyrimisulfan, sulcotrione, thidiazuron, topramezone, trifloxysulfuron, tritosulfuron. Los copartícipes de mezclado E), las sulfonilureas A) y los protectores B) se pueden aplicar juntos (como una mezcla preparada o como una mezcla en tanque) o sucesivamente en cualquier secuencia. Los copartícipes de mezclado preferidos E) son bromoxynil (E1 ) en todas sus formas de uso, incluyendo las sales y esteres, por ejemplo bromoxinil-octanoato (E1.1), bromoxinil-heptanoato (E1.2), bromoxinil-butirato (E1.3), bromoxinil-sódico (E1.4) y bromoxynil-potásico (E1.5); 2,4-D (E2) en todas sus formas de uso, incluyendo las sales y esteres, por ejemplo 2,4-D-butotil (E2.1), 2,4-D-butilo (E2.2), 2,4-D-dimetilamonio (E2.3), 2,4-D-dietanolamina (E2.4), 2,4-D-2-etilhexil (E2.5), 2,4-D-isooctiIo (E2.6), 2,4-D-isopropilo (E2.7), 2,4-D-sódico (E2.8) y 2,4-D-trietanolamina (E2.9); dicamba (E3) en todas sus formas de uso, incluyendo las sales y esteres, por ejemplo dicamba-sódico (E3.1), dicamba-potásico (E3.2) y dicamba-dimetilamonio (E3.3); fenoxaprop (E4) en todas sus formas de uso, incluyendo los esteres, por ejemplo fenoxaprop-etílico (E4.1) y fenoxaprop-P-etílico (E4.2); fluroxypyr (E5) en todas sus formas de uso, incluyendo las sales y esteres, por ejemplo fluroxypyr-meptyl (E5.1 ) y fluroxypyr-2-butoxy-1-metiletil (E5.2); MCPA (E6) en todas sus formas de uso, incluyendo las sales y esteres, por ejemplo MCPA-sodium (E6.1), MCPA-potásico (E6.2), MCPA-2-etilhexil (E6.3), MCPA-butotil (E6.4) y MCPA-dimetilamonio (E6.5); iodosulfuron (E7) en todas sus formas de uso, incluyendo las sales y esteres, por ejemplo iodosulfuron-metílico (E7.1) y iodosulfuron-metílico-sódico (E7.2); mesosulfuron (E8) en todas sus formas de uso, incluyendo las sales y esteres, por ejemplo mesosulfuron-metílico (E8.1) y mesosulfuron-metílico-sódico (E8.2); propoxicarbazona (E9) en todas sus formas de uso, incluyendo las sales y esteres, por ejemplo propoxycarbazone-sódico (E9.1). Las combinaciones preferidas (A), (B), (E) de conformidad con la invención son, por ejemplo: (E1) + (A1.1) + (B1), (E1) + (A1.1) + (B2), (E1) + (A1.1) + (B3), (E1 ) + (A2.1) + (B1), (E1) + (A2.1) + (B2), (E1) + (A2.1) + (B3), (E1 ) + (A3.1 ) + (B1), (E1) + (A3.1) + (B2), (E1) + (A3.1) + (B3), (E1) + (A4.1) + (B1), (E1) + (A4.1) + (B2), (E1 ) + (A4.1 ) + (B3), (E1) + (A1.2) + (B1), (E1) + (A1.2) + (B2), (E1 ) + (A1.2) + (B3), (E1) + (A2.2) + (B1 ), (E1) + (A2.2) + (B2), (E1) + (A2.2) + (B3), (E1) + (A3.2) + (B1), (E1) + (A3.2) + (B2), (E1) + (A3.2) + (B3), (E1) + (A4.2) + (B1), (E1) + (A4.2) + (B2), (E1) + (A4.2) + (B3), (E1 ) + (A1.1) + (A1.2) + (B1), (E1 ) + (A1.1 ) + (A2.1 ) + (B1 ), (E1) + (A1.1) + (A2.2) + (B1), (E1) + (A1.1) + (A3.1) + (B1), (E 1) + (A1.1) + (A3.2) + (B1), (E1) + (A1.1) + (A4.1) + (B1), (E1) + (A1.1) + (A4.2) + (B1); (E1) + (A1.2) + (A2.1) + (B1), (E1) + (A1.2) + (A2.2) + (B1), (E1 ) + (A1.2) + (A3.1) + (B1), (E1) + (A1.2) + (A3.2) + (B1), (E1) + (A1.2) + (A4.1) + (B1), (E1) + (A1.2) + (A4.2) + (B1); (E1 ) + (A2.1 ) + (A2.2) + (B1), (E1) + (A2.1) + (A3.1) + (B1 ), (E1) + (A2.1) + (A3.2) + (B1), (E 1) + (A2.1) + (A4.1) + (B1), (E1) + (A2.1) + (A4.2) +
(B1); (E1) + (A2.2) + (A3.1 ) + (B1), (E1) + (A2.2) + (A3.2) + (B1 ), (E1)
+ (A2.2) + (A4.1) + (B1), (E1) + (A2.2) + (A4.2) + (B1); (E1) + (A3.1) + (A3.2) + (B1), (E1) + (A3.1) + (A4.1) + (B1), (E1) + (A3.1) + (A4.2) + (B1); (E1) + (A3.2) + (A4.1) + (B1), (E1 ) + (A3.2) + (A4.2) + (B1), (E1) + (A4.1) + (A4.2) + (B1); (E1) + (A1.1 ) + (A1.2) + (B2), (E1) + (A1.1) + (A2.1) + (B2), (E1) + (A1.1) + (A2.2) + (B2), (E1 ) + (A1.1 ) + (A3.1) + (B2), (E1 ) + (A1.1 ) + (A3.2) + (B2), (E1) + (A1.1) + (A4.1) + (B2), (E1) + (A1.1) + (A4.2) + (B2); (E1) + (A1.2) + (A2.1) + (B2), (E1) + (A1.2) + (A2.2) + (B2), (E1)
+ (A1.2) + (A3.1) + (B2), (E1 ) + (A1.2) + (A3.2) + (B2), (E1 ) + (A1.2) + (A4.1) + (B2), (E1) + (A1.2) + (A4.2) + (B2); (E1) + (A2.1) + (A2.2) + (B2), (E1) + (A2.1) + (A3.1) + (B2), (E1) + (A2.1) + (A3.2) + (B2), (E1 ) + (A2.1 ) + (A4.1) + (B2), (E1 ) + (A2.1) + (A4.2) + (B2); (E1) + (A2.2) + (A3.1) + (B2), (E1) + (A2.2) + (A3.2) + (B2), (E1) + (A2.2) + (A4.1) + (B2), (E 1) + (A2.2) + (A4.2) + (B2); (E1) + (A3.1) + (A3.2) + (B2), (E1) + (A3.1) + (A4.1) + (B2), (E1) + (A3.1) + (A4.2) + (B2); (E1 ) + (A3.2) + (A4.1) + (B2), (E1 ) + (A3.2) + (A4.2) + (B2), (E1) + (A4.1) + (A4.2) + (B2); (E1) + (A1.1) + (A1.2) + (B3), (E1) + (A1.1) + (A2.1) + (B3), (E1) + (A1.1) + (A2.2) + (B3), (E1 ) + (A1.1) + (A3.1) + (B3), (E1 ) + (A1.1) + (A3.2) + (B3), (E1 ) + (A1.1) + (A4.1) + (B3), (E1) + (A1.1) + (A4.2) + (B3); (E1) + (A1.2) + (A2.1) + (B3), (E1) + (A1.2) + (A2.2) + (B3), (E1) + (A1.2) + (A3.1) + (B3), (E1) + (A1.2) + (A3.2) + (B3), (E1) + (A1.2) + (A4.1) + (B3), (E1) + (A1.2) + (A4.2) + (B3); (E1) + (A2.1 ) + (A2.2) + (B3), (E1) + (A2.1 ) + (A3.1) + (B3), (E1) + (A2.1) + (A3.2) + (B3), (E1) + (A2.1) + (A4.1) + (B3), (E1) + (A2.1) + (A4.2) + (B3); (E1) + (A2.2) + (A3.1) + (B3), (E1 ) + (A2.2) + (A3.2) + (B3), (E1) + (A2.2) + (A4.1) + (B3), (E1) + (A2.2) + (A4.2) + (B3); (E1) + (A3.1) + (A3.2) + (B3), (E1) + (A3.1) + (A4.1 ) + (B3), (E1) + (A3.1) + (A4.2) + (B3); (E1) + (A3.2) + (A4.1) + (B3), (E1 ) + (A3.2) + (A4.2) + (B3), (E1) + (A4.1 ) + (A4.2) + (B3); (E1.1) + (A1.1) + (B1), (E1.1) + (A1.1) + (B2), (E1.1) + (A1.1 ) + (B3), (E1.1 ) + (A2.1) + (B1), (E1.1) + (A2.1) + (B2), (E1.1) + (A2.1) + (B3), (E1.1) + (A3.1) + (B1), (E1.1) + (A3.1) + (B2), (E1.1) + (A3.1) + (B3), (E1.1) + (A4.1) + (B1), (E1.1) + (A4.1) + (B2), (E1.1) + (A4.1) + (B3), (E1.1 ) + (A1.2) + (B1), (E1.1) + (A1.2) + (B2), (E1.1) + (A1.2) + (B3), (E1.1) + (A2.2) + (B1), (E1.1) + (A2.2) + (B2), (E1.1) + (A2.2) + (B3), (E1.1) + (A3.2) + (B1), (E1.1) + (A3.2) + (B2), (E1.1) + (A3.2) + (B3), (E1.1) + (A4.2) + (B1), (E1.1) + (A4.2) + (B2), (E1.1 ) + (A4.2) + (B3), (E1.1) + (A1.1) + (A1.2) + (B1), (E1.1) + (A1.1) + (A2.1) + (B1),
(E1.1) + (A1.1 ) + (A2.2) + (B1), (E1.1) + (A1.1) + (A3.1) + (B1), (E1.1) + (A1.1) + (A3.2) + (B1), (E1.1) + (A1.1) + (A4.1) + (B1), (E1.1) + (A1.1) + (A4.2) + (B1); (E1.1) + (A1.2) + (A2.1) + (B1), (E1.1) + (A1.2) + (A2.2) + (B1), (E1.1) + (A1.2) + (A3.1) + (B1), (E1.1 ) + (A1.2) + (A3.2) + (B1), (E1.1 ) + (A1.2) + (A4.1) + (B1), (E1.1) + (A1.2) + (A4.2) + (B1); (E1.1 ) + (A2.1) + (A2.2) + (B1), (E1.1 ) + (A2.1) + (A3.1) + (B1), (E1.1) + (A2.1) + (A3.2) + (B1), (E1.1) + (A2.1) + (A4.1) + (B1), (E1.1) + (A2.1) 3
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(B1), (E2) + (A3.1) + (B2), (E2) + (A3.1) + (B3), (E2) + (A4.1) + (B1), (E2) +
(A4.1) + (B2), (E2) + (A4.1) + (B3), (E2) + (A1.2) + (B1), (E2) + (A1.2) + (B2),
(E2) + (A1.2) + (B3), (E2) + (A2.2) + (B1), (E2) + (A2.2) + (B2), (E2) + (A2.2) + (B3), (E2) + (A3.2) + (B1), (E2) + (A3.2) + (B2), (E2) + (A3.2) + (B3), (E2) + (A4.2) + (B1), (E2) + (A4.2) + (B2), (E2) + (A4.2) + (B3), (E2) + (A1.1) + (A1.2) + (B1), (E2) + (A1.1) + (A2.1) + (B1), (E2) + (A1.1) + (A2.2) + (B1), (E2) + (A1.1) + (A3.1) + (B1), (E2) + (A1.1) + (A3.2) + (B1), (E2) + (A1.1) + (A4.1) + (B1), (E2) + (A1.1) + (A4.2) + (B1); (E2) + (A1.2) + (A2.1) + (B1), (E2) + (A1.2) + (A2.2) + (B1), (E2) + (A1.2) + (A3.1) + (B1), (E2) + (A1.2) + (A3.2) + (B1), (E2) + (A1.2) + (A4.1) + (B1), (E2) + (A1.2) + (A4.2) + (B1 ); (E2) + (A2.1) + (A2.2) + (B1), (E2) + (A2.1) + (A3.1) + (B1), (E2) + (A2.1) + (A3.2) + (B1), (E2) + (A2.1) + (A4.1) + (B1 ), (E2) + (A2.1) + (A4.2) + (B1); (E2) + (A2.2) + (A3.1) + (B1), (E2) + (A2.2) + (A3.2) + (B1), (E2) + (A2.2) + (A4.1) + (B1), (E2) + (A2.2) + (A4.2) + (B1); (E2) + (A3.1) + (A3.2) + (B1), (E2) + (A3.1) + (A4.1) + (B1), (E2) + (A3.1) + (A4.2) + (B1); (E2) + (A3.2) + (A4.1) + (B1), (E2) + (A3.2) + (A4.2) + (B1), (E2) + (A4.1) + (A4.2) + (B1); (E2) + (A1.1) + (A1.2) + (B2), (E2) + (A1.1) + (A2.1) + (B2), (E2) + (A1.1) + (A2.2) + (B2), (E2) + (A1.1) + (A3.1) + (B2), (E2) + (A1.1) + (A3.2) + (B2), (E2) + (A1.1) + (A4.1) + (B2), (E2) + (A1.1) + (A4.2) + (B2); (E2) + (A1.2) + (A2.1 ) + (B2), (E2) + (A1.2) + (A2.2) + (B2), (E2)
+ (A1.2) + (A3.1) + (B2), (E2) + (A1.2) + (A3.2) + (B2), (E2) + (A1.2) + (A4.1) + (B2), (E2) + (A1.2) + (A4.2) + (B2); (E2) + (A2.1) + (A2.2) + (B2), (E2) + (A2.1) + (A3.1) + (B2), (E2) + (A2.1) + (A3.2) + (B2), (E2) + (A2.1) + (A4.1) + (B2), (E2) + (A2.1) + (A4.2) + (B2); (E2) + (A2.2) + (A3.1) + (B2), (E2) + (A2.2) + (A3.2) + (B2), (E2) + (A2.2) + (A4.1) + (B2), (E2) + (A2.2) + (A4.2) + (B2); (E2) + (A3.1) + (A3.2) + (B2), (E2) + (A3.1) + (A4.1) + (B2), (E2)
+ (A3.1 ) + (A4.2) + (B2); (E2) + (A3.2) + (A4.1) + (B2), (E2) + (A3.2) + (A4.2) + (B2), (E2) + (A4.1) + (A4.2) + (B2); (E2) + (A1.1 ) + (A1.2) + (B3), (E2) + (A1.1 ) + (A2.1 ) + (B3), (E2) + (A1.1) + (A2.2) + (B3), (E2) + (A1.1) + (A3.1) + (B3), (E2) + (A1.1) + (A3.2) + (B3), (E2) + (A1.1 ) + (A4.1 ) + (B3), (E2) + (A1.1 ) + (A4.2) + (B3); (E2) + (A1.2) + (A2.1) + (B3), (E2) + (A1.2) + (A2.2) + (B3), (E2) + (A1.2) + (A3.1) + (B3), (E2) + (A1.2) + (A3.2) + (B3), (E2) + (A1.2) + (A4.1 ) + (B3), (E2) + (A1.2) + (A4.2) + (B3); (E2) + (A2.1 ) + (A2.2) + (B3), (E2) + (A2.1) + (A3.1 ) + (B3), (E2) + (A2.1) + (A3.2) + (B3), (E2) + (A2.1) + (A4.1) + (B3), (E2) + (A2.1) + (A4.2) + (B3); (E2) + (A2.2) + (A3.1) + (B3), (E2) + (A2.2) + (A3.2) + (B3), (E2) + (A2.2) + (A4.1) + (B3), (E2) + (A2.2) + (A4.2) + (B3); (E2) + (A3.1) + (A3.2) + (B3), (E2) + (A3.1) + (A4.1) + (B3), (E2) + (A3.1 ) + (A4.2) + (B3); (E2) + (A3.2) + (A4.1 ) + (B3), (E2) + (A3.2) + (A4.2) + (B3), (E2) + (A4.1) + (A4.2) + (B3); (E2.1) + (A1.1) + (B1 ), (E2.1) + (A1.1 ) + (B2), (E2.1) + (A1.1 ) + (B3), (E2.1) + (A2.1) + (B1), (E2.1) + (A2.1) + (B2), (E2.1) + (A2.1) + (B3), (E2.1) + (A3.1) + (B1), (E2.1) + (A3.1) + (B2), (E2.1) + (A3.1) + (B3), (E2.1) + (A4.1) + (B1), (E2.1) + (A4.1) + (B2), (E2.1) + (A4.1) + (B3), (E2.1) + (A1.2) + (B1), (E2.1) + (A1.2) + (B2), (E2.1) + (A1.2) + (B3), (E2.1) + (A2.2) + (B1), (E2.1) + (A2.2) + (B2), (E2.1) + (A2.2) + (B3), (E2.1) + (A3.2) + (B1), (E2.1) + (A3.2) + (B2), (E2.1) + (A3.2) + (B3), (E2.1) + (A4.2) + (B1 ), (E2.1) + (A4.2) + (B2), (E2.1) + (A4.2) + (B3), (E2.1 ) + (A1.1) + (A1.2) + (B1 ), (E2.1) + (A1.1 ) + (A2.1) + (B1), (E2.1) + (A1.1) + (A2.2) + (B1), (E2.1) + (A1.1) + (A3.1) + (B1), (E2.1) + (A1.1) + (A3.2) + (B1), (E2.1) + (A1.1) + (A4.1) + (B1 ), (E2.1) + (A1.1) + (A4.2) + (B1); (E2.1) + (A1.2) + (A2.1) + (B1), (E2.1) + (A1.2) + (A2.2) + (B1), (E2.1) + (A1.2) + (A3.1) + (B1), (E2.1) + (A1.2) + (A3.2) + (B1), (E2.1) + (A1.2) + (A4.1) + (B1), (E2.1) + (A1.2) + (A4.2) + (B1); (E2.1 ) + (A2.1) + (A2.2) + (B1), (E2.1 ) + (A2.1) + (A3.1) + (B1 ), (E2.1) + (A2.1) + (A3.2) + (B1), (E2.1) + (A2.1) + (A4.1) + (B1), (E2.1) + (A2.1) + (A4.2) + (B1); (E2.1) + (A2.2) + (A3.1) + (B1), (E2.1) + (A2.2) + (A3.2) + (B1), (E2.1) + (A2.2) + (A4.1) + (B1), (E2.1) + (A2.2) + (A4.2) + (B1); (E2.1) + (A3.1) + (A3.2) + (B1), (E2.1) + (A3.1) + (A4.1) + (B1), (E2.1) + (A3.1) + (A4.2) + (B1); (E2.1) + (A3.2) + (A4.1) + (B1), (E2.1) + (A3.2) + (A4.2) + (B1), (E2.1) + (A4.1) + (A4.2) + (B1); (E2.1) + (A1.1) + (A1.2) + (B2), (E2.1) + (A1.1) + (A2.1) + (B2), (E2.1 ) + (A1.1 ) + (A2.2) + (B2), (E2.1) + (A1.1 ) + (A3.1) + (B2), (E2.1 ) + (A1.1) + (A3.2) + (B2), (E2.1) + (A1.1) + (A4.1) + (B2), (E2.1) + (A1.1) + (A4.2) + (B2); (E2.1) + (A1.2) + (A2.1) + (B2), (E2.1) + (A1.2) + (A2.2) + (B2), (E2.1) + (A1.2) + (A3.1) + (B2), (E2.1) + (A1.2) + (A3.2) + (B2), (E2.1) + (A1.2) + (A4.1) + (B2), (E2.1 ) + (A1.2) + (A4.2) + (B2); (E2.1) + (A2.1) + (A2.2) + (B2), (E2.1) + (A2.1) + (A3.1) + (B2), (E2.1 ) + (A2.1) + (A3.2) + (B2), (E2.1) + (A2.1 ) + (A4.1) + (B2), (E2.1 ) + (A2.1 ) + (A4.2) + (B2); (E2.1 ) + (A2.2) + (A3.1) + (B2), (E2.1) + (A2.2) + (A3.2) + (B2), (E2.1) + (A2.2) + (A4.1) + (B2), (E2.1) + (A2.2) + (A4.2) + (B2); (E2.1) + (A3.1) + (A3.2) + (B2), (E2.1) + (A3.1) + (A4.1) + (B2), (E2.1) + (A3.1) + (A4.2) + (B2); (E2.1) + (A3.2) + (A4.1) + (B2), (E2.1) + (A3.2) + (A4.2) + (B2), (E2.1) + (A4.1) + (A4.2) + (B2); (E2.1) + (A1.1) + (A1.2) + (B3), (E2.1) + (A1.1) + (A2.1) + (B3), (E2.1) + (A1.1) + (A2.2) + (B3), (E2.1) + (A1.1) + (A3.1) + (B3), (E2.1) + (A1.1) + (A3.2) + (B3), (E2.1) + (A1.1) + (A4.1) + (B3), (E2.1 ) + (A1.1 ) + (A4.2) + (B3); (E2.1 ) + (A1.2) + (A2.1) + (B3), (E2.1) + (A1.2) + (A2.2) + (133), (E2.1) + (A1.2) + (A3.1) + (B3), (E2.1) + (A1.2) + (A3.2) + (B3), (E2.1) + (A1.2) + (A4.1 ) + (B3), (E2.1 ) + (A1.2) + (A4.2) + (B3); (E2.1) + (A2.1) + (A2.2) + (B3), (E2.1) + (A2.1) + (A3.1) + (B3), (E2.1) + (A2.1) + (A3.2) + (B3), (E2.1) + (A2.1) + (A4.1) + (B3), (E2.1) + (A2.1) + (A4.2) + (B3);
4
(E2.1) + (A2.2) + (A3.1 ) + (B3), (E2.1) + (A2.2) + (A3.2) + (B3), (E2.1) + (A2.2) + (A4.1) + (B3), (E2.1) + (A2.2) + (A4.2) + (B3); (E2.1) + (A3.1) + (A3.2) + (B3), (E2.1) + (A3.1 ) + (A4.1) + (B3), (E2.1) + (A3.1) + (A4.2) + (B3); (E2.1) + (A3.2) + (A4.1) + (B3), (E2.1) + (A3.2) + (A4.2) + (B3), (E2.1 ) + (A4.1 ) + (A4.2) + (B3); (E2.2) + (A1.1) + (B1), (E2.2) + (A1.1) + (B2), (E2.2) + (A1.1) + (B3), (E2.2) + (A2.1) + (B1), (E2.2) + (A2.1) + (B2), (E2.2) + (A2.1) + (B3), (E2.2) + (A3.1) + (B1), (E2.2) + (A3.1) + (B2), (E2.2) + (A3.1) + (B3), (E2.2) + (A4.1) + (B1), (E2.2) + (A4.1) + (B2), (E2.2) + (A4.1) + (B3), (E2.2) + (A1.2) + (B1), (E2.2) + (A1.2) + (B2), (E2.2) + (A1.2) + (B3), (E2.2) + (A2.2) + (B1), (E2.2) + (A2.2) + (B2), (E2.2) + (A2.2) + (B3), (E2.2) + (A3.2) + (B1), (E2.2) + (A3.2) + (B2), (E2.2) + (A3.2) + (B3), (E2.2) + (A4.2) + (B1), (E2.2) + (A4.2) + (B2), (E2.2) + (A4.2) + (B3), (E2.2) + (A1.1) + (A1.2) + (B1), (E2.2) + (A1.1 ) + (A2.1) + (B1), (E2.2) + (A1.1) + (A2.2) + (B1), (E2.2) + (A1.1) + (A3.1) + (B1), (E2.2) + (A1.1) + (A3.2) + (B1), (E2.2) + (A1.1) + (A4.1) + (B1), (E2.2) + (A1.1) + (A4.2) + (B1); (E2.2) + (A1.2) + (A2.1) + (B1), (E2.2) + (A1.2) + (A2.2) + (B1), (E2.2) + (A1.2) + (A3.1 ) + (B1), (E2.2) + (A1.2) + (A3.2) + (B1), (E2.2) + (A1.2) + (A4.1) + (B1), (E2.2) + (A1.2) + (A4.2) + (B1); (E2.2) + (A2.1) + (A2.2) + (B1), (E2.2) + (A2.1) + (A3.1) + (B1 ), (E2.2) + (A2.1) + (A3.2) + (B1), (E2.2) + (A2.1) + (A4.1) + (B1), (E2.2) + (A2.1) + (A4.2) + (B1);
(E2.2) + (A2.2) + (A3.1) + (B1), (E2.2) + (A2.2) + (A3.2) + (B1), (E2.2) + (A2.2) + (A4.1) + (B1 ), (E2.2) + (A2.2) + (A4.2) + (B1 ); (E2.2) + (A3.1 ) + (A3.2) + (B1 ), (E2.2) + (A3.1) + (A4.1) + (B1 ), (E2.2) + (A3.1) + (A4.2) + (B1); (E2.2) + (A3.2) + (A4.1) + (B1), (E2.2) + (A3.2) + (A4.2) + (B1), (E2.2) + (A4.1) + (A4.2) + (B1 ); (E2.2) + (A1.1) + (A1.2) + (B2), (E2.2) + (A1.1) + (A2.1) + (B2), (E2.2) + (A1.1) + (A2.2) + (B2), (E2.2) + (A1.1) + (A3.1) + (B2), (E2.2) + (A1.1) + (A3.2) + (B2), (E2.2) + (A1.1) + (A4.1) + (B2), (E2.2) + (A1.1) + (A4.2) + (B2); (E2.2) + (A1.2) + (A2.1) + (B2), (E2.2) + (A1.2) + (A2.2) + (B2),
(E2.2) + (A1.2) + (A3.1) + (B2), (E2.2) + (A1.2) + (A3.2) + (B2), (E2.2) + (A1.2) + (A4.1) + (B2), (E2.2) + (A1.2) + (A4.2) + (B2); (E2.2) + (A2.1) + (A2.2) + (B2), (E2.2) + (A2.1) + (A3.1 ) + (B2), (E2.2) + (A2.1) + (A3.2) + (B2), (E2.2) + (A2.1 ) + (A4.1) + (B2), (E2.2) + (A2.1) + (A4.2) + (B2); (E2.2) + (A2.2) + (A3.1) + (B2), (E2.2) + (A2.2) + (A3.2) + (B2), (E2.2) + (A2.2) + (A4.1) + (B2), (E2.2) + (A2.2) + (A4.2) + (B2); (E2.2) + (A3.1) + (A3.2) + (B2), (E2.2) + (A3.1) + (A4.1) + (B2), (E2.2) + (A3.1) + (A4.2) + (B2); (E2.2) + (A3.2) + (A4.1) + (B2), (E2.2) + (A3.2) + (A4.2) + (B2), (E2.2) + (A4.1 ) + (A4.2) + (B2); (E2.2) + (A1.1) + (A1.2) + (B3), (E2.2) + (A1.1) + (A2.1) + (B3), (E2.2) + (A1.1) + (A2.2) + (B3), (E2.2) + (A1.1 ) + (A3.1) + (B3), (E2.2) + (A1.1) + (A3.2) + (B3), (E2.2) + (A1.1 ) + (A4.1) + (B3), (E2.2) + (A1.1 ) + (A4.2) + (B3); (E2.2) + (A1.2) + (A2.1) + (B3), (E2.2) + (A1.2) + (A2.2) + (B3), (E2.2) + (A1.2) + (A3.1) + (B3), (E2.2) + (A1.2) + (A3.2) + (B3), (E2.2) + (A1.2) + (A4.1) + (B3), (E2.2) + (A1.2) + (A4.2) + (B3); (E2.2) + (A2.1) + (A2.2) + (B3), (E2.2) + (A2.1) + (A3.1) + (B3),
(E2.2) + (A2.1) + (A3.2) + (B3), (E2.2) + (A2.1) + (A4.1) + (B3), (E2.2) + (A2.1) + (A4.2) + (B3); (E2.2) + (A2.2) + (A3.1) + (B3), (E2.2) + (A2.2) + (A3.2) + (B3), (E2.2) + (A2.2) + (A4.1) + (B3), (E2.2) + (A2.2) + (A4.2) + (B3); (E2.2) + (A3.1) + (A3.2) + (B3), (E2.2) + (A3.1) + (A4.1) + (B3),
(E2.2) + (A3.1) + (A4.2) + (B3); (E2.2) + (A3.2) + (A4.1) + (B3), (E2.2) + (A3.2) + (A4.2) + (B3), (E2.2) + (A4.1) + (A4.2) + (B3); (E2.3) + (A1.1) + (B1 ), (E2.3) + (A1.1) + (B2), (E2.3) + (A1.1 ) + (B3), (E2.3) + (A2.1) + (B1), (E2.3) + (A2.1) + (B2), (E2.3) + (A2.1) + (B3), (E2.3) + (A3.1) + (B1), (E2.3) + (A3.1) + (B2), (E2.3) + (A3.1) + (B3), (E2.3) + (A4.1) + (B1), (E2.3) + (A4.1) + (B2), (E2.3) + (A4.1) + (B3), (E2.3) + (A1.2) + (B1), (E2.3) + (A1.2) + (B2), (E2.3) + (A1.2) + (B3), (E2.3) + (A2.2) + (B1), (E2.3) + (A2.2) + (B2), (E2.3) + (A2.2) + (B3), (E2.3) + (A3.2) + (B1), (E2.3) + (A3.2) + (B2), (E2.3) + (A3.2) + (B3), (E2.3) + (A4.2) + (B1), (E2.3) + (A4.2) + (B2), (E2.3) + (A4.2) + (B3), (E2.3) + (A1.1) + (A1.2) + (B1), (E2.3) + (A1.1) + (A2.1) + (B1), (E2.3) + (A1.1) + (A2.2) + (B1), (E2.3) + (A1.1) + (A3.1) + (B1), (E2.3) + (A1.1) + (A3.2) + (B1), (E2.3) + (A1.1) + (A4.1) + (B1), (E2.3) + (A1.1) + (A4.2) + (B1 ); (E2.3) + (A1.2) + (A2.1) + (B1), (E2.3) + (A1.2) + (A2.2) + (B1), (E2.3) + (A1.2) + (A3.1 ) + (B1), (E2.3) + (A1.2) + (A3.2) + (B1), (E2.3) + (A1.2) + (A4.1) + (B1), (E2.3) + (A1.2) + (A4.2) + (B1); (E2.3) + (A2.1) + (A2.2) + (B1), (E2.3) + (A2.1) + (A3.1) + (B1),
(E2.3) + (A2.1) + (A3.2) + (B1), (E2.3) + (A2.1) + (A4.1) + (B1), (E2.3) + (A2.1) + (A4.2) + (B1); (E2.3) + (A2.2) + (A3.1) + (B1 ), (E2.3) + (A2.2) + (A3.2) + (B1), (E2.3) + (A2.2) + (A4.1) + (B1), (E2.3) + (A2.2) + (A4.2) + (B1); (E2.3) + (A3.1) + (A3.2) + (B1), (E2.3) + (A3.1) + (A4.1) + (B1),
(E2.3) + (A3.1 ) + (A4.2) + (B1); (E2.3) + (A3.2) + (A4.1) + (B1), (E2.3) + (A3.2) + (A4.2) + (B1), (E2.3) + (A4.1) + (A4.2) + (B1); (E2.3) + (A1.1) + (A1.2) + (B2), (E2.3) + (A1.1) + (A2.1) + (B2), (E2.3) + (A1.1) + (A2.2) + (B2), (E2.3) + (A1.1 ) + (A3.1) + (B2), (E2.3) + (A1.1) + (A3.2) + (B2), (E2.3) + (A1.1) + (A4.1) + (B2), (E2.3) + (A1.1) + (A4.2) + (B2); (E2.3) + (A1.2) + (A2.1) + (B2), (E2.3) + (A1.2) + (A2.2) + (B2), (E2.3) + (A1.2) + (A3.1) + (B2), (E2.3) + (A1.2) + (A3.2) + (B2), (E2.3) + (A1.2) + (A4.1) + (B2), (E2.3) + (A1.2) + (A4.2) + (B2); (E2.3) + (A2.1) + (A2.2) + (B2), (E2.3) + (A2.1) + (A3.1) + (B2),
(E2.3) + (A2.1) + (A3.2) + (B2), (E2.3) + (A2.1 ) + (A4.1 ) + (B2), (E2.3) + (A2.1) + (A4.2) + (B2); (E2.3) + (A2.2) + (A3.1) + (B2), (E2.3) + (A2.2) + (A3.2) + (B2), (E2.3) + (A2.2) + (A4.1) + (B2), (E2.3) + (A2.2) + (A4.2) + (B2); (E2.3) + (A3.1) + (A3.2) + (B2), (E2.3) + (A3.1) + (A4.1) + (B2), (E2.3) + (A3.1) + (A4.2) + (B2); (E2.3) + (A3.2) + (A4.1) + (B2), (E2.3) + (A3.2) + (A4.2) + (B2), (E2.3) + (A4.1) + (A4.2) + (B2); (E2.3) + (A1.1) + (A1.2) + (B3), (E2.3) + (A1.1) + (A2.1) + (B3),
(E2.3) + (A1.1) + (A2.2) + (B3), (E2.3) + (A1.1) + (A3.1) + (B3), (E2.3) + (A1.1 ) + (A3.2) + (B3), (E2.3) + (A1.1 ) + (A4.1 ) + (B3), (E2.3) + (A1.1 ) + (A4.2) + (B3); (E2.3) + (A1.2) + (A2.1 ) + (B3), (E2.3) + (A1.2) + (A2.2) + (B3), (E2.3) + (A1.2) + (A3.1 ) + (B3), (E2.3) + (A1.2) + (A3.2) + (B3), (E2.3) + (A1.2) + (A4.1) + (B3), (E2.3) + (A1.2) + (A4.2) + (B3); (E2.3) + (A2.1) + (A2.2) + (B3), (E2.3) + (A2.1 ) + (A3.1) + (B3), (E2.3) + (A2.1) + (A3.2) + (B3), (E2.3) + (A2.1) + (A4.1) + (B3), (E2.3) + (A2.1) + (A4.2) + (B3); (E2.3) + (A2.2) + (A3.1) + (B3), (E2.3) + (A2.2) + (A3.2) + (B3),
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(B3), (E2.4) + (A2.1) + (B1), (E2.4) + (A2.1) + (B2), (E2.4) + (A2.1) + (B3), (E2.4) + (A3.1) + (B1), (E2.4) + (A3.1) + (B2), (E2.4) + (A3.1) + (B3), (E2.4) + (A4.1) + (B1), (E2.4) + (A4.1) + (B2), (E2.4) + (A4.1) + (B3), (E2.4) + (A1.2) + (B1), (E2.4) + (A1.2) + (B2), (E2.4) + (A1.2) + (B3), (E2.4) + (A2.2) + (B1), (E2.4) + (A2.2) + (B2), (E2.4) + (A2.2) + (B3), (E2.4) + (A3.2) + (B1), (E2.4) + (A3.2) + (B2), (E2.4) + (A3.2) + (B3), (E2.4) + (A4.2) + (B1), (E2.4) + (A4.2) + (B2), (E2.4) + (A4.2) + (B3), (E2.4) + (A1.1) + (A1.2) + (B1), (E2.4) + (A1.1) + (A2.1) + (B1),
(E2.4) + (A1.1) + (A2.2) + (B1), (E2.4) + (A1.1) + (A3.1) + (B1), (E2.4) + (A1.1) + (A3.2) + (B1), (E2.4) + (A1.1) + (A4.1) + (B1), (E2.4) + (A1.1) + (A4.2) + (B1 ); (E2.4) + (A1.2) + (A2.1) + (B1), (E2.4) + (A1.2) + (A2.2) + (B1), (E2.4) + (A1.2) + (A3.1) + (B1), (E2.4) + (A1.2) + (A3.2) + (B1), (E2.4) + (A1.2) + (A4.1) + (B1), (E2.4) + (A1.2) + (A4.2) + (B1); (E2.4) + (A2.1) + (A2.2) + (B1), (E2.4) + (A2.1) + (A3.1) + (B1), (E2.4) + (A2.1) + (A3.2) + (B1), (E2.4) + (A2.1) + (A4.1) + (B1), (E2.4) + (A2.1) + (A4.2) + (B1); (E2.4) + (A2.2) + (A3.1) + (B1), (E2.4) + (A2.2) + (A3.2) + (B1),
(E2.4) + (A2.2) + (A4.1) + (B1), (E2.4) + (A2.2) + (A4.2) + (B1); (E2.4) + (A3.1) + (A3.2) + (B1), (E2.4) + (A3.1) + (A4.1) + (B1), (E2.4) + (A3.1) + (A4.2) + (B1); (E2.4) + (A3.2) + (A4.1) + (B1), (E2.4) + (A3.2) + (A4.2) + (B1), (E2.4) + (A4.1) + (A4.2) + (B1); (E2.4) + (A1.1) + (A1.2) + (B2), (E2.4) + (A1.1) + (A2.1) + (B2),
(E2.4) + (A1.1) + (A2.2) + (B2), (E2.4) + (A1.1) + (A3.1) + (B2), (E2.4) + (A1.1) + (A3.2) + (B2), (E2.4) + (A1.1) + (A4.1) + (B2), (E2.4) + (A1.1) + (A4.2) + (B2);
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(B1); (E4) + (A2.2) + (A3.1) + (B1), (E4) + (A2.2) + (A3.2) + (B1), (E4)
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1
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1
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(E9) + (A2.2) + (A3.1) + (B1), (E9) + (A2.2) + (A3.2) + (B1), (E9) + (A2.2) + (A4.1 ) + (B1), (E9) + (A2.2) + (A4.2) + (B1); (E9) + (A3.1 ) + (A3.2) + (B1), (E9) + (A3.1) + (A4.1 ) + (B1), (E9) + (A3.1) + (A4.2) + (B1); (E9) + (A3.2) + (A4.1) + (B1), (E9) + (A3.2) + (A4.2) + (B1), (E9) + (A4.1) + (A4.2) + (B1); (E9) + (A1.1) + (A1.2) + (B2), (E9) + (A1.1) + (A2.1) + (B2), (E9) + (A1.1 ) + (A2.2) + (B2), (E9) + (A1.1) + (A3.1) + (B2), (E9) + (A1.1) + (A3.2) + (B2), (E9) + (A1.1) + (A4.1) + (B2), (E9) + (A1.1) + (A4.2) + (B2); (E9) + (A1.2) + (A2.1) + (B2), (E9) + (A1.2) + (A2.2) + (B2), (E9) + (A1.2) + (A3.1 ) + (B2), (E9) + (A1.2) + (A3.2) + (B2), (E9) + (A1.2) + (A4.1 ) + (B2), (E9) + (A1.2) + (A4.2) + (B2); (E9) + (A2.1) + (A2.2) + (B2), (E9) + (A2.1 ) + (A3.1 ) + (B2), (E9) + (A2.1) + (A3.2) + (B2), (E9) + (A2.1) + (A4.1) + (B2), (E9) + (A2.1) + (A4.2) + (B2); (E9) + (A2.2) + (A3.1) + (B2), (E9) + (A2.2) + (A3.2) + (B2), (E9)
+ (A2.2) + (A4.1) + (B2), (E9) + (A2.2) + (A4.2) + (B2); (E9) + (A3.1) + (A3.2) + (B2), (E9) + (A3.1) + (A4.1) + (B2), (E9) + (A3.1) + (A4.2) + (B2); (E9) + (A3.2) + (A4.1) + (B2), (E9) + (A3.2) + (A4.2) + (B2), (E9) + (A4.1) + (A4.2) + (B2); (E9) + (A1.1) + (A1.2) + (B3), (E9) + (A1.1) + (A2.1) + (B3), (E9)
+ (A1.1) + (A2.2) + (B3), (E9) + (A1.1) + (A3.1) + (B3), (E9) + (A1.1) + (A3.2) + (B3), (E9) + (A1.1) + (A4.1) + (B3), (E9) + (A1.1) + (A4.2) + (B3); (E9) + (A1.2) + (A2.1) + (B3), (E9) + (A1.2) + (A2.2) + (B3), (E9) + (A1.2) + (A3.1) + (B3), (E9) + (A1.2) + (A3.2) + (B3), (E9) + (A1.2) + (A4.1 ) + (B3), (E9) + (A1.2) + (A4.2) + (B3); (E9) + (A2.1 ) + (A2.2) + (B3), (E9) + (A2.1 ) + (A3.1) + (B3), (E9) + (A2.1 ) + (A3.2) + (B3), (E9) + (A2.1) + (A4.1) + (B3), (E9) + (A2.1 ) + (A4.2) + (B3); (E9) + (A2.2) + (A3.1 ) + (B3), (E9) + (A2.2) + (A3.2) + (B3), (E9) + (A2.2) + (A4.1) + (B3), (E9) + (A2.2) + (A4.2) + (B3); (E9) + (A3.1) + (A3.2) + (B3), (E9) + (A3.1 ) + (A4.1) + (B3), (E9) + (A3.1) + (A4.2) + (B3); (E9) + (A3.2) + (A4.1) + (B3), (E9) + (A3.2) + (A4.2) + (B3), (E9) + (A4.1) + (A4.2) + (B3); (E9.1) + (A1.1) + (B1), (E9.1) + (A1.1) + (B2), (E9.1) + (A1.1) + (B3), (E9.1) + (A2.1) + (B1), (E9.1) + (A2.1) + (B2), (E9.1) + (A2.1) + (B3), (E9.1) + (A3.1) + (B1), (E9.1) + (A3.1) + (B2), (E9.1) + (A3.1) + (B3), (E9.1) + (A4.1 ) + (B1), (E9.1) + (A4.1) + (B2), (E9.1) + (A4.1) + (B3), (E9.1) + (A1.2) + (B1), (E9.1) + (A1.2) + (B2), (E9.1) + (A1.2) + (B3), (E9.1) + (A2.2) + (B1), (E9.1) + (A2.2) + (B2), (E9.1) + (A2.2) + (B3), (E9.1) + (A3.2) + (B1), (E9.1 ) + (A3.2) + (B2), (E9.1 ) + (A3.2) + (B3), (E9.1) + (A4.2) + (B1), (E9.1) + (A4.2) + (B2), (E9.1) + (A4.2) + (B3), (E9.1) + (A1.1) + (A1.2) + (B1), (E9.1) + (A1.1) + (A2.1) + (B1), (E9.1 ) + (A1.1 ) + (A2.2) + (B1), (E9.1) + (A1.1) + (A3.1) + (B1), (E9.1 ) + (A1.1) + (A3.2) + (B1), (E9.1) + (A1.1) + (A4.1) + (B1), (E9.1) + (A1.1) + (A4.2) + (B1); (E9.1) + (A1.2) + (A2.1) + (B1), (E9.1) + (A1.2) + (A2.2) + (B1), (E9.1) + (A1.2) + (A3.1) + (B1 ), (E9.1 ) + (A1.2) + (A3.2) + (B1 ), (E9.1) + (A1.2) + (A4.1) + (B1), (E9.1) + (A1.2) + (A4.2) + (B1); (E9.1) + (A2.1) + (A2.2) + (B1), (E9.1) + (A2.1) + (A3.1) + (B1), (E9.1) + (A2.1) + (A3.2) + (B1), (E9.1) + (A2.1) + (A4.1) + (B1), (E9.1) + (A2.1) + (A4.2) + (B1); (E9.1) + (A2.2) + (A3.1) + (B1), (E9.1) + (A2.2) + (A3.2) + (B1), (E9.1) + (A2.2) + (A4.1) + (B1), (E9.1) + (A2.2) + (A4.2) + (B1); (E9.1) + (A3.1) + (A3.2) + (B1), (E9.1) + (A3.1) + (A4.1) + (B1), (E9.1 ) + (A3.1) + (A4.2) + (B1); (E9.1) + (A3.2) + (A4.1) + (B1), (E9.1) + (A3.2) + (A4.2) + (B1), (E9.1) + (A4.1) + (A4.2) + (B1); (E9.1 ) + (A1.1) + (A1.2) + (B2), (E9.1) + (A1.1) + (A2.1) + (B2), (E9.1 ) + (A1.1) + (A2.2) + (B2), (E9.1 ) + (A1.1 ) + (A3.1) + (B2), (E9.1) + (A1.1) + (A3.2) + (B2), (E9.1) + (A1.1) + (A4.1) + (B2), (E9.1) + (A1.1) + (A4.2) + (B2); (E9.1) + (A1.2) + (A2.1) + (B2), (E9.1) + (A1.2) + (A2.2) + (B2),
(E9.1) + (A1.2) + (A3.1) + (B2), (E9.1) + (A1.2) + (A3.2) + (B2), (E9.1) + (A1.2) + (A4.1) + (B2), (E9.1) + (A1.2) + (A4.2) + (B2); (E9.1) + (A2.1) + (A2.2) + (B2), (E9.1) + (A2.1) + (A3.1) + (B2), (E9.1 ) + (A2.1) + (A3.2) + (B2), (E9.1 ) + (A2.1 ) + (A4.1) + (B2), (E9.1 ) + (A2.1) + (A4.2) + (B2); (E9.1) + (A2.2) + (A3.1) + (B2), (E9.1) + (A2.2) + (A3.2) + (B2), (E9.1 ) + (A2.2) + (A4.1) + (B2), (E9.1) + (A2.2) + (A4.2) + (B2); (E9.1) + (A3.1) + (A3.2) + (B2), (E9.1) + (A3.1) + (A4.1) + (B2), (E9.1) + (A3.1) + (A4.2) + (B2); (E9.1) + (A3.2) + (A4.1) + (B2), (E9.1) + (A3.2) + (A4.2) + (B2), (E9.1) + (A4.1) + (A4.2) + (B2); (E9.1) + (A1.1) + (A1.2) + (B3), (E9.1) + (A1.1 ) + (A2.1) + (B3), (E9.1) + (A1.1) + (A2.2) + (B3), (E9.1) + (A1.1) + (A3.1) + (B3), (E9.1) + (A1.1) + (A3.2) + (B3), (E9.1) + (A1.1) + (A4.1) + (B3), (E9.1) + (A1.1) + (A4.2) + (B3); (E9.1) + (A1.2) + (A2.1) + (B3), (E9.1) + (A1.2) + (A2.2) + (B3), (E9.1) + (A1.2) + (A3.1) + (B3), (E9.1) + (A1.2) + (A3.2) + (B3), (E9.1) + (A1.2) + (A4.1) + (B3), (E9.1) + (A1.2) + (A4.2) + (B3); (E9.1 ) + (A2.1 ) + (A2.2) + (B3), (E9.1) + (A2.1) + (A3.1) + (B3),
(E9.1) + (A2.1) + (A3.2) + (B3), (E9.1) + (A2.1 ) + (A4.1 ) + (B3), (E9.1) + (A2.1) + (A4.2) + (B3); (E9.1) + (A2.2) + (A3.1) + (B3), (E9.1) + (A2.2) + (A3.2) + (B3), (E9.1) + (A2.2) + (A4.1) + (B3), (E9.1) + (A2.2) + (A4.2) + (B3); (E9.1) + (A3.1) + (A3.2) + (B3), (E9.1) + (A3.1) + (A4.1) + (B3),
(E9.1) + (A3.1) + (A4.2) + (B3); (E9.1) + (A3.2) + (A4.1) + (B3), (E9.1) + (A3.2) + (A4.2) + (B3), (E9.1) + (A4.1 ) + (A4.2) + (B3). Todas las combinaciones anteriormente mencionadas también pueden comprender más compuestos agroquímicamente activos (E), en particular dos o tres compuestos activos (E), preferiblemente seleccionados a partir del grupo que consiste de (E1), (E1.1), (E1.2), (E1.3), (E1.4), (E1.5), (E2), (E2.1), (E2.2). (E2.3), (E2.4), (E2.5), (E2.6), (E2.7), (E2.8). (E2.9), (E3), (E3.1), (E3.2), (E3.3), (E4), (E4.1), (E4.2), (E5), (E5.1), (E5.2), (E6), (E6.1), (E6.2), (E6.3), (E6.4), (E6.5), (E7), (E7.1), (E7.2), (E8), (E8.1 ), (E8.2), (E9), (E9.1). Las combinaciones preferidas (A), (B), (E) con dos o tres compuestos activos (E) que comprenden, como un componente (E), (E1.1 ) + (E1.2), (E1.1) + (E1.2) + (E6.3), (E1.1) + (E1.2) + (E2.6) o (E5.1) + (E6.3). Con preferencia particular, los componentes (A) y (B) contenidos en las combinaciones anteriormente mencionados se combinan con los componentes (E) (E1.1) + (E1.2), (E1.1 ) + (E1.2) + (E6.3), (E1.1 ) + (E1.2) + (E2.6) o (E5.1 ) + (E6.3). Los auxiliares y aditivos usuales (componente F) los- cuales pueden estar contenidos en las composiciones herbicidas de conformidad con la invención son, por ejemplo: agentes tensioactivos, tales como emulsificantes y dispersantes, espesantes y agentes tixotrópicos, agentes humectantes, agentes anti-flujo, adhesivos, penetrantos, conservadores y agentes anticongelantes, antioxidantes, solubilizantes, llenadores, vehículos y colorantes, antiformadores de espuma, fertilizantes, inhibidores de evaporación y agentes los cuales modifican el pH y viscosidad. Los emulsificantes adecuados y dispersantes son, por ejemplo, emulsificantes no iónicos y dispersantes, por ejemplo: 1) alcoholes alifáticos polialcoxilados, preferiblemente polietoxilados, saturados y no saturados, • que tienen de 8 a 24 átomos de carbono en el radical alquilo, los cuales se derivan a partir de los ácidos grasos correspondientes o a partir de los productos petroquímicos, y • que tienen de 1 a 100, preferiblemente de 2 a 50, unidades de óxido de etileno (EO), siendo posible que el grupo hidroxilo libre se encuentre alcoxilado, • los cuales están comercialmente disponibles, por ejemplo como serie Genapol® X y Genapol® O (Clariant), serie Crovol® M (Croda) o como serie Lutensol® (BASF), 2) arilalquilfenoles polialcoxilados, preferiblemente polietoxilados, tales como, por ejemplo, 2,4,6-tris-(1-feniletil)fenol(tristirilfenol) que tienen un grado promedio de etoxilación de entre 10 y 80, preferiblemente de 16 a 40, tales como, por ejemplo Soprophor® BSU (Rhodia) o HOE S 3474 (Clariant), 3) alquilfenoles polialcoxilados, preferiblemente polietoxilados, que tienen de uno o más radicales alquilo, tales como, por ejemplo, nonilfenol o tri-sec-butilfenol, y un grado de etoxilación de entre 2 y 40, preferiblemente de 4 a 15, tales como, por ejemplo, serie Arkopal® N o serie Sapogenat® T (Clariant), 4) hidroxiácidos grasos polialcoxilados, preferiblemente polietoxilados, o glicéridos los cuales contienen hidroxiácidos grasos, tales como, por ejemplo, ricinina o aceite de ricino, que tienen un grado de etoxilation de entre 10 y 80, preferiblemente de 25 a 40, tales como, por ejemplo, la serie Emulsogen® EL (Clariant) o la serie Agnique® CSO (Cognis), 5) esteres de sorbitano polialcoxilados, preferiblemente polietoxilados, tales como, por ejemplo, Atplus® 309 F (Uniqema) o la serie Alkamuls® (Rhodia), 6) copolímeros di- y tri-bloque, por ejemplo a partir de óxidos de alquileno, por ejemplo a partir de óxido de etileno y óxido de propileno, que tienen masas molares promedio de entre 200 y 10 000, preferiblemente de 1000 a 4000, g/mol, la proporción en masa del bloque polietoxilado varía entre 10 y 80%, tales como, por ejemplo, la serie Genapol® PF (Clariant), la serie Pluronic® (BASF), o la serie Synperonic® PE (Uniqema). Los emulsificantes no iónicos preferidos y dispersantes son, por ejemplo, alcoholes polietoxilados, triglicéridos polietoxilados los cuales contienen hidroxiácidos grasos y copolímeros en bloque de óxido de polietileno/óxido de polipropileno. La proporción total de emulsificantes no iónicos y dispersantes en las composiciones herbicidas de conformidad con la invención generalmente es entre 0 y 20% en peso. Si los emulsificantes no iónicos y dispersantes están presentes, además de sus propiedades emulsificantes/dispersantes, también utilizadas para incrementar la efectividad biológica, por ejemplo como penetrantes o adhesivos, su proporción en las. composiciones herbicidas de conformidad con la invención se puede incrementar hasta 60% en peso. También son adecuados los emulsificantes iónicos y dispersantes, por ejemplo: 1) emulsificantes/dispersantes polialcoxilados, preferiblemente polietoxilados, (cf. componente) los cuales están iónicamente modificados, por ejemplo mediante la conversión de la función hidroxilo libre terminal del bloque óxido de polietileno hacia un éster de sulfato o de fosfato (por ejemplo como metal álcali y sales de metal terreo alcalino), tales como, por ejemplo, Genapol® LRO o dispersant 3618 (Clariant), Emulphor® (BASF) o Crafol® AP (Cognis), 2) metal álcali y sales de metal terreo alcalino de ácidos alquilarilsulfónicos que tienen una cadena de alquilo de cadena recta o ramificada, tales como fenilsulfonato CA o fenilsulfonato CAL (Clariant), Atlox® 3377BM (ICI), o la serie E piphos® TM (Huntsman), 3) polielectrolitos, tales como lignosulfonatos, condensados de naftalensulfonato y formaldehído, poliestirensulfonato o polímeros sulfonados no saturados o aromáticos (poliestirenos, polibutadienos o politerpenos), tales como la serie Tamol® (BASF), Morwet® D425 (Witco), la serie Kraftsperse® (Westvaco) o la serie Borresperse® (Borregard). Los emulsificantes/dispersantes iónicos preferidos son, por ejemplo, sales de ácidos alquilarilsulfónicos y polielectrolitos a partir de la policondensación de naftalensulfonato y formaldehído. La proporción total de emulsificantes y dispersantes iónicos en las composiciones herbicidas de conformidad con la invención generalmente es entre 0 y 20% en peso, en particular entre 0 y 8% en peso. Los espesantes adecuados y agentes tixotrópicos son, por ejemplo: 1) silicatos naturales modificados, tales como bentonitas químicamente modificadas, hectoritas, atapulgitas, montmorilonitas, esmectitas u otros minerales de silicato, tales como Bentone® (Elementis),
Attagel® (Engelhard), Agsorb® (Oil-Dri Corporation) o Hectorite® (Akzo
Nobel), 2) silicatos sintéticos, tales como silicatos de la serie
Sipemat®, Aerosil® o Durosil® (Degussa), la serie CAB-O-SIL® (Cabot) o la serie Van Gel (R.T. Vanderbilt), 3) espesantes basados en polímeros sintéticos, tales como espesantes de la serie Thixin® o Thixatrol® (Elementis), 4) espesantes basados en polímeros naturales y aceites naturales, por ejemplo a partir de la serie Thixin® o Thixatrol® (Elementis). Los espesantes preferidos y agentes tixotrópicos son, por ejemplo, filosilicatos modificados y espesantes basados en polímeros sintéticos. La proporción de espesantes y agentes tixotrópicos en las composiciones herbicidas de conformidad con la invención generalmente es entre 0 y 5% en peso, en particular entre 0.2 y 3% en peso. La composición herbicidamente activas o combinaciones de sulfonilurea/protector de conformidad con la invención se pueden preparar mediante procesos usuales los cuales ya se conocen, por ejemplo mediante mezclado de los diversos componentes con la ayuda de agitadores, vibradores, molinos o mezcladores (estáticos). En esta conexión, un breve calentamiento de las mezclas en algunos casos puede ser ventajosa con el objeto de lograr la disolución completa de todos los componentes implicados. Se da preferencia a las composiciones herbicidamente activas de conformidad con la invención que comprende: A) 0.1 a 30% en peso de una o más sulfonilureas a partir del grupo que consiste de (A1.1), (A1.2), (A1.3), (A1.4), (A2.1 ), (A2.2), (A2.3), A2.4), (A3.1), (A3.2), (A3.3), (A3.4), (A4.1), (A4.2), preferiblemente a partir del grupo que consiste de (A1.1 ), (A2.1), (A3.1 ), (A4.1), A) 2 a 40% en peso de uno o más protectores a partir del grupo que consiste de (B1), (B2), (B3), (B4), (B5), (B6), (B7), (B8), (B9), preferiblemente a partir del grupo que consiste de (B1 ), (B2), (B3), (B8), particularmente preferiblemente (B1), (B2), (B3), muy particularmente preferiblemente (B1), (B2), especialmente (B1 ), A) 20 a 80% en peso de uno o más solventes, preferiblemente a partir del grupo de los hidrocarburos alifáticos, las mezclas de hidrocarburos aromáticos y alifáticos y los aceites vegetales, tales como metil éster de aceite de colza, 0.5 a 30% en peso de uno o más sulfosuccinatos, preferiblemente a partir del grupo de metal álcali di(C4-C?8)alquilsulfosuccinatos, tales como di(C4-C-?.)alquilsulfosuccinato sódico, B) 1 a 20% en peso de uno o más compuestos agroquímicamente activos diferentes a A) y B), C) 0 a 40% en peso de auxiliares y aditivos usuales, preferiblemente de 0 a 20% en peso de uno o más emulsificantes no iónicos y dispersantes, 0 a 8% en peso de uno o más emulsificantes iónicos y dispersantes y de O a 3% en peso de uno o más espesantes y agentes tixotrópicos. La presente invención también provee un método el cual comprende aplicar los componentes (A) y (B) de la composición herbicidamente activa de conformidad con la invención juntos o separadamente a las plantas dañinas, cosechas vegetales, semillas vegetales o al área en la cual crecen las plantas, si es apropiado en combinación con componentes adicionales, por ejemplo junto o separadamente con los componentes (C), (D), (E) y (F). En la presente invención, uno o más protectores del grupo (B) (preferiblemente en una cantidad antídoto efectiva) se pueden aplicar antes, después o simultáneamente con la sulfonilurea(s) (A) a las plantas, semillas vegetales o el área en la cual crecen las plantas. Las composiciones herbicidamente activas de conformidad con la invención también se pueden emplear para controlar plantas dañinas en cosechas de plantas conocidas genéticamente modificadas o plantas genéticamente modificadas a ser desarrolladas. Como una regla, las plantas transgénicas se distinguen por propiedades particularmente ventajosas, por ejemplo mediante resistencia a ciertos agentes para protección de cosecha, resistencia a enfermedades vegetales o hacia agentes que ocasionan enfermedades vegetales tales como insectos o microorganismos específicos tales como hongos, bacterias o virus. Otras propiedades particulares se refieren por ejemplo a las cosechas cosechadas con respecto a la cantidad, calidad, propiedades de almacenamiento, composición y constituyentes específicos. Por lo tanto, se sabe que las plantas transgénicas tienen un contenido incrementado de almidón o una calidad modificada de almidón, o aquellos con una composición diferente de ácido graso de la cosecha cosechada. Se prefiere el uso de combinaciones de conformidad con la invención en cosechas transgénicas económicamente importantes de plantas útiles y ornamentales, por ejemplo de cereales (tales como trigo, cebada, centeno, avena), mijo, arroz, cassava y maíz, o cualesquiera cosechas de remolacha azucarera, algodón, frijol de soya, aceite de semilla de colza, patata, tomate, chícharo y otros vegetales. Cuando las combinaciones de conformidad con la invención se utilizan en cosechas transgénicas, frecuentemente se encuentran efectos además de los efectos a ser observados en contra de plantas dañinas en otras cosechas, las cuales son específicas para la aplicación en la cosecha transgénica particular, por ejemplo un espectro modificado o específicamente más amplio para maleza la cual se puede controlar, relaciones de aplicación modificadas las cuales se pueden emplear para la aplicación, preferiblemente en una buena combinación con los herbicidas a los cuales la cosecha transgénica es resistente, y un efecto sobre el crecimiento y producción de las cosechas vegetales transgénicas. Por lo tanto, la invención también se refiere al uso de la composición herbicidamente activa de conformidad con la invención para controlar plantas dañinas en cosechas vegetales transgénicas o cosechas vegetales las cuales son tolerantes como un resultado de la cruza selectiva. Los protectores del grupo (B) y las sulfonilureas (A) se pueden formular juntos o separadamente, si es apropiado en combinación con componentes adicionales, por ejemplo los componentes (C), (D), (E) y (F), en diversas formas, dependiendo de los parámetros biológicos y/o fisicoquímicos predominantes. Las posibilidades adecuadas de formulación son, por ejemplo: polvos humectables (WP), concentrados emulsificables (EC), polvos solubles en agua (SP), concentrados solubles en agua (SL), emulsiones concentradas (BW) tales como emulsiones de aceite-en-agua y agua-en-aceite, soluciones o emulsiones que se pueden asperjar, suspensiones en cápsula (CS), dispersiones basadas en aceite o en agua
(SC), suspoemulsiones, concentrados en suspensión, polvo (DP), soluciones que son miscibles en aceite (OL), productos para revestimiento de semilla, granulos (GR) en la forma de microgránulos, granulos para aspersión, granulos revestidos y granulos para adsorción, granulos para aplicación en suelo o siembra al voleo, granulos solubles en agua (SG), granulos que se dispersan en agua (WG), formulaciones ULV, microcápsulas y ceras. Estos tipos de formulación individual se conocen en principio y se describen, por ejemplo, en: Winnacker-Küchler, "Chemische Technologie" [ingeniería química], Volumen 7, C. Hauser Verlag Munich, 4a Ed., 1986;
Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker N.Y., 1973; K.
Martens, "Spray Drying Handbook", 3a Ed. 1979, G. Goodwin Ltd. Londres. Los auxiliares para formulación que se pueden requerir, tales como materiales inertes, agentes tensioactivos, solventes y aditivos adicionales se conocen similarmente y se describen, por ejemplo, en: "Handbook of Insecticide Dust Diluents and Carriers", 2a Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2a Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvents Guide"; 2a 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, "Grenzfláchenaktive Áthylenoxidaddukte" [Adductos de óxido de etileno activos en superficie], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie", Volumen 7, C. Hauser Verlag Munich, 4a Ed. 1986. Basándose en estas formulaciones, las combinaciones con otros compuestos agroquímicamente activos, por ejemplo protectores para cosecha tales como insecticidas, acaricidas, herbicidas, fungicidas, o con protectores, fertilizantes y/o reguladores para crecimiento también se pueden preparar, por ejemplo en la forma de una mezcla preparada o una mezcla en tanque. Los polvos humectables son preparaciones las cuales se dispersan de manera uniforme en agua y los cuales, además del ingrediente activo, comprenden adicionalmente agentes tensioactivos iónicos y/o no iónicos (humectantes, dispersantes), por ejemplo alquilfenoles polioxietilados, alcoholes grasos polioxietilados, aminas grasas polioxietiladas, éter sulfatos de poliglicol de alcohol graso, alcanesulfonatos, alquilbencensulfonatos, lignosulfonatos sódicos, 2,2'-dinaftilmetano-6,6,-disulfonato sódico, dibutilnaftalensulfonato sódico, o cualquier oleoilmetiltaurinato sódico, además de una sustancia diluyente o inerte. Para preparar los polvos humectables, los ingredientes activos, por ejemplo los ingredientes activos herbicidas y/o los protectores, se muelen finalmente, por ejemplo en aparatos usuales tales como molinos de martillo, molinos de ventilador y molinos de aire a chorro, y simultáneamente o subsecuentemente mezclados con los auxiliares para formulación. Los concentrados emulsificables se prepararon, por ejemplo, mediante la disolución del ingrediente activo, por ejemplo el ingrediente activo herbicida y/o el protector, en un solvente orgánico, por ejemplo butanol, ciciohexanona, dimetilformamida, xileno o cualesquiera hidrocarburos de alto punto de ebullición tales sustancias alifáticas o alicíclicas como saturadas o insaturadas, sustancias aromáticas o mezclas de los solventes orgánicos con adición de uno o más agentes tensioactivos iónicos y/o no iónicos (emulsificantes). Los siguientes son ejemplos de emulsificantes los cuales se pueden utilizar: alquilarilsulfonatos de (Cß-C-is) calcicos tales como calcium dodecilbencensulfonato, o emulsificantes no iónicos tales como esteres poliglicólicos de ácido graso, éteres poliglicólicos de alquilarilo de (C2-C?8)-, éteres poliglicólicos de alcohol graso, condensados de óxido de propileno/óxido de etileno, poliéteres de alquilo, esteres de sorbitano tales como, por ejemplo, esteres de sorbitano de ácido graso o esteres de polioxietilen sorbitano tales como esteres de polioxietilen sorbitano de ácido graso.
Los polvos se obtienen en general mediante la molienda del ingrediente activo, por ejemplo el ingrediente activo herbicida y/o el protector, con materiales sólidos finalmente divididos, por ejemplo talco, arcillas naturales tales como caolina, bentonita y pirofiüta, o tierra diatomácea. Los concentrados en suspensión se puede basar en agua o en aceite. Estos se pueden preparar por ejemplo mediante molido con húmeda por medio de molinos en lecho comercialmente disponibles, si es adecuado con la adición de agentes tensioactivos como, por ejemplo, ya se ha listado anteriormente en el caso de otros tipos de formulación. Las emulsiones, por ejemplo emulsiones de aceite-en-agua
(EW), se pueden preparar por ejemplo por medio de agitadores, molinos coloidales y/o mezcladores estáticos utilizando solventes orgánicos acuosos y, si es apropiado, agentes tensioactivos que, por ejemplo, ya se han listado anteriormente en el caso de otros tipos de formulación. Los granulos se pueden producir ya sea mediante aspersión del ingrediente activo, por ejemplo el ingrediente activo herbicida y/o el protector, sobre material inerte granulado absorbente o mediante la aplicación de concentrados del ingrediente activo a la superficie de vehículos tales como arena, caolinita o de material inerte granulado por medio de aglutinantes, por ejemplo alcohol polivinílico, poliacrilato de sodio u otros aceites minerales. Los ingredientes activos adecuados también se pueden granular de manera que es convencional para la producción de granulos de fertilizante, si se desea como una mezcla con fertilizantes. Como una regla, los granulos que se dispersan en agua se prepararon mediante el método usual tales como secado mediante aspersión, granulación en cama fluida, granulación en disco, mezclado por medio de mezcladores de alta velocidad, y extrusión sin material inerte sólido. Para preparar el disco, cama fluida, extrusor y granulos para aspersión, véase, por ejemplo, los métodos en "Spray-Drying Handbook" 3a ed. 1979, G. Goodwin Ltd., Londres; J.E. Browning, "Agglomeration", Chemical and Engineering 1967, páginas 147 y subsecuentes.; "Perry's Chemical Engineer's Handbook", 5a Ed., McGraw-Hill, New York 1973, pp. 8-57. Para detalles adicionales sobre la formulación de los agentes para protección de cosecha véase, por ejemplo, G.C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc., New York, 1961 , páginas 81-96 y J.D. Freyer, S.A. Evans, 'Weed Control Handbook", 5a Ed., Blackwell Scientific Publications, Oxford, 1968, páginas 101-103. Las formulaciones preferidas son formulaciones líquidas, tales como suspensiones en aceite, un concentrado de suspensión oleosa, suspoemulsiones, concentrados de suspoemulsión, emulsiones, por ejemplo concentrados de emulsión basada en W/O- o en O/W, microemulsiones, concentrados de microemulsión, concentrados emulsificables, y licores en aspersión obtenidos a partir de estos, preferiblemente licores acuosos en aspersión. Un tipo de formulación líquida particularmente preferida es un concentrado para suspensión oleosa, por ejemplo concentrados para suspensión basados en solventes orgánicos, y formulaciones obtenidas a partir de éstos mediante la dilución, tales como soluciones, emulsiones, suspoemulsiones y suspensiones. En el concentrado de suspensión oleosa, uno o más compuestos activos se suspenden en el solvente orgánico; los compuestos activos adicionales se pueden disolver en el solvente orgánico. En un concentrado preferido de suspensión oleosa, el herbicida (A) está presente en forma suspendida en los solventes orgánicos. Esto significa que la mayor proporción (en % en peso) de sulfonamida realmente no se encuentra disuelta en una forma altamente dispersa y una porción menor de la sulfonamida puede estar presente en forma disuelta. Preferiblemente, más de 80% en peso, particularmente preferiblemente más de 90% en peso, de la sulfonamida se suspende en el solvente orgánico, en cada caso basado en la cantidad total de sulfonamida en un concentrado de suspensión oleosa de conformidad con la invención. Como una regla, las preparaciones agroquímicas comprenden de 0.1 a 99% en peso, en particular de 0.1 a 95% en peso, de compuestos activos, por ejemplo compuestos protectores activos (B), o sulfonilurea (A), o la mezcla activa de herbicida/protector de conformidad con la invención que comprende sulfonilureas (A) y compuestos protectores activos (B), y a partir de 1 a 99.9% en peso, en particular de 5 a 99.8% en peso, de un aditivo sólido o líquido y de 0 a 25% en peso, en particular de 0.1 a 25% en peso, de un agente tensioactivo.
En los polvos humectables, la concentración del ingrediente activo es, por ejemplo, de aproximadamente 10 a 90% en peso, el remanente del 100% en peso estando compuesto de componentes comunes para formulación. En el caso de los concentrados emulsificables, la concentración del ingrediente activo es una cantidad de aproximadamente 1 a 80% en peso. Las formulaciones en la forma de polvos comprenden de aproximadamente 1 a 20% en peso de ingredientes activos, soluciones que se pueden asperjar a partir de aproximadamente 0.2 a 20% en peso de ingredientes activos. En el caso de granulos tales como granulos que se dispersan en agua, el contenido de ingrediente activo depende parcialmente de si el compuesto activo se encuentra en forma líquida o sólida. Como una regla, el contenido del compuesto activo en los granulos que se dispersan en agua es entre 10 y 90% en peso. Además, las formulaciones de ingrediente activo mencionadas comprenden, si es apropiado, los adhesivos, humectantes, dispersantes, emulsificantes, penetrantes, conservadores, agentes anticongelantes, solventes, llenadores, vehículos, colorantes, anti formadores de espuma, inhibidores de evaporación, reguladores de pH y reguladores de viscosidad los cuales son convencionales en cada caso. Para aplicación, las formulaciones comercialmente disponibles están opcionalmente diluidas de manera convencional con agua, por ejemplo en el caso de polvos humectables, concentrados emulsificables, dispersiones y granulos que se dispersan en agua. Las formulaciones preferidas que se diluyen con agua son, por ejemplo, formulaciones líquidas tales como suspensiones en aceite, concentrados de suspensión oleosa, suspoemulsiones, concentrados de a suspoemulsión, emulsiones, por ejemplo basadas en W/O- o O/W, concentrados de emulsión, microemulsiones, concentrados de microemulsión, y concentrados emulsificables. Las preparaciones en la forma de polvos, granulos para aplicación en suelo o siembra al voleo así como soluciones que se pueden asperjar usualmente no se diluyen con sustancias inertes adicionales antes de su aplicación. La relación de aplicación necesaria de los herbicidas (A) varía con las condiciones externas tales como, entre otros, temperatura, humedad y el tipo de herbicida utilizado. Esto puede variar dentro de límites amplios, por ejemplo entre 0.001 y 10.0 kg/ha o más de la sustancia activa, pero preferiblemente es entre 0.005 y 5 kg/ha. Los ejemplos que siguen ilustran la invención:
A. Ejemplos de formulación a) se obtiene un polvo mediante la mezcla de 10 partes en peso de una sulfonilurea (A) o un protector (B) o una mezcla de compuesto activo de una sulfonilurea (A) y un protector (B) y 90 partes en peso de talco como sustancia inerte y pulverizando la mezcla en un molino de martillo. b) un polvo humectable el cual se dispersa fácilmente en agua se obtiene mediante la mezcla de 25 partes en peso de una sulfonilurea (A) o un protector (B) o una mezcla de compuesto activo de una sulfonilurea (A) y un protector (B), 64 partes en peso de cuarzo que contiene caolina como material inerte, 10 partes en peso de lignosulfonato potásico y 1 parte en peso de oleoilmetiltaurinato sódico como humectante y dispersante y mediante molido de la mezcla en un molino con disco tipo rodillo. c) un concentrado el cual se dispersa fácilmente o se suspende en agua se obtiene mediante la mezcla de 20 partes en peso de una sulfonílurea (A) o un protector (B) o una mezcla de compuesto activo de una sulfonilurea (A) y un protector (B), 6 partes en peso de éter poliglicólico de alquilfenol (©Tritón X 207), 3 partes en peso de éter poliglicólico de isotridecanol (8 EO) y 71 partes en peso de aceite mineral parafínico (intervalo de punto de ebullición por ejemplo de aproximadamente 255 a 277°C) y mediante el molido de la mezcla en un molino de balón hasta una finura por debajo de 5 mieras. d) un concentrado emulsificable se obtiene a partir de 15 partes en peso de una sulfonilurea (A) o un protector (B) o una mezcla de compuesto activo de una sulfonilurea (A) y un protector (B), 75 partes en peso de ciclohexanone como solvente y 10 partes en peso de nonilfenol oxietilado como emulsificante. e) los granulos que se dispersan en agua se obtienen mediante mezclado 75 partes en peso de una sulfonilurea (A) o un protector (B) o una mezcla de compuesto activo de una sulfonilurea (A) y un protector (B), 10 partes en peso de lignosulfonato calcico, 5 partes en peso de lauril sulfato de sodio, 3 partes en peso de alcohol polivinílico y 7 partes en peso de caolina, El molido de la mezcla en un molino con disco tipo rodillo y la granulación del polvo en una cama fluida se a spejó sobre agua como un líquido para granulación. f) los granulos que se dispersan en agua también se obtienen mediante la homogenización y prepulverizando 25 partes en peso de una sulfonilurea (A) o un protector (B) o una mezcla de compuesto activo de una sulfonilurea (A) y un protector (B), 5 partes en peso de 2,2'-dinaftilmetan-6,6'-disulfonato sódico, 2 partes en peso de oleoilmetiltaurinato sódico, 1 parte en peso de alcohol polivinílico, 17 partes en peso de carbonato de calcio y 50 partes en peso de agua En un molino coloidal, subsecuentemente el molido de la mezcla en un molino de cama y atomización y secado de la suspensión resultante en una torre de aspersión por medio de una boquilla particular de la sustancia. g) Se obtuvo un concentrado de la suspensión oleosa, por ejemplo, mediante la mezcla de los componentes, por ejemplo mediante la preparación de una premezcla en donde opcionalmente se disuelve un sulfosuccinato D) en el solvente C) y, opcionalmente, auxiliares y aditivos adicionales F) se añaden a esta solución. Cualesquiera protectores solubles B) y compuestos agroquímicamente activos E) utilizados se disuelven posteriormente en la premezcla. Después del término del proceso de disolución, la sulfonilurea sólida A) y cualquier protector insoluble B) y compuestos agroquímicamente activos E) utilizados se suspenden en la mezcla. La suspensión gruesa se somete, si es apropiado después del premolido, a un molido fino. En otra modalidad para la preparación de un concentrado de suspensión oleosa, sulfonilurea sólida A) y cualesquiera componentes insolubles B), E) y F) utilizados son suspendidos en el solvente C) el cual opcionalmente contiene un sulfosuccinato D) y se muele. Cualesquiera compuestos activos solubles B) y E) utilizados y también auxiliares y aditivos a partir de F) los cuales no requieren molido o no se requieren para el proceso demolido se añaden después del molido. En una modalidad adicional para la preparación de un concentrado de suspensión oleosa, en el cual espesantes se utilizan como auxiliares y aditivos F), el espesante inicialmente se mezcla con el solvente C). Los compuestos activos A), B) y opcionalmente E) y cualesquiera auxiliares y aditivos adicionales F) y sulfosuccinatos D) se añaden posteriormente, y la mezcla se muele, por ejemplo en un molino. h) preparación de un concentrado específico de suspensión oleosa Solvesso® 200 ND, Bentone® 34 y carbonato de propileno se añaden a un molino y se mezclan intensivamente hasta que se obtiene una pasta. Los otros componentes (auxiliares y aditivos y compuestos activos) se añaden posteriormente de manera sucesiva con agitación, y la mezcla resultante se homogeneiza subsecuentemente en un molino tipo balón. El cuadro A a continuación muestra las proporciones de los componentes de la formulación (en % en peso) de un concentrado de suspensión oleosa preparado de esta manera.
CUADRO A
Notas: Tritón® GR-7M-E es di-2-etilhexilsuIfosuccinato-sódico,
Emulsogen® EL400 es un aceite de ricino etoxilado que tiene 40 unidades de óxido de etileno, Etocas® 10 es un aceite de ricino etoxilado que tiene 10 unidades de óxido de etileno, Genapol® PF 10 es un agente tensioactivo polimérico (copolímero en bloque de óxido de etileno y óxido de propileno), Morwet® D 425 es un dispersante aniónico polimérico, Bentone® 34 es un espesante (basado en filosilicato modificado), Rhodorsil® 454 es un anti formador de espuma de silicón, Solvesso® 200 ND es un solvente aromático que tiene un alto punto de ebullición.
B. Ejemplos biológicos
1. Evaluación del daño El daño a las plantas se evalúa visualmente en comparación con las plantas control, de conformidad con una escala de 0 a 100%: 0% = efecto no perceptible en comparación con la planta no tratada, 100% = planta tratada muere
2. Acción del herbicida post-surgimiento Las semillas de malezas monocotiledóneas y dicotiledóneas y de cosechas vegetales se colocan en suelo de tierra negra arenosa en macetas de plástico, se cubren con tierra y se cultivan en un invernadero bajo buenas condiciones de crecimiento. Tres semanas después de la siembra, las plantas prueba se tratan en la etapa de 3-4-hojas. Las diferentes dosis de los compuestos activos indiciduales de conformidad con la invención, se formulan como concentrados en emulsión, se asperjan individualmente o como mezclas en relaciones de aplicación de 300 I de agua/ha (convertida) sobre las partes verdes de las plantas, y después de que las plantas han pasado 3 semanas en el invernadero bajo condiciones óptimas de crecimiento, el efecto de la preparación se evaluó visualmente en comparación con controles no tratados. Como se muestra por los ejemplos, las combinaciones de conformidad con la invención de sulfonilureas y de protectores son capaces de controlar efectivamente un amplio espectro de malezas, y el daño a ias cosechas vegetales disminuyó considerablemente, en comparación con el uso de sulfonilureas individuales sin protector. Los resultados prueba para las cosechas vegetales se compilan en los cuadros a continuación. Se establece el grado respectivo de daño a las cosechas vegetales y la reducción del daño por las combinaciones del herbicida/protector de conformidad con la invención en porcentaje, en comparación con el herbicida aplicado solo.
CUADRO 1 Maíz, cultivar "Lorenzo"
herbicida A1.1 : metsulfuron-metílico; herbicida A2.1 : thifensulfuron-metílico; herbicida A3.1: tribenuron-metílico; herbicida A4.1 : chiorsulfuron; protector B2: isoxadifen-etílico
CUADRO 2 Cebada, cultivar "Baronesse"
herbicida A1.1 : metsulfuron-metílico; herbicida A4.1 :
chiorsulfuron; protector B1 : mefenpyr-dietílico; protector B2: isoxadifen-etílico;
protector B3: cloquintocet-mexílico CUADRO 3 Cebada, cultivar "Duett"
herbicida A2.1 : thifensulfuron-metílico; protector B1 : mefenpyr- dietílico; protector B3: cloquintocet-mexílico
CUADRO 4 Trigo, cultivar "Triso'
herbicida A1.1 : metsulfuron-metílico; protector B1 : mefenpyr-dietílico; protector B2: isoxadifen-etílico
CUADRO 5 Trigo, cultivar "Kanzler"
herbicida A1.1 : metsulfuron-metílico; herbicida A2.1 : thifensulfuron-metílico; herbicida A3.1 : tribenuron-metílico; protector B1 : mefenpyr-dietílico; protector B2: isoxadifen-etílico; protector B3: cloquintocet-mexílico.
Claims (10)
1.- La formulación líquida en la forma de un concentrado de suspensión oleosa o un licor acuoso para aspersión que se obtiene a partir de éste, que comprende (A) una o más sulfonilureas a partir del grupo que consiste de metsulfuron, tifensulfuron, tribenuron, chiorsulfuron y sus sales y esteres, (B) uno o más protectores a partir del grupo que consiste de mefenpyr, ¡soxadifen, cloquintocet, fenchiorazole y sus sales y esteres, (C) uno o más solventes, preferiblemente solventes orgánicos.
2.- La formulación líquida de conformidad con la reivindicación 1, caracterizada además porque comprende (D) opcionalmente uno o más sulfosuccinatos.
3.- La formulación líquida de conformidad con la reivindicación 1 ó 2, caracterizada además porque comprende adicionalmente (E) uno o más compuestos agroquímicamente activos diferentes a (A) y (B).
4.- La formulación líquida de conformidad con una o más de las reivindicaciones 1 a 3, caracterizada además porque comprende (F) auxiliares y aditivos usuales.
5.- La formulación líquida de conformidad con una o más de las reivindicaciones 1 a 4, caracterizada además porque comprende una cantidad herbicidamente efectiva de una o más sulfonilureas (A) y una cantidad antídoto efectiva de uno o más protectores (B).
6.- Un método para controlar plantas dañinas en cosechas vegetales, el cual comprende aplicar los componentes de la formulación líquida de conformidad con una o más de las reivindicaciones 1 a 6 conjuntamente o separadamente a las plantas dañinas, cosechas vegetales, semillas vegetales o al área en la cual crecen las plantas.
7.- El método de conformidad con la reivindicación 6, caracterizado además porque las plantas de cosecha son a partir del grupo que consiste de maíz, trigo, centeno, cebada, avena, arroz, sorgo, algodón y frijoles de soya.
8.- El método de conformidad con la reivindicación 6 ó 7, caracterizado además porque las plantas vegetales son trangénicas o tolerantes adecuadas para cruza selectiva.
9.- El uso de una formulación líquida de conformidad con una o más de las reivindicaciones 1 a 5 para controlar plantas dañinas en cosechas vegetales.
10.- Un procedimiento para la preparación de una formulación líquida de conformidad con una o más de las reivindicaciones 1 a 5, dicho procedimiento comprende la mezcla de los componentes.
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